BRITISH CHEMICAL ABSTRACTS
A.-PURE CHEMISTRY
FEBRUARY, 1935.
General, Physical, and Inorganic Chemistry. Excitation of Balmer series by electrodeless Heat of dissociation of hydrogen molecule discharge. H. N a g a o k a , Y. S u g iu r a , and T. deduced from a new ultra-violet resonance band Mish im a (Proc. Imp. Acad. Tokyo, 1934, 10, 450— sequence. Heats of dissociation of HH2, Hi;, and 451).—Dry II2 was circulated at low pressure through HC1. H. B e u t l e r (Z. physikal. Chem., 1934, B, atube 10 cm. diam., surrounded bya coil of thick wire. 27, 287— 302).—Discharge through A containing Discharges from a 125-kv. transformer of frequency traces of H2 reveals lines due to H2 which constitute C X 106 cycles per sec. were passed between Zn balls. aresonance-band system leading from 2pa1SJ, v' — 10, C. W. G. K' = 2-— ^lsaiS+.v" = 1 -1 4 , 11" = 1 and 3. Excit Influence of the Stark effect on the fine struc ation i3 effected by absorption of the A line 1066-4 A. ture of the Balmer lines of hydrogen. N. P. by mols. at the level«" = 2, K" = 1. The extension He y d e n b u r g (Physical Rev., 1934, [ii], 46, 1069— of the scries of vibrations v" by v" = 13 and 14 shows 1075).—The possibility of small electric fields, present the no. of v" vibrational levels to be finite and permits in a discharge tube, accounting for the discrepancies a more exact extrapolation giving heat of dissociation between observed and calc, doublet splitting of the of H2, 102-68 ± 0-12kg.-cal. Thevals. 103-50 ± 0-12, Balmer lines is investigated. Doppler curves are 104-48 i 0-12, and 101-63 ± 0-22 kg.-cal. are calc, plotted for each component and superimposed. For for the heats of dissociation of HH2, H2, and HC1, the Hg line, fields > 100 volts per cm. do not explain respectively. R. C. Houston’s results (cf. A., 1934, 467). A field of 500 Fine structure of H2a. F. H. Sp e d d i n g , C. D. volts per cm. agrees with Gibbs’ results (cf. ibid., 575) S h a n e , and N. S. G r a c e (Physical Rev., 1933, [ii], for H„, but not for H^. N. M . B . 44, 58).— Spectroscopic measurements of H20 con Spectrum of the hydrogen molecule. I. The 3, taining 50% HiO show that H1« and H2a are widely 4§?S,n, A— >- 2p3n, and 3s3E— 2p3II systems. separated, each showing its own system of interference 0. W. R ic h a r d s o n and T. B. R y m e r (Proc. Roy. fringes. Preliminary vals. for e/m are < 1-758 X 107 Soc., 1934, A , 147, 24— 47).— Several new bands e.m.u. L. S. T. and a new band system ending on the lowest triplet Spectrum of deuterium ? F. S a n f o r d (Science, state are described. These include : (1) the 1934, 80, 478). L. S. T. 4d3Att— >-2y3n system; (2) the substitution of new Influence of the polarisation of the inner o' ■= 2 and 3 levels for those given by Richardson and electron in the field of the outer [electron] on the Davidson (A., 1933,1219); (3) the non-diagonal lines spectral terms of a two-electron system (especi of 4
Wave-lengths, term vals., and the series limit are 176).—The absorption spectrum and pleochroism calc. The ionisation potential of Be in is 153-012 of rhombic S between 4000 and 5800 Ä. have been volts. L. S. T. observed for 4 directions of the electric vector of the incident light relative to the crystal axes. The Ionisation potential of Be ill. B. E d l e n differences of the fractional transmissions for (Physical Rev., 1933, [ii], 4 4 , 778).—New investig ations confirm the author’s previous val. (A., 1931,539) the various directions are relatively small, despite the for the series limit, which is Is2 1S0 = 1,241,180 cm.4 marked anisotropic structure of the crystals, but the (see above). L. S. T. change in the long wave-length limit of the ultra violet absorption exhibits marked variations. Magnetic dipole radiation and the atmo H. F. G. spheric absorption bands of oxygen. J. H. Structure of discontinuities in the absorption V a n V l e c k (Astrophys. J., 1934, 8 0 , 161— 170).— of some gases in the region 1 0 —1 0 0 Ä . J. A. The atm. bands of 0 2 are best interpreted as magnetic P r in s (Physica, 1934, 1, 1174—1180; cf. A., 1934, dipole radiation rather than as ordinary dipole or 712).—Measurements for A, CC14, and N2 are recorded quadrupole radiation. L. S. T. and discussed. H. J. E. Regularities in the radiation emitted by the Hyperfine structure of spectrum lines of man positive column in the neon discharge. H. ganese arc in vacuum. I. W. M o h a m m a d and K r e f f t and E. 0. Se it z (Physikal. Z., 1934, 35, P. N. Sh a r m a (Phil. M ag., 1934, [ v i i ] , 1 8 , 1144— 1149; 9S0—983).—The spectral energy distribution of the cf. White, A., 1930, 970).— Structure data for 20 lines red Ne lines in the positive column is characteristic in the visible region are reported. N. M. B. and easily reproducible, but the abs. efficiency depends on experimental conditions. A. J. M. Persistence of some lines due to impurities in iron. R. B r e c k p o t and A. M e v is (Ami. Soc. Sei. Widening and displacement of absorption Bruxelles, 1934,5 4 , B, 290—298).— In connexion with lines. C. F u c h t b a u e r [with P. S c h u l z , A. F. quant, spectral analysis, the spectra obtained when B r a n d t , and F . G o ssler ] (Physikal. Z., 1934, 3 5 , known amounts of impurities (Cu, B a , Pb, Bi, Sn, Sb) 975—977).—The displacement of the absorption line in an Fe base are used in the method (A., 1934, 857, of the principal series of K, Na, and Cs up to the 23rd 858> are examined. A. J. M. and 26th members by the addition of He, Ne, and A was investigated. The curves for He and Ne show Hyperfine structure of the arc lines of molyb max. in the violet, whilst A produces only red dis denum and copper. L. Si b a i y a (Proc. Indian placement. The limiting vals. are the same for Na Acad. Sei., 1934,1, A , 321— 324).—Lines arising from and K. The effective cross-section of He for very slow transitions to the ground state in the arc spectra of electrons obtained from the above data is 15-5 cm.2 Cu and Mo in a Schüler tube are self-reversed, but give per cm.3 The effect of A and He on the width of the correct vals. for the hyperfine structure components. higher series lines of Na was investigated. The width Cu63 and Cu65 each have a nuclear spin of 3/2, and the attains a max at about Is — 6p. A. J. M. m2D terms show positive isotope shift. The Mo lines 4fZ54s7$3 — H1P2.za and 4rf54s7/S3 — z7P%34 are all Isotope effect in the spectrum of neon. II. singlets, whereas a nuclear moment of i for Mo9| H. N a g a o k a and T. M ish ima (Sei. Papers Inst. Phys. and Mo97 demands at least two satellites. It is Chem. R es. Tokyo, 1934, 25, 223—231; cf. A., 1930, concluded that the interval factors are negligibly 1337).—The relative intensities of the lines of N e 20 small. J. W. S. and N e 22 arc not in the ratio of the relative amounts present. The isotope effect (Sv/v) is 47-2 X 10~7 for Standard wave-lengths in the copper spectrum l5a — 2pn terms and is almost const, at 34-8 X 10~7 in the region 8 0 — 6 5 0 Ä . F. S. C o o p e r and P.’ G. for ls3„j,5 — 2ph terms. The relative intensities of K r u g e r (Physical Rev., 1933, [ii], 4 4 , 324).— Several some lines, especially the 5852 A. (ls2 — 2p^) line, hundred lines in the spectrum of Cu vi, vn, vm, vary with changes in frequency of excitation between and ix have been photographed, and standard wave 50 and 107 cycles. Lines of the N e isotopes form good lengths calc. The spectra of Co, Ni, Cu, and Zn have wave-length standards if the difficulty of self-reversal also been photographed in this region, and a partial is overcome. J. W. S. analysis has been made. L. S. T. Effect of pressure on the higher terms of the Absorption spectrum of arsenic. G . E..G ibson alkalis. E. A m a l d i and E. SEGRi: (Nuovo Cim., and A. M a c f a r l a n e (Physical Rev., 1934, [ii], 46, 1934, 11, 145—156; Chem. Zentr., 1934, ii, 724).— 1059— 1068; cf. Swings, A., 1933, 823).—Data and Data for the displacement of the higher terms in the vibrational analyses for 80 band heads in the range Na and K absorption series, due to addition of H2, N2, 2200—2750 A., when ultra-violet light is absorbed by He, and A, are recorded and discussed. H. J. E. As vapour heated to 1100°, are given. N. M . B.
Pressure displacement of the higher lines of Arc spectrum of selenium. J. E. R u e d y and spectral series. E. F e r m i (Nuovo Cim., 1934, 11, R.C. G ib b s (Physical Rev., 1934, [ii],46,880— 888).— 157— 166; Chem. Zentr., 1934, ii, 724).—A theoretical Measurements for 510 lines in the range 300— discussion of Amaldi and Segrfe’s results (see above). 11,000 Ä. of the arc spectrum of Se excited by a H. J. E. positive column discharge in He, and classifications Absorption spectrum of rhombic sulphur in for 391 of these lines, are tabulated. All known Sei polarised light. H. G. S m it h and R. H. Cr a d d o c k terms and numerical vals. and perturbations are (Trans. Roy. S o c. Canada, 1934, [iii], 28, III, 173— listed. N. M. B. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 137
Arc spectrum of selenium. K. R. R a o and Structure of spectra of hafnium and tungsten. S. G. K rishnamurty (Current Sei., 1934, 3, 200).— A. T. W il l ia m s (Compt. rend., 1934, 199, 1201— Four of the levels of Se I previously reported (A., 1934, 1202).—Data are classified. H. J. E. 935) are now definitely assigned. L. S. T. Second spectrum of hafnium (Hf II). W. F. M e g g e r s and B. F. S c r ib n e r (J. Res. Nat. Bur. Resonance series in selenium vapour. I. S. Stand., 1934, 13, 625— 6 5 7 ).— Data for > 1000 lines Pasierbi&ski (Acta phys. polon., 1932,1, 503— 511 ; and Zeeman data for 207 lines are tabulated and Chem. Zentr., 1934, ii, 199).—Three new resonance classified. The ionisation potential of Hf is 14-8 volts. series are recorded. H. J. E. H. J. E. Spectrum of niobium IV . R . J. L a n g (Physical Hyperfine structure and nuclear spin of tant Rev., 1933, [ii], 44, 325).—The spectrum of Nb has alum. N. S. G r a c e and E. M cM il l a n (Physical been photographed from 2500 to 250 Â. in the vac. Rev., 1933, [ii], 44, 325, 949— 950).— Most of the Ta spark and from 2500 to 1250 Â. in the spark in N2. arc lines have structure. The structures of the lines, The lines of Nb m and Nb iv have been separated, especially of 5997-24 and 6020-69 A., show that the and further terms for Nb rv located. L . S. T. nuclear moment of Ta is 7 /2 . L. S. T. Hyperfine structure and nuclear moment of Hyperfine structure and nuclear moment of gold. J . W u l f f (Physical Rev., 1933, [ii], 4 4 , niobium. N. S. G r a c e and S. S. B a l l a r d (Physical 512).—Many of the lines in the spectra of Au i and Rev., 1933, [ii], 44, 128).—The hyperfine structure of Au n show four components. The levels involved the lines 4059,4675,5344, and 4672 Â. in the spectrum can be relegated to a hyperfine term system if a of Nb i indicates a nuclear moment ^ 7 /2 for Nb. nuclear moment of 3 /2 be assumed (cf. A., 1931,1103). L. S. T. The interval rule is better satisfied in a no. of levels for Nuclear spin of iodine. S. T o l a n s k y (Nature, a val. of 5 /2 , but from the nature of the coupling 1934, 134, 851— 852).—The greater detail given by involved this val. is unlikely. The splitting of the the arc and spark spectra of I excited in a cooled resonance lines agrees with previous results. hollow cathode discharge establishes the nuclear spin L. S. T. as 5/2 (cf. A .,1932, 787). L. S. T. High series terms in the arc spectrum of mercury. I. W a l e r s t e in (Physical Rev., 1934, Absorption of light in gases. R. W. D it c h - [ii], 46, 874— 879).—Wave-lengths, wave-nos., and burn and H. J. J. B r a d d i c k (Nature, 1934, 134, term vals. are tabulated for the higher members in the 935).—Addition of He reduces the absorption of light singlet and triplet diffuse and sharp series in the by Cs vapour. In general, the absorption of a gas spectrum of luminous Hg vapour drawn into a low- cannot be assumed oc the concn. of the active atom or pressure chamber. The 3SV 1SQ, 1D, and 3D terms mol. (cf. this vol., 138). Many photochemical and develop as series following a Ritz formula. astrophysical calculations may thus need revision. N. M. B. L. S. T. Paschen-Back effect. II. JJ-coupling (ap Series of cæsium atoms in an electric field prox.). J. B. G r e e n and R. A. L o r in g (Physical N T. ZÉ and C. S. Piaw (Nature, 1934,134, 1010). Rev., 1934, [ii], 46, 888— 8 9 3 ; cf. A., 1934, 467).— —The effect of an electric field on the absorption The Paschcn-Back effect of the XX 5789— 5790, 3662— spectrum of Cs is described. L. S. T. 3663, 3131— 3132, and 2967-—2968 Hg lines was in Hyperfine structure of the rare earths. N. S. good agreement with Houston’s theory. The red Grace (Physical Rev., 1933, [ii] 44, 603).—A dis shift of the central component of X 5790 at several cussion of King’s results (A., 1931,7, 780 ; 1932,440). field strengths approx. oc (field strength)2, g-vals. are L. S. T. calc, from Zeeman effect measurements of several Arc spectrum of europium. H. N. R ussell other Hg lines. N. M. B. and A. S. King (Physical Rev., 1934, [ii], 46, 1023— Role of absorption of the exciting line in 1024).—Term vais, and lines, intensities, and temp, resonance spectra. W . K e s s e l (Acta phys. polon., classifications are tabulated. The principal ionisation 1933, 2, 91— 9 5 ; Chem. Zentr., 1934, ii, 198).— The potential is 5-64 volts. N. M. B. contribution of the various components of the green Hg line to the excitation of the resonance series of I Nuclear moment of thulium (Tu169), y ttriu m and Te vapour has been examined. H. J. E. (Y89), and rhodium (Rh103). H. S c h ü l e r and Second-order Zeeman effect in the arc spec T. S chm idt (Naturwiss., 1934, 22, 838—839).— Hyperfine structure investigations of the spectrum of trum of mercury. J. B. G r e e n and R. A. L o r in g lu in the wave-length range 6500— 4000 Â. indicate (Physical Rev., 1933, [ii], 44, 325). L . S. T. that the splitting is considerably smaller than in the Physical properties of the radiation from the case of other rare-earth elements of odd at. no., the discharge in mercury vapour. H. R r e f f t greatest val. being 55 x 10~3 cm.*1 Many lines (Physikal. Z., 1 9 3 4 ,35, 978— 980).—The abs. radiation consist of two equally strong components. The efficiency of 29 series lines in the Hg discharge was nuclear moment of Tu is J. It is probable that Tu has determined for definite current strengths, the pressure & ' ery small nuclear magnetic moment (I). Within the of the Hg vapour being varied continuously between same wave-length range the spectra of Y and Rh show 0-01 and 1000 mm. The radiation emission is a o trace of a structure. These elements must have reproducible property of the Hg discharge with respect a very small (I). A. J. M. to spectral energy distribution and abs. efficiency. 138 BRITISH CHEMICAL ABSTRACTS.— A.
Tlie behaviour of the continuous background with enhanced. The last two may be identical with the regard to changes of v.p. and current strength was Rayleigh bands X 1 and X , of the night sky, and investigated. A. J. M. possibly of the aurora. L. S. T. Re-emission in the fluorescence bands of Spectra and latent energy in flame gases. mercury vapour. (Miss) A. F a t e r s o n (Bull. A. E g e r t o n and A. R. U b b e l o h d e (Nature, 1934, Acad. Polonaise, 1934. A, 239—241).—Hg vapour at 134', S4S).—The luminosity or afterglow of flame gases 450° and 100 nun., excited by Zn and Cd sparks, is probably due to metastable mols., but the energy shows re-emission of the 2139, 2100, and 2164 A. Zn associated with them is probably < that ascribed to lines and of the 2144 A. Cd line, all in the region of them by David (A., 1934, 128S). L. S. T. intense mol. absorption. The re-emission varies in Spectra and latent energy in flame gases. intensity with pressure in the same way as the W. T. D a v id (Nature, 1934, 134, 848).—A reply (see fluorescence bands. The phenomenon is not due to above). L. S. T. anomalous at. diffusion because the separation of re- emitted and resonance lines is too great (200 A.). Sparking potentials at low pressures. S. S. J. W. S. C e r w in (Physical Rev., 1934, [ii], 46, 1054—1056).— Effect of hydrogen on the afterglow in mercury Sparking potentials were determined as a function of vapour. M. M. MaHK and W. M. Nielses (Physical air pressure in the range 1—0-06 mm. for spark lengths Rev., 1934, [ii], 46, 991—994).—With no potential 2— 10 mm. between outgassed Ni electrodes in air, applied to a grid in the luminous Hg vapour stream, and gave vals. up to 80,000 volts, agreeing approx. the introduction of H2 at a pressure > 4 x 10*4 mm. with Paschen’s law. N. M. B. slightly decreased the intensity of the afterglow; at Classical analogue of electron spin. W . W es- lugher pressures the lines increase in density. With s e l (Z. Physik, 1934, 92, 407—424). A. B. D. C. grid potentials of 3-5— 4 volts, H2 at a pressure > 4 x 10-4 mm. markedly decreased the intensity of the Origin of Ita satellites. E. H . K e n n a r d and afterglow. N. M. B. E. R a jib e r g (Physical Rev., 1934, [ii], 46, 1040— 1046).—Proposed explanations and conditions affect Influence of nitrogen and carbon dioxide on ing these are examined for various elements. the absorption spectrum of mercury vapour. N. M. B. R. W . W ood and H. W . St r a u b (Physical Rev., 1933, Structure of the Ii line of beryllium and con [ii . 44, 1030).—The absorption spectra of Hg vapour ductivity electrons. A. H a u t o t (Compt. rend., with added gases has been investigated at 170—370°. 1934, 199, 1399—1401).—The width and intensity' of A broad absorption band appears on the short-wave the K line of Be can be interpreted satisfactorily on side of the resonance line 2536 A. when CO., or N„ is the hypothesis of free electrons. J. W. S. added. L" S. T“ Self-consistent field and some X-ray terms of Isotope shift of thallium. G. B r e it (Physical the sodium atom. E. H . K e n n a r d and E. B am R e v ., 1933, [ii], 44, 41S— 119).— Shifts are appreci b e r g (Physical Rev., 1934, [ii], 46, 1034— 1040).- able only for 6pV2 and 6pa,2 and are nearly the same Self-consistent field functions are tabulated for neutral for these two terms (cf. A., 1933, 2, 760). L. S. T. Na and for six internally ionised states. The corre Forbidden lines in the arc spectrum of lead. sponding calc. at. energies lead to agreement within H. N iewodkiczanski (Physical Rev., 1933, [ii], 44, 0-1% for the observed and calc, frequency of Na Kz. S54).—The forbidden lines 4618-0, 5312-7, 4659-4, and N. M. B. 7330 A. have been observed when undamped high- Direct and fluorescence excitation of the K frequency discharges are excited in rarefied Pb vapour level in thick copper targets. K . B. St o d d a r d + He or A. L. S. T. (Physical Rev., 1934, [ii], 46, 837— S42; cf. A., 1933, 657). N. M. B. Specific isotope effect in the lead spectrum. B. H. D ic k in so n (Physical Rev., 1933, [ii], 44, 329).— Depth distribution of origins of characteristic The sp. isotope effect for the separation of Pb206 and X-rays from thick targets. P. K ir k p a t r ic k and Pb20S levels in four different configurations of the Pb D. G. H a r e (Physical Rev., 1934, [ii], 46, 831—S36). atom has been calc. L. S. T. N. M. B. Widths of the L series lines and of the energy Spectrum and ionisation potential of radium. levels of A u (79). F. K. Richtm yer, S. W. Barnes, H. N. R u sse ll (Physical R e v ., 1934, [ii], 46, 9S9— and E. Ramberq (Physical Rev,, 1934, [ii], 46, 843— 990).—Term vals. an d designations confirm a new 860).—An expression is found, based on the Weisskopf- interpretation of the connexion between the two groups Wigner theory of the shape of spectral lines, for the of terms in Ra I (cf. Rasmussen, A., 1934, 340). The shape of an X-ray absorption discontinuity. Data first ionisation potential is 5-252 volts. N. M. B. are given, in the range 7-6— 20-8 volts, on the widths Bands at 4450 and 4180 A. in the spectra of the of 23 Au L series lines; from these the widths of the night sky and of the aurora. H . H a m a d a (Nature, several L, M, N, and 0 states of Au are calc. 1934, 134, Sol).— In addition to well-known bands, N. M. B. the spectrum of N2 excited by weak currents at low Probabilities of L ionisations of Au by cathode pressure has bands at 4728-5 (weakest), 4432-3, and rays. D. L. W e b s t e r . L. T. P o c k m a n , and P- 4165-9 A., each with apparently four intensity max. K ir k p a t r ic k . (Physical Rev., 1933, [ii], 44, 130— Addition of H e or Ne has no effect, but A almost 131).—Probabilities of ionisation of L%, and ¿21 quenches the bands. At low temp, their intensity is electrons have been measured as functions of cathode- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 139
ray energy by intensities of the La. and L$x lines from high energy. G. W a t a g h in (Z. Physik, 1934, 9 2 , Auleaf. L. S. T. 547—560). A. B. D. C. Secondary structure of X-ray absorption edges Elastic electron scattering in potassium. J. H. from elements in certain cubic crystals. G. P. M cM i l l e n (Physical Rev., 1934, [ii], 46, 983—988).— Brewington (Physical Rev., 1934, [ii], 4 6 , 861— An improved method of measuring slow electron 864).—The K X-ray absorption spectra of K, Cl, Ca, scattering in vapours was applied to obtain angular and S were photographed, using KF, KC1, KBr, K I, distribution curves from 25° to 160° for 5- to 150-volt LiCl, NaCI, RbCl, and CaS. Separation data for electrons elastically scattered by K atoms. Character secondary structure on the short wave-length side of istic shifting max. and min., similar to those of A for the K edge of each element are tabulated. energies > 50 volts, were obtained. N. M . B. N. M. B. Sensitivity of light counters. M. W K a r e v and X-Ray absorption coefficient of xenon. T. N. S. F. R o d io n o v (Z. Physik, 1934, 9 2 , 615—621).— W hite (Physical Rev., 1934, [ii], 4 6 , 865—867).— Spectral electron emission efficiency of light counters Mass-absorption coeSs. for the range 0-18—1-5 A. are registering single electrons was determined for Al, tabulated and plotted, and an equation is deduced. and compared with photo-current efficiency. N. M. B. A. B. D. C. A'-Ray levels and atom ic constants. H. R. Experiments with positrons. E. R u p p (Phys R o bin so n (Phil. Mag., 1934, [vii], 18, 1086—1099; ikal. Z., 1934,35,999— 1003).—A satisfactory artificial cf. A., 1934, 1149).—Energy data for photo-electrons source of positrons (I) is described. A thin layer of Li characteristic of various X-ray levels of Au, Pt, W, on Al foil is bombarded with fast protons. Photo Sn, Ag, and Cu are tabulated from magnetic spectro graphs of the tracks of the rays were obtained by means meter measurements, using Cuifa and Cr Ka radi of the cloud chamber method. The majority of (I) ations in turn. Comparisons with X-ray data and had velocities between 800 and 1000 kv. An appara relations with at. consts. are discussed. N. M. B. tus for the determination of 'e/m for (I) is described. Ionised gases. T. V. I onescu (J. Phys. Radium, The ratio of e/ra for (I) to that for electrons (II), both 1934, [vii], 5, 578—584).—Mathematical. A study of of 800 kv. velocity, is 0-95 ± 0’05. A slight modific self-induction and capacity is applied to the investig ation of the e/m apparatus serves to separate (I) from ation of the characteristic frequency of ionised gases, (II) of equal energy. Diffraction experiments with the action of positive grid gas-filled lamps, and the (I) at Al and Au foils gave only a continuous scattering. propagation of energy in tubes of ionised gas. The proportion of elastically to inelastically scattered 3ST. M. B. particles is much smaller in the case of (I) than (II) Measurement of shot voltage used to deduce of the same velocity. The absorption cocffs, of (I) the magnitude of secondary thermionic emis and (II) of 800 kv. velocity were obtained for Al, Cu, sion. E. B. Moullin (Proc. Roy. Soc., 1934, A, and Au. The absorption of (I) cc mass, to a first 147, 100—118).—The theory of shot effect is re approximation. The velocity loss in Al was deter newed, and the experimental method is described and mined for various velocities. (I) give, with all sub illustrated by measurements of the electron charge, stances investigated, almost pure monochromatic in conditions where secondary emission is absent, both X-rays with absorption coeffs. 0-18 ± 0-08 cm.-1, one in the presence and absence of space charge. absorbed (I) giving 1-8—2-2 X-ray quanta. (I) give L. L. B. 35—50 times more X-ray quanta than the same no. of Direction of polarisation and selectivity of (II). A. J. M. external photo-electric effect of metals. F. Artificially excited positrons. E. R u p p (Z. HluCka (Z. Physik, 1934, 92, 359—366).—Normal Physik, 1934, 9 2 , 485—512).—Positrons were emitted and tangential light components have sensitivity max. by Li, less by Mg and Be, and not at all by Cu, Hg, at different wave-lengths for the metals Ag, Au, Pt, and Au, on bombardment by fast protons; an Al-N Cu, and Zn. The absence of parallel component layer on Al is a particularly good emitter. Absorption nias. for alkali metals is due to their optical properties. measurements are given for positrons. For each A. B. D. C. positron absorbed two quanta of X-rays are emitted. Velocity distribution of photo-electrons in thin elm for positrons is 0-95 ± 0-05 that for electrons. metal foils. E. Vasser (Physikal. Z. Sovietunion, A. B. D. C. 1934, 5, 645—658).—The proportion of high velocities Production of the positive electron. J. R. increases with increase in time under vac. With O p p e n h e im e r and M. S. P l e s s e t (Physical Rev., change of thickness a Fermi distribution is obtained. 1933, [ii], 44,53—55; cf. A., 1934, 468).—Theoretical. C h . A b s . (e) L. S. T. Electron-optical images with photo-electric- Recombination of electrons and positrons. ally liberated electron s. J. P o h l (Physikal. Z., E. F e r m i and G. E. U h l e n b e c k (Physical Rev., 1933, 1934, 35, 1003—1005).—An apparatus for obtaining [ii], 44, 510—511).—Theoretical. The explanation of images of photo-cathodes with the electrons liberated the hard component observed by Gray and Tarrant from them is described. The method was applied to (A., 1932, 791) as due to the destruction of positrons It.to discover the effect of absorption of gas, and cannot easily be reconciled with the Dirac theory. crj'stal structure, on the geometrical distribution of L. S. T. ‘ight and thermo-electric emission. A. J. M. Dirac’s theory of the positron. W . H e is e n Relativistic quantum electro-dynamics and b e r g (Z. Physik, 1934, 9 2 , 692).—A correction (cf. radiation emission on collision of electrons of A., 1934, 1150). A. B. D. C. 140 BRITISH CHEMICAL ABSTRACTS.— A.
Formation of negative ions in gases by elec homogeneous crystals;, their thermionic properties tron attachment. I. NH3, CO, NO, HC1, and are much superior to those of the above mixture. Cl2. N. E. B r a d b u r y . II. C02, N20, S02, The nature of the lattice changes accompanying H,;s, and H„0. N. B. B r a d b u r y and H. E. T a t e l emission of positive ions has been determined by (L Chem. Physics, 1934, 2, 827—834, 835— 839). X-ray analysis. L. S. T. —I. The gases were ionised by a stream of electrons from a photo-electric source, accelcrated by X volts Production of intense beams of positive ions. per cm., in an apparatus previously described (A., R. D. F o w l e r and G. E. G ib s o n (Physical Rev., 1934, 126), and the probability h of capture of an 1934, [ii], 4-6, 1075—1086).—Theory of excitation and electron by a mol. of gas at pressure p mm. was apparatus for the production of beams of several determined. X/p was plotted against h. In NH3 milliamps. of ions from H2, He, N2, and C02 from negative ions are formed for X/p > 7-5. It is the low-voltage arc arc described. Data on the assumed that the gas dissociates first to NH and H2 influence of gas pressure and c.d. in the arc, and of and NH then combines with an electron. CO does extractor voltage on the density of the beams, are not form negative ions and has, therefore, no electron given. Electrostatic divergence and magnetic con affinity. NO forms negative ions by direct electron vergence and magnetic analyses of the beams are attachment, h increasing with decrease in X/p. discussed. Beams from H2 consist of HJ, H3l„ There is also a linear variation of h with p which is H3t2, H i, H „t1; and H+, depending on pressure. explained by collision of an electron with a lightly N. M. B. bound polymeride N202. NO~ is formed and the At. wt. of tantalum. 0. H o n ig s c h m id and R. remaining NO mol. carries off the excess energy. Sc h l e e (Z. anorg. Chem., 1934, 2 2 1 , 129— 141).—The Negative ions are formed in HC1 and Cl, h increases mean of 14 determinations of the Br content of with X\p, indicating that dissociation of the mol. TaBr5 by nephelometric titration with AgN03 gives probably occurs, due to the excess energy produced Ta 180-88+0-01, in agreement with Aston’s val. in the electron attachment process. Of the possible F. L. U. methods of dissipation of the excess energy in electron At. wt. of radium. 0. H o n ig s c h m id and R. attachment, that most generally occurring appears to S a c iit l e b e n (Z. anorg. Chem., 1934, 2 2 1 , 65—S2), be the removal of the energy by a third body involved —The at. wt. of Ra has been determined from the in the process. ratio RaBr2 : RaCl2 using a comparatively large II. No negative ions are formed in C02. In N20 quantity of highly purified RaBr2. The mean of they are formed when X/p is > 2, with probable 8 determinations gave Ra=226-05 (Cl=35-457, dissociation, N20 + e — > N2+ 0 _ . In S02 attach Br=79-916). The pure RaCl2 was afterwards used for ment definitely occurs for electrons of low energy, the prep, of standards. M. S. B. and increases rapidly as the energy of the electrons Masses of the lithium isotopes. K . T. B a in - decreases, indicating a true electron affinity and a b r id g e (Physical Rev., 1933, [ii], 4 4 , 56— 57).—The radiation process for the dissipation of energy. As mass of Li® referred to O16, measured from five spectra X/p increases h decreases to a min. and then increases, by comparison with H2 by the doublet method, is due to dissociation and formation of SO- . H2S 6-0145+0-0003; that of Li7 is 7-0146+0-0006. The probably forms HS- for X/p > 6 and H20 gives mass ratio of the Li isotopes obtained does not agree HO- for X/p > 10. Negative ion formation in with the val. from band spectrum analysis (A., 1933, H20 is also observed at low X/p for sufficiently high 994), but agrees with that obtained from earlier mass- vals. of p. This may be due to the formation of spectrograph measurements (A., 1925, ii, 1021). negative ions from small mol. aggregates existing L. S. T. near the point of condensation of H20. M. S. B. Redetermination of the mass ratio of the Intensities of molecular rays diffracted by lithium isotopes from the band spectrum. rigid crystal surfaces. W. L e n z (Z. Physik, 1934, F. A. J e n k in s and A. M cK e l l a r (Physical Rev., 9 2 , 631—639).—Tho geometric-optical and Huygen’s 1933, [ii], 4 4 , 325—326).—From new spectrograms methods are applied to diffraction by an ideal rigid of the 1II -<— bands of Li2, accurate wave-length periodic surface. A. B. D. C. data for the (0,0), (0,1), and (0,2) bands from both Geometric-optical and wave-theoretical the isotopic mols. Li7Li7 and Li°Li7 have been methods of calculating intensities of diffraction obtained. The mass ratio Li7/Li6 is 1-1690+0-0003, of molecular rays by rigid crystal surfaces. E. which is > previous vals. Using 7-015 as the mass B r a n d t (Z. Physik, 1934, 9 2 , 640—660; cf. pre of Li7, this gives 6-001 for Li®. L. S. T. ceding abstract).—The wave method is applied, and Relative abundance of the isotopes of lithium, practical approximations are given for the two potassium, and rubidium. A. K . B r e w e r and methods. A. B . D. C. P. D. K u e c k (Physical Rev., 1934, [ii], 4 6 , 894—897). Sources of positive ions. Thermionic proper From mass-spectrograph measurements, using arti ties of the system Li20-A l20 3-S i0 2. E . J . J o n e s ficial A1 silicates of Li, K , and Rb as a source of ions, and S. B. H e n d r ic k s "(Physical Rev." 1933, [ii], 4 4 , the abundance ratio, mass ratio, m of the two isotopes, 322).—The mixture 3Li20+ A l203+3S i02 gives const, and packing fractions p are : Li7/L i«= 12-14+0-4, emission of large currents (4 x 10“4 amp. per sq. cm.) w=7-016+0-002 and 6-016+0-002, «=23+3 and for 40 hr. A similar mixture containing K is a satis 26+3; K39/K41= 13-88+0-4, m=38-96+0-003 and factory source of K" ions. The various compounds 40-96+0-003, ^=-9-85+0-9 and -9-37+0-9; of Li20, Si02, and A1203 have been prepared as Rb85/Rb87=2-59+0-04, wi=84-8S and 86-88, p = GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 141
— 14-li0-7 and —13-8±0-7. Vais, for Rb diverge for air, He, Ne, A, Xe, and Kr. Velocities corre from those due to Aston. N. M. B. sponding with max. ionisation are calc. N. M. B. Isotopic constitution of lithium in the sun. Disintegration of beryllium by y-rays. W. E. McM il l a n (Physical Rev., 1933, [ii], 44, 240). G e n t n e r (Compt. rend., 1934, 199, 1211— 1213). —Microphotometric measurements of the Li line of —Szilard and Chalmers’ result (cf. A., 1934, 1152) the sun-spot spectrum show that the whole line was confirmed using a mesothorium source. The 6707-8 A. can be accounted for by Li7 alone. The optimum y-ray energy was 0-9 X 10® e.v. The calc, presence of Li® cannot definitely be confirmed, but if mass of Be9 was 9-013. H. J. E. present its relative abundance is not much > on y-Rays accompanying artificial nuclear dis earth. L. S. T. integrations. E. M cM i l l a n (Physical Rev., 1934, Relative abundances of elements of even and [ii], 46, 868— 873).— The excitation function and odd mass number and atomic number. T. E. absorption of y-rays from the bombardment of F, Sterne (Physical Rev., 1933, [ii], 44, 238—239). Li, B, and Be by protons, and of y-rays and neutrons —Band spectra of homonuclear mols. indicate that from the bombardment of Be, C, Li, B, F, M g, and nuclei of even mass no. obey the Einstein-Bose A1 by deutons were investigated, as was the absorption statistics and those of odd mass no. the Fermi-Dirac of the “ annihilation radiation” accompanying the statistics. This explains the general preponderance radioactivity excited in C. N. M . B. of nuclei of even mass no. and even at. no. pointed Absorption of y-rays of radium by radioactive out by Harkins. L. S. T. salts. F. Behouneic (Z. Physik, 1934, 92, 533— Faraday effect at high frequencies. G. P. 542).—Absorption of Ra-C y-rays is given for a no. Ha r n w e l l , W. B l e a k n e y , S. N. V a n V o o r iiis , and of compounds, and the absorption eoeff. is related to the no. of electrons per c.e. A similar relation is J. B. H. K u p e r (Physical Rev., 1933, [ii], 44, 785). —Preliminary experiments show the feasibility of shown to hold for elements. A. B. D. C. investigating the Faraday effect for isotopes with y-Radiation from slow neutrons. R. F l e is c h - continuous oscillations. L. S. T. m a n n (Naturwiss., 1934, 22, S39).—The absorption of Spectro-analytical investigations. XIII. y-rays and neutrons from Be-f-Rn was investigated. On passage of the rays through paraffin, H20, or Spectrographic test of purity of the new primary substances containing HaO, the proportion of y-rays radium standard. W. G e r l a c h and (F r l .) E. was considerably increased. The intensity of the R iedl (Z. anorg. Chem., 1934, 221, 103— 108).—A y-rays at first increases rapidly with the thickness of method for the spectral analysis of very small quan paraffin traversed up to 2-5 cm., reaching saturation tities of an element is described. Using 0-61 mg. of at 6 cm. and then decreasing. The radiation from the RaCl2 prepared by Honigschmid as standard (cf. the paraffin is the same in both forward and backward this vol." 140), the Ba content was found to be 0-002—0 004 at.-%, the actual quantity detected being directions. The neutrons pass through a certain thickness of paraffin where they are rapidly retarded, 1-Ox 10"9 g. M. S. B. and combine with H1 nuclei to form H2 nuclei, with Failure to detect radioactivity in beryllium liberation of y-rays, thus accounting for the rapid with the linear amplifier. R. D. E v a n s and M. C. increase in intensity. A. J. M. Henderson (Physical Rev., 1933, [ii], 44, 59).—-The Fermi effect. M. D ą n y s z , J. R o t b l a t , L. radioactivity of Be reported by Langer and Raitt W ertenstein, and M. Ż y w (Nature, 1934, 134, (this vol., 6) could not be confirmed using a linear amplifier responsive to the a-particles emitted from 970— 971),—The intensities of the Fermi effect obtained under identical geometrical conditions when a granite containing 10~12 g. of Ra per g. of rock. screens of Pb and Au are placed between the Be-Rn The results indicate that Be is stable. L. S. T. source and Si, Al, Ag, or I, in which the effect is Failure to detect the radioactivity of beryllium cxcited, arc recorded. With Ag and I, the eSect with the Wilson cloud chamber. D. M. G a n s , increases when the screen is interposed, showing a W. D. H a r k in s , and H . W. N e w s o n (Physical Rev., transformation of the exciting rays. It is concluded 1933, [ii], 44, 310).—The radioactivity of Be recently that the capture of a neutron (I) by a heavy nucleus reported (this vol., 6) could not be confirmed (see without emission of a heavy particle takes place only above). L. S. T. when the energy of (I) is > a certain val. If the energy Energies of a-, [3-, and y-rays. H. A. W i l s o n of (I) is too high it loses in a nuclear encounter a part (Proc. R oy. Soc., 1934, A, 147, 240—250; cf. A., of its energy, which is emitted as a y-radiation. The 1934, 579).—The energies of (3-rays from elements increased effect observed with Ag and I would then with the same at. no. are approx. equal, in accordance be due to the production of slow (I) in a no. > the with theory. Pairs of (3- and y-ray energies having loss of primary slow (I) due to absorption. sums equal to multiples of 3-85 are found for several L. S. T. elements. The internal conversion coeffs. for Ra-C' Emission of a-particles from various targets y-rays are consistent with theory. L. L. B. bombarded by deutons of high speed. G. N. L e w is , M. S. L iv in g s t o n , and E. 0 . L a w r e n c e Ionisation curves of P o a-rays in rare gases. (Physical Rev., 1933, [ii], 44, 55— 56).— Using H3 R. Naidu (J. Phys. Radium, 1934, [vii], 5, 575— 577 ; containing 5 0 % H i H!H2! ions have been given cf- A., 1934, 1053).—Curves for the velocity variation energies of 2 x 1 0 ® volts. On striking a target these along trajectories and for retarding effect are given yield 6-6 x l O -5 volt-protons and 1 -3 3 X 1 0 -® volt-H2 142 BRITISH CHEMICAL ABSTRACTS.— A.
nuclei, deutons. When bombarded by theso particles Experimental proof of layers of neutrons in the N from a target of NH4N03 yields approx. 100 the nucleus. W. Y e h (Compt. rend., 1934, 199, a-particles (1) of range 6-8 cm. per 109 deutons and 1209—1211).—The reciprocal of the log. of the period the min. deuton energy for this disintegration is of radio-elements produced by neutrons plotted against 6 x 105 volts. Li from a LiF target gives a large no. the no. of protons in the nucleus shows a periodic of (I) of 8-2 cm. range probably due to the accom variation for a series of elements. The interpretation panying protons, and some of 14-5 cm. range of of nuclear structure from this observation is discussed. 12-5 X 10® volts energy. Assuming the process H. J. E. Li6+ H 2 — >- 2He4, the total energy liberated is Radioactivity induced by neutrons. W . Y e h 23-4xl06 volts. With a Be target (I) of range (Compt. rend., 1934, 199, 1404— 1406; cf. preceding 3-3 cm. are obtained and the no. of disintegrations per abstract).—When 10/log T (27=half-life period of the deuton is •< 100 times the no. per proton. The bom atoms) is plotted against the no. of protons contained barding particle probably causes disintegration of the in radioactive elements formed by the inductive unstable Be nucleus without capture. A1 and Mg action of neutrons, the curve shows max. corresponding targets, and CaF2 and NaCl give a small no. of with the end of each complete layer of neutrons in the particles. Si02, NaP03, C, CuS, Ca(C103)2, Au, Pt, nucleus, the max. decreasing with increasing no. of brass, and mica give no detectable (I). L. S. T. layers of neutrons. The val. for K accords with theory. J. W. S. Emission of protons from various targets bombarded by deutons of high speed. E. 0. Nuclear structure and artificial radioactivity. L a w r e n c e , M. S. L iv in g s t o n , and G. N. L e w is G . G u é b e n (Ann. Soc. Sci. Bruxelles, 1934, 54, B, (Physical Rev., 1933, [ii], 44, 56).—When deutons (I) 215—223).—The nuclear constitution of elements of 6 x l0 5—1-33x10® volts are directed against produced artificially which show radioactivity is different targets (see above), in addition to a-particles deduced in terms of a-particles (a), diplons (tt2), protons with ranges up to approx. 40 cm. are emitted protons (re), and neutrons (n). Those elements which in large nos. Each target, including Au and Pt which disintegrate with emission of a positive electron have are unlikely to undergo disintegration, gives protons nuclei of the form (za+rc), (a:a+-2), or (a:a+-2-f“), of approx. 18 cm. range. This group can be ex where x is an integer. Those which disintegrate with plained only by assuming that the (I) breaks up, pre emission of a negative electron have nuclear con sumably into a proton and a neutron. In all cases, stitutions of the type (æa-j-T2+zw,), z being even. The proton emission is not observed when the (I) energy fact that these particular arrangements are unstable is < 8 x l0 5. L. S. T. may be used to predict nuclear changes. A. J. M. Liberation of neutrons from beryllium by Disintegration of the elements by swiftly hard X-rays. Production of radioactive moving protons. M. S. L i v i n g s t o n , M. C. H e n elements. A. B r a s c ii, F. L a n g e , A. W a l y , d e r s o n , and E. O. L a w r e n c e (Physical Rev., 1933, T. E. B a n k s , T. A. Ch a l m e r s , L . S z il a r d , and [ii], 44, 316).—When bombarded by 6 XlO5 to F. L . H o p w o o d (Naturwiss., 1934, 22, 839, and 1-6xl06 volt-protons, all the elements investigated Nature, 1934, 134, 880).— 1*5X106-volt X-rays were give evidence of disintegration. Li yields a-particles passed on to Be, and the neutrons liberated were (I) of 8-9 and 9-1 cm. range with 6X105 and l-4 x 10° directed on to CHBr3, which was then found to have volt-protons, respectively. The process involves cap mols. containing radioactive (I) and ordinary Br. ture of the proton. Be yields 3-3 cm. (I) and a few (I) has a half-life period of G hr. Increase of voltage of ranges up to 6T cm. NaCl yields (I) of ranges on the X-ray tube caused a much more powerful up to 3-4 cm. with 1-1 x l0 G volt-protons: Al and activity; with both Br and I, activity sufficiently Mg give a few 2-7 cm. (I) and NH4N03 still fewer powerful to be indicated on an electroscope could be 2-2 cm. (I) with 7-5 x 105 volt-protons. L. S. T. obtained. A. J. M. Three types of nuclear disintegration of cal Neutrons from a beryllium-radon source. cium fluoride by bombarding protons of very L a w r e n c e J. R. D u n n in g and G. B. P e g r a m (Physical Rev., great energy. E. O. and M. S. 1933, [ii], 44, 317).—Absorption curves for C, Al, Pb, L i v in g s t o n (Physical Rev., 1933, [ii], 44, 316— Cu, and paraffin up to 21 cm. in thickness and single 317).—When bombarded by protons CaF2 yields points for other elements have been obtained. Scat a-particles (I) of 2-8 cm. range with 6— 9-5 xlO 5 tering measurements have been made for C, Al, Cu, volt-protons, 2-S cm. and 5-6 cm. (I) with 9-5x lO 5— Sn, and Pb at angles between 35° and 135°. A beam 1-35X10° volt-protons, and an additional (I) group of of neutrons is not deflected by passage through a 6-8 cm. range with 1-35— 1-60 X 106 volt-protons. The magnetic field of 104 gauss, indicating that it does not excitation threshold is sharp and the yields increase possess the properties of a free magnetic pole of any rapidly in a linear manner with an increase in proton large multiple of unit strength. L. S. T. range above the threshold val. L . S. T. Atom disintegration, atomic structure, and Interaction of neutrons and protons. I. T a m m (Nature, 1934, 134, 1010— 1011).—The emission or artificial radioactivity. H. M a r k (Oesterr. Chem.- Ztg., 1934, 37, 200—203).—A lecture. absorption of two neutrinos by the neutron or proton, although less probable than emission of a y-ray by the Artificial radioactivity and the scheme of excited proton, may possibly occur. The electric L a n d e . I- K iirtschatov (Compt. rend. Acad. Sci. charge and the spin of the heavy particle would be U.R.S.S., 1934, 4, 202—207). E. S. H. unchanged. This would not be the case when a GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 143 single neutrino is given off, as postulated by Fermi m. long and comparing band photographs of CH4, to account for the emission of ¡3-rays by some radio approx. 40 rotation-vibration bands in the spectra of active materials. L. S. T. these planets are identified as due to CH4, which Neutrons from beryllium bombarded by appears to be the major constituent of their atm. The absence of appreciable amounts of other hydro deutons. M. S. L iv in g s t o n , M. C. H e n d e r s o n , carbons is shown. N. M. B. and E. 0. L a w r e n c e (Physical Rev., 1933, [ii], 44, 782—783; cf. A., 1934, 6).—-Neutrons (I) result from Constitution of elementary particles and the disintegration of Be bombarded by deutons (II), nuclear forces. W . M. E l s a s se r (Compt. rend., apparently from the disintegration of Be9 with cap 1934, 199, 1213—1215).—Theoretical. H. J. E. ture of a (II) to form Be10 and a (I). The yield of Genesis of the elements. G. N. L e w is (Physical (I) increases linearly with the range 1— 9 cm. of (II). Rev., 1934, [ii], 46, 897—901).—It is suggested that Hence the probability that (II)-will disintegrate the a large part of the matter in the universe is com Be nucleus on collision is independent of (II) energy, posed, like the metallic meteors, chiefly of Fe and and the increase in yield with (II) range is due only Ni, and that such material, thermodynamically stable to the increased frequency of collisions. L . S. T. against spontaneous transmutations except at very Mass of the neutron. W. D. H a r k in s and D. M. high temp., is superficially attacked by cosmic radi Gans (Nature, 1934,134, 968—969).—For the present ation to produce the material represented by the it is suggested that the val. 1-006 should be used for earth’s crust and by stony meteors. This view is the mass of the neutron. A probable lower limit is supported by comparison of the relative abundance 1-0052. L . S. T. of the chief at. spccies in the two types of meteors. Passage of very fast protons through matter. The main disintegration processes undergone by the Fe and Ni nuclei are: splitting off of 0 2, splitting H. J. B h a b h a (Nature, 1934,134, 934).—-Theoretical. L. S. T. into two identical parts, and splitting of He from Investigations of ultra-radiation corpuscles. the products of the preceding processes. N. M. B. H. Ku len k am pff (Physikal. Z., 1934,35,996—997).— Jacyna’s selection theorem for helium. V. The absorption of ultra-radiation corpuscles (I) in Fe J a c y n a , S. D e r e v j a n k in , A. O b n o r s k i, and T. placed between or above two counter-tubes was P a r f e n t j e v (Z. Physik, 1934, 92, 675—679).—The investigated. The weakening of (I) on passing through selection theorem is verified for He (cf. A., 1934, an absorbent is due to gradual energy loss, absorption 1070). A. B. D. C. processes playing only a subordinate part. Wave theory of the neutrino. G. R u m e r A. J. M. (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4, 21—24). Cosmic ray nuclear disintegrations. W. F. G. A. B. D. C. Swann and C. G. M o n t g o m e r y (Physical Rev., 1933, Mass of the neutrino. T. T a k e u c h i (Proc. [ii], 44, 52— 53). L. S. T. Phys.-Math. Soc. Japan., 1934, 16, 294— 295).—The Absorption of cosmic rays by different sub mass of the neutrino differs from that of the anti stances. H. T ie l s c h (Z. Physik, 1934, 92, 589— neutrino by the mass of a photon (4x 10~04 g.). The 6H).—Absorption measurements are given for Pb, spins are -J and respectively. C h . A b s . (e) Hg,Fe,Al,H20, air, and C. A. B. D. C. Equivalence of mass and energy. K. T. Counter calibration and cosmic-ray intensity. B a in b r id g e (Physical Rev., 1933, [ii], 44, 123). J-C. Str ee t and R. H . W o o d w a r d (Physical Rev., L. S.T. 1934, [ii], 46, 1029— 1034).—Observations with a set Expression for [energy] density in terms of pf counters calibrated absolutely gives tho no. of the new theory of the photon. L . d e B r o g l ie ionising cosmic rays as 0-80±0-028 per cm.2 per min. (Compt. rend., 1934, 199, 1165—1168; cf. A., 1934, from unit solid angle at the vertical at sea level. 1054).—Theoretical. H. J. E. TheRo. of rays from all directions is l-4S±0-055 Relativistic invariant perturbation theory of cm.-2 min.-1, giving an average sp. ionisation of the Dirac electron. I. Scattered and retarded 100x3-7 ion pairs per cm. path of a ray. radiation. E . C. G. Stueckelberg (Ann Physik, N. M. B. 1934, [v], 21, 367—389). A. J. M. Distribution of cosmic ray nuclear disinte Atomic energy relations. I. R.F.B a c h e r and gration in tim e. C. G. M o n t g o m e r y and D. D. S. G o u d s m it (Physical Rev., 1934, [ii], 46, 948— JIo xtg o m e ry (Physical Rev., 1933, [ii], 44, 779).— 969).—Mathematical. Approx. energies of at. levels Experimental results support the hypothesis that the are calc, from linear relations which express the nuclear disintegrations produced by cosmic rays are unknown energy in terms of observed energy vals. randomly distributed in time. L. S. T. of the atom and its ions. Results are tabulated for Structure of ionised layer of the atmosphere. s and p electrons and are applied to the spectra of L , scu and C. Mihul (Compt. rend., 1934, 199, C, N2, and 0 2. N. M. B. 1301—1303). -T - H . j ’ E. Collision of two light quanta. G. B r e it and Constitution of the atmospheres of the giant J . A. W h e e l e r (Physical Rev., 1934, [ii], 46, 1087— P-ianets. A . A d e l and V. M, Slipher (Physical 1091).—Mathematical. The production of positron- s C\5 Pi]> 46, 902— 906).—By duplicating the electron pairs as a result of collision of two light pectra of the gaseous envelopes of Jupiter, Saturn, quanta, and the formation of photons due to recom ranus, and Neptune, using an absorption cell 22-5 bination, are examined. Results are applied to the 144 BRITISH CHEMICAL ABSTRACTS.— A. collision of high-energy photons of cosmic radiation Em ission and fluorescence spectra of sulphur with the temp, radiation of interstellar space. dioxide. H. D. Sm y t h (Physical Rev., 1933, [ii], N. M. B. 44, 690).—A comparison of the results of Chow Breakdown of the Coulomb law for the hydro (A., 1933, 1227) and Lotnmr {ibid., 886). L. S. T. gen atom. E. C. K e m b l e and R. D. P r e s e n t Molecular spectra of boron and aluminium (Physical Rev., 1933, [ii], 44, 1031—1032). halides. E. M ie s c h e r (Helv. phys. Acta, 1934, 7, L. S. T. 462— 464; Chem. Zentr., 1934, ii, 908—909).—Band Magneto-ionic theory. H. G. B o o k e r (Proc. spectrum data for BC1, BBr, A1C1, AlBr, and All Roy. Soc., 1934, A, 1 4 7 , 352—382),—Several new (in a Geissler tube) are recorded. H. J. E. features of Appleton’s magneto-ionic theory of the propagation of wireless waves in the ionosphere Band spectra of the halides of aluminium. (A., 1932, 670) appear if damping due to electronic F . H. Cr a w f o r d and C. F . F f o l l io t t (Physical Rev., collisions be taken into account, and incidence is 1933, [ii], 44,'953—954).— A1C13 gives a well-developed not necessarily vertical. L. L. B. group of red-degraded bands (approx. 75) from 2550 to 2900 A., and AlBr3 one from 3065 to 2745 A., Electronic states of the N2+ molecule and their presumably due to AlBr. A1I3 gives an intense con energies of dissociation. H. H. B r o n s (Proc. K. tinuous spectrum with a faintly-banded appearance ! Akad. Wetensch. Amsterdam, 1934, 3 7 , 793—801).— in places extending from the visible to 2300 A. Potential cnergy-distance curves have been calc, for L. S. T. the electronic states of N2+. The products of dis Spectroscopic investigation of indium halide sociation and the symmetry of the states are dis vapours and gallium halide vapours. M. cussed. R. S. B. W e h r l i and E. M ie s c h e r (Helv. phys. Acta, 1934,
Magnetic moment of the proton. A. L a n d e 7, 298—330, 331—359; Chem. Zentr., 1934, ii, (Physical Rev., 1933, [ii], 44, 1028— 1029).—The 725—727).—Data on the emission and absorption ; magnetic properties of higher nuclei indicate that the spectra of InCl, InBr, and Ini are recorded and magnetic moment, of a proton is approx. two mag classified. Three band systems were observed in j netons. This differs from Stern’s val. (A., 1933, each case. A new In isotope of mass 113 was 996) by 20%. The proton appears to circle around detected. Data for GaCl, GaBr, and Gal are also inside or on the surface of the neutron shells. recorded and classified. The bands resemble those 1 L. S. T. of In halides. H. J. E. Calculation of the perturbation of a hydrogen- Absorption spectrum of thallium fluoride oid atom by a free electron. P. B r ic o u t (Compt. vapour. Z. V. B o i t z o v a and K. V. B utkov rend., 1934, 1 9 9 , 1392— 1394).—Mathematical. (Pliysikal. Z. Sovietunion, 1934, 5 , 765— 776).—At J. W. S. low temp, a continuous absorption, attributed to Planck quanta and the atomic field of force. T12F2, was observed. A t higher temp, the spectrum M. B billotjin (Compt. rend., 1934, 199, 1345— of T1F is observed. The dissociation energy of TIP 1349).—Mathematical. J. W. S. is 106 kg.-cal. C h. A b s . (e)
Electronic at. wt. and e/m ratio. R. C. G ib b s Absorption spectra of the samarium ion in and R. C. W il l ia m s (Physical Rev., 1933, [ii], 4 4 , solids. V. Absorption spectrum and energy 1029).—The at. wt. of the electron, determined from levels of the SmH+ ion as it exists in monoclinic measurements of the interval between corresponding crystals of Sm 2(SO4)3,8H0O. F . H. S p e d d in g and components of the Hxa and H2a lines (A., 1934, R, S. B e a r (Physical Rev., 1934, [ii], 46, 975— 983; 575), is (5-491+0-002) X10-1. This gives a val. of cf. A., 1934, 1154).—Full data for the spectra at 20°, (l-757±0-001)xl07 e.m.u. per g. for e/ni for the 78°, 169°, and 298° abs., and an energy level diagram electron. L. S. T. are given. Results are similar to those for SmClg,6H20. The existence of low-lying levels separated from the Band spectra measurements of mass. A. basic level by 160, 188, and 225 cm.-1 is proved. B r a m l e y (Physical Rev., 1933, [ii], 44, 309—310).— N. M. B. A discussion. L. S. T. Transparency of the atmosphere in the ultra Chemical reactivity and absorption of light. violet and a possible means of extending the N. R. D h a r and P. N. B h a r c a v a (Nature, 1934, Solar spectrum in the regions 2200—2000 A. 1 3 4 , 84S— 849).—Absorption in the visible region for K. R. Ramanathan and L. A. R a m d a s (Proc. Indian mixtures of reacting substances, e.g. H2+C12, H2+ B r2, Acad. Sci., 1934, 1, A, 308— 314).—The absorption MeOH+Br,, and EtOH +Br2, is > that by the band of 0 3, which produces the short-wave limit of separate constituents. Increased absorption may be the solar spectrum, has relatively low intensity at a measure of the reactivity of a system, and is due 2200— 2000 A., whilst the Schumann-Runge ab to the weakening of the binding forces of the mols. sorption band system of 0 2 begins at about 2000 L. S. T. A. Hence it is calc, that, provided that the sun emits Spectrum of 0 16H2. H. L. J o h n s t o n and black-body radiation, and there is no other absorb D . H. D a w so n (Physical Rev., 1933, [ii], 44, 1031).— ing agent present in the atm., it should be possible Approx. 500 new lines (8 bands) have been identified to detect solar radiation between 2200 and 2000 A- and assigned in the spectrum of OH2 produced in at heights of < 16 km. in the tropics. J. W. S. H„0 vapour containing 35% of the H as H2. Ultra-violet absorption of methane. A. B. F- L. S. T. D u n ca n and J. P. H o w e (J. Chem. Physics, 1934, 2. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 145
851—852).—CH4 shows true continuous absorption plastid in ordinary solution. Intensities have been in the region 1450— 850 Â., and all excited states up determined in aq. colloids and paraffin-oil solutions to the first ionisation potential are repulsive. Con and measurements of diffusion in different solvents tinuous ultra-violet absorption spectra may be general have also been made. From absence of fluorescence for mois, with tetrahedral symmetry. M. S. B. in the colloidal solution, it is probable that (I) is not Absorption of ultra-violet light by some present in the colloidal state in plastid. M. S. B. organic substances. X XX V II. L . M a r c h l e w s k i Temperature classification of infra-red iron and J. Z g l e c z e w s k i. XXVIII. W. G o s l a w s k i and lines. A. S. K i n g (Astrophys. J., 1934, 80, 124— L. Ma r c h l e w s k i (Bull. Acad. Polonaise, 1934, A, 135).—The spectrum of Fe from 6400 to 10,500 Â. 256—260, 261—279).— X X X V II. o-Hydroxyearb- has been observed at temp, between 2100° and 2700° anilide and its JV-Et ether show similar absorption in the vac. furnace and in the arc, and 367 lines have curves, that for the latter being shifted slightly been classified according to temp. L . S. T. towards longer X. The 0 -Et ether shows weaker Temperature variation of infra-red absorption absorption, and a different type of absorption curve, of crystals. I. Fluorspar and calcite. F. with two max., indicating a difference in structure M a t o s si and H. B r i x . II. Sulphates and micas. from the parent compound and its iV-ether (cf. A., F. M a t o s si and H. K in d l e r (Z. Physik, 1934, 92, 1926, 9). 303—311, 312—336).—I. Transmission spectra were XXXVIII. Methyl-, ethyl-, amyl-, meta-, methyl- obtained from —168° to 300° in the near infra-red. meta-, acetyl-, and alkali-lignins all show strong Combination bands become less intense and broader absorption bands with max. at 2795-T-2835 Â. The with rising temp., due to damping effects exceeding absorption increases with increased concn. of acid excitation of the fundamental ; for calcspar this is used in prep, of lignin, the length of time of reaction, at 41-4 ¡X. and rise of temp. With the alcohol-lignins it in II. Absorption spectra are given for muscovite, creases with rise of temp, and pressure of formation. clinochlore, anhydrite, celestine, and baryta from 0 The selective absorption is unaffected by acidity, but to 20 ¡JL, and between —125° and 300°. the continuous absorption is increased considerably A. B. D. C. in alkaline solution. J. W. S. Infra-red spectrum of heavy ammonia, NH% Spectrum of acraldehyde. H. W. T h o m p so n S. S il v e r m a n and J. A. Sa n d e r s o n (Physical Rev., and J. W. L in n e t t (Nature, 1934, 134, 937— 938).— 1933, [ii], 44, 1032).—Calc, and observed vais, of the The ultra-violet spectrum of acraldehyde (I) lias a four bands of the infra-red spectrum of 90% NH“ region of absorption from 4000 to 2800 Â. approx. are recorded. L . S. T. consisting of bands with no overlapping continuum, Infra-red spectrum of methyl chloride. A. H. and a region of continuous absorption from 2300 Â. N ie l s e n and E. F. B a r k e r (Physical Rev., 1934, to higher frequencies. The relation of these bands [ii], 46, 970—974).— Data are tabulated for new infra to mol. structure is discussed. Illumination of (I) red absorption bands mapped in the region 0-7—7-0 ¡x. vapour at room temp, with light of wave-length Theoretical predictions and anomalous spacing are corresponding with the first region leads to a poly confirmed. Bands at 5900 and 4200 cm.-1 indicate merisation. L . S. T. interaction between the levels vx and 2v4 thought to Ultra-violet absorption of binary liquid mix exist in some Me compounds. N . M. B. tures. V. System acetone-hexane. M. P e s - Polarisation and intensity measurements in temer (Monatsh., 1934, 65, 1—5; cf. A., 1934, 952).—Results for the whole range of compositions the Raman spectrum of carbon dioxide. A. of the system support the conclusions reached in the L a n g se t h and J. R. N ie l s e n (Physical Rev., 1934, examination of other binary systems. E. S. H. [ii], 46, 1057— 1058; cf. Dickinson, A., 1929, 1215; Hanson, A., 1934, 1056).— For the principal Raman Band position of chlorophyll in different m edia. bands at 1286 and 1389 cm.-1, the depolarisations (for Hubert (Proc. K. Akad. Wetensch. Amsterdam, unpolarised incident light) are 0-18 and 0-14, respec 1934, 37, 694— 699).—Determinations of the absorp tively, and the relative intensities 0-61. N . M. B. tion band max. of chlorophyll (I) in different solvents indicate that the shift follows Kundt’s law. Com Raman spectrum of gaseous carbon dioxide. parison with the shift in leaves indicates that, if (I) A . A d e l (Physical Rev., 1933, [ii], 44, 691 ; cf. A., >3 dissolved in plastid, it must be in a medium of 1933, 661). L . S. T. Tery high refractive index. Certain observations Raman spectra of some linear triatomic mole av°ur the adsorption theory. M. S. B. cules. A. L a n g s e t h and J. R. N ie l s e n (Physical Rev., 1933, [ii], 44, 326; cf. A., 1933, 208).— Raman Chlorophyll spectrum . L. G. M. B a a s -B e c k - spectra of N20, C02, CS2 uq.» and the ions SCN' and K g and (Miss) H. C. K ondtg (Proc. K. Akad. Wetensch. Amsterdam, 1934, 37, 674— 678).— Pre N3' in aq. solution have been photographed with high liminary. The approx. positions of the absorption dispersion, and the depolarisations of certain lines and relative intensities measured. The results support a and fluorescence bands of solutions of chlorophyll (I) ln different org. solvents have been determined. In linear structure for these mois. L . S- T. general Kundt’s rule is obeyed, since the higher is Raman effect with triatomic molecules. VI. he refractive index the greater is the shift of the Constitution of nitrite ion. A. L a n g s e t h and and max towards longer wave-lengths. The results E. W a l l e s (Z. physikal. Chem., 1934, B, 27, 209— indicate that (I) cannot be present in the living 218; cf. A., 1931, 1353).—Raman lines 1331-3;£10, 146 BRITISH CHEMICAL ABSTRACTS.— A.
1240±2, and 813-2±l-0 cm.-1 have been observed, extreme wings arise from groups which cannot rotate, with NaN02, and their states of polarisation measured. but oscillate about their equilibrium positions. The relative intensities are the same at 15° as at 95°. J. W. S. The results indicate that NO,' is isosteric with 0 3 Examination of molecularly scattered light and has a ring structure. N 02' is apparently pale with a Fabry-Perot etalon. I. Liquid benzene. yellow. R. C. B. V. R. R a o (Proc. Indian Acad. Sci., 1934, 1, A, Raman spectrum of deutero-methyl alcohol 261—268).—Two fine structure components have been identified in the Rayleigh fine due to mo), and deutero-chloroform. 0. R e d l i o h and F. scattering in C6H0, their displacement being in P o r d e s (Natunviss., 1934, 22, 808).— Tlie Raman agreement with theory. The variation of the fre spectrum of MeOH2 indicates that the frequency to quency shift of the displaced components from the be ascribed to the OH vibration in the ordinary mol. main line with the frequency of the incident radiation is 3388 cm.-1 For CH2C13 lines were found at 649, is in agreement with Brillouin’s equation (Ann. 905, and 2253 cm.-1 The results do not agree with Physique, 1922, [ix], 17, 88). J. W. S. those calc, on the basis of the central force system of Bjerrum and Dennison. A. J. M. Rotational Ram an scattering in benzene vapour. S. C. S i r k a r (Nature, 1934, 134, S50— Raman spectra [of n- and scc.-butylamine and S51).—Measurements of the distribution of intensity n-heptylam ine]. P. L. B a y l e y (Physical Rev., in the rotational wing due to C6H,; at 210° and approx. 1933, [ii], 44, 510).—Frequencies and relative inten 16-6 atm. support thetheory of Placzek and Teller sities are recorded. A weak line at approx. 2725 cm.4 (A ., 1933, 446). L. S. T. is new for amines. Preliminary vals. for the fre quencies of furan are also given. L. S. T. Raman spectrum of fluorobenzene. J. W. M u r r a y and D . H. A n d r e w s (J. Chem. Physics, Raman spectra of tartaric acid and tartrates 1934, 2, 890).—The data of Crawford et al. (A ., 1934, in aqueous solution. I. P e y c h e s (Compt. rend., 1155) for the Raman frequencies of PhF differ from 1934, 199, 1121— 1123).—-Data are recorded for the those of the authors (ibid., 473) for 4 of the lines. acid and for Li, Na, NH4, K, Rb, Cs, and Et tartrates. The former used a filter of I in CC14 which does not H. J. E. permit an unambiguous assignment of some of the Raman effect of acetylenes. I. Methyl-, di lines. A numerical error in the earlier paper is corr. methyl-, and vinyl-acetylene. G . G l o c k l e r and Polarisation data are given for the Raman lines of H. M. D a v is (J. Chem. Physics, 1934, 2, 881—S89).— PhF. M . S. B. An improved technique has resulted in slightly Raman effect. XXXVII. Raman spectra of different vals. for the CMeiCIi frequencies (cf. A., molecules of the type XCOY. K. W. F. Koift- 1933, 1229). Frequencies are also given for the other R A trscn and A. P o n g r a t z (Z. physikal. Chem., 1934, two compounds and the modes of vibration discussed. B, 27, 176— 195).—The Raman spectra of compounds Faint rotation lines accompany the C:C vibration in of the type XCOY, principally amides and crotonyl liquid CMe-CMe. They are interpreted as due to derivatives and compounds having X = B r or SH and rotation of the 6 H around the figure axis of the mol. Y=alkyl, have been studied. Normal vibration The moment of inertia is 10-39 g.xem .2 M. S. B. frequencies are identified by means of approximation Linking frequency of heavy acetylene formulas for a valency-force system (cf. A., 1933, 209). Y. M o r in o (Sci. Papers Inst. Phys. Chem. Res. The effect of X and Y on the CO frequency appears Tokyo, 1934, 25,232—234).—Theoretical. Assuming to bo connected with their dipole moments. R. C. the force consts. to be the same as for C2H.j, and Raman effect. XXXVI. Raman spectrum of the mass of II2 to be 2-014, the frequencies of C2H;j organic substances. (Poly-substituted benz are calc. A hitherto unobserved Raman line at enes. V.) K. W. F. K o h l r a u s c h and A. Pox- 26S0 cm.-1 and an infra-red absorption band at g r a t z (Monatsh., 1934, 65, 6— 17 ; cf. A., 1934,1290). 2408 cm.-1 are predicted. J. W. S. —Data are recorded for 1 :3 :5 - , 1 :2 :3 - , and Raman spectra of cyc/opentene derivatives. 1 : 2 : 4-C6H3Me3, 1 : 2 : 4 : 5- and 1 : 2 : 3 : 0- Synthesis of A1-benzylci/ciopentene. L. Piaux C6H2Mc4, CeHMes, C6Me6, 1 :2 -, 1 : 3-, and 1 :4- (Compt. rend., 1934, 199, 1127— 1128; cf. A., 1934, C6H4(OH)2, 1 : 2 ; 3- and 1 : 3 : 5-C6H3(OH)3, PhQifei 942).—Data are recorded for A1-eyclopentenylmethyl 1 :2 -, 1 :3-, and 1 : 4-C6H4(OMe)2, 1 :2 :3 - and acetate, b.p. 73—75°, and bromide (I), b.p. 56—59°, 1 : 3 : 5-C6H3(OMe)3. E. S. H. and b.l-l-benzylcyc\opentene, b.p. 113— 117° [from (I) Combination scattering and association of and MgPhBr, or from cycZopentanone and CH2PlrMgCl molecules. S. I. L e it m a n and S. A. U c h o d ix and dehydration of the resulting l-benzylcyclopetitanol, (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4,12— 14).— m.p. 54—55°]. H. J. E. Scattering was investigated for solutions PhNOj Rotational Raman effect in liquids. A. V. in CC14, and AcOH in H20 ; a displacement at R a o (Proc. Indian Acad. Sci., 1934,1, A , 274—280; 623 cm.-1 is ascribed to association of the AcOH cf. A., 1934, 345, 1056).— C6H6, CS2, cycZoliexane, mols. A. B. D . C. molten salol, and CClj all show a high intensity near Rayleigh scattering in crystals. F. M atossi the Rayleigh line, and a weak but definite extension (Z. Physik, 1934, 92, 425-461).—The theory of of the wing beyond the theoretical limit. The intensity depolarisation is developed for rhombic, trigonal, distribution remains almost unchanged at temp, hexagonal, and tetragonal crystals; trigonal crystals near the b.p. of the liquids. It is suggested that the do not show symmetry normal to the single optic GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 147 axis, as elastic consts. have a lower symmetry than Kunsman anode (mixture of Fe203, A1203, and alkali optical consts. Depolarisation was observed for glass, salt) was used to investigate the variation of velocity rock-salt, topaz, calcspar, and quartz; quartz shows (I) of Cs ions emitted from it with temp. (I) was const, the lower symmetry of elastic consts. A. B. D. C. between 650° and 900°, increased by 0-5 volt between Topography of surfaces deduced from the 900° and 1100°, and was again const, from 1100° to coefficient of diffusion of light. Application in 1300°. The variation of (I) is due to a change in the thermo-electric emission work, a satisfactory the study of corrosion. F. Ca n a c (Compt. rend., 1934,199, 1117— 1118).—The reflexion of light by the explanation for which has not been found, although surface is correlated with the surface conditions. it may be connected with the p-y Fe transformation H. J. E. in the anode. A. J. M. Fluorescence of platinocyanide solutions. I. A. Outer photo-electric effect of composite photo Ch v o s t ik o v (Compt. rend. Acad. Sci. U.R.S.S., 1934, cathodes at low temperatures. R. S u h r m a n n 4,14—20).-—Fluorescence of K, Ba, and Mg salts was and D . D e m p s t e r (Physikal. Z., 1934, 3 5 , 973—975). observed. The K salt fluorescence appears as bands —Photo-electric cells with K -K H -K (I) and at 525 and 555 m|i, absorption bands appearing near K -C 10H8-K (II) cathodes show increased sensitivity 254, 279, and 350 mjx. Variation of polarisation with at the temp, of liquid air, when irradiated with fight viscosity is used to calculate the half-life period of of the selective max. [430 m(i for (I), and 290 mji for emitting centres. A. B. D. C. (II)]. It is assumed that the increased sensitivity is duo to the presence in excited states of light- Crystallisation fluorescence. H. D o r in g absorbing centres, of which the life is considerable at (Naturwiss., 1934,2 2 , 838).— CaC204, freshly separated from plant cells, shows fluorescence, whilst more aged low temp., but is shortened at room temp, crystals do not. A similar phenomenon is observed owing to thermal vibration. A. J. M. in the separation of thymol and similar phenols, and Photo-electric conductivity in silver chloride. vanillin, from supercooled melts. A. J. M. A. A r s e n ie v a (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4 , 118— 120).—The photo-electric current is Luminescence and crystal structure of solid independent of temp, between —110° and —170°. ified gases. L. V e g a r d (Proc. K. Akad. Wetensch. E. S. H. Amsterdam, 1934, 3 7 , 780—788).— The bands in the Radiation from cells formed of semi-con luminescence spectrum produced by bombarding ductors. G. DicHiiNE (J. Phys. Radium, 1934, solid Kr and A with cathode rays have been studied, [vii], 5, 553—562).—The emission of absorbable and many have been referred to an impurity of No- electromagnetic radiation is confirmed. Investigation The infra-red luminesccnce from A, A - f 3-5% N2, of the absorption in air, and analysis by the tangent and N2, in the solid state, has also been studied. grating method, showed that semi-conducting cells of From X-ray measurements solid P-N2 has a hexagonal yellow HgO, PbCl2, and Na2C03 emit an ionising elementary cell, containing 2 mols. capable of radiation situated in a region 12— 600 thick; rotation in the lattice, with a 4-039 A., c/o 1-651. A. its suggested origin is the thin air film in contact with In a-N2 the mols. are fixed on trigonal axes, space- the semi-conductor. N. M. B. group Ta, and the mol. centres are approx. arranged in a face-centred cubic lattice. It is suggested that Barrier layer cells. R. H. V a r i a n (Physical in ct-N2 the excited state is kept undisturbed for Rev., 1934, [ii], 4 6 , 1051— 1054).—Frenkel and sufficient time for transition to the normal to occur, Joffe’s theory of the photovoltaic effect in cells con and a band system is emitted, but with p-N2 no taining a semiconductor (I), a thin barrier to the phosphorescence can be emitted, since the excited passage of electrons, and a metal, docs not adequately state is disturbed by rotation. Solid 0 2 exists in explain the direction of current flow, but can be two forms, I stable between —229° and the m.p., made adequate if the difference in the rate of loss of II from —249° to —229°. There is some indication velocity of- photo-electrons in (I) and in the metal is that the mols. rotate in form I. R. S. B. taken into account. N. M. B. Efficiency of chemiluminescence accompany External photo-electric effect and chemical P o c h e t t in o ing the Wedekind reaction. W. L. A s l in g and constitution. A. (Nuovo Cim., 1934, “ • I - DtJp°Ri) (Physical Rev., 1933, [ii], 4 4 , 315).— 1 1 , 213—223; Chem. Zentr., 1934, ii, 910—911).— Ihe chemiluminescence (I) accompanying the re Data are recorded for several C6H6 derivatives action between chloropicrin and certain Grignard using X 2536 A. for irradiation. The presence of a ^gcnts has been quantitatively investigated. The CgHc ring combined with one or more other 6-rings, efficiencies, which range from 4-4 xlO -8 to 10~9%, or containing active groups (e.g., NH2), is necessary are discussed in relation to the possible origin of (I). for a high photo-effect (I). Halogens, COaH, N 0 2, L. S. T. or :C:0 produce a low val. For isomerides the Luminescence on agitating mercury in im substances with the highest dipole moments have the pure neon at low pressure. G. D e j a r d i n an d highest (I), except when N 02 is present. In C10HS derivatives the val. is higher with a- than with llio^') ScHW^GLER (Compt. rend., 1934, 199, 110 1112).—The spectrum, which contains mainly [3-substitution. Some dyes were studied and showed and bands, resembles the aurora spectrum. a high effect. H. J. E. p H. J. E. Motion of ionic lattices of insulators at extreme Experiments the Kunsman anode. G. field intensities. A. G u n t h e r -S c h u l z e and H. UtLLE (Ann. Physik, 1934, [v], 21, 443-^56).—The B e t z (Z. Physik, 1934, 92, 367— 374).—Unaged oxide 148 BRITISH CHEMICAL ABSTRACTS.— A. layers on A1 and Ta show three regions of current Refractivity of cellulose and its derivatives. flow : a pure electron current at low field intensities, III. Influence of adsorbed water on refractivity and an electron and ion current of the same order at of cellulose fibres. IV. Refractive indices of higher intensities; at still higher intensities the ionic cellulose nitrate and cellulose acetate. K . K a n a - current follows a different exponential law. The m a r u (Helv. Chim. Acta, 1934, 17, 1425— 1429, ionio current is due to interpenetration of metal 1429— 1440; cf. A., 1934,1292).—III. During absorp and 0 ions. A. B. D. C. tion of H20 by dried ramie fibres the refractive index perpendicular to the fibre axis (na) remains approx. Ionisation of liquid carbon disulphide by const., whereas ny (parallel to axis) passes through a X-rays. F. L. M o h l e r and L. S. T a y l o r (J. Res. min. An explanation is suggested. Nat. Bur. Stand., 1934, 13, 659— 664).—Data are IV. The linear relationship between double re recorded. The no. of ions produced in the liquid per fraction and N content of cellulose nitrate has been quantum absorbed is approx. the same as in the established by direct measurement of na and nr vapour, but the current resulting from the ionisation The relationship is observed only when the nitration is much reduced by intracolumnar recombination. process gives rise to a homogeneous product. When H. J. E. cellulose (I) is acetylated so as to preserve the fibre Photovoltaic effect. R. T. D u e f o r d (Physical structure the product is always heterogeneous, and Rev., 1933, [ii], 44, 315; cf. A., 1933, 915).—The consists of a mixture of the triacetate with unchanged behaviour of photovoltaic cells, especially those con (I). The diminution of na and nY on esterification of taining Grignard reagents, is compared with that of (I) indicates that n is influenced by the polarity of the other types of cell. Current theories of electrode side-chains. F. L. U. potential must be extended in order to explain the Corrections to the refractive indices of quartz results. L. S. T. in the infra-red. D . G. D r u m m o n d (Nature, 1934, Effect of temperature and of visible and 134, 937).— Corr. vals. for n are given for wave [near] infra-red radiation on the electrical lengths between 3 and 3-8 ¡¿. L. S. T. resistance of boron. R . F r e y m a n n and A. Optical anisotropy, form, and inner move St ie b e r (Compt. rend., 1934, 199, 1109— 1110).— ments of organic molecules. H. A. St u a r t and Weintraub’s results for the temp, effect are confirmed H. V o l k m a n n (Physikal. Z., 1934, 35, 988— 990).- (cf. Ind. Eng. Chem., 1913, 5, 112). The resistance The optical anisotropy of n- and branchcd-chain diminishes on irradiation. H. J. E. hydrocarbons (C2—C12) in the vapour state, calc, Ionic mobilities in dielectric liquids. I. from the Kerr const., indicates that these mols. do not form extended zig-zag chains, and are not spiral. A d a m c z e w sk i (Bull. Acad. Polonaise, 1934, A, 217—230).—A third ion has been detected in ionised The introduction of polar groups (-0-0, !C‘0), however, CgHu , and three ionio mobilities each in C5H12, causes an extension of the chain. A. J. M. C7Hj8, and C8H18. The ionic mobilities are related Anisotropy of the optical polarisation field in empirically with the viscosity coeff. X-Rays furnish liquids. M. R a m a n a d h a m (Proc. Indian Acad. Sci., a better source of ions than Ra preps, for mobility 1934, 1, A, 281— 287).—The refractivities of a no. of investigations, owing to the stronger ionising effect org. vapours, calc, from the vals. of n for the liquid and the absence of errors due to mechanical dis state on the basis of the theory of the anisotropic turbance. J. W. S. polarisation field developed by Raman and Krishnan (A., 1928, 113), agree with observed vals. better than Atomic polarisation of carbon monoxide. those calc, by the Lorentz formula. J. W. S. L. A. M a th e so n (Physical Rev., 1933, [ii], 44, 604).— A discussion. L. S. T. Ultra-violet rotatory dispersion of camphor in sulphuric acid solution. J. L e c o m p t e and J. Dipole moment of heavy water. F . H . M u l l e r P e r r i c h e t (Compt. rend., 1934, 199, 1202— 1205).— (Physikal. Z., 1934, 35, 1009— 1011).—The dipole Data are recorded for varying concns. for XX 4047, moment of IliO in C6H6 solution determined by a 3650, 3341, 3130, 3022, and 2967 A. Measurements modified Williams method is l-78±0-02D, which in conc. H2S04 indicate that a third form or a com agrees within experimental error with the val. for pound of camphor exists in the solution. H. J. E. H20. The theoretical consequences are discussed. Magnetic rotation of salts of higher fatty acids A. J. M. and evidence in favour of the formation of ionic Determination of dipole moment of sucrose. micelles. S. S. B h a t n a g a r and P. L . K a p u r (J. E. L a n d t (Naturwiss., 1934, 22, 809).—The dipole moment of sucrose in polar solvents has been de Indian Chem. Soc., 1934, 11, 767— 772).—M[w] of termined In C5H5N the val. is 2-8, in NH,Bua 3-4, Na and K oleates in H20 in the conen. range 3—-19% and in NHEt2 3-4 (all x 10-18). Interaction with the vary in a manner consistent with the formation of solvent is neglected. A. J. M ionic micelles. J. G. A. G. Verdet constant of heavy water. F. G. S la c k Refractive index and molecular refractivity (Physical Rev., 1934, [ii], 46, 945— 947).—Verdet of hydrogen selenide for the D3 line (5875-6 A.). consts. for HaO containing 0, 31-1, and 9 9 -7 % H2, 9 ' anc^ O. H a s s e l (w ith J . L o h n e ) (Z. measured for XX 5893 and 5460-7 A. at 20°, give a physikal. Chem., 1934, B, 27, 316—318).— (na- 1) val. for the const. 3 -9 3 % < that of H20 for both X 10« measured at 8—27 mm. pressure is 788-0 wave-lengths. Non-linearity of the Verdet const.- mol. refractmty is calc, as 11-77. R q concn. relation gives an apparent const, for H1H20 GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 149
0-85% < that for H20. Vais, of the relative mol. obtained with aq. PbCl2 by the magneto-optic rotatory power and magnetic rotatory dispersions method. L. S. T. are given. v N. M. B. Constitution of hypophosphoric acid. A. Superposition of electric and magnetic bire H a n t z sc h (Z. anorg. Chem., 1934, 221, 63—64).— fringence. M. S c h e r e r and A. P i e k a r a (J. Phys. The reactions of H4P206 and its Na salt support Radium, 1934, [vii], 5, 568—570).-—Investigations Nyl6n and Stelling’sformula'(A., 1934, 854) (H 0)4P20 2. on CS2, PhMe, l-CJ0H7Me, and solutions of PhN02 It is not a mixed acid anhydride of H3P03 and in PhMe show that the two effects are without mutual H3P04. M. S. B. influence, agreeing with Pockels’ theory. N. M. B. Magnetic properties of free radicals. Xanthyl- Magnetic double refraction of organic liquids. a-naphthylmethyl. (M m e .) S. A l l a r d (Compt. rend., 1934, 199, 1125— 1126).—Measurements of E. Ma t u l l (Ann. Physik, 1934, [v], 21, 345—366).— The Cotton-Mouton consts. (I) of PhMe, C6H6, and the susceptibility are used to calculate the degree of dissociation in C6H6 solution of dixanthyldi-a- CHCl3,7-28,6-80, and— 0-77 (all X 1 0 13); respectively, differ from those recorded. The principal magnetic naphthylethane. H. J. E. polarisabilities (II) were calc, from (I). For CC14, Dependence of the diamagnetism of water on the three vals. of (II) are identical, confirming the tem perature. A. P. W il l s and G. F. B o e k e r tetrahedral form of the mol. For CHC13, the negative (Physical Rev., 1934, [ii], 46, 907—909).—Anomalous sign of (I) indicates that the max. optical polaris results previously reported (cf. A., 1933, 212) are abilities and (II) are coincident. The axis of max. partly explained. Variation of susceptibility with (II) lies in the plane of the three Cl atoms, whilsttemp, is plotted for the range 20—66°, and a parabolic that of least (II) coincides with the direction of the formula is deduced. N. M. B. C-H moment. For C6H6, (I) is relatively large, indicating considerable magnetic anisotropy. The Diamagnetic susceptibilities of salts forming ions with inert gas configurations. I. Halides max. optical polarisability and (II) are perpendicular to each other. A. J. M. of sodium and potassium. F. E. H o a r e (Proc. Roy. Soc., 1934, A, 147, 88— 100).—The diamagnetic Thermal variation of magnetic birefringence susceptibilities of the Na and K halides have been of paramagnetic solutions of rare-eartb salts. measured at 20—-22° by Gouy’s method, in which the C. Ha en n y (Compt. rend., 1934,199, 1207— 1209).— force on the specimen in an unhomogeneous magnetic Vals. are recorded for salts of Ce and Tb. field is measured with a sensitive balance. H. J. E. L. L. B. Allison m agneto-optic effect. L. B . S n o d d y Nickel cyanide and complex derivatives : (Physical Rev., 1933, [ii], 44, 691).—Modifications in magneto-chemical studies. L. Ca m b i, A . Ca g - technique are described. L. S. T. n a s s o , and E. T r e m o l a d a (Gazzetta, 1934, 64, Isotopes of hydrogen by the m agneto-optic 758—772).—Ni(CN), and its complex salts containing method. Existence of H3. W. M. L a t im e r and H20, NH3, (CH2-NH2)2, and other org. bases give H. A. Y oung (Physical Rev., 1933, [ii], 44, 690).—A vals. of XNi=H Weiss magnetons approx., whereas s°mtion of HC1 in H20 gives min. at 15-74 and 15-85 for the halides N iX, and their complex salts the vals. Allison units; the latter, due presumably to H1, is = 16 approx. It is suggested that the complex much stronger. With H|0 (2 and 4%) as solvent, cyanides contain the complex cation [Ni,»M], which these two min. are practically equal in intensity. is paramagnetic with xsi= 16 (M =a mol. of NH3 etc.), A third min. at 15-65 corresponds with H3. Similar and the complex diamagnetic anion Ni(CN)4. results are obtained when HBr replaces HC1. 0. J. W. L. S. T. Magnetic susceptibility of the ferrous salts Isotopes of ch lorin e. E. R. B is h o p and F. of pyridine- and quinoline-2-carboxylic acids. Allison (Physical Rev., 1933, [ii], 44, 4 1 9 ^ 2 0 ).— L. C a m b i and A. Ca g n a sso (Gazzetta, 1934, 64, ' lien HF, H3P04, or K B r is added to a saturated 772—773; cf. A., 1934, 241).—The data given for solution of Cl2 in H20, min. corresponding with Cl the Fe salt of quinolinic acid in the previous paper uoride, Cl phosphate, and B r chloride, but not Cl are wrong. The correct val. of xf« for the compound momide, respectively, were obtained by the magneto- Fe(C7H404N)2,3H20 is 26-7 Weiss magnetons at °Ptlc niethod. C12-H 20 gives min. corresponding 291° abs. “ 0. J. W. with Cl chloride. The min. observed are due to Cl35, Paramagnetic rotation of tysonite. J . H . V a n u > and probably Cl39. L. S. T. V l e c k and M. H . H e b b (Physical Rev., 1934, [ii], Isotopes of ca lciu m by the magneto-optic 46, 929; cf. A., 1934, 944).—A correction. ethod. W. M. L a t im e r and H. A. Y o u n g (Physi- N. M . B . d ;eT-’ 1933, [ii], 44, 61).—Many of the min. What is known of ferromagnetism with small ported by Allison (A., 1930, 1541) have been con- changes of field ? H. J o r d a n (Ann. Physik, 1934, / " f f . With Ca, a third faint min., probably due [v], 21, 405— 424).—A criticism of the work of Gans 10 U « is always obtained. L. S. T. and Wittke (A., 1934, 14). A. J. M. T by the magneto-optic method. [What is known of ferromagnetism with small L (Physical Rev., 1933, [ii], 44, 420).— In changes of field?] R. G a n s (Ann. Physik, 1934, s cement with other investigators (A., 1933, 204) [v],-21, 425).—A reply to Jordan (preceding abstract). mili. between 36 and 38 Allison units have been A. J. M-. 150 BRITISH CHEMICAL ABSTRACTS.— A.
Chemical linking, (a ) R. F . H u n t e r and R. 333—345).—Mathematical. The equations of vibra S a jiu e e (Nature, 1934, 1 3 4 , 971). ( b ) A n o n , (ibid., tory motion of the diamond lattice are formulated. 971— 972).—Polemical. L. S. T. A typical factor of the secular equation corresponds Models for the demonstration of the exact with the vibration of the two face-centred cubic lattices composing the diamond lattice relative to one another, space occupied by molecules. H. A. St u a r t (Physikal. Z., 1934, 3 5 , 990—991).—Models in which this vibration being triply degenerate. This vibration parts of spheres are used instead of complete ones is Raman-active but optically inactive, since all are described. A. J. M. atoms arc liomonuclear, and accounts for the principal Raman frequency (1332 cm.-1) being absent from the ; Constants of the HC1 molecule. P. G om ba s infra-red spectrum. J. W. S. and T. N e u g e b a u e r (Z. Physik, 1934, 9 2 , 375— 384).—Theoretical. The ionic model with Hartree’s Nuclear forces. W. M. E l s a s s e r (Compt. rend., proper function leads to an interat. separation 3-8% 1934, 1 9 9 , 1406—1408).—Theoretical. J. W. S. too great, a dipole moment 19% too great, and Effect of dispersion and of lattice distortion fundamental frequency 3-9% too small. on the atomic scattering factor of copper for A. B. D. C. X-rays. G. W. B r i n d l e y and F. W. S p ie r s (Nature, Interatomic forces and oscillation frequencies 1934, 1 3 4 , 850).—The at. scattering factor (I) for of atoms in lattices. S. F r a n c h e t t i (Atti R. the (220) spectrum at room temp, of Cu pptd. from j Accad. Lincei, 1934, [vi], 2 0 , 186— 191).—Mathem CuSO.j by Zn is > that of Cu filings from chill-cast atical. 0. J. W. rod or hard-drawn wire. Distortions in a metal Role of the electron in chemical combination. thus lower the val. of (I). The lowering of (I) due J. S a v a r d (Helv. Chim. Acta, 1934, 1 7 , 1466— to dispersion is 3-3. L. S. T. 1480).—A lecture in which simple mols. are con Angular variation of the refractive index for sidered from the point of view of ionisation potential X -ra ys. J. A. P r i n s (Z. Physik, 1934, 9 2 , 690— (cf. A., 1934, 11, 347, 577, 584, 943). F. L. U. 691).—Polemical, against Jentzsch (A., 1934, 1295). Collision phenomena in the recombination of A. B. D. C. hydrogen atoms to molecules. H. S e n f t l e b e n Measurement of absolute X-ray intensities and and W. Hein (Physikal. Z., 1934, 3 5 , 985— 986).— absolute sensitivity of X -ray film with a Geiger- The effect of pressure and addition of inert gases on Müller counter. G. L . L o c h e r (Physical Rev., ; the recombination of II to H2 has been investigated. 1934, [ii], 4 6 , 1047— 1051).—A special counter con The reaction is one involving triple collisions. The taining Kr is described, and a “ standard beam ” of activity of the third participant in the reaction varies fluorescent Zr X-rays is calibrated. Using this with its nature, and it is found that the heavier inert beam, the min. exposure of X-ray film for detectable gases (A and Kr) are more effective than the lighter blackening is 0-72x10° quanta cm.-2, incident on (He and Ne) and H2 itself. A. J.'M. the film, or 4-1 xlO 4 quanta cm.-2, absorbed in the Electronic configuration of molecules and emulsions. The total absorption coeffs. of the film, their electron affinity. N. E. B r a d b u r y (J. celluloid, and emulsion, for Zr X-rays, are 8-63, 1-06, Cliem. Physics, 1934, 2 , 840).—The relation between and 13-0 cm.-1, respectively. N. M. B. the electronic configuration of a mol. and its ability Structure determination by the F o u rier to form a stable negative ion by electron attachment method. A. H e t t i c h (Z. Physik, 1934, 9 2 , 52S— is discussed. M. S. B. 532).—The Fourier method may be applied in general Fundamental oscillations of molecules of the to structural and chemical problems of crystals. type X G and X GYG. M . v a n d e n B o ssc h e and C. A. B. D. C. M a n n e b a c k (Ann. Soc. Sci. Bruxelles, 1934, 54, B, Property of structure analysis. N. Seljakoy \ 230—279).—Mathematical. The general method of (Z. Physik, 1934, 9 2 , 543—546).—X-Ray photo symmetrical co-ordinates is used to calculate the graphs taken by the rotating-crystal method depend frequencies of the fundamental oscillations of mols. very much on the crystal position for both large and of the type X G and X 6Y6 (CGH6). The forms of the small angles of reflexion. A. B. D. C. degenerate motions are also obtained. It is proposed Significance of surface forms for determin to utilise the results to calculate the fundamental ation of symmetry and habit of crystals. G. frequencies of CGHG. A. J. M. K a l b (Z. K r is t ., 1934, 8 9 , 400—409).—The general Reactions of atoms. W . H e l l e r and M. geometry of a crystal is not always sufficient to fix P o l a n y i (Compt. rend., 1934, 1 9 9 , 1118— 1121).—A its symmetry completely; an additional study of summary and discussion. H . J. E. surface forms (including etch markings) is necessary. Intramolecular statistics, especially for chain Detailed examples are given. B. W. R- molecules. I. E. G u t h and H. M ark (Monatsh., New evidence, setting an upper limit of 500 A. 1934, 65, 93—121).—Theoretical. M. S. B. or less, to dimensions of mosaic blocks (if any) Potential function for the vibrations of di in a crystal. H . E . B u c k l e y (Z. Krist., 1934, atomic molecules. M . F . M a n n in g an d N . R o s e n 8 9 , 410— 415).— Crystal plates (order of 0-3 nun. (P hysical Rev., 1933, [ii], 44, 953).— Mathematical. thick) can be grown or cleaved so perfectly as to giye L. S. T. interference bands in monochromatic light between Dynamical theory of the diamond lattice. I. front and back surfaces over considerable areas. N . S. N . N a t h (Proc. Indian Acad. Sci., 1934, 1, A, This is taken to disprove the existence of mosaic GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 151 structures such as have been required by various system. III. Limit of X-ray reflexion. M. authors. B. W. R. I s h ih a r a (J. Soc. Clicm. Ind. Japan, 1934, 37, 562— X-Ray investigations at high pressures. 566b , 566— 568b , 568— 570b ).— Mathematical. J. W. S. W. M. C o h n (Physical Rev., 1933, [ii], 44, 326— Crystallisation of polymorphous substances. 327).—Changes in the modifications of crystals occurring in a Bridgman bomb at pressures up to I. K. L a r k -H o r o v it z and S. E. M a d ig a n (Physical 3000 atm. have been investigated by means of X-rays. Rev., 1933, [ii], 44, 320).—-The cubic form of ZnS L. S. T. has been evaporated in a vac. at temp. < the transition point a->ß-ZnS and deposited on different surfaces Theory of real crystals. A. Sm e k a l (Z. Krist., 1934, 89, 386—399).—A summary of existing theories, at 20°. The deposit is cubic on all surfaces with a cubic lattice (Cu, Al, diamond, etc.), on amorphous with special reference to strength properties of crystals. surfaces such as glass and fused quartz, and on Zn, B. W. R. mica, and cryst. quartz. A mixture of the hexagonal Theory of real crystals. A. G. Sm e k a l (Physi with excess of the cubic modification is formed on cal Rev., 1933, [ii], 44, 308—309).—Polemical (cf. this vol., 19). L. S. T. ZnO. On hexagonal CdS (I), the deposit is also wholly hexagonal (wurtzite). When deposited Strength and real structure of crystals. E. simultaneously on (I) surrounded by Cu, the ZnS is Orow an (Z. Krist., 1934, 89, 327— 343).—A perfect hexagonal on (I) and cubic on the Cu. When evapor lattice cannot explain such properties as crystal ated in a vac., wurtzite is deposited on cubic surfaces breaking strength, plastic slip, and electrical strength, as Zn blende, but remains hexagonal on hexagonal nor can any regularly modified lattice {e.g., block or ZnS. L . S. T. secondary structures). The crack-broadening theory of Griffith with certain modifications is more satis Transition of antimony into the vitreous factory when applied to these properties. am orphous state. G. T a m m a n n and W. M ü l l e r B. W. R. (Z. anorg. Chem., 1934, 221, 109— 112).—By the X-Ray reflexion and real structure in rock- addition of Sb2Se3 to molten Sb the crystallisation salt. M. R e n n ig e r (Z. Krist., 1934, 89, 344— velocity may be reduced, so that, by rapid chilling 374).—With a double-crystal spectrometer the re to — 180° of droplets of approx. 0-4 mm. diameter, flexion width and the integrated intensity wrere amorphous particles are formed. By heating for determined for various crystals and surfaces of rock- \ hr. at 520° the particles become cryst. This result salt. An artificial crystal gave the theoretical width is not obtained in the absence of Se. M . S. B. and intensity; i.e., over regions of order 1 mm. the Nucleus formation on crystals of copper lattice was perfect. This is discussed in relation to sulphate pentahydrate. N. F. H. B r ig h t and the usual theories of secondary structure. W. E. G a r n e r (J.C.S., 1934, 1872— 1877; cf. A., B. W. R. 1934, 720).—The no. of nuclei (I) formed on the Theory of the plasticity of crystals. G. I. (110) face of crystals of CuS04,5H20 when dehydrated Ta y lo r (Z. Krist., 1934, 89, 375—386).—The ob in a high vac. wras determined. After an induction served strength of crystals is highly dependent on period (II), (I) increases linearly with time. As a the past history, i.e., on previous plastic distortions. rule a few visible (I) are present during (II). (I) A simple picture of plastic distortion is suggested, were star-shaped, with two main directions of growth in which “ dislocations ” move through the lattice in the (110) face, and a third into the crystal in the as slipping takes place. The dislocation moves form of a thin disc making an angle of 56° with the freely only in a perfect lattice, and has a “ mean face. The occurrence of (II) indicates that (I) when free path ” ; this leads immediately to (a) a parabolic small do not grow at a uniform rate. The crit. stress-strain relationship agreeing with experiment, increment of (II) is 16 kg.-cal. A. J. M. and (6) a “ mean free path ” of about 10^ cm., agree ing with the spacing of the dislocations or cracks Cell dimensions of ordinary and “ heavy " ice. postulated by. Goetz, Zwicky, Smekal, et al. H. D. M egaav (Nature, 1934, 134, 900— 901).—The B. W. R. structure of cryst. HaO is the same as that of ordinary Group phenomena in metal crystals. A. ice, the difference between the cell dimensions being Goetz (Z. Krist., 1934, 89, 310— 326).—A survey extremely small. There appears to be a small, real pi the experimental distinction between real and difference (< 0 -l% ) in a at 0°. Ordinary H20 has ideal crystals, especially referring to metal crystals, its mols. more closely packed than H!jO, which has proper verification of a groiip or swarm theory is a more ice-like structure. L. S. T. difficult, but an assumption of this kind removes many arbitrary hypotheses which are otherwise Difiuse scattering of X-rays from sylvine. required. B. W. R. G. E. M. J atjncey and W. D. Clatts (Physical Rev., 1934, [ii], 46, 941— 945).— Improved experimental Hooke's law and crystal structure. A. E. determinations of S vals. agree with calc, results. Caswell (Physical Rev., 1933, [ii], 44, 320).— N. M. B. theoretical. * L. S. T. . Crystal structure of LaMg and CeMg. A. A'-Ray rotation crystal and fibrous structure Rossi (Gazzetta, 1934, 64, 774— 778).-—LaMg and diagrams. I. Expressions of the X-ray spot CeMg have a cubic-centred lattice with a 3-952, and the crystal plane. II. Expressions of the 3-884 Ä., d0i„. 4-36, 4-48, 4-36, 4-63, respectively. A-ray spot and the crystal plane in triclinic The Hume-Rothery rule is discussed. 0 . J. W. 152 BRITISH CHEMICAL ABSTRACTS.— A.
Crystal structure of PrSn3 and PrPb3. A. Acad. Polonaise, 1934, A, 246—255).— Crystallo R o ssi (Gazzetta, 1934, 64, 832— 834).—PrSn3 and graphic data are given. J. W. S. PrPb3 have the same face-centred cubic structure Crystal lattice of oxalic acid dihydrate and the as the corresponding La compounds (A., 1933, 1003) structure of the oxalate radical. W. H. Z a c h a with a 4-704, 4-857 A., d0}x. 7-60, 10-60, d^c. 7-SS, r ia s e n (Z. Krist., 1934, 8 9 , 442— 447).—This is 10-98, respectively. 0. J. W. monoclinic, o0 6-12, b0 3-61, c0 12-03 A., p 106° 12', Crystal structure of stannite Cu2FeSnS4. L. 0. space-group P21/n\ The 12 parameters (neglecting B r o c k w a y (Z. Krist., 1934, 8 9 , 434— 441).— The the H atoms) are uniquely and accurately determined. cell is tetragonal, a0 5-46, c0 10-725 A., containing The oxalate radical is planar. B. W. R. 2 mois, of Cu2FeSnS4. Space-group chosen as D $ ; Ar-Ray studies of the molecular arrangement there is, however, a possibility of a structure based in liquids. S. K a t zo f e (J. Chem. Physics, 1934, on the point-group SA. At. positions are deduced 2 , 841— 851).—An improved method for taking X-ray from intensity considerations. The structure re diffraction photographs of weakly absorbing liquids sembles, but is not identical with, that of chalcopyrite. is described. Photographs of H20, C7H16, C10IL,2l B. W. R. C6H6, and C6H12 have been made. The results are Crystal lattice of ammonium persulphate, explained on the assumption that adjacent mols. (NH4)2S20 8, and the structure of the persulphate in a liquid are held together similarly to those of a group! R. C. L. M o o n e y arid W. H. Z a c h a r ia s e n crystal, but are otherwise of random arrangement. (Physical Rev., 1933, [ii], 44, 327; cf. A , 1934, M. S. B. 1060).—NH4 and Cs persulphates, monoclinic, have AVRay investigation of crystals of m-azotolu- 4 mois, per unit cell; space-group P2Jn (Clh). ene. M. P r a s a d and P . H. D a l a l (Current Sci., (NH4)2S2Os has a 7-80, b 7-98, c 6-12 Â., p 95^9'. The 1934, 3 , 200—201).—The rotation method gives a S208 group can bo regarded as 2 S04 joined together 11-88, b 13-75, c 7-52 A .; space-group Ql1. L. S. T. by a linking across a centre of symmetry between 2 O atoms. Each S is tetrahedrally surrounded by Cholesteryl salicylate. S. B. H e n d r ic k s (Z. 4 0 at a distance of 1-50 Â. The distance between Krist., 1934, 8 9 , 427— 433).—The prep, of the pure the 2 0 connected by the valency linking is 1-31 Â., salicylate is described; X-ray data give a0 9-68, and the angle between the two linkings of these O b0 12-52, c0 6-31, a 92° 56-5', (3101° 58-5', y 95° 14', for is 12S°. NH4 is surrounded by 12 0 at a mean the cell, which is triclinic, space-group PI. There distance of 3-15 A. L. S. T. are possible alternative units, and it is argued that in general the dimensions of units of structure are not Crystal structure of sodium thioantimonate. necessarily related to the mol. dimensions. The Ch in g -Y e u n g Hui (Physical Rev., 1933, [ii], 44, salicylate forms a liquid crystal phase below its m.p., 327).—X-Ray investigations show that Na3SbS4,911,0, perhaps due to the presence of orthogonal N and 0 cubic, a 11-835 A., has 4 mois, per unit.cell; space- valencies. B. W. R. group P2j3 (2Ti) ; d 1-927. L. S. T. M.p. and long crystal spacings of the higher Crystal structure of potassium uranyl acetate. primary alcohols and ?i-fatty acids. S. H. I. F a n k u c h e n (Physical Rev., 1933, [ii], 44, 327).— P it e r , A. C. Ch ib n a l l , and E. F. W il l ia m s (Bio- X-Ray investigations indicate that K uranyl acetate is cliem. J., 1934, 2 8 , 2175—2188).—'The m.p. and long dimorphous, both forms being hexagonal. One has crystal spacings of several pure C26 to C36 alcohols, a 14-38, c 25-80, and the other a 13-99, c 27-70 A. acids, acetates, and Et esters and binary and ternary Both body-centred unit cells have approx. the same mixtures of known composition are recorded. Methods val. and contain 16 mois. ; space-group, probably are indicated for using the data in determining the I 4j2 (D\°). The U atoms are approx. in a face-centred composition of mixed alcohols and acids present in lattice 0-25 the height of the actual unit cell. waxes. C. G. A. L. S. T. Crystal structure of ir!g(NH3)2Cl2. J. M. Crystals of hydrochlorides, hydrobromides, B ij v o e t and C. H. M acG il l a v r y (Nature, 1934, and hydriodides of methylephedrine. Crystallo 134, 849— 850).—The unit cell, 4-06 A.3, contains graphic relations between rfi-compounds and only 0-5 mol. Structure is discussed. L. S. T. their components. B. G o s s n e r and H. N eff (Z. Krist., 1934, 8 9 , 417— 426).—Crystallographic Crystal structure of chalcopyrite. S. Kôzu descriptions, d, cleavage, consts. of unit cell (X-ray), and K. T a k a n é (Proc. Imp. Acad. Tokyo, 1934, 10, and space-group are given for the hydrochloride and 498—501).—The cell dimensions and axial ratio of hydrobromide of I- and dZ-methylephedrine, and the crystals from Arakawa, Ugo, Japan, are a0 5-28, eZZ-hydriodide. Two modifications of the dZ-hydro- c„ 5-22 A c0/a0 0-9S9; space-group F3; 2 mois. bromide are described. The constitution of these CuFeS2 in unit cell. C. W. G. racemates is discussed from the viewpoint - of a Structural fine-structure of barium succinate. “ double salt ” of the d- and ¿-compounds. E. H e r t e l and G. H. R ô m e r (Z. physikal. Chem., B. W. R. 1934, B, 27, 282—286).—The unit cell has I„ 7-57, X-Ray observations on lower and higher poly I c 10-28 A. and contains 4 BaC4H404 mois.; space- peptides. K. H. M e y e r and Y. Go (Helv. Chim. group The lattice is a typical ionic lattice. Acta, 1934, 17, 1488—-1492).—Powder diagrams of R. C. w-glycylglycine (n = 3—7), compared with those of a Guanidine mono-, di-, and tri-chromates. polyglycylglycine of mol. wt. about 2000, show that Crystallographic study. A. Swaryczewski (Bull. as n increases the arrangement of atoms in the former GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 153 approximates to that in the latter. The atoms are points at —14°, —9°, and —2° range from 98 to mostly arranged in lattice planes at a distance of 180( X 10~6). g is approx. 2, indicating that the para 4-15 A. F. L . U. magnetism of the Ni is due to spin alone, as in the Structure of rubber as shown by the time lag ferromagnetic state. L. S. T. of fibering. W. E. Sin g e r , J. D. L o n g , and W. P. Magnetostriction of pure and alloyed Bi single Da v e y (Physical Rev., 1933, [ii], 44, 319).—X-Ray crystals. A. W o l e and A. G o e t z (Physical Rev., investigation shows that there is a time lag between 1934, [ii], 46, 1095—1107).—The existence of a the time rubber is stretched and the time a fibre magnetostrictive effect for steady moderate fields is structure is produced. The view that rubber consists shown. Using 99-97% Bi single crystals the modulus of a tangle of spiral or zigzag-shaped mols. with firmly of magnetostriction is -j-5-7 x 10 16 parallel to the fixed ends, the lengths of which can be temporarily trigonal axis, and —7-0 X 10~16 normal to the trigonal untangled by application of an external force, explains axis. Bi crystals with Pb, Sn, and Te in concn. the properties of the time lag. L . S. T. within the solubility range were studied. Sn and Pb Directional effects in electron diffraction from first diminish the contraction normal to the trigonal axis, and with increasing concn. cause an elongation, single crystals. G. A. M o r t o n (Physical Rev., 1933, [ii], 44, 952).—Electron diffraction photographs Sn being four times as effective as Pb. Parallel to from the cleavage surfaces of NaCl and NaF show that the axis small concns. of Sn decrease, and larger the resolution of the diffracted spots varies with the concns. increase, the elongation; the effect of Pb is azimuth of the crystal. L. S. T. small. Te causes a much larger sp. effect, but no change in sign. The change of the stress co'eff. of Interpretation of electron-diffraction photo the susceptibility with the concn. of foreign atoms is graphs of gas molecules, with results for benz discussed. Results support the assumption of the ene and carbon tetrachloride. L. P a u l in g and existence of two types of insertion of foreign atoms in L. 0. B r o c k w a y (J. Cliem. Physics, 1934, 2, 867— the crystal lattice: selective adsorption for small 881).—The accuracy of the visual method of inter concns. and vol. absorption for larger concns. preting electron-diffraction photographs has been N. M. B. tested in 4 different ways. When carefully applied Electrical properties of materials at high it can give vals. of intcrat. distances accurate to radio frequencies. J. S. M cP e t r ie (Nature, 1934, about 1 % . The regular plane hexagon model for 134, 897— 898). L. S. T. the C6HG mol. has been verified. The C-C separation Mechanism of electrical conductivity. R. W. in C6H6 is 1-390 ± 0-005 A. and the C-Cl separation P o h l (Z. Metallic., 1934, 26, 217—219).—A brief in CC14 is 1-760 ± 0-005 A. M . S. B . account of recent work of the author and his collabor Bloch theory applied to the study of alloys ators with especial reference to electronic condition in and of the properties of bismuth. H. J o n e s salt crystals. A. R. P. (Proc. Roy. Soc., 1934, A, 147, 396-417).—The Direct determination of the free paths of Bloch theory is applied to binary alloys which form electrons in metals. A. E u c k e n and F . F o r s t e r e- and r,-phases both having a close-packed hexagonal (Z. Metallk., 1934, 26, 232—235).—An apparatus is structure, and to alloys of Bi with small concns. of described for determining the diameter (d) of very thin other metals in solid solution. A Brillouin zone is metal wires by measuring the torsional vibration in found for Bi containing 5 electrons per atom. The vac. If the sp. electric resistance of the wire (p^) is conductivity of Bi-Sn and Bi-Pb alloys, and the then determined, the free path (I) of the electrons diamagnetic properties of the solid solutions of Sn, is given by pd = pK (1 + 8l/3nd). For Bi at 0° I is Pb,Te, Se, in Bi are considered. L. L. B. 11 ¡x, showing that the no. of free electrons at this temp, Ferromagnetic transformation and catalytic is only 1 for every 10® Bi atoms, i.e., that the classical activity. J. A. H e d v a l l , R. H e d i n , and 0. theory and not the Sommerfeld-Femri theory (I) Persson (Z. physikal. Chcm., 1934, B, 27, 196— applies to Bi. For Ag at 0° I is 57-7 X 10~7 cm. 208).—-A more detailed account of work already ( ± 1’5%), a val. which is in accordance with (I) and reported (A., 1934, 608). There is no evidence of a shows that every Ag atom provides a free electron. change in the macro-structure of Ni at the Curie point At very low temp, the equation does not apply, the (cf- A., 1933, 574). There is an increase in the rate const. 8/3— being replaced by another factor varying of oxidation of Ni at this point. R. C. with the temp. A. R. P.
Thermal expansion and the ferromagnetic Interaction of electrons in metals. E . W ig n e r change in volume of nickel. C. W illia m s (Physi (Physical Rev., 1934, [ii], 46, 1002—1011; cf. A., cal Rev., 1934, [ii], 46, 1011—1014).—The coefl. of 1934, 1283).—Mathematical. N. M. B. expansion of single and polycryst. specimens of Ni Reflexion of light from silver mirrors on ,°* known (varying) purity was measured at 2-5° transition from the amorphous to the crystalline 'ntervals in the range 200—500°. The ferromagnetic state at low temperatures. R. S u h r m a n n and ™®ngoinvol. per unit vol. of pure Ni is 3-24 ± 0-15 X G. B a r t h (Physikal. Z., 1934, 35, 971— 973).—The 1(H- N. M . B. electrical resistance and reflexion of thin layers of Gyromagnetic effect for a ferromagnetic sub Ag formed by vac. condensation at 20° abs. were stance above its Curie point. W. S u o k s m it h determined up to 390° abs. The variation of resist (mature, 1934, 134, 936)).—The mass susceptibilities ance is parallel to that of reflecting power (I). As 0 three Ni-Cu alloys (Ni approx. 56%) with Curie the resistance decreases (I) increases first in the long- 154 BRITISH CHEMICAL ABSTRACTS.— A, wave region, and later in the visible and ultra-violet. S and Se into the respective stable forms takes place In the transition from the amorphous to the metallic above 0, but not below. M. S. B. state, first the weakly bound, and then the more Thermo-electric force of thin films. E. A. strongly bound, electrons play the part of metal J o h n s o n and L; H a r r is (Physical Rev., 1933, [ii], electrons. A. J. M. „'V ...... 44, 944— 945).— The e.m.f. of thin sputtered thermo Susceptibility measurements of aluminium couples of Sb and Bi varies with the- thickness of Bi (Sb 3 X 10-5 cm.) up to 10-4 cm. Varying the m ixed crystals. H. A u e r (Z. Physik, 1934, 92, 283—290).—The susceptibility of A1 with small thickness of Sb (5 x 10-6 cm. to 10-4 cm.) has no quantities of Mn, In, Ge, Ga, Cu, Ag, Zn, Li, and Mg effect with 2 x 10-4 cm. of Bi. Thicknesses > 10"* does not follow the additivity law; deviations are cm. give a thermal e.m.f. corresponding with that of towards diamagnetism, and are dependent on the massive Bi-Sb. Different cryst. orientation in thin solvent metal. Extent of impurity may be deter layers of Bi may be the cause of this effect. L. S. T. mined spectroscopically, so that these measurements Thermal conductivities of bismuth single can be used to elucidate metallic constitution. crystals as influenced by a magnetic field. A. B. D. C. M. T. R o d in e (Physical Rev., 1934, [ii], 46, 910— Reflecting power of aluminium and its alloys 916).—Thermal and electrical conductivities of two in different regions. D. H. C l e w e l l and J. specimens of Bi single crystals were determined as a W u l f f (Physical Rev., 1933, [ii], 44, 952).—The function of temp., in the range —170° to —50°, and reflecting powers of Al, Be, Mg, Si, and Ag alloys have orientation of magnetic field relative to the crystallo- been measured throughout the region 2000—7000 A. graphic axes. N. M. B. and compared with those of films of the same metals. Electrical resistance of gold, copper, and lead L. S. T. at low temperatures. W . J. d e H a a s , J. de Absorption and reflexion of gold between 380 B o e r , and G. J. v a n d e n B e r g (Physica, 1934, 1, and 1400 A. I. L i b e n and H. M. O’B r y a n (Physi 1115—1124).—Measurements are recorded between cal Rev., 1933, [ii], 44, 952).—Reflexion from Au 1° and 20° abs. The val. for Au has a min. at 3-70° mirrors at various angles of incidence, and trans abs. The transition temp, of Pb is 7-20° abs. mission of thin Au films, have been, determined in a H. J. E. vac. spectrograph. Sputtered Au mirrors give more Superconductivity of thin films. E. F. B u r t o n , reproducible reflexion than evaporated surfaces. J. 0. W i l h e l m , and A. D. M is e n e r (Trans. Roy. Soc. L. S. T. Canada, 1934, [iii], 28, III, 65—79).—The temp, of Use of model substances for the investigation transition (I) to the superconducting state of thin of metal mechanics. A. S m e k a l (Z. Metallk., films of Sn varies with the thickness, there being a 1934, 26, 220—224).—Ail account is given of the limiting thickness (about 2 X 10~5 cm.) for which (I) results obtained in studying the elastic properties and is < 2° abs. The anomalous behaviour of such thin recrystallisation of NaCl and of their application to films is not due to irregularities of structure. The the problems of the mechanism of metal deformation pronounced sensitivity to current strength varies with and recrystallisation. A. R. P. the thickness. A superconducting film < 40 X 10-5 Elastic moduli of rock-salt. L. B a l a m u t h cm. thick is no longer superconductive (above 2° (Physical Rev., 1934, [ii], 46, 933; cf. A., 1934,836).— abs.) when it is covered with non-superconducting A correction. N. M. B. metal. Since alloy formation could not have occurred under the conditions of the experiment, it appears Elastic moduli for different textures of regular that a free surface is necessary for the occurrence of metals. D. A. G. B r u g g e m a n (Z. Physik, 1934, superconductivity, although a layer of definite 92, 561—588).—Elastic moduli for polycryst. solids thickness is also required. H. F. G. may be calc, from vals. for the single crystal. Superconductivity. A. P a p a p e t r o u (Z. Physik, A. B. D. C. 1934, 92, 513—522).—Theoretical. A. B. D. C. X-Ray analysis of the deformation textures of metallic materials. F. W e v e r (Kolloid-Z., Recent work on superconductivity. W. 1934, 69, 363—36S).—A review of published work on M e is s n e r (Physikal. Z., 1934, 35, 931—938).—A the X-ray structure of cold-worked metals. E. S . H. review of recent work on the occurrence of super conductivity in metals, thin metallic layers, and Allotropy and crystallisation of vitreous sub alloys, and the magnetic behaviour of superconductors, stances. P. M o n d a i n -M o n v a l (Ann. Chim., 1935, with a discussion by various investigators. [xi], 3, 5—72).—An abrupt change in the thermal A. J. M. expansion and sp. heat of vitreous Se and S takes Thermodynamics of the superconducting state. place at the softening temp. 0 (080 = 32°; 03 = C. J. G o r t e r and H. C a s im ir (Physikal. Z., 1934, 35, —29°). 0 has been determined by following the rate 963—966).—The assumption that the superconducting of change of penetrability of the substance by a metal phase is a two-phase system is extended. point with change of temp. Below 0 the rate of A. J. M. penetration, and therefore the fluidity, is practically Electronic theory of superconduction. B- zero. . 0 has also been determined for a no. of other S chachenmeier (Physikal. Z., 1934, 35, 966— vitreous substances (sucrose, glycerol, B203, a black 969).—In a superconductor, the two outer electrons wax, colophony, and glass). It is found that the are supposed to have different functions. One is transformation of the metastable cryst. varieties of attached to the core, the other is a conductivity GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 155 electron (I), this being responsible for the super has been investigated at 27-80° and 26-25° abs. conductivity. The wave-function corresponding with Cp and Cv at these temp, and at pressures 0—1 atm. (I) is unchanged by the application of a weak magnetic have been calc. M. S. B. field. A. J. M. High-frequency sound waves in Kundt’s tube. Excitation of nuclear vibrations of oxygen by O. B r a n d t and H. F r e u n d (Z. Physik, 1934, 92, molecular collision (according to determinations 385—389). A. B . D. C. of absorption of sound). H. 0. K n e s e r (Physikal. Difference between the specific heats of solid Z., 1934, 35, 983—984).—The connexion between and liquid tin in the neighbourhood of the m.p. excitation of nuclear vibrations and absorption of L . D ’O r and C. D e g a r d (Bull. Soc. chim. Belg., sound waves (I) is discussed. The dependence of 1934, 43, 510—512).—By application of Fischer’s (I) in 0 2 on the frequency of the waves and on the equation (cf. A., 1927, 615) to Sn-Bi solid solutions purity of the gas has been determined. With very it is calc, that Cp (solid)—Cv (liquid) = +0-44^0-06 pure 0 2 there is no (I), but when foreign gases are g.-cal. per g.-atom for Sn. E. S. H. present (H20, EtOH, NH3, C6H6, C2H2, H2S, H2, He) (I) increases to a max. and then decreases to zero Properties of condensed heavy hydrogen. as the eonen. of impurity (II) is increased. Extra K. Cl u siu s and E. B a r t h o l o m e (Physikal. Z., 1934, polation of the (I)—(II) curve to zero eonen. indicates 35, 969— 971).—The following data have been ob that the cessation period of the vibrational heat in tained for HJ and H“ (first val. in each case refers pure 0 2 is < 0-001 sec. The probability of collision to HJ) : m.p. 13-95°, 18-59° abs., heat of fusion between two 0 2 mols. is very small, but is greater 28-0, 47-0 g.-cal., pressure at triple point 58-3, 127 between 0 2 and foreign mols. A. J. M. mm., mol. vol. at triple point 26-13, 23-15 c.c., characteristic temp. 0 for Cp (solid) 91°, 89°. The Collision excitation of intramolecular vibra differences in these vals. are explained by the difference tions in gases and gas mixtures studied by in zero-point energy of the two gases, and the anharm- sound dispersion measurements. I. Experi onieity of the lattice vibrations. A. J. M. mental m ethod and results of precise m easure ments of velocity of sound in ultrasonic region. Phase equilibria of the third kind. E . J u st i II. Dispersion of sound at various temperatures and M. v o n L a u e (Physikal. Z., 1934, 35, 945— in chlorine and carbon dioxide, pure and with 953).—Phase equilibria of the third kind, as shown by admixed foreign gases. A. E u c k e n and R. 0 2 at the transition point (44° abs.), are considered. Becker (Z. physikal. Chem., 1934, B, 27, 219—234, Transformations of the NH4C1 type (NH4 salts, HI, 235—262; cf. A., 1933, 554).— I. An apparatus for HBr, PH3), where the sp. heat-temp. curve shows a the precise determination of the wave-length of sharp max., are considered. A. J. M. ultrasonic wraves and depending on the principle of Transformations of state of a higher kind. A. the acoustic interferometer is described. This may E u c k e n (Physikal. Z., 1934, 35, 954— 959).—The be used even with corrosive gases over a wide temp, continuation of the v.-p. curve above the crit. point range. The derivation of the vals. of cP/cv reduced is discussed as an example of a transformation of to zero pressure for the components of a gas mixture the third kind. Phase transformations (I) of the from the velocity of sound is described, the error NH4C1 type are considered as masked (I) of the first being 0-4— 1%. kind. They are due either to changes in the mol. II. The velocity of sound of frequencies 58, 145, arrangement in the crystal, or to the appearance or and 292 kilohertz has been measured in Cl2 and C02, disappearance of rotation in the mols. Since in these pure and with admixed foreign gases, at —33° to cases the rotational state changes over a very small 145°. The results show that the no. of collisions temp, range, the rotational hindrance exerted by necessary to withdraw one energy quantum from a the mols. on each other is the smaller the more mols. vibrating mol., Z, is very high for pure Cl2 and C03 there are rotating. The variation of sp. heat with at room temp., but may be reduced considerably by temp, of mixed crystals of CH4 and A has been the presence of reactive foreign mols. It is deduced investigated. It was found that the max. was theoretically that Z cc l/T’1', where n' depends on displaced to lower temp, and its width was considerably the index of repulsion of the mols. and a quantity increased, showing decreased hindrance. A. J. M. expressing the increase, on mutual approach of the F.p. of gallium. W. F. R o e s e r and J. I. H o f f mol. centres, of the probability of loss of a vibrational m a n (J. Res. Nat. Bur. Stand., 1934,13, 673—676).— quantum. The experimental data confirm this con The f.p. was 29-780±0-005°. Ga does not dissolve clusion. In general, light mols. are more effective its oxide appreciably. H . J. E. than heavier mols. in inducing excitation bv collision. R. C. Experimental determination of the heat Velocity of sound in neon gas. W. H. K e e s o m capacity of explosive gases. A correction. B. and J. A. van Lammeren (Proc. K. Akad. Wetenseh. L e w is and G . v o n E l b e (J. Chem. Physics, 1934, Amsterdam, 1934, 37, 614—615, and Physica, 1934, 2, 890).—The heat capacity of 0 3 cannot be calc, 1161—1170).—The velocity of sound in No has by the method previously given (A., 1934, 846). been measured by a resonance method between 0° M. S. B. and the temp, of liquid Ne (—247°). A new vapour Determination of the specific heat of gases cryostat has been designed for the lower temp. at high temperatures by the sound velocity Uown to liquid 0 2 temp. CP/CV calc, for p = 0 is 1-667 method. I. Carbon monoxide. G. G . S h e r - to ± 0-2%. The dependence of sound on pressure r a t t and E. G r if f it h s (Proc. Roy. Soc., 1934, A, 156 BRITISH CHEMICAL ABSTRACTS.— A.
147, 292—30S).—Working with > one frequency and curve. P. W. B r id g m a n (Physical Rev., 1934, [ii], correcting the data for the effect of frequency on 46, 930—933).—The pressure-temp. co-ordinates the velocity of sound in the gas, the sp. heat of CO of the melting curve and change of vol. were measured determined up to 1800° is in good agreement with up to 5500 kg. per sq. cm., and latent heats of fusion that deduced from spectroscopic data. The dis are calc. There is no evidence of a crit. point between crepancy, even at fairly high temp., between sp. liquid and cryst. phases, or of a max. or of an asymp heats determined by sound velocity methods and totic temp. N . M. B. those deduced from spectroscopic data is attributed Isotopic ratio in hydrogen. Precise density to the use of a single frequency. L. L. B. comparisons on water from various sources. II. Heat capacity of gadolinium sulphate octa- H. J. E m e l e u s , F. W. J a m e s , A. K in g , T. G . P e a r hydrate below 1° abs. W. F. G ia u q u e and D . F. s o n , R. H. P u r c e l l , and H. V. A. B risc o e (J.C.S., M a c D o u g a ll (Physical Rev., 1933, [ii], 44, 235— 1934, 1948— 1950; cf. A., 1934, 1062).—A no. of 236).—The heat capacity has been determined by samples of H20 have been found, by the flotation means of a series of adiabatic demagnetisations at method, to be heavier than normal H20. The vals. 1-7° to 0-287° abs. in fields up to 8000 gauss. The of A yd (p.p.m.) for the different samples are : Polar results are compared with a theoretical curve obtained H20, +1-36 and +4-2, the more northerly being by considering the interaction of two G d"‘ ions the heavier; deep-seated H20 from the Asmari treated as simple magnets. L. S. T. limestone of the Persian oilfields, + 1-9; H20 ob Real gases according to the thermodynamic tained by burning permanent gas driven off from equation of state. III. Specific heats c„ and charcoal absorbers used for extracting CGHG from and the compressional and expansion coeffi coal-gas, +4-6; ox-blood, +2-10, +2-52, -f-2-31; cients, [3 and a, of helium. V. J a c y n a (Z. Physik, ox-bile, -j-1-47; H20 from combustion of Trinidad 1934, 92, 661—674).—Theoretical (cf. A., 1934, cane-sugar, -}-7-56. The distribution of heavy H 1070). A. B. D . C. of beet-sugar and mixed molasses after fermentation was also investigated. A. J . M. Thermal behaviour of metals at very low tem peratures. W. H. K e e so m (Physikal. Z., 1934, Density of liquid iodine. T. N a y d e r (Bull. 35, 939—944).—The vals. of 0=7-745TC'-i (C==at. Acad. Polonaise, 1934, A, 231— 238).—Liquid I has heat), which should be const, if the Debye T3 law is ¿ 12° 3-94916 (buoyancy method), and its temp, coeff. accurate, show an increase and then a sudden fall -0-003267 per 1°. J. W. S. as the tomp. is decreased below 4° abs., in the case Thermal expansion of bismuth single crystals of Ag, Zn, Sn, Pb, and Bi. The effect is not due to near the m.p. J . W. B u c h t a and A. G o e t z (Physi the desorption of He used in the cooling from the cal Rev., 1934, [ii], 46, 1092— 1095; cf. A., 1932, surface of the metal. The corresponding increase in 796).—Highly purified B i single crystals showed no sp. heat at very low temp, is due to free electrons. decrease in the coeff. of expansion as the m.p. was The sudden change of sp. heat of a metal on transition approached. Traces of impurities (Pb, Ag, Cd, Sn) from the superconducting to the ordinary state was caused a decrease to negative vals. in a range of 10° investigated for Sn and Tl, and the results are com or 20° below the m.p. Discrepancies between pared with thermodynamic theory. A. J. Ml previous data are discussed in the light of these Discontinuities in the energy and the specific results. N . M. B. heat. A. B i j l (Physica, 1934, 1, 1125— 1142).— Interpretation of the pressure-volume-tem- A general theoretical discussion of association, perature relations of single and composite gases. illustrated by reference to gaseous condensation and G . A. L in h a r t (J. Physical Chem., 1934, 38, 1091— the transition of NaN03 at 275°. H. J. E. 1097).—A formula previously deduced for the jy-v-T Rate of vaporisation of molybdenum in a relations of several gases over a large range of temp, vacuum. L. N o r r is and A. G. W o r t h in g (Physi and pressure (A., 1933, 668) has been applied to cal Rev., 1933, [ii], 44, 323).—The changes in wt. mixtures of these gases and over a much larger of various long filaments of Mo heated in a vac. to pressure range. M. S. B. various incandescence temp, give an empirical equation Pressure-volume—temperature relations for of the form log m—A-rBT-^+CT-- for the rate of six [mineral] oils. R. B. Dow (J. Washington evaporation (m ). Contrary to the case of W , operation Acad. Sci., 1934, 516—526).—Relative vols. at 25°, at const, current results in a const, temp. 40°, and 75°, and pressures nearly up to apparent L. S. T. solidifying pressures, have been determined for Effect of a magnetic field on the passage of 6 light oils of different composition. Compressibility, heat through gases. H. Se n f t l e b e n and J. thermal expansion, and various thermodynamic P ie t z n e r (Physikal. Z., 1934, 35, 986—988).—The functions have been deduced. Similar vals. are, variation of the effect of a magnetic field on the in general, found for all the oils. Thermal expansion thermal conductivity of a gas with the nature of varies most with temp, and pressure, and in a manner the gas is investigated. This effect increases until contrary to that for pure liquids at low pressures. the lines of force are perpendicular to, and then M. S. B. decreases as they become parallel to, the direction of Molecular size of crystalline carbon tetrachlor heat flow. A. J. M. ide and tetrabromide, and of ethylene dichloride Melting parameters of nitrogen and argon and dibromide. E. 0. K. V e r s t r a e t e (Bull. Soc. under pressure, and the nature of the melting chirn. Belg., 1934, 43, 513—544).—The v.p. of CBr4 GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 157 at low temp, and the f.p. of solutions of CBr4 and Viscosity and conductivity of molten glasses. CC14 in CHCL, and C2HC15 have been determined. K . L a r k -H o r o v it z and C. L . B a b c o c k (Physical The m.p. of the stable forms of CBr4 and CC14 have Rev., 1933, [ii], 44, 321).—The conductivity and been obtained by extrapolation and the heats of 7] of molten glasses as a function of temp, have been transformation calc. The d of the modifications determined at 50° intervals up to 1400°. There is of CBr4, CC14, C2H4Br2, and C2H4C12 have been no sudden break in the curves. Resistivity and tj determined. The results indicate that the two can, in most cases, be represented by -ri~ApB for forms of CC14 and CBr4 are bimol. and the two modific temp, from the softening point to 1400°. A and B ations of C2H4Br2 unimol. E. S. H. change from glass to glass. L . S. T.
Vapour pressure of hydrocarbons. S c h m it t Transport phenomena in Einstein-Bose and (Compt. rend., 1934, 199, 1299— 1301).—Vais, for Ferm i-D irac gases. II. E. A. U e h l in g (Physi n-C6H14, methylq/cZopentane, CGHG, and PhMe are cal Rev., 1934, [ii], 46, 917—929; cf. A., 1933, represented by formulae. H. J. E. 551).—Mathematical. Equations for the heat con Dependence of vapour pressure on temper ductivity and viscosity cocffs. of gases as a function of temp, and density are obtained for the case of ature above the critical point. J. E. V e r s c h a f - mols. acting as rigid elastic spheres, and are evaluated felt (Physikal. Z „ 1934, 35, 1013— 1014).—The continuation of the v.-p. curve above the crit. point for H and He. N. M. B. observed by Trautz and Ader (A., 1934, 723) is Evaporation of binary liquid mixtures. A. derived analytically. A. J. M. P a k s c h v e r and G. L tjrie (Chem. Fabr., 1934, 7, 448— 452).—The velocity of evaporation of a Statistical mechanics applied to the calcul binary mixture of const, composition is expressed ation of the entropy of rigid gas m olecules. in terms of its surface area, the v.p. of the components, (Ml l e .) G. S c h o u ls (Bull. Acad. roy. Belg., 1934, [v], and the atm. pressure. The speed of evaporation in 20, 1014— 1022).—Mathematical! N. M. B. an air stream of velocity v follows the empirical law Two-dimensional equation of state and struc F = F 0(1-|-k ^ v ), where A: is a coeif. dependent on ture of surface layers. II. Surface layer of temp, and on the composition of the mixture. The pure liquids. B. T a m a m u s h i (Bull. Ghem. Soc. theory has been verified for E t0H -E t20 mixtures. Japan, 1934, 9, 475—493; cf. A., 1934, 1304).—An J. W. S. equation of state for the surface layer of pure liquids Volatility at 20° of heptane-alcohol-benzene is developed in which the surface tension (a) is repre mixtures. R. S a l m o n i (Annali Chim. Appl., 1934, sented as the sum of the static cohesion, thermal 24, 539— 549).—The two binary EtOH systems show energy, and intermol. forces. Eôtvôs’ formula is marked max. volatility (I) in the EtOH-poor region, derived, and the const, shown to depend on temp, owing to dissociation of the associated EtOH mols. and on the nature of the substance, increasing with on dilution with the inert component. The triangular increase in cohesional forces. The abnormal diagram for the ternary mixtures shows that the behaviour of anisotropic liquids is explained, and (I) of binary mixtures containing 20% of EtOH is vais, of the dipole moment of y-azoxy-anisole and further increased by addition of 20% of CcH6. At -phenetole agreeing with those experimentally deter 20° the (I) of all the mixtures is sufficient to give an mined are calc, by assuming that at the transition inflammable air-vapour mixture and, with mixtures temp. c=cohesional forces. F. L. U. rich in C6HG or C7H16, much > sufficient. The ternary Equation of state. I. R. B e c k e r (Z. Physik, mixtures are of val. especially for starting up a motor 1934, 92, 680—682, 689). G. S c h w e ik e r t (ibid., engine at about 0°. T. H. P. 683—68S, 689).—Polemical. A. B . D. C. Azeotropism in relation to polymerisation and General form of the equation of state for a solvation, and negative azeotropism from the monatomic ideal g a s. G. P o l v a n i (Physical Rev., functional viewpoint. M. L e c a t (Ann. Soc. Sci. 1933, [ii], 44, 123).—A claim for priority (cf. A., Bruxelles, 1934, 54, B, 283—290).—The connexion 1933, 551). L. S. T. between positive (max. in v.p.-composition curve) (I) and negative (min. in curve) (II) azeotropism and Fusion. K. F. H e r z f e l d and (Miss) M. G. the mol. condition of the components is discussed. M ayer (Physical Rev., 1934, [ii], 46, 995— 1001 ; Polymerisation may give rise to either (I) or (II), cf. A., 1934, 241).—Mathematical. As a type of and not exclusively (I). The effect depends on the the simplest crystal, the equation of state of frozen degree of polymerisation. Solvation is not strictly A is developed. The pressure as a function of the necessary for (II), but is favourable to it. All vol. at a given temp, has a min., indicating the break negative binary azeotropic mixtures (about 200 are down of the crystal. The temp, for this min. at known) contain either an acid, an organic halogen zero pressure is interpreted as the m.p. The case of derivative with > 1 halogen atom, or a phenol. He and substances of high m.p. is considered. These are discussed in detail. A. J. M. N. M. B. Compressibility of helium gas between 2-6° Frequency of azeotropism without the Ban and 4-2° abs. W. H. K e e s o m and H. H. K r a a k croft point, and limited azeotropism. M. L e c a t (Troc. K. Akad. Wetenseh. Amsterdam, 1934, (Ann. Soc. Sci. Bruxelles, 1934, 54, B, 212—215).— 37, 746—747).—Isotherms of He have been deter Theoretical. A. J. M. mined at 4-224°, 3-095°, and 2-581° abs., and virial Temperature-viscosity measurements in the coefis. calc. R. S. B. systems CaO-SiOa and Ca0-Si02-CaF2. C. H. 158 BRITISH CHEMICAL ABSTRACTS.— A.
H e r t y , jun., F. A . H a r t g e n , G. L. F r e a r , and 10, 532—554).—Al and Mg are mutually sol., forming M. B. R o y e r (Bur. Alines, Rept. Invest., No. 3232, a- and e-phases. The y, and S intermetallic phases 1934, 31 pp.).—The concentric-cylinder method for consist mainly of Al8Mg5, AlMg, and Al3Mg4, respec high-temp. r) determinations has been applied to tively. Ch. A b s . (e) the mixtures Ca0-Si02 (36—57% CaO, 1464— Equilibrium relations in alimiinium-nickel 1688°) and CaO-SiO,-CaF2 (12-64—61% CaO, 10-6— alloys of high purity. W . L. F i n k and L. A. 52-5% Si02, and 0-39—76-7% CaF2, 1010— 1740°). W i l l e y (A m er. Inst. Min. Met. Eng., Inst. Met. There is a ridge of max. r, sloping from the 50 : 50 Div., Tech. Publ. 569, 1934, 11 pp.).—Alloys with Ca0-Si02 binary towards the CaF2 apex. The de 0— 18% Ni have been examined. NiAl3 and solid crease in -q with fluorspar content is continuous over solution form a eutectic mixture (639-9°, 5-7% Ni). the range studied, but is greatest near the Ca0-Si02 The solid solubility of Ni in Al decreases from 0-05% binary line. Ch . A b s . (e) at the eutectic temp, to 0-005% at 500°. Al-Ni Active oxides. LXXXII. Changes in the alloys exhibit age-hardening. Ch . A b s . (e) magnetic properties of mixtures of Cd0/Fe20 3, Effect of quenching strains on lattice para Cu0/Fe20 3, and PbO/Fe2Os during chemical meter and hardness values of high purity K it t e l com bination. H. (Z. anorg. Chem., 1934, aluminium-copper alloys. A . P h il l ip s and R . M. 221, 49—55).—On heating, the magnetic susceptibil B r ic k (Amer. Inst. Min. Met. Eng., Inst. Met. Div., ities remain fairly const, until combination of the Tech. Publ. 563, 1934, 19 pp.).— Quenchcd Al-Cu oxides begins to take place, generally above 500°, alloys of high purity may have abnormally large when paramagnetism increases. At still higher lattice parameters which increase with rapidity of temp, ferromagnetism appears, indicating the presence cooling, specimen diameter (up to 0-5 in.), and with of a ferrite. M. S. B. Cu content of the solid solution. Alloys with 5-4% Mobility of gold in solid lead. W. S e it h and Cu in solution when rapidly quenched have a max. H. E t zo ld (Z. Elektrochem., 1934, 40, 829— 832; age-hardening capacity at room temp. The greater cf. A., 1933, 1110).—The diffusion coeff. of Au in is the degree of strain the sooner does pptn. occur solid Pb, measured between 113° and 300°, oc at 275—325°. Ch . A b s . (e) e-u,oooirt^ an(j js not affected by pressures up to High zinc region of the copper-zinc phase- 1000 atm. When a current is passed through a equilibrium diagram. E. A . A n d e r s o n , M. L. rod of homogeneous Pb-Au alloy at 150— 180°, Au F u l l e r , R . L. W il c o x , and J. L. R o d d a (Amer. accumulates at the positive end. The transport no. Inst. Min. Met. Eng., Inst. Met. Div., Tech. Publ. of Au in solid Pb at this temp, is about 10"10. 571, 1934, 29 pp.).—Data obtained by X-ray, elec F. L. U. trical conductivity, and microscopical methods are Compression of metals in the formation of recorded, confirming earlier results. Ch . A b s . (e) intermetallic compounds. W. B il t z (Z. Metallic., 1934, 26, 230—232).—Differences between the mol. Equilibrium in the lead-zinc system with vol. of intermetallic compounds and the sum of the special reference to liquid solubility. R K. at. vols. of their components show that readily W a r in g , E. A . A n d e r s o n , R. D. Sp r in g e r , and compressible metals undergo a considerable con R. L. W il c o x (Amer. Inst. Min. Met. Eng., Inst. traction on combination; the contraction is slight Met. Div., Tech. Publ. 570, 1934, 10 pp.).—The when the metals are much less compressible. solubility is > and the temp, of complete miscibility A. R. P. < previously reported. The monotectic temp, is Character of metallic solid solutions and 417-8° (0-7% Pb). C h . A b s . (e) com pounds. U. D e h l in g e r (Z. Metallic., 1934, Magnetic, electric, and spectroscopic investig 26, 227—230).—Recent work on the nature of ation of gold-silver alloys. H. A u e r , E. R ie d l , intermetallic compounds is critically reviewed with and H. J. Se e m a n n (Z. Physik, 1934, 92, 291— 302).— especial reference to the influence of valency and Magnetic susceptibility and electrical resistance show affinity. A. R. P. no change after heating in vac. or in N2, or after A'-Ray analysis of iron-aluminium alloys. II. remelting in vac. (cf. Shimizu, A ., 1933, 455). A. O s a w a (Kinz. no Kenk., 1933, 10, 432— 445; A. B. D. C. cf. A., 1934, 137).—From X-ray analysis the phases Ternary system copper-silver-cadmium. L. existing at room temp, are a-Fe, FeAl, (rhombohedral; L o sa n a and C. G o r ia (L’lnd. Chimica, 1934, 9, a 6-314 A., a 87° 24' 28"; 18 atoms per unit cell), 1603— 1615).—M.-p. data and photomicrographic Fe2Al5 (monoclinic; a 9-910, b 10-811, c 8-S24 A., observations are recorded and a few X-ray photo (3 124° 59' 53"; 56 atoms per unit cell) and FeAl3 graphs are appended. No ternary compounds are (rhombic ; a 15-804, b 11-870, c 8-088 A .; 104 atoms formed. The structure of the alloys is influenced per unit cell). (FeAl),, (parameter 5-980 A .; 16 considerably by the rate of cooling. The composition atoms per unit cell) was obtained by quenching from of several alloys which are particularly resistant to > 1080° in H20. The parameter of the a-solid oxidation is given. D. R. D. solution increases from 2-854 A. for Fe to 2-S91 A. Ternary aluminium-silver-magnesium alloys. with 46-7 at.-% Al. No deformation structures such B . O t a n i (Kinz. no Kenk., 1933, 10, 262—276).— as Fe3Al or FeAl are present in the a-solid solution. The equilibrium diagram for mixtures of Al with Ch . A bs. (e) AgMg is recorded. The ternary compound AlAgMg Equilibrium diagram of aluminium-magnes- is formed at 570°. Its solubility in Al is 14% at ium system. M. K a w a k a m i (Kinz. no Kenk., 1933, 538° and 0-4% at 300°. The combined effects of GENERAL, PHYSICAL, AND. INORGANIC CHEMISTRY. 159
AgMg and Cu, Si, Mn, and Ni on A1 have been ex determined between —70° and 70°, and of Ba(NOs)2 amined. The alloy with AgMg 6 and Cu -4% has between —27° and 51°. With both substances excellent mechanical properties after suitabfe heat- unstable (probably tetra-)ammoniates are formed. treatment. Ch. Abs. (e) F. L. U. New magnetic alloy with a very large coercive Solubilities and activity coefficients of the three nitroanilines in aqueous solutions of typical force. V. D r o z z in a and R. J a n u s (Nature, 1935, 135, 36—37).—Nd containing approx. 7% Fe is salts at 85°. J. N P e a r c e and L. J. G a r w o o d strongly ferromagnetic. The large coercive force, (Proc. Iowa Acad. Sci., 1932, 3 9 , 161).— Solubilities which is > that of Fe or its alloys, indicates that a have been determined at 25° in H20, and in aq. new alloy is present. L. S. T. NaCl, BaCl2, K 2S04, and MgS04. Activity coeffs. are calc. These increase for the four salts in the Critical solution temperatures of some hydro above order and also increase with salt concn. carbons in sulphur dioxide. R. T L e sl ie (J. Res. C h . A b s . (e) Nat. Bur. Standards, 1934,' 13, 589—597).—From Velocity of crystallisation of sucrose. K. miscibility temp, curves for various hydrocarbons Sm o l e ń s k i and A. Z e l a z n y (Bull. Acad. Polonaise, the following crit. solution temp, in S02 have been 1934, A, 172—1S9).—The formation of secondary determined: w-C5H12 2°, p-methylpentane 10°, n- germ crystals after inoculation is attributed to the CcH14 12°, methylci/cZopentane 8°, cj/cZohexane 12°, presence of crystal dust. Crystallisation of super [i-nicthylhexane 18°, w-C7H1G 19°, methylcj/cZohexane saturated solutions of sucrose (I) induced by the 15°, (3-methylheptane (I) 24°, ethylq/cZohexane 25°, addition of (I) crystals of known size and no. has n-C8H18 25-5°, nonanaphthene (II) 27°, hexahydro- been followed refractometrically. For pure un mesitylene (III) 30-5°, ?i-C9H20 32°, n-C10H22 36-5°, stirred solutions at 25°, dx/dt=KF(n0—x)2/n0, where 42°, and n-C12H2r> 47°. Vais, for NH2Ph n0 is the initial crystallisable (I), F is the surface, are (I) 75°, (II) 57°, and (III) 56-9°. S02 and NH3 and x the amount of (I) crystallised, per 100 g. of are considered unsuitable for separating const. - H ,0, after t min. dx/dt is diminished by impurities. boiling mixtures of hydrocarbons, but NH2Ph is R. S. more promising. A. R. P. Distribution of trichloroacetic acid between Distribution equilibrium between alcohol, two contiguous liquid phases. N. A. d e K o l o - benzine, and water. F. S p a u s t a (Mitt. tech. Ver- s o v sk i and F. S. K u l ik o v (J. Gen. Chem. Russ., suchsamtes, 1933, 22, 9— 17; Chein. Zentr., 1934, 1934, 4, 915—926).—The partition coeff., y, of ii, 1559). H. J. E. CC13-C02H for the systems H20-PhMe, -cumene, -CHC13, -CC14, -EtBr, -PhNOa, -n- and sec.-C5Hn -OH, Passage of helium through apparently com and -CH2PlrOH, at 25° is given by y=Jc1c—k2, pact solids. (L o r d ) R a y l e ig h (Nature, 1935, where k} and k2 are consts., and c is the total concn. 135, 30).-—He passes through gelatin, celluloid, and of CC13-C02H. “ R. T. Cellophane at room temp., probably by penetration between the constituent crystals. It does not pass Role of intergranular fissures in the occlusion through single crystals of quartz; beryl, which has and evolution of hydrogen by palladium. D. P. a more open crystal structure, appears to be per Sm it h and G. J. D e r g e (J. Amer. Chem. Soc., 1934, meable. L . S. T. 56, 2513—2525).—The absorption and desorption of Solubility of lead sulphate in water and H2 have been studied, particularly with respect to aqueous solutions of sulphuric acid. H. D. time of decay, annealing temp., rate of cooling, Crockford and D. J. B r a w l e y (J. Amer. Chem. grain size, effect of air, and deformation. Variations Soc., 1934, 56, 2600—2601).—Data are recorded for in the metal other than those, caused by mechanical 0°. 25°, 35°, and 50°. The solubility falls rapidly deformation affect absorption and desorption in the "lth the addition of minute quantities of H2S04, same sense. Mechanical deformation may affect ab but increases again at about 70% H2S04. The solid sorption and desorption in the same or opposite senses, pbase in equilibrium throughout is PbS04. according to its severity. The rate of absorption E. S. H. at atm. temp, and pressure is independent of time Saturated solutions of carbam ide in liquid for both worked and unwarked metal. Diffusion ammonia. Vapour pressures and com positions appears to occur primarily along slip-plane fissures from - 2 6 - 4 0 to 101-0°. W. S c h o l l and R O. E. and secondarily through the unstrained lattice. Davis (Ind. Eng. Chem., 1934,2 6 , 1299— 1301).—The E. S. H. compositions and v.p. of saturated solutions of Sorption of sulphur dioxide by active char ^0(NH2)2 iii NH3, determined by use of an iso- coal. II. Effect of heating on the sorptive teniscope, agree well with the data of Janecke. A power of coconut charcoal. III. Sorption equi break occurs in the temp.-coinposition curve at librium at high temperatures. IV. Hysteresis. «•6° and 74-6% CO(NH2)2, corresponding with the K . A r i i (Bull. Inst. Phys. Chem. Res. Tokyo, 1934, transition from CO(NH2);,NH3 to CO(NH2)2; a 1 3 , 1428— 1434, 1435—1438, 1439— 1445; cf. A ., similar break occurs in the temp.-pressure curve. 1934, 1066).—II. The absorptive power of coconut A. G. charcoal (I) activated at 690° increases with time of Ammoniates of calcium and barium nitrates. activation. A t 800°, max. activity is reached in pu P o r t n o v and B. B. V a s s il ie v (Z. anorg. 2 hr. and is unchanged on further - heating. (I) m-, 1934, 221, 149— 153; cf. A., 1934, 1185).— activated at 990° for 30 min. has very high adsorption, ihe solubility of Ca(N03)2 in liquid NH3 has been but the activity decreases on further heating. X-Ray 160 BRITISH CHEMICAL ABSTRACTS.— A.
analysis and the change in magnetic susceptibility Effect of air on the condensation of water show that the loss of activity is due to graphitisation. vapour. E. F. M. v a n d e r H e l d (Physica, 1934, III. The adsorption isotherm of S02 at low pres 1, 1153—1160).—Theoretical. The retarding effect sures is expressed by a = 10-47p0135 and 2-67^°-917 of air on condensation is attributed to the resistance at 90° and 100°, respectively. offered to diffusion by an air-rich boundary layer. IV. A hysteresis effect is observed at 20— 30° H. J. E. ■with (I) activated at 800° for 1 hr. This is attributed Adsorption of phenol and resorcinol from to difficulty in escape of SO, from the interior of (I). aqueous solution by carbon. A B o u t a r ic and J. W. S. (M l l e .) P. B e r t h ie r (Bull. Soc. chim., 1934, [v], Chemisorption on charcoal. V. Influence of 1 ,1549—1560).—The adsorption by animal, activated, ultraporosity on adsorption. A. K in g (J.C.S., vegetable, and gas C has been investigated inter- 1934, 1975— 1980; cf. A., 1934, 1067).—It is sug ferometrically. There is no evidence of discontinuities gested that activation of charcoal by 0 2 or C02 in the adsorption isotherms, which in all cases conform increases the pore diameter in agreement with the to the Freundlich equation and not to that of Perrin. result that the max. size of mol. adsorbed increases In general, added solutes which are only weakly with the degree of activation. The density also adsorbed by C do not affect the adsorption of PhOH increases with the time of oxidation. Traube’s rule (I) and resorcinol (II), but > 0-53 g. per litre of K phos is obeyed if the pores are sufficiently enlarged by phate (III) diminishes the adsorption, although (III) oxidation or evacuation. The theory of sp. adsorp is adsorbed to only a small extent. The diminished tion by charcoals is discussed. R. S. adsorption of (I) and (II) in the presence of > 0-25 g. Vapour pressure isotherms of water on active of BzOH (IV) and > 0-5 g. of succinic acid (V) per charcoal applied to its behaviour towards litre is probably related to the marked adsorption of carbonyl chloride. H. E n g e l h a r d and W. St i l (IV) and (V). J. G .A. G. l e r (Z. Elektr ochem., 1934,40,833—836).—Specimens Interchange of adsorbed ions. E. J. W. of active C containing equal quantities of adsorbed V e r w e y (Cliem. Weekblad, 1934, 3 1 , 789-795).- H ,0, prepared (I) by dehydrating wet material and A review of recent work on the interchange of ions (II) by allowing previously dried material to absorb between a solution and an adsorbed laver. H20, are not equally effective in removing C0C1, ' D. R. D. vapour from air; (II) becomes ineffective sooner than Adsorption and catalysis. I. Carbon di- (I). The difference in the resistance times [i.e., sulphide-water reaction. L . A. M uniio and duration of capacity to remove COC1, beyond the J. W. M cC u b b in (Trans. Roy. Soc. Canada, 1934, limit of detection under standard conditions) corre [iii], 28, III, 29—33).—The quantity of CS2 adsorbed sponds with the difference between the v.p. shown by from saturated air at 25° by A1203 gels of different the adsorption and desorption isotherms of the H20 contents, and the quantity of H2S produced, C-H ,0 system. This behaviour is considered to have been determined. The adsorption rises to a be due to liquid H20 partly blocking the pores in (II) pronounced max. (at about 8%) with decrease of the and thus hindering entry of the vapour. F. L . TJ. H20 content, but the catalytic activity is a max. Equation for the kinetics of activated ad at 9— 16% H20 and shows no direct relation to the sorption. S. R o g in s k y (Nature, 1934,134, 935).— adsorptive power. H. F. G. The equation q—ar1 log ( i + y - f C , where q is the amount of gas adsorbed during time t, and a and C Surface and interfacial tension of mercury are consts. for a given system, reproduces the data by the sessile drop and drop-weight methods. of various investigators for the sorption of gases on H. B r o w n (J. Airier. Chem. Soc., 1934, 56, 2564— metals or metallic oxides. It does not agree with 2568).—A modification of the sessile drop apparatus Taylor’s theory of activated adsorption. L. S. T. is described, and the results obtained thereby are compared with those of the drop-wt. method. The Sorptional and catalytic properties of active interfacial tension of Hg against H20 is 374-3 dynes manganese dioxide, with reference to vapours per cm. at 25°; the surface tension of Hg in dry and gases. I. E. V. A l e x e e v s k i and Z. E. air or in vac. is 473 (±0-3% ) dynes per cm. at 25°. G o l b r a ic h (J. Gen. Chem. Russ., 1934, 4, 936—947). Irreversible adsorption effects and the difference —The adsorptive power of active Mn02, prepared between results obtained by static and dynamic from KMn04 and MnS04, increases with the mol. wt. methods are explained on the basis that surface of the members of a homologous series of adsorbates. oxidation of Hg in air occurs only in the presence of For CC14 and PhCl, breaks in the adsorption isotherms H20 vapour. E. S. H. indicate capillary condensation. NH2Ph is converted into NPhiNPh (48% yield at room temp.) by MnO,, Validity of Antonow’s rule for the solid-liquid which is reduced to Mn304, whilst PhCN is hydrolysed interface, and the measurement of the surface to NH,Bz. CgH14 and C5H12 at 40° react violently tension of solids. R. L o m a n and N. P. Z w i k k e r with Mn02, with production of CO, CO,, H20, and (Physica, 1934, 1, 11S1—1201).—Antonow’s rule of small quantities of unsaturated hydrocarbons; has been verified by measurements of angles of xinder analogous conditions, MeOH yields CO, CO,, contact for H20 and Hg drops on 56 stones, minerals, H ,0, and traces of CH20, whilst PliMe affords PhCHO. ctc. The relation is applied to calculate the surface NH3 is adsorbed witfiout oxidation at 0°, whilst at tension of specimens of Fe, steel, and granite. The >50° the reaction 4NH3-|-9Mn02— >-2N2-f3Mn304-f- pre-treatment of the solid surface is discussed. 6H20 takes place. " R. T. H. J. E. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 161
Influence of atmospheric carbon dioxide on as the mols. are flat and the films gaseous. The val. the surface tension of aqueous solutions of is much lower for these groups when the mols. are sodium salts of fatty acids. A . Lottermoser standing on end (in the condensed state). For and B. Baumgurtel (Kolloid-Beih., 1934, 41, 73— alcohols, Me ketones, and aldoximes, jjl changes but 94).—In solutions of Na salts of the lower fatty slightly on transition from the expanded to the con acids, C02 reduces the surface tension (I) slightly, densed state. It thus appears that there is no the effect increasing with increasing concn. of the necessary reorientation of the end groups as the mols. solution, whilst with the soaps C02 reduces (I) come closer together. L. L. B. markedly, the effect decreasing with increasing Electron microscope and its application, concn. of the soap. In all cases after a time (I) begins especially to the study of thin films on metals. to rise again. The influence of temp, and concn. E. B r u c h e (Kolloid-Z., 1934, 6 9 , 389— 394).— has been studied quantitatively. 0 2 reduces the Apparatus and technique are described and the (I)'of Na oleate solutions only slightly, whilst C02 application of the method to the study of metallic reduces (I) markedly. The influence of temp, and surfaces is illustrated. E. S. H. concn. on the (I) of Na oleate in absence of 0 2 and C02 has been determined. C02 coagulates Na abietate Spreading of complex proteins. E. G o r t e r , and causes a slight rise of (I). E. S. H. H. v a n O r m o n d t , and T. M . M e i j e r (Biochem. J., 1935, 2 9 , 38— 47).—The influence of the introduction Interface equilibria and inner equilibria in of a prosthetic group into a protein mol. on its spread heterogeneous systems. III. Significance of ing (I) is studied. Combination of tartrazine (II) with molecular structure of salt-like compounds for ovalbumin (III) does not influence the (I) at the iso charging adsorption on their surfaces. L. I m r e electric point (IV), whilst the min. at pa 2-7— 3-0 dis (Z.physikal. Chem., 1934,171,239— 256; cf. A ., 1933, appears. Combination of spermidine (V) with pepsin 671).—Measurements of the adsorption of P b " on (VI) decreases (I) on the acid side of (IV) and increases BaSO,, and sparingly sol. Pb salts at low concns. of it on the alkaline side. Nucleic acid is without in adsorbate have shown that the elementary vol., v, fluence on the (I) of (III). Acetylation of (VI) modi occupied by each adsorbed ion on the various adsor fies the min. on the acid side of (IV). Additions of bents falls in the order BaS04>PbS04>PbCl2> (II) and (V) produce similar effects with (III) and (VI), PbI3>PbBr2. The abs. vals. of v deduced by means respectively. These effects are similar to those pro of Boltzmann’s distribution law, however, are the duced by adding negative and positive bivalent ions, normal at. dimensions. The explanation is that in respectively. H. D. applying the Langmuir-Hiickel isotherm to such systems the vol. term involved is not the vol. of the Influence of time on the spreading of proteins. solution, but the much smaller phase vol. of the dis E. G o r t e r and G . T. P h i l i p p i (Proc. K. Akad. solved mols. Theoretical considerations show that Wetensch. Amsterdam, 1934, 3 7 , 788— 793).—The the more polar is the lattice the larger is v, and this is velocity of spreading of ovalbumin on acetate buffer confirmed experimentally. B-. C. has been determined by following the boundary of the film by means of a Po electrode. The time for the Structure investigations of interfaces by boundary to reach its final val. is a min. at pK 1-0, pa means of X-rays and electrons. E R u p p (Kol- 13-0, and at the isoelectric point, and reaches high vals. loid-Z., 1934, 69, 369—378).— Published work is on both sides of this point. This explains the W - reviewed. E.' S. H. shaped curve obtained when area, reduced to zero Energetics of surface phenomena. W. K o s s e l pressure, is plotted against pa and the measurements (Ann. Physik, 1934, [v], 21, 457— 480).—The mechan are made at a const, time after the formation of the ism of the growth of crystals according to the Gibbs film. R . S. B. theory and the mol. theory is discussed. A. J. M. Spreading of myosin. E. G o r t e r and H. v a n Laminar system s. I. U ni- and m ulti-m ole O r m o n d t (Biochem. J., 1935, 2 9 , 48—52).—Myosin is cular sulphide and hydroxide layers at phase made to spread on H20 by previous treatment with boundaries. S. G. M o k r u s c h i n (Kolloid-Z., 1934, trypsin (I ); the area-time curve is dependent on (I) 70, 48—55).—Published work is reviewed, and pre concn. and the time of treatment with (I). H. D. liminary observations of the characteristics of sulphide Effect of carbonic acid on the spreading of and hydroxide films formed on metals are recorded. ovalbumin on the surface of water and vari E. S. H. ations in the thickness of these films in uni- Orientation of oxide films on metals. R. F. molecular layers. H. D e v a u x (Compt. rend., E- L. M c C a n d l e s s , and F. N. R h i n e s (Nature, 1934, 1 9 9 , 1352— 1354).—The variations observed in 1934,134,1009).—Thin films of FeO and Cu20 grown the spreading of ovalbumin on pure H20 are due to fV ? anc^ Cu, respectively, have an at." arrangement variation in pB, the observer’s breath yielding sufficient definitely related to the lattice structure of the metal C02 to cause inaccuracies. Unimol. films can be °n which they are formed. L. S. T. obtained which vary from 0-9 to 8 mix in thickness, Structure of surface films. XXI. Surface according to the ps . If these variations are due to Potentials of dibasic esters, alcohols, aldoximes, orientation, the albumin mol. must be long and and ketones. N. K. A d a m , J. F. D a n i e l l i , and narrow. J. W. S. 4Qchi H id in g (Proc. Roy. Soc., 1935, A, 147, 491— Flow potentials of barium sulphate. H. R . const- vali of ¡z is obtained for mols. with K r u y t and R. Ruyssen (Proc. K . Akad. Wetensch. - tUjkt groups at opposite ends of a long chain, so long Amsterdam, 1934, 3 7 , 624— 632).— Measurements 162 BRITISH CHEMICAL ABSTRACTS.— A.
were made on natural barytes and on 4 differently decreases in intensity with dilution. It indicates a prepared samples of pptd. BaS04. All the samples more or less regular arrangement of the ions in the had exactly the same cryst. structure, but the degree liquid. This effect is not observed with aq. AgN03, of development of the active surface differed and Pb(N03),, or Ba(N03)2. Aq. Lil, LiBr, RbBr, and influenced the electrokinetic potential (£). Natural other alkali halides give a broad ring, unaffected by barytes retained a negative charge in presence of aq. dilution, and this is attributed to interference between BaCl2 and the i-concn. curve is similar to that of the scattering from a heavy ion and that from paraffin. Pptd. BaS04, of dimensions 10 [i approx., adjacent H20 mols. H. J. E. has a negative charge in contact with pure H„0, but Refractometric investigation of the formation is charged positively by BaCl2 and negatively by sol. of compounds in acjueous solution, hitherto sulphates. Chlorides of Sr, Ca, Mg, Zn, and Cd impart designated as double salts. G. S pactt and E. a positive charge, whilst NaCl and KC1 increase the P o p p e r (Bui. Soc. Stiinte Cluj, 1934, 7, 400—520; negative charge. M. S. B. Chem. Zentr., 1934, ii, 704).— Data are recorded for Theory of cataphoresis and electro-osmosis. aq. solutions of 16 pairs of salts (e.g., HgCl2+NaCI, J. J. Bikerman (Z. physikal. Chem., 1934,171, 209— HgCl2+ K 2Cr20 7, CdCl2+K Cl, NaN03+ K N 0 3) in 220).—The rate of formation of the double layer has varying proportions. H. J. E. been derived from considerations based on the theory of the diffuse double layer. The relation between Observation of the Brownian movement with cataphoretic and electro-osmotic velocity, the i-poten- the unaided eye. E. L a u and J. Johannesox tial vals. deduced from electro-osmotic measurements (Physikal. Z., 1934, 3 5 , 1013).—A similar observation with membranes having very fine pores, and the effect to that of Andreev (A., 1934, 361) has been made. of proximity to the wall on surface conductivity and If a point source is viewed through a thin layer of the methods of measuring it are examined. R. C. milk between tw’o glass plates, a variation in the light scattered by the milk is observed. If, however; Does electrokinetic potential measured by the cell is placed horizontally, the variations cease, the electro-osmotic method with ceramic dia showing that they are not due to the Brownian phragms vary with the current strength ? J. movement, but to alteration in the position of the VeliSek and A. VaSiCeic (Z. physikal. Chem., 1934, scattering centres caused by currents. It is suggested 171, 281—285).—Measurements with aq. KC1 solu that Andreev’s observation is similarly explained. tions have shown that the amount of solution trans A. J. M. ported in 1 sec. cc the current strength, I, so that, Linear problems of the theory of Brownian contrary to Schonfeldt’s findings (A., 1933, 776), the movement. III. G. A. K r u t k o v (Compt. rend. X, potential calc, in the usual way is independent of I. Acad. Sci. U.R.S.S., 1934, 4 , 120— 124).—Theoretical. R. C. E. S. H. Spherites. A. W i e l e r (Kolloid-Z., 1935, 70, Ultracentrifugal measurem ents with synthetic 79—94).—The production of spherites and pptn. highly polymerised substances. R. Signer membranes by the interaction of solutions is described, (Kolloid-Z., 1935, 70, 24—26).— Observations on the and their relation to org. forms is discussed. influence of concn. and mol. wt. on sedimentation of E. S. H. polystyrenes are reported. The variation of mol. wt. Theory of apparent molecular volume. III. in the fractions of a specimen of polystyrene having a Apparent molecular volume of sucrose. 0. mean mol. wt. 80,000 has been determined. R e d l ic h and H . K l in g e r (Monatsh., 1934, 6 5 , 137— E. S. H. 140).— In agreement with theoretical considerations, X-Ray and electron analysis of disperse the apparent mol. vol. of sucrose in dil. solution systems, fibres, films, and interfaces. Wo. varies linearly with the sucrose concn. (c) and not O s t w a l d (Kolloid-Z., 1934,6 9 , 264— 266).—A lecture. with \/c as is the case with strong electrolytes. E. S. H. Deviations from the linear relation are found when c X-Ray analysis of difform and disperse is large. M. S. B. systems (with special reference to electron Cryoscopy and association in p-chlorotoluene. interference). E. S c h i e b o l d (Kolloid-Z., 1934. R . P. B e l l , E . C. B a u g h a n , and M. W . V a u g h a n - 6 9 , 26G—301).—A lecture. E. S. H. J a c k s o n (J .C .S ., 1934, 1969— 1972).— The cryoscopic Determination of particle size by A'-ray and const, of p-C6H4MeCl (I) is 5-53° per kg. CH2C1-C02H, electron analysis. R B r i l l (Kolloid-Z., 1934, 69, CHC12'C02H, and CC13*C02H are bimol. and the mol. 301— 312).—A lecture. E. S. H. refractivities are const, in (I) over the range 0-05—0-35 mol. per kg. R . S. X-Ray and electron analysis of inorganic gels, Diffusion of copper sulphate. L. W. Oholm especially hydroxides and oxides. R. F r i c k e (Kolloid-Z., 1934, 6 9 , 312—324).—A summary of (Finska Kem. Medd., 1934, 4 3 , 121— 135; cf. A., 1934, 1170).—The diffusion coeffs. for Cu, Zn, Cd, published work. E. S. H. and Mg sulphates have approx. the same val. X-Ray analysis of organic gels. F. H alle R. S. (Kolloid-Z., 1934, 6 9 , 324—340).—A lecture. X-Ray diffraction in ionic solutions. J. A. E. S. H. Press (Physica, 1934, 1, 1171— 1173).—The diffrac X-Ray analysis of protein fibres. W. T- tion pattern of saturated aq. Th(N03)4 and U 02(N03)2 A s t b u r y (Kolloid-Z., 1934,69,340— 351).—Published shows a ring, which shifts to smaller angles and work is reviewed. E. S. H. GENERAL, PHYSICAL, AND INOEGANIC CHEMISTRY. 103
X-Ray analysis of lamellar disperse systems. particles between 8° and 40° are expressed by i]= U. Hofmann (Kolloid-Z., 1934, 69, 351— 357).— A 12,740e-°04649< (cf. Busse and Karrer, A., 1934, 28). review of published work, especially on graphite and A. J. H. certain minerals. • E. S. H. Particle form in colloidal rubber solutions. I. S a k u r a d a and K. T a n a k a (J. Soc. Chem. Ind. Highly polymerised compounds. Cl. Con Japan, 1934, 37, 470— 473b).—Measurement of the nexions between solvation, solubility, and vis variation of the sp. viscosity with the concn. of rubber cosity of polystyrenes. H . S t a u d i n g e r and in 8 different solvents shows that tho colloidal par W. H e u e r [with E. H u s e m a n n ] (Z. physikal. Chem., ticles are nearly spherical; particles of masticated 1934,171, 129— 180).—The solubility, S, of two poly rubber arc uniform in shape, but not spherical or styrenes in various solvents has been examined by chain-like. A. J. H. determining how much MeOH or COMe2 must be added to the solutions just to cause pptn. Good sol Colloid chemical researches on soaps. W. vents for polystyrenes (I) solvate all the groups of the P r o s c h (Kolloid-Z., 1935, 70, 106— 108).— A discus mol., whilst poor solvents solvate principally the sion. E. S. H. aromatic groups. S for polymeric-homologous (I) falls Colloid chemistry of metal soaps, II. Struc with rising mol. wt., M, very rapidly with the hemi- ture viscosity in benzene solution. Wo. O s t - colloids and slowly with the meso- and eu-eolloids. w a l d and R . R i e d e l (Kolloid-Z., 1935, 70, 67— 74 ; The sp. viscosity, of a solution in a good solvent cf. A., 1934, 1305).—The viscosity and structure is > that of an equally cone, solution in a poor sol viscosity of A1 soaps in C6H6 at 25° have been deter vent. A mixture of a good solvent and a precipitant mined . With the middle members (laurate and myrist- behaves like a poor solvent. For a given solute in ate) the increase of viscosity with concn. is very various solvents, the vals. of lUm/c; where c is the basic marked, and the abs. viscosity shows a pronounced molarity, for a given temp., T, approach as T rises. max. in very dil. solutions (0-006673/) and at high The vals. for the M of a given solute deduced from concns.; these members form gels at concns. at which T,Sp for solutions in CGH6 and COMeEt by -q,P/c= the other members are fluid. These anomalies are KmM agree for hemi- and meso-colloids, but discussed in relation to dielectric properties. not for eucolloids. For gel solutions and conc. sol E. S. H. solutions log (v)sp/c)= if5(.c-)-[log (i)sp/c)]c^.0, where Hydration of the crystalline fibres of soap for a given (I) K Sl has a const, val. independent curd. J. W. M c B a i n , H. I. B u l l , and L. S. of solvent and temp. This leads to a now equation for S t a d d o n (J. Physical Chem., 1934, 38,1075— 1084).— the M of (I): ilf=(Z5i-0-17)/l-5xl(h5. Cone, The dew-point method of measuring v.p. has been em solutions of homopolar org. substances with thread ployed to determine the hydration of curd fibres of mols. are associated sol solutions if M is > 1000 and NaP (P=palmitate) and NaL (L=laurate) at 20°. In gel solutions if M is larger. R. C. presence of saturated aq. Na2C204, NaP fibres have Viscosity properties of synthetic highly poly the composition NaP,2-6H20 and NaL fibres probably merised substances. I. S a k u r a d a (J. Soc. Chem. NaL,l-2H20. Dehydration curves in absence of a salt Ind. Japan, 1934, 37, 473— 474b).—The character of indicate the existence of NaP,8— 10H20, NaP,30H20, viscous solutions of complex synthetic (polystyrene and and possibly NaP,2-6H20, but part of the apparent polymerised w-hydroxydecoic acid) (I) and natural HaO of hydration may be adsorbed H20. Curd fibres (cellulose nitrate, starch, and rubber) (II) substances is obtained from liquid-cryst. anisotropic soap solution compared by means of the consts. a and
Precipitation of ferric oxide hydrosol in solu (I)-K 2Cr04-A gN 03 in the presence of a limited concn. tions of moranyl. H: G o l d i e (Compt. rend. Soc. range of sp. impurities, and it is inferred that these Biol., 1934, 117, 622— 624).—Fe203 hydrosol is pptd. must give a ppt. with AgN03. The impurities are from EeGlg solutions containing moranyl (I) in the pa divided into three classes : (1) those which induce zone 5—7, in the form of heavy yellow hydrophobic ring formation in washed (I) include KC1, KBr, and flakes (II), negatively charged, and poor in inter- KCN, which are effective in the ranges 0-5—2%, micellary liquids containing acid FeCl3. This pptn. 1—5%, and 2—8%, respectively, and afford data occurs in (I) solutions as dil. as 1 :100,000, and can be conforming to Jablczynski’s relation, (2) those which used to detect traces of (I) in protein-free solutions. are without influence, e.g., NaF, and (3) those which Cone, strong acids interfere by destroying (I), conc. prevent ring formation in unwashed (I), e.gr., Na2S203, strong alkalis by changing the structure of the micelles. which dissolves AgCl, and K I which reacts with A (I)-frce suspension of (II) in H20 “ sensitises ” chromate. J. G. A. G. Fe203 to pptn. in the acid zone as (II), a phenomenon Fluidities of thixotropic gels. Bentonite sus not exhibited by suspensions of brown alkali-pptd. pensions. H. A . A m b r o s e and A . G. L oomis Fe203 hydrosol. R. N. C. (Physical Rev., 1933, [ii], 44, 320).—Flow measure Coagulation of colloids. X. Viscosity vari ments on bentonite suspensions (I), showing the ation during mutual coagulations of positive property of thixotropy and of fluidity varying with ferric oxide sol and colloid arsenious sulphide, shearing stress, have been carried out in capillary manganese dioxide, and antimony sulphide. tubes, brass pipes, and a rotary apparatus (II) of S. S. J o s h i and K. P . N. P a n n i k k a r (J. Indian special design. (II) showed that the structure of such Chom. Soc, 1934, 11, 797—304; cf. A., 1934, gels must be broken down or built up until an equili 1171).—When Fe203 sol is mixed with the oppositely brium state of flow is reached in order to obtain charged colloids As2S3, MnOs, and Sb2S3 coagulation reproducible measurements. No slip at the walls usually occurs with comparable quantities of the two occurs in non-plug flow. Turbulent flow of (I) was colloids. In the case of slow coagulation there is an also investigated. (I) behave as a viscous liquid in initial fall in of approx. 6-5% and the yj-time the turbulent region, and the vol. of flow at any curve shows irregularities. For rapid coagulation pressure gradient may be assumed to be the same as the initial fall in yj is insensible, and 7j increases that of H20. L . S. T. rapidly with time without irregularities. In some Swelling of gelatin in deuterium oxide. H. Q. cases variations in t¡ occur when no coagulation is W o o d a r d and L. C . C h e s l e y (J. Amer. Chem. apparent, and it is suggested that -r¡ is a more sensitive Soc., 1934, 56, 2562—2563).—Gelatin swells less in property for studying coagulation than degree of HaO than in HoO. The ratio is S6% (wt.) in 90% turbidity. R. S. B. HjO and 93% (wt.) in 42% H?,0. E. S. H.
Theory of coagulation. N. F u c h s (Z. physikal. Relative flocculation value of alcohols towards Chem., 1934, 171, 199—20S).—The fundamental protein solutions. W. S. E i s e n m e n g e r (Kolloid- equation of Smoluehowski’s theory of rapid coagul Z., 1935, 70, 94— 96).—The flocculating power ation has been deduced by a new method, and doubts (I) of the aliphatic alcohols increases with increasing of its validity are unfounded. An important correc mol. wt. and show's a relation with the b.p. In a tion is, however, required in the theory, the magni series containing the same no. of C atoms, (I) decreases tude of which depends on the val. of x/a, where a in the order n, iso, sec., tert., w'hich is also the order of is the particle radius and X the mean path of the par decreasing toxicity. CH2Ph-OH has a particularly ticle in a particular direction. For dispersions with high (I) towards blood serum. E . S. H. a liquid dispersing medium the correction is negligible, Precipitation power and dielectric polarisation but for aerosols it cannot be neglected. Smolu of alcohols. Wo. O s t w a l d (Kolloid-Z., 1935, 70, ehowski’s theory of slow coagulation requires complete 96—100).—1The relative pptn. power a of alcohols reconstruction. Whereas Smoluchowski assumed the for protein solutions (cf. preceding abstract) increases rate of coagulation, v, to be oc to the fraction, a, of the rapidly with increasing polarisation in accordance collisions which are effective, it is found that v de with the expression ( a - f P 2)= k 2, w'here P\ pends less on a as x/a diminishes. This is important is the limiting polarisation for the highest homologous for the interpretation of experimental data on the alcohol sol. in H20, P 2 the mol. polarisation of the stabilisation of sols. Harper’s theory of coagulation pure alcohol in question, and and k2 are consts. (A., 1934, 960) is rejected. R. C. characteristic of the protein solution. E. S. H.
Reversible opalescence changes in gum sols. Aqueous solutions of proteins. M. P ie t t k b , N. P e s k o v and E. P r e is (Kolloid-Z„ 1935, 70, 62— A. B o u t a r ic , and M. R o y (Compt. rend., 1935, 67).—The opalescence-temp. curves of the sols 200, 94—95).—The degree of polymerisation of the exhibit hysteresis. The S-shaped character of the following proteins, as determined by the amount of curves is less pronounced the greater is the EtOH charcoal necessary for complete adsorption from content of the dispersion medium. E. S. H. solution, increases in the order given : serum-albumin Influence of the nature of impurities on the (ox), lactalbumin, serum-albumin (heifer), mammary formation of Liesegang rings in gelatin (silver albumin, myosin, liver-albumin, ox serum-myxo- chromate). M . F . T a b o u r y and R. E c h a r d (Bull. protein, ovalbumin, ricin. C. G. A. Soc. chim., 1934, [v], 1, 1525—1531 ; cf. A., 1933, Pressure and the water relations of proteins. 224, 225).—Rings are produced in the system gelatin I. Isoelectric gelatin gels. (Miss) D. J. L l o y d GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 165
and T. M o r a n (Proc. Roy. Soc., 1934, A, 147, 382— of NaCl, EtOH, and AcOH, alone or in pairs, has been 395).—When isoelectric gelatin gel is submitted to studied by the methods previously described (A., pressure, pure H20 is forced out of the gel, and the 1932, 910). The presence of > 1 protein is indicated, concn. of the residual gel is a function of the pressure. and methods for their separation are suggested. The effects of varying the pressure (up to 48,000 lb. R. T. per sq. in.), the temp. (0° and 20°), and the initial Physical chemistry of starch and bread concn. of the gel (4-5— 41-4%). have been examined. making. XXIV. Hindering of A"-ray diagram The relationship between the activity of H20 and retrogression of starch paste and starch solu concn. of gel, calc, by applying the Katz equation to tions by heating. J. R. K a t z and A. W e i d i n g e r the pressure data, agrees with that obtained from an (Z. physikal. Chem., 1934, 171, 181— 189; cf. this analysis of the f.p.-concn. curve of gelatin gel (A., vol., 33).—Retrogression is hindered by rise of temp, 1932 , 694). The results confirm the suggestion that and inhibited above 60°. At each temp, a state of the H20 in gelatin gels is to be regarded as existing equilibrium is ultimately reached. At higher temp, in two states : (1) firmly held II20, most of which is the equilibrium state is the fresh state, at lower removed only at low activities (< 0 -2 ), and (2) temp, the retrogressed state; at 20—60° the X-ray loosely held H20, present only at high activities diagram shows superimposed V- and 5-spectra. The (> 0’7). The nature of the forces holding the different increases on retrogression in opacity, viscosity, and types of H20 to the gelatin mol. is discussed. proportion of substance resisting malt run approx. L. L. B. parallel with the change in X-ray diagram. R. C. Crystalline proteins : hormones and enzymes. Fine structure of wood. I. Volume swelling —See this vol., 122. of pine wood and lignin in different media. H. Effect of hydrogen ions and thrombase on the S a e c h t l in g and H. Z o c h e r (Kolloid-Beih., 1934, coagulation of fibrinogen. G. C r u t (Compt. rend., 40, 413—448).—The swelling phenomena of wood 1935, 200, 95— 98).—Fibrinogen is sol. at pH 1—2-6. are discussed in the light of the spiral arrangement At higher pn there is pptn. (different from the normal of anisotropically swelling cellulose micelles. The coagulation) which is max. at pK 4-4— 4-6. Above dimensional changes have been measured during Pa 6 the solution remains clear. Up to pa 6 the swelling in CGH6, Et20, COMe2, C5H5jST, MeOH, and phenomena are the same in presence of thrombase, H20. The amount of the swelling liquid taken up but above pn 6 coagulation occurs, with max. velocity increases in the order given, excepting C5H5N, between pa 7 and 8. Coagulation is followed by which has a sp. effcct probably connected with its fibrinolysis. ,C. G. A. basic character. E. S. H. Colloidal behaviour of sericin. VII. H. Use of photo-cells for the determination of the Kahbko (Bull. Chem. Soc. Japan, 1.934, 9, 510—520; degree of dissociation in the gaseous equi <£ this vol., 33).—The different forms of N present librium N 20 4 2 N 0 2 from the degree of ab in the hydrolysis products of sericin-^4 and -B have sorption of light. K. B e r g w i t z and O. E. been determined. A summary of previous papers is S chweckendiek (Physikal. Z., 1935, 36, 35).— The given. F . L. U. method allows the simultaneous variation of pressure and temp., the amount of N 02 present at any temp, Plant colloids. XL. Reaction of starches being determined by the intensity of the light absorbed with proteins. M. S ajuec [with A. D u r j a v a ] by it. A. J. M. Mloid-Beih., 1934, 40, 449—457; cf. A., 1934, W3).—Amylopectin, pptd. from starch solution by Chemical equilibrium between hydrocarbons. clectrodialysis, neutralises solutions of gelatin or VIII. Equilibria of the reactions C6H14 ==±= ovalbumin, reducing the H' activity to 10~°A7. CcH j2+ H 2 ; C8H 18 q = i C8H18-)-H2. A.A.V e d e n s k i Simultaneously the viscosity falls, and the solution and P. J. I v a n n i k o v (J. Gen. Chem. Russ., 1934, 4, becomes more easily pptd. by EtOH and less easily 975— 978).—Empirical formulæ connecting the equili by electrodialysis. E. S. H. brium const, with temp, are given. R. T. Colloid ch em istry of ch lorop h y ll. H. A. Relation between molecular interaction and 1 cr)KKER (^>roc- K. Akad. Wetensch. Amsterdam, the thermodynamic properties of solutions. 37, 688—694).— Cataphoresis of a suspensoidR. P. B e l l and 0. G a t t y (Phil. Mag., 1935, [vii], °f chlorophyll (I) in H20 showed it to be negatively 19, 66—82).—Theoretical. H. J. E. charged. Flocculation by electrolytes was observed Chemical constitution and the dissociation depended on the valency. A suspensoid of constants of monocarboxylic acids. II. J. F. J. P 'sophytin also showed a negative charge. A D i p p y and F. R. W il l i a m s (J.C.S., 1934,1888— 1892 ; «orescent sol and coacervate of lecithin (II) with (I) cf. A., 1934, 364).— Classical and thermodynamic ,a'e been prepared. Since lecithinoids may be dissociation consts. of AcOH, BzOH, _p-anisic acid, j!|nP°r|.ant components of plastid, it is not impossible o- and m-chloro-, o-bromo-, m-nitro-, 2:4-dinitro-, at (I) may occur as coacervate of (II) in the living p-methoxy-, and 3 :4-dimethoxy-phenylacetie acid plant- M. S .B . are given. K is increased by introduction of a 3- Application of physico-chem ical analysis to alkoxy-group into BzOH or CH2Ph*C02H, but e mvestigation of peptisation. II. Peptis- diminished by a 4-alkoxy-group. R. S. ion of wheat-flour proteins. A. D u m a n s k i and Anomalous strength of salicylic acid. G. E. K. 95lllq- HEL0VA Gen- Chem. Russ., 1934, 4, B r a n c h and D . L. Y a b r o f f (J. Amer. Chem. Soc., 957).—The peptising action on wheat proteins 1934, 56, 2568—2570).— The dissociation consts. of 166 BRITISH CHEMICAL ABSTRACTS.— A. o-, m-, and jj-0H*C6H4*C02H, and o-, m-, and p- Seward (J. Amer. Chem. Soc., 1934, 5 6 , 2610—2612). OMcCyH.j'CO.jH in 25% EtOH at 25° have been —The solubility of NMe4Cl in C2H4C12 in the presence determined. That of salicylic acid (I) is abnormally of quaternary NH4 salts has been determined at 25°. large. An explanation based on H linking, which The decrease in the activity coeff. varies with the gives rise to a chelate ring, is put forward; this added salt and is greater the smaller are the added ions. explains also the low second dissociation const, of E. S. H. (I). E. S.H. Cyanide solutions. R. M. WlCK (Monthly Rev. Amer. Electroplatèrs’ Soc., 1934, 20, No. 10, 10—16). Dissociation constants of acetoacetic, gly- — Solutions of K Ag cyanide contain Ag(CN)3" and collic, and acetic acids in solutions of sodium Ag(CN),', thé relative amounts depending on [CN']. chloride. K. J. P e d e r s e n (J. Physical Chem., C h . A b s . (e) 1934, 3 8 , 993— 99S).— The ratios of the dissociation Condition of sodium dissolved in fused sodium consts. of CBUAc'COaH (I) to those of AcOH (II) hydroxide. F. H a l l a and H . T o m p a (Z.' anorg. and 0H>CH2*C02H (III), respectively, have been Chem., 1934, 2 2 1 , 18—20).—The authors’ previous determined by the quinhydrone electrode at 0° conclusions (cf. A., 1934, 1166) are in agreement with and 1S° in aq. NaCl of concn. 0—0-5M. The dissoci Rinck’s observations (A., 1933, 228) on the variation ation consts. at 0° and 18° and at infinite dilution of the equilibrium const, of the reaction NaOH-fK have been calc.: (I) 2-57 and 2-62 x l(H , (II) 1-70 ^ Na+KOH. The upper temp, limit for which the and 1-79 X10-5, (III) 1-36 and 1-48 x lCH. M. S. B. equilibrium const, for the reaction K20+ N a = N a 20-f Dissociation constants of formic and acetic K can be determined is 400°. M. S. B. acids in concentrated salt solutions. A. v o n Compound of glucose and potassium chloride. K is s and A. U r m a n c z y (Z. physikal. Chem., 1934, S. M a t s u u r a (Sci. Rep. Hirosima Higher Tech. 171, 257—267).—The dissociation consts., K c> in School, 1929,1,217—221).—The system glucose-KCl- solutions of various neutral salts have been determined H ,0 reveals no mol. compound such as is found with at 25° by e.m.f. measurements. At salt concns. NaCl (A., 1927, 518). Ch. Abs. (r) < N, log Kc is a linear function of the concn. Except for CaCl2, the salts show the same order in respect of Constitution of phosphate complexes of iron the neutral salt effect for both acids. The ratio and aluminium. K. A. J e n s e n (Z. anorg. Chem., K a/Ke for AcOH, compared with that for HCO,H, 1934, 2 2 1 , 1—5).—The solubility of FeP04 and A1P04 varies with the salt and its concn. R. C. in acid solution containing Cl' and P 0 4"' increases with the concn. of P0 4"', but is practically independent Strengths of phenolic ketimines and their of the concn. of Cl'. The phosphate complexes formed methyl ethers as bases. J. B . C u l b e r t s o n , contain, therefore, no Cl. The rapid increase in mol. P. B i e b e r , and A . Z a v o d s k y (Proc. Iowa Acad. conductivity, with dilution, of aq. FeCl3 decomposed Sci., 1932, 39, 177).—The ionisation consts. of by H3P04 appears to be due to the formation of col monohydroxydiphenylketimines and their Me ethers loidal FeP04 and free acid. M. S. B. are recorded. C h . A b s . (r) Condensation reactions of boric acid. W. C. Combination scattering and “ association of S ch u m b and W. H. H artford (J. Amer. Chem. Soc.. m olecules." S. I. L e i t m a n and S. A. U k h o l i n (J. 1934, 5 6 , 2613—2615).—The prep, of Mo03 and W03 Chem. Physics., 1934, 2, 825—826).—The association is described, and their solubilities at 28° have been of PhNO, in CC14 and of AcOH in H20 has been studied determined. Solubility and pn measurements for by the combination-scattering (Raman spectrum) saturated solutions of Mo03 and W 03 in aq. Na,B407, method. Although PhNO, is known to be associated Na2C03, and Na-3P04, respectively, show that boro- in CC14 the solution shows no evidence of the formation molybdate ions do not exist, although the existence of of complexes. In the spectra of aq. AcOH, however, borotungstate ions is demonstrated. E. S. H. the lines corresponding with the wave-no. 623 cm.4 change in relative intensity with change of concn. Complex formation between aniline and This wave-no. appears, therefore, to be characteristic picrate ion. Solubility measurements. K. J- of complex mols. of AcOH. Reasons for the difference Pederson (J. Amer. Chem. Soc., 1934, 5 6 , 2615— in behaviour of the two solutions are discussed. 2619).—Two forms of anilinium picrate have been pre M. S. B. pared ; the metastable form is 28% more sol. in H20 Association of phenol in different solvents. at 18°. From solubility data it is concluded that the F. A. P h il b r ic k (J. Amer. Chem. Soc., 1934, 5 6 , picrate ion forms complexes with 1 and 2 mols. of 2581—2585).—By a modification of the K Br03-K I NH2Ph. There is no evidence of complex formation procedure, 3— 10 mg. of PhOH can be determined to between NH2Ph and NH3Ph\ E. S. H. within rh0’05%. The distribution of PliOH between Dielectric constants of solutions of amphoteric H20 and PhJVle, PhCl, C6He, PliNO,, and CC14, electrolytes. I. Existence of zwitter ion. 0. respectively, at 25° shows that PhOH is present in B l ü h . I I . O. B l ü h and J. Kroczek (Z. physikal. these solvents as single and double mols. Differences Chem., 1934, B , 2 7 , 263—269, 270—281).— I- Pub; in the calc, association consts. are ascribed to solvation lished data for the dielectric const., e, of solutions of of single PhOH mols.; the effect of substituents in the amphoteric electrolytes and its bearing on the exist benzene ring is in the order : Me, Cl, (H), NO,, OH. ence of zwitter ions are reviewed. Reasons are given E. S. H. for rejecting the claim that the s of an aq. solution of Activity coefficients of salts in ethylene di an aromatic amphoteric electrolyte is < that of the chloride from solubility measurements. R. P. solvent. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 167
II. Measurements of the e of aq. solutions of ampho III. Addition of CH20 to (I) produces a decrease in teric aromatic electrolytes (A., 1923, ii, 823) have been electrical conductivity and an increase in viscosity, to repeated using a method permitting comparison with a degree depending on the age of the solution. The solutions o f strong electrolytes of the same high- CH20 undergoes a stepwise reaction with the three frequency conductivity. The s' of almost all the bound CS(NH2)2 groups. solutions is > that of HoO, proving the presence of IV. The following compounds have been prepared zwitter ions. In solutions of jj-NH2‘C6H4-S03H and by direct replacement of Cu in ( I ) : MnCl2,10CS(NH,)„ »¡-NHg'CgH^'COgH these are present in considerable ZnCl2,10CS(NH,)2,2CdCl2,5CS(NH2)2, m.p. 203—206°, amount, whilst in solutions of o- and ¡»-NHvCrjH t-C02H PbCl2,4CS(NH2)2, decomp. 116-120°, and liippuric acid there are few, if any. R. C. 2SnCl2,5CS(NH2)2,2H20, m.p. 175° (decomp.). Colours appearing in the systems cupric V. Measurements of the potentials of Cu, Ag, Cd, chloride-hydrogen halide-water-alcohol (ether, and Zn in solutions of their complex CS(NH2)2 salts aldehyde, ketone, acid, ester). E. B e u te l and show that the Cu and Ag complexes are stable, whilst A. K u t ze l n ig g (Monatsh., 1934, 65, 82—90);— Many those of Zn and Cd are resolved into their components, alcohols, ethers, and other org. liquids give a green especially in dil. solutions. These measurements and colour with CuCl2 and HBr under certain conditions, observations of chemical deposition show that in such leaving a purple residue after evaporation; sec.- and solutions the electrochemical series is : Ni, Ag (Fe, feri.-alcohols give the effect at room temp. Cone. HC1 Sn, Pb), Cu, Cd, Zn. The Cu and Zn complex solu gives a yellow colour, whilst HF discharges the colour. tions are suitable for the electrolytic deposition of the The influence of temp, and concn. of the reagents on metals. E. S. H. these effects has been studied. E. S. H. Diagram of state for mixtures of any number Complex salts of 2 : 2'-dipyridyl with bivalent of constituents, V. F i s c h e r (Ann. Physik, 1934, copper. II. F. M. J a e g e r and J . A. v a n D ijk [v], 21, 426— 432).—A plane orthogonal isobaric (Proc. K . Akad. Wetensch. Amsterdam, 1934, 3 7 , diagram is constructed for a mixture of any no. of CIS—623; cf. A., 1934, 1317).—If an EtOH solution constituents, and is applied to N ,-0 ,-A -C 0 mixtures. containing 1, 2, or 3 equiv. of dipyrydyl (dip) is added A.J.M. to aq. Cu(N03)2 the corresponding complex (dip) salts Two co-existent phases. A. K. V lcjek (Chem. arc deposited on slow evaporation, viz., Listy, 1934, 28, 262—268, 282—283).—Theoretical. [Cu(dip)(H20)2](N03)2,H20 (I), dark blue, dichroitic, R. T. thick, tabular crystals or smaller needles; F.p. of mixtures of H20 and H5O. Latent [Cu(dip)2](N03)2,H20 (II), dark blue, weakly di heat of fusion of B|0 . V. K . L a M e r and W . N. chroitic, thick, imperfect, triclinic crystals; B a k e r (J. Amer. Chem. Soc., 1934, 5 6 , 2641—2643). [Cu(dip)3](N03)2,6H20 (III), flat, hexagonal, dark blue —-B y extrapolation of the experimental data the crystals, plastic owing to gliding planes, and red in f.p. of pure H|0 is 3-802°. The calc, latent heat of thin layers. Crystallographic data are given. (II) fusion of HjO is 1510 g.-cal., which is estimated to be and (III) are much less sol. than (I). From aq. at least 10 g.-cal. too low. E. S. H. Cu(0Ac)2 with 1, 2, or 3 equiv. of (dip) the following Absorption of nitrogen on fusion of iron in the «site are obtained : [Cu(dip)(H20)2](0Ac)2,3H20 (IV), arc and the iron-nitrogen diagram. A. P o r - (lark blue prismatic needles with reddish reflexions; t e v t n and D. S e f e r i a n (Compt. rend., 1934, 199, [Cu(dip) (H2O)0.G6](OAc)2,5H2O or a mixture of 1613— 1615).—The absorption has been studied in an 1 mol. of (IV) with 2[Cu(dip)2](0Ac)2,6H „0; arc containing at. N, when Fe4N is formed. An [Cu(dip)1.38(H20)1.24](0Ac)2,2H20. " “ M. S. B. equilibrium diagram for the system aFe-Fe4N Complex metal-thiocarbamide salts. II. (0— 10% Fc4N) is described, differing from that of Equilibrium in trithiocarbamide-cuprous chlor Fry (B., 1923, 1074). The Curie point (I) of Fe is ide solution. III. Conductivity and viscosity lowered by the presence of Fe4N, the (I) of which is measurements on trithiocarbamide-cuprous at 480°. ” H. J. E. chloride solu tion s. IV. Direct displacement System pyridine-acetic acid. II. M.p. L. E. of copper in trithiocarbamide cuprous chloride S w e a r i n g e n and R. F. Ross (J. Physical Chem., hy other metals. G. W a l t e r and E. S t o r f e r . 1934, 38, 1085— 1089).—M.-p. data for mixtures of V. Electrochemical relations of complex m etal- C5H5N and AcOH indicate the presence of the «uocarbamide salts. G. W a l t e r , M. A d l e r , and compounds C5H5N,AcOH, m.p. —59°, and w R eim er (Monatsh.. 1934, 6 5 , 21— 35, 38—52, 53— C5H5N,4 or 5AcOH, m.p. approx. —42°. The com «8, 59-81; cf. A., 1931, 831).—II. Cuthi3Cl (I) in position of the second compounds also corresponds conc. solution is pptd. by aq. KC1 or HC1; at lower with the composition of max. viscosity. M. S . B. f'Qncns. Cuthi2Cl (II) is pptd., and CuthiCl (III) is pptd. from dil. solutions. Small quantities of CH20 ppt. Solid-liquid equilibria in system p-naphthol- > i- in presence of medium amounts of CH20 [i-naphthylamine. K. H r y n a k o w s k i and M. S z m y - addition of KC1 causes pptn. of (III). In presence of t 6 w n a (Z. physikal. Chem., 1934, 171, 234— 238).— cone. CH20, KC1 ppts. (Ill) from freshly prepared The components are miscible in all proportions in the solutions of (I), but not from old solutions. On age- solid state and the liquidus and solidus curves touch mg, the conductivity and [H‘] of the solution vary; at a min.; no compounds are formed (cf. A., 1919, ii, Pa is on the acid side, and the conductivity changes 54). R. C. anomalously with dilution. It is suggested that Redetermination of thermal dissociation solutions of (I) contain (II) and (III). equilibria of inorganic compounds. IV. Deter 168 BRITISH CHEMICAL ABSTRACTS.— A. mination of dissociation equilibria of strontium M.-p. diagram of the system AlCl^-NaC1-KC1. and barium hydroxides with high-temperature L. W a s i l e w s k i , A. K a c z o r o w s k i, and M. D y n k in vacuum balance. V. Determination of dissoci (Przemsyl Chem., 1934,18, 608—617).—The recorded ation equilibria of hydrates of strontium and eutectic data are : A1C13 66, NaCl 34, 93°, A1C13 71, barium hydroxides with high-temperature KC1 29,114°; A1C13 66, NaCl 20, KC114,70°. Transi- vacuum balance. S. T a m a r u and K. S i o m i (Z. tion point data are : A1C13 50, NaCl 50,146°; A1C13 50, physikal. Chem., 1934, 171, 221—228, 229—233; cf. KC1 50, 241°; A1C13 43-5, NaCl 43-5, KC1 13, 123°; A., 1932, 1204).— IV. The dissociation pressures, p, A1C13 54, NaCl 31, KC1 15, 110°. Composition is of Ba(0H)2 at 500—750° and Sr(0H)2 at 390—670° expressed in mol.-%. R. T. are given by log p ——25,100/4-575T+6-906 and log Equilibria in the mutual system Na2S 0 4- p ——25,190/4-575T-f8-531, respectively. Ba(OH)2 NH4H C 0 3-H 20 at 0°. A. P. B e l o p o l s k i, S. J. forms liquid and solid solutions with BaO. S c h p u n t , arid M. T. S erebrenikova (J. Appl. Chem. V. For Sr(0H)2,8H20 ^ Sr(0H)2,H20+ 7 H 20 and Russ., 1934, 7, 669—686).—The solid phases are Ba(0H)2,8H,0 — Ba(OH)2,H20+ 7 H 20 log p( mm.)== Na2S04,10H00 (I), Na2S04, (NH4)2S04,4H20 (II), -1 3 ,200,/4-57571+ 10-80 and log p (m m .)= -13,600/ (NH4)2S04 (III), NH4HC03 (IV), and NaHC03 (V). 4-575T+10-84, respectively. No evidence could be At the 3 invariant points the solid phases are (II), obtained for the existence of Sr(0H)2,2H20, (III), and (IV) (0°); (I), (II), and (IV ); and (I), (IV), Ba(0H)2,3H20, and Ba(0H)2,16H20. R. C. and (V,). The cryst. fields of (I) and (V) diminish with fall in temp. R. T. Effect of pressure on the dissociation of a solid. T. E. F i e l d (J. Amer. Chem. Soc., 1934, Metal displacement equilibria in fused halides, 56, 2535).—The effect of piston pressures up to 105 oxides, and pyrophosphates. K. J e l l i n e k and atm. on the dissociation pressure of BaCl2,8NH3 has H. S i e w e r s (Z. Elektrochem., 1934, 40, 871—884; been determined. The mol. fraction of NH, in equi cf.- A., 1933, 783).—Equilibria in the following re librium at 31-85° and at various pressures of H2 up to actions have been determined : Cu-f-AgCl(Br) ^ 150 atm. has been determined by approaching the Ag+CuCl(Br), Zn+CdCl2(Br2) — Cd+ZnCl2(Br„), equilibrium from both sides. At every pressure the 3Pb + Bi203 = Bi2 + 3PbO, Zn + PbCl2 = Pb + product of mol. fraction and total pressure is > ZnCl2, 2Pb-j-Ag2P20 7 — 2Ag2+ P b 2P20 7. The law the pressure calc, from the Poynting equation, of mass action is followed in all but the two last. assuming that the inert gas has a pressure effect only Differences between the normal potentials of the two on the activities of the solids, and the divergence is metals in their respective compounds are given for the greater the higher is the pressure. E. S. H. each system except the last. Bi is diat. in molten Pb. F. L. U. Alkali aluminium silicates. VIII. Validity Double decomposition in absence of a solvent. of Hiittig's equation for permutites. E. G r u n e r (Z. anorg. Chem., 1934, 221, 142— 148; cf. A., 1933, XXVI. Mutual system Ba(NOa)2+2K C l BaCl + 2 K N 0 3. A. P. R o s t k o y s k i (J. Gen. Chem. 579).—V.-p. isotherms for H-, Na-, and Ca-permutite 2 have been determined from 69° to 184°. Hiittig’s Russ., 1934, 4, 1010— 1020).—The phase diagrams formula lo g ,p = logepa—knln' is not valid for per indicate formation of K N 03,KC1 and BaCl0,2KCl. mutites without H20 of hydration, but gives vals. R. T. which are very high and not const. If n' is diminished System MgCl2-K C l-M g S 0 4-K 2S 0 4-H 20 at by a const, quantity representing those H20 mols. 100°. A. N. C a m p b e l l , K. W. D o w n e s , and C. S. which exercise a purely chemical function in the S a m is (J . Amer. Chem. Soc., 1934, 56, 2507—2512).— mol., the expression becomes valid, and &£=1. In the quaternary system the stable double salt is F. L. U. langbeinite. Kainite does not occur. E. S. H. Equilibrium relations in system calcium Heat of formation of ammonia and nitric oxide-sulphur dioxide-water (acid region) at acid. G. B e c k e r and W . A. R o t h (Z. Elektro- pressures below atmospheric. F. H. C o n r a d chera., 1934,40, 836— 843).—New determinations give and W. L. B e u s c h l e in (J. Amer. Chem. Soc., 1934, ll-0 li0 -0 7 and 14-84±0-08 kg.-cal. per mol. of NH3 56, 2554—2562).—The system has been examined at and dil. aq. HN03, respectively, at 20° and const, 15° and 25°, and at pressures up to 1 atm. The pressure, the latter substance from N9, 0«, and H20. solid phase in equilibrium appears to be 2CaS0 3,H20. “ F. L. U. E. S. H. Heat of combustion of standard sample benzoic Phase-rule studies on metallic thiocyanates. acid. R. S. J e s s u p and C. B. G r e e n (J . Res. Nat. III. The systems Ba(NCS)2-NH,NCS-H20 and Bur. Stand., 1934,13, 469— 495).—A brief description Ba(NCS)2-AgNCS-H.,0 at 25°. V. J. O c c l e - of a standard bomb calorimeter and of the method s h a w (J.C.S., 1934, "1892— 1895; cf. A., 1934, of using it is given, followed by tabulated results for 1091).—The compounds Ba(NCS)2,NHtNCS,H20, a large no. of tests made on BzOH. The mean val. Ba(NCS)2,AgNCS,2H20, Ba(NCS)2,2AgNCS,2H20, obtained for the calorific val. of pure BzOH is 26,419 and Ba(NCS)2,3AgNCS,2H20 are recorded and some international joules per g. (wt. corr. for air buoy crystal properties described." The double salts decom ancy) when the sample (I) is burned at 25° in 0 2 at pose when recrystallised from water. The solubility 30 atm. abs. in a bomb (II) of const, vol., the mass curves of NH4NCS and Ba(NCS)2,3H20 intersect at a of (I) and of the HjO in (II) each being 3 g. per litre of metastable invariant point, but the" results do not the vol. of (II); this val. is within 0-03% of recent conform with Kuklin’s theorem. R. S. determinations of other workers. A. R. P- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 169
Thermochemical researches on diazo-deriv- 1934, 13, 689—697; cf. B., 1933, 752).— Data are re atives of p-chloroaniline and a few other amines. corded from 30° to -40° for 15—45% H2S04. The M. W ojciechowski (Bull. Acad. Polonaise, 1934, A, composition of solutions of max. resistivity depends on 280—292).—The mol. heats of diazotisation of NH2Ph, the temp. An empirical relation between resistivity, p-C6H4Cl-NH2, i?-NH2-C6H4-S03H, and H-acid are kinematic viscosity, and abs. temp, is given. 22-74, 21-64, 18-38, and 21-66 kg.-cal. per mol., H. J. E: respectively. Diazotisation is not quant, for the first Electrolytic conduction by proton jumps: two unless 20% excess NaN02 is present, but with transference number of barium hydrogen sul the two last it is quant. The heat of. reaction phate in solvent sulphuric acid. L . P. H a m m e t t of ^-C6H4C1-N2C1 with NaOH increases with [NaOHj, and F. A. L o w e n h e im (J. Amer. Chem. Soc., 1934, probably owing to tautomeric change. The heats 5 6 , 2620—2625).—The apparent transference no. of involved in the change of diazonium hydroxides into Ba" in solutions of Ba(HS04)2 in H2S04 is 0-012. their isomerides and their heats of reaction with Using CC13-C02H as reference solute the true trans P-C10H7‘OH have also been measured. The heat of ference no. is shown to be about 0-006. Conduction reaction of £>-CGH4Cl’NH2 with HC1 is 6-49 kg.-cal. in these solutions does not depend on simple ionic per mol. J. W . S. migration, and supports the theory of conduction by Optical method for determination of heats of intcrmol. proton jumps. E. S. H. dissociation of organic molecular compounds High-frequency conductivity of an electrolyte of the type A B 2. G. B r i e g l e b and J. Iv a m b e i t z (Z. in the region of anomalous dipolar absorption physikal. Chem., 1934, B, 27, 161— 175).—The deter of the solvent. M. K u b o (Bull. Inst. Phys. Chem. mination of the heat of dissociation of org. mol. Res. Japan, 1934, 13, 1415— 1427).—A method for compounds in solution from measurements of extinc the measurement of high-frequency conductivities is tion coeff. is described. The method has been applied described and applied to glycerol and aq. glycerol to compounds of C6H3(N 02)3 with stilbene, tolane, solutions of NaCl between —80° and 80°, where and dibenzyl. R. C. anomalous dispersion is shown by the solvent. J. W. S. Integral heats of dilution, relative partial Single electrode potentials and the e.m.f. of molal heat contents, and heat capacities of dilute a cell. E. H u t c h is s o n and A. L. R o b i n s o n aqueous sodium chloride solutions. E. A. G t t l- (Physical Rev., 1933, [ii], 44, 323).—The o.m.f. of a b ra n s e n and A. L. R o b i n s o n (J. Amer. Chem. Soc., cell has been obtained by summing the p.d. at the 1934, 5 6 , 2637— 2641).—Data covering the range metal-liquid and metal-metal interfaces (electrolyte 0-0001—0-816Af and 10—25° are recorded. at unit activity) calc, by applying a Born-Haber- E. S. H. Fajans cycle. L. S. T. Osmotic pressure and the thermal effect of chemical reactions from the viewpoint of tech Applicability of Nernst’s electrochemical law to extremely dilute solutions. Normal poten nical thermodynamics. C. G r a b o w s k i (Przemysl Chem., 1934,18,385—397).—Theoretical. R, T. tials of bismuth and polonium. M. H a i s s i n s k y (Compt, rend., 1934, 199, 1397— 1399).—The crit. Behaviour of electrolytes in mixed solvents. potential (I) for the cathodic deposit from dil. Bi(N03)3 VI. Electrical conductivities of some salts in solutions has been studied with the apparatus of water-ethyl alcohol solutions. L. C. C o n n e l l , Joliot (A., 1930, 713), using Ra-i? and Th-C as radio R. T. H a m il t o n , and J. A. V. B u t l e r (Proc. Roy. active indicators of Bi deposition. (I) is independent Soc., 1935, A, 147, 418—433).—Data for LiCl and of the material of the cathode (Au or Ag) and is Kl in a series of H20-E t0 H solutions are recorded. sensibly the same for HN03 and AcOH solutions. The change of A0 cc the fluidity of the solvent up Initially, Bi deposit« on the cathode at much lower to 20 mols.-% EtOH, but beyond this increasing potentials than is suggested by theory, but this divergence is found, and this is ascribed to solvation deposit redissolves slowly and redeposition occurs of the ions by EtOH mols. The Kohlrausch equation only when the potential reaches the theoretical val. A=Ap— is obeyed in all the solvents. From the This phenomenon is especially marked for concns. fact that Onsager’s equation applies more exactly in < 10-8i\T. The normal potential of B i/B i"’ at 18° is the mixed than in the pure solvents, it is inferred +0-226±0-015 volt. The normal potentials calc, for that the former arc better ionising media. Measure the electrodes Po/Po’” " and Po/Po’" are -f0-77o± ments for ZnC^ suggest that it is completely dis 0-015 and +0-53±0-03, respectively. J. W. S. sociated, even in conc. solutions, whilst in EtOH it Electrochemistry of magnesium. II. S. B o d - behaves as a weak uni-univalent electrolyte with FORSSandH. K a j m e r (Z. physikal. Chem., 1934,171, *o=4 x 10-8. In the mixed solvents the ionisation 190— 198; cf. A., 1931,435).—The electrode potential, for each salt concn. seems to be complete up to about E, of different samples of Mg in buffer solutions has 40 mols,-% EtOH; it then falls to about 1% in pure been measured. With decrease in from ~ 7, E PtOH. In more conc. solutions (c—0-01— 0-5) EtOH becomes increasingly negative and passes through a depresses the ionisation more readily. The extent of max. Rotating the electrode shifts the E -pK curve complex ion formation in the alcoholic solutions is towards higher pa. The curve also depends on the estimated. L. L. B. anion of the buffer, and the effect of NH4 salts, Resistivity of sulphuric acid solutions and its fluorides, and pyrocatechol has been studied. The relation to viscosity and temperature. G. W. rate of evolution of H2 from Mg in buffer solutions is 'INAL and D. N. Craig (J. Res. Nat. Bur. Stand., for each buffer oc to the amount of acid and prac- 170 BRITISH CHEMICAL ABSTRACTS.— A. tically independent of the acid/salt ratio, observations Determination of the dissociation constants which agree fairly well with Kilpatrick and Rushton’s of weak bases by the silver iodide electrode. results (A., 1934, 605). R. C. B. B. O w e n (J. Amer. Chem. Soc., 1934, 56, 2785— 2786).—The possibilities of the Agl electrode are Thermodynamic study of potassium amal discussed. E. S. H. gam s. M. H. A r m b r u s t e r and J. L. C r e n s h a w (J. A in e r. Chem. Soe., 1934, 56, 2525—2534).—The Stannous-stannic oxidation-reduction poten e.m.f. of the cell K(c2)(amalgam)|KCl(aq.)|K(c1)(amal- tial. C. S. H u e y and H . V. T a r t a r (J. Amer. gam) has been measured at 15°, 25°, and 35° over a Chem. Soc., 1934, 56, 2585—2588).—The e.m.f. of wide range of concn., using dropping electrodes. cells of the type Hg|HCl,SnCl2,SnCl.t|HCl|H2,Pt has Reproducible’results arc obtained when the amalgams been determined at 15°, 25°, and 35°. The normal contain 0-01—0-40 g. of K per 100 g. of Hg. The oxidation-reduction potential of Sn“-Sn'"' at 25° is influence of variations in technique is discussed. The —0-154 volt. The change in heat content for Sn” — )- calc, standard electrode potential of K is 2-9243 volts Sn“ "-j-2e (in 1-lJf-HCl) is 120 g.-cal. E. S. H. at 25°. The solubility of K in Hg has been deter Oxidation-reduction potentials of hypo- mined between 0° and 35°. E. S. H. xanthine xanthine and xanthine ==s= uric acid. S. F i l i t t i (Nature, 1935, 135, 35).—A reply Glass electrode. III. Statistical explanation to criticism (A., 1934, 1257). L. S. T. of the alkaline solution behaviour. M. D o l e (J. Chem. Physics, 1934, 2, 862—866).— Gurney’s quan Oxidising agents and vat-dyed cotton. H. A. tum-mechanical theory of electrode potential (A., 1932, T u r n e r , G. M. N a b a r , and F. S c h o l e f ie l d (Nature, 26, 669), when applied to the glass electrode, gives 1935,135, 68).—Evidence of a simple relationship be the same equation previously obtained by application tween the e.m.f. of a Pt electrode in a dil. solution of of the liquid-junction theory (ibid., 126, 1207), but NaOCl and the action of the latter on cellulose fibres makes unnecessary any assumptions concerning the dyed with a reduced vat dye has been obtained. mobility of H' and Na\ It also explains other diffi L. S. T. culties inherent in the earlier theory. Negative ions Occurrence and position of the principal have no effect on glass electrode potentials because inflexion point in certain acid-base titration the form of the glass lattice is such that large repulsive curves. E . D . E a s t m a n (J. Amer. Chem. Soc.; forces for negative ions come into play and these 1934, 56, 2646—2648).—Mainly a reply to criticism have not sufficiently high energies to reach the glass (A., 1932, 1101). E . S. H. surface. Gross and Halpern’s theory (A., 1934, 601) Electrometric titration of lecithin and kephalin. is criticised. M. S. B. T. H. J u k e s (J. Biol. Chem., 1934,107, 783—787).— Influence of sucrose on the p a of alkaline Kephalin (I) in 98% EtOH behaves towards NaOHasa solutions. K . S m o l e ń s k i and W. K o z ł o w s k i monobasic acid with j)Ka' val. of 8-9, very close to (Bull. Acad. Polonaise, 1934, A, 160— 171).—Sucrose that of +NH3Et. Lecithin (II) shows no base-binding (I) behaves as a poly basic acid and reduces the pu. power. Both lipins show acid-binding power at very The val. of the dissociation equilibrium const. K low pa vals. (I) and (II) form zwitter ions which depends on the ratio [NaOH]/[sucrose]. Assuming should be represented as RO-PiO^’CH^CH^-NRV (I) to be dibasic, Jv,=3—4 x 10-13 and i i 2=0 -3 x where R '= H for (I) and Me for (II). A. E. 0. 10-13. R. S. Electrometric titration of zein and iodozein. Platinum electrode potentials in mildly alkal A. N e u b e r g e r (Biochem. J., 1934,28,1982— 1992).— ine sugar solutions, the electromotively active The acid-binding power for different preps, of zein (I) reductant present, and the catalytic eSect of in 90% EtOH varies between 16-6 and 20-1 arid the iron on its oxidation. J. M. O r t and M. H. base-binding power between 46-2 and 54-6 x 10~5 inols. R o e p k e (J. Physical Chem., 1934, 38, 1061— 1074).— per g. of protein. From titrations at different temp, Pt electrodes in alkaline sugar solutions do not give and concn. of EtOH it is shown that the titration curve exactly reproducible potentials. This is attributed to of (I) is determined by the no. of free C02H, phenolic, adsorption of an oxygenated glucose ion, GO', at the iminazolc, and guanidino-groups. The I of iodozein surface of the electrode. Oxidation or reduction (II) is found exclusively in the C(1Hfi ring of tyrosine appears to remove it. The electromotively active (III). Titration curves of (II) confirm that the base- reductant accumulating in such solutions appears to binding power of (I) is due to the (III) groups. be H2. On addition of excess of oxidant H2 is oxidised, C. G. A. GO' is formed, and finally G02', giving a high oxid Titration constants of some amides and di ation potential. Finely-divided Pt and Fe do not peptides in relation to alcohol and formaldehyde catalyse the rate of formation of the reductant (cf. A., titrations of amino-N. J. M e l v i l l e and G. M. 1932, 345), but they catalyse the oxidation of GO' to R ic h a r d s o n (Biochem. J., 1935, 29, 187— 195).— GO./, and then the oxidation of H3 by G 02' giving GO' Titration consts. at 25° are given for rf-glutamine, d- and H20. A formula is given for the relation between isoglutamine, Z-tsoasparagine, rf-glutaminylglycine, d- time and reduction potential after the reduction of glutaminyl-
by the direct method and in each case to break the of the containing vessel, a chain mechanism is probably circuit at the same point on the film. The results involved. The velocity oc a power of [NH2Me] give no indication of the existence of a transfer or between 1 and 2 and approx. the first power of [02]. surface resistance, thus confirming previous con Foreign gases have no marked influence. Above a clusions (A., 1932, 701). M. S. B. definite limiting pressure, determined by the temp., Passivity of iron and steel in nitric acid solu ignition occurs. It is a thermal process and results tions. Ill, IV. Y . Y a m a m o t o (Bull. Inst. Phys. in a series of products different from those in the Chem. Res. Japan, 1934, 13, 1446— 1500, 1501— slow reaction. Greatly increased proportions of 1517; cf. A., 1934, 736).—III. HN03 containing H2, CO, and N, are found. There is an initial period CO(NH2), does not render Fe and steel passive. of induction. Thermal decomp, of NH2Me does not This is attributed to the removal of H N 02, which become appreciable until 500° is attained. It con acts as an 0 2 carrier to the surface of the metal. Fe sists mainly of the two reactions N’H2Me==HCN+2H2 in HN03 loses its passivity on addition of CO(NH2)2 and NHjMe-f H2=CH 4+N H 3. Since oxidation in a short time. HN03-resistant stainless steel is readily takes place at. 250° these reactions cannot attacked severely by HN03 containing CO(NH2)2. take part in the oxidation process. M. S. B. IV. The effect of HN03 in making Fe passive is Slow oxidations at high pressures. I. Meth increased by addition of NaN02, but the passivity ane and ethane. II. M ethyl alcohol, ethyl of Fe immersed in HNO, is not destroyed by sub alcohol, acetaldehyde, and acetic acid. D. M. sequent addition of NaN02. J. W. S. N e w i t t and P. S z e g o (Proc. Roy. Soc., 1935, A, Photovoltaic cells and photo-electric cells with 147, 555—571).—By using hydrocarbon-02 mixtures containing < 5% of 0 2 and a flow method in which an irreversible layer. G. A t h a n a s it j (Compt. rend., 1934, 199, 1604— 1607).—A discussion. The the gaseous medium is passed rapidly at 50 atm. assumption of an irreversible layer, as in Cu-Cu20 through a reaction zone maintained at a suitable photo-electric cells, is shown to be inapplicable to temp, between 340° and 430°, the proportion of photovoltaic cells in general. H. J. E. primary product (alcohol) surviving is increased, until with CH4 it corresponds with 50% and with Determination of flame velocities of mixtures C2H6 with 62-6% of the hydrocarbon burnt: there of inflammable gases.—See B., 1934, 53. is no trace of peroxidation. Additional evidence Equation for hydrogen-oxygen explosion supporting the hydroxylation theory of hydrocarbon lim its. H. H. S t o r c h and C. W. M o n t g o m e r y combustion is obtained by studying the slow oxidation (J. Amer. Chem. Soc., 1934, 56, 2644— 2646).—An and thermal decomp, of each of the principal inter equation representing the explosion limits as a mediate oxidation products of C2H6 (EtOH, MeOH, function of the partial pressures of the reactants is MeCHO, AcOH) at appropriate temp, and pressures. derived. E. S. H. The oxidation of AcOH in a SiO, vessel at 426— 486°/200 mm. proceeds uniformly without an in Spark ignition of methane-oxygen mixtures. duction period, the products consisting of CO, C02, G . A. G im m e l m a x and M. B. N e im a n (Compt. rend. CH4, H.,0, and traces of MeOAc and COMe,. Acad. Sci. U.R.S.S., 1934, 4, 35—41).— Capacity and L. L. B. potential producing the spark, pressure, electrode Significance of proknocks in hydrocarbon separation, and reaction temp, were varied; the com bustion. A. R. U b b e l o h d e and A. E g e r t o n efficiency of the spark varies as CV2, and not as CV, (Nature, 1935, 135, 67).—Org. compounds which in agreement with Semenov’s equation. can disrupt to give radicals thus: EtO--OEt, A. B. D. C. EtO-'-OH, AcO— OH, EtO— NO, have a pronounced Kinetics of the reaction between gaseous proknocking effect in concns. as low as 10-5—10~6 methyl alcohol and nitrous oxide. E. W. R. mol. fraction. Peroxides and N 02-compounds which S t e a c ie and R. D. M c D o n a l d (J. Physical Chem., do not disrupt in this manner show no such marked 1934, 38, 1031— 1043).—The reaction between gaseous effects. ‘ L. S. T. MeOH and N20 has been studied at 500— 570°. The velocity is much > that of the thermal decomp, of Thermal decomposition of acetaldehyde. N20 and approx. oc [N20], but is independent of C. N. H in s h e l w o o d (Nature, 1935, 135, 67).—New [MeOH]. The apparent heat of activation is approx. data confirm the homogeneous nature of the reaction 60,000 g.-cal. Velocity oc surface area, indicating under conditions of previous work (cf. A., 1934, that the reaction is either heterogeneous or a chain 1294, 1312), and show that the pressure increase process. The latter alternative is doubtful, since it measures the actual rate of disappearance of MeCHO- was not found possible to cause an explosion by L. S. T. raising the temp. The main reaction is probably Thermal decomposition of acraldehyde. Me0H+3sT20=CH„0-fH,0+N„ CH.,0=H,+C0. H. W. T h o m p s o n and J. J. F r e w in g (Nature, 1934, M. S. B. 134, 900).—The decomp, of acraldehyde has been Thermal oxidation of methylamine. L. J. studied at 550°. Three independent “ bimol.” regions J o l l e y (J.C.S., 1934, 1957— 1966).—The slow homo occur over the approx. ranges 15— 40, 40—200, geneous reaction between gaseous NH2Me and - 0.,, and 200—600 mm. The energy of activation, which examined between 250° and 600°, consists of a serie“s is of the order of 5 x l0 4 g.-cal., is different in the of consecutive reactions giving mainly a mixture of several regions (cf. A., 1934, 1311). L. S. T. CHjjO, CO, C02, HCN, XH3, and H.,0. Since the Vapour-phase hydrolysis. S. Y a m a s a k i and reaction is retarded by increase in the ratio surface/vol. T . T i t a n i (Bull. Chem. Soc. Japan, 1934, 9, 501— GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 173
504).—There is no detectable hydrolysis of CH2PhCl in solution as if it exists in 2 forms in equilibrium, vapour when heated for 5 hr. with H20 vapour at only one being saponifiable. H. J. E. 130° or 200°, or of EtOAc vapour after 150 hr. at Kinetic considerations regarding the Riesen- the same temp. F. L. U. feld test in the investigation of the nature of Rate of reactions in solution. R. S. B r a d l e y a peroxy-compound. H. A. L i e b h a f s k y (Z. (J.C.S., 1934, 1910— 1917).—Formulae for uni- and anorg. Chem., 1934, 221, 25—32).—By using a buffer bi-mol. reactions in liquids, which take into account solution in the Riesenfeld test, i.e.', the reaction of the mol. structure of the liquids and avoid the intro peroxy-compounds (I) with KI, a clear distinction duction of viscosity, are calc. Agreement with ex may be made between true,(I) such as K 2S2Og and perimental data is found in a no. of cases. For apparent (I) such as H202. In the former case bimol. reactions the formula applies to reactions liberation of I progresses continuously and in the between mols. and large ions which are not strongly latter the liberation of I soon reaches a stationary solvated, as well as to reactions between mols. The state and evolution of 0 2 takes place at a rate cor same conceptions may be applied to the study of responding with the rate of destruction of (I). (I) diffusion in solutions. M. S. B. of an intermediate character behave like mixtures of Kinetics of oxidation of nitrous acid by chloric H202 and K 2S20 8. M. S. B. and bromic acids. W. G. L o w e and D. J. B r o w n Kinetics of the interactions of sodium hydr (Z. anorg. Chem., 1934, 221, 173— 176).—The re oxide with penta- and hexa-chloro- and -bromo- action between C103' and H N 02 is of the second ethane in aqueous and ethyl-alcoholic solutions. order; k cc [H‘], Alteration of [Cl'] produces no W . T a y l o r and A. M. W a r d (J.C.S., 1934, 2003— significant change in fe. The reaction with Br03' 2010).— In aq. EtOH-NaOH at 25° and 35° the is similarly unaffected by changing [Br'], whence halogen compounds, C2HX 6 (X=C1 or Br), lose H X it. is inferred that oxidation of Br' to Br plays no immediately and C2X6 lose X 2 very slowly. Both part. F. L . U. types give C2X4, the latter undergoing a further Kinetics of the reaction between potassium very slow elimination of X. On the assumption permanganate and oxalic acid. II. H. F. that the reactions are all bimol., ratios of the velocity Latjner and D. M. Y o s t (J. Amer. Chem. Soc., 1934, coeff. k for the compounds C2H2X4 and C2HX 5 have 56, 2571—2577; cf. A., 1932, 1002).—Reaction been determined by a competitive method. Elimin between Mn04' and C204" is extremely slow, whilst ation of X from C2X6 and C2X4 is essentially bimol., that between M n"" or Mn’n and C204" proceeds but complications, varying with the character of X, at a measurable rate. Mn"“ is present in equilibrium are caused by oxidation of EtOH by X. The com with Mn04', Mn'“ , and Mn” ; a solution containing pounds C2H6_„X „ are classified into two groups, no Mn of low valency reacts slowly or not at all with according to whether they undergo slow or immediate H2C204. The mechanism of reaction proposed varies elimination of X. Observed vals. of k have been according to the concn. of the reagents; the inter compared with those calc, from crit. increments. mediate formation of C02' is assumed. E. S. H. M. S. B. Velocity of decomposition of diazo-compounds Kinetics of the decomposition of ammonium D e y r u p in water. XVI. E. Y a m a m o t o (J. Soc. Chem. am algam . A. J. (J. Amer. Chem. Soc., Ind. Japan, 1934, 37, 687— 690b).;— The rate of 1 9 3 4 ,5 6 ,2594— 2599).—The decomp, of NH4amalgam decomp, of aq. a-C10H7*N2Cl is unaffected by the at —20° and — 30° follows the rate law dx/dt— addition of MgS04, A12(S04)3, CaCl3, or Pb(OAc)2; k2(a—x)^x. Decomp, is mainly heterogeneous, oc it is slightly increased by CuS04 (after an induction curring at the surface of bubbles of the reaction period), FeS04, or NaOAc, and greatly increased by product, which consist of spherical shells of liquid NaOH or Na2C03. A. G. NH3 enclosing gaseous H2. The heterogeneous reaction is probably an electrode reaction obeying Kinetics of sucrose inversion by adiabatic the laws of overvoltage; it is completely inhibited temperature measurements. S. S. Joshi and by > 0-005J/-LL The homogeneous decomp, G. R. P h a n s a l k e r (J. Indian Chem. Soc., 1934, 11, measured at 0°, 10°, and 20° follows the rate law 751—766).—The velocity of the initial stages of the dx/dt^k^a—x)2, which may be explained by effective inversion of aq. sucrose (I) (2— 30 g. per 100 c.c.) collisions between two NH4 ions and two electrons. by 0-4—0-9AT-HCl has been determined by the rise The energy of activation of the homogeneous reaction of temp, measured under adiabatic conditions. The is 22,400 g.-cal. E. S. H. Telocity coeff., k, is a function of [HC1], and with const. [HC1], k increases with increasing [(I)]. The Local element effect in corrosion processes. sp. heat of aq. (I) diminishes with increase of [(I)] I. S t e r n and N . N e k r a s o v (Physikal. Z. Soviet- and the heat of dilution of aq. HC1 in ELO is > in union, 1934, 5, 729—745).—A theoretical relationship a
electrolyte on the deposit has been determined. for ignition in proportion to the ability of these gases The effect of the citrate is to displace the electrode to retard the rate of diffusion. 25% H2-75% 0 2 is potentials to “ baser ” vals., the shift being greatest the mixture most easily ignited in the positive column. for Cu and least for Fe. F. L. U. Rise in temp, causes a relatively large increase in ignitability. This is also increased by increasing Electrolytic production of lithium. L. W a s i the length of the positive column, but is decreased l e w s k i and J . Z . Z a l e s k i (Przemysł Chom., 1934, by the approach of a surface to the path of the dis 18, 628—633).—A fused 6 : 4 mol. mixture of LiCl charge if the distance is > about 1 cm. A glass and KC1 is electrolysed at 410° in a special apparatus, surface has a lowering effect < that of Ag. These using graphite anodes, and hollow, conical cathodes, results may be interpreted on the basis of the reaction from which the fused Li, containing > 2% K, is chain hypothesis previously given (this vol., 45). periodically removed. R. T. The energy of the gas surrounding the discharge Electrodeposition of chromium under must, for the positive column, be very much > for pressure.— See B., 1935, 2S. the condensed discharge. M. S. B. Electrolytic oxidation. VI. Anodic oxidation Electrothermal production of nitric oxide in of acetates : mechanism of the Kolbe and Hofer- the light of researches on dissociation. W. Moest reaction in aqueous solution. S. G l a s - D o m in ik (Przemysł Chem., 1934, 1 8 , 367—373).— s t o n e and A. H i c k l in g (J.C.S., 1934, 1878— 1888).— The formation of NO and NH3 from their elements The electrolysis of aq. solutions of acetates and AcOH at high temp, is ascribed to combination between with smooth and platinised Pt, Au, Ni, and C anodes dissociated mols. of N2, 0 2, and H2, and not to the has been studied under different conditions. greater stability of NO or NH3 at higher temp. N2 Catalysts for the decomp, of H202, e.g., Pb", Ag‘, is calc, to be 0-65% dissociated at 2000°, 3-6% at Mn", Cu'*, Co” , and Fe", inhibit the formation of 3000°, and 8-3% at 4000°. R. T. C2H6 by the Kolbe synthesis, whilst Na", K", NH4", Combination of hydrogen and oxygen in Ca", Sr", Ba", Mg“ , Zn” , Ni", and U 02", which do direct-current discharges. E. M. G u e n a u l t and not decompose H202, allow the formation of C2H6 R. V. W h e e l e r (J.C.S., 1934, 1895-1901).- to take place. Poisoning the platinised Pt anode for Measurements of the rate of combination of H2 and H202 decomp, increases the yield of C2H6. Au and 0 2 in the d.-c. discharge have confirmed the results Ni anodes become coated with oxides which decom of earlier investigators. The temp, at different pose H202 and, therefore, do not yield C2H6. The points in the path of the discharge varies system Kolbe synthesis is also inhibited by the anions F', atically with the conditions of the experiment. In C104', Ń 03', P04'", Cl', S04", or Fe(CN)e'". The comparative experiments, in which N2, A, or He was effect oc the mobility of the ions. The results do used as a diluent, the relative rates oc the temp, not agree with previous theories of the Kolbe re produced in the mixture by the discharge, and not cc action. It is suggested that H202 is formed by the the effect each diluent gas would have on the degree union of discharged OH' and reacts with AcO' to of ionisation. The combination of H2 and 0 2 in the give C2H6. If the [H202] or [AcO'] is kept low, d.-c. discharge is not primarily due to its ionising formation of MeOH occurs, probably with A c02H effect, but the chemical reaction as a result of electron as an intermediate product. Alkalinity is not excitation is probably considerably augmented by necessary for MeOH formation. Anode potential its thermal effect. M. S. B. is merely a secondary indication of the particular Action of an electric discharge on nitric oxide. reaction taking place, and not a primary factor in Production of active nitrogen. C. Z e n g h e l is and determining it. M. S. B. S. Evangelides (Compt. rend., 1934, 1 9 9 , 1418— Electrolytic reduction of acetophenone. S. 1419).—When an ozonising discharge is passed S w a n n , jun., and G. H. N e l s o n (Trans. Electro- through NO, the latter is decomposed into N2 (partly chem. Soc., 1935, 6 7 , 49—54).— COPhMe when as active N) and 02 (partly as 03) as well as into reduced electrolytically in aq.-Et0H-H2S04 with N 02. As a second phase oxidation occurs to N03 Cd, Sn, Pb, Hg, Al, Zn, C, N i, Cu, and Fe cathodes, and N20 6; in the third stage of the action these at 65—70° and c.d. 0-054 amp. per sq. cm., gives combine with NO and NO,, to form N,Or. acetophenonepinacone (I), (CHPhMe)aO, and a resin ■ J .W .S . of unknown composition. A Pb cathode gives the Active chlorine. E. J. B. W i l l e y and S. G. best yield of (I), but the cathode material has very F o o r d (Proc. Roy. Soc., 1934, A, 1 4 7 , 309—332).- little influence on the course of the reaction. The activation of Cl2 in the silent discharge is not R. S. B. accompanied by a vol. change. No change in the Chemical action in the glow discharge. XIV. absorption spectrum of activated Cl2 could be de Ignition of hydrogen-oxygen mixtures. A. K. tected. Experiments were carried out using a spark B r e w e r and P. D. K ite c k (J. Physical Chem., 1934, discharge between C electrodes, and also with the 38, 1051— 1059).—Ignition in the positive column silent discharge. Active Cl2 reacts with H20 giving is different from that in the condensed discharge an increased amount of HC1. No difference (from (A., 1931, 44), but there is a distinct analogy between ordinary Cl2) could be detected in the oxidation of the latter and the reaction in the negative glow. In FeCl2, but with FeS04 the amount of Cl2 reacting the positive column there is a hyperbolic relation decreased. No difference was observed in the oxid between power input and pressure. The addition ation of H2C204, but an increase in reaction was of foreign gases lowers the power input necessary found with AcOH in the case of the sparked CL GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 177
Active Cl2 reacts with C6H0 giving both substitution reaction rate varies with pressure and has a large and additive compounds. The effect of traces of temp, coeff. A mechanism of reaction is suggested. impurities, 0 2, N2, and air, and of irradiation of the E. S. H. Cl2 was investigated. The nature of active Cl2 is Photochemical reactions. Action of phos discussed, the balance of evidence suggesting that it phorous and hypophosphorous acids on uranyl is at. L. L. B. salts. F. D ik n e r t and F. V il l e m a in e (Compt. rend., 1934, 199, 1113— 1114).—Reduction occurs Heterogeneous chemical reactions in the on illumination in a Pyrex vessel. The product is silent electric discharge. X I. S. M iy a m o t o a U phosphate, its composition varying with the (Bull. Chem. Soc. Japan, 1934, 9, 505—510; cf. A., light intensity and the acidity. H. J. E. 1934, 739).—H2 reacts with the following solid substances : KAg(CN)2, ICONS, Ca(CNS)2, NH4CNS, Influence of salts on intermittent photographic Na2S203, 'MgS203, BaS203, Ba(C103)2. Details are exposures. T. H. J a m e s , J. M. B l a ir , and F. E. E. given. F. L. U. G e r m a n n (J. Physical Chem., 1934, 3 8 , 1023— 1030).—Intermittent exposures of a photographic Photochemistry. M. B o d e n s t e in (Naturwiss., emulsion produce developable densities which are 1935, 23, 10— 16).— A lecture. different from, and usually < , those produced by Decomposition of ozone photosensitised by equal continuous exposures. The influence of different chlorine. R. G. W. N o r r i s h and G. H. J. N e v i l l e ions on this intermittent effect is similar to their (J.C.S., 1934, 1864— 1872).—The decomp, of 0 3, influence on the Herschel effect (cf. Narbutt, A., photosensitised by Cl2, lias been studied using light 1930, 1385). M. S. B. of X 365 mu at 25°. It is a chain reaction, and Mechanism of the desensitisation of photo quantum efficiencies, y, up to 10 may be obtained. graphic plates. M. B l a u and H. W a m b a c h e r The law y oc J-05, whore I is the light absorbed, is (Z. wiss. Phot., 1934, 33, 191— 197).;—Plates treated approached when the pressure of 0 3 is high and those with pinakryptol-yeilow (I) are more sensitive to of Cl2 and 0 2 are low. When the pressure of Cl2 a-particles and slow protons; treated plates are or 02 is high, y is independent of I, the reaction is of also sensitised to high-speed protons, if exposed in zero order with respect to 0 3, and the rate oc the first vac. or in N2. With visible light the desensitisation power of I. For const. I and increasing pressure normally produced by (I) decreases with the degree of 02 and Cl2 y is depressed towards a limiting val. of vac. obtaining during the exposure, and is almost of 2. Foreign gases have no effect. At high Cl2 entirely removed in an atm. of N2, C02, or other and 0 3 pressures a red liquid (C103)„ is obtained. 0 2-free atm. The effect is not obtained by evacuation When this does not separate, the results are uniform after exposure, and only weakly when the plate is and reproducible, and there is no indication of after kept in vac. until just before exposure. Other effects when irradiation is discontinued. After desensitisers (pinakryptol, induline-scarlet, pheno- separation, however, it continues to decompose in safranine, etc.) show the effect, but not pinaflavol. the dark, causing an increase of pressure. A re The effect is less with the more strongly dyeing action mechanism involving the propagation of chains reagents. Desensitisation is hence considered as by Cl and CIO is suggested, and applied also to the an oxidation of reduced AgBr, the desensitiser being thermal decomp, of 0 3 sensitised by Cl2. reduced by photochemical action, but reoxidisable M. S. B. by atm. 0 2 to re-form the dye, which can then again Photochemical reaction between chlorine and oxidise Ag. The presence of H20 is also necessarv. formaldehyde. Preparation of formyl chloride. J. L. K. B. K h a u s k o p f and G. K. R o l l e f s o n (J. Amer. Relation between exposure and photographic Chem. Soc., 1934, 5 6 , 2542—2548).—The reaction blackening on exposure to Röntgen rays. E. occurs in two steps. The first is an exothermic, H o f e r (Z. wiss. Phot., 1934, 3 3 , 198—200).— long-ohain process, involving no pressure change, Mathematical. The formula
( III) and of the products of reaction in the emulsion. Photo-bromination of a-phenylcinnamic acid. (Ill) adapted to over- (under-)exposed plates exert A. B e r t h o u d and D. P o r r e t (Hclv. Chim. Acta, only the, latter (former) effect. The successive use 1934, 17, 1548— 1557).—The speed of this reaction, of (III) for over- and under-exposed plates leads to at 25° and in blue light, is greatly increased if the a considerable extension of (II) in both directions CC14 used as a solvent is first acted on by Cl2 in the (compensational development). R. T. light for 8 hr., treatment which appears to destroy a negative catalyst present in material purified in Autophotographic location of radioactive ions, the usual way. The velocity oc 7089[Br2][^ ]070 for in gelatin. (M l l e .) S. V e il (Compt. rend., 1934, total absorption and / 0'77[B r2]1,i6[^[]0 70 for weak 1 9 9 , 1044— 1046; cf. A „ 1933, 1005; 1934, 961, absorption (7=intensity, A =unsaturated acid), the 1172).—When radioactive ions are concerned in the reaction thus differing from other similar bromin- formation of diffusion figures in gelatin, additional ations. The difference is attributed to simultaneous data can be obtained from the pattern obtained on reactions leading to the formation of more highly a photographic plate in contact with the gelatin brominated compounds. F. L. U. film. The colourless Th(N03)4 aureole has thus been shown to have distinct diffusion zones. The auto- Combined action of ultra-violet light and photographic pattern of a gelatin film, impregnated platinum on transformation of fumaric and with BaCl2 solution containing Ra, after electrolysis maleic acids and their salts. F. B erezovskaja , to almost zero conductivity, shows a distribution of M. K o g o n , and E. M oskalenskaja (Compt. rend. radioactive material corresponding with the relative Acad. Sei. U.R.S.S., 1934, 4, 50—56).— Conductivity opacity of the film. J. W. S. measurements show that this combined action does not transform fumaric (I) into maleic (II) acid, but Photo-decomposition of gaseous ethyl iodide produces decomp, by adsorption at the Pt surface; and a comparison of the photo-change in the a similar effect was observed with (II) and the Ba gaseous and condensed states. W . W e s t and salt of (I), but the Ba salt of (II) showed no decomp. E. G in s b u r g (J. Amer. Chem. Soc., 1934, 5 6 , 2626— A. B. D. C. 2630).—The quantum yield (1) is < 0-01 in the con Photochemical decomposition of glycine. In tinuous spectrum, about 2600 A., increases to about fluence of the medium and wave-length. V. 0-1 at 2026 A. in the band spectrum at about 90 mm. H e n r i, C. W e iz m a n n , and Y. H ir s h b e r g (Compt. pressure, and is lower in this region at 0-1 mm. In rend., 1934, 1 9 9 , 1205— 1207; cf. A., 1934, 264).- the continuous region, liquid EtI and its solution in Thc decomp, rate has a max. at pB 3 and a min. at hexane have much higher (I) than the gas (about pn 6. The effective wave-length is < 2478 A 0-6), whilst at 2026 A. (I) in the liquid is about 0-24. Extinction coeff. measurements before and after Rise in temp, by 10° does not appreciably change irradiation are recorded. H . J. E. (I) at 2026 A. The mechanism is discussed. Photosynthesis of am ino-acids. N. R. Diiar E. S. H. and S. K. M u k h e r j i (J. Indian Chem. Soc., 1934, Photochemical studies. XX. Photochemical 1 1 , 727— 735).— Details are given of results already decomposition of acetone in the Schumann published (A., 1934, 1208). Coloured inorg. salts region. W. M. M a n n in g (J. Amer. Chem. Soc., increase the photosynthesis. Of several NH4 salts 1934, 56, 2589—2594; cf. A., 1933, 792).—The of org. acids, only the lactate affords an NH2-acid proportion of CO, H,, CH4, C2H4, and C2H6 produced on illumination in presence of T i02. J. G. A. G. at different initial pressures has been determined. The products and rate of reaction vary with the Kinetics of photosynthesis. E. C. C. B aly (Nature, 1934, 134, 933).—A reply to criticism (A., pressure. More H2 is produced by decomp, in the 1934, 1078). L. S. T. Schumann region than when light in the near ultra violet is used. E. S. H. Mechanism of the action of light on selenium electrolytic photo-cells. R . A u d u b e r t and J. Photochemical changes of t-aspartic acid, R o u l l e a u (J. Chim. phys., 1934, 3 1 , 553—558).—A /-asparagine, and chemically related sub detailed account of work already noted (A ., 1934, stances by A'-rays and ultra-violet light. J. P. 584). B e c k e r (Strahlenther., 1934, 5 0 , 357— 363; Chem. Lithium cobaltinitrite. S. K i k u c h i (Compt. Zentr., 1934, ii, 1422).—¿-Aspartic acid (I) when rend., 1934,. 199, 1414— 1416).—On mixing aq. irradiated with X-rays and dissolved in O-liV-NaOH LiN02 [prepared from Ba(N02)2,H20 , 82 g., and gave an absorption max. at 2650 A., not observed Li2S04,H20, 43 g.] with aq. Co(N03)2 (28 g.) and with ¿-asparagine (II), ¿-malic acid, or cinnamic acid acidifying with 5 0 % AcOH (20 c.c.), an orange- after similar treatment. Irradiation of (II) in yellow solution is obtained which on evaporation solution gave a similar max. at 2750 Ultra-violet A. under reduced pressure deposits orange-yellow prism illumination of an aq. NaOH solution of (I) gave a atic crystals of Li cobaltinitrite, Li3C o(N 02)6,8H20, max. absorption at 2650 A. H. J. E. decomp. < 100°. It is very hygroscopic and is sol. in Photochemical process for measuring ultra EtOH and E t0H -E t20 mixtures, but not in pure Et20. violet radiation. H. Sc h r e ib e r (Meteorolog. Z., On addition of a K salt to its aq. solution a ppt. of 1933, 399—402; Chem. Zentr., 1934, ii, 986).—The K 3Co(N02)6 is formed even when the L i : K ratio COMe2 method of Friedrich and Bender (Meteorolog. is 200 : 1. J. W. S. Z., 1930, 285) has been tested and is discussed. Interaction of alkali chlorides with calcium H. J. E. nitrate in liquid ammonia. A. G u y e r , A. B ie l e r , GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 179 and E. S c h m id (Helv. Chim. Acta, 1934, 17, 1538— thus : 2CPh3Cl+2NaI+2COMe2 ---- >• CP1i3*OH-{- 1544; cf. this vol., 2(S).—The reaction 2NaCl-f CHPh3+2N aC l+I2+CMe2:CH-COMe. J. G. A. G. Ca(N03)2=?2NaN0|'tf CaCl2' is nearly quant, at 0° in Action of potassium iodide on fairly insoluble NH3 containing > 15% of H20 , owing to formation com pounds. E. M o n t i g n i e (Bull. S oc. chim., 1934, of CaCl2,8NH3 which is only slightly sol. in NH3. [v], 1, 1405—1407).—Aq. KI reacts with PbS04, The concn. must be such that ,NaN0 remains dis 3 AgCl, T1C1, Cu(CNS)2, Ag3As04, Ag2Cr04, Hg2Cr04, solved. At lower temp., and with anhyd. NH3, HgCr04, Tl2Cr04, and Bi2(Cr04)3, but not with BaCr04 the reaction is more rapid in consequence of the or PbCr04. , F. L . U. greater solubility of NaCl arid, below —20°, of NaCl,5NH3. The reaction with KC1 is incomplete Action of potassamide on sulphur in liquid and much slower. F. L. U. am m onia. F. W. B e r g s t r o m (Z. anorg. Chem., 1934, 2 2 1 , 113— 123; cf. A., 1934, 1110).—When Preparation of pure sodium fluoride. I. S is added gradually to KNH2 dissolved in liquid Ta n a n a e v (J . Appl. Chem. Russ., 1934, 7 , 729— NH3 at —33° in presence of Fe as catalyst, a yellow 730).—40—45 g. of impure NaF arc dissolved in ppt. is at first formed which dissolves on further 1000 c.c. of H20, 15—20 g. of KC1 added, and the addition of S. The reaction at first is GKNH2+3S = solution is filtered after 2—-3 days. The filtrate is 2K2S+ S(NK)2,NH3+3N H 3, and subsequently 6KNH2 free from Na2SiFfi if the red colour obtained by adding + 1 2S= 2K2S4+ S4(NK)2 -f- 4NH3. If the reaction takes a drop of 0-1AT-Na011 and of phenolphthalein per place slowly K 2S3 is formed. F. L. U. sists after boiling; if not, more KC1 should be added. The filtrate is coiic. to 100 c.c. in a Pt vessel and the Compounds of magnesium chloride with pptd. NaF washed free from 01' and dried at 150°. organic compounds. I. Compounds with Yield 55—60%. R. T. alcohols and acetic acid. L. J. O l m e r and (M l l e .) M . L. Q u i n e t (Bull. Soc. chim., 1934, [v], Synthesis of sodium cyanamide and sodium 1, 1579— 1584).— Optimal conditions for preparing cyanide under pressure. I. Sodium cyan anhyd. MgCl2 (I) from MgCl2,NH4Cl,6H20 are defined. amide. K. Sakurazawa, M. H a n d a , and R. By evaporating or by adding Et20 to solutions of (I) H ara (J. S oe. Chem. Ind. Japan, 1934, 3 7 , 701— in the appropriate alcohol, the following compounds 702b).—Approx. 100% yields of Na2CN2 may be were obtained : MgCU,6MeOH (II), m.p. 115— 120°, obtained by the reaction NaCN+Na-j-0-5N2— >• MgCI2,6EtOH (III), m.p. 72—77°, MgCl2,6Pr“OH, Na2CN2 under suitable.conditions, e.g., 620°, 83 atm., MgCU,6BunOH, m.p. 55—60°, and a substance 120 min., with Fe as catalyst. The equilibrium containing (I) and CH2Bu^*OH. Et20 ppts. from pressure rises rapidly with % Na2CN2 in the mixture. a mixture of alcohols the compound containing the A. G. alcohol with the lowest mol. wt. In vac., thermal Action of halogen compounds on alkali decomp, of (II) and (III) affords variable proportions iodide solutions. A. P e r r e t and R. P e r r o t (Bull. of HCl, the alkyl chloride, MgCl2, MgO, MgC03, Soc. chim., 1934, [v], 1 , 1531— 1548):—The oxidising and C. MgCl2,6H20 and AcCl or Ac20 afford powers of the halogen compounds have been investig MgCl2,GAcOH (IV),"m.p. 85—90°, at low temp, and ated by means of the I liberated or determined in the MgCL,±AcOH (V), m.p. 110°, at >80°. At the m.p. reactions with neutral, acid, and alkaline aq. and (IV) changes into (V), which is decomposed by heat C0Me2 solutions of K I or Nal alone, and with excess into variable proportions of MgCl2, Mg(OAc)2, HCl, of Na2S,0.,, and by means of LiBr in COMe». The MgC03, and C. J- G. A. G. reaction" S2C12+ 2 K I— >2S+2KC1+L, proceeds to Dissociation of magnesium chromate. I. G. completion in 2A;-HC1 andinKI with excess of Na2S20 3. hiCCI4, the reaction is S2Cl2-f 2Na,S20 3— >-Na2S40 6+ Riss and R. G. U r i t z k a j a (Compt. rend. Acad. Sci. 2S-f2NaCl. With neutral KI, the process CCL-SCl-f- U.R.S.S., 1934, 4, 213—217).—The prep, of pure anhyd. MgCr0 is described. Thermal decomp. 2KI— >CSCl2-[-I2-f2KC1 is complete in 20 hr., 4 follows the reactions 2MgCr04=2Mg0,Cr203+ l-5 0 2; and with a mixture of K I and Na2S,03, 2-4— 3-1 2MgO,Cr 0 = MgO+ MgO,Cr 0 3. H reacts at 300° Cl atoms of CSC14 arc available. SOCl2 and KI 2 3 2 2 afford S, and the quantity of I liberated varies with with inflammation. The dissociation pressure of the acidity. The competing reactions are considered. MgCr04 is given by log —16,488/r-)-23-271; the heat of dissociation is 75,370 g.-cal. per mol. of The I rapidly liberated from alkaline Nal by S0,C12 oxidises the S03" produced. 81% of the PhS02Cl 0 2. E. S. H. w a mixture of Nal in aq. COMe2 and excess of Na.,S20 3 Hydrates of calcium aluminates, sulphato- reacts: PhS02C l+ 2NaI— > PhS02Na+ 12+ NaCl, and aluminates, and chloroaluminates. J. L e f o l jinSO.,-), is not formed. With CC13-S02C1, I is (Compt. rend., 1934, 1 9 9 , 1412— 1414; cf. A., liberated quantitatively from Nal in COMe2 thus : 1934, 31, 853).—Al203,4Ca0,12H20 passes into CCL-S02Gl+2NaI— CCl3-S02N a + I2+NaCl. By Al20 3,4Ca0,8H20 in a dry atm. The reaction is analogy with the action of COCl2 on Nal, BzCl reversible. Al20 3,3Ca0,6H20 , cubic, is very stable '™ ales small quantities of I from Nal in anhyd. and does not lose H20 oven at a relatively low H20 v t Although I is not liberated by treating aq. v.p. Al20 3,2Ca0,8H20 gains or loses H20 readily 1 n k (-COC1)*, the reaction in anhyd. COMe2 is according to the H20 v.p. in the atm. The hydrate (•tOa)2+ 2NaI — ^ 2NaCl+I2+2CO. Whereas ICN Al20 3,2Ca0,5H20 has been identified, but its form and BrCN liberate I quantitatively from acid JKI, ation is not reversible. Al203,3CaO,3CaS04,30H20 p,e^ is a deficiency with C1CN owing to hydrolysis. and Al20 3,3CaO,CaCl2,10H20 are stable hydrates ^CCl reacts with Nal in anhyd. COMe2 mainly which in a dry atm. pass into Al20 3,3Ca0,3CaS04,7H20 180 BRITISH CHEMICAL ABSTRACTS.— A. and Al203,3Ca0,CaCl2,6H20, respectively. The change the addition of much Bi(N03)3. Pure Tb is prepared is reversible for the latter compound, but not for the by preliminary concn. as bromate and fractional former. J. W. S. crystallisation of the Me2 phosphates. The possible influence of changes of lattice dimensions during Brick-red zinc oxide. A. K u t z e l n ig g (Z. fractionation is discussed. M. S. B. anorg. Chem., 1934, 2 2 1 , 4 6 ^ 8 ; cf. A., 1933, 239).— The red ZnO formed by dissolution of white ZnO Double sulphates of the rare-earth and alkali in fused NH4N03 and explosion is not due to the metals. Sulphates of praseodymium and potass presence of an unknown N compound, since the ium, of praseodymium and rubidium, of praseo N205 content is 0-25% and the loss in wt. on calcin dymium and cæsium, and of samarium and ation only 0-28%. Under the microscope the cryst. sodium. S. R e s t a in o (Atti R. Accad. Lincei, 1934, form is similar to that of ZnO prepared by the decomp, [vi], 2 0 , 192—200).—Investigation of the systems of Zn(N03)2. The magnetic susceptibility of the red M2S04-P r2(S04)3~H20 and Na2S04-Sm2(S04)3-H 20 at ZnO is —0-20 X 10~6 with 4 amp. and —0-25x10-* 25° (M =K , Rb, Cs) shows the formation of the com with 5 amp. The temp, of formation is > 300°. pounds xPr2(S04)3,yK2S04,zH20 with x, y, z= l, 5, 1 ; By heating above this temp, up to 540° the colour is 1,4-5, 0; 1 ,4 ,1 ; i, 3, 2 ; 2, 3, 8 ; and 1, 1, 2, respec gradually destroyed. No similar coloured oxide could tively ; Pr2(S04)3,Rb2S04,8H20 ; be obtained by replacing ZnO by MgO, BeO, Sn02, Pr,(S04)3,Cs,S04,8H20 ; Sm2(S04)3,Na,S04,2H20 ; or Si02, or NH4N03 by NH4C104. By decomp, at a and 4Sm2(S04)3,5Na2S04,8H20. " O. J. W. lower temp, the residue from the evaporation of aq. Reactivity of solids. III. Combustion o! Zn(C103)2 or Zn(C104)2 a S-yellow compound is carbon. K. F is c h b ë c k (Z. Elektrochem., 1935, obtained. M. S. B. 4 1 , 60— 66).—A review. Complex [cadmium and zinc] compounds Carbonyl fluoride COF2. 0. R u f f and G. [with pyridine and quinoline].—See this vol., 222. M iltschitzky (Z. anorg. Chem., 1934, 2 2 1 , 154— Preparation of metallic barium and its amal 158).— CO and F2 combine explosively when sparked gam s. V. D. P o l j a k o v (J. Appl. Chem. Russ., at atm. pressure, and COF2 can be prepared by feeding 1934, 7, 731—735).—Ba amalgam, prepared by F2 into CO through a spark gap. 0 2 present in the F2 electrolysing saturated aq. BaCl2 with a Hg cathode forms C02 which cannot afterwards be separated from (Mo connexion) and a graphite anode (0-28 amp. the COF2. Pure COF2, obtained by passing CO over per sq. cm. of Hg surface for 3 hr.), is vac.-distilled AgF2, has m.p. —114-0^0-3°, b.p. —83-li0-5°. in an Fe apparatus for 6 hr., gradually raising the V.p. is given by log 25=7-3231— 843-05¡T (mm.) and temp, to 850°, when a product containing 10% Hg d=l-809—0-00420?’. C0F2 is hydrolysed with ex remains. This is gradually heated to 1000° in a treme readiness. Other chcmical properties are second still (8 hr.), with a vac. of 10*3 mm. The resi described. F. L. U. due, containing 0-02—0-2% Hg, m.p. 650°, is sealed Action of titanium tetrachloride on organic in Cu tubes under A. H2 combines very energetically nitrogen compounds. O. C. D e r m e r and W. C. with Ba or its amalgam. ~ R. T. F e r n e l iu s (Z. anorg. Chem., 1934, 2 2 1 , 83—96).— Boron arsenate. W. C. S c h u m b and W. H. The following mol. compoimds have been obtained by H a r t f o r d (J. Amer. Chem. Soc., 1934, 5 6 , 2646).— the addition of an org. base to a solution of TiCl4 BAs04, prepared by boiling an aq. solution containing in CGHfi or CHC13 : TiCl4,NHPh2, TiCl4,2NAcPh2, H3As04 and H3B03, has d 3-40, ?iD 1-66. It is readily TiCl4,2(CH2-CO)2NH, TiCl4,C6H4Me-S02-NH2(p), hydrolysed and is slightly decomposed at red heat TiCl4,CHPh:NPh, TiCl4,CPh„:NPh, 3TiCl4.2NPh:NPh, without melting. E. S. H. TiCl4,NPh:N-C6H4*OBz, ‘ TiCl4,NPh:N-NHPh, 3TiCl4,2PhN:N-NPh2, TiCl4,2C5H5N, TiCl4>2C„H7N, Preparation of pure gallium. J. I. H o f f m a n TiCl4,4C6H7N (y-picoline), TiCl4,C5Hi0N. LiquiclTiCl4 (J. Res. Nat. Bur. Stand., 1934, 1 3 , 665—672).— and C6H2(N02)3-0H give Cl Ti[0-C H (N02)3]2. By A HC1 solution of the specimen is extracted with 2 6 2 the action of NH(CH2Ph)2 and excess of CS2 on TiCl4 a Et20, which dissolves the chlorides of Ga, Mo, Au, Fe, Ti[S-CS’N(CH2Ph),]4 is obtained. NPh2K Tl, and traces of other elements. Sb, As, Bi, Cd, Cu, compound, and TiCl4 give Ti'[iVPA2]4. " The mol. wts. of GPhjINPh; Ge, Au, Hg, Ag, and Sn and most of the Pb, Mo, and Rh are pptd. with H2S from an acid solution of the COPh2, and NPhlNPh in boiling TiCl4 have been deter Et20 extract. Fe and Tl are then pptd. with aq. mined, but owing to the volatility of the solute too NaOH and filtered off, Ga being deposited electro- high vais, have been obtained for the first two. lytically on Pt from the alkaline filtrate. Final M. S. B. purification from traces of Pb and In is effected by Zirconium and hafnium tetrafluorides. G. fractional crystallisation. Pure Ga separates first. v o n H e v e s y and W. D u l l e n k o p f (Z. anorg. Chem., 1934, 2 2 1 , 161— 166; cf. A., 1930, ).—The Recovery of the Ga residues is described. H . J. E. 1362 crystallographic characters of ZrF4 and HfF4 are Preparation of pure europium, gadolinium, recorded. The electrical conductivity of solid ZrF4 and terbium compounds. J. K . M a r s h (J.C.S., has been measured and found to be due almost entirely 1934, 1972— 1974).—Pure EuS04 can be separated to F ions. HfF4 can be partly separated from ZrF4 by quantitatively from a mixture of earths containing 3% fractional sublimation, or by distillation of their Eu by electrolysing once, or at most twice, with an solution in fused K2ZrF6. They are conveniently amalgamated Pb cathode of large area. Gd may be separated from Fe and other impurities by sublimation. purified by fractionation of double M g nitrates with GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1S1
N03F, an explosive compound. G. H. C a d y its fine state of division. Analysis leads to the formula (J. Amer. Chem. Soc., 1934, 56, 2635—2637).—Re Te3N4 as previously surmised (A., 1926, 137); it is action of F2 with dil. HN03 produces a gaseous com therefore not analogous to the S and Se compounds. pound, NO3F, b.p. —42°, which explodes when heated. The reaction with Br is very incomplete and yields NO3F reacts slowly with H20, liberating 0 2, and liber chiefly TeBr4. When the substance is suspended in ates I from aq. KI. E. S. H. Et.20 and treated with Br, the resulting HBr forms (NH ) TeBr6. Dry HC1 reacts with the solid to give Nitrogen selenide. W. St r e c k e r and H. E. 4 2 (NH ) TeCle. F. L. U. Schw arzkopf (Z. anorg. Chem., 1934, 221,193— 198). 4 2 —Pure (NSe)x can be prepared by the action of dry Hydrolysis of inorganic salts and chemistry NHj 011 Et2Se03 or Me2Se03 dissolved in C6H6, and of high-molecular hydrolysis products (includ removal of the accompanying Se02 and Se by 10% ing iso- and hetero-poly-compounds. I. G. J a n - KCN. The product is usually orange-red and amor d e r and K. F. J a h r (Kolloid-Beih., 1934,41,1—57).— phous, and has been obtained cryst. in monoclinic A summary of published work, especially on the com prisms analogous to N4S4 on one occasion only. It is plex oxy-acids of W, Mo, V, Ta, and Si. E. S. H. highly explosive. Chlorination yields mainly SeCl4. Oxidation of manganous sulphate by hydro Dry HC1 gives SeCl4, NH4C1, (NH4)2Se03, and H2Se. gen peroxide in an alkaline medium. P . D u b o is The Cl2 and HC1 used in these reactions must be greatly (Compt. rend., 1934,199, 1310— 1313).—The effect of diluted with C02. F. L. U. iW [H 20 2],.:[aq. NH3], and [KOH] on the composition Absorption of oxygen by phosphorus. C. T. of the ppt. was studied. With aq. NH3 or KOH the K djg zett (Analyst, 1934, 59, 816; cf. A., 1934, 11S6). ppt. is hydrated Mn20 3. With excess of KOH the —Attention is directed to previous work by the author composition varies between MnO^ and MnOj.g, and (J.C.S., 1880, 37, 792). E. C. S. the ppt. retains KOH after washing. Excess of H20 2 Production of pure, finely-divided vanadium. gave the same results. H. J. E. T. Doring and J. G e il e r (Z. anorg. Chem., 1934, 221, Hydrate and allotropic forms of manganese 06—62).—A method for the prep, of very pure V by sesquioxide. P . D u bo is (Compt. rend., 1934, 199, the reduction of VC13 with pure H2 at approx. 900° is 1416— 1418).—Oxidation of MnS04 by H20 2 in described. M. S. B. presence of NH3 yields Mn20 3 in a form which appears Decomposition of arsine by fine fibrous colloidal, but is cryst. to X-rays. When heated in air this tends to yield Mn02, but the reaction is never materials. G. L o c k e m a n n (Z . anal. Chem., 1934, complete. In absence of air, the oc-form of Mn 0 is 99, 178— 1 8 0).—Polemical against Gangl et al. (A., 2 3 1934,1084). ° J. S. A. formed, this being oxidised on heating in air. When heated to 600°, however, it passes into the normal Preparation of pure oxygen for laboratory use. ¡3-form of Mn20 5, which is not oxidised by heating in J. K rutzsch and H . K a h l e (Chem. Fabr., 1934, 7, air. The X-ray diagram of a-Mn20 3 is very similar to 452—453).—The decomp, of H 20 2 in a vessel of that of Mn30 4 resulting from the thermal decomp, of relatively small vol., leaving little free gas space, is p-Mn203. J. W. S. accelerated by the presence of beads. An apparatus suitable for generating 10— 50 c.c. per hr. is described. Complex sulphates. H. B r in t z in g e r and H. J. W. S. O s sw a l d (Z. anorg. Chem., 1934, 221, 21—24).—By Oxygen preparation from sodium peroxide. dialysis of solutions of the sulphates of bi- or ter- valent metals containing excess of alkali or NH sul G. H. Ch e e s m a n and D. R. D u n c a n (Nature, 1934, 4 134, 971).—An explosion under conditions similar to phates it is shown that the following ions exist: those previously described (this vol., 51) is reported. [M2(S04)4]" " (M=Mn, Fe, Co, Ni, Cu, Zn, Cd, or Mg) L. S. T. and [Fe3(S0 4)6]'". The possibility that the effects Yellow coloration of hydrochloric acid con observed may be due to heavily hydrated metallic ions is excluded by experiments to be described later. taining selenium. H. D it z and F. U l l r ic h (Z. anorg. Chem., 1934, 2 2 1 , 33—45).—Although Se is M. S. B. practically insol. in pure conc. HC1, it dissolves in HC1 Frictional oxidation [of metals]. F. R o l l and solutions of Se02 giving an intense yellow coloration W. P u l e w k a (Z. anorg. Chem., 1934, 221, 177— 181). due to the formation of Se2Cl 2 in solution. The extent — Oxidation occurring when a metal specimen is of the reaction may be studied quantitatively by pressed against a revolving steel plate has been studied titrating solutions of Se02 in HC1 with SnCl2 until a with respect to pressure and speed of rotation. The hunt cloudiness due to the separation of Se appears, zones of Fe20 3 and Fe30 4 formed are related to the i ® fo rm e d by reduction of Se02 redissolves giving temp, produced by the friction, contrary to the state oe2Cl2. In approx. 37% HC1 the Se2Cl2 formed is ment of Fink and Hoffmann (Ay, 1933, 241). about 90% of the theoretical quantity. This freshly F. L. U. leduced Se is more sol. than powdered or pptd. Se. Preparation of [iron-tin] alloys. P . P i n g a u l t (Compt. rend., 1934, 199, 1223— 1225).—The com rn .. . M.S.B. pound FeSn (I) is formed by heating Sn with aq. i eUurmm nitride. W. St r e c k e r and C. M a h r (Z. 2 anorg. Chem., 1934,221, 199—208; cf. A., 1926, 137). ZnCl2 containing 340 g. of FeCl2 per litre at < 300°. *>y the long-continued action of liquid NH3 on (I) is also formed by the direct action of FeCl2 on Sn ri a yellow powder is obtained which, after re at < 300°. H. J. E. moval of NH3, explodes on contact with H20. The Intermediate compounds between ferro- er property is due to heat of wetting resulting from cyanides and ferroammines. A. G. B a r b ie r i 182 BRITISH CHEMICAL ABSTRACTS.— A.
(AttiR. Accad. Lincei, 1934, [vi], 2 0 , 273—278).—By the compound [Pt ae2Cl3], and in acid solution liberates the action of KCN on [Fe(C,qH8N2)3]Br2,6II20 in solu 1 atom of I per atom of Pt from KI. (II) is con tion reddish-violetcn/sfo/s of [l,1e(CJ0H8N2)2(CN)2]3H2O verted by Na2PtCl6 in cold solution into the com (I) are obtained. Prolonged warming of (I) with conc. pounds, [Ptae4][PtCl6] and [Ptae4Cl2][PtClG]. With aq. KCN gives orange-brown crystals of excess of K 2PtClG (II) is completely transformed into [Fe(C10H8N2)(CN)4]K2,3H2O (II). From a solution the sparingly sol., violet-red compound of (II) the free acid, [Fe(C10H8N2)(CN)4|H2,2H2O is [Ptae„][PtCl4]. (II) and Ag,C,04 afford the salt obtained as a yellow ppt. by the addition of a mineral [Pt ae4]C204. “ H. W. acid. With o-phenanthrolinc instead of dipyridvl Varying valency of platinum with respect to the comjwunds corresponding with (I) and (II) have mercaptanic radicals. VIII. (S ir) P. C. R ay been prepared. Magnetic susceptibility measurements and N. N. G h o s e (J. Indian Chem. Soc., 1934, 11, for the above compounds are recorded. 0. J. W. 7 3 7 — 7 4 2 ; cf. A., 1928, 44, 751).— The product of the Influence of temperature on the formation interaction in EtOH solution of (SEt’CH2-)2 (=es) of additive compounds. G. Sc a g l ia r in i and M. and H2PtCl6 is PtesCl3 (I), m.p. 180— 182° (decomp.), R agn o (Atti R . Accad. Lincei, 1934, [vi], 2 0 , 278—- which is converted into PtesCl2 (II) by heating with 282).—From solutions of CoX2 (X=C1, Br) in C5H5N NPliMe2and into the compound PtesCl4 (III), m.p. 230° which have been kept at 70—80° for several hr., the (decomp.), by heating with fuming HC1 and compounds CoX2,2C5H5N crystallise out, whereas C5H5N and (I) afford [Pt(C5H5N)]Cl2 (IV) and the from cold solutions the compounds CoX2,4C5H5N are substance Pt(C5H5N)Cl3, m.p. 2 6 1 — 26 5 ° (decomp.), (II) obtained. The transition points for the changes gives (IV), and (III) yields [Pt(C6H5N)2Cl4]. M(SCN)2,4H20,2C6H12N4— M(SCN)2,4H20,CGHloN4 (•CH2’NH2)2 (—en) produces [Pteh2]Cl2 with (I), (II), (M=Co, Ni, Fe) and MX2,10H20,2C6H12N4 — and (III), whilst aq.NH3 and(III)afford [Pt(NH3)4]Cl2. MX„,4H20,2C6H12N4 (MX2=C oB r„ CoCl2, or NiCl2) The results show that (I) is neither a mixture nor a are < 80°. " " O. J. W. mol. compound of (II) and (III), and (II) and (III) are probably best represented by the formula [esPtCl,] Influence of substituents in bases and anions on the co-ordination index of a metal. VI. Ad and [esPtCl4], respectively. J. G . A. G. ditive products of benzylamine and phenylhydr- New indicators and other reagents employed azine with the nickel salts of substituted acetic in volumetric analysis. A. D. M i t c h e l l (Inst. acids. A . A b l o v (Bull. Soc. chirn., 1934, [v], 1, Chem., 1934, 21 pp.).:—A lecture. 1489—1494; cf. A., 1934, 1083).—The following com Polarimetric methods in chemistry. T. M. pounds are described : Ni(0Ac)2,4CH,PlvNH„H„0; L o w r y (Nature, 1934, 1 3 4 , 920— 921, 958— 960).- (CH2Ph-C02)2Ni,4CH2Ph-NH.,; ' " An address to the British Association. L . S. T. (CH,Cl-C0.,)2Ni,4CH2Ph-NH;; Methylal as a solvent in analytical chemistry. (CHCl2,C02)2N[i,4CH2Ph'NH2: L. E s f i l (Bull. Soc. chim., 1934, [v], 1,1502— 1503).— (CCl3"C0o)2Ni,4CH2Ph'NH2: The purification of technical methylal (I) is described. (CN-CH2,C02)2Ni,4CH2Ph-NH2: The range of complete miscibility with H20 of (I) is Ni(OAc)2,4NHPh-NH2; of Et20 (II). (I) extracts AcOH, lactic, succinic, (CHoPh-C00),Xi,4NHPh-NH2,3H.,0;r (CH2Cl-C0o)2Ni,4NHPh-NHo; citric, malic, and tartaric acids from aq. solution acidified with H2S04, and the process is faciliated (CHClo'C02)2Ni.4NHPlrNH2; by saturating with Na2S04. The advantages of (I) (CCl3-C02)2Ni,4NHPh-NH2; over (II) are emphasised and distribution data are (CN,CH2-C02)2Ni,4NHPlrNH2. These salts probably recorded. J. G. A. G. have the constitution [Ni(base)4]X 2, and the con stancy of the no. of base mols. co-ordinated (cf. the Determination cf small concentrations. VII. variable no. of C5H5N which co-ordinate; A., 1934, Potentiometric acid and alkali determinations. 1084) is attributed to the higher energy of addition E. V. Teis and O. R. V a g n e r (J. Gen. Chem . Russ., of CH2Ph*NH, arising from the. greater deformability 1934, 4 , 9 2 7 — 9 3 5 ).— The potentiometric titration of of the -NH2 group. J. G. A. G. acids by alkalis (Cu and W electrodes) gives more Constitution of thiosemicarbazide compounds accurate results than when alkalis are titrated, in of nickel. See this vol., 202. particular when carbonates are present. R. T. Colorimetric determination of p n with the Thiosemicarbazide compounds of bivalent Pulfrich photometer. I. S. H a h n e l (Svensk palladium and platinum .—See this vol., 202. K e m . Tidskr., 1 934, 4 6 , 2 6 2 — 2 7 9 ).— Details of a Red tetraethylamminoplatinum chloride. H. method for two-colour indicators using two wave R e ih l e n and E. F l o h r (Ber., 1934, 6 7 , [B], 2010— lengths are given. With sulphonephthalein indicators 2017 ; cf. Hantzsch et ah, A., 1930, 440).— Treatment the p£ can be calc, from the measured absorption of aq. K2PtCl4 with 2 mols. of NH2Et at 15—20° vals. by the theoretical equations. With thymol-blue until the solution becomes colourless and with a in acid solution and with Me-red empirical equations further 2 mols. at 65—70° affords tetraethylammino- must be used; this is probably due to the existence platinum chloride (I), [Pt ae4]Cl2,2H20 (ae=NH2Et) of > two forms of the indicator. A series o f indic in 93% yield. (I) is transformed by 3% H202 and ators is given for measurements from pn 1-0 to 10-0. 5iV-HCl into the red salt (II) R. P. B. [Pt ae4]Cl2,[Ptae4Cl2]Cl2,4H20, m.p. 177°, which does Potentiometric and conductometric studies. not react with dil. HN03, is transformed by HC1 into II. Conductometric. J. P i e p e r (Z. Elektrochem., GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 183
1934, 40, 844—857).— Graphical methods of deter Cl' or N 03' is present, the NaC104 should be extracted mining the equivalence point in conductometric titra by means of dry COMe2, the solution evaporated, the tions are discussed critically, and it is shown how NaC104 redissolved in EtOH, and the C104' pptd. as more satisfactory results may be obtained by cal KC104. If C103' is present, it should first be reduced culation. Both methods being empirical, the pro to Cl'. D. R. D. cedure to be followed in a particular experiment must Detection of chlorine and bromine in air, gas bo established by a preliminary titration with stand mixtures, and solutions by formation of iris- ardised solutions, and as far as possible identical blue. H. E i c h l e r (Z. anal. Chem., 1934, 99, 272— conditions maintained. The neutralisation point in 275).—Free Br and Cl2 convert resorufin (I) into non- NaOH containing Na2C03 can be determined only fluorescent halogenated iris-blue. (I) is used as its with difficulty, and the transition of Na2C03 to 0-1% solution in aq. Na2C03. An approx. quant, NaHC03 not at all. The choice of apparatus is also determination of Cl2 or Br in gases may be made by discussed. F. L. U. determining the vol. of gas (e.g., measured roughly Mercurimetric determination of halogens. with a rubber pinch bulb) necessary to destroy the A. I o n escu -M a t iu and S. H e r s c o v ic i (Bull. Soc. fluorescence of a measured amount of (I). J. S. A. chim., 1934, [v ],l, 1379— 1386; cf. A., 1933, 1023).— Cyanide-formaldehyde reaction, and new volu The authors’ method has been applied to the volu metric analytical applications. A. M u t s c h in metric determination of the halogens, including F. (Z . anal. Chem., 1934, 99, 335—348).—CH20 reacts The procedure is described in detail. The degree of reversibly with KCN, giving OH-CH2-CN (I) (cf. precision attained is i the same as in the classical A., 1925, ii, 1009). A 3-fold excess of CH20 is neces methods. F. L. U. sary to remove CN' quantitatively. Reaction in acid Semi-micro-volumetric determination of halo solutions is slow. Hydrolysis of (I) takes place only gens. (Sodium-higher alcohol method.) W. extremely slowly, and is not accelerated by MgS04 Kbiu r a (J. Soc. Chem. Ind. Japan, 1934, 37, 590— (cf. A., 1925, ii, 606). Cl', Br', I', or CNS' in presence 591b ; cf. A., 1928, 8 2 ).—The halogen compound is of CN' may thus be determined by adding excess of reduced with Na and a higher alcohol (best CH20 to the neutral or alkaline solution, neutralising CH2Ph*0H). The resulting Na halide is determined against Me-red, and titrating with AgN03. CH20 volumetrically by Volliard’s method. H. N. R. may be determined by adding excess of KCN, and Influence of higher alcohols and of ether on converting the excess into BrCN by means of Br-H20. the titration of halogens by Volhard’s method. Excess of Br is removed with N2H4,H2S04, K I added, and the BrCN then determined iodometrically. W. Kim u r a (J. Soc. Chem. Ind. Japan, 1934, 37, J. S. A. 589—590b ).—The influence is negligible. H. N. R. Application of cyanogen bromide as universal Accurate quantitative analysis of chlorides in standardisation material. M . M i l l e r (Z. anal. presence of thiocyanates. E . C o h e n and K. Chem., 1934, 99, 351—354).—BrCN, readily obtained Pebpenbroek (Z. anal. C hem ., 1934, 99, 258— 269).— and preserved in analytical purity, may be used for Schulek’s iodometric method (A., 1923, ii, 591), and standardisation (a) of Na2S203, against the I liberated oxidation of CNS' by means of HN03 according to on dissolution in IQ , (b) of acids, (c) of AgN03. For RosanoS and Hill (A., 1907, ii, 984) are satisfactory. (b), BrCN is hydrolysed by KOH to CNO'. The solu Oxidation of CNS' with H20.2 in acid solution (cf. tion is acidified, and C02 boiled off. The NH3 formed A., 1915, ii, 124) gave accurate results only w'hen the is liberated by NaOH and distilled into the acid. The amount of acid was reduced to 1 c.c. of 4Ar-H2S04 in excess of acid is then titrated back. For (c), BrCN GO c.c. of liquid. J. S. A. is dissolved in NaOH, and the solution neutralised. Determination of perchlorates. C. S m e e ts Br' so formed is titrated with AgN03. J. S. A. (Natuurwetensch. Tijds., 1934, 16, 262—266).—The Determination of bromide ion in presence of best conditions for determining C104' in presence of large quantities of chloride ion. F. P. Z o r k in various interfering ions have been investigated. If (J. Appl. Chem. Russ., 1934, 7, 852—856).—Szabo’s onl3’ Li, Na, Ni, Co, Zn, Cd, Pb, Al, Cr, and/or Fc are method (A., 1931, 811) is preferred. R. T. present, a sample containing 0-2—0-3 g. of perchlorate may bo dissolved in > 10 c.c. of EtOH (< 96% and Sensitivity of the starch-iodine reaction. I. M. preferably abs.) and 5—7 c.c. of cold saturated KOAc K o r e n m a n (J. Appl. Chem. Russ., 1934, 7, 847— 851). in EtOH added. After a short time, the pptd. KC104 —The sensitivity of the reaction is a function of the 13 collected and dried at 130°. This method cannot be concns. of K I , I , and acid or alkali in the solution; “sed in presence of Ag, Mg, Ca, Sr, Ba, Cu, or Mn, for a given [I], N G =k, where N is the concn. of acid or to the insolubility of their acetates in EtOH, nor alkali, C the [K I ], and k a const, for the given acid or jo presence.of NH4 or other NH3 derivatives, owing to alkali. The colour obtained changes from blue to red- he insolubility of their perchlorates. In these cases, dish-violet as the [K I ] rises from 1 to 10%. R. T. j. S- of the sample is moistened with 0-1 c.c. of Potentiometric determination of minimal « e d H20, 0-2—0-3 g. of Na2C03 in 0-2 c.c. of H20 quantities of iodine. R. F l a t t (Helv. Chim. Acta, added, and the mixture is evaporated to dryness. In 1934, 17, 1494—1513).—The solution containing I', ais way the metals are converted into insol. carbon acidified with HC1, is titrated with K B r03, whereby I' ates and the NH3 is volatilised. The NaC104 formed is oxidised first to I (I) and then to ICI (II). A break a then extracted by means of EtOH and the C104' is in the potential curve occurs at the completion of (I) PP d. as KC104. C03" and S04" do not interfere. If and a sharper one at the completion of (II). A micro- o 184 BRITISH CHEMICAL ABSTRACTS.— A. method by which the I in 1 c.c. of liquid can be deter S==S203"-t-H‘ , and is itself determined in the manner mined with a max. error of 5 x 10~8 g. is described. already described. F. L. U. Apart from the high precision attainable, an advantage Determination of ammonia in water and air. of the method is the absence of I from the reagents A . K r o g h (Biol. Bull., 1934, 67, 126— 131).—The introduced, and the consequent possibility of repeated H20 sample is treated with 0-2oiV-Na0H to 9—11 determinations on the same sample, after reduction of and then distilled under reduced pressure. NH3 the IC1 by CrCI2. F. L. U. evolved is absorbed in dil. HBr, the aq. NH4Br is M icro-iodom etry. J. R e n a u d in and (M m e .) treated with a definite vol. of standard aq. NaOBr at J. R e n a itd in (J. Pharm. Chim., 1934, [viii], 30, 516— pa 8-5—9, and the excess of NaOBr titrated with 527).— Conditions and precautions for accurate work 0-0005A7-naphthyl-red solution, which is decolorised with 0-01jY solutions aro defined. The solutions as long as NaOBr remains. 0-05—2 X 10~6 g. of N should be neutral. A. E. 0. may be determined. NH3 in air is determined by Determination of fluorine in phosphorites and first absorbing it in dil. HBr. C h . A b s . (e) apatites.— See B., 1935, GO. Drop reaction for arsenic with A7-ethyl-8- Microchemical colour reaction of elementary hydroxytetra [hydro jquinoline hydrochloride sulphur. A. Sc h o n b e r g and W. U r b a n (Ber., (kairin). W. R e p p m a n n (Z. anal. Chem., 1934, 1934, 67, [iS], 1999—2003).—The finely-powdered 99, 180— 182).—A drop of solution containing Asm, material (I) is placed in a m.p. capillary tube, covered on filter-paper, is moistened with HC1 and 0-5% aq. with about 10 times its wt. of benzyliminodi-'p-anisyl- jV-ethyl-8-hydroxytetrahydroquinolinc hydrochloride. methane, m.p. 93° [obtained by the successive action A drop of aq. FeCl3 is added, and the test paper of SOCU and NH2-CH2Ph on CO(C0H4-OMe)2], and warmed. In presence of As a reddish-brown color the tube is sealed. The contents are mixed by ation results; limit, 6 X10-10 g. Hg, Pb, and Cu repeatedly inverting the tube and then heated at interfere. J. S. A. about 210° for 5 min. The cold product is dissolved Apparatus for the detection and determination in boiling C6HG, which if free S is present in (I) becomes of arsenic by the Gutzeit and Beck-Merres blue owing to the formation of CS(C6H4'OMe)„. The methods. R . St e in b r u c k (Pharm. Zentr., 1935, intensity of the colour is diminished by adding a 76, 5—6).— Gnessin’s statements (this vol., 53) are crystal of HgCl2, which becomes red superficially. criticised. Alteration of the Beck-Merres apparatus Reaction is not given by Se or by compounds of S. is unnecessary and the addition of the substance and H. W. the acid all at once is not a fault. The necessity for Potentiometric determination of sulphates. the evolution of H2 to be const, and also for the use I. I. S h u k o v and C. G. R aichinschtein (J. Gen. of 10% HC1 is emphasised. The max. of 0-07 g. As Chem. Russ., 1934, 4, 902—968).—50 c.c. of EtOH, is too low. 10-° g. can be detected, but amounts of 0-2 c.c. of 0-00251i-K4Fe(CN)6, and 2 c.c. of 0-13/- 1, 2, and 3 x l0 -6 g. cannot be easily differentiated. K3Fe(CN)6 are added to 30 c.c. of aq. Na2S04 (approx. E. H. S. 0-1JV), a Pt electrode is introduced, and the system Determination of small (juantities of arsenic. is connccted with a HgCl electrode and titrated with (Determination of arsenic in iron ore, soot, etc.) 0-ljV-Pb(NO3)2; the results differ by > 0-04% from L. W. S t r o c k (Z. anal. Chem., 1934, 99, 321—335).- the theoretical. Salts enhancing the solubility of As is rcduced by nascent H to AsH3, which is absorbed PbS04 cause high, and of Pb2Fe(CN)6 low, results to in 2—6% aq. HgCl2. The yellow ppt. formed does be obtained. R, T. not contain the total As, but decomposes to H3As03-f Detection of hyposulphites and sulphoxylates Hg2Cl2. For small amounts of As (0-01— 1 mg.), and of nascent hydrogen with resazurin. H. NaHC03 is added to the solution+ppt., and exactly E ic h l e r (Z. anal. Chem., 1934, 99, 270—272).— neutralised with HC1 (Me-orange). Hg2CI2-j-H3As03 Hyposulphites and sulphoxylates, also freshly pptd. are then titrated with 0-01A,'-I, requiring”8 I per atom Fe(OH)2 and Sn(OH)2, but not S203'' or S03", in of As. With larger amounts of As (1— 10 mg.), the alkaline (Na2C03) solution reduce the blue solution ppt. is allowed to decompose completely, Hg2Cl2 is of resazurin (I) (fluorescing a weak brownish-red) to removed by filtration, and H3As03 titrated iodo- non-fluorescent hydroresorufin, which oxidises in con metrically after exact neutralisation, as before. Fe tact with air to the vividly yellowish-red fluorescing ores etc. are fused with 2 parts of Na2B40 7+4 parts rcsorufin. In acid solution, S03", S,03", and nascent of Na2C03, dissolved in H2S04 containing Na2HP04, H also reduce (I). “ J. S. A. and AsH3 is at once generated from the considerably Analysis of reducing acids of sulphur. E. diluted solution before pptn. of Si02 occurs. Metallic Fe and org. material (soot, humus, etc.) are dissolved Ch e r b u l ie z and A. H e r z e n s t e in (Helv. Chim . Acta, 1934, 1 7 , 1582— 15S7).— In the analysis of mineral in H,S04+ H 202. J. S. A. waters H2S can be determined in presence of other Volumetric determination of arsenates. F. 1-reducing substances by treatment with suspendedT a b o u r y and H. A u d id i e r (Bull. Soc. chim., 1934, CdC03 and iodometric titration of the CdS produced. [v], 1, 1570— 1578).—The effects of concn. of reagents In dil. (> 10-4N) solution S203" is determined by and time of boiling on the reduction of As04"' to means of its catalytic effect on the interaction of A s0 3" ' by K I in H2S04 solution have been investig NaN3 and I, for which a simple iodometric method is ated. The reduction is complete when a mixture of described. S03" is determined by adding colloidal 10 c.c. of 0-001—0-0165J/-A s20 5 with 2 c.c. of H2S04 S at pa 6, when S203" is formed according to S03H '+ (d 1-8) and 0-8 g. of K I is heated at 100° for 10 min. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 185
The I liberated is exactly titrated with Na2S203 and, Direct colorimetric determination of sodium. after adding excess of NaHC03, the As03'" is titrated 0. M. S m ith and H. B l a i r (Proc. Oklahoma Acad. with I. The method is used for analysis of Pb Sei., 1 934, 1 3 , 3 3 — 3 5 ).— Caley and Foulk’s method arsenate after pptg. the Pb as PbS04. J. G. A. G. (cf. A., 1929, 900) was tested on 140 H20 samples, and Rapid determination of silica in water-glass.— is accurate to approx. 0 -3 5 mg. Na. C h . A b s . (e) See B., 1935, 60. Rapid spectroscopic determination of metals. Determination of dissolved organic carbon 1. Lithium. A. P. S n e s s a r e v (J. pr. Chem., and nitrogen in sea-water. A. K r o g h and A. 1934, [ii], 1 4 1 , 327—330).—The min. concn. K e y s (Biol. Bull., 1934, 67, 132— 144).—A sample of (0-0000010728 g. per c.c.) of Li which can be detected the H ,0 is evaporated in a Ag tube, which is heated spectroscopically is first determined; the unknown at 500° in a stream of H2. The NH3 evolved is solution is then diluted to the same concn. Results absorbed in dil. HBr, and determined, together with are reproducible and compare favourably with those residual NH3, by the NaOBr method (cf. this vol., obtained by Gooch’s method. H. B. 184). C is determined by acidifying to remove Use of phosphomolybdic acid in chemical C03", and pptg. most of the Cl' with T12S04. The analysis. J. W. I l l in g w o r t h and J. A. Sa n t o s H20 is then evaporated to dryness, and heated with (Nature, 1934, 1 3 4 , 971).—Phosphomolybdic acid conc. H2S04, K2Cr,0,, Ag2Cr04, and Cr03. C02 detects 1 part of Cs in 5 x l0 5 of H20 and ppts. 1 of evolved is absorbed in aq. Ba(OH)2 and excess K in 104 of HaO. The ppt. of K 3PMo12O40,mH2O, titrated with HC1. C h . A b s . (e) where n is >2 (probably 0), is stable at 120°. Application of perchloric acid to the indirect L. S. T. determination of carbon dioxide in carbonates. Systematic potentiometric analysis. II. Deter P. Vojf& (Chem. Listy, 1934, 28, 299—301).—The mination of A g, Bi, Pb, Cu, Cd. W. H i l t n e r and non-volatility of HC104 and the solubility of its salts W. G it t e l (Z. anal. Chem., 1934, 9 9 , 169—178; cf. render it preferable to HC1 for expelling C02 from this vol., 55).—Ag, Bi, Pb, Cu, and Cd are separated carbonates. R. T. by pptn. as sulphides and dissolved in H N 03. Ag is Determination of carbon dioxide in the atmo titrated potentiometrically with HC1 at room temp. sphere of a closed system. C. Z. R o s e c r a n s Excess of 0-liV-HCl is added, and the solution boiled (Science, 1934, 8 0 , 483— 484).—Attention is directed and neutralised to Congo-red by 2iV-NaOAc, thereby to advantages of the thermal conductivity method of pptg. BiOCl quantitatively. The ppt. is collected, determination (cf. A., 1934, 1190). L. S. T. dissolved in HN03, and titrated with AgNOs. Pb is pptd. from the filtrate as PbCr04, and this dissolved Determination of carbon disulphide in air.— in HC1. A measured excess of 0-2JV-SbCl3 is added, See B., 1935, 47. and titrated back with KMn04. Excess of Cr04'', Sensitiveness of detection of the alkali metals and Cu” in the filtrate are reduced with N2H4,H2S04, in the a rc sp ectru m . P. U r b a i n and M. W a d a and Cu is pptd. as CuCNS. The ppt. is dissolved in (Compt. rend., 1934, 1 9 9 , 1199— 1201).—The limits NaOH, and CNS' titrated with AgN03. Cd in the for spectrographic detection of Li, Na, K, Rb, and remaining solution is titrated with Na2S. J. S. A. Cs in the Cu arc were 2, 70,1200, 2600, and 8000 X 10~° Determination of silver by photometric titra mg. respectively. H. J. E. tion. S. H ir a n o (J. Soc. Chem. Ind. Japan, 1934, Rapid determination of potassium. K. N o w a k 3 7 , 7 5 4 — 75 6 b ).— Ag can be titrated photometrically (Przemysł Chem., 1934,1 8 , 509—510).—5 c.c. of clear, with NaCl, preferably in a coloured beaker and with neutral solution, containing about 0-05 g. K 20, and the addition of starch as a protective colloid; Cu free from N H 3, arc added to 17 c.c. of reagent (I) in does not interfere. A. G. a special centrifuge tube, the bottom of which is Applicability of potentiometric silver titration drawn out into a capillary, and previously filled with in determining silver in practice. E. R atjb (Mitt. HjO. The solution is centrifuged for 15 sec. at 21— Forsch.-Inst. Probieramts. Edelmet. Schwab. Gmünd, 23' and 1000 r.p.m., and the K content is read 1934, 8, 11 pp.; Chem. Zentr., 1934, ii, 1168).— directly on a scale on the capillary from the height of A discussion. The potentiometric method is more the column of ppt. (I) is prepared by dissolving accurate. In determining Ag in material insol. in ^50 g. of NaNOo in 800 c.c. H20, adding the solution HNOs, Cl is first removed, Pb is added to concentrate after 24 hr. to 250 g. of Co(OAc)3 in 800 c.c. of H20, the Ag, and the Ag determined potentiometrically diluting to 2 litres, and adding 65 c.c. of H20 and in the Pb-Ag mixture. In alloys containing Au ® c.c. of AcOH to 100 c.c. of the solution so obtained. Cu must be added until Au : other metals is < 1: 3. R. T. H. J. E. Application of spectrum analysis to determin Volumetric [micro-Jdetermination of calcium ation of alkalis and alkaline earths. IV. Micro- and magnesium in water.—See B., 1 9 35, 48. determination of potassium and calcium. W. H. Application of photo-elements to the deter Jansen, J. H e y e s , and C. R ic h t e r (Z. physikal. Uicm., 1 9 3 4 ,1 7 1 , 268—280).—The method previously mination of salts in natural waters.—See B., 1935, described (A., 1934, 745) is used, the sensitivity being 48. 'ncreased by utilisation of an improved atomiser Analysis of limestone.—See B., 1 9 35, 60 . , ‘ch makes it possible to cany out a determination Determination of magnesium as magnesium ■on/® C-C‘ dil* solution. The precision attainable oxide in presence of ammonium salts.—See B., ls«% for K and 10% for Ca. R. C. 1935, 21. 186 BRITISH CHEMICAL ABSTRACTS.— A.
Determination of magnesium using 8-hydroxy- Soc. chim., 1934, [v], 1, 1356—1357).—A weighed quinoline. M. J a v i l l i e r and J. Lavollay (Bull. excess of solid K2SnCl4 is added to the solution of Cu" Soc. Chim. biol., 1934, 1 6 , 1531— 1541).—The deprived of dissolved 0 2 and strongly acidified with technique of a method for the determination of Mg HC1. CuCl is ’pptd., and the residual K 2SnCl4 is by pptn. at pa 8 of the complex (I) which it forms titrated with I. F. L. U. with 8-hydroxyquinoline (II) is described. Ca (a ) Determination of mercury applicable to may be removed by preliminary pptn. as oxalate, mercury cyanide, (b ) Application of the mer and Fe, Al, Mn, Zn, and Cu, when present in small curic sulphate reagent. G. D e n i g e s (Bull. Soc. quantity, may be separated by extraction of (I) Pharm. Bordeaux, 1934, 7 2 , 5— 13, 13—18; Chem. with EtOH. Interference of Fe and Al in larger Zentr., 1934, ii, 1499).—a. To 20 c.c. of the solution amounts may be avoided by a preliminary pptn. (> 0-3% Hgn) 20 drops of the HgI2,2KI reagent (ef. with (II) at pa 5—6. A. L. A., 1932,355) and 10 drops of HC1 are added. Hgl2 is Precipitation of zinc salts by alkali metal pptd. and is titrated with 0-ljV-Na2S203 at 20° until chromates in a gelatin medium. Discrimin just redissolved. Non-ionised Hg(CN)2 reacts quantit ation of zinc and cadmium. ( M l l e . ) S. V e i l atively on adding the HC1, and may be determined in (Bull. Soc. chim., 1934, [v], 1, 1358—1359).—Zn presence of Hg". forms a banded ppt. of chromate in gelatin, whilst b . The reagent (5 g. of red HgO in a mixture of Cd does not. F. L. U. 100 c.c. of H20 and 20 c.c. of cone. II2S04) can be used Electrolytic determination of cadmium. J. for the microchemical detection of halides, halogen- ates, and cyanuric acid by adding an equal of vol. of S e b o r (Chem. Listy, 1934, 28,290—291, 297—299).— The well-stirred solution (400 r.p.m.), containing aq. NH3 to the reagent instead of using a cone, acid 12 g. of K2C204, 3 g. of NaOAc, and 3 c.c. of 20% solution. H. J. E. AcOH per 120 c.c., is electrolysed at 70— 80°, using Determination of alum inium in aqueous 0-1—0-2 amp. and > 2-9 volts, when all the Cd aluminium acetate. M. Dominikiewicz (Arch. is deposited as an adherent, cryst. deposit after 0-5— Chem. Farm., 1934, 2 , 64— 68).—5 g. of solution are 1 hr. In presence of Zn a current of 0-1 amp. at 2 volts heated at 100° with 4 c.c. of conc. HC1 and 20 c.c. of is recommended. R. T. an aq. suspension of filter-paper pulp, 5—6 drops of 30% H202 and excess of aq. NHS are added, and the Fluorescence analysis of minerals. H . H a b e r - suspension is filtered after 1 hr. The residue is washed, l a n d t (Sitzungsber. Akad. Wiss. Wien, 1934, Ila, dried, ignited, and weighed as A1203. R. T. 1 4 3 , 11—13; Cliem. Zentr., 1934, ii, 1496).— Certain yellow specimens of topaz show a yellow fluorescence, Titrimetric determination of aluminium sul whilst others, initially colourless, become yellow phate and sulphuric acid present together. G. and fluoresce after irradiation with Ra. Certain B l r s t e i n and J. K r o n m a n (Przemysł Chem., 1934,18, scheelite and zircon specimens after heating show 317—321).—A series of colour standards matching the fluorescence lines of the rare earths. Some skapolites colours given by thymol-blue with a scale of concns. gave the fluorescence spectrum of U compounds. of A12(S04)3 (I) is prepared by mixing 0-5jV-CoC12 and H. J. E. -FeCl3 in various proportions. The solution, the (I) Sensitive drop reaction for copper. A. S. content of which is approx. known, is titrated with Komarovski and N. S. Poltjektov (J. Appl. Chem. 0-27A7’-Ba(OH)2 to the same shade as the appropriate Russ., 1934, 7 , 844—846).—A drop of saturated standard, and the H2S04 content hence calc. The solution of hydroxyquinoline (I) in 80% AcOH, solution is further titrated with 0-5Ar-NaOH at 100° to a drop of the solution under analysis, and a second a colour change from yellow to blue, and the (I) con drop of (I) are placed on the same spot on filter-paper, tent hence calc. R. T. followed by a drop of 25% aq. KCN, when a bluish- Determination of small quantities of alumin red coloration indicates < 0-4 x 10-® g. of Cun. The ium in complex media. Application to plants. coloration is due to C2N, formed from Cu11 and CN'. P . M e u n i e r (Compt. rend., 1934,1 9 9 , 1250— 1252).- H g n , Pb, Bi, Cd, Sbm, Snn, Mn04', W 04", V 0 3', Conditions for pptn. and colloidal ppt. formation for Al Niu, and Co11 do not interfere. Fen gives a black with cupferron (I) (cf. Pinkus and Martin, A., 1927, spot under the above conditions, and should previously 406) have been studied. Opacity measurements are bo pptd. as Fe(OH)3. R. T. described for the determination of 0-01—0-06 mg. of Determination of copper in copper sulphate.— Al per g. of dried plant. The elimination of other See B„ 1935, 60. metals (e.g., Fe, Cu, or Ti) by pptn. with (I) at con Detection and determination of copper in trolled pa is described. H. J. E. pharmaceutical preparations.—See B., 1935, 45. Rapid determination of aluminium in iron Determination of copper in organic com ores.—See B., 1935, 63. pounds. N. N. M e l n i k o v (Z. anal. Chem., 1934, Determination of small quantities of alumin 9 9 , 182—184).—The compound is completely oxidised ium in special iron-containing copper-zinc by adding EuMn04 to its H,>S04 solution at 70—90°. alloys.—See B., 1935, 64. Excess of KMn04 is removed with H ,02 or H2C204, Behaviour of aqueous ammonium sulphide and Cu determined iodometrically. J. S. A. towards manganous ions. D. T o to iescu (Z. Potassium staxmochloride in the volumetric anorg. Chem., 1934, 2 2 1 , 182— 1S6).—Aged solutions determination of copper. E. Voyatzakis (Bull. of (NH4)2S often give no ppt. with Mn“ in presence of g e n e r a l , p h y s ic a l , a n d in o r g a n ic c h e m is t r y . 187
NH4 salts or of KCN. The cause is traced to the obtain a sharp end-point, with which Fo and Mn at gradual disappearance of SH' through oxidation. moderate concns. do not interfere. A similar method F. L. U. is applicable for the determination of Cr203 in H2Cr04. Benzoate method for the separation of iron, R. S. B. aluminium, and chromium. Suggested changes Determination of chromium in tungsten steels. for its application to qualitative analysis. L. -—See B , 1935, 63. Lehrm an and J. K r a m e r (J. Amer. Chem. Soc,, 1934, Potentiometric determination of chromium, 56, 2648—2649).—Modified procedure is recom vanadium, and molybdenum present together.— mended (cf. A., 1934, 621). E. S. H. See B , 1935, 63. Precipitation of aluminium with 8-hydroxy- Volumetric determination of chromium, man quinoline in presence of iron, nickel, cobalt, ganese, and vanadium in steel.—See B., 1935, 64. copper, chromium, and molybdenum. T. Weighing of molybdenum as silver molybdate. Heczko (Chem.-Ztg, 1934, 58, 1032— 1033).—The alloy is dissolved, tartaric acid and excess of NH3 are L. W. M c C a y (J. Amer. Chem. Soc, 1934, 56, 2548— added, and the metals other than A1 are converted by 2549).—Mo in alkali molyhdates can be determined by adding KCN into complexes from which they are not conversion into x\g2Mo04, which is slightly sol. in H20, pptd. by 8-hydroxyquinoline (I). If Fe is present H2S but insol. in H20 containing AgN03. E. S. H. is also passed. A1 is pptd. by adding a solution of (I) in Determination of small quantities of van 10% EtOH. E. S. H. adium in uranium preparations.—See B , 1935,60. Application of flotation to qualitative analysis. Laboratory apparatus for conducting pyro- A. M. B e lo u so v and A. G. B e l o u s o v a (J. Appl. Chem. genesis. J. D o l iń s k i (Przemysł Chem, 1934, 18, Russ., 1934, 7, 837— 838).—The ppt. of Ni dimethyl- 366).— Si02 apparatus is described. R. T. glyoxime is masked by Fe(OH)2 when Fen is present; Calorimetric apparatus. K . K l in g and J. it may be separated by shaking with ¿so-C6Hn *OH (I), P f a n h a u s e r (Przemysł Chem, 1934,18, 420—424).— "'lien it undergoes concn. at the H20-(I) interface. The calorimeter bomb is enclosed within a Dewar flask The mixture of Al(OH)3 and FeS obtained by adding (I), and the heat of combustion is calc, from the ex (NH4)2S to aq. salts of A1 and Fe is separated by adding pansion of the air within the (I). The method involves alizarin-red (II) and (I), arid shaking, when the an error of 50— 100 g.-cal, but is suitable for most A!(0H)3-(II) complex is suspended in the (I) layer. technical purposes. R. T. PbS, Sb2S3, and As2S3 can be separated from S by shaking the suspension with (I), when S remains in the Autographic thermal expansion apparatus. aq. layer. R. T. W. S o u d e r , P. H id n e r t , and J. F. Fox (J. Res. Nat. Bur. Stand, 1934, 13, 497—513).—A descrip Titration of oximes of nickel and copper. B. tion is given of an autographic expansion apparatus Tougarinoff (Ann. Soc. Sci. Bruxelles, 1934, 54, B, utilising the optical lever method of recording con 314—324).—Ni dimethylglyoxime (I) is pptd. in the tinuous expansion curves photographically. The usual way, and is then hydrolysed by boiling with dil. results obtained with the apparatus for low-, medium-, H:S04. The NHaOH liberated is determined by and high-expanding materials are compared with addition of excess of acidified Fe2(S04)3 and titration those obtained with the previous apparatus of the of the FeS04 formed by 0-lAr-KMn().,. The method is Bureau of Standards; for steels the error is 6% applicable to the determination of Ni in alloys, e.g., between 20° and 100° and 3% between 20° and 500°. German silver, Ni steel, and coinage inetal, if (I) is pptd. A. R. P. in presence of tartaric acid. For the determination of Magnetic method of producing low temper Cu , the compound with salicylaldoxime is pptd. and atures. P. D e b y e (Physikal. Z , 1934, 35, 9 23 — determined in a similar way. The method is directly 9 2 8 ).—A summary of the results of the method using applicable to Cu alloys. A. J. M. adiabatic demagnetisation of rare-earth salts and Cr Separation of nickel and cobalt by means of alum is given. Consideration of entropy-temp. alkali phosphates. A. C o l a n i (Bull. Soc. chim., diagrams shows that 0° abs. is not attainable by this 1934, [v], 1, 1478— 1479; cf. A., 1934, 747).—Polem- method. Since the nuclear moment is about 10~3 X !cal and historical. Other methods are more trust the Bohr magneton, the former will be of great worthy. J. G. A. G. importance in the range 0 001— 0-01° abs, and hence [Separation of nickel and cobalt by means of direct results on nuclear magnetism may be expected alkali phosphates.] H. Wunschendorff and from observations within this range. A. J. M. (Mans,) P. V a l i e r (Bull. Soc. chim., 1934, [v], 1 , 14S0). Simple and inexpensive thermoregulator. A. A reply (cf. preceding abstract). J. G. A. G. R a ig n ie r (Natuurwetensch. Tijds, 1934, 16, 267— Determination of tervalent chromium in 268).—The expansion of Et20 in a closed metal chromic acid and in chromium-plating baths. vessel operates a lever controlling a Hg break. An n. H. W il l a r d and P. Y o u n g (Trans. Electrochem. accuracy of ± 1 ° may be obtained. D. R. D. 1 °c., 1935, 67, 55—64).— Cr'" in Cr-plating baths in Automatic temperature control of thermo ! ! ® nce of H2Cr04 may be determined by adding stats, ovens, etc. by means of an alternating- .n\ °3 and excess of 0-liV-Ce(S04)2, heating at 50—55° current valve relay. A. L. D e l a u n o is (Natuur lor 5 mm, and titrating with 0-05Ar-NaN02 at 50—55°, wetensch. Tijds, 1934, 16, 268—270).—A modific ie end-point being determined potentiometricallv. ation of Fonteyne’s d.-c. apparatus (A, 1934, 162) itle n electrode must be cleaned in K 2Cr20 7-H 2S0 4 to is described. D. R. D. 188 BRITISH CHEMICAL ABSTRACTS.---- A.
Determination of the heat of combustion by 716).—The effect of variation of sensitivity of these means of the micro-bomb. J. J. V r u u n g (Chem. cells should be diminished by reducing the thickness Weekblad, 1935, 32, 20—22).—The method is de of the So layer and reducing the effect of the external scribed and data for BzOH and various fuel and surface of the layer. J. W. S. lubricating oils, agreeing well with macro-determin Monochromatic filter. W. H. A u g h e y and ations, are recorded. D. R. D. W. D. Lansing (Physical Rev., 1933, [ii], 44, 326).— Investigation of photographic-photochemical Photographic plates treated with a NaOH solution processes with the aid of the electro-optical Kerr of p-methylajsculetm transmit only X 4358 A. from a effect. A. N a r a t h (Physikal. Z., 1934, 35, 992— Hg arc. This filter is only a photographic, and not 996).—A method for the determination of the inten a visual, monochromat. L . S. T. sity and wave-length of actinic light using the electro- Precision photom etry. P. C o p e l (J. Pli3’3. optical Kerr effect is described. A. J. M. Radium, 1934, [vii], 5, 563—567).— Considerations Combined recording microphotometer, densi on measurements with an accuracy of 1 mm. are tometer, and comparator. P. A. L e ig h t o n , S. discussed. N. M. B. Sm it h , and F. C. H e n so n (Rev. Sei. Instr., 1934, [ii], Microphotography and radiation studies with 5, 431— 434).—Full constructional details of an in various wave-lengths of monochromatic ultra strument incorporating a radiometer are given. violet radiation. A . J. A l l e n , R. F r a n k l i n , and C. W. G. E. M cD o n a ld (J. Franklin Inst., 1934, 218, 701— Self-registering microphotometer. L. A. 716).—A detailed account of work already noted W o o d w a r d and R. G. H o r n e r (J. Sei. Instr., 1935, (this vol., 124). L . S. T. 12, 17—22).—The photometer unit moves bodily Temperature control system for use in the across a magnified image of the plate under examin study of the Raman effect of liquids. A . H. ation, moving uniformly and without vibration under L e c k ie and W . R. A n g u s (J. Sci. Instr., 1935, 12, gravity controlled by an oil leak. C. W . G. 22—23).—Heated H20 from the jacket circulates by Photometric stage for the study of emission convection through a bath kept at a controlled temp. spectra. R. B r e c k p o t (Ann. Soc. Sei. Bruxelles, C. W. G. 1934, 54, B, 299—314).—An apparatus in which the Cuprous oxide rectifiers. W. C. v a n G e e l spectrum is projected on to a horizontal screen, in (Physica, 1934, 1, 1143— 1152; cf. Z. Physik, 1931, the centre of which is an opening over a photo 69, 765).— Current-voltage characteristics are re electric cell, is described. A. J. M. corded between 20° and 134°. The mechanism of Ultra-violet microscope for the examination rectification is discussed. H. J. E. of opaque objects. B. K. J o h n s o n (J. Sci. Instr., Temperature-control box for saturated stan 1934,11, 384—394).—A new form of reflecting micro dard cells. E. F. M u e l l e r and H. F. STiMSOir scope utilises a lens-mirror objective in place of an (J. Res. Nat. Bur. Stand., 1934, 13, 699—704).— object glass. Opaque objects can be examined with The cells are contained in a small A1 box, placed out introducing back-reflected light from the lens inside and thermally insulated from a larger A1 box, system. Ultra-violet transmissions and reflecting in the wrall of which is a Hg thermoregulator control powers for several substances are recorded. ling an elcctrical heater. The temp, was const, to C. W. G. ±0-01°. H. J. E. Johann’s JV-ray spectrometer for high vacuum Life tests of commercial type standard cells. with concave crystal. II. A. S a n d s t r o m (Z. T. T. Sm it h (Rev. Sci. Instr., 1934, [ii], 5, 425—427). Phvsik, 1934, 92, 622—630; cf. A., 1933, 1036). —No definite time eoeff. can be applied. Measure A. B. D. C. ments with a single cell should not be trusted for Source of the Lyman continuum for use with accurate work. C. W. G. spectrographs of high dispersion. G. Co l l in s Field combinations for velocity- and mass- and W. C. P r ic e (Rev. Sci. Instr., 1934, [ii], 5, 423— 425).—A Lyman discharge tube is so made that the spectrography. III. W. H e n n e b e r g (Ann. capillary can easily be replaced when enlarged by Physik, 1934, [v], 21, 390—404; cf. A., 1934, 341, use. • C. W. G. 713).—The use of a superposition of a cylindrical electric field, a homogeneous magnetic field, and a Photo-electric densitometer. E. O b e r m e r magnetic dipole field as a focussing lens for electrons (Chem. and Ind., 1934,1077).— Colorimetric biochemi and positive rays is described. By a special arrange cal analyses of blood, urine, foeces, and food are ment, a non-focussing “ prism ” may be produced. mentioned. C. W. G. A. J.M . Electrical characteristics of barrier-layer Cataphoresis apparatus. H . T h e o r e l l (Bio- photo-cells. P. R. G l e a s o n (Physical Rev., 1933, chem. Z., 1934, 275, 1— 10).—A description is given [ii], 44, 315).—The resistance of barrier-layer photo of an apparatus which may be used for accurate cells has been detennined over a wide range of determination of ionic mobilities, for the separation illumination and for currents in the same directions of the constituents (I) of mixtures [including those as and opposite to the photo-currents. L. S. T. in which (I) move in the same direction], and for Use of selenium unidirectional layer photo other purposes. W. McC. cells in the measurement and record of very Precision recording cosmic-ray meter. A . H. intense illuminations. G. L ia n d r a t (Compt, C o m pto n , E. 0. W o l l a n , and R. D . B e n n e t t (R ev . rend., 1934, 199, 1394— 1395; cf. A., 1934, 272, Sci. Instr., 1934, [ii], 5, 415— 422).—The steel ionis- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 189 ation chamber holds 19-3 litres of A at 50 atm. lying on the Mo. On heating until the Mo and the Balancing current is supplied by ionisation by ß-räys NaN02 react, heat is evolved sufficient to melt the from U in an auxiliary chamber. C. W. G. Ag, which flows over the surface of the Mo, to which Amplifying and recording small e.m.f. H. E. hard and soft solder will then adhere C. W. G. Mokgan, L. T. De Y o r e , and R. F. B a k e r (Physical Device for water circulation. A. B. B u r c h Rev., 1933, [ii], 44, 324).—The p.d. to be measured and R. M. E a k in (Science, 1934, 80, 563—564).— is applied to a sensitive galvanometer which causes A simple air pump maintaining a continuous circul a beam of light to play across the cathode of a photo ation of clean aerated H20 is described. L. S. T. electric cell. L. S. T. Determination of the specific gravities of Increased resolving power of the electron- liquids. E. A. B e c k e r (Farben-Ztg., 1934, 39. optical immersion objective. E. B r ü c h e and 1311— 1313).—The vol. of liquid delivered by one W. K n e c h t (Z. Physik, 1934, 92, 462—466).-—The complete stroke of certain medicinal syringes is electron microscope together with an oil-immersion sufficiently reproducible to enable them to replace objective can resolve to 1-5 (¿. A. B . D . C. a pyknometer. It is much easier to avoid air bubbles Camera for electron diffraction. J. A. D a r b y - in this way. G. H. C. shire and E. R.. Co o p e r (J. Sei. Instr., 1935, 12, Recording dilatometer of high sensitivity. A. 10—14).—The instrument is suitable for both re G o e t z , J. W. B u c h t a , and T. L. Ho (Rev. Sci. flexion and transmission. C. W. G. Instr., 1934, [ii], 5, 428— 431).—Expansion is ampli Portable Geiger-Müller tube. K. G r a n t and fied by an optical lever and thermocouple, actuating M. Il iffe (J. Sei. Instr., 1935, 12, G-—8).—Full con a galvanometer. C. W. G. structional details are given. 1 mg. of Ra can be Visco-conductimeter. C. L. B a b c o c k and J. V. detected at 50 ft. C. W. G. H o f f a c k e r (Physical Rev., 1933, [ii], 44, 320—321). Quinhydrone micro-electrode. F. L. V o d r e t —The apparatus is suitable for determining of (Rend. Sem. Fac. Sei. Cagliari, 1933, 3, 55—60; ordinary liquids at room temp, and of silicate glass Chem. Zentr., 1934, ii, 1165).—A Pt wire fused into up to 1400°. L. S. T. a capillary is mounted in an open glass tube con Separation of neon into its isotopic com stricted at the lower end. The use of the electrode ponents by means of rectification. W. H. is described. H. J. E. K e e s o m , H . v a n D i j k , and J. H a a n t j e s (Proc. Apparatus for uninterrupted p u determination. K . Akad. Wetensch. Amsterdam, 1934, 37, 615, M. SI. M uschkatblat and I. M . B r u s k in (J. Appl. and Physica, 1934,1,1109— 1114).—A glass rectifying Chem. Russ., 1934, 7, 857— 863).—Apparatus for the apparatus for the separation of the Ne isotopes in measurement of continually changing pH [e.g., dis relatively large quantities has been constructed. solution of ZnO in aq. H2S04) is described. R. T. Fractions of at. wt. 20-091 and 20-574 (normal at. wt. Simple micro-burette. R. F l a t t (Helv. Chim. 20-183) have been obtained. The efficiency of the Acta, 1934, 17, 1513— 1516).—The burette consists rectifying column is about 50% of theoretical. of a U-tube in which one limb (a) is of wide bore, M. S. B. and the other of about 1 mm. bore bent over at the New glass apparatus. I. Siphon with top and drawn to a fine point. There is no tap, the attached filter. II. Filter reagent glass. H. titration liquid being confined between the delivery B a r sc h (Pharm. Zentr., 1935, 76, 20—21, 21).— point and a surface of Hg. Liquid is expelled by I. A sintered glass filter forms the siphon inlet. admitting Hg to (a) from a dropping funnel. The II. A sintered glass filter crucible with a curved vol. can be measured to within 0-2 cu. mm. rim fits into a rubber ring placed in the top of a F. L. U. filtering tube. E. H. S. Apparatus for continuous extraction of High-vacuum cut-off. G . W. L o b b and J. B e l l aqueous solutions by non-miscible solvents. (J. Sci. Instr., 1935, 12, 14— 17).—N a -B i and Li-Bi A. A. P o l ic a r d and R. F a v ie r (Bull. Soc. chim., amalgams at temp, just > m.p. are suitable for use in 1934, [v], 1, 1523— 1525).—The rod of a stirrer (I) cut-off seals; they have Hg v.p. about 10~8 mm. situated axially in the flask (II) is surrounded by a C. W. G. tube down which flows the solvent (III) from a Two demonstration experiments with liquid condenser fed by solvent vapour from an auxiliary hydrogen. K . Cl u s iu s (Physikal. Z., 1934, 35, flask (IV). The (III) flowing into the aq. solution 929—930).—An apparatus using liquid and solid H, just above the vanes of (I) is broken into fine drop by means of which a temp, of 9-5° abs. may be reached, lets which rise and flow back to (IV) by way of a and its use for the demonstration of superconductivity side tube in the neck of (II). J. G. A. G. in Nb carbide (transition point 10-2° abs.) is described. Microbalance to weigh to 10-® g . M. Ziegler- An apparatus for demonstrating the differences in W ellm an x (Chem. Fabr., 1934, 7, 472—473).— v.p. and m.p. of HJ and H“ is also described. A direct-reading null instrument on the torsion A. J. M. principle using spiral hairsprings is described. Symbol for hydrogen-ion concentration. T. D. R, D. Hennig (Chem.-Ztg., 1934, 58, 1021).—A question Soldering molybdenum to copper. A. M ü l l e r of nomenclature. E. S. H. ‘}nd R. E. C la y (J. Sei. Instr., 1934, 11, 405).—A Heavy water in chem istry. M. P o l a n y i small chip of Ag is placed on a layei of NaN02 (Nature, 1935, 135, 19—26).—A lecture. L. S. T. 190 BRITISH CHEMICAL ABSTRACTS.— A.
Geochemistry. Analysis of the water of the Boniface spring Radioactivity of the geological layers of the at Morszyn. S. J u r k o w s k i (Arch. Chem. Farm, Rhine valley. E. R o t h 6 and F. St o e c k e l (Compt. 1934, 2, 41—61).—The rise in concn. of salts per kg. rend, 1934,199, 1330— 1332).—Data are recorded. of H20 since 1881 is : K 5-7 to 23-9, Na 14-25 to 64-2, H. J. E. Mg 3-8 to 22-9, Cl 17-8 to 131-7, Br 0-004 to 0-075, New mineral containing metals of the and S04" 28 to 75-8 g. R. T. platinum group. O. E. Z v j a g in z e v (Compt. Fluorine content of French mineral waters. rend. Acad. Sci., U.R.S.S, 1934, 4, 176— 179).— “ Aurosmirid,” a solid solution of Au, Os, and Ru in Ir, R . Ch a r o n n a t and (M l l e .) S. R oche (Compt. rend, 1934, 199, 1325— 1328).—Numerous determinations has been isolated in the residue remaining after dis based on de Boer’s colorimctrio method (A , 1926, solving Pt in aqua regia. The substance is very hard 40) are recorded. H. J. E. and brittle, and has a cubic lattice. E. S. H. Anohaline stratification of the chemical con Molybdenite-quartz veins of Shih-ping-chuan, stituents of Lake Osoresanko, Aomori Prefec Tsingtien, Chekiang. H. M . M e n g and K. C hang ture, Japan. S. Y o s h im u r a (Proc. Imp. Acad. (Contr. Nat. Res. Inst. Geol, Sinica, 1933, No. 4,47— Tokyo, 1934, 10, 475— 478).—Temp, and salinity of 58).—Porphyry, lamprophyric apophyses, and veins this acid lake both decrease towards the bottom. are described, and the paragenesis and genesis of the C. W. G. latter discussed. Ch . A b s . (e) New sulphur constituent of the thermal Ores in middle East Bothnia and the Skellefte waters of Pistany (Czechoslovakia). E. C h e r - area. M. Sa k s e l a (Suomen K em , 1934, 7, A, bttliez and A. H e r z e n s t e in (Helv. Chim. Acta, 129—132).—Ores described are principally Fe, Cu, and 1934,17, 1587—1592; cf. this vol., 184).—A residual As pyrites, Pb glance, and Zn blende. Considerable I-reducing effect observed in these waters after proportions of Au ore occur in some areas. A. G. P. allowing for the H2S present, not due to H ^ O s, is Zinc-lead lode at Rosebery, Tasmania. F. L. ascribed to an unstable S acid. The chemical behaviour St il l w e l l (Proc. Austral. Inst. Min. M et, 1934, No. of the substance, which has not been isolated, 94, 43—67).—A description is given of the mode of resembles that of Na2S204. F. L. U. occurrence and characteristics of the following Radium in field waters and petroleum of minerals of the lode: Zn blende, galena, pyrite, Bibi-Eibat oil-field. B. A. N i k i t i n and M . S. chalcopyrite, mispickel, tetrahedrite, bournonite, and M e r k u l o v a (Trav. inst. état radium, U.S.S.R, native Au. The gangue contains quartz, spessartite, 1933, 2, 160—176).—The Ra content was variable, rhodoclirosite, sericite, chlorite, barytes, and but decreased with depth. The U and Ra contents ilmenite. A. R. P. were not interdependent. The Ra in H20 is due Petrography of Sardinia. Characteristic ker- only to the leaching of minerals. Ch. Abs. (e) santitic vein with prasinitic “ facies” from Origin of radium in oil-field waters. L. V. Sarrabus. II. A. Ca v in a t o (Atti R. Accad. K o m l e v (Trav. inst. état radium, U.S.S.R, 1933, 2, Lincei, 1934, [vi], 20, 205—209).—The mineral 207—-223).—Leaching of solid rocks (granodiorite) (chloritic prasinite, ovardite; Si02 53-90, T i02 T06, with distilled H20 removes about 15% of Ra at slightly A120310-21, Fe203 9-00, FeO 7-76, CaO 1-59, MgO 7-18, elevated temp, and with long contact. A q . BaCl2 K ,0 1-00, Na20 4-40, H20 4-90, total 101-00%) is extracts Ra rapidly at room temp. The Ra, Ms-Th, described. 0. J. W. and Th-X in field H20 arise from the leaching of Mindigite, a new [copper] cobalt hydroxide. rocks. Ch. A b s . (e) L . d e L e e n h e e r (Natuurwetenseh. Tijds, 1934, 16, Radioactivity of waters from the oil-fields of 237— 241).—This mineral, found in the Belgian Congo, Dagestan, Kuban, and Azerbaïdjan. L. V. 9Co203,2Cu0,16H2O, d 3-07, hardness 2-5, colour dark K o m l e v , P. M y a t e l k x n , and V. Sa v c h e n k o (Trav. brown, is non-magnetic. Its apparently amorphous inst. état radium, U.S.S.R, 1933,2,176—207).—Data character is confirmed by X-ray powder diagrams. are recorded. The Rn in the natural gas was > that Curves are given for the loss of H20 on heating at required by the equilibrium conditions. different temp. At high temp, it loses 0 2, forming C h . A b s . (c) Co304 and CoO. Its optical properties are given. Thorium-X content of water from well No. 1 D. R. D. in Ukhta oil-field. P. L. B o b in (Trav. inst. état Composition of titaniferous silicates, especi radium, U.S.S.R, 1933, 2, 157— 159).—Average con ally astrophyllite. B. G o s s n e r and E. R e in d l tents of Ra and Th-X were 7-58 x 10~9 and 2-86 x 10-3 (Zentr. Mineral, 1934, A, 161— 167; Chem. Zentr, g. per litre, respectively. Ch. A b s . (e) 1934, ii, 747).—Astrophyllite, {[Si20 7]2[(Ti>Zr)(0H,F)2](Fe;iIn)4(KJNa)2}, is rhombic Sorption b y snow. Y . K a u k o an d V . M a n t e r e (a 11-70, b 5-40, c 21-10 A .; 4 mols. in unit cell). (Suomen Kem , 1934, 7, B, 97—98).— Snow has con H. J. E. siderable adsorptive power for CO,. A. G. P. Hornblende synthesis at low pressures. Occurrence of lithium on the earth. F. Her K. H. S c h eu m a n n and W . L u d k e (Ber. Verh. sachs. m a n n (Metallbörse, 1934,24,535 ; Chem. Zentr, 1934, Akad. Wiss. Leipzig, math.-phys. K l, 1933, 85, 273— ii, 1433).—The mean Li content of the earth’s crust is 278; Chem. Zentr, 1934, ii, 747).—Tremolites identi 4 X 10-®%. The occurrence is discussed. H. J. E. cal with the natural products have been prepared by ORGANIC CHEMISTRY. 191 heating at 900° a mixture of silicofluorides and H VERDiii, G. Sil o r e t , and J. F . d e FEfiRrfc&E (Ami. carbonates pressed into pastilles with SiO, gel. Agron., 1934, 4, 732—769).—The formation, analysis, H. J. E. classification, and practical usage of these soils are Product of [radioactive] transformation' of discussed. A. G. P. potassium. G. v ox H e v e s y and W. D u l l e n k o p f Soil formation on the coloured clays of Trans- (Z. anorg. Chem., 1934, 221, 167— 172).—The extrac ural. L. N. A l e x a n d r o v a (Trans. Dokuchaiev tion of Ca from a very old Norwegian biotite is de Soil Inst., 1934, 10, No. 3, 23—46).—The clays were scribed, and explanations are proposed to account for formed by the sialitic weathering of massive cryst. the apparent identity of the specimen so obtained rocks during the Tertiary period. The content of with ordinary Ca (cf. A., 1934, 825). F. L. U. bases is low, whilst that of R 203 is high. The HCl-sol. Composition and age of crystalline uraninite fraction is small in comparison with that of laterites. from Katanga. C. S. H i t c h e n and R. v a n A u b e l The present soils are of the podsolic type, but are (Compt. rend., 1934, 199, 1133— 1135).— Spectro- thin and with no great humus accumulation. graphic analytical data are recorded and discussed. A.M. H. J. E. [Origin of] natural oil. J. M . M a c f a r l a n e Exhalation of radon from the soil. P. R. (Science, 1934, 80, 478— 479).—Polemical (cf. A., Z to a n c io (Terrestr. Mag. and Atm. Elec., 1934, 39, 1934,1198). L. S. T. 33—46).—-The method of collection and measurement Petrographical investigation of lignite, petrol is described. The average amount of Rn exhaled was eum , etc. R. PoTONiis (Braunkohle, 1934, 33, 23xlO~18 curie per sq. cm. per sec.- The amount 209—212; Chem. Zentr., 1934, ii, 1060— 1061).—A increases with rise of soil temp. Ch. A b s . (e) discussion. H. J. E. Iodine contents of the soils in Japan. A. Radioactivity and the age of meteorites. R. D. Itano and Y. Tujt (Proc. Imp. Acad: Tokyo, 1934, E v a n s (Physical Rev., 1933, [ii], 44, 131). 10, 524—527).—The I content of 120 samples of L. S. T. Japanese soils is between 0-49 and 56-53 p.p.m., Relative abundance of the oxygen isotopes average 7-41. I contents decrease in the order clay, 016 : Qis in stone m eteorites. S. H. M a n i a n , H. C. loam, sand, sandy loam. The higher is the pa the U r e y , and W. B l e a k n e y (J. Amer. Chem. Soc., 1934, greater is the I content. C. W. G. 56, 2601—2609).—Methods for converting the O of silicate rocks and stone meteorites into CO, by heat Italian volcanic soils. L. R ig o t a r d (Ann. ing with CC14 at 1000°, thence by reduction with H2 Agron., 1934, 4, 770—780).—The composition of to H20 and by electrolysis to 0 2, have been devised. deposits of varying age is examined. A. G. P. The ratio O16 : 0 18 is the same, within the experi Soils of the lower Charente. Relations mental error ±2-5% , in the terrestrial and extra between pedology and local designations. H. terrestrial specimens. E. S. H.
Organic Chemistry. Electron diffraction and its application to the is determined (method : A., 1934, 276) to be 100±6 study of organic compounds. J. J. T r t l l a t kg.-cal. The first step in the decomp, is probably (Kolloid-Z., 1934, 69, 378—388).—A review of pub CH4 — >- M e + H ; the H then combines on the walls lished work, especially on paraffins, fatty acids, of the vessel or reacts thus : CH.-J-H — M e+H 2. cellulose and its derivatives, and caoutchouc. h . b : E. S. H. [Preparation of ethylene.] V. N. I p a t ie v (Ber., Isomerism. I. F. P. A. T e l l e g e n (Chem. 1934, 67, [.B], 2018; cf. A., 1934, 864).—A reply to Weekblad, 1935, 32, 3—5).—A discourse on the three Sakmin (ibid., 508, 1198). H. W. types of isomerism. S. C. Combustible liquid obtained from ethylene. Catalysis in preparative organic chemistry. K . S m o l e ń s k i and S. K o w a l e w s k i (Bull. Acad. k. Y oshikaw a (Sci. Papers Inst. Phys. Chem. Res. Polonaise, 1934, A, 315—328).—The polymerisation lokyo, 1934, 25, 235—301).—A detailed report on of C2H4 was studied by slowly heating it at initial experiments described previously (cf. A., 1931, 693; pressures, P, of 34, 51, and 90 atm. The variations 1932, 918; 1934, 1102, 1206). J. W. S. of pressure with temp, showed that polymerisation Thermal decomposition of organic compounds begins at 300—340°, according to P. The liquid from the view point of free ra d ica ls. X II. De hydrocarbons (yield, 80—97% according to P) ob composition of methane. F. O. R i c e and M. D . tained contain paraffins, defines, and aromatic com ^ootEY (J. Amer. Chem. Soc., 1934, 56, 2747—2749). pounds : the relative proportions of light and heavy The gases formed during thermal decomp, of CH4 (lubricating oil) fractions depend on P. The yield m quartz at low pressures (cf. A., 1932, 1108) are of liquid product is diminished by heating above 420° Passed over a Te mirror; Te2Me2 (but no TeCH2) is when depolymerisation occurs, and by heating the jras obtained, showing the production of Me and the products with H2, which increases the proportion of •absence of CH2 (cf. Kassel, A., 1932, 1209). The paraffins in the product. A1203 has no appreciable nation energy of the dissociation into free radicals catalytic effect. H. G. M. 192 BRITISH CHEMICAL ABSTRAOTS.— A.
Polymerisation of isobutylene with alumina Brj-derivatives (from butene and HBr evolved during on silica gel as a catalyst, and addition of hydro reaction) are also formed. Dehydration of Bua0H gen chloride to the reaction products without over pumice-H3P04 at 350—400° gives (I) (27-5%) catalyst. H. I. W a t e r m a n , J. J. L e e n d e r t s e , and and (II) (72-5%), whilst sec.-BuOH affords (I) (47-5%) A. J. d e K o k (Rec. trav. chim., 1934, 53, 1151— and (II) (52-5%); the results of King (J.C.S., 1158).—'The products (di-, 2 tri-, tetra-, and penta- 1919, 1 1 5 , 1404) and of Young and Lucas (A., 1930, merides, separated by fractional distillation) obtained 888) arc incorrect. H. B. by polymerisation of isobutylene in the vapour phase Formation of butadiene and acetylene by the with a Si02 gel-Al203 catalyst (activated at 350°) action of the high-frequency discharge on ethyl at > 40° are similar to those obtained with ene. A. A. B a l a n d i n , J. T. E idtjs, and N. G. H2S04 (Tongberg et al., A., 1932, 1109) or floridin Z a l o g in (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4, (Lebedev et al., A., 1930, 316) as catalysts. They are 132— 135).—In a closed system treatment of C2H4 mono-olefinic, those obtained with A1C13 being more with a high-frequency discharge produces H2, satur cyclic. The (n2—l)/d(n2—2) vais, for the low-b.p. ated hydrocarbons, and a thick oil, mol. wt. about fractions are > the theoretical vais, for the olefines, 500. In a circulatory system the product contains as also are those of the saturated paraffins obtained butadiene (I) and C2H2. The amount of (I) formed by their reduction with H2-Ni at 190° underpressure. is dependent on the velocity of circulation and on The Br vais. (Macllhiney) for the polymerides are the amount of H2 added to C2H4. A chain mechanism much < the theoretical C„H2n vais., and are not is proposed. H. N. R. considered trustworthy as a measure of unsaturation. This discrepancy is possibly due to elimination of Effect of peroxides and acids on reduction of HBr, since the trusobutylene fraction, completely olefines in alcohol solution with platinum oxide saturated by addition of dry HC1 in C5H12 at —78°, catalyst. G. T h o m so n (J. Amer. Chem. Soc., 1934, 5 6 , 2744—2747).—The time required for 91—95% readily loses HC1 above 0°. J. W . B. reduction of CHMe!CMe2 (I) by H2 and an Fe-contam- Isomérisation of n-butenes. V. N. I p a t ie v , ing Pt02-Pt-black catalyst (II) in EtOH-MeOH H. P in e s , and R. E. S c h a a d (J. Amer. Chem. Soc., (95 : 5) is shortened considerably by addition of 0-001 1934, 56,2696—2698).—When A^-butene (I) is passed mol. of Bz202 or furoyl or succinyl peroxide (III) through 100% H3P04, isomérisation to A^-butene (II) (which are probably reduced to the corresponding occurs to the extent of 4% at 26°, 12% at 78°j 34% acids), 0-002 mol. of BzOH or furoic or succinic acid, at 100°, and 60% at 135°. Passage of (I) or Bu“OH or (best) 2 drops of AcOH or conc. HC1. Using a through a mixture of Al(OH)3 (1 mol.) and H3P04 (II) which effected only 27% addition of H2 to the (T6 mois.) in a Pyrex tube at 427° gives a mixture of freshly distilled (over Na) (I), the % reduction can (I) (20—30%) and (II) (70—80%). When (I) is be increased by preliminary shaking of the (I) with passed under pressure through diatomaceous earth air; a peroxide (IV), which decomposes to C0Me2 impregnated with H3P04 at 249°, quant, conversion and MeCHO (oxidised further to AcOH), is probably into (II) occurs (36—94% isomérisation is found at formed. (IV) may be reduced to OH,OHMe-CMe2-OH; 100—200°); the catalyst loses its activity when re addition of pinacol or mannitol has only a small action is continued for a long time at 250—325° and accelerating effect. The reduction of amylene and then causes 70—80% conversion. A second sample anethole (cf. Kern et al., A., 1925, i, 625) is similarly of the catalyst gave (probably) an equilibrium mix accelerated by (III) and AcOH, respectively. A ture [containing 72—79% of (II)], irrespective of the mechanism to explain the offset of the poisoning contact time. The amounts of (I I ) formed when (I) effect of Fe bv small amounts of acids is discussed. is passed through 70—72% HC104 at 21°, aq. 75% H. B. PhS03H at 76°, and aq. 75% ZnCl2 at 100° are 21, Polymerisation of olefines formed by the 13, and 5%, respectively; AcOH, CH2C1-C02H, and action of sulphuric acid on methyl/sopropyl- CHC12-C02H at 100° do not cause isomérisation. A carbinol. G. M. K l in e and N. L. D r a k e (J. Res. mixture of 6-6% of (I) and 6% of cis- and S7-4% of Nat. Bur. Stand., 1934, 1 3 , 705—712).— CHMePrs-0H irams-(II) is obtained when trans-(H) is passed through at 80° with 75% H2S04 yields A^-ySee-tetramcthyl- 100% H3P04 at 100°. The various mixtures are liexene and A^-yee-trimethylheptene. Whitmore's analysed by Podbielniak’s method (A., 1933, 690). theory of define polymerisation (A., 1932, 1016) does H. B. not explain this result without postulating a com Catalytic dehydration of butyl alcohols. V. plicated rearrangement. A theory is proposed in K o m a r e w s k y , W. J o h n st o n e , and P. Y o d e r (J. which the trimethylethylene behaves as if it were Amer. Chem. Soc., 1934, 56, 2705—2707).—Dehydra activated to -CH^+CMcICHMe. It is applied to tion of Bu°OH over AJ203-H 3P04 at 250° gives a explain the formation of di- and tri-j’sobutylenes from mixture of 45% of A°- (I) and 55% of Ae- (II) -butene ; isobutylene. H. J. E. sec.-BuOH similarly affords (I) (24-1%) and (II) Preparation and physical properties of ali (75-9%), whilst Bu^OH gives isobutene (III) as the phatic acetylenes. F. R. M o r e h o u s e and O. Maass sole product. (I)— (III) are identified by low-temp. (Canad. J. Res., 1934,11, 637—643).—The imp., b.p., distillation (Podbielniak column) ; (III) is character d, y, v.p., and the parachor and other consts. derived ised further by addition of HBr in AcOH and hydro from these vals. for pure C2H2, C2HMe, C2HEt, C2Me2, lysis (H20) of the resulting mixture of Bu^Br and and C2HPr» (prepared by "alkylation” of the Na BuyBr (thus removed as BuvOH). Analysis of (I)— derivatives obtained in liquid NH3) are tabulated and (III) as dibromides is inaccurate, since Br3- and discussed in relation to the vals. of the similar consts- ORGANIC CHEMISTRY. 193 in the corresponding CnH^ and C„H2,H2 series. autoclave at various temp, and for various times, In general the properties of the CnH2)1_2 series differ affords mainly aliphatic substances. The yield of from those of C„Ho„ and CaH2n+2, due, it is suggested, gaseous products is increased at higher temp. The to the polarity of the triple linking. Symmetry in max. yield of oily liquid products is obtained at 450° the mol. decreases unsaturation. J. W. B. with an initial concn. of EtOH of 3-5 g.-mol. per litre. Acetylenes. I. Preparation of A°-heptinene An A1203 catalyst increases the yield of liquid hydro carbons, which now consist mainly of aromatic and by dehalogenation m ethods. G. B . B a c h m a n and unsaturated compounds. H. G. M. A. J. H ill (J. Amer. Chem. Soc., 1934, 5 6 , 2730— 2732).—Me «-amyl ketone and PCl5in C6HB at < 1 0 ° Reaction of ethylene oxide with acetylenic and then at room temp, give fifi-dichloroheptane (I), Grignard reagents. J. P. D a n e h y , R. R. V o g t, b.p. 77°/25 mm., and fi-chloro-Aa-heptene (II), b.p. and J. A. .Nie u w l a n d (J. Amer. Chem. Soc., 1934, 7F/75 mm.; with P C l3B r2 in C6H6, Me a-brcmio-, 5 6 , 2790;’ cf. Faucounau, A., 1934, 1199).— (CH2)20 b.p. 80°/9 mm., and aa-dibromo-, b.p. 118— 120°/9 and CR-C-MgX give Av-noninen-a-ol (I), 8-pheny!-Av- mm., -n-amyl ketones result, a$-Dichloroheptane (III), butinen-a-ol (II), and Ay-octinen-a-ol (III), b.p. b.p. 68—72°/7 mm., is best prepared from A“-heptene 97°/15 mm. (II) is accompanied by an approx. and S02C12. When (III) and aa-dicliloro- (IV) and equal amount of the H20-sol. 2-phenyl-4 : 5-dihydro- a!3-dibromo- (V) -heptanes are passed with N2 over furan, b.p. 55°/15 mm .; similar compounds are formed soda-lime at 420°, Aa-heptinene (VI) is obtained (cf. with (I) and (III). H. B. A., 1928, 269) in isolable yields of 3, 23, and 3%, Action of Aspergillus niger on n-ap-diols. A. respectively. Dehalogenation of the following with W a l t i (J. Amer. Chem. Soc., 1934, 5 6 , 2723—2726).— powdered KOH in mineral oil at 250° (cf. Guest, ibid., ¿Z-OH-CHR-CH2-OH (I) (R=M e, Et, Pr) are converted 988) gives (VI) (isolable yield quoted): (III) 33% ; by A. niger (II) under sterile conditions into (IV) 40%; (V) 64% ; a-chloro- 37%, a-bromo- COR-CH2-OH (II I); the recovered a(3-diols are 88%, and aa-dibromo- (VII) 21%, -Aa-heptenes; optically active (— when R =M e and -f when bromoheptene mixture [obtained by dehalogenation R = E t or Pr) and rotate in the same direction as those of (V)] 65%. (VI) is not similarly obtained from obtained by reduction of (III) or OH-CHR-CHO (I) or (II). (VI) polymerises readily at 300°; the with yeast (A., 1932, 143). Infected (II) under non- polymeride cracks at 400°, but does not regenerate sterile conditions also converts (I) (R = E t, Pr) into (VI). (VI) is not rearranged by soda-lime at 200— (II I); the recovered diols are, however, laworot- 250° (cf. Guest, loc. cit.). aa-Dibromoheptane could atory. Hexane-aP-diol, b.p. 100°/5 mm., from (V) not be prepared by Bruylants’ method (Ber., 1875, 8, (below) and H20 at 180° (sealed tube), is unaffected by 409), by reduction of (VII), or from (I) and NaBr in (II). The following are described: ]-propane-o.fj- MeOH-COMe2 containing I and KI. H. B. diol, m.p. 146°, [a]£J +9-3° in EtOH, d-, m.p. 117— Identification of a lk y l h alides. AT-A lkyl-p- 118°, [a]g> +3-7° in EtOH, and 1-, m.p. 118°, [a]g> bromobenzenesulphon-p-anisidides. H. B. G i l —0-47° in EtOH, -butane-a^-diol, and d-, m.p. lespie (J. Amer. Cliem. Soc., 1934, 56, 2740— 100— 101°, [a]“ +1-2° in EtOH, and 1-, m.p. 102°, 2741),—The following iV-alkyl derivatives of p- [«]» -2 -3 ° in EtOH, -pentane-x$-diol di(phenyl- brouiobenzenesulphon-p-anisidide, m.p. 142° (from carbamates) ; a-hydroxybutan- (3-one-2 : 4-dinitrophenyl- P-C6H4Br-S02Cl and p-OMe-CgHfNH,, in C5H5N), hydrazone, m.p. 150°; v.-hydroxypenlan-fi-one-Z : 4- arc obtained with the appropriate alkyl halide (I) in dinitrophenylhydrazone, m.p. 165°; a$-oxidopentane aq.EtOH-KOH : Me, m.p. 96—97°, Et, m.p. 113-5°, (IV), b.p. 91— 92°, from OH-CHPr-CH2Cl and warm if1 m.p. 75°, Pr&, m.p. 107°, Bua, m.p. 74-5°, Bvft, m.p. conc. aq. NaOH; a$-oxidohexane (V), b.p. 118— 120°, '8—79°j il.j m_p_ 88-5°, and iso-, m.p. 52-5°, -amyl, from OH-CHBu-CH2Cl and powdered NaOH or n-hplyl, m.p. 56°, allyl, m.p. 82°, benzyl, m.p. 167-5°, KOH in Et20. (IV) and H20 at 90° (sealed tube) P-hydroxyethyl, m.p. 92— 93°, and |3-hydroxypropyl, give pentane-ap-diol, b.p. 96— 99°/ll mm., and a ®-p. 92°. These derivatives arc useful for the little dihydroxydiamyl ether, b.p. 130— 132°/7 mm. identification of (I). H. B. (IV) and aq. 30% NHMe2 at about 0°—room temp, afford a-dimethylaminopentan-fi-ol, b.p. 165— 166°/762 Preparation of higher aliphatic bromides. mm. [methiodide (=(3-n-propylcholine iodide), m.p. J- R. Ruhoff, R. E. Burnett, and E. E. R eid (J. 198°]. a-Bromohexan-(3-ol, b.p. 89—90°/13 mm., is Amer. Chem. Soc., 1934, 56, 2784).—The alcohol (I) obtained from (V) and cold 48% HBr. H. B. >s saturated with dry HBr [simplified prep. (cf. Baxter and Coffin, A., 1909, ii, 397) described] at Preparation of ethylene glycol from dichloro- about 100° and the crude product washed success ethane. A. L. K l e b a n s k i and I. M. D o l g o p o l s k i ively with conc. H2S04 [removes unchanged (I)], dil. (J.Appl. Chem. Russ., 1934,7,790—806).— (-CH2-OH)., MeOH-NHg, and dil. MeOH. ci/cZoHexyl, M-heptyl, (I) is obtained in 87—90% yield from C2H4C12 by and do-, tetra-, and octa-decyl bromides are thus pre heating for 20—25 min. with a 5% excess of 15% pared in yields of 73, 88,89,89, and 90%, respectively. Na2C03 at 185— 190°/100 atm.; CtI2:CHCi, a by H. B. product of the reaction, is best absorbed by xylene Compounds of magnesium chloride with from the reaction gases. Using aq.-EtOH HC02Na alcohols and acetic a cid .— See this vol., 179. in place of Na2C03 80% yields of (I) are obtained by heating at 160— 170°/18 atm. for 5-5 hr. R. T. Pyrogenic transformations of ethyl alcohol. p Smolenski and S. K owalewski (Bull. Acad, Di-tertiary diols derived from diacetone «lonaise, 1934, A, 304— 314).—EtOH, heated in an alcohol (p-hydroxy-p-methylpentan-s-one). R. 194 BRITISH CHEMICAL ABSTRACTS.— A.
Jacqttemain (Compt. rend., 1934,199,1315— 1317).— Preparation and determination of ethylene Diacetone alcohol with the appropriate Grignard oxide. W. D o m in ik and J. B artkiewiczówna compound gives fiS-dihydroxy-pS-dimethyl-hexane, b.p. (Przemysł Chem., 1934, 18, 373—375).— (CH2)20 98°/5 mm., -heptane, b.p. 107— 108°/5 mm., -octane, is obtained hi 90% yield by dropping aq. EtOCl on to b.p. 116— 117°/5 mm., -nonane, b.p. 123— 124°/2 mm., CaO in a flask heated on an oil-bath, and fitted with $8-dihydroxy-$&e-irimethylhexane, b.p. 103— 106°/2 a reflux condenser connected with a manometer. mm., -p8%,-trimethylheptane, b.p. 105— 106-5°/2 mm., The yield of (CH2)20 is ealc. from the rise in pressure and ^■q-lrimethyloctane, b.p. 119— 120°/4 mm., which in the flask. Lower yields are obtained when aq. readily lose H20. J. L. D. NaOH is substituted for CaO. R. T. Molecular changes of the a-disecondary oxides Constitution of polyhydroxy eye iobexane. I. of the aliphatic series, and of normal structure, i-Tetrahydroxymannocyclitol. Y. H a m a m u r a M. F a v o r s k i, M. T chitchonkin , and I . I vanov (Proc. Imp. Acad. Tokyo, 1934, 10, 459— 462).— (Compt. rend., 1934, 199, 1229—1230).—a-Hethyl-fi- avDi-iodo-cf-mannitol PySe-tetrabenzoate (I) (ef. A;, ethylethylene oxide (I), b.p. 79— 82° (prepared through 1932, 928) with Ag in dioxan at 125—130° affords a CHMelCHEt and its monochlorohydrin), with fused syrup, hydrolysed [5% MeOH-Ba(OH)2] to 1 :2 :3 :4 - ZnCl2 at 315—320° gives COMePr“. Similarly, a-ethyl- tetrahydroxycyclohexane (II), m.p. 146— 147°, [a]“ Çi-propylethylene oxide, b.p. 131—132°, is converted —27-7° in H20 (ef. A., 1932, 834) {Ac derivative, 4 into COEtBu». Tho C atoms nearer the periphery m.p. 79°), which absorbs Br in AcOH, does not possess the greater affinity for 0, so CO is situated as reduce Folding's solution, and with H2 (Pd-BaS04) near the end of the chain as possible. J. L. D. at room temp, gives a$y8-teirahydroxy-n-hexane, m.p. 123— 125° (CPh3 etlier, m.p. 124— 125°), the Specificity of phosphatase.— See this vol., 122. oxidation product (PrOH) of which confirms its Spontaneous decomposition of lecithin and structure. (I) with Zn-AeOH at 100° gives a product its bearing on determination of isoelectric point. which is converted into [iySe-tetrahydroxy-n-hexane (?), H. F isc iig o l d and E. Ch a in (Biochem. J., 1934, m.p. 150°, which does not reduce KMn04 or absorb 28, 2044—2051).—Lecithin (I) is titrated electro- Br, and differs from (II). J. L. D. metrically in 99% EtOH, with NaOH, giving a curve similar to that of the solvent alone ; back titration Mannitol. IV. Acetone- [»'sopropylidene-] with HC1 shows slight buffering at p3 7-5. Back mannitols and mixed esters of mannitol. P. titration after keeping 66 hr. in excess of NaOH shows B r ig l and H. G r ü n e r (B er., 1934, 67, [73], 1969— the formation of anew group, pK 7-5. Fresh and old 1973; cf. A., 1934, 1199).—Mannitol is shaken with props, of (I) are titrated in CGH6-EtOH (19:1) H B02 (or H3B03) and conc. H2S04 in COMe2 until with HC104 and also with NaOEt. On the acid dissolution is complete. The solution is conc. to side no significant change in the titration occurs a syrup, which is repeatedly evaporated with MeOH with age, whilst on the alkaline side an increase to remove H B02. The residue is extracted with in the groups titratable by NaOEt occurs. The pK ligroin, from which dii'sopropylidenemannitol of stearic acid in 90% EtOH at 25-7° is 7-36. After separates. Triisopropylidenemannitol (I) is obtained émulsification of (I) in H20 and subsequent addition from the mother-liquors, whilst treatment of the of HC1 and Fe(OH)2 choline chloride (II) is not- present material insol. in ligroin with EtOH leads to iso- in the supernatant fluid. Fatty acids are present propylidenemannitol. aßevDii.sopropylidenemannitol in an EtOH extract of an old prep, of (I) after pptn. is converted by ;p-CfiH4Me,S02Cl in” C5H5N at 35° with CdCl2, but not of a fresh prep. A solution of into aße'C-du soprop ylidenemannitol yS-di-Tp-toluene- (II) in H20 was neutral. The titration curve of (II) sulphonate, m.p. 120— 121°, [a]D -j-9-3° in CHC13, is identical with its blank correction curve. From the which is hydrolysed and then transformed by BzCl Pn of a solution of (II) in O-lxV-NaOH a val. of 14 in C5H5N into mannitol vX^-dibenzoate, yS-di-’p-ioluene- for its pK is obtained, giving a theoretical isoelectric sulphcmate, m.p. 145— 146°, [a]D -{-42-20 in CHC13, point of (I) at pu 7-5 approx. H. D. whence (Ac20 in C5H5N) mannitol ße-diacetate oiZ,-dibenzoate yS-di-Tp-toluenesulphonate, m.p. 142°, Isoelectric points of lecithin and sphingo Md +55-9° in CHC13. Mamiitol a^-dibenzoate is myelin. E. C h a in and I. K e m p (Biochem. J-> converted by COMe and conc. H2S04 into isopropyl- 1934, 28, 2052—2055).—A fresh prep, of lecithin has idenemannitol a^-dibenzoate, which is transformed an isoelectric point (I)'at fn 6-74;0-2 as determined by y-C6H4Me-S02Cl and C5H5N at 15—20° into by the min. cataphoretic velocity of dispersions in yS-isopropylidenemannitol at,-dibenzodie fie-di-p- aq.-EtOH media. (I) is independent of the buffers toluenesulphonate, m.p. 96— 97°, [cc]d -r27-0°inCHCl3> used and the ionic strengths of the solutions; in hydrolysed to mannitol ?Z,-dibenzoate fie-di--p-toluene- 0-05iV-BaCl2 strong adsorption of Ba” occurs. The sulphonate, m.p. 76—77°, [a]? —27-8 in CHC13, whence (I) of preps, of sphingomyelin increases from a val. mannitol yH-diacetate aZ,-dibenzoate pe-di-j)-toluene- < 2 to a val. > 6 with successive purifications t hrough sulphonate, m.p. 121°, [a]D +56-4° in CHC1S. The the Cd salt. H. D. compound of Müller et al. (A., 1933, 931) is therefore Mechanism of chlorination of aliphatic acid mannitol ye-diacetate aX,-dibenzoate ßS-di-'p-toluene- chlorides. I. Dark reaction.— See this vol.. 174. sulphonate. yS-Diisopropylidenemannitol, m.p. 84— S5°, [a]J,s +30-4° in H20, is readily obtained by partial Oxidation of fatty acids.— See this vol., 114. hydrolysis of (I) with" AeOH-H20 at 15—20°. Rotatory dispersion curves of a-substituted H. W. u-carboxylic acids.—See this vol., 14. o r g a n ic c h e m i s t r y . 195
Preparation of formyl chloride.—-See this vol., X V (cf. A., 1933, 934). Tho orientation of addition 177. of HBr to vinyl- (V) and allyl- (VT) -acetic acids in Organic reactions with boron fluoride. VIII. hexane is unaffected by anti oxidants [H2,p-C6H4(OH)2, Condensation of propylene with acids. T. B. NHPh2]. Addition to (VI), but not to (V), in the absence of solvent is reversed by admixture of 1% Dorris, F. J. S o w a , and J. A. N ie u w l a n d (J. Amer. B z20 2. Chem. Soc., 1934, 5 6 , 2689—2690).—Pr^O Ac, of Addition to stale samples of (VI) in the CH2Cl-CO2Pr0, CHCi2-C02Pri*, and CCl3-C02Pr^ are absence of solvent occurs in the same direction as to obtained in yields of 16-8, 38-8, 48-6, and 57-8%, fresh samples. The orienting effect of solvents in the respectively, from the acid, Pr^OH, and BF3 (cf. above examples is not considered to be due to A., 1932, 728) ; the yields are in the reverse order variations in the peroxide effect. H. G. M. witH HC1 as catalyst (Sudborough and Lloyd, J.C.S., Arachidonic acid and its quantitative deter 1899, 75, 467). Pr^OBz (I) is similarly obtained in mination. W. C. A u l t and J. B. B r o w n (J. Biol. 60% yield. The esters are also prepared in yields Chem., 1934, 1 0 7 , 615—622).—Specimens of Me of 7, 34-2, 39-5, and 48-8%, respectively, from the arachidonate (I) prepared by fractional distillation, acid, C3H6, and BF3 at 60—70°. The solubility of by the Li soap-COMe2 method, and by reduction of CoH„ in the acids and esters increases with the no. Me octabromoarachidonate all have the same poly of Cl atoms. (I) is obtained in 88% yield from bromide no., 86-5. By use of this no. as described by BzOH [in (I)], C3H6, and BF3 at 20—30°; ring- Brown (A., 1928, 208), (I) and arachidonic acid (II) substitution does not occur (cf. A., 1934, 1349). may be determined. (I) has b.p. 200—205°/l—2 m m .; H.B. (II) has m.p. —49-5°. C. G. A. Hetero-formato-salts of calcium. J. V. Dübskÿ and J. T r t î l e k (Publ. Fac. Sci. Univ. Unsaturated fatty acids and their derivatives. Masaryk, 1934, No. 196, 1—6).—The compounds X. Constitution of clupanodonic acid. Y. [Ca2R2]Cl2,8H20, [Ca2R2][CeH2(N02)3-0-]2,4H20, m.p. I n o u e and H. K a t o . XI. Configuration of 160°, [Ca2R2]Cr04,2H20, CaR2,K3Fe(CN)6, and eruco- and brassido-dibromobehenic acid. T. [Ca2R2](OAc)2, in which R=HCO,-, have been M a r u y a m a (Proc. Imp. Acad. Tokyo, 1934,1 0 , 463— prepared. . ” R. T. 466, 467—469; cf. A., 1932, 252; 1933, 145).— X. Decabromobehenic acid (I) [from clupanodonic acid Olefinic acids. X III. Ay-n-Hexenoic acid and (II)] with K I in CbH6-H 20 gives the octabromide “ hydrosorbic ” acid. R . A. L e t c h and R . P. (III), m.p. 98—98-5°, reconverted into (I) with Br, Lik stead . XTV. Preparation and additive re and with 0 3, followed by hydrolysis, gives hexabromo- actions of A5-w-hexenoic acid. Unusual isomeric octadecanedicarboxylic acid (IV), m.p. 65° [Me ester change in the three-carbon system. XV. Effect (V), m.p. 52—52-5°, similarly obtained from the of peroxides on orientation of addition of hydro Me ester of (I) or Me hexabromoclupanodonate gen bromide to vinyl- and allyl-acetic acids. (VI)]. (IV) and (V) when debrominated and hydro S. P. L in s t e a d and H. N. R y d o n (J.C.S., 1934, genated (Pd-BaS04) both give hexadecane-aoi- 1994—1995, 1995—2001, 2001—2003).—X III. “ Hy- dicarboxylic acid (Pb salt), and ozonisation in each drosorbic ” acid (A., 1928, 868, 1214) contains case affords Pr“C02Ag. Because both (VI) and Ay- (I) and A^-m-hexenoic acids. Hot alkali partly (III) give (I), the centres of unsaturation are the same, converts the latter into the A“-isomeride, which may but (VI) must have a triple and (III) a double linking. ho separated by partial esterification. After two (II) with fuming HN03 affords an a-diketone, and repetitions of the whole process pure (I) remains. with conc. H2SO,j and H20 affords monoketotri- The acid thus obtained is identical with that prepared hydroxybehenic acid, decomp. 128° (oxime, decomp. by other methods (A., 1897, i, 13, 590; 1901, i, 63; 150°). 1929, 1271). yS-Dibrojno-n-hexoic acid has m.p. 84°. XI. Erucic acid with Br gives eruco-dibromo- XIV. Decarboxylation of b?-n-butenylmalonic acid, behenic acid (VII), which with the calc, amount m p. 92° [from a-bromo-Ay-«-butene (II) (improved of EtOH-KOH at 80° affords [¡.-bromo-i^-behenic acid prep.) and CHNa(C02Et)2], gives A5-n-hexenoic acid (VIII), m.p. 33°, the Mo ester of which when oxidised (ill), which after regeneration from the p-toluidide, gives octoic acid (IX) and Hetero-compounds of glycollic acid. J. V. Treatment of Z-(araóo)-trihydroxyglutaric acid with D u b s k £ and D. V inogradsova (Publ. Fac. Sci. Univ. excess of CH,N2 in Et20 gives a product containing Masaryk, 1934, No. 196, 7— 16).—The salts CuR2, 45-4% OMe, transformed by Ag20 and Mel into Me, NiR2, MgR2,2H,,0, BaR.„ ZiiR2,2H,0, CdR„,2H20, l-(arabo)-trimethoxyglutarate, b.p. 74— 76°/0-005 mm., PbR2, MnR2,2H20, GoRa,2H20, CuR2,2NH3, Mi? +32-2° in MeOH [Z-(araZ>o)-trimethoxyglutardi- [Cu2R2]C12,3H20, [ % 2R2]CJ2,3, m.p. 282°, and 4H20, methylamide, m.p. 173— 174°, [a]J? -f-59-4°-h0-9° in [Ca!R2]Cl2!5, m.p. 188°, and 6H20, m.p. 128“! H20], in 60% yield. With excess of CH2N2 (xylo)- [Ba2R2]Cl2,3H20, m.p. 275—280°, [Hg,R,]Cl2, trihydroxyglutaric acid affords essentially Me., hydr- |Pb2R|]Cl2, [Mn.,R2]Clo,4H20, m.p. 162— 164°, oxydimethoxyglutarate, b.p. 97—99°/0-003 mm., hydro [Ni2R2]CI2"6H20, m.p. 126— 128°, CoCl„CoClR,10H,0, lysed to a mixture of an acid and the monolactone of m.p. 52°, [Co2R2]C12,5-5H20, m.p. 86—90°, a-hydroxy-a'p-dimethoxyglutaric acid, m.p. 109-5— [Ca2R2](N03)2,8Ho0, m.p. 174°, [Zn0R2](N03)o,4H20, 110-5°. ¿-Tartaric acid is converted hy an excess of m.p. 119°, [Pb2R2](N03)2,decomp, at 160°, [Cu2R2]RR', CH2N2 into Me2 cZ-dimethoxysuccinate, b.p. 130— [Cu2R2]R',,H20, 3ZnRo,2ZnR'o,llH„0, m.p. 230°, 132°/12 mm., in 95% jdeld; the same substance is [Ba2R"2](N03)2,4H„0, [BaiR''4](N03)2,2H20, and produced by vigorous action, but in somewhat lower [Pb,R"2](N03),,HoC), m.p. 182— 187°, have been pre yield, from Me2 rf-tartrate. Mucic acid, probably by pared (R = 6 H-CHv CO, ; R'=NH ,-CH ,-C02; R " = reason of its sparing solubility, reacts so slowly with HC02). “ R. T. CH2N2 in Et20 that complete esterification is not Hydroxy-acids obtained by the atmospheric attained. ¿-Saccharic acid reacts vigorously, acquir ing about 4Me, but apparently undergoing complex oxidation of paraffin. II. P. P. S c h o r ig in and change. H. W. A. P. K r e s c h k o v (J. Gen. Chem. Russ., 1934, 4 , 988—994).—The product of oxidation of paraffin by Identification reactions for i-ascorbic acid atm. 0 2 consists of a mixture of OH-acids (I), their (vitam in-C).—See this vol., 130. anhydrides, lactones, and lactides, carboxylic acids, and unidentified, unsaponifiable substances. The (I) Types of lactones formed from monobasic sugar acids under varying conditions. J. M. were converted into Me esters with Me2S04, the mix ture of esters fractionally distilled, the fractions hydro B r a c k e n b u r y and F. W. U p so n (J. Amer. Chem. lysed with aq. KOH, the individual (I) fractionally Soc., 1934, 5 6 , 2659—2662; cf. A., 1933, 808).—The pptd. as Cd salts, and the acids OH-C0H18-CO„H, rate of lactone formation by various acids in (usually) AcOH, 0-5iV-H2S04, and H20 at 25° is studied 0H*C11_j7H22_ai-C02H, OH'C20H40’COoH (2 isomer- ides), 0H-C21H42-C02H, 0H-C26H52“C02H, and polarimetrically. (Z-Mannonic acid is converted more 0H-C31H62-C02H isolated; OH is chiefly, but not slowly but to a greater extent into the S-lactone in exclusively, in the fi-position, and the C chain is AcOH than in H20, and gradual conversion of the 8- probably branched in every case. R. T. into the y-lactone (isolable from the equilibrium mixture; the change is also established independently) Combined action of ultra-violet light and occurs; Z-rhamnonic acid shows a similar behaviour. platinum on transformation of fumaric and (Z-Gluconic acid lactonises to a greater extent in AcOH maleic acids and their salts.—See this vol., 178. than in H20 ; the mam constituent of the equilibrium Preparation of pimelic acid. A . M u l l e r mixture is (probably) the S-lactone (which is isolable). (Monatsh., 1934, 6 5 , 18—20).— Pimelic acid is ob a-cZ-Glucoheptonic acid (I) is also converted more tained in 50% yield by treating 0-0H-CeH4-C02H with slowly but to a greater extent into the S-lactone (II) Na in boiling amyl alcohol. H. W. in AcOH than in H20 or dil. acid; reaction is slower at 0° and gives an equilibrium mixture of (I) and (II). Muconic and hydromuconic acids. VI. cfs- a-Z-Rhamnolieptonic acid resembles (I); its S-lactone and tr«i»s-Aa-Dihydromuconic acids. E. H. has a — rotation in accordance with Hudson’s lactone F a r m e r and L. A . H u g h e s (J.C.S., 1934, 1938— 1940; rule (A., 1910, i, 220). 8-Lactone formation by cf. ibid., 1923, 123, 2531).—The mixture obtained by arabonic, talonie, and galactonic acid is not much > heating A^-diliydromueonic acid (I) with hot aq. NaOH in AcOH than in H20. H. B. contains unchanged (I) and trans-Aa-dihydr Synthesis of hamamelonic acid. 0. T. Sc h m id t arabonic acid (phenylhydrazide, m.p. 194— 195°, [a]“ and K. H e in t z (Annalen, 1934, 515, 43—64, 65—76, + 8 3 + 5 ° in H20) and a-hydroxymethyl-Z-ribonic acid 77—96; of. A., 1930, 197; 1931, 70).—III. A mix ('phenylhydrazide, m.p. 204°, [a]},8 —33+4° in H 20). ture of a-fructohcptonic acid (I), [a]J? —20-26+0-5° (Z-Araboketose, [a]D —12-4°, similarly prepared from in H20, —1T58+0-40 (as Na salt in H20) {brucine ri-arabinose, and HCN afford a-hydroxymeth yl-(Z- salt (II), m.p. 162° (Kiliani, A., 1928, 47); phenyl arabonic acid (phenylhydrazide, m.p. 194— 195°) and hydrazide, m.p. 164°, [a]},8 + 9-6+0-50 in H20 (Kiliani hamamelonic (a-hydroxymethyl-cZ-ribonic) acid and Diill, A., 1890, 596); amide, m.p. 175— 176°, (phenylhydrazide, m.p. 202—203°, [a]J,8 + 3 4 + 4 ° in [a]J? —9-3° in H20 ; anilide, m.p. 164— 165°, [a]},8 H20). Hamamelose is, therefore, an a-hydroxymethyl- -f 22-5+0-5° in H20 ; lactone, [a]»,8 +82-15° in H20}, (Z-ribose (IV). and (3-fructoheptonic acid (III), [a]j,8 + 1 -4+0-4° in Further investigation of the action of C5H5N on H20, +2-1+0-3° (as Na salt in H20) {brucine salt (Z-xylose (V) [3-5-dinitrobenzoylhydrazone (VI), m.p. (+2-5H20), m.p. (anhyd.) 143— 145° (not sharp); 194°, [cx]Jf +35-4° (final val.) in C5H6N] shows that phenylhydrazide (IV), m.p. 190— 191°, [a]“ -3 0 -7 5 + (I) is accompanied by a little lyxose; the initial 0-5° in H20 (cf. Kiliani, A., 1922, i, 1111)}, is obtained reaction product can be freed from (V) with 3 : 5- from fructose and HCN by Kiliani’s method (loc. cit.); CHO (N02)2CgH3-C0-NH-NH2 [thus giv- (I) is separated from the mixture as (II), and (III) nTT.ru . X m *nS (VI); ketoses do not react], is then isolated from the filtrate as (IV). (Ill), H'C-OH an(I (after treatment with PhCHO) obtained as a syrup, is converted by repeated evapor H-C-OH (I) can then be isolated as the ation with aq. HC1 into an anhydrolactone, C7H10OG, ptt .nir p-bromophenylhydrazone (loc. cit.). m.p. 189— 190°, [cx]i« +100-7° in H20 (free acid, [a]]8 2 The production of (I) from (V) is + 8-4+0-4°); the anhydride ring does not undergo ' ' contrary^ to the results of Levene fission with acid or alkali. (I) docs not give an and Hill (A., 1933, 1278). The composition of mix analogous compound. Interconversion of (I) and (III) tures of aldo- and keto-pentoses cannot be determined could not be effected by boiling C5H5N or quinoline. by titration with I in alkaline solution (cf. Levene The nitrile, m.p. 105°, of Kiliani and Diill (loc. cit.) and Hill, loc. cit.). (V) undergoes quant, oxidation (the m.p of different preps, is found to be 95—-117°) with I in aq. KHC03 after 12 hr.; (I) similarly con is hydrolysed to (I). Comparison of the [JJ/]D of (I), sumes I s 65% of aldose. H. B. (III), gluconic, mannonie, arabonic, ribonic, and Thiodiisobutyricacids. E.L a r s so n (Ber., 1934, hamamelonic (V) acids and their derivatives shows 67, [5], 2109—2111; cf. A., 1934, 870).—Et (3-bromo- that (I) and (III) are a-hydroxymethyl-gluconic and i'sobutyrate (I) and SH'CMog'COaH are converted by -mannonie acid, respectively. (V) (cf. Part V) shows NaOEt-EtOH and subsequent hydrolysis into thio- the same optical behaviour as (I). a(3'-dii'sobutyric acid, m.p. 151°. Et a-bromotsobutyr- IV. Lutz and Jirginson’s method (A., 1932, 720) ate and Na2S in EtOH-C6HG afford thio-aa'-ditso- of determining the configuration of a-OH-acids fails butyric acid, m.p. 142°, whilst similar treatment of with aldonic acids. Investigation of the optical (I) yields thio-pp'-diwobutyric acid, m.p. 115°. The rotatory changes occurring when the following acids assigned constitutions (loc. cit.) are thus confirmed. (as Na salts) are mixed with varying amounts of H. W. ^a.,Mo04 (I) and the solutions then treated with acid or Application of Raman spectrography to the alkali, shows th at trustworthy results are obtained only study of the allylic transformation and of cis- when the mol. ratio Na aldonate : (I) is 2 :1 : gluconic, trans isomerism of crotonyl derivatives. ( M l l e .) galactonic, talonic, mannonie, rhamnonic, a- (II) and B. G r e d y and L. P ia u x (Bull. Soe. chim., 1934, [v], 1, ?- (Ill) -fructoheptonic, 4-methylmannonic, arabonic, 1481— 1489).—Raman spectra prove the following: lyxonic, ribonic, and hamamelonic (IV). The results CH2:CH-CH2-CHO and Charon’s CH2:CH-CH2-CH2-OH f°r (II), (III), and (IV) confirm the constitutions (I) contain only a little cis-compound. Acetylation assigned from rotation measurements. of (I) and of CHs:CH*CHMe-OH (II) is completely V. ¿-Xyloketose (I) (A., 1934,173), aq. HCN, and a “ normal.” (I) with HBr and (II) with PBr3 give the little aq. NH3 at 0°—room temp, for 3 days give same mixture of iraw5-CH2!CH,CH2,CH2I}r (80%) [after hydrolysis with Ba(OH)2] a-hydroxymethyl-rf- and 10% each of the other two ingredients, which lyxonic acid (II) (phenylhydrazide, m.p. 155— 156°, with NaOAc in AcOH gives a mixture of about equal Md —32-7+0-7° in H20) and galactonic acid [which amounts of the acetates of (I) and (II), hydrolysed arises from eZ-lyxose, formed by the action of the NH3 “ normally ” by alkali to a corresponding mixture on (I)], purified through the Ca salts and separated of (I) and (II). R. S. C. as the phenylhydrazides. In the absence of NH3, (I) similarly affords (II) and a-hydroxymethyl-d-xylonic [Aldehyde of violet leaves.] E. S p a t h and F. acid (Ca salt; phenylhydrazide, m.p. 194— 195°, [<*]£? K e s z t l e r (Ber., 1934, 67, [B], 2099—2100).—A t56+7° in H20). Z-Arabinose (III) is boiled with reply to Walbaum et al. (this vol., 66). H. W. auhyd. C5H5N and the resulting mixture is crystall- Allyl change. Studies by the Raman effect. ■sed from Et0H+Et20, whereby the bulk of un A. K irrmajstn (Compt. rend., 1934, 1 9 9 , 1228— changed (III) is removed; treatment of the residue 1229).— Crotonaldehyde with PC15 gives a mixture 'nth CH^Ph-NPh-NHo gives some (Ill)-phenylbenzyl- (I) of Cl-compounds which cannot be separated by nyarazone. Subsequent treatment of the residual fractional distillation. (I) with NaOEt affords a- product with PhCHO in H20 and extraction with chloro-y-ethoxy-A°-butene, the spectrum of which 2^ affords an aq. solution of Z-araboketose, [a]” shows only one double linking. (I) gives two fractions, + 12'7 • This and HCN give a-hydroxymethyl-Z- b.p. 120— 123° and 124— 125°, each of which shows 198 BRITISH CHEMICAL ABSTRACTS.— A. the same lines (1666 and 1620 cm.-1) but of different Cu> steel or brass. The rate (k) of. alcoholysis of intensities. (I) is mainly the ¿rans-compound; very various COMe-CHR-COR' is measured by inter little of the cis-isomeride is formed. J. L. D. rupting the reaction before completion and determin Polymerisation of dihydroxyacetone. H. H. ing the amounts and ratio of the products formed; S t r a i n and W. H. D o r e (J. Amer. Chem. Soc., 1934, reactions are carried out in glass (in which k is < in 56, 2649—2650).—Unimol. CO(CH2-OH)2(I), m.p.72°, brass vessels). The effects of R and R ' on k and (A) polymerises completely to the bimol. form, m.p. are discussed. Some of the results are correlated ■with 78—81°, during 25—30 days at room temp.; the rate the polar effects of the substituent groups and the of polymerisation is determined by X-ray diffraction mechanism previously given (A., 1934, 759). H. B. patterns (II) and is independent of the radiation. Polymerides, m.p. 130— 133°, 230—260° (decomp.), Hydrogenation and hydrogenolysis of a y -d i and 230—250° (dccoinp.), obtained when (I) is kept keton es. J. M. S p r a g u e and H. A d k i n s (J. Amer. for many months, show definite (II). H. B. Chem. Soc., 1934, 56, 2669—2675).—Reduction [H2 (usually 1-6— 1-9 mois.) at 150—200 atm.; Preparation of ay-diketones by the Claisen Raney Ni; Èt20] of COR-CH^COR' (^4) at 125° and reaction. J. M. Sprague, L. J. Beckham, and COR-CHAlk-COR' (B) at 50—60° usually gives a H. Adkins (J. Amer. Chem. Soc., 1934, 56, 2665— good yield of the corresponding glycols. In several 2668).—The following COR-CHVCOR' are prepared eases fission (hydrogenolysis) of C’C (leading to, (in 50—70% yield) from COMeR, R'C02Et, and e.g., RCH O +C0R',CH2Alk and/or their reduction (usually) NaOEt (prepared in Et20 or xylene) in products) and C-0 (giving e.g., COR-CH2-CH,R' Pr^oO or PhMe (except when large excess of ester is and/or OH-CHR-CH2-CH2R') occurs. Definite con used), and purified by fractional distillation (Widmer clusions could not be reached regarding C-C fission column): CH2Ac-COPriS; CH„Ac-COBu>’ (I); and the enol content of (A) and (B). The order of CH,Ac-COBu0; CH2Ac-COEt; " CH2Ac-COPi-; facilitation (as determined by temp, required) of CH,Ac-COBua; CH2AcCOBu(sec.); hexahydro- C-C fission by various groups is : M e>Et>Pr^> benzoylacetylmethane; furoylacetylmethane; tetra- Buv > Ph, 2-furyl > OH > 10 > CH2-OH > -CHR;0H > hydrofuroylacetylmethane, b.p. 95—97°/8 mm. (from •COR. The relative labilities of the 2 C-C linkings in COMe2 and Et tetrahydrofuroate); CH2BzAc; (A) appear to bo the samo in alcoholysis, hydrolysis, 2 : 4 : 6-trimethylbenzoylacetylmethane, m.p. 46— or hydrogenolysis. 47°; benzoylfuroylmethane, m.p. 68°; p-phenyl- CH2Ac2 is thus reduced to pentane-pS-diol (80%) benzoylacetylmelhane, m.p. 156— 157° (from EtOAc and EtO H +PrW H ; CH2Ac-COPri gives (at 25°) and p-C0H¡Ph • COMe). CH2Ac2 is best prepared by EtOH, $-methylhexane-ye-diol (I) (73%), b.p. 123— using Na as condensing agent. COMe-CHNa-COR 124°/24 mm., and (probably) (3-mcthyl-As-hexen-y- and R'Hal in (usually) COMe2 or dioxan (cf. Weygand, one (9-6%), b.p. 135— 139° [semicarbazone, m.p. A., 1928, 643) give COMe-CHR'-COR; the following 180— 190° (decomp.)], whilst at 125°, (I) (60%) and are new : a-benzoyl-a.-acetyl-pentane, b.p. 156— 160°/10 COIVPr/3 (30%) result ; CH2Ac-COBuv affords (at 60°) mm., and -octane, b.p. 178— 183°/8 m m .; a-acetyl-a- EtOH, COMeBuy (5-4— 6-7%), ^-dimethyl-As-hexen- trimethylacetyl-propane, b.p. 77—78°/17 mm., and Y-one (16-3—62%), b.p. 153— 155° [oxidised (KMn04) -pentane, b.p. 113— 117°/11 m m .; a-acctyl- 0-liY, but increases rapidly above this. An empirical glucoside, sucrose, raffinose, and lajvulan.. Native relationship between the velocity of M and pa is cellulose (I) contains 0-282% of C02H (±1-4% ). The established. A. G. P. possibility that (I) adsorbs NaOH is excluded by the Preparation and enzymic fission of basic observations that (1 ) the results are independent of the temp, between 0° and 25°; at > 25° the data glycosides. II. B . H e l e e r ic h and F. P h il ip p (Annalen, 1934, 514, 228—233).—m-Cresol-^-d-gliicos- are influenced by evaporation of the H20 ; (2) ident ical results are obtained in presence or absence of ide tetra-acetate (I), in.p. 137— 139° (corr.),[a]D0 —19-61° in CHClg, obtained by the method previously de Humectol CA ; (3) identical results are obtained with (I) from cotton wool in fibrous form or as powder scribed (A ., 1933, 379) from w-cresol, glucose penta- after pptn. from CuO-NH or from cellose B crushed acetate, and p-CGH4Me-S03H at 100°, is brominated 3 (method: A., 1934, 282) to w-bromo-m-cresol-$-d- or as powder. Since the vals. obtained by the titra ghtcoside tetra-acetate, m.p. 122— 124° (corr.), [a]^° tion of (I) with AT/44:NaOH in presence of thymol- —20-4° in CHC13, which is converted (aq. EtOH-NH3; phthalein accord with those obtained conductometric- cf; loc. cit.) into m-aminomethylghenol-fi-d-glucoside ally, the hypothesis that the Na salt of (I) is decomp, (II), m.p. 196-5— 199° (corr!), [a]“0 -68-52° in aq. by excess of NaOH into celluloses containing less C02H cannot be maintained. In the direct titration AcOH (1 mol.). The Ac. derivative, m.p. 96—97° (corr.), OK -19-95° in CHC13, of (II) is hydrolysed only ash-free cellulose can be used. The electro dialysis of cellulose is described; the products contain (jY-NaOH in COMe2) to m-acelamidomethylphenol-$-d- glucoside (III), m.p. 176— 177° (corr.), [«]” -62-6° 0—0-6% of ash which does not influence the con ductometric process. H. W. in H20, whilst (I) is hydrolysed [MeOH-NaOMe (trace)] to m-cresol-fi-d-glucoside (IV), m.p. 183—184° Osmometric investigation of dilute solutions (corr.), [a]„ -69-7° in H ,0. m-Cresol-fi-d-galactoside of polymeric carbohydrates. VI. Mol. wt. of (V), m.p. 166— 168°, [a]l3 -44-3° in H20 , and its crystalline cellulose acetates. II. K. Hess and tetra-acetate, m.p. 81— 83°, [ajj,1 +2-7° in CHC13, are M. U lm a n n - (Ber., 1934, 67, [5], 2131—2145; cf. A., similarly prepared. (Ill) is hydrolysed (emulsin) 1934, 841).—Limit dextrin acetate I (I) is as resistant much more rapidly than the 0- and £>-isomerides to fractionation as the corresponding II (II) derivative (A., 1934, 282) and (II) (and its 0- and p-isomerides); (loc. cit.), which it resembles very closely in composi (IV) is hydrolysed more rapidly than (V) but less tion and rontgenographic behaviour, whilst differing rapidly than its o-isomeride (loc. cit.). H. B. somewhat in optical activity. Osmometric measure ments establish a step-wise degradation of (I) from Polysaccharides. XVIII. Constitution of even multiples of (C0)2 to (C6)2 dependent on the xylan. W. N. H a w o r t h , E. L. H ir s t , and E. concn., but the simpler forms persist at a higher Oliver (J.C.S., 1934,1917— 1923; cf. A., 1932, 44).— concn. in the case of (I) than of (II). The stepwise Xylan (I) (from esparto celluloses of different origin) transitions of (I) occur with measurable rapidity which on hydrolysis gives arabinose; on methylation and is greater than with (II). A further difference is subsequent hydrolysis it gives 2 : 3-dimethylxylopyr- found in the occurrence of the (C0)4 stage in the case anose (90%), 2 : 3 : 5-Z-arabofuranose (about %), 6 of (I), whereas with (II) (C0)2 appears to pass imme and a monomcthyLxylose (II). (I) therefore contains diately and reversibly into (C6)8. In contrast to (II), an Z-arabofuranose unit (^4) as a terminal group the electrolytic conductivity of (I) increases with attached to a chain of xylopyranose units (B) (one of dilution at concn. > 0-1 % and in this region *4 is associated with 18—20 of B). The nature of the solutions of (I) do not follow van’t Hoff’s law ; it is other terminal group, which is not C02H (cf. A., 1932, considered that at this dilution a complex of (I) and 934), is discussed with regard to the facts that the solvent dissociates into ions. In this respect (I) above cleavage products contain (II) but no tri- resembles cellobiose acetate. The behaviour of an methylxvlose, and that (I) is non-reducing. early fraction obtained in the purification of (II) is H. G. M. less clearly defined than that of (II) over the whole Crystalline erythrodextrin.— See this vol., 133. region of concn. in consequence of adherent impurities. Reaction of starches with proteins.— See this H. W. vol., 165. Acetylation of cellulose. D. K r u g e r , M. L u d t k e , and F. O b e r l i e s (Angew. Chem., 1934, 47, Determination of the carboxyl groups of 806—810).—When lower acetates of cellulose (I) cellulose b y con d u ctom etric titration. E. ( < 3Ac per C6H10O5) are prepared using feebly Schmidt, M. H e c k e r , W. J a n d e b e u r , and M. catalysed acetylating mixtures, all the chain mols. of Atterer [with W. Sim so n and R. S c h k e g g ] (Ber., (I) are equally acetylated. When a strongly catalysed 1934, 67, [jB], 2037—2049).— Cellulose is treated with mixture is used, the rate of reaction is fast compared an excess of NaOH in presence of Humectol and con- with the rate of diffusion into micelles, and the exposed ductometrically titrated with OTiV-acid. The graph chain mols. are preferentially acetylated j if the pro consists of 3 sections, the first representing the cess is interrupted before equilibrium is reached the neutralisation of the excess of NaOH, the second material is micro-heterogeneous. A. G. depicting the liberation of the cellulose acid from its anc^ third being due to the further Cellulose diacetate. I. S a k u r a d a and T. K i t a - addition of HC1. The validity of the process is estab b a t a k e (J. S o c . Chem. Ind. Japan, 1934, 37, 604— lished by comparative experiments with lauric, palm- 605b).— Cellulose 2 : 3-diacetate was prepared by pro- “ ic cholic, and anthraquinone-2-carboxylic acids and tecting the primary OH with •CPh3 from acetylation. with pentaerythritol, fi-glncosan, mannitol, a-methyl- Treatment with CPh3Cl showed that ^ of the free OH 202 BRITISH CHEMICAL ABSTRACTS.---- A. groups in commercial COMe2-sol. cellulose diacetate with resolidification) (block),' which with the appro were primary, and hence that Ac was equally easily priate aldehyde gives its dibenzylidene, decomp. eliminated from each of three positions 2, 3, and 6. > 360°, difurfurylidene, m.p. > 360°, and diiso- A. G. propyli.de.ne, decomp. 330° (block), derivatives. With Thioanhydrides of cellulosexantkic acid. 1 mol. of N2H4,H20 (II) gives its monohydrazide, S. N. D a n il o v and D . S. B rochxna (J. Gen. Chem. m.p. 179° (decomp. with resolidification), from which Russ., 1934, 4 , 995— 1002).—BzCl and Na cellulose- the mono-benzylidene, m.p. 229°, -anisylidene, m.p. xanthate (I) in aq. Na2C03 or C6Hq afford the thio- 229°, -piperonylidene, m.p. 254°, and -furfurylidene, anhydride of (I), which eliminates H2S in acid, and m.p. 247°, derivatives are obtained. (I) similarly regenerates (I) in alkaline solutions. R. T. affords its monohydrazide, decomp. 220°. With the Asymmetric nitrogen atom. LX. Optical appropriate NH2R in boiling aq. EtOH (II) gives a activity of ammonium salts as a means of monoamide, m.p. 2 1 1 °, and monomethylamide, m.p. detection of double decomposition in non 207-5° [hydrazide, m.p. 305° (benzylidene derivative, m.p. 335°)]. J.W.B. ionising solvents. E. W e d e k i n d (Ber., 1934, 67, [i?], 2007—2009).—The optical activity of Reaction of aliphatic diazo-compounds with ?-NPhMcPro(CH.,Ph)-NO.! in CHC13 (in which it is mercury salts. A. N. N e s m e j a n o v and G. S. P ovch optically stable when alone) gradually diminishes (J. Gen. Chem. Russ., 1934, 4 , 958—961).—Et diazo- after addition of an inactive NH4 halide. The rate acetate and HgCl2 yield CH,Cl’C02Et, N,,, and of decay of the optical activity of the corresponding Hg[-CCl(HgCl)-C02Et]2. R. T. inherently unstable halides is retarded by the addition Constitution of thiosemicarbazide compounds of nitrate to a labile limiting val. The occurrence of of nickel. K. A. J e n s e n (Z. anorg. Chem., 1934, an equilibrium active nitrate (optically stable)+ halide 2 2 1 , 11— 17).—The compounds Ni(COSN2H3)2, active halide (optically unstable)-f-nitrate is Ni(CS2N„H3)„ and [Ni(0Et-CS-N0H.)3](N03), (I) have supported by the concurrence of fall in [a] with been prepared from SH-CS-NH-NHj SH-CO-NH-NH2, diminution of halogen titre. Similar results are and OEt-CS-NH-NH2, respectively. The similarity obtained with active phenjdbenzylmethylallyl- of these to thiosemicarbazide compounds previously ammonium nitrate (I) and inactive NPhMe2EtI. obtained confirms the formula in which the metal The optical activity of (I) in CHCL is not affected by is bound to S and the N,H4 group. The aq. solution EtI. ‘ H. W. of (I) gives with NH3 the compound Ni(bEt'CS*N2H2)2; Action of secondary amines on epichloro- [Ni(SCN3H5)2]S04 has been obtained in two different hydrin. N. S. D r o z d o v and O. M. T s c h e r n t z o v modifications which may be cis- and /rans-isomerides. (J. Gen. Chem. Russ., 1934, 4 , 969—974).—Epichloro- M. S. B. hydrin (I) and aq. NHEt2 at 28—30° give diethyl- Thiosem icarbazide com pounds of bivalent aminoepihydrin (65% yield), b.p. 55—60°/15 mm., palladium and platinum. K. A. J e n s e n (Z. which when heated at 100° for 30 min. with MeOH- anorg. Chem., 1934, 2 2 1 , 6— 10).—The following NH3 gives 70% yields of NH2-CH2-CH(OH)-CH2-NEt2, compounds have been prepared : (M =Pd or Pt; b.p. 118—1230/15 mm. (I) and aq. NHMe2 at 30° y=C SN 3H5), [MTC12], [MT2]C1„ [MT2]S04, and afford a polymeride, charring at 210°, of dimethyl- M(CSN3H4)2. (P dr2]Cl2 and Pd(CSN3H4)2 have aminoepihydrin, whilst piperidine and (I) give differently coloured cis- and ¿rans-modifications. piperidinoepihydrin (70% yield), b.p. 86-5—88715 M. S. B. mm., from which y-amino-a-'N-pipcridino-$-hydroxy- Varying valency of platinum with respect to propane, b.p. 133°, is obtained as above. R. T. m ercaptanic radicals. V III.—See this vol., 182. Mercury alkyl derivatives. M. C. H a r t and Glutathione. Its reaction with alkali and H. P. A n d e r s e n (J. Amer. Chem. Soc., 1934, 56, some A- and S-derivatives. B. C. Sa u n d e r s 2752—2753).—The following are prepared from (Biochem. J „ 1934, 28, 1977— 1981).—The abnormal HgAlk-OH and the acid or phenol in EtOH : HgEt reaction of glutathione (I) and CH2PhCl in presence salts of -, m.p. 75—76°, and pt-, m.p. 177— 178°, of NaOH is due to oxidation of (I) and dismutation 0 -OH-C H -COoH, PhOH, m.p. 115— 116°, o£-C] Hv-OH, of the product to give (I) and higher oxidation products 6 4 0 m.p. 78—79°, m-C6H4Me-OH, m.p. 54-5—55-5°, together with H2S and S. (I) with 1 :2 :4-C6H3Cl(N02)2 m-CGH4(OH)„, m.p. 191— 192° (also formed from in alkaline solution gives cryst. S - 2 :4 -dinitrophenyl- «i-OH-C6H4-OAc), m-OH-C6H4-OMc, m.p. 72—173°, glutathione (II), m.p. 211°, which with 2-Cj0H7-SO2C1 p-hydroxy-, m.p. 139— 140°, and 4 : 4'-dihydroxv-, gives W?^phthalene-2-stdphotyyV-S-2: 4-dinitrophenyl- m.p. 201—203°, -diphenyl, ^-OH-CgHi'COjMe (?), glutathione, m.p. 158°. S- 2 :4 -Dinitrophenylcysteine, m.p. 85-5—86-5°, C(iH,I -OH, m.p. 169—170°, m.p. 148— 154°, is similarly prepared. C. G. A. 3 CGH2Br3-OH, m.p. 107°, C6H2C13-0H, m.p. 60—61°, Esters of ethylene-a£J-dioxamic acid and its 0- and i)-C6H4Bi-OH, both "m.p. 98— 99°, chloro- derivatives. J. v a n A l p h e n and (in part) H. d e n ci/c/ohcxyphenol, m.p. 79-5—80-5°, 5-chloro-2-hydroxy- O t t e r (Rec. trav. chim., 1934, 53, 1159— 1166).— diphenyl, m.p. 10 1— 102°, vanillin, m.p. 100—101°, Dropwise addition of (*CH2\NTH2)2 hydrate to R 2C20 4 3-nitro-jJ-cresol, m.p. 89— 90°, 0-, m.p. 76—77”, (R=M e or Et) in abs. EtOH affords a starch-like and p., m.p. 122— 123°, -M V C 6H4-OH, clilorothymol, substance (not ethvleneoxamide) and Me2 (I), m.p. m.p. 81— 82°, o-NH2-C6H4-CO,H, m.p. 81— 82°, 168°, or Et2 (II), m.p. 129°, ethylene-afi-dioxamate j)-KH2,CGH4,S03H, 6-chloro-m-cresol, m.p. 77-5—78-5°, (CO,,R-CO-NH-CH2-)2, converted bv N2H4,H ,0 in 0-, m.p. S3—84°, and p-, m.p. 108°, -C^Cl'OH , boiling EtOH into the dihydmzide, m.p. 295° (decomp. phenolphthalein, m.p. 198— 199°, o-cresolsulphone- ORGANIC CHEMISTRY. 203 phthalein, m.p. 128— 131°, plienolsulphonephthalein, Fulvenes in ionone series. E. P. K o h l e r and m.p. 118—121°, and thymolsulphonephthalein, m.p. J. K a b l e (J. Amer. Chem. Soc., 1934, 5 6 , 2756— 145—155°; HgMe salts of m-CGH1(0H)2, 2757).—c?/cioPentadienc (I) and (5-ionone in MeOH- 0-0H‘C6H4*C0 2H, m.p. 119— 120°, and m-cresol NaOMe give 2 -(y-cyc\opentadienylidene-/\a-bute7iyl)- m.p. 84—86°; HgPr salts of ra-CGH4(OH)2, m.p. 1:3: 2-trimethyl-k1 -cyc\ohexene (II), b.p. I l l — 113°/ 161—162°, 0-0 H-CGH4-C0 2H, m.p. 75°, and m- 0-5 mm. (cf. Willstaedt, A., 1934, 641), which absorbs cresol, m.p. 61— 62°; HgBu salts of m-C6H4(OH)2, 10 H on complete reduction (H2, P t02, EtOH) and is m.p. 148°, o-OH-CgH4'CO,H, m.p. 51—52°, and oxidised (03 in CC14) to geronic acid. a-Ionone and m-cresol; IIg amyl salts of m-CGH4(OH)2, m.p. (I) similarly afford G-(y-cycloj)cntadienylidene-Arl- 132-5—133-5°, and 0-0 H-CGH4-C0 2H, m.p. 4 6 -^ 7 °; butenyl)-! : 5 : 5-trimethyl-A1-cyclohexene (III), b.p. Hg hexyl salt of ?«-CGH4(OH)2, m.p. 128— 129°. 107— 109°/5 mm., which also absorbs 10 H. (II) and Few of the salts are bactericidal (towards S. aureus) ; (III), which are orange-coloured oils, are regenerated the bacteriostatic properties are quite high (variation when piperidine solutions of their colourless H2- of R and R ' in HgR-OR' has a very limited influence). derivatives are shaken with air. 0-Ionone and (I) H. B. givo the red K-c.yc\opentadienylidene-%-dimethyl-6>0 - Conversion of open-chain molecules into cyclic undecatriene (IV), b.p. 139— 141°/0-5 mm., which also compounds. E. P u x e d d u (Rend. Seminar Fac. affords a colourless dihydro-derivative and absorbs Sci. Cagliari, 1933, 3 , 61— 63; Chem. Zentr., 1934, 12 H on complete reduction. (II)— (IV) give blue ii, 1437).—Theoretical. H. N. R. colours with SbCI3 and undergo ready autoxidation; cryst. adducts could not be obtained with maleic Ring closure and radical formation. VI. anhydride. H. B. 1 :1 :2 :2-Tetraphenyleyciopropane. G . W i t t i g and B. O b e rm a n n (Ber., 1934, 6 7 , [5], 2053—2060; Internal energy relationships among carbo- cf. A., 1933, 944).— OH-CPh2-CH2Bz is converted cyclic compounds. II. Stability and reactivity by MgPhBr into COPh2 and COPhMe (whence of cyclic polyolefines. O. S c h m id t (Ber., 1934, CPhj-OH and CPh2Me-OH, respectively). The mol. 6 7 , [5], 2078—2080; cf. this vol., 73).— On the basis is ruptured by LiPh at 15—20°, whereas at —80° of the Heitlei-London theory it is shown that C6He 'ttyy-letra'phenylpropane-oiy-diol (I), m.p. 112— 113-5°, is the first cyclic define [CHICH],, capable of existenco is produced. (I) is transformed by MeOH-HCl at and also the most stable, since the electron ring has room temp, into a.y-dimethoxy-a.iyy-tetraphenylpropane, the greatest possible distance from the outer C ring. m.p. 174—175°, converted by K-Na in dioxan into H. W. 'xy- C6C16 (I) is treated with F2 in CC14 in a glass apparatus d 1-5, gives 4-chloro-5-nitro-o-xylene (A., 1891, 921; (loc. cit.) first at 0° and then at room temp., the pro 1934, 644) and a solid, m.p. 111°. Nitration of (III) duct is freed (vac. distillation) from (I), then treated gives 3 : 4-dichloro-5 : 6-dinitro-o-xylene, m.p. 172°. with F2 (no solvent) in a Cu vessel (loc. cit.) at 0°, and H. G. Mi finally fractionated. When emulsions of the fractions, Highly-arylated aromatic compounds. IV. b.p. 135— 160°/1 mm, and 100— 115°/7 mm., with Tetraphenylbenzenes. W. Dilthey and G. Hur- H20 are kept in the cold, hexachlorotetrajl%iorocye\o- t i g (Ber., 1934, 6 7 , [£], 2004—2007; cf. A., 1934, hexene, m.p. 113—114°, and hexachlarohexafluorocyclo- 641; this vol., 213).—4 : 5-Diphenylc?/c£opentonolone hexane, m.p. 94—96°, respectively, are obtained. is converted by tolane at 275° into a greatly resinified H. B. mass from which 1:2:4 : 5-tetraphenylbenzene, m.p. Vapour-phase hydrolysis.—See this vol., 172. 262—263°, is isolated in small amount. It is also obtained from 2 :3 : 5-triphenylcÿcZopentadienone and Nitration of alkylbenzenes. III. Orient CH-CPh and is identical with the “ hexaphenylbenz- ation of dinitro-p-fert.-butyltoluene. 0. L. cne ” of Durand et al. (A., 1931, 207). COMo-CHJPh B r a d y and J. K. L ah eri (J.C.S., 1934, 1954— 1957; and benzil in MeOH-KOH afford 2 : 3 : 4-triphenyl- cf. A., 1934, 286).—The orientation of 2 : 6-dinitro- cyclopent&nolone (I), m;p. 165°, transformed by 4-fert.-butyltoluene (I) [obtained by nitration of CH-CPh into 1 : 2 : 3 : 4-tetraphenylbenzene, m.p. 2}-ferf.-butyltolucne (cf. A., 1897, i, 514; 1899, i, 424; 190— 191°, obtained also from (I) and CPh':C-COaH. 1917, i, 34)] is established by the following reactions. (I) and tolane at 280° afford CeHPh5, m.p. 251° (corr.). (I) is reduced by (NH4)2S in boiling EtOH to -nitro- 6 TetraphenylcycZopentadicnone and tolane at 225— 2 -amuwA-tei't.-butyltoiucne [hydrochloride (II), m.p. 315° give C Ph6, m.p. 426°, which can readily be 210° (decomp!); Ac derivative, m.p. 138— 139°]. 6 halogcnated, stffphonàted, and hexanitrated. The (II), by the diazo-reaction, gives 2-nitro-4-iert.-butyl- corresponding hexa-amine can be diazotised. toluene (III) (A., 1924, i, 1176) [reduced (Sn-HCl) to H. W. 2-amino-4-tert.-butyltoluene] and G-nitro-2-hydroxyA- Phenomena of isomérisation in the cracking tesrt.-butyltpjuene, m.p. 128°. (Ill) is oxidised (AcOH- of decahydronaphthalene with aluminium Ac20 -H 2S04-C r03) below 10° to an aldehyde diacetate, chloride. N. D. Z e l i n s k i and M. B. T u ro v a - hydrolysed to 'l-nitroA-tert.-butylbenzaldehyde (2:4- P o l j a k (J. Appl. Chem. Russ., 1934, 7 , 753—756).— dinitrophenylhydrazone, m.p. 228°), obtained as a On heating with A1C1 at 175—210° cw-decahydro- semi-solid mass which gave the Baeyer-Drewson 3 indigo reaction. (II) is converted (Sandmeyer) into naphthalene is transformed into the ¿raws-isomeride, and this into dimethyldicÿcZopentane ; at the same G-nitro-2-cyano-4:-tei't.-butylloluene, m.p. 83°, hydro time cyclo-pentane and -hexane hydrocarbons are lysed to 6-nitro-4:-tevt.-biityltoluene-2-carboxylic acid, formed. R. T. m.p; 219°, oxidised [HN03 (3 c.c., d l-5)-H20 (12c.c.) at 200° during 8 hr.] to 5-nitro-tert.-butylbenzene- Nitration of 2-bromonaphthalene. J. S a l k ix d 3 : i-dicarboxylic acid, m.p. 365° (decomp.), which and F. Filtnov (J. Gen. Chem. Russ., 1934, 4, 979— forms an anhydride, m.p. 147— 149°, insol. in cold 981).—2-Bromo-l-nitro-, m.p. 110— 111°, and -l-nitro- 2Af-Na2C03. H. G. M. naphthalene are obtained by nitrating 2-C10H-Br. D ichloro-o-xylenes. II. L. E. H inkel, E. E. R. T. Ayling, and T. M. W alters (J.C.S., 1934, 1946— Fractionation and purification of organic sub 1948).—3 : 6-Dichloro-o-xylene (I), m.p. 29°, b.p. stances by chromatographic adsorption. IV. 234°/760 mm. [from 6-chloro-o-3-xylidine (A., 1934, Polycyclic aromatic hydrocarbons. A. W in ter- 644)], is not identical with the compound, m.p. 68°, s t e in and K. Sc h o n . V . Anthracene, chrysene, obtained from the chlorination of o-xyleho (A., 192S, and pyrene. A. W in t e r s t e in , R. Sc h ô n , and H. 995, 1238). Chlorination of (I) gives 3 : 4 : 5 : 6- V e t t e r . VI. 1 :2-Benzpyrene. A . W in ter stein tetrachloro-o-xylene, m.p. 226°. 3 : 6-Dichloro-i-nitro- and H. V e t t e r (Z. physiol. Chem., 1934, 230, 146— o-xylene, m.p. S4° [from (I); also from 6-chloro-4- 15S, 158— 169, 169— 174).— IV . The following pairs nitro-o-3-xylidine (A., 1934, 644)], is reduced to the of hydrocarbons are separable using A120 3 (activated) corresponding amine (Ac derivative, m.p. 146°). as adsorbent : anthracene (I)-C10H8 (not adsorbed) ; 3 : G-Dichloro-4 : 5-dinitro-o-xylene, m.p. 174°, is-pre (I)-chrysenc (II) ; (I)-phenanthrene (III) ; (I)-pyrene pared from (I) and HNO:!, and is reduced to the (IV); (III)-(IV); (II)-(IV) ; (IIj-1 : 2-benzpyrene corresponding diamine (phenazine derivative, m.p. (V); perylene-(V). Mixtures of C10H8, (I), and 2:3- above 250°). (I) with Br gives 3 : 6-dichloro-4 : 5- benzanthracone, and of 1 : 2 : 5 : 6-dibenz- (VI), 1: 2- dibromo-o-xylene, m.p. 23S°. 4 : 5-Diehloro-o-xylene benz-5 : 6-2' : 3'-naphth- [prepared (cf. Cook, A., 1931, (II), m.p. 76° (cf. A., 1928, 995), is synthesised from 612) from anthracene-2-carboxyl chloride and 2- 1:2:5: 4-C6H,Me2ChNH2 (A., 1934, 644) and affords C10H,Mc (Friedel-Crafts), pyrolysis of the resulting 4 : 5-dichloro-3 : G-dibromo-o-xylene, m.p. 232°. 4 : 5- ketone, and adsorption on A120 3], and 1 : 2 : 5 : 6-di- Dichloro-o-3-xylidine (A., 1934, 644) gives 4:5- 2' : 3'-naphth-anthracenes are similarly separable. dichloro-3-bromo-o-xylene, m.p. 1 1 1 ° (lit. 90°). Inspection of the chromatograms in ultra-violet light Chlorination of 3-chloro-o-xvlene (from o-xylidine) shows (usually) varying coloured zones. The deeply gives 3 : 4-dichloro-o-xylene (III) [cf. A., 192S, 995; coloured hydrocarbons are most r e a d i ly adsorbed; also obtained from 3-chloro-o-4-xylidine (A., 1934, thus, the yellow 1 : 2 : 6 : 7-dibenzanthracene (VII) is 644)]. Chlorination of 4-cliloro-o-xylene (IV), f.p. adsorbed more readily than the colourless (VI). The -6-25°, b.p. 1947755 mm. [lit, 191-5° (corr.) and 195°] mixture of (VII) and 1:2:3 : 4-dibenz- and 1:2-1' :2’- (from o-4-xylidine), gives (II). (IV) with H N 03, naphth-anthracene obtained from phenanthrene and ORGANIC CHEMISTRY. 205 o-CgH^Me'COCl with subsequent pyrolysis (Clar, A., [Di-radical formula of rubene and constitution 1929, 922), is readily separable; so is the mixture of of its dissociable peroxide.] C. D u f r a i s s e (Ber„ (VII) and 1 : 2-2': 3'-naphthanthracene, m.p. 255— 1934, 6 7 , [B], 2018; cf. A., 1934, 882).—A question 257° (lit. 265°), formed by the method of Clar et al. of priority (cf. Schonberg, ibid., 997). H. W. (ibid., 689) from £>-C0H4(COCl)2 and o-C6H4Mo*MgBr. Triphenylmethanes with linked benzene rings. 1 :2-Benz-5 : 6-2': 3'- and -6 : 7-1': 2'-naphthanthra- VIII. Reduction products of trimethylenetri- cenes could not be separated, but the closely related phenylmethane triketone. R. W e is s and F. anthrodianthrene and awiidrperidibenzcorbnene are M u l l e r (Monatsh., 1934, 6 5 , 129— 136).—The blue separable. triketonc C22H 10O3 (I) (A., 1925, i, 560) exists in its V (cf. A., 1934, 643). Adsorption of a “ benzine ”anthranol form, since with ^-C0H4Me-SO2Cl and boil solution of technical anthracene (I) on activated ing C5H5N it gives a p-loluencsulphonyl derivative, A120 3 gives 3 well-defined zones (visible only in ultra decomp. 220° [hydrolysed by KOH-EtOH to (I)]. violet light), from which by extraction with Et20 Reduction of (I) with red P-H I (d 1-7) affords a and repetition of the process pure (I), m.p. 219° brown, KOH-sol. (0 //)3-derivative, C22H12<14)0 3 + (corr.; Berl), naphthacene (2 : 3-benzanthracene) (II), AcOH and -(-MeOH (II) (Ac.j derivative, turns blue m.p. 337° (corr.), and carbazole are isolated; the at 285°), and the hydrocarbon (III), m.p. 182°. With filtrate contains varying amounts [according to purity of (I)] of paraffin and C10H 8 derivatives. The blue fluorescence of pure (I) is almost inhibited by0-00001% and prevented by 0-000033% of (II). Small amounts of (II), 1 : 2-benzcarbazole, and a S-compound are similarly separated from chrysene (III); pure (III), m.p. 255—256° (corr.; Berl), is obtained in only 10— 20% yield. Pyrene is shown to contain (II), 1:2: 6 :7- dibenzanthracene, 2 : 3-1': 2'-naphthanthracene (IV), and dibenzcoumarone (2 : 3-benzdiphenylene oxide). Crude picene contains (II), (IV), and (probably) 1 : 2- Zn dust-IV-KOH (02 excluded) and subsequent benz benzpyrenc and 1:2-benz-6:7-l':2'-naphthanthracene. oylation (II) affords a Bz2 derivative (IV), C36H22Ot, VI. 1 : 2-Benzpyrene (I), m.p. 177° (corr.; Berl) decomp. 200°. In the prep, of di-o-toiylphthalide [quinone, m.p. 292—293° (corr.; Berl) (cf. Cook et al., (be. cit.) is obtained a second modification, m.p. 176°, A., 1933, 601)], is prepared by dehydrogenation (Se also reduced to C02H-C6H4-CH(CGH4Me)2, identical at 320—340°) of 4'-keto-l': 2 ': 3 ': 4'-tetrahydro-l: 2- with a specimen obtained by similar reduction of the benzpyrene, and purified by adsorption on A1,03+ form, m.p. 128°. J. W. B. A1,03-C (whereby a little 4'-hydroxy-l : 2-benzpyrene, m.p. 180°, is separated). (I) is carcinogenic. Addi Action of sodiomalonic ester on diphenylthio- tion of (I) (in COMe2) to hot aq. 20% Na deoxycholate carbamide and carbodiphenylimide. V. E. gives a solution containing 2 mg. of (I) per c.e. Tischtschenko and 1ST. V. K o s c h k in (J. Gen. Chem. Absorption curves for (I) in various solvents are Russ., 1934, 4 , 1021— 1026).— CS(NHPh)2 (I) or given. H. B. C(:NPh)2 (II) and CHNa(C02Et)2 (III) in CGH„ yield tho substance (IV) NPh!C(NHPh)’CH(C02Et)2, m.p. Synthesis of alkylphenanthrenes. VIII. At 166— 167°, giving on hydrolysis with NaOH-EtOH tempted synthesis of 4 :5-dimethylphenanthrene. diphenylacetamidine, NPhlCMe-jSfHPh, m.p. 131— 132°. The reaction is probably (I) — y (II)+H,,S ; R. B. H a w o r t h and G. Sh e l d r ic k (J.C.S., 1934, 1950—1952).— 8-Methyl-2-naphthyl CH2Br ketono (II) + (III)—^(IV). R. T. [from the Me ketone (I) and Br in CHC13] and Reactions of unsaturated compounds. III. CHNa(C0 2Et)2 in C6H 6 give, after hydrolysis with Addition of arylamines to butadiene. W. J. JleQH-KOH and decomp, of the resulting acid at Hickinbottom (J.C.S., 1934, 1981— 1984; cf. A., 180°, $-(8 -methyl-2 -naphthoi/l)2n'opionic acid, m.p. 1932, 1242; 1934, 644).—Butadiene (I) with excess 113-115° (Me ester, m.p. 87— 88°, b.p. 185— 190°/ of NH2Ph and NH2Ph,HCl (or HBr) at 220—260° 0-5 mm.), which is reduced (Clemmensen) to y-(8- during 4—25 hr. affords mainly a-p-aminophenyl- inethyl-2-naphthyl)butyric acid (Me ester, b.p. 170— bP-butene (II), b.p. 135—136°/24 mm. (hydrochloride ; l75°/0*3 mm.). This is cyclised to a product, b.p. suljphate), tho Ac derivative of which, m.p. 98—99°, 180—19070-5 mm., considered to be impure l-Jceto- is converted by Br in CHC13 into {iy-dibromo-a-i>- 5-methyl-l : 2 : 3 : i-tctrahydroanthracene (II), which on acetamidophenylbutane, m.p. 127— 128°, reduced (H2- treatment with MgMel followed by dohydration and Pd) to i?-CGH4Butt-NHAc (which indicates that aryl is dehydrogenation (Se at 280—300°) gives 1 : 5-di- attached to the terminal C of the butenyl group), nethylanthraeene, m.p. 139— 140° [jn crate, m.p. 166— and oxidised (KMn04) to MeCHO (which indicates a 167°; quinone, m.p. 190°, which does not react with Py double linking) and p-NH2-C6H4‘C02H. The di o-C6H4(NH2)2]. The formation of (II), instead of a azonium derivative of (II) with (3-C10H--OH gives an pnenanthreno derivative, is explained on steric azo-derivative, m.p. 100— 101°, and a-anilino-As- grounds. (I) was prepared by Clemmensen reduction butene (III), purified through its nitrosoamine. The °* P-p-anisoylpropionic acid, followed by cyelisation Ac derivative, b.p. 165— 168°/28 mm., of (III) reacts and dehydrogenation to 7-methoxy-I-methylnaphthal- slowly with Br and. H2 and is oxidised (KMn04) to ; the OMe group then successively converted into MeCHO. NHPh2 and 2 : 3-dimethylindole are also NH2, CN, and COMe. H. G. M. isolated. (I) with excess of j?-CGH4Me‘NH and 206 BRITISH CHEMICAL ABSTRACTS.— A. p - C 6H4Me -NH2, HC1 (or HBr) affords u-'p-toluidino-AP- Monoethyl-o-toluidine and rhodamines ob butenc, b.p. 135°/33 mm. [platinickloride, m.p. 200— tained therefrom. H. E. Fierz-David and J. P. 201° (decomp.); nitrosoamine], and k-butenylamino- R u f e n e r (Helv. Chim. Acta, 1934,1 7 , 1452— 1459).— 3-butenyltoluene, b.p. 185°/30 mm. (nitrosoamine), and o-C6H4Me*NH2 (I) (380 g.), EtOH (195 g.=20% a small amount of di-p-tolylamine and 2:3: 5-tri- excess), and conc. H2S04 (57 g.) are heated for 12 hr. methylindole (picrate, m.p. 188— 189°). Tho reactions at 200°. The bases are liberated by NaOH and described aro distinct from those of the Diels-Adler distilled through a Frey column, whereby 0- diene syntheses because a catalyst is necessary to C6H4Me-NHEt (II), b.p. 95-5°/10 mm., is obtained in bring about reaction. The formation of indoles may 66% yield. The preliminary fractions contain (I) be due to a Py-reaction of (I). J. L. D. and (II) whereas o-CGH4Me-NEt2 (III) is not produced. d of mixtures of (I) and (II) in varied proportion has Preparation of nitrogen-substituted sulphon-o- been determined. The separation of (II) from toluidides. G. H. Y o u n g (J. Amer. Chem. Soc., (III) is not readily effected through the hydrochlorides, 1934, 56, 2783—2784).—The following JV-alkyl deriv the sulphonic acids, or their salts. The solubilities atives of ;p-toluenesulphon-o-toluidide are described of the sulphonic acids and their Na and K salts is (cf. A., 1934, 1342): Me, m.p. 87— 87-5° (lit. 119— recorded for 2 : 1 : 4-R-C6H3Me,S03H, where R = 120°), Pr°, m.p. 72—72-5°, Prt>, m.p. 92—92-5°, Bu°, NHo, NHMe, NMe2, NHEt, NEt2. Rhodamine-2?, -G, m.p. 82-5—83°, Bvfi, m.p. 106— 106-5°, and 11-, m.p. and -GP have been transformed into their Me, Et, 80—80-5°, and iso-, m.p. 95—95-5°, -amyl. H. B. Pr1, Pr&, Bua, BnP, amyl, hexyl, octyl, benzyl, and Action of titanium tetrachloride on organic cycloliexyl esters. H. W. nitrogen com pounds.—See this vol., 180. Addition of methyl alcohol to methyl o-nitro- p-Bromophenylthiocarbimide as a reagent for styrylcarbamate with formation of methyl a(?)- the identification of aromatic amines. P. P. T. methoxy-p-o-nitrophenylethylcarbamate. F. Sah, S. H. C h ia n g , and H. H. L e i (J. Chinese Chem. S c h e n c k (Ber., 1934, 6 7 , [2?], 2035—2036).—The Soc., 1934, 2 , 225—228; cf. A., 1934, 997).-^»- protracted action of NaOCl on o-nitrophenylcinnam- C6H4Br-NH2 with boiling CS2-EtOH during 3—4 hr. amide in M e0H-H20 leads to the formation of Me gives dibromodiphenylthiocarbamide, decomposed by a( ?)-methoxy-$-o-nitrophenyleihylcarbamate, m.p. 12 1°, boiling Ac20 to ^-bromophenylthiocarbimide (I), converted by dll. H2S04 into o-nitrophenylacetalde- which gives sharply melting derivatives with many hyde. The ester is considered to react in its tautomeric amines. The -p-bromophenylthiocarbamides from the form, N 02-C6H4-CH,-CH:N-C02Et. H. W. following amines are described : NH2Ph, m.p. 150— Preparation of arylcarbim ides. D. V. X. 151°; p-bromo-, m.p. 186— 187°, £>-chloro-, m.p. 189— H a r d y (J.C.S., 1934, 2011).—_p-Xenylamine (I) 190°, 0-, m.p. 60—61°, m-, m.p. 163— 164°, and in boiling PhMe with C0C12 affords (cf. A., 1931, 834) ^-nitro-aniline, m.p. 164— 165°; 0-, m.p. 147— 148°, p-xenylcarbimide (II) and «-di-p-xenylcarbamide m-, m.p. 147— 148°, and p-CGH4Me-NH2> m.p. 174— [by interaction of (I) and (II)], but the hydrochloride 175°; m-bromo-p-toluidine, m.p. 158— 159°; a-, m.p. of (I) with COC1, gives only (II). Similarly, 165— 166°, and p-C10H7’NH2, m.p. 175— 176°; 0-, NH2Ph,HCl affords only PhNCO. J. L . I). m.p. 131— 132°, and n-aininophenol, m.p. 163— 164°. J. L. D. Manufacture of derivatives of diazo-com- Identification of metanilic acid and sulphanilic pounds.—See B., 1935, 14. acid. R. B. F o r st e r (J.S.C.I., 1934, 53, 358t).— Action of chlorine, bromine, and iodine mono- These acids can be identified by conversion into the chloride on aryl azoacetoacetates and related corresponding chlorobenzenesulphonic acid (diazo- com pounds. F. D. C h a t t a w a y and R. D. A sh reaction), arylamine salts of which have sharp m.p. w o r t h (J.C.S., 1934, 1985— 1988).—The following m-CpHjCl-SOyNa with NH2Ph,HCl in H20 gives the are described (cf. A., 1933, 705; 1934, 182): Et aniline salt, m.p. 206—207°. Similarly prepared, the 2: ‘i-dinitrobenzeneazoacetoacetate (I), m.p. 10S°, 2:4- j)-toluidine, -p-chloroaniline, m-xylidine, a.-naphthyl- dinitrobenzeneazo-benzoyl- (II), m.p. 203°, and -acetyl- amine, and benzidine salts have m.p. 199—200°, acetone (III), m.p. 176°, Et a.-bromo- (IV), m.p. 122°, 195—196°, 151— 152°, 207—208°, and > 320° and a.-amino-glyoxylate-‘l : i-dinitrophenylhydrazone. (decomp.), respectively. NH2Ph, m.p. 222—223°, m.p. 169°. (I) with Br in AcOH-NaOAc at room temp, p-C6H4Mo-NH2, m.p. 207—209°, 2>-C6H4Cl-NH2, m.p. gives (IV), but in boiling AcOH it affords Et 2:4- 210—211°, and benzidine salts, m.p. >320° (decomp.), dinitr6benzeneazo-y-bromoacetoacetate, m.p. 141°. Cl2 of -jp-CgHjCl-SOjH are described. J. L. D. is without action 011 (I) in cold or boiling AcOH or CHCI3, but in cold AcOH-NaOAc, Cl2 gives Et m-Toluidine-6-sulphonic acid. M. S. S h a h , ix-chloroglyoxylate-2 : ■i-dinilrophenylhydrazone, m.p. C. T. B h a t t , and D. D. K a n g a (J.C.S., 1934, 2010— 2011).— m-C,;H,Me-NH2 with oleum at 125° gives 120°, and in dry CHC13 it affords Et 2 :4 -dinitro- only m-toluidinc-6-sulphonic acid, the diazonium benzeneazo-y-chloroacetoacetate (V), m.p. 143°. Simi derivative of which with boiling H20 gives m-cresol-6- larly, (II) and (III) with Cl2 in cold AcOH-NaOAc sulphonic acid (cf. A., 1888, 280), identified by several give oi-ch loroph enylylyoxa I -, m.p. 177°, and u-cldoro- derivatives (A., 1933, 1292). J. L. I). x-ketopropaldehyde-2 : i-dinitrophenylhydrazone,, m.p. 159°, respective^. The action of IC1 depends partly Additive products of benzylamine and phenyl- on the nature of the substituents in the Ph nucleus. hydrazine with the nickel salts of substituted Et 2:4:6-tribromo-, 2:4-dibromo-, ^j-bromo-, p-nitro-, acetic acids.—See this vol., 182. or o-nitro-benzeneazoacetoacetate (which are not ORGANIC CHEMISTRY. 207 easily aeetylated) with ICI in AcOH afford Et 2:4:6- functions as an anionoid reagent (cf. A., 1929, 1313)], Iribramo-, m.p. 104°, 2 :4 -dibromo-, m.p. 127°, p- and with EtOBz it affords C02, Et diphenyl-4- (I) bromo-, m.p. 114°, p-nitro-, m.p. 154°, and o-nilro- and -3-carboxylate, which accords with the less definite benzeneazo-’y-iodoacctoacetate, m.p. 128°, respectively, distinction between the o- and p-directive influence of which also result when the corresponding y-Cl- or C02Et, as compared with the almost exclusively -Br-compounds react with KI. The y-I-compounds m-directing N 02. Na benzenediazoate with EtOBz with KOAc afford pyrazoles (cf. A., 1932, 1125; gives mainly (I), but also smaller amounts of the 3- 1933, 1156). (I) with ICI in cold AcOH gives (V), and 2-C02Et-compounds (cf. A., 1924, i, 1295). which is unchanged by excess of ICI. Et benzene- Benzeneazotriphenylmethane (II) with boiling C6H6 azoacetoacetate with ICI in AcOH gives Et oi-chloro- gives CHPh3, Ph2, and CPh4; and again (II) with glyoxylate-p-iodophenylhydrazone, m.p. 176°, which PhCl gives CPh4, CHPh3, and 4-chlorodiphenyl, which is reduced (Sn-HCl) to ;p-C6H4IrNH2. Et ^-chloro- indicates that decomp, of (II) involves the formation benzeneazoacetoacetate similarly affords Et a-chloro- of free Pli radicals (cf. A., 1922, i, 772) which can glyoxylate-p-chlorophcnylhydrazone (cf. A., 1932, react with a neutral aromatic compound (this vol., 1125). a-Ketopropaldehyde-o-nitrophenylhydrazone 78). (II) with PhNO, at 100° gives some CHPh3, a with ICI in AcOH at 40° gives fi-iodo-a-ketopropcdde- phenol, and a substance, m.p. 240—-241°. J. L. D. hyde-o-nitrophenylhydrazone, m.p. 174°. Similarly, Azides. II. 3 :5-Dinitrobenzazide as a re the 2 :4 : 6-tribromophenylhydrazone gives co-chloro-a- agent for the identification of phenols. P. P. T. ketopropaldchyde-2 : 4 : 6-tribromophenylhydrazone (cf. A., 1934, 998). The arylazo-acetyl- and -benzoyl- Sah and T. S. Ma (J. Chinese Chem. Soc., 1934, 2 , acetones do not react with ICI. o-Bromo-a-keto- 229—233; cf. A., 1934, 997).— 3 : 5-Dinitrobenzazide propaklehyde-o-nitrophenylhydrazone with K I in (I) when heated in PhMe affords 3 : 5-dinitrophenyl- boiling EtOH gives the «-/-compound, m.p. 189°. carbiviide, m.p. 92—93°. (I) with many phenols in boiling PhMe gives aryl 3 : o-diniirophenylurethanes Similarly prepared are (a-iodo-a-ketopropaldehyde-2 :4- (II). The following phenols were tested [m.p. of (II) dibromo-, m.p. 169°, and -2:4:6-tribroino-phenylhydr- in parentheses]: PhOH (192— 193°); o- (140— 142°), azone (VI), m.p. 150°. fSpo-Tribromo-a-ketopropalde- m- (188—189°), and p-nitro- (200—201°), o- (182— hyde-2: 4 : 6-tribromophenylhydrazone with KI in AcOH at 100° gives (VI), which is similarly obtained 183°) and p-chloro- (197— 19S°), o- (253—254°) and from the $y-dibromo-analogue, m.p. 134° (prepared by j?-amino-phenol (266—267°); o- (205—206°), m- (209— 210°), and p -c r e s o l (184— 185°); thymol (154— 155°); brominating a-ketopropaldehyde-2 :4 : 6-tribromo a- (228—229°) and P-C H7-OH (238—239°); >cresol- phenylhydrazone). The ^-acetates of Et 2:4:6-tri- 10 o-aldehyde (227—228°); Me (180— 181°), Et (145— bromo- (VII) and 2:4:6-trichloro-benzeneazoaceto- acetate (VIII) (cf. A., 1932, 377) with excess of Br 147°), and benzyl salicylate (172— 173°). J. L. D. in boiling AcOH give Et 2:4:6-tribromo-, m.p. 178°, Bromination of benzoates of phenolic com and 2 :4 : Q-trichloro-benzene,azo-yy-dibromoacetoacetate- pounds. L. C. R a x fo r d and J. E. Milbery (J N-acefate, m.p. 141°, respectively, identical with the Amer. Chem. Soc., 1934, 5 6 , 2727—2729).—During Ac derivatives of Et 2:4:6-tribromo- and 2:4:6-tri- bromination of ArOBz [Ar=Ph,C6H4Me,j)-CHO-Cr,H1, chloro-benzeneazo-yy-dibromoacetoacetate. N- Acét 2 : 4-(OMe)(CHO)C6H3,]) Br enters the ^-position (if ylation of (VII) and (VIII) prevents the replace available) of Ar; o-substitution occurs less readily, ment of Ac by Br (see above). J. L. D. whilst m-substitution was not found (cf. Claus and Hirsch, A., 1889, 389). In many cases, the HBr The azochromophore. VI. J. S. P. B lu m - evolved caused hydrolysis to BzOH and ArOH (sub bergeu (Chem. Weekblad, 1935, 3 2 , 6— 8).— Absorp tion spectra of pm'-hydroxyazo-dyes (I) of the type sequently brominated); PhOBz thus gives p- C H Br-OBz, s-CGH Br -OH, and BzOH. The methods 1:8-aminonaphthol->a-C10H7-NH2 in neutral and 6 4 2 3 alkaline solutions, in which a bathochromic colour of bromination used are: (i) a modification of Kauschke’s (A., 1895, i, 280) using I as catalyst at change (chromophore inversion) takes place, show that ‘he OH and N:N groups in (I) form a conjugated < 60° in open vessels; (ii) Br in AcOH containing NaOAc and I at about 40° for 48 hr.; (iii) Br in hot system similar to that present in o-hydroxyazo-dyes (A, 1933, 946). Absorption curves are given for the AcOH containing NaOAc, I, and the catalyst described by Fierz-David (A., 1929, 273). The bromoaryl following dyes : 1: 8-aminonaphthol-3 : 6-disulphonic benzoates are also synthesised. i-Bromo-2-methyl-, acid (II)^a-C10H 7-NH2, (II)->1 : 6-NH2-C10H r;SO,H m.p. 67— 68°, - and 3-bromo-i-methyl-, m.p. 71—72° I1*!), 1 :8-aminonaphthol-3 : 5-disulphonic acid->(III), 2 J:5- and 2 :5-aminonaphthol-7-sulphonic acid->(III), and 75—76°, respectively, 2-bromoA-nitro- (I), m.p. 131— 132°, and -p-bromomethyl- (II), m.p. 109— 110°, 1:7-aminonaphthol-4-sulphonic acid->(III), 2:8- -phenyl benzoates are new. A 1 : 1-mixture, m.p. 113— ^onaphthol-6-sulphonic acid->-(III), jj-C6H4(NH2)2 117°, of (I) and p-N02-C6H4-0Bz (III) is obtained by t) 1 ' and 2-naphthol-3 : 6-disulphonic acid, repeated crystallisation of the bromination product <^)->l : 4-OH-C10H6-S03H. S. C. from (III). (II), obtained in 14% yield from p- Amphoteric aromatic substitution. II. Re C6H4Me-OBz by method (iii), is converted into stions of benzoyl peroxide and benzeneazotri- p-benzoyloxybenzylpyridinium bromide (-|-H20), m.p. P^aylmethane. D. H . H e y (J.C.S., 1934, 1966— (anhyd.) 174— 175°. O-Benzoylvanillin (IV) gives ,cf- A-> 1926, 286, 612).—B z 20 , with PhCl at [method (ii) for 6 days] the 6-^r-derivative, m.p. 00 gives C02, BzOH, and 4-chlorodiplienyl. Simi- 117— 118° (hydrolysed to 6-bromovanillin), whilst ? . . Bz20 2 with PhN02 gives C02, 4- and 2-nitro- nitration affords 70% of the 2- and 4% of the 6-N02- c ‘phenyl [which indicates that the substituting agent derivative. (IV) and PBr5 at about 100° give i-benz- 208 BRITISH CHEMICAL ABSTRACTS.— A. oyloxy-3-methoxybenzylidene bromide, m.p. 108-5— cryst. H3P 04 at 100° (bath) give 4 : 4'-dihydroxytri- 109-5°. jp-Benzoyloxybenzaldehyde, m.p. 90° (lit. 72°) phenylmethane (leucobenzaurin), m.p. 161°; p- [•p-bromophenylhydrazone, m.p. 179—180° (decomp.)], OH-CbH4-CHO and (I) similarly afford 17% of tri-p- could not be brominatcd [method (ii); in contact hydroxyphenylmethane (leucoaurin), m.p. 240°, with air p-0Bz-CBH4-C02H results], indicating that and 35% of a phenolic substance; o-C6H4(CH0)2 in (IV) the active directing group is OMe, and the yields a-jj-liydroxyphenylphthalide, m.p. 148°; activity of OH is suppressed by acylation. Similarly, 0-N0 2-CrH4-CH0 furnishes 2-nitro-4': 4 "-dihydroxy- 4-0-, m.p. 103—104°, -m-, m.p. 95—96°, and -p-, m.p. triphenylmethane (about 70%), amorphous, m.p. about. 117— 118°, -chloro-, 4-m-bromo-, m.p. 114—115°, and 92° [also prepared by diazotisation of the 4 ': 4"- 4-p-nitro-, m.p. 199—200°, -benzoyloxybenzaldehydes (NH2)2-derivative] [Ac2 and Bz2, m.p. 155° (not sharp), could not be brominatcd; 4-0-, m.p. 215—216°, -m-, derivatives; Me2 ether], reduced (Zn dust, aq. EtOH, m.p. 217— 218°, and -p-, m.p. 239—240°, -chloro- and little CaCl2) to the amphoteric 2 -aminoA': 4"-di- 4-m-bromo-, m.p. 211—212°, -benzoyloxybenzoic acids hydroxytriphcnylmcthane, m.p. 195° (not sharp) (Bzz are described. H. B. derivative, m.p. 110°); m-NO2-C0H4-CHO gives (cf, Stereochemistry of dicyclic ring systems. X. De Varda and Zenoni, A., 1891, 1346) about 50% of Stereochemistry of hydrindane and its deriv Z-nitro-i' : 4 "-dihydroxytriphenyhnethane, m.p. 90— atives. II. Derivatives of cis-hydrindane with 91° (Bz2 derivative, m.p. about 89°; Me2 ether, m.p. substituents in the six-membered ring. W. 70°), similarly reduced to 3-aminoA’ : 4 "-dihydroxy- H u c k e l and E . G o th (Ber., 1934, 6 7 , [ 5 ] , 2104— triphenylmethane (-f-EtOH), m.p. 114° (decomp.) (ft3 2107; cf. Linstead et al., A., 1934, 1002).— Catalytic derivative); p-N 0 2-C6H4-CH0 affords 4-nitro-4': 4"- hydrogenation of 5-hydroxyhydrindene (Pt sponge- dihydroxytriphenylmethane (II), m.p. 130° (previous AcOH; P t02-Ac0H ; colloidal Pt-H 20) in all cases sintering) (cf. Danckwortt, A., 1909, i, 938; King yields a similar mixture of isomerides in which and Lowy, A., 1924, i, 646) {Bz2 derivative; l/e2 cis-5-hydroxyhydrindane (I), m.p. 41° (H succinate, m.p. ether), reduced to 4-amir\o-4! : 4"-dihydroxytriphmyl- 81-5°; normal succinate, m.p. 90°; phenylurethane, methane (III), m.p. 110° (Bzs derivative). When a m.p. 125°), greatly predominates and is accompanied solution of (II) in 25% KOH is kept for 24 hr. and by as-5-hydroxyhydrindane (II) (phenylurethane , m.p. then acidified (HC1), 4-nitro-4'-hydroxyfuchsoni 74°). Oxidation of (I) with Cr03 in AcOH gives the (+ H 20), carmine-red with green reflex (Bz deriv corresponding lcetone (III), b.p. 103°/17 mm. (semi- ative) [reduced (as above) to (III)], is obtained. carbazone, m.p. 208°), and cis-cyclope?ito«e-l : 2 -di- Nearly all the above compounds are amorphous. acetic acid, m.p. 173°, also obtained in very small H. B. yield when (III) is oxidised with KMn04 or, together Apiole. H. W in d is c h (Mcrcks Jahresber., 1934, with an acid, m.p. about 100°, when (I) is dehydrated 47, 56—57; Chem. Zentr., 1934, ii, 1171).—A method with KHS04 and the unsaturated hydrocarbon, b.p. for the isolation of apiole and myristicin as their Br 165—170°/730 mm., is oxidised with KMn04. Hydro additive compounds, m.p. 118— 120° and 126—129°, genation of 5-acetamidohydrindene (IV) (Skita) gives respectively, is described. H. N. R. a mixture of products from which, after hydrolysis, cis- and fraus-Chlorohydrins of 1 -methyl-A1- Bz derivatives, m.p. 165° (V), 145°, and 143°, respect ci/ciopentene. P. D. B a r t l e t t and R. V. W hite ively, are isolated. (V) is hydrolysed to an amine (j. Amer. Chem. Soc., 1934, 56, 2785; cf. A., 1934, (VI), b.p. 86°/I2 mm., the Ac derivative, m.p. 107— 1221).—2-Chloroci/c/opentanonc and MgMeBr give 2- 10S°, of which is obtained by the Willstatter hydro chloro-\-methylcyc\op&ntanol (I), b.p. 50—57°/S mm., genation of (IV). Treatment of (VI) with HN02 whilst 1 -methyl- A1-ci/cZopentene and HOC1 afford an affords (II). Hydrogenation of 4-hydroxyhydrindene isomeride (II), b.p. 61—64°/7 mm., m.p. 35—37°, and (Skita) does not give a homogeneous hydrindanol. Cl-containing material (which does not react ■with Oxidation of 4-hydroxyhydrindane with Cr 0 3 in AcOH EtOH-alkali) (cf. Chavanne and de Vogel, A., 1928, gives imperfectly homogeneous cis-hydrindan-4-one 745). (I) is converted by KOH in E t,0 or aq. 33% (VII), b.p. 100°/l7 mm. (semicarbazone, m.p. 193°); NaOH into 2-methylci/cfopentanone; (II) similarly the corresponding, non-cryst. oxime yields two Bz gives 1 : 2-oxido-l-methylci/cZopentane. H. B. derivatives, m.p. 114° (cis-compound), and m.p. 92° Preparation of cyc/ohexanol. N. A. O rlo v . (? iran-s-compound). Oxidation of (VII) with H1\03 M. F. Schostakovski, and V. V. S c h a b a r o v (J- yields only (•CH2-C02H)2. H. W. Appl. Chem. Russ., 1934, 7, 760—763).—cyclo- 4-Iodopyrocatechol. E. F o u r n e a u and J. Hexanol is obtained in 96% yield by heating PhOH D e u e y (Compt. rend., 1934, 199, S70— 872).— Iodo- and H2 at 265°/100 atm. for 7 hr. in presence of pyrocatechol diacetate (I), b.p. 148—15070-8 mm., is 4—6% of Ni20 3. R. T. prepared by diazotisation of 4-aminopyrocatechol di Esters of hydrogenated phenols. J. S. Sal- acetate and treatment with KI. Hydrolysis of (I) iu n d and M. G . G e r c h ik o v (Plast. ]\Iassi, 1934, with HC1 in MeOH yields 4-iodopyrocatechol, m.p. 92° No. 3, 37— 40).—The esterification of ci/cZohexanol and 50° (dimorphous), which gives a green coloration with AcOH, HC02H (85— 90% yield with 95% aria with FeCl3, becoming red with Na,C03 and reddish-, in cold without catalyst for 1 day), and H2C204, and violet with NaHC03. " A. G. P. of methylcT/cZohexanol with AcOH, is described. Hydroxytriphenylmethanes. Condensation of Ch. A b s. (r) aromatic aldehydes and phenols with phosphoric Reaction of magnesium dimethyl and diethyl acid. I. T a n a s e s c u and T. Sim o n e s c u (J. pr. Chem., with cyeiohexene oxide. P. D. B a r t l e t t and 1934, [ii], 141, 311—326).—PhCHO, PhOH (I), and C. M. Berry (J. Amer. Chem. Soc., 1934, 56, 2683" ORGANIC c h e m i s t r y . 209 2685).—The residue after removal of Et20 from picrate, decomp. 195°]. (II) is transformed by NH3 cj/cZohexene oxide and Et20-M gEt2 (Noller and into the substance (?) * Hilmer, A., 1932, 837) is heated at 100° (hath) and NH[CH(C6H4-NMe2)-CH:CH-C6H4-NMe2]2, m.p. 193°. then hydrolysed (dil. HC1); im?w-2-ethylc«/cZohexanol (II) shows an absorption max. at 689 mji, that of (I) (contaminated with some impurity) is thus obtained Michler’s hydrol in AcOH bemg at 609 mix. When in 42% yield. Slightly impure ¿ra?is-2-methylq/cZo- (I) is heated in AcOH from which all trace of oxidising hexanol is similarly prepared using MgMe2. (I) is agent has been removed, a small amount of (II) (as oxidised to 2-ethylc?/cZohoxanone. No rearrangement acetate) is formed, together with some tetramethyl occurs in the above reactions. H. B. benzidine. Leuco-erystal-violet undergoes a similar Preparation of amino-alcohols. I. J. T. change in AcOH, forming Michler’s hydrol acetate. A bram s and P. S. K ip p in g (J.C.S., 1934, 1988— H. W. 1991).—CH2Bz-C02Et, Et a-benzoy 1-propionate, Resolution of some cyclanediols. M . G o d c h o t , •butyrate, and -isobutyrate (I) areprepared by Claisen’s M . M o u s se r o n , and R . R ic h a u d (Compt. rend., method [cf. J.C-.S., 1909, 9 5 , 2042; criticisms (A., 1934, 1 9 9 , 1233—1235).— ira?w-cycZoPentane-l : 2-diol 1930, 212 and 1932, 944) are unfounded] and give with H2S04 at —15° affords the di-sulphuric ester, the [except (I)] with conc. aq. NH3 the corresponding strychnine salt of which when fractionally crystallised, amides, m.p. 112— 113°, 153° (lit. 145— 146°), 155° followed by hydrolysis, gives the optical isomerides, (lit., 148— 149°), respectively, which with Al-IIg in [“Isso ±33-60°. Similarly, cis-1 -mcthylq/cZohexanc- H20-EtC)H give, respectively, (3-hydroxy-P-phenyl- 3 : 4-diol (A., 1923, i, 1082) gives d- and 1 -compounds, propionamide (II), m.p. 118— 119°, and its a-Me (III), Mcio ±18-10°, and the £ra?w-diol (A., 1923, i, 101), m.p. 134— 135°, and a-Et, m.p. 134— 135°, derivatives isomerides, [a]|}9 ±19-40°. J. L. D. [and a dia&tereoisomeride (?), m.p. 128— 131°, of the j>-Fluorophenacyl alcohol and some of its last]. (II) and (III) are converted by NaOBr below esters. R. M. H a n n and J. P. W e t h e r il l (J. 0° into [i-amino-a-phenyl-ethyl (cf. A., 1914, i, 677) Washington Acad. Sci., 1934, 24, 526— 528).— Con and -propyl alcohol (IV) [also some bromoamide (?), densation of CHoCl-COCl with PhE and A1C13 in CS2 m.p. 116—117°, which is converted by NaOH into affords p-fluorophenacyl chloride (I), m.p. 48°, con (IV)], isolated as the hydrochlorides. J. L. D. verted by fused NaOAc-AcOH-aq. EtOH into the Ephedrine. II. Ndtv benzyl homologues. acetate, m.p. 48-5— 49°, hydrolysed by BaC03-H 20 S. D. W i l s o n and L. H. SuN (J. Chinese Chem. Soc., at 100° to p-fluorophenacyl alcohol, m.p. 114° [o-, m.p. 1934, 2 , 243—256).— CH2PlrCHBrCOPh with excess 74-5°, m-, m.p. 105°, and Tp-nitrobenzoate, m.p. 134°, of NH2Me in C6H 6 at room temp, during many hr. from the C0H4(NO2)-CO2H and (I) in iV-NaOH], gives Ph o.-methylamino-$-phenylethyl ketone hydro J. W. B. chloride, m.p. 225—226°, reduced (H2-P t-P t oxide) in Structure of cholesterol. R . R o b in s o n (Chem. EtOH at 40— 50° to dl-p -methylamino-ay-diphenyl- and Ind., 1934, 1062— 1063).—The suggestion (this propanol, an oil (hydrochloride, m.p. 204—205°; vol., 81) that the Me group of cholesterol (I) now sulphate, m.p. 1S4— 185°; pier ate, m.p. 172— 173°), usually placed at C10 is better placed at C9 was made which is resolved (tartaric acid) into the d-, [a]” by the author (A., 1932, 1245), but is not in accord +10-9° in 2% EtOH (hydrochloride, m.p. 194—195°; with chemical evidence. The accepted C skeleton of i-tartrate, m.p. 202—204°), and the 1 -form, [a]J? —11-0° (I) can be constructed without rearrangement from {hydrochloride, m.p. 192—193°; d-tartrate, m.p. 175— difarnesyl (tail to tail; 2 : 6 : 10 :15 : 19 : 23-hexa- 1”6°). Similarly prepared, Ph a.-benzylamino-$- methyltetracosane) by elimination of the C10, C15, and phenylethyl ketone hydrochloride has m.p. 206—207°, C23 side-chains and junction of C7 and C10 to C23, of and is reduced to dl-$-benzylamino- Acetyldiphenylchloroacethydrazide. H . A s p e - T. R. S e s h a d r i (J. Indian Chem. Soc., 1934,11, 743— lund and A . M. A ugitstson (Acta Acad. Aboensis 749).—o-Coumaric acid (I) and its 5-N02- (II) and math, phys., 1933, 7, No. 10, 1—7; Chem. Zentr., 4-OMe- (III) -derivatives (modified preps.), when 1934, ii, 1455).—Benzilic acid hydrazide and Ac20 heated, give the styrene and C02, but the Me and Et yield acetylbenzilhydrazide, ra.p. (-)-2H20) 190— 191°; esters undergo: ring-closure rapidly. Both acids and this, with CPh2Cl-COCl, affords acetyldiphenylchloro- esters give the coumarin in light, the ease of reaction acethydrazide, m.p. 94°, which with EtOH yields being (II)> (I)> (III). The following are de acetyldiphenylethoxyacethydrazide, m.p. 154°. EtOAc scribed : Me, m.p. 137°, and Et o-coumarate, m.p. and N2H(,H20 at 130° for 4 hr. give a good yield of 86°; Et 5-nitrocoumaratc, m.p. 170— 172°; 7-methoxy- -l-amino-3 : 5-dimethyl-l : 2 : 4-triazole, m.p. 196° coumarin, m.p. 117— 118° [from umbelliferone (modi H. N. R. fied prep.) or malic acid and ?n-0Me-CrH4-0 H ]; Me; Preparation of (3-benzylidene-a-o-nitrobenzyl- m.p. 138°, and Et 4-methoxycoumarate, m.p. 109°. idene- and a-benzylidene-(3-o-nitrobenzyl- R. S. C. idene-propionic acid. F. S ch en cic (J. pr. Chem., cyc/oPentane-1: 2-diacetic acid. W. H u c k e l , 1934, [ii], 141, 299—300).—CHPh:CH-CH2-C02Na, E. G o t h , andG. D e m m l e r (Ber., 1934,67, [5], 2102— 0;NO2-CeH4-CHO, and Ac20 at 125— 130° (bath) 2103; cf. Linstead et ah, A., 1934, 1002).—Treatment give y - phenyl - a - o - nitrobenzylidene - A® - butenoic of Et c/ycZopentanoneacetate with CH2Bi-C02Et and ($-benzylidene-a.-o-nitrobenzylidenepropio7iic) acid, m.p. Zri in CgH 6 gives a mixture of OH-ester, unsaturated 180—181°. y-o-Nitrophenyl-kP-butenoic acid, m.p. ester, oily acids, and other products. Fractionation 112-113° [from 0-N02-CfiH4-CH2-CH0 and and hydrolysis of the ester mixture leads to cyclo- CH2(C02H)2 at 100° (bath) and finally at 110°], and ‘iitenc-1 : 2-diacetic acid (I), m.p. 182— 183°. PhCHO similarly afford y-o-nitrophenyl-a-benzylidene- ydrogenation (Pt sponge in AcOH or EtaO ; P t02- As -butenoic (a.-benzylidene-p-o-nitrobenzylidenepropionic) gMeOH) leads mamly to ci,s-c?/ctopentane-l : 2-diacetic acid, m.p. 167— 168°. H. B. acid, m.p. 172— 173° (monoanilide, m.p. 129— 131°; o-Phenyldiphenyls and “ synchronised rot dianilide, m.p. 225—226°), whereas treatment in presence of Pd-C-EtOH or (as Na salt) with Pd-C- ation." A. M. S a d l e r and G. P o w e l l (J. Amer. Chem. Soc., 1934, 5 6 , 2650—2653).—o-Iododiphenyl, H20 yields essentially ¿raws-c?/cfopentane-l : 2-di o-C6H4Br'C02Et (I), and Cu-bronze at 270—275° give acetic acid, m.p. 132— 133-5° (monoanilide, m.p. 144— 2 :2'-didiphenylyl, b.p. 193— 195°/1 mm., m.p. 117— 146°; dianilide, m.p. 236—237°). H. W. 119°, and a product, b.p. 169— 175°/1 mm., which Steric course of addition and substitution re when hydrolysed (KOH in 5% EtOH) affords 2-phenyl- actions. I. Stereochemistry of diene syn diphenyl-2'-carboxylic acid (II), m.p. 143— 144-5° thesis. K. A l d e r and G. St e in [with F . v o n (strychnine, m.p. 215°, [«]&, - 4 2 to -4 3 ° in CHC13, B u d d e n b r o c k , W. E c k a r d t , W. F r e r c k s , and S. and phenylethylamine, m.p. 115— 116°, [a]^61 —4-1 ° S c h n e id e r ] (Aiinalen, 1934, 514, 1—33).—The in in EtOH, salts). o-Cf)H4Ph2 is obtained when the Ag vestigation (A., 1933, 941) on the steric configurations salt of (II) is heated. (II) could not be resolved; of the dic?/cZopentadienes is being extended to the a model of (II) has a plane of symmetry when the determination of, e.g., configurations in the camphor plane of the 2-Ph group is perpendicular to the plane group. Preliminary work on the addition of maleic of the Ph, groups. 2-Iodo-2'-methyldiphenyl (III) anhydride to cf/cfo-pentadiene and -hexadiene, and [prepared by Mascarelli and Gatti’s method (A., the occurrence of exo- and mfo-isomerism in the 1932, 607)] and (I) similarly afford 2-o-tolyldiphenyl- adducts, is now reported. 4-Bromo-5-hydroxy-cis- 2 -carboxylic acid (IV), m.p. 130-5— 131-5° [strychnine 3 : 6-e?2 HC02H and PhCl give a 2% yield of y-C6H4QlfjlpHO; Michael condensation. II. Reactivity of the a resin is the main product. J. L. D. addendum. R. C o n n o r and D. B. A n d r e w s (J. Friedel-Crafts reaction. Preparation of Amer. Chem. Soc., 1934, 5 6 , 2713—2716; cf. A ., ketones and keto-acids. P. H. G r o g g in s and 1934, 72).— Three types of products formed in the R. H. N a g e l (Ind. Eng. Chern., 1934, 26, 1313— Michael condensation are recognised: (1 ) normal 1316).—Interaction of Ac20 with C6H6 containing product, e.g., (G02Et)2CMe-CHMc-CH2-C02Et from A1C13 is not facilitated by Fe or Al, whereas KC103 CHMe(C02Et)2 (I) and CHMe:CH-C02Et (II) in pre and S0C12 markedly retard the reaction, which prob sence of a little NaOEt or piperidine (cf. Michael and ably proceeds through the formation of AcCl from Ross, A ., 1931, 67); (2) rearrangement product, e.g., AcOH and A1C13; the second AcOH residue (from (C02Et)2CH-CHMe-CHMe*C02Et from (I) and (II) in Ac20) is also partly available for reaction. 3 mols. presence of 1 equiv. of NaOEt (cf. Michael and Ross, of A1CL are employed which probably (a) form AcCl lee. cit.; Holden and Lapwrorth, ibid., 1272); (3) re- and AlCl2'OAc by double decomp., the latter of which arrangement-retrogi-ession products, e.gf-.CHoBz-COaEt with AIC13 gives AcCl and A10C1; (6) AcCl and A1C13 and CHPh;CMe,C02Et, formed by a reversed Michael form a salt which is the active acylating agent. AcCl condensation from C02Et-CHMc-CHPh-CHBz-C02Et affords less pure products than Ac20 , but in as good [the rearrangement product (cf. 2) from (I) and CHPhiCH-COPh (III)]. The addition of various com- yield, and SOCl2, KC103, and Fe have no effect on * the reaction. AcCl and PhMe give impure products pounds containing an active CH2 to (III) under con with > 1 mol. of A1C13, but with Ac20 the use of 3-3 ditions (1) and (3) is studied; the reactivity of the mols. results in but little side-chain chlorination. addendum cannot be correlated with the no. of Oxyhalogen compounds decreaso the yields of 4'- activating groups attached to C* or from the amount methyl-(or chloro-)2-benzoylbenzoic acids. Cast iron of enolisation. The reactivity of any given structure vessels have no deleterious effect on the reaction or is decreased by introduction of substituents on C *; reaction product. J. -Ł. D. the effect of Me is much < that of higher alkyi a-Hydrinden-4-one from 8-ketosebacic acid. groups. The original must be consulted for details. W. Hu c k e l and R. S c h l u t e r (Ber., 1934, 6 7 , [jS], Et a.y-dibenzoyl-$-phcnylbutyrate, m.p. 135— 135-5° 2107—2109).—Oxidation of 1-ketodecahydronaphth- [from CH2Bz-C02Et and (III)], and Et 3 : 5-diphenyl- alene with KMn04 at 100° gives S-ketosebacic acid, 6-ethyl-A2-cyclohexenone-6-carboxylate, m.p. 135— m.p. 116°, converted by distillation with Ac20 into 135-5° [from CHEtAc-C02Et and (III) or Et y-benz- a-hydrinden-4-one (I) (semicarbazone, m.p. 255°; oyl-a-acetyl-p-phenylbutyratc and EtI in EtOH- oxime, m.p. 136°). (I) is hydrogenated (Pd-C-EtOH) NaOEt; in both cases intramol. dehydration is to cw-a-hydrindan-4-one (Bz derivative of oxime, m.p. involved], appear to be new. H. B. 112°). H. W. Acyl derivatives of phenylcyciohexane. D. Y. Pregnan-20-ol-3-one. A. B u t e n a Nd t and J. Chang (J. Chinese Chem. Soc., 1934, 2, 216—-220).— S c h m id t (Ber., 1934, 6 7 , [B], 1893— 1896).—Partial Phenylq/cZohcxane (I) with A c,0 in boiling CS2 con hydrolysis of pregnan-3: 20-diol diacetate by MeOH- taining A1C13 during 1 hr. affords ^-acetylpfienyl- KOH at 15—20° leads to the (20-)monoacetate (I), oyclollexane (cf. A., 1929, 550). Similarly, (I) with m.p. 170-5°, the constitution of which follows from (EtC0)20 and (PraC0)20 gives, respectively, p-prop- mo CHMe-OAc ue R ionyl-, b.p. 191— 196°/20 mm. (oxime, m.p. 106°; fhnylhydrazouc, an oil), and p-butyryl-jjhenylcyclo- hmiie, b.p. 208—214°/20 mm. [oxime, m.p. 112— 113°; phenylhydrazcme, m.p. 85° (decomp.)]. J. L. X). Formation of benzanthrone from antbraquin- one and glycerol. J. S. T u r s k i (Przemysł Chem., 1934,18, 605—607).—The view that benzanthrone is formed by condensation of aldehyde with anthra- its energetic oxidation by Cr03 to the acetoxydicarb- hydroquinone is advanced. R. T. oxylic acid, m.p. 272° (II; R=-CHMe-OAc), hydro- Chlorobenzophenoneoximes. C. W . P o r t e r lj-sed to the Oil-acid, m.p. 346° (II; R=-CHMe*OH), « 4 H. B. W ilcox (J. Amer. Chem. Soc., 1934, 5 6 , which is transformed by gentle oxidation into the 2688—2689).— Oximation of o-CrH4Cl-COPh gives two keto-acid, m.p. 271° (II; R = A c) obtained previously oximes, m.p. 131° (I) and 96—97°, re-solidifying with from pregnandiol. Cautious oxidation of (I) affords a.p. 13Q— 1 3 1 ° (II) (in pre-heated bath), separable the keto-acetate, (III; R=-CHMe-OAc), m.p. 142—- »y fractional crystallisation from aq. MeOH. When 142-5°, hydrolysed to pregnan-20-ol-3-one (I I I ; R = (h) is heated it changes rapidly into (I). Beckmann -CHMe-OH).m.p. 152° (semicarbazone, m.p. 203—204°). ^arrangement of (I) and (II) gives o-CeH4Cl,CO,NHPh The last-named compound is not identical with the 0-C6H4C1 -ISTHBz, respectively. (I) and (II) are similarly composed material from the corpus luteum. unaffected by 30% ŃaOH at room temp., but in the : H. W. pot both afford the same indoxazen; cis-trans isomor- aifoPregnan-3-ol-20-one, a companion of the jsation may precede elimination of HC1. Indoxazen corpus luteum hormone. A. B u t e n a n d t and formation is no guide to the structure of the oxime L. M a m o l i (Ber., 1934, 67, [I?], 1897— 1901}.— (cf. Meisenheimer and Meis, A., 1924, i, 433). 3-Hydroxybisnorcholenic acid is hydrogenated (Pt H. B. in AcOH) to 3-hydroxybisnoraZtocholanic acid, m .p . Q 216 BRITISH CHEMICAL ABSTRACTS.— A. Me ester, m.p. 152-5°, of which is trans dimethylaminophenyl-, m.p. 230—231°, and 2:3:5- formed by MgPhBr in Et,0 triphenyl-A-p-diphenylyl-, m.p. 215°, -4-anisyl-, m.p. into the [ carbinol ( I ; R = 213—214°, and -4-p-dimethylamirwphenyl-, m.p. 220— •CHMc-CPlvOH ; R '=O H ), de 2 2 1-, -cyclopentadienones are prepared from hydrogenated and acetylated CO(CH2Ph)2, the appropriate benzil, and NaOMe hy boiling AcOH to the un- in boiling EtOH. The colours of these ketones and saturated acetate (II) (R = tetraphenylci/cZopentadienone (I) (A., 1931, 91) and •CMe:CPh2; R '=O A c), m.p. their solutions in C6HG and conc. H2S04 are given. 238-5° [corresponding alcohol, Introduction of positive groups into the ^-positions m.p. 163-5°, rc-acetylated to (II)]. Ozonisation of of the 3- and 4-Pli groups is accompanied by a hypso- (II) affords COPh2 and a.\\opreg7ian-3 -ol-2 0 -one acetate, chromic effect (which increases with the positivity m.p. 144-5°, hydrolysed to &\\opregnan-3-ol-2-one of the auxochromes and is a max. for SPh). An (I; R —COMo; R '= O H ), m.p. 194-5° (oxime, m.p. analogous hypsochromic effect is observed by intro 224°), identical with the product derived from the duction of ¿j-OMe or 4 : 4'-(OEt)2 into benzil; the corpus lutcum (see following abstract). H. W. results parallel those with stilbenes (A., 1928, 627). Constitution of the hydroxyketone, C21H 340 2, Ph and SPh exert a bathochromic action on the from corpus luteum. E. F e r n h o l z (Z. physiol. halocliromism, whilst Aik, OAlk, and NMe2 cause a Ohem., 1934, 230, 185—189).—Me acetoxybisnor- hypsochromic effect; these results are not similar flZ/ocholanate (A., 1933, 1290) and MgPhBr give to those shown by the substituted benzils or distyryl the carbinol (I) (A, R = ketones. Since 3:4: o4ri'phenyl-2-anisylcy(i[openta- •CHMe-CPh2-OH), m.p. 207° dienone (II), m.p. 189—190°, dissolves in conc. (monoacetate, m.p. 197°). Dis H2S04 to a greenish-blue solution, whilst (I) affords tillation of crude (I) at about a violet-blue solution, C2 is considered to be positive 1 mm. affords the compound + . - (see A ) ; the OMe in (II) thus exerts a (A, R='CMe'CPh2), m.p. 168° vp 3jjC bathochromic effect. Alternative structures {chloride, m.p. 199°; acetate C\ yG ^or salts are discussed. Dcoxybenzoin, (II), m.p. 246° [oxide. (Ill), \ / Ph yj-methoxystyryl ketone, and MeOH- m.p. 225°, from (II) and Bz02H in CHC13]}. Dehydr Y+ (-1-) NaOMe give cie-dil'eto-a^e4riphenyl-y-anisyl- ation of (I) with AcOH, Ac20, or AcOH-HCl gives 0~ pentane (III), m.p. 155°, and (probably) (II), an isomeric acetate, m.p. 263°, and resin. Oxid a$-dibenzoyl-$-2ihenyl-y-anisylpropane, m.p. 143—144° ation (03 in CHC13) of (II) affords (III) (trace) and (oxime, m.p. 218°). (Ill) is reduced (Zn dust, AcOH) ' the acetate, m.p. 145° (semicarbazone, m.p. 273°), to 1:2: 3 - triphenyl - 4 - anisylcyclopentane -1 : 2-diol, of Z-hydroxyaWomtiocholyl Me ketone (IV) (A, R = in.p. 126— 127°, dehydrated (HC1 in MeOH) to 3 : 4 :5- COMe), m.p. 195° [oxime, m.p. 227°; semicarbazone, tripthenyl-2-anisylQ,yc\opentadiene, m.p. 125—126°. m.p. 253° (decomp.)]. (IV) is probably identical with This and p-NO-CGH4-NMe2 with piperidine in C3H5N- the hydroxyketone, C21HM02, isolated by Butenandt EtOH give the p-dimethylaminoanil, m.p. 204—205°, et al. (A., 1934, 1039, 1268) from corpus luteum (see of (II). 4 : 4'-Diphenylthiolbenzil, m.p. 104—105°, preceding abstract). H. B. is prepared from Ph2S, ("0 0 0 1)2, and A1C13 in CS2. Conversion of pregnandiol into the corpus 4-Chloro-4'-dimethylamino-benzii, m.p. 143—144“, luteum hormone. A. B u t e n a n d t and J. S c h m id t is obtained (cf. Jenkins, A., 1931, 1158) by oxidation (B er., 1934, 6 7 , [B], 1901— 1904).—Pregnanol-3-one (Fchlmg’s solution) of the -benzoin. H. B. is converted by B r in AcOH at 15—20° into the Additive reactions of alkylated naphthacjuin- R brornoketo-alcohol (I; R = Me •CHMe-OH), m.p. 185° (de- ones. L. F . F i e s e r arid A. M, S e l ig m a n (J. Araer. Chem. Soc., 1934, 5 6 , 2690—2696).—3 : 7-Dimethyl- conrp.), oxidised by C r 0 3 in AcOH at 15—20° to Br-diketone 1 : 2-naphthaquinone (I) (improved prep.; cf. Weiss- (II) ( I ; R=COMe), also ob gerber and Kruber, A., 1919, i, 315) and N H 2O H , AcOH tained by cautious oxidation in aq. MeOH give the 2-oxime, m.p. 222° (decomp.), of pregnandione. (II) in boiling since reduction (alkaline Na2S,04) does not afford l-amino-3 : 7-dimethyl-p-naphthol (N-^4c derivative, C5H-N passes into the corpus luteum hormone, m.p. 121° or 128-5° [oxime, m.p. m.p. 107-5°, obtained from the hydrochloride and Ac20 in aq. NaOAc), but yields an unstable amine 244° (decomp.)]. H. W. [? Ac3 derivative, m.p. 245° (not sharp)]. Successive Corpus luteum horm ones .—See this vol., 127,128. treatment of (I) with aq. NaHS03, dil. H2S04 (boiling), Heteropolarity. XXIV. Colour and halo- aq. K 20r20 7, and aq. KOI gives K 3 :7 -dimethyl- chromism of deeply coloured aromatic five-ring1 1 : 2-naphthaquinone-4:-sulphonate (+ H 20), whilst (I) ketones. W. D i l t h e y , 0 . T r o s k e n , K . P l u m , and Ac20-conc. H2S04 at 10° and finally at 60° and W. S c h o m m e r (J. pr. Chem., 1934, [ii], 141, afford 1:3: i-triacetoxy-2 : Q-dimethyhiapihthalene, m.p. 331 -349).—2 : 5-Diphenyl-3 : 4-idi'-p-tolyl, m.p. 218— 161°, converted (aq. EtOH-NaOH) into 3 -liydroxy- 219 -3 : ^-di-p-i&opropylphenyl-, m.p. 214°, -3 : 4- 2 : Q-dimethyl-l : i-naphthaquinone, m.p. 194° (acetate, di-p-diphenylyl-, m.p. 258—259°, -3 : 4-dianisyl-, m.p. m.p. 75—76°; Me ether, m.p. 1 0 8 °). (I) also reacts 222 223°, -3 : i-di-p-elh oxyphenyl -, m.p. 19S— 199°, readily with EtOH-NH2Ph and p-C GH4M e-S02H, -3 : ‘i-di-p-phenoxyphenyl-, m.p. 219—220°, -3:4- but not with CH2N2. 2 : 6-Dimethyl-l : 4-naphtha- di-p-phenylthiolphenyl-, m.p. 199°, -3 : i-di-n-bromo- quinone (II) (loc. cit.) undergoes littfe or no reaction phenyl-, m.p. 244—245°, and -3-p-chlorophmyU-p. with Ac20-conc. H2S04, NaHS03, NH2Ph, or A i-S 0 2H ; ORGANIC CHEMISTRY. 217 with Et20-CH 2N2 in C6H G at 100° (sealed flask), hydrolysed to 1 : 4-dihydroxy-9-anthrone (II), m.p. 3 : 7 : 3' : 7' - tetramethyl -2 : 2' - dinaphthylmethane - 227° (decomp.). (I) or (II) is converted by hot Ac20 in 1:4:1': 4'-diquinone, m.p. 300°, results in 40% presence of NaOAc or C5H5N into 1 : 4 : 9-triacetoxy- yield. 3 : 7-Dimethyl-P-naphthyl acetate is oxidised anthracene, m.p. 2 1 1 —2 12 °. (I) and BzCl in warm (Cr03, AcOH) to 1 -acetoxy-2 : 6-dimethyl-1 : 4-naphtha- C5H5N afford \-acetoxy-4 : S)-dibenzoyloxyanthra.eene, quinone, m.p. 171°, which with Zn dust and Ac20 m.p. 240—241°, oxidised by Cr03 in AcOH to 1 -acet- followed by NaOAc (if this is present throughout the oxy-4:-benzoyloxyanthraquinom, m.p. 195— 196°. 5 : 8- reaction an unidentified substance, m.p. 149—150°, Dichlorodiacetylquinizarin is reduced by Na2S20 4 to results) gives 1:4: 7-triacetoxy-2 : G-dimethylnuph- 5 : 8-dichloro-4;-hydroxy-l-acetoxy-d-anthrone, m.p. thakne, m.p. 139° Sy-Dimcthylbutadiene (III) and 222—223° after softening, whence 5 : 8-dichloro- (II) in EtOH at 100—105° 1:4: d-triaeetoxyanthracene, m.p. about 228°. Di- O Jie H2 (sealed tube) give the tetra- acctylchrysazin yields 5-hydroxy-4-acetoxy-9-anthrone, ^ \ / \ / \ Me methylietrahydroanthraquinone m.p. 247—248°, whence 4 : o-dihydroxy-9-anthrone, (IV) (R=H, R'=Me), m.p. m.p. 292—293°, and 4:5:9-triacetoxyanthracene, 1 75—11° (semicarbazone, m.p. m.p. 2 2 1—222°. Diacetylalizarin gives 4-hydroxy-S- mo / R 'J h 2 263°), reduced (Clemmensen) acetoxy-9-anthrone (+ 1 H 20), m.p. 187— 189°, whence (IV.) to the tetramethylhexahydroan- 3 : 4-dihydroxy-9-anthrone and 3:4: 9-triaeetoxy- thracene [(IV) with R=H, R '= anthracene, m.p. 193°. 4-Hydroxy-3-methoxy-9- Me, and both 0 = H 2], and dehydrogcnated (S) to anthrone, m.p. 203—205°, results from acetylalizarin 2:3: 6-trimetliylanthraquinone, m.p. 232° [lit. 240° 2-Me ether; 3-methoxy-4 : 9-diacetoxyanthracene has (corr.)]. (I) and (III) similarly afford a tetrametliyl- m.p. 189— 191°. 1-Acetoxyanthraquinone is trans telraliydrophe.nanthraquwione (?), m.p. 106°, which formed into 4-liydroxy-9^-anthrone, m.p. 239—240° (de- undergoes deep-seated decomp, on attempted dehydro- comp.), converted by I or 2 mols. of jJ-C^HYMe-SOgMe gcnation. 2 : 3-Dimetliyl-l : 4-naphthaquinone and in C6H4C12 containing NaHC03 into 4-methoxy-(j- (III) give the tetramethyltetrahydroanthraquinone (IV) anthrone, m.p. 132— 133°, and 4 : 9 - dim ethoxyan th ra c - (R=Me, R '= H ), an oil; 2-methyl-l: 4-naphthaquinone ene, m.p. 86—87°, respectively. (I) is easily trans affords an adduct, an oil, dehydrogenated to 2:3- formed by boiling MeOH-eonc. HC1 into 1 -hydroxy-4- dimethylanthraquinone, whilst thymoquinone yields methoxy-6-anthrone (III), m.p. 156— 157°, which gives 6:7: 9-trimethyl-Z-isopropyl-5 : 8 : 9 : 10-tetrahydro- 4-methoxy-l : 9 - diacetoxyan th ra cent, m.p. 178°, with 1: 4-naphthaquinone (?), an oil. H. B. AcoO and c 5h 5n. l-IIydroxy-4-ethoxy-9-anthrone, m.p. 146— 147°, and 4-ethoxy-l : 9-diacetoxyanthrac- Alkannin. III. H. R a u d n it z and E. St e in ene, m.p. 160— 161°, are described. (Ill) and (Ber., 1934, 6 7 , [ 5 ], 1955— 1959; cf. A., 1932, 396; o-chloroisatin-2-^-chloi'oanil in C5H 5N at 100° afford DieterleeiaZ., A., 1931,1297; Betrabotei aZ., A., 1933, 2-[4-methoxy-9-anthrone]-2'-[o' - chloroindole] - indigotin. 1165, 1217).—Technical alkannin dissolved in warm Oxidation of (II) or, preferably, of (I) with FeCl leads EtOH is treated with Ni(OAc)2. The Ni salt is 3 to l-hydroxy-4 : 9-anthraquinone (IV), decomp, about extracted successively with boiling EtOH and CGHG 200° after softening. 5 : S-Dichloro-l-hydroxy-4 : 9- to remove wax and decomposed with the necessary anthraquinone (V) has m.p. 257°. l-Aeetoxy-4:9- amount of 1 % HCl-McOH, whereby alkannin (I), anthraquinone (VI), decomp, about 200°, is obtained C!17H180 5, is obtained as crystals, m.p. 109°. Since from (I) by FeCl and HC1 in EtOH or from (IV), (I) is a derivative of naphthazarin (loc. cit.), 10 C are 3 involved. A further C is present in OMe, the remain Ae20 , and C5H5N. Bromoanthrone is readily prepared from acetyl- ing 6 in a side-chain which contains a double linking, (VII) or phenylacetyl-, m.p. 102— 103°, -anthranol by since (I) absorbs 7H2 in presence of Pt. Ozonolysis the action of Br in hot AcOH. 10-Chloro-9-anthro?ie, (I) in AcOH leads to the formation of 0-7 mol. of decomp. 233°, is obtained from CI and (VII) in cold C0Me2. Reductive acetylation of (I) gives dihydro- 2 AcOH, whereas benzoylanthranol and Br in AcOH c&kannin tetra-acetate, m.p. 133— 134°. (I) is there afford 10-bromo4)-benzoykinthranol, m.p. 214—215°. fore 5 : 8-dihydroxy-3( ?)-methoxy-2-S-methyl-Ay- IQ-Bromo-l : 4-diacetoxy-9-anthrone (VIII), decomp. pentenyl-1 : 4-naphthaquinone. H. W. 183° after becoming discoloured, is transformed by 1:4-Dibydroxy-9-anthrone and 1-hydroxy-4:9- boiling C0Me2-H 20 into 1 0 hydroxy-1 : 4-diacetoxy-d- anthraquinone. K. Z a h n (Ber., 1934, 6 7 , [5], anthrone, m.p. 140° in a pre-heated bath. (VI) is 2063—2078).—Reduction of a-acetoxyanthi‘aquinone converted by Ac20 containing conc. H2S04 or ZnCl2 is accompanied by loss of an a-Ac I’esidue and elimin into 1:4: 10-lriacetoxy-d-anthrone, m.p. 179°, also ation of the vicinal meso-O; the following scheme is obtained from (VIII) and KOAc in boiling AcOH, and transformed by boiling Ac20 containing KOAc or suggested: CGH4< ^ > C GH3-OAc(2) — > C5H5N into 1:4:9: 10-tetra-acetoxyanthracene, m.p. 240—242°. 10-Chloro-l-aceloxy-4 : 9-anthra- C6H3*OAc « ■ v < cSÍoI !> g^--oa« quinone, m.p. 196— 197°, is described. (VI) and butadiene in EtOH at 75—S0° yield the WO < c h 2 > c «h »-°h ■ adduct G20H16O4, m.p. 181— 182°, transformed by air in alkaline solution into 9-hydroxynaphthacenequin- H *OH. Thus, diacetylquinzarin is con 6 3 one and by boiling Ae20 and KOAc into 9:11: 12- certed by H2 at 85—90°/40 atm. in presence of Ni or triacetoxy-1 : 4-dihydronaphthacene, m.p. 225—227°. }y *a2S20 4 in H ,0-A c0H at 65° into 4-hydroxy-1- (VI) is transformed by boiling A1 :3-c//cfohexadiene acefoxy-9-anthrone“ (I), m.p. about 208° (decomp.), into the siibstanvce. C20H iCO3, m.p. 160— 161°, whence 218 BRITISH CHEMICAL ABSTRACTS.---- A. Jiydroxi/-1 : i-endoeihtjlene-l : i-dihydronaphthacene- CHO of strophanthidin which replaces a Me of (I) quinone, which loses C2H4 when heated and yields and must occupy C10. The position of the OH 9-hvdroxynaphthaeenequinone. groups in ring I follows naturally. H. W. (IV) is converted by Br in warm AcOH into 2 : 3- Saxatilic acid. G. K o l l e r and A. K lein dibromo - 1 - hydroxy -2:3- dihydro -4:9- anthraquinone, (Monatsh., 1934, 6 5 , 91—92).— Comparison of the decomp. about 1579, transformed by Ac20-conc. Ac3 and Ac6 derivatives establishes the identity of H2S04 into the Ac.derivative C16H10O4Br2, m.p. about saxatilic and salazic acids. H. W. 197° (decomp.), also obtained from (VI) and con Constituents of red sandal-wood. Ptero- verted by KOAc in boiling A c0H -H 20 into 2(3)- carpin. H. L e o n h a r d t and K. F a y (Arch. Pharm., bromo-l-acetoxy-4: : 9-anthraquinone (IX), m.p. 230°. 1935, 2 7 3 , 53— 60).—Pterocarpin (I) (modified prep.), The position of Brin (IX) follows from its reduc Ci H 0 (0Mé)(;0 CH2) (lit. C H 0 4), dimorphic,m.p. tion by HI and AcOH and subsequent acetylation by 4 9 2 2 14 12 165° arid 156—157° [/Jr-derivative, m.p. 165° (de Ac20 -C 5H5N to a bromotriacetoxyanthracene, m.p. comp.) ; 2 : 4:-dinitrophenylhydrazone, decomp. about 203—204°, oxidised by Cr03 and then hydrolysed by 305°], contains no OH, but, when hydrogenated conc. H,S04 to 2-bi'omoquinizarin, m.p. 232—233°. (Pd-C) in EtOAc, affords, by opening of an O-ring, 2(3)-Bromo-l-hydroxy-i : d-anthraquinone has been dihydropterocarpin, C H 0 5, m.p. 141—-142° [Ac, prepared. 2:3: lO-Trichloro-l-hydroxy-2 : ‘¿-dihydro- 17 16 m.p. 96—97°, and Bz derivative, m.p. 128-5°; Me 4, : $-anthraquinone (X), m.p. 178— 179° (decomp.), and ether, m.p. 107— 108° (Br derivative, m.p. 136— its Ac derivative, m.p. 146— 148°, are described. 137-5°)]. KOH fusion of (I) gives m-C H (OH)2, and 0 2(3) : lO-Dichloro-l-hydroxy-i : 9-anthraquinone (XI), 6 4 3 affords an ozonide decomposed by H 0. Homoptero- m.p. about 190°, from (X) and KOAc in boiling 2 carpin gives a :4 -dinitrophcnylhydrazone. R. S. C. AcOH or in boiling PhCl, readily passes into 2-chloro- 2 quinizarin, is converted by Ac20 in C5H5N into the Artemisic and dihydroartemisic acids from A c derivative, m.p. 230°, and by Ac20 -H 2S04 into dcsniotropossLntonin. P. P. B e r t o l o (Atti 2-chloroquinizarin diacetate. (XI) and boiling NH2Ph Congr. naz. Chim., 1933, 4, 396—401 ; Chem. Zentr., afford 2(3) : IQ-dianilino-l-hydroxy-i : 9-anthraquin 1934, ii, 951— 952).—The Et ester of dihydroartemisic one, slow decomp. > 220°. acid (I) (Ba salt) yields an Etx ether, m.p. 68—70°, Quinizarin is transformed by S0C12 at 135— 140° and a monoacetate, m.p. 72°. Both (I) and artemisic into 10-chloro-l-hydroxy-4 : 9-anthraquinone, con acid (II) yield 1 : 4-dimethyl-7-ethyl-(±-naphthol on verted by A c,0 in C5H5N into the Ac derivative, m.p. fusion with KOH ; it is thus not possible to ascertain 174—175°, hydrolysed by warm, conc. H2S04 to whether the acid obtained from desmotroposimtonm 2 : 4-dichloro-l-hydroxyanthraquinone, m.p. 241— is (I) or (II). H. N. R. 242°. H. W. Constitution of resin phenols and their bio- Constitution of tannins. IV. Absorption genetic relationships. I. Pinoresinol. H. spectra of natural pblobatannins and synthetic E r d t Ma n (Svensk Kein. Tidskr., 1934, 4 6 , 229— 233). flavpinacols. A. B u ss e l l , J. T o d d , an d C. L. —Pinoresinol, C20H22OG (I) (not C19H20O0, Zinke et W ilso n (J.C.S., 1934, 1940— 1945).—The absorption al., A., 1924, i, 1088), is best purified by the action spectra of synthetic flavpinacols are entirely similar of Ac20 -C 5H5N on its K salt to give an Ac2 deriv to those of typical natural phlobatannins, consisting ative (II), m.p. 165-5— 167-5°, [a]D 55-8°, hydrolysed o f 2 sharply defined bands at X 2700 and X 2800— and benzoylated to the Bz2 derivative, m.p. 162—164° 2900. The parent chalkones also show 2 bands in (loc. cit., 159°), [a]D +42-8° [i?r2-derivative, approx. the same positions, but have in addition a C20H18O4Br2(0Bz)2, [a]D +37-1°]. Hydrolysis and broad characteristic band in the violet region, differ méthylation of (II) affords a Me2 ether, m.p. 98—99°, entiating the spectra very sharply from those of the Md + 66-0°, of (I), affording a l-j5r2-derivative, m.p. flavpinacols. * F. R. S. 171— 172°, and (with HN03-Ac0H) a (AT0 2)2-deriv- ative, m.p. 210—212°, and oxidised by KMn04 to Structure of the cardiac aglucones. W. A. veratric acid, and by HN03 to trimethylveratrol (50% J a co bs and R. C. E l d e r f ie l d (Science, 1934, 8 0 , yield). The biogenetic i-elationships of (I) and other 533—534).—The Me arid Et esters of the acid obtained compounds of the coniferyl type as derivatives con by the degradation of digitoxigenin (this vol., ) are 88 taining two guaiacol residues are discussed, (I) being identical with those of setiocholanic acid. These represented by the partial formula (>CR-0-)2(C4H8) results arid those of Tschesche (A., 1934, 1354) show [R==4 : 3-C6H3(OH)(OMe)], the two O atoms having that the cardiac aglucones possess the sterol ring ether linkings. All [a]D vais, are in COMe,. system. Revised partial formulas for strophanthidin J. W. B. and related aglucones are given. L. S. T. Pyro- and hydro-abietic acids. A. G r e t h Uzarigenin. G. A. R. K on (Chem. and Ind., (Angew. Chem., 1934,4 7 , 827—-830).—Abietic acid (I), 1934, 1008).—If the identity of the acid obtained by obtained from colophony by the action of acids, passes Tschesche (A., 1934, 1354) from uzarigenin (I) with at 230° into a lævorotatory acid which has not allosttiocholanic acid is finally established, it follows attained the final stage of isomérisation by heat and that the lactone ring of the cardiac aglucones is is either an isomeric abietic acid or an intermediate directly attached to the 5-membered ring IV in acid between (I) and pyroabietic acids. At 250—260° position C17, and that, apart from the lactone ring, the d- and Z-pyroabietic acids are produced. (I)« their C skeleton is identical with that of the sterols whether obtained by heat or by acid isomérisation, is and bile acids. Tschesche’s work confirms that of hydrogenated (Pt-sponge) to tetrahydroabietic acid (II), Bernal et al. (ibid.) and confirms the position of the m.p. 174—175°, [a]D -fl5°. Pyroabietic acid affords ORGANIC CHEMISTRY. 219 dihydropyroabietic acid, m.p. 170— 171°, [a]D +45° or mm., m.p. 25°, [«Imso -35-6° in CGH6, isolated as its +34-5°, and a H4-acid, m.p. 170— 171°, [a]D -(-37-5° H phlhalate, m.p. 155°, [a]5)(,0 — 16-S° in CGHG, from or +28°, provisionally regarded as identical with (II). which it is obtained by hydrolysis with aq. NaOH. The same acid appears to be isolable from the products (I) has almost no action on EtOAc, only traces of of the hydrogenation of colophony at 300°/200 atm. camphane, dibornyl, bomylene, and a substance, b.p. The course of pyrogcnation is discussed. H. W. 120— 130°/13 mm. [giving a substance, m.p. 249—250° Constituents of ammoniacum resin. I. K. (corr.), with NH2,NH,CO‘NH2], being isolated. K tinz, H .W e id l e , and K. F is c h e r (J. pr. Chem., 1934, J. W. B. [ii], 141, 350—35G; cf. Luz, A., 1896, i, 249; Casparis Steric course of addition and substitution re et al., Pharm. Acta Helv., 1928, 3, 25, 41).— actions. III. eiido-ecco-Isomerism [of nor- .The resin is extracted with Et20 and the solution bornyl compounds]. I. K. A l d e r and G. St e in then extracted with 5% Na2C03; the material [with E. R o l l a n d and G. S c h u lze ] (Annalen, 1934, obtained by acidification (HC1) of the alkaline extract 514,211—227).—The Me ester of 2 : 5-ewiZomethylene- is acetylated (Ac20) to diacelylammoresinol (I), hexahydrobenzoic acid (endo) (I) (this vol., 2 1 1 ) CjgH^Og, m.p. 102°. (I) is hydrolysed by 2JV-Na2C03 is converted (to the extent of 70—80%) by conc. in MeOH to the NaOH-sol. acetylammoresinol, m.p. MeOH-NaOMe into 2 : ¡j-cndonmthylenehexahydro- 129—130°, and by 6% EtOH-KOII to ammoresinol, benzoic acid (exo) (II) (A, R = C 0 2H, R '= H ) , m.p. m.p. 109° [Bz2 (II), m.p. 75°, and di-p-chlorobcnzoyl, 48° (amide, m.p. 187— 188°; anilide, m.p. 130°); in.p. 93-5°, derivatives]. Reduction (H2, Pt02 or the change occurs through an intermediate enolic Pd-BaS04, AcOH) of (I) gives a hexahydro-derivatiyc, form (cf. Hiickel and Goth, A ., 1925, i, 402). The m.p. 64°. (I) and (II) consume approx. 10 Br (6 for chloride of (I) with activated NaN3 (Nelles, A ., 1932, addition; 4 for substitution) in AcOH. (I) is OMe-free. 1118) in CGH6 followed by hydrolysis (conc. HOI) Oxidation (H20 2, AcOH) of (I) affords y-rcsorcylic acid gives emfonorbomylamine (III) (A, R=H, R'=NH2) (III); NaOH-KOH-fusion gives [3-resorcylie acid (IV). (hydrochloride, m.p. 295°; Ac derivative, m.p. 124°) Ozonolysis of (I) gives an aldehyde, C14H 120 7, degraded (no details) to (III) and (IV). H. B. Poisonous substance in croton oil. II. Con ch, „ : stitution of crotophorbolone. B . F l a s c h e n- A& (exo) trI ger and F . F . v o n F alkenhausen (Amialen, (A.) >R ' (endo) (V.) 1934, 514, 252—260; cf. this vol., 64).—Crotophorbol one (I) (previously designated anhydrophorbol), (cf. Komppa and Beckmann, A., 1934, 1105); crulo- C20H2GO5, m.p. 228°, [ Preparation and properties of furyl phenyl and pptd. therefrom by C02, it does not contain a ketimine. J. B. C u l b e r t s o n and B. D a v is (Proc. C02H or lactone ring. By CH2N2 or Me2S04 (I) gives Iowa Acad. Sci., 1932,39,177).—Furyl phenyl ketimine. the Me5 etlier (IV), m.p. 203° (oxime), which with (I) is prepared from furonitrilc and MgPhBr. The hot 5% KOH-EtOH rapidly yields an iso-derivative hydrochloride is rapidly hydrolysed to furyl Ph (V), m.p. 136° (dioxime; Ac derivative, m.p. 158°), ketone; the velocity of this hydrolysis and the previously called (IV). With Me2S04 (V) gives basic strength of (I) arc recorded. Ch . A b s . (r) iso'fukugetin MeQ ether, m.p. 188°, Hydropyran nucleus. II. Bromo-derivatives OH CO stable to KOH, but giving with of tetrahydropyran. R. P a u l (Bull. Soc. chim., ptt HC1 (IV); the isomcrisation of 1934, [v], 1, 1397— 1405; cf. A ., 1934, 1225).— g p (IV) to (V) is due to change of With dry Br in Et20 at —17° dihydropyran (I) (VI.) ° < S c O *» -CO'CfOHJXH-. affords 2 : 3-dibromotelrahydro- (II), b.p. 96—989/9 mm. [contaminated with (III)], converted by distillation KOH fusion of (I) gives phloro- at 25 mm., or better by NPhEt2, into 3-bromo-t> : 6- glucinol, protocatechuic acid, and AcOH. (I) is, dihydro-pyran (III), b.p. 65°/25 mm. With HBr (I) therefore, (VI) [R = 3 : 4-CGH3(OH)2; R ' and R "= gives 2-bromotetrahydropyran, b.p. 61°/16 mm. (resini- H and respectively, or vice fics in air). With NaOH in presence of Pb(N03)2 (II) affords 3 -bromo-2-hydroxytetrahydropyran (IV), m.p. versa], Garcinin is inipure (I). R. S. C. 79—80° (reduces Fehling’s solution or NH3-AgN 03), but with H20 at room temp, is obtained the ether Constitution of hydroxy-derivatives of di- phenylene oxide. K . T a t e m a t s u and B. K ubota (C H ,< gg^ r^CH-)20, m.p. no® (block) (no (Bull. Chcm. Soc. Japan, 1934, 9, 448^—457).— reducing properties), also obtained by interaction of The compound obtained by heating resorcinol with equimol. quantities of (II) and (IV). J. W. B. W30 8 (A., 1925, i, 809) is 2-hydroxydiphenylene oxide (I), m.p. 138— 138-5° [Ac derivative, m.p. Attempts to synthesise 5 : 6-dihydroxyflavone I l l —111-5°; Me ether, m.p. 97— 97-5°; (iY02)2- (primetin). W. B a k e r (J.C.S., 1934, 1953— 1954). derivative, m.p. 216—217° (decomp.)], obtamed by —2 : 6-Dibenzoyloxyacetophenone, m.p. 105° (simplified diazo-reaction from 2-aminodiphenylene oxide (II), prep, of 2 : 6-dihydroxyacetophenone), with K 2C03 m.p. 99— 99-5° (lit., m.p. 94° ; cf. Cullmane, A., 1931, in PhMe gives 5-hyciroxy-3-benzoylflavone, m.p. 96) [^c derivative (III), m.p. 176-5— 177°]. Bromin- 177° (cf. Sugasawa, A., 1934, 1107). 2 : 4-Diacetyl- ation of (I) affords d-bromo-2 -hydroxydiphenylene oxide resorcinol dibenzoate, m.p. 123°, with KOAc-EtOH (IV), m.p. 113— 113-5° (Me ether, m.p. 147— 148°). yields a small amount of 5-hydroxy-G-acetylflavone Bromination of (III) affords ‘¿-bromo-2 -acetamido- (I), m.p. 201°, also obtained from 5-acetoxyflavone diphenylene oxide, m.p. 195— 195-5°, hydrolysed to and A1C13 in P1iN02. Quinacetophenone and NaOAc- the corresponding amine (V), m.p. 129— 130°, which A c20 form 5-0-acetylquinacetophenone. (1) cannot be gives (IV) by diazo-reaction. Replacement of NH, oxidised with H20 2 or BzO, to primetin. F. R. S. in (V) by H gives 3-bromodiphenylene oxide (Mayer Constitution of fukugetin. II. M . M u r a k a m i et al., A., 1922, i, 746). (V) affords (Sandmeyer) and T. I r ie (Proc. Imp. Acad. Tokyo, 1934, 10, 2 : 3-dibromodiphenylene oxide (VI), m.p. 150— 150-5°. 568—571; cf. A., 1933, 398).—Fukugetin (I) (H 3-Nitro-2-aminodiphenylene oxide (VII) (A, 1924, i, sulphate), CaiH1G0 9 (loc. cit., C22H 160 8), with 50% 161) affords (diazo-reaction) 2 -bromo-3 -nitrodiphenylene KOH gives fukugenetin, garcinol (II), and 3:4- oxide, m.p. 171— 172°, reduced to 2-bromo-3-amino- C6H3Ac(OMe)2. (II), C15H10O5 (lit., C16H120 5) (deriv diphenylene oxide, m.p. 172— 172-5°, which gives atives give depressions of the m.p., when mixed with (VI) (Sandmeyer). The constitutions of (IV) and those of 5 : 7-dihydroxy-3-j>-hydroxyphenyleoumarin), (VII) were thus established [cf. Cullmane, loc. cit,, readily gives a / / 2-derivativo (catalytic reduction) who supposes the N 02 in (VII) to be in the 1 -position]. and with Me2S04-K 0 H affords, by opening of the H. G. M. lactone ring, “ pentamethylgarcinol hydrate ” (III), m.p. Pyrenium compounds. XXIV. 2 : 3 -Benzo- 142— 143°, Which is synthesised. ^-OMe-C8H4-CHO xanthone and 9-phenyl-2 : 3-henzoxanthenol. W. and «-chloro-2 : 4 : 6-trimethoxyacetophenone give D il t h e y and F. Q u in t (J. pr. Chem., 1934, [ii], 141, 306—310; cf. A., 1934, \2 2 1 ).— 3 -Plienoxy-$- the substance, 0 < ^ H -C ^ C aEU(OMe)3’ m p‘ 115— 11G°’ naphthoic acid, m.p. 183— 184° (obtained together which yields successively fi-p-anisyl-y.-2 : 4 : 6-tri- with an acid, m.p. 132— 133°, from NaOPh, 3 :2- methoxyphenyl-lactic acid, amorphous, the anhydride, C10H6I-CO2K, and Cu-bronze), is converted by OMe-C6H4-CH:C(CO2Ac)-C0H2(OMe)3, m.p. 100— 103°, PC15 in C6H G into 2 : 3-benzoxanihone (I), m.p. and x-carboxy-2 : 4 : 6 : i ’-tetramethoxystilbene, m.p. 201—202°, which is more yellow 188—188-5°, the Me ester of which is (III). (II) is, CO than the 1 : 2- and 3 : 4-iso- therefore, 2-p-hydroxybenztjlideneA : G-isocoumarone. merides. (I) and MgPhBr in Atr (I) affords by Ac20 - EtO-CfiH6 give 9 -phenyl-2 : 3- /v NaOAc the Ac, deriv- œ benzoxanthenol (II), m.p. 157-5— p-OH-C6H4-CH:Q----- / \ ative. m.p. 273-274°, (I.) 158-5° [corresponding perchlorate,, OCx 1 'OH and by Me2S04 the m.p. 271—272° (decomp.)], which (H.) il/e4 ether, m.p. 252— affords green salts. The 2 : 3-bcnzo-group has a 254°, of anhydrofuku- bathochromic action (cf. Dutta, A., 1934, 1013). getin, C24H 10O4(OH)4. Since also (I) is sol. in KOH (II) is reduced (Zn dust, AcOH) to 9-phenvl-2 :3- ORGANIC CHEMISTRY. 221 benzoxanthen (Kaufmann and Egner, A., 1914, i, 2 : 4-dimethylpyrrole-5-aldeliyde. (I) with 39). The compound described: as. (II) by Gomberg C0Cl,CH2-C02Et yields Et 3 : 5-dimcthyl-2-pyrroyl- and Schoepfle (A., 1917, i, 551) is ,,9-phenyl-1 :2- acetate (III), in.p. 95° (semicarbazone, decomp, about benzoxanthenol. H. B. 170°); from (III), 5-acetyl-2 : 4-dimethylpyrrole, Varying valency of platinum with, respect to 3 : 5~dimethyl-2-pyrrylphenylpyrazolone, m.p. 141°, mercaptanic radicals.—See this vol., 182. and, using NH2Me, 3 : 5-diviethyl-2-pyrr&ylmethylacct- amide, m.p. 156°, are prepared. E. W. W. Poisonous constituents of the seeds of Teph- rosia vogelii. K. W. Merz and G. Schmidt (Arch. Mixed functional derivatives of 2 :4-dimethyl Pharm., 1935, 273, 1— 21; cf. A., 1932, 888).—These pyrrole. F. I n g r a f f ia (Gazzetta, 1934, 64, 784— seeds, freed from protein (39%) and oil (10-5%) by 792).— (I) (preceding abstract) with CH2C1-C0C1 ligroin, yield to COMe2 a mixture containing dehydro- yields 5-chioroacetyl-2: 4-dimethylpyrrole, which deguelin (I), aliotephrosin (II), C^H^O?, m.p. 194— gives the following products : with KOH, 3 : 5-di 195°, and isodeguelin (III), C^H^O,-,, m.p. 107— 168°. methyl-2-pyrroylcarbinol, m.p. 208° (Ac derivative, The Ac derivative, m.p. 119-5— 120-5°, of (II) loses m.p. 108°), oxidised (KMn04) to (II) ; with KCN, AcOH at 180° to yield isodehydrodeguelin (IV), m.p. 3 : 5-dimethyl-2-pyrroylacetonilrile, m.p. 195°; -with 235—236°, colourless; with -C6H4Me-S0 3Me it gives aq. NH3 and NH2Me at 100°, 5-aminoacetyl-, m.p. (I) and with 0-03iV-K()H-aq. EtOH gives isoallo- 203° [hydrochloride; picmte, m.p. about 195° (de tephrosin (V), C23H220 7, imp. 202°. Hydrogenation comp.)], and 5-methylaminoacetyl-2 : ‘i-dvmethylpyr- (Pt02) of (II) in AcOH gives impure dihydrooMo- role, decomp. 260° (hydrochloride), respectively. (I) tephrosin, the Ac derivative, m.p. 266°, of which with and BzCl yield 5-benzoyl-2 : 4-dimethylpyrrole (A., ])-C6H4Me-S03Me affords dihydrodchydrodeguelin. 1915, i, 990) (picrate, m.p. 92°; iodate, m.p. 109°). (II) with KMn04-C0Me2 gives aliotephroshulicarb- E. W. W. oxylic acid, C23H220 11, m.p. (+ ? H20) 122— 124°, Reaction between phthalic anhydride and the (anhyd.) 171°, hygroscopic, isomerised by H20 2-K 0 H magnesium derivative of 2 : 4-dimethylpyrrole. to an acid, m.p. 210—211° (decomp.). With f l2S04- F. I n g r a f f i a (Gazzetta, 1934, 64, 714—718).—This AcOH (1 : 2) at 60—65° (II) yields (I), but with reaction yields 3 : 5-dimethyl-2-pyrrylenephthalide (I), boiling Ac20-N a0A c (IV), which with KOH-Zn m.p. 207° (4-i>e?Keneazo-clerivative, m.p. 76°), and dust affords deguelic acid (VI) [Me ester, m.p. 125— 3 : 5 - dimethyl - 2 - pyrrylenephenylcarbinol - o - carboxylic 126°; oxime, m.p. 168—169° (decomp.)]. (II) and ■ j /TT> CO,H‘C6H4‘C(OH):C'CMc\r,TT 1QQO acid (II), ■» NICMe^ ’ m-P’ cold RH3-EtOH give (V), the Ac derivative of which, 2 6 8 when heated above the m.p., 193—194° (decomp.), (Ag salt); (I) with KOH gives (II). E. W. W. gives AcOH and (IV). Hydrogenation of (V) gives Pyrrole derivatives. I. I. J. R i n k e s (Rec. l. acetyldihydroiso&Wotephrosin, m.p. 193— 194°, and trav. chim., 1934, 53, 1167— 1174).—2-Acetylpyrrole dehydration by H2S04-Ac0H gives (IV). (Ill), with Ac20 -H N 03 (d 1-51) at — 10° to —15° gives a a 0° (oxime, m.p. 233—234°), gives by hydrogenation mixture of its 4- (I), m.p. 197°, and 5-N02- (II), m.p. dihydrodeoxydeguelin, G^H^Os, m.p. 153— 154°, by 156°, -derivatives (cf. Ciamician et al., A.,1886, 718). K3Fe(CN)6 (IV), and by Ac20 -C 5H sN (I). Aerial Me pyrrole-2-carboxylate with 1-5 mols. of HNOa oxidation of (III) in NaOH-COMe2 affords (V), whilst also gives its 4- (III), m.p. 197°, and 5-N02-, m.p. in Et20-aq. NaOH a mixture is rapidly formed, 181— 182° (lit. 178°), -derivatives, also obtained (after wherefore it is concluded that (II) may be formed esterification) together with 2-nitropyrrole (IV), m.p. from (III) during isolation from the plant. The 55°, by Ac20-HN"03 (1-25 mol.) on the corresponding formula- given is assigned to (IV) and it is considered acid. Nitration of pyrrole with Ae20 -H N 0 3 (1-25 that tephrosin and isotephrosin are cis- and trans-7- mols.) at —10° gives (IV) (21% yield), but with 2 mols. MeO of HN03, 2 : 4- (V), m.p. 149— 150°, and 2 : 5-(N02)2-, m.p. 173°, -derivatives [also by similar nitration of (IV)] are obtained. With HN03 (d 1-51) at —10° (III) gives (V). When heated with 25% H N 03 (I) and (II) are converted, respectively, into 4 : 4'-, m.p. 219°, and 5 : 5'-, m.p. 176°, -dinilro-2 : 2'-dipyrryl- dinitrosacyl (cf. Holleman, A., 1892, 971), hydrolysed CO by hot aq. NaOH, respectively, to 4-, m.p. 217°, and y\cH/v 5-, m.p. 160— 161°, -nitropyrrole-2-carboxylic acid. 0 \ HOl (VI.) J. W. B. Thiolpyrrolecarboxylic acids. K. N e is s e r CH2-CO„H (Ber., 1934, 67, [5], 2080—2083).—Et 2 : 4-dimethyl- and (II) and (V) cis- and ¿rans-S-hydroxydeguelins, and pyrrole-3-carboxylate is transformed by Cu(CNS)2 in that deguelin and (III) are cis-trans-ring isomerides. boiling MeOH into Et 5-thiocyano-2 : i-dimethylpyr- The change of (IV) into (VI) is assumed to proceed by role-3-carboxylate, converted by cautious hydrolysis of (4 ) and (B). R, S. C. into Et o-thiol-2 : 4.-dimethylpyrrole-3-carboxylaie, m.p. Ketonic acids with pyrrole nucleus. F. In- 107— 108°, which loses H2S and NH3 under the action oraffia (Gazzetta, 1934, 64, 778—784).—The Mg of aq. KOH. The product obtained by the action JfA®'af e (I) of 2 : 4-dimethylpyrrole reacts with of C02 on the pyrrole-Grignard compound is pyrrole- (-0Cl-C02Et to give Et 2 : 4-dimethylpyrrole-5-gly- 2-carboxylic acid (I), m.p.. 207°, and a dimorphous oxylate, of which the acid (II) gives on decomp. modification (II), m.p. 161°, incorrectly regarded as 222 BRITISH CHEMICAL ABSTRACTS.— A. pyrrole-3-carboxylic acid, since (I) and (II) do not ketonocarboxylic acid (III) as is obtained (Noelting give a depression in mixed m.p., and yield identical Me and Herzbaum, A., 1911, i, 917) from (I) and (II) in esters (III), m.p. 72-5—73°, and Me Br3-esters, m.p. alkali. Di-indone and (I) in boiling iV-NaOH also 208—210°; hydrolysis of the ester from (II) gives afford (III); in AcOH, a substance, m.p. 310° (Cu (I), and (I) is obtained when the solution of (II) in block), results. H. B. H20 is seeded with (I). Cautious bromination of Synthesis of Bs-tetrahydroquinolines. II. U. (III) gives Me dibromopyrrole-2-carboxijlatc,, m.p. 164— B a su (Annalen, 1934, 5 1 4 , 292—298; cf. A., 1934, 165°. (Ill) is transformed by Cu(0NS)2 in boiling 1 1 1 1 ).—6-Methyl - 2 - hydroxymethylenecycZohexanone MeOH into Me 2-thiocyanopyrrole-5-carboxylate, m.p. and Et (3-aminocrotonate at 100° give Et 2 : 8-di- 107°, converted by cautious hydrolysis into 2-thiol- methyl-5: 6 :7 : 8-telrahydroquinoline-3-carboxylate, b.p. pyrrole-5-carboxylic acid, m.p. 173° (decomp.) [Me 166°/11 mm. (picrate, m.p. 127°); the free acid, m.p. ester, m.p. 83—84°], not identical with the product 214° (decomp.), distilled with soda-lime in a vac. obtained by Windaus et al. (A., 1934, 1415) from affords 2 :8-dimethyl-5: 6 :7 : 8-tetrahydroquinoline, b.p. vitamin-B v H. W. 227—228°/754 mm. (picrate, m.p. 118°; platinichlor Fission of pyridine. H. F r e y t a g (Ber., 1934, ide, m.p. 182—183°; mercurichloride, m.p. 136°). 67, [JS], 1995—1998).—Addition of BzCl to C5H 6N - 2 : (¿-Dimethyl-5 : 6 : 7 : 8 -tetrahydroquinoline-3 -carb- H20 followed by acidification of the solution leads to oxylic acid [Et ester, b.p. 170—171°/9 mm. (cf. loc. BzOH and glutacondialdeliyde (I) [identified by the cit.)] similarly affords 2 : 6-dimethyl-5 : 6 : 7 ; 8 -tetra “ fluorescence test ” (II), which consists in adding hydroquinoline, b.p. 235— 236°/752 mm. (cf. von 2)-NH2;C0H4,CO2Et and HC1 to the solution and Braun et al., A., 1924, i, 553) (picrate, m.p. 146°; extraction with amyl alcohol, thus giving a solution platinichloride, m.p. 185°); the 2 : 7-Me2 derivative with green fluorescence]. The presence of (I) in (loc. cit.) gives a mercurichloride, m.p. 151°, and a hydro C5H5N which has been exposed to moist air but not chloride, m.p. 168—169°. 4 : 5-Dimethyl-2-hydroxy- in freshly distilled C5H5N and also in the products methylenecycZohexanone similarly affords Et 2:6:7- of the action of NaOH and CHC13 on C5H 5N is trimethyl-5 : 6 : 7 : 8-teirahydroquiribline - 3 - carboxylate, established by (II). H. W. b.p. 172°/13 mm. [freeacid, m.p. 135—136° (decomp.)]; 2 : 6 : 7-trimethyl-5: 6 :7 : 8-tetrahydroquinoline (picrate, Influence of temperature on the formation of m.p. 105°; platinichloride, m.p. 187°) has b.p. 239— additive com pounds.—See this vol., 182. 240°/752 mm. 2-Hydroxymethyleneq/cZohexanone (I) Indoleacetic acids. F. E . K in g and P.L’ E c u y e r and [3-aminocrotononitrile at 100° give 3 -cya?w-2- (J.C.S., 1934, 1901— 1905).—2-Carboxyindole-3-acetic methyl-5:6 :7: S-tetrahydroqu inoline (II), m .p. 107—108° acid, obtained by hydrolysing the Et ester, gives at (picrate, m.p. 160—161°), and a substance, m.p. 235°; its m.p. skatolo, but in quinoline at 195° loses 1 mol. (II) is hydrolysed (75% H2S04) to the 3 -carboxylic of C02 to give indole-3-acetic acid in small yield. acid (loc. cit.) (platinichloride, m.p. 120— 12 1 °). (I) NHPh*NHMe (I) and a-ketoglutaric acid afford 2- and acetylacetoneimine at 100° afford 3 -aeetyl-2- carboxy-l-melhylindole-3-acetic acid, m.p. 234°, decarb- methyl-5 : 6:7:8 -tetrahydroquinoline, m.p. 55° (picrate, oxylated in quinoline to l-methylindole-3-acotic acid m.p. 155°; semicarbazone, m.p. 195°); Z-acetyl-2 : 0-, (II). Et 2-carboxy-l-methylindole-3-acetate, m.p. 184°, b.p. 165°/15 mm., m.p. 65° (picrate, m.p. 168°; semi at 190—200° gives Et l-methylindole-3-acetate, b.p. carbazone, m.p. 215°), and -2 :1 -dimcthyl-o : 6 : 7 : 8- 165°/1 mm., hydrolysed to (II) [best method of prep, tctrahydroquinoline, b.p. 169— 170°/16 mm. (picrate, for (II)]. (I) and acetonedicarboxylic ester form m.p. 169°; semicarbazone, m.p. 214°), are similarly (HC1) Et 3-carbethoxy-l-methylindole-2-acetate, m.p. prepared. Benzoylacetoneimine and the appropriate 90°, hydrolysed to 3-carboxy-\-methylindole-2-acetic hydroxy methylenecf/dohexanone give 3 -benzoyl-2- acid, m.p. 262°, or to 3-carbethoxy-l-methylindole-2- methyl-, m.p. 73° (picrate, m.p. 184°), and - 2 : 6-di acetic acid, m.p. 170°. The lialf-ester at 180— 190° methyl-, m.p. 76—77° (picrate, m.p. 170°), -5 : 6 : 7 : 8- gives Et 1 : 2-dimethylindole-3-carboxylate, further tetrahydroquinolines. The above Ac derivatives are hydrolysed to the acid. " F. R. S. accompanied by HCl-insol. by-products. H. B. Condensation of isatin and 1 :3-indanedione. The complex compounds [MX2,2A] and W. M. F isc h e r and A. Cirtjlis (Annalen, 1934, 5 1 4 , [MX,]H 2,2A. J. V. DuBSKi and V. D ostal (Publ. 261—267).—Isatin (I) (1 pt.) and 1 : 3-indanedione Fac. Sci. Univ. Masaryk, 1934, No. 196, 17—23).— (II) (2 pts.) in MeOH at room temp, for 5 days give a The prep, and properties of the compounds: little of a blue compound, m.p. 263° (insol. in aq. [CdCl4]H „P y2; CdCl2,Q2, m.p. > 300°; NaOH), and (mainly) the NaOH-sol. 2-keto-Z : 3-di- CdCl2,Q,HCl,H20, m.p. 280°; CdCl„Py2, m.p. >350°; (1': 3'-diketo-2'-indanyl)-2 : 3 - dihydroindole, MnCl2,Q2,3H20, m.p. > 350°; [MnCl4]H2,Q2i2H20, m.p. 144°, and its isomeride, m.p. 105°; CoC12,Q2, m.p. -^H 173—175° (decomp.); picrate, m.p. 245—246°; Ac, m.p. 247° (decomp.), hydrolysed (conc. aq. NH3) to m.p. 149— 150°, and NO-,-m.p. 144°, derivatives], the I-Ac derivative, m.p. 236° (decomp.), and thence obtained by heating COPhMe with to (II). (I) and boiling Ac20 -C 5H 6N or Ac20 at »i-C6H4Me-NH-CS-NHPh at 180—205° and finally at 160-—170° (bomb) give 5-acetamido- (III) (A., 1926, 300°, is proved by its hydrolysis with KOH-EtOH at 414) and a little 5-diacetamido-, m.p. 100° (uncorr.), 200° to ‘k-hydroxy-2-phenyl-5-methylquinoline, m.p. -l-acetyl-3-methylhydantoin. (Ill) is converted by aq. 281°, different from the known -7-Me isomeride, m.p. basic Pb acetate at 100° into 5*acetamido-3-methyl- 270°. Condensation of CH2Ph-COPh with CS(NHPh)2 hydantoin (IV), re-acetylated (Ac20-conc. H2S04) to at 190—220° and then at 280° affords 4:-anilino- (III). (Ill) or (IV) and conc. aq. jSTH3 give NHi 2: Z-diphenylquinoline, m.p. 196— 197° [hydrochloride, a.-acetamido-M-methylhydantoate, m.p. 178— 180° (de m.p. 279°; nitrate, m.p. 185° (dccomp.); picrate, m.p. comp), converted by basic Pb acetate into (IV) and by 259—260°; and iTO-derivative, m.p. 153— 154° (de Ac20 into (III). 1 : 8-Dimethylallantoin (V) or its comp.)], similarly hydrolysed to 4-hydroxy-2 : 3-di- Ac2 derivative and boiling Ac20 afford 5-acetyl- phenylquinoline. J. W. B. methylamino-l-acetyl-3-methylhydantoin, m.p. 128— Direct introduction of amino-groups into 130°, whilst the 6-Ac derivative of (V) similarly gives aromatic and heterocyclic nucleus. II. Re i-ethoxy-3 : G-diacetyl- 1 : 8 -dimelhylacetylenediureine, action of isoquinoline with alkali and alkaline- earth amides in liquid ammonia. F. W. B e r g - CO^ m e ^ 0OEt)-NAc^>CO’ m,p- 155~ 156°> hydro stkom (Annalen, 1934, 515, 34—42; . cf. A., 1934, lysed (EtOH-NH3) to the G-Ac derivative, m.p. 185° 1110).—1-Aminoisoquinoline (I), m.p. 122— 123°, is (decomp.); the OEt is probably introduced during obtained in 60—75% yield from isoquinoline (II) and crystallisation of the reaction product from EtOH. an excess of KNH2 (III) in liquid NH3 at room temp.; All m.p. are corr. unless stated otherwise. H. B. the reaction mixture is freed from NH3 and then Constitution of porphyrindine ; magnetic treated with Cf,H6 and H20. NaNTI2 similarly gives proof of an organic bi-radical. R. K u h n , H . 20^—30% of (I) and resin. Little reaction occurs K a t z , and W. F r a n k e (Naturwiss., 1934, 22, 808— between (II) and LiNH2, Ca(NH2)2, or Mg(NH2)2. 809).—Porphyrindine is paramagnetic and is a true Ba(NH2)2 reacts rapidly but somewhat less readily bi-radical (cf. A., 1934, 718). This is in agreement than (III); reaction is accelerated by Ba(CNS)2. Of with the constitution given by Piloty (A., 1903, i, 523). the complex ammono-salts investigated, only H. G. M. BaKNT,2NH3 and K 2NaN,2NH3 react with (II) to Amidations with sodium and potassium give (I); dissociation probably occurs to some extent. amides in the alkaloid series. II. a- and H. B. a'-Aminoanabasine. M. I. K a b a t sc h n t k and M. M. Preparation of 3 : 6-dicarboxybenzoyl-A7-ethyl- K a t z n e l s o n (Compt. rend. Acad. Sci. U.R.S.S., 1934, carbazole. V. A. Ignatiuk-M ajstrenko and N. S. 4, 47— 50; cf. A., 1934, 538).—Anabasine and Tichonov (Anilinokras. Prom., 1934, 4, 473— 475).— NaNH2 in NHMe2 at 135— 145° afford 2-(2'-amino-3'- A1C13 is added to a 1 : 4 : 20 mol. mixture of iV-ethyl- pyridyl)-, m.p. 109° (cf. A., 1934, 422), and 2-(2'- carbazole, o-C6H4(00)20, and PhCl, the mixture amino-5’-pyridyl)-piperidine, m.p. 85-5— 90°, the diaz- heated at 50—70°, poured on ice, made acid with onium compounds of which are converted into the HC1, and PhCl removed by steam-distillation. The 2'-Ci-compounds, m.p. 99-5— 100° and 58-5— 59-5°, residue is dissolved in aq. NaOH, the solution filtered, respectively. These are oxidised (KMnO,,) to 2- 3-mono- (I) and 3 : 6-di-carboxybenzoyl-9-ethylcarb- chloropyridine-3- and -5-carboxylic acid, respectively. azole are pptd. by HC1, and separated by C8H G, which J. L. D. dissolves only (I). R. T. Complex salts of 2 :2'-dipyridyl with bivalent New iY-substituted C-derivatives of barbituric copper.—See this vol., 167. acid. E. Gryszkiewioz-Trochimowski (Arch. Intermediate compounds between ferrocyan- Chem. Farm., 1934, 2 , 1 — 8).—The following com ides and ferroam m ines.— See this vol., 181. pounds are obtained from NEt2,CH2,CH2Gl and the Na salts of various substituted barbituric acids (I) in Cyanine dyes. VII. Synthesis of pentameth- EtOH at the b.p. : 3-$-diethylaminoethyl-5 : 5-diethyl-, inecyanines. T. O g a t a (Proc. Imp. Acad. Tokyo, an oil (hydrochloride, m.p. 225— 226°); -5-ethyl-5-n- 1934, 10, 572—574).— In a new method of preparing bufyl-, an oil (hydrochloride, m.p. 212— 213°); -5-A1- 1 : 3 : 3 : 1' : 3': 3'-hexamethylindodicarbocyanine ^\ohexenyl-\ : 5-diethyl- (II) (hydrochloride, m.p. iodide, the product obtained by condensing 1 mol. of 150—151°); -5-phenyl-5-ethyl- (III) -barbituric acid diphenylformamidine with 1 mol. of 2 :3 :3-tri- [tydrochloride, m.p. 245—246°). (II) and (III) have methylindolenine methiodide is heated with Ac20, only a feeble analgesic and narcotic action as com together with CH(OEt)3 or the K salt of a carboxylic pared with the corresponding (I), but greatly depress acid. Similar preps, of 2 : 2'-diethylthiadicarbo- Wood pressure. R . T . cyanine iodide are described. The course of the reaction is not clear. F . M . H. Degradations of allantoins. H. B i l t z and L. «Mswb (J. pr. Chem., 1934, [ii], 141, 284—298).— Cyanine dyes containing an isoquinoline 3-Methylallantoin (I) and Ao20-conc. H2S04 give nucleus. (Miss) N. I. F is h e r and (Mi s s ) F . M . (probably) the 1 : 6-Ac2 derivative, H a m e r (J.C.S., 1934, 1905— 1910).— 1-Chloroiso- quinoline, b.p. 160— 165°/20— 30 mm. (improved 189°, is similarly prepared. The ethiodide with NH3 m.p. 184°, and does not react with Ac20, BzCl, or forms 1-amino-, m.p. 194°, and with NH.,Ph 1- ketonic reagents. The constitution (I) is supported by anilino-Koquinoline. ethiodide, m.p. 192— 193°. 1- its transformation by MgPhBr into the compound (II), Bromo\mquinoline ethobromide, m.p. 128°, and 1- m.p. 149° [hydrochloride, m.p. 130° after softening at iodoisoquinoline n-propiodide, m.p. 116— 117°, are 122°; picrate, m.p. 139° (decomp.); methiodide, similarly obtained. Quinaldine methiodidc (I) and m.p. about 96° (decomp.); Ac derivative, m.p. 176°]. Na in EtOH give 1 : 2'-dimethyl-2 :1 '-cyanine iodide, Similarly (I) and CH2PlrMgCl give the substance m.p. 234°, and by use of the appropriate reagents C19H16ON2, m.p. 132° [picrate, m.p. 128° (decomp.); 2'-methyl-l-ethyl-, m.p. 250°, 1 : 2'-diethyl-, m.p. 258°, Ac derivative, m.p. 139°]. (II) gives a methiodide, 6 : 2'-dimethyl-1-ethyl -, m.p. 234°, and 2'-methyl-1- m.p. 213° (decomp.) [corresponding perchlorate, m.p. ethyl-5 : G-benz-2 : 1'-cyanine iodide, m.p. 250°; 2'- 208° (decomp.), and picrate, m.p. 200°], oxidised by methyl-l-ethyl-4 : 1 '-cyanine iodide, m.p. 210 ° [from K 3FeC6Nfi in alkaline solution to the compound (III), lepidine ethiodide and (I)], and 2 : 2'-diethylthia-, m.p. 181°, which is converted by MgPhBr into a m.p. 246° (from 1-mcthylbenzthiazole ethiodide and substance, m.p. 264°, and a compound [picrate, m.p. 1 -iodojsoquinoline ethiodide), 2-ethyl-2'-i\-p ropyl t hi a -, 170° (decomp.)]; 3-Hydroxy-2-tetrahydroxybutyl- m.p. 237°, 2'-methyl-2-ethyl-ii : 4-benzthia-, m.p. 235° quinoxaline is transformed by dehydrating agents [from 2-methyl-fl-naphthathiazole ethiodide and (I)], into a substance, m.p. 255°. H. W. 2'-methyl-2-ethyl-5 : G-benzthia-, m.p. 233°, and 2'- Photochemical formation of 6 : 7-dimethyl- methyl-2-ethylselena-, m.p. 238° [from 1-methyl- aUoxazine from lactoflavin. R. K u h n and H. benzselenazole ethiodide and (I)], and 4 : 2'-dimethyl- Rudy (Ber., 1934, 67, [B], 1936—1939).—The 3-ethylthiazolo-1 -cyanine iodide, m.p. 235° [from 2 : 4- formation of 6 : 7-diinethylalloxazine by irradiation dimethylthiazole ethiodide and (I)], are obtained. of lactoflavin in neutral or weakly acidic solution is The cyanines containing an isoquinoline nucleus are, established by treatment of the product with CH2N,, in general, definitely weaker as photographic sensi- whereby 1:3:6: 7-tetramethylalloxazine, m.p. 250° tisers than those containing a quinoline nucleus. (corr.), is produced. H. W. M.p. are also decomp, points. F. R. S. Synthetic compounds of the lactoflavin group. New phenazine synthesis. Phenazhydrins. R. K u h n and F. W e y g a n d (Ber., 1934, 67, [5], I. G. R. C l e m o and H. M cIlwain (J.C.S., 1934, 1939— 1941).—Halogeno-o-nitro-benzenes and -xyl 1991— 1993).— cj/c/oHexane-1 : 2-dione and o- enes are condensed in presence of tert.-bases (C5H5N) C6H4(NH2)2 condense (AcOH-NaOAc) to 1 : 2 : 3 : 4- with the amines NH2,CH2*[CH‘OH]3"CH2,OH ob telraliydrophenazine, m.p. 92-5°, dehydrogenated with tained by reduction of the oximes of i-arabiriose and I in AcOH to phenazine. 1-Methyl-1 : 2 : 3 : 4- ¿-xylose, and the products are reduced (SnCl2) in telrahydrophenazine (I), b.p. 160—165°/20 mm., m.p. presence of a large excess of alloxan, whereby leueo- 37°, similarly prepared, is dehydrogenated to 1- flavins are produced which are oxidised by air to the metlvylphenazine, m.p. 108°, which is oxidised by flavins. These behave similarly to lactoflavin with H,Cr04 to phenazine-1-carboxylie acid. Oxidation respect to solubility, formation of lumilactoflavin by (H2Cr04) of (I) yields an acid, Cn H 10N2(CO2H)2,H2O, irradiation in alkaline solution, absorption spectrum, m.p. 114— 117°, subliming at 1 mm. to a dehydrated dependence of fluorescence on pa, and formation of a acid, m.p. 187°. Phenazhydrins between the phenazines red radical when reduced in mineral acid solution. and dihydrophenazines are obtained by heating with H. W H2 and platinised asbestos at 325°: phenazhydrin, Synthesis of tetrahydroharman derivatives C13H 10N2,C13H 12N2, between methylphenazine and under physiological conditions. I. G. Hahn its H.,-derivative, m.p. 116°, between phenazine and and H. L u d e w i g (Ber., 1934, 67, [B\, 2031—2035).- dihydrophenazine, m.p. 209° (decomp.), and between Tetrahydroharman is obtained ill almost quant, yield phenazine and methyldihydrophenazine, m.p. 157— from tryptamine (I) and MeCHO at 25° and pa 5*2, 160°. The constitution of the compounds is discussed. 6-2, or 7-0. Similarly (I) and CH2Ph‘CHO afford F. R. S. 3-benzyl-3 : 4 : 5 : 6-tetrahydronorharman [hydro Synthesis of heterocyclic compounds from chloride (II), m.p. 278° (decomp.)]. (I) and o-diamines and sugars. K. M a u r e r and B. CH2PlrC02H afford tryptamine phenylacetate, m.p. Sc h ie d t (Ber., 1934, 67, [B], 1980— 1985).— Con 178° (decomp.), which passes, at 180— 190° into densation of o-C6H4(NH2)2 with glucose, fructose, or, phenylacet-tryptamide (III), m.p. 144°. (Ill) with preferably, sucrose in boiling H20 -A c0 H gives P0C13 in boiling C6HB gives 3-benzyl-5 : 6-dihydro- 2-aPyS-tetrahydroxybutylquinoxaline, m.p. 188°, con norharman [picrate, m.p. 225° (decomp.)], from which verted by H2S04 at 100° into a substance C12Hg0 2N2, (II) is obtained by reduction with Na and EtOH and m.p. 159°, and a compound (I), m.p. 104°. (I) is addition of HC1. H. W. N y-Triazines. XXV. Property of o- and p- nitrophenyliminoketotriazidines (o- and p-nitro- benzylideneguanylcarbamide) of giving platini- V'X n/'S V N sj/V “ octachloride besides the normal platinihexa- chloride. First two complexes of quadrivalent v l : 0 Uph U:o platinum with co-ordination number eight. A (i.) (n.) (m.) Ostrogovich and V. Bena Median. XXVI. D i- optically inactive, does not reduce Fehling’s solution, hydroxytriazinylform aldoxim e and its salts. rapidly decolorises KMn04, yields a hydrochloride, A. Ostrogovich and V. G ra s u . XXVII. Syn ORGANIC CHEMISTRY. 225 thesis of phenacetylbiuret and its transform 136°, derivatives ; 1 : 3 : 9-trimethylspiVodihydantoin ation into dihydroxybenzyltriazine. A. Ostro- similarly affords the 7-Ac derivative, m.p. 110— 120° goyich and I. Tanislait (Gazzetta, 1934, 64, 792— (decomp.) (all m.p. except this are corr.), whilst 3 : 7- 800, 800—824, 824— 832).—X XV . Iminoketo-o-nitro- dimethylspù'odihydantoin (II) gives only a Ac2 deriv ative, m.p. 178° (cf. A., 1926, 962). (I) is ethylated phenyltriazidinc, N H < £ j ^ ^ | > C H C 6H4-N02 (CHMeN2) to the 3 : 7-Et2 derivative, m.p. 123°, (M), in Ar-HCl gives a normal platini chloride, whilst f^feYodihydantoin similarly gives a EtA deriv [PtCl6](H-M)2, m.p. 249—250°, which in 2.V-HC1 gives ative, b.p. 120—140°/0-02 mm. ; cryst. products could the abnormal [PtCls](H\M)4, new m.p. 229—230° not be obtained from (II) and l-acetyl-3-methyl- and (cf. A., 1929, 827). The ^-isomeride similarly gives 3-metliyl-spirodihydantoins. 3 : 7-Dimethylcaffolide the normal, new m.p. 244— 245° (cf. loc. cit.), and the (i.soa^jocafleine) similarly affords the 1 -Et derivative abnormal platinichloride. A„ of the compounds is m.p. 110°. H. B. determined. XXVI. N203 converts dihydroxymethyltriazino Action of acetic anhydride on uric acid glycols into dihydroxytriazinylformaldoxime, and their ethers. II. 9-Methyluric acid [glycol]. III. 3 : 9-Diniethyluric acid [glycol]. < 0 H ™ > C’CH:N'0H (I) [H sulPhate’ hydro H. B i l t z and L . L o e w e (J. pr. Ghem., 1934, [ii], chloride; Na (+ H aO), Na2 (+ 2H 20), Na3 (+ H 20), 141, 246—267, 268—283; cf. this vol., 96).— II. K (+ H 20), NHt, and Ag (+II20) salts; Ba salt, 9-Methyluric acid glycol is converted by short treat (C4H;j03N,,)2Ba (+ 2 H 20 or -j-3H20) (II) ; Fe salt, ment with boiling AcaO into l-acetyl-3-methylsj)ii'odi- (C4H303N4)2Fc (+ 2H 20); Gu salts, C4H203N4Cu hydantoin (I), decomp. 195°, and a trace of l-acetyl-3- (-fH20), and (C4H203N4)2Cu2 (+ 4 H aO)]. Crystallo- methylaUantoin (II), m.p. 255° (decomp.) (all m.p. arc graphic data for (I) and (II) are determined. corr. unless stated otherwise). (I) is acetylated XXVII. CH2Ph-COCl and biuret give phenyl- further to the 1 : 9-Ac2 derivative (III), m.p. 170°, acetylbiuret, m.p. 199—200° (dccomp.), converted by and is methylated (Et20-M e0H -CH 2N2) to tetra- KOH into dihydroxybenzyltriazine, m.p. 251—252° methylsp/rodihydantoin (IV). (I) and pure CH2N2 (decomp.) [hydrochloride, m.p. 258—259° (decomp.) ; (cf. A., 1931, 853) give 9-acetyl-l : 3 : 7-trimethyl- Na, m.p. 236—237°, Ag, m.p. 264—265°, and Ba, m.p. s^nYodihydantoin, m.p. 185— 186°. (II), obtained 254-256°, salts (all decomp.)]. E. W. W. also from (I) and H20 at 60— 100°, is hydrolysed (conc. HC1) to, and prepared by acétylation of, Constitution of dimeric indoles. O. Schmttz- 3-methylallantoin (V). (II) is reduced (HI) to Dumont (Annalen, 1934, 514, 267—279).—Nitrosodi- 3-methylhydantoin. (I) is converted by boiling 3- (I) and -7- (II) -methylindoles are shown to be N- MeOH into Me l-acetyl-3-methylallanloin-5-carboxyl- and not O-NO- derivatives by the methods of Lehin- ate (VI), m.p. 223—225° (decomp.), hydrolysed stedt (A., 1927, 1062) and Clauser fA., 1903, ii, ISO), (conc. HG1 or MeOH-HCl) to (V) and a little (VIII) and by the formation of NO (with small amounts of (below) ; (I) is unaffected by boiling EtOH. (Ill) N20 and/or N2) when (I) and (II) are warmed with is hydrolysed (piperidine in-Et20) to a little (I) and AcOH. (I) is reduced (Zn dust, EtOH-conc. HC1) is ethylated (CHMeN2) to a mixture of 3-rneihyltri- to di-3-methylindole (III) [Ac derivative, m.p. 178— ethyl-, m.p. 110— 115°, and 1 : 9-diacetyl-3-methyl-7- 179°, readily hydrolysed (aq. EtOH-KOH) (cf. Oddo, ethyl-, m.p. 105— 110°, -spirodihydantoin. Impure A., 1934, 419) to (III), thus indicating the presence 3-methyl-7-ethyhiph'odihyda?itoin has m.p. 115° (un- of N- and not C-Ac]. (II) is converted by. EtOH- corr.). (I) is converted by EtOH-NH3, dil. aq. NH3, KOH or -NaOEt in N2 into a compound, C18H15N3 or aq. NH4HCO:! into \-acetyl-Z-methylallantoin-5- -Nr-----OH [PTObaWy (IV)], m.p. carboxylamide (VII) (-fH 20), m.p. 220° (decomp.), ,TV, I 200°; with EtOH- m.p. (anhyd.) 240—245° (decomp.), also prepared ' / y JL NaOEt in air, a com- from (VI) and dil. aq. NH3; (III) similarly gives f ,TT Ç H / if pound, m.p. 237—238°, 1 : Q-diacctyl-3-meÜiylallantoincarboxylamide, m.p. tr^>C-GH— — 'I J results. The formation 245°. The Ac group in (VI) and (VII) is removed of oximino-2 ; 3-di-7- only with difficulty; hydrolysis (aq. HC1) of (VII) methylindole (A., 1933, affords (V) and (VIII). (Ill) is hydrolysed (conc. 958) is not observed in any experiment. Nitrosodi- HC1 at 100° or conc. aq. NH3 at room temp.) to indole and EtOH-KOH or -NaOEt in N2 give a com 3 -methylspirodihydantoin'(VIH) (-f-0‘5H2O), m.p. 155° pound analogous to (IV) and a substance, m.p. 227— (loss of H20), re-solidifying with m.p. 180— 190°, -30° (decomp.). Indole and 3- but not 2-methylindole m.p. (anhyd.) 210° (decomp.) (sinters at 200°), which are polymerised [to tri-indole and (III), respectively] is acetylated to (III), methylated (CH2N2) to (IV), *hen solutions in aq. EtOH-HCl are kept at 30°. and converted by aq. basic Pb acetate at 100° into (V). Ine above results support the constitution previously The Ag salt, m.p. about 265° (decomp. ; uncorr.), of assigned (A., 1933, 958) to di-indole, but not that of (VIII) and Mel give 3 : 7-dimethylsjnrodihydantoin Wdo (loc. cit.). H. B. (IX), m.p. 297° (ef. A., 1917, i, 290), also methylated Acétylation and éthylation of 1 : 9-dimethyl- to (IV). 1 : 7-Dimethyl- and 1 : 3 : 9 - tri m e thy 1 - spiro - spirodihydantoin and related experiments. H. dihydantoins and (VIII) titrate as monobasic acids; Jwltz and L. Loewe (J. pr. Ghem., 1934, [ii], 141, Sÿirodihydantoin and its 1 : 9-Me2 and 1 : 9-Ac2 deriv ,-V -245).— 1 ; 9-Dimethylspirodihydantoin (I) (sim atives act as dibasic acids, whilst its 1 ; 3 : 7-Me3 plified prep.; cf. A., 1917, i, 290) and boiling Ac20 derivative and (IX) have practically, no acidic gnre the 3-^4c, m.p. 176°, and then the 3 : 7-Ac2, m.p. properties. 226 BRITISH CHEMICAL ABSTRACTS.— A. III. 3 : 9-Dimethyluric acid glycol Me2 ether (4 : 5- derivative, m.p. 170°, converted by HN02 into dimethoxy-3 : 9-dimethyl-4 : 5-dihydrouric acid) is NPli &piïenÿU,3 : 4-pyridino-i 8 : 9-triazole acetylated (boiling AcaO) slowly to the 7-Ac deriv (IV), m.p. 110°. The product obtained ative, m.p. 223°, w’hilst the 5-Mex ether gives 4-acei- from (III) and SnCl2-conc. HC1 gives, oxy-5-methoxy-, m.p. 187— 189°, and ‘i-aceioxy-5 -melh- with HN02, (IV) and its 6-Ci-derivative, oxy-7-acetyl-, m.p. 145—148°, -3 : Q-dimethyl-4: : 5-di- m.p. 164— 165°. (IV) and HN0, hydrouric acid and 5-methoxy-l : 7-diacetyl-Z-methyl- (IV.) (d 1-4) in conc. H2S04 at 50° afford the 4'-N02-, m.p. 222—223°, reduced (SnCl2, conc. hydantamide (I), ^[^Qo^C(OMe)-CO-NHAc, m.p. HC1) to the 4'-AW2-derivative (V), m.p. 206—207°. 170— 173°, according to the time of reaction. (I) is The Ac derivative, m.p. 235—236°, of 3-miro-4-p- hydrolysed by EtOH-NH3 to 5-methoxy-3-methyl- aminoanilinopyridine, m.p. 163° [from (II) and hydantamide (A., 1921, i, 614), and is accompanied 2)-C6H4(NH2)2 in EtOH-KOAc], is reduced (aq. by a little 5-methoxy-l-acetyl-3-me.thylhydantamide (?), Et0H-Na2S204) to 3-aminoA-^-acetamidoanilivjo- m.p. 212° (sinters at 205°). 3 : 9-Dimethyluric acid pyridine, m.p. 159°, converted (HNO,) into 9-p- glycol [4 : 5-Ac2 derivative, m.p. 158-—160° (decomp.), acetamidophenyl-3 : 4-pyridino-l : 8 : 9-triazole, m.p. prepared using cold Ac,0-conc. H2S04] and boiling > 295°, which is hydrolysed (EtOH-conc. HC1) to Ac20 give 3 : 9-diacetyl-1 : 7-dimethylspiYodihtjdantoin (V). Z-Nitro-4:-2'-pyridylaminopyridine, m.p. 131— (II), m.p. 137°, hydrolysed (EtOH-NH3) to, and 132° [from (II) and 2-aminopyridine], is reduced prepared also by acetylation of, 1 : 7-dimethyl.s|»rodi- (aq. Na2S204) to the 3-A7// 2-derivative, m.p. 148—149”, hydantoin (III) (modified prep.; cf. loc. cit.). (II) is convertible into 9-2'-pyridyl-3 : 4-pyridino-'l : 8 :9- hydrolysed (boiling H20) to the 9-.4c derivative, m.p. triazole, m.p. 194°. 3-NitroA-(6'-methoxy-S'-quinolyl- 232—234° (decomp.), and a mixture of 6-acetyl- (IV), ■amino)pyridine, m.p. 203° [from (II) and 8-amino-6- m.p. 197—200° (decomp.), and 3 : 6-diacetyl- (V), m.p. methoxyquinoline], which, like (III), does not 180— 185° (decomp.), -1 :8 -dimethylallantoin; the give a iV-NO-derivative, is reduced (Na2S204, aq. amounts of (IV) and (V) [hydrolysed (EtOH-NHg) to GOMe2) to the 3-NH2-derivative, m.p. 163—164° (IV)] are diminished when hydrolysis is effected with (darkening) (p-dimethylaminobenzylidene derivative, 50% AcOH. (IV) and basic Pb acetate give 1 : 8-di m.p. 234— 235°). (IV) heated in paraffin oil at 320— methyl allantoin [also prepared similarly (cf. A., 1921, 350° affords 5-carboline, m.p. 231—232° (picrate, i, 893) from (III)], which is reduced (HI) to 1-methyl- m.p. 250°) (Robinson and Thornley, A., 1924, i, hydantoin. The spirodihydantoin ring system is very 1349), in nearly quant, yield; the other pyridinotri stable towards acids, but is readily converted into an azoles undergo résinification. H. B. allantoin by alkali. H. B Syntheses of drugs. IX. Benzthiazolecarb- Syntheses of drugs. VIII. [Use of] complex am id es. H. P. K a u fm a n n [with P. S c h u l t z and compounds in the synthesis of drugs. I. Cal (in part) W u r l ] (Arch. Pharm., 1935, 273, 31—52).— cium theobromide-calcium nitrite. H. P. K a u f p-NH,-C6H4-NHAc and (SCN)2 (from NH4SCN and m a n s [with K u c h l e r ] (Arch. Pharm., 1935, 273, Br) in AcOH give 1 -amino-5-acctamidobenzthiazolt 22—31).—The salt, Ca"[T2Ca(H20)2(N02)2]" (T=theo- (I), m.p. 239°, hydrolysed (dil. H2S04) to the 1:6- brominc), is prepared and its homogeneity demon (jV£T2)2-compound (II), m.p. 207°, which (diazo- strated. The absorbability of drugs is changed by reactions) affords 5-chloro-l-aminobenzthiazole (III), administration as complex compounds. R. S. C. m.p. 198°, and 5-Tp-aminobenzeneazo-\-aminobenzthi- Compound of theophylline and di(hydroxy- azole, m.p. 245° [reduced by Sn-HCl to (II)]. 1-Amino- ethyl)amine.—See B., 1935, 46. 5-ethoxybenzthiazole (IV) and HCNO in CHC13 give the 1-carbamate, m.p. 2S9°; 1-carbamates of the Graebe-Ullmann carbazole synthesis and its application to Ar-substituted pyridinotriazoles. following are similarly prepared : (III), m.p. 325°; (II), m.p.about 315° ; a-naphthathiazole, benzthiazole, 0. B r e m e r (Annalcn, 1934, 514, 279—291).— and (I), m.p. > 3 0 0 °.; C0C12 affords ~XN'-di(benz- 4-Bromo-4'-nitro-2'-aminodiphenylamine and NaN02 thiazolyl-l-)carbamide, m.p. 325°, and its 5 :5 -Cl2- in EtOH-HCl‘give 5-nitro-, m.p. 222°, reduced (SnCl,’ AcOH-HCl) to 5-amino-, m.p. 171°, -1-p-bromophenyl- derivative, m.p. 241°. By PhCNO in CHC13 are 1 :2 : Z-benztriazole. 4'-Nitro-2'-anhno-4-methoxy- obtained N-phenyl-'N'-benzthiazolyl-, sublimes > 200°. diphenylamine, m.p. 144— 145° [prepared (cf. Gallas -5-ethoxy-, m.p. about 243°, -5-cliloro-, m.p. > 325°, and Alonso, A., 1930, 1571) by reduction (EtOH- and -6-nitro-benzthiazolyl-l-carbamide, m.p. > 300°. and-a.-ruiphthathiazolyl-1-carbamide,m.p. > 325°. Allyl NaHS) of the 2 ': 4'-(N02)2-derivative], similarly thiocyanate yields ~N-5-ethoxybenzthiazolyl-l-W-allyl- affords 5-nitro-, m.p. 244—245°, and 5-amino-, m.p. 157°, -1-anisyl-l : 2 : 3-benztriazole. -5-Nitro-, m.p. carbamide, m.p. 185°. PhCNS gives Ik-phenyl-Is'- 171°, and 5-amino- (I), m.p. 117°, -1-p-fofyZ-l : 2 : 3- .benzthiazolyl-l-thiocarbamide, m.p. 207°, and its 5-Cl- benztriazole are prepared. (I) heated in paraffin derivative, m.p. 174°. The carbamides have yery oil at 320—350° gives a good yield of 3-amino-6- slight anæsthetic action, but (IV) is intermediate methylcarbazole, m.p. 252°; 5 : 4'-diamino-1-phenyl - between cocaine and novocaine. R. S. C. 1 : 2 : 3-benztriazole similarly affords a trace of Cactus alkaloids. XII. Constitution of an- 3 : 6-diaminocarbazole, whilst the other NH2-triazoles h alam in e. E. S p a th and F. B e c k e (Ber., 1934, undergo decomp. 4-Chl oro-3-nitrop\Tidine (II) 67, [ 5 ] , 2100—2102).—Anhalamine (I) is treated (Koenigs: and Freter, A., 1924, i, 990) and NH2Ph at with EtI and NaOEt and the product is acted on 130' give S-nilro-i-anilinopyridine (III), m.p. 118°, successively with Ag20 and KMn04, whereby 4:5- reduced (Na2S204 in aq. COMe2) to the 3-NH2- dimethoxy-3-ethoxy-o-phthalic anhydride, m.p. 106— ORGANIC CHEMISTRY. 227 107° after softening, is produced. (I) is therefore in H20 (ef. Jarzynski et al., A., 1933, 1312), and a 8-hydroxy-G : 7-dimethoxy-l : 2 : 3 :-4-tetrahydrowb- second component, possibly a stereoisomeride. The quinoline. H. W. salts of apoquinine are dihydrochloride, m.p. 261°, Alkaloids of Anabasis aphylla. X I. H of- [a]j>° -224-4° in H20, hydrobromide, m.p. 284°, di mann degradation of aphyllidine. A. O r e k h o v hydrobromide, m.p. 255°, [a]},0 —180-9° in H20, II and S. K o r k i n a [with T. M a x im o v a ] (Ber., 1934, 6 7 , sulphate, soft platelets, sinters 90° or 170— 190°, and [5], 1974— 1979; cf. A., 1932, 405).—Aphyllidine (I) hard plates, m.p. 203—208°, [a]„ -193-6° in H20, is transformed by Mel in MeOH into the methiodide, and acid dianisoyl-d-tartrate, m.p. 235-5°. apoQuinine m.p. 223—225°, [a]D +9-8° in H20, converted by Me ether, m.p. 183— 185° (no decomp.), [a][f —201-2° boiling KOH-MeOH into de-IV-methylaphyllidine (II), in EtOH, forms a hydrochloride, m.p. 249—251°, [a]},5 m.p. 120— 121°, [a]D — 18-1° in MeOH, the methiodide, —196° in H20, and the Et ether, m.p. 195—197° (no m.p. 224— 225°, of which passes when treated with decomp.), [a]},5 —199-7° in EtOH, gives a hydro KOH-MeOH into a mixture of bases (III), b.p. chloride, m.p. 247—250°, [a]i>8 -191-7° in H20. 230—23S°/5 mm. Dissolution of (III) in HC1 and Quinidine (99-5% pure) and 60% H2S04 form treatment with NaCIO,, gives the.. sparingly sol. dextrorotatory ;\poqui?iidine (70%) and isoapogimwd- perchlorate, m.p. 180—182°, of the optically inactive ine, m.p. 245° (no decomp.), [a]“ +25-6° in 0-liY- deÆ-dimethylwphyllidine (IV), b.p. 240—242°/5 mm. H2S04 or —12-6° in EtOH (hydrochloride, m.p. 255°, Tho corresponding methiodide, m.p. 121—122°, passes [°0d —40-2° in H20 ; dihydrobromide, m.p. 280° [a]},5 when treated with AgOH and then distilled into + 18-6° in H?0 ; and II sulphate, decomp. 235—240°, NMe3 and hemiaphyllidene. Although a double [*]» +17-6° in H20), and not cupreidine as stated by linking has been shown to occur in (I), catalytic Ludwiczakowna (A., 1933, 1312). M.p. are also hydrogenation (Pt02) of (II) leads only to dihydroda-'N- decomp, points except where stated. F. R. S. methylaphylUdine, m.p. 118— 120°, the methiodide, Eserine. III. Synthesis of d- and l-eserethole m.p. 234—235° (decomp.), of which is degraded to methiodide. T. H o s h in o and T. K o b a y a s ih (Proc. ail oil of indefinite b.p., from which dihydrode-~S- Imp. Acad. Tokyo, 1934, 10, 564—567; cf. A., 1934, iimethylaphyllidine, b.p. 218—220°/5 mm., is obtained 667).—The substance, m.p. 79— 80° [picrato, m.p. through the perchlorate, m.p. 209—210° [methiodide 150—151° (lit., 139—140°, 140—141°)], previously (V), m.p. 194— 195°] ; it is not hydrogenated (Pt02) called dZ-eserethole (A., 1934, 1236, 667), is C^H^Oi^ at 15—20°. It can also be obtained by hydrogenation (macro-analyses are faulty), dl-methyleserethole. The (Pt02) of (IV). Treatment of (V) with AgOH and following corrected data are given : H ¿-tartrates of subsequent distillation yields NMe3 and dihydro-, 1-, m.p 166— 167°, [o|d —73-9°, and cZ-dinorescrethole, hmiaphyllidine, b.p. 206—207°/8 mm., hydrogenated m.p. 164— 165°, [a]|2 -¡-235-1°, and of I- (I), m.p. to hexahydrohemiaphyllidine, b.p. 206—207°/8 mm. 190— 191°, [a]“ —53-3°, and ci-noreserethole (II), m.p. (I) and CNBr in anhyd. C6H6 afford the compound 188— 189°, [a]“ +202-1°, (I) and (II) with Mel in CI6H22ON3Br, m.p. 116-—117°, readily transformed (Zn cold Et20 give I- (III) and ¿-eserethole (IV) meth dust-AcOH or H2-Pd-CaC03) into -the corresponding iodide, m.p. 168— 169°, respectively (mixed m.p. about cyanoamide, hydrolysed with difficulty by 70% H2S04 155°). The methopicrates of (III) and (IV) have at 165—170° to a substance, m.p. 260—265°. H. W. m.p. 189° (mixed m.p. about 173°), the corresponding Composition of amorphous quinine iodobis- ¿¿-derivative (V) having m.p. 190—191°. The picrate, muthates. G. V i t a and L. B r a c a l o n i (J. Pharm. m.p. 184— 185° (loc. cit. and ibid., 89), is dl-noresereth- Chim., 1934, [viii], 20, 512—516 ; cf. B ., 1932, 622).— ole picrate, the other product, m.p. 192—193°, being The composition of quinine iodobismuthate prepared (V). Tho criticisms of Robinson et al. (loc. cit.) are by the method of François and Seguin (A., 1925, i, refuted.' R. S. C. 1084) varies with the ratio Bi/quinine in the reactants. Organic arsenic compounds. XVII. Poly The products corresponding with ratios 2-05 and meric phenylarsenoxide and reactions of m- 078 have the following % compositions : Bi, 25-8 phenylenediarsinic acid. W. Stein k o pjf, S. and 21-01; quinine, 14-12 and 22-42; I, 57-4 and Sc h m id t , and H. P e n z (J. pr. Chem., 1934, [ii], 141, 56-2; H20, 0-19 and 1-30, respectively. A. E. 0. 301—305).—Reduction (S02) of PhAs03H2 in dil. Modified cinchona alkaloids. I. op o Quinine H2S04 gives PhAsO, m.p. 142— 145° (lit. 119—120° ^d apoquinidine. T. A. H e n r y and W. S o l o m o n to 145— 147°), and (probahly) the dimeride, (J.C.S., 1934, 1923— 1929).—Quinine is demethylated AsPh<^Q^>AsPh, m.p. 210—220° (converted by conc. ®y AlClg (cf. Oberlin, A., 1927, 681) to crude “ apo- luinine,” m p 175o. ^ _ 177<> in MeOH, which is HC1 into PhAsCl2). to-CgH4(As03H2)2 is converted an equimol. mixture of C19H2202iSi2 and C ^ H ^ O ^ C l, (usual method) into m-phenylenedi(dichloroarsine), Preserved in a dihydrochloride, m.p. 225°, [a]“ m.p. 43-5° (previous sintering), which with MgMeBr v-204-1° in H20, and a zincichloride, m.p. 242°. gives m-phenylenedi(dimethylarsine), b.p. 140— 141°/ ™m the mixture by crystallisation from MeOH- 12 mm. This and CNBr in Et20 afford m-phenylene- chlorodihydroapoquinine (H sulphate, m.p. di(dimethylarsine. hydroxybromide), > [fjo- —206-7° in H20) is obtained, and bym-C6H4(AsMe2Br-OH)2, m.p. 161— 162°. H. B. 'Crystallisation of the dianisoyl-ei-tartrate, impure apo- Arsenical derivatives of organic sulphides. luinine acid dianisoyltartrate may be prepared. Pure S. M. S c h e r u n and A. J. J akubovitsch and (in part) » e and 60% H„S04 yield apoquinine, froths at L. E x e m p l a r s k y (Bull. Soc. chim., 1934, [v], T, 1367— .1* - Hd -2 8 1 ° in 0-1iV-H2SO4, or -214-8° in EtOH, 1373).—A sC13 reacts with diazotised p-NH2*C6H4-SEt Elated as the hydrochloride, m.p. 265° [a]|° —154-5° to give p-ethylthiolphenylarsinic acid (I), not melting' 228 BRITISH CHEMICAL ABSTRACTS.---- A. at 200°, reduced by S02-HC1 to -p-ethylthiolphenyldi- Colorimetric test for compounds containing chloroarsine, m.p. 39-5—40°, re-oxidised by CC13-N02 CH, CH2, or CH3 contiguous to negative groups. in EtOH-NaOH to (I). Oxidation of (I) with warm M . G o s w a m i, A. Sh a h a , and B. M u k e r j e e (J. Indian 30% H202, or with KMn04-Ac0H , affords \i-ethyl- Chcm. Soc., 1934,1 1 , 773—115).—28 compounds con sulphonylphenylarsinic acid, not melting at 280°, con taining CH, CH2, or CH3 adjacent to a negative group verted by S02-reduction into the corresponding di- (usually CO) give red or brown colours with slightly chloroarsine, m.p. 116— 118-5°. With aq. H3P02 the alkaline, alcoholic picric acid. CH20, PhCHO, ctc. ]STa salt of (I) affords pp'-rfiethylth iolarsenobenzene. give no colour. Bitto’s reagents give similar colours. Similar diazotisation of p-NH2-CfiH4-SCISr in presence R. S. C, of A sC13 in Me0H-H2S04 gives a 50% yield of jj-thio- Cyanide-formaldehyde reaction, and new cyanophcnylarsinic acid, reduced by S02-HC1 to volumetric analytical applications.—See this vol., p-thiocyanophenyldichloroarsine, b.p. 193— 195°/7— 8 183. mm., m.p. 55— 56°; and with AsPhCl2 in place of Detection of diazonium salts and of primary AsC13, phenyl-ii-thiocyaiwphenylarsinic acid, m.p.138— amines with resorufin. H. E ic h l e r (Z. anal. 139° (decomp.), is obtained, but reduction of this Chem., 1934, 9 9 , 348— 350).— Slightly acid solutions affords only AsPhCL (oxidised to PhAsO.dl.,). of diazonium salts give with the brightly fluorescent J. W. B. resorufin (I) brown insol. products not fluorescing Furan arsenicals. H. G ilm a n and W. H. when made alkaline. Aromatic NH2 groups may be Kirkpatrick (Proc. Iowa Acad. Sci., 1932,3 9 , 176).— detected by diazotising and then testing the solutions Furan arsenicals may be prepared from furan mer with (I). Free HNOa in diazo-solutions may be curials and AsCl3, and from furan Grignard reagents detected with Magdala-rcd (cf. A., 1934, 269). Fluor and A s halides. C h . A b s . (r) escein behaves like (I), but with certain diazonium Methyl ester of phenylphosphorous acid. A. E. salts only. J. S. A. A r b u z o v (J. Gen. Chcm. Russ., 1934, 4, 898— 900).— Micro-determination of carbonyl groups. F. PPhCl2 and NaOMe yield a mixture of PPh(OMe)2, v o n F alkenhausen (Z. anal. Chem., 1934, 9 9 , 241— b.p. 101— 102°/15 mm. (CuBr salt, m.p. 139-5—140°), 257).—5— 15 mg. of substance are allowed to react and PPhMe-OMe, b.p. 139— 140°/15 mm. R. T. quantitatively at 100° with a weighed excess of Diphenyl- and di-o-tolyl-guanidinium poly- NHPh-NH2,HCl in 67% aq. C5H5N; excess of selenides. R. L. McCleary and W . C. Fernelius NHPh-NH, (I) is then decomposed by mixing with (J. Amer. Chcm. Soc., 1934, 5 6 , 2499).— Treatment Fehling’s solution+C6Hf, at 100°, and the vol. of N2 of the solution from diphenylguanidine and H2Se in so evolved is measured in a micro-gas burette. An air-free EtOH with Se (excess) gives di(diphenyl- empirical correction for spontaneous decomp. of (I) guanidinium) tetraselenide, C2(jH28N6Se4, decomp. must be introduced. The method fails -with certain 152— 156°; di(di-o-tolylgiianidinium) tetraselenide, ketones. J. S. A. C30H.!6Nf)Se4, decomp. 170— 174°, is similarly pre Sensitive and specific reaction for ergosterol. pared. These are readily decomposed by dil. acids J. B r u c k n e r (Biochem. Z., 1934, 274,' 465).—An to H2Se and amorphous black Se. ” H. B. addendum (A., 1934, 910). This reaction is obtained Lecithins of egg-yolk. Y. Yokoyama (Proc. only when “ acetonum puriss. Merck,” and not when Imp. Acad. Tokyo, 1934, 10, 582— 585).—The prep, “ acetonum pro analysi Merck ” is used, and must of a- (I) and ¡3-lecithin (II) from egg-yolk is described. depend on the presence of some impurity in the former (I) yields oleic (III) (72), clupanodonic (2), and iso- solvent. P. W . C. palmitic (IV) (m.p. 57-57-5°; 26%) acids. (II) A cidim etric m ethod for determining sali gives (III) and (IV) only. With Br (I) affords the cylic acid and its salts. C. N. T h o m as (Praktika, diisopalmitate, cryst., dioleate tetrabromide (3HgCl^- 1933, 8, 281—286; Chem. Zentr., 1934, ii, 811).- derivative, cryst.), and oleate clupanodonate dodeca- The free acid is extracted from acidified solutions of bromide, m.p. 1S0° (decomp.). (II) gives similarly salts with Et20, and after removal of solvent is the oleate isopalmitaie dibromide (3£T‘ m.p. 191— 193°. Photomicrographs are given. (Rec. trav. chim., 1934, 5 3 , 1145— 1150).—Applic R. S. C. ation of the method used by Gnadinger et al. (B ., 1929, Hydrolysis of blood-albumin.— See this vol., 230. 996) for pyrethrin to determine small amounts (0-01— Determination of copper in organic com 0-02 g.) of rotenone (I) (x mg.) in 95% EtOH [free pounds.—Sec this vol., 1S6. from other reducing substances (II), CHC13, or CC1J BIOCHEMISTRY. 229 is described. The (I) solution is treated as in a modi Excess of AgN03 is titrated back with NH4CNS. fied Folin’s determination (A., 1926, 648) for glucose Alternatively, (I) may be titrated directly with (III), and the solution compared colorimetricaliy with AgN03, using dichlorofluorescein as adsorption a similarly treated standard (III) solution (y m g.); indicator. J. S. A. then . y=0-6195—0-006858a;+0-008371a;2. The Detection of scopolamine and atropine in the accuracy is 0-2%. Owing to the presence of (II) the presence of phenol. 0. F r e y (Wiss. Mitt, ôsterr. method is not applicable to the determination of Heilmittelstelle, 1934, 12, 3—4; Chem. Zentr., 1934, •the (I) content of derris root. J. W. B. ii, 1500).—The alkaloids are first extracted with Et20 Argentometric determination of 2-thiolhenz- from alkaline solution. H. N. R. thiazole. M. I. U s o h a k o v and A. S. G a l a n o v Electrometric titration of lecithin and keph- (Z. anal. Chem., 1934, 99, 185— 195).—The 2-thiol- alin.— See this vol., 170. .benzthiazole (I) is dissolved in aq. NH3, and excess of AgN03 added. Aq. NH3 is added to dissolve other Electrometric titration of zein and iodozein.— Ag salts, and the Ag salt of (I) then filtered off, dried See this vol., 170. at room temp., and weighed. Volumetrically, an Titration constants of some amides and di excess of OTiV-AgNOy is added to (I) in EtOH- peptides in relation to alcohol and formaldehyde NH3 solution, followed by an equal vol. of Et20. titrations of am ino-nitrogen.—See this vol., 170. Biochemistry. Carbon dioxide balance between maternal Osmotic properties of the erythrocyte. V. and fcetal bloods in goats. A . B . K e y s (J . Rate of haemolysis in hypotonic solutions of Physiol., 1934, 80, 491—501).—Fcetal blood has a electrolytes. M . H. J a c o b s and A. K. P a r p a r t greater C02 capacity, alkali reserve, and C02 content, (Biol. Bull., 1932, 63, 224—234).—Within certain but is less acid than maternal blood. limits the rate of haemolysis (I) of ox-blood and the C h . A b s . (p) concn. of the solution are related by simple osmotic Solubility of oxygen in red blood-corpuscles. laws. The permeability const, for H20 in these E; F. Y a n g (Chinese J. Physiol., 1934, 8, 365—382).— limits is { —J- of that for non-electrolytcs. Retard The solubility of 0 2 in blood-cells, after conversion of ation of (I) by dil. solutions of electrolytes increases haemoglobin into cyanohaemoglobin (I) by N 02' and rapidly with the valency of the cations present. CN', follows Henry’s law and is not affected by the pK. Ch. A b s . (p) The coeff. of 0 2 absorption for horse-, sheep-, dog-, Osmotic pressure and mol. wt. of the hsemo- and cow-cells are 0-0228, 0-0259, 0-0272, and 0-0298, erythrin of Sipunculus. A. R o c h e and J. R o c h e respectively. Since the val. for (I) solution is only (Compt. rend., 1934, 199, 1678— 16S0).—Determin slightly < that of H20, the high coeff. for the cells ation of the mol. wt. of the haemoerythrin by the must be due to the presence of lipins. H. G. R. method of Adair (A., 1925, ii, 965) (M=10RT/-k0\ Solubility of nitrogen in corpuscles. E. F. 7r0=val. of the osmotic pressure/concn. extrapolated Yang (Chinese J . Physiol., 1934, 8 , 383—397).—The to infinite dilution) is approx. 66,000, i.e., of the same coeff. of the absorption of N2 for the cells of horse, order as that of the haemoglobins. Dialysis of the dog, and sheep are 0-0100, 0-0151, and 0-0120, cryst. pigment at 0° increases the mol. wt., probably respectively. Some dialysable substance in blood (I) due to aggregation. j . W. B. gives a high and variable val. for the coeff. in whole Prosthetic group of Limulus haemocyanin. (I) and in serum. H. G. R. J. B. C o n a n t , F. D e r s c h , and W. E. M y d a n s (J. Haemoglobin and blood-cell relations as deter Biol. Chem., 1934, 107, 755—766).—The prosthetic mined by iron and oxygen capacity methods. group (I) formed by decomp, of the haemocyanin by 0- B r o u n and A . P. B r ig g s (J. Lab. Clin. Med., alkali, followed by purification by dissolution in AcOH, 1934, 19, 886—892).—Average vals. for men and is a black substance containing 14% Cu and 6% S. ^omeh, are, respectively, haemoglobin 16-6, 14-0 g. (I) with aq. NH3 yields a Cu-free, colourless, amor per 100 c.c,; cell vol. 46-57, 40-3%. C i i . A b s . phous polypeptide (II) from which tyronine and l- leucine were isolated. (II) is probably composed of Osmotic behaviour of red cells. I, II. E. 3 mols. of serine + 1 each of leucine and tyrosine. (I) Ponder (Cold Spring Harbor Symp. Quant. Biol., is the Cu salt of (II) (viz., C^H^OjoN jCu) united to a 1933, 1, 170— 177, 178— 183).— I. The erythrocyte .S-containing substance, probably C7H150 5N2S2. The is unchanged in an isotonic solution of NaCl, same kind of (I) is also present in octopus haemocyanin h • or glucose. In a hypertonic solution they (cf. A., 1931, 497, 753). A. E. 0. eal^ an(* in a kyp°tonic solution they swell < , Ammonia formation and respiration in the ,.?• Erythrocytes from different animals have erythrocytes of birds. A. A. B a e v (Compt. rend. l”erent crit. vols. Human or rabbit cells are more Acad. Sci. U.R.S.S., 1934, 4, 69—73)— Pigeon resistant to distension than ox or sheep cells. The erythrocytes in Ringer’s solution containing glucose cell membrane is regarded as a fluid or semi-fluid liberate 40 X lO-8 g. of NH3-N per c.c. of cells per hr. , permeability of which is governed by a few when respiration is restricted by small amounts of %ers of mols. .. C h . A b s . HCN, CO, and phenylurethane, or a N2 atm., the 230 BRITISH CHEMICAL ABSTRACTS.— A. normal rate being 0-25—2X10*6 g. per hr. The exhaustion. It becomes completely extractable if restriction has a similar effect on dephosphorylation. Na2S04 solution is added to the serum. There are no Most of the NH3 is formed in the first hr. The definite grounds for postulating two different indirect N : H3P04 ratio is variable (0-5—0-25). J. L. D. bilirubins. R. N. C. Influence of bone-marrow extract of normal Micro-determination of cholesterol in whole and splenectomised animals on the synthesis blood, serum, and plasma. J. K a m l e t (J. Lab. of haemoglobin. V. B a e n a (Biochem. Z., 1934, Clin. Med., 1934, 19, 883—884).— 0-2 c.c. is dried on 274, 358—361).—The view that bone-marrow extract filter-papcr at 35— 40° for 20— 30 min., and extracted (I) contains a factor which accelerates the synthesis for 2 hr. at room temp, with CHC13 (10 c.c.). The of hfemoglobin in vitro is confirmed, and it is shown Liebermann-Burcliard procedure is then used. that (I) of splenectomised has a greater effect than (I) Ch . A b s . of normal animals. This confirms the view that the Control of blood-cholesterol by the kidney. spleen exerts an inhibitory action of the function of H. M iy a z a k i (J. Chosen Med. Assoc., 1934, 24, 263— the marrow. P. W. C. 277).— Injection of 2 c.c. per kg. of renal venous Detection of true nucleal substance in thrombo blood-serum of a normal rabbit into another rabbit cytes. K. V o it and H. K e m p a (Z. Biol., 1934, 95, causes a fall in blood-cholesterol; arterial blood or 635—638).—Thymonucleic acid is detectable in the .auricular venous blood-serum causes no change. blood-platelets of men and horses by Feulgen’s The action is due to a hormone secreted from the nucleal reaction (A., 1924, i, 905). F. 0. H. epithelium of the kidney tubules. The hormone reduces hypercholesterolemia in experimental neph Blood-proteins of children. Distribution of ritis or nephrectomy. Ch . A bs. total nitrogen in whole blood, red blood-cells, and serum-proteins from the same specimen. Determ ination of uric acid in hum an, bovine, A. B e r n h a r d , J. S. L e o p o l d , and I. J. D r e k t e r and avian blood. G . H. P r it h a m and A . K. (Amer. J. D is. Children, 1934, 47, 1256—1260).—The A n d e r s o n (J. Lab. Clin. Med., 1934, 19, 892— N contents of whole blood (I), red cells (II), and serum 896).—Any method involving isolation of uric acid (III) are recorded. Vais, for (I) and (II) are < and is satisfactory for human or avian blood. Benedict’s for (III) > in adults. Ch. A b s . (p) direct method and Folin’s method for unlaked blood are satisfactory; - for bovine blood Folin’s direct Refractometric determination of serum- method is preferred. Ch . A bs. proteins. M. P a i<3 and V. D e u t s c h (Compt. rend., 1934, 199, 1306—1308),—A modification of Reiss’ Electro dialysis as method of separation and method is described. Changes in n with temp, of determination of bases in biological fluids. II. serum are substantially the same as those for H ,0. Determination of total bases in blood, serum, A.G.“P. and erythrocytes. N. P. M e s c h k o v a and S. E. Pn of heat-inactivated serum. P. L. d u N oiIy Se v e r in (Z. physiol. Chem., 1934, 230, 114— 121).- and V. H a m o n (Compt. rend. Soc. Biol., 1934, 117, The cathode fluid obtained from protein-free (using 337— 338).—When heated above 56° the pa falls to a a limited amount of CC13-C02H) blood (2 c.c.), min., usually at 60°, after which it fluctuates feebly, erytlirocytes (2 c.c.), and serum or plasma (1 c.c.) is in some cases rising again. The mean initial fall is treated with 0-01iY-H2S04 (excess of which is then 0-05. R. if. C. determined iodometricallv). The error is > 2%. H. B. Hydrolysis of blood-albumin by autoclaving Electrolytes in the serum of the rat. P. K- in 2% potassium carbonate solution. V. S. S m it h and A. H. Sm it h (J. Biol. Chem., 1934, 107, Sa d ik o v , V. R o z a n o v a , and G. N o v o s e l o v a (Compt. 673—680).—Vais, are recorded for the concn. of C02, rend. Acad. Sci. U.R.S.S., 1934, 4, 217—221).— Cl, inorg. P 04"', Ca, Mg, K, Na, and protein in the Hydrolysis for 2 hr. at 180° with 2% K2C03 yields a serum of albino rats. The Ca, Mg, and P 04'" are > small proportion of free NH2-aeids, with a predomin and the Na, HCO,', and protein < in man. ance of heterocyclic and ci/cfopeptide material, the C.G.A latter being removed by extraction with Et20 and Physical chemistry of the blood. D. D. VAif CHC13. 24-14% of the total N was lost as N H 3 and Sl y k e (Cold Spring Harbor Symp. Quant. Biol., amines. H. G. R. 1933, 1, 184— 189).—Plasma and lymph contain Clearing agent for blood. Application to about 18 times as much Na* as K ‘ ; cellular tissues determination of blood-sugar. M. P a g e t and have a relative excess of K\ N a '+ K ' (I) in blood D u po n t (Compt. rend. Soc. Biol., 1934, 117, 881— and tissue cells is a little > hi blood-plasma. 0-33 882).—Blood is deproteinised by a mixture of suitable 0-75 of (I) in the cell is neutralised by complex acids conens. of K4Fe(CN)6 and Zn(OAc)2. The clear which are buffered and indiffusible colloids. The solution contains the sugar, which reduces Baudouin’s ratio cell-: serum-Cl' is < 1 by an amount which cc solution. r . if. the amount of base as hsemoglobinate in the cells. Indirect bilirubin of serum and its extraction Ch . A bs. by chloroform. Techniques proposed by de Blood-calcium and -magnesium of the cow in Castro, and by Kerpola and Leikola. B. V a r e l a - health and disease. W. M. A l l c r o f t and H. H. F u e n t e s , C. V ia n a , and P . R e c a r t e (Compt. rend, G r e e n (Biochem. J., 1934, 28, 2220—2228).—The roini 1934, 117, 903—908).—-Extraction with normal range of serum-Ca and -Mg in 139 clinically CHClg of the indirect bilirubin of both normal and healthy cows is S-65—11-65 mg. and 1-85—3-17 mg. icteric sera is incomplete, even when continued to per 100 ml., respectively. No marked change occurs BIOCHEMISTRY. 231 ill cases of Brucella abortus infection, but in advanced sera contain the antibodies (only the alexin being generalised tuberculosis hypomagnesæmia (I) occurs. destroyed), and are completely sol. in 10% Na2S203, (I) is associated with lactation tetany (II) and hypo- the solution so obtained exhibiting the same bio calcæmia with milk fever. The Ca/Mg ratio is not logical properties as the original serum. J. W. B. the determining factor of (II). C. G. A. Excretion of antibody through the urine. O. Relation between the ossification of the skele S u z u k i (Sei-i-Kwai Med. J., 1933, 52, No. 9, 31—40, ton and the state of the blood-calcium of fish. 41—62).—Excretion through the urine and intestinal M. F o n t a in e (Compt. rend., 1934, 199, 1452— 1454). fluid is the main cause of loss of antibody from the —The proportion of blood-Ca which is adsorbahle on serum. C h . A b s . BaS04 is greater for fish with much ossified cartilage Inactivation of the third component of alexin than for those with little, and within the latter class by yeast. O. Bier (Compt. rend. Soc. Biol., 1934, greater for those with much cartilage than for those 117, 720—722).—Guinea-pig serum (I) peptonised with little. R. S. C. with physiological salt solution and treated with a Blood-iodine. II. Normal iodine content of yeast suspension at 37° lost the third component of human blood. C . B. D a v i s , G. M. C u r t i s , and the alexin. Under the same conditions (I) pepton V. V. C o l e (J. Lab. Clin. Med., 1934,19, 818—830).— ised with K I remained active. A. L. I is a const, constituent of human blood (normally 12 X10-6 g. per 100 e.c.). Vais, in summer are > in Magnetic properties of animal fibrous tissues. H. G. C l a m a n n (Z. Biol., 1934,95, 639—640).— Whilst winter. C h . A b s . celluloid and cocoon-fibres are paramagnetic, wood, Blood-iodine content of normal and thyro aq. and dry gelatin, neck-fibres, tendons, liver, bone, toxic individuals. Iodine-tolerance test. H. J. spleen, hair, fibrin, muscle, and powdered fibrinogen Pe r k in , B . R . B r o w n , and J. L a n g (Canad. Med. arc diamagnetic. F. O. H. Assoc. J., 1934, 31, 3G5—3G8).—Blood is heated with K2C03 in a Ni crucible at 260° for 5 hr. The ash X-Ray spectrographic structure investigations is extracted with EtOH, filtered, and the filtrate on biological objects and human tissues. E. evaporated to dryness. The residue is dissolved in S a u p e (Kolloid-Z., 1934, 69, 357—363).—A lecture. H,0,1' is oxidised to I 0 3', and the latter determined E. S. H. by treatment with K I and titration with Na2S203. X-Ray diffraction studies on nerve. F. O. c h m it t l a r k r g u d i c h Ch . A b s !” (p ) S , G. L. C , and J. N. M (Science, Is thrombin a calcium compound? 0. K a s t l 1934, 80, 567—568).—X-Ray photographs indicate a (Biochem. Z., 1934, 274, 452—460).—The view of fundamental similarity between the fine structure of Loucks and Scott (A., 1930, 802) that thrombin (I) is the axis cylinder of nerve and other fibres such as hair, a “ Ca-tissue-juice ” compound, inactivatable by tendon, and muscle. Details of the patterns are décalcification with H2C204, is not confirmed. More discussed in relation to their possible chemical over, the method employed by these authors is now significance. L. S . T. known not to lead to complete décalcification. (I) Cyto-chemistry of incinerated nerve-cells. J. preps, obtained from sera rigorously decalcified by K r u s z y n s k i (Bull. Acad. Polonaise, 1934, B, 105— the more recent techniques of Kramer-Tisdall and of 116).—Paraffin sections (> 3|x) of nerve-tissue (fixed Schimmelpfeng have the same activity as (I) from with 85—90% EtOH) are mounted in the usual Ca-containing serum. P. W. C. manner, and the slide is heated to give the ash- Effect of hydrogen ions and thrombase on the picture (“ spodogram ” ) of the cell-structure formed coagulation of fibrinogen.— See this vol., 165. by its mineral constituents. Subsequent treatment with 2% H2S04, 10% H2PtClg, Na2HP04, or NH4SCN Opacificationreaction in the serum of sensitised indicates the distribution of Ca, K , Mg, and Fe, rabbits. P. Vallery-Radot, G. M a u r i c , and A. respectively. F. O. H. Hugo (Compt. rend. Soc. Biol., 1934, 117, 1091— 1093).—The opacifying power (Î) of rabbits’ serum Chromosome behaviour in terms of protein J* affected to different degrees in different animals pattern. D. M. W r i n c h (Nature, 1934, 134, 978—■ by sensitising with liorse-serum. There is no con 979).—An attempt to correlate the properties of nexion between (I) and the appearance or non- chromosomes and the facts of genetics with protein appearance of anaphylactic shock. R . N. C. structure. L. S. T. Opacification reaction and precipitins in the New fixing-mixtures revealing the morpho sensitised rabbit. P . V a l l e r y -R a d o t , G. M a u r i c , logy of chromosomes. G. A. L e v i t s k i (Compt. and A. H u g o (Compt. rend. Soc. Biol., 1934, 117, rend. Acad. Sci. U.R.S.S., 1934, 4, 143— 144).—A 1093—1095).—There is no parallelism between the no. of new CH„0 fixing-mixtures are described. sensitised state and the appearance of precipitins. H. N. R. R. N. C. Approximate determination of proteins of Reversibility of certain metalloprotein pre muscle. E. C. S m it h (J.S.C.I., 1934, 53, 351— cipitations by the action of sodium thiosulphate. 3 o4 t ).—The minced muscle is extracted 6 times at Serological behaviour of the complexes from 0° with 10% aq. NH4C1. Myosin (I) is determined hemolytic and syphilitic sera. H . D ia c o n o by- pptn. from the extract by dilution with 19 parts (Compt. rend., 1934, 199, 1686— 1687).—The pptd. of H20, a correction being applied for the amount of Metalloprotein complexes formed by addition of (I) remaining in solution [12% of the total (I)]. u'10/o HgCl, or CuSOj to hiomolytic and syphilitic Collagen in the residue after extraction is converted R 232 BRITISH CHEMICAL ABSTRACTS.— A. into gelatin (II) by autoclaving at 121° for 2 hr. Cu is determined either by the C5H5ii-thiocyanate (II) is extracted with boiling H20, and the residue is (I) or the chromotropic method (II). In (I), the liquid, digested with trypsin to remove and determine after centrifuging, is incinerated (wet) with HN0, residual intracellular protein. The final residue and H2S04, and the clear neutral solution treated consists of elastin (cf. B., 1927, 264). Typical analyses with NH4CNS and C5H5N. The green of rabbit- and ox-muscle are given. E. C. S. Cu(C5HBN)2(CNS)2 complex is extracted with CHC13 Determination of lactic acid in muscle. C. P. and determined colorimetrically. In (II) the Cu St e w a r t , J. P. D ic k s o n , and R. G a d d ie (Biochem. is titrated with nitrosochromotropic acid, a colori J., 1934, 28, 1945— 1948).—AcCHO should be re meter being employed to determine the end-point. moved by distillation prior to treatment with CuS04+ Aq. humour contains 0-14—0-1S mg. Cu per litre. CaO for removal of sugar, otherwise the lactic acid R. N. C. content found by oxidation with KMn04 to MeCHO Antiscorbutic action of the eye lens and its will be too high. CuS04+C a0 convert AcCHO reductone and thiol content. H. v o n E ulee into a substance oxidised by KMn04 to MeCHO and M . M a l m b e r g (Z . physiol. Chem., 1934, 230, (2 : 4-dinitrophenylhydrazone, m.p. 161°; not 148° 225—230; cf. A., 1933, 1090).—The no. of mg. as in lit.) and other substanccs which combine with of ascorbic acid (I), determined by titration with NaHS03. A. E. 0. 2 : 6-dichlorophenol-indophenol at 2-5 [at ps 5-5—6-5, (I)+SH-compound is found], in 1 g. Combined or free potassium in muscle. E . (unless stated otherwise) of lens (II) from the following E r n s t and J. F r i c k e r (Pfliiger’s Archiv, 1934, are : human, 0-2; human (cataract), 0—0-5 per 2 3 4 , 360—368).-—An aq. COMe, extract of a frog’s (II); ox (III), 1 per (II); Salmo salar, 1-04; Gadus gastrocnemius (I), rendered rigid by heat or electrically minutus, 0-53; G. callarius, 0-48; G. merlangus, stimulated, contains a proportion of the muscle-K > 0-45; Labrus exoletus, 0-32. The presence of (I) in that extracted from a similar (I) frozen immediately (III) is confirmed by biological tests. (Ill) appear after excision, suggesting that muscle-K is converted to contain a substance which is toxic to guinea-pigs. into a more diffusible form by heat-rigor (II) or Administration of C10H8 and 2 : 4-(NO2)2C6H3-0H fatigue (III). The increases in diffusible K correspond to rabbits does not affect the (I) content of the (II). with 0-10% of total alkali calc, as NaCl in (II), H. B. and 0-05% in (III). R. N. C. Variations in glycogen and accompanying Pentose polynucleotide of the pancreas. E. substance of active and hibernating snails. J o r p e s (Biochem. J ., 1934, 2 8 , 2102—2108).— L. S e m ich o n (Compt. rend. Soc. Biol., 1934, 117, The substance has a pentanucleotide structure contain 774—775).—The glycogen (I) content of the vesicular ing 3 mols. of purine pentose nucleotides and 2 mols. cells of conjunctive tissue of snails approaches zero of pyrimidine nucleotides. It contains 2 mols. during hibernation, whilst the hyaline substance of guanylic acid (I) per mol. of adenylic acid. The accompanying (I) remains more const. E. O. H. titration curve of pancreas nucleic acid (II) is similar to that of thymus (II), showing that the substance is Galactogen. VII. Galactogen and glycogen not a mixture of (I) with yeast (II). H. G. R. contents of starved snails. VIII. Detection oi galactogen in animals and man. F. M a y (Z. Biol., Determination of adenine in the presence of 1934, 95, 606—613, 614— 634).—VII. During starv guanine. E. J o r pe s (Biochem. J ., 1934, 28, 2097— ation of vineyard snails, galactogen (I) is converted 2101).—Guanine is oxidised by KMn04 in acid solution, into glycogen (cf. A., 1933, 380). determinations of purine-N being made before and VIII. (I) occurs in the eggs [36% of the total after the reaction by pptn. with Cu II sulphite reagent. polysaccharides (II)] of snails (Limacidce), in the H. G. R. sexual glands (51-8%) of fresh-H20 mussels (Anodonta), Vitreous body. I. W. S. Duke-Elder, E. B. in carp’s roe (1-2, 9-84%), in adult (but not young) Robertson, and H. D a v s o n (Biochem. J., 1935, rabbits (7%) after removal of ovaries, uterus, brain, 2 9 , 72—75).—The vitreous body (I) does not show mammary glands, and liver [all of which are free uptake of H20 at 8, nor does swelling occur in from (I)], and in human placenta (approx. !%)• presence of 1% Na oleate or Na laurate. This does Traces of (I) occur in the carp before maturation of not eliminate swelling of (I) as the cause of intra the ova; organs other than the ovaries are approx. ocular pressure in glaucoma simplex, as the behaviour free from (I). The nature and function of (II) in of (I) is different in vivo and in vitro. C. G. A. the organism are discussed. F. 0. H. Polysaccharide of the vitreous humour. K. Liver-glycogen. Blood-sugar level. M. C. M e y e r and J. W. P a l m e r (J. Biol. Chem., 1934,107, H r u b e t z and L. B. D o t t i (J. Biol. Chem., 1934,107, 629—634).—A polysaccharide of high mol. wt. 731—733).— Correlation coeffs. are calc, for liver- has been obtained from the vitreous humour of cattle glycogen, liver-wt., and body-wrt. Blood obtained eyes by pptn. with COMe, and fractionation from acid by decapitation has a sugar content significantly EtOH. It has an acid equiv. approx. 450 and a > blood obtained by venesection. A. E. 0. dissociation const. 4-58 xlO -5 at 32°. It contains a uronic acid, an NH2-sugar, and a pentose. Galactose Spreading of com plex proteins.—See this vol.. is absent. ~ C. G. A. 161. Determination of copper in the aqueous Substance resembling acetylcholine in ad humour. I. I. N it z e s c u and I. G e o r g e s c u renals and other organs. F. P la ttn er (Pfliiger’s (Compt. rend. Soc. Biol., 1934, 117, 1135—1137).— Archiv, 1934, 2 3 4 , 258—263; Chem. Zentr., 1934, ii, BIOCHEMISTRY. 233 1149).—Repeated evaporation of solutions does not in highly cone, form, b.p. 120— 140°/5 mm. (C 75-45, cause loss of acetylcholine (I). The (I) of a cat H 10-65%), free from vitamin-^4, and unaffected by adrenals is not increased by stimulation of the fuming HXO., at 130°. The B contents of 14 oils splanchnic nerve. The brain, pituitary, and lachrymal are given. The toxic action of A is destroyed by glands contained 1—4x10-® g. of the substance per hydrogenation (I), but that of B is unaffected by (I), g. Smaller amounts occur in spleen and liver. oxidation, or saponification. C is narcotic. Para- A. G. P. lithodes camschatica liver-oil contains C and possibly Choline or acetylcholine content of human A ; the body-fat of sardines contains only A. Cod- placenta. E. St r a c k , H. G eissendorfer , and E. liver oil contains A, B, and C. R. S. C. Neubaur (Z. physiol. Chem., 1934, 229, 25—36).— Fatty acids of the phosphatides of ox adrenals. Only a small amount of choline is present in the W. C. A u l t and J. B . B ro w n (J. Biol. Chem., 1934, placenta before parturition, but this is considerably 1 0 7 , 607—614).—The fatty acids of the phospholipins increased on interruption of the blood-flow, and the of ox adrenal have been fractionated by way of the choline content becomes greater the longer the Me esters, and pure palmitic, stearic, and arachidic placenta remains in the uterus. J. H. B. acids isolated. Some myristic acid may be present. Hydrocarbon in basking shark. I. M. T s u j i - The principal unsaturated acids are oleic and arachid- moto (J. Chem. Soc. Japan, 1934, 5 5 , 702— 741).— onic, the latter being present to the extent of 22%. Isolation is described of an unsaturated hydrocarbon, C. G. A. "zamene,” C1SH3G, 0-8006, n™ 1-4500,1 val. 78-4. Lecithin and kephalin of egg-yolk.—See this C n . A b s . (p) vol., 228. Hydrocarbons of pig liver. H. J. Channon, J. Flavin content of animal tissues under differ Devise, and J. V. Loach (Biochem. J., 1934, 28, ent conditions. A. J. C h a r it and N. W. K h a u - 2012—2025).—-The unsaponifiablo matter from 63 kg. s t o v (Bioebem. J., 1935, 2 9 , 34— 37).—The tissue is of pig liver yielded 52 g. of a sterol-free oil which washed with H20, extracted with aq. MeOH (1 : 3), was fractionated by Et20 and MeOH into an insol. and the solution extracted with CHC13. The MeOH fraction (I) of I val. 266 and a sol. fraction (II) of I solution is compared colori metrically with a standard val. 140. (I) yielded 70% of an unsaturated hydro K 2Cr04 solution. The method is not applicable to carbon (29 mg. per 100 g. of liver), C45H70 or Cf0TT81, blood and tissues containing yellow pigments. The from which the bromide and hydrochloride were pie- distribution of flavin in the tissues of the rabbit and pared. 10% of (I) consists of a saturated hydro cat is determined, and agrees with the results of carbon not yet obtained pure and a further 10% of a Euler and Adler (A., 1934, 544). A small decrease compound containing O. (II) contains a third hydro occurs in the liver-flavin (I) of rats deficient in carbon with one double linking reacting with I. vitam in-/l; neither avitaminosis-C nor a rich protein C. G. A. diet influences the (I) of rats. H. D. Body-fats of the pig. IV. Progressive hydro genation as an aid in the study of glyceride struc Constitution of pectenoxanthin. E. L e d e r e r (Compt. rend. Soc. Biol., 1934, 1 1 7 , 411— il3).—1The ture. T. P. H il d it c h and W. J. St a in s b y (Bio chem. J., 1935, 2 9 , 90—99).—The increase of fully cryst. material, C40H54(±2)O3, has the properties of a saturated glycerides in pig, ox, and sheep dep6t-fats xanthophyll; it contains 11 double linkings and 2 and cow milk-fats, in which the total content of OH. It is very similar to 3-carotene, but does not saturated fats progressively increases, is very similar act as provitamin-^. H. G. R. to that displayed by pig back-fat (I) artificially Carotenoids of three Ascidicc (Halocynthia hydrogenated to varying stages of saturation. (I) papillosa, Dendrodoa grossularia, Botryllus contains about 15% of tri-C18-glycerides, other than Schlossen). E. L e d e r e r (Compt. rend. Soc. Biol., tristearin, which is absent, probably consisting mainly 1934, 1 1 7 , 1086— 1088).—H. papillosa contains a of stearodioleins. The monopalmito-compounds are hypophasie ester of astaeene (I), m.p. 228—230° (large largely, or solely, (3-palmitoglycerides. JPalmito-di- band at 500 m[i in C5H5N), and a xanthophyll, ®saturated compounds (chiefly palmitodiolein) con cynthiaxanthin, m.p. 188— 190° (bands at 517, 483, stitute 42—57% of the fat, and palmitostearo-oleins 452 ni[i in CS2), which resembles zeaxanthin closely, 21—36%. C. G. A. but differs in adsorbability. D. grossularia 'contains Abdominal fat of the Western range horse. an cpiphasic ester of (I), m.p. 230° (large band at 500 rri[j. in C5H5N). B. Schhsseri contains capsorubin, H-A. Sc h u e tte , T. Mi G a r v in , and E. J. S c h w o e g l e r (J. Biol. Chem., 1934, 1 0 7 , 635—639).—The acids of capsanthin, and pectenoxanthin. Carotenes are pre the glycerides of the abdominal fat contain the sent only in traces in all three species. R. N. C. following: palmitic 26-28%, stearic 4-50%, oleic Yellow pigment of the thalamo-subthalamic ‘*>'86%, linoleic 11-88%, and lmolenic 4-48%. No region. G. R o u s s y and M . M o s in g e r (Compt. rend. heptadeeoic acid was present. C. G . A. Soc. Biol., 1934, 1 1 7 , 1054— 1056).—A yellow pig Toxic components of fish liver-oils. K . K a w a - ment of the lipochrome type is present in varying quan and I. Y a m a m o t o (Bull. Inst. Phys. Chem. Res., tities in certain parts of the thalamus and hypo tokyo, 1934, 1 3 , 86—88).—Liver-oil toxins are of thalamus in adult man. R . N. C. «reekinds, A, B, and C. A occurs in the saponifiable Origin of the colours in the plumage of birds. traction and causes nutritive disturbances. B and C C. V. R a m a n (Proc. Indian Acad. Sei., 1934, 1, A, pceur m the unsaponifiable fraction. B causes cramp 1—7).— Observations on the feathers of a jay, Coracias 111 rats, when injected subcutaneously; it is obtained indica, show that the tints may range over the whole 234 BRITISH CHEMICAL ABSTRACTS.— A. spectrum; a simple Tyndall effect explanation is thus taining pituitary hormone, nor that Br metabolism is insufficient. Possible explanations are discussed. a factor in mental disease. C. G. A. N. M. B. Deterioration of shells when stored in oak Micro-chemistry of the pigmentation of the cabinets. J. R. N ic h o l l s (Chem. and Ind., 1934, ear-lobes of the cock. R. L o u v ie r (Compt. rend. 1077— 1078).—Traces of AcOH emitted from oak Soc. Biol., 1934, 1 1 7 , 328—330).—The situation and attack shells on which they are absorbed by moisture staining reactions of the typical granular pigment collected on hygroscopic sea-salt. C. W. G. ation (due to purine bases) are described. F. 0. H. Composition of amniotic fluid. A. R. Occurrence of iron in the milk glands of the T a n k a r d , D. J. T . B a g n a l l , and F. M o r r is (Analyst, rat and the mouse. A. S c h u l t z (Arch. Gynakol., 1934, 5 9 , 806—808).—The d, acidity, Pn, and f.p., 1934, 1 5 5 , 479—489; Cliem. Zentr., 1934, ii, 977).— and the % of total solids, ash, Cl, albumin, and urea, Microscopical examination shows the presence in the are given. E. C. S. milk glands of ratsand mice of Fe, which disappears Modes of stimulation of gastric secretion during pregnancy and lactation. R. N. C. B . P. B a b k in (Nature, 1934, 1 3 4 , 1005).—A Chemical constitution of bone salts of healthy summary. L. S. T. and rachitic animals, (a ) R. E l e m e n t , (b ) J. Influence of temperature on the conductivity M a r e k , 0. W e l l m a n n , and L. U r b a n y i (Z. physiol. of m ilk. E. M e s s n e r (Compt. rend. Soc. Biol., 1934, Cliem., 1934, 2 2 9 , 22—24, 24).— (a ) Polemical against 1 1 7 , 897—899).—Empirical equations are given for Marek et al. (A., 1934, 1133). calculating the sp. conductivity^ at 25° from that (b ) A reply. J. H. B. observed at any different temp. R. N. C. Chemical composition of teeth. I. Deter Combination curves, hydrogen-ion regulating mination of fluorine : fluorine content of normal powers, and equivalents of lactalbumin and its teeth. J. H. B o w e s and M . M . M u r r a y (Biochem. non-identity with serum-albumin. S. E. W oods J., 1935, 2 9 , 102— 107).—F as determined by the (Biochem. J., 1934, 2 8 , 2034—2038).—Titration Zr-alizarin method constitutes 0-02% of the human curves show that lactalbumin (I) is not identical with enamel in the London area. The teeth of rats fed on serum-albumin (II). (I) requires less acid to bring it a diet not designed to be F-free contained 0-02— to a given pn than either (II) or ovalbumin. Above 0-03% of F. C. G. A. Pn 10-5 the buffering power of (I) is > that of (II). C. G. A. Copper content of teeth. E. T i e d e and H. Extraction from urine of a substance possess C hom se (Bor., 1934, 67, [5], 1992— 1995).—The sup ing the biological properties of Oriel’s “ sub position that the discoloration observed in the residue stance P.” H. T h ie r s (Compt. rend. Soc. Biol,, (I) obtained by strongly igniting teeth in air is due 1934, 1 1 7 , 940— 943).— Oriel’s method is modified. to the presence of minute amounts of Cu is supported Urine is acidified, shaken with -J—| its vol. of Et20, by the prep, of similar materials from liydroxyapatitc and left for i hr. The E t,0 is evaporated at 50° and containing Cu (100,000 : 1). Further, addition of (I) coagulated mucus removed by centrifuge. The liquid to pure ZnS leads to ZnS-Cu phosphors. Electrolysis is treated with 5 vols. of EtOH, and then with of a solution of (I) in 7% HN03 gives Cu, 1-2 X10“5 g. Na2C03 until alkaline to phenolphthalcin. The ppt- of which is obtained from 1 g. of ox tooth. H. W. is separated by filtration after 10 min., washed with Luminescence of teeth. E. T i e d e and H. EtOH, dried at 37°, dissolved in H20 with a drop of Ch om se (Bcr., 1934, 67, [5], 1987— 1992).—Addition NaOH, and the insol. residue is removed. The of traces of activating metals to hydroxyapatite (I), solution is pptd. at alkaline pn with 5—6 vols. of Ca]0(OH)2(PO4)6, followed by ignition of the products EtOH, and the ppt. washed with EtOH and dried. at 430° or 710° does not lead to preps, with luminescent R. N. G. properties comparable with those of natural teeth (II). Extraction from bile of a substance possessing Addition of small amounts of glycine, tyrosine, the biological properties of Oriel's “ substance hippuric acid, leucine, gelatin, or collagen from teeth P .” H. T h i e r s (Compt. rend. Soc. Biol., 1934,117, to (I) gives materials the luminescence of which is 943— 944).—Bile is treated with 4 vols.,of 95% EtOH greatly increased by heating at 430° and then very and 1 vol. of 20% CClj-COJI, and the ppt. removed. closely resembles that of (II). The colour depends The clear liquid is made alkaline to phenolphthalcin less on the added substance than on the temp, and with Na2C03, and the ppt. washed with EtOH, dried, experimental conditions. Extraction of (II) with dissolved in O-lJV-NaOH, and the insol. residue re alkaline glycerol does not remove org. matter suffi moved by centrifuge. The solution is pptd. with ciently to inhibit luminescence; this effect is pro 5 vols. of 95% EtOH. The ppt. is sol. in H20 or duced by H202-NH3. Treatment of (II) with S% artificial serum, and has the biological properties of HC1 removes inorg. matter, leaving collagen, which Oriel’s “ substance P .” R. N. C. fluoresces and phosphoresces even when dried. Fatty Determination o f bile-salts in body-fluids matter in (II) is not concerned with luminescence. based on bile-salt haemolysis. S. S. L i c h t m a S H. W. (J. Biol. Chem., 1934, 1 0 7 , 717—730).—The hauno- Bromine in tissues. T. F . D i x o n (Biochem. J ., lytic activity of bile-salts (I) on a standard suspension 1934, 2 9 , 86— 89).—The Br content of blood and of sheep’s red cells previously stabilised by treatment pituitary is variable and is thought to be dependent with P 0 4"' buffer is determined in presence of on food intake. There is no evidence of a Br-con- citrate, which enhances haemolysis by (I), but inhibits BIOCHEMISTRY. 235 the hsemolytic activity of soaps, thus rendering Composition of glomerular urine. XII. Con possible the determination of the (I) content of centration of chloride in glomerular urine of body-fluids. The order of activity of (I) is Na frogs and Necturi. B. B. W e s t f a l l , T. F i n d l e y , deoxycholate (II) (the standard) > taurocholate > and A. N. R i c h a r d s (J. Biol. Chem., 1934, 107, glycocholate>cholate. The activity of mixtures of 661— 672).—The sensitivity of Isaac’s colorimetric (I) is strictly additive. Vais, are given for tho (I) method for Cl' is sufficiently increased by use of content of normal blood, urine, and bile and for 5-diphenylcarbazide to enable determination to be cadaver gall-bladder bile. The first two fluids contain made of 0-001 mg. of NaCl with an accuracy of 3% in 0-5—4-0 mg. of (II) (or its equiv.) per 100 c.c. urine or plasma. The [Cl'] of the glomerular urine A. E. 0. and blood-plasma is approx. equal in both frogs and Colloidal solution of acid bilirubin. Prepar Necturi. C. G . A. ation and properties. B. V a r e l a -F h e n t e s and Excretion of copper in urine and faeces and its P. R e ca r te (Compt. rend. Soc. Biol., 1934, 117, 900—902).—A colloidal solution of bilirubin (I) is relation to the copper content of the diet. S. L. obtained from a filtered, saturated COMe2 solution by T o m pse tt (Biochem. J., 1934, 28, 208S—2091).— a process of repeated dilution and vac. evaporation. The average daily intake of Cu is 2-0—2-5 mg., which It is stable in the dark, and contains only traces of is balanced by the total excretion. Human urine C0Me2, removal of which ppts. the (I). Various contains 0-08—0-48 mg. of Cu per litre. H. G . R. properties are recorded. Small quantities of alkali Routine determination of fat in faeces. E. C. convert (I) into H20-sol. bilirubate. P. N. C. W o o d and T. W . Sim pso n (Analyst, 1934, 5 9 , 817— Bilirubin excretion of the liver. T. O k a d a 818).—The material is acidified with HC1, dried with (Trans. Japan. Path. Soc., 1933, 23, 567—571).— Na2S04, and extracted with light petroleum. Fatty The bile of the newborn infant consists chiefly of acids and neutral fats are determined consecutively bilirubin I, and that of the adult of bilirubin I and II. in the extract. Free fatty acids and soaps may be C h . A b s . differentiated by repeating the determination on a Clinical tests for bilirubin in urine. E. G. new sample, omitting the addition of HC1. Specimen Godiried (Biochem. J., 1934, 28, 2056—2060).— analyses are given. E. C. S. Hunter’s test (A., 1931, 863) for bilirubin is modified. Application of emission spectrum analytical To the urine acidified with AcOH arc added BaCl2 and methods to problems of social medicine. W a l - (M4)2S04 and the ppt. is washed with H20. Abs. t h e r G e r l a c h and W e r n e r G e r l a c h (Angew. Chem., EtOH, saturated aq. (NH4)2S04, 6% Na2HP04, and 1934, 47, 825—827).—A lecture. H. W. diazo-reagent are added. When the colour has deve loped CHC13 is added. The lower layer contains the Energy requirement of an acromegalic giant. azobilirubin, and is compared with a standard Co A. W . R o w e (Science, 1934, 80, 482— 483).—Respir solution. H. D. atory data demonstrate an established level of hypo- Action of light on lyochromes. W. K o s c h a r a function. L . S. T. (Z.physiol. Chem., 1934, 229, 103— 111).—Aquoflavin Cholesterolsemia in experimental infectious (I) may be isolated from the lyochrome concentrate of anaemia in the horse. G . G u il l o t and J. G u il h o n urine by chromatographic analysis. It is eluted by (Compt. rend. Soc. Biol., 1934, 117, 320—321).—In H20 or aq. NaOAc. Irradiation of (I) in alkaline colts inoculated with infectious anaemia the blood- solution with ultra-violet light (II) gives aquolumi- cholesterol remained normal until the onset of fever, flavin (III) insol. in CHC13. (Ill) is eluted by 5% aq. when it increased steadily until death. R. N. C. C5H5N. Irradiation of uroflavin in alkaline solution gives, as by-product, a CHCl3-insol. pigment re Respiration of red blood-corpuscles of normal sembling (III). Neither visible light nor (II) acts on the subjects and in various forms of anaemia. W. feuco-form of lactoflavin in alkaline solution. Irrad D e u t sc ii (Biochem. J., 1934, 28, 2002—2011).— iation of tho pigments in aq. Na2C03 in air yields pro Since no formation of methsemoglobin (I) is observed ducts resembling deuteroflavin. In aq. NaOH the when red blood-cells (II) are mixed with liver extract Foments are irreversibly bleached. H2S03, inactive and examined spectroscopically or by respiration of the dark, reduces uroflavin in the light to the (II), tho (I) test cannot replace the clinical determin kuco-compound. Other H2-donators are also effect- ation of hsemopoietic potency. Saline extracts of 1Ve' J. H. B. fresh rat-liver-produce a slight and limited loss of O capacity when mixed with haemoglobin (III), without Chromogen of melanuria. L. Linnell and production of (I). The stimulating effect (IV) of H. S. R a p e r (Biochem. J., 1935, 29, 76—85).—The the “ respiratory supplement ” on the respiration of ®Momogen (I) of human melanuria can be separated from urine by pptn. -with Pb or Hg acetate. Admin (II) in pernicious and secondary anaemias is highest istration of 5 :6-dihydroxyindole (II) to rabbits at the time of reticulocyte crisis, and then falls to the causes excretion of a melanogen in the urine the val. for normal blood. (IV) is independent of the (III) content of (II). C. G . A. properties of which suggest identity with (I). 5 : 6- whydroxyindole-2-carboxylic acid does not produce Effect of inorganic iron with and without ®elanuria. (I) appears to be a simple derivative of ultra-violet irradiation on prevention and cure >|1), possibly a sulphate or glycuronate. The syn- of nutritional anaemia. E. J. A n d e s and H. D. hesis of the 7v0 disulphate of (II) is described. B e a r d (Amer. J. Physiol., 1934, 108, 91—98).— C. G. A. Irradiation (I) accelerated the curative action of low 236 BRITISH CHEMICAL ABSTRACTS.— A. but not of high dosages of Fe. (I) affects the erythro preps, are stabilised (for many months) by rapid cyte rather than haemoglobin regeneration. drying and subsequent storage, both at low temp. Ch. A b s . (p) A. E. 0. Active principle of liver extract in recovery Influence of potassium and calcium chlorides from anaemia due to bleeding. T. A sao (A ich i and sodium , potassium , and calcium acetates Ig. Zasshi, 1933, 40, 313, 863).—The third fraction of on the flocculation of hydrosols (organ extracts) the Et20 extract of liv er (Levene, Sueyoshi) was the by human serum. M. L. Chevrel-Bodin and M. most effective in curing anaemia in rabbits. A n Cormier (Compt. rend. Soc. Biol., 1934, 117, 764— extract of erythrocytes was similarly active. Brain 765).—With normal and canccr sera as controls, the extract was inactive. The active substance was flocculation of syphilitic sera when mixed with an absent from fisli-liver. Ch . A b s . (p) (EtOH) extract of ox-heart at pn 6-8 is sp. in presence of Na' or K ‘, but not of Ca". F. O. H. Italian work on liver therapy. H. I. G o l d s t e in (Science, 1934, 80, 561).— Concerning priority. Fat-soluble vitamins and dental caries in L. S. T. children. C. D . M. D a y and H. J. Se d g w ic k (J. Bence-Jones protein in serum. D. M. K y d d Nutrition, 1934, 8, 309— 328).—Feeding of vitamin- (J. Biol. Chem., 1934, 107, 747—753).—Bence- A and -D had no influence on the progress of caries. Jones protein (I) begins to bo pptd. when [P04'"] A. G. P. reaches 1-983/, whereas globulin is pptd. at l-4Sjli. Effect of diet on the course of experimental The various sections of the discontinuous solubility coccidiosis in chickens. E. E. Jones (J. Amer. curve are extrapolated logarithmically to zero and Vet. Med. Assoc., 1934, 38, 193—206).—Vitamin-i the various individual serum-protein contents deter in the diet did not affect the course of infection of mined (cf. A., 1933, 293). (I) from urine is identical E. tenella. Infected chickens maintained live wts. with (1) from serum. (I) exists in the serum of nearer to thoso of controls when fed a high-protein myelomatous individuals and may or may not appear than when fed a low-protein (I) diet. Immunity to in the urine. A. E. 0. reinfection developed more rapidly in chickens re Hormones in cancer. IX. Resistance factor ceiving (I). A. G. P. in normal urine affecting carcinoma 256. F. Therapeutic effect of total ablation of normal B isc h o f f and L. C. M a x w e l l (J. Pharm. Exp. Ther., thyroid on congestive heart failure and angina 1934, 52, 378—382).— Injection of crude callicrein pectoris. VIII. Relationship between serum- preps. (I) increased the no. of takes of carcinoma 256 cholesterol values, basal metabolic rate, and in rats and the rate of tumour growth. Purified clinical aspects of hypothyroidism . D. R. Gilu- preps, of (I) failed to produce these effects. H. D. o a n , M. C. V olk, D. Da™, and H. L. B lu m g a e t (Arch. Int. Med., 1934, 54, 746—757).—After removal Influence of vitamnwl and -D on the frequency of the thyroid, serum-eholesterol (I) increases to 300 of tumours in mice. E. H a r d e and N. K o b o z ie f f mg. per 100 c.c. as the basal metabolic rate decreases. (Compt. rend. Soc. Biol., 1934, 116, 848— 849).— (I) is significantly decreased by thyroid medication Increased dietary Ca and vitamin-4 and -D decreased and may be used as an index of hypothyroidism. the appearance of tumours. Ch. A b s . (p) ' H. G. B. Action of ascorbic acid on tumour metabolism. Fur dermatitis. S. A. W o o d h e a d (Analyst, D. L. W o o d h o c se (Biochem. J., 1934, 28,1974— 1934, 59, S15).—A fur, suspected of causing derm 1976).—Injection of ascorbic acid, although having atitis, contained 110 dye, but contained 0-7S% of no effect on the induction period for the production H2S04 and 12-43% of solids sol. in boiling H20, of of tar warts in mice, exerted a stimulating effect on which 4-89% was NaCl. E. C. S. the proliferation of the tumours. A. E. 0. B lood-potassium in different form s of diabetes Blood changes following snake-venom treat mellitus. F. R a t h e r y and J. B e r t o l ia t t i (Compt. ment of cancer. J. V e l l a r d and M . M ig u e l o t e - rend. Soc. Biol., 1934; 117, 875—878).—Plasma-K V ia n n a (Compt. rend., 1935, 200, 98—100).—The (I) and total blood-K (II) were normal in simple lethal dose of Lachesis atrox venom for the normal diabetes (III). (I) was raised in cases of (III) with rat is 4 mg. and for the cancerous rat 1-5 mg. In foot-gangrene or hepatic lifchiasis, but not with cervical man repeated small injections (0-1— 1 mg.) cause abscess. Insulin had scarcely any effect on (II), even intense lysis of red blood-eells and leucocytes, decrease after several months. In some cases of diabetic coma of fibrinogen and complement, and increase of the (IV) results were too variable to indicate a definite coagulating power of the serum. Hepatic and renal relation between (II) and (IV). In bronzed (III), troubles may also occur. C. G. A. (II) was normal. R. N. C. Stabilisation and purification of specific anti Lumbar and sub-occipital cerebrospinal fluids cancer bodies. T. L u m s d e n and T. F . M a c r a e in experimental poliomyelitis in monkeys. P. (Biochem. J., 1934, 28, 1968— 1973).—Anti-cancer M o l l a r e t and B. E r b e r (Compt. rend. Soc. Biol, sera can be highly conc. by fractional pptn. of the 1934, 117, 1098—1100).—Fatal forms of poliomyel euglobulin (J. Path. Bact., 1932, 35, 441) and sub itis (I) in monkeys produce increases in albumin sequent adsorption on Al(OH)3 and elution at ps 7-5, (II) and leucocytes (III) in the cerebrospinal fluid when 40—o0% of the antibodies (I) are eluted. (I) (IV ); Cl remains normal, and the pptn. curve for are pptd. in solutions containing 12% EtOH, but colloidal benjoin (V) broadens. The modifications C0Me2 is ineffective as a precipitant. Antibody begin 48 hr. before the appearance of symptoms, at BIOCHEMISTRY. 237 which point they attain their max., and remain thus Nitrogen and sulphur metabolism in Bright’s until death. In curable (I), the modifications are disease. V. Metabolic study of a patient with similar. The increased (II) persists longer than oedema of unknown origin. G. P. G r a b f ie l d , M. (III), and suboccipital (IV) becomes normal again D r isc o l l , and M. G. G r a y (Arch. Int. Med., 1934, before lumbar (IV). The same modifications appear 54, 764—769).—Non-nephritic, non-cardiac oedema in abortive (I). Anti-(I) vaccination produces a %vas accompanied by a negative S balance together broadened (V). R. N. C. with some retention of N. The diuresis produced by urea comes from within the cells. H . G. R. Lumbar and sub-occipital cerebrospinal fluid in experimental yellow fever in Macacus rhesus. Glycogen. I. Nasal polypus. S. H o r ie (Sei- 'P. M o l l a r e t and G. J. Stefanopoulo (Compt. rend. i-kwai Med. J., 1933, 52, No. 9, 1—30).—The distrib Soc. Biol., 1934, 117, 1101—1103).—Animals with ution of glycogen in the various cells has been yellow' fever (I) show an increased lymphocyte re investigated. Ch . A b s . action of the cerebrospinal fluid, but albumin and Phosphoric acid exchange in the blood of the the colloidal benjoin pptn. curve are scarcely cliangcd. pregnant w om an. E. M o m ig l ia n o (Arch. 1st. The same modifications appear in animals with Biochim. Ital., 1934, 6, 351— 408).—The inorg. nervous (I), and immunised animals inoculated with (I), total acid-sol. (II), and total P 04"' (III) in the either form. B>. N. C. blood are increased in pregnancy (IV), but the Protein exchange in relation to hepatic func increase is not always oc the stage of (IV) ; P20 7"" (V) is unchanged. Reducing hexose phosphoric tion. R. M e s s in a (Arch. Farm, sperim., 1934, 58, 280—302).—Persons with normal fiver function (I) esters are present in the placental tissues, indicating show a serum-albumin (II) > -globulin (III). In enzymic control of sugars and P 04'" in their trans cases of atrophic cirrhosis (IV) and luetic hepatitis placental passage. (I), (II), and (III) are all increased (V), (II) falls and (III) rises until the (II)/(III) ratio during the expulsive period of parturition (VI), is inverted. The change is more marked in (V) but the increases are independent of uterine con than in (IV), and increases with (I) deficiency, traction. In several cases where cæsarian section but the inverted (II)/(III) ratio always remains near was carried out, no difference was found in uterine unity; Total serum-protein is diminished in (IV). arterial and venous P. During puerpérium, (I) The blood-sugar curve is higher and more prolonged only is increased, the other fractions oscillating in (I) deficiency. R. N. C. irregularly and variably. (I), (II), and (V) in the fœtal blood are considerably increased, particularly Metabolism in hepatic diseases. VI. Blood- in the umbilical artery, but lipin-P04"' is decreased, sugar. Y. Kin (J. Chosen Med. Assoc., 1934, 24, whilst (III) is the same for foetus and mother. 208—220).—Of 37 hepatic patients, 15 had blood- R. N. C. sugar (I) > 0-12% and 5 <0-07% , the former being Diagnosis of pregnancy from the urine. W. associated with jaundice or liver abscess. In coma H o f f m a n n (Deut. mod. Wocli., 1934, 60, 822—824; (I) rises, but cerebrospinal fluid-sugar fluctuates. Chem. Zentr., 1934, ii, 1148).—The growth of wheat Ch. Abs. or barley (I) is accelerated by urine (II) of pregnant Lipin antigens of organs in sero-diagnosis. women, and retarded or prevented by (II) of non- New antigen of seroflocculation in leprosy. pregnant women. Flowering is not affected; in M. C. R u b in o (Compt. rend. Soc. Biol., 1934, 117, summer-(I) the HaO-treated controls flow’er earlier. 894—S97).—Aq. EtOH extracts of spinal marrow, The effects are not destroyed by boiling the (II), liver, and CH20-treated corpuscles, suspended in 0-9% nor by removing the nutritional salts by dialysis. NaCl solution after evaporation of EtOH, exhibit a R. N. C. sp. flocculating effect with leprosy sera (I). If Influencing of the antidiuretic and chlorine- diluted without evaporating the EtOH, the specificity releasing action of the posterior pituitary hor of the effect for (I) disappears or is diminished, showing mone by the blood-serum of pregnant and non- that (I) flocculates a sp. group of lipins. Thé group pregnant women. (Posterior pituitary theory is absent from kidney extracts ; brain extracts show of pregnancy toxicosis.) W. B ic k e n b a c h and a diminished effect, due probably to the presence in H. R u p p (Arch. Gynakol., 1934, 155, 572—584; large quantities of stabilising lipins. R . N. C. Chem. Zentr., 1934, ii, 792—793).—Mixtures of pituitrin (I) with sera of pregnant or non-pregnant Adrenal cortex and electrolyte metabolism. women generally weaken or suppress the antidiuretic R. L. Z w e m e r (Endocrinol., 1934, 18, 161— 169).— and Cl-releasing actions of (I), the pregnancy sera Oral administration of Na salts prolongs the life of showing the greater effect. Sera of pre-eclampsia adrenalectomised cats. Ch. A b s. show the same property. R . N. C. Blood chemistry of adrenal insufficiency in Experimental renal insufficiency produced by cats. R. L. Z w e m e r and R . C. S u l l i v a n (Endo partial nephrectomy. III. Diets containing crinol., 1934,18,97— 106).—Adrenalectomy is followed whole dried liver, liver residue, and liver extract. by early loss of Na, lowered C02 capacity, and A. Ch a n u t in (Arch. Int. Med., 1934, 54, 720— 745).— increase in K and non-protein-N. Before death, A low-protein diet causes albuminuria and polyuria, blood-sugar and -Cl are lowered; -P and -Mg are with little retention of N and a delay of hypertension, raised. Injection of extract of adrenal cortex into whereas a high-protein diet causes an increased adrenalectomised animals reverses the chemical excretion of dil. urine (I). The amount of protein changes occurring in adrenal insufficiency. Ch. A b s. excreted has no relation to the vol. of (I). H. G. R. 238 BRITISH CHEMICAL ABSTRACTS.— A. Examination of urine in renal disorders. H. as conditions improve. As exudative tuberculosis G ib b o n s III (Arch. Int. Med., 1934, 54, 758—763).— develops, ultrafilterable (I) vals. increase. A. L. Tho method shows the rate at which cells and casts Apparatus for measuring the gaseous meta are excreted in tho urine (I). Tables are given showing bolism of dogs. F . F o l d e s (Biochem. Z., 1934, the cells, casts, and protein in normal and patho 275, 66—73).—A simple valveless apparatus for use logical (I). H. G. R. under physiological conditions is described. The Colorimetric test for renal function using error is ± 3 to ± 4 % . W. McC. intravenous iodine preparations. R . H . H e r b s t Metabolism of ducks (Anas platythyncka, L.). and G. 0. B a u m r u c k e r (J. Urol., 1934, 32, 131— II. Gas metabolism and respiratory quotient. 140).—After injection of Neoskiodan, I in urine is T. C. S h e n and S. M. L i n g . III. Carbohydrate' determined colorimetrically by oxidation with K N 03- metabolism. S. M. L in g and T. C. S h e n (Chinese H2S04 and extraction with CHC13. The method is J. Physiol., 1934, 8, 307—333, 335—349).— II. After applicable to any substance of the uroselectan group. feeding, Oa consumption and C02 production increase Ch . A b s . (p) due to a conversion of carbohydrate into fat: R.Q. Effect of rickets on the structural character increases, reaching a max. in about 5 hr. istics of bone. G. L. Cl a r k and J. N. M r g u d ic h III. Liver-glycogen runs parallel with the R.Q. (Amer. J. Physiol., 1934, 108, 74—79).—The X-ray and a linear relationship was found between the diffraction pattern of rat humerus shows crystals glycogen (I) and the wt. of tho liver (II). Of the total oriented lengthwise in normal animals. In rachitic carbohydrate ingested, 54% is utilised for energy animals the collagen is broken down and no longer production, 24% for fat, and 22% is stored as (I), holds crystals in this position. Ch . A b s . (p) whilst 12% of the last amount is temporarily Comparison of the antirachitic action of accumulated in (II). H. G. R. methyl phosphates, glycerophosphates, and Ability of fresh-water fish to extract oxygen lecithin. R . L e co q and M. L . B a r b a n (Compt. at different hydrogen-ion concentrations. A. H. rend. Soc. Biol., 1934, 117, 671—673).—Tho P 04"' W ie b e , A . M . M cG a v o c k , A . C. F u l l e r , and H. C. in CaMe phosphate has an antirachitic activity (I) M a r k u s (Physiol. Zool., 1934, 7, 435—448).—In < that in Ca glycerophosphates, but with Mg the normal ranges of the initial 0 2 content of the H20 reverse is the case. The fatty acids and choline do did not influence the 0 2 content at death. Beyond not decrease the (I) of the glycerophosphate in egg- normal pn ranges 0 2 concn. at death increased with lecithin. A. L. the initial 0 2. Ch . A b s . (p) Antirachitic action of glycophosphates. M. L. Effect of oxygen tension on oxygen con B a r b a n (Compt. rend. Soc. Biol., 1934, 117, 999— sumption of a developing egg (Orthoptera). 1001).—The glycophosphates of Na and Mg have a J. H. B o d in e (Physiol. Zool., 1934, 7, 459— 463).— similar antirachitic activity, but that of tho Ca salt With 0 2 tensions (I) of 25— 160 mm. Hg, 0 2 consump is less. Their activities, however, are < that of the tion (II) of M. diffcrenlialis is independent of (I)- corresponding Me phosphates. A. L. With (I) < 25 mm., (II) declines rapidly. Eggs in Chlorine and phosphorus contents of the brains diapause are stimulated to higher (II) by 380—760 of normal and starved guinea-pigs and of those mm. (I). Ch . A b s . (j>) suffering from chronic and acute scurvy. Mag Iron content and oxidation rates of a develop nesium content of striated muscle. A . M ic h a u x ing egg (Orthoptera). J. H. B o d in e and J. E- (Compt. rend., 1934, 199, 1460— 1462).—The Cl W o l k in (Physiol. Zool., 1934, 7, 464— 469).—The and P contents of the brain of normal and starved total Fo in eggs of M. differentialis is unchanged guinea-pigs (I) aro the same, but increase during during development, but embryo-Fe (I) increases serious attacks of chronic or acute scurvy; the at the expenso of yolk-Fe. During diapause 02 P content is affected only in prolonged cases. The consumption (II) is low and (I) is const. On resumed M g content of striated muscle of (I) does not decrease growth (I) increases with (II). The degree of satur during scurvy, unless the muscle is very hsemorrhagic. ation of the Fe is less in diapause than in active R. S. C. growth. Ch. A b s . (p) Blood-lipase and other conditions in tuber Calculation of the permeability of the cell culosis. S. R yu (J. Chosen Med. Assoc., 1934, 24, surface to oxygen. N. R a s h e v s k y (Physical Rev., 305—313).—In severe tuberculosis blood-lipase is 1933, [ii], 44, 322).—An attempt to calculate the reduced. Ch. A bs. permeability of the [living?] cell surface to 0 2 from Calcium, potassium, ultrafilterable calcium 0 2-pressure-02-consumption curves at low pressures content, and the ratio of calcium to potassium has been made. L. S. T. in the blood in pulmonary tuberculosis. A. d e Micro-determination of calorific value of foods. M. S a r m e n to and M. J. B. d a Co s t a (Compt. rend. V. S. I v l e v (Biochem. Z., 1934, 275, 49—55).—The Soc. Biol., 1934,117,741—744).—Fibrous tuberculosis food is oxidised with excess of OTiY-K^C^O? (3 vols.) is associated with reduced vals. for ultrafilterable and 0-lA7'-Ag2Cr20 7 (1 vol.) in H2S04 and the excess serum-Ca (I). Ultrafilterable serum-K (II) and (I) of H2Cr20 7 is determined. Since protein (I) is not increase in amount as the disease progresses. Pul completely oxidised, a correction must be applied. monary tuberculosis, on the other hand, is associated Since the amount of heat produced on consumption with increased vals. for (I), (II), and ultrafilterable of 1 g. of 0 2 varies little when the proportions of (I), the last decreasing, and the ratio (I)/(II) increasing food constituents [fat, carbohydrate, (I)] change, a BIOCHEMISTRY. 239 general “ cal. coeff.” is used to calculate the calorific 12).—Oral administration of NaH2P04 increases the val., but where the (I) content is unknown a N 0 2 consumption in muscular work. The average losses determination (micro-Kjeldahl) is made. W. McC. of body-wt. and of H ,0 through sweating are Balanced diets, net energy values, and specific diminished. Diuresis is reduced more by small doses than by large doses. Blood-hsemoglobin in most dynamic effects. H. H. M it c h e l l (Science, 1934, 80, 558—561).—A discussion. L. S. T. cases decreases. Blood-Cl is unaffected, but sweat-Cl falls, whilst urinary Cl rises. Large doses of NaH2P04 Permeability and ion concentration in muscle administered 9— 10 hr. before the work period have excitation. E . E r n s t and J. F r ic k e r (Pfliiger’s no effect. R. N. C. Archiv, 1934,234, 399-—405).—Perfusion of a Laewen- Trendelenburg frog prep, with Ringer’s solution with Chemical reactions in muscle. J. K. P a r n a s , indirect stimulation of one gastrocnemius (I) does not P . O s t e r n , and T. M a n n (Biochem. Z., 1934, 275, alter muscle-K. With a solution with increased 74— 86; cf. A., 1934, 1027, 1394).— Inorg. phosphate K:Ca ratio, which raises the pormeability (II), undergoes esterification in the absence of adenosine- muscles give oil K on stimulation. In a KCl-rich triphosphoric acid in frog-muscle pulp poisoned with perfusion solution, the stimulated (I) always contains CH2I-C02H. In such pulp phospliocreatine is syn less K than the unstimulated (I). Stimulation does thesised from added phosphoglyceric acid (I), but not not increase muscle-(II). R. N. C. from added phosphate, and added creatine is phos- phorylated. From (I) AcC02H is produced. A frog Permeability of frog's muscle under the in heart, poisoned with CH2I-C02H, is kept beating by fluence of different substances involved in addition of (I). Many of the chemical changes which muscle metabolism. P. B e c k m a n n (Pfliiger’s occur in muscle are depicted in a scheme which is in Archiv, 1934, 234, 469— 475).—The permeability (I) harmony with the views of Embden, Meyerhof, Loh- of the frog’s abdominal muscle is steadily and revers- mann, and the authors. The interacting substances ibly increased by lactic acid, fructose, and Na fructose frequently behave as sp. phosphate donators and diphosphate, malonate, glycerophosphate, propionate, acceptors. W. McC. and citrate (II). The increase in (I) cc the increased output of AcC02H (III) from breakdown in the Mechanism of poisoning [of muscle] with iodo- muscle of all these substances except (II). (Ill) also acetic acid. P. O s t e r n (Biochem. Z., 1934, 275, increases (I). R. N. C. 87— S9; cf. A., 1934, 1394).— In muscle pulp CH2I-C02H affects neither the production of hexose Seasonal variations of the permeability and diphosphate and adenylic acid (I) from adenosinetri- metabolism of the muscle of the cold-blooded phosphoric acid (II) and glycogen nor the resynthesis animal. (Effect of creatine on the frog's of (II) from (I) and phosphocreatine, but it prevents muscle.) B. K a t z (Pfiiiger’s Archiv, 1934, 234, the production of phosphoglyceric acid from fructose- 492——509).—The effect of creatine (I) on the muscle diphosphoric acid. W. McC. (II) is dependent on the season, and on the general metabolic condition of the (II) cells. In normal Decrease of glycolysis and increase of readily frogs, (I) is either ineffective or produces a passing hydrolysable acid-soluble phosphorus in blood relaxation of (II), and a marked increase in resting after prolonged fatiguing work. Z. D is c h e and respiration, whilst in frogs with low carbohydrate K. Sach s (Biochem. Z., 1934, 274, 346—357).—The reserve after hibernation, or in normal animals glycolytic power of the blood of an adult dog after treated with toxic doses of insulin, (I) produces a exhaustive wrork decreases, but of a growing dog may contraction of (II), probably accompanied by an increase or decrease considerably. The concn. of increased synthesis of creatinephosphoric acid. readily hydrolysable acid-sol. P always increases, but R. N. C. not in amount corresponding with the decrease of Action of monophosphate on the blood and the glycolysis. The relationship of phosphorylation (I) of sugar, dephosphorylation of and subsequent (I) to circulation in physical w ork. A. K r e s t o v n i- adenosinetriphosphoric acid, and the velocity of glyco K°v, A. K o r ia k in a , E. K o s s o v s k a ja , P. R e t e l - skaja, and S. S c h ir o b o k o v (Arbeitsphysiol., 1934, lysis is discussed. P. W. C. -13—19).—Administration of smalldoses of NaH2P0 4 Influence of cortical hormone and ascorbic immediately prior to physical work causes a smaller acid on the chemistry of active muscle. V. rise of blood-lactic acid (I). Inorg. P 04"' shows only B a e n a (Biochem. Z., 1934, 274, 362— 366).—The time an insignificant increase compared with controls (II); required for complete exhaustion of rats in a~ tread ? is not raised by small doses. Blood-sugar mill under standard conditions (cf. A., 1934, 332) is shows no increase over that of (II). The alkali greater when the animals receive both adrenal-cortex reserve is also unaffected. NaH2P0 4 decreases produc- hormone (I) and ascorbic acid (II) and the decrease of lou of leucocytes, but increases that of lymphocytes; glycogen at exhaustion is < whon they receive (I) y-eIf is no parallelism between the changes due to alone. The increase of residual N in fatigued muscle irffu* i 4 ^le white-cell and chemical composition is almost completely inhibited by administration of 0 the blood. XaH2P04 accelerates resynthesis of (I) (I)+(H). P. W. C. after work. R. N. C. Blood-lactic acid and oxygen consumption Influence of phosphate on the distribution of during and after muscular work in man. O. ater and salts in muscular work. A. D a n il o v , B a n g (Arbeitsphysiol., 1934, 7, 544— 554).—The 0 2 irnv jAKTNa ’ K o s s o v s k a j a , A. K r e s t o v n i- supply (I) during hard work of short duration, and > and A. F o m i6 o y (Arbeitsphysiol., 1934, 8, 1— at first during more prolonged work, is insufficient. 240 BRITISH CHEMICAL ABSTRACTS.---- A. The greater part of the accumulated lactic acid (II) in for a short time, slightly > , and subsequently the muscles is removed as soon as cessation of work definitely < , that with a glucose or sucrose diet. 1 increases (I), (II) being partly oxidised and partly loss of 40—50% of ingested lactose may occur in so reconverted into glycogen. A small part of (II) far as wt. or energy relationships are concerned. diffuses into the blood, from which it is afterwards A. G. P. taken up by the resting muscle or oxidised and Quantitative changes of glycogen in the liver resynthesised in the liver. This quantity of (II) is of the foetus and of the new-born infant. S. not always large enough to alter the 0 2 consumption M it a n i (Trans. Japan. Path. Soc., 1933, 23, 245— (III). The increased (III) during and after work 247). Ch . Abs. depends chiefly on oxidation in the working and Available carbohydrate of fruits. Determin recovering muscles, and has no immediate quant, ation of glucose, fructose, sucrose, and starch, relation with blood-(II). R. N. C. E. M . W id d o w s o n and R. A. M cCa n c e (Biochem. J., Formation of pyruvic acid from lactic acid in 1935, 29, 151— 156).—The glucose (I), fructose (II), muscle. E. A u b e l and E. Sim o n (Compt. rend. sucrose (III), and starch (IV) contents of 41 varieties Soc. Biol., 1934,117, 658—659).— Chopped muscle in of fresh fruit have been determined. All fruits presence or absence of 0 2 is capable of converting (except bananas) contain negligible amounts of (IV). lactic acid into AcC02H. A. L. Most fruits contain approx. equal amounts of (I) and First type of formation of lactic acid in (II). Cherries, grapes, figs, tomatoes, pomegranates, the tissues in oxido-dynamic metabolism of and mulberries contain no (III), whilst (III) is the chief sugar present in apricots and peaches. (II), but hexoses : glucose and • maltose. M. W i e r not (I), is partly destroyed by boiling 5% HC1. z u c h o w s k i and F . Se k u r a c k i (Compt. rend. Soc. Biol., 1934, 117, 915—918).— Continuous intravenous A. E. 0. injection of glucose or maltose results in an increase (a ) Absorption by intact organs of glucose, in the lactic acid (I) of the afferent and efferent maltose, and galactose injected at constant rate blood-vessels of the liver, muscles, intestines, and into the blood-stream. (b ) Assimilation by the head-tissues, the (I) being produced in all these except organs of fructose introduced into the blood the liver, which retains it. Galactose does not pro stream at constant rate. M. W ierzuchowski duce this effect. This type of (I) formation is termed and H . F is z e l (Compt. rend. Soc. Biol., 1934, 117, “ hepatopetal.” R. N. C. 1019— 1022, 1022— 1025).— (a ) A comparison is made of the carbohydrate content of tho femoral blood Second type of formation of lactic acid in the vessels, the portal and hepatic veins, and the carotid organism during the combustion of hexoses, artery and jugular vein of dogs during fasting (I) and accompanied by specific dynamic action : fruc during the continuous separate injection of glucose tose. M. W ierzuchowski and F. S e k u r a c k i (II), maltose (III), and galactose (IV) at const, rate. (Compt. rend. Soc. Biol., 1934,117, 919— 922).— Con During (I) the liver produces considerable quantities tinuous intravenous injection of 0-9% NaCl, inositol, of (II), whilst the other organs, particularly the head, Na lactate, or MeCHO does not alter the “ hepato absorb it. In the head 13%, and in the muscles 48%, petal ” cycle of lactic acid (I) circulation. Fructose of (II) taken up is converted into lactic acid. Where causes a formation of (I) winch occurs chiefly in tho as during injection of (II) and (III) the muscles liver, and is hence termed “ hepatofugal.” absorb the greatest amount of (II) and the intestine R. N. C. least, during (IV) the absorption in the head is greatest Cellulose in the diet of rats and mice. C. M. and that in the intestine least. M cK a y [with C. C. K u , J. C. W o o d w a r d , and B. S. (b ) The (II) balance of the blood-vessels of fasting Se h g a l] (J. Nutrition, 1934, 8, 435— ¿47).—Rats dogs is unaffected by tho introduction of physiological receiving a diet containing 10—20% of cellulose (I) salt solution, Na lactate, MeCHO, and inositol into produced normal growth. The digestibility of crude the blood-stream. When fructose (V) is injected, fibre from beet pulp, bran, and regenerated (I) was the organs arranged in order of decreasing absorption 40, 20, 20%, respectively. Feeding of (I) increases of (V) are the liver, the muscles, the intestine, and the faecal dry matter to an extent > can be ascribed to head. The liver produces (II) at its normal rate, and the amount ingested. A. G. P. whilst the head absorbs (II) it does not stop the Exogenous m elituria in m an. B. G. E d w a r d s circulation of (V). A. L. and M. R. E v e r e t t (J. Nutrition, 1934, 8, 253—267). Balance of water in the organs during the —Ingestion of toast results in urinary excretion of injection of carbohydrates and related sub an unknown product which is neither dextrin (I) nor stances. M. W ierzuchowski and H. Fiszed anhydro-sugar (II). After ingestion of glucose syrups (Compt. rend. Soc. Biol., 1934, 117, 1025—1028).- -(III) urine contains an unknown non-fermentable, A comparison is made of the haemoglobin content reducing saccharide of low mol. wt., which occurs in of the blood-vessels of the liver (I), muscles (Il)> the “ isomaltose fraction ” of (III). (I) and (II) have intestine (III), and head (IV) of dogs during fasting no relation to the hydrolysable sugar of normal urine, (V) and during the separate continuous injection broketose is probably a product of intermediate (under amytal anaesthesia) of 2 g. per kg. per hr. of metabolism. A. G. P. physiological salt solution, Na lactate, MeCHO, Nutritive value of lactose. A . E. K o e h l e r inositol, glucose, maltose, and galactose (VI). During and S. E. A l l e n (J. Nutrition, 1934, 8, 377—383).— (V) and with all the injections except (VI) the haemo The gain in wt. of rats receiving a lactose diet was, globin content of the blood from (I), (II), and (HI)13 BIOCHEMISTRY. 241 increased; that from (IV) is almost unchanged. (II) (pn 7-4) in absence or presence of Cu (cf. Wind, In general the incroase is < that during (V). No A., 1925, ii, 1174) proceeds with a R.Q. of 0-2—0-3. relationship could bo established between the actual The rate of oxidation of (I) in (II) -j- 0-0004i/-CuS0.1 vals. obtained and the amount of assimilation or the is increased by addition of (CHO)2 (III) and is max. lactic acid production of the organs. A. L. with 20 mols. (30—40 mols. cause almost complote Specific dynamic action and oxidation of inhibition); the R.Q. is 0-37 and 1-14 with 1 mol. and hexoses introduced into the circulation of amytal- 16 mols., respectively, of added (III). (Ill) alone is not oxidised in (II). The amount of C02 produced ansesthetised dogs. M. W ierzttchowski (Compt. rend. Soc. Biol., 1934, 117, 909—912).—The sp. is not oc added (III). Similar increased oxidation dynamic actions, mol. heats of oxidation, and R.Q. for occurs when CHO-CO,H (IV) or AcC02H (V) is added glucose, fructose, and maltose in dogs arc of the same to (I). (Ill) or (IV) also causes increased oxidation of order, and are not altered in amytal anaesthesia. CO(CHvOH)„. Oxidation of (I) is retarded by R. N. C. EtC02H, PrC02H, 0H ,CHMe,CH2-C02H (VI), or valeric Intravenous assimilation of hexoses in nar acid. Glyceric, crotonic, and glycollic (VII) acids, (•CH2*OH)2 (VIII), glycerol (IX), and crotonalde- cosis provoked by amytal. M. W ierzuchowski hyde have no effect. Oxidation of (I)+ (III) is and H. F is z e l (Compt. rend. Soc. Biol., 1934, 117, 913—915).—Narcosis (I) raises slightly the % of unaffected by added EtOH or (IN), but oxidation glucose (II) and maltose (III) assimilated from the of (I)-j-(V) is retarded by (IX) (not by EtOH). blood, the non-assimilatcd (III) being excreted partly Oxidation of AcCHO is increased by (V) and retarded as (II). With fructose (IV), the % assimilated is slightly by (VII), (VIII), or (VI). Oxidation of reduced by (I). Exposure of the blood-vessels and fructose is greatly retarded by (III), (IV), or (V). withdrawal of samples of blood during (I) reduces the Biological oxidationsof carbohydrates arc undoubtedly % assimilation considerably for (II) and (III), but influenced by the formation of trioses as intermediate only slightly for (IV). Galactose is assimilated only products. H. B. moderately, (I) showing the same effects as for (II) Effect of a high-fat meal on the respiratory and (III), whilst inositol is not assimilated. quotient and heat production of normal and R. N. C. obese individuals. B . D . B o w e n , F. R. G r if f it h , Carbohydrate metabolism of the liver. IV. jun., and G . E. Sl y (J. Nutrition, 1934,8,421— 434).— Sugar output in amytalised cats. C. T s a i and The post-absoiptive R.Q. was in obese < in normal G. L. Yi (Chinese J. Physiol:, 1934, 8, 399— 409).— subjects. The sp. dynamic action of the fat was The concn. of hepatic sugar (I) was > that of the portal similar in both cases, but was greater in obese (I) and of the arterial (I). During aniytalisation the diabetic individuals. A. G . P. (I) output does not materially increase, and the fall in liver-glycogcn is due to inhibition of glycogen Seasonal variation in butter-fat. II. Seasonal formation. H. G. R. spectroscopic variation in the fatty acid fraction. Carbohydrate metabolism at high altitudes. R. G . B o o t h , S. K . K o n , W. J. D a n n , and T. M o o re II. Action of adrenaline (and content of K and (Biochem. J., 1935, 29, 133— 137).—Fatty acids (I) from summer butter-fat (II) always show an absorp Ca in the blood). V. F. M a d o n and E. S a p e g n o (Atti R. Accad. Lincei, 1934, [vi], 20, 119— 125; tion at 230 ni|x > twice as intense as that of (I) from cf. A., 1932, 885).—With individuals acclimatised on winter (II) (cf. A., 1933, 1087). This increase oc increased inhibiting power (III) of the fat in the high mountains, the rapidity of action of adrenaline SbCl3 reaction for vitamin-^1, but the substanccs on the equilibrium conditions of the carbohydrates is increased, as is that of the reaction of the organism responsible for (III) are much more sensitive to to the consequent hyperglycscmia. No definite oxidation and irradiation than those responsible for increased absorption. A. E. O. modification in the concns. of K ' and Ca" in the serum is detectable. T. H. P. New spectroscopic phenomenon in fatty acid Biological oxidation of inositol. B. C. G u h a metabolism. Conversion of “ pro-absorptive" and N. D a s (Current Sci., 1934, 3, 157— 158).— into “ absorptive ” acids in the cow. W. J. Oxidation of inositol in vitro at pa 7-4 and 37-3° is D a n n , T. M o o r e , R. G . B o o t h , J. G o l d in g , and effected by brain, heart muscle, kidney, and (more S. K. K on (Biochem. J., 1935, 29, 138— 146).— slowly) liver tissue of adult albino rats fed on a When cod-liver, sardine, rape, or linseed oil is fed to standard mixed diet. J. W. B. cows in the winter, the resulting butter-fat (I), although somewhat less in relative amount, shows Control of carbohydrate metabolism by the absorption at 230 m;x much > in summer. In-vivo kidney. H. M iy a z a k i (J. Chosen Med. Assoc., 1934, conversion of “ pro-absorptive ” into “ absorptive ” 24> 1—22).—The epithelial cells of the urinary tubes fatty acids has taken place, not accompanied by a secrete a hormone, of the nature of sterol, which fall "in the I val., i.e., not caused by oxidation of controls carbohydrate metabolism by increasing the unsaturated “ pro-absorptive ” acids (II). Prolonged combustion of glucose by the tissue. C h. A b s. boiling of (II) from these oils with EtOH-KOH also Significance of coupled reactions of lower results in a similar increase in absorption, but similar aliphatic compounds for carbohydrate and fat treatment shows that “ absorptive ” winter (I) degradation. R. M e ie r and K. B a l l o w i t z (Z. contains no “ pro-absorptive” acids. Ingested Physiol. Chem., 1934, 230, 122— 138).— Oxidation foreign fats are very rapidly secreted in the milk. (Oj) of glyceraldehyde (I) to C02 in phosphate buffer A. E. O. 242 BRITISH CHEMICAL ABSTRACTS.— A. Fat metabolism. V. Degradation of un Metabolism of I- and di-cystine in growing saturated fatty acids in man. P. E. V e r k a d e dogs maintained on diets of various protein and J. v a n d e r L e e (Z. physiol. Chem., 1934, 230, content. J. A. St e k 'o l (J. Biol. Chem., 1934, 107, 207—215).—After ingestion of tri-A‘-undecenoin 641—648).—Z-Cystine-S is practically completely (which may cause mild nephritis) together with ade oxidised and excreted as inorg. S04" in the urine of quate carbohydrate, sebacic acid is excreted in the pups maintained on Cowgill’s diet. Much of the urine; direct oxidation at the double linking thus S is retained by pups on other diets. cZZ-Cystine fed occurs. Definite decomp, products were not isolated to pups on low-protein diets is not so well retained, after ingestion of olive and rape oils. H. B. much of the S appearing in the urine as neutral S. Fat metabolism in fishes. IV. Mobilisation Z-Cystine may be used as an indicator of the min. of depot-fat in the salmon. V. Fat of the protein requirement for growth and maintenance of salmon in its young fresh-water stages. J. A. dogs. C. G. A. L o v e r n (Biochem. J., 1934, 28, 1955— 1960, 1961— Effect of fasting, refeeding, and variations 1963).— I V . Compared with other fish-fats, salmon in the cystine content of the diet on the com body-fats exhibit low palmitoleic acid (I) content position of the tissue-proteins of the white rat. and high content of C22 acids, and low degree of W. C. L e e and H. B. L e w is (J. Biol. Chem., 1934, unsaturation of C20 acids. Mobilisation of the depot-fat 107, 649—659).—Neither fasting nor subsequent (II) is almost non-selective in the females, but in the refeeding results in significant change of the com males acids of low mol. wt. are preferentially mobilised position of the muscle or kidney of growing or adult and the (I) content falls steadily. Ova-fat is more rats, or the proteins of these tissues. The N and S unsaturated than (II), and a high degree of selectivity of the livers increased after fasting, but the change is displayed in its formation. is not due to alteration of the composition of the liver- V. In the parr stage, the fat of the young salmon proteins. The S of all tissues is higher in young rats is of the fresh-water type (III), but the fat of the smolt receiving adequate cystine (I) than in those receiving appears to be at a transitional stage between (III) a deficiency of (I), although the composition of the and the special fat of the adult salmon. A. E. 0. proteins is the same in each group, the excess being Variation in nutritive properties of skimmed due to non-protein-S. C. G. A. milk with habituation to milk-assimilation. Urea formation in the liver. H. A. K r e b s (Z. P. M a z e , P. J. M a z e , jun., and R. A n x io n n a z (Compt. physiol. Chem., 1934, 230, 278—279; cf. A., 1932, rend. Soc. Biol., 1934, 117, 751—752).—Rats fed 1059).—The conclusions of London et al. (A., 1934, for a long period on a complete diet including normal 1392) are not in agreement with their results. H. B. or skimmed milk (I) are able to synthesise the vita mins (II) necessary for fertility when fed on diets [Urea formation in the liver.] E. S. L ondon containing (I) but deficient in (II), which apparently (Z. physiol. Chem., 1934, 230, 279).—A reply to occur as precursors in (I). Oxidation (Cl) or ultra Krebs (preceding abstract). H. B. violet irradiation partly corrects the deficiency of Factors in cellular multiplication. P. J oyet- (I).’ F . 0 . H . L o v e r g n e (Compt. rend., 1934, 199, 1339— 1341).— Assimilation of albumin by normal dogs and The function of glutathione and vitamin-/! in the dogs with Eck fistulee. S. L iv ie r a t o , M . V a g - growth, reproduction, regeneration, and proliferation l ia n o , and A . D e r v e n a g a (Compt. rend. Soc. Biol., of cellular tissue is discussed. A. G. P. 1934, 117, 1088—1090).—Dogs with Eck fistula Effect of variations in the diet on absorption show increases in total non-protein-, urea-, NH2-acid-, of food in absence of pancreatic digestion. M. B. and NH3-N (I) after ingestion of ovalbumin. Normal H a n d e l s m a n , L. A. G o l d e n , and J. H . P r a t t (J. dogs show only a slight increase of (I). R. N. C. Nutrition, 1934, 8, 479—495).—After exclusion of Effect of feeding carrot on rat serum-protein. pancreatic juicc from the intestine dogs absorbed A. L. Bloom field (J. Exp. Med., 1934, 59, 687— 698). large proportions of ingested foods including fats, — On exclusively fresh carrot diet serum-protein although faecal N and fat were abnormally high. falls; a similar effect is produced by carrot powder Gains in body-wt. resulting from increased diets are only after addition of H20 and agar. Ch. Abs. influenced by factors other than the amounts of Synthesis of creatinine and creatine during ingested fat, carbohydrate, and protein. A. G. P. protein starvation. G. M o u r o t (Compt, rend., Action of prolonged administration of food 1934, 199, 1341— 1343).—Examination of creatinine grown with and without artificial manuring. (I) excretion during protein starvation confirms the A. Sc h e o n e r t , M. S a c h s se , and R. Sp e c h t (Biochem. synthesis of considerable amounts of (I) under these Z., 1934, 274, 372—396).— Rats fed on a diet of which conditions. Creatine disappearing from the organism the materials had received artificial manuring during (rat) appears as (I) in the urine. A. G. P. growth were superior in fertility and length of life Measurement of creatinine clearance. R. F. to others receiving food grown without such fertilisers. H a n z a l and J. M. H a y m a n , jun. (Proc. Soc. Exp. P. W. C. Biol. Med., 1934,31,730—733).—After administration Method of partial regression in analysis of of creatinine, dil. urine and blood-plasma are treated comparative feeding trial data. II. E. W. with picric acid arid centrifuged. The clear liquids Cr a m p t o n and J. W. H o p k in s (J. Nutrition, 1934, are mixed with NaOH and compared colorimetrically. 8, 329— 339).— Interpretation of statistical analyses Ch. A b s . (p) is discussed. A. G. P. BIOCHEMISTRY. 243 Inorganic salts in nutrition. X. Electrolyte dairy cows. C. Y. C h a n g , P . H . P h il l ip s , and balance in the serum of rats receiving a diet E. B. H a r t (J. Dairy Sci., 1934, 17, 695—700).— deficient in inorganic constituents. A . H . S m it h All tissues examined contained F, max. proportions and P. K . Sm it h . XI. Changes in composition occurring in bones (I) and teeth (II). Ingestion of of the whole animal induced by a diet poor in F (in rock phosphate) increased the storage of F in salts. A. E. L ig h t , P. K . Sm it h , A. H . Sm it h , and (I) and (II) (16—-25 times normal) and in internal W. E. A n d e r so n (J. Biol. Cliem., 1934,107,681—688, organs, tendons, and hair (twice normal). 689—695).—X. Animals recoving only 0-32 milli- A. G. P. equiv. of base per day maintain a normal electrolyte Iodine metabolism. III. T. Y u z u r ih a (Trans. balance in the scrum, but cease to gain wt., take in Japan. Path. Soc., 1933, 23, 96—100).— In the control less food, and excrete NIT3 in the urine instead of of I metabolism the reticulo-endothelial system and fixed base. the thyroid are synergetic; the former is the more XI. In rats on salt-poor diets (I) there is loss of fat, important. Cn. A b s . little or no change of ash content, slight increase of Heavy water in the animal body. E. J. protein, and slight loss of Ca, Mg, and P. There is M cD o u g a l l , F. V e r z a r , H. E r l e n m e y e r , and H. no appreciable loss of Na or Cl. Compared with G a e r t n e r (Nature, 1934, 134, 1006— 1007).—Using animals of the same age on an adequate diet rats on HaO as indicator, it has been shown that H aO injected (I) have lower Ca, P, and Ca : P ratio. C. G. A. into fasting rats is distributed throughout the body Significance of phosphatase determinations in in 1 hr. L. S. T. the adult fowl. D. W. A u o h in a c h ie and A. R. G. Dosage above the pharmacopoeial maximum. Emslie (Biochem. J., 1934, 28, 1993—2001).—It is A. F. H u r s t (Lanect, 1934, 227, 1379—1383).—A suggested that the plasnia-phosphatase activity of lecture. L. S. T. normal hens may be little affected by egg-laying, but that marked changes may be expected in eases of Hypoglycaemic action of yeast extracts, especi vitamin-D or Ca deficiency. Anomalies arc discussed. ally the relation of yeast extracts to true hor C. G. A. mones . I. Influence of yeast extract on normal Results of ingestion of cod-liver oil and yeast and adrenaline blood-sugar balance. II. Rel on calcium and phosphorus metabolism of ation between the effect produced on blood- women. H . A. H u n s c h e r , E. D o n e l s o n , B. N. sugar by yeast extract and insulin : influence of Erickson, and I. G. M a c y (J. Nutrition, 1934, 8, the thyroid. K. M a e h a r a (Folia Endocrinol. 341—346).—Retention of Ca and P was not consist Japon., 1934, 9, 34—35, 36).— I. Aq. and acid (0-5% ently affected by feeding cod-liver oil or yeast. HC1) EtOH extracts of yeast lower the blood-sugar " A. G. P. level. Adrenaline hyperglycsemia is retarded. Salivary glands and calcium metabolism. II. Insulin hypoglycemia is increased by injection T. Matsuo (Trans. Japan. Path, Soc., 1933, 23, 254— of extracts. Hypoglycemia resulting from injection 257).—Serum-Ca was increased by extirpation of the of extracts is checked by feeding thyroid and increased parotid gland, and decreased by injection of parotid by thyroidectomy. Ch . A b s . (p) venous blood-serum. Ch . A b s . Blood-sugar variations in rabbits poisoned by Calcium metabolism of the fœtus. T. M a t s u o ingestion of carbon tetrachloride. P. M . D e r - (Trans. Japan. Path. Soc., 1933, 23, 257—261).— v il l e e and R. Ca st a g n o u (Compt. rend. Soc. Biol., Fœtal blood is higher in Ca than the blood of the 1934, 117, 365—367).—Ingestion of CC14 produced mother or of the umbilical cord. Ch . A b s . considerable hypoglycemia during the first day, Calcium in the fœtal liver of the calf in em followed by slow recovery if the animal survived. bryonic development. G . R o u s s e l and Z. G r u - R. N. C. œwska (Compt. rend. Soc. Biol., 1934, 117, 863— Modifications of blood-sugar and liver-glyco- SW).—Liver-Ca rises to max. in the 4th and 8th gen in splenectomised animals. D. Z o r zi (Arch. months of gestation, afterwards falling to normal. Farm, sperim., 1934, 58, 253—269).—Blood-sugar in R. N. C. rabbits rises irregularly to a max. at the end of the Iron m etabolism . III. T. K o s u z i, K . U m e d a , 1st month after splenectomy (I), thence falling very E- Le e , S. T a c h ib a n a , and C. L e e (Trans. Japan. gradually to normal at the end of the 5th month. Path. Soc., 1933, 23, 203—205).— Oral administration The alimentary glycaemic curve (II) is normal 5 days of Fe compounds accelerates the metabolism through after (I); at 20 days from (I) it falls to a min. at the the entero-hcpatic circulation. Ch . A b s . 2nd hr. after feeding, afterwards rising to its original val. At 30 days from (I) the fall is still greater and Relation between salts and acidosis. G. is preceded by a slight rise, which is more pronounced Suzuki (Aichi Ig. Zasshi, 1933, 40, 1152).—No at 60 days, (II) afterwards tending to return to relationship was apparent between acidosis (I) normal. (II) provoked by injection of adrenaline or alkalosis, and sefum-Cl'. Production of (I) by glucose is not altered by (I). Liver-glycogen falls in lowered NaCl consumption results from smaller intake the first few days from (I), afterwards rising to > of Na rather than of Cl'. In the Gerson and other normal. R. N. C. treatments (I) is duo to the low carbohydrate and high fat contents of diet and not to absence of NaCl. Effect of hepatic denervation on the stability Ch . A b s . [p) of liver-glycogen. P. D e m a n t (Compt. rend. Soc. Effect of feeding raw rock phosphate on the Biol., 1934, 117, 323—326).—Hepatic dencrvation Uuorine content of the org an s and tissues of reduces liver-glycogen (I) and the hyperglycemia (II) 244 BRITISH CHEMICAL ABSTRACTS.— A. provoked by ingestion of glucose. Splanchnic section Appearance of an acetylcholine-like substance reduces (I) but raises (II); (I) disappears entirely if in the perfusion-liquid from perfusion of the the adrenal nerve supply is interfered with. Glycos isolated small intestine of the cat. W. F e l d b e r g uria does not occur. R. N. C. and H. K w ia t k o w s k i (Pfltiger’s Archiv, 1934, 234, 333— 341).—Perfusion of the isolated intestine with Influence of hepatic stimulation on exogenous physiological NaCl solution gives no result, but if and endogenous hypercholesterolaemia in the eserine (I) is added an acetylcholine (Il)-like sub rabbit. M. Eck and J. D e s b o r d e s (Compt. rend. stance, destroyed by alkali but not by acid, and Soc. Biol., 1934, 117, 081—6S3).—Hypercholesterol possibly (II) itself, can be detected in the emergent emia (I) induced in rabbits by administration of a liquid. On re-perfusion with NaCl the effect decreases lipin-rich diet was increased by injection of the after 20—25 min. (II) added to the perfusing solu extract of Cynara scolymus (II). (I) induced endo tion without (I) is destroyed in the intestine, so that genously by adrenaline injection was reduced by (II). the action of (I) is to inhibit the tissue-esterase A. L. without causing (II) production. Nicotine has no Choline and the 11 cholesterol V fatty liver. effect on (II) production. R. N. C. H. J. Ch a n n o n and H. W il k in s o n (Biochem. J., 1934, 28, 2026— 2033).—Feeding choline (I) does not Substance sensitising muscle to acetylcholine cure the “ cholesterol ” fatty liver of rats previously formed in the vagus nerve by electrical excit fed on a diet containing fat and 2% of cholesterol. ation. L . B in e t and B . M in z (Compt. rend. Soc. (I) has no obvious effcct in causing a decrease of any Biol., 1934, 117, 1029— 1031).—Electrical excitation of the lipoid constituents except the glyceride fraction. of a piece of the vagus nerve isolated from a dog C. G. A. causes the liberation of a thermostable and oxidisable Lecithin, kephalin, and duration of haemor substance which sensitises the dorsal muscle of the rhage. J. R o s k a m and S. C o m h a ir e (Compt. rend. leech to the action of acetylcholine. A. L. Soc. Biol., 1934,117,802—804).—Injection of lecithin, Biological significance of the linkings in free from kephalin (I) and allied substances, into adenosinetriphosphoric acid. J. H. G ille s p ie rabbits increases the duration of bleeding by 30—50%, (J. Physiol., 1934, 80, 345—359).—The action of the whilst injection of (I) decreases it by approx. 30% acid on heart and uterus of guinea-pigs is > that of (cf. A., 1922, i, 697). F. O. H. any of its derivatives. Removal of P 04'" from the Influence of hydrogen- and hydroxyl-ion con mol. affects its activity < deamination. Scission of centration on intestinal tonus. M. T e f f e n e a u pentose from the purine base destroys biological A b s. ( ) and D. B r o u n (Compt. rend. Soc. Biol., 1934, 117, activity. Ch. p 1002— 1004).—The inhibiting action of adrenaline and Micro-determination of ethyl alcohol in organs. atropine on the isolated guinea-pig intestine increases O. M o l l e s t a d (Biocliem. Z., 1935, 275, 136— 146).— as decreases, and inversely. On the other hand, By using a special flask in which solid matter is finely the accelerating effect of acetylcholine, pilocarpine, ground the procedure of Widmark (A., 1922, ii, 789) histamine, anterior pituitary extract, and BaCl2 is made applicable to the determination of EtOH in decreases as pn decreases, and inversely. A. L. organs. W. McC. Chemical transmitter at synapses in a sym Alcohol. II. Concentration in blood. M. S c h m id t (J. Ind. Hyg., 1934,16, 355—365).—Typical pathetic ganglion. W. .F e l d b e r g and J. H. G a d d u m (J. Physiol., 1934, 81, 305—319).—The curves of the changes in blood-EtOH (I) after inges superior cervical ganglion of a cat, perfused with tion of EtOH (0-6 c.e. per kg. body-wt.) by habitual Locke solution containing eserine, liberated acetyl users (II) and abstainers (III) are given. Max. vals. choline (I) on stimulation of the cervical sympathetic. (0-04—0-08%) of (I) are attained more rapidly with Liberation of (I) forms the mechanism by which (II) than with (III) (average times of approx. 36 and nerve impulses pass the synapse. Ch . A b s . (p) 48 min., respectively7), whilst a return to normal levels generally occurs within 4— 5 hr. for both (II) and Chemical transmitter of vagus effects to the (III). The psychological effects of EtOH are related stomach. H. H. D a l e and W . F e l d b e r g (J. to (I). ' F. 0. H. Physiol., 1934, 81, 320—334).—Acetylcholine (I) acts Concentrations of ethyl alcohol in the blood as the chemical transmitter of vagus effects to the and its rate of oxidation in the organism. E. L e stomach. Following injection of eserine and stimul B r e t o n (Compt. rend. Soc. Biol., 1934, 117, 707— ation of the vagi to cause contractions of the stomach 709).—The equations of Widmark for determining wall (II) the (I) content of venous blood from (II) the quantity of EtOH oxidised by man can be applied increases by 400%. Ch . A b s . (p) to the rat, but not to the rabbit. Vals. of P Appearance of an acetylcholine-like substance (decrease in [EtOH] per min.) and r (total [EtOH]/ in the portal blood of the cat. I. D o n o m a e [EtOH] in blood) are const, for the individual animal (Pfliiger’s Archiv, 1934, 234, 318—324).— On injection and the species, respectively. A. L. of eserine (I) or prostigmine, an acetylcholine-like Rate of diffusion of ethyl alcohol in the organ action in the portal blood can be demonstrated by ism . E. L e B r e t o n (Compt. rend. Soc. Biol., contraction of leech muscle in Ringer’s solution, or by 1934, 117, 704—707).—Determinations are made of its depressor effect-, inhibited by atropine. Larger the decrease (I) with time in [EtOH] after injection quantities of (I) produce the same effect to a small of animals with EtOH, and when (I) becomes const, extent in the vena iliaca. R . N. c. for unit time equilibrium (II) is assumed to be BIOCHEMISTRY. 245 attained. The time taken for (II) to be reached is 685).—Examination of the urine of dogs, injected used as a basis for the comparison of the rates of with PhOH, for phenolsulphonates gave negative diffusion of EtOH in rats, mice, and rabbits according results. A. L. to the method of admmistration. The order of Denervated kidney. II. Action of sodium decreasing [EtOH] in the organs is always the same, salicylate on uric acid, allantoin, sodium chlor namely, blood, brain, carcase, liver. A. L. ide, and total nitrogen excretion in dogs. M. G. Influence of diet on the rate of oxidation of G r a y and G . P. G r a b f ie l d (J. Pharm. Exp. Ther., ethyl alcohol. E. Le B r e t o n (Compt. rend. Soc. 1934, 52, 383— 389; cf. A., 1934, 324).—Section of Biol., 1934, 117, 709—712).—Rabbits receiving the renal nerves (I) depresses the increased excretion EtOH after ingestion of Witte peptone or alanine of N, has no effect on the allantoin output, and oxidise more EtOH per kg. of body-wt. than fasting decreases the uric acid output produced by Na animals or those having received glucose. A. L. salicylate (II). (I) has no effect on the changed Barbiturates. II. Methods of barbital re vol. : [Cl'] relationship produced by (II). H. D. search. T. K o p p a n y i, J. M . D i i a e , W. S. M u r p h y , Action of various hyperthermic agents on the and S. K r o p (J. Amer. Pliarm. Assoc., 1934, 23, respiration of cells of starfish tissues. P. 1074—1079).—Improved methods of extraction from C r e a c ’h (Compt. rend. Soc. Biol., 1934, 117, 367— urine, blood, and tissues are described. Colorimetric 36S).—Respiration is increased by basic vital stains methods of determination using Co(OAc)2 and (I) of rH >8, and decreased by (I) of rH < 8, and acid LiOH, Ba(OH),, or NH2Pr^ are equally sp., the only indigo stains. It is scarcely affected by 2 :4 - other CHGlj-sol. substances showing positive tests C6H3(N 02)2,0H (II), but increased by reduced (II), being theobromine, theophylline, thymine, and leci whilst Me-blue reduces it. R. N. C. thin. The micro-tost (using LiOH) can be performed Action of vital stains and nitrophenols on the only in CHC13 solution. A. E. 0. respiration of oyster-tissues and blood-cells of Hasmatological changes produced by poison Sipunculus. M. C h a f h e a u (Compt. rend. Soc. ing with barbiturates. R. E. C a r r a t a l a (Semana Biol., 1934, 117, 370—371).—Vital stains of rH >8 m6d., 1934, II, 402— 405).— Chemical changes include increase the respiration, whilst those of rH <8 have decreased Ca, Mg, and P and increased NaHC03 no effect. 2 : 5- (I) and 2 : 4-C6H3(N02)2'0H (II), in the blood. Cir. A b s . (p) when reduced, increase the respiration of the blood- (a) Prolongation of narcosis by piperidino- cells of Sipunculus; unreduced (I) is ineffective, and methylbenzdioxan and related derivatives. D. unreduced (II) acts only very slowly. Oyster-tissues are not affected by (I) or (II), either normal or reduced. Bovet and A. Sim o n , (b ) Central analgesic and sedative action of the aminomethylbenzdioxans, R. N. C. aminocoumarans, and phenoxyethylamines. D. Elimination of theobromine and caffeine from the circulation. R. A. H a t c h e r and N. T. K w it (J. Bovet, A. Sim o n , and F . D e p ie r r e (Compt. rend. Soc. Biol., 1934,117,958—960,961— 963).— (a) Preliminary Pharm. Exp. Ther., 1934,52,430— 436).—Immediately injection of piperidino- (I) and diethylamino-methyl- after the injection of caffeine (I) or theobromine (II) benzdioxan (II) prolong the narcosis in rabbits pro the concns. of (I) and (II) in the blood fall rapidly duced by paraldehyde and Na 5-c?/cZohexyl-l-methyl- and more slowly after 5 min. The concns. of (I) barbiturate. The duration of anaesthesia produced and (II) 30 min. after administration are the same PJ Na tetraethylbarbiturate in sticklebacks is whether given intravenously or orally. H . D. increased by (II) and particularly by allyaminomethyl- Action of certain alkaloids on the physio benzdioxan (III). The aminocoumarans are also logical polarity of infusoria. A. S e r f a t y (Compt active in this respect, especially the 0-OMe-dcrivatives; rend. Soc. Biol., 1934, 117, 1077— 1079).—The *^t2,CH2,CH2'OPh is inactive, although polarity is reversed by choline, pilocarpine, and ^to’CHj-CHg'O'CgHj-OMe is active. atropine in decreasing order of potency. R. N. C. (b) (I) and its related derivatives, particularly the Curarising poisons and muscular fatigue. O. coumarans, possess comparable analgesic properties; D e h e n n o t (Compt. rend. Soc. Biol., 1934,117, 318— diethylaminophenetole is, however, inactive. (I) 320).— Curare has no effect on the fatigue of frogs’ diminishes the emetic action of opomorphine and muscles, sparteine raises the fatiguability (I) in digitalis. (I) and (III) injected into rabbits at the doses < the min, curarising dose (II), whilst KC1 ™se of the fourth ventricle cause a pronounced does not affect it in doses < (II). Eserine in (II) narcosis indicating that their action is of central increases (I) in respect to indirect excitation (II I); origin- A. L. with direct (III) variable results are obtained. Results “Adrenolytic” action of a dioxan deriv are compatible with the hypothesis of acetylcholine ative (933F). Z. M. Bacq and H. F r e d e r i c q formation by nervous (III). R. N. C. SUmpt. rend. Soc. Biol., 1934, 117, 806—SOS).— [Pharmacology of] morphine, codeine, and Ihe typical reactions of adrenaline in the organism derivatives. VII. Dihydromorphine (paramor- 2re inhibited by administration of 933F (2-piperidyl- phan), dihydromorphinone (dilaudid), and di- ffiethylbenzdioxan hydrochloride), the action of hydrocodeinone (dicodide). N. B. E d d y and ^inch is better described as “ adrenolytic ” than J. G. R e id (J. Pharm. Exp. Ther., 1934,52,468—493). as svmpathicolytic.” F. O. H. -—The effects of hydrogenation and methylation of Phenolsulphonates in the urine of dogs. Y. the phenolic OH, and of the introduction of the '-»akeeau (Compt. rend. Soc. Biol., 1934, 117, 683— keto-CO in morphine and codeine are in accordance 246 BRITISH CHEMICAL ABSTRACTS.— A. with the rules which hold for the other alkaloids against T. ñagana. (I) and (III) were the only studied (A., 1934, 805). H. D. effective compounds on staphylococci and B. coll. Morphine acidosis. N. R a k ie t e n , H. E. Him- These compounds all contained two N 02-groups w ic h , and D. Dubois (J. Pharm. Exp. Ther., 1934, (IV) and a phenolic OH, the 2 : 5-positions for (IV) 52, 437— 444).—Dogs given 25 mg. per kg. body-wt. being specially favourable for activity. R. N. C. of morphine sulphate showed a decrease of blood-jJn Chemical nature and biological activity of of approx. 0-2 unit accompanied by an increased methylphenarsazine dihydroxide and its deriv serum-C02, -d, and -total solids, and a decreased atives. V. M. K a r a s ik and M. M. L ichatsch ev alkaline reserve. No changes were produced in the (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4, 161—163). lactic acid, total base, or [Cl'] of the blood. H. D. —Methylphenarsazine dihydroxide (I) (the Ac deriv Changes in the physical and chemical charac ative of which has no trypanocidal action) causes teristics of the blood-sera of opium addicts. augmented reflex action and convulsions in white R. N. Ch o p r a and S. N. M u k h e r j i (Current Sci., mice and frogs. Replacement of Mo by Et and, 1934, 3, 201—202).— In opium addicts, the pK of especially, by Pr increases the effect. Dimethyl- blood-serum is near the lower limit of normal Indian phenarsazine hydroxide (II) is much more toxic than adults and the buffer action is lowered. tj is diminished (I) and exerts a central paralytic action. The nitrate and a is increased. The albumin fraction and of (II) is less toxic than (II), but more rapid in its euglobulin content are increased, whilst pseudoglobulin action. H. N. R. and total proteins are < normal. L. S. T. Comparative toxicity of sodium and diethyl- amine derivatives of 3-acetamido-4-hydroxy- Blood-sugar of opium addicts. S. C h o (Folia Pharmacol. Japon., 1934, 17, No. 2, 230—242).— phenylarsinic acid. R. P o t t ie r and F. v a n den Yals. aro normal, but rise slightly during abstinence. B r a n d e n (Compt. rend. Soc. Biol., 1934, 117, 830— Adrenaline produces greater hyperglycfemia in addicts 832).—The ratio of the toxicities to rabbits of intrav during abstinence. Pilocarpine has the usual effect; enously administered Na salt and NHEt2 derivative atropine sometimes lowers and again slightly raises of stovarsol is 1 : 1-25. F. O. H. blood-sugar. Ch . A b s. Anthelmintics. I. Effect of hydrogen per Effects of intravenous injections of colloids. oxide and som e oxygenated terpene hydro I. Deposition of acacia in the liver and other carbons on Ascaris lumbricoides. L . W. B u tz organs and its excretion in urine and bile. M. and W. A. L a L a n d e , jun. (J. Amer. Pharm. Assoc., 1934, 23, 108S— 1094).—H202 and the products A n d e rsc h and R. B. G ib so n (J. Pharm. Exp. Ther., 1934, 52, 390—407).— In rabbits 50% of the total obtained by the oxygenation of a-pinene, turpentine, acacia (I) injected intravenously was recovered in and d-limonenc are very toxic to A. lumbricoides. the livers; in dogs about 30%. (I) is removed from The active constituents of the oxygenated hydro the liver very slowly. Injection of (I) into the gall carbons are probably not peroxides or ketones. bladder decreases the excretion of bile acids and A. E. 0. bilirubin (II) and (II) is replaced by a yellow pigment. Anthelmintic constituent of leaves of Caly- H. D. copteris floribunda. A. N. R atnagiriswakas , Poisonous constituents of the seeds of Teph- K. B. S e h r a , and K. V enkataraman (Biochein. J., rosia vogelii.—See this vol., 221. 1934,28,1964— 1967).—A yellow flavone, calycopterin, C18H180 8 (I), with anthelmintic properties was Toxic principle of poison ivy. G. A. H il l , isolated in 0-1% yield by COMe2 extraction of the V. M a t t a c o t t i, and W. D. G r a h a m (J. Amer. dried leaves of C. floribunda, Lamk. (I) contains Chem. Soc., 1934, 56, 2736—2738).—The bark (I) of 4 OMe and 2 OH, and yields Ac2, m.p. 129°, Bz¡¡, m.p. Rhus toxicodendron is extracted with boiling 95% EtOH 165°, and Me2 derivatives, m.p. 131° (sintering at for 4 days; slow cooling of the cone. extract ppts. 127°). Demethylation with HI yields the parent wax and gum (removed by filtration). Saturation hexahydroxyflavone, calycopteretin, C15H10O8, m.p. of the residual extract with NaCl and extraction 310° (sintering at 294°) [Acs derivative, m.p. 212° with xylene gives urushiol (II), b.p. 210°/0-5 mm. (sintering at 207°)], not identical with gossypetin, (Majima, A., 1922, i, 262). (I) gathered in winter is myricetin, or quercetagetin. Boiling aq. K0H practically free from (II). The M e2 ethers of (II) on (I) in H2 yields jJ-OH-Ce||^OJB[; hence (I) must and dihydrourushiol are non-toxic (cf. ibid., 263). H. B. be represented as OH*(OMe)3C^£Q_^,Q|^4 Toxic properties of greasewood. Physio * A .E .O . logical action of oxalic acid and its soluble salts. Elim ination of water from the human body. V. A. W il l so n (J. Amcr. Vet. Med. Assoo., 1934, G. v o n H e v e s y and E. H o f e r (Nature, 1934, 134, 38, 76—81).-—Toxicity is due to Na and Iv oxalates 879).—The d of H20 prepared from urine after (Na : K = 4 :1). Ch . A b s . (p) the intake of dil. BJO has been determined after Chemotherapeutic testing of nitro-derivatives. different intervals of time have elapsed. Using V. F isc h l (Z. Immunitat., 1934, 82, 146— 153).— HjO as indicator, it is found that 30 min. after the Of 60 N 02-compounds tested for chemotherapeutic beginning of the intake of H20, some of it (approx. effect on trypanosomes in mice, 2 : 5-CBH3(N 02)2-0H. 0-2%) is found in the urine. Most of the H20, however, Victoria-yellow, picric (I), picramic (II), and picro- leaves the body slowly. Approx. 9 days elapse before lonic (III) acids, and sun-yellow showed very weak half is eliminated. The average time a mol. of H20 effects on T . recurrens. (II) was also slightly effective spends in the human body is 13±l-5 days, and this BIOCHEMISTRY. 247 is explained by assuming that most of the H20 hr. to Hg-saturated (6—7 mg. per cu.m.) air. A taken becomes completely mixed, with the total high content (21—88x10-® g. per g.) of Hg sub Ha0 of the body. L. S. T. sequently occurs in the lungs (II) and kidneys (III), whilst that of the liver (IV), heart, spleen, brain, etc. Fibrillation in tbe chicken embryo heart in is generally < the blood level (5-7—20-0x10-® g. per vitro. I. Effects of excess potassium, calcium, g .); relatively small amounts occur in the urine. magnesium, and sodium, and of high and low Curves are given for the accumulation of Hg in (II), osmotic pressures. II. Character and mechan (III), and the remainder (V) of (I) and also for the ism of the fibrillation. P. D. F. M u r r a y (Proc. diminution in Hg content after cessation of adminis Soe,, 1935, B, 116, 434^-451, 452—478). tration. The retention of Hg by (III) persists for Control of cyanide action : cyanohydrin equi several weeks. The blood-N indicates a toxic action libria in vivo and in vitro. E. EL. M a r s h a l l , jun., of Hg on (III). Absoiption of Hg through the and M . R o se n f e l d (J. Pharm. Exp. Ther., 1934, alimentary tract is < that through (II) and produces 52, 445—461).—-The protective val. of aldehydes and a rapid rise in the Hg content of (III), those of (IV) ketones against CN' poisoning varies directly with and (V) increasing slightly and remaining approx. their rate of cyanohydrin formation (I) and inversely const., respectively. F. O. H. with the magnitude of their cyanohydrin equi Detection of mercury in bullet wounds. G. librium const. (II). Initial respiratory stimulation (III) varies directly with (II) and inversely with (I). G u a r e sc h i (Deut. Z. ges. geriehtl. Med., 1934, 23, Prolonged (III) is produced by cyanohydrins with 89—96; Chem. Zentr., 1934, ii, 102).—Material cut from around the wound is treated with HN03, diluted small (II). A cC0 2H is particularly effective in (III). H. D. with H20, filtered, and tested for Hg with SnCl2. A Antitoxic effect of glutathione in cyanide microscopical method of detection is also applicable. H. J. E. poisoning. M. T. R é g n ie r (J. Pharm. Chim., Amino-aciduria and ammoniuria in the course 1934, [viii], 20, 501— 512).— In the guinea-pig, the of acute uranium nephritis in the dog, rabbit, injection of glutathione (0-5 mol.) has a direct and and rat. R. Devize (Compt. rend. Soc. Biol., immediate effect in arresting asphyxia due to HCN 1934, 117, 1111— 1112).— U02(iT03)2 nephritis (1 mol.). The effect is not due to formation of SON'. A. E. 0. produces in all species an increased NH2-acid excre tion. NH3 excretion varies with the species, being Nitrite-thiosulphate combination as a remedy scarcely affected in the rat, increased in the rabbit, £or cyanide poisoning in sheep. H. B u n y e a , and decreased in the dog. R. N. C. J. P. Co u c h , and A. B . Cl a w s o n (J. Washington Acad. Sci., 1934, 24, 52S—532).—Prompt intraperi- Organic-aciduria in the course of acute uran toneal injection of NaN02-N a2S203 is generally an ium nephritis in the dog, rabbit, and rat. R. elective antidote for sheep poisoned by administra D e v i z e (Compt. rend. Soc. Biol., 1934, 117, 1113— 1114).—Excretion of org. acids is increased in all three tion (per os) of 2-75 xmin. lethal dose of KCNV The safest therapeutic dose is 1 g. of NaN02 for 35—40 kg. species in U 02(N03)2 nephritis, the increase being body-wt. ; doses of 0-095 g. per kg. body-wt. may largely due to lactic acid. Hippuric acid excretion themselves prove fatal, and 0-05 g. per kg. doses are is diminished. R. N. C. dangerous. Increase of the Na2S203 (1— 3 g-) is Renal origin of albuminuria in nephritis pro possibly advantageous, and is not itself toxic. duced by uranium nitrate. R. W e e k e r s (Compt. J. W. B. rend. Soc. Biol., 1934, 117, 817—818).—Perfusion of Bibliography of the more important heavy nephritic kidneys with normal or nephritic blood metals occurring in food and biological material, produces the same degree of albuminuria (I). Hence 1921—1933 (Soc. Public Analysts, 1934, 30 pp.).— the blood plays no part in (I) due to U 02(N03)2. Very brief abstracts are included in many cases under F. O. H. each of the 13 metals. Variations in blood-gases after Röntgen irradi ation of the spleen. I. Variations after irradi Determination of traces of lead in biological ation of various regions of the body with small materials, with special reference to bone. G. R. and large doses. T. A b e (Tohoku J. Exp. Med., Ltkch, R . H. Sl a t e r , and T. G. O s l e r (Analyst, 1934, 23, 394— 414).— Changes in blood-02 and -C02 1934, 59, 787— 806).—After wet oxidation, the Pb is depend on the site and size of the dose. extracted with diphenylthiocarbazone, and deter g e d colorimetrically as PbS. Special precautions C h . A b s . (p ) Blood-sugar modifications in hyperthermal ■oust be taken to exclude Bi, if present. The Pb and radioactive media. M . Se n d r a i l , R. M o l i- content of 20 normal bones was 14-5— 146-0 p.p.m. n e r y , and J. A v e r s e n q (Compt. rend. Soc. Biol., of fresh tissue, that of the teeth of 5 normal persons 1934, 117, 322—323).— Hypoglycsemia (I) is wide *-5—247-5 p.p.m. The method has been applied spread among miners in galleries in volcanic rocks, 0 marrow, organs, blood, urine, and fæces. where the air is affected by deep mineral hot springs . E- C- S- charged with H2S and Rn. The greatest (I) was •'«sorption and distribution of mercury in shown by diabetics. R. N. C. finals. A. St o c k an d F . C u c u e l (Angew. Chem., 1934> 47, 801— 806; cf. A., 1934, 862, 1257).—The Possible action of cosmic rays on living races of Hg present in various tissues of normal organisms. R. B. E n g e l s t a b and N. H. M o x n e s guinea-pigs (I) are increased by exposure for 10—24 (Nature, 1934,134, 898).—The only detectable differ- 248 BRITISH CHEMICAL ABSTRACTS.— A. ence in mice is a greater mean \vt. of animals shielded chem. Z., 1934, 274, 321—328).—The reversibility from cosmic rays. L. S. T. of the oxido-reduction process in the system EtOH- dehydrogenase (prep, from washed dried yeast)- Enzyme reactions from the viewpoint of MeCHO is demonstrated in a series of potential heterogeneous catalysis. W. F ranicenburger (I) determinations at 30°. The equimol. (I) at (Ergebn. Enzymforsch., 1934, 3, 1—22; Chem. Pn 7-45 amounts with the normal H2 electrode (II) Zentr., 1934, ii, 952—955).—A theoretical discussion. to E0'——0-090 volt, or with a (II) of the pa of the A parallel is drawn between the heterogeneous cata enzymic system to ¿= 0-356 volt. P. W. C. lysis of gas reactions and enzyme reactions. H. N. R. Xanthine-oxidase. XII. Oxidation of nucle Enzymic histochemistry. K . L in d e r s t r q m - osides. M. D ix o n and R. L e m b e r g (Biochem. J., L a n g and H . H o l t e r (Ergebn. Enzymforsch., 1934, 1934, 28, 2065—2079).—Xanthine-oxidase oxidises 3, 309—334; Chem. Zentr., 1934, ii, 1144).—Dis inosine (I), inosinic acid (II), adenosine (III), muscle tribution of proteinase, peptidase, carbohydrase, de- adenylic acid (IV), and cozymasc, due to the liber amidase, and esterase among various organs and ation of hypoxanthine (V) by other enzymes. Oxid tissues is examined. A. G. P. ation of (I) is brought about by a nucleosidase, sp. towards the purine part of the mol., which liberates Proportionality studies on catalase. G. W. free (V). The action on (III) is shown to be deamin M a r k s (J. Biol. Chem., 1934, 107, 623—627).— ation by a third enzyme to form (I) with subsequent pa curves are given for the catalases (I) from A mphiroa formation of (V). Since (II) and (IV) behave like aspergillum forma nana, Corallina officinalis (II), (I) and (III), respectively, the presence of a phosphat and Pikea calif'omica. For (I) from (II) the quantities ase is indicated. ' H. G. R. of H202 decomposed oc (I) concn. and are independent of H202 concn. over a pn range 4-5— 10-0. Sharp Effect of X- and y-rays on indophenol-oxidase. changes occur in the slopes of some of the curves. R. E. H a v a r d (Brit. J. Radiol., 1934, 7, 296-304).- C. G. A. Indophenol-oxidase was not affected by irradiation Inhibitors of catalase reaction. D. K e il in under the conditions examined. Ch. A b s . (p) and E. F. H a r t r e e (Nature, 1934, 134, 933— 934; [Nature of] the respiratory co-enzyme of red cf. A., 1934, 1136).—NaN3 is a sti’ong inhibitor of blood-cells. H. T h e o r e l l (Biochem. Z., 1934, catalase. O-OlS-M-Dimethylglyoxime treated by 275, 11—18; cf. A., 1934, 1136; Warburg et al, the method of Sevag and Maiweg gives approx. ibid., 109).— Cataphoresis cannot be used to purify 0-O241i-NH2OH, which is a known catalase inhibitor. the co-enzyme (I), but it indicates that (I) is an acid L. S. T. (probably a phosphoric acid) which dissociates in Peroxidase specificity. M. D ix o n (Biochem. two stages. (I) contains no conjugated OH groups. J., 1934, 28,2061—2064).—Pyrocatechol, guaiacol (I), W. McC. guaiacum, and pyrogallol are readily oxidised by Acid groups of the respiratory co-enzyme. S20 8" in the presence of milk-peroxidase (II) but not H. T h e o r e l l (Biochem. Z., 1934, 275, 19—29).— when (II) is replaced by liorseradish-peroxidase Measurements in the cataphoresis apparatus show that (III) or hsematin. Bz202 oxidises all the usual per the co-enzyme is a tetrabasic acid, probably a di- oxidase reagents with (II) or (III) except (I). H. D. phosphorie ester, 2 H being liberated at each stage of dissociation. W. McC. Peroxidase. A. K. B a l l s and W. S. H a l e (J. Biol. Chem., 1934, 107, 767—782).—A method of [Nature of] mixtures of respiratory enzymes determining peroxidase (I) based on iodometric with substrates. H. T h e o r e l l (Biochem. Z., 1934, titration of residual H20, is described. The increase 275, 30—36).—At pR 7-4 the intermediate respiratory in (I) content during dialysis of sliced horseradish enzyme (I) and the co-enzyme (II) react with the roots (cf. A., 1929, 1106) depends on the absence of substrate (III) (hexosemonophosphoric acid), but (I) air in the H20 used. pR optima for various substrates does not react with (II). All the components of the were determined. In the enzymic oxidation of system [yellow enzyme, (I), (II), (III)], and hence pyrogallol (II), aerated (II) may replace H202, hence (presumably) all combinations of them are negatively it is possible to determine (I) in presence of catalase charged. W. McC. if (II) is also present. (I) is able to combine with Active group of the yellow enzyme. H. almost any amine or phenol, but successful oxidation T h e o r e l l (Biochem. Z., 1934, 275, 37; cf. A., 1934, takesplace only when the substrate mayyield a quinone 1136).—No yellow enzyme (I) is produced when at a min. oxidation-reduction potential rather > lactoflavin is added to the inactive constituent of that necessary to reduce o-chlorophenol-indophenol (I). The constituents of (I) are separated by adding at pft 7, i.e., the substrate must be an o- or p- 3 vols. of MeOH to aq. (I), the protein constituent, disubstituted C 6H 6 derivative, with either one which contains no P, being pptd. 1 mol. of the active substituent OH, or both NH2. In presence of H20 2, yellow constituent contains 1 P. The active group (I) is either destroyed or irreversibly bound in the of (I) is probably a monophosphoric ester, a nucleotide attempt to oxidise an unfavourable substrate. The in which the purine base is replaced by dimethylall- possibility of “ oxidative synthesis” by the action oxazine (Karrer, et al., A,, 1934, 1233). W. McC. of (I) is mentioned. * A. E. 0. Reduction of nitric oxide b y oxidising enzymes- Biological oxidation-reduction potential. O. M e y e r h o f and W. S c h u l z (Biochem. Z1-, 1934, Potential determinations in the system alcohol— 275, 147— 161).—Yeast maceration juice (I) jn dehydrogenase-acetaldehyde. J. L e h m a n n (Bio- presence of oxidisable substrates (II) (especially BIO CHEMISTRY. 249 hexose phosphates) and the yellow respiratory 1136).—The amylase (I) is purified at about 0° by enzyme (III) in presence of hexose monophosphate dialysis of extracts of batate and adsorption of (I) reduce NO to N20, (II) being oxidised at the same or on Al(OH)3. The degree of adsorption is independent at a greater rate than by atm. 0 2. With (I) C02 of the concn. of (I), but increases with increasing purity is produced and the R.Q. is the same as when atm. of (I). The optimum pn for adsorption is 3-7—4-2. 02 is the oxidising agent, but the 0 2 uptake is 1J times (I) contains carbohydrate but no protein. as great with NO as with 0 2. Reduction of NO W. McC. occurs only with such (II) as are enzymically oxidised Development of amylase during germination with 0 2. The extent of reduction varies considerably of barley. H. L u e r s and W. R u m m l e r (Woch. with the (II) used. W. McC. Brau., 1935, 5 2 , 9—12).—Using barley extract, with or without papain digestion, liquefying and dextrin- Reduction of glutathione by the Warburg- ising action could not be demonstrated, and the Christian system . N. U. M e l d r u m and H. L. A. appearance of an amylokinase during germination Tarr (Biochem. J., 1935, 29,108— 115).—Glutathione could not be confirmed. Destruction of saccharogen- (I) is reduced both aerobically and anaerobically by amylase (S) by heating extracts to 70° had little effect the Warburg-Christian enzyme-co-enzyme system on liquefying power, but decreased dextrinisation (II), derived from brewer’s top yeast, baker’s yeast, markedly, suggesting that the two reactions are due or rat’s blood, in presence of hexosemonophosphoric to different factors. Investigation of S activity, in acid (III), less readily with phosphohexonic acid normal and papain-digested extracts, suggested that and fructosediphosphoric acid, and not by diphospho- 3 factors are active during germination, and not S glyccric acid, glucose, or fructose. (I) acts as 0 carrier and dextrinogen-amylase only. I. A. P. when (III) is oxidised by (II) in presence of 0 2; the velocity of oxidation cc the amount of (I), the Biochemical micro-methods. VI. Photo limiting factor being the rate of reoxidation of (I). metric determination of amylase and maltase. Cystine (IV) also acts as 0 carrier in the same system, B. J. K r ijg sm a n (Z. physiol. Chem., 1934, 2 3 0 , 190— the rate being independent of (IV) concn. as the 198).—The amylase content of saliva is determined limiting factor here is the rate of reduction of (IV). by an adapted Rona and van Eweyk’s method (A., C. G. A. 1925, i, 1264); the max. error is 2-5%. The method Salts of base from co-enzyme preparations. previously described (A., 1933, 845) for determin 0. Wa r b u r g and W. Ch r is t ia n (Biochem. Z., 1934, ation of blood-sugar is adapted for the maltase activity 275,112—113; cf. this vol., 121).—The base (I), m.p. of yeast and pancreas extracts using maltose as sub 125°, yields a picrolojuite, m.p. 220° (decomp.), a strate; the max. error is 2-8%. H. B. hydrochloride (II), m.p. 224°, and a platinichloride, Degradation of glycogen in muscle. II. m-P- > 300° (decomp.). 1 mol. of (II) reduced with Effect of muscle compounds on the activity of M tH 2 takes up 3 H2. (I) is obtained from (II) by amylase. III. Action of amylase in presence shaking with A g 2C 0 3 ; it has mol. wt. about 120 of m yosin. S. J. v o n P r z y l e c k i and B. F il tpo - (Rast’s method gives 154). 100 litres of horse blood w ic z (Biochem. Z., 1934, 2 7 5 , 56—61, 62— 65; yield 10—20 mg. of (I). W. McC. cf. A., 1932, 193).—II. The degradation of starch or Michaelis constant for fum arase. F. B. glycogen (I) by amylase (II) is only slightly or not at Pereira and A. D a Cr u z (Compt. rend. Soc. Biol., all affected by addition of nucleic acid, nucleotides 1934, 117, 723—726).—Results of determinations of (guanylic, adenylic, xanthylic acids), or muscle fumarase activity at 37°, 22°, and 5° indicate that extract (rabbit). Hence the reactions which lead to there is no change with temp, in the val. for the great and rapid increase in degradation of (I) are not substrate concn. below which diminution in enzyme the cause of the increased activity of (II), which results activity takes place. The dissociation const, of the rather fron spatial changes (III). (Ill) bring (I) fumarase-fumarate complex is only slightly affected and (II) into direct contact or separate them. »J' change of temp. (0-0017 at 22° and 0-0035 at 37° III. The degree of activation of ptyalin (IV) by a^5°). A. L. myosin (V) is slight at the isoelectric point (VI), but increases with the distance from (VI). (V) does Temperature coefficient of fumarase. K. P. not adsorb (IV). Polysaccharoproteins (VII) are «acobsohn and A. Da Cr u z (Compt. rend. Soc. Biol., degraded with much greater difficulty than are free 1934,117j 726—728).—The Arrhenius const, for the polysaccharides (VIII). Hence hydrolysis of (VIII) “ydration of fumaric acid by' fumarase is the same decreases following production of (VII) at physio asthat for the reverse reaction, viz., 10,000. A. L. logical pa and salt concn. W. McC. Ainylosynthease. XXIV. Reaction velocity. Presence of a kinase of amylase in trypsin jH' T. ill n a g a wa (J. Agric. Chem. Soc. Japan, preparations. T. C h r z ^ szc z and J. J a n i c k i (Bio **” ■ 10, 550—553).— Dextrin is polymerised with chem. J., 1934, 2 8 , 1949— 1954).—Trypsin (I) ™wulty by yeast extract, but relatively easily if increases both the saccharifying and dextrinising %lase is previously removed from the extract, functions of barley, the effect on the latter being very ■toylosynthcase, purified by pptn. with (NH4)2S04, marked. Inactivated (I) partly protects the amylase Pplymerises a- and ¡3-dextrins (from starch by taka- against inactivation by shaking. A. E. O. astase and various amylases) with equal facility. . C h . A b s . {■}>) Influence of aeration on the diastatic activity of _ Arnyla.se of batate (Ipottlcea batatas). K. V. barley during steeping. R. H. R. R au and V. (Biochem. Z „ 1934, 275, 106— 111; cf. A., 1934, S ubrahmanyan (Proc. Indian Acad. Sci., 1934, 1, B, 250 BRITISH CHEMICAL ABSTRACTS.— A. 1—9).—Steeping of barley diminishes the diastatic S c h a f f n e r and E . B a it e r (Naturwiss., 1934, 22, activity (I) (due to anaérobiosis) for approx. 24 hr., 855—856).—The co-enzyme of horse’s blood-cells whilst continuous steeping for 2— 4 days in presence can be replaced by that of yeast for phosphorylation or absence of air increases (I). The development of (I). (I) is connected with a dehydrogenation, since (I) is independent of the capacity for germination. Warburg’s intermediate enzyme is necessary for it F. O. H. to occur. R. S. C. Dilatometric studies in the enzymic hydro Production of an optically active phospho lysis of polysaccharides. I. Inulin. M . S r e e n i - glyceric acid by glycolysis in muscle. G. v a s a y a , H . B . S reeranoachar , and 1ST. K . I y e n g a r . E m b d e n , H. J. D e u t ic k e , and G. K r a f t (Z. physiol. II. Hydrolysis of starch by malt diastase. Chem., 1934, 230, 12—28).—Treatment of minced H. B. S reerangachar and M. S reenivasaya (Proc. rabbit muscle (I) with 0-5ilf-Na ¿Z-lactate containing Indian Acad. Sci., 1934, 1, B, 43—47, 101— 105).— 0-4% of wheat-starch and 2% of NaHC03 at 11—13° I. For equal substrate concns., hydrolysis of inulin (I) gives (—)-ß-phosphoglyceric acid (II), [a]D —11-91° {determined by dilatometer (A., 1932, 880) or by the in H20, 4-11-390 (as Na3 salt), isolated as the cryst. rate of liberation of fructose (II)] at 30° and ps 3-8 in citrate buffer by inulinase (Penipiüium extract) Ba salt (+ H 20). (II) is hydrolysed (dil. H2SO.,) with difficulty to d- (—)-glyceric acid (Ba salt) and H3P04. is > that of starch (A., 1934, 109). Liberation of (II) is also produced from (I) and Na2C204 or NaF; (II) is accompanied by a relatively high contraction the amount is much increased by addition of Na in vol., viz., 7-9 cu.mm. per millimol. of (II), a val. hexose diphosphate [which is probably an inter independent of the concn. of (I). mediate in the above production of (II)]. H. B. II. The hydrolysis of sol. starch (005—2-0%) by malt diastase at 30° and jhi 5-3 in P 04"' buffer gives Significance of phosphoglyceric acid for a dilatometric contraction which oc the amount of glycolysis in muscle. G. E m b d e n and H. J. maltose liberated (3-9 cu.mm. per millimol.) and also D e u t ic k e (Z. physiol. Chem., 1934, 230, 29— 49).— oc the diminution in a (6-8 cu.mm. per 1°). Phosphoglyceric acid (I) (as Na salt) is converted by F. O. H. minced rabbit muscle (II) into H3P0 4 and AcC02H Lucerne emulsin. K. H i l l (Ber. Verh. sachs. (III). Little lactic acid (IV) is formed when glycero- Akad. Wiss. Leipzig, Math-Phys. Kl., 1934, 86, 115— phosphoric acid (V) (as Na salt) is added to (II), but 128; Chem. Zentr., 1934, ii, 1142— 1143).—Prep, of addition of (I)-f(V ) produces much; (V) is the the emulsin is described and its specificity examined H-donator in the change (III)— >- (IV). (II) does in respect of mannose, a- and S-galactose. Com not effect the change (II I)— 5-(IV); subsequent parison is made with almond emulsin. A. G. P. addition of (V) accelerates reaction. AcCHO is not considered to be an intermediate. The following Emulsin. XVII. Action of ozone on almond- scheme for the production of (IV) is given : (i) hexose- emulsin. B . H e l f e r i c h , S . W i n k l e r , E . S c h m i t z - diphosphoric acid is synthesised from polysaccharide, H i l l e b r e c h t , and H . B a c h (Z. physiol. Chem., 1934, hexose, or hexosemonophosphoric acid and H3P04; 229, 112— 116; cf. A., 1934, 1402).—When emulsin (ii) P 0 3H,-0-CH,-C0-[CH(0H)]3-CHo-0-P03H, —> is progressively inactivated by 0 3, its tryptophan is 0H-CH2-C0-CH2-0“P03H2 (VI)+ destroyed at about the same rate. The activity CHOCH(0H)-CH2-0-P03H2 (V II); (iii) dismutation towards ¡3-d-glucosidc, -isorhamnoside, and -galactos- of (VI) and (VII) to (I) and (V ); (iv) ide is lowered to about the same extent in a treated C0,H-CH(0H)-CH2-0-P03Ho — > A cC0 2H+ H 3P04; orep, but the activity towards a-d-mannoside (I) to (v) 0H-CH2-CH(0H)-CH2-0rP03H2+AcC02H — > a greater degree, indicating that a different enzyme 0H-CHMe-C02H+ (V II).“ ‘ H. B. is responsible for (I) hydrolysis, as previously shown. J. H. B. Action of fluoride and bromoacetic acid on Relation between the re-synthesis of adenos- interm ediary processes in glycolysis in muscle. inetriphosphoric acid and the reaction of pyruvic G. E m b d e n and H. J. D e u t ic k e (Z. physiol. Chem., acid and dihydroxyacetonephosphoric esters. Z. 1934, 230, 50— 62; see preceding abstracts).— Minced rabbit muscle (I) treated with NaF and D i s c h e (Naturwiss., 1934, 22, 855).—Theoretical. R. S. C. NaHC03 converts added hexose diphosphate (II) into Phosphorylated intermediate product of phosphoglyceric acid (III), but specifically inhibits carbohydrate fission and its enzymic equi the conversion of (III) into AcC02H (IV) and H3P04; reduction of (IV) by glycerophosphoric acid (V) to librium. 0. M e y e r h o f and W. K i e s s l i n g (Natur wiss., 1934, 22, 838).—d-a-(2-)Phosphorylglyceric lactic acid is similarly unaffected, but less “ hydro acid (I) (Ba salt, [a]D -j-24-3°), is isolated from the lysis ” of (V) occurs [than with normal (I)]- © crudo p-(3-)acid (II), prepared enzymically. treated with CH2Br-C02Na does not convert (11) and dl-(Il) are obtained from glycerol-[3- and -a-phos- into triosepliosphoric acids and also retards the above phoric acids, respectively, and' Br. With dialysed reduction of (IV); conversion of (III) into (I^J muscle extract the biologically inactive d-(I) and occurs. H. B. ?-(II) are unaffected, whereas the active Z-(I) and Isolation of glycerophosphoric acid from d-(II) enter into equilibrium with each other, k for fluoride-poisoned muscle. G. E m b d e n and T. Z-(II)/d-(II) being 3-0 at 28° [75% of (II)]. I c k e s (Z. physiol. Chem., 1934, 230, 63—£8).-" R. S. C. Glycerophosphoric and phosphoglyceric acids (see Relation between phosphorylation and oxido- above) are formed from minced rabbit muscle, re duct ion in fermentation and glycolysis. A. NaF+NaHCOa, and Na hexose diphosphate; separ- BIOCHEMISTRY. 251 ation is effected through the 'differing solubilities of N2 are probably different; the former is activated the Ba salts. H. B. and the latter inhibited by K\ A. E. O. Intermediate stages in glycolysis in striped Phosphatases. II. Liberation of phospho- muscle. G. E m b d e n and H . J o s t (Z . physiol. esterases from liver. E. B a m a n n , E. R i e d e l , Chem., 1934, 2 3 0 , 69—89).—Minced rabbit muscle and K. D ie d e r i c h s (Z. physiol. Chem., 1934, 2 3 0 , (vertebral and leg) with ¿¿-(3-phosphoglyceraldehyde 175-—184).— Of the methods studied, natural auto (I) (Fischer and Baer, A., 1932, 364) in 2% NaHCOs lysis of fresh liver (I) gives an autolysate containing saturated with C02 at 37° gives a preponderance of max. amounts of the phosphoesterases [(II) (max. (-f)-lactic acid (II) after a short reaction time. More activity a tp u 5-5) and (III) (max. activity at pa 9-5)] ; prolonged reaction leads to an excess of (—)-lactic liberation of (II) and especially (III) is incomplete. acid (III), probably owing to hydrolysis of unreacted Dehydration of (I) with C0Me2 causes loss of enzymes. (I) to AcCHO, which is then converted (as is shown Neutral solutions of (II) and (III) do not lose their experimentally) into (III). These results are con activity when kept at 6°; (II) is stable in 0-025iV- trary to those of Barrenscheen and Beneschovsky AcOH, whilst (III) is stable in 0-025A-NH3. Lyo- (A., 1933, 1202); they also show that cZ-(I) is an and desmo-complexes in (III) are characterised. intermediate in glycolysis in muscle. (II) is similarly H. B. produced from AcC02H+glycerophosplioric acid (IV) Phosphatases. III. Separation of the two or phosphoglyceric acid+(IV ); cW-glyccraldeliydc isodynamic phosphoesterases of animal organs affords (III). Dihydroxyacetonephosphoric acid by a selective inactivating process. E. B a m a n n (Langheld, A., 1912, i, 415) and CO(CH2-OH)2 are not and K. D ie d e r i c h s (Bcr., 1934, 67, [J5], 2019—2021). converted into lactic acid (V) even in presence of (I). —The alkaline phosphoesterase of pig’s liver is stable The above results support the scheme suggested only in neutral or weakly alkaline solution and above for the production of (V) from carbohydrates. becomes inactivated in the presence of acid. The H. B. reverse is true of acid phosphoesterase. The difference Action of fluoride on intermediary processes in behaviour is so pronounced that it is possible to in glycolysis in yeast. E. L e h n a r t z (Z. physiol. obtain the individual enzymes from mixtures of them Chem., 1934, 2 3 0 , 90—95; cf. Neuberg and Kobel, by selective inactivation. H. W. A., 1933, 982; Meyerhof and Kiessling, A., 1934, Composition and properties of esterases. H. 328).—Phosphoglyceric acid, [a]g* —11-3° in H20 [Ba K r a u t and W. v o n P a n t s c h e n k o -J u r e w i c z (Bio salt (+1'5H 20)], identical with that isolated from chem. Z., 1934, 2 7 5 , 114—135; cf. A., 1928, 671; muscle (see above), is obtained during fermentation Willstatter, et al., A., 1934, 913).—Liver-esterase of glucose with dry brewer’s yeast in presence of (I) is purified by adsorption on Pb3(P04)2 (which phosphate, Na hexose diphosphate, NaF, and MeCHO first adsorbs impurities) and elution with dil. AcOH. (absence of this leads to a diminished yield). (I) and other enzymes are “ symplexes ” (II) con H, B. sisting of an active constituent “ agon ” (III) and a Anaerobic glycolysis in kidney. H. J o s t (Z. carrier “ pheron ” (IV). (II), (III), and (IV) are physiol. Chem., 1934, 2 3 0 , 96—108).— (+)-Lactic subject to the law of mass action; in the case of acid is formed from minced ox kidney (I) and the (I) large excess of (IV) must be present to maintain following substances in 2% NaHC03 saturated with (III) in (II) and removal of free (IV) destroys the C02 at 37°: dZ-fS-phosphoglyceraldehyde (provided activity by disturbing the equilibrium. Free (III) a small concn. is used), phosphoglyceric acid (II), changes into an inactive “ anagon ” incapable of g'ycerophosphoric acid (Ill)-f(II), AcC02H (IV), re-forming (II), but other enzymes may have agons (III)-HIV). (—)-Lactic acid is similarly obtained which are also active when free. Free (IV) [in (I) from AcCHO and glyceraldehyde. (I), unlike muscle, at least] is not a true protein. New (I) is produced contains a substance [probably (III)] capable of acting when (I) rich in (IV) is added to pancreatic lipase as a H-donator to (IV). The production of lactic (V) rich in (III), and new (V) is produced when (I) acid (V) from carbohydrate (VI) in the kidney is con rich in (III) is added to (V) rich in (IV). Hence (I) sidered to involve the same changes as in muscle and (V) have the same (III) but different (IV). (Embden and Jost, above). (V) is not similarly Differences in specificity amongst esterases are a produced from CO(CH2'OH)2. Preliminary work on function of (IV). Activation of (V) with albumin is the possibility of the production of (V) from (VI) by due to synthesis of a new (II) with excess of (III). way of non-phosphorylated: compounds [e.ff., (IV)] is In the same manner explanations are provided for discussed. H. B. many properties of enzymes and (possibly) for those Effect of potassium on the glycolysis of brain of vitamins and hormones. W. McC. tissue with reference to the Pasteur effect. C. A. Fixation of enzymes by cells. I. Proto Ashford and K. C. D ix o n (Biochem. J., 1935, 29, plasmic fixation of liver-esterase. E. B a m a n n 157—168).—Addition of K salts (but not Na salts) and J. N. M u k h e r j e e . II. Isolation of esterase reversibly increases aerobic glycolysis (I) and 0 2 from liver. E. B a m a n n , J. N. M u k h e r j e e , and uptake, and irreversibly inhibits anaerobic (I) by L. V o g e l (Z. physiol. Chem., 1934, 2 2 9 , 1— 14, 15— wain slices. cW-Glyeeraldehvde inhibits the raised 21).— I. Only about 1% of liver-esterase (I) is imme (I) occurring in the presence of 0-1IV-KC1, whilst diately sol. in glycerol (II). Extraction of (I) by Pyruvate does not modify the action of K'. The H20-(II) mixtures from the fresh organ progresses oxidative removal of lactic acid (II) is not affected by slowly and ceases when 30— 40% of (I) is dissolved. ^ • The mechanisms of (II) production in 0 2 and The rest, bound to high-mol. carriers, is liberated by 252 BRITISH CHEMICAL ABSTRACTS.---- A. autolysis at alkaline reaction. Solutions of (I) are Details are given of the isolation of cryst. trypsinogen more readily obtained from COMe2-dried preps. (I) from the mother-liquor obtained from the chymo- H20 or (II)-H 20 dissolve 45—<35% of the (I) present, trypsinogcn crystallisation (A., 1934, 1260) and its the rest being liberated by acid or alkali without conversion into cryst. trypsin by treatment with autolysis. Distilled H20 containing C02 is less cone. aq. MgS04 at pa 7-0—8-0. (-I) 'is a protein efficient than C02-free H20. with no proteolytic activity. The activation reaction II. A rapid quant, isolation is,attained by subject is autocatalytic. L. S. T. ing the fresh minced organ to autolysis in alkaline medium for 3—4 days (which renders 50—60% of Development of rennin-like and proteolytic the esterase sol.), and subsequent treatment with activity of trypsin-kinase. M. G u i lla u m e dil. AcOH. The enzyme may be purified by dialysis. (Compt. rend. Soc. Biol., 1934, 117, 354—357).— J. H. B. The rennin-like activity (I) of trypsin-kinase develops at a faster rate than the proteolytic activity (II), (a ) Reversible inactivation of papain and cathepsin. (b) Activation phenomena of papain the rate for (I) depending on the quantity of entero- kinase (III) present. The max. (I) attained is in and cathepsin. A. P u r r (Biochem. J., 1935, 29, dependent of the quantity of (III), and when attained 5—12,13—20).— (a ) The proteinase activity of papain (I) extracts is completely inactivated by alloxan it is unaltered by the addition of sufficient (III) to (II), AcCHO (III), milk xantliine-oxidasc+liypo- bring (II) to its max. R. N. C. xanthine+milk peroxidase in the presence of 0 2, Activity of extracts of the pancreas of Scyl- and by H202. Cathepsin (IV), from rats’ livers, is lium catulus with added enterokinase. M. inactivated "by (II), (III), and CH2I.-C02H (V) ; G u il l a u m ie (Compt. rend. Soc. Biol., 1934, 117, reactivation by cysteine or H2S is not obtained after 747—750).—The proteolytic action (I) of extracts inactivation by (V) ; in this case EtOH reactivates. of the pancreas of dogfish (II) is increased by addition A parallelism exists between the disappearance of of enterokinase (III) preps, from dogs, rabbits, or •SH from (I) or (IV) and inactivation except with (II). With low concns. of (III), (I) oc (III) concn. (V). Large quantities of inactive (IV) are prepared Following attainment of max. activity, the milk- by extraction of liver with COMe2 and Et20, and curdling action diminishes more rapidly than (I). extraction of the residue with 85% glycerol. F. O. II. (b ) Vitamin-C-t-Fe” (VI) fails to activate purified Enzymic liberation of arginine from proteins. preps, of (I)," whilst both (VI) and AcC02H-(-Fe” F. L ie b e n and H. L ie b e r (Biochem. Z., 1934, 275, (VII) activate an impure (I). Pure (I) is activated 38— 48).—Arginine (I) liberated from proteins (casein- by fixed -SH+-S-S- proteins (VIII) (A., 1923, i, 167), ogen, gelatin, serum-albumin) by enzymes (pepsin, (VI), (VII), and succinic acid + Fe“ in the presence trypsin, papain) is best determined by pptn. with of (VIII). The activation by (VI) and (VII) results fiavianic acid or, colorimetrically, by a modification from the reduction of ’S'S- to -SH. -S-S- glutathione of the method of Lang (A., 1932, 834). By means activates (I) in presence of (VI). The activation of sulphosalicylic acid (II), (I) is separated into a phenomena of (IV) are similar except that (VIII)+ fraction of high mol. wt. pptd. by (II) and another (VII) does not increase activity. H. D. (III) which contains free (I) and peptides of low mol. Absorption of ultra-violet radiation by crystall wt. The arginase method determines free but not ine pepsin. F. L. G a t e s (J. Gen. Physiol., 1934, combined (I). Sources of error in other methods of 18, 265—278).—Pure cryst. pepsin (I) in OTAr-NaOAc determination are indicated and figures are given for buffer at pa 5 gives progressive changes in the ultra the amounts of (I) obtained. The vals. decrease if violet absorption curve (II), especially in higher X, alkaline digestion is prolonged, possibly because resyn on irradiation for increasing periods. Increasing the thesis and racemisation then occur. W. McC. X of the radiation has similar effects. There is no significant difference between the (II) of active and Behaviour of animal proteolytic enzymes with heat-inactivated (I). The log. % of (I)-activity plant proteins. V. S. Sa d i k o v and V. N. M en- as determined by the Anson-Mirsky method (A., s c h ik o v a (Compt. rend. Acad. Sci. U.R.S.S., 1934, 4, 1932, 1166) oc time of exposure. An essential agree 138— 142).—The process of isolation of proteins ment obtains between the determined activity and changes their behaviour towards enzymes; the that deduced on the assumption of a one-quantum native proteins of many seed meals are unattacked relationship, and the destruction curve (III) coincides by animal proteolytic enzymes. The results caimot with (II). However, considerably more energy must be ascribed to the presence of oil, since completely be absorbed at 250-9 and 271-9 mjj. to produce 50% defatted soya-bean meal behaves similarly. The inactivation than at 235-7 mu. The (III) of (I) is action of dil. HC1 and Na2C03 on the meals under similar to that of urease. H. D. different.conditions is described. H. N. R. Temperature coefficient of inactivation of Relative actions of pancreatin on caseinogen crystalline pepsin by ultra-violet radiation. and gelatin. P. E f e n d i (J. Physiol. U.S.S.B., F. L. G a t e s (J. G on. Physiol., 1934,18, 279—2S2).— 1934, 17, 45—51).-—Caseinogen (“ acid protein ”) The temp, coeff. of inactivation of pepsin by ultra is digested better by 0-5% pancreatin than is gelatin violet radiation at 253-7 riifi is 1-02. H. D. (“ basic protein ” )." Ch. A b s . (p) Isolation of crystalline trypsinogen and its Ultrafiltration of urease using membranes of conversion into crystalline trypsin. M. K u n it z graded porosity. P. G r a b a r and A. R i e o e r T and J. H. N o r t h r o p (Science, 1934, 80, 505—506).— (Compt. rend. Soc. Biol., 1934, 117, 712—714).— BIOCHEMISTRY. 253 Urease is completely retained by a membrane having Sa r ic (Compt. rend. Soc. Biol., 1934, 1 1 7 , 368—369). pores of 30 m^ diam. A. L. —Dinitrophenols produce no hicrease of respiration of either yeasts or B. Delbriicki. R. N. C. Sugar fermentation. C. N e u b e r g and M. K obel (J. Bact., 1934, 28, 461— 471).—The mechan Results of irradiating Saccharotnyces with ism of the enzymic changes is discussed. A. G. P. monochromatic ultra-violet light. II. Influence of modifying factors. III. Absorption of ultra Influence of p n on the rate of yeast growth in a violet energy by yeast. R. H. O s t e r (J. Gen. synthetic medium containing asparagine. C. Physiol., 1934, 1 8 , 243—250, 251—254; cf. A., 1934, T a x n e r (J. Inst. Brew., 1935, 4 1 , 27—30).—To a 1262).—II. Old yeast-cells (I) are more resistant to basal mineral-salt medium (without N) an extract ultra-violet irradiation (II) than young proliferating of malt rootlets was added to supply “ bios,” and pa cells; the temp, coeff. of the rate of destruction is was adjusted to the required val. with NaOH and 1-1. No toxic substances are liberated by cells killed lactic acid, the pa changes during the periods or damaged by (II) nor is any effect on the subsequent investigated being relatively small. Glucose was growth of (I) produced by the (II) of the malt-agar added daily to maintain a concn. of 2%, and aspara medium. gine was added whenever N fell below 0-005% in III. An approximation to the ultra-violet absorp the medium. The initial pB (I) was of greater effect tion curve (III) of the absorbing substance responsible on the yeast growth than that reached later. The for the death of (I) is obtained by plotting the incident optimum (I) for growth was 3-57—3-87, there being energies required to cause the death of 50% of (I) here a lag, however, compared with growth at more against X. A min. energy requirement between alkaline vals., the increased growth being shown 260 and 270 nijj. and one below 230 inn are found. later. The cultures were continuously aerated. The curves obtained resemble the (III) of cytosine I. A. P. and uracil. H. D. Assimilation of nitrogen by brewers’ yeast. Extraction of zymoflavin by methylal. L. R. H. H o p k in s (J. Inst. Brew., 1935, 41, 30— 33).— The yeast growth obtained by Taxner (preceding G e n e v o is and L. E s p il (Bull. Soc. chim., 1934, [v], abstract), was somewhat > that obtained in brewers’ 1, 1498— 1502).—Fresh yeast is shaken with methylal wort (I), and enormously > that usually given in (I) for 30 min. and the liquid decanted. The paste synthetic media. This is only partly due to the is extracted with H20 [saturated with (I)] and conditions of pa, aeration, and sugar concn. employed, filtered. The (I) is removed by evaporation at 30°. and to the presence of “ bios.” The low [N] main Sugars are removed from the resulting aq. solution tained is also effective in increasing growth. It by yeast. The solution is then conc. in vac. and some appears necessary to distinguish between “ potentially NH,-acids (II) are pptd. by Pb(OAc)2. The product assimilable N ” (II) and “ immediately assimilable contains zymoflavin. (Ill) and some (II) and other N” (III). For max. growth, it seems that (III) impurities. (Ill) is not affected by substitution of should be maintained at a low val. With excessive the NH2 or SH of (II). The fluorescence of (III) (III), growth is rapid at first, but later declines. In is const, between pK 3 and 10; it is destroyed by (I), (II) reaches a relatively high val., but, in effect, Na2S204, by which (III) can thus be determined. steadily supplies (III) only in small quantities. R, S. C. I. A. P. Potentiometric determination of oxido-reduc- Dehydrase system o f yeast. R. Sonderhoff tion processes in fermenting yeast extract. (Ergebn. Enzymforsch., 1934, 3, 163— 184; Chem. F. L ip m a n n (Biochem. Z., 1934, 2 7 4 , 329—340).— Zentr., 1934, ii, 1141— 1142).—Dehydrase activity The author’s earlier work (A., 1934, 451) on potentio of yeast is discussed. A. G. P. metric determinations in Lebedev’s maceration extract is extended, vals. for oxido-reduction potential being Role of ferrous and ferric ions in the ferment given using Pt electrodes in a vac., in air, and in pure ation and oxidation processes of yeasts. A. 0 2 in presence of traces of a series of indicators, and Ualkow (Zentr. Bakt. Par., 1934, 91, II, 161— 163).— the results being discussed in reference to the fer Addition of F o"‘ to cultures resulted in formation of menting system. P. W. C. greater dry-wt. of yeast and less EtOH than when Potentiometric experiments on the formation an equal wt. of Fe" was used. Fermentation in of reducing substances during fermentation. presence of Fe” ' is independent of aeration. F. L ip m a n n (Biochem. Z., 1934, 2 7 4 , 412— 422).— A. G. P. The potential (I) during fermentation is measured Effect of liver extract on fermentation by with polished Pt electrodes, a const, air stream yeast. K. Z ip f and K. R a t h e r t (Biochem. Z., being passed and a trace of thionine or methylene-blue 1934, 275, 90—96).— In liver extracts anti-ancemic being added. (I) decreases slowly in slow ferment activity (I) oc power (II) to stimulate fermentation ations (glucose alone), quickly in rapid fermentations oy yeast. The substances responsible for (I) and (glueose-j-hexose diphosphate), to a min. of + 0 03 (II) seem to be identical or closely related, since they to 0-04 volt (pK 6-4). (I) decreases most quickly very often occur together and have similar properties on adding glucose+phosphoglyceric acid whilst with [stable to heat and to mild acid hydrolysis, not pptd. glucose+AcC0 2H it falls but only after a latent by Pb(OAe),, pptd. bv 70% aq. EtOH, not adsorbed period, and with glyceric acid phosphate (concn. V animal C] " W .McC. 0-00151/) the fermentation begins with almost max. Action of dinitrophenols on respiration of velocity. After complete utilisation of the P 0 4"' yeasts and la ctic b a cilli. L. G e n e v o is and R. (I) increases and the whole process may be repeated. 254 BRITISH CHEMICAL ABSTRACTS.— A. By addition of A sO /", (I) falls and does not again by (II). Crude algin contains (I) and a lignin-like increase as long as glucose is present. In presence of complex [pptd. in the culture medium as a humus-like F', (I) falls on addition of substrate at the same rate complex during the action of (II)]. H. B. and to the same level as under normal conditions whilst in presence of CH2Br*C02H the addition of Maintenance of vigorous mould stock cultures. substrate is almost without action on (I). P. W. C. H. C. G r e e n e and E. B. F r e d (Ind. Eng. Chem., 1934, 26,1297— 1299).—The maintenance of morpho Chloric acid : only a limited plant poison. logical and physiological characters of 10 moulds on H. K ijn z-K r a u s e (Pharm. Zentr., 1935, 76, 3— 4).— malteagar, potato-agar, sterilised bread, and steril The growth of S. glutinus, Fresenius, on 5% KC10S ised soil (I) media has been studied. Little variation solution is instanced. E . H. S. was observed except with Aspergillus sydoivi, in Oxytrophy and nutrition of flagellated leuco- which the wt. of dried mycelium produced under phytes. A. Lvov and H. Dusi (Ann. Inst. Pasteur, standard conditions varied by 34%. Cultures on (I) 1934, 53, 641—653).—The nutrition of Polytoma showed reasonable constancy. The prep, of stock uvella, Euglena gracilis, Astasia Chattoni, and Chilo- soil cultures is described. E. C. S. monas paramecium indicates that the necessity for fatty acids (I) having < C7 (A., 1933, 536, 647) is Conversion of guanidine into urea by moulds. related to the presence of plastids and the absence of T. Ch r za szc z and M. Z a k o m o r n y (Biochem. Z ., 1934, chlorophyll. (I) can bo replaced by starch. 275, 97— 105; ef. A., 1934, 1263; Ivanov et al., A., F. O. H. 1931, 524).-—Guanidine (I) is degraded by many Relation of certain amino-acids to carbon di different species (II) of mould with production of urea oxide and mycelium production of Fusarium and NEU, the amounts of urea varying greatly accord oxysporum . A . K. A n d e r s o n and K. E m m ar t ing to (II) and to the kind of nutrient medium. In (Plant Physiol., 1934, 9, 823—829).— Glycine (I), some cases the urea produced is rapidly degraded leucine (II), tyrosine (III), and aspartic acid (IV) further. Although the degradations often proceed failed to increase the C02 production of the fungus. concurrently they are entirely separate functions of (I) and (IV) were utilised for C02 production, which the moulds. Low concn. (0-1 %) of glucose accelerates was retarded by (II) and (III). (I), (III), and, the degradation of (I) leading to greater accumulation notably, (IV) were more effective than glucose for of urea, but higher concn., EtOH, and Ca(OAc)2 mycelium production. A. G. P. restrict urea accumulation. In the production of urea from peptone by moulds (I) is probably an inter Carotenoids of some fungi. E . L e d e r e r mediate. Possibly in the production of urea from (Compt. rend. Soc. Biol., 1934, 117, 1083—1185; arginine the precursor of urea is (I). W. McC. cf. A., 1934, 220).—Torulene (I), m.p. 183—185° (blue colour with SbCl3 with a strong band at 657 m¡x Respiration and metabolism of moulds. S. and a weaker one at 435 mil), is present in red Torulce M ic h a e l (Biochem. Z ., 1934, 274, 397— 407).—An (II), and also in Sporobolomyces (III) and Lycogala apparatus is described for following the acid form epidendron; [3-carotene (IV) is present in all these ation (I), 0 2 utilisation, and C02 elimination of a mould except (III). The acid pigment (V) of (II) shows (A. niger) during growth. In a medium maintained faint bands at 583,543, and 500 mu in CS2, and at 530, neutral with CaC03, the C02 : 0 2 ratio is approx. 1. 494, and 460 m¡x in light petroleum and MeOH; it In the early period only 3% of the glucose used is is present in (II) and (III), and also in Puccinia coroni- utilised for respiratory purposes, the chief reaction fera, together with the three carotenes. Tremella mes- being an oxidation to gluconic acid. The ratio of enterica contains (IV) alone, whilst Coleosporium senec- respired C02 to C02 set free from CaC03 is therefore ionis contains the three carotenes without (V). The very small, but increases considerably as citric and absorption curve of (I) in C6H,, is given. oxalic acids are formed. In a non-neutral medium R. N. C. the R.Q. falls during (I) to about 0-7, but returns to Decomposition of polyuronides by fungi and 1 as (I) slackens. P. W. C. bacteria. II. Decomposition of alginic acid by bacteria and formation of the enzyme alginase. Growth and nitrogen assimilation of Asper S. A . W a k s m a n and M. C. A l l e n (J. Amer. Chem. gillus niger under the influence of g ro w th Soc., 1934, 56, 2701— 2705; cf. A., 1933, 1082).— regulators and of vitamin-ii. E. B u n n in g (Ber. Alginic (=polymannuronic) acid (I) (from Fucus deut. bot. Ges., 1934, 52, 423— 444).—Dry-matter vesiculosas) is not decomposed to any appreciable production (I) by A. niger is accelerated by growth- extent by Aspergillus, Trichoderma, or Fusarium substance-U (synthesised by the fungus) but not by (cf. loc. cit.). (I) is hydrolysed by sp. bacteria (II) -A. Both substances accelerate the degeneration (from soil and sea-water) to simpler groups of uronic of mycelium, favour the resorption of NOs', and acids (III) (not pptd. by Ca), which are then decom restrict that of NH4\ In N1I4N03 media the latter posed further or oxidised to C02; simple (III) are effect results in increased pK in the nutrient and a not formed to any appreciable extent. (II) grown on more rapid formation of conidia (III). Vitamin-5, liqiiid media (containing NaN03) produce enzymes affects the growth of A. niger only in initially neutral which hydrolyse (I), starch, and other polysacchar media, in which a small beneficial action is recorded. ides; the alginase (max. action at pB 7 and 40° in Vitamm-^2 causes a 30— 40% increase in (I). Both presence of 2% NaCI) converts (I) into (III). The vitamins influence 1ST assimilation, the reaction of hydrolysable and non-hydrolysable fractions of (I) media, and (III) formation in the same manner as the are both attacked (the former somewhat more readily) growth-substances. A. G. P. BIOCHEMISTRY. 255 Mould tissue. VI. Factors influencing resistant substance which stimulates the production amount and nature of fat produced by A sper of lactic acid by L. caucasicus in milk-serum. gillus fischeñ. E. A. P r il l , P . R. W e n c k , and Ch . A b s . (p) W . H. P e t e r s o n (Biochem. J., 1935, 29, 21— 33).— B. xylinum cultures in lactic acid. M. Cozio Different strains of A.fischeri, incubated with an inorg. (Compt. rend. Soc. Biol., 1934, 117, 371—372).— salt médium-(-glucose for 10 days, showed variations in The lactic acid (I) is oxidised to AcC02H (II). The the fat content (I), sterols (II), lipin-P (III), and the anaerobic equilibrium potential (III) between (I) and I val. of the fatty acids (IV). A given strain shows (II) -with B. xylinum is equal to (III) between glycerol an increase in the fat content by increasing the and dihydroxyacetone, and to the Wurmser-Mayer- glucose in the medium, and a decrease in (II) and (IV). Reich (III) between (I) and (II) with lactic bacteria Increasing the [NH4N03] decreases the yield of mould (cf. A., 1933, 850). R. N. C. per g. of glucose utilised, (II), and (IV). Increasing Comparative dissimilation of xylose and the pa of the medium from 2 to 8 increases growth, glucose by Escherichia coli and Citrobacter % of fat, and (II). Raising the temp, decreases the anindolicum. O . L. O sbtjrn and C. H. W e r k - % of fat, whilst aeration increases the mould growth. m a n (Proc. Iowa Acad. Sci., 1932, 39, 134— 135).— Continued incubation of the mould after all the glucose Differences in the proportions of the end-products lias been utilised decreases the % of fat and (III), (H2, C02, AcOH, HC02H, lactic and succinic acids) but (IV) is unchanged. H. D. of the fermentation of the two sugars are recorded. Influence of a buffer on the activity of A sp er No evidence was obtained of the formation of AcC02H at any stage of the dissimilation. Tho xylose mol. gillus. V. B o lcato (Giorn. Chim. Ind. Appl., 1934, 16, 552—555).—Fe and N compounds inhibit the splits into fractions other than those containing 2 and formation of citric acid by Aspergillus, H2C204 and 3 C. Ch. A b s . (p) C02 being formed instead. Addition of Ña citrate Dehydrogenase activity of B. coli communis destroys this inhibitive action. D. R. D. on higher aliphatic acids. II. F. P. M a z z a and A. Cim m in o (Atti R. Accad. Lincei, 1934, [vi], 20, Influence of calcium on the development of 113— 118; cf. A., 1934, 221).—Methylene-blue (I) Aspergillus niger in a medium deficient in may act as H-acceptor in this dehydrogenation, but potassium. C. P o n ttllo n (Compt. rend. Soc. Biol., the process is then far slower than the aerobic 1934, 117, 647—650).—The presence of Ca activates process. If the concn. of (I) is > 0-001 mol., de- the utilisation of carbohydrate by A. niger grown hydrogenation of stearic acid is inhibited, owing to on a medium deficient in K. A. L. adsorption of (I) on the surface of the bacteria and Influence of anti-oxidants, of methylene-blue, consequent prevention of contact with the substrate. and of 2 :4-dinitrophenol on the growth and The dehydrogenase (II) is inactivated by heating sooner than the enzymes effecting the normal oxid energy output of Aspergillus niger. R. B o n n e t ations of B. coli, and probably requires no oxygenase and R. J a c q u o t (Compt. rend., 1934, 199, 1334— to catalyse its action. (II) resembles the dehydro 1336).—The growth and composition of the organism genases of succinic, lactic, and acetic fermentations, were not affected by various agents influencing the 02 exchange. A. G. P. but is more sensitive to the action of CO ; in its resistance to PhMe (II) resembles Quastel and Wool Classification of acetic acid bacteria and dridge’s formic (II) (A., 1925, i, 1217). T. H. P. oxidising bacteria isolated from fruits. M ethod T oxin of Bacillus proteus. H. R a n d o l p h (J. of classifying oxidising bacteria. I. T. A s a i (J. Lab. Clin. Med., 1934,19, 870—875).—Broth filtrates Agrie. Chem. Soc. Japan, 1934, 10, 621—629).— Cell contain a sol. exotoxin capable of producing an membranes of oxidising organisms give no blue colour antitoxin in rabbits. Ch . A b s . with neutral or acidified solutions of I in ICI. Biological oxidation of carbohydrates. IV. Ch. A b s . (p) Phosphorus requirements of percolating filters. Physiological characteristics of propionic acid S. H. J e n k in s (Biochem. J ., 1935, 29, 116— 132).— bacteria. E. R. H it c h n e r (J. Bact., 1934, 28, Tho amount of P 04"' required to ensure rapid oxid f73—479).—The catalase activity of these organisms ation of a sugar solution depends on the size and shape ls < is usually supposed. Succinic acid (I) as a sole of the filter medium, sufficient being required (together source of C is not utilised by any of the species, but with adequate N supply) to establish a continuous volatile acids may be produced from (I) by some film of the organism, but not enough to cause choking. strains in media containing fermentable carbohydrates, When the film is established less P 04"' and N are e-?-, glucose. A . G. P. necessary7. Excess of P 04"' passes the filter un Lactobacillus bifidus. J. E. W e iss and L. F. changed, no org. P compounds being produced. The Rettger (J. Bact., 1934, 28, 501—521).—L. bifidus org. P compounds in beet press-watcr are only slowly ®ay constitute 90—95% of the intestinal flora of available to the filter organisms. Unless adequate breast-fed infants. Growth conditions, sugar-fer available N is present the full effect of P 04'" is not menting ability, and tolerance to indole and PhOH evident. The increase of acidity of the effluent with °f the organisms are examined. A. G. P. increase of P 04"' is due to removal of NH3 from NH4C1 with production of HCI, and not to org. acids. Activator of lactic acid fermentation. A. K. C. G. A. Savin (Mikrobiologiya, 1933, 2, 266— 276).—Extracts Flavin transformation by bacteria. L. B. of French beans contain a H20-sol., dialysable, heat- P e t t (Nature, 1935, 135, 36).—A bacterial species 25G BRITISH CHEMICAL ABSTRACTS.— A. which changes the green fluorescence (I) of a lacto- b l o c k i (Compt. rend. Soc. Biol., 1934,117, 789—791, flavin solution to blue has been isolated. The green 792—794).— (a ) Cultures of typhus bacilli are repeat (I) is restored by shaking in air. The EtOH extract edly kept at —10° for 18 hr. and then at 37° for 6 hr., of the dried bacteria gives only a blue (I). The blue the final product being centrifuged and filtered through fluorescent material can be extracted from CHC13 a Chamberland candle. Small doses (0-1—0-5 c.c.) by alkaline H20 and the blue (I) disappears at of the filtrate produce marked toxic reactions in men, pK < 5. Brewers’ yeast, Clostridium acetobutylicum, guinea-pigs, rabbits, and mice. and Mycoderma cerevisiœ do not effect a similar (b ) The preps, are fairly thermostable and contain change in flavin solutions. L. S. T. no protein or cholesterol and only traces of N ; their Histo-chemistry of pigments of organisms immuno-properties and the ability to produce anti producing septicaemia. I. Bacillus per- bodies (agglutinins and preeipitins) are, however, well marked. The residue from filtration contains living fringens. E. D a l o t j s , J. F a b r e , H. P o n s , and but morphologically changed bacilli. F. O. H. BouLiCATrD (Compt. rend. Soc. Biol., 1934, 117, 765—767).—The histochemical reactions of the Antigenic power and properties of staphylo brown pigment produced by B. pëffringens indicate coccus anatoxin. J. T r a v a ss o s (Compt. rend. Soc. a melanin- and thioamino-type containing only Biol., 1934, 117, 717— 719).—Staphylococcus toxin traces of Fe. F. 0. H. modified by CH20 is grouped with the Ramon anatoxins. A. L. Origin of the pigment in Azotobacter chroo- coccum . E. U n g e r e r (Z. Pflanz. Diing., 1934, A, Preparation of diphtheria anatoxin. M. I sa- 36, 287—290).—T3rrosine occurs in the bacterial cell. b o l in s k i, I. L e v z o v , and V. B a t a n o v (Z. Immunitat Pigmentation is associated with the appearance of exp. Thor., 1934, 82, 16—25; Chem. Zentr., 1934, NH3 and increased ps in the medium. A. G. P. ii, 789).—Treatment of the toxin with 0-5—3% aq. S02 or HC1 in aq. NaCl at 40° for 15—30 days pro Nitro-effect. 0. A c k l in (Wasser u. Gas, 1934, duces an anatoxin having 7-8— 8-2. A. G. P. 24, 323—333; Chem. Zentr., 1934, ii, 1176).— Chiefly theoretical. The connexion between nitro- Chemistry of anti-bodies and serum-proteins. reduction and other biological processes is discussed. I. Nitrogen distribution and amino-acids. II. The determination of the nitro-effect is described. Protein-carbohydrate groups. L. F. H ewitt H. N. R. (Biochem. J., 1934, 28, 2080—2087).—I. No marked Comparative toxicity of sulphuric and acetic difference was observed in the Hausmann no., or in acids for R and S varieties of mammalian the cystine, tyrosine, or tryptophan content of cryst. albumin, the globulin fractions, and diphtheria tubercle bacilli. A. Sa e n z , M. Sa d e t t in , and L. toxin-antitoxin floccules. Co s t il (Compt. rend. Soc. Biol., 1934, 117, 308— II. It was not possible to distinguish between 311).— Cultures of B. tuberculosus R an d S o f hum an, serum-globulin (I) and diphtheria or streptococcus bovine, or BCG origin were all killed by 5% AeOH, antitoxin by determination of carbohydrate (II) but tolerated ïï2S04 in conens. < 20%. R. N . C. groups. Both (I) and serum-albumin can be fraction Comparative toxicity of sulphuric and acetic ated into portions of different (II) content, that of the acid solutions to the R and S varieties of avian more sol. fractions being greater. H. G. R. tubercle bacilli. A. Sa e n z , M. Sa d e t t in , and L. Synthesis of a growth factor by a micro C o s t il (Compt. rend. Soc. Biol., 1934, 117, 1072— organism. W. Sc h o p f e r (Compt. rend., 1934,199, 1075).— H 2S0.j is practically non-toxic, but AcOH 1656— 1658).—Although the growth of Phycomyces destroys both strains in conens. > 5 % . R. N . C. blakesleeanus (I) on a synthetic medium (glucose, Activation of the filterable form of tubercle asparagine, MgS04, KH2P04) is inhibited by the bacilli by acetone extracts of Koch’s bacilli. complete absence of vitamin-i?! (II), growth readily H. D. B oer (Compt. rend. Soc. Biol., 1 9 3 4 ,117, 772— occurs if a small amount of culture of (I), grown on 774).—The results of Nègre et al. (A., 1933, 1334) are a medium containing (II), is added, a similar effect confirmed. F. 0. H. being produced by similarly grown cultures of other Antigenic fixatives of tubercle bacilli. I. In fungi of the same species. (I) can thus synthesise a lipin-containing extracts of heat-killed bacilli. growth factor which is not (II), since it can also M . A. M achebcetjf and G. Lévy [with M . Ciia m b a z ] accelerate the growth of Saccharomyces cerevisitx (Ann. Inst. Pasteur, 1934, 53, 591—597).—Amongst which is not sensitive to (II), vitamin-.Bo, or lactofiavin. the various lipin fractions from heat-killed tubercle " J. W. B. bacilli (A., 1934, 564, 929), only two (one sol. in hot Enzymes of bacteria and bacterial meta or cold EtOH, the other only in hot EtOH) fix com bolism . A . I. V i r t a n e n (J. Bact., 1934, 28, 447— plement in presence of tubercular sera to a marked 460).—A review. A . G. P- extent. Further fractionation by solvents indicates Action of carbon dioxide on putrefactive micro that the fixation is due to a substance (containing organism s. F. M. C h is t y a k o v (Mikrobiologiya, approx. 5% P but no glycerol) sol. in Et20 and CHC13 1933, 2, 192—210).—Of 35 species of putrefactive but insol. in C 0 M e2, common to both. F. 0. H. bacteria examined, only 5 were not adversely in Endotoxin of typhus bacilli prepared by re fluenced by C 0 2. Ch. A b s. (p) peated freezing, (a ) Preparation. B. Z a b l o c k i Influence of cations on bacterial viability. and J. M o r z y c k i. (b) Physico-chemical and C. E. A. Winslow (Quart. R e v . Biol., 1934, 9, antigenic properties. J. M o r z y c k i and B. Z a - 259—274),—Stimulation by low and inhibition by BIOCHEMISTRY. 257 high concns. of cations results from influence on “ solganal,” “ uclarsyl,” and isamine-blue proved diffusion, the effects being paralleled by the position active. A. L. of the cation in the electromotive series (Na, K, low). Gram staining method. P . L a s s e u r and M. The action of anions is mainly exerted through their B e n o it (Compt. rend., 1934, 199, 1680—1682).— effects on pa. Ch . A b s . (p) The no. of plastids (B. mesentericus and B. subtilis) Tropical soil microbiology. II. Bacterial stained by the Gram method decreases from pn 2 to numbers in the soil of the Malay peninsula. Pn 12 when the pB in the pretreatment is varied using A. S. Co r b e t (Soil Sci., 1934, 38, 407—416; cf. A., Macllvaine’s buffer, and from pa 8 to pa 12 when 1934, 453).—Bacterial counts indicate that the no. of ]Sra2C03 buffers are used. With a Davis buffer soil organisms is controlled by temp, and H20 content. (citric acid + alkali citratc) the no. stained increases Decomp, of org. matter in these soils is mainly fungal. slightly from pa 2-2 to j)a 6-5, the increase being more A. G. P. marked with H2S04 (12% at pa 1-7 to 82% at pK Preservation of stock cultures of micro 5-3). Uniform staining occurs if the dimensions are organisms. A. C. T h a y s e n (J. Inst. Brew., 1934, 0—2 u. ; very old plastids (2-5—3 ¡¿) are not coloured, 40, 469— 471).— Cultures of a no. of micro-organisms, but the cytoplasm, after rupture of the membrane, prepared by methods previously described (B., 1924, is stained. J. W. B. 485), have remained in a viable condition for 12 Bacterial staining with potassium perman years. I. A. P. ganate ; spore staining. F. Sa n d e r (Z. Hyg., Determination of reducing sugars in bacterio 1934, 116, 334—336).—Use of H2S04-K M n04 for logical media. E. J. M cCr e a r y and H. G. Sm it h staining is described. A. G. P. (Proc. Iowa Acad. Sci., 1932, 39, 171— 173).—The Detection of gold in spirochsetes and trypanos- work of Magee and Smith (A ., 1930, 643) is confirmed. om es. V. F is c h l , J. K o t r b a , and E. S in g e r (Z. Use of Lloyd’s reagent for clarification causes less Hyg., 1934, 116, 69—71).—A spectrographic method variation in results than that of basic Pb acetate or is described. A. G. P. Zn(0H)2. Discrepancies are reduced by dilution of Use of drugs in vitro. E. S in g e r and V. F is c h l the solution prior to clarification. Clarifying agents (Z. Hyg., 1934, 116, 356—360).—The intake of As affect results by absorption of glucose and also by from atoxyl solutions by spirochoetes, trypanosomes, removal of interfering substances. CuS04 removes and other micro-organisms is increased by previous all non-sugar reducing agents from blood filtrates, but digestion of the solution with liver extract. Digestion not from beef broth. Ch . A b s . (p) With glutathione produces much greater activation. Agglutination of various bacteria by lemon Ascorbic acid-thiourea mixtures are lethal to spiro- juice. P. L a s s e u r and M. A. R e 'n a u x (Compt. choetes. A. G. P. rend., 1934, 199, 1454— 1456).—This is shown to be Antiseptic properties of esters of rhodamine-G . due to the low pn of the juice. R . S. C. Role of surface tension and phenomena of Catalase of filtrates of bacterial cultures after photosensitisation. D. B o v e t (Helv. Chim. Acta, lysis by bacteriophage. I. L o m in s k i (Compt. 1934, 17, 1460— 1465).—The absorption spectra of a rend. Soc. Biol., 1934, 116, 839— 841).— Catalase series of esters of rhodamine-6-’P, -G (1), and -B content of filtrates through Chamberland L .3 candles [prep. (Fierz-David) not yet described] are recorded. of cultures of Staphylococcus after lysis oc initial nos. The antiseptic action of esters of (I) towards staphylo of bacteria. Ch. A b s . (p) cocci increases progressively from the Me to the Preparation of graded collodion membranes heptyl ester and then declines markedly. The effect and their use in stu dy of filterable viru ses. J. H. is parallel to that exerted by the substances on the Bauer and T. P. H u g h e s (J. Gen. Physiol., 1934, surface tension. The simpler esters have a marked 18, 143—162).— Collodion membranes (I) were pre- photosensitising action (II) and are more active in paro using as a stock collodion a solution of Parlodion the light than in the dark; this phenomenon is not shreds in EtOH, Et20, COMe2, and aH ^-O H . The presented by the higher members. The (II) of two pore size (II) was varied by addition of II20 or glacial substances which are very similarly constituted and AcOH. Average (II) were calc, by application of have almost identical absorption spectra may differ toiseuille’s law. In the filtration of yellow-fever widely. H. W. v'rus (III) adsorption of proteins was eliminated by Bactericidal action of colloidal solutions. M. passing a hormone broth at p n 8 first. Suspensions P r ic a (Z. Hyg., 1934, 116, 385—396).— Colloidal (III) passed through (I) of (II) equal to 70, 55, solutions of SiO, such as may be obtained in H20 and 50 mu. showed clearly decreasing infective powers. left in contact with fine sand for some months are he min. (II) for the filtration of sheep and monkey toxic to B. coli, B. paratypliosus, and S. 'pyogenes o^yhasmoglobin (IV) and ovalbumin (V) were 8 and aureus. Colloidal Fe(OH)3 and Al(OH)3 have a similar - m^., respectively. Using Svedberg’s vals. for the action. The natural purification of H20 is discussed mo -sizes, a pore : particle ratio of 1-5 : 1 for both (IV) from this aspect. A. G. P. and (V) was obtained. H. D. Callicrein. IX. Detection and occurrence of Action of antiseptics on the poliomyelitic callicrein in urine. H. K r a u t , E. K . F r e y , E. in vivo and in vitro. G. H o r n us and P. W e r l e , and F . S c h u l t z (Z. physiol. Chem., 1934,2 3 0 , (Compt. rend. Soc. Biol., 1934, 117, 656— 259—277; cf. A., 1930, 1069, 1624; 1932, 547).— )' poliomyelitic virus is very resistant to Dialysis of human urine (I) through Cellophane antiseptics. Among several substances examined, against H20 removes heat-stable depressor substances 258 BRITISH CHEMICAL ABSTRACTS.— A. from the callicrein (II), which is then assayed using Action of parathormone. H.K. G o a d b y and R.S. dogs [the (I) of which contains much (II)] (cf. Weese, S t a c e y (Biochem. J., 1934, 28, 2092— 2096).—Para A., 1933, 1335). Purified (II) is inactivated by short thormone increases excretion of P in urine independ heating at 60°; human (I) does not lose all its (In ently of the concn. of inorg. P in the plasma. activity even after 30 min. at 90—95°, probably H. G. R. owing to the presence of thermo-stabilisers (remov Oral and duodenal administration of single able by dialysis). The (II) in dialysed human (I) is large doses of pure thyroxine. Comparison of inactivated much more readily by serum (III) (differ calorigenic effects with those of monosodium ent types of which contain varying amounts of thyroxine and thyroxine in alkaline solution. inactivator) or extracts of the lymph (IV) or parotid W. O. T h o m p so n , P. K. T h o m p so n , S. G. T a y l o r III, glands of the ox. The (I) of dogs is not inactivated and L. F. N. D ic k ie (Arch. Int. Med., 1934, 54, 818— by (IV) or pancreas (dog); (III) largely inactivates 828).— Oral and duodenal administration of thyroxine the undialysed (I). Dialysed (I) of cats is inactiv has no effect on the basal metabolic rate (I) in myx- ated by (III) but not (IV). The amount of (II) in oedema, 10 mg. of the Naj salt increase the the (I) of adults varies from 0-04 to 0-6 unit per c.c. (I) 7, 20, and 32 points when administered orally, (mean val. 0-22); 56—550 units arc excreted daily. orally in alkaline solution, and intravenously in Much less (II) is excreted by infants, children, and old alkaline solution, respectively. H . G. R. people. The horse excretes little (II). H. B. Biological demonstration of the thyroid hor Villikinin content of different parts of the mone in the blood of pregnancy. Limitation of intestine. G. d e L u d a n y (Compt. rend. Soc. Biol., the activity of the thyrotropic hormone of the 1934, 117, 974—975).—Villikinin (I) previously anterior pituitary, according to investigations isolated from the duodenum is present also, but in on thyroid-deficient animals. P. T h ie s s e n (Arch. smaller amount, in the mucosa of the large intestine, Gynakol., 1934, 156, 454—458; Chem. Zentr., 1934, the ileum, and the stomach. (I) is not destroyed by ii, 963).—The increase in metabolism produced in trypsin or pepsin; it diffuses easily, and is not adsorbed rats by injection of pregnancy serum is not due to the by animal C. A. L. thyrotropic hormone in the serum, as it occurs in Renal activity. VII. Effect of adrenal cortex. thyroidectomised animals. R. N. C. Y. M iz u n e (Sei-i-kwai Med. J., 1933, 52, No. 9, Effect of the epithelial cell and colloidal sub 63—79).—Acceleration of renal activity is demon stance of the thyroid gland on excretion of strated by determining urinary: blood-urea-N in iodine in urine. G. T a n a k a (Folia Endocrinol. rabbits fed with urea with or without injection of interrenin, and by a renal function test with phenol- Japon., 1933, 9, 32— 33).—Normal excretion of I was increased by injection of KI. The cffcct was accentu sulphonephthalcin. Ch . A b s . ated by injection of aq. extracts of epithelial cells Ovarian stimulation by adrenal extracts. and restricted by extracts of colloidal substance. L . E. Ca s id a and A. A. H e l l b a h m (Endocrinol., Ch . A b s . (p) 1934,18, 249—253).—Adrenal (but not blood, serum, Effects of extracts of thyroid gland obtained by liver, or ovary) extracts (I) from non-pregnant mares treatment with acid alcohol on iodine excretion and geldings, and (I) from pregnant mares caused the in urine. G . T a n a k a (Folia Endocrinol. Japon., formation of large follicles or corpora lutea in rats. 1933, 9, 33—34).— I excretion was retarded and Ch . A b s . decreased by small doses and frequently unaffected Variation in blood-calcium fractions caused by larger doses of the extract. Ch . A b s . (p) by adrenaline. C. R osso (Clin, pediatr., 1934, 16, No. 3).—Intravenous injection of adrenaline causes Effect of the thyrotropic hormone on the transition of colloidal Ca into an ultrafilterable form. ketonic substances in the blood. F . S i l b e r s t e i n , Ch. A b s . (p) F. G o t t d e n k e r , and E. H o h e n b e r g (Klin. Woch, Antagonism of potassium and magnesium ions 1934, 13, 595—596; Chem. Zentr., 1934, ii, 793).- in adrenaline secretion. R . H a z a r d and L. Injection of 1000 units of the thyrotropic hormone W u r m se r (Compt. rend. Soc. Biol., 1934, 117, 864— (I) in cats produces a rise in blood-ketones (II), 866).—KC1 injected intravenously excites the adrenal lasting several hr. Injection of 500 units causes a glands to secrete; MgCl2 inhibits the effect. rise, followed by a fall below normal. (II) is simi R. N. C. larly but not uniformly influenced by (I) after ad Muscle-phosphorus compounds in adrenal ministration of oil. v R. N. C. insufficiency. E. L h n d s g a a r d and A. T. AVilson I Endocrine glands and calcium metabolism. (J. Physiol., 1934, 80, 29—30p).—Inorg. P 0 4"', H . Z w a r e n s t e in (Biol. Rev. Cambridge Phil. Soc., , phosphagen, pyrophosphate, and liexose phosphate 1934, 9, 299—331).—Thyroidectomy, hyper- and in muscles of adrenalectomised cats were substantially normal. Ch. Abs. (p) hypo-thyroidism, administration of thyroid gland or thyroxine did not affect the serum-Ca (I) level. Variations in blood-calcium fraction caused Adrenaline had no const, action. The adrenal cortex, by parathyroid hormone. A . C a b it t o (Clin, pituitary, thymus, and possibly ovaries are con pediatr., 1934, 16, No. 3).—The total Ca (I) is in cerned in Ca metabolism (II). Administration of creased except when the initial level is high. Ultra- insulin with or without glucose increased (I). Pan‘ filterable Ca varies with (I). Changes in colloidal Ca createctomy had no consistent effect on (II). are independent of (I). Ch. A b s . (p) Ch . A b s . (p) BIOCHEMISTRY. 259 Inactivation, of growth hormone. I. In increased in eclampsia. Pituitrin can be used to adequate refrigeration. II. Exposure to air. produce a lasting H20 and Cl retention in pregnancy. H. S. R u b in s t e in (J. Lab. Clin. Med., 1933, 19, R. N. C. 63—66,404— 405).—The potency of anterior pituitary Synergism between cestrin and pituitrin. E. extracts is lowered by inadequate refrigeration or atm. M o l l e r -C h r is t e n s e n (Lancet, 1934, 227, 1388— oxidation. Ch. A b s . 1389).—The injection of cestrin into infantile guinea- Iodine metabolism. VII. Effect of the mid pigs gives rise to increased sensibility of the uterus brain and the pituitary on iodine metabolism. to pituitrin in vitro. L. S. T. A. St u r m (Z. ges. exp. Med., 1934, 93, 490—501; Biological assay of folliculin. H . H in g l a is Chem. Zentr., 1934, ii, 792).— Cessation of the func and M. H in g l a is (Compt. rend. Soc. Biol., 1934, tions of the tuber cinereum, lower hypothalamus 117, 1005— 1008).—Using the technique of Allen region, infundibulum, and posterior pituitary pro and Doisy 0-1x10-° g. of folliculin is equiv. to duced no change in total I metabolism. Destruction of the Allen and Doisy rat unit and not J as has been or removal of the anterior pituitary (I) produced previously thought. A change of the international hyperiodaemia and hyperioduria for a week, followed unit is suggested. A. L. by a slowly progressing hypoiodiemic phase due to Folliculin content of normal and ectopic stoppage of the activity of the thyroid following the testicles. R. C o u r r ie r (Compt. rend. Soc. Biol., interruption of the thyrotropic effect of (I). 1934, 117, 1117— 1120).—The folliculin content (I) R. N. C. of horse-testicles is > that of ox-, but < that of Effect of pituitary extracts on the viscosity hog-testicles (II). Normal and ectopic (II) show of blood, and its antagonistic effect on insulin. similar (I). R. N. C. K. A. T z o n i (Praktika, 1933, 8, 249—252; Chem. Zentr., 1934, ii, 1148).—Simultaneous injection of Absorption and excretion ratios of folliculin pituitary extract and insulin in rabbits produced an in m an. T. K em p and K . P e d e r s e n -B j e r g a a r d antagonistic effect of the two hormones on the (Endokrinol., 1934, 13, 156—167 ; Chem. Zentr., viscosity of the blood. R. N. C. 1934, ii, 1147).—Normal growing persons excrete daily < 10 mouse units per litre of folliculin (I) in Lactic acid content of the muscle of hypophys- the urine, and 30—70 units in the fæces, which ectomised toads. A. D. M a r e n z i (Compt. rend. probably originates from food. After peroral admin Soc. Biol., 1934, 117, 1035— 1036).—The lactic acid istration about 6% is eliminated in the urine, and after content (I) of the gastrocnemius of normal toads (II), subcutaneous injection about 3%. Blood-(I) at the of those deprived of the posterior (III), and of those end of pregnancy is 5-6—7-6% of that of the urine, deprived of the anterior pituitary gland (IV) was (I) being distributed equally between corpuscles 10-24, 11-06, and 10-35 mg. per 100 g. of muscle, and plasma. R. N. C. respectively. (I) after 2 min. electrical excitation of the sciatic nerve was in (II), (III), and (IV), 129, Metaplasia of uterine epithelium produced 88, and 53 mg. per 100 g., respectively. After implant by chronic cestrin administration. H . Se l y e , ation of both glands and (III) alone, (I) increased D. L. T h o m so n , and J. B. C o l l ip (Nature, 1935,135, to 126 and 106 mg., respectively. A. L. 65—66).—The effect has been observed in castrated Melanophore hormone. IV. Isolation of the female rats injected with oil solutions of œstrone. L. S. T. hormone. F.G.D ie t e l (Klin. Woch., 1934,13,796— Regeneration of testes degenerated by men- "97; Chem. Zentr., 1934, ii, 792).—The hormone isstable to Ba(OH)2, which destroys oxytocin and vasopressin. formone, spontaneously and by use of the gonadotropic hormone. S. E. d e J o n g h and E. To obtain a highly-purified prep, posterior pituitary L a q u e u r (Nedcrl. Tijdschr. Geneesk., 1934, 78, powder is extracted at room temp, with 50 times its 3030—3035; Chem. Zentr., 1934, ii, 1147).—-Young 'ft- of aq. Ba(OH)2, insol. material removed, and the rats’ testes (I), the hormone production of which is solution acidified with H2S04 and filtered after 2 hr. stimulated by the gonadotropic hormone of pregnancy The filtrate is boiled down to j vol. at neutral reaction, urine (II), are not or very little > those of untreated any ppt. removed, and 5 vols. of COMe2 are added; the ppt. containing the hormone is collected after animals. Menformone (III) causes shrinkage of (I), 24 hr., dried, taken up in H20, and evaporated recovery of wt. being more rapid under administration of (II). (II) has a more marked effect on the Leydig to dryness. The residue is extracted thrice with cells (IV) than on (I). Prolonged treatment with boiling EtOH and the extract conc. The amorphous (III) causes a temporary decrease in the no. of residue is sol. in H20 ; the solution is not pptd. by CC13-C02H or o-SH-C6H4-C02H, and the Pauly (IV). R- N. C. reaction is negative. The anterior lobe appears to Constituents in normal urine producing the contain inhibiting or sensitising substances. hyperglycæmia previously attributed to prolan. R. N. C. B. L. D a v is , jun., J. C. H in s e y , and J. E. M a r k e e Effect of the posterior pituitary hormone on (Endocrinol., 1934, 18, 382—386).—Hyperglycæmia the water and chlorine excretion of the pregnant in rabbits following injection of urine extracts is organism with reference to the hormonal theory due to urinary constituents other than prolan. of the origin of eclampsia. H. R u p p and W. Ch . A b s . Bickenbach (Arch. Gynakol., 1934, 156, 420— 427; Emmenin. J. B . C o l l ip , J. S. L. B r o w n e , and Uem. Zentr., 1934, ii, 963).— Injection of posterior D . L. T h o m so n (Endocrinol., 1934, 18, 71—74).— Pituitary extract reduces Cl excretion, which is Emmenin is a hydrolysable complex containing 260 B R ITISH c h e m i c a l a b s t r a c t s .—A. trihydroxycestrin. It does not appear to bo ovary- Pregnan-20-ol-3-one. ai JoPregnan-3-ol-20- stimulating, and its active principle may be converted one, a companion of the corpus luteum hor into a more potent form in presence of ovarian mone. Conversion of pregnandiol into the tissue. Ch . A b s . corpus luteum hormone.—See this vol., 215, 216. Hormonal function of the unfertilised egg. A. Male hormone as obtained from urine. T. F. W e st m a n (Arch. Gynakol., 1934, 156, 550—565; G a l l a g h e r and F. C. K och (Endocrinol., 1934, 18, Chem. Zentr., 1934, ii, 962).—Luteinisation of granu 107— 112).—Testicular hormone (I) in urine extracts losa cells of rabbit follicles is not dependent on a is purified by removal of acids and phenols and by hormonal action of unfertilised eggs. A. G. P. distillation at > 150°. The residue is fractionated with aq. EtOH, light petroleum, and CC14, and then Preparation of the corpus luteum hormone again distilled at 150—200°. The distillate (10,000 fromstigmasterol. E. F e r n h o l z (Ber., 1934, 67, units per g.) differs chemically, but not biologically, [5], 2027—2031).—3-Hydroxybisnorchplenic acid is from (I) from ox testis. Ch. A bs. degraded to the OH-ketone (I), the dibromide of which is oxidised and debrominated to the diketone Vitamins of olive oil. F. S. Girona (Bull. Mat. (ii), m.p. 129°, [a]“ +200° in CHC13 (dioxime, m.p. Grasses, 1934, 18, 281—286).—The characteristic 246— 248° when rapidly heated), identical with the absorption from the red, blue, indigo, and violet corpus luteum hormone. Dehydrogenation of (I) regions of the normal spectrum indicates that the to (II) by CuO at 310° is described. (II) is converted vitamin contents of dark cod-liver oil (I) and olive oil (II) are > that of clear cod-liver oil and that (II), unlike (I), contains vitamin-5. Normal residue oil and (II) heated to 150° contain no vitamin-^, -B, or -D. F. O. H. Production of vitamins by a pure culture of Chlorococctim grown in darkness on a synthetic m edium . M. F. G u n d e r s o n and C. E. S k in n er into the variety, m.p. 121°, [a]“ +200° in CHC1S, when (Plant Physiol., 1934, 9, 807—815).—Vitamin-il, air is aspirated through its solution in H20-E t0 H - or the provitamin, was produced hi considerable E t,0. The reverse transformation is effected by amounts on a mineral salt-glucose medium. Smaller crystallisation from MeOH. H. W. amounts of -B, and -B„ but no -G were formed. • Preparation of the corpus luteum hormone A. G. P. from stigmasterol; constitution of the corpus Purification of biosterol (vitamin-yl) and a luteum hormone. A. B u t e n a n d t and U. W e s t - crystalline derivative thereof. S. H a m a n o (Bull. phal (Ber., 1934, 6 7 , [J3], 2085—2087; cf. A., 1934, Inst. Phys. Chem. Res., Tokyo, 1934, 13, S9).— 1268).—The OH-ketone (I) (loc. tit.) is cautiously Theragra clialcogramma liver-oil yields vitamin-4 treated with Br in AcOH and the product is directly (C.L.O.U. 8300); the maleic anhydride addvd, oxidised with Cr03; mild treatment of the oily C30H36O8, of the Ac derivative thereof has m.p. substance (II) thus obtained with AcOH and Zn dust 261—262°. R. S. C. yields A4-pregnene-3 : 20-dione (III) (A ; R = 0 ) ident- Vitamin-^L. I. M. H e il b r o n (Chem. and Ind., 1934, C03VIe*ca* natural corpus 1063).— A correction (A., 1934, 1269). R. S. C. ' luteum hormone and with that I Y I obtained from pregnandiol. Vitamin-/I content of herring. A. Sch eu n ert Mo ------' The A4 position of the double and M. S c h ie b l ic h (Z. Unters. Lebensm., 1934, 68, linking follows from the optical 409— 411).— Herring roe contains Vitamin-Jl, the hard behaviour of (III) and from roe > the soft. The -A content is not diminished by the oxidation of (I) to a di- smoking. E. C. S. kctone. More drastic treatment of (II) with Zn and Relative biological efficiencies of the vitamin-.'l AcOH leads to the deoxy-hormone, C21H320 [( ?) A ; and carotene of butter. R. G. B o o t h , S. K . K on, R —Ha], m.p. 105°, [a]n +96-4°, which is physio and A. E. G illa m (Biochem. J., 1934, 28, 2169— logically inactive. H. W. 2174).—The carotene (I) and vitamin-4 (II) contents Polymorphous modifications of the corpus of the butters of Shorthorn and Guernsey cows have luteum hormone. A. B u t e n a n d t and J. S c h m id t been determined speetrophotometrically and tlic (II) (Ber., 1934, 6 7 , [5], 2088—2091).— It is considered activities biologically. Although the total biological that there is only one corpus luteum hormone, C21H30O2, activity is the same for butters of both breeds, the which exists in several polvmorphous forms. Whether contributions from (I) and (II) vary considerably the modification (I), imp. 121°, or the form (II), with the breed, from which it is calc, that (II) is 6 m.p. 128-5°, is obtained from the gland, from stigma times as potent as (I). C. G. A. sterol, or from pregnandiol is a matter of accident. Fat-soluble vitamins. XLI. Carotene and (I) and (II) can bo interconverted by crystallisation vitamin-^l content of colostrum. J. S e m b , C. A. from suitable solvents, they have identical analytical B a u m a n n , and H. Steenbock. XLII. Absorp composition, absorption spectra, and optical activity, tion and storage of vitamin-^L in the rat. C. A. yield identical derivatives, and, according to the B a u m a n n , B . M. R iis in g , and H. S t e e n b o c k (J. Clauberg test, have the same physiological activitv, Biol. Chem., 1934, 107, 697— 703, 705—715).- identical with that of the natural hormone. H. W. The carotene (I) and vitamin-4 (II) content of fat BIOCHEMISTRY. 261 prepared from colostrum is much higher than that W . C. R u s s e l l , M . W . T a y l o r , and D. E. W il c o x of fat from ordinary milk, but decreases rapidly (J. Biol. Ghem., 1934, 107, 735—746).—To produce during the first week of milk secretion. The blood normal bone ash and body-wt. in chickens at 8 weeks stream may function as a significant storage reserve of age, < 1 4 4 times as much vitamin-D (I) must be for (I). fed in the form of irradiated ergosterol (II) as in the XLII. The (II) content of new-born rats is very form of cod-liver oil (III). Storage of (I) in the liver low but is increased slightly by raising the (II) is the same for each source of (I). The (I) content intake of the mothers during pregnancy, and markedly of the blood and long bones of cockerels is the same by raising their (II) intake during lactation. 95% of whether (I) is supplied as (III) (1% of the ration) or the total (II) in the rat is stored in the liver, and as (II) equiv. to 24% of (III). Pullets fed with (II) (II) storage is greater when (II) is fed to normal did not show the persistence in laying exhibited by animals than when it is fed to (Il)-depleted rats. birds receiving (III) under identical conditions. The min. daily dose of (II) necessary to produce The antirachitic potency of the egg-yolk from birds storage is 25—50 blue units. Absorption and storage receiving (III) was much < that from birds receiving mostly take place within 6 hr. after ingestion. Loss (II). As regards body-wt., feathering, and general of (II) due to destruction in the digestive tract is appearance, 1% of (III) is equiv. to the (I) content large, but feecal elimination of (II) is small. A. E. 0. of 24% of (III) supplied as (II). (I) from either Vitamin-/1 and carotene. XII. Elimination source is not lost by excretion in the bile. A. E. O. of vitamin-yl from the livers of rats previously Relative efficiencies of irradiated ergosterol given massive doses of vitamuwl concentrate. and irradiated yeast for the production of A. W. D a v ie s and T . M o o re (Biochem. J., 1935, vitamin-D milk. W . E. K r a u s s , R. M . B e t h k e , 29, 147— 150).—Rats with sufficient vitamin-^4 (I) and W . W il d e r (J. Dairy Sci., 1934,17, 685—693).— stored in their livers to last theoretically for 100 years The transference of vitamin-D from ingested irradiated lose the greater part of their stored (I) in 12 weeks ergosterol to milk was approx. two thirds of that from when restricted to a (I)-free diet. A stable storage irradiated yeast. A. G. P. level of 400 B.U. per g. is then reached. Carotene Relation between vitamin-E and sex horm ones. (in vegetables) is an efficient substitute for preformed G. S p a g n o l (Rev. sud-amer. endocrinol. inmunol. (I) in diets suitable for the building up of a large quimioterap, 1934, 17, 553—565).— Hormone pro (I) store in the rat’s liver. A. E. 0. duction is independent of vitamin-i? (I), but (I) is Influence of vitamin-/l on the metabolism of necessary for physiological processes produced by rats and guinea-pigs. A. C h e v a l l ie r and H. hormones. C h. A b s. (p) Baert (Compt. rend. Soc. Biol., 1934, 1 1 6 , 1037— Utilisation of energy-producing nutriment and 1039).—Absence of vitamin-^4 from diet increases protein as affected by individual nutrient de basal metabolism especially in young animals. ficiencies. II. Effects of vitamin-B deficiency. Ch. A b s. ( >) 2 F . J. M cCl u r e , L. V o r is , and E. B. F o r b e s (J. Carotene and vitamin-/L requirem ents of Nutrition, 1934, 8, 295—308).— Deficiency of vitamin- white Leghorn chicks. W . O. F r o h r in g , an d J. B resulted in depressed appetite but no change in Wyeno (J. Nutrition, 1934, 8, 463—477).— The min. wt.-increase per unit of food, decreased fat and requirement of chicks a'pprox. 8 weeks old was 65 energy gains, lower body temp., slightly increased units per day. Vitamin-^4 deficiency did not induce digestibility of protein but not of energy foods, “ slipped-tendon.” A. G. P. lowered efficiency of utilisation of metabolisable Vitamins. XIX. Assimilation of carotene energy, increased energy out-go in heat and urine, and vitamin-/l in presence of mineral oil. R. A. increased C : N ratio in urine, and depression of Pftch er, P. L. H a r r i s , E. R. H a r t z l e r , and oxidative processes of the organism. A. G. P. N. B. G u e r r a n t (J. Nutrition, 1934, 8, 269—283).— The vitamiriyl potency of butter-fat is depressed in Alimentary imbalance caused by Senegal gum. the presence of mineral oil (I), the effect varying R. L e co q (Compt. rend. Soc. Biol., 1934, 117, with the proportion of (I) used. The potency of 994— 996).—Pigeons fed on an adequate diet relatively cod-liver oil was not affected by (I). Faecal excretion high in vitamin-jB developed polyneuritis when °f carotene is relatively high when (I) is fed. Senegal gum (I) was added to the diet. The galactose in (I) was probably responsible. A. L. A. G. P. Determination of vitamin-4 values by a Optical investigation of the antineuritic Method of single feeding. H. C. S h e r m a n and vitam in(-Bv). A. Sm a k u l a (Z. physiol. Chern., h at. T o d h u n t e r (J. Nutrition, 1934, 8, 347—356).— 1934, 230, 231—239).—The absoiption spectrum (I) Rats depleted of stored vitamin-^ receive a single of vitamin-I?! (II) shows max. at 260 and 245 mjx J(ling of test material. Subsequent wt. curves are (cf. Windaus et al., A., 1932, 310 ; Peters and Philpot, compared with those obtained by feeding carotene, A., 1933, 645). The (I) of the fission product fne area of growth curves for males was > that C7Hu 0 5N3 (III) (Windaus et al., A., 1934, 1415) for females. Fresh kale contained 200 units per g. has max. at 261 and 225 mjx and is identical with A. G. P. that of 6-hydroxy-2-methylpyrimidine. The (I) Fate of the antirachitic factor in the chicken. of the fission product CGH702NS (IV) (loc. cit.) Effective levels and distribution of the has max. at 257 and 198 mjx ; (IV) probably contains actor from cod-liver oil and from irradiated a pyrrole ring. Superposition of the (I) of (III) and ergosterol in certain tissues of the chicken. (IV) gives a curve, similar to that of (II) ; (II) contains 262 BRITISH CHEMICAL ABSTRACTS.— A. 2 chromophores separated by a saturated hydro 457—462).—Mice receiving a vitamin-J52-deficient carbon group. The (I) of the following are also given : diet consumed approx. 60% of the normal caloric hydrolysis product (probably C12H1502N3S) of (II); intake. The body-wt. remained unchanged, neutral Me pyrrole-2-carboxylate; 2-thiopyrrolidone; Me fats disappeared from the body, but phospholipins 4-thiol-3 5-dimethylpyrrole-2-carboxylate; glyoxal- were unaffected. Bones developed subnormally, nos. ine; 2-methylglyoxaline-4-carboxylic acid; Et of red blood-cells declined, and the eoncn. of glyoxaline-4-acetate; pyrrole; 6-hydroxy-4-ethoxy- haemoglobin and of serum-protein was < normal. 2-methylpyrimidine; 4 : 6-dihydroxy-2-methyl- -Bx and -B2 are necessary to maintain normal pyrimidine; C5H5N; thiophen. H. B. appetite. A. G. P. Brain respiration, a chain of reactions as Colour test for vitamin-C. J. H. R oe (Science, revealed by experiments on catatorulin effect. 1934, 80, 561).—When ascorbic acid is boiled with R . A. P e t e r s , H. R y d in , and R . H. S. T ho m pso n HC1 furfuraldehyde (I) is formed and C02 is liberated. (Biocliem. J., 1935, 2 9 , 53—62).—Minced brain tissue The pink colour produced with (I) and NHzPh cau of pigeons (I) prepared while kept warm showed a rate then be used for its determination. Pentoses, of oxidation in Ringer’s solution-(-lactate or AcC02H pentosans, hexoses, and hexosans interfere. L. S. T. > when prepared in the cold. Addition of glutathione Ascorbic acid and thiosulphate in urine. M. to the cooled (I) was without influence. Vitamin-#! v a n E e k e l e n (Nature, 1935, 135, 37).—S203" is (II) had its greatest effect on warm (I). Avitaminous present in the urine (I) of diabetics and of cats and, (I) was incubated for 2 J hr. in Ringer solution+ to a smaller extent, in that of dogs and normal persons. P207"" (II). Addition of lactate produced an Its interference with the determination of ascorbic increased 0 2 uptake only when (II) was present. acid in (I) by the 2 : 6-dichlorophenol-indophenol H. D. method can be prevented by its removal with Relation of pyruvic acid in brain to certain Hg(OAc)2 or Ba salts. L. S. T. tissue poisons. R . A. P e t e r s , H. R y d i n , and R . H. S. T h o m pso n (Biochem. J., 1935, 2 9 , 63—71).— Ascorbic acid content of the intestine of the Fluoride (I) and iodoacetate (II) reduce 0 2 uptake guinea-pig. S. S. Z il v a (Biochem. J,, 1935, 29, equally. Each largely reduces the catatorulin effect 100— 101).— Ascorbic acid injected into the jugular [extra 0 2 uptake in presence of added vitamin-I^ vein or given per os (as a mixed diet) to scorbutic (III)], both together eliminating it. (I) decreases guinea-pigs is selectively absorbed by the tissues of the pyruvate (IV) accumulation by avitaminous the intestinal tract, particularly in the small intestine. brain and (II) increases it. Glutathione produces only C. G. A. partial restoration of the vitamin effect in presence Vitamin-C in Indian food-stuffs. B. C. GuiU of (II). Disappearance of (IV) in presence of (III) and A. R. G h o sh (Current Sci., 1934, 3, 210).—The results from some other change, the poisons influencing guava, the mango (I) (langra variety), and the lichi a preparatory stage for oxidation. C. G. A. are the richest sources of vitamin-C (II ); they con tain 1-04,0-69, and 0-48 mg. of (II) per g., respectively. Effects of the composition of the diet on the Different varieties of (I) differ in their (II) contents. vitamin-Zf! and -B 2 requirements of the growing The (II) of kancha-mung (Pha-scoins mungo) is increased rat. N. B. G u e r r a n t and R. A. D u t c h e r (J. 7-S times by germination. .The process of develop Nutrition, 1934, 8, 397—420).—Addition of fats to ment of these fruits appears to involve progressive the ration slightly retarded the depletion of reduction in (II) content. L. S. T. vitamin-1?! in rats, but did not affect that of -Bz. The -B2 requirement increased with the amount of Chinese citrus fruit. VI. Vitam in-C content mineral salts ingested. Addition of fibre to the diet of Tsun Chii and Chao Kan. P. P. T. Sah and economised the utilisation of -Bl and -B2. Sucrose T. S. 3VIa (J. Chinese Chem. Soc., 1934, 2, 257—259; increased and dextrin lowered the -B1 and -B2 cf. A., 1933, 755; 1934, 1042).—Tsun Chii is > twice requirements. The latter were not influenced by the as rich as Chao Kan in vitamin-C, and is equal in level of dietary protein. A. G. P. antiscorbutic activity with Fu Chii and Hsiu Mi Chii. J. L. D. Synthetic vitamin-#,,. R. K u h n and F. W ey- Vitamin-C content of Peiping summer fruit g a n d (Ber., 1934, 67, [£], 2084—2085).—The com and vegetables. P. P. T. Sa h , T. S. M a , and H. C. pound C17H20O6N4, obtained from Z-arabinose as Ch a n g (J. Chinese Chem. Soc., 1934, 2, 260—265; cf. A c4 derivative, has the same growth-promoting A., 1934, 1042).—The vitamin-C (I) content of many action as natural vitamin-i^, whereas the substance summer fruits and vegetables is recorded. Prolonged Ci5H160 6N4 is inactive (cf. this vol., 94). H. W. boiling of vegetables rich in (I) results in a large los3 Non-identity of vitamin-Ji2 and flavins. C. A. in nutritional properties. J. L. D. E lv e h je m and C. J. K o e h n , jun. (Nature, 1934,1 3 4 , 1007— 100S).—Vitamin-2?,, and flavins are not ident Isolation of vitam in-C from Chinese iris- Y. F. Ch i and B. E. R e a d (J. Chinese Chem. Soc., ical. ' L. S. T. 1934, 2, 271—273).—The yield (isolation described) Photochemical formation of 6 : 7-dimethyl- is small, although titrimetric determinations indicate alloxazine from lactoflavin.—See this vol., 224. a high vitamin-C content. J- L. D. Synthetic compounds of the lactoflavin group. Vitamin-C and the adrenal gland in dogs. —See this vol., 224. H. M. V a r s and J. J. P f if f n e r (P roc. Soc. Exp- Inanition as a factor in vitamin-JS, deficiency. Biol. Med., 1934, 31, 839—841).—Adrenaleetomised D. G. R e m p and F. C. B in g (J. Nutrition, 1934, 8, dogs receiving cortical hormone survived 15—33 BIOCHEMISTRY. 263 months without developing scurvy on a diet which changes of fluorescence of living leaves. In was scorbutic to guinea-pigs. Feeding of large fluence of temperature on the fluorescence amounts of vitamin-C (I) did not affect the require curve. H. K a u t s k y and H. Sp o h n (Biochem. Z., ment of cortical hormone. The adrenal gland is 1934, 2 7 4 , 423—434, 435—451).—I. Change of in not concerned with the synthesis or metabolism of (I). tensity of chlorophyll fluorescence on irradiation is a Ch. A b s. (p) general characteristic of green leaves of many plants Is the ascorbic acid content of adrenals and and is probably related to assimilation of C02 by the liver under control of nervous system ? A. B. L. leaves. Beznak and Z. H a r is s (Biochem. J., 1934, 2 8 , II. A detailed description of the apparatus is given. 2039—2043).—No significant change (i.e., within The velocity of increase of fluorescence on irradiation ±15%) is produced in the ascorbic acid content of is probably determined by the intensity of the irrad the adrenals (I) and liver (II) on stimulation or iating light, and is not altered by change of temp., degeneration of the splanchnic nerve of the cat or by whereas the velocity with which fluorescence falls perfusion of (I) and (II) with solutions of adrenaline away after irradiation varies greatly with the temp. or acetylcholine. H . D. P. W. C. Effect of ascorbic acid on the thyroid and Chlorophyll spectrum.—See this vol., 145. adrenals of guinea-pigs. D. Ma r i n e , E. J. Colloid chem istry of chlorophyll.— See this vol., Baum ann, and S. H. R o se n (Proc. Soc. Exp. Biol. 165. Med., 1934, 3 1 , 870—873).— Oral administration of ascorbic acid produced smaller thyroid glands in Biochemistry of chlorophyll-defective barley guinea-pigs receiving a goitrogenic diet and anterior mutants. H. v o n E u l e r and R. W e ic h e r t (Svensk pituitary extract than in control animals. Kem. Tidskr., 1934, 46, 301— 306; cf. A., 1932, 550). Ch. A b s . (p) —1Three new mutants (I) [normal (II) and chlorophyll- Enzymic reduction of dehydroascorbic acid. defective (III)] contain the base CUH14N2 (A., 1933, E. Pf a n k u c h (Naturwiss., 1934, 2 2 , 821).— In juice 877) not found in ordinary barley or other green expressed from potato (I), the vitamin is in the form plants. For two (I) the catalase content (IV) of (II) of dehydroascorbic acid (II), owing to the activity of considerably exceeds that of (III) in samples grown oxidases. If cysteine (III) (about 0-3%) is added to in light, but there is less difference in etiolated samples. (I), (II) is reduced to ascorbic acid (IV). The re For the third, (IV) in (III) is > in (II). The dehydrase duction is enzymic. In the presence of much (III), content (V) of barley seedlings on the 4th day is. > (IV) must be titrated in presence of a citrate buffer on the 6th—9th days. In a mutant irradiated with of pa 5-3—5-5, after addition of HgCl2 and KC1. X-rays (V) in (III) is 100% > in (II). W . McC. A. J. M. Respiratory rate and enzyme activity as Biological genesis of vitamin-C. J. M o s o n y i (Z. physiol. Chem., 1934, 2 3 0 , 240—244).—The related to the hardened condition of plants. increase hi the ascorbic acid (I) content of the adrenals S. T. D e x t e r (Plant Physiol., 1934, 9, 831—837).— of rats after administration of y-hydroxyhexane-[ie- Respiratory rates of wheat and cabbage seedlings dione (II) (Henze et al., A., 1933, 88, 377) is approx. decrease continuously during storage (I) at 2°, the same as when the.same amount of (I) is given. irrespective of their sugar content or condition of (II) is considered to be an intermediate in the hardiness. Oxidase activity was unchanged. In biological synthesis of (I). H. B. cabbage, catalase activity (II) was not affected by (I) for 5 days, although plants hardened and had Proportions of chloroplast numbers and increased proportions of sugar. In wheat (II) de chlorophyll concentration in Elodea densa. H . creased in lighted and increased in darkened conditions. vos Euler, B. Bergman, and H. H ellstrom (Ber. A. G. P. deut. hot. Ges., 1934, 5 2 , 458-462).— The clioro- Temperature characteristics for metabolism phyll (I) content per chloroplast (II) and the no. of (II) of Chlorella. II. Rate of respiration of cultures Per cell are p ra ctica lly con st. A . G . P. of C. pyrenoidosa as function of time and tem Development of chlorophyll and carotenoid perature. C. S. F r e n c h , H. I. K o h n , and P. S. Pigments in etiolated plants. R. J. N o r r i s (Bull. T a n g . III. Catalytic decomposition of hydro Basie Sci. Res., 1933, 5, 23—32).—Exposure of gen peroxide by C. pyrenoidosa. C. S. F r e n c h etiolated plants to artificial light resulted in the (J. Gen. Physiol., 1934, 1 8 , 193—207, 209— 213; ranation of chlorophyll (I) and xanthophyll (II) in cf. A., 1934, 1262).—II. The 02 consumption (I) ^ • proportions. Carotene (III) decreased at of C. pyrenoidosa in Knop’s solution in the dark tat, Dh\after 4—5 hr. increased more rapidly than decreases with time; the R.Q. also falls from an initial y snd (XI^ With increasing 0 2 in the atm. (Ill) val. of 0-95 to a const, val. 0-65; hence it is concluded ^e/°ped still more rapidly, but formation of (I) and that two substances, A and B, are responsible for < ) reached a niax^with 20% 02. The proportion (I). The plot of rate of (I) against (I) is linear in the aU pigments increasecT'with rising [C02] in the atm. initial stages only; a similar curve for C02 con P to 3—5%, but subsequently declined. sumption (II) runs parallel to this; curves of (I) p * Ch. Abs. (p) and (II), corr. for the oxidation of A only, coincide, ^uiiorophyll fluorescence and assimilation of indicating an R.Q. equal to 1 for this component. conic acid. I. Fluorescence behaviour of The R.Q. of B is 0-65. The Arrhenius const, of (I) ¡pen plants. H. Kautsky and A. Hirsch. II. of A is 3500 g.-cal. above 11-5° and 19,500 g.-cal. Pparatus fo r com parative m easu rem en t of below, whilst that of B is 5600 with no critical temp. T 264 BRITISH CHEMICAL ABSTRACTS.— A. I ll, The decomp, of H20 2 by C. pyrenoidosa at S. R . R is k in a (Trans. Central Sci. Res. Inst. Sugar pa 6-72 is unimol. only in the initial stages. The plot Ind, U.S.S.R., 1933, No. 12, 36—43).^-The increase of log. initial d[B.2Oz\/dt against 1 /i is linear, giving in enzyme content of germinating seed (1 —8 days) an Arrhenius const, of 10,500 g.-pal. H. D. is irregular, but characteristic of seed type. Variations in forage-beet are less irregular than in sugar-beet. Respiration of conjugating Sjiirogyra with Ch. A b s. (p) special reference to fat metabolism. N. L. P a l (New Phytol., 1934, 33, 241—273).—During conjug Substance in fleshy fruits inhibitory to germin ation. A. K o c k e m a n n (Ber. deut. bot. Ges., 1934, ation C02 evolution and the R.Q. decline. The 0 2 intake rises in the early stages, but decreases later. 52, 523—526).—The Et20-extract of apples, pears, Oil globules appear only in conjugating filaments. tomatoes, etc. contains a H20-sol., heat-resistant Starch is present at all times except the final stage substance (“ blastokolin ”); which is decomposed by of zygote formation, when it is converted into fats hot NaOH and by H20 2, and inhibits the germination and oils. Light energy is essential to the latter of seeds. A. G. P. process, which is reversed in darkness. A. G. P. Metabolic changes in geotropically stimul ated seedlings. P. M e t z n e r (Ber. deut. hot. Ges., Metabolism of plant and insect waxes. A. C. 1934, 52, 506—522).—The hypocotls of 'Helianthiis Ch ib n a l l and S. H. P ip e r (Biochem. J., 1934, 28, 2209—2219).—A general scheme for the metabolism seedlings, after keeping horizontal for some time, exhibited changes in the composition of expressed of waxes is based on the hypotheses (1 ) that the saps. Sap from the under side had higher d, osmotic primary alcohols are formed by the reduction of the pressure, [H‘], and reducing sugar content than corresponding acids, and the paraffins, sec.-alcohols, that of the upper side. A. G. P. and ketones by indirect decarboxylation of the corresponding w-fT acid, and (2) that the saturated, Action of salts of beryllium, zirconium, and keto-, and OH-acids are formed from unsaturated palladium on the geotropic sensitivity of roots. acids synthesised from shorter products. C. G. A. V. B a m b a c io n i-M e z z e t t i (Atti R. Accad. Lincei, 1934, [vi], 20, 125— 128).—0-1% PdCl solutions Physiology of sugar accumulation in sugar- 2 (in tap-H 0) completely paralyse the geotropic beet. I. Transformation of sugars in leaf 2 sensitivity of roots of Vida sativa; some roots resume scions. II. Influence of different sugars on growth subsequently and then show irregular curv photosynthetic energy. A. L. K o r s a k o v and ature. 0-1 %ZrCl4 solutions inhibit geotropic curvature M. N. K a z a k o v a (Trans. Centr. Sci. Res. Inst. Sugar for hr.; most of the roots dry without the plants Ind. U.S.S.R., 1933, No. 12, 3— 13, 13—26).— I. 8 dying, but some, after 24— 48 hr., show geotropic A 3% solution of glucose (I) filtered through leaf scions is partly converted into fructose (II). Some and ageotropic curves. 0-1 % BeCl2 solutions have less effect. Apparently geotropic curvature depends synthesis of sucrose (III) occurs. A 3% solution of less on the faculty of growth than on unequal dis (II) is partly transformed into (I) under these con tribution of the growth hormones. T. H. P. ditions and (III) is also formed. Solutions of (III) (8%) were not affected by this treatment. Absorptive function of roots and concentration II. The action of sugar solutions on photosynthetic of culture media. P. M a z e , P. J. M a z Is, jun., and activity indicates that in beet sugars are translocated R. A n x io n n a z (Compt. rend. Soc. Biol., 1934, 117, in the simple forms, and sugar storage is limited by 753—754).—Maize plant roots immersed in aq. insufficiently rapid photosynthesis. Ch. A b s . (p) KI, KC1, or N aC l absorb these salts to an extent Seasonal cycle of nitrogenous and carbo cc their concn. in the media. Hence the absorptive hydrate materials in fruit trees. II. Cycles of power of roots varies with the properties and com alcohol-soluble materials and of carbohydrate position of the protoplasm (cf. B., 1933, 1027). fractions and lignin in wood, bark, leaves, and F. 0. H. portions of terminal shoots of apple trees under Factors in elongation and expansion [of plants] two cultural systems—grass plus annual spring under reduced light intensity. F. E. C l e m e n t s nitrate, and arable without nitrogenous fertil and F. L . L o n g (Plant Physiol., 1934, 9, 767—781).— The supply of H20 is the dominant factor in stem iser. E. S. Sm it h (J. Pomology, 1934, 12, 249— 292).— Seasonal variations in all constituents are elongation, and that of light in dry-matter production. recorded, those for bark (I) and wood being similar. Grassland trees receiving NaN03 had higher pro Variations in composition of protein of ripen-ra portions of reducing sugars in spring and summer and, ing wheat grains. A. K ie s e l and M. K asteup» in general, higher carbohydrate : N ratios. Other (Z. physiol. Chem., 1934, 230, 216—224).—Tlio^total, constituents were not appreciably affected by differ protein, and H20-sol. N, gliadin (I). -globtriu>r- ences in cultural treatment. Carbohydrates are glutenin, and H,0-sol. protein (II) of the dry, and the H ,0 content of the fresh, grains are determined a translocated principally through (I). Sucrose in shoots acts as a primary reserve (II) rather than a various intervals during growth. The composition of (I) and (II) obtained at the various stages varies. medium of translocation. Complete disappearance of starch in winter does not occur. Hemicellulose is EtOH -sol. and -insol. (I) appear to have the same probably not a (II), but has a structural function. chemical composition. / H. i>. A. G. P. Root stock effects with cherries. S e e d a n d Variations in enzymic content of different phyton propagation. M. B ." Cummings, E. >'• varieties of sugar-beet at the germination period. J e n k in s , and R. G. D u n n in g (Vermont Agric. Exp- BIOCHEMISTRY. 265 Sta. Bull., 1933, No. 352, 36 pp.).—Effects of the Influence of humic acid on the absorption of stock on the development of tree and fruit and on the mineral salts by plants. A. V. B l a g o v e s t - sugar and acid contents and j)a of fruit are examined. s c h e n sk i and A. A. P rosorovskaja (Biochem. Z., A. G. P. 1934, 2 7 4 , 341— 345).—Humic acid preps, from peat Production of ethylene by some ripening stimulate the growth of flax seedlings in H20 culture, fruits. R. G a n e (Nature, 1934, 1 3 4 , 1008).— The increasing considerably the dry wt. and % of N, but gas given off by ripe apples contains small amounts decreasing the % of P (increase of protoplasm but of C2H4. In the absence of 0 2 its production ceases not of nuclear material). Tables show the N, P , and or is much diminished. L. S. T. K contents of stalks and roots as a % of the dry wt. Carbohydrate-nitrogen ratios with respect to with varying nutrition. P . W. C. the sexual expression of hemp. P. J. T a l l e y Phosphorus metabolism in the leaves of (Plant Physiol., 1934, 9 , 731—748).— Staminate mistletoe. E. M ic h e l -D u r a n d (Compt. rend., plants have higber % of total carbohydrates, poly 1934, 9 9 , 1653— 1655).—Determination of P in the saccharides, sugars, and reducing sugars, but lower ignited residue of the EtOH- and EtaO-sol. [lipin-P (I)], N, than pistillate plants. A. G. P. and the EtOH-sol. Et20-insol. [residual sol. P (II)] Phytohormones. H. v o n E u l e r , D. B u r s t r ö m , fractions of the dried leaves of mistletoe, and of the and G. G ü n t h e r (Svenk Kem. Tidskr., 1934,4 6 , 250— 10% CC13-C02H extract (III) [total sol. P (IV)], the 256).—The retarding action of egg-yolk and malt phytin pptd. by Ca(OAc)2 from (III) [phytin-P (V)], extracts and of urine on the root-growth of barley and in the Mg phosphates from the (III) filtrate mutants grown in saline solution is as pronounced [mineral P (VI)] of the fat-freed leaves, gives an with chlorophyll-defective mutants (albina 1 ) as with approx. measure of the relative types of P present at those (I) of normal chlorophyll content. No re different periods between May and September tardation is caused by ovalbumin, pollen extract, (results tabulated), sol. org. P (VII) being given by methylene-blue, flavin, or the base Cn H 14N2 present (IV) — (V)—(VI), and the residue from (III) giving in (I). No differentiation is observed in the effect of residual insol. P (VIII). During this period (I) factor-Z (yeast extract) on the growth of large or diminishes slightly during leaf fall, (I)-j-(II) shows a small plants of Antirrhinum atardata (Stubbe). Ex slight increase, (IV) a slight continuous decrease, traction of factor-Z from Stockholm brewer’s yeast (VIII) remains const., (V) and (VI) exhibit a parallel (cf. Borchardt et al., A., 1934, 1035) and from barley and marked decrease, whereas (VII) undergoes a embryos (best sourcc) is described. J. W. B. corresponding increase, (V), (VI), and (VII) being the most affected by the fall of the leaves. J. W. B. Electrical behaviour of large plant cells. W. J. V. O s t e r h o u t (Cold Spring Harbor Symp. Forms of nitrogen in infusions of maize, Quant. Biol., 1933, 1, 125—130).—Phase-boundary timothy, red clover, tobacco, and red top. W. S. potentials and potentials in living tissues due to E is e n m e n g e r (J. Agric. Res., 1934, 4 9 , 375—378).— Donnan constraints are usually small. Oxidation- Analytical data show the N partition in the various reduction potentials do not account for the electrical infusions. In all cases NH3-, protein-, and proteose-N behaviour of cells. Diffusion potentials have been were present. A. G. P. studied for multi-nucleate cells. The non-aq. surface Chemical composition of certain aquatic appears to be a mixture of substances, some of which plants. H . J. H a r p e r and H . A. D a n ie l (Bot. may be removed and still leave a non-aq. layer. Gaz., 1934, 9 6 , 1S6— 189).—The N, P, and Ca Anesthesia may be produced by removing certain contents of a no. of species are recorded. The substances from the cell. Ch . A b s . influence of algae on the classification of natural waters Osmotic pressure in relation to permeability is discussed. A. G. P. in large plant cells and in models. W. J. V. Seasonal variation of hydrocyanic acid in Osterhout (Cold Spring Harbor Symp. Quant. Molinia ccerulea, Moench. A. J u il l e t and R. Biol., 1933, 1, 166— 169).—The plant ccll maintains Z it t i (Compt. rend., 1934,1 9 9 , 1150— 1152).— Details a higher osmotic pressiire inside by manufacture of are recorded of the distribution of HCN in the various sugar or sol. salts, and by accumulation of inorg. parts of the plants and of its variation with the course such as KC1. ' Ch. A b s . of the season. Desiccation and preservation cause Permeability of protoplasm to alcohols. H. marked diminution of the cyanogenetic complex. Zihetner (Jahrb. wiss. Bot., 1934, 8 0 , 505—560).— The quantity of HCN disengaged by an organ is not „^Parison is made of the penetration of EtOH and modified by addition of emulsin to the macerated cells and the mechanism of the process is mass, whereas contusion, previous to maceration “ seussedX A. G. P. which precedes distillation, does not permit the action balance of'ionic sodium and calcium and cell- of the enzyme on all the glucoside. H. W. o m £ s (Compt. rend. Soc. Drift of the potassium and calcium content %!•, 1934, 1 1 7 , 796—797).—Aq. NaCl or CaCl2 with age in plants. A. H. K. P e t r ie (Austral. Penetrates sections of turnip root to an extent such J. Exp. Biol., 1934, 1 2 , 99— 110).—The total K - a \r^e, is the same with both salts. With in Lolium perenne rises to a max. at maturity or -i- ÄaCl-}-CaCl2 in varying proportions, max. pene- during senescence and then declines, whilst Ca rises .on of Cl' and min. toxicity (as indicated by the until late senescence without appreciable subsequent survival period of the tissue) occur with Na*: C a "= decline. The relative amount of K declines during the aPprox. 19:1. F. O. H. life-cycle; that of Ca declines during adolescence, 266 BRITISH CHEMICAL ABSTRACTS.— A. subsequently remaining const, or slightly rising. n a r d (Contr. Boyce Thompson Inst., 1934, 6, 297— The mechanisms involved in the drifts of K and Ca are 302).— By a system of in-arch grafting and pruning, discussed. W. 0. K. salts and elaborated foods may be made to move both Significance of manganese in plants. N. C. upwards and downwards in stems. A. G. P. Nag (Trans. Bose Res. Inst., 1932— 1933, 8, 179— Chemotropic sensitivity of dicotyledonous 194).—The Mn content of the leaves of various species seedlings. J. K is s e r and I. B e e r (Jahrb. wiss. of Coniferie increases markedly during female flower Bot., 1934, 8 0 , 301— 335).—Deviation of seedling production; the cones also have a high Mn content. stems following the application of salt solution to an In Abies balsamia the Mn content rises from 155-0 incision on one side of the stem depends 011 the concn. p.p.m. in October to 430-5 during female inflorescence. of the solution used and the period of treatment. The Mn content of chlorotic leaves is < that of normal High concns. caused a positive curvature (I) in all green leaves. P. G. M. cases as a result of mechanical and osmotic effects. Symptoms of malnutrition manifested by With small concns. negative (I) observed is due to sugar cane grown in culture solutions from unequal growth following chemotropic response. The which certain essential elements are omitted. latter was most marked with LiCl, NH4C1, and MnCl,. J. P. M a r t in (Hawaiian Planters’ Rec., 1934, 38, 3— less with NaCl and KC1, and did not occur with CaCl2, 31).—The effects of deficiencies of N, P, K, Fe, M n, SrCl2, BaCl2, or MgCl2. A. G. P. M g, and Ca on the development of the various plant Salt concentration and reversibility of ice organs and on chlorosis are recorded. Pylhium root form ation as related to the hardiness of winter rot was severe in plants deprived of P and of S, but wheat. S. T. D e x t e r (Plant Physiol., 1934, 9, very slight where N was omitted. Ch. A b s . (p) 601— 618).—Withdrawal of H20 by ice formation in Boron deficiency in sugar cane. J. P. M a r t i n wheat crowns is not a fully reversible process, but (Hawaiian Planters’ Rec., 1934, 38, 95— 107).—Nor reversibility increases as hardiness (I) develops. The mal growth occurred in the presence of 0-22 p.p.m. of proportion of H20 remaining unfrozen (II) decreases B (as H3BO3) in media. Depressed growth with with the freezing temp. Increasing (I) of plants with distorted and chlorotic leaves due to B deficiency re the advancing season is associated with a declinc in semble symptoms of “ pokkah bceng ” disease. sol. salt content of the tissues and a marked decrease Ch. A b s. (p) in the salt concn. of (II). A. G. P. Effect of boron on development of sugar-beet Accum ulation of electrolytes. VII. Organic in water cultures. M. A. B e l o v s o v (Trans. Centr. electrolytes. I. A. G. J a c q u e s (J. Gen. Physiol., Sci. Res. Inst. Sugar Ind. U.S.S.R., 1932, No. 8, 1934, 1 8 , 235—242; cf. A., 1934, 1049).—The 50— 59).—The presence of H 3B 0 3 (0-5— 10-0 mg. cation : anion ratio of the inorg. constituents of the per litre) favourably affects the growth of beet. saps of Rheum rhaponticum, Rumex acetosella, and Absence of B prevents growth. Concns. > 25 mg. per litre are injurious. The injurious action of heavy Oxalis corniculata varied between 1-8 and 5-3. H. D. metals is counteracted by addition of H 3B 0 3 to the Elementary com position of som e cultivated medium. Ch. A b s . (p) plants. G . B e r t r a n d and V. G h it e s c u (Compt. [Report on] botany research [sugar-cane]. H. rend., 1934, 1 9 9 , 1269— 1273).— Complete analyses E v a n s (Mauritius Rept. Agric. Sugar Cane Res. Sta., are recorded of rape, lucerne, buckwheat, and oats. 3rd Ann. Rep., 1932, 29—46).— Cane arrows, cut and A. G. P. placed in H20, wilt in 12 hr. because the vessels are Relationships of soils to manganese deficiency blocked with reddish-brown substance produced by of plants. G. W. L e e p e r (Nature, 1934,1 3 4 , 972— oxidase and peroxidase. Reducing agents (H2C20 4 or 973).—A method for determining the available Mn S02), also H3P 0 4 and H2S04, prolong Hfe, but are toxic is described and a mechanism for absorption by plants later. Invert sugar is less effective. Germination of suggested. Healthy soils contain > 100 p.p.m. Mn cane cuttings is increased by soaking in aq. Ca(OH)2 deficiency diseases occur with < 15 p.p.m. L. S. T. (I) for 8— 12 hr. Cane borer larva; in cuttings are killed Determination of sm all quantities of alumin by (I) alone or containing MgS04. Ch . A b s . (p) ium in plants.—See this vol., 186. Pathological effects of deficiency or excess of “ Stony” concretions in the trunk of Cliloro- certain ions on citrus leaves. J. D u f r e n o y and pliora excelsa, Bth. L. A d r ia e n s (Bull. Agric. H . S. R e e d (Ann. Agron., 1934, 4 , 637— 653).— Salts Congo Beige, 1934, 2 5 , 86—90).—Brown concretions of Zn and Fe have a sp. effect on the assimilatory func in the cavitv and trunk wood contain Mn and tion of leaves. Cytological examination of leaves of Zn- 94% of CaCOg. Ch. „ deficient trees is recorded and discussed in relation to mosaic disease. A. G. P. Composition of juice of oranges from girdled Biology of halophytes. I. Physiology of and normal trees. C. G. C h u r c h (Calif. Citro- graph, 1933, 1 8 , 348— 349).--Juice of fruit from germination. E. Sc h r a t z (Jahrb. wiss. Bot., 1934, girdled trees had higher proportions of sol. solids, 8 0 , 112— 142).—Retarded germination caused by NaCl solutions and sea-HaO is due to the high concn. total and reducing sugars. Sucrose and citric acid of salts rather than to any sp. action of NaCl contents were normal. Ch. Abs. (?) A. G. P. Bog-moss. I. Chemical composition of Reversal of direction of translocation of solutes Sphagnum firnbriaturn, Wils." (Himemizugoke)- in stems. P. W. Z b im e r m a n n and M. H. C o n - M. Sh ik a t a and M. W a t a n a b e (Proc. Imp. Acad- BIOCHEMISTRY. 267 Tokyo, 1934, 10 470— 471).—The composition is bark furnishes 0-1% of an alkaloid, C23H260 4N2, m.p. compared with that of wood-pulp. J. L. D. 27.0° (decomp.), which yields an unstable hydrochloride, completely decomposed at 240°. The symptoms of a Amanita toxin. J. R e n z (Z. physiol. Chem., dermatitis caused by the leaves are described. 1934, 2 3 0 , 245—258).—The most active prep, of the toxin (I) is obtained by adsorption of inactive A. E. 0. substances from the MeOH extract (of Amanita Pigment of “ Adsuki bean." C. K u r o d a and M. W a d a (Proc. Imp. Acad. Tokyo, 1934, 1 0 , 472— phalloides, Fr.) on Si02 gel and Al(OH)3, subsequent pptn. with phosphotungstic acid (II), fractional 474).—A purple-coloured material, decomp, at 235° (Pb salt), and substances, m.p. 157° and decomp, decomp, of the ppt. with basic Pb carbonate in H20, and final dialysis. (I), thus obtained, gives no ppt. at 235°, which are found in the testa (isolation des with (II) or Hg(OAc)2 (cf. Raab, A., 1932, 785) cribed) give, with alkali, s-C6H3(OH)3 and proto- except in presence of KOI, NaCl, or NH4C1, but is catechuic acid. A phlobatannin-like substance, pptd. by Ba or K Bi iodide. (I) gives Pauli’s diazo- decomposed by alkali to s-CfiH3(OH)3 and gallic acid, is also isolated. J. L. D. reaction, reduces KMn04 (not Fehling’s solution), could not be reduced (H2, PtO,, MeOH), does not Anthocyanin plant colours and yield in maize. react with CH2N2, and gives no colour with ninhydrin. R. A. B r in k (J. Amer. Soc. Agron., 1934, 2 6 , 697— Appropriate acylation of (I) in C5H 5N affords the 703).—Relationships between inheritable yielding Bz, M about 800 (hydrolysed with difficulty), anisoyl, capacity and the presence of plant pigments are rn.p. about 175° [readily hydrolysed (EtOH-NaOEt examined. A. G. P. or -KOH) without much loss of activity], and (probably) the ON-^lc, derivative (III), m.p. 190— Indian acorn oils. S. V. P u n t a m b e k a r and S. 195° (decomp.; sinters at 158°) [not hydrolysed by K r is h n a (J. Indian Chem. Soc., 1934, 1 1 , 721— 2iY-H2SO,, at 30°; hydrolysis with conc. acid or 726).—The oil from the acorn kernels of Quercus MeOH-KOH gives an inactive product]; these are incana, Roxb., yields palmitic (17-1), oleic (and amorphous H20-insol. [except (III)] powders. (Ill) isomeric) (82), and (?) lignoceric (0-9%) acids, and and conc. KOH in N0 at 130° give NHMe2 and contains a small amount of (?) sitosterol, m.p. NH3. “ H. B. 126— 128°. R. S. C. Differentiation of the toxin ricin and of an Chinese citrus fruit. VII. Isolation of essen allergen in castor-oil seeds. Preparation of tial oils from Fu Chii and Chao Kan. P. P. T. ricinallergen. P. G r a b a r and A. K o u t s e f f S a h and H. Y. F a n g (J. Chinese Chem. Soc., 1934, 2, (Compt. rend. Soc. Biol., 1934, 1 1 7 , 700—701, 702— 266—270; cf. A., 1933, 755).— CgHe containing some 704).—Seeds of Ricinus zanzibariensis contain the CHC13 extracts an essential oil and a substance, toxin ricin (I) and the allergen ricinallergen (II), m.p. 60° (which contains no N), from F u Chii (I) and whilst the rind of the seeds contains only (II). (I) Chao Kan (II). The oil from (I) contains cZ-limonene is destroyed by heating to 60° and by EtOH, (II) (III), and has a high sap. val. and N content, remaining unaffected. (I) and (II) may be separated whereas that from (II) is about 94% (III). J. L. D. from one another and from the dried and oil-free seeds by ultrafiltration or pptn. with (NH4)2S04. Essential oil in the ripe Fu Chii [tangerine] A method for separating a non-toxic prep, of (II) is fruit. W. S. T a o and C. M. C h u (J. Chinese Chem. described. A. L. Soc., 1934, 2 , 282—287).—Light petroleum or Et20 Pharmacologically valuable constituents of extracts from the skins an essential oil (3-8— 4-9%) Rixa orellana, L . P. W. F r e is e (Pharm. Zentr., which contains mainly d-limonene and some aldehyde. 1935, 76, 4—5).—Proximate analyses of the fruit, J. L. D. husk, and seeds are given and also the medical Constitution of the primary alcohols, fatty application of preps, of the fruit pulp, whole seeds, acids, and paraffins present in plant and insect seed husk, unripe fruits and their husks, and of the waxes. A. C. C h ib n a l l , S. H. P ip e r , A. P o l l a r d , fresh leaves. E. H. S. E. F . W il l ia m s , and P . N. S aeiai (Biochem. J., 1934, 2 8 , 2189—2208).—Analysis by use of the data given Entandro )hragma jiahistris, Staner. L. 2 previously (this vol., 264) of many plant and insect Tdion (Bull. Agric. Congo Beige, 1934, 2 5 , 21—25).— waxes shows that the alcohols are mixtures of the The bark contains resin, fluorescent material sol. in even-no. members from C24 to C36, the acids mixtures ■■HQ, pyrocatechol, an alkaloid, a tannin (catechuic of even-no. w-fatty acids from C24 to C34, and the ■ tf), and certain phlobaphens. Ch. A b s . (p) paraffins mixtures of the odd-no. members from ICohatituents of] Ceanothus velutinus. L. W. C25 to C37. Even-no. paraffins do not occur. The «■CHARDS'and E. V. L y n n (J. Amer. Pharm. Assoc., approx. composition of the various waxes is indicated. 1 3.?’ 332^336).—The leaves of C. velutinus pre- C. G. A. rnicroscopicaHy^a,_pecuhar structure, not found in Odorous principles of green tea. III. Acids Ci«er species, which may be related to the charac- of raw tea oil. S. T a k e i , Y. S a k a t o , and M. O no enstic balsamic coating. They furnish 0-14— 0-21% (Bull. Inst. Phys. Chem. Res. Japan, 1934, 1 3 , 1161— 0 an oil which consists chiefly of Et and cinnamyl 1168; cf. A., 1934, 571).—The oil from fresh tea-leaves cianamates, with smaller amounts of salicylaldehyde, contains AcOH, EtC02H, PrC02H, valeric, w-hexoic «rpenes, and esters of an unidentified alcohol (di- (I), and palmitic (II) acids. The oil from manu nylurethane, m.p. 56°; phthalate, m.p. 204—205°) factured green tea contains only (I), (II), and heptoic V1tn cinnamic and probably valeric acids. The root acid, and 0-0 H-C6H4*C0 2Me. R. S. C. 268 BRITISH CHEMICAL ABSTRACTS.— A. Crystalline principles from Indian species of eosin and erythrosin are utilised for staining cellulose Artem isia. A n o n . (Pharm. J., 1935, 1 3 4 , 3—5).— in plant sections. Liquefied tissue, cork, and pith From various species of Artemisia were isolated cells are unstained. The free base of methylene-blue santonin, ¡3-santonin (A., 1934, 1225), and ^-san is similarly used for staining liquefied membranes. tonin, m.p. 184— 186°, [a]20 -172-5° in CHCL. A. G. P. F. 0. H. Chemical composition of ripe Huang Yen Chii Marrubiin content of some Labiatic. J. B a l a n - [Citrus species]. W. S. T a o , S. Y . Y a o , and C. T. s a r d (Compt. rend. Soc. Biol., 1934, 1 1 7 , 1014— Liu (J. Chinese Chem. Soc., 1934, 2, 274—281; 1015).—Marrubiin (I) is present in a large no. of cf. A., 1934, 818).—In Chu Hung Chii the acid, indigenous Labialce. The active principle, m.p. reducing sugar, pentosan, and cellulose contents 188— 189°, of Tenerium scordium is, however, not (I). are > in the variety Shih Chii. J. L. D. A. L. Structure of proteins. M. A. L is it z u in (Bull. Heteroside of Primula acaulis, Jacq. A. G o r is Appl. Bot. Genetics, Plant Breeding U.S.S.R., 1934, and H. C a n a l (Compt. rend., 1934,1 9 9 , 1675— 1677). A, No. 9, 5—16).— Globulins of peas, beans, and soya —The isolation of pure primulaveroside (I), beans are examined and classified as “ proto-acids.” C18H220u (0Me)2-f-H20 and anhyd., m.p. 179-5— 180° Ch . A b s . (p) (corr.”), [a]D —57-74° in H20, from the rhizomes of Protein. XIII. Proteins of soya bean. T. P. acaulis, and its separation from the volemitol H ib in o (J. Chem. Soc. Japan, 1934, 55, 655—692).— present, are described. Enzymolysis of (I) with the The isolation of albumin, glycinin (I), and glutelin sepal powder of P. officinalis, L. (II), affords prime- is described. The hydrolysis of (I) at different temp, verose and Me 2-hydroxy-5-methoxybenzoatc and pn yields varying proportions of sol. protein, (structure confirmed by synthesis). (I) is accompanied proteose, and peptone and of insol. substances. by traces of a ketonic substance [2 : 4-dinitrophenyl- Min. amounts of sol. matter are obtained at 120° hydrazone, m.p. 230° (decomp.)]. (I) occurs with at the isoelectric point. The reaction at 150° is primcveroside in (II). J. W. B. reversible. C h . A b s . (p) Glucoside and a hydrolysing enzyme in the Protein content of barleys at different stages bark of Pcriploca grceca, L. T. S o l a c o l u and of m aturity. K. G. S c h u l z and G. K unisch H e r r m a n n (Compt. rend. Soc. Biol., 1934, 1 1 7 , (Woch. Brau., 1934, 51, 321— 323).—The protein 113S— 1140).—Pcriplocymarin (I), m.p. 149— 152°, content (I) of barley is influenced by the rainfall during occurs in the bark (II) with periplocin (III), from the principal period of development of the plant, by which it is formed by loss of 1 mol. of glucose. The the nature of the previous crop, and by the soil. In ratio (I) : (III) in (II) is approx. 0-02%. (II) also most of the samples examined, a low proportion of contains an enzvme which hydrolyses (III) to (I). available H20 (judged from soil and rainfall statistics) R. N. C. gave high (I), and vice versa. I. A. P. Polysaccharides of Iridcea laminaribides. T. Chemical properties of proteins of Iridcea T a d o k o r o and K. Y o s h im u r a (J. Chem. Soc. Japan, laminarioides. T . T a d o k o r o and K. Y osiiimura 1934, 5 5 , 617—621).— Hydrolytic products of a (J. Chem. Soc. Japan, 1934, 55, 525—527).—Two 35% EtOH extract included pentose, methylpcntose, proteins arc examined, (i) a chromoprotein, sol. in and arabinose. A hot-H20 extract contained in salt solutions and 30—35% EtOH, with N-containing addition galactose, glucose, and fucose. products of hydrolysis unlike those of phycoerythrin, C h . A b s . (p) (ii) sol. in hot H20 and 2% NaOH, similar to pro Spruce holocellulose and composition of its lamine. Ch. A b s . (p). easily hydrolysable fraction. E. F. K u r t h and Proteins of the seeds of the tobacco plant. G. J. R i t t e r (J. Amer. Chem. Soc., 1934, 5 6 , 2720— 2723).—The holocellulose (I), isolated from the saw G. I l j i n (Biochem. Z., 1934, 273, 350—353).—The dust by a slight modification of the method previously fat-free seed (I) contains 7-8% of albumin, 8-5% of described (B., 1934, 12), contains all the Ac (cf. globulin (II), and 2-75% of glutenin. The N content Hiigglund, A., 1934, 819), all C02-forming material, of (I) is > that of (II) from other plants. The P about 12% of the OMe, and nearly all the pentosans contents of the separate proteins differ considerably, of the extracted (EtOH-C6H6 and hot H20) wood whilst the S contents are similar. W. McC. (II). Hydrolysis (2-5% H2S04) of (I) or (II) gives Phosphorus in vegetable proteins. I. Glob HC02H [0-56% based on (I)] and AcOH (about ulins of Lathyrus sativus and Vicia sativa, vap 1-95%). Hydrolysis (1% H2S04) of (I) removes a augustifolia. Y. Y. S. R a u (Proc. Indian .^ a . fraction (hemicellulose) [=10-3% of (II)] of the Sci., 1934, 1, B, 73—79).— Data are giveu^ 1---^0 following composition: mannose (17-7%), glucose N, P, and S contents and the N distribution in the (8%)> galactose (7-8%), arabinose (12-5%), and globulin and albumin of L. sativus (khesari) and m xylose (20-9%) anhydrides; OMe (3-2%); uronic the globulin of V. sativa (akta). The l a t t e r contains anhydride (14-6%); volatile acids (8%). The no P, a small fraction [separated by (NH4)oSU4] residue [ = 61% of (II)] from the hydrolysis appears containing approx. 10% P being probably an albumin. to be identical with the Cross and Bevan cellulose. / p. 0. H. H. B. Preparation of white zein f r o m yellow c°rn- Substitution staining with free dye-acids and I. D. M a s o n and L. S. P a l m e r (J. Biol. Chem., 1934’ -bases._ R. C. M c L e a n (New Phytol., 1934, 33, 107, 131— 132).—Fat and pigments are extracted 316—317).—Solutions in xylene of the free acids of with C2H4C12 from 95% EtOH solution. H. G. R. BIOCHEMISTRY. 269 Feulgen's nucleal reaction. A. E ic h h o r n and examined the min. concn. inhibiting G was lowest in R. F r a n q u e t (Compt. rend. Soc. Biol., 1934, 117, buffered solutions of quinol, followed in increasing 326—328).—The results of staining cell nuclei, order by o-cresol, anisic and benzoic acids, pyro- chromosomes, etc. of various plant tissues are dis catechol, guaiacol, and PhOH. In unbuffered solu cussed (cf. A., 1933, 105). No interaction between tions the influence of pa accentuates the effects. nucleolus and chromosomes during mitosis is evident. Expressed juices from wheats exhibited inhibitory P. 0. H. effects which showed varietal differences. No re Distribution of non-protein-nitrogen in the lationship was apparent between the inhibitory action Alaska pea. S. L. J o d i d i (J. Franklin Inst., 1934, of the juice and the resistance of the variety to rust 218, 581—591).—The acid-amide-N (7-58—8-13%) infeotion. A. G. P. of Alaska pea seeds grown on untreated soil is increased Effect of mildew and rust infection on dry to 9-02 and 10-89— 11 -43% by fertilising with NaN03+ weight and respiration of excised clover leaflets. (NH4),S04 and KC1, respectively; the NH2- and C. E. Y a r w o o d (J. Agric. Res., 1934,49, 549—558).— peptide-N vals. are S-43—8-59, 9-72, 6-04—7-92, Infection decreased the dry wt. and markedly increased and 39-08— 41-83, 33-28, 36-06—37-64%, respectively. respiration (I) in clover leaflets. Dusting with S The bearing of the data on the vals. of nutritive increased the (I) of healthy and infected leaflets. non-protein-N is discussed (cf. A., 1932, 312). A. G. P. F. O. H. Chemistry of vegetable tumours. IV. Per Occurrence of organic bases, especially of oxidase in the tumours. G. K l e in and W. Z ie s e cadaverine in potato tubers. K , Y o s h i m u r a (Biochem. Z ., 1933, 267, 22—25; cf. A., 1933, 315).— (Biochem. Z., 1934, 274, 408-^11).—From 20 kg. The peroxidase content (I) of tumours (II) in horse of fresh materials the following bases were isolated : radish roots (III) is much (up to 100%) > that of adenine (as picrate) 0-2 g .; trigonelline (as chloride) roots of the healthy plant and the (I) of the thick 0-2 g.; cadaverine (as chloride) 0-1 g .; choline as upper parts of (III) is > that of the small branches of aurichloride 0-5 g. Histidine and arginine were also the roots. Young (II) have lower (I) than old. present. P. W. C. W. McC. Preparation of aqueous extracts of soluble Nature of injury to forage legumes by the nitrogen from plant tissues. O. W. D a v id s o n , potato-leaf hopper. H. W. J o h n s o n (J. Agric. H. E. Cl a r k , and J. W. S h iv e (Plant Physiol., 1934, lies., 1934, 49 , 379— 406).—Yellow and reddened 9. 817—822).—Boiling the material with H20 for leaves of lucerne and clover caused by leaf hopper 20 min. followed by washing on a filter cloth was as injury have higher contents of dry matter, reducing effective as cold-HaO extraction after grinding with sugars, sucrose, starch, total hydrolysable matter, and sand. Loss of N from cyanogenetic material in peach EtOH-sol. N, but lower total N, than normal green was minimised by the boiling method. A. G. P. leaves. Also the osmotic pressure of the sap is in creased. Similar changes arc produced artificially Variations of the quantity of tannin during by girdling the stems. Coloration of leaves of infested the development of the gall-nuts of the oak. plants is due to excessive accumulation of carbo H. Grossu -H e r r m a n n (Compt. rend. Soc. Biol., hydrates in areas in which vascular tissues are injured 1934, 117, 1127— 1131).—-Tannin in Dryophanta folii by the insects. A. G. P. gall-nuts rises to a max. in midsummer, falling to a Photodynamic action of methylene-blue on the min. in early autumn. In Cynips hungarica the virus of a plant disease. H. H. St o r e y (Ann. tannin reaches its max. in late summer. In both Appl. Biol., 1934, 21, 588— 589).—The virus of streak species the max. occurs simultaneously with max. disease in maize is inactivated by exposure to light morphological development. R. N. C. in the presence of methylene-blue and 0 2. A. G. P. Quantity of oil in linseed and hemp seed dur Fungi associated with blight diseases of cer ing different periods of maturation and germin tain cultivated leguminous plants. A. Sa t t a r ation as well as in birch and lime trees during (Trans. Brit. Mycol. Soc., 1934, 18, 276—301).—- different phases of winter. J. D m o c h o w s k i Growth of Ascochyta jnTwdella, A. jnsi, Mycospliaerella (Polish Agric. Forest. Ann., 1934, 3 2 , 35— 77).— Dur- pirioides, and Phylloslicta rabieri was fairly rapid in !ng normal maturation the oil (I) of linseed and hemp the pa range 4-0—8-8 (optimum, 7-0), declined rapidly ^creases to a max. as the seeds dry. No increase between 4-0 and 3-0, and ceased between 3-0 and 2-4. occurs during drying of shelled seed under germinating C h . A b s . (p) ^(litions. (I) declines and disappears in 24 hr. H20 Virus causing foliar necrosis of the potato. is for transformation of oil. In birch and F. C. B a w d o n (Proc. Roy. Soc., 1934, B, 116, tree>“changes in (I) and H20 content during 375—395).—A new potato virus “ D ” (I) is described. ^ier and spring are inversely related. In some species this causes foliar necrosis and in others w ^ C h . A b s . (2>) •Nature of rust-resistance in wheat. VI. top-necrosis. (I) confers a resistance to further infec ect hydrogen-ion concentration, phenolic tion with virus “ X ” and vice versa, the extent of ompounds, and host extracts on germ ination which depends on the species of the host. H. G. R. urediniospores of Puccinia graminis tritici, Photodynamic action of methylene-blue on 21. J, a . A n d e r s o n (Canad. J. R es., 1934, plant viruses. J. M. B ir k e l a n d (Science, 1934, ■ oG /—686).—The optimum pa for spore germin- 80, 357—358).— In general, plant viruses such as 1 10n (G) was 5-8— 6-5. Among a no. of compounds tobacco virus and streak virus are more resistant to 270 BRITISH CHEMICAL ABSTRACTS.— A. the photodynamic action of methylene-blue (I) than of n and d, and by observation of the fluorescence in are animal viruses or bacteriophage. Ringspot virus, ultra-violet light. E. C. S. however, in presence of (I) is quickly inactivated by exposure to electric light. L. S. T. Blood-iodine. III. Reservoir burette. F. J. P h il l ip s and G. M. C u r t is (J. Lab. Clin. Med., Serum reaction as an aid in the study of filter 1934, 1 9 , 896—898).—A 0-2-c.c. Kahn pipette, able viruses of plants. H. P. B e a l e (Contr. Boyce graduated in 0-001 c.c., is attached to the reservoir Thompson Inst., 1934, 6, 407— 435).—Serological tube of a Koch burette by means of a 3-way stopcock. reactions of tobacco mosaic virus are examined and Ch . A b s . a method is described for determining the antigenic Iodometric determination of sugar in presence content of saline extracts of virus. A. G. P. of thiocyanate. D. K r u g e r and E. T schirch (Biochem. Z., 1934, 2 7 4 , 34— 41).—The influence of Action of high-frequency sound waves on pa and concn. of K I , Cu, and CNS' on the titration of tobacco mosaic virus. W. M. St a n l e y (Science, Cu is investigated and the most suitable composition 1934, 8 0 , 339—341).—-The data given indicate that of the required solutions is outlined. P. W. C. the inactivation of the virus by supersonic radiation (A., 1934, S22) is associated with expulsion of dissolved Galactosuria test of Fiessinger. Application gas and with the presence of extraneous matter in of the method of Fleury and Marque to the the untreated juice. Intense high-frequency sound determination of galactose in urine. R. H azard, waves have practically no cffect on virus purified M. H e r b a in , and C. V a il l e (J. Pharm. Chim., 1935, under a high vac. L. S. T. [viii], 2 1 , 61— 71).— The K I - H g I 2 method of Fleury and Marque (A., 1929, 292) may be used for the Spreading in a unimolecular film. Method determination of galactose in urine. W. 0. K. for biological problems. E. G o r t e r (Amer. J. Dis. Children, 1934, 47, 945— 957).—Technique of Determination of phenol. G. B a r a c (Compt. du Nouy and Langmuir is applied to determinations rend. Soc. Biol., 1934, 1 1 7 , 259—261).—A modific of lipase activity, fat, and lipins in blood, and protein ation of the method of Theis and Benedict (A., 1924, in solutions. Ch . A b s . (p). ii, 708) is used for the determination of PhOH in blood or urine. A. L. Accurate, adjustable gas-mixing apparatus for measurements of biological liquids. H. Colorim etric m icro-determ ination of chole S c h a d e and H. v o n P e in (Z. ges. exp. Med., 1934, sterol. S. G o r t z (Biochem. Z., 1934, 2 7 3 , 396— 7 6 , 540—548; Chem. Zentr., 1934, i, 1530). 412).—By combining the advantages of the methods L. S. T. of Rappaport and Engelberg (Klin. Woch., 1931, 700) Determination of the pa of normal and malig and Milbradt (A., 1933, 624) a simple procedure for nant tissues with the glass electrode and vacuum determining cholesterol in biological fluids, e.g., tube null indicator. H. M. P a r t r id g e , J. A . C. 0-1 c.c. of blood, is obtained. AcCl is used to produce B o w l e s , and A . G o l d f e d e r (J. Lab. Clin. Med., the strong, very persistent colour. The average 1934, 1 9 , 1100— 1105). Ch . A b s . (p) error is about 2% . W. McC. Electrical method for checking physiological Biochemical gravimetric methods. IV. salt solution. J. H. G r a h a m (Amer. J. Pharm., Micro-determination of cholesterol by the 1934, 1 0 6 , 325—327).—The concn. of physiological torsion balance. L. J e n d r a s s ik and A. B ok- NaCl solution (0-85%) is best checked by determin r £ t a s (Biochem. Z., 1934, 2 7 4 , 367— 371).—-A ation of its sp. conductivity. J. W. B. simplified method is described in which the pptn. is carried out at room temp, with dil. EtOH solutions Determination of iron in biological materials. of digitonin (I) and the ppt. collected on a Seitz T. G. K l u m p p (J. Biol. Chem., 1934,107,213—223).— asbestos filter and weighed. The method gives Knecht and Hibbert’s TiCl3 method (A., 1903, ii, 217, accurate vals. for blood-serum. By heating cholesterol 509) is modified and adapted to determination of Fe a substance arises which is no longer precipitable by in blood, food, facces, and urine. C. G. A. (I), but is still detected colorimetrically. P. W. C. Micro-detection of insoluble calcium salts in Determination of lactic acid by the method of tissues. G . G o m o r i (Virchow’s Archiv, 2 8 6 , 682— Mendel and Goldscheider. R. N o r d b o (Biochem. 689; Chem. Zentr., 1934, i, 3500).—The solubilities of Z., 1934, 2 7 5 , 162).—In the process described in A., Ag3P0 4 and Ag2C03 are < those of the corresponding 1934, 1050, the colour comparison is made after Ca salts. Immersion of tissue in 1-5% aq. AgN03 keeping the solution for 60 rain, in ice-H20. / for 6— 10 days results in transformation of Ca into Ag f ~v__ salts the presence of which is detectable by the hypo- Nephelometric investigation of protein solu phosphite test. The prep, is fixed in aq. Na2S203 tions. II. E. M. Mystkowski (Biochem. Z., 1934, and Ca is removed by sulphosalicylic acid. 2 7 4 , 461—464; cf. A., 1934, 1306).—A table sum A. G. P. marises the varying degrees of turbidity, determine« Identification of glass splinters. N. A. M a r r is nephelometrically, of an electro-dialysed solution ot (Analyst, 1934,5 9 , 686— 687).— The probable identity ovalbumin as compared with a commercial preP’ of two samples of glass, one of which was in the form at varying pa and in presence of NaCl, CaCl2, MgW»» of minute splinters, was established by determination MgS04, and Na2S04. P- W. 0.