BRITISH CHEMICAL ABSTRACTS
A —PURE CHEMISTRY
MARCH, 1936.
General, Physical, and Inorganic Chemistry.
Absorption spectrum of hydrogen. II. The Excitation of the auroral green line by meta D state in the term scheme of hydrogen from stable nitrogen molecules. J. K a p la n (Physical photographs of H 9 and D2. H. B e u t le r , A. Rev., 1936, [ii], 49, 67— 69; cf. A., 1934, 827).— Deubner, and H. 0 . J ü n ger (Z. Physik, 1935, 98, Jhc excitation in tubes which show the two new 181—197; cf. A., 1935, 1291). ' A. B. D. C. afterglow spectra of N2 is described. The conditions Ground state of (H2), the molecular ion (H2<), of excitation are compared with those in the night- and wave mechanics. 0. W. Richardson (Proc. sky and in the aurora borealis, in which cases, it is Roy. Soc., 1935, A , 152, 503— 514).— The agreement suggested, the LSq state of 0 which is responsible between the vals. of the fundamental consts. of the for the green line is produced by collisions of O atoms ground state of the H 2 mol. (i) as determined by and metastable N2 mols. in the A 8S state. experiment, and (ii) as calc, by wave mechanics, is N. M. B. discussed. The properties of the mol. ion (H2+) Hopfield’s Rydberg series and the ionisation as predicted by wave mechanics are compared with potential and heat of dissociation of nitrogen. those predicted empirically from a study of various R. S. M u llik e n (Physical Rev., 1934, [ii], 46 144 - excited states of (Ii2). ' . ' L. L. B. 146; cf. A., 1931, 1343). L. S. T. Fine structure of Da with increased resolution. Predissociation of the oxygen molecule. P. J R. C. Williams and R . C. G ibbs (Physical Rev., F lo r y (J. Chem. Physics, 1936, 4, 23— 27).— Opticai 1936, [ii], 4 9 , 40; cf. this vol.. 127).—A correction. data for 0 2 are interpreted as indicating that the N. M. B. initial process in the photochemical reactions of 0 2 Energy states of doubly excited helium. T. Y. due to light in the region of Schumann-Runge band Wu (Physical Rev., 1934, [ii], 4 6 , 239). L. S. T. absorption is the formation of normal 3P atoms by predissociation rather than the reaction of an optically Doubly-excited states in helium. F. G. Fender excited mol. with a normal, mol., as hitherto supposed and J. P. V in ti (Physical Rev., 1934, [ii], 46 , 77— M. S. B. 78)' L. S. T. Arc spectra of fluorine and potassium. B. Absorption of fluorspar [transmitted] ultra E d lü n (Z. Physik, 1936, 98, 445—460).— 85 F i violet light by carbon black, gold, and rhombic lines between 6000 and 9500 A. are tabulated. sulphur. G. R a th e n a u (Physica, 1936, 3 , 42— 60). A. B. D. C. 0 black has an absorption max. at approx. 2500 A., Intensity measurements in the spectra of and a min. at approx. 1700 Ä .; Au has an absorption neon and argon excited by electron collision. niax. at about the latter A. S layers, transparent to O. H errm a n n (Ann. Physik, 1936, [v], 25, 143— n tra-violet light, were made by vaporisation in vac. 165).—Efficiency determinations for the excitation o?J;0»a k'aF2 plate at —80°. S absorbs at about of the Xe and A spectra by electron collision have been A., and there is another band at 1800 A. The made by an abs. method. The scattering of electrons results are discussed in relation to the at. and mol. and their angular distribution are taken into account. spectra, A . j . M. The abs. yield and excitation probabilities for 54 A Light yield in the nitrogen spectrum excited lines, and the excitation functions for 52 A and 16 Ne f ™ ° n collision. O. Herrmann (Ami. Physik, lines are recorded. Comparison of the abs. yields of 7 36, [v], 25, 166—•184).—-The excitation function X e and 7 A lines belonging to the same term shows no simple connexion between the two gases. vi ,, ,neSa^ve bands of the X spectrum and the abs. } ie d for 3 negative and 5 of the second positive A. J. M. gioup of N2+ and X 2 band spectra have been deter- Intensity distribution of neon lines. E. Lau (Physikal. Z., 1936, 37, 110).—Polemical against mmed- " A. J. M. Schütz el al. (A., 1935, 907). A. J. M. Dependence of intensities of rotation lines of band on the conditions of excitation. 0. [Intensity distribution of neon lines.] W. R errsiann (Physikal. Z., 1936, 37, 100— 103).— S ch ü tz (Physikal. Z., 1936, 37, 110— 111).— A reply to the above. A. J. M. ^ IC Iincs in the II branch of the j ,an °.f t*le negative X, group at 3914 A. have Absolute transition probability of potassium. ... -1 determined for excitation with electrons of E. F. M. van d e r H e ld and J. H. H eierm an (Physica, various velocities. A. J. M. 1936, 3, 31— 41).— The abs. intensity of light emitted 261 I {a, b) 262 BRITISH CHEMICAL ABSTRACTS.— A. by K atoms in a C2H2-air flame, the flame temp., New “ bright” method for investigation of and the no. of emitting particles have been deter the Stark effect with a homogeneous field. W. mined, and the abs. transition probabilities of the Stettbtng and J. A. S c h a e d e r (Ann. Physik, 1930, resonance lines of Iv calc. The abs. transition prob [v], 25, 97— 123).— The method enables very bright abilities were also obtained for the sharp and diffuse spectra to be produced in a measurable homogeneous series by photographic comparison with the resonance electric field, and makes it possible to examine the lines, using light of known colour temp. A. J. M. Stark effect of some atoms and mols. which are difficult to excite by other methods. A. J. M. Arc spectrum of rubidium. K. W. M e is s n e r Analysis and interpretation of the nebular (Z. Physik, 1935, 98, 353—354). A. B. D. C. spectrum of Nova Herculis. M. B lo c h and J. Fine structure in the (2D) series limit terms D u e a y (Compt. rend., 1935, 201, 1463— 1465).— o f the 1+ sp ectru m . S. T o la n s k y (Proc. Physical Lines are due to H i, He I, He n , O n , N n , C ii, Soc., 1936, 48, 49— 56; cf. A., 1935, 137).— Classi 0 m , N m , and probably C m . T . G. P. fications and fine-structurc data are tabulated for Absorption of monochromatic X-ray beams, I +, and fine structure analyses of 14 lines of the -D of wave-length in the region 50—20 X units, in system and interval factors for 12 terms are given. lead, tin, copper, and iron. J. R e a d (Proc. Roy. Large interval factors associated with the 5d electron Soc., 1935, A , 152, 402—417; cf. A., 1934, 577).— terms of the iS and 2Z> systems are correlated with A curve relating the absorption coeff. of Pb and the observations for Sn rt, and are due to perturbation Xhas been obtained. The photo-electric absorption by torms with large fine structure. Two types of coeffs. calc, from this are 7— 20% > corresponding perturbation in the fine structures arc observed. vals. obtained from Gray’s empirical law (A., 1931, 1 N. M. B. 281). L. L. B. Nuclear spin of iodine. II. Fine structure in Fluorescence X-ray yields from K shells of the arc spectrum and a fine structure perturb atom s. R. J. Stephenson (Physical Rev., 1934, a tion effect. S. T o la n s k y (Proc. Roy. Soc., 1935, [ii], 46, 73—74).—A criticism and a revision of vals. A, 152, 663—672; cf. A., 1935,137).—The fine struc (cf. A., 1934, 577). L. S. T. tures of 13 of the classified lines of the I arc spectrum Dose measurement of very soft X-rays. E. (6300— 4760 Á.) have been measured. The nuclear W il h e lm y (Pliysikal. Z., 1936, 37, 103— 107).—The spin is confirmed as 5/2. The 6s4P5/2 is perturbed. method employs an ionisation chamber of sufficient L. L. B. length to absorb the rays almost completely. Absorption spectra of cerium, neodymium, b A. J. M. and samarium. P. W. P aul (Physical Rev., 1936, Effects of chemical binding on the X-ray [ii], 49, 156— 162; cf. King, this vol., 2).—Data for Iiali2 doublet lines of sulphur studied with a XX and intensities of 600 Ce, 450 Nd, and 1500 Sm two-crystal spectrometer. L. G. P a r r a t t (Physi lines are tabulated in the region 12,000— 2500 A. cal Rev., 1936, [ii], 49, 14— 16).— Using FeS, Cu2S, N. M. B. MgS04, BaS04, and PbS targets, ionisation curves Absolute intensities in the spectrum of a were recorded, and effects of binding on X, on the low-pressure quartz mercury-vapour discharge a, a2 separation, and on the doublet contour were burner. A. J. M a d d o c k (Proc. Physical Soc., 1936, measured. The X shift of the S A a ,i2 lines from 48, 57—62).—Abs. intensities of tho main XX in the sulphates to sulphides was observed in the process of range 6000—2400 A. are tabulated and discussed shifting. N. M. B. theoretically in relation to results for high-pressure arcs (cf. A., 1935, 800). Therapeutic effects are Excitation potential of Iia 34 satellite lines. examined. Ar. M- L. G. P a r r a t t (Physical Rev., 1936, [ii], 49, 132— 139).— The 11% satellite lines intensity-A-ray tube Collision-induced emission. W . M. P r e s t o n voltage curve has been determined for the Ti A'%t (Physical Rev., 1936, [ii], 49, 140— 144).— A new lines. For voltages > 1 1 kv. the ratio satellite continuous spectrum associated with the weak intensity ¡TiK%1 line intensity is 2-21%; the ratio forbidden Hg 2269-80 A . line has been found in a of peak intensities a4/aj is 0-69%. The Ti A%,i low-pressure Hg discharge with a few cm. pressure excitation potential is 5450 ¿100 volts, in good agree of A or He added. It is attributed to radiation from ment with the calc, voltage, 5455, required to pro excited Hg atoms in the 3P2 metastable state perturbed duce a state of K L m ionisation in the Ti atom, by the close approach of rare gas atoms. N. M. B. and supporting the Wentzel-Druyvesteyn theory oi Thallium II spectrum. C. B. E l l i s and R . A. satellite line origins. N. M. B. Sa w y e r (Physical Rev., 1936, [ii], 49, 145— 150). A b so rp tion ra tio w ith in the JO-shell. H- The T1 spectrum from the hollow-cathode discharge S ch w a rz (Ann. Physik, 1935, [v], 23, 571— 588).-- in He has been photographed in the range 9250— Measurements of the fluorescence radiation of bn 600 A. Full data, classifications, and assignments excited by the K% lines of Cr (2-285 A.), Cu (1-54 A), for 115 previously known lines and 160 new lines and Mo (0-71 A .) lead to intensity ratios for the which locate 35 new levels are tabulated. N. M. B. three lines, which correspond with the three h- levels. A. J. M- Hyperfine structure and the depolarisation of resonance radiation by a magnetic field. A. Asymmetry of the electric charge distribution in the 80H g 201 nucleus. H. SoHULERandT. Schmidt E llett (Proc. Iowa Acad. Sci., 1934, 4 1, 251). Ch . A bs. (e) (Z. Physik, 1935, 98, 239— 251). A. B. D. 0. (I b-d) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 263
Emission constants of single- and poly-crys atoms. Total cross-sections for elastic scattering talline materials. A. R eoknagel (Z. Physik, 1935, are calc, in terms of three parameters related with • 98, 355—362).—Theoretical. Richardson’s emission band spectroscopy. Results for incident electron const. A for a single crystal can be double that for velocities 0 -4 0 volts for N2, 0 2, and H„ are in good polycryst. samples of the same material. A. B. D. C. agreement with experiment. “ N. 31. B. Thermionic emission from tungsten and thori- Electron attachment and ion formation in ated tungsten filaments. W. B. Nottingham g a s e s . W . R o g o w s k i (Z. Physik, 1935, 98, 399— (Physical Rev., 1936, [ii], 49, 78— 97).— Electron 414). The mass action law is applied with success emission has been investigated as a function of applied potential from a few volts retarding to 1400 volts to formation of ions in gases. A. B. D. C. accelerating. The electron energy distribution was Energy losses by positive ions to probes in deficient in slow electrons. The negative temp, the plasma of gas discharges. W. M o lt h a n (Z. coeff. of the work function for pure W is 4-3 xlO -5 Physik, 1935, 98, 227— 238).— Probe heating cc probe volt per degree. Electron emission data in acceler potential to 200 volts, indicating that the accommod ating fields show large deviations from the Schottky ation coeff. for the ions is much < 1, and that there mirror image theory. N. M. B. is a negligible electron emission from the probe. Photo-electric effect for the ¿-shell. H . H a l l . A. B. D. C. and W. R a r it a (Physical Rev., 1934, [ii], 46, 143) Retardation of hydrogen positive rays by metals. H. BAtzner (Ann. Physik, 1936, [v], 25, o , . ' L - S. T. Spark potential for electrolytic valve action. 233 262).—The velocity decrease of H+ particles W. Bär (Z. Physik, 1935, 98, 267— 279). with 4— 60 e.lcv. in passing through films of Al, Cu, Ag, Sn, and Au has been measured. The relative A. B. D. C. Shot effect of secondary emission. I. M. at. retarding powers for this energy region depend on the at. vol. rather than on the at. no., in contrast to Ziegler (Physica, 1936, 3, 1— 11).— A method of measuring fluctuations in the current in a vac. the relation for high energy. Vais, for the range of the particles in Al are calc. L. J. J. tube by comparing them with the definite fluctuations brought about in another tube by the pure shot Negative atomic hydrogen ions. W. H. B en - effect is described. a. J. M. NETT^and P. F. D a r b y (Physical Rev., 1936, [ii], Electron-microscopic investigations of elec 49) 9^ 99). Negative at. H ions have been directly tron emission from cold metals. A. W ehnelt observed at the heads of striations in discharges in and W. S c h illin g (Z. Physik, 1935, 98, 2S6— 287).— HoO vapour; they form readily in these regions of A cold Mo cathode emits electrons from independent high density of slow electrons, but are easily lost points; these centres last for several mm. and then by collision. j\f. yp g suddenly cease to emit, whilst new centres appear. Determination of the conditions for inelastic . A. B. D. C. collision with the aid of slow K>- ions. O. Electron-optical structural image and emis S chm idt (Z. Elektrochem., 1935, 42, 8— 21).—Theo sion from barium-nickel cathodes. E. B r ü c h e retical. The significance of experimental results (Z. Physik, 1935, 98, 77— 107).— Changes in heated (A., 1934, 863, 937) is discussed. E. S. H. cathodes during electron emission have been followed Collision of K+ ions with inorganic and organic by the electron microscope. A. B. D. C. gases. III. Effective cross-section [of part Electron-optical images of emitting wires. icles] and area of mass-spectrographic dis fl. M ahl (Z. Physik, 1935, 98, 321— 323).— Images tribution curves. O. Schmidt (Ann. Physik, 1936, ot VV and Mo wires are reproduced. A. B. D. C. [v], 25, 92— 96 ; cf. A., 1935, 5).— For const, max. Pressure of a degenerate electron gas and intensity, the area JP of the curve of scattering oc related problem s. (S ir) A. E d d in g t o n (Proc. pressure of tho gas and is related to the effective *%• Soc., 1935, A , 152, 253— 272).— A straightfor cross-section Q. For pure scattering in similar gases ward deduction of the formula P —Kam (P =m in. F l Q = a = const. (Xe, Kr, A, and C02, N2, MeCl). electron pressure corresponding with an electron For other gases, the val. of a and the loss of energy density a) from relativistic principles is given. The on impact either increase (inert gases) or decrease Pressure is found directly, and not by way of the (paraffins and olefines and He) with decreasing mass. amutonian. The usual (Dirac) theory of at. L. J. J. phenomena follows from the present basis. The Relative at. wt. of oxygen in water and in air. « s are applied to a determination of the val. M. D o le (J. Amer. Chem. Soc., 1935, 57, 2731).— ° the cosmical const. The existence of a vast no. The at. wt. of O in air is 16-00008 if that of O in 0 occupied negative energy levels is one of the Lake Michigan H20 is 16-00000. E. S. H. essential consequences of the analysis. L. L. B. At. wt. of gallium. G. E. F. L h n d e l l and Reflexion coefficient of electrons. M. J. C o p le y J. I. H o ffm a n n (J. Res. Nat. Bur. Stand., 1935, and P. E. Phipps (Physical Rev., 1934, [ii], 46,144). 15, 409—420).—Conversion of pure Ga into Ga203 L S T through Ga2(S04)3, Ga(OH)3, or Ga(N03)3 and ignition Scattering of slow electrons by diatomic at 1200— 1300° gave at. wt. of Ga 69-74. Ga20 , has molecules. J. B. E isk (Physical Rev., 1936, [ii], d 5-95. A. R . P. • 13).—Mathematical. The Ramsauer effect At. wt. of rubidium. E. H . A r c h ib a ld , J. G. s reated by a method analogous to that used for H o o le y , and N. W. F. P h illip s (Trans. R oy. Soc. I (d, e) 264 BRITISH CHEMICAL ABSTRACTS. A.
Canada, 1935, [iii], 29, III, 155— 162, and J. Amer. electron-pair in Kr by y-rays from Th-C" (/¿v=2-6 X Chem. Soc., 1936, 58, 70— 72).— The at. wt., deter 106 ev.) is about & of the probability of production mined from the Ag : RbCl ratio, and using Johnson’s of Compton electrons with energy > 1-25 x l0 e ev. method of determining the nephelometric end-point, Examination of 300 Wilson photographs gave 51 was 85-48 (of. A., 1931, 584). H. J. E. Compton electrons of the above energy, and 4 electron- pairs. -A- J- M- Mass ratio of hydrogen and deuterium from band spectra. W. W. Watson (Physical Rev., Determination of neutron intensities by means 1936, [iiJ, 49, 70— 72).— Corrections of B e rotational of Fermi electrons from rhodium. R. D o p e l const3. for uncoupling terms and interactions between (Physikal. Z., 1936, 37, 96— 100).— The Fermi effect nuclear and electronic motions for some diat. hydride with Rh has been investigated with a view to its and deuteride mols. are calc. If H —1-0081, D must use for determining the intensity of a weak beam of be > the generally accepted val. 2-01423, and is neutrons mixed with strong y-rays. There are two approx. 2-0148 (cf. Aston, A., 1935, 677). N. M. B. emissions of electrons, half-life 35 sec. and 3-8 m. The initial intensity ratio of the short- to the long-lived Mass ratio of the lithium isotopes from the is 6-7, and lialf-val. thickness of Al for absorption spectru m of Li„, G. M. A lm y and G. R. Ir w in of the electrons is 0-45 mm. for both emissions. (Physical Rev., “l 936, [ii], 49, 72— 77; cf. ibid., The optimum conditions for the determination of 1935, [ii], 48, 104).— Rotational and vibrational neutron intensities are examined, and the prep, of analyses of the ->■ Li2 band system are tabulated. neutron standards for comparative work is described. The mass ratio Li7/'Li° calc, from the observed isotope A. J. M. effect is 1-16640±0-00016, and the mass coeff. Neutrons from the disintegration of deuterium 1 -04077 :t:0-00004. A small electronic isotope shift, by deuterons. T. W. B o n n e r and W . M. B ru —0 064±0-010 cm.-1, has been found. N. M. B. b a k e r (Physical Rev., 1936, [ii], 4-9, 19— 21; cf. Alpha-particle yield from lithium under pro this vol., 6 ; Crane, A., 1934, 714; McMillan, A., 1935, ton bombardment. N. P. Heydenburg, C. T. 559).—The excitation functions for the emission of Zahn, and L . D. P. K in g (Physical Rev., 1936, neutrons from D and Be by D2 were investigated in [ii], 49, 100— 101).— Observed thick film yields for the energy range 0-5— 0-9 m.e.v. The yield of neutrons the proton energy range 40—225 kv. are in good from a D3P04 target varied nearly linearly, and from agreement with those of Herb (cf. A., 1935, 1186) a Be target nearly exponentially, with the bombarding at higher voltages. N. M. B. energy. The no. of neutrons from Bo increases from Measurement of p-radiation from radium in i to 3 times as many as from D3PO,, in the range. »•-units. H. S m e re k e r and K . J u r is (Strahlen- The neutrons from D are nearly homogeneous, with ther., 1935, 52, 327— 337; Chem. Zentr., 1935, i, 2-55 m.e.v. max. energy. The energy of the dis 3249).—Measurement by the method described shows integration is 3-21^0-13 m.e.v. N. M. B. the unfiltered fi-radiation to bo 200 times as strong as Absorption of residual neutrons. J. T u tin the y-radiation. J. S. A. (Nature, 1936, 137, 34).— Neutrons may be captured Quantum energy of some nuclear y-rays. in energy levels outside the nucleus. L. S. T. R. Fleischmann (Naturwiss., 1936, 24, 77— 78).— Absorption law for slow neutrons. F. Rasetti, The quantum energy of y-rays emitted by neutron E. S e g re , G. F in k , J. R. D u n n in g, and G. B. bombardment was determined by the coincidence P egram (Physical Rev., 1936, [ii], 49, 104).— The method of Bothe et al. (A., 1929,116), to avoid scatter validity of the Fermi-Bet he absorption law was tested ing effects. The absorption of secondary electrons by measuring the absorption of neutrons by a thin emitted by the action of the y-rays on Al was deter film of C'd and of Ag on the edge of a disc rotating mined. The quantum energies arc > those obtained at high velocity with and against, respectively, the by the direct absorption method (this vol., 6). neutron beam.' For Ag the law is obeyed, but for Quantum energy shows dependence on at. no. similar Cd a change of 6-3% in the absorption coeff. indicates to the packing fraction. A. J. M. that the capture cross-section varies with the velo Emission of y-quanta on disintegration of city less rapidly than 1/v, where v is the neutron lithium by fast protons. K. Alexopoulos (Z. velocity (cf. following abstract). N. M. B. Physik, 1935, 98, 336—341).— y-Quanta are emitted Velocities of slow neutrons. G. A. Finic, J. R. on bombardment with protons of 450 e.kv. D u n n in g, G. B. P egram , and D. P. M it c h e l l (Physi A. B. D. C. cal Rev., 1936, [ii], 49, 103; cf. A., 1935, 1441).- Rayleigh scattering of hard radiation by heavy Velocity distribution curves for slow neutrons from a tom s. W . F r a n z (Z. Physik, 1935,98,314—320).— sources at room temp, and liquid air temp, are given Theoretical. Rayleigh scattering of 4-7 X y-radiation and discussed. N. M. B. by Pb should amount to 1% of the Klein-Nishina Slowing down of neutrons. G. C. W ic k (Physi scattering. A. B. D. C. cal Rev., 1936, [ii], 49, 192— 193).— Fermi’s state Scattering of the Th-C" y ra ys. C. C. L a u r it- ment, that an impact of a neutron with a proton se n and J. R . Oppenheimer (Physical Rev., 1934, reduces, on an average, the neutron energy by l/«> [ii], 46, 81). L. S. T. is explained (cf. A., 1935, 910). N- M. B. Production of electron-pairs by y-rays in Influence of the velocity of slow neutrons on k rypton . M. N. S. Imm elman (Naturwiss., 1936, their capture by certain nuclei. P. P r e i s w e r k 24, 61—62).—The probability of production of an and H. v o n i f at,ran, jun. (Nature, 1935,136,1027). I (e-sO GENERAL, 1'HYSICAL, AND INORGANIC CHEMISTRY. 205
The radioactivation of Ag by neutrons from a B e+R n Fluctuations in cosmic-ray ionisation as given source at different temp, after traversing paraffin by several recording meters at the same station. wax with a Cd shield interposed at various distances R. L. D oa n (Physical Rev., 1936, [ii], 49, 107— indicates that the cross-section for neutron capture 122).— Intensity variations over 10 weeks are re varies inversely as the velocity of the neutrons corded and analysed. Statistical agreement is found. relative to the Ag atoms. Contrary to Moon and The barometer effect is 1—2% per cm. Hg. Marked Tillman (A., 1935, S02), cooling the paraffin wax to ionisation increase during rainfall is probably due 90° abs. increases the radioactivity induced in I by to y-radiation from active deposits brought down from 10%. ' L. S. T. ‘ the upper atm. Time distribution of ionisation Energy of disintegration of radio-phosphorus bursts is purely random, with no evidence of baro [P30]. C. D. E l l i s and W . J. H e n d e r s o n (Proc. meter effect on burst frequency. N. M. B. Roy. Soc., 1935, A , 152, 714— 723).— The energy Super-Novae and cosmic rays. W. B a a d e and of the upper limit of the positrons from [P3®] is found F. Z w ick y (Physical Rev., 1934, [ii], 46, 76— 77). to bo 2-9¿0-1 X 10® volts, corresponding with the L. S. T. formation of the product nucleus Si30 in its ground Penetrating power of asymmetric component state. Assuming that this energy determines the of cosmic radiation. S. A. K o r e e (Physical Rev., difference of internal energy of Si30 and P30, it is 1934, [ii], 46, 7 4 -7 5 ). L. S. T. found, on the basis of existing data, that the differ ence in mass of Al27 and Si30 is the same whether calc, Analysis of ultra-radiation. B. G ross (Physi- from 13Al27+ 2He4-> 14Si30+ 1H1, or from the two kal. Z., 1936, 37, 12— 18).— Theoretical. The energy stages 13Al27+ 0He4- » 15P3®+0wi and 15P30 -> of a primary ray is calc, as a function of depth anil 14Si30-f-e+. L. L. B. range. A. J. M. New artificial radioactive elements. II. O. Excitation function of lithium under proton D A g o s tin o (Gazzetta, 1935, 65, 1071— 1087; cf. bom ba rd m en t. M. Ostroesky, G. B r e it , and A., 1935, 276).—The identification of 17 active ele D. P. J oh n son (Physical Rev., 1936, [ii], 49, 22— ments obtained by neutron bombardment of Li, B, 31).—The yield of a-particles in the bombardment Na, Al, P, Cl, K , Mn, Cu, Zn, Ga, As, Se, Ag, Cd, In, of Li with protons for different depths and widths ob, I, Ba, W , and R e and some experiments on the of the “ potential well,” and the asymptotic form of separation of radioactive isotopes are described. the dependence of the collision cross-section on velo city at low velocities, are calc. Estimates of the „ . . . ’ O. J. W . Radioactivity produced in thorium and in theoretical variation of the yield with velocity are uranium by means of neutron bombardment. made for Li7-pH2. The “ well ” for the quant, 0. D A g o s t in o and E. S e g r e (Gazzetta, 1935, representation of the a-particle reaction is compared 65, 1088— 1098; cf. A., 1934, 826).— In the Tli with the mass of Be8, and both can be fitted by activity produced by neutron bombardment two attributing the formation of Be8 from Li7 to the addi periods have been established, viz., 1 mill, and 24min. tion of a proton into a p level. N. M. B. The latter is due to a new isotope of Th. The 13 Radiative collision between fast charged and 100 min. activities of U are not duo to any ele particles. C. M o ll e r (Proc. R oy. Soc., 1935, A , ment of at. no. 80— 92, but to an element 93 or 94 152, 481—496).—Mathematical. A correspondence and at. wt. 239. O. J. W. method, which is relativistically invariant and forms an immediate generalisation of the method previously Angular distribution of the products of arti used in the treatment of the non-radiative collision ficial nuclear disintegration. J. Giarratana and of fast particles, is developed for the treatment of C G. B r e n n e c k e (Physical Rev., 1936, [ii], 49, 35— the radiative collision between two particles. (Cf A w). Using special technique, measurements, accur 1931, 1109.) L. L. B. ’’ ate to ± 8 % , of the angular distribution of a-pacticles rom the disintegration of Li by fast protons showed Apparent failure of the photon theory of that the emission is random in direction. N. M. B. scattering. R. S. S iia n k la n d (Physical Rev., 1936, Capacity of the elements for disintegration, [ii], 49, 8— 13).— Using Ita-C y-radiation and air, results of old and new methods. G. Stetter Al, Be, filter-paper, and paraffin scatterers, coincident ( hysikal. Z., 1936, 37, 88— 95).— A critique of the discharges were recorded in special Geiger-Muller scintillation method of investigating at. disintegration, electron and photon counters at various angles. and discussion of results obtained by more modern There were fewer coincidences in the correct positions methods. A . J. M . than expected, and those observed could be accounted for as chance coincidences due to the finite resolving Production of cosmic-ray showers at a con time of the apparatus. Results do not agree with the siderable depth below ground-level. D. II. photon theory of scattering. N. M. B. 10°wfTTArand J - D - Cea w sh a w (Nature, 1935, 136, Exchange forces and the structure of the ,.(U '■ Much of the radiation which penetrates nucleus. J. H. B a r t le t t , jun. (Physical Rev., 1936, electron must consist of positive or negative [ii], 49, 102 ; cf. Feenberg, this vol., 134).— The possi L. S. T. bility of a Heisenberg exchange followed by a T.Se,Cv0ndary e®ect °f cosm ic rays. A. S ciiw eg - Majorana exchange, i.e., an interchange of spin Physik, 1935, 98, 288; cf. A., 1935, 1297). co-ordinates and not of space co-ordinates, is examined. A. B .D .C . N. M. B. 266 BRITISH CHEMICAL ABSTRACTS.— A.
Interaction of light nuclei. II. Binding ener as a function of impact parameter is investigated, gies of the nuclei and He23. H. S. W. M assey and various cases are treated which have not been and C. B. 0. M o h r (Proc. R oy. Soe., 1935, A , 152, considered before. Most of the formulas can be 693—705).—The validity of the variation method derived by a method similar to that given by Weiz as applied to H x2 is examined by comparing results säcker (A., 1934, 712). L. L. B. obtained by its use with exact solutions. The method Light aberration and the Doppler effect. K. must bo used with caution in determining binding P a r e l l o (Z. Physik, 1936, 98, 490— 495).— Aberration energies due to short-range hiteractions. The bind of light from stars depends on the distance of the star ing energies of II]3 and He23 can be explained by from the earth, and the relative or abs. velocity of introducing attractive forces between the neutrons the observer, indicating that the velocity of fight on the one hand and the protons on the other. The is a function of time. A. B. D. C. attraction between two neutrons must be much < that between a neutron and a proton, so the Orbits of electrons in magnetrons with space existence of a stable n02 nucleus is precluded. The charge. H. A w e n d e r , A. Thom a, and D. M. anomalous attraction between two protons at small Tom bs (Z. Physik, 1936, 98, 534— 535).— A correction distances must also be much < that between a neutron (cf. this vol., 4). A. B. D. C. and a proton, and cannot be sufficient to produce a Probability of radiative processes for very stable nucleus He23. (Cf. A., 1935, 274.) L. L. B. high energies. L. W. N o r d heim (Physical Rev., Energies of nuclear reactions. H . A. W ils o n 1936, [ii], 49, 189— 191).— Mathematical. The pre (Proc. R oy. Soc., 1935, A , 152, 497— 502).— The ener sent theory (cf. Bethe, A., 1934, 1150) is modified gies of 17 nuclear reactions arc discussed, and in for high energies and cosmic-ray phenomena. order to make the reaction equations consistent, the N. M. B. vals. of some of the energies are revised. The at. Temperature dependence of free electron sus wts. of the 13 light elements involved are calc, from ceptibility. E. C. S t o n e r (Proc. Roy. Soc., 1936, the reaction energies, and vals. obtained in good A, 152, 672— 692).—Mathematical. Various formulas agreement with those of Bethe (Physical Rev., 1935, required in the application of the Fermi-Dirac [ii], 47, 634) and of Oliphant et al. (A., 1935, 803). statistics to the calculation of magnetisation are given L. L. B. in a convenient form, and calculations are made of Recombination of neutron with proton. S. the magnetisation as a function of H and T for the K ik u ch i, K . Husimi, and H. A oki (Nature, 1936, spin and diamagnetic effects considered separately 137, 30—31).-—From the relative intensities of the or together, at both low and' high temp. Under y-rays emitted under neutron bombardment by certain conditions the formulae derived will hold ap H20 and aq. H3B03 and an aq. solution of a Cd prox. for electrons in metals. L. L. B. salt, the mean cross-section found for tho recom Magnetic moment of the neutron. A. LandIs bination of neutron with proton lies between 8-3 X 10~26 and D. R . I n g lis (Physical Rev., 1934, [ii], 46, 70).— and 3-0x 10-26 cm.2 L. S. T. Disagreement with Schueler’s val. of —1-65 magnetons Spontaneous disintegration of proton or neu (A., 1934, 580) is expressed. L. S. T. tron according to the Fermi theory. H. C. Interpretation of present values of nuclear W o l f e and G. E. U h le n b e c k (Physical Rev., 1934, [ii], 46, 237). L. S. T. m om en ts. G. B r e it and I. I. R a b i (Physical Rev., 1934, [ii], 46, 230— 231).— A discussion of recent Neutron collisions and the |3-ray theory of speculations on the magnetic moment and nature of F erm i. A. N o r d s ie c k (Physical Rev., 1934, [ii], the neutron and proton. L. S. T. 46, 234— 235). L. S. T. Progression of nuclear resonance levels with Energy of removal of neutrons and a-particles atomic number. H. M a rgen a tt and E. P o lla r d from nuclei and a-instability below the radio (Physical Rev., 1934, [ii], 46, 228; cf. A., 1935, 804). elem en ts. E . D. E astm an (Physical Rev., 1934, L. S, T. [ii], 46, 238—239).—A discussion emphasising the a- Disintegration of H 2 and the stellar abundance instability of elements of relatively low at. no. (cf. of H 2 and H3. H. H. G o ld s m ith (Physical Rev., A., 1934,'939). L. S. T. 1934, [ii], 46, 78— 79). L. S. T. Hydrogen atom. V. F o c k (Z. Physik, 1935, 98, Electric quadrupole moments of some atoms 145—154).—Group theory describes very simply and the magnetic moment of the proton. H. many of the phenomena associated with the II atom, S c h ü le r and T. Schm idt (Z. Physik, 1936, 98, 430— including the Compton effect for bound electrons. 436).—Lack of symmetry shown by Cu, As, Eu, Lu, A. B. D. C. Hg, and Bi nuclei indicates rod- and plate-like electric Singular magnetic poles. B. O. G ro n b lo m (Z. charge distribution, and gives a magnetic moment Phvsik, 1935, 98, 283— 285).— Theoretical. of 1-5 for the proton in these nuclei. A. B. D. C. A. B. D. C. Creation of electron pairs by fast charged Relativistic self-consistent field. (Miss) _B. particles. H. J. B habha (Proc. Roy. Soc., 1935, S w ir le s (Proc. R oy. Soc., 1935, A , 152, 625— A, 152, 559—586).—Mathematical. The creation 649).—Mathematical. A relativistic treatment of of electron pairs by the collision of fast charged a many-electron atom on the lines of the self-con particles is calc., taking into account the effect of sistent field method with “ exchange ” is developed. screening. The probability of the creation of a pair Tables are given from which the expression for the I (g), II (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 267
total energy of tan atom containing s, p, d electrons both Br79 and Br81. Analyses are confirmed by the may be constructed. L. L. B. respective isotope shifts; ail the bands degrade to the Band spectrum of OH". F. W. Loom is and red. N. M. B. W. H. B ran dt (Physical Rev., 1936, [ii], 49, 55— End-isotope effect for triatomic molecules. 67).—Full data are given for two bands at 3332 and M. W e iir li (Naturwiss., 1936, 24, 14— 15).— The 3565 A . in the eleetrodeless discharge in pure H20 end-isotope effect has been investigated for vapour (cf. Rodebush, A., 1934, 39) and for new bands TeClg, the relative abundance of the mols. being at 3695 and 3893 A., which are, respectively, the TeClf : TeCl33Cl37: TeClf=1:0-32 :0-10. In contrast (1,0), (0,0), (1,1), and (0,1) bands of OH+. Rbta- to diat. mols. there is no simple connexion between tional analysis shows that they correspond with the isotopic splitting, Av, and the frequency, except in a 3n -> 3£_ transition in which the 3n state is in two special band series, one due to excitation of verted. Multiplet intervals in both states are de symmetrical vibrations only, and the other to ex termined from the 9 strong branches and the satellite citation of the antisymmetrical and deformation branches. A-typo doubling and perturbations are vibrations. The isotopic factor, f v is 0-0131 (theory examined. The 3S_ state concerned in the trans for linear mol. 0-0139). A. J. M. ition and the perturbing state are mol. levels which Absorption spectra of the chlorides and oxy- dissociate into the ground states of 0 and H + and 0 + chlorides of sulphur. R. K. A s u n d i and R. and H, respectively. N. M. B. Sam uel (Proc. Physical Soc., 1936, 48, 28— 34; Rotation constants B , D , and Y for the 3fl cf. A., 1935, 680).—Absorption curves, in the visible terms of TiO, C„, CO, PH, A1H, and NH. A. and ultra-violet, are given for the vapours of SCI2. Btjd6 (Z. Physik, 1936, 98, 437—444). S2C12, S0C12, and S02C12. Heats of formation and A. B. D. C. linking energies are derived, and results are corre Absorption spectrum of copper hydride. B. lated with photodissociation processes. N. M. B. Grrndstrom (Z. Physik, 1935, 98, 128— 132) Spectrophotometric studies. II—V.—See this A. B. D. C. Strontium deuteride and hydride spectra. vol., 221. W. W. W a tso n , W . R . Fredrickson, and M. E. Extinction of mesomorphic liquids in a mag Hogan, jun. (Physical Rev., 1936, [ii], 49, 150— 155; netic field. Y. Bjornstahl (Z. physikal. Chem., cf. A., 1932, 439; 1935, 1443).— Analyses of the B 1935, 175, 17-—37).— Melts of p-azoxyanisole, p- and C band systems of SrD and of part of the D azoxyphenetolc, and p-azoxyanisolephenetole have system of SrH arc reported. N. M. B. been examined. The extinction coeff., e, is unaffected Isotope effect for gold hydride (AuH/AuD). by a transverse field, and there is no dichroism in the field. The depolarisation of linearly polarised light T. Heimer (Naturwiss., 1936, 24, 78).— The arc emis sion band spectrum of AuD has been examined, and by the liquid is changed in the field. In a longi compared with results for AuII. A. J. M. tudinal field e decreases with increasing field strength, F, ultimately approaching a limit. If e is measured Anomalous rotation of HgH molecules. F. F. with rising and falling F, hysteresis may appear. Rieke (Physical Rev., 1934, [ii], 46, 236— 237). For moderate F e decreases in jumps with rising F. L. S. T. In a given longitudinal field e is independent of the Absorption bands of gaseous HI. D. E. K ir k - temp. It is difficult to account for these observations wtrick (Physical Rev., 1936, [ii], 49,104).— Measure on the swarm theory of mesomorphic liquids. Orn- ments of the centres of the 1 -£- 0 and 2 - 4 0 absorption stein’s theory (A., 1935, 20) is criticised. R . C. bands gave the vals. 2260±30 and 4416±75 cm d, m agreement with Salant (cf. A., 1931, 545) and Absorption spectra of tautomeric selenazoles. -Nielsen (cf. A., 1935, 806). N. M. B. R. F. H u n te r (Nature, 1935,136, 1030).—The ultra violet absorption curve of 1-hydroxylbenzselenazole Band spectra of BiBr, BiCl, BiF, and Bil in (I) in MeOH is practically identical with that of absorption. F. M o rg a n (Physical Rev., 1936, [ii], l-keto-2-methyl-l : 2-dihydrobenzselenazole and dis 49, 41—46).—Data and vibrational analyses are tinct from that of the O-Me ether. In aq. NaOH the reported. BiBr has two systems for each of the iso curve of (I) is moved to the left (deformation) and topes Br79 and Br81 with origins at 4045-7 and 4869-1 there is a decrease in the max. due to the production A., the latter system degrading to the red. BiCl “as a system in the range 3600—4000 A . for both of the ion CGH4<[jq-^>CO on which tautomeric change 61 and Cl37, in addition to a system at 4300— 5500 A . depends. 1-Thiolbenzselenazole shows marked simi (of- Saper, A ., 1933, 207). Vibrational analyses are larity to thiazole analogues in the ultra-violet region; confirmed by the respective isotope shifts. A system the curve for MeOH solution is similar to that of floO—4900 for BiF, and a system 4150— 4300 A . l-thio-2-methyl-l : 2-dihydrobenzselenazole. tor Bil have been observed and analysed. N. M. B. L. S. T. Absorption spectra of PbF, PbCl, and PbBr. Ultra-violet absorption spectra of some com Morgan (Physical Rev., 1936, [ii], 49, 47— 50).— plex aromatic hydrocarbons. I. W. V. May- ata and vibrational analyses are given. PbF n e o r d and E. M. F. R o e (Proc. Roy. Soc., 1935, A, ias a single system of double-headed bands in the 152, 298—324).—An investigation has been made of 4100— 5300 A. PbCl has a system with origin the ultra-violet absorption spectra of EtOH solutions Pin i ^or eack the isotopes Cl35 and Cl37. of C6H6, C]0H8, anthracene, 1 : 2-benzanthracenc, bBr has a system in the range 4400— 5400 A . for 1:2:5: 6-dibenzanthracene, phenanthrene, and their 268 BRITISH CHEMICAL ABSTRACTS.— A. derivatives, and of clirysene, picene, pyrene and its V e r l e g e r (Z. Physik, 1935, 98, 342— 352).— Re derivatives. The spectra of chemically related solved vibration bands are given for MeCl, MeBr, and compounds are compared, and the effects of the addi Mel, and give moments of inertia for the axis normal tion of various groups are noted. Changes have to the symmetry axis of 60, 80, and 90 X lO-40 g.-cm.2; been observed in the absorption spectra on cooling that about the symmetry axis is 4-1 X10-40 for all the solutions to —183°. L. L. B. three. A. B. D. C. Ionic dispersion in the extreme infra-red. Infra-red evidence for the existence of an C. H. Cartwright (Physical Rev., 1936, [ii], 4 9 , 101— isomeric form of HCN. D. W illia m s (J. Chem. 102).—A study of the absorption coeflf. and reflecting Physics, 1936, 4, 84).—The infra-red spectrum of a power curves of H20 and of KI and KC1 solutions saturated solution of HCN has a strong band at 4-76 g indicates that the dispersion of electrolytes in the and a much fainter band at 4-95 g. Since a shift of extreme infra-red can be pictured classically, accord approx. 0-2 g represents the difference between the ing to Maxwell’s equations, by considering the ions band for org. cyanides and their isomeric forms at to follow in translation the alternations of electro 4-5 g the absorption at 4-95 g is attributed to a small magnetic waves. The motion of the ions decreases quantity (about 2%) of the isomeride HNC. in amplitude, because of inertia and friction, with M. S. B. increasing frequency of radiation. In electrolytes Relations between electrochemical constants, of KC1 and K l the ions seem to move with respect infra-red spectrum, and reaction properties. to the H20 mols. except for friction. N. M. B. F. V le s (Compt. rend., 1935, 201, 1475— 1477).— Choice of spectral reference rays in the study The >.x of the bands calc, from the previous relation of every infra-red region (photographic infra ship (A., 1935, 444) for BzOH, N H 2Ph, anthranilie red), especially for the determination of fluor acid, and methylene-blue, and for the decomp, of escence spectra. C. DHimi: and 0 . Biermacher CO(NH2)2 by urease, are ascribed to sp. groups of (Compt. rend. Soc. Biol., 1935, 120, 1162— 1166).— atoms. T. G. P. Standard reference lines for the infra-red are A Infra-red spectra of amino-acids and poly 912-4 and 1064 mg, Hg 1014 and the combined He, peptides. E. H e in tz (Compt. rend., 1935, 201, Cu, and Ag spectra for 500— 850 mg. Acid por 1478— 14S0; cf. A., 1935, 1053).— Data are recorded phyrin solutions show fluorescence bands between for glycine, (¿¿-alanine, Z-cystine, cysteine, Z-leucine, 667-8 and 728-2 mg, coincident with the two Cu (Z-glutamic acid, (7-arginine, (ZZ-proline, tyrosine, lines. R . N. C. Z-histidine, phenylalanine, three peptones, and an Infra-red absorption spectrum of water and albuminose of casein. The vals. confirm the previous alcohols in non-polar solvents. E. L. K in s e y relationship (A., 1935, 444). T. G. P. and J. W . E l l i s (Physical Rev., 1936, [ii], 49, 105).— Absorption curves in the range 1-0— 2-5 g for H 20 Raman spectrum of deuterium. II. Inten dissolved in CS2 and for MeOH in CC14, compared with sity and polarisation characters. S. B hagavan- those for liquid and vapour I120 and MeOH, show tam (Proc. Indian Acad. Sci., 1935, 2, A, 477—482; vapour-like characteristics and strong OH bands, cf. A., 1935, 1415).— Data are recorded and classified. indicating that the interaction between mols. in the Vibration lines are polarised; rotation lines are nearly liquid is weakened or destroyed in solution, and that completely depolarised. H. J. E. the interaction affects, relatively, only the polar Raman spectra of carbon and silicon tetra part of the mol. N. M. B. chlorides. R. Ananthakrishnan (Proc. Indian Rotation-vibration spectrum of acetylene in Acad. Sci., 1935, 2, A , 452— 458).— Two new lines of the photographic infra-red. G. W. F u n k e and low intensity were found for CC114 (434, 145 cm.-1). G. H e rz b e h g (Physical Rev., 1936, [ii], 49, 100).— A new line at 440-5 cm.-1 was found for SiCl4. The Data and interpretations of 3 new _L and 6 new || origin of these lines is discussed. H. J. E. bands are reported and discussed. N. M. B. Raman spectrum and fundamental vibration Quantitative absorption measurements of the frequencies of silane (SiH4). F. B. S t it t and CH overtones for simple hydrocarbons. I. D. M. Y o s t (J. Chem. Physics, 1936, 4, 82).— Two Halogen derivatives of methane, ethane, and Raman lines have been found for SiII4 and, com bined ethylene. B. Timm and R. Mecke (Z. Pliysik, with the infra-red data of Steward and Nielsen 1935, 98, 363—381).—Photometer measurements (A., 1935, 914), have led to the following arrange are given for the third CH overtone in spectra of ments of fundamentals: v4 2187, v2 97S, v3 2183, CHCL, CH2C12, McCl, CHBr3, CH,Br2, MeBr, CVHCL, and v4 910 cm .-1 M. S. B. Ca>HoCI„ C2H3C13, G,H.,C1„ EtCl, Pr“Cl. C2H„Br4, Raman spectra of some formates and the con C2II4Br2, EtBr, C2HC13, C2H2C12, and C2H3C1. “ Ab stitution of formic acid. C. S. Venkateswaran sorption intensity oc to the no. of CH groups, the (Proc. Indian Acad. Sci., 1935, 2, A, 615—620).—The halide atom having little influence on the electrical Raman spectra of H C 02Na, (IIC02)2Ca, (HC02)2Cd, properties of an aliphatic CH linking. Transition and (HC02)2Pb have been measured for the solids arid moments are calc, and used to determine variation their aq. solutions; average frequencies for the IIC02 of dipole moment with nuclear separation in a homo- ion are 2834, 2732, 1717, 1534, 1347, and 857 cm.'1 polar linking. A. B. D. C. These frequencies are compared with those of HC02H, Rotation-vibration spectra of methyl halides HC02Me, AcOH, and NaOAc. The existence of the in the photographic infra-red to 1-11 g. H. lines 2834 and 2732 cm.-1 proves the presence of the 11(a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 2G9
CH group. The 1534 cm .-1 line, of doubtful origin, Raman spectra of benzene and its derivatives. is characteristic of formates. J. W . S. K. W. F. Kohlrausch (Physikal. Z., 1936, 37, 58— Raman spectrum of oxalic acid. W . R . A n g u s 79).— A review. A. J. M. and A. H. L e c k ie (J. Chem. Physics, 1936, 4, 83— Partial interpretation of the Raman and infra 84).—Contrary to Hibben’s conclusion (this vol., 9), red spectra of benzene. E. B. W ils o n , jun. the frequencies 1661 and 1759 are present in the (Physical Rev., 1934, [ii], 46, 146— 147).— Raman- spectrum of solid H 2C20 4,2H20 and are as strong as active and infra-red-active fundamentals of C0H 0 the corresponding frequencies in aq. solution. This have been assigned to definite modes of vibration agrees with Rao’s data (A., 1935, 807) on the assump of the regular plane hexagon model. The doublet tion that the latter were obtained from the 2H20 at 1600 cm .-1 in the Raman spectrum is explained crystals. M. S. B. on the basis of quantum-mechanical resonance between v8 and Vj+vfi. The suggestion that the Raman spectrum of dioxan. A. Simon and F. spectra of C0H 6 arc incompatible with hexagonal F eher (Ber., 1936, 59, [£], 214— 217).— Repeated symmetry is not justified. L. S. T. freezing and melting of dioxan causes a gradual lowering of the m.p., apparently due to the formation Molecular scattering of light: Cabannes- of a polymeric form. Evidence of isomerisation Daure effect, critical opalescence of binary m ix to acctaldehyde ethylene diacctal is not obtained. tures. A. R o u s s e t (Ann. Physique, 1936, [xi], 5, The Raman spectrum of dioxan gives results correcting 5— 135; cf. A., 1934,473, 830,1302).—The continuous and expanding those of Villars (A., 1931, 145). spectrum surrounding the exciting line in the scatter H. W. ing of light by liquids (Cabannes-Daure effect) is Raman effect of acetylenes. II. Di-iodo- attributed to part of the anisotropic scattering due to acetylene, liquid acetylene, and deuteroacetyl- variations of mol. orientations. The arrangement of enes. G. G l o c k l e r and C. E. M orrell (J. Chem. cybotactic groups limiting the relative orientations Physics, 1936, 4, 15— 22; cf. A . , 1935, 146).— A new of the axes of the mols. changes the statistical wt, type of apparatus is described. Data are recorded for of the rotational levels so that the intensity max. of C2I2, liquid C2H2, and gaseous C2H 2, C2HD, and C2D2. the P and R branches are approx. identical with that -»larked differences between the spectra of liquid and of the fundamental line. In presence of strong gaseous C2PI2 indicate mol. distortion in the liquid permanent moments the anisotropic scattering of a state,^ so that the mol. is no longer linear. Free vibrating mol. is wholly in the Q branch, explaining energies have been calc, and the equilibrium const, the weak intensity of the Cabamies-Daure effect for C2H2+ CJ )2 2CJ1D has been determined at in strongly polar mols. Measurements of the de polarisation factors p for H 20-Pr^C 02H, CeH u - temp. 273— 700° abs. M. S. B. PhN 02, NH2Ph-cyc?ohexane, and H 20 -N E t3 show Fundamental frequencies of acetylene. G. that on approaching the crit. temp, of complete G lockler and C. M o r r e l l (Physical Rev., 1934, miscibmty p reaches a min. and increases rapidly M> 46, 233).— The frequencies 382 (5), 618 (2), near the crit. point, indicating that the scattering j)31 (5), 1762 (1), 1959 (10), 3338 (5) cm.-i have been due to variations of the mol. field increases more found by Raman scattering in liquid C2H2. L. S. T. slowly than the opalescence near the crit. point. Spectrum and force constants of the ethylene The sharp rise of p is attributed to a partly depolarised Molecule. L. G. B o n n e r (J. Amer. Chem. Soc., secondary scattering increasing more rapidly in D3G, 57, 34—39).-—The Raman and infra-red ab intensity than in the case of the primary scattering. sorption spectra in the photographic region have The law of variation of opalescence ■with A is deduced, been reinvestigated. Three new Raman lines and intensity of scattering in two directions relative to 1 new infra-red absorption bands have been found, the incident beam and variations of XX are examined, frequency vals. have been assigned to all the 12 and results are discussed in relation to available undamental vibration modes of the C2H4 mol., theory. N. M. B. on t he basis of the new data, and 8 of the force const s. Raman spectra of amino-acids and related °t the mol. have been obtained. E. S. H. compounds. I. Ionisation of the carboxyl group. J. T. E d s a l l (J. Chem. Physics, 1936, 4, Jp0nstitution of the ap-dihalogen derivatives of 1— 8).—Raman spectra have been determined for ethane. H. C. C h e n g (J. Chim. phys., 1935, 32, four NH2-acids, their hydrochlorides and Et esters of lQ W ^ )'—^a^annes an
time, and the effect of heating the crystal and then Acad. Sci., 1935,2, A, 630— 636).—Measurements have treating with X-rays are interpreted theoretically. been made with a Eayleigh type interferometer at R . S. B. room temp, and for XX 4359—6440 A . Combining Mitogenetic radiation. J. B. B ateman (Biol. with dielectric const, data (this vol., 139) the vals. Rev. Camb. Phil. Soe., 1935, 10, 42— 71; Chem. of the electronic and at. polarisation are deduced. Zentr., 1935, i, 3294).—A crit. review. The existence (CF3N )2 and B3N3HG have appreciable vals. of at. of mitogenetic radiation is unproven, and its alloc polarisation. From the variations of n with pressure ation to the ultra-violet region is improbable. the compressibilities of the gases have been deduced. J. S. A. J. W . S. Relation between the photo-potential and the Refractometric investigations in the series of chemical properties of photo-sensitive organic saturated normal nitriles. B. D a ra g a n (Bull. substances. H. T. N ga (J. Chirn. phys., 1935, 32, Soc. chim. Belg., 1935, 44, 597— 624).— d\ vals. for 725—740).— As with inorg. electrodes, the photo various temp., and n20, nBii, w74, and n9S for the electric potential of org. substances appears only in E erc(j, Heycnow, Hegreen, Hcvj0]et, Ha, D, lb?. and presence of H 20. The effect appears instantaneously H y lines are recorded for the series MeCN to only with mols. containing atoms of variable valency, C13H 27-CN. The mol. refractions are calc, and the the NH2-group being the most active. All compounds increments for each CH2 deduced. The results are containing this group are not photo-sensitive, nor in accord with data for paraffins (A., 1934, 132), but arc their leuco-derivatives, but a mixture shows the diverge from those for glycols. J. W. S. effect, as does a dye to which is added the leuco-baso Rotatory dispersion of aliphatic aldehydes. of a less readily reducible dye. It is concluded that P. A. L e v e n e and A. R o th e n (J. Chem. Physics, in these compounds the effect is due to displacement 1936, 4, 48— 52; cf. A., 1934, 12, 1293).— Rotatory of the oxidation-reduction equilibria, produced by dispersion curves of aldehydes of the type the primary photolysis of H 20 . J. W . S. ' CHMeEt-[CH2]„-CTIO have been determined in the Flow method applied to space charge and visible and ultra-violet regions. The -CHO band at ionic processes in oil. K. C h ris t (Z. Physik, 1935, X 2950 is active and the sign of its contribution changes 98, 23—65).—The method of a fluid flowing at right as n changes from 0 to 1 and higher members. The angles to an electric field lias been applied to dielectric magnitude of the contribution varies periodically liquids; it shows the transference of a positive with the no. of C between the -CHO and the asym charge from metal to oil, and the presence of space metric C. M. S. B. charge when an electric current passes through the Photographic measurement of the magnetic oil. It can be used to measure ionic mobilities. rotatory dispersion of water. I. T. P ie r c e and A .B .D . C. R. W. R o b e r t s (Phil. Mag., 1936, [vii], 21, 164— ¡superposition of field distribution and con 176).—The magnetic rotation of H20 for 11 lines ductivity^ W. 0 . Sch u m an n (Z. Physik, 1935, 98, of the Hg spectrum from 5780 to 2483 A . has been if—74).—Theoretical discussion of inhomogeneous determined, and a formula has been derived for the dielectrics. A. B. D. C. dispersion of the Verdet const. A. J. M. determination of dielectric constants* of Magnetic birefringence in solutions of organic organic liquids at radio-frequencies. I. Car substances. I. S. W . Chinchalkar (Proc. Indian ton tetrachloride and chloroform . E. M. Davies Acad. Sci., 1935, 2, A, 525— 531).— Data are re ■ 1 1936, [vii], 21, 1— <41).— The resonant corded for several aromatic hydrocarbons with two circuit method was used to obtain the dielectric or more CG rings in the mol., dissolved in CC14, EtOH, cons s. of CC14 and CHC13, CGIi 6 being employed as E t20, or EtOAc. For Ph2 and most of its simple randard. Vais, obtained at 20° and 25°, respectively, derivatives the mol. magnetic birefringence is approx. ; °C14 2-2360, 2-226,; CHC13 4-7964, 4-7080. 4 times, for m-C6H4Ph2 approx. 9 times, and for n A. J. M. C6H3Ph3 approx. 16 times that of CGHG, indicating that uenshy and molecular polarisation of menthol the C6 rings in these mols. aro either coplanar or nd borneol. H. H arm s (Z. physikal. Chem., 1935, parallel. When the Cc rings are condensed, the ’ , “ >440— 442).— The dipole moments of Z-menthol magnetic and optical anisotropies are > when they are (I-C2±0-03)x 10-18 and (l-65± are separate. H. J. E. e.s.u., respectively. The association in ntr , . icopwuiveiy. i.ne association ] Thiele’s theory of partial valency in terms of ® g solutions has been examined. E. C. electrons. F. E. R a y (Proc. Iowa Acad. Sci., 1934, Molecular volu m e of alkanes.— See this vol., 309. 41, 157— 160).— A discussion. Ch. A bs. (e) thp1cnerfi°n of air' krypton, and xenon in Theory of liquids. V. T. S. W h e e le r (Proc. >h6 ultra-violet. W. K ro n jâg er (Z. Indian Acad. Sci., 1935, 2, A , 466— 476; cf. A., to A — 22).—Dispersion is given down 1935, 119S).— The application of the theory in the ~ . A.B.D.C. calculation of surface tension, internal pressure, co m ^ aCti Ve 1x1(11065 dispersions of volatile cohesion, mol. vibration, internal latent heats, and tet.r-ifi Un<^j fluorine and boron. Carbon compressibilities is reviewed. H. J. E. carHn U° r -1, ’ nitrogen trifluoride, fluoroform, Parachors and chemical constitution. VI. boron n ,gen ?omP°und of fluorine (CF3N )„ Quadrivalent tellurium compounds. B. S in g h hydride nitrogenous boroii and R . K r is h e n (J. Indian Chem. Soc., 1935, 12, 1 3^ jHg. K . L. Eam aswam y (Proc. Indian 711— 714; cf. A., 1928, 355).— The parachors of 272 BRITISH CHEMICAL ABSTRACTS. A.
a-dimethyltelluri-dichloride, -dibromide, and -di Dependence of interatomic distance on single nitrate have been determined and are in good agree linking-double linking resonance. L. P auling, ment with vais. calc, on the basis of a shell of 10 Te L. 0 . B rock w a y, and J. Y . B each (J. Amer. Chem. valency electrons. R. S. Soc., 1935, 57, 2705— 2709).— Using experimental vals. for C-C linkings, a function showing the depend Parachor and molecular refraction of hydraz ence of interat. distance on linking character for single ine and [its] aliphatic derivatives. L. D. B ar- double linking resonance is plotted. The electronic ric x , G. W. D ra k e , and H. L. L o ciite (J. Amer. structure of mols. containing double or triple linkings Chem. Soc., 1936, 58, 160— 162).—-Vais, for para- or aromatic nuclei and of mols. containing C-Cl chors (figures given after compound ) agree with those linkings adjacent to double linkings, and the depend calc, from Sugden’s consts. (A., 1024, ii, 662), but differ ence of linking angles on single-double linking considerably from those calc, from the consts. of Mum- resonance are discussed. E. S. H. ford and Phillips (A., 1929, 1219) : N ,H , 90-7, (CMe2:N-)2 302-2, (CMeEt:N-)2 379-8, (-NHPÏ-0), 327-1, Radial distribution method of interpretation (-NH-CHMeEt)o 400-8, (tNPr^), 318-4, (IN-CHMeEt), of electron diffraction photographs of gas mole 395-5, CMe2:NvNHPr0 313-7, CMeEtlN-NH-CHMeEt cu les. L. P a u lin g and L. 0 . B ro c k w a y (J. Amer. 387-6, 3 : 5 : 5-trimethylpyrazoline 28S-4. The mol. Chem. Soc., 1935, 57, 2684— 2692).— Tests on CC14 refractions of these compounds agree with the calc, and other tetrahalides, Br, Cl2, CGHG, CS2, and COS vais, provided (i) each N in the N-N and N!N linkings show that the radial distribution function given by is given the primary amine val. and (ii) the C!N a sum of Fourier terms corresponding with the rings linking is given the val. of C!C and the N that of a of an electron diffraction photograph of gas mols. sec.-amine. H. B. provides vals. of the important interat. distances accurate to 1 or 2%. Revised vals. of interat. Predissociation limit of CO at 11-6 volts. R. distances and linking angles for several substances Schmid (Physikal. Z., 1936, 37, 55— 56).— New are given. " E. S. Ii. spectral evidence is given for the existence of a pre- dissociation limit for CO at 11-6 volts (cf. A., 1935, Effect of electric and magnetic fields on the 1299). A. J. M. properties of gases. A. A. Z a itz e v (Uspek. Fiz, Nauk. U.S.S.R., 1934,14,1009— 1019).—A discussion. Highly dilute flames of K-I2. E. E. R o th Ch . A bs. (e) (Magyar chem. Fob, 1934, 40, ”65— 81; Chem. Dissociation of some molecules with free Zcntr., 1935, i, 2311).—The heat of tlie secondary valencies. H. Lessiieim and R. S am u el (Phil. gas reaction is sufficient to excite only the red, but Mag., 1936, [vii], 21, 41— 64; cf. A., 1935, 1057).— not the violet, E doublet. The heat of dissociation In the case of the mols. BeF, MgF, CaF, SrF, BeO, of K 2 is calc, as 187 kg.-cal. from the diminution MgO, CdF, BeCl, MgCl, and CaCl, there is good in light intensity on superheating the reaction zone. agreement between the energy of excitation of the J. S. A. products of dissociation and the terms of the metal Plano-radiate compounds. H. J. B a c k e r atom if the ground level of the mol. is correlated to (Chem. Weekblad, 1936, 33, 67— 71).— A survey of the sp:iP term of the metal. Correlation of the ground published data indicates that, whilst in compounds level to the repulsive term s21S is also possible in some of the type CX4 the X are distributed symmetrically of these mols. A. J. M. in space, in compounds of the type C6X G (C6=benzene ring) they take up a symmetrical radial arrangement Statistical perturbation theory. II. Perturb in the plane of the Cfi ring. The resultant compounds ation calculations with exchange for the Thomas- are characterised by high m.p., readiness to crystallise, Fermi theory. P. Gombas (Z. Physik, 1936, 98, chemical stability, and volatility. D. R. D. 417—429; cf. this vol., 134). A. B. D. C. Polymerisation and condensation. E. K- Exchange of energy between diatomic gas R id e a l (Trans. Faraday Soc., 1936, 32, 3— 10).— molecules and a solid surface. J. M. Jack son A general review of the present state of knowledge- H o w a rth and A. (Proc. Roy. Soc., 1935, A , 152, regarding types of linking, mechanical properties, 515—1>29).—The theory of the accommodation coeff. swelling and dispersion, and mol. wt. of highly developed by Jackson and Mott for monat. gases (A., polymerised substances, and the kinetics of their 1932, 1074) has been extended for diat. mois. The production. F. L. U. gas mol. is treated (a) as an oscillator, when the ex change of energy between the rotations of the gas Influence of van der Waals forces and primary mol. and the vibrations of the solid is negligible, linkings on binding energy, strength, and orient and (b) as a plane rotator, when the effect" of thé ation, with special reference to artificial resins. rotations is small for H 2 and larger for 02. L. L. B. J. H. d e B o e r (Trans. Faraday Soc., 1936, 32, 10— 37; cf. A., 1934, 727).— The mutual orientation Distance between molecules and the deter of C6Hg rings parallel to their planes is discussed mination of the volume they occupy in the with reference to the van der Waals and repulsive liquid state (by density). A. E. M a k o v e tzk i forces. In calculating the tensile strength of either (Trans. Kirov Inst. Chem. Tech. Kazan, 1935, No. NaCl or synthetic resins of the P liO H - or »z-cresol- 3, 83— 102).— Expressions are derived for calculating CHaO type, the inclusion of van der Waals forces intermol. distances in liquids, the results differing still further increases the discrepancy between theor\ from those derived from van der Waals’ equation. and observation, which is attributed to weakness due Ch . A b s . (e) respectively to defects in the lattice and to the II (g), III (a, b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 273 smallness of the no. of OC linkings actually formed G r a to n and H. J. F r a s e r (J. Geol., 1935, 43, 785— compared with the no. possible. In the case of 909).—The geometry of close-packing is discussed. well-oriented cellulose derivatives the calc. vals. agree L. S. T. with experiment. Calculation of the relative posi Orientation of molecules of liquids from the tions of CGHr, rings in polystyrene indicates that they X-ray scattering pattern. A. P e t e r li n (Physikal. will tend to lie perpendicular to the direction of the Z., 1936, 37, 43— 52).— The theoretical scattering aliphatic C chains, a conclusion in agreement with the curve for CC14 is calc., and agrees'-weU with the ex observed strongly negative fluxional birefringence. perimental curve of Pierce (A., 1932, 12). A. J. M. F. L.U. Schiller structure. R. T. C olon y ' (Amer. Min., Absolute measurement of efficiency of X-ray 1935, 20, 828— 837).— A discussion. L. S. T. fluorescent screen. 0. G'aertner (Z. tech. Phys., 1935, 16, 9— 12; Chem. Zentr., 1935, i, 3100; cf. Tabulation of crystal forms and discussion of A., 1935, 273).—A Cd tungstate screen absorbed form-names. A. F. R o g e r s (Amer. Min., 1935, 20, 50% of the incident X-radiation, and emitted 0-54% 83S— 851). L. S. T. as visible light. J. S. A. Metallic surfaces and thin films with particu lar reference to aluminium. Britlsh Aluminium Intensity of interference lines in Debye X-ray diagrams. N. S e lja k o v , A. Steeanovski, and J. Co. (Intelligence Memo., 49 pp.).—An exhaustive Hurgin (Z. Physik, 1935, 98, 66—71).— Variation review. of the lattice area covered by the incident beam when Disperse structures. I. Systematics. V. S. its angle is varied accounts for anomalous intensities Veselovski. II. X-Ray investigation of the dis of different orders of reflexion from chemical cata perse structures of graphitic substances. V. S. lytic lattices; these anomalies measure the extent Veselovski and K . V. V a s ilte v (J. Phys. Chem. of defects in the lattice. A. B. D. C. U.S.S.R., 1934, 5, 977— 981, 982— 995).— I. A review of crystal structure and classification. Precision measurements with the Debye- II. X-Ray data for graphitic substances are dis Scherrer method. II. M. Straumanis and A. cussed. Ch. A rs. (e) If,vinS (Z. Physik, 1936, 98, 461—475; cf. this vol., 181).—The film is extended to give interference Crystalline horon. S. von Naray-Szab6 (Natur- rings around the incident and exit portions of the wiss., 1936, 24, 77).— Cryst. B (Merck) consists primary beam; this allows measurement of the film chiefly of the adamantine form, together with ir to be made independently of camera and film curva regular hexagonal leaflets of the graphitic form. ture dimensions. Accurate lattice consts. are X-Ray investigation gave for the adamantine form tabulated for Al, As203, Au, Pe, Pc20 3, MgO, NaCl, (tetragonal), a 12-55, c 10-18, identity period along Fb, Pb(N03)2, Si, T1C1, W , and W 0 3. A. B. D. C. [110], 17-61 A ., and for the graphitic form (rhombic), a 17-64, b 25-0, c 10-26 A . A. J. M. Relation between mechanical strain and in tensity of X-rays reflected by a quartz plate. Crystal structure of solid oxygen. L. V e g a r d IH. E. E uk u sh im a (Bull. Inst. Phys. Chem. Res. (Z. Physik, 1935, 98, 1— 16).— y-0 2 has a cubic -Japan, 1936, 15, 1—14; cf. this vol., 15).—The structure, space-group T ah, the unit cell containing increase in intensity of the interior reflexion of X-rays 8 rotating mols. ordered in pairs; the pair centres transmitted through a quartz plate under the in form a face-centred cubic structure of closest spherical fluence of heterogeneous strain has been studied packing for the pairs. (3-02 has a rliombohedral cell theoretically. R. S. B. of 6 mols. A. B. D. C. Crystalline properties and magnetic aniso Effect of temperature on the reflexion of tropy of distilled bismuth. A. Goetz, O. Stier- A’-rays by crystals. I. Isotropic crystals. C. s ta b t , and A. B. F o c k e (Z. Physik, 1935, 98, 118— Zbsek and G. E. M. J a u n c e y . II. Anisotropic 127).—High-vac. distillation of Bi produces a micro- crystals. C. Z e n e r (Physical Rev., 1936, [ii], 49, cryst. layer 0-5— 0-1 mm. thick carrying a macro- II—18, 122— 127).— I. A short derivation of the cryst. conglomerate of similarly oriented crystals. Debye-Waller temp, factor in the reflexion of X-rays A. B. D. C. from isotropic crystals is given. Isomorphism of Mg 3A l2 and a-manganese. II. Mathematical. The temp, factor eril is a F. L aves, K. L o h b e rg , and P. R a h lfs (Nachr. Ges. 'unction of reflexion plane orientation. The case Wiss. Gottingen, 1934, [ii], 1, 67— 71; Chem. Zentr., °f metals with hexagonal symmetry is treated, 1935, i, 3103).— Complete analysis of the crystal ■toe ratio of the const. M for reflexion _L to and || to structure of “ Mg3Al2 ” shows the space-group to be me principal axis is 1-80 and 1-73 for Zn and Cd, 'J’l, a 10-54 A ., with 58 atoms per unit cell, giving a respectively. N. M. B. true formula Mg17Al12. J. S. A. -Y-Ray studies of crysta ls v ib ra tin g p iezoelec- Structure of aluminium carbonitride, A15C 3N . trically. C. V. B e r ts c h (Physical Rev., 1936, [ii], M. von Stackelberg and K . F. Spiess (Z. physikal. 49, 128—132; cf. Colby, A., 1934, 1296).—Intensity Chem., 1935, 175, 140— 153).— A15C3N has a hexa investigations for quartz and Na K tartrate, using gonal structure; a 3-280, c 21-55 A ., Z = 2 , space- auo patterns and regular reflexion from the crystal group (?!„, The lattice consists of hexagonal at. surfaces, are reported. N. M. B. planes, 5 Al planes interleaved with 3 C planes and Systematic packing of spheres, with particular 1 N plane forming a layer, which consists of two relation to porosity and permeability. L. C. parts similar in structure to A140 3 and AIN, respect- 274 BRITISH CHEMICAL ABSTRACTS.— A. ivcly. The lattice of AIN has a 3-104, c 4-965 A. pa1h1mbllo- The Sr salt shows twinning (cf.- ibid., 2-15 A . is deduced by Zachariasen’s method as the 70). ” E. E. A. mean “ univalent radius ” of the N "' ion. Apparently Fine structure of plant chitin. G. van Iterson, AIN is able to hold some A14C3 in solid solution. jun., K . H. M e y e r , and W . L o tm a r (Rec. trav. chim., R . C. 1936, 55, 61— 63).— X -R ay examination of plant Crystal structure and colloid-chemical pro chitin from Phycomyces is described and the results perties of vanadium pentoxide. J. A. A Kete- are compared with those previously recorded for e a a r (Cliem. Weekblad, 1936, 33, 51 57). V 20 5 animal chitin (cf. A., 1935, 753). An arrangement forms hemimorphic rhombic crystals of space-group of the acetylglucosamine residues in the elementary CL, with 2 mols. in the unit cell; a 11-48, b 4-360, cell of plant chitin fibres is suggested. E. E. A. c 3-555 A ., and dm,0 3-37. The structure is built up X-Ray spectrography of polymerides, par of chains of 0 tetrahedra linked by shared corners, accounting for formation of elongated micelles in ticularly those having rubber-like extensibility. J. R . K a tz (Trans. Faraday Soc., 1936, 32, 77—94).— colloidal solution. D- R- ®- A general discussion of the interpretation of X-ray Structure of thin films of metallic oxides and. spectrograms of cryst. and amorphous polymerides. hydrates. N. Sm ith (J. Amcr. Chem. Soc., 1935, Synthetic rubbers should be made under control by 58, 173—179).—Electron diffraction indicates that X -ray analysis. No polymeride of isoprene has yet oxide films removed from heated metals are poly- been found to have the X-ray characteristics of cryst., showing no evidence of preferred orientation natural rubber. Spectrographic data indicate that or pseudomorphism. The film on Ni is NiO, Cu20 the extensible units in rubber and in polymerides on Cu, and Fe30 4 mainly on Eo. Hydroxide ppts. with similar properties are single mols. F. L. U. from salt solutions are cryst., but show evidence Dependence of cybotactic groups on specific of distortion. E- S. H. volume. R. D. S p a n g le r (Proc. Iowa Acad. Sci., Complex nitrites of iron, cobalt, nickel, and 1934, 41, 253— 254; cf. A., 1935, 1297).— X-Ray copper : structure and magnetic susceptibility. diffraction data are recorded for EtaO near its crit. L. Cambi and A. F e r r a r i (Gazzetta, 1935, 65, 1162— point. The cybotactic groupings depend more on 1190).—The prep, of 15 compounds MlMn[F c(N 02)8] sp. vol. than on temp. The indications of groups is described (MI=K, NH4, Tl; Mn=Ba, Sr, Ca, disappear at about the crit. sp. vol. Ch . A bs. (e) Pb, Hg, Cd). Vais, of lattice consts. and d^c., obtained from X-ray measurements, are given. Comparison Efiect of crystal size on lattice dimensions. with previous data shows that the mol. vols. of the G. I. F in c h and S. F o r lh a m (Proc. Physical Soc., complex ions [Fe(NOo)e]"", [Co(N02)6]"", anc^ 1936, 48, 85— 94).— Lattice consts. of the Li, ha, [Ni(N02)6]" " are 120-3,123-5, and 128-9, respectively. and K halides are determined by the electron- Magnetic susceptibility measurements show that diffraction method. Slight divergences from results [Fen(N02)G]"" is predominantly diamagnetic like by X-ray diffraction indicate that crystal size [CoIU(NO2)0]",> whereas [CoTI(N02)G]'"' is para appreciably influences lattice dimensions. N. M. B. magnetic (1 Bohr magneton) like [Cun(N02)6]"". Electron-diSraction investigation of carbonyl 0 . J. W . chloride, the six chloroethylenes, thiocarbonyl Crystallography of hexa-co-bromomethyl- ch lorid e, a-m eth ylh yd roxylam in e, and nitro- benzene. J. B ein tem a, P. T e r p s tr a , and W . J. methane. L. 0. B r o c k w a y , J. Y . B e a ch , and L van Weerden (Rec. trav. chim., 1935, 54, 962— P a u lin g (J. Amor. Chem. Soc., 1935, 57, 2693— 969).—The hexagonal unit cell of CG(CH2Br)G con 2704) —The C— Cl distances determined vary be tains 3 mols. and has a 11-373, c 5-377 A ., but the tween 1-67 and 1-73 A ., which is 5— 20% < the norma crystal has a rhombohedral lattice with a 9-621 and single linking val. The decrease is due to the partial a 116° 36'. It is concluded that the atoms of each double linking character caused by resonance re mol. are coplanar, and that each Br lies on a circle sulting from the conjugation of an unshared pair of of radius 3-75 A . J. W . S. electrons on the Cl atom with the adjacent double X-Ray study of symmetrical trinitrotoluene linking. The vals. for the angle Cl-Cl-X are smaller and cwclotrimethylenenitroamine. R. H u lt g r e n than the tetrahedral val. for the angle between a (J. Chem. Physics, 1936, 4, 84).— CGH 2M e(N 03)3 single and a double linking for the same reason. is orthorhombic with a 14-85, b 39-5, c 5-96 A . For The vals. for other interat. distances are in good 16 mols. per unit cell dCJx!c_ is 1-710 (lit. 1-654). The agreement with the accepted covalent radii.^ ^ ^ crystals of cycZotrimethylenenitroamine are also orthorhombic. X-Ray analysis gives a 11-5, b 13-2, Diffuse rings produced by electron scattering- c 10-6 A. For S mols. per unit cell d ^ . is 1-82. L. H. G e rm e r (Physical Rev., 1936, [ii], 49, 163 M. S. B. 166; cf. A., 1933, 657).— Two diffuse diffraction Alkaline-earth cacodylates. II. R. T io lla is rings have been obtained by electrons scattered ho (Bull. Soc. chim., 1936, [v], 3, S7— 95).— Cacodylates vaporised ZnS, and from unpolished surfaces of 1' of Ca, Sr, and Ba belong to the monoclinic system, and Cu20, contrary to the view that such ring» with a : b ; c=3-363 :1 2-414, 1-813 : 1 : 2-335, from polished metal surfaces are evidence that 1-5737 :1 : 1-3332, respectively. Forms found pre surfaces are amorphous. The possibility of an anio sent are Ca : pJipn and pa^hpn, Sr : pwbiitft-Jh.iz and phous layer on polished metals is not excluded. Pm
Structure of ice II. R. L. McFarlan (J. on deviations from Ohm’s law show that these Chem. Physics, 1936, 4, 60— 64).— X -R a y analysis deviations are due to the presence of a high-voltage of ice II indicates a side-centred orthorkombic cell, polarisation. a R p> q a 7-30, b 4-50, c 5-56 A . The cell contains 8 mols., has the symmetry of space-group V5—C222v and /Variation of alternating-current resistance of gives d 1-21. The transition from ice I to II breaks nickel in longitudinal magnetic fields. M. M. S en up the H20 mol. and gives an ionic crystal for II. G upta, H. B. M oh a n ti, and S. S iia ra n (Z. Physik M. S. B. 1935, 98, 262— 266).—A.-c. measurements are free Structure of ice. W. H. B a r n e s (Trans. Roy. from many irregularities found with d.c. Hysteresis Soc. Canada, 1935, [iii], 29, H I, 53— 60).— A crit. is less for a.c. (cf. A., 1935, 267). A. B. D. C. discussion of the structure proposed by Bernal and Phenomenon in transformations [in metals Fowler (A., 1933,1106). H. J. E. and alloys] extending over a temperature range. Structure and entropy of ice and of other A. Schulze (Z. Metallic., 1935, 27, 251— 255).— crystals with some randomness of atomic Magnetic transformations and the change from regular arrangement. L. P a u lin g (J. Amer. Chem. Soc., to random orientation of the atoms in the lattice 1935, 57, 2680—2684).—The H20 mols. in ice are aro preceded by inflexions in the curves of electrical so arranged that each is surrounded by 4 others, resistance, temp, coeff. of resistance, and thermal each mol. being oriented so as to direct its 2 H towards expansion. This anomaly is shown by Fc, Ni, and two of the four neighbours, forming II linkings. Ni-Fe alloys (magnetic transformations) and by Only one H lies near each 0-0 axis. There are Au-Cu and (3-Zn-Cu alloys (lattice reorientation). (3/2)iV such configurations for N mols., giving a A. R. P. residual entropy of R log, 3/2=0-805 e.u., in good Magnetic behaviour of nickel wire under high agreement with the experimental val. E. S. H. torsion. R. Gan s (Ann. Physik, 1936, [v], 25, 77— 91).—-Theoretical. L. L. J. Crystal structure from data on magnetic susceptibilities. O. M. J o r d a h l (Physical Rev., Processes of technical magnetisation. I. 1934, [ii], 46,79).— Experimental results on the crystal Weiss' theory of the technical magnetisation structure of CuS0.„5H20 (A., 1934, 243) agree with curve. K. H. R. W e b e r (Z. Physik, 1935, 98, the conclusions of the author (ibid., 241) deduced 155— 180). " A. B. D. C. from an analysis of the magnetic data. L. S. T. Relation of spontaneous and true magnetis X-Ray investigation of the solid solution ation to [optical] emissivity. W. G e r la o h (Ann nature of nitrate-contaminated barium sulphate Physik, 1936, [v], 25, 209— 212).— The anomalous precipitates. G. H. W a ld e n , jun., and M. U. resistance-temp. curve of Ni in the neighbourhood of Oohen (J. Amer. Chem. Soc., 1935, 57, 2591— the Curie point is associated with a similar anomaly' ? J- Apparatus and technique for determining in the emissivity-temp. curve for long XX, in accord the lattice parameters of powdered crystals with a ance with the Hagen-Rubens relation. Both effects precision of 0-01% are described. A study of the are quantitatively related to the spontaneous mag lattice parameters of BaS04 ppts., containing N03' netisation ; data for XX 24 ¡x and 8-7 ¡x are recorded m absence of all foreign cations other than H*, from 100° to 310°. True magnetisation depresses shows that the contaminant enters the BaS04 lattice the emissivity, in further agreement with theory. with, formation of a solid solution. The general L. J. J. problem of ppt. contamination is discussed in the [Optical] emissivity of nickel. E. L o w e (Ann. ught of the results. E. S. H. Physik, 1936, [v], 25, 213— 222; cf. preceding ab stract).—Measurements of total radiation and radi Crystal structure and constitution of BF 3,2H 20 . ation at a series of XX from < 4-5 to 24 \i. for polished ■ J. Klinkenberg and J. A. A. K e t e la a r (Rec. Ni between 100° and 450° are recorded. Magnetisation rav. chim., 1935, 54, 959— 961).— BF3,2H ,0 is has no effect on the total emission, but for x > 8— amorphous with N H 4C104, its orthorkombic unit 10 (i the emission at the Curie point is depressed 0 -6 % containing 4 mols. and having a 8-744-0-06, in a field of 4000 gauss. L. J. J. o i-j-o.03^ c 7-30-j-O-lO A . These cell dimensions 0™ ™ °? identical with those of NH4BF4, viz., Effect of tension on magnetisation [of nickel] ± 0*0o, 5-68¿0*05, and 7*21 ¿0*03 A ., respectively. above the Curie point. G. S c h a r f f (Ann. Physik, uJS, Is ud-erPreted as indicating that the formula 1936, [v], 25,223— 232).— The Curie temp, is independ Id be written (OH3)(BF3OH). J. W. S. ent of tension. Ferromagnetic and true magnetis ation can be distinguished by the effect of tension, Physical investigations on alkali halide crys- since the former is depressed, the latter unaffected. R. H ilsch (Angew. Chem., 1936, 49, 69— 73). Ferromagnetisation can be detected up to 12° above Dmr, e,. rc on published work concerning optical the Curie point. L. J. J. i 3 and electrical conductivity, especially of ystais containing excess of alkali or halide ions. Transverse magnetic effect. J. E. Verschaf- E S H f e l t (Wis. nat. Tijds., 1934, 7, 53— 66; Chem. =««*<* thermal and mechanical tempering Zentr., 1935, i, 3638).— Theoretical. J. S. A. voliorf electromotive force and current- Surface magnetisation in ferromagnetic UEitof1^ CUrves, of rock-salt crystals. A. Ven- crystals. L. W. M cK e e h a n and W . C. E lm o re 108—m f 11 m? R ‘ D rirtna (z - Physik, 1935, 98, (Physical Rev., 1934, [ii], 46, 226— 228; cf. this vol., I'h Ihe effects of tempering NaCl crystals 145). L. S. T. III (c-f), IV (a) 276 BRITISH CHEMICAL ABSTRACTS.— A.
Variation of volume magnetostriction and sion is relaxed, with consequent shortening of the Weiss’ factor with temperature and lattice con specimen. I'- L. U. stant. M. K o r n e t z k i (Z. Physik, 1935, 98, 289— Constitution of the crystallised part of cellul 313). —Fcr r omagnctic substances showing vol. mag ose. TV. Elasticity of cellulose. K. II. M eyer netostriction should have Curie points that vary with and W . L o tm a r (Helv. Chim. Acta, 1936, 19, 68— vol. Measurements on Fe, Fe-Ni, and Ni-Cu alloys 36).— The influence of moisture, temp., orientation, between 20° and 90° confirm this. A. B. D. C. and tension on the modulus of elasticity E of several natural cellulose (I) fibres and some derivatives Behaviour of single crystals of aluminium of of (I) has been determined using Polanyi’s dynamo different degrees of purity prepared from the meter and also an acoustic method of measurement. molten metal and by recrystallisation. F. G isen The temp, coeffs. of the tension are zero or negative (Z. Metallk., 1935, 27, 256— 261).— Single crystals except for (I) acetate, which gives a positive val. like 0f 99.5—99-998% A1 can be prepared (i) by maintain rubber, because of its amorphous structure. In the ing the metal at 800—820° until all nuclei disappear, other fibres, with a cryst. network, the attractive then cooling very slowly without disturbance to < forces between the atoms, or the deformation of the the m.p., or (ii) by drawing rod to 40—45% reduction, valency angles, are responsible for the elasticity. annealing at 250° for 15 hr. to obtain a fine-grained E for natural fibres of high orientation, such as ramie, structure, stretching 0-5— 1 %, and slowly heating hemp, and linen, approaches a val. of approx. 11,000 from 430° to 480° during 45 hr. The cnt. shear kg. per sq. mm. ± 10% , which is close to the val. strength of crystals prepared by method (ii) decreases calc, for the (I) model if the angular forces are 20% almost linearly with decreasing purity from about of the principal valency force. Artificial (I) fibres 300 g. per sq.' mm. for the 99-998% metal to 70 g. or (I) derivatives have vals. of E between 100 and per sq. mm. for the 99-5% metal, whereas that of 5000 kg. per sq. mm. M. S. B. crystals prepared by method (i) is < 20 g. per sq. Crystal plasticity. V. Completion of the rate mm. irrespective of the purity. This difference is of slip formula. 15. O ro w a n (Z. Physik, 1935, 98, ascribed to the more pronounced mosaic structure 382— 387; cf. A., 1934, 949).— A term is added to of crystals prepared by method (ii); A-ray examination the earlier rate of slip formula to take account of confirms this theory. A. It. P. forces arising in the crystal opposed to the applied force : these are likely to be significant for org. Strength and modulus of elasticity of amor crystals. A. B. D. C. phous materials, related to their internal struc tu re. R. H o u w in k (Trans. Faraday Soc., 1936, 32, Variation of the adiabatic elastic moduli oi 122— 131).— The internal structure of asphalts, resins, rock-salt between 80° and 270° abs. F. C. Rose and glass is discussed, and their tensile strengths (Physical Rev., 1936, [ii], 49, 50— 54).— Balamuths and vals. of Young’s modulus are compared. Smekal’s method for measuring Young’s modulus of a cubic theory of “ Lockerstellen ” is adopted to account crystal (cf. A., 1935, 154) is extended to the measure for the discrepancy between calc, and observed ment of all the elastic moduli of any solid crystal strengths, weaknesses in macromols. of an insol. below 0°. Data for the variation with temp, of Ph0H-CH20 resin being due to non-reaction between the adiabatic and isothermal elastic moduli and elastic such reactive groups as happen to be out of alinement. consts. of rock-salt in the range 80—270° abs. are F. L. U. given. N. M. B. High elasticity of three-dimensionally poly Relation between heat of transition and transi merised amorphous materials in relation to tion point of enantiotropic modifications. J. A. M. their internal structure. R. H ouavink (Trans. van Liempt (Rec. trav. chim., 1935, 54, 934— 936).— Faraday Soc., 1936, 32, 131— 143; cf. preceding An equation is derived connecting heat of transmission abstract).—“ High elasticity,” i.e., elastic deformation with the temp., and the at. frequencies and densities which > 1% , is observed in asphalts and glass, of the modifications at the transition temp. Direct | in which it may reach 20% and is connected with a confirmation is lacking owing to absence of data, viscosity range of 1011— 10*3 poises. In hardening but by substituting the ratio of the at. frequencies resins at about 120° it reaches 240%. A relation by the ratio of the abs. temp, at which the forms between the conditions for high elasticity and the have equal sp. heats, the calc, transition tell'Pj formation of insol. elastic three-dimensional networks for Sn and S are of the same order as the experiment3 is shown, and calculations are given to explain vals. J. W. b. changes of Young’s modulus, yield val., and strain Rates of vaporisation of metals in a gaseous at the vield val. when such structures are formed. atmosphere. J. A. M. van Liempt (Rec. trav. F. L. U. chim., 1936, 55, 1— 6).— A formula is d e r i v e d whicu Inorganic substances with rubber-like pro is in agreement with experimental data and "i perties. K. H. M e y e r (Trans. Faraday Soc., 1936, Weber’s formula. The deviations which are o»- 32, 148— 152; cf. A., 1935, 1450).— The elastic served at high pressures are explained. E. E. A. behaviour and A-rav patterns of elastic S and of polyphosphonitrilic chloride are described. They Mol. wt. of polystyrenes and shape of the present many analogies with org. polymerides, molecules in solutions. R. S ig n e r (Trans, l'ara day Soc., 1936, 32, 2 9 6 — 3 0 7 ).— Experiments on and their extensibility is attributed to long flexible chains of mols. which become straight when stretched, mol. wts. of polystyrenes as determined by u r centrifuging and on their fluxional birefringence e. and undergo flexion by Brownian movement when ten IV (a, b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY.
to the conclusion that in certain solvents the mols. of superconductivity by a magnetic field is treated are linear, straight for the fractions of lower, and thermodynamically (A., 1935, 689). A threshold curved for those of higher, jmol. wt. (cf. A. 1933 ‘>3 val. of the c.d. and not of the magnetic field is the 902; 1935, 162, 700). ' F. L. U. ’ decisive quantity. p, p p Rendering visible standing ultrasonic waves Superconductivity of thin m etallic film s. A. D. in transparent solid substances. III. Optical M isen er and J. O. W ilhelm (Trans. Roy. Soc' strain analysis of elastic vibrations. E. H ie d e - Canada, 1935, [iii], 29, III, 5— 11).—The transition hann and K. H. II oesch (Z. Physik, 1935, 98, 141— temp, for Pb films falls rapidly as the film thickness 144; cf. A., 1935, 1312).— Longitudinal and trans is decreased below 9xl0 5 cm. The films were de verse waves give different patterns. A. B. D. C. posited electrolytically on constantan wire cores Determination of ultrasonic velocity in 52 XT« . r . H.J. E. organic liqu id s. S. P arthasaratiiy (Proc. Indian Effect of magnetic fields on the supercon Acad. Sci., 1935, 2, A , 497— 511).— Data for 52 ductivity of thin films of tin. A. D. Mis e n e r , liquids (hydrocarbons, alcohols, ketones, halogen H. G. Sm ith, and J. O. W ilhelm (Trans. Rov Soc’ derivatives, etc.) at 23— 24-5° are given. Aromatic Canada, 1935, [iii], 29, III, 13— 21).—The crit! compounds in general gave higher velocities than did magnetic field necessary to interrupt the super aliphatic compounds. Mols. with electric moment, conducting state of Sn is greater for thin films than or long mols., also gave high velocities. Adiabatic for massive Sn. Hysteresis effects occurred in thin compressibility data are tabulated. H. J. E. films- H. J. E. Longitudinal thermoelectric effect. VI. Mer- Magnetic anisotropy of naturally occurring cury. J. L. Ch ’e n and W. B a n d (Px-oc. Physical substances. I. Mother of pearl. P. N il a k a n - Soc., 1936, 48, 164— 167; cf. A., 1935, 1312).— The tan (Proc. Indian Acad. Sci., 1935, 2, A , 621— Benedicks e.m.f. in Ilg in an unconstricted glass 629).—From measurements of the abs. susceptibility tube undergoes a reversible decrease with risin« and magnetic anisotropy of the nacre of Turbo, temp. It is suggested that there is an anisotropic Ilaliotis, M . margaratifera, Mytilus viridis, and’ quasi-cryst. arrangement of the surface mols. depend Nautilus pompilius it is concluded that the c axes ing on temp. N .M . B. are in each case normal to the elementary lamina. Thermomagnetic properties of nickel. II. The a and b axes are probably in some cases distri W. Band and Y . K . Hsu (Proc. Physical Soc,, 1936, buted at random and in others the a axis is approx. 48, 168— 177 ; cf. ibid., 1935, 47, 910).— Curves ai-e along the line of growth. J. \y. S. given for the homogeneous thermoelectric e.m.f. in Magnetism and polymerisation. J. F a r q u - pure Ni wire 1 mm. diameter for tensions > 8 kg. iiarson (Trans. Faraday Soc., 1936, 32, 219— 226).— Benedick coeffs. are found as functions of magnetic Polymerisation is accompanied by a change in dia field and tension. An antisymmetric part of the magnetic susceptibility, measurement of which can e.m.f. with respect to the magnetisation has been be used to find the mol. wt. of the product with an discovered. Evidence suggests that the homogeneous accuracy which decreases with increase in the degree effect is controlled by the regularity of the micro- of polymerisation. Results of experiments with ervstals in the wire. ' X. M. B. (CH2:CMe-)2, .eyefopentadiene, CNC1; and PliNO are Ionic com p lexes of p o ly m eric com p ou n d s. Siven- F. L. U. "• W alter (Trans. Faraday Soc., 1936, 32, 396— Electrical resistance and magnetic suscept p i Determination of the electrical conductivity ibility of sugar carbon submitted to various 1 “ ®°; and poly-meric methylenecarbamides in thermal treatments. P. Co rriez (Compt. rend. iit02H in conjunction with that of the mol. wt. in 1935, 201, 1486— 1488; cf. this vol., 143).— Vals! we same solvent and of the NIL, end-groups reveals are recorded for specimens heated from 1000° to file presence of ionic complexes. The role of the latter 2000°. T G P in the formation of resins from CO (NI L,), and GILO Character of linking in the carbon monoxide ts discussed. F. L. U m olecu le. R . I. J a n u s and J. S. Sch u r (Physikal Electrical conductivity of alkali metal flames. Z. Sovietunion, 1935, 7, 19— 25).— A simple method r i Kisselmann and A. B ecker (Ann. Physik, 1936, of measuring the magnetic susceptibility of gases j'J, 25, 49—73).— The conductivity of Li, Na, K, is described. The val. for CO is — 1 1 8 ± 6 x 10-7. A and Cs chloride vapours in the Mcker burner CO contains a triple linking. Ch . A bs. (e) nnie at 1250— 1950° abs. has been investigated. Diamagnetism and change of state. P. S. I . 0 metal-free flame the conductivity-temp. V aradaghari (J. Annamalai Univ., 1935, 5 , -18__ e atton corresponds with electron emission by a 26).—Evidence is given that the decreased magnetic otnponent of ionisation potential 2-50 volts. For susceptibility of many aromatic compounds on solidi c m®tal vapour, the conductivity oc the square fication is due to the decomp, on fusion of polymerides j 0 ^he total metal concn.; the conductivity- present in the solid state. The sharp lines in solid mp. relation is independent of the concn., and corre- C0H 6 and Ph20 (cf. Gross, A., 1935, 564) may be due -1 oncis approx with electron emission by free metal to such polymerides. H20 is considered in the light nis formed by chemical dissociation. L. J. J. of Raman data. Differences between the susceptibil J ^ a®®"®i[uilibrium. of su percon d u ctors in a ities of the liquid and vapour states of org. compounds A ^ field . H. L o n d o n (Proc. Roy. Soc., 1935, are eliminated if the v.d. is taken into account in > , 650 663).—Mathematical. The disturbance calculating mol. susceptibility. N. M. B. U IV (b, d) BRITISH CHEMICAL ABSTRACTS.— A. 278
Magnetochemistry of rhenium : metallic rhen to data for CO, N.„ and S in the range 100— 5000° ium and septavalent rhenium. N. P e r r a k is and abs. L. K a p a tos (Praktika, 1934, 9, 121— 125; Cliem. Rotation and entropy of hydrogen sulphide. Zentr 1935, i, 3110).— Measurement of the magnetic K. C lu siu s and A. F r a n k (Naturwiss., 1936, 24, susceptibility of Re20 7 gives for ReTO the same val. 62).—There is no difference between the entropy of as found by Albrecht and Wedekind for metallic H„S calc, thermodynamically and statistically, in Re. For Re prepared by reduction of NH 4R e 0 4, contrast with H 20- There is therefore no zero- the author’s previous val. was confirmed, x ^or point rotation of Its o-modification. This difference K R e0 4 and NH 4R e0 4 are recorded. J. S. A. between H „0 and H„S is connected with the existence of a no. of solid phases of H 2S under ordinary pressures, Diamagnetic susceptibilities of salts forming whereas only one stable form of H20 exists. ions with inert gas configurations. II. Alkal A. J. M. ine halides. G. W. B r in d le y and P. E. H o a r e Thermal data on organic compounds. XV. (Proc. R oy. Soc., 1935, A , 152, 342— 353).— The Heat capacity, entropy, and free energy data for method previously described (A., 1935, 149) has been the iso m e ric b u ten es. S. S. T o d d and G. S. Parks used to determine the diamagnetic susceptibilities of (J. Amer. Chem. Soc., 1936, 58, 134— 137; cf. A„ the halides of Li, Rb, and Cs. The results indicate 1935, 825).— The heat capacities of the four isomeric that the susceptibilities are additive within the limits butenes have been determined between liquid-air of experimental error except for LiCl, LiBr, and Lil, temp, and their respective b.p. The mol. entropies and CsCl, CsBr, and Csl. It is suggested that the and free energies of formation have been calc, rue low vals. in the latter cases are due to deformation thermodynamic stability varies considerably with of the ions produced by (a) the close approach of the the configuration of the mol. E. S. H. negative ions in the Li salts, and (6) the change of crystal structure in the Cs salts. A series of ionic Glass. XII. New heat capacity data for susceptibilities for ions in crystals of the rock-salt organic glasses. Entropy and free energy of type is derived. P- L. B. ill-lactic acid. G. S. P a rk s, S. B. Thom as, and D. W . L ig h t . XIII. Glass formation by a Temperature coefficient of susceptibility of hydrocarbon polymeride. J. D- F e r r y and G. o. tetrahydronaphthalene . B. Is. R a o (Current Sci., P a rk s (J. Chem. Physics, 1936, 4, 64— 69, 70— 1935, 4 , 404— 405).— The susceptibility, studied in 75) —XII. Sp. heat measurements have been made the range 23—70°, showed no temp, effect. The abs. on BiGOH, didactic acid (I), and y-methylhexane in val. w a s —0-688 X 10% showing no variation with glassy, liquid, or incompletely cryst. states by Nernst s field strength. N- method. As with other glass-forming substances Temperature of the Langmuir hydrogen flame. (cf. A., 1930, 1359), there is a transition region over H. von Wartenberg and H. J. R e u sch (Nachr. a temp, interval of 8— 20°, depending on the in1 tine Ges. Wiss. Gottingen, 1934, [ii], 1, 141— 145; Cliem. of the glass and its thermal history. Through this Zentr., 1935, i, 2654).— The temp, of an at. H flame temp, interval the material passes from a hard g ass was determined by the reversal of lines of the Li to a more or less viscous liquid, whilst the sp. hen flame, using the solar image as comparison. Near rises rapidly. The sp. heat of cryst. (I) has also been the electrode 4600— 4S00° was recorded. J. S. A. determined at different temp. The heat of fusion Temperature rise in a material of which the of the crystals at 2S9-90 abs. is 30-1 g.-cal. per g. 11» thermal properties vary with temperature. J. H. entropy and free energy of formation of (I) ha\ e eei A w b e ry (Proc. Physical Soc., 1936, 48, 118— calc. 124).— Mathematical. N. M. B. X III. Polyisobutene, average mol. wt. 4000, forms a glass of nature similar to those of low mol. wt. » Polymorphism. H. E. P hipps and J. II. R e e d y transition region, through which the sp. heat increases (J, Physical Chcm., 1936, 40, 89— 100).— An accurate by 32% , is 192— 202° abs. The expansion coen. method for determining the transition temp, of sol. has been measured at 160— 300° abs. and increases substances by means of a dipping rcfractometer is by 200% between 185° and 205° abs. In agreemen described. Examination of NH4N 0 3 III petro- with the behaviour of other glass-forming substances, graphically indicates that it is orthorhombic. Re- y], at the mean transition temp., is approx. 1013 poises- determination of the transition point of CCl4by heating The influence of mol. structure on glass formatm and cooling curves gives —47-66±0-2°. The effect is discussed: M. 5- ■ of impurities on this is much > on the m.p. r M. S. B. Purification and physical properties of organs Temperature dependence of free electron compounds. XII. Lower aliphatic bronn e specific heat. E. C. S to n e r (Phil. Mag., 1936, [vii], E. L. S kau and R. M cCulloch (J. Amer. Chem. 21, 145—160).—Mathematical. The Ferini-Dirac 1935, 57, 2439—2440; cf. this vol., 290).—Re^ .I statistics are applied to obtain the variation of energy data for the b.p., f.p., and d of. Et, Pr®, P1 > and sp. heat over the whole temp, range, the range BuS, BuY, and n-amyl bromides are recorded- E. o. -W-* of validity of the formulae being specially considered. A. J. M. Regularities in the m.p. of polyenes. P- Equation for approximating heat capacities of and C. G rundm ann (Ber., 1936, 69, [B], 224— gases calculated from spectral data. 1. N. The same regularities are observed in the absorR . and fluorescence spectra of the p u r e l y alip i G o d n e v (J. Amer. Chem. Soc., 1936, 58. 180— 181). The proposed equation has been applied satisfactorily polyenes and of the oxf-diphenylpolyenes. In exj IV (d,f-h), V (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 279
ation of further physical regularities it is found that (J. Chem. Physics, 1936, 4, 3 0 -3 3 ).— /) is nearly a the m.p. of polyenes are to a first approximation a linear function of d. An expression relatino- fluidity linear function of the no. of conjugated double linkings. to the increase in d over that of ordinary H„0°is shown The inclination of the graphs is nearly identical for to be valid to 0-006% over the whole concn. range aldehydes, carboxylic acids, and their Me esters, but whilst Bingham’s equation is valid to 0 -01%. is steeper for the alcohols. Among cis—trans-isohi- erides the cis-forms (H2C20 4, nialeic, cis-ci’s-muconic . . , . m ' s . b . Absolute measurement of the viscosity of acid) show a different sequence of m.p., and the 2- W i d tm - A. J. L ew is (Proc. Physical Soc., 1936 furylidenepolyene-aldchydes and -carboxylic acids do * 8 , 1 0 2 -1 1 0 ; cf. Stott, A., 1933, 895).— Using the not conform to the scheme. The following new or capillary flow method, -/¡, with independent correction amended m.p. are recorded : sorbaldehyde, m.p. sor6ate, m.p. 15°; decatetraenoic acid, oo1- oo/w was measured for the temp, range ¿¿o 330 . The temp, variation of -q and the val. m.p. 226-5°. h . W. at the f.p. agree with Andrade’s theory (cf. A. 1934 Time of melting of thin fuses. II. J. A. M. 35°)- ' N. M. B. vax Liempt and J. A. d e V rien d (Z. Physik 1935 Association of substances which are solid at , 13on ~ -40; Cf' A ' ’ 1935’ 289).— Currents, I, ordinary temperatures [determined] hy the up to 20 times the limiting current require a time fluidity method. E. C. B ingham and J. E H a t r, for fusion, where / 2£=const. A. B. D. C. f i e l d (Physics, 1935, 6 , 64—68).—The fluidities of m Thermochemical properties of nitrous oxide. BzOH C10H 8, CII2Ph-OBz, Me2C20 4, Et2C20 4, m Soi'ton, IL R. Ambler and G. W. Williams, ll-2C2U4, and succinic, glutanc, and adipic acids (Proc. Ihysical Soc., 1936, 48, 189— 202).— The con and of mixtures of BzOH and C10l l 8 with CH2Ph-OBz ditions of initiation and of pressure under which were measured. A viscosimeter bath suitable for use direct decomp, will propagate progressively and up to 230° is described. Cji. A bs. (e) explosively through N20 are examined. The heat Molecular dimensions from viscosity studies « formation, determined by explosive thermal R. M. T iieis and H. B. B u l l (J. Physical Chem.' decomp, at 42 atm., is -19-52±0-l g.-cal. per mol. 1936, 40, 125— 131).— The viscosity of stearic acid at const, pressure. A simple method for comparing and lecithin in CC14 has been determined arid a linear ft-for two gases is applied to N20 and CO„ over 10— 45 relation observed between cq0/(-q—»„) and c, where atm' “ N. M. B. v)0 and -/j are the viscosities of the solvent and solution, Continuation of vapour-pressure curve above respectively. The possibility of applying Eisen- wl -p1^ 1 F‘ Kruger (Physikal. Z., 1936, schitz’ equation (A., 1932, 121) to determine the ratio \ ) 1T £ lleoretical- The methods of Eucken of the length of the solute mols. to their diameter is & 1934, . 062) and of Trautz and Ader (ibid., discussed. jq 5 j> «) gave identical results in the neighbourhood of d>e cnt. point. A j M; Partial molal volumes of ammonia and hydro gen in liquid ammonia-hydrogen mixtures Vapour pressure of glycols . 0 . J. Schierholtz under pressure at 1Q0°. R. W ie b e and T. II 57 (J- Amer- Chem. Soc., 1935, T rem ea rn e (J. Amer. Chem. Soc., 1935, 57, 2601— 2 2709— 2711).— V.p. (10— 760 mm.), and d 2603).—Data are recorded and their thermodynamic ecoided for ethylene, «¡3- and ay-propylene, significance is discussed. E. S. H. '/•and py-butylene glycols. E. S. H. Density of solutions of alkali metal halides in Isopiestic m ethod of determining the vapour liquid ammonia. W. C. J o h n s o n and R. 1 Pressures o f s a lt s o lu t io n s . A. .Taxis (Proc. Roy. M a rte n s (J. Amer. Chem. Soc., 1936, 58, 15— 18).— i iii]’ 29’ I n > 87— 89).— A modi- Data are recorded for solutions of the chlorides, iamni • ^inc^air s method for use with larger bromides, and iodides of Li, Na, and K in liquid NIL ■ mples is described (cf. A., 1933, 587). H. J. E. between -—32° and —60° over as wide a concn. range °f exPansion of silver iodide and as solubility permits. E. S. H. v m i S of th a lliu m - G. Jon es and F. C. [Refractive index of] mixtures of piperine and 1 Iffi ilUn1er- Chem- Soc- 1!)35, 57, 2532— 2536).— iodides. S. Grum-Grshimailo (Trans. Inst. Econ. tanen «N ?ifc' cll|atometer, which acts simul- Min. U.S.S.R., 1934, Ho. 61, 21— 23, 27— 28).__ foiw;, / as il thermo-regulator, is described. The The vals. of n recorded for piperine, Sbl3, and Asl3 determ tneaii pubical coeffs. of expansion have been differ from those given by Larsen (U.S. Geol. Siirv. l0'3 AaT 1* « yrex gIass 9'8 5 x l0 ‘ °> PhMe 1-111 X Bull. 679, 1921). Ch. Abs. (e)
111 1 3 5 X1 o ’i X G’ T1C1 ?'69 x 1(H * T1Br 1-53X10-*, Raman effect in mixtures of oleum and nitric acid. J. CnkDiN (Compt. rend., 1936, 202, 220— Ken ei!fa ^ curves an 70’4 x1~ 32: ? \~±. cf- XI.,A - 1935, 100156),;.--- teristic spectral effects are very different from those at nrpqi.,Uiira1 K *changes‘ c anffes on melting were determineddeterminea accompanying the association“ of SO. and IL SO, werH"•ere calc llre\ V UP ' 1!/ *0% 9000 atm-atm' TheT!le heats of fusionfusic in H 2S20 7. ' T. G. P. Visc 1 ( ~J data are given. Ch. A bs. (e) Magnetic susceptibilities of nitric acid solu "ithw°at!i !*f or“ teri ™ oxide and its mixtures tions. S. P. Ranganadhan and M. Q u r e s h i (Cur at 2o . G. Jones and B. J. Fornvalt rent Sci., 1935, 4, 404).— The susceptibility-concn. 280 BBITISH CHEMICAL ABSTRACTS. A. curve over the range 4—65% HiSr0 3 shows marked 65 at.-% Au; for 47—53% it can be obtained only departure from linearity. The g.-ionic susceptibility by quenching from 420°. The relations between the of the NO, ion is —20-83x10-«. Min. in the curve lattice structures, and the influence of heat-treatment, correspond with HN03+ 50H,0, -J-6H,0, +4H 20 , are discussed. In the region 65—80 at.-% Au a and 2HN03+ 5 H ,0 . ' N. M. B. cubic structure is found. The sp. resistance for the entire range has been measured. L. J. J. Constitution of liquid zinc amalgams. H. A. L ie b h a fsk y (J. Amcr. Chem. Soc., 1935, 5 7 , 2657— Ferromagnetic increment of resistance of 2662).—Analysis of published e.m.f. data shows that copper-nickel alloys. B. S v e n s so n (Ann. Physik, the deviations can be explained on a polymerisation 1936, [v], 2 5 , 263—271).—Data are recorded for the hypothesis which assumes the existence of Zn2 and sp. electrical resistance of nine Cu-Ni alloys with Zn3 in equilibrium with monat. Zn. E. S. H. II— 90 at.-% Ni betw-een 0° and 500°. The ferro magnetic component of the resistance has a max. Binary mixtures. IV. L. P ia tti (Angew. val. at approx. 80 at.-% Ni. L. J. J. Chem., 1936, 49 , 77— 78; cf. A., 1934, 1301).— The b.p. of binary mixtures (0— 100% ) of o-, m-, and p- Solid solubility of magnesium in aluminium. crcsol with C0Me2 and CcH 0, respectively, have been S. K ish in o (J. Chem. Soc. Japan, 1935, 56 , 322— determined. The“ vals, are < those calc, from the 324).—The determination of the solubility of Mg in mixture rule. E. S. H. Al by microscopic examination, or by electrical Azeotropic and constant evaporating mix resistance measurements, is difficult for < 5% of Mg. Ch . A b s . (e) tu res. S. I. Sk lja b k n k o and M. K. B a r a n a je v M.p. of eutectics. Lipowitz alloy and Wood's (Z. physikal. Chem., 1935, 1 7 5 , 203—213; cf. this m eta l. S. J. F b e n c h (Ind. Eng. Chem., 1936, 28, vol., 281).— It is deduced that r 1/r2= ( p 1/p2)V(-®i/A)> III— 113).—The cooling and melting curves of the where vx and v2 are the rates of evaporation of the Lipowitz allov (Bi 50, Pb 27, Sn 13, Cd 10%) and components of a binary liquid mixture having the W ood’s metal (Bi 50, Pb 25, Sn 12-5, Cd 12-5%) diffusion coeffs. D1 and I)2 and partial v.p. p x anc* Pi- coincide approx. over the greater part of the const.- A mixture in which x 1 and x2 are the mol. fractions temp. region, giving the same m.p. and f.p., viz., of the components will evaporate without change in 71-7° and 69-7°. The former approaches the quater composition if x 1[x2—(p1lp2)\/(D1ID2), an equation nary eutectic more closely than does Wood’s metal. which has been confirmed by experiment. Mixtures Discrepancies in published vals. may be due to under for which the vapour given off at a particular temp, cooling or to Hg as an impurity. It is suggested that has the same composition as the liquid do not, in names for the alloys should be discarded, and that general, evaporate without change of composition composition and m.p.—f.p. range should be sub at that temp. B- C. stituted. R . S. B. Orthobaric azeotropes. Esters-hydrocarbons. Ternary diagram of aluminium—copper-silicon M. L e c a t (Ann. Soc. Sci. Bruxelles, 1935, 5 5 , B, 253— system. K. M atsu yam a (Kinz.-no-Kenk., 1934,11, 265; cf. A., 1930, 680).— 315 binary systems involving 461— 490).—The Al-Cu, Cu-Si, and Al-Si diagrams 44 hydrocarbons and. 72 esters have been studied. have been reinvestigated. In the system Al-Cu-Si The b.p., composition, and heats of formation of the there are 18 monovariant curves and S nonvariant azeotropes are given. R. S. points. The a, ß, y, and S solid solutions of the B.p. and composition of the vapour phase of systems Cu-Al and Cu-Si are contiguous. In the the ternary system ethyl acetate-ethyl alcohol- solid state there are 9 monovariant curves and 2 water. V. A. K ir e e v , I. J. K lin o v , and A. N. nonvariant points. Ch . A bs. (e) Gkigoboyltsch (J. Chem. Ind. Russ., 1935,1 2 , 936— 940).—B.-p. data and the composition of the vapour System iron-cementite-manganese carbida- manganese. R. V ogel and W. D öbing (Arch. phases are recorded. R. T. Eisenhiittenw., 1935— 1936, 9 , 247— 252).— Contrary Viscosity measurements of the ternary system to previous statements, Mn and Mn3C do not form a diopside-albite-anorthite at high temperatures. continuous series of solid solutions, but a complicated S. K ózü and K. K ani (Proc. Imp. Acad. Tokyo, series of reactions occurs during cooling. The liquidus 1935, 11 , 383—385).—Data are recorded for the curve passes through a min. at 3-5% C, 1160°, and temp, range 1150— 1575°. In a homogeneous melt, Mn3C undergoes a transformation at 1050°, the temp- v) varies linearly with the temp, but the slope in of which is gradually decreased by addition of Mn to creases suddenly when the primary phase begins to 920° at 3-5% C (eutectoidal point). At 740° in alloys crystallise. E. S. H. with > 1 -2 % C the y-Mn solid solution undergoes X-Ray and electrical investigation of the a eutectoidal transformation into a-Mn+a-Mn3C- copper-gold system. C. H. J o h a n s so n and J. 0 . The y-ß-transformation point of Mn is lowered L in d e (Ann. Physik, 1936, [v], 2 5 , 1— 48; cf. A., by addition of C from 1140° to 840°, whereas the 1926, 112; 1927, 400).—A new regular structure ß—oc point is raised from 740° to S40° (0-9% C). The (CuAu n) in the region 50 at.-% has been identified, complete diagram and micrographs showing charac and its lattice dimensions are measured. CuAu n has teristic structures of alloy's within the various fields rhombic symmetry, and is a modification of the are included. In the ternary system Fe-Mn-C the tetragonal form (CuAu i). The unit cell is the 4-atom equilibria resemble those in the Fe-C sy'stein up to face-centred cell repeated 10 or 11 times. CuAu n 60% Mn; in alloys with a higher Mn content com is stable at low temp, for the regions 36— 47 and 53— plicated reactions occur due to the allotropic changes V (a, b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 2S1
in Jin and Mn3C; thus the section through 70% Mn of air vJv^(pJp2)V{V\i(B-lPi)VlD2(B~fa)]}, contains 17 phase fields. In the Mn corner of the where tq and v2 are the rates of evaporation, and D l ternary diagram there are 4 planes of four-phase and D2 the diffusion coeffs. of the vapours, and B is equilibrium, one of which corresponds with a ternary the barometric pressure. R . C. eutectoidal change : y-M n = a-M n + y-F e+ a-M n 3C; Dependence of rate of evaporation on nature the eutectoid contains Fe 25, Mn 77-95, C 2-05% of gas flowing over the surface of the evaporating (040°). A. R, P. liquid. S. I. Skljarenko and M. K . B a r a n a je v (Z. Properties of the oxides of nitrogen. II. physikal. Chem., 1935, 175, 214— 21S; cf. preceding Binary system N 20 3-H ,0. III. Pseudo-binary abstract and this vol., 280).—If the vapour of the system N 20 .,-H 20 . T. M. L o w r y and J. T. L em on. liquid is heavier than the gas passing over the surface, IV. Formation of two liquid layers in mixtures vi/vo~\/(D 1iD.i), where u, and v0 are the rates of of nitrogen peroxide and water. T. M. L o w r y , evaporation into, and D 1 and D0 the diffusion coeffs. E. L lo y d , and W. V. L lo y d (J.O.S., 1930, 1— 0, of the vapour into, the gas and air, respectively. 6—10, 10— 17).—II. Two liquid phases are formed If the vapour is the lighter, as in the evaporation of over a wide range of mixtures. The limiting mixtures H20 into air, allowance must be made for convection correspond with 42— 97 w t.-% N.20 3 at 0° and 48— currents. R.. C. 95% at 20°. A max. temp, of separation was ob Principles of gas exsorption. III. A. G u y e r , served at 55° and 05% N 203. Escape of NO into the B. -T o b le r, and H. F a rm er (Chem. Fabr., 1930, 9, gaseous phase lowers all the temp, and the crit. 5— 7; cf. A., 1934, 592, 1005).— The apparent solution temp, is possibly 20° > that recorded. " evasion coeff.” and rate of loss of gas from falling A quaternary point, at which the gaseous and two drops of I120 is independent of the height of fall, and liquid phases arc in equilibrium with ice, occurs at therefore of the velocity of fall. The relative loss of -33-3° and 30% N203, and another, with N20 3 as gas increases with increasing height of fall. The the solid phase, may occur below' — 103° at > 98% N203 relative loss of gas from a H2G stream falling against an air resistance increases with the height of fall and III. Two liquid phases are formed over a wide with decreasing cross-section of the stream. Reduced range. A max. temp, of separation was observed at pressure has only a slight influence on the loss of gas. 67° and 89% N20 4. Escape of NO into the gaseous This is related to the degree of disturbance of the H ,0, phase probably lowers the temp. Homogeneous aq. udiich is a function of the air pressure. J. W . 8 1 solutions deposit ice dowm to —50° and up to 33% X 0 4 and a compound of unknown composition over Diffusion of gases through metals. II. Diffu a narrow range down to —56° and up to 44% N20 4. sion of hydrogen through aluminium. C. J. Son-homogeneous mixtures containing > 44% N20 4 S m ith e lls and C. E. R a n s le y (Proc. Roy. Soc., deposit I1N03,3H20 from the upper aq.-acid layer, 1935, A , 152, 706— 713; cf. A., 1935, 692).— The at temp, up to a max. of —22-5°. The lower laver rate of diffusion of H 2 through A1 above 400° depends of liquefied gas deposits N20 4, either in the ordinary on the state of the surface. The highest rate is given stable form or in a metastable form which melts 11° with a surface freshly scraped in H2, but it rapidly lower. falls, and after several hr. reaches a steady vah IV. The composition of the two liquid layers which is only 0-1 of the initial rate. This low' rate is ms been determined by analysis. The limits within obtained with an anodically oxidised surface. The which two liquid layers are formed in the system effects of temp, and pressure are represented by Ha0—N20 3-N 20 5 at 0° and 20° are shown on triangular Richardson’s equation. L. L. B. diagrams. E. E. A. Diffusion of water vapour through copper. Solubility of gas mixtures in liquids under J. H. d e B o e r and J. D. F a s t (Rec. trav. ehim., Pressure. I. S olu b ility in w a ter of ca rb on 1935, 54, 970— 974).— At about 800° II20 vapour dioxide fr o m a dm ixtu re w ith h yd rogen at 2 0 ° diffuses at the rate of about 1-9 x 10~12 g.-mol. per siid 30° and under total pressures up to 30 kg. sq. cm. per sec. through Cu 1 cm. thick, when the Per sq. cm. I. R. Kritschevski, N. M. S h a v o r o x - pressure difference is 1 atm. The rate of diffusion and V. A. Aepelbaum (Z. pliysikal. Chem., of II2 under similar conditions is 230 x l ( H 2 g.-mol. U35, 175, 232—238).—A thermodynamic method is per sq. cm. per sec. The diffusion of N2 through described for calculating the solubility of components Cu, if existent, is very slow'. H20 vapour" does not gas mixtures in liquids in the case where the thermo diffuse through chrome-Fe, whilst at 900° the rate of dynamic potential of the dissolved gas is not affected diffusion of N2 is > 6-9X10-12 g.-mol. per sq. cm. ov the presence of other dissolved gases. The per sec. J. W. S. experimental results show' that if the pressure is not Diffusion of helium through fused silica, oo high the solubility of CO, in H20 at a given E. 0 . B r a a te n and G. F. C la r k (J. Amer. Chem. ugacity is the same whether the gas is pure or mixed Soc., 1935, 57, 2714— 2717).— Measurements at 1 R .C . —78° to 562° show that the rate of diffusion oc pres Ratio of rates of evaporation of different sure and inversely oc the thickness of Si02. Two quids in moving air. S. I. Skljarenko and vals. for the activation energy have been obtained,* %'_ ■ Baranajev (Z. physikal. Chem., 1935, 175, depending on the temp, region. E. S. H. ' 0 '-02).—It is deduced theoretically and confirmed Diffusion of silver in glass. 0. Kubaschbw'ski xpenmentallv that for two liquids of v.p. j)l and p 2 (Z. Elektrochem., 1936, 42, 5— 7).— The rate of evaporating under the same conditions in a current diffusion and variation with temp, have been v (b, c) 282 BRITISH CHEMICAL ABSTRACTS— A. determined- The amount of Ag taken up depends of pptn. centres. If the stabilising effect of the primarily on the availability of 0 2, showing that it ion of variable concn. is very great, or there is con is not a case of simple diffusion of Ag*. E. S. H. siderable tendency to complex formation, the first max. only is observed, whilst if both ions have but Equilibrium between strontium sulphate and a slight stabilising effect the second max. only is e T? C water at various temperatures. G. Gallo (Annali present. JS'- L- Chim. Appl.. 1935, 25, 628— 631).— The solubility Distribution of thorium-C" in thallium salt of SrS04 in H 20 increases from 0-0121 (g. per 100 c.c. of solution) at 5° to 0-0141 at 40°, then decreases solu tion s. J. ZiRKLER (Z. Physik, 1935, 98, 75— to 0-0113 at 95°; both pptd. SrS04 and calcined 76).— The separation of the Tl isotope Th-C" from eelestine give similar vals. The influence of N II4C1, a solution containing Tl’ and Tl does not depend on NBLNO,, and (NH|)2S 0 4 on the solubility is studied. the total mass of the ions present, but on the amounts E. W . W . of Tl205 and Tl2«3. A. B. D. C. Re-determination of the solubility of chloro- Adsorption of hydrogen and deuterium on pentammine cobaltic chloride. F. J. Ga r ric k copper at low pressures. R. A. B e e b e , G. R. (Nature, 1935, 136, 1027—1028).— The compound Low iun., E. L. W ild n e r , and S. Goldwasser (J. purified by an improved method (A., 1935, 1335) Amer Chem. Soc., 1935, 57, 2527— 2532).— At -7 8 ° gave 0-00925 and 0-0211 g.-mol. per litre at 0 -20° and 0— 2 mm. the rate of adsorption is less for D, and 25-00°, respectively. L. S. T. than for Id2, but equal amounts arc adsorbed at equili brium. At 0° LI, is more strongly adsorbed, but at Solubilities and free energies of some metallic 125° it is adsorbed < D ,. The differential heats su lph ides. S. E. R a y itz (J. Physical Cliem., 1936, of adsorption are identical for H, and D,. E. S. II. 4 0 . 61— 70).— The solubility data for the sulphides of Zn, Pb, Cu, Tl, Ag, and Cd have been examined Adsorption of hydrogen on tungsten. J. K. and the solubilities recalc, with the help of recent R o b e r t s (Proc. R oy. Soc., 1935, A, 152, 445— 4=83).— activity data. Free energies of formation have also The method used depends on the fact that the accom been calc. M. S. B. modation coeff. of Ne is different for a bare surface and for a surface with an adsorbed film on it. Satur Solubility of oxalic acid and oxalates of the ation occurs at a partial pressure of H 2 of the order alkaline earths in mineral acids. I. H. Trapp of < 10_1 mm. and the process is one of chenii- (J. pr. Chem., 1936, [ii), 144. 193— 210).— The solu sorption, which takes place rapidly at these low pres bility of H2C20 4 in 0— 16-46% HC1, 0—46-96% H 2S 04, sures at 79° abs. The heat of adsorption and amount and‘0—29-35% H3P 0 4 at 204-2° is recorded. With of gas adsorbed have been measured 011 a single K „S 04 and CaS04 it forms KHC20 4,H2C20 4, and fine wire. The film is stable at negligibly low pres CaC,04,2H20, respectively, until the concn. of H 2S 04 sures at room temp. There is strong evidence for is 12 and 13%, respectively, at 204-2°- Lower the view that the H 2 is adsorbed as atoms, with one concns. of H2S 0 4 suffice to dissolve the salts at higher atom for each W atom in the surface. The binding temp. NaCl" and MgS04 form Na2C20 4,H2C20 4,2H20 is of the same type as that of 0 2 on W. The bearing and MgC20 4,2LI„0, respectively. BaCl2 gives of the data 011 the general problem of H 2 adsorption BaC20 4,H2C20 4,2H20 until the concn. of HC1 is and on that of activated adsorption is considered. 4-5% and above this concn. BaC,04,H ,C„04,3H20 . L. L. B. " " R . S. C. Composite films of oxygen and hydrogen on Equilibrium in the system lithium phthalate- tungsten. J. K. R o b e r t s (Proc. Roy. Soc., 1935, p hthalic a cid -w a ter. S. B. Sm ith, W. A. Sturm , A, 152, 477— 480).—When an 0 2 mol. is adsorbed on and E. C. E ly (J. Amer. Chem. Soc.. 1935, 57, 2406— a W surface already covered with H2, a mol. of H, 240S).—Solubility data at 0°, 25°, and 50° have is ejected into the gas phase. The behaviour of Hi been obtained. The compound LiHG8H40 4,2H20 in the presence of a surface partly covered with 0, is formed at these temp, and can be crystallised is also considered. The data support the theory that at temp. -t 60°. E. S. H. activated adsorption of H 2 is connected with the inter Solubility of metals in crystals of halides. G. action between H 2 and surface 0 2, either adsorbed T am m any (Z. anorg. Chem., 1935, 228, 92— 96).— or forming an integral part of the solid lattice^ ^ Solutions of metals in their solid halides (e.g., Na in NaCl, Ca in CaF2) are discussed from the point of Adsorbed films of oxygen on tungsten. J-jL view of their similarity to solutions of one metal in R o b e r t s (Proc. R oy. Soc., 1935, A , 152, 464—47/. crystals of another. F. L. U. cf. preceding abstract).—Experiments show that a Precipitation processes. I. Connexion be second mol. film of 0 2, which is quite stable a tween ratio of concentrations of reactants and room temp., is formed on top of the well-known stable precipitation of silver thiocyanate and cyanide. film (A., 1931, 782). The heats of adsorption and no. B. Tezak (Z. physikal. Chem., 1935, 175, 219— of mols. adsorbed in each film have been measure/ • 231; ef. A., 1934/593).—The pptn. curve (graph of Consideration of the process of building up an im turbidity 4 min. after mixing the reacting solutions mobile film » bv„ j the adsorption of------the two atoms ot >• , 'against reactant concn.) exhibits two max. if the stab diat. mol. on neighbouring solid atoms shows that ilising effects of the two reacting ions are large but such a film necessarily has gaps in it. The no. 0 approx. equal. The max. at the lower concn. is due these gaps has been measured, and the amount 0 to the isoelectric point, and the other to the reduction O, in the second film found to correspond uj 1 in solubility and stability and to the rapid formation adsorption on the gaps in the first. The possi e v (c) g e n e r a l , p h y sic a l , an d in o rg an ic c h e m istr y . 283
rôle of these gaps in the diffusion of 0 2 into W is different active charcoals. H. Brintztnger, A. discussed. The accommodation coeffs. for Ne S c h a ll, and H. G. B e ie r (Kolloid-Z., 1936, 74, 29— striking the at. and the mol. film are deduced. 32).— Max. adsorption is defined as the amount of L. L. B. substance adsorbed at a given temp, by 1 g. of the Sorption of ammonia and other gases by adsorbent from a saturated solution. Determinations arsenic trisulphide. N. M o r ita (J. Cliem. Soc. with salicylic acid and quinine are reported. Japan, 1935, 56, 325—332).—The sorption velocity E. S. H. of NH3 by As2S3 varies with the mode of prep, of the Adsorption of lead nitrate by metastannic As2S3. The product at room temp, corresponds acid. A. G. B osin and M. M. S h ilk in a (J. Appl. with As2S3,NH3. The behaviour of N H 2Et is similar. Chem. Russ., 1935, 8 , 1287— 1290).— When Sn-Pb Ch . A b s . (e) alloys are dissolved in H N 03 part of the Pb(NO.,).> Adsorption of gases by virgin salt surfaces. formed is adsorbed on the Sn02; the amount (C'J F. D urau and A. H o r n (Z. Physik, 1935, 98, 198— of Pb adsorbed by a const, amount of Sn02 is given 226).—Observations have been made with NaCl, by C2= ‘iy 'C 1, where C1 is the amount of Pb found in CdCl2, and N aN 03 which were melted, freed from the solution. R, p. impurities, and powdered in high vac. A. B. D. C. Adsorption at the interface between two fluids. Adsorption on chromite catalysts. J. C. W. I. Adsorption of methylene-blue, methyl- Frazer and C. G. A l b e r t (J. Physical Cliem., 1936, orange, Congo-red, and orange II at benzene- 40, 101—112).—The “ activated adsorption” of 0 2 water and chlorobenzene-water interfaces. C. W. and CO on Cu chromite (I) at 100— 200°, as distinct G ib b y and C. C. A d d iso n (J.C.S., 1936, 119— 127).— from the van der Waals adsorption, has been deter The adsorption, at various concns. in H 20 , at H 20 - mined in order to see what relation it bears to the CgHg and H 20-PhCl interfaces and the interfacial catalytic activity of (I) in the oxidation of CO. tensions have been measured. The results show Activation energies of the adsorption have been marked quant, deviations from the predictions of calc. The activated adsorption of 0 2 increases with Gibbs’ equation in all cases, although this equation rise of temp., but that of CO attains a max. and then gives vals, of approx. the right order and in closer falls. This behaviour may be due to entirely separate agreement wit h the observed results than with Lewis’ processes taking place at the surface of (I). The results data. Two types of concn.-adsorption curve are suggest that it is the activated adsorption of 0 2 found. The type differs according to the adsórbate, which determines the catalytic activity of the surface. but is independent of whether the interface is H 20 - Possible mechanisms are discussed. M. S. B. C6H g or H 20-P1iC1. Curves for Congo-red and Me-orange have the qual. features of a Gibbs curve; Adsorption at crystal-solution interfaces. those for methylene-blue and orange II have not. VIII, Influence of dyes and other organic com The area of the interface occupied by the adsorbed pounds on the crystal habits of barium and lead mol., reckoned as monomeric, in the region of max. nitrates. (Miss) P. P. D avis and W . G. Fk4n ce adsorption is calc. For methylene-blue and orange (J- Physical Cliem., 1936, 40, 81— 87).— The habit II, the adsorbed layer, on either interface, is uriimol., assumed by crystals of Pb(N03)2 and B a(N 03)2, but for the other two dyes, the surface concn. on Separating from pure solutions arid solutions contain- CfiHfi is < , and on PhCl about twice as great as, that *g dyes or other org. substances, indicates that which is represented by a unimol. layer. E. E. A. 'ney approximate most closely to the distorted CaF2 structure. The results arc in general agreement with Kinetics of adsorption of vapours by highly tne theory previously put forward to account for active adsorben ts. M. V. P o lja k o v , I. E. N ei- adsorption and habit'modification (cf. A., 1933, 20). m ark, and I. M. M a lk in (J. Phys. Chem. U.S.S.R., Je effect of a mixture of two dves is approx. 1934, 5, 1079— 1081).— Data for the adsorption of tive. - m . SMB. C6Hg and PhMe by a mixture of C and Si0 2 gel at 0— 36° are recorded. The change in the character of the Adsorption of dyes on previously ignited gels. isotherm with fall in temp, is attributed to the onset Splîchal (Coll. Czech. Chem. Comm., 1935, 7 , of capillary condensation. Ch. A bs. (e) . 536).—Basic dyes, e.g., metlivlene-blue, Me- Ai/nu are not ^sorbed from aq. solution by ignited Application of Polanyi’s potential theory to ‘ gel (I). The adsorption of acid dyes, the van der Waals adsorption of gases on iron ■9; Congo-red (II), eosin, and Bordeaux-red, is high, synthetic ammonia catalysts. P. H. Em m ett and ut decreases to very low vais, as the drying temp, of S. B r u n a u e r (J. Amer. Chem. Soc., 1935, 57, 2732— [) is raised to 1200°. Ignited F e(0 H )3 gels behave 2733).—Isotherms for the adsorption of A and N2 nuterly. An unstable space lattice of the y-Al20 3 by Fe20 3-A l„0 3 catalysts arc in accordance with the , .'^heated. The adsorption on bauxites (III), theory* ' E. S. H. of an ° a sma^er internal surface than (I), and Specific heat and binding conditions of ad ( I) on (I), decreases as the grain size increases, sorbed argon on charcoal. H. M. Cassell (J. ^adsorptive power of (III), heated at 1000°, Amer. Chem. Soc., 1935, 57, 2724).— Published sp. creases towards basic dyes, probably owing to an heat evidence suggests that the adsorbed atoms are rease of the internal surface of the grains. capable of one-dimensional vibration only. J. G. A. G. E. S. H. ti0 axjmal adsorption. I. Maximal adsorp- Temperature dependence of the surface ten sparingly soluble acids and bases by sion of solutions. R. V. Mertzlin and N. A. 284 BRITISH CHEMICAL ABSTRACTS.— A. V(c)
T r ifo n o v (J. Phys. Chem. U.S.S.R., 1934, 5, 1146— formation of a surface film. If overcrowding of the 1163; cf. A., 1935, 928).— Data are recorded, for the surface mols. is produced by shifting the barrier, systems PhMe-Pr°C02H (12— 100°), C5H 5N -N PhE t2 the surface tension increases with time. The ob (18— 100°), alIylthiocarbimide-NPhEt2 (16— 130°), served rate of accumulation of solute mols. is far < the quinoline-Bu^OH (0— 140°), tliymol-EtOAc (15—70°) calc, collision frequency and is > doubled for 20° temp, Ch . A b s . (e) rise, in agreement with the view that the adsorption Effect of light on surface tension of soap is of the activated type. N. M. B. solutions. II. L. D. M a h a ja n (Z. Physik, 1935, Collapse of unimolecular films of palmitic 98, 388— 395; cf. A., 1931, 1228).— Max. lowering acid on acid solutions. R. J. M y e rs (J. Amer. by irradiation is observed with 6-25 X1(H g. of Na Chem. Soc., 1935, 57, 2734— 2735).— The curve ob oleate per c.c., and with ultra-violet light. tained when the collapse pressure vals. arc plotted A. B. D. C. against p a is S-shaped. The mid-point of the Electrokinetics. XVI. Streaming potentials curve differs from that of the neutralisation curves in small capillaries. H. B. B u l l and L. S. M o y e r for fatty acids. This appears to indicate increased (J. Physical Chem., 1936, 40, 9— 20).— A mathema activity of palmitic acid when oriented at a H20 tical treatment is given for the streaming potential surface. E. S. H. in capillaries < those to which Smoluehowski’s theory in its simple form applies. The change in the Periodic phenomena in diffusion and adsorp viscosity of li 20 with capillary size is discussed and tion. I. Use of membranes. H. W a e ls c h , S. an equation is derived to show the relationship bo- K i t t e l , and A. B u sztin (Kolloid-Z., 1936, 74, 22— tween the back pressure produced by electro-osmotic 29).—Periodic variations in concn. have been ob effects and the mechanical pressure. A method for served in the diffusion of salts in blood corpuscles determining the average pore radius is described. and plasma. Similar periodicity has been obtained For quartz and glass diaphragms, the theoretical crit. in a colloid model by allowing KC1 to diffuse from pore radius is not the same as that found experiment aq. solution into a gelatin sol, from which it is separ ally. The potential-concn. and flow-concn. curvcsare ated by a membrane. E. S. H. anomalous for quartz and glass diaphragms with Effects of some factors on rhythmic crystal pores < the crit. size, but normal for cellulose. lisation . M. J. MacMasters, J. E. Abbott, and M. S. B. C. A. P e t e r s (J. Amer. Chem. Soc,, 1935, 57, 2504— Wetting and spreading properties of aqueous 2508).—The periodic crystallisation of aq. K,,Cr,0r. solutions. Oleic acid-sodium carbonate mix Na2Cr207, and (KH4)2Cr20 7 has been investigated. tures. H. L. C u p p les (Ind. Eng. Chem., 1936, 28, Differences in temp, and concn. have little effect, 60— 62; cf. B., 1935, 1129).— The surface tensions but the phenomenon may be inhibited by foreign and interfacial tensions against mineral oil have anions, the effect increasing in the order C1' shaken with freshly-pptd. PbSO., is independent of mp in aq. solution at 20° and 25° remains const., the speed of agitation so long as the ppt. is prevented in presence of foreign salts independent of the salt from settling. The speed of ageing of PbS04 in aq. concn., c, up to concns. beyond those at which the Pb(N03)2 is independent of the amount of ppt. ionic properties influenced by electrostatic inter and the speed of agitation. The recrystallisation actions, e.g., conductivity, vary appreciably with c. is not an Ostwald-ripening process. E. S. H. At higher salt concns. (c > 0-01) the absorption Influence of nature of the membrane and bands of (I) shift, but the magnitude and direction temperature on the osmotic system of water of the shift arc an individual property of the foreign and oxalic acid. F. A. H. Schreinemakers, salt present. At these concns. there is no parallelism (Miss) J. C. L a n zin o, and C. L. d e V r ie s (Proc. K. between the change of e with c and the change of the Akad. Wetensch. Amsterdam, 1935, 38, 1067— activity coeff. of (I) with c. The effects cannot he 1074; cf. A., 1931,1007; 1932,334, 691).—The system explained by deformation by the cations accumulating H,0-membrane-aq. H 2C20 4 has been investigated in the ionic atmosphere or by ionic association. In when one of the liquids is maintained invariant. general, the salt anion has a sp. effect on e com With Cellophane at 20°, H 20 and H 2C20 4 diffuse in mensurate with that of the cation. The effects of opposite directions, with pig’s bladder both H 20 salts on the optical properties of an ion seem to depend and H2C20 4 diffuse to the left at 0 °, but at 20° with on the interaction between the ion and the solvent, invariant aq. H2C204, H20 and H 2C20 4 diffuse to rather than on direct deformation in the Coulomb the left until the H 20 contains approx. 5 % of H2C20 4 field of force of the added ions. Calculation shows that and then H20 diffuses to the right. The relations small changes in the field of force due to ion-dipole at 0° and 20° are discussed. . J. G. A. G. interaction will have optical effects as large as de formation in the Coulomb field of the ions. The Osmotic complex with two stationary liquids. optical effects of non-electrolytes on (I) are similar P. A. H. Schreinemakers and J. P. W e r r e (Proc. to those of electrolytes. The effect of temp, on the K. Akad. Wetensch. Amsterdam, 1935, 38, 982— long-wave absorption hand of (I) suggests an electron 988).—Changes in composition with time have been affinity spectrum. A review of the entire optical investigated for the system A \B\C\D, where A is data for aq. solutions of electrolytes indicates that H,0, I) is a NaCl solution of definite concn., and B at small and moderate concns. the solute is present and C represent solutions of NaCl and Na2C03. as isolated solvated ions, the mutual"deformation of The concn. of NaCl in B passes through a min. which is largely negligible compared with their J. W . S. interaction with the H20 mols. R. C. Osmotic complexes in which one or more Optical rotation and circular dichroism, and liquids proceed along a closed curve during absorption and refraction in solutions. W. K u h n osmosis. I. P. A. H. Schreinemakers and C. L. (Z. physikal. Chem., 1935, B, 30, 356—378).— The de V ries (Rec. trav. chim., 1935, 54, 945—955).— non-sp. part of the effect of tlic solvent results hi the The changes of composition with time in systems circular dichroism, D, and the optical rotation, a, each consisting of solutions in series contact through being multiplied by the factor (?i2-)-2)/3 on passage semipermeable membranes are discussed, with special from the gaseous to the dissolved state, whilst the reference to aq. N aC l+N a2C 03 solutions, H20 contribution of an absorption band to the normal forming one invariant phase. J. W. S." absorption and sp. refractive power, rL, is multiplied Electrodialysis. G. S. V ozdvishenski (Trans, by the factor 7v = [(n2+ 2 )/3 ]2/n. Consequently, re jhitlerov Inst. Chem. Tech. Kazan, 1934, No. 1, 99— lations between D and a and between rL and absorp | |)~If the H20 in the electrode spaces in eloetro- tion are not changed by going over from the gaseous (halysis is left unchanged, the c.d. and rate of dialysis to the dissolved state, provided that the magnitudes ^crease, even if the voltage is kept const. Gluten for the appropriate state are consistently used. containing NaCl (ash. content 1-70%) was elcctro- This is confirmed by existing experimental data. ' tlysed by this method, using a parchment mem The anisotropy-activity factor observed with a brane. It took 5 hr. at 30 volts, or 1 hr. at 100 volts, solution must be multiplied by (?i2-)-2)/3?i to reduce to obtain a product with 0-14% of ash. it to the gaseous state. In calculating / vals. from Ch. A bs. (e) the intensity of absorption hands in solutions, Simple lyotropic effects (viscosity). E. M. allowance must be made for the factor K. R. C. "Rdins (Rec. trav. chim., 1936, 55, ” 13— 16).— Dielectric constants of strong electrolytes and Different lyotropic formulae are discussed and the the Debye-Falkenhagen theory. M. Jezewski moa of crit. ions is explained. The viscosities of 0-25N (Physikal. Z., 1936, 37, 52— 55).— New measurements solutions of electrolytes containing (1, 1)-, (1, 2 )-, of the dielectric consts. of strong electrolytes by a (4 |)-, and (2 , 2 )-valent salts can be calc, from a resonance method show that the Debye-Falkenhagen angle formula. E. E. A. theory is in agreement with experiment for dil. Optical behaviour of dissolved ions and its solutions. At higher concns. and higher temp, the s|gniflcance for the structure of solutions of change of dielectric const, is < that given by the e ectrolytes. I. Influence of temperature and theory. A. J. M. tect of salts on optical absorption of 2 : 4 -d i- Form and dielectric behaviour of thread-like natrophenoxide ion. G. K o r tü m (Z. physikal. molecules in solutions. W. K u h n (Z. physikal. en'u?1 ’ TV 30, 317— 355).— The extinction Chem., 1935, 175, 1— 16).— The dipole moment of en > s, of the 2 : 4-dinitrophenoxide ion (I) at 436 a zwitterion oc y'Z, where Z is the chain length, and 286 BRITISH CHEMICAL ABSTRACTS. A. V (d, e) r2 oc Z, where r2 is the mean square distance between J. W. M cB ain and R. F. Stu e w er (Kolloid-Z., 1936, the positive and negative charges on the ion. r%, the 74, 10— 16).—Apparatus, technique, and applications mean square of the distance between the ends of the are described, with some preliminary results on the mol. taking account of the attraction between the sedimentation velocity of agar sols and swelling pres two charges, increases slightly more rapidly than cc Z, sure of the gels. E. S. H. which agrees with the observation that dD/dc oc Z Effect of heat-treatment on hydrous chromic (Z)—dielectric const., c=concn.). Only when Z > 25 oxid e sols. G. H. A yr es (J. Amer. Chem. Soc., does the difference between r% and r2 fall below about 1936, 58, 18— 22).— The effect of heating the sols 40%. The calc, orientation polarisation on applying at temp, up to 260° is to decrease -t\ in the lower a field to a solution containing zwitterions is the same temp, ranges, but to increase -q at the higher temp. whether the zwitterions are supposed to behave as At 250—260° conc. sols set to rigid gels and dil. rigid dipoles capable of rotating, but not of changing sols are finally pptd. Heat-treatment reduces the in length in the field, or whether the variation in the stability of the sols towards flocculation by KoS04. distance between the charges with the field strength E. S. H. is taken into account. The internal field in aq. Electrolytic double layer. E. J. W. V erwey solutions of NH2-acids is much weaker than (4-/3JP (Wis. nat. Tijds., 1934, 7, 89— 100; Chem. Zentr., (cf. A., 1934, 959, 1291). R. C. 1935, i, 3640).— The formation of a double layer with Diffusion of compounds of high mol. wt. A g l sols is discussed. H. J. E. IV. Rod-like molecules. M. Taniguchi and T. Sakurada (J. Soc. Chem. Ind. Japan, 1935, 38,. Viscosity relationships in emulsions contain 728— 730b ; cf. A., 1935, 1072).-—The diffusion ing milk fat. A. L ev ito n and A. L eigh to n (J. consts. (/)) of squalene and fractions crystallised from Physical Chem., 1936,'40, 71— 80).— The viscosity solid paraffin have been determined in C6II 14 and 7] of emulsions containing milk fat does not vary, Et20 . D —t)kT (log Z/cZ j-0-69)/27t7, where I and d within the limits of experimental error, with variations arc the mol. length and thickness, 75== viscosity of the in the degree of dispersion of the fat phase, provided medium, and &=gas const. For squalene Z =-31-2, that fat clusters enclosing a portion of the continuous d—5-3 A., and for the paraffin fractions (=29-2— 39-7, medhyn are not formed. Such formation causes a <7=4-0 A. These vals. are in good agreement with rise in -q. An empirical expression for the relation those deduced From X-ray measurements. between -q and the fat content of these emulsions has been found. For low concns. of fat it reduces to R, S. B. Spierer lens and colloidal structure. W. Sei- Taylor’s equation (A., 1932, 1195). The apparent vol. of the continuous medium associated with the eriz (Ind. Eng. Chem., 1936, 28, 136— 140).— A reply to criticism of the use of the lens (A., 1926, fat clusters per unit vol. of dispersed fat represents 931) in the study of colloidal structure. R. S. B. the clumping index of cream and ice-cream mixes. It is determined from -q vals. of the mix and the Preparation of colloid solutions by the silent continuous medium. M. S. B. electric d isch a rg e . IV. S. M iyam oto (Kolloid-Z., 1936, 74, 32— 35; cf. A., 1935, 932).— The prep, of Relation between absorption and scattering hydrosols and alcosols of Cu20 and Cu2S, and also of of light in white sols. B. T e z a k (Kolloid-Z., 1930, hydrosols of Hg and HgS from corresponding salt 74, 16—22).— Determinations of absorption and scat solutions is described. The relative stability of the tering of light in different spectral regions by sols sols is indicated. E. S. II. of colophony and cellulose acetate of different concn. are in accordance with the Lambert-Beer law. The Water-soluble colloidal lead. A. F. G erasim ov influence of X, particle radius, and polydispersity is and B. M. K ozu irev (Trans. Butlerov Inst. Chem. discussed. E. S. 11- Tech. Kazan, 1934, No. 1, 119— 125; cf. A., 1930, 1114).—The prep, of a substance containing 16-5% Dispersion of the Kerr effect of certain colloidal of Pb is described. The properties of a 1% colloidal solutions. Time of relaxation of the electro- Pb solution after dialysis are described. kinetic potential. J. E r r e r a , J. T. G. O v e r b e e k , Cii. A bs. (e) and H. S a c k (J. China, phys., 1935, 32, 681— 704 : Emulsification of mercury. L. J. Krehnev cf. A., 1929, 135).— The electrical birefringence of (J. Phys. Chem. U.S.S.R., 1934, 5, 1051— 1061; colloidal solutions of V20 5, benzopurpurin (I)- cf: A., 1934, 729).— Suspensions of oxides and certain polystyrene (II), and p-azoxyanisolc (III) has been slightly sol. salts stabilise the Hg globules by forming measured at frequencies 103— 6 x l 07 cycles per sec. protecting layers. Results obtained with oxides The birefringence of V 2Og sols increases with increasing or hydroxides of Ca, Mg, Ba, Zn, Hg, Pb, Cu, Fe, field towards a saturation val., and it also increases and Si, and Hg.2Cl2, H gl2, IIgBr2, ZnC03, PbS04, with increasing concn. and age. The dispersion sug BiONO;!, and IigS in association with various electro gests that there are two components, one positive lytes are described. Stabilisation is also produced and decreasing rapidly at frequencies > 10l> and the by Prussian-blue, Congo-red, night-blue, benzopur- other negative and decreasing at frequencies > 10 • purin-4B, benzopurpurin-lOB, and chrysophenin. The dispersion of the dielectric const, (e) of thc»e In presence of oxidising or chlorinating agents, sols is confirmed and the negative part of the bire- HgO or Hg2CI2 can act as an emulsifier for Hg. fringcnce is attributed to high vals. of s. The bire Ch . A bs. (e) fringence of (I) is negative and diminishes rapidly Application of a simple air-driven spinning- at frequencies >10°, whilst that of (III) is positive top centrifuge to colloid-chemical problems. and accompanied by marked dichroism. No birc- V(e) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 287 fringence could be detected with (II). The disper sions at > 1 0 0 cycles per sec. can be explained in solutions. The shape of the curve, but not the terms of the time of relaxation of the electro-kinetic general rate, is influenced by addition of electrolytes. potential. j w g> E S H Heat of imbibition of cellulose in water and in Maxwell effect in colloids. A. M. T a y lo r certain technical organic solvents at 25°. K P (Trans. Faraday Soc., 1936, 32, 307— 310).— Methods Mjschtschenko and M. Z. Pronina (J. Appi. Chem. are suggested for discriminating between theories Russ. 1935, 8 , 1164— 1169).— The heat of imbibition of streaming double refraction which assume on the ot cellulose> has been measured In an ice calorimeter one hand optical anisotropy of the particles and on the oi H 20 , IICOoH, MeOH, and triacetin. Vaseline other hand the production of elastic strain in particles oil gives no heat effect, whilst the rate of evolution normally isotropic. F L U of heat in (•CH2-OH)2 and glycerol is too slow to permit measurement. pv q, Constitution of hydrous oxide sols from X -r a y diffraction studies. H. B. Weiser and W G' Interaction of cellulose esters with solvents. Milligan (J. Physical Chem., 1936, 40. 1—7).— A I. Okatov and Z. I. Emmanuilova (J. Appl A-Bay diffraction photographs of moist A1„0,, Chem. Russ., 1935, 8, 1248— 1264).— When S io ' . ]2, a' J'hO-t gels prepared from the hydrous gel is immersed in HaO or C8H0, heat is evolved in and Tn° 0 f^ e„the E^erns for y-Al20 3,H20 , Sn02, two stages which correspond with wetting of the li i - i 2 2 j respectively. In sols containing surfaces and with swelling of the gel. When cellulose chloride this is not present as basic salt, but is nitrate is placed in EtOH-Et20 , the greatest heat effect adsorbed. ^ g -g is obtained for equimol. mixtures, which have also the greatest negative heat of mixing; the evolution _ Constitution of hydrous oxide gels and sols. of heat in this case involves a third factor, viz dis L S SEooan£ 5 ‘ ° ‘ Milltgan (Trans. Faraday ruption of aggregates to yield sols. Imbibition i j’ , 3, ’ 32, 358 374).—A review of evidence proceeds most rapidly at low temp, and high pres- leads to the conclusion that gelatinous ppts. of oxides suics, whence it follows that the most homogeneous consist of agglomerates of minute crystals of oxide films would be obtained by cold-pressing the partly or hydroxide which hold large amounts of FLO by solvated product. p> adsorption and capillary forces. In hydrous "oxide Mb containing chloride the latter is adsorbed, not Dependence of the swelling power of potato bound in the form of basic salts or Werner complexes. starch in warm water on the kind and amount of cations contained therein. E. W ie g e l (Kolloid- 7j ., 1936, 74, 58— 66).— The effect of acid treatment a S ° id^Te? ^ al Pr0cesses at high temper- S. I- D ijatschkovski (Kolloid-Z., 1936, 74 on the viscosity (vj) of starch sols has been investig ated. After neutralisation with alkalis the sol atG°! r -effect °f heatinS several hydrosols Tv™ i , 111 f !1 autoclave has been investigated, a if r relatively greater initial ^ and a lower end /¡. ipical hydrophobic sols undergo coagulation; hydro Alkalme-earth cations cause a relatively lower initial philic sols undergo complex changes, involving loss 0, but scarcely change the end val.; the sols are more oi electrolyte and desolvation. Fc(OH)., is re- turbid and less sensitive to electrolytes than those containing alkali ions. The practical significance l V h0 }iiglr St temp' Used' V2° o passes 0 a mol. form, leading to crystallisation of HVOo. of the results is discussed. F. S. H. ESI 1 ' 1 Relation between the chemical and colloidal Acclimatisation phenomenon in colloid-chem- structure of proteins. A. F o do r and S K uk j* P^cesses V N Krestinskaja (Kolloid-Z., (Kolloid-Z., 1936, 74, 66—87).—Results obtained by i 74, 45 ol).—Pubhshed work is discussed. non-hydrolytic degradation of gelatin and casein by E S H glycerol at 930— 150° are further discussed (cf. A. chloermti0n 1 ° rganic anions with basic thorium 1933, 730). e_ g_ H _ sahs of ti ynr? ° 1S- Reversal of charge with Laws of motion of thixotropic plastic liquids. i m hydroxy-acids and with nitric acid M. B unin (J. Phvs. Chem. U.S.S.R., 1934, 5, 996— Soc JoHr°M^ aadooa K eem er (J- Amer. Chem. 1003).— A discussion. ' Ch . A bs. (e) Srse f t If 2538-2541).-Hydroxy-org. anions thorate ' charge of the sol, producing aniono- ^ Lyophilic colloids. XXVI. Coacervation. III. bv tmV ™',-, Negative sols are also produced Complex coacervation of the system gum arabic- Ptptismg lh 0 .2,rH20 with K salts of the above gelatin. II. H. G. B. d e J ong (Kolloid-Beih., 1936, 43, 213—271; cf. A., 1935, 821).—The composition f LitF" ,^ ^ ‘^ver^lhe T1C1 1 T , Ihe order of ¿eolation of basic of the two layers formed by mixing aq. gum arabic ^lutVns Jhi subsequent formation of crystalloid and gelatin sols has been investigated. Under HXo conc' inorS- acids is H ,S 0 4> H C 1> optimal conditions of coacervation the coacérvate “ E. s. H. contains the components in the same ratio as in the whole system for a series of isohydrie mixtures. Of e-unf n aif d reactivation in vitro. I. A gein g The H20 content of such a coacérvate is at a min. 74, ss- -Ofm p K o ts o v s k y (Kolloid-Z., 1936, between p u 3-3 and 3-5. Addition of a desolvating is inversph- 'Un!, ara .c s°ls age at a rate which non-electrolyte (e.g., EtOH) increases the colloid tension tim ^ ,e of solution- The surface content of the coacérvate, but addition of neutral the am,,fip LCU7 C1 ®h|Rrirre^ ar.Periodic variations, salts decreases it. The coacérvate can take up excess 1 'tude of which is greater in dil. than in cone. of one of the components. The aq. layer also con y (e), VI (a) 28S BRITISH CHEMICAL ABSTRACTS. A. tains gum arabic and gelatin ; the conditions deter- ehem. Z., 1936, 283, 280—291; cf. Büchner et al, rninine the amount of these components are discussed. A., 1931, 1125).— The effects of small amounts of E. S. H. NaCl, N al, and NaCNS on the salting-out- of edestin Silicic acid gels. VI. Influence of temper by Na2SO.j are similar to those produced in the case of gelatin, there being no antagonistic effects, but ature and acid on the time of set. C. B. Hurd (J. Physical. Chem., 1936, 40, 21— 26).— The times KE has an antagonistic effect on peptisation by NaCl, of set of silicic acid gels made by mixing aq. Na adsorption of F ' being then negative. The antagonism silicate with aq. AcOH, tartaric, citric, or succinic observed between NaCl and multivalent cations prob acids of varying concn. have been determined at ably has another cause (effect of oppositely charged 25-1°, 38-4V and 03-0“. The relation between log centres, auto-complex action). W . McC. (time of set) and 1 jT° abs. is shown to bo linear and Plant colloids. XLII. Influence of crystal heats of activation have been deduced. The average loids on the state of amyloses, with special vais, for the four acids are 17,140, 17,530, 16,940, and reference to thread-forming power. M. S ämeo 17,190 g.-cal., respectively (cf. A., 1932, 1202). [with P. Benkoviö] (Kolloid-Beih., 1936, 43, 272— M. S. B. 286; cf. A., 1935, 165).— The viscosity of dil. amylose Diffusion coefficient and apparent radius of solutions is lowered by small amounts of electrolytes, the cupric ion in silica gels. W. G. E versole but raised by larger amounts; the spontaneous and E. W. D oughty (J. Physical Chem., 1936, 40, coagulation by ageing is retarded by electrolytes or 55— 60 ; cf. A., 1935, 702).—The rate of diffusion of org. crystalloids. Cone, amylose solutions (6%) CuCl2 into Si02 gels has been determined by a photo increase in consistency as the concn. of the added metric method. The most probable val. of the crystalloid is increased; at a certain stage the mix diffusion coeff. of Cu" in H20 is 4-6x10-° sq. cm. per tures have good thread-forming properties. sec. The effective radius of hydrated Cu" appears E. S. II. to be approx. 5-2 XK P8 cm. M. S. B. Phase rule in colloid chemistry. W. D. Ban croft (J. Physical Chem., 1936, 40, 43— 45). Theo Influence of neutral salts on the optical rotation of gelatin. III. Effect of the halides of lithium, retical. M- k- B. sodium, rubidium, and cæsium. IV. Rotatory Exchange reactions with deuterium. I. Deut dispersion of gelatin in sodium iodide solutions. e r iu m and hydrogen chloride. P. C. Cross and D. C. Car pe n ter arid E. E. L ovelace (J. Amer. Chem. P. R. Leighton (J. Chem. Physics, 1936, 4, 28 - Soc., 1935, 57, 2337— 2342, 2342— 2346).— III. The 30).— An apparatus for measuring exchange equilibria [ electrolytes (A., 1927, C26) is valid if the ordinary of the anhydrides mannitan, maimide, and dulcitan. Coulomb forces between the ions are assumed. fsoMamiide has no effect. M. S. B. The deviations from the inverse square law, due to saturation and hydration effects on the II20 Hydrogen-ion dissociation curve of the crystall dipoles, and to the polarisation, van der Waals, ine albumin of the hen's egg.—See this vol., 360. and exchange forces between two typical ions’ Physico-chemical properties of mercurous per are accounted for by means of a correction term in the chlorate solutions. E. N e w b k r y (Electrochem expression for the energy of interaction. L. L. B. Soc. Preprint, 1936, 69, 57— 73).— The prep, and puri fication of Hg2(C104)2 is described. The existence Transition cases in the distribution of ions. of the totrahydrate is confirmed and this is shown R. M. Fuoss (J. Amer. Chem. Soc., 1935, 57, 2604— to be stable below 36°. From 36° to > 100° the stable 2607).—A crit. concn. exists, above which free and hydrate is 2H20. The transition point is lowered in pair-associated ions become indistinguishable (cf. strongly acid solution. Hydrolysis occurs in three A., 1935, 488). At higher concns. the simple laws stages the products being Hg20,Hg,(C10,)., (I), of dil. electrolyte solutions are no longer obeyed hrg2(OH)-Clp4 (II), and TlgO, respectively." The E. S. H. degree of hydrolysis is 2-5% in 0-llf solution. In Hydration of ions. 0. Sciim itz-D um ont (Z. more conc. solution the hydrolysis is > anticipated auorg. Chem., 1935, 226, 33—45).— Theoretical. because (I) is a weaker base than (II). The degree Brintzingcr’s method (A., 1935, 579, 582, 824) based of ionisation (a) of the salt appears to increase with on the coeff. of dialysis does not enable electro the concn. Conductivity data suggest that a=128% statically bound H20 to be distinguished from that in the saturated solution (3-93i¥) at 25°. The view present as an aquo-coinplex. ' E. L. U. is expressed that in dil. solution the basic salt formed Sourness of acids. R. M. B e a t t y and L. H. by hydrolysis is non-ionised and that, in very conc. Craog (J. Amer. Chem. Soc., 1935, 57, 2347— 2351).— solutions, iig 2" is dissociated into 2Hg' by the action Sourness is defined in terms of the normality of aq. of the negatively charged ions present in largo concn. HC1 of equal sourness. The sourness of unbuffered Hg1 perchlorate may be used for a Hg coulometer, solutions of some org. acids is given by xlK , where x for sp. gr. determinations in mineralogy, for cleaning is the vol. of a P 0 4"' buffer required to bring a unit Hg, for the prep, of pure Hg2Cl2 or' Hg2S04, and vol. of the acid to p a 4-4, and K is a const, character as a reagent for halogens, S04", P 04'", AsO,'", and istic of the buffer used. E. S. H. Cr04". M. S. B. Monoalkyl phosphites and their hydrolysis.— Equilibria in solutions of tri-ionic electrolytes. See this vol., 312. K. J ablczyn ski and R. L egat (R ocz. Chem., 1935, 15, 351—359).—Cryoscopic and conductivity data Effect of tem p eratu re on the ion isation con are applied in the estimation of the equilibria const, stants of some dibasic acids. I. J ones and E. G. for the ionisation of Ba, Sr, Ca, and Mg chlorides in g3per (J.C.S., 1936, 133— 137).— When the distance accordance with the general formula MCI, \p between the ionising centres is > 4-0 A., corrections M-+2C1'. R qy tor anisotropy and compressibility may be ignored vnthout appreciable error, and it has been possible Carbamate equilibrium. I. Equilibrium of to determine r for many symmetrical dibasic acids amino-acids, carbon dioxide, and carbamates various temp. The p n changes during the neutral in aqueous solution ; with a note on the Fer- isation of cis-caronic acid (I) show no marked guson-Roughton carbamate method. W C ispneement with temp, change, and with phenol- Sta die and H. O’B r ie n (J. Biol. Chem., 1936, P itlialein, contrary to the observation of Baeyer, 1 1 2 , 723— 758).— It is the amphanion COO~-R\NTL ifte is no indication of monobasicity at room temp., and not the zwitterion COO--R\NH3+ of NH2-acids a though temp, markedly affects the inflexion point which forms carbamates with CO,. The ionisation of these, which behave as dibasic salts at p a > 7, J the second neutralisation. The second ionisation roust, of (I) is 0-49 X 10~s, and the disappearance of is discussed. Mass-action equations for the carbam ate equilibrium of NH,-acids and C02 in aq. solution 1, -V i .i°n higher temp, is attributed to increased b iolysis of the salt. To obtain a sharp end-point are given, together with consts. calc“ under various conditions. By the use of carbonic anhydrase, 11 he titration of such weak acids, titrations should made at low temp. For a const, val. of r, the the Ferguson-Roughton carbamate method can be used when much free CO, is present. J. N. A. ■ 10 °‘ the first and second ionisation consts. K 1/K2 »eases with temp, for all acids studied, except those Activity coefficient of ions. (Ml l e .) M. Q u in t in aving cis-structures, and possible causes of this (Compt. rend., 1936, 202, 123— 125; cf. A., 1935, e uscussed. Values of K l x 105 for (I) and trans- 826).— The e.m.f. of the cells Cd (amalgam, two ?1UC acid are 459 and 15-2 respect. Caronic phases) |CdCl2(m)|KCl sat. KClO-liV H g A Hg and i is compared with other dicarboxylic acids. Ag|AgCl|CdCl2(m)|KCl sat. KC10-liV Hg,CI Hg have Eff E. E. A. been measured at 25° for »»==0-001— 0-1. From the a i °f certain sugar alcohols and their data the calc, radii (Debye a) of Cd++ and Cl~ are T ri i-ri<^es °n the dissociation of boric acid. 5-4 and 2 A., respectively. The former val. agrees A ■ tvrantz, jun., (Miss) M. Oakley, and C. J. C a r r with the 6 ± 1 A. calc, from data using CdSO, (A b- Physical Chem., 1936, 40, 151— 154).— The two 1927,729). T. g"p. effpri i ahphols, maimitol and dulcitol, have an A ctivity coefficients of lead ch loride in aqueous on the titration curve of H3BO, much > that solutions of barium nitrate. H. D. Crockford BRITISH CHEMICAL ABSTRACTS. A. VI (a-c) 290 in each system. Solubilities, eutectic temp., and ami H. 0 . F a r r , jun. (J. Amcr. Chem. Soc., 1936, compositions are approx. those calc, for ideal solutions. 58, 87 -89). Activity cocffs. and the a parameter E. S. H. have been calc, from e.m.f. determinations of the Physical-chemical properties of the chloro- cell Pb fig (2-phaso)|PbCl2 (m,), Ba(NOs), (m2)JAgCl- hydrin and of the dichloride of A^-butene. I. X. Ag. E- S- H- B usciimakin, M. M. G olidm an, and K. I. K ubtschix- Activity coefficients of sulphuric acid in ska ja (Sintet. Kautschuk, 1935, 4, No. 1, 33 35).— anhydrous ethyl alcohol from electromotive Equilibrium data are recorded for the binary and forco data. A. W. Sch o ll, A. VV. H u t ch iso n , and ternary systems formed with H 20 . Ch . A b s . (e) (1, 0. Ch andler (J. Amcr. Chem. Soc., 1935, 57, Solid-liquid equilibria in ternary systems in 2512 2544).- -The data have been obtained from which incongruently melting compounds are e.m.f. measurements of the cell H2|H ^04, Hg2S04(s)| formed. III. K. H r y n a k o w s k i and M. Szmyt (Z. | |g, E. S. Id. physikal. Chem., 1935, 175, 83— 98).— The systems Fundamentals of chemical thermodynamics. salicylic acid-CO(NH2)2-urethane and PhOH- P. van RyssklbeRohe (Chem. Rot., 1935, 16, 37— C0(NH2).,-urethane each exhibit one eutectic point 51). - A review. Ch . A b s . (e) and two peritectic points. B. C. Exact significance of the thermodynamic quan (a ) Lower transition point of the mutual tities A F and A F°. P. v a n R yssk lberoiie (Chem. system Na2S 04-NH4HCQ3—H20. (b ) M utual Rov,, 1935, 16, 29 35).—Theoretical. aqueous system Na2S04-NH4HC03-H20 at Ch . A b s. (e) — 17°. A. P. B elopolski and S. J. Sohpunt (J. Independent components in the phase rule. Appl. Chem. Russ., 1935, 8 , 1126— 1135, 1136 A F C kraSIMOV (Trans. Butlerov Inst. Chem. 1142).— (a ) The transition point, corresponding with Tech. Kazan, 1934, No. 1, 114— 119).— A discussion. the equilibrium 2Nu,,SO4,10H2O + 2N II4HCO3 Cit. A b s. (e) Na2S 04.(NH.1)2S 04,4H20 (I)+2NaHC03+16H20, is Integrated form of the equation for calculating shown by solubility measurements to be at / . clmnee of equilibrium with temperature. J. B. ( b) Equilibrium relations liavc been determined A u s t in (.1, Amer. Chem. Soc., 1935,57,2428— 2434). at — 17°. (I), which is unstable at < —16°, can exist The equations relating change of solubility with temp, at lower temp, in presence of NII4HC03. R. T. are eon verted into a more convenient form. Ex- Equilibria in tlie systems (a) M gCO3-N a2C0:!- peri montai vais, fall on a straight line when plotted H „0 , (b) Na3P 0 4-NaCl-H20 . A. P. Obuchoy against temp., or the reduced temp., on double (J. Appl. Chem. Russ., 1935, 8 , 1143— 1148, H49 logarithmic co-ordinates. The approx. equation for 1151).— (a) [with E. I. G o rd o n ], The double silt v.p. loads directly to the rules of Ramsay and Young Na2C 03,MgC0o crystallises from an aq. solution and of Dilhring. E - of Na2C 03 which lias been saturated with MgC03 at System stannic chloride-hydrogen chloride. 35°. A. Chrétien and G. V arga (Compt. rend., 1935, (b ) [with M. N. M ichailova], Equilibrium data 2 0 1 . 1491 1493).—Thermal data show the formation are recorded for the systems at 25 and 105 . T tc of SnCl,.51101. m.p. -94-7°, and SnCl.„2HCl, m.p. solubility of Na3P 0 4 'falls rapidly with increasing 85°, and three outectie points. T. G. P. Nar*n ‘ R. I- System antimony iodide sodium iodide— System cobalt chloride, ammonium chloride, water. F. F r a n ç o is (Compt. rend., 1935, 201, ammonia, water. M. C h a t e le t (Compt rend-, 1489 - 1491). Isotherms at 15 , 35°, and 60 in 1936, 202 . 216—217).—The formation of the ions dicate the formation of SbI3,2Nal,8H20 and [CoNHg] and [Co(NH3)3] is said to have been detected SM 3,NnT,6H£0. T. G. P. by colorimetric measurements. T • G. i . Thermal analysis of the systems iodine Lil, Determination of change of free energy m reactions of type A(s)+B(s)=AB(s) and applic KÏ, Rbl, or -Til. J. A. Fialkov and G. A. ation to dolomite problem. F. Halla [w^u ■ K uzmenko (Mem. Inst. Chem. Ukrain. Aead. Sei., 1935,2, 127 139).— Polviodides are not formed when R itter] (Z. physikal. Chem., 1935, 175, 63 S-). A method for determining the change in free energj, the iodides are fused with I. indicating that the pre AF, in the formation of double compounds by solu sence of a solvent is essential for their formation. R . T. bility measurements is described. Application Purification and physical properties of organic the formation of dolomite (I) from its solid component» compounds. X. F .p. diagram for the system shows that under 1 atm. this occurs spontaneous acetanilide propionanilide. E. L. Skau and L. F. above - 34J and AF° is 590 ¿5 0 g.-cal. at 2o ana 740- 30 g.-cal. at 3S-S°, and that AH is -2 S 4 0 x 3 w R ow e (J. Amor. Chem. Soc.. 1935. 57. 2437— 2438: ,r .cal. at 25— 32°. . For dolonutisation, 2CabU3 , of. A., 1935. 1077). -The Beckmann method is un A F = — 190¿50+1430 log (p I satisfactory, A static method shows that the [Ms”]) g.-cal. at 25° and 120± 3 0 - 136o lofc system forms a compound with ineongruent m.p. E. S. H. ([Ca“ [ [Mg"]) g.-cal. at 3S-S°. The direction of thu Binary systems of p-dichlorobenzene with process is" therefore determined almost entire!} the ratio [C V ]: [Mg"] in the solution, and under tn d ip h e n y l, naphthalene, and triphenylme thane. conditions of temp, and concn. prevailing m t U, K. M orris and \W A. Cook (J. Amer. Chem. Soc., dolonutisation should occur spontaneous!'. 1935, 57, 2103 2406).- A simple eutectic is shown VI (c), VII (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 291 following solubility products have been obtained : ation of dienes and of benzene. G. B. Kistia- MgC03, 1-8x10-8 at 25°, 1-6x10-8 at 38-8°; CaCO„ k ow sk y , J. R. R u h o ff , II. A. Sm ith, and W. E. 3-83x10-9 at 38-8°; (I), 3x10-” at 25°, 1-8x10-” V augh an (J. Amer. Chem. Soc., 1936, 58 137__ at 38-8 . Lewis and Randall’s sp. ionic activity 145 146— 153; cf. A., 1935, 825).— Ill, Heats of coeffs. have been successfully used to calculate hydrogenation (in g.-cal. per mol.) are recorded for solubility product from a single solubility. The AMieptenc (-30,137 ±37), ns-methylethylethylene 3 variation in solubility of MgC0 ,3H20 with temp (—28,491+36), A+pentenes (cis and trails) (—27 954+ is given by m=0-4344-0-0illi+0-0>53f2. Heats (—27,997+24), cydohexene of dissolution in 22V-HC1 have been measured. (—-3o9w+10), CMe2.CHMe (—26,920+10), and 11. C. CMe2.CMe2 (-26,633+19). With increasing no. Heats of dissolution of ferric chloride in water of substituent alkyl groups the heat of hydrogen and in aqueous hydrochloric acid. W. Kangro ation is progressively lowered, and the differential and R. F lü g g e (Z. physikal. Cliem., 1935, 175, effect decreases with increasing no. of substituents. 187—194).— Differential and integral heats of dis This effect is independent of the chain length of solution and dilution at 20° have been determined. substituent w-alkyls, but branched groups have a The heat of dissolution in aq. HC1 falls rapidly with greater influence. increasing [HC1], When [HC1] is > ~ 10% the de IV. Heats of hydrogenation are given for allene+ crease is quantitatively accounted for by fall in the 2H2 (—71,280+103), ay-butadiene+2H2 (—57,067 + activity of the H 20, but at higher concns. there are 28), aS-pentadiene+2H2 (-60,790+64), oe-hcxa- discrepancies, which are probably connected with diene+2H 2 (-410,525+43), Ai+CyCfohexadiene+2 H , association. Sp. heats of aq. FeCI3 solutions have (-55,367+56), C8H 0+ 3 H 2 (-49,S02 +44), cych- been determined at 20°. R Q pentadicne+2H, (-50,865+47 g.-cal. per mol.). Hydrazine. Heats of dissolution of hydrazon- The data are discussed. jj. S. H. ium salts at 2 5 3. II. E. C. Gil b er t and Y . C. Single linking energies. I. C-C linking in Bushnkll (J. Amer. Cliem. Soc., 1935, 57, 2611— hexaphenylethane. II. E. B e n t, G. R. C u t h b e r t- -612, cf. A., 1935, 303).— Data for liydrazonium so n , M. D orfm a n , and R. E. L e a r y . II. C-C (hbromide (anhyd. and hydrated) and sulphate are linking in hexaphenylethane. II. E. B e n t and tecorded. Partial mol. heats of dissolution of solute G._R. Cuthbertson (J. Amer. Chem. Soc., 1936, 58. and solvent (H20) have been calc, for the bromide, 170, 170 1/3).—I. Apparatus and technique the heat capacity of aq. liydrazonium sulphate at for determining heats of reaction, especially for easily -a” has been determined. E. S. H. oxidised substances, are described. Tlie v.p. of Thermochemistry of azoimide. P, Günther, A“-heptene (I) has been determined from 0° to 90° K. M eyer, and F. M üller-Skjold (Z. physikal! and the heat of vaporisation calc. The heat ofhydro- 'em., 1935, 175, 154— 169).— (1X.. is conveniently genation of (I), the heat of oxidation of (■CPh3)2, prepared by heating NaN, with stearic acid in vac and the heats of dissolution of the compounds in and condensing at not below -7 5 ° . When the gas volved in these reactions have been determined. explodes under reduced pressure very little NIL The dissociation of (-CPh3)2 is due to weakening of 'stormed. The heat of formation of the gas at const, the C-C linking and the stabilising 'effect of the re r -’fi.- 70'9±0-5 kg.-cal. per mol. The v.p. of the sonance energy of CPh3. 'quid has been determined from near the triple point II. The heat of hydrogenation of (-CPh3)2 to form G "ear the b.p. (35-7°). At 12-4° the mol. heat of CPh3 is —40-5 kg.-cal. for solids and -34-8 kg.-cal evaporation is -7-3+0-1 kg.-cal. The total heat in EtOAc solution. The C-C linking is weaker than w dissohition of the gas to give a 0-16A solution is a normal linking by about 30 kg.-cal. E. S. H. ^±0-1 kg.-cal. per mol. These data confirm the Electrical conductivity of potassium chloride Worded heat of formation (Roth and Midler, A. 1929 in certain mixed solvents. R. N. Agarwala and too). For the liquid at 0— 21° ¿=1-126/(1 +0-0013i)! D. C. Manderville (J. Indian Chem. Soe., 1935, R. C 1 2 , 699—705).—Viscosities and sp. conductivities Heat of combustion of isobutane. F. D. Ros- of H20-Me0H, H„0-Et0H, and H 20-C 0M e2 mix Ifih ( rk,Re,s- Nat- Bur‘ Stand., 1935, 15. 357— tures have been determined together with equiv. w — Hie heat of combustion of Ao-C.H,n in 0 , conductivities A of the corresponding HC1 solutions. i rÜr-'o, 2 (gas) and H2° (liquid) at 25°/l atim The plot of A against [KCT]1'2 is linear for H20 and 6^31±°;13 kg.-cal. per mol., hence the heat of H 20-Et0H, but regularly spaced max. and min onnation of i«>-C4H ]0 at 25° is 32-2+0-43 and the appear in the case of H 20-Me0H and H 20-C 0M e2 eat oi conversion of the »- into the i.so-form is 1-63 + which bear no relation to the viscosity. An explan ’ “ g.-cal. per mol. r p ation involving “ dipole association” chains of hydr carHoxylation of carbon compounds. ated COMe2 etc. between the ions has been advanced Wn o e energy of benzoic acid at 522 abs. R. S. Electrical conductivity of solutions of electro Soc ioo°XibER and R - K in n e y (J. Amer. Chem. gf||1935, 57, 2 4 0 2 -2 4 0 3 : cf. A., 1933, 1159).— lytes in methyl alcohol and acetone at high , | ut'on from published data gives AEf.„= -3 6 491 tem peratures. P. C. B lo k k e r (Ree. trav. chim., * 1 ' E. S. H. 1935, 54, 975— 987).— The conductivities and sp. vols. of solutions of LiCl, LiBr, Lil, Nal, KI, Cal„ °f organic reactions. III. Hydrogen- and (P+[GH2]2)4NI in MeOH and COMe2 have been 11 of some higher olefmes. IV. Hydrogen measured at temp, up to 21S° in special soft steel BRITISH CHEMICAL ABSTRACTS.— A. VII (a-c) 292 bombs lined with Pt. The equiv. conductivities Mercury-mercuric oxide-saturated barium of these solutions show max. at temp, which are the hydroxide and calcium hydroxide electrodes. lower the higher is the salt concn. It is shown that G. J. Samuelson and D. J. B row n (J. Amer. Chem. the max. are caused by decrease in the dielectric Soc., 1935, 57, 2711— 2714)— The potential const. J. W . S. Hg|HgO(s),Ba(OH),(s) with reference to the A-H2 electrode is -j-0-1462—0-00060(f—25)i0-0002 volt; Conductivity of calcium, strontium, and bar that of Hg|HgO(s),Ca(OH)2(s) is 4-0-1923 +0-000lbx - ium chlorides in anhydrous glycerol. J. Szper (i—25) ±0-0010 volt. The ease of prep., constancy, and Z. Gajkw ski (J. Chim, physj, 1935, 32, 705— reproducibility, and temp, coeff. of the electrodes' 714).— Poe i — 1/10 molar solutions and at 25—200 , have been studied. E. S. H. the mol. conductivities of CaCl2, SrCl2, and BaCl2 in anhyd. glycerol follow the Kohlrausch law — Av = Potential of the Ag(s)IAg 2C r 0 4(s)|Cr04" elec k'K/c. The limiting mol. conductivity is 3-67 x H H trod e. J. Y. Canx and G. B. M heller (J. Amer. at 25° and 35° for all three salts. The mobilities of Chem. Soc., 1935, 57, 2525— 2527).—E.m.f. measure the cations increase with the mol. wt. The mol. ments of the cell Ag(s)|Ag,Cr04(s)|K2Cr04 (aq.)|KCl conductivity increases exponentially with temp, (aq.)|AgCl(s)|Ag(s) at 25° give -0-44 63 volt for£tho at low temp., hut above 130° increases linearly. normal electrode potential of Ag(s), Ag2Cr04(s), J. W . S. Cr04"; AE°=20,596 g.-cal. E. S. H. Electrochemical investigation of the ternary Volta effect of electrolytic solutions against system AlBr.r AsBr 3-benzene. V. A. P lo tn ik o v water, and characteristics of acidity and basicity. and S. I. J akubson (Mem. Inst. 'Chcm. Ukrain. (M lle .) S. V e il (Compt. rend., 1936, 202, 121— Acad. Sei., 1935, 2, 99— 109).—Thermal analysis does 123).——The electrometrio potentials. of the system not suggest compound formation, but freshly pre Pt-HoO (gelatin)-salt solution-Pt- have been measured pared solutions of the salts in CttHc conduct electricity, (A., 1935,822). They depend on the concn. and nature the conductivity falls rapidly to a const, val. after of the salt, and are positive at pn <7. T. G. P. 23 days. The unstable compound AlBr3,AsBr2 is postulated. E. T. Anomalous redox potentials of thiol-disul- Determination of transference numbers in phide systems. J. W. H. L ugo (J. Indian Chem. dilute solutions from limiting ionic conduct Soc., 1935, 12, 706—711).— A theory involving the formation of an ionisable compound between Kb ances. B. B. Ow e n (J. Amer. Chcm. Soc., 1935, 57, 2-141).—Theoretical. E. S. H. and the electrode surface is suggested. R- S. Ionic mobility. J. J. H erm ans (Z. Physik, 1935, Oxidation-reduction potential of reductone. 9 7 , 681—689).—An equation is obtained for the R. W urm ser and N. M a y e r (Compt. rend., effect of solvent dipoles on ionic mobility, and is 1935, 201, 1366— 1368; cf. A., 1934, 1072).—1Hie solved for infinite dilution. Extension to finite oxidation-reduction potential of the system dilution shows that the mobility cc (concn.)1/2. OH-CH:C(OH)-CHO ^ CO(CHO)2 at 38° has been A. B. D. C. studied between p a 2 and 9. E0 at p u 0 is + 0-28-' Electrical transport of an active deposit of volt. T. G. P- radium in some organic liquids. Z. Klemen- Oxidation-reduction potentials. II. Invest siewicz. and K. P rojkkt (Acta Phys. Polon., 1933, igation of a coupled oxidation-reduction equi 2, 109—415).— Solutions in C61I14, C0H G, PhMe, lib riu m b y p h oto-electric m ea su rem en t of light E t20, C0Mc2, and EtOII have been examined in an extin ction . G. H olst (Z. pkysikal. Chem., 1935, eloctric field. The amount of Ra deposited on the 175, 99— 126; cf. A ., 1934, 968).—The mol. extinc electrodes decreases with rise in the dielectric const, tion coeff., a, of methylene-blue (I) at 20° in 0 -01A- and the viscosity of the liquid. Ch. A b s . (e) HC1 for >.= 546.mg increases with the dye concn. Absolute single potential of [calomel] elec PhNlN-SOoK (II), as a result of chemical interaction, trod e. K . H ikota and T. M u r a t a (Bull. Chcm. depresses a, whilst NHPh‘NH-S03K (III) does no , Soc. Japan, 1935, 10, 594—596).— The variation affect a. The equilibrium (I) + (III) leucomethj - of p.d. with interfacial tension (cr) of Hg has been ene-blue (IV) -[-(II) is reversiblv displaced by Mg1'1' studied by forcing the Hg upwards through a fine In (M)lV-HCl at 20° the equilibrium const, of tfte orifice immersed in KNO;s. The height of the jet dark reaction is S-2. Irradiation with blue hg varies approx. parabolically with the p.d. between shifts the equilibrium towards larger concns. of W> jot and the Ar-calomcl electrode, tho’min. correspond yellow light has the reverse|cffect. T h e a o f the mixture ing with the position of max. a. The mean val. equilibrated in the dark increases during irradiation for the Ar-calomel electrode is 0-563±0-004 volt at when the (I) concn. is small and falls when it is large, 20-6°. in agreement with vals. determined by the in either case it attains a limiting val. as irradiation * dropping Hg electrode. R- S. B. continues. The p.d., AE, between the two reactm,. Unknown property of the calomel half-cell reduction-oxidation systems at 20—40° is com ■ and the determination of bromide-chloride m ix at 0 027 volt, corresponding with an equihbriu tures. F. I- H ahn (J. Amer. Chem. Soc., 1935, 57, const, of S-5 at 20°. This val. of AE is ^ t h a t r ' 2537).—The potential is strongly influenced by even corded by Clark et al. (U.S. Hyg. Lab. Bull., lJ-■> very small amounts of Br' in the KC1. The effect No. 151), a discrepancy which may be coiuiec mav he adapted to the determination of Br'. with the variation of potential with dye c04‘:,' E. S. H. The heat changes for (lI)-*-H2 ==== (111) and ( Jt VII (c-e), VIII (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 293 H2^==(IV) (at p„ 2-0) are 30'3 and 31-5 kg.-cal., from NH2Ph and C5H SN show that these are relatively respectively. R . (J. much less stable, E. E. A. ‘ Decomposition potential of solutions of brom Energy levels in electrochemistry W . D. B a n ides of m etals in fused ca d m iu m b ro m id e . croft and J. E. M agoffin (J. Amer. Chem. Soe., V. A. Izb e k o v and G. J. Zachartsciienko (Mem. 1935, 57, 2561— 2565).— The oxidation of dil. aq Inst. Chem. Ukrain. Acad. Sci., 1935, 2, 121— 126).— H2S 03 or Na2S 03 is irreversible because, for reduc The decomp. potentials of a no. of bromides in fused tion to occur, the system must pass through an CdBr2 fall in the order Zn takes place with an energy-rich peroxide radical, has been calc, statistically, assuming that the liomo- Mc-[CH.2].,02 -> OH-CH Kinetics of the synthesis of ketones by Friedel 177— 186).— In the usual method of determining and C rafts’ m eth od . S. C. J. Ol iv ie r (R oc. trav. the crystallisation velocity, v, of a non-metallic chim., 1935, 54, 943— 944).— The conclusions of substance in a tube the temp, of the solid-liquid Ulich and Heyne (A., 1935, 1207) were anticipated interface rises with the distance from the wall. by the author (A., 1918, i, 228), but no irregularities This is responsible for the presence on the graph of v in the reaction const, were observed. J. W. S. against amount of supercooling of a portion of const. Kinetics of gaseous Diels-Alder reactions. v, followed by an abrupt fall, whilst the true curve G. B. Kistiakowsky and J. R. L a c h e r (J. Amcr. must exhibit a sharp max. A method of determining Chem. Sop., 1936, 58, 123— 133).— Rate coeffs. the true form of the curve is described. R. O. have been determined as follows : acraldehyde and Atmospheric corrosion of metals. Iron. I, cyc/opentadiene, k = 1 -50 X 109e-15’200,ii:r; acraldehyde II.— See B., 1936, 150. and isoprene, ¿= 1 -02 X 109e-18 700/'fr ; acraldehyde and Kinetics of reactions in heterogeneous sys butadiene, k— 1 -46 x 109e-19'700//ir; crotonaldehyde and tems. I. Reaction between carbon disulphide butadiene, /r= 0-90 x 109e-22’000//ii’. The reactions are and alkali. II. Reaction between benzoyl of the second order, homogeneous, and only slightly chloride and water. D. K arve and K . K . D ole complicated by side reactions. The product of the (J. Indian Chem. Soc., 1935, 12, 719— 732, 7 3 3 - first of the above reactions, endomethylenetetra- 739).—I. The influence of speed of shaking, temp., hydrobenzaldehyde (A., 1928, 1019), is unstable at amount and concn. of alkali solution, and amount and elevated temp.: the rate of decomp, is given by k = concn. of CS2 alone and in petroleum, light petroleum, 2 '2 x]0 1V 33(i00//i'/'. E. S.'H. PhMe, xylene, PhCl, and PhBr has been studied. Constitution and reactivity. XV. Kinetics of Reaction occurs chiefly in the homogeneous a q. the nitration of aromatic compounds in sul phase and to a smaller extent heterogeneously. phuric acid. K. L a u e r and R. O d a (J. pr. Chem., The rate is increased by addition of H 202, but de 193(1, [ii], 144, 176— 192; cf. A., 1935, 1465).— The creases with additions of NaCl, and does not follow rate of nitration of anthraquinone (I) by HN03 a simple kinetic law. or KNO.j, measured in 87—-100% H 2S04 at 15°, II. The reaction is purely heterogeneous and the 20°, and 25°, is a max. in 89% H 2S 0 4r Q is about velocity is increased by shaking. Solutions of BzCl 21,750 g.-cal. for H N 0 3 and 5 nitrates in 87— 95-6% in CC14, xylene, CS2, PhCl, PhBr, and CHCLj react HsSOf but only 13,300 for KN0 3 in 100% H 2S 0 4. according to a unimol. law and with velocities which The “ action const.” varies with the concn. of the decrease in the order named. R. S. acid, being a min. for 87% acid, and is thus respon Hydrolysis rates of some monoacid triglycer sible for the variation in k. The rate of nitration ides under the influence of pancreas extract. is affected by the nature of the cation in the order, I. Influence of the fineness of division of the H increasing [N2] : [02] ratio in the bomb, but there is Polymerisation of phosphorus. H. W. M el evidence that the HN03 first formed tends to oppose v ille and S. 0. Gr a y (Trans. Faraday Soc., 1936, 32, the further oxidation of N2. The results also in 271—285).—P4 mols. dissociate to P2 when passed dicate that there is a negative catalyst for the re through a Si02-glass jet at 500—800°, or by contact action present in cylinder 0 2, and that its concn. with a hot W filament. If P2 thus formed is con increases as the pressure in the cylinder decreases. densed under such conditions that it cannot com J. W . S. bine to P4, the product is red P. The kinetics of Polymerisation of gaseous formaldehyde and dissociation on hot W have been studied in detail. acetaldehyde. J. E. Ca r r u th e r s and R. G. W. It is shown that only P2 mols. are in equilibrium N orrish (Trans. Faraday Soc., 1936, 32,195— 208).— with red P, and that discrepancies in the thermal Polymerisation of gaseous CII20 is promoted by data regarding the interconversion of red and white IIC02H vapour. The reaction occurs only on the P are removed by taking into account the thermal walls of the vessel, and is complete at 18°. At change accompanying the dissociation P, 2P2. higher temp, depolymerisation takes place simul F. L. U. taneously and leads to an equilibrium, whilst if the Change of magnetic and catalytic properties whole vessel is at 100° only the monomeric form can during the transformation of a mixture of be detected. Polymerisation is bimol. with reference calcium oxide and ferric oxide into calcium to the CH 20 ; that of MeCHO vapour is also pro ferrite. G. F. Huttig, J. Funke, and II. Kittel moted by HC02E but not by AcOH, and that of (J. Amer. Cliem. Soc., 1935, 57, 2470— 2477).— Pro CH20 is promoted by AcOH. With (•CHO)2 and ducts obtained by heating Ca0-j-Fe20 3 and CaC03+ HC02H reaction does not go beyond the formation Fe20 3 in mol. ratio at different high temp, under of an additive compound. The results are explained varying conditions have been investigated with regard by a branching chain mechanism in which the HC02H to catalytic activity in the decomp, of N20 , magnetic is responsible for both initiation and branching. The susceptibility, powder d, colour, and C02 content. ease with which depolymerisation occurs indicates The heat of activation and no. of active centres are that the simple mols. are linked through 0. The given for each product. An “ active intermediate,” results support Staudinger’s theory of the catalysis. which no longer possesses the properties of the F. L. U. original mixture nor those of the cryst. CaFo20 4, is Acid-catalysed enolisation of see .-butyl ket formed. The most active samples contain up to 60% on es.— See this vol., 317. of the intermediate, which has a magnetic suscept Kinetics of Friedel-Crafts reaction and activity ibility of 51-5x 10-° and heat of activation (for of m ix ed ca ta lysts.— See this vol., 322. decomp, of N20) of 20,000—25,000 g.-cal. The inter mediate is formed as a film at the surface of the Enzymic hydrolysis of glucosides in heavy particles. E. S. H. w a ter.— See this vol., 377. Platinum catalysts on metallic carriers.—See Adsorption and heterogeneous catalysis. B., 1936, 101. E. C. C. B a l y (J.S.C.I., 1936, 55, 9— 12T).— The equa System vanadic acid-cupric oxide-silicic acid tions already developed (A., 1935, 1084) are extended as catalyst in the formation of sulphuric acid.— to cases involving supported catalysts. On certain Sec B., 1936, 144. assumptions, the reaction velocity is a function of one half of the total energy of activation of the Is sintering the cause of inactivation of reaction. A supported catalyst has a max. efficiency b a riu m -v a n a d iu m ca ta ly s ts ?— See B., 1936, 101. when of a sp. composition, e.g., a unimol. layer of Catalytic air-oxidation of petroleum in the Al(OH )3 on kieselguhr (I), or a termol. layer of NiO va p ou r p h ase.— See B., 1936, 83. or CoO on (I) (cf. A., 1935, 1070). The structure of Catalytic hydrogenation of phenolic oil in low- these surfaces is discussed. J. G. A. G. tem p eratu re tar. II.— See B., 1936, 132. Polymerisation in monolayers. G. G ee (Trans. Condensation of benzyl chloride and benzene. Faraday Soc., 1936, 32, 187— 195).— Changes occur — See B., 1936, 138. ring during the “ dryingof the compound of Ternary catalyst Cu-Zn0-Cr 20 3 as a hydro p-elseostearin with maleic anhydride have been fol gen ation catalyst. S. S. B a l ia sn i (Mem. Inst. lowed by measuring the surface pressures at different Chem. Ukrain. Acad. Sci., 1935, 2, 175— 182).-—-Re areas per mol. of a unimol. film on 0-01V-H2S 0 4. duction of COPhMo to PhEt is catalysed more The initial reaction gives rise to an unstable peroxide efficiently by Ni than by 91-8 : 6-5 : 1-7 Cu-Zn-Cr20 3 which may polymerise either directly or after trans at 250°, whilst at 284— 289° the latter calalyst has formation into a more stable form, according to no hydrogenating activity. B- T. the experimental conditions. The velocity curves indicate that polymerisation proceeds by a chain Decompositions of esters and acids by an mechanism in which the chains are terminated h yd rou s zin c ch lo rid e.— See this vol., 313. by a sterie factor. Addition of inert substances like Electrolytic preparation of deuterium and the Me*[CH2]13‘C02Et to the film inhibits polymerisation separation coefficient a. M. P. A it l e b e y and G. by breaking the chains, but does not affect the Ogden (J.C.S., 1936, 163— 168).— The large discrep oxidation. The polymerisation stage is also acceler ancy between the observed and the theoretical vals. ated by CoS04, and retarded by quiriel. Activation of a (= [D 2] in gas/[D2] in liquid phase) is discussed, energies are calc. F. L. U. and the following principles are adopted in the design VIII (e, d) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 299 of cells for producing I)2() : (a) the electrode metal Hardness of electrolytic chromium. II.—See must be a poor catalyst for the exchange reactions, B., 1936, 152. (b) the II2 evolved must be removed rapidly from the Effect of imprisonment of resonance radiation electrode surface, and (c) local conen. of D 20 at the in the decomposition of ammonia and of deutero- electrode must be avoided. With very low [D20 ], ammonia. H. W. M elville (Proc. Roy. Soc., 1935, vals. of a the calc. vals. (0-05—0-10) were obtained, A, 152, 325— 341; cf. A., 1934, 1078, 1183),— but this is not necessarily a proof that quantum- Velocity coeffs. in Hg-photosensitised reactions mechanical leakage is an important factor in the are usually determined by comparison with the difference of reactivity of H and D atoms, since the mean life of the Hg atom, which is assumed to observed val: of a is controlled by the uncertain val. he const. At high Hg-vapour pressures, however, of [D] in standard H 20 . J. G. A. G. at which experiments are usually made, there is Direct introduction of deuterium into benzene appreciable imprisonment of resonance radiation by high-frequency current. J. H o r iu t i and T. with the result that the effective mean life is much Koyano (Bull. Chem. Soc. Japan, 1935, 10, 601).— > its actual val. of 10-7 sec. A re-examination of Pure C6H„ in presence of 8 % I)20 and Pt-black the Hg-photosensitised decomps, of NH3, ND3, after standing on a pole of a Tesla coil for 10 hr. at PHg, and PD3, under conditions where reabsorption room temp, acquired a I) content of 0-69%; no is negligible, leads to lower velocity coeffs., in agree change in temp, occurred. In a second experiment ment with expectation. It is suggested that the the pure CBHf) wns kept between the poles of a high- decomps, of NH3 and ND3 are brought about in frequency oscillator of A 4 in., and was cooled, the % collisions between NH3 (ND3) and metastablc atoms, of D rising from 0 to 041. CBH 6 similarly treated derived from quenching collisions between 3 P ( with ordinary H 20 gave no change in d and f.p. atoms and NH3 (ND3). The former collisions are No exchange occurred at room temp., even with an equally efficient for NH3 and ND3. To account for oscillator, unless a catalyst was present. It. S. B. the greater reactivity of NH3, secondary reactions, unconnected with Hg atom processes, are assumed Preparation of oxyg'en by electrolysis of to occur. The suggested mechanism is supported baryta. E. M. St o d b a r t (Proc. R oy. Soc., 1935, by the fact that in the direct photo-decomp. NH3 A, 152, 273— 277).— Electrolysis of Ba(OH)2, using also reacts more quickly, and that the decomp, of Ni electrodes, does not always give pure 0 2 at the ND3 is more susceptible to inhibition by D than is that mode. After some time H,, is liberated as well, of NH3 by H. " L. L. B. probably owing to the reaction 0H-S-0H=H 2-}-0 2. Ibis can be prevented by coating the anode with a Mathematical representation of photographic Vr of Ni(OH)2. L. L. B. blackening curves deduced from the coagulation theory of latent images and using the funda Influence of sm all am ounts of agar-agar and mental hypothesis of Bose--Einstein statistics. gelatin o n t h e K G 1 of the anode deposit of silver G. U ngar (Z. Physik, 1936, 98, 517— 533).— The equa peroxide. A. Gla zu n o v and K . V a l e r k a (Chem. tion deduced permits closer correlation of blackening I-isty, 1935, 29, 359— 361).—The velocity of crystall with properties of the emulsion. A. B. D. C. isation of Ag20 2 at the anode in electrolysis of AgNO., falls with increasing concn. of agar-agar or gelatin Mercury-photosensitised polymerisation of from 0 to 0-15%. R. T. acetylene. H. W. M elville (Trans. Faraday Soc., 1936, 32, 258— 271).— Kinetic analysis of results ob Spectroscopic studies of luminescence at tained in polymerising C2H 2 by light from a quartz- cathode d u r i n g e le c t r o ly s is . I. U iia r a (Bull, Hg lamp in presence of Hg vapour (pressure > 0-0003 '-“cm. Soc. Japan, 1935, 10, 559—563).—The spec- mm.) indicates that excited Hg atoms form with a inun of the luminescence at a Pt wire cathode on C2H2 mol. a complex which then adds on more C2H 2 electrolysis of 1— 3A-salt or -acid solutions shows mols". by a chain mechanism. The chain length is lines identical with those of the arc, and in some independent of the C2H2 pressure, of surface, and of eases the spark, spectra of the metals forming cations. the rate at which chains are started, and exhibits I he lines of H and H 2 are observed, but anions have a max. (100) at 250°. Cessation of growth is due no influence on spectra. It is suggested that no to collision between a C2H 2 mol. and the growing luminescence occurs until the c.d. is sufficient to form polymeride, but of a different kind from that causing a film of H on the cathode. The metals which give propagation. The pressure and temp, ranges were msol. hydroxide and consequent disappearance of the 0-05—10 mm. and 20—500°. Polymerisation of luminescence with d.c. give prolonged luminescence C,H4 also occurs under the same conditions, but is with 100 volts a.c. R. S. B. preceded by formation of C2H 2 and H 2, the final Electrolytic manufacture of alum inium -m ag- product being partly hydrogenated. F. L. U. nesium alloys.— See B., 1936, 151. Explanation of the course of photolysis of Electrodeposition of bronze.— See B., 1936, 151. fructose in quartz light using long-wave ultra violet light. R. Ca n t ie n i (Helv. Chim. Acta, 1936, Electrodeposition of zinc and cadmium on 1 9 , 86— 93).— In long-wave ultra-violet light (glass- aluminium and alum inium alloys.— See B., 1936, filtered quartz light) fructose with the ketone struc ture decomposes with the evolution of CO, whilst, _ Electrodeposition of cadm ium .— See B., 1936, simultaneously, the ring structure in equilibrium m2. gives CO,. In long- and short-wave ultra-violet BRITISH CHEMICAL ABSTRACTS. A. VIII (d) light (unliltered quartz light) H2 is obtained in addi higher in AeOH and particularly in CGHG. The photo- tion, but polariinetric nieasurements also indicate reaction is parallel to the displacement of the absorp that some of the fructose undergoes change without tion spectra, and double linkings in the solvent have any evolution of gas. M. S. B. a distinct, accelerating action on the change. Connexion between decomposition velocity III. Bromination of anthracene in (I) or (II) takes and concentration of fructose in long-wave place relatively slowly and at about the same rate u ltra-violet light, it. CJantihni (Helv. Ghim. Acta, in each solvent. In CGH 6 and EtOH it is equally 1011(1, 19, 04— 00 ; of. preceding abstract).— The rate rapid at 10°, but about twice as fast in EtOH as in of depomj). of fructose by long-wave ultra-violet CGHG at 15°. In (I), (II), and CflHfl (dipole-free light, as measured by gas evolution, reaches a max. solvents) the change occurs with a uniform energy for a fructose conen, of 150 g. per 100 c.c. of H 20. of activation (about 6800 g.-cal.) and the greater Above this conen. the rate of decomp, remains rate in CGH 6 is due to the higher action const. In const., at least up to 200 g. por 100 o.c. of II20 . EtOH and AeOH the energies of activation are The gas evolution from such a solution is approx. 18,600 g.-cal. and 10,850 g.-cal., respectively, and the half that from an equal vol. of solution of conen. action consts. are considerably higher, hence the 1 : 10 irradiated hv unliltorod quartz light. greater rate of change. M. S. B. IV. The heat of dissolution of Br in (I), AcOlI. Acidity and yellow coloration of fructose at and EtOH, respectively, is determined at dilutions higher temperatures in quartz light. R. Can- and temp, similar to those used in the bromination of anthracene. These vals. subtracted from the heats tiioni (Helv. Chim. Acta, 193(1, 19, 96—98).—The acid formation which takes place in fructoso solution of activation gave a very nearly const, val. which is under the influence of ultra-violet light, and more regarded as the energy val. of the action, anthracene- rapidly at shorter XX, is probably duo to iIC02H Br, in the absence-of solvent. It is considered that formed by the oxidation of the CH20 proved to bo the solvent without dipole exerts an “ impact action ” produced by ultra-violet light. The yellow coloration which affects the no. of successful collisions of the is due to a dark reaction accelerated by the presence reacting mols.; whether this is a numerical or spatial of acid and requiring the addition of heat, either action remains undecided. Dipolar solvents, in directIv or by the transformation of light enorgv into addition to this action, cause also a change in the heat heat. ' ' M. S'. B. of activation of the subsequent reaction due to alteration in the energy conditions on dissolution Influence of solvent on the course of chemical of the reaction partner (“ energy action ” ). H. W. reactions. I. Absorption spectrum of anthrac Photochemical stability of crotonaldehyde. ene in various solvents. K. La u e r and M. H o rio . F. E. B lacet and J. G. R oof (J. Amer. Chem. Soc., II. Photochemical reaction, anthracene di 1936, 58, 73— 75).— Although ultra-violet light is anthracene, in various solvents. III. Kinetics absorbed by the vapour phase, no .decomp, or of bromination of anthracene in various sol appreciable polymerisation was observed. The con vents. IV. Changes in energy of activation cept of a predominating reverse reaction is put forward and action constants in substitution reactions as an explanation. E. S. H. of organic compounds as effect of solvent. K. La h e r and R. Go A (Bor., 1936, 69, [B], 130— 137, Photochemical decomposition of nitrated 137 140, 111— 145, 146— 148).— I. Examination of phenols. J. M o l x a r (Compt. rend., 1935, 201. the absorption spectrum of anthracene in hexane 1482— 14S4).— At p a > 13-0 picric acid is decom (1), oyidohexane (11), cyctohexene (H i). CGHG. EtOH, posed in ultra-violet light to give picramic and iso- and AeOH shows that solvents containing double purpuric acids, HNO.,, NH3, and HCN, whilst the usual linkings cause displacement of the absorption max. yellow form existing at p H < 13-0 in unaffected. An of dissolved aromatic compounds without dipole analogous reaction occurs with 2 : 5-0H-C6H3(X 02)>. character or polar groups towards the region of longer o- and y-X 0 2-CeH4-0H, 2 :4- and 2 :6-OH-C8H3(X02)^. X. Dipolar solvents have so little effect, on these and 2 : 4-dinitro-o-cresol decompose at p a where the solutes that the displacements are within the limits red forms exist, the rate of decomp, increasing with of experimental error. Solvents with double linkings pn■ T. G. P- but without dipole act on polar mols. in such a manner Catalysed photo-reduction of vat dyes. K. that the spectrum proper to the polar group and that W e b e r (Xaturwiss., 1935, 23. 849— S50).— If due to the aromatic portion of the solute is displaced 0-001% aq. solution of thionine (Lauth's violet) (I) towards the longer X. Dipolar solvents have a greater containing a small amount of FeS04 and H2S04 h> influence than dipole-free solvents on that part" of the cooled to 10° and exposed to the light of a powerful spectrum due to the dipole of the solute and a less, arc lamp, the dye is rapidly bleached. The process though distinct, influence on the aromatic portion is reversible. The bleaching takes the longer the of the spectrum. The displacements are always in higher is the temp, and the weaker the light. Methyl the same sense as those caused by the linear anellation ene-blue (H), Nile-blue, phenosafranine, and neutral- of C6H 8 nuclei to CGHG. red, all of which have negative normal reduction II. The rate of the photochemical reaction, potentials, do not behave similarly. (I) has a positive anthracene ' dianthraeene. has been determined reduction potential. In the case of (H) photo- in (I), (11), (III), 0 GHG. EtOH, and AeOH. Within reduetion takes place if the FeS04 is replaced by the limits of experimental error it has the same val. K 4Fe(CX)G, which has a more negative reduction in (I), (11), (H I), and EtOH, but is considerably potential. The phenomenon can be explained by VIII (d, e), IX GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 301 supposing that the photo-excited dye mol. F* lias a Br2, F2, (N03)2, (OAc)2, (0-C0Et)2, (0-C0Pr)2 are more positive reduction potential than the unexcited described. J. S. A. mol. F. The systems F-leuco-base, and F*-Jeuco- Aluminium carbide, A14C3, and aluminium base are both present. In the dark, F e" does not carbonitride, Alr,C3N . M. von Stack elbk ko , E. react, but in the light the potential of F* becomes Sohnorrenberg, R . P au lus, and K. F. S piess (Z. more positive than that of the Fo” '—Fe" system, and physikal. Chem., 1935, 175, 127— 139).— The com equilibrium is reached by the formation of leuco-base pound AI6C3N, almost indistinguishable in appear and Fe“ ’. The max. of the absorption band of (1.) is ance and properties from A14C3, is formed by regulated at GOO mjx, corresponding with an absorption of admission of N2 to a mixture of A1 and C at 1800°, energy > sufficient for the above change. (II) has being an intermediate product in the nitridation of a more negative reduction potential than (I) and its carbide to nitride, 5 A14C3 - 10N2= 4 A15C3N + 3C+ 8N2 absorption max. is at higher X). ; consequently the =20A1N+15C. A14C3 takes up at high temp, excess energy absorbed is in this case insufficient for the of Al, which separates again on cooling, and the reaction to occur. The fact that the photo-reduction supposed carbides AI9C3 and A13C2 (A., 19134, 600) aro does not occur in alkaline solution is explained on merely finely disperse mixtures of AI4C3 and Al, whilst similar grounds. A. J. M. AIsC9 is a mixture of Al and A12C3. “ Amorphous ” Radiochemical decomposition of deutero- A14C3 (A., 1933, 917) is identical with the cryst. ammonia. J. C. J un gers (J. Physical Chem., 193G, variety. R. C. 40, 155— 158).— The rate of decomp, of ND3 by Carbonyl chloride. A. P erret and R. P errot a-radiation is < that of NH3 and also increases more (Bull. Soc. d ’Encour., 1935, 134, 552—560).—The slowly, relatively, with rise of temp. M. S. 13. reactions of 00C12 are summarised and its action on Action of radioactive substances on proteins. the blood is discussed, especially with reference to 9 J. L oiseleur (Compt. rend., 1935, 201, 1511— 1513). the analogy between the effects of COCl and of CO. —Proteins are first hydrolysed^ and flocculation b J. W. S. follows in the presence of electrolytes. T. G. P. Colour reaction between nitroprusside and sulphite (Bodeker’s reaction). G. Scagliaiuni Heavy hydrogen and heavy water. H i M a r k (Atti R. Accad. Lincei, 1935, [vi], 22, 155— 159).— and M. W ald (Protoplasma, 1935, 23, 109— 127).— Treatment of equimol. aq. mixtures of Na nitro A review. prusside and Na2S03 with conc. aq. Zn, Cd, or Production and identification of helium of Ni acetate and (CH2)8N4 affords the compounds mass three. W . B l e a k n e y , G. P. H a r n w e l l , (Zn or Cd)2[Fe” (CN)5(NO-SO3)],2C0H 12N4,12H2O and W. W. L ozier, P. T. Sm ith , and H. D. Smyth Ni2[Fe"(CN)5(N 0-S03)],2C8H 12N4,8II20 (see A., 1896, (Physical Rev., 1934, [ii], 46, 81— 82; cf. this vol., i, 197). F. 0. H. 130).—Evidence for the production of He3 from D2 Germanium chlorofluorides. H. S. B ooth and in a mass spectrograph is advanced. The life of the W. C. M orris (J. Amer. Chem. Soc., 1936, 58, 90— H3 and He3 produced is at least 108 years. No 93).—By reaction of GeCl4 with SbCl3 in presence of evidence of the production of He4 was obtained. SbCL, there are formed GeCl^F, b.p. 37-5°, m.p. Attempts to find Pie3 and He5 in ordinary He were —49-8°, GeCl2F2, b.p. —2-8°, m.p. —51-8°, GeClF.,, unsuccessful. L. S. T. b.p. —20-3°, m.p. —66-2°, and GeF4. The chloro fluorides hydrolyse in moist air more readily than Purification and spectroscopic evidence for does GeCl4; they are unstable, tending to rearrange He;. G. P. H a r n w e l l , H. D. Sm y t h , and W. D. to GeC!4 and GeF4 even at —78°. Under certain Hhki (Physical Rev., 1934, [ii], 46, 437).— The puri conditions they are reduced explosively by Cu to fication and isolation of small amounts of He3 from circulating in a canal-ray discharge tube are Ge11 salts. PL S. H. described (cf. preceding abstract). L. S. T. Lead ferrites. L. I. P a ra m on ov (Tzvet. Metal., 1934, No. 3, 79— 88).— Formation of P b0,F e20 3 (I) Preparation of calcium chromate in the wet by heating PbO with Fe20 3 begins at 665°, and is a Wa7- J. Mil b a u e r and J. D o sk a r (Sborn. Masaryk. max. at 725°. Addition of Si02 favours the decomp, Akad. Brace, 1934, 8 , 42— 59; Chem. Zentr., 1935, i, of (I). CaO decomposes (I) at 600—800° and com 3259; cf. B., 1933, 963).— Full details are given. bines partly with the PbO. CO begins to reduce J. S. A. PbO from (I) at 400°. The reduction is complete at Common occurrence of trimercury group 550°. Ch . A b s. (e) (HgXÆg,) in complex compounds of mercury (family of turpeths). G. Denigès (Bull. Trav. Soc. Ammonium salts of arsenic, phosphoric, and Pham. Bordeaux, 1933, 71, 97— 109; Chem. Zentr., antimonic acids, and direct determination of *335, i, 3260).— Basie Hg compounds with 3 atoms of heats of oxidation of arsenic. A. d e P a s s i l l Ic (Ann. Hg per mol. are referred to a common structural Chim., 1936, [xi], 5, 83— 146).— Full details of the author’s prep, of pure As (cf. A., 1934,742) and work on nnit Hg < | : ^ ; > A , where X = 0 , S, Se, NH, N R or NH4 phosphates and arsenates (cf. ibid., 377,966; 1935, XH20H, X 2H4, and CO(NH2)2 residues; A=C12, Br2, 344j 936) are given. The prep, of NH4Sb03,3H20 (I) °r a dibasic acid. The compounds are termed is described. (I) readily loses H 20 and NH3 afford turpeths” (turpeth mineral, A = 0, X = S 0 4), and ing probably HSb03,0-5NH3 at 110 , and Sb20 5 at he compounds with X = 0. A=(NO,)„ Se04. Te04, 270°. When As is burned in 0 2 at 15— 40 atm., the (Er03),, (I03)2, Cl2, and Br2; X = S , A = S 0 4, CL, ratio As20 5 : As20 3 increases with [02]. The heats 302 BRITISH CHEMICAL ABSTRACTS. A. IX, X of formation from As metal are : As20 3 (cubic) 154-7 [RuCl2(NH2Et)4]Cl, and [Ru(OH)CI(NH2Et)4]Cl. The and As20 5 (cubic) 218-3 kg.-cal. ' J. G. A. G. analogues of (I) are less strongly coloured than (I). Dehydrogenating action of sulphur monoxide. J. G. A. G. B. S. R ao and M. R . A . R ao (Current Sci., 1935, 4, Detection and separation of sparingly soluble 406).— On absorption in paraffin or decalin at low compounds by concentrated hydriodic acid. temp. SO yielded H 2S. C2C14 gave no result, the SO E. R . Ca l e y and M. G. B urford (Ind. Eng. Chem. being comparatively stable in solution, but yielding [Anal.], 1936, 5 8 , 63— 67).— Examples of the use of H,S on adding paraffin or decalin. SO gave H2S conc. H i in the detection and separation of compounds readily on treatment with MeOH, and more slowly that are insol. in IICl, HN03, or aqua regia are given. with EtOH. Micro-analysis confirmed the reaction E. S. H. 2 S 0 + M e 0 H = H 2S-|-CH20 + S02. The general de Calculating the blank [in volumetric deter hydrogenation is“ R H 2-f2SO=R“-f H 2S+S02, or pos minations]. B. P a r k (Ind. Eng. Chem. [Anal.], sibly in some cases RH„-|-SO = RO -f H,S. 1936, 8 , 32).—Arithmetical procedure is described. N. M. B. E. S. H. Fluorination of sulphuryl chloride : sulphuryl Theory of titration in stages of mixtures of chlorofluoride. H. S. B ooth and C. V. H e rrm a n n acids and bases. S. K ilpi (Z. physikal. Chem., (J. Amer. Chem. Soc., 1936, 58, 63— 66).— S 02ClF, 1935, 1 7 5 , 239— 254; cf. A., 1935, 1214).— The con b.p. 7-1 rt0-l°, m.p. —-124-7;L0To, has been pre ditions for the titratability of such mixtures and of pared by the action of SbF3 on S 02C12 in presence of ampholytes have been derived. R. C. SbCl5 under pressure. The latent heat of vaporisation Colorimetric chemical analyses by means of at the b.p. is 6338 g.-cal. At 0° the liquid has d photo-electric cells. F. Ca r r a n za (Bob Soc. Quim. 1-623 and surface tension 17-2 dynes per cm. The Peru, 1935, 1 , No. 5, 7—27).—The % of the gas is hydrolysed by H,0 and readily absorbed by incident light transmitted by the unknown solution aq.NaOH. “ E.S.H. is determined by means of a photo-electric cell and the concn. deduced by comparison with solutions Preparation of selenic acid. L. I. Gilbertson of known concn. The sensitivity may be increased and G. B. K ing (J. Amer. Chem. Soc., 1936, 58, 180).— Se02 is oxidised by reiluxing with aq. H ,0„ or decreased by the use of filters of complementary or similar colour, respectively, to the solution. E. S. H. Examples are given of the determination of KMn04 Molybdenum-blue. F. H e i n , I. B u r a w o y , and in aq. solution, of NH2-acids (glycine) by means of the H. Sc h w ed ler (Kolloid-Z., 1936, 75, 35—45).— ninhydrin reaction, and of vitamin-A in cod-liver The reduction of heteromolybdic acids by SnCl2 has been studied colorimetrically. This reaction oil. D. R , D. and titration of the Mo-blue with KMnO., indicate Volumetric determination of water in liquids that the product is Mo4On. E. S. H. and so lid s.— See B., 1936, 127. Mixed molybdates. F. G a r e l li and A. T e t ta- Argentometric titration of halide, thiocyanate, m an zi (Gazzetta, 1935, 65, 1009— 1015; cf. A., 1934, selenocyanate, and cyanate with adsorption in 1208).—The prep, of the following compounds is dicators. R. R lpan-TTlici (Z. anal. Chem., 1936, described : (NH 4)5NHR.,Mo70 „, ,411 „0 ; 1 0 4 , 16—22).— CN' is titrated with AgN03 by Liebig’s (NH4)4(NHR3)2Mo70 ;4,4H20 ; method, and the titration of Cl', SCN', SeCN', CN0', (NH4)3(NHR3)3Mo70 „4,4H20 (R=C,R,-OH). etc. continued using fluorescein as indicator. O. J. W. J. S. A. Action of chlorine and bromine on chlorites. Determination of sulphuric acid in solutions G. R. L e v i and M. T ab e t (Gazzetta, 1935, 65, containing aluminium, chromium, and ferric 1138 1144).— The action of Cl2 on aq. solutions sulphate. III. S. A. T o lk atsch ev and J. G. of Ca(C10,)2 is quant : 2C102'+C 12==2C1'+2C102. T itova (J. Appl. Chem. Russ., 1935,8,1271— 1283).— With Br a similar reaction takes place in the initial 25 ml. of aq. A12(S04)3 are titrated with 0 -5N-NaOH, stages, but is followed by an oxidation-reduction an excess of 12 ml. of which is then added; the solu process: 3C102'=2C 103'+C1', nearly all the Br tion is diluted to 100 ml., and saturated with C02 at remaining in the free state. O. J. W. the b.p., cooled, and diluted to 250 ml., filtered, and excess of alkali in an aliquot part of the filtrate is Residual affinity and co-ordination. XXXVI. titrated with 0-5Ar-H2SO4 (Me-orange). Cr2(S04)3 is Constitution of "ruthenium-red.” G. T. M or determined analogously, an excess of 10 ml ."of 0-5N- gan and F. II. B u rstall (J.C.S., 1936, 41— 45).— NaOH being added per 0-1 g. of Cr20 3 in the solution. Ru-red (I) is best prepared by treating RuC13 with In the case of Fe2(S04)3 treatment with CO, is not conc. aq. NH3. The constitution of (I), necessary; the excess of alkali should be 8 ml. per [Ru(0H)C1(XH3)4]C1,H20, is supported by the prep, 0-1 g. of Fe203. The mean error is ¿0-2—0-3%. therefrom of the following cmnpounds : R. T. [RuC12(NH3)4]C1,2H20, [RuC1(N03)(NH3)4]N 03,4H20, Stabilisation of 01AT-sodium thiosulphate [Ru(OH)Br(N.H,)4]Br.H,0, [RuBr,(NH3)4]Br H„0, solu tion .— See B., 1936, 144. [Ru(OH)C1(NH3)41I, [Ru(OH)I(NH3)4]I, “ and [RuI2(NH3)4]I. The following analogues of (I) and Determination of selenium in sulphur. —See derivatives have been prepared : [Ru(OH)Cl en„]Cl, B., 1936, 101. [Ru(OH)I en2]I, [RuCL enJCl, Source of loss of ammonia in Kjeldahl distill [Ru(OH)C1(C5H 5N)‘4]C1, [RuC12(C5H 5N)4]C1, ations. Method of eliminating this loss. H. S. X GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 303 M ille r (Ind. Eng. Chem. [Anal.], 1936, 8, 50— 51).— cobaltinitrite which dissolves completely when treated Dilution of NH3 with air in the initial stages causes with conc. NaOH followed by AcOH, K* is absent, low absorption, giving an average loss of 1-26% N. whilst if a yellow ppt. remains, K* is present. In By using a modified delivery tube, provided with portion B, Na* is detected as Na2H 2Sb20 7,6H20. holes which cause the air bubbles to be broken up, (CH2)6N4 interferes with other qual. tests for K*. this loss can be reduced to 0-06% N. E. S. H. E. W . W. Titrimetric determination of phosphoric acid Methyl-red as an adsorption indicator. D. M. in perchloric acid solution as bismuth phosphate. M u k iierjee (J. Indian Chem. Soc., 1935, 12, 748— 749).— The p u and the sp. conductivity of the solution J. H arms and G. J a n d e r (Angew. Chem., 1936, 49, have been determined after pptn. of AgCl in presence 106—109).—The conductometric titration of I13P 0 4 and in absence of Me-red. R. S. in HC104 solution with aq. Bi0C104 has been inves tigated in presence of Mg, Ca, Cu, Zn, Ni, EeTI, Mn, Determination of the radium content of rocks. Al, small amounts of EeUI, N 0 3, Cl, H 2Si03, and in W. D. U r r y (J. Chem. Physics, 1936, 4, 40— 48).— The artificial fertilisers. W ith suitable precautions, the differential method for determining Ra has been method is rapid (10— 15 min.) and satisfactory. applied to rock analysis. The apparatus has an T. G. P. observational limit of 5-5 X 10~14 X w~0'5 g. Ra for n Influence of fluorine on precipitation of phos hourly readings. He, Ra, U, and Th, and age data phoric acid with molybdic acid. H. T. B u c iie r e r are given for Kcweenawah trap rocks from different and p. W. M e ie r (Z. anal. Chem., 1936,104, 23— 28). levels, and also data for a geological time scale. —Quant, results for P20 5 by the molybdate method M. S. B. of Lorenz, or in presence of 8-hydroxyquinoline, D etection of ca d m iu m . E. I. T risch in (J. Appl. cannot be obtained in presence of E, which must Chem. Russ., 1935, 8 , 1269— 1270).— Ag, Pb, Hg, Bi, first be removed. J. S. A. Ee, Al, Cr, Mn, and Sn are pptd. by adding dil. aq. Micro-determination of arsenic in must and KI, conc. aq. NH3, and 5—6 drops of H 20 2 to 1 c.c. of solution, the solution is filtered, and excess of wine.—See B., 1936, 119. KCN and a few drops of aq. Na2S are added to the Determination of silicon in aluminium alloys. filtrate (containing Zn, Co, Ni, Cu, and Cd), when a -See B., 1936, 151. yellow ppt. is obtained in presence of < 0-00056 mg. Determination of free carbonic acid in waters of Cd. H- T. containing h u m u s. Y . K a u k o (Ann. Acad. Sci. Salts of thiolbenzthiazole.— See this vol., 215. fenn., 1934, 39, A, No. 2 ; Chem. Zentr.', 1935, i, 3177).—The method previously described (A., 1935, Direct detection of lead with diphenylthio- 31; this vol., 159) is applied to soft surface waters. carbazon e. M. K asa h a ra and T. K asa h ara (Klin. Decomp, of dissolved H carbonates introduces an Wocli., 1934, 13, 1857— 1858; Chem. Zentr., 1935, i, enor if applied to hard waters. J. S. A. 3320).—A colorimetric variation of the method of Bohnenkamp and Linneweh (A., 1934, 1030) is System of qualitative analysis for the [com described. DU N. R. moner] anions. J. T. D o bbin s and H. A. L ju n g (J. Chem. Educ., 1935, 1 2 , 586—588).—The anions Use of the iodine monochloride end-point in are separated into six groups, the detailed analysis of volumetric analysis. III. Titration of thallous which is described. Group I, containing C03", E', salts with permanganate, iodate, and eerie sul ^0,", S03", As03'", As04"', P04"', and tartrate, is phate. E. H. Sw ift and C. S. Ga r n e r (J. Amer. Pptd. as the Ca salts in alkaline solution; II, S04" Chem. Soc., 1936, 58, 113— 115; cf. A., 1930, 561).— and Cr04", as the Ba salts from alkaline solution; KM n04 and Ce(S04)2 are unsatisfactory. ^ The use ffl, CN', B03"', Ee(CN)G"', S", and Ee(CN)0"", as of KIOs is recommended. E. S. H. Ihe Zn sap;S jn alkaline solution; IV, S203", CNS', Iodometric determination of copper. Adjust Br', and I', as the Ag salts from slightly acid ment of hydrogen-ion concentration. W. R. (ffif0a) solution; V, CIO/, NO/, OAc' and VI, Cr o w e l l , T. E. H il l is, S. C. R it ten b e r g , and h03' are identified without pptn. Sensitivities are R. F. E venson (Ind. Eng. Chem. [Anal.], 1936, recorded. L. S. T. 8 , 9— 11).— Park’s procedure (A., 1931, 454) is Use of formaldehyde for the elimination of modified. K II phthalate has no material effect ammonia and of a m m on iu m salts in qualitative on p a of the solution and may be omitted. E. S. H. and quantitative analysis. II. Application to Spectrophotometric determination of copper detection of m etals of the six th g rou p . A. in ores and mattes.— See B., 1936, 105. Hkmmbler (Annali Chim. Appl., 1935, 25, 610— 617). Separation of precipitated mercuric sulphide ~~HH4 salts, and their disturbing effect on group VI and sulphur in the gravimetric determination analysis, may readily be removed by adding CHaO, of mercury. E. R. Oal ey and M. G. B u rford rhus converting them into (CH2)6N4 (cf. A., 1934, (Ind. Eng. Chem. [Anal.], 1936, 8 , 43).— The HgS-S 1189). The group V filtrate so treated is divided into mixed ppt. is dried and weighed; HgS is dissolved portions A and B. To A, conc. aq. or solid NaOH is by treatment with cold, conc. HI, and the residual added and Mg(OH)2 completely pptd.; in half the S weighed. filtrate Li* is detected in the usual way. In the remainder, K* is detected by adding AeOH to neutral Gravimetric determination of cerous salts. l y (phenolphthalein) followed by freshly prepared P. Spacu (Z. anal. Chem., 1936, 104, 28— 30). CeIU salts give with K 4Fe(CN)6 at room temp, a ■Aa3Co(NO)6; if there is no ppt., or one of (CFI2)aNi 304 BRITISH CHEMICAL ABSTRACTS. A. X,XI ppt. of vCeK[Fe(CN)6],4H20 which may be weighed D. A. W ils o n (J. Amer. Chem. Soc., 1936, 58, 67— as such or dried to the trihydrate at 100°. J. S. A. 70).—A method for determining UIY in presence of Volumetric determination of indium. H. B. H2C20 4 and U02‘‘ is described. In the photolysis H ope, M. R oss, and J. F. S k e lly (Ind. Eng. Chern. of actinometer solutions the complex undergoing [Anal.], 1936, 8 , 51—52).—In acetate is titrated unimol. decomp, is U0 2(C20 4)2", and the source of with Iv4Fe(CN)G, using diphenylbenzidine as in UIV is U 0 2C204. The ionisation of the complex is ternal indicator. Cl' must be absent. E. S. H. discussed. E. S. II. Determination of rhenium. I. Qualitative. Oxidation of stannous chloride by perman L. C. H urd (Ind. Eng. Chem. [Anal.], 1936, 8 , 11— ganate. V. V. Z a c iia r o v and N. V. Z a ch a rova 15).— In the Prescott and Johnson system of analysis (J. Appl. Chem. Russ., 1935, 8 , 1284— 1286).— SnCl., Re concentrates with As. Confirmatory tests for may be titrated with KMnO, in presence of FeS04 and Re are described. E. S. II. H 3P 0 4. R. T. Standardisation of permanganate solutions Determination of the thorium content of rocks. with sodium oxalate. R. M, F o w le r and H. A. W . D. U r r y (J. Chem. Physics, 1936, 4, 3 4 -4 0 ).— B r ig h t (J. Res. Nat. Bur. Stand., 1935, 15, 493— A method of measuring Th in quantities of the order 501).—Titration of Na2C20 4 with K M n04 at 60— of 10-5— 10-® g. by determining the a-particle activity 90° gives vals. for the normality of the latter which of thoron (Tn) in a streaming gas by a counter is may be 04% high. 90—95% of the KMn04 solution described. It is possible to make a simultaneous should be added to the aq. Na2C20 4 (+ 5 % of H 2S 0 4) determination of the Pa/Ra ratio in common rocks. at 25—30°, the solution warmed to 55—60°, and the M. S. B. titration completed as usual. H. J. E. Organic compounds as analytical reagents. Colorimetric determination of manganese [in II. Cinchonine iodide as reagent for determin s o ils] in presen ce o f titan iu m .— See B., 1936, 114. ation of bismuth. J. B. F ic k le n , I. L. N ew ell, and N. R. P ik e (Z. anal. Chem., 1936,104, 30— 34).— Determination of manganese and magnesium Cinchonine iodide is not strictly sp. for Bi. Data are in soils and silicate ro c k s.— See B., 1936, 114. given as to the interfering effect of other cations. Use of potassium stannochloride dihydrate J. S. A. K 2SnC l4,2H.,0 in determination of iron. E. Stable standardised gold solution. W. C. Voyatzakis “(Praktika, 1934, 9, 108— 111; Chem. W illia m s (J. Lab. Clin. Med., 1935, 80, 545— 549).— Zentr., 1935, i, 3317).— To the strongly acid (HC1) F e"' Patterson’s method (A., 1932, 225) is modified by solution, NaHC03 is added, and then an excess of use of 0-02JV-KOH, the acid Au salt, and a solution K 2SnCl4,2II20 (I) (prep, described). The excess of of edestin for standardisation. Ch. A bs. (p) (I) is titrated back with 0-01N-I. J. S. A. Calorimetric apparatus. W . A . R oth (Chem. Determination of iron in phosphorites and Fabr., 1936, 9, 10— 12).— A summary of recent apatites.— See B., 1936, 144. developments in calorimetry. J. W. S. Oxidimetric determination of molybdenum. Maquenne block. R. P. Jacquemain (Bull. Soc. I. Vanadate method. R . L a n g and S. G ottlieb chim., 1936, [v], 3, 142— 143).— The disadvantages (Z. anal. Chem., 1936,104, 1— 16).— A neutral M o04" of the usual Maquenne block are reviewed. A Cr solution is acidified with 15—20 vol.-% of conc. block is recommended. E. E. A. HC1, and 0-2A-SnCl2 is added until no further brown coloration occurs on each addition, reducing MoVI Combined hydrogen and helium liquefier. to M o '. The excess of SnCl2, but not Mov, is B. V. R o l l i n (Proc. Physical Soc., 1936, 48, 18—27). —An apparatus needing only liquid air for the initial oxidised by adding aq. Br+KBr, Br being removed cooling, and designed for low-temp. laboratory experi by an equal vol. of 0-3N-As2O3. NaF is added, ments, is described. N. M. B. and then NHPh2 in H 3P 0 4 as indicator. Mov is oxidised by addition of 0 jiV -N H ,V 0 3 (I), the excess Semi-micro-Cottrell b.-p. apparatus. M. L. of which is titrated back with FeS04. Alternatively, W il la r d and D. E. C r a b tr e e (Ind. Eng. Chem. after addition of As203, the Mov may be titrated [Anal.], 1936, 8 , 79—80).—The apparatus can be directly with (I), previously oxidised diphcnylamine- used with 5 c.c. of liquid and gives results accurate sulphonic acid being added as indicator shortly before to 0-1°. E. S. H. the end-point. The acidity during reduction must Electrically-heated m .-p. apparatus. E. Dow- be as stated to avoid reduction to Mo111 or MoIT, z a rd and M. J. R usso (Ind. Eng. Chem. [Anal.]. which oxidises directly to MoVI with Br. Neutral 1936, 8 , 74— 75).—The apparatus avoids the use of salts or non-reducible metals do not interfere. In heating liquids and is suitable for substances with presence of Fe and V the method is impracticable, m.p. > 310°, with a reproducibility of 0-5°. due to oxidation of Mov by FeIIT and Vlv. Large E. S. H. amounts of Cu interfere similarly. Mo may be Stem correction for mercury thermometers. determined in presence of W by adding NaF before M. E d en h olm and G. O lsso n (IVA, 1935, 5— 10; reduction to keep W 0 3 in solution; a trace of Cu Chem. Zentr., 1935, i, 3692).— The formula Af= is added to catalyse the reoxidation of W compounds n i(ta—te)/(k—n1-{-te), where t,.=temp, of exposed by Br. ‘ J. S. A. stem, observed temp., ?i4=length of exposed stem Reduction of uranyl ion in the uranyl oxalate in degrees, and l/&=apparent coeff. of cubical actinometer. E. C. P itz e r , N. E. G o r d o n , and expansion, is proposed. H. N. R- XI GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 305 General source of radiation for the visible (Rev. Sci. Instr., 1936, [ii], 7, 26— 30).— Reflected or and infra-red sp ectru m . A. H. P f u n d (Science,, transmitted electron beams from a hot-filament 1935,82,597— 508). L. S. T. cathode or from a discharge tube can be used. A Curved quartz crystal X-ray spectrograph. wide range of temp, and exposures is available. C. W . G. J. W. M. D uM ond and B. B. W atson (Physical Rev., Ion sources for mass spectroscopy. A. J. 1934, [ii], 46, 316— 317). L. S. T. D empster (Rev. Sci. Instr., 1936, [ii], 7, 46— 49; cf. Large-aperture spectrograph suitable for the A., 1935, 677).—A high-frequency alternating spark ultra-violet. A . A r n u l f and B. L yo t (Compt. coupled inductively to a primary oscillating spark rend., 1935, 201, 1480— 1482).— A quartz spectro circuit is a more convenient source than a vac. graph, aperture / l , lias been constructed using a vibrator or a large condenser discharge. C. W. G. spherical A1 mirror in place of the usual objective. T. G. P. Measurement of the breakdown and current- Self-rectifying gas A'-ray tube. R. W. G. voltage characteristics of liquid dielectrics with W yckoff and J. B. L agsdin (Rev. Sci. Instr., 1936, direct potentials. E. B. B a k e r and H. A. B oltz [ii], 7, 35—37).-—An instrument previously described (Rev. Sci. Instr., 1936, [ii], 7, 50— 58).— Currents from (Radiology, 1930, 15, 42) is improved. C. W. G. 10 18 to 10"3 amp. can be measured. C. W . G. Simplified apparatus for fluorescence analysis. High-speed, high-sensitivity photo-electric A. K a rsten (Zement, 1935, 24, 158— 159; Chem. potentiometer. R. W. Gilbert (Rev. Sei. Instr., Zentr., 1935, i, 3315).—An apparatus, using activated 1936, [ii], 7, 41— 46).— The response to changes of metal electrodes, is described. H. N. R. input is instantaneous. C. W . G. Application of photo-electric methods to the Electro-ultra-filtration apparatus. E. J. Czar- Duboscq colorimeter. G. Bernheim and G. Re- n e tzk y (Science, 1935, 82, 625— 626).— An apparatus mllon (Ann. Falsif., 1936, 29, 5— 10).— The photo for the prep, of solutions of protein-Hg compounds electric cell described has a range of sensitiveness is described. L. S. T. similar to that of the human eye, and consists of a small Fe plate supporting semi-conductors which are Mounting cell for the bulb type of glass elec covered (by cathodic treatment) with a thin layer of trode. J. H . H ig h berg er (J. Ainer. Leather Chem. an alloy of a precious metal. One of these is inserted Assoc., 1936, 31, 32— 34).— The apparatus described under each of the eyepiece prisms of the Duboscq previously (A., 1935, 1097) is modified to permit the colorimeter, the two being connected through a flushing of the saturated aq. KC1 and the electrode imlliammeter in opposition. Solutions tested and the chamber. D. W. corresponding max. relative matching errors are 0 -6 % Modified Gouy’s balance for the accurate and 1 2, 0-05% K M n04 10, 2 % CuS04 (in aq. NH3) 6 , and 10 mg. per litre of methylene-blue 2-2%. J. G. quick measurement of diamagnetic suscept ibilities. M. B. N evgi (Current Sci., 1935, 4, 403).— Determinations with registering spherical The modified instrument consists of two tubes, one cadmium cells. M. B e n d e r (Physikal. Z., 1936, of which is sealed and contains the paramagnetic 37,107—110).— Cd photo-cells can be used for deter substance and acts as a stopper to the other tube mining the ultra-violet in sunlight. A. J. M. containing the diamagnetic specimen. An equation Differential refractom eter. D. R a u and W . E. is deduced, and calc, results for nine org. substances Roseyearf. (Ind. Eng. Chem. [Anal.], 1936, 8 , 72— are in good agreement with available data. 73).—The apparatus uses white light and has a N. M. B. sensitivity of 5 x 10'7. It has been used to determine Utility of broken automatic pipettes. B. N. the eonen. of aq. solutions with w=0-0004— 0-002 > n Singh and P. B. M athur (Science, 1935, 82, 626). for H20. The scale readings are nearly a linear L. S. T. function of the difference in n. E. S. H. Apparatus for sugar and other titrations. E. S. W est (Ind. Eng. Chem. [Anal.], 1936, 8 , 62). Visual conductometry. L. W olf (Chem. Fabr., E. S. H. 1936, 9, 46—49).—Two galvanometer-Se-rectifier in Precision pyknometer for liquids. S. T. Yus- struments are used, one in series with the titration te r and L. H. R eyerson (Ind. Eng. Chem. [Anal.], cell and the other in parallel. The current in the 1936, 8 , 61— 62).— A modified apparatus is described. main circuit is kept const, and the deflexion of the E. S. H. second galvanometer is observed after each addition Method of obtaining perfectly polished metallic °f alkali. The accuracy can be increased by taking surfaces. P. J acqu et (Compt. rend., 1935, 201, readings with different currents in the main circuit. 1473— 1475; cf. B., 1935, 730).— The Cu specimen, R. S. polished in the ordinary way on fine emery, is made Directionally selective ion counter. L. M. the anode in the electrolysis, at a suitable c.d., of aq. Danger and R. T. Cox (Rev. Sci. Instr., 1936, [ii], 7, H3P 0 4 or H 4P20 7 containing at least 400 g. per litre, 31—33).—A particle passing between a pair of parallel and maintained between 15° and 25°. T. G. P. wire electrodes in a direction parallel to them pro duces a greater total discharge than one passing in Q uick m eth od of depositin g p olon iu m on. another direction. C. W. G. silver. M. D. W h it a k e r , W. B jo r k st e d , and Universal camera for electron diffraction at A. C. G. Mitchell (Physical Rev., 1934, [ii], 46, 10 100 kv. H. J. Y e a r ia n and J. D. H owe 629— 630). ‘ L. S. T. 306 BRITISH CHEMICAL ABSTRACTS.— A. XI, XII, XIII Safety device for use with gas-heated Soxh- Automatic recording balance. D, S. B inning- lets. J. C. M acrae (Chem. and Ind., 1936, 53).— ton and W . F. Ged d es (Ind. Eng. Chem. [Anal.], The device cuts off the gas supply if the H20 supply 1936, 8 , 76— 79).— The balance is electrically oper to the condenser or bath begins to fail. E. S. H. ated, fitted with oil damping, and counterbalanced Efficient fume hood [for laboratories], G. W. for an initial load of 100 g. W t. losses up to 17 g., M uhleman (J. Chem. Educ., 1935,12, 591). with an accuracy of 0 01 g., are recorded without L. S. T. manual attention by an automatic device which Apparatus for producing vapours of constant places wts. on the pan. A continuous record is ob concentration by evaporation of mixtures of tained on a paper chart by the use of a timed spark. j liquids of different b.p. E. V. A l e x e e v s k i and E. S. H. ! G. M. Ciiram ov (J. Appl. Chem. Russ., 1935, 8,1319— Micro-Dumas generation of carbon dioxide. 1320). R. T. W . S. I de (Ind. Eng. Chem. [Anal.], 1936, 8 , 56).—- MgC0:i is introduced into the closed end of the micro Stirring apparatus for small amounts of combustion tube. Before combustion, air is removed liquid. K. Packendorff (J. pr. Chem., 1936, [ii], from the tube by heating the MgC03. E. S. H. 144, 211—213).— An electrically operated plunger- stirrer, suitable for mixing small amounts of liquid Check valve. E. L. Gr e e n (Ind. Eng. Chem. in a gas-tight or evacuated tube, is described. [Anal.], 1936, 8 , 40).—The device is designed to R. S. C. prevent the sucking back of liquids when passing Low-pressure measurements. W. Gaede (Z. a gas through them. E. S. H. tech. Physik, 1934,15, 664— 668; Chem. Zentr., 1935, Ball mill. L. L. Q u il l (Ind. Eng. Chem. [Anal.], i, 3164).—A piece of A1 foil is suspended by a quartz 1936, 8 , 27). E. S. H. fibre in a glass vessel, the pressure and mol. \vt. of Determination of the wall correction for the the gas in the apparatus being deduced from observ falling-sphere viscosimeter. E. I. F ulmer and ations of the vibration and damping of the Al. The J. C. W illiam s (J. Physical Chem., 1936, 40, 143— range of operation is 10— 10' 7 mm. Hg. H. J. E. 149).—Viscosity data have been obtained in the fall Laboratory hints. A. V osmaer (Chem. Week- ing-sphere viscosimeter for castor oil, glycerol, blad, 1936, 33, 61— 62).— The best methods for cutting solutions of colophony in turpentine, and two samples different kinds of glass tubing and for cutting and of honey. An equation has been derived giving the boring glass plate are described. D. Ri D. wall correction for vals. of r/R up to approx. 0-500. Laboratory hints. W. v a n T o n g e re n (Chem. r and R are the radii of the sphere and the inside Weekblad, 1936, 33, 62).— A hole bored in the rubber of the cylinder, respectively. M. S. B. ejector bulb of a wash-bottle is closed during use by Surface tension by the ring method. Applic means of a finger. D. R. D. ability of the Du Nouy apparatus. R. M acy (J. Ultramicrometer. C. L. U tt e r b a c k and H. Chem. Educ., 1935,12,573—576).—Methods by which W irth (Physical Rev., 1934, [ii], 46, 328).— Changes data obtained by this method can be brought into in pressure of the order 10~3 dyne per sq. cm. can be line with those given in the International Critical measured by the arrangement described. L. S. T. Tables are described. L. S. T. Organic liquids suitable for cloud expansion Practical application of lifting plate method work. D. D. L o u g h r id g e and H. C. T ru eb lo od to determination of surface tension. W. De- (Physical Rev., 1934, [ii], 46, 323).— 28 liquids have k e y s e r (Wis. nat. Tijds., 1934, 7, 107— 118; Chem. been studied with reference to their min. expansion Zentr., 1935, i, 3640— 3641).—An expression is ratio for condensation on a-particle tracks. developed for the accurate determination of surface L. S. T. tension from the force required to lift, a disc from the Amplifier and recording apparatus for a-part- surface of a liquid. J. S. A. icles, high-speed protons and neutrons. M. C. Determination of surface tension of saturated H enderson (Physical Rev., 1934, [ii], 46, 324). aqueous solutions. F, d e B lo ck (Wis. nat. L. S. T. Measurement of very low relative humidities. Tijds., 1934, 7, 80— 88; Chem. Zentr., 1935, i, 3641).-—A lifting-disc method is applied to the de A. Simons (Proc. Physical Soc., 1936,48,135— 144).— An apparatus for measuring dew points down to termination of the surface tension of saturated solu —40°, corresponding with 0-5— 10% R.H., and a tions, and its dependence on temp. J. S. A. hygrometer using wet and dry thermocouples are F u rth er applications of ch em istry to archae described. Calibration curves for the hygrometer olog y . W . F oster (J. Chem. Educ., 1935,12, 577— for 0-5— 10% R.H. and 10— 90° air temp, are given. 579).—Ancient mortars and cements (Mayan), bees N. M. B. wax, and Pb are described. L. S. T. Geochemistry. Temperature of atmospheric ozone. J. D e - Penetration of solar and cosmic rays into v a u x (Compt. rend., 1935, 201, 1500— 1501; cf. fresh -w a ter lakes. G. A. L in h a r t (J. Physical A., 1932, 108).— Infra-red spectra indicate a temp. Chem., 1936, 40, 113— 119).— An equation previously < 0°, which does not suffer appreciable diurnal or deduced (Amer. Math. Month., 1935, 42, 224) m seasonal variation. T. G. P. applied. M. S. B. XIII GEOCHEMISTRY. 307 Origin of bore-hole water. N. V. T ageeva Si02, and H20 are formed. (I) forms clinoenstatito (Neft. Clioz., 1934, 26, No. 7, 63— 65).— Analyses at 1200°, and amorphous Si02 forms cristobalite at are given. The H20 originated from the ocean, 1300°. H. J. E. and was later changed by contact with minerals. Ejected blocks of the Laacher See district. Ch . A b s . (e) G. K alb (Tsch. Min. Petr. Mitt., 1936, 47, 185— 210). R adium m in era ls. V. Ch a r r in (Rev. ind., 1935, —d'he sanidinites derived from cryst. schists are of 65, 19— 20; Chem. Zentr., 1935, i, 3701).— A review two types : aegirine-augite-sanidinite (fenite) formed of the occurrence and extraction of Ra. J. S. A. by pneumatolytic injection metamorphism with a Occurrence of minerals in Hungary. R. phonolitic magma; and biotite-sanidinite formed by R eichert (Foldtani ICozlony., 1934, 64, 348— 356; pneumatolytic contact metamorphism with an alkali- Chem. Zentr., 1935, i, 3651).— Microscopic, chemical, trachyte magma. L. J. S. and crystallograpliic data are given concerning Aphrosiderite from the granite of the Tatra Hungarian occurrences of marcasite, quartz in pyr M ts. B. Ma u r it z (Mat. Term. Erfc., 1935, 53, oxene andesite, hornblende and biotite, and phillips- 238— 247, and Tsch. Min. Petr. Mitt., 1936, 47, ite. J. S; A. 262— 269).—Analysis of a chloritic mineral coating a Crystallographic data for Hungarian copper block of granite identifies it with aphrosiderite. pyrites. Szá va-K ováts and K . R esch (Foldtani L. J. S. ICozlony, 1934, 64, 334— 341; Chem. Zentr., 1935, Yellow rock-salt from Hall in Tirol. K. Rr z i- i, 3651).— Measurements on Cu pyrites from four bram (Nature, 1936, 137, 107— 108).—The discovery sources are given. J. S. A. by Schauberger of light-sensitive yellow rock-salt from this locality supplies the link, hitherto missing, in Granodiorite deposit of Sténovic (near Pilsen) the formation of natural blue rock-salt. The absorp and its relation to neighbouring massifs. A. tion spectrum is the same as for rock-salt coloured Orlov (Vest. stát. Geol. Ust. Cesk. Repub., 1934, artificially by Ra rays. The salt shows thermo- 10,97— 103; Chem. Zentr., 1935, i, 3651).— The oligo- luminescence, and on exposure to Ra rays it colours clase granodiorite of Sténovic contains plagioelase quickly; the artificial colour is likewise sensitive to (of ohgoclase type, with zoned structure) 50%, light. L. S. T. quartz 20%, and orthoclase 10%, with amphibole and biotite. J. S. A, Petrology of common volcanic rocks of Japan. S. T suboi (Proc. V Pacific Sci. Congr., 1934, 3, 2271— Chemical-mineralogical investigation of erup 2273).—The alkali-lime index for the Japanese tive rocks of the central Sahara and the Sudan. volcanic rock series is 65-5. The compositions of V. E. D e n a e y e r (Bull. Soc. franq. Min., 1934, pyroxenes are plotted. Ch . A b s. (e) 57, 284— 337; Chem. Zentr., 1935, i, 3651).— A comprehensive résumé of chemical and mineral- Chemical composition of the Deccan trap ogical data. J. S. A. • flows of Linga, Chhindwara District, Central P rovin ces. L. L. F e rm o r (Rec. Geol. Surv. India, Hohmite and bayerite. H. L eh l (J. Physical 1934, 6 8 , 344—360).—The minerals are described. Chem., 1936, 40, 47— 54).— Four definite cryst. Analyses are given. Ch . A b s. (e) forms of A1 hydroxide are known. Diaspore, gives a-corundum on removal of H 20. Occurrence of sphalerite at Ellsworth, Ohio. The other three forms, on losing H 20, give cubic G. U. Green e (Amer. Min., 1935, 20, 8S2— S83).— y-Al203. They are, in order of increasing stability, Sphalerite associated with barite or calcite is described. pohmite, Alo0 3,H90, bayerite, AL0o,H 20, and gibbs- L. S. T. ltc> AÍ¿03,3H2O. " M. S. B. Morphology of phenacite from two new occur Helium content of minerals not emitting rences [at Klein-Spitzkopje, South West Africa, and the Morefield mine, Winterham, Amelia “■rays and its explanation. H. J. B orn (Natur- Co., Virginia]. F. H. R ou gh (Amer. Min., 1935, wiss., 1936, 24, 73—76).—The origin of He in beryl 20, 863— 874). L. S. T. and in alkali halides, particularly sylvine, is discussed. Hie He content of beryl is probably duo to the action Vectorial chemical alteration of crystals. G. of y-rays on 4Bc° giving 4Be8 and 0nl, the 4Be8 break F rondel (Amer. Min., 1935, 20, 852— 862).— Vec ing down to 22He4. Sylvine and rock-salt often con torial chemical alteration of crystals occurring in tain Pb, and the difference in He content of these nature is described for pyrite (to hiematite), enargite, Minerals may depend on the concn. of U, Ra, and stibnite (probably to wurtzite), and tourmaline. Ra-1) in the H20 from which they were originally With barite and celestite, a partial overgrowth of a deposited. Primary rock-salts contain only minute white opaque substance of later generation may amounts of He. Those containing greater amounts simulate a vectorial alteration. Chemical changes in have all been in contact with H20 at some later crystals may be affected by twinning, zoning in period, and the high He content is connected with composition, and the physical nature of the bounding the high [Ra] in deep waters. A. J. M. surface. Nucleation on crystal edges or surface imperfections is described for the topoehemical alter Thermal decomposition of talc. R. H. E w ell, ation of azurite to malachite. L. S. T. H X. B unting, and R . F. G e lle r (J. Res. Nat. Bur. stand., 1935, 15, 551— 556).— W t. losses and X-ray MonticelHte from San Bernardino County, ata are given. No change in.crystal structure occurs California, and the monticellite series. W. T. np to 800°. A t 800— 840°, enstatite (I), amorphous Schaller (Amer. Min., 1935, 20, 815— 827).— Small 308 BRITISH CHEMICAL ABSTRACTS. A. XIII grains of monticellite (I) disseminated throughout a Ca by kin11 and of A1 by Mn111. The varied coloration dolomite from the Dewey mine are the purest samples of Mn minerals and the occurrence of Mn in different of-(I) so far described. The FeO and MnO replacing kinds of rocks are discussed. L. J. S. MgO is < 1-50%. a 1-641, p 1-649, and y 1-655 are Pyrometasomatic vein deposits at Tepezala, < any other recorded vals. The components of the Aguascalientes, Mexico. A. W a n d k e and T. G. series MgO,Ca0,Si02(I)-Fe0,Ca0,Si0 2-Mn0,Ca0,Si02 M oore (Econ. Geol., 1935, 30, 765—782).— The rock (glaucochroite) are discussed and their refractive types and ore deposits are described. CaO-silicate indices given. L. S. T. minerals occur both as products of wall rock alteration Experimental study of the porosity and per and as gangue minerals in the veins proper. The meability of clastic sediments. H. J. F r a ser (J. sulphide ore, chiefly chalcopyrite with minor amounts Geol,, 1935, 43, 910— 1010). L. S. T. of pyrite, sphalerite, and galena, is associated with Biotite system. A. N. W in c h e ll (Amer. Min., abundant diopside (I), hedenbergite (II), garnet, 1935, 20, 773—779).—A revision of data and diagrams epidote (III), fluorite, quartz (IV), etc. as vein gangue (cf. A., 1925, ii, 592; 1926, 494). L. S. T. minerals. The marginal alteration associated with the veins consists of an intcrgrowth of (I), (II), (III), Occurrence and origin of celestite and fluorite and (IV). This alteration affects both intruded at Clay Centre, Ohio. R. B. M orrison (Amer. and intrusive rock and is probably the first work Min., 1935, 20, 780— 790).— Descriptive. L. S. T. of the solutions as they rose in the fractures. The Enargite and plumbojarosite at Picher, Okla sequence of mineral deposition is discussed, and a homa. A. L. R a n s o m e (Amer. Min., 1935, 20, 799— comparison with other pyrometasomatic districts is 805).—Crystals of enargite and plumbojarosite in a made. The deposits are considered to be of Tertiary specimen from the Barr mine are described. age. L. S. T. L. S. T. Iron ore deposits of the Ilimpeia River, East T hulite in New Mexico. S. A. NoRTHRor (Amer. ern Siberia. V. Sobolev (Econ. Geol., 1935, 30, Min., 1935, 20, 805— 807).— Thulite, d 3-15, occurs in 783— 791).— The geology and petrology of the dis quartz, associated with some aetinolite, at Pilar Post trict are briefly discussed. The Fe ore deposits, Office, Taos Co., New Mexico. An analysis is given. which present a new instance of a special typo of L. S. T. magnetite deposits, are described and analyses are Quartz paramorphs after tridymite and cristo- given. Their origin also is discussed. L. S. T. balite. R. S. M o eh lm an (Amer. Min., 1935, 20, 808—810).—Abnormal forms of quartz, probably the Kaldurga conglomerates and the iron ore result of inversion from tridymite and cristobalite, series of the Bababudans, Kadur district, have been observed in Miocene volcanic rocks south M y sore, (a ) M. B. R. R ao . (b ) C. S. P icha- west of Ouray, Colorado. L. S. T. m uthu (Current Sci., 1935, 4, 415— 417, 417— 418).— Composition of asbestos and other fibres of ( a ) A criticism of Pichamuthu (cf. A., 1935, 1479).. Thetford district, Quebec. H. C. Cooke (Trans. (b ) A reply. N. M. B. Roy. Soc. Canada, 1935, [iii], 29, IV, 7— 19).— Some deposits of lead ores in the state of Several analyses are given of carefully selected Minas Geraes. B. A. W e n d b b o r n (Bol. Min. chrvsotile of different degrees of softness and harsh Agric. [Brazil], 1935, 24, 35— 77).— The geology of the ness, and these are interpreted as mixtures of ser region studied (a zone of 1100 km. from Sete Lagoas pentine (H4Mg3Si209), chlorite, talc, brucite, peri- through Pirapora to Montes Claros, and about 10— clase, etc. Harshness seems to be connected with 20 km. wide) is described with especial reference to, excess of Si02 and the presence of more talc and pcri- and analyses of, the Pb ores found. E. L. clase and less H 20. Analyses of fibrous materials occurring on slickensided surfaces and in faults Lead-bismuth ores in Bleka, Svartdal, Nor show that these may range from serpentine to brucite. w ay. C. B ugge (Econ. Geol., 1935, 30, 792— 799).— L. J. S. The ore (analyses given) occurring at Bleka in quartz Manganese concretions in Nova Scotia lakes. (I) veins in a gabbro dyke is mainly galenobismutite E. M. K in d le (Trans. R oy. Soc. Canada, 1935, [iii], with small amounts of bismutite (Bi2S3) and traces 29, IV, 163— 180).— The nodular or more often of galena. Emplectite has also been found. Au- disc- or saucer-shaped concretions (3— 6 in. across) bearing veins also occur and the gangue consists of are formed around pebbles on the bottom of tlie dominant (I), barite, brown spar, tourmaline, and lakes, and contain MnO, 35-29, Fe20 3 16-56%. traces of fluorspar. Chalcopyrite is also important. They have probably been formed by the action of L. S. T. algse extracting Mn and Fe from the lake water. Spectrographic evidence on origin of ores of L. J. S. Mississippi Valley type. L. C. Graton and G. A. Role of manganese in minerals. H. Otto H arcourt (Econ. Geol., 1935, 30, 800— 824). (Tsch. Min. Petr. Mitt., 1935, 47, 89— 140).— Several Spectrographic examination shows that sphalerites new chemical analyses together with optical data are from many deposits of the so-called Mississippi given of various manganese-bearing minerals (phos Valley type appear to contain amounts of Fe, Cu, phates and silicates), and the results are plotted, and Pb, and of the less common elements, especially together with data from the lit., shoving a decrease Cd, Ga, Ge, and In, commensurate with those found in n with isomorphous replacement of Fe11 by Mn11 in deposits formed by. solutions of magmatie origin. and an increase with replacement of Zn, Mg, Li, The geochemistry of the latter group of elements XIII, XIV (a) ORGANIC CHEMISTRY. 309 in this connexion is discussed. A definite and system slope of the Ural mountains. A. A. V a r o v (Neft atic serial relationship between these sphalerites Choz., 1934, 26, No. 7, 32— 37).— The shales contain and those of hydrothermal sphalerites of a magmatic T i0 2 0-2 0-3, Mn > 2-23, Fe20 3 > 2, total S 2 - 3 , group is indicated. L. S. T. S 04" 0-2— 0-3%. The P20 5 (0-1— 0-5%) is higher’ Steigerite, a new vanadium mineral. E. P. in the carbonate shales than in the siliceous shales. H enderson (Amer. Min., 1935, 20, 769— 772).— Ch . A bs. (e) Steigerite (I), A120 3,V20 5,6-5H20, similar to fervanite Lithology of the clay facies of the carbonifer (II), has been found in the U -V deposits of the Gyp ous in the Samara U-bend of the Volga river. sum Valley, San Miguel Co., Colorado. (I), n 1-71 dr L. A. G u lja e v a (Neft. Clioz., 1934, 26, No. 7 , 26— 0'005, has V20 6 44-44, A120 3 25-14, Fe20 3 1-50, 31).— The clay from various depths (> 1000 m ) H20 — 8-08, H 20 + 21-04, total i00-20%. It is bright contained alkalis 6— 10, C02 < 6, Mg 1—3%. It was canary-yellow in colour, insol. in H 20 , and is easily low in Mn, Cl, and H 2S04. Ch . A b s . (e) decomposed by mineral acids. X-Ray examination Enrichment of titania in clays. A. Salm in e n shows that (I) is cryst. giving a pattern different from (Suomen Kern., 1936, 9, A , 1—4).— The average TiO„ that of (II). ji. S. T. content of 27 Finnish clays was 0-68%; that of 12 Pegmatite minerals from near Amelia, Vir sands was 0-40%. S. M. N. ginia. J. J. Glass (Amer. Min., 1935, 20, 741— Geological aspects of recent research on coal. 768).—31 mineral species have been identified from — See B., 1936, 82. the pegmatites of Amelia and eight of these, viz., bertrandite, biotite, clialcopyrite, phenacite, pyro- Geology and presence of petroleum in north lusite, topaz, triplite, and zinnwaldite, are described ern Ferghana. G. I. S c h a to v (Neft. Choz., 1934 in detail for the first time. The physical and optical 26, No. 10, 2 1 -2 2 ). Ch . A b s. (e) properties of the two varieties of microlite which occur Geological characterisation of the Tschiki- are compared, and several varieties of sericite (with schlyar oil-hearing district in Turkmenia. A. I. analyses) are described. The zinnwaldite has SiO, IIo su ig in (Neft. Choz., 1934, 26, No. 7, 49— 55).— 43-70, A120 3 22-96, F e ,0 3 0-59, EeO 11-67, TiO, 0-32, Analytical data aro given for various volcanic, MgO 0-03, CaO 0 -02, Na20 0-74, K 20 9-58, H .O - and other, gas and oil producers, on the east shore of 0-0S, H20 + 1-35, MnO 1-95, F 5-52, Li20 1-92, the Caspian Sea. Ch . A bs. (e) «b20 1-04, Cs20 0-10, total 101-58, (less O 2-32) 99-26%. New optical determinations and other pro Athabasca oil sands : apparent example of perties of nearly all the minerals which occur at local origin of oil. M. W. B a l l (Bull. Amer. Assoc Amelia are tabulated. The less common elements, Pet, Geol., 1935, 19, 153— 171).— The oil occurs as identified by spectrographic analyses in many of these a film around each grain of sand. It is of asphaltic minerals, are recorded. L. S. T. base, very heavy, high in S, and is readily cracked at < the normal temp., yielding 20— 35% of gasoline. Lithology of the p recip ita tion of ‘ ‘ d om an ic ' ’ It is probably a young oil, which has not been geo shales from the upper Devonian of the western logically cracked. Ch . A b s. (e) Organic Chemistry Comparison and critical analysis of physical that the state of the Si02-glass surface influences the Properties of homologues and isom erides. Mole nature of the reaction. ~ F. L. U. cular volume of alkanes. G. Ca lin g a e r t and Development of the intermolecular and intra t ” ■ H lidky (J. Amer. Chem. Soc., 1936, 58, 153— molecular chains in oxidation of »-hexane. y • A series of parallel curves is obtained by plotting W . M. Z a ik o v sk y (Physical Rev., 1934, [ii], 46^ vol. against no. of C atoms in the longest chain; 329). Analytical data of the oxidised air—n-hexane ■i111 % rary scale is used. Certain irregularities mixture are discussed. L. S. T. 1 die need of new data are discussed. II. B. Isomérisation of «-heptane. G. Calin g ae rt Combustion of hydrocarbons I, II.— See this v°l-» 294. and II. A. B e a tt y (J. Amer. Chem. Soc., 1936, 58, 51— 54 ; cf. A., 1935, 843).— n-C7H16 heated with Occurrence radicals in the thermal decom A1C13 gives pentanes (-flower hydrocarbons) 64-6% position of molecules and the reaction C H -A -H ,. (of C7H 16 reacting), p- and y-methylpentane 34 and "See this vol., 293. 2% , respectively, w-CGH 14 0 4 % , pS-dimethylpentane Formation of condensation products from 1-5%, p Py-trimethyl butane 0-5%, yy-dimethyl- iunple hydrocarbons. M. W . T r a v e r s (Trans, pentane 04% , P- and y-methylhexane 1-2 and 1-6%, n n k r v j ,c‘’ 1936> 32> 236—246).—Work previously respectively, and polymerisation products 244%. The aurl i 1935, 40) on the pyrolysis of C2H 6 above % are deduced from vais, of n, b.p., and crit. condensation of C2H 4 is reviewed. In presence solution temp, in NH 2Ph. II. B. S s f i b 500 ° ™ e:CH2 y^lds C2H4 and CH4, Highly polymerised compounds. [Viscosity ... . 10 same time condensation proceeds from of solutions of aliphatic hydrocarbons.] .H. c eimtmlreactions2C3H G=(C 3H G)2andC3H B+C 2H4= Stau din ger (Ber., 1936, 69, [B], 203—208).—A reply s io- Preliminary experiments with C2H2 indicate to Meyer et al. (A., 1935, 1318). H. W . X IV (a) 310 BRITISH CHEMICAL ABSTRACTS. A. 4 8 Paraffin hydrocarbon from urine of preg of the C H prepared by catalytic decomp, of Bu“OH are ascribed to the effects of catalyst and temp, n a n c y .— See this vol., 362. rather than to analytical procedure. H. B. Mechanism of addition of halogens to ethylenic Application of the structure theory of reac lin k in g s . R. A. Ogg, jun. (J. Amer. Chem. Soc., 1935, 57, 2727—2728).—The following mechanism, tions to Lebedev’s synthesis of butadiene from alcohol and to Rice's theory of pyrolysis.— Sec which applies to reactions in solution and in the dark, x — Br-Br this vol., 167. is suggested : CHR.CHR+Br- CHRBr'CHR — Polymerisation of A“v-butadiene in presence CHRBr-CHRBr+Br". Addition is thus catalysed of metallic sodium.— See this vol., 296. by Br- ; evidence (lit.) supporting this view is given. Since the intermediate cafbanion has a stablo con Induced substitution of pentene by chlorine. figuration, stcreoisomerides should be formed from T. D. Ste w a r t and B. W eiden ba u m (J. Amer. Chem. Soc., 1936, 58, 98— 100).— The following reactions cis- and irans-isomeridcs; the theories of Carotliers 2 in CC14 at —10 (A., 1924, ii, 814) and Ingold (Chem. Reviews, 1934, occur between A3-pentene and Cl or 25-1°: CHEt:CHMe+Cl2 -> CHEtChClIMeCl; 15. 225) lead to identical additive products. The CHEt:GHMe+Cl2-> CHEt:CH-CH2Cl (I)-f HCl. Sub above theory also explains the generally observed stitution is favoured by decreasing the [Cl2] ; addi trans addition of Hal. H- ®- tion of HoO, HC1, or powdered glass has no effect. Mechanism of polymerisation.— See this vol., Substitution also occurs, but to a smaller extent, 295. with CH2:CH-CH2Ph but not with CH2:CMeCl (II). Polymerides and polyfunctionality.— See this A reaction mechanism is discussed. The pseudo vol., 295. uni mol. velocity coeffs. (mols. per litre at 25°) of Formation of high polymerides of unsaturated quaternary salt formation between NMea (ten-fold substances.— See this vol., 295. excess) and (I), CH2!CH'CH2C1, (II), and CC14 are 0-109, 0-045, 0, and 0, respectively. H. B. Polymerisation of unsaturated hydrocarbons. Dicrotyl [A&-octadiene]. R. L espieau and P. H I W aterm an and J. J. L een dertse (Trans. Faraday Soc., 1936, 32, 251— 257; cf. A., 1935, H eitzm ann (Bull. Soc. chim., 1936, [v], 3,273— 277).— 480).—A review of work previously published. CHMeiCH-CIIyMgBr and H20 give a mixture of F. L. U. dicrotyls [A«-octadienes], b.p. 122—125° [does not Peroxide effect in addition of reagents to add I ; hydrogenated to ?i-C8H 1R; oxidised to AeOH unsaturated compounds. XI. Solvent effect in and (-CH2-C02H)2], trans-trans-dtcroti/f, b.p. 124°/747 addition of hydrogen bromide to isobutene. mm., m.p. about —76° (tetra-bromide, m.p. 84— 84-5 , and -iodide,, decomp, about 100°), and trans-y-md/ii/!- M S K harasoh and W. M. P otts (J. Amer. Chem. Soc., 1936, 58, 57— 59; cf. A., 1934, 792).— Addition A“ -heptadiene, b.p. 115°, m.p. about —57° (di-iodide, of HBr to isobutene in a vac. in presence of antioxi m.p. 155— 156°; oxidised to H 2C20 4 and dants and solvents (pentarie, CS2, E tC 02H, EtBr, C 02H-CH2-CHMe-C02H ; hydrogenated to y-methyl- PhCN, PhN02, H 20) gives 80—92% yields of BtVBr. heptane, b.p. 118-5). R- S. 0 . In presence of ascaridole (O'03—0-04 mol.) and the Mercury-photosensitised polymerisation of same solvents a mixture of Bu3Br (75—87% except a ce ty le n e .— See this vol., 299. in CS2 when 100%) and BuvBr (13— 25% ) results. Peroxide effect in addition of reagents to The data now obtained confirm the conclusion (loc. unsaturated compounds. X. Addition of hydro cit.) that solvents affect the velocity, but not the direc gen brom ide to methylacetylene (allylene). M. S- tion, of addition. H. B. K h arasch . J. G. M cN a b , and M. C. M cN a b (j . Amer. Photoiodination of ethylenic linking at low Chem. Soc., 1935, 57, 2463— 2465).— ‘ -'Normal temperatures. G. S. F orbes and A. F. N elson addition (in a vac. in absence or presence of anti- (J. Amer. Chem. Soc., 1936, 58, 182— 183).— Illumin oxidant) of HBr to CHiCMe (I) gives CMe2Br2. Ia ation (through- 10 cm. H 20) of an cquimol. mixture presence of ascaridole (II), CHMeBr*CH2Br is formed; of A“-butene (0-013/ in C11C13) and I at —70° to —60° the HBr must be passed into the (I) + (II) at —40° to with light from incandescence lamps causes 98% — 33°. (I) is not very sensitive to 0 2. H. B. disappearance of I after 3 hr. (90% in 0H.,C12 at 90° Divinylacetylene and its derivatives. P. V to —60°); I does not react with the solvent. Sub Shavoronkov, A. P. A le c h in a , and R. S. Schteb sequent exposure of the solution in quartz to light (Sintet. Kautschuk, 1934, No. 2,12— 14; cf. A., 1933, from a W-steel spark causes quant, elimination of 694).—Divinylacetylene (I), b.p. 46— 47°/200 mm., the I within 1 hr.; when the solution is kept at 20°/ obtained as a by-product in the prep, of chloroprene 100 hr., 84% elimination of I occurs. H. B. from C2H2, polymerises in 7— 8 days in air to a gel Dibromide method of determination of butene which explodes on drying and cannot be used in the m ix tu r e s . W . G. Y o u n g and S. W in ste in (J. production of protective films. Antioxidants retarc Amer. Chem. Soc., 1936, 58, 102— 104).— Contrary the formation of explosive films, whilst chlorination to Pines (A., 1933, 1138) and Komarewsky ct al. gives “ safety ” films. (I) yields vinyl allyl ketone, (A., 1935, 192), the reaction rate-dibromide method b.p. 85— S6°/20 mm., by the addition of H 20. (A.’ 1930,888) is trustworthy. Conversion of mixtures Ch. Abs. (r) into dibromides (composition not altered by distillation Reaction of butylacetylene with oxygen. C. - • at atm. pressure) does not cause an appreciable Y oung, R. R. V ogt, and J. A. N ieu w lan d (J. Amer. change in composition. Differences in composition Chem. Soc., 1936, 58, 55— 56; cf. A., 1935, 325).— XIV (a, b) ORGANIC CHEMISTRY. 311 CH-CBu, freed from olefine by regeneration from containing (3y-dimethyl-A0-butene (about 70%) yy- GBuiCAg,AgN03 with aq. NaCN, forms a peroxide dimethyl- A°-butene (about 3%), and Py-dhnethvl- {attempted isolation by distillation caused decomp.); A“-butene (about 27%). The formation of a radical when kept in 0 2 at 35— 45°/3 months, valeric acid and its immediate isomerisation, CH„:C*-CMe, — (8 g. from 123 g.) and polymeric material are produced. GH2.CMe-C*Me2 C*H2-CMe!CMe2, is assumed, H. B. hydrogenation at the expense of Buy occurring at C* Catalytic dechlorination of tetrachloroethane. atoms. The dehydration of methylterf.-butylcarbinol I. Decomposition by active carbon. II. Order is explained similarly. ‘ j j yy of the decomposition reaction of tetrachloro ethane. S. Y am a gu ch i (J. Chcm. Soc. Japan, 1934, Fission and isomerisation of olefmes which 55, 1227— 1231, 1232— 1235).— I. The effect of contain a tertiary radical. I. N. N asarov (Ber. temp, and of various added materials is described. 1936, 69, [B], 21— 24).—Methyh'sopropylferi. - butyl- II. The reaction 2C2H 2C14 2C2HC13+HC1 is carbinol (I) is transformed by distillation with' a of the second order in the presence of active C. trace of I. into y-methylene-¡3 ¡38-trimethylpcnt an e Ch . A bs. (r) smoothly transformed by 1 : 4-CJ0H 6Br-SO3H into Constitution of the aß-halogen derivatives of ¡3-methyl-Aa-propene and ¡3-methyl-A^-butone, also ethane.— See this vol., 269. obtamed directly from (I). ElhyURopropyltcrt.-biUi/l- carbmol, b.p. 188— 191°, is dehydrated by I to 88- Allylic rearrangements. I. Crotyl and ditnethyl-y-isopropyl-A0-buienc, b.p. 153— 158°, which methylvinylcarbinyl bromides. S. W in st e in is transformed by 1 : 4-C10HfiBr-SO3H into ¡3-methyl- and W. G. Y oung (J. Amer. Chem. Soc., 1936, 58, A -propene and, apparently, (3-methyl-A^-pcnteno 104—107).— Largely a more detailed account of and P-methyl-A“-pentene. JJ. W. work previously reviewed (A., 1935, 1480). Mix tures of CHMe:CH-CH2Br, b.p. 2°/5 mm., and Pyrolysis of geraniol and citral. J. D ceuvre CHJCH-CHMeBr (I), b.p“. -2°/14 mm., 31°/93 mm., and R. D esmule (Bull. Soc. chirn., 1936, [v], 3 , 196— are separated by fractional distillation at low temp, 206).—Li presence of Pt or glass wool at 505—510° in a vac.; higher temp, cause rearrangement. Slow geraniol (p-xenylnrethane, m.p. 69°) gives much iso- distillation/atm. pressure of a mixture [13% (I)] prene and CMe2ICH-CHO [semicarbazone, m.p. 240° gives a product containing 87-5% of (I) (cf. loc. cit.). (block); p-nitro-, m.p. 161°, and 2 : 4 -dinitro-phenyl- hydrazone, m.p. 187— 188°1, with C H ,0, MeCHO. H. B. Mechanism of the catalytic conversion of CHMe.CH'COgH, (?) C ^ ^ .C H ’CHg’OH, and a mixture alcohols into diethylene hydrocarbons. S. V. of (?%- and K-)dimethyl-AK-octadicnes, b.p. 67— 68°/20 mm., all of which arise by fission of the 8s- Lebedev, J. A . G o rin , and S. N. Chutoretzkaja (Sintet. Kautschuk, 1935, 4, No. 1, 8— 27).— Cata linking or formation and fission of an internal y- lytic decomp, of a mixture of EtOH and MeCHO oxide. Citral gives much CH0!CHMe and other «'fiords butadieno (I). The influence of varying con gases with a complex mixture containing %-dimethyl- ditions on the yield of (I) is described. Catalytic Aac-no7iadiene, b.p. 141— 143° (eorr.)/750 mm., a uecoinp. of a mixture of EtOH and Et20 yields (I), hydrocarbon, C10H ]g, b.p. 66°/19 mm.,' a little iso- prene, and a trace of CMe2:CH-CHO. R. S. C. together with C2H4 and (!CHMe)2, the proportions depending on the conditions. Mixtures of EtOH with (a ) Hexadecenol and tetradecenol in sperm r*~4> H20, H2, and BuOH behave similarly; the head oil. Y. T oyam a and T. T su c h iy a . (b ) H exa nmuenco of varying conditions on the yield of (I) decenol in sperm blubber oil. Y . T oyam a and ¿escribed. Ch. A bs. (r) G. A k iy a m a (Bull. Chem. Soc. Japan, 1935, 10. 572— 579, 579— 584).— (a ) Fractionation of the Ac Action of sulphuric acid on s e c .-butyl alcohol. derivatives of the unsaponifiable matter, b.p. < 180°/ * • D. Drake and F. P. V eitch , jun. (J. Amer. Chem. 15 mm., of sperm head oil, conversion of the unsatur- J°c,I935, 57, 2623— 2625).—sec.-BuOH and 75% ated acetates into their bromides, debromination, at 80°/48 hr. under pressure give a mixture and refractionation of the unsaturated acetates i° r ec-'Bu)20 and y8-dimethyl-A0-hcxene (I) [ozono- affords the A c derivative, b.p. 195—198°/15 mm ^ f^ d u cts, MeCHO, AcOH, and Me sec.-Bu ketone (oxidised by KMn04-AcOH to m-C6H 13-C02H and t It • ' m.p. 71-2°)]. Dis- 0Ac-[CH 2]8-C02H), of A‘-hexadecen- a-ol (I) (zootnaryl 1 :!tl0.n (I) with a trace of acid gives substances alcohol), 1 val. 98-6, and the A c derivative, b.p. in Ä r m?L wt: (T1) is oxidised (NaOBr) to a- 165—170°/15 mm. (oxidised to a-C8H 17-C02H and (Oi’ i ac^ (p-phenylphenacyl ester, m.p. y-liydroxyvaleric acid), of At-tetradecen- ethylidene peroxide. A complete mechanism for COMe.,, has in.p. 45°, I val. 20-5, sap. vak 66-9, the autoxidation of Et20 is suggested. T. C. P. falD -flo'l 0 in CHCJ3. Hydrolysis (5% EtOH- KOH in N2) gives glycerol, trehalose, optically active Preparation of ketals of alkylacetylenes with higher fatty acids, and a dibasic OH-acid, C70H 138O6, higher alcohols. D. B. Killian, G. F. HennioN, m p 56— 57°, [«]„ +6-1° in CHCL, [Ac derivative, and J. A. Nieuwland (J. Amer. Chem. Soc., 1936, m p. 40—41°; Me ester, m.p. 49° {Ac derivative, 58, 80— 81; cf. A., 1934, 867).— Addition of CHiCBu ni.p. 41°)]- The unsaponifiable matter consists to ROH (R=Et—hexyl) containing small amounts almost entirely of higher alcohols’ since treatment of CCL-COoH and a catalyst (prepared from red HgO with o-C6H4(CO)20 gives nearly quant, conversion and BF3,Et20 in MeOH) at > 70° gives CMeBu(0R)2, into H phthalates. Fractional crystalhsation ot which are hydrolysed (dil. H ,S 0 4) to GOMeBu. the alcohols (from MeOH) and their phenylearbamates (JS-Diethoxy-, b.p. 68— 69°/18 mm., ^-dipropoxy-, affords d-eicosan-^-ol (I), m.p. 62-5—63°, [a]D +4-2 b.p. 95—97°/18 mm., ffl-dibutoxy-, b.p. 115— 117°/18 in CHCL (acetate, m.p. 35—37°; benzoate, m.p. 39— nun., fifi-diamyloxy-, b.p. 141— 143°/18 mm., and 40°; , m.p. 78— 78*5°, solidifies at W-dihexyloxy-, b.p. 143—144°/8 mm., -hexanes are 76° and rcmelts at 81°; H in, p. 60— 61 ), described, pp-Dietlioxy-, b.p. 81— 83 /IS mm., P3- and d -octadecan-fi-ol (II), m.p. 56°, Mg +^‘7 in dipropoxy-, b.p. 107— 109°/18 mm., $$-dibutoxy-, CIICL (phenylcarbamate, m.p. 72— 73 , solidities b.p. 134— 136°/18 mm., and ^-diamyloxy-, b.p. at 66° and remelts at 76—77°). (I) is oxidised 148— 150°/17 nun., -heptanes are similarly prepared (CrO,-AcOH, 30—40°) to eicosan-P-one, m.p. 58— from AMieptinene. Ketals could not be prepared 59° (oxime, m.p. 73—74°; scmicarbazone, m.p. from branched-chain AlkOH. H. B. 128°), which is also prepared by alkaline hydrolysis Thermal decomposition of methyl hydrogen of the product from «-heptadecyl bromide and p erox id e.— See this vol., 164. CHNaAc-C02Et. (II) is similarly oxidised to> orta- Monoalkyl phosphites and their hydrolysis. dccan-fi-one, m.p. 52° (scmicarbazone, m.p. 127-0 ), P. NylI?n (Svensk Kem. Tidskr. 1936, 48, 2— 22). also synthesised from w-heptadccoyl chloride and The following monoalkyl phosphites, prepared by the ZnMeL H - B - action of NaOH on the appropriate dialkyl phosphite, Stability of pinacolates in liquid ammonia are isolated as their Na salts: Me, m.p. 125 (de solution. C. B. W ooster and D. S. L atham (J. com p.); Et, m.p. 183— 185°; Pra, m.p. 195 196 , Amer. Chem. Soc., 1936, 58,76— 7S).— (-CMeyOH), (I) PrP, m.p. 132— 133°; Bua, m.p. 177-5— 178-5. and (-CPhMe-OH).. (II) with NaNHL (or CNaPlu) m K for these H esters is determined in 3-98il/-NaCl at liquid NHo give the colourless (•CRMe*ONa)2, which at 25°. Only the undissociated H ester is oxidised by are hydrolysed (NH4C1) to the pinacols but no acid 1; the anion is stable towards I. A method CORMe; ketyl formation [as with (•CPh2-UH)2 for following the hydrolysis of the esters by acids and (cf. Kraus and Bien, A., 1933, 1120)] does not occur. alkalis is described, and the equilibrium of the system I) and (II) can bo titrated with NaNH2 using CHPh3 H3P0.,-Et0H-EtH 2P 0 3-E t 2H P 0 3-H 20 is determmed, as indicator. (I) and Na in liquid NH3 give The structure of the mono- and di-alkyl phosphites 0 H ■ CMe2 ■ CMe.y 0 Na; (II) undergoes fission to is discussed. J- N. A. CHPhMe-ONa. Hydrobenzoin is too insol. m liquid Hydrolysis of the phosphoric ester of starch ■ ■*T -»ttt H. B. NH 3 to react with NaNH2. and glycogen .— See this vol., 243. Compounds of bivalent carbon. XIV. Bromo- Formation of high polymerides by condens dimethoxymethane (formyl bromide dimethyl ation between metal polysulphides and dihalo- acetal) and its reaction with sodium triphenyl- genated hydrocarbons and ethers. J. C. P atrick methyl. II. Sc h eibler and H. J. Sch m id t (Ber., (Trans. Faraday Soc., 1936, 32, 347— 357). Ali 1936, 69, [jB], 12— 1 5 ; cf. this vol., 66).— phatic hydrocarbons and ethers having a halogen (0Me)2CH-C02H is readily converted by Br in warm on each of the terminal C condense with metal polv- CHCL in direct sunlight into bromodimetlioxymrMianc sulphides, e.g., Na2S4, to form linear polymerides of (I) b.p. 55°/12 mm., and M e II oxalate, b.p. 75°/12 high mol. wt. with the respective empirical formula mm. (K salt). (I) and CNaPh, in Et20 under N2 C2H 4S4 and C4H 8OS4. Both types frequently exhibit yield the unstable triphenylacetaldehyde Me., acetal, rubber-like properties. By treatment with PiaUxi which immediately decomposes into CHPh3 and half the S is removed, the residual substance losing (not-isolated) dimethoxy methylene (CO M e2 acetal). its rubbery nature if formed from a hydrocarbon, H. W. but retaining it if formed from an ether. S can be Small-scale experiments on the autoxidation re-introduced, and (in the former case) rubbery of ether. A. R ie o h e and R. M e is t e r (Angew. properties restored, by a process analogous to the Chem., 1936, 49, 101— 103).— PhCHO treated with vulcanisation of rubber. Theories of chemical struc IIo02, followed by CH2Ph-0II and P 20 6, yields ture and of the mechanism of the h e a t -vulcanisation dibenzyl ether peroxide, (CH2P1i-0-)2, J11-?- 77 X are advanced. E. L. U. OH-CHMe-OoH (I) dehydrated with P2Os in Me20 Preparation of lower alkanesulphonic acids. at low temp, yields the compound (CHMe-0,ti)2U. D. L. V iv ia n and E. E. R eid (J. Amer. Chem. Soc., (I) treated with MeCHO and H 20 2 in Et20 at 20 , 1935, 57, 2559— 2560).— Anhyd. Alk-S03H are ob the mixtme cooled in EtjO-solid C02, and MeCl tained from cone. aq. solutions after 4— 5 distillatioi added followed by P20 5 yields u-ethoxyethylH per oxide, which under appropriate conditions of decomp, at 1 mm.; the pure acids soon darken even m a vac. The following are described: «-propane-, gives EtOH, MeCHO, AcOH, H 20 2, and polymerised XIV (b, c) ORGANIC CHEMISTRY. 313 b.p. 136°/1 nun., m.p. 7-5°, w-butane-, b.p. 147°/0-5 3 •«6 ;-mC9 A ’ -18188, 11G8)-— Treatment of ap-C4H 8Br, mm’’ ~ 15'2°’ «-pentane-, b.p. 163°/1 mm., with NaNH2 m kerosene, followed by passage of CO, m.p.o lo-9 , and «-hexane, b.p. 174°/1 mm., m.p. gives a 46% yield of Aa-pentinenoic acid, b.p. 81— 16-1 , -sulphonic acids. The alternation in. m p resembles that for Alk-C02H. H . B. ' m-P- 50-6°. The prep, from COMeEt and PC15, followed by NaNH2 and CO,, gave only Interaction of diazonium salts and acetone- poor yields. Gii. A b s. (r) sulphonic acid. G. D. P a r k e s and S. J. M. F ish e r (J.G.S., 1936, 83— 85).— Diazotised p-CGH 4Br-NH, Tetradecenoic and dodecenoic acids in sperm oil. I. Tetradecenoic and dodecenoic acids in and Na acetonesulphonate give Na methylglyoxal-v- sperm blubber oil. II. Dodecenoic acid in oroniopheiiylhydrazone-to-sulpho7iate, m.p. 224° (de comp.) The following are similarly obtained : Na ,hea(i °il. Y. T o yam a and T. T su ch iy a methylglyoxal-phenyl-, m.p. 195° (decomp.), -p-chloro- (Bull. Chem. Soc. Japan, 1935, 10, 563— 569; 570— phemjl- .ni.p. 228° (decomp.), -2 : ‘i-dichlorophenyl-, 573).—I. After fractionation of their Me esters and m.p. 2/0 (decomp.), -2 : ‘i-dibromopJienyl-, m.p. hydrolysis, the fatty acids (2-4%) of sperm blubber (decomp.), -o-mtroplienyl-, m.p. 256° (decomp.), oil (from Physeter macrocephalus, L.) are separated -m-nilrophenyl-, m.p. 251° (decomp.), and -p-nitro- into fractions (i) b.p. 172— 177°/15 mm., and (ii) p/i(myI-hydrazom-co-sulphonate, m.p. 265° (decomp.). h-P- lp2 197'/15 mm. By the Pb-soap method (i) affords A«-dodecenoic acid (I), termed denticctic Aa methylglyoxalphenylhydrazone-co-sulphonate with nr (1 or 2 mols.) yields co-bromometliylglyoxal-«- acid, converted into a Me di hydroxylaurate which gives m-GgH „-C 02H and glutaric acid (II) when oxid bromophenylliydrazone, with 3 mols. of Br gives ised with I Catalytic hydrogenation of acid chlorides in Drying of oils and related unsaturated com “ e vapour phase at atmospheric pressure. N. pounds. R . S. M orrell and W. R . D avis (Trans ai?d G- G- B an ov (J. pr. Chem., 1936,’ Faraday Soc., 1936,32, 209—215; cf. this vol., 298).— of II 217—224).—Hydrogenation (Pd-asbestosj Of the possible combinations between maleic an P,.nT?r>appropriate acid clll°ride at the b.p. gives hydride and a- and (3-ekeostearic acids, only one is somo CHPr“:CHEt-CHO), wovaler- formed with each, viz., at the pair of conjugated cinvla-°n' yd}’dyrolactonc (54%; from suc- double linkings remote from the C02H in the a- and id nn u r^ ek ^ hC!^ 0 (89% )’ CH2Ph-OH+PhEt, nearer the C02II in the (3-acid. The former (I) does bp r.nci54} S and P compounds must not, and the latter (II) does, exhibit “ drying ” rely absent. Raney Ni cannot be used. pioperties at room temp. Changes occurring in R S C both compounds have been studied by measurements Catalysis in organic chemistry. V. Decom- of the O, absorbed, peroxide val., I val., and viscosity, chlorid? °TTeSw STTnd acids by anhydr°us zinc and by examination of the chemical structure of the Biim fr a r i UNni:Rwoon, jun., and 0 . L. products. In (I) only the etlienoid linking in the AIBPn u ^ er- 9 hera‘ Soc-> 1935> 5 7. 2729— 2730).— aliphatic chain is oxidised, yielding a product with unnffp p i f a their Me, Et, Pr, and Bu esters are ■CO'CH(OH)', which undergoes no further change. 5 l 0. i bypunhyd- ,ZnC1* (II) Constitution of isopropylidenefurtondicarb- b.p 62°/13 mm.; amide, m.p. 117°), identical oxylic acids. H. O h le and N. S e n g e r (Ber., 1936, with a specimen synthesised by condensation of 69, [J3], 160— 170; cf. A., 1929, 913; 1931,72; 1932, GHEtBr-C02Et-Zn-EtCHO to give the OH-ester 144, 148).— Oxidation of p-dusopropylidenefructose b.p. 107—122°/18 mm., converted by PCI- and (I) with KMn04 (ss40) gives K,, fi-isopropylidene-l- subsequent hydrolysis with KOH-EtOH into furlondicarboxylic acid, ( + H 20) (II), [a]j* +53-2° in CHEt.CEt-C02H. The amides of tiglic, m.p. 77°, H20 [corresponding Ay,, (+ 2 H 20), Ba (+1-5H,0), and of Pfi-dimethylacrylic acid, m.p. 108°, were and Cla ( + 6H20) salts]. (II) is transformed by prepared for comparison. Glaucanic acid (I) mp pyridine-l-sulphonic acid in C5H5N into Ks P-iso- 188°, [a]2? +189-6° in CHC13, has equiv. 83, and gives propylidene-Z-furtondicarboxjdate 1-sulphate (ill) (loc. a Er/.j salt which, with Mel-MeOH affords only a cit.), so that (II) is the parent of (III). Methylation M e2 ester, m.p. 145°. (I) gives a compound, of the Ag salt of (II) affords ap-isopropylidenedioxy- Gi8H2i06N, m.p. 207— 208°, with NH2OH, and a P-carbomethoxymcthoxy-y-butyrolactone (IV) m p compound, C20H32O4H4, m.p. 122°, with NHPh-NH,. 89-5°, [a® +56-6° in MeOH, +64-2° in CBH6, which Reduction of (I) with Zn-AcOH affords (mainly) a regenerates (II) when hydrolysed by alkali, and Me dicarboxylic acid, C18H270 7, m.p. 209° (.Me2 ester, ■y-methoxy-a.(3- isopropylidenedioxy-y-carbomethoxymetli- m.p. 161°), and traces of an acid, C20H24(28)O7, oxy-n-butyrate, b.p. 140° (bath)/0-05 mm., [a]22 +33-8° m.p. 201 (Me ester, m.p. 193— 194°), and a neutral in MeOH, hydrolysed by KOH-MeOH to K 2 substance, C18H220 G, m.p. 192°. (I) is stable to most y-melhoxy-afi-isopropylidehedioxy- y- carboxymethoxy-n- oxidising agents, but with NaOCl-NaOH it gives a butyrate (V), [a]y -f-45-850 in H20 (corresponding Ag2 substance, C18H20(22)O4Cl2, m.p. 200°. The structure ?i7t ' contains an active H of unknown location. of (I), which probably contains the system When hydrolysed by acid it evolves C02 with much greater difficulty than does (II). When treated with 0H-(xj<£°:go reduced to >0 heated with Ag20 it is oxidised (with partial hydro between enolisation and alkyl substitution. The lysis) to citrylideneacetic acid, h.p. 115— 120°/0-002 vals. of kR and kT for menthone {ibid., 153) are revised. mm., hydrogenated (Pt02) to dl-SO-dimethyldecoic H. B. acid, b.p. 160— 162°/12 mm. (p-bromophenacyl ester, Reactions of tagetone. I. T. G. H. J ones m.p. 56°). Treatment of it with Al(OPr<3)3 affords (Proc. Roy. Soc. Queensland, 1934, 45, 45—49: cf. A., citrylidene-ethyl alcohol (zz-dimetliyl-Aft°-decatrienyl 1926, 72).— Tagetone (I) is represented as a tauto alcohol), b.p. 102—105°/0-03 mm. H. W. meric mixture: COBus-CHvC(CH„)-CH!CHS Detection of methylglyoxal and fission of oh-cbu/?:ch-c(ch2)-ch:ch 2 — caoutchouc by ozone. R. Pummerer, G. Mat COBuP-CH:CMe-CH:CH2. Reduction of (I) with Na- thäus, and W. Soctas-Vinals [with, in part, P. EtOH yields dihydrolagetol, C10H 20O, b.p. 197°/760 Braun] (Ber., 1936, 69, [E], 170— 183).— The pos mm., which is not y0-dimethvl-A°-octen-E-ol. Re sibility of recognising AcCHO in presence of lævul- duction of (I) with Zn dust and EtOH-NH4Cl yields aldehyde (I), McCHO, and CH20 (as products of a non-liomogeneous dihydroiagetone (II), C10H 18O, ozonisation of caoutchouc) is impeded by the impos b.p. 186— 190°, with two dimeric products, C„0H,,O, sibility of separating (I) and AcCHO by means of b.p. 115— 120°/4 mm., and C20H34O27, b.p.“ 140— (N02)2C6H3-NH-Nir2. The pptn. of Ni methylgly- 150°/4 mm. (II) on oxidation yieids BuPCO,H and oxime is not sufficiently complete in .dil. solution. a CO-acid, CflH lfi0 3; it is, therefore, The most suitable reagent is NH2-CO-NH-NH2, which COBus• CH„■ CMe!CilMe containing a little in very dil. solution gives 91% yields of methyl- COBu/!-CHyCHMe-CIi:CH2. Reduction of (I) with glyoxaldisemicarbazone (II) without co-pptn. of Zn and EtOII-NaOH yields a monoketonc, C.,0H34O2, lævulaldeliydesemicarbazone. (II) is subsequently b.p. 140— 150°/4 mm. (monoxinie), and an isomeric transformed by 17 % H2S04 into methylglyoxal-2 : 4- dikctonc, b.p. 160— 170°/4 mm. (diox¿me), together oinitrophenylosazone (yield (95%). A more complex with a little low-boiling liquid (sernicarbazone, m.p. separation of AcCHO and (I) is effected by p- 92-5°). Reduction of (I) with Na-Hg and EtOII or h 0 /C(;H4-XH- NH,. Comparative experiments with with Al-H g and Et20 affords intractable mixtures 03 and mesityl oxide in CC14 and H20 givo only 7-4% of pinacols. Treatment of (I) with Ii2S in NH3- and 18% yields of AcCHO, which are increased to EtOH yields a S-containing substance ~ b.p. 90°/4 29% in ÔHCLj at 0° followed by very cautious fission mm. With Ba-(OH), in MeOH (I) affords a CO- of the ozonide by S02. The mean yield of MeCHO alcohol, C]0H l8O2, b.p. 75—80°/4 mm., with COMeBuA from caoutchouc is 1%, but this is observed only (I) with MgMel yields a substance, b.p. 66°/3 mm., and after over-ozonisation. If the action of 03 is inter two polymerides, G,0H3O02, b.p. 130—140°/4 mm. rupted as soon as the CHC13 solution has become and 150—160°/4 mm. “With NH2OH in alkaline «able to Br, the production of AcCHO is > 0-1% in solution an oxiino is formed, whilst in dil. H 2S04 an any case. The view that AcCHO is a secondary oximinoketone, b.p. 100— 102°/4 mm., is produced. product is discounted by the observation that, after Ch . A b s. (r) a certain period, further over-ozonisation does not Steric transformation of sugars. E. J ust (Z. affect the yield of AcCHO. If aq. S02 is used for Spiritusind., 1936, 59, 25, 33— 34).— A review of ^sion of the ozonide, AcCHO is not detected even the methods used in effecting steric transformation a ter prolonged ozonisation. A terminal isoprene of sugars leads to the conclusion that Walden inversion group with a conjugated system is therefore not during fission of the O bridge in anhydro-sugars is Present in 1000 fsopentene groups of caoutchouc, more promising preparatively than treatment of the uttapercha behaves similarly, giving no AcCHO with sugars with alkali or C5H5N or of unsaturated sugar r without over-ozonisation if S02 is used for fission derivatives with Bz0 2H. H. W. Sw ■ ozonidG and about 1% of AcCHO if 11,0 at Structure of d-xylomethylose. P. A. L e v e n e th 13 Cj‘Ploye(l' '-BHo occurrence of MeCHO among and J. Com pton (J. Biol. Chem., 1936, 112, 775— e products of ozonisation is unexplained. Methyl- 783).—isoPropylidene-d-xylomethylose and Mel- eP enone when ozonised or over-ozonised and then Ag20 at 50° give the 3-Ale ether, b.p. 5S—60°/0-3 created with S02 does not give AcCHO. Over- mm., [a]„ —49-4°, hydrolysed by hot 1% H 2S04 to .îiisataon and subsequent treatment with 11,0 at Z-methyl-d-xylomethylose, b.p. 101— 102°/0-8 mm.; gives 0-6—0-8% of the C skeleton as AcCHO and [“]» +8-1° (phenylosazone, m.p. 128— 130°), which ua almost equiv. amount of H,C204. H. W. with HCl-MeOH affords a-, b.p. 58—62°/0-3 mm., [a]jf +124-5°, and (i-methyl-3-melhyl-d-xylomethyloside, ra^°^fation as directed- by acid and basic 7SÎS; , Acid-catalysed énolisation of b.p. 72—75°/0-3 mm., m.p. 48—50°, [a]“ -127-9°. , c.-butyl ketones. P. D . B artlett and C. H. These with M el-A g20 at 50° yield a-, m.p. 34— 35°, b.p. 39—41°/0-5 mm., [a]“ +154°, and [i-methyl- 2äST|I''FIt (J ' Amer. Chcm. Soc., 1935, 57, 2580— 2 : 3-dimethyl-d-xylomethyloside, b.p. 38— 40°/0-5 mm., Tl-\ i rates of racémisation (JcR) and iodination M b — 102-4°, respectively, both oxidised by conc. b Q0A7w C0Ph'CHÄIeEt in AcOH containing UNO, HNOs to +[-CH(0Me)-C02H]2. d-Xylomethylose (I) /■ a 1 ,(catalyst) at 36-75° are identical. Similarly, and Ag20-H 20 at 80° give only AgOAc. The rate Me iii determined for d-COR-CHMeEt (R= of lactonisation of d-gulomethylonic acid indicates teirm u I, and cycZohexyl) at 25° (and other formation of y- and S-lactones. The structure of ¡,,J] '. , competitive rates of the énolisations (I) is thus confirmed, [a] are in H 20 . R . S. C. h° H of °H #E t and R are calc. The doesV f “ 1 Prcvi°usly advanced (A., 1934, 607) Ring closure in sugar benzoates. M. L. W ol- 0 permit an explanation of the relationship fr o m and C. C. C hristm an (J. Amer. Chem. Soc., 318 BRITISH CHEMICAL ABSTRACTS.— A. X IV (/) 11)30, 58, 39—43).—Successive treatment of l- saccharide at 100°. The amount increases rapidly arabinose Et2 mercaptal with CPh3Cl and BzCl in with rise of temp, up to 0-3 at 170°. Sucrose is C5HrN at room temp, gives 5-triphenylmethyl-1- stable up to 130°. 0H-CHMe-C02H was not found in arabinose El., mercaptal tribenzoate, m.p. I l l — 112°, the liquors. S. M. N. [a]2!> —25° in CHCL,, converted by AcOH-HBr followed Constitution of osazones. L. L. Engel (J. by C'dCO, +H gC l2 in aq. COMe2 into 1 -arabinose Amer. Chem. Soc., 1935, 57, 2419— 2423).— The 2 :3 : à-trlbc7izoate (I), m.p. 162— 163°, [a]J,° (in absorption spectra of the osazones (I) of various C5H5N) +143° -> +196°. EquUibration of i-arab- sugars {e.g., glycerose, glucose, lactose, 3:4:6- inose in C5H6N and subsequent treatment with trimethyl-, tetra-acetyl- and -benzoyl-glucose) are BzCl affords a-1 -arabinose tetrabenzoate (II), m.p. all markedly similar; the group responsible for the 160— 161°, [a]ÿ +112-5° in CHCL, [also prepared by sp. absorption is considered to be benzoylation of (I)], converted by cold AcOH- HBr into benzobromo-l-arabinose, m.p. 144— 145°, NHPh-N:CH-C(:N-NHPh)-CH*OR (R=H , alkyl, or [a]„ +203° in CHC13, which is hydrolysed (method : acyl). The difference between the curves for (I) Fischer and Noth, A., 1918, i, 225) to (I). p+ and the osazones of AcCHO and A c2 (both of which Arabinose tetrabenzoate has m.p, 173— 174°, [a]„ are almost identical) is" ascribed to the C3-0 in (I). +325° in CHCL, (cf. Gehrke and Aichner, A., 1927, The mutarotation of (I) may be due to the establish 544). The abovo reactions are considered to support ment of an equilibrium between (I) and their hydrolysis the pyranoso structure of (II). d-Galactose Et2 products. A related equilibrium appears to be estab mercaptal tetrabenzoate, m.p. 127— 128°, [a]ff — 16-5" lished between 3 :4 :6-trimethylglucosephenyl- in CI1C13 [from the 6-CPh, ether (III) (A., 1935, 734) osazone, [a] —48-8°-> +61-5° (after 188 hr.) (in and ÀcOH-HBr], with CdC03+HgCl„ in aq. COMc., EtO H -CsH 5N), and NHPh-NH2 (16-3 m ols.); the gives à-galactose tetrabenzoate (+M eO H ), m.p. 112— change [a] —50-6° —> + 3 0° (after 155 hr.) being 113°, [«]“ (in CHClj) - 1 0 ° -> +6-5°. HBr converts observed. (III) (in CHC13) into O-bromo-d-galactose Et2 mercaptal Acetylation (Ac20, C5H5N) of glucosephenylosa- tetrabenzoate, m.p. 103— 104°, [agj, — 1-4° in CHC13. zono (II) and fructosephenylmethylosazone (III) a-d-Galactose pentabenzoate, m.p. 128— 129°, [a]„ gives the A c4 derivatives, m.p. 102— 104° (corr.). + 187° in CHCL,, is prepared by Levene and Meyer’s [a]“ —58-5° in 95% EtOH, and m.p. 126—127’ method (A., 1928, 398). Triphenylmethyl-à-mannose (corr.), [ag7 -184-8° in 95% EtOH. (Ill) and Et2 mercaptal tetrabenzoate, m.p. 105— 106°, [a]2* NHPh-NH2 in MeOH at room temp, afford glucose- 0°, [a]g“6l — 10-5° in CHCL, (corresponding tetra phenylphenylmethylosazone; the p-nitrophenylphenyl- acetate, m.p. 133-5— 134-5°, '[a]*? + 3 6 ° in CHCL,), 7iiethylosazone, m.p. 223-5— 224-5° (corr.), is similarly is converted [as for (III)] into à-mannose Et2 mercaptal prepared using p-N 02-C6H4-NH-NH2. isoPropylidene- tetrabenzoate, m.p. 116— 117°, [a]“ —5° in CHCL,, galactosephe7iylosazone, m.p. 183-5— 184-5° (corr.), and thence into à-mannose tetrabenzoate, [a]“ —115° is formed from the galactosazone, COMe2, and P205 in CHC13. Glucose Et2 mercaptal pentabenzoate at 0°. Acet7jlglycerose-2 : 4,-dinitropliemjlosazonc, m.p. (Brigl and Muchlschlegel, A., 1930, 1022) with 196— 197° (corr.), is obtained from CO(CH2-OAc)2 CdC03+HgCl2 in aq. COMo2 gives ald-ehydoglucose [prep, by oxidation (Na2Cr20 7, AcOH—H2S04) of pentabenzoate, m.p. 81—82°, [a]J* +40° in EtOH diacetin described]. Methylation (various conditions) (cf. loc. cit.). Kunz and Hudson’s method of hydro of (II) gives non-homogeneous products. Votofek lysis (A., 1926, 941) is applicable to sugar benzoates and Valentin’s results (A., 1931, 1274) on the muta provided they are appreciably sol. in H20. H. B. rotation of (III) could not be confirmed. H. B. Esters oi aldehydrol form of sugars. M. L. Photolysis of fructose in ultra-violet light.—- W o lfr o m (J. Amer. Chem. Soc., 1935, 57, 2498— Sec this vol., 299, 300. 2500).— aldchydoGiilnctose penta-acetate Et hemi- Hydrolysis of glucosides and of certain organic acetal (A., 1930, 1023) with AcHal gives aldehydo-1- compounds by ultra-violet rays.—See this vol., chloro-, m.p. 174— 175°, [a]j,7 —44° in CHCL,, -1- bromo-, m.p. 179— 181°, [a];,7 —79° in CHCL,, and 171. -l-iodo-, m.p. 152— 153°, [«]“ -1 1 1 ° in CHC13, Synthesis and properties of (i-alkylglucosides. -d-galactose hexa-acetates ; these compounds are the S. V e ib e l and F. E rtksen (Bull. Soc. chim., 1936, open chain analogues of the cyclic halogenosugar [v], 3, 277— 283).— (3-Methyl-, -ethyl-, m.p. 81—83 , acetates. Acétylation (AcaO and C5H5N or ZnCl2 [a]™ —38-6° in IIo0 (tetra-acetate, m.p. 105— 106 ■ at room temp.) of aldehydo-d-glucose penta-acetate [a]“ -29° in C„H6 or EtOH), -propyl-, forms, m.p- affords the hepta-acetatc, m.p. 11S-5— 119-5°, [a]jf 77_78° (I) and 102—103° (II), respectively, [afc +S° in CHC13 ; rtWe%tfo+arabinose tetra-acetate -39-3° in H20 [(I)-M U) at 90—95°; (II)-> W gives the hexa-acetate, m.p. S9-5°, [ajÿ —27° in CHC13. in PliMe slowly at 30° and rapidly if boiled and then These +,11(0Ao)2 derivatives are much more stable cooled to 70°; tetra-acetate, m.p. 102— 103°, [«lb than the aldehydo-iorms. H. B. —27° in EtOH], and -isopropyl-glucoside, m.p. 128 Action of hot alkali solutions on carbo 129°, [a]b° —40-9° in H„0 (tetra-acetate, m.p. 136— h ydrates. R. S. H ilb e r t and A. W o l t e r (Angew. 137°, [a]'| —30-6° in EtOII), are prepared (a) from Chem., 1936, 49, 54— 55).— Carbohydrates are heated penta-acetylglucosidyl bromide and subsequen with aq. NaoC03, and the amount of acid produced is hydrolysis by a trace of NaOMe and (6) by emulsin from determined from the C02 evolved. This varies from glucose with removal of the excess of glucose y zero for gum arabic to 0-18 g. of C02 per g. of mono- yeast. M.p. are corr. B- XIV (/, g) ORGANIC CHEMISTRY. 319 Synthesis of 1-d-glucosidocytosine. G. E. H il and nitriles, like hydrocarbons and esters, exist in bert and E. F. J ansen (J. Amer. Chem. Soc., 1936, solution as thread mols. with the most extended 58, 60—62).—2 : 4-Diethoxypyriinidine and aceto- form; from these the crystals are formed and m.p. bromoglucose at 65° give 2-keto-i-cthoxy- 1-tetra- and solubility of the soiids depend greatly on the acetyl-d-glucosido-1 : 2-dihydropyrimidine, m.p. 206° length of the chains. Nitriles have a somewhat higher (corr.), [a]j)J + 36-1° in CHGL, converted by EtOH- m.p. (about 9°) than hydrocarbons with the same no. HC1 into 1-d-glucosidouracil (I) (A., 1931, 100) of chain links. Primary amines and primary alcohols and by EtOH-NH3 at 80°/96 hr. in sealed tube into have the same m.p. (20— 30° > that of the correspond l-d-<7 lucosidocytosine (II) (+JE tO H ), m.p. 197— ing hydrocarbons); their mols. are therefore co- 199° (sinters at 192°) [picrate, m.p. 216—218° (de ordinatively united but so weakly that the union comp.) ; nitrate (+H 20), m.p. 143° (decomp.)], is broken in solution. The very low m.p. of fcri.-amines which when kept in a moist atm. passes into a hydrate, is explained by their branched structure, sec.- m.p. about 128° (decomp.). Crystallisation from 90— Amines with two long chains have m.p. slightly7’ 95% EtOH gives a hydrate-alcoliolate, m.p. 194— < the corresponding hydrocarbons due to the slightly 195° (decomp.). Anhyd. (II) is hygroscopic and has less regular structure, whilst Me-substifuted tert'.- Mg +25-6° in H20. (II) with 25% H2S04 at 150° amines have m.p. similar to that of hydrocarbons gives (probably) a mixture of (I/and (II). l-Acetyl-\- containing Et attached to the central C. ' The follow tetra-acetylglncosidocytosine has m.p. 225°, [a]Jf +38-1° ing compounds are incidentally described : dimyr- in CHClg. H. B. istylamine, m.p. 56— 58-5°; dicetylamine, m.p. 65— Influence of crystalloids on the state of amyl- 66°; dimethylmyristylarhine, liquid at 0°; dimethyl- oses.—See this vol., 288. cetylamine, m.p. about 12°; dimethylstearylamine, m.p. about 25°; methyldimyristylamine, m.p. 24— Plant colloids. XLIII. Influence of chlorine 25°; methyldicetylamine, m.p. 34— 35°; methyldi- dioxide on the chemical reactions of potato- stearylamine, m.p. 40°; trimyristxylamine, m.p. 33— and wheat-starch. M. Samec (with F. U lm ] 34°; tricetylamine, m.p. 42—43-5°; tristearylamine, (Kolloid-Beih., 1936, 43, 287— 294).— When treated m.p. 54-5°. H. W . with CI02 solutions, starch loses P and N. A con siderable amount of P in potato- (but not wheat-) Possible rearrangement reactions of mono- starch resists this action. The treatment also renders chloroamine and Grignard reagents. G. H. tne starch more sol., and in some cases causes feeble Coleman and R. A. F orrester (J. Amer. Chem. oxidation. E. S. H. Soc., 1936, 58, 27— 28).— CH2Ph-MgCl and NH2C1 give 92% of CHYPh-NHo; a-C10H7-CH2-MgCl affords Kinetics of lo n g chain d isin tegration applied 47% of a-C10H7-CH2-NH2; CHPhlCH-CHyMgCl (at fo cellulose and starch.—See this vol., 295. -20°) yields 14% of CHPh:CH-CH2-NH2. No indic Origin of nitrous oxide and hydrogen cyanide ation of the formation of rearrangement products formed by certain methods of decomposition of (viz., o-C6H4Me-NH2, 1 : 2-C10H6Me*NH2, and cellulose nitrate. H. M u r a o u r (Bull. Soc. chim., NH2-CHPh-CHlCH2, respectively) was obtained 936, [v], 3, 265— 267).— Decomp, of cellulose nitrate H. B. oads to HNO, which at low temp, gives N20 and at Kinetics of ring formation and polymerisation nigh temp, reacts with CH4 to produce HCN. in solution.— Sec this vol., 296. R S C Reduction of organic compounds by ethanol- H ig h ly polymerised compounds. CXXIII. am ines. M. jMeltsn er, C. W o h lber g , and M. J. measurements of the viscosity of aliphatic K leiner (J. Amer. Chem. Soc., 1935, 57, 2554).— *?™nes with long chains. H. Staubinger and Reduction of anthraquinone, (!NPh)2, and COMe2 a. Kossler (B er, 1936, 69, [B], 49—60).—Deter- occurs when these are heated with N(CH2-CH2,OH).| mations of the viscosity of long-chained aliphatic (I); anthranol, NH2Ph, and Pr^OH, respectively, are n'es and primary and sec.-amines show the com formed. Mixtures of the azo-, azoxy- (II), and NH2- pounds to be unimol. in C6HG and CC14, since the derivatives are similarly produced from PhN02 and served v),p- (1-4%) vals. agree with those calc, from o-C8H4Me-N02 with (I), NH2-CH2-CH2-OH, or, prefer me expression Y]ip. (1-4°/0)= n y . The temp, coeff. ably, NH(CH2,CH2'OH)2 in presence of aq. NaOH; ne same as that of hydrocarbons. With short- (II) is not fonned in absence of NaOH. Chrysoidine ■ am eompounds the observed vals. are < the calc., is reduced [ ? by (I)] to 1:2: 4-C0H3(NH2)3. Aq. ,mce the abs. viscosity of the dissolved substance solutions of Ag, Pb, Hg, and other metal salts are n°t- sufficiently high in comparison with that of the also reduced. H. B. n Y u The amine mol. has therefore the form M ixed m olyb d a tes.— See this vol., 302. A riTt, not N H R ,. tert.-Amines with three long [Derivatives o f] ru th en iu m -red.— See this vol., chains have the mol. structure R ’^ 'R , not N ^ R , and 302. Preparation and properties of fi-n-alkylcholine viso^ff- comparable with the glyceryl esters. The chlorides and their acetyl esters. R. T. Major solr° ^ jong-chained amines in heteropolar and H. T. B onnett (J. Amer. Chem. Soc., 1936, 58, u eri, ?. Is 9uite irregular and is little affected by 22— 24).— OH-CHR-CH2-NMe2 (from OH-CHR-CH2Cl is nnf *• , electrolytes. Since micelle formation and NHMe2 in C6H6 at 115— 120°) are converted . lnvplved, an adequate explanation of the high (Mel followed by AgCl) into 0H*CHR7CH2'NMe3Cl iscosity in AcOH is not forthcoming. Amines (R=Et—w-C7H13), which are acetylated (method : 320 BRITISH CHEMICAL ABSTRACTS.— A. XIV (¡7, ¡1) A , 1932, 257) to OAc*CHR-CH2-NMc3Cl. The follow Acid hydrolysis gave methionine (carbamide, m.p, ing are described : u.-chlorononan-$-ol, b.p. 114-5— 171— 172°; hydantoin, m.p. 117—118°). H. D. 116-5°/13 mm. (prep. : Levene and Haller, A., 1928, 737) ; a-dimethylamino-Ç>-hydroxybutane, b.p. 142:— Determination of the stereochemical purity of 144°/7G0 mm., -liexane,, b.p. 89—90°/25 mm., -octane, i-cysteine. G. T o e n n ie s and (Miss) M. A. B e n n e tt b.p. 99—101°/10 mm., and -nonam', b.p. 104— 106°/ (J. Biol. Chem., 1936, 1 12, 497— 502).— Z-Cysteine 5 mm. ; $-ethylcholine chloride, m.p. 174— 176° (acetate, (modified prep.), [a]f,°g + 9-68±0-05°, [a]j,° -j-7-6rir0-l m.p. 144— 146°), and iodide, m.p. 162— 163°; (3-n- (M solution in A-HC1; da/dt==— 1 % between 23° propylcholine chloride, m.p. 115— 117° (acetate, m.p. and 33°), is determined within ±0-25% by oxidation 168— 169°), and iodide, m.p. 198— 200°; p-n-butyl- with H „0 2 (2 % excess) in iV-HCl in presence of choline chloride, m.p. 100-5— 102° (acetate, m.p. 186— 0-003Ji-CuS04 and determination of the max. [a] 187°), and iodide, m.p. 90— 92°; p-n-amylcholine (due to cystine) during 1 hr. R. S. C. chloride, m.p. 72—74° (acetate, m.p. 182— 184°), and iodide, m.p. 98— 100° (lit. 106— 108°) ; (3-n-liexyl- Detection of cysteine in presence of cystine. choline chloride, m.p. 69— 71° (acetate, m.p. 169— 171°), C. B. d i Capua (Boll. Soc. ital. Biol, sperim., 1935, and iodide, m.p. 109— 110° ; $-n-licptylcholine chloride, 1 0 , 428—429).—Grothe’s reagent can be used for m.p. 97— 99° (acetate, m.p. 176— 177°), and iodide, detection of cysteine, but the supposed blue cystine (I) m.p. 122-5— 123-5°. Pharmacological data are given; coloration appears in acid solution without (I) and is none of the acetates is as active as probably due to formation of Prussian-blue. R. N. C. OAc-CHMe-CH2-NMe3Cl (cf. Simonart, A., 1932,1284). H, B. Highly polymerised compounds. CXXIV. Equilibrium of amino-acids, carbon dioxide, Measurements of the viscosity of amides and and carbamates in aqueous solution.—Sec this anilides of fatty acids. H. Staudinger and K. vol., 289. R o s s le r (Ber., 1936, 69, [13], 61— 73).—-The m.p. of the normal fatty amides is considerably > that of the Feeding experiments with purified amino- corresponding acids; the lower m.p. of sec.- and led.- acids. V III.— See this vol., 233. amides may be caused by the presence of branched Synthesis of a-amino-p-hydroxy-n-butyric chains. Correspondingly the methylamides and more acids. H. E. Ca r t e r (J. Biol. Chem., 1936, particularly the dimethylamides are more freely sol. 1 12, 769—773).—The mixture of isomerides, in C8H 6, CC1.„ or CHC13 than the simple amides. 0H-CHMe'CH(NH2)-C02H (I), of Abderhalden et al. The relatively high m.p. of primary amides depends on (A., 1934, 638) has no physiological activity. Formyl peculiarities of structure as well as on the formation ation gives a-formamido-fi-methoxy-n-butyric acid, m.p. of co-ordinative mols. Measurements of r„r. 173— 174°, which after épimérisation by hot A c20 - dimethylamides in CGHG gives vals. > expected, which NaOH and hydrolysis with HBr yields a mixture of do not depend on concn. Since the temp, effect is stereoisomerides of (I), which has about 25% of the normal the CO-NH2 group causes exaltation; this activity of the natural acid. R. S. C. view is confirmed by the behaviour of the piperidides. Canavanine. VI. 3VI. K itacaava and A. T a k a n i Similarly, *^,p. of amides and methylamides in CHClj (J. Agric. Chem. Soc. Japan, 1935,11,1077— 10S2).—- is > expected. Methylanilides in CGHG, CC14, or The similarity in properties of 0NH 2-CH2-C02H and CHC13 behave similarly to the dimethylamides. On canalino confirms the structure of the hypothesis that mols. in solution assume the 0N H 2-CH2-CH2-CH(NH2)-C02H. Guanidation of «- longest possible form, the normal mols. of anilides have O benzoylcanalinc with methyKsocarbamide followed by the structure Co-ordinahve hydrolysis yields (as flavianate) canavanine, which Me-[CH2]|C— NHPh. therefore is mols. can have the structure XH,-C(NH)-N(OH)-CH2-CH2-CH(NH2)-CO,H (cf. A., Me-[CH„]„-C(:0)-NH • • • HN-(0)C-[CH2]„-Me or 1934, 993). "F. 0 . H. Ph t h Specific rotation of i-cystine in relation to ^COR dependent on whether or not degree of neutralisation and p B. G. T o e n n ie s , Me’[CH,]„-CO is longer than Ph. Support for this T. F. L a v in e , and (Miss) M. A. BenS^tt (J. Biol. view is found in the observation that the m.p. of fatty Chem., 1936, 112, 493— 496).— [a]“™-31’3 at p a 0— 10-6 acid anilides passes through a min. at octoanilide. arc recorded for 0-005iV4-cystine, prepared from 7)ip_ of anilides in C6H G, CHC13, or C5H SN shows pro 98—99% pure Li cystinate by adding varying gression similar to that of the m.p. In AcOH the amounts of LiOII and/or HC1. [a]Hg is —225° at p n viscosity of anilides appears to depend on the ion°- about 0-1, —97° at p a 11-6, and —325° at p a 3—7 genic groups rather than on the chain length. The (theisoelectric range). d[a]/diis +1-5° between 19-3° following compounds are incidentally described ■ and 32-05°. R . S. C. •methylamides of undecenoic, myristic (I), and palmitic New synthesis of methionine and a scheme (II) acid, m.p. 48—49°, 78—79b, and 86°, respectively; relating certain a-amino-acids. E. M. H il l and dimethylamides of lauric (III), (I), (II), and stearic W . R obson (Biochem. J., 1936, 30, 24S— 251).— acid (IV), b.p. 180°/15 mm, m.p. 18—20°, b.p. 210- Et y-chloro-a-benzamidobutyrate, m.p. 45°, prepared 213°/15 m m , m.p. 31— 32°, m.p. 41° and m.p._50sj— by treatment of a-benzamido-y-butyrolaetone with 51-5°, respectively; stearpiperidide, m.p. 37—-3c , HC1 in EtOH, gave benzoylmethionine on treatment methylanilides of (III), (I), (II), and (IV), b.p. 1“' 1 with NaSMe and subsequent alkaline hydrolysis. 0-2 m m , m.p. 15°, b.p. 204-5— 206°/0-5 m m , m.p- XIV (Jir-m), X V (a) ORGANIC CHEMISTRY. 321 29—30°, b.p. 202— 203°/0-01 mm., m.p. 40—45° and BuO-PCL, is converted by NaOBu into (BuO)2PC1; m.p. 48-5— 49-5°, respectively. H. W. this, with (BuO)2P-ONa, affords butylpyrophosphorous Condensation of carbamide and formaldehyde. acid, b.p. 175— 176°, which, with H aO, yields G. W a lt e r (Trans. Faraday Soc., 1936, 32, 377— 395). (BuO)2P’OH, and, with Br, a Br4-compound. —A summary of work previously published (cf. B., Ch. A bs. (r) 1931, 357; A., 1932, 150). F. L. U. Acetoacetic acid O-phosphoric ester. P. K a r - RERand H. B en d as (Helv. Chim. Acta, 1936,19, 98— Coloured compound formed in Sullivan reac 99).— Cautious treatment of ONa-CHMciCH-COoEt tion for guanidine. M. X . S u lliv a n and W . C. with P0C13 give Ets aceloacetate O-phosphate, isolated Hess (J. Amer. Chem. Soc., 1936, 58, 47—48; cf. as the salt P 0 3Ba-0-CMe'CH-C02Et. The corre this vol., 195).— The compound, decomp, about 250°, sponding Na2 salt is hydrolysed to the compound (I), formed from guanidine (I) and Na 1 : 2-naphtha- P 0 3Na2* O • CMe.CII• CO2Na. Hot, dil. acids convert quinone-4-sulphonate in aq. NaOH at 90°, followed by (I) into CH2A c,C 02H or COMe2 ; kidney phosphatase acidification (conc. H C l+conc. H N 0 3), is considered readily removes -0P0 3Na2 from (I) at pa 9. H. W. to be (II) since it is hydrolysed (conc. H 2S 0 4, 95% EtOH) to 2-hydroxy-l : 4-naphthaquinone. (II) is Phosphate transferences by means of phospho- pyruvic acid in alcoholic fermentation of sugar. O — See this vol., 246. OH Preparation of boron alkoxy-halides and their or reaction with metals. C. It. K in n e y , II. T. n -C(:n h )-n h 2 Thom pson, and L. C. C h en ey (J. Amer. Chem. Soc., ~ ( ii). C :n h 1935, 57, 2396—2397).—A mixture of trh'soamyl borate (I) (2 mols.) and BC13 (1 mol.) is kept for 24 hr. rose-coloured in acid, purple in alkali, and forms N ib , and then fractionated; B diisoamyloxy-chloride m.p. 285— 288°, and Na, m.p. 297— 300°, salts. 1 : 2- (II), b.p. 110— 115°/14 mm., is obtained in 45% Napkthaquinone, (I), and a little H N 0 3 in aq. EtOH yield. (II) and Na in C6H 6 at 70° give HC1, iso- give the compound, 1 : 2-O:C10H 0:N-C(:NH)-NH2, m.p. pentcne, II2, (I), and B 203. BCl(OEt)2 warmed with 265—267° (decomp.), hydrolysed (20% HC1) to Na or Zn dust similarly affords B(OEt)3 and B 20 3. «-C10H/OH. H. B. H. B. Reduction of nitroguanidine. II. Prepar Colour reaction for detection of cyciopenta- ation and properties of nitrosoguanidine. V. J. diene. B. N. A fa n a s ie v (Ind. Eng. Chem. [Anal.], Sabetta, D. H im m iclfarb, and G. B. L. Smith. 1936, 8 , 15).—A violet colour is produced when one m. Synthesis of aminoguanidine. G. B. L. drop of cycfopentadiene dissolved in CHC13 (1 c.c.) «mth and E. Anzelmi. IV. Preparation of and AcOH (1 c.c.) is treated with conc. H 2S 04. A mtrosoguanidine by catalytic hydrogenation [of similar coloration is obtained with higher "terpenes mtroguanidine]. E . L ie b e r and G. B. L. S m th but only when Ac20 is used, S. C. (I Amer. Chem. Soc., 1935, 57, 2478— 2479, 2730, Ozonisation of hydrogenated diphenyls. C. R. -rl'!)r 2480).—II. Slightly impure nitrosoguanidine N o l l e r and G. K. Kaneko (J. Amer. Chem. Soc., (1). detonates at 161°, is obtained in 40— 60% yield 1935, 57, 2442— 2443).— 1-Phenyl-A1-cycZohexenc (I) % reduction (Zn dust and aq. NH 4C1 at < 50°) of and di-A1:r-c)/c/ohexenyl add 1 and 2 mols., respect ™roguanidine (H). Methods for the determination 01U) are given. ively, of 0 3, indicating that steric hindrance in the 1 and 1' positions is not the factor involved in the failure . Methyl ¿sothioearbamide sulphate and N2H 4,H20 of Ph2 to give a hexaozonide (cf. Harries and Weiss, one ileSH and the sulphate (yield 90%) of amino- A., 1906, i, 22S). Decomp, of the ozonidos affords guamdine (ArB 1-1 x 10'3), the H carbonate of which is S-benzoylvaleric and adipic acid, respectively. The ® A H 2co 3. tetrahydrodiphenyl obtained (cf. Bamberger and H. Reduction [H 2 (slightly > 1 m ol), P t0 2 or Lodter, A., 1888, 292) by reduction (Na, amyl alcohol) Raney Xi, H 20] of (II) affords 36—62% of (I). " of Ph2 is mainly (I). . H. B. Vinyldiazomethane. C. D. H u r d and S. C. Lui Dehydration of benzylcyclohexanols. J. W. t". Amer. Chem. Soc., 1935, 57, 2656—2657).— Vinyl- C ook and C. L. H e w e tt (J.C.S., 1936, 62— 71).— infZ?-1^ ane (d)> obtained from nitrosoallylurethane 2-Methylcycfohexanone and CH2Ph-MgCl (I) give iQln • o RreP') bV Nirdlinger and Acree’s method (A., impure l-benzyl-2-methylq/cZohexanoI, b.p. 115°/ • ,y b.341), with BzOH gives allyl benzoate. Appre- 0-8 mm., dehydrated (KHS04 at 160— 175°) to 1- aifri v- '^e’rncrisation of (I) to pyrazole (cf. Adamson benzyl-2-methyl-i^-cyc\ohexene, b.p. 158— 160°/19mm., ation lner’ ^ ’ ^35, 479) occurs during its distill- converted by A1C13 in CS2 at 0 ° into a saturated H. B. hydrocarbon, C14H18, b.p. 141°/18 mm., which could not be dehydrogenated (Se at 300— 320°; Pd-C at J -c h o r and molecular refraction of hydraz- 300°) and is oxidised (dil. H N 03 at 180— 185°) to 2~0 and its aliphatic derivatives.—See this vol., 0-C0H 4(CO2H)2. Tetrahydrocarvone and (I) afford 1-benzyl-2-methyl-5-isopropylcyclohexanol, b.p. 140— ^ibutylphosphorous acid chloride and pre- 142°/0-6 mm., dehydrated (ZnCl2 at 160°) to 1- a ion of butylpyrophosphorous acid from it. benzyl-2-methyl-b-isopropyl-t±.l-cyc\ohexcne, b.p. 159°/ Tnof ’ [ u ETJSOV an(^ ^ • S. Abramov (Trans. Butlerov 12 mm., similarly converted into a saturated hydro- • Chem- Tech. Kazan, 1934, No. 1, 28— 33).— carbon, C17H24, b.p. 160— 161°/13 mm., which could 322 BRITISH CHEMICAL ABSTRACTS.— A. X V {a, b) not be dehydrogenated. PhenylcycZohexylcarbinol benzoic acid (X), m.p. 105— 107°, better prepared (II) and 1- (III) and 2-benzylcyc\ohexanol, b.p. 154°/ by reduction (Na, amyl alcohol) of o-CGH 4Ph-C02H 11 mm., m.p. 75-5—76° (prepared by reduction [the acid obtained by catalytic reduction (Ranedo of the hcxanone with Na and H20 in Ët20 ), are all and León, A., 1925, i, 665) is not a stereoisomeride converted by P20 5 at 150° into 30— 70% of 2 :3 - of (X) but is o-cycZohexylbenzoie acid, m.p. 104°, benz-1 : 3 : 3-dicyclo-A2-nonene (IV), b.p. S5°/0-3 mm., oxidised (alkaline KMn04) to o-CGH4(C02H )2]. The r C0Ph*0GH4Me,AlCl3,FeCl3, is given. The variation H2S04 at about 40° affords the 5 : 6 - CL-derivative, of the velocity coeff. with concn. is of the same order m.p. 78— 80°, b.p. 165— 170°/15 mm. [Ac, m.p. 165° as that found by Olivier (A., 1918, i, 228) for the re (corr.), and Bz derivative, m.p. 173° (corr.)], con action between CGH 6 and BzCl. The velocity coeff. verted (diazo-reaction) into 2 : 3-dichloro-p-xylene. for the reaction between PhMe and CH2PhCl is greatly Hot chlorination of (III) affords 3:5: 6-trichhroacet- increased by a small % of FeCl3; a subsequent p-xylidide, m.p. 220°, and thence the base, m.p. 206°. decrease occurs when substantial amounts are pre Dyes obtained by coupling each of 10 diazotised sent. The results support the reaction mechanism xylidines with 9 2-hydroxy-l-naphthxylidides and 9 proposed by Steele {loc. cit.). H. B. naphthols are described. The fastness of these dyes Decomposition of di-o-tolyliodonium iodide. to light, Cl2, and washing is good. The following H. J. L ucas, E. R . K e n n e d y , and C. A. W ilm ot are prepared: 2-hydroxy-1 -7iaphth-xylidide, m.p. 200°, (J. Amer. Chem. Soc., 1936, 58, 157— 160).— o- -3 -, m.p. 230°, -5'-, m.p. 258°, and -Q'-chhro-, m.p. (VH4Me,IO, o-CGH4Me'I02, and Ag20 [which cata 180°, -3'-, m.p. 150° (decomp.), -5'-, m.p. 255° (de lyses the reaction C7H 7I 0 + C 7H 7I 0 2 -> (C7H 7)2I+ + comp.), and -6'-nitro-, m.p. 145°, and -3' : 5'-, m.p. I03~ ] are triturated in CHC13-f -successive small amounts 223°, -3' : 6'-, m.p. 250°, and -5' : G'-dicJiloro-'p-xylidide, of H20 ; treatment of the combined aq. extracts with m.p. 233°. R. S. C. S02 or KI gives di-o-tolyhodonium iodide (I). De comp. of (I) at 155° (bath) affords only o-CGH4MeI Jacobsen reaction. TV. L. I. Sm ith and C. L. (which is converted into o-CGH4Me-MgI and thence M o y le (J. Amer. Chem. Soc., 1936, 58, 1— 10).— The into o-CGH4Me-C02H) : (o-CGH4Me)2I-I -> Jacobsen rearrangement is not a general reaction; ®-C0H4MeI-|-o-CcH4Me+-)-I_. Physical data for the it is limited (with few exceptions) to CGH2Me4, G6H4MeI are given. * H. B. CGHMe5, CGHEt5, and halogeno-derivatives of CGHG and methyl benzenes. Labile groups are Cl, Br, I, Chloro-derivatives of xylene. H. W a h l (Ann Me, Et, and S03H ; no rearrangement occurs when Chirn., 1936, [xi], 5, 5— 82).— Partly a detailed N 0 2, A c, OMe, or C02H is present. In general, account of work already reported (A., 1933, 815; except when Hal is present, «*: 4 substituents must 1931, 177, 181, 772, 878; 1935, 739). The following be in the CGHG nucleus to obtain rearrangement; the is new. Chloro-p-xylene (I) and H2S 0 4 give 2-chloro- course (and ease) of the reaction is determined by y-zylcneA-sulphonic acid, + 2 H 20 ,“ m.p. about 100° the substituents. Results now and previously ob ja®1 + H 20 , and Ca salts, -f-3H20 ; chloride, m.p. tained (A., 1933, 600) show that for all the CGHMe4Cl w ; amide, m.p. 185°; anilide, m.p. 155°), obtained and CGHMe4Br, the ease of migration is B r> pazo-reaction) also from p-xylidine-5-sulphonic acid Me>Cl, whilst for CGH 2Mc3Cl and CGH 2Me3Br the m converted by H N 0 3-H 2S 04 at 50— 60° into a order is Br>Cl>Me (when rearrangement occurs). Mixture of 65— 70% of 2-chhro-3-nitro-r>-xylene-5- There appears to be some correlation between the Mpfomc acid (K , Ca, + 4 H 20 , and Na, + 2 H „0 , ease of hydrolysis of ArS03H and its ability to ®) and 20% of 2-chloro-?> : 5-dinitro-p-xylene (II), undergo rearrangement, Whenever rearrangement mP- 95° [also obtained from 2-chloro-3- and -5-nitro- occurs, side reactions leading to amorphous solids or P-xjlene and H N 0 3 at about 10° and (diazo-reaetion) tars and S 02 also occur. Attempts to rearrange ifom 3 :5-dinitro-p-xylidinc]. Reduction (Fe-HCl) CGMe5*S03H, using conditions designed to avoid such «tords 3-chloro-p-xylidine-Q-sulphonic acid, + H 00. reactions, failed; rearrangement could not be effected mC umo* m.p. 36° {Ac derivative, with reagents [e.g., PhS03H, H 3P 0 4, CaCl2, Mg(C104)2] •P- DO ), and 5-N02-derivatives of acet-p-xylidide other than H 2S04. The constitutions of the com in C^' -' *le third aldehyde (phenylhydrazone, pounds described below are established by conversion 101°’ or)’ ohtninecl by nitration of (I), ‘has m.p. into known or proved derivatives. Jo3 ■ hloro-6-nitro-p-xylene and HN03 at about Chlorodurene (from durene and Cl2 in CHC13 at 0°) ^n!e --chloro-5 : G-dinitro-y-xylene, m.p. 101°, re- and conc. H 2S04 at 65° give 99% of chloropenta- uced by Zn and AcOH-EtOH to the {NH2)2-com- methylbenzene (I), m.p. 154-5— 155° [reduced (red P, •w.-o1 ’ 'U'P‘ 60°, which affords a phenanthrazine, m.p. 45% H I, 220°) to CGHMe5], and 81% of 3-chIoro-^- Gh loro a ce t -p - xy Ii d id e (III) and H N 0 3 give cumene-5-sulphonic acid (II) [also prepared by short i ; S ^ i'WC!<-P -^ ^ 'rfe>m-P-200-200-5°,hydro- treatment of 3-ehloro-0-eumene (III) With oleum], 101° i n 'i i) t°5-c/i7oro-3-wib'o-p-a-i/Zi£/mc, m.p. 100— Chlorotsodurene, b.p. 139°/41 mm., m.p. —1° to 1° is nr . m-P- 160°), the structure of which (obtained with a little of the CZ2-derivative, m.p. The p| f C0Ilversi°n into 2-chloro-6-nitro-p-xylene. 188°, from ¿sodurene and Cl2 in CHC13), similarly 1 ° %e chloronitro-p-xylenes is unreactive affords (I) (96-4%), (II) (70%), and a little of a 2 - „ g to steric hindrance. The K salts, + H 20 , of compound, C20H24C12, m.p. 209-5°, whilst chloropreh- ri„’ ri';ian. 2 : 6-dichloro-p-xylenesulphonic acids are nitene, b.p. 131— 132°/24 mm., m.p. 24°, and approx. the (1 Yn j3 : 5-Dichloro-p-xylene and HNOs give 14% oleum at 25— 30° yield (I) (98%) and (II) [or, mm , 2~denvative, m.p. 95°, b.p. 155— 160°/15 by hydrolysis, (III)]. At least two rearrangements are 8 >1-, reduced (Fe) to the 6 -W fif derivative, m.p. considered to occur with the above CGHMe4Ci. derivnU" 160°/15 mm. {Ac, m.p. 198°, and Bz 5-Chloro-i/,-cumene, m.p. 70-5— 71° [formed with (111) 3 S l f ’ mp- 203°)- (HD and Cl2 in AcOH give from fcumene and Cl2 in CHC13 at 0°], and 20% he £ ? m-P- 172°, hydrolysed to oleum at 65—70° give (II) (71%) and tar. (II) (44%) aUvc m m‘?^48°’ b P- 160-162°/15 mm. {Bz deriv- and a small amount of an unidentified product, m.p. 2 : 6-rlini F' 180°), which (diazo-reaction) yields 148— 153°, are formed from 6-chloro-^-cumene (IV), l oro-p-xylene. p-Xylidine with Cl2 in conc. b.p. 127— 128°/20 mm. [3 : 5-(N02)2-derivative, m.p« XV (6) 324 BRITISH CHEMICAL ABSTRACTS.— A. 162° (lit. 162° and 169— 170°)], and approx. 15% derivative, m.p. 196-5°, of 4-bromohemimellithenc, oleum at 25—30°. Intramol. migration of Cl thus b.p. 103— 103-5712 mm., 229-5°/750 mm., m.p. 1°, occurs in both cases. (IV) is prepared by deamin on reduction (SnCl2, HC1) and treatment with (IX) ation of 6-chloro-5-^-cumidinc [from 0->/>-cumidine (V) gives 10 : 11 : l2-trimetliylplienanthrophe7iazine, m.p. (in EtO H -I) and • Cl2 (in CHC13)]. Chloromesitylene 311°. H - B- [SOgll derivative (Na salt +0-5H 20 ; amide, m.p. Oxidation in benzene series by gaseous oxy 105-5— 166°)] and 4-clilorohemimellithene, b.p. S6— gen. V. Oxidation of tertiary hydrocarbons. 87°/10 mm. [5 : 6 -B?y derivative, m.p. 229—230°], H. N. S tep h en s and F. L. Roduta.(J. Amer. Chem. prepared from hemimellithene and Cl2 in CHC13-I at Soc., 1935, 57, 2380—2381).— Slow oxidation (02) of 0°, do not rearrange; sulphonation occurs with 20% CIIPhMeR (R=Et, Pra, Bua) at 119° (bath) gives oleum at 70—75°. Bromomesitylene [S03H deriv COPhMe but no COPhR; CHPh2Me and CHPh3 ative (Na salt +0-5H 2O ; amide, m.p. 160— 160-5°)] similarly afford C0Ph2. These reactions, unlike that and 20% oleum at 25—30° give dibromomesilylene, with CH2Ph2(-> COPh2) (cf. A., 1928, 1233), are not m.p. 65-5°, and 2 : 4 : 6-CGH,Me3-S03H (not isolated; inhibited by H 20 . H. B. hydrolysed to s-CeH 3Me3) ; at 70°, tribromomcsitylenc, Reactions between organom ercury compounds m.p. 223-5— 224°, is formed in 68-5% yield. 5-Bromo- and nitrosyl compounds. L. I. Sm ith and F. L. li-cumene [from ^-cumene-5-sulphonic acid (VI) and T a y lo r (J. Amer. Chem. Soc., 1935, 57, 2460— 2463). Br in aq. EtOH] and 20% oleum at 25—30°/6 weeks —Acetoxymercuridurene (I) (in CHC13) and N0C1 afford a little tribromo-i/i-cumcne, m.p. 232°, and 90% (from EtO-NO and AcOH-conc. HC1) give nitroso- of 3-bronio-r/l-cumene-5-sulphonic acid [Na salt, also durene (II), m.p. 160° (decomp.) (rapid heating). propared from the Na salt of (VI) in EtOH with Br NUroso-isodurene (III), m.p. 134°, -pentamethyl- in CHClg], hydrolysed (dil. H 2S04 at 145°) to 3-bromo- benzene, m.p. 160° (decomp.) (rapid heating), -preh- ^1-cumene. The f ollowing compounds did not undergo nitene, m.p. 72°, -mesitylenc, and - ArN0+ or" oleum : (V), hemimellithene, 5-nitro-i/i-cumene, HgXCl. (I) and (II) are both converted by HN03 2 : 3-C10H GMe2, 25-CGH4PhBr, pentamethylci/c/ohexane, (d 1-26) at 70° into nitrodurenc, m.p. 112— 113°; (III) b.p. 98—98-5°/38 mm., 188°/730 mm. [prepared by and acctoxymcrcuriisodurene (IV) similarly .afford reduction (H2, Ni-kieselguhr, 225°) of CGHMe5], and nitroisodurene, m.p. 38— 39°, also prepared from (Iff) M e pentamethylbenzenesulphonate, m.p. 91— 91-5°(from and N 0 2 in CHC13. N20 3 distilled into (IV) (in CHCljl CGMe5-S02Cl and MeOH-NaOMe). gives a colourless ppt". of (probably) nitritomercun- Reduction (Zn, dil. HC1) of 3-chloro-^-cumene-5- tsodurene contaminated with Hg(N02)2, which subse sulplionamide, m.p. 1S2°, affords i/r-cumene-5-sulphon- quently redissolves; a brown ppt. is then formed and amidc, m.p. 180°. Na 3-chloro-i/r-cumene-5-sulpkon- the CHC13 contains (III) [similarly obtained from (IV) ate (VII) is reduced (Na-Hg, H,0) to Na fcumene- and NO,]. The reaction between HgPh, and. b-A 5-sulphonate (nitrated to trinitro-i/r-cumene, m.p. (Bamberger, A., 1897, i, 28S; 1900, i, 145) is con 183-5°), is converted by red P and 45% H I into j>- sidered to give PhNO as the primary product; cumene, and is hydrolysed (dil. H 2S04 at 135— 155°) PhN ,-N 03 is then formed from PhNO and h0- to 3-chloro-i/i-cumene, b.p. 127°/61 mm. [5 : 6-(N 02)2- Diazonium nitrates are formed only when N ,03+hO derivative (VIII), m.p. 173-5— 174°, also formed by (excess) act on Hg compounds. H. B. nitration of (VII)]. ‘¿-Chloro-5 : 6-diamino-p-cumene, m.p. 136-5° [from (VIII), SnCl2, and EtOH -conc. Reaction between chlorodiphenylmethane and HC1], and phenanthraquinone (IX) in EtOH-AcOH ethyl alcohol. F. G. KLny-Jones and A. M. Ward afford 12-chloro-10 : 11 : Vi-trirncthylphenanihrophen- (J. Amer. Chem. Soc., 1935, 57, 2394— 2396). Re azine, m.p. 330-5— 331°, whilst reduction (SnCl2, HC1) examination of the method previously used (A., 1927, of (VIII) in AeOH gives G-chloro-2 : 4 : 5 : 7-teira- 1061) in greater detail again shows that the reaction, methylbenziminazole, m.p. 250— 251°. 'i-Chloro-b : 6 - CHPh2Cl4-E tO H C H P h ,-O E t4 -H C l, is irreversible dibromo-ip-cumene, m.p. 224°, is obtained from (VII) (cf. Norris and Morton, A., 1928, 1000). H. B. and Br in AcOH at 70°. 2-Chloro-i: Q-diamino- Polystyrene and the m echanism of polymeris ■mesitylene, m.p. 137— 138°, is prepared by reduction a t io n . G. S. W h it b y (Trans. Faraday Soc., 1930, (SnCl2) of the (N 02)2-derivative. 3-Bromo-5 : 6-di- 32, 315— 323).— Evidence is presented for the vie" nitro-^-cumene is reduced (SnCl2, EtOH-HCl) to that polymerisation of unsaturated compounds is due 5 : 6 -diamino-i/r-cumene, which with (IX ) yields to successive additions to the double linking presen 1 0 :1 1 : Yi-trimethylphenanthraphenazine, m.p. 253°; in the monomeride or the preceding polymeric stage, a reduction in AcOH affords 2 :4 :5 : 7-tetramethyl- H atom going to one side of the double linking and the benziminazole, m.p. 233°. 6 - Br o m o-iA - c u m 0 ne, b.p. rest of the addendum to the other. F. L. u. 117°/17 mm., 233° (corr.)/724 mm., is obtained by deamination of 6-bromo-5->p-cumidine, m.p. 69° [from Highly polymerised compounds. C XX I. In soluble polystyrene. H. S ta u d in qb r [with • (V) (in dil. HC1) and Br in AcOH]. 4-Chloro-5 : 6- dinitrohemimellithene, m.p. 183°, is similarly reduced Heuer and E. Hesemann] (Trans. Faraday Soc, to the (NH2)2-derivative, m.p. 137— 137-5°, which 1936, 32, 323— 332).— When styrene (I) is P0lP with Ac, and (IX) gives S-chloro-2 : 3 : 5 : 6 : 7-penta- merised in presence of p-divinylbenzene (II) o' metliylquinoxaline, m.p. 160-5°, and 13-c/doro- product, although highly tuxgescible, is insol. m tn 10 :1 1 : Vl-trimethylplienanthraphenazine, m.p. 346-5— usual solvents. The proportion of (II) n e e d e d render the resulting polystyrene (III) insol. decrease 347°; reduction in AcOH yields l-chloro-2 : 4 : 5 : 6- tctrameihylbenziminazole, m.p. 288-5°. The (NO,),- as the chain-lengtli of (H I) increases, being, e.g. WJI XV (b) ORGANIC CHEMISTRY. 325 (I)=1/50,000 for a highly polymerised product. The (dry 0 2 in CGH4Me2 at 140°) gives 52% of COPli,, insol. product is thus chemically indistinguishable (apart from products derived from the CGH4Me2). (I) from sol. (Ill), and the striking difference in physical could not be oxidised by Pb02; with 0 3 the products properties is due to the relatively small no. of “ bridges ” previously reported (loc. cit.) and BzOH are obtained. effected by (II) between the long chains of (III), con The hydrocarbon C42H46 [obtained (ibid., 496) from verting a linear into a three-dimensional polymeride. CMeEt2*C:OCPh2Br] is also oxidised (0 2) to G’OPh., The results are discussed with reference to sol. and (38%); definite products could not be isolated from insol. caoutchouc, and to highly polymerised biological the hydrocarbon prepared by Moureu el al. (A., 1927 materials. p p pj 355) from (CPh;C-CPh2-)2. Reduction of diphenyl- Synthesis of diacetylene derivatives. J. S. tert.-butylethinylcarbinol with TiCl3 gives (I) and a Salkind and F. B. F u n d yle r (Ber., 1036, 69, \B\, compound, C38H39C1, m.p. 201°. Reduction (Na, 128—130).— CPhiCH is converted by heating with a amyl alcohol) of (I) affords hydrocarbons, C oJLF,,) feebly acidified solution of NH4C1 and excess of CuCl m.p. 132 (II), and C38H44 [described previously (A., into the compound, C16H10CuC1, immediately decom 1932, 505) as C19H22], m.p. 182°; with red P and 47% posed by Et20 into ocS-diphenyl-A“v-butindi-inine (I), H I in AcOH, a hydrocarbon, C30H42 (III), m.p. 210— m.p. 86—87°. The change appears to be balanced. (I) 211° [which may be the dimeride“of 3-phenylindene is hydrogenated (Pt-sponge) to aS-diphenylbutane. (Blum-Bergmann, A., 1931, 208)], results. The The liberated H is involved in the formation of hydrocarbon, C38H38, m.p. 176°, obtained (cf. loc. cit.) resinous material ( ?)C1GH14. Analogous reactions are from (I) and AcOH-HCl, is not oxidised by K 2Cr„07 given by y-hydroxy-y-metliyl-Aa-butinene and hydr- in AcOH, docs not give a Na alkyl with 40% Na-Hg, oxyq/cZohcxylacetylene. H. W. but is reduced (P, HI, AcOH) to (III). (I) and 40% Na—Hg in Et20 and N2 afford a product (A) containing Rearrangements of polyinenes. V I I . F o r m CNaPh2-CiCBuy [since treatment with CO, gives a ation of allenes. J. H. F o r d , C. D. Thom pson, little CBuy:C,CPh2'C02H (A., 1932, 50)] and an adcli- and C. S. M arvel (J. Amer. Chem. Soc., 1935, 57, tive compound C38H38Na2 [since the action of H„0 ’-619 2623).— GOPhBu7 (I) (2 : A-dinitrophenylhijdr- affords a hydrocarbon, C38H40 (IV), m.p. 163° (loc. cit.), ojoae, m.p. 194— 195°), prepared in 67% yield from whilst ClC02Me gives an ester, C38H38(C02Me)2, m.p. MgPhBr and BiffCOCl in Et20 and X , with 173°, which when (partly) hydrolysed (MeOH-KOH) UJu’sC'MgBr gives phenyitert.-butyltert.-butylethinyl- and then heated passes into an ester, C38H3,yCO,Me p-n b.p. 125—128°/4 mm., converted by m.p. 162°]. Oxidation of (IV) with KM n04 in COMe.’ : n in light petroleum into the carbinyl bromide (III), gives a neutral compound, C33H30O2, m.p. 217— 218°; PF 115—117°/1 mm., and by AcOH-conc. H2S04 with K 2Cr20 7 in AcOH, a neutral compound, C,3H280 3 mto y-phcnyl-WQ4etramethyl-Av-heptan-z-one, b.p. (V), m.p. 169°, results. Reduction (Na, amyl alcohol) t>—97 /I mm., m.p. 30-5° (2 : 4-dinitrophenylhydr- of (IV) affords a hydrocarbon, C38II42 (VI), m.p. 197°, n'0!'c, m P- 150— 151°). A hvdrocarbon could not be and a mixture (B) of (VI) and a more fusible isomeride; Prepared from (II) and TiCl3 or from (III) and Ag or the hydrocarbon, C38H42, m.p. 181— 182°, previously rp (^I) and moist Ag,0 in COMe, give (II). described (A., 1932, 505), is identical with (B). (VI) H n°n'P‘ °f the Grignard reagent (A) from (III) with is also obtained by successive treatment of (IV) with , affords the allenic hydrocarbon y-nhenyl-$$t£- 40% N a -H g and H20. The hydrocarbon, C38H38, r ^ thyl-An -heptadiene (IV), b.p. 78— 80°/l rain. m.p. 179— 180° (loc. cit.), prepared from (A) and Lozondysis products, BuyCO,H and (I)]. ClC02Me C2Me4Br2, is oxidised (K2Cr2()7, AcOH) to (V), is \vsi 8hnilarly give M e y-phenyl-[i$X4etrarriethyl- reduced (Na, amj-l alcohol) to (VI) and an isomeride, “ -nepiadiene-z-carboxylate, b.p. 116— 120°/2 mm. m.p. 155— 156°, and is converted by successive ree acid, m.p. 160— i61°, also formed from (A) and treatment with 40% Na-Hg and H„0 into (IV). »,7 i is oxidised (0 3) to the Me ester (2 : 4-di- The Na alkyl from ota-diphenji-SS-dimethyl-A^- ™nptenylbydmzone, m.p. 205—206°) of trimethyl- pcntadiene (A., 1932, 50) and 40% N a-H g with 171° '?;5ac*d ^ ■ ^-dinitrophenylhydrazone, m.p. 169— C2Me4Br2 gives a hydrocarbon, C38H40, m.p. 143— 144°; ill, i ,ecomP-)]. (HI) d°es not give a stable Na the dimeride (VII) (loc. cit.) similarly regenerates (VII), X 1 " hen treated with 40% Na-Hg in Et20 and N ,; but decomp, with H20 affords a hydrocarbon, C38H44, necomp. of the product with H20 affords (IV) and tw“o m.p. 133° [probably formed also by reduction (Na, bomenc hydrocarbons, C34H46, m.p. 148— 149° and amyl alcohol) of (VII)], which differs from (II). Re tinn p?'0 i dhe same mixture is obtained by reduc- duction (red P, 47% HI, AcOH) of (VII) affords a t-Ph 7 ’. ®tOH) of (III) or treatment with Li. hydrocarbon, C3SH42, m.p. 134— 135°, whilst oxidation nirJ,nJ/l'W'dimethyttutyric acid, m.p. 105°, is pre- (K2Cr20 7, AcOH) gives a little of a neutral compound, E 70m C°2 and CHPhBiff-MgBr. The acids and C2GH2602, m.p. 227°, but no COPh,. H. B. OR-n tr°m metallic derivatives of the type mtAR. ,M may all be C0,R"-CR:C:CR'2. H. B. Mol. compounds of polycyclic hydrocarbons and their quinones with polynitro-compounds of polyinenes. V I I I . F o rm - and with metallic salts. K. B rass and K. F a n ta U , 0 d/allenes. E. D. F a r le y and C. S. M a r v e l (Ber., 1936, 69, [B], 1— 11).—Examination of many earh^eri.? iem- Soc’> 1936> 58> 29—34).—The hydro- compounds fails to confirm Bruni’s view (A., 1906, i, buivWr i1Ile?. I"2 , 505) from diphenylieri.- 491) that the power of adding N02-compounds now or, lnGeayt)inyl bromide and Ag or Cu-bronze is depends essentially on the CGHG nucleus and that the Aa&f ;,.n'S,. ere t° be xyZ,Z,-lelrapheny[-y3-ditert.-butyl- no. of added mols. is in the limit equal to the no. of in -hexaletraene (I), (CPlCCiCBiff-),, since oxidation dependent CGHG nuclei present in the hydrocarbon 326 BRITISH CHEMICAL ABSTRACTS. A. XV (6) and that polynuclear condensed mols. add only 1 Synthesis of compounds related to sterols, mol. of X02-compounds. Perylene does not add bile acids, and cestrus-producing hormones. dipicric acid (I), but with styphnic acid (II) gives a VIII. C. L. H e w e t t . IX . A. Co h e n , J. W. Cook, compound (1 : 1), m.p. 211°. 2 : 3 : 10 : ll-Dibenz- and C. L. H e w e t t. X. Ruzicka’s hydrocarbon perylene affords the compounds, C„8HIfi,2C6H30 7N3, “ C 21H 10 " from cholic acid. W. E. B achmann, m.p. 240° (decomp.), 0,oH16,2GGHi0 ^ 3, decomp. J. W . Cook, C. L. H e w e t t, and J. I ba ll (J.C.S., 236°, C28H 16,SbCl5, and C28H 16,SnCl4. 1 : 12-Benz- 1936, 50— 52, 52— 53, 54— 61).— V III. Dihydrores- perylene does not add (I), hut affords the substances, orcinol (I) (1 mol.) and CH2PhCl (1 mol.) in EtOH- C22H12,C6H30 7N3, m.p. 267 , C22H12,C0H3O8N3, m.p. HaOEt (1 mol.) give some benzylcyclohexane-2 : 6- 234°, 2C22H12,SbCl3, and C22H ]2,2SnCl4. 2 : 3-Benz- dione, m.p. 184— 185°, converted by conc. H2S04 at anthracene does not unite with picric acid (III), — 15° into a SOsH derivative (+1120), m.p. 193— dibromopicric acid (IV), (I), or (II), but gives the 194°. p-m-Mdhoxyphenylethyl bromide (II), b.p. 138°/ substances, 2C18H 12,SbCl5 and C18H 12,2SnCl4. A ddi 12 mm., and (I) similarly afford (mainly) the (S-m- tion of (I), (II), (III), or (IV) to 2 : 3-benzanthraquin- methoxyphenylethyl ether, b.p. 205— 207°/0-5 mm., of one is not observed, but the compounds, (I) and a little p-m-methoxyphenylethylcycZohexane- C18H10O2,2SbCl5 and C18H10O2,2SnCl4, have been 2 : 6-dione, m.p. 149— 150° (cf. Robinson and Schittler, isolated. 1 : 2-Benzanthracene gives the compounds, A., 1935, 1498), which is best converted into 1-keto- C18H 12,C0H3O7N3, m.p. 141-5— 142-5°, 7-methoxy-l : 2 : 3 : 4 : 9 : 10-liexahydrophenanthrene C18H 12,C6H30 8N3, m.p. 153°, and 2C18H 12,SbCl5. (loc. cit.) by 80% H2S04 at 100° (bath), a- 1 : 2-Benzanthraquinone does not add (I), (II), (III), C10H7-CH2-CH2Br and (I) give Z-lcelo-^-cyclohexenyl or (IV), but affords the substances, C18H10O2,SbCl5 $-\-naphthylethyl ether, m.p. 138— 139°, hydrolysed and 2C18H 10O2,SnCl4,CHCl3. (Ill) is not added by (aq. EtOH-KOH or NH20H,HC1 in C5PI5N at 100c) 3-isopropyl-, m.p. 154— 155°, 7-isopropyl-, m.p. 114°, to a-C10H7-CH2-CH2-OH. Hydrolysis (dil. IICl) of 4-methyl-, m.p. 168— 169°, 5-methyl-, m.p. 173-5— the product from m-OMe-C6H4-MgBr and (CH2)20 at 174-5°, or 6-methyl-, m.p. 174°, -1 : 2-benzanthra- 100° (Et20 removed first) gives p-m-mcthoxyphenyi- quinone. Additive compounds of 9 : 9'-dianthryl ethyl alcohol, b.p. 150— 155°/18 mm. (3 : 5-dinitro- with (II), (III), or (IV) could not be isolated; SnCI4 benzoate, m.p. 106-5— 107-5°), converted by PBr3 in causes halochromism, whilst SbCl5 affords the sub CC14 into (II). Modified preps. stance, C28H j8,SbClr(. 9 : 9'-Dianthranylquinone does of ra-C8H4Br-OH (from a- not add (I), (II), (III), or (IV), but gives the compounds, C6H4Br-NH and m-CGH4Br-0JIe ■Ca8H 10O2,2SbCl5 and C28H 160 2,2SnCl4. H. W. are given. 2-Acetyl-l-methyl-A1- cycZopentene (from 1-methyI-A1- Action of oleum on decahydronaphthalene. cycZopentene and AcCl in CS,-SnCl4) E. I. P rokopbtz (J. Appl. Chem. Russ., 1935, 8, and CH2Ph-CH2-CH(C02Et)2 in 1214— 1215).— W hen cts-Zrans-decahydronaphthalene EtOH-NaOEt afford a little of (probably) the acid is shaken with 20% oleum, only the ds-isomeride is (III), m.p. 242°. oxidised, leaving the pure iraws-isomeride. R . T. IX. ¡3-6-Methoxy-l-naphthylethyl bromide and CH K (C02Et)2 in PhMe at 120— 130° give the Et Rubrene problem. A. Sch on berg (J. Amer. ester, b.p. 200— 205°/0-3 mm., of (i-G-methoxy-l- Chem. Soc., 1936, 58, 182; cf. A., 1934, 643).— naphthylethylmalonic acid, m.p. 160° (decomp.), de- A question of priority (cf. Eck and Marvel, A., 1935, carboxylated at 190° to y-6-methoxy-l-naphthyl- 1492). H. B. butyric acid, m.p. 150— 151° [Et ester (I), b.p. 169°/ Attempts to obtain rubenes soluble in water. 0-2 mm.]. l-Keto-7-m ethoxy-l : 2 : 3 : 4-tetrahydro- Hexabromotetraphenylrubene ; its transform phenanthrene (Butenandt and Schramm, this vol., ation into rubenepolycarboxylic acids. C. Dtr- 76) and a little of the 7-OH-ketone are formed from fr aisse and L. V elluz (Bull. Soc. cliim., 1936, (I) and 80% H 2S0 4 at 100°. The product from (I) [v], 3, 254—265).—p-C6H4Br-C!C-MgBr and and Et2C204 in Et20+ K 0E t is converted by warm CO(C0H4Br-p)2 give ayy-tri-p-bromophenylpropinen- 80% H2S04 into 1-methoxy-Z : Mdihydrophenanthrene- y-ol, m.p. 141— 142° (Me ether, m.p. 101— 102°); this 1 : 2-dicarboxylic anhydride, m.p. 217-5— 218-5°, which with H2S04-Bu20 gives p-Cfliflir pp'-dibmmohydr- is demethylated [HBr (d 1-48) in AcOH] to 7-hydroxy- indenylmethyl ketone, m.p. (+ C fiH 0) 114— 115° and 3 : i-dihydrophenanthrene-l : 2-dicarboxylic anhydride, (anhyd.) 135— 136°, which with PC13 in ligroin affords m.p. 275— 278° (previous sintering), and dehydrogen the chloride, m.p. 130— 131° (dimeride, m.p. 273— ated (Pt-black at 300°) to 7-methoxyphenanthrene- 275°), converted in quinoline at 100°/15— 16 mm. into 1 : 2-dicarboxylic anhydride, m.p. 260—261° (corr.) (cf. 5 : 5'- (or 5 : 6'-)dibromo-l : 3 : 1' : 3'-tetra-p-bromo- this vol., 71). plicnylrubene (bisindenyl formulation), m.p. 401— X (cf. A., 1935, 1359). The carbinol from 2- 402° (cryst. peroxide loses 75% of its 0 at 150— methylhydrindone and a-C10H7-CH2-CH2-MgBr (I) >s 200°). Eour Br readily and the last two very slowly dehydrated (KHS04 at 160°) (general procedure) to react with Mg; C02 then leads to an amorphous 3-p-l'-naphthylethyl-2-methylindene. m.p. 99— 99-5° ( (decomp.) [the Et ester, b.p. 203—210°/26 mm., is gives a-1 -najihthylisopropyl alcohol, b.p. 148— 155°/ /,\ prepared from p-CGli4Me-CH2Br 25 mm. [3 : 5-dinitrobcnzoate, m.p. 171— 172°; chloride ■ x and CNaMe(C02Et)2 in EtOH], is (VI), b.p. 131°/6 mm.]. Cyclisation of a fraction, decarboxylated at 180° to (3-p- b.p. 195—215°/0-8 mm., obtained from 2-methyl- tolyl-a-methylpropionic acid, b.p. hydrindone, the Grignard reagent from (VI), and 181— 182°/23 mm., m.p. 30— MgEtBr (1 mol.) gives aS-di- 1-naphthyl-^y-dirnethyl- 31-5°, the chloride, b.p. 139— butane, m.p. 131—132° (removed as picrate), and 141°/21 mm., of which with resinous material, dehydrogenated with Se to a little A1C13 in ligroin gives 2 : 6-di- 4-methyl-2' : l'-naphtha-l : 2-jluorene, m.p. 202—203° methylhydrindone, b.p. 145— (corresponding fluorenone, m.p. 214— 215°). All 148°/21 mm. [phenylhydrazonc, m.p. 173— 175° (de the methylnaphthafluorenones give intense purple comp.)]. This and' (I) lead to 3-P-T-?laphthylethyl- colours, gradually changing to magenta, with conc. 2 : 5-dimethylindenc, m.p. 81— Sl-5° (dipicratc, m.p. H2s o 4. 144—144-5°), converted into 6 :10-dimethyl-3'A:lQ.11- Comparison (m.p.; colour with H2S04) of (V) and iclrahydro-2': l'-naphtha-l : 2-jluorene, m.p. 106-5— the ketone obtained by oxidation of the hydrocarbon, 107° (semipicrate, m.p. 133-5— 134°), and thence into C21H16 (VII), of Ruzicka et al. (A., 1933, 278; 1934, Q-methyl-2' : V-naphtha-! : 2-jluorene, m.p. 330° (varies 398) shows their identity. Powder photographs of with rate of heating), which is oxidised (K2Cr20 7, (IV) and (VII), which are first fused under identical AcOH) to the -1 :2 -jluorenone, m.p. 225—226 . conditions, are very similar; the slight difference is m-Methylbenzylmethyhnalonic acid, m.p. 152— 153° ascribed to impurity in (VII). Crystallographic data (decomp.), is similarly converted through (3-m-tolyl- for (III) and (IV) are given. The production of (VII) z-methylpropionic acid, b.p. 178— 179°/20 mm. (chlor [i.e., (IV)] from cholic acid is due to simple cyclisation ide, b.p. 137— 138°/21 mm.), into 2 : 5-dimethyl- of the side-chain during dehydrogenation. H. B. hydrindone, b.p. 142— 144°/21 mm. [2 : 4-diniiro- 'phenylhydrazone, m.p. 225—226° (decomp.)], which Alkali fusion. I. Fusion of potassium sul- with (I) gives 3-$-V-naphthylethyl-2 : G-dimethylindene, phanilate with alkali. N. N. V oroschcov and b.p. 184—186°/0-05 mm., cyclised to 7 : 10-dimethyl- M. M. Sciiem jakin (Ber., 1936, 69, [71], 148— 152).— 3:4: 10 : U-letrahydro-2' : l'-naphtha-l : 2-jluorene, p-NH2-C6H4-S03K when heated with a large excess ffi.p. 134-5— 135° [accompanied by some aS-di-1- of KOH at 350—355° in N2 gives NII3 (76-7%); the naphthylbutane, m.p. 101° (dipicrate, m.p. 174— 175°), normal exchange of -S03K for -OK occurs to only a which is undoubtedly present as an impurity in the slight extent since only 1-5% of S03" is observed. indene; it is now prepared from a-C10H7-CH2-CH2Br A t higher temp. ( > 400°) the yield of S03" increases and Mg], 1-Methyl-2' : l'-naphtha-l : 2-jluorene, m.p. but the product becomes carbonised. Although jh—336°, Qis oxidised to the -1 : 2-jluorenone, m.p. p-N H 2-CGH4-S03K enters almost quantitatively into —176-5°. o-Meihylbenzylmethylmalonic acid, m.p. reaction the product does not contain NH2Ph, PhOH, E-;5—123°, similarly yields $-o-tolyl-u.-methylprop- or NH„-CgH4-OH. p-0H-C6H4-S03H is formed in !®Acaci’d, b.p. 179— 180°/20 mm. (chloride, b.p. 137— 77-53%”yield. H. W. oS/21 mm.), and thence 2 •A-dimethylhiydrindone, Action of sodium on aromatic nitro- and .p. 147—149°/20 mm. [semicarbazone, m.p. 224— 225° nitroso-compounds. V. O. L ukaschevitsch (A11- iteomp.)]. This and (I) lead to 3-(3-1'-naphthylethyl- nalen, 1936, 521, 19S— 214).— The Na compounds of ■j-dmethylindene, m.p. 96°, resolidifying with m.p. aryl NO,- and NO-derivatives (Schmidt, A., 1900, i, m i ) 11'*0, cy cbsed to 8 : 10-dimethyl-3 : 4 : 10 : 11- 20) are best prepared by the action of 0-5% Na-Hg wmyiro.2' : l'-naphtha-l : 2-jluorene, m.p. 121— 122° on the N 02- or NO-compound in dry Et20, C6HG, or W’nipicrate, m.p. 130-5— 131-5°), dehydrogenated to PhMe (N2 atm.). The structures R-N(ONa)2 (I), and : l'-naphtha-l : 2-jluorene (III), m.p. 281— R-NNa-ONa (II), respectively, are suggested. The re f 0ly (corr.) (jluorenone, m.p. 237—238°). Hydro- actions (I)-t-R'N02 R'N(0Na)2+RN02 [A), and ^deOH-KOH) of the product from (H )-fR 'N O === R'NONa2-|-RN0 (B), are reversible, 1 Jile(C02Et)2 and 4-bromo-3-bromomethyltoluene, but the reaction (I)+R'NO -> R'N0Na2+R N 02 (C) 148~ 152° (from m-C6H4Me-CH2Br, Br, and Ee proceeds only from left to right. These relationships 0 , ,er at 0°), or a mixture of 4-bromo-2- and are established by investigation of the products of 19V sr-°Qmet^yltoluenes (Fieser and Seligman, A., interaction of (I) or (II) (or mixtures in accordance y,u> gives 2-bromo-5-mcthylbenzylmethylmalonic with equations A , B, or G) with BzCl, dil. H2S04, or 01 ra-P-_179— 180° (decomp.), converted through H20, numerous examples being given. Thus with Mo r°7jw'!j~rnethylbenzylpropionic acid, m.p. 84— 85° BzCl (I) reacts: (I) -f-2BzCl -> RN(OBz)2 -> Bz20 + dim°u. P" —174°/20 mm.), into 4-bromo-2 : 7- RNO, which then reacts as G to give (II), which with amwr?" ly VIII. As diazotised amines decompose in presence m.p. 118°; «î-OH-C6H4-, m.p. 194° (lit. 184°); eu- of NaOH they lose their power to couple with ¡3- genyl; woeugenyd, m.p. 130° ; 2 :4-(OMe)(CHO)C6H,- ; Cjpllj-OH, and take progressively longer to give a 0-, m.p. 142° (lit. 119°), m-, m.p. 138°, and (delayed) blue coloration with starch-KI paper. m.p. 120° (lit. 114°), NO,-CfiH4-; G-chloro-m-tolyl, Both reactions are negative when N2 has ceased to be m.p. 112°; 0-CJ1J-, m.p. "95°; p-CfiH4I- ; 0 -, m.p. evolved; their progressive decrease with decomp, of 99°, m-, m.p. 75°, and p-, m.p. 126°, C.H .Cl-; 32 diazotised amines is tabulated, and the oxidising 2:4:.C6H3Ch-, m.p. 119°; 2 :4 :6 -CeH,CT3-, m.p. action discussed. 136°; 0 -, m.p. 89°, and p-, m.p. 141 °, CeH .B r ; IX. fsoDiazotates (I) are reconverted into normal 2 : 4-C6H3Br,-, m.p. 135°; 2 :4 :6 -C6H»Br3-, m.p. diazotates (II) by the action of heat or light (sun, 135°. ~ H. B. ultra-violet, or electric). Azo-pigments are formed when (I) are mixed with 1% (3-C10H /O H in 1% NaOH m-2-Xylyl a-naphthylcarbaniate. C. D. H u rd and exposed to light. The reaction is given by (I) and M. A. P o lla c k (J. Amer. Chem. Soc., 1936, from NH2Ph, o-4-xylidine, and o-, m-, and p- 58, 181).— The xylenol obtained (A., 1932, 857) by- C8H4X-NH2 (X=C1, Br, or I), but not by those from pyrolysis of furfuraldéhyde is 2 : 6-CGH3Me2,OH o-C6HtMe-NH2, m-4-xylidine, ^-cumidine, or mesidine. \'j.-naphlhylcarbmnate, m.p. I76-50). H. B. The interconversion is represented : NRjN-ONa (II) Synthesis of alkyl- and aryl-cryptophenols. ^ NRIN-ONa (I). Application of (I) to dyeing, M. E. M cGreal and J. B. N ie d e r l (J. Amer. Chem. and to “ diazotype ” photographic printing, is Soc., 1935, 57, 2625— 2627).— ClMe2Pr^OH (1 mol.), discussed; good prints have been obtained using (I) PhOH (1 mol.), and ZnCl2 (1-5 mois.) at 180° give from p-C8H4Br-NH2 or from p-CfiH4TNH2. (3-p-liydroxyphenyl-^y-dimethylbutane, m.p. 105° (45) ; X. (I) may be rapidly prepared by adding solutions CMc2Bu“-OH similarly affords |3-p-hydroxyphenyl- p- of diazonium salts to 1-6% NaOH heated to 100°, and methylhexane, b.p. 280°/760 mm., but (iSS-tri methyl- keeping at 100° until (after a few min.) coupling power pentan-p-ol yields p-C8H4Buy-OH (I) ; the methyl- is completely lost (P-CjqH/OH paper). Yields are : cyctohexanols give p-2-, m.p. 107° (50), -3-, m.p. from NHgPh, 2 9 % ; from its m- and p-Me, p-Br-, 101° (105), and -4-, m.p. 108° (70), -methylcydo- P-I-, and m -N02-derivatives, 31, 8, 39, 52, and 61% ; hexylphenols, but 4-fer<.-octylcyc/ohexanol affords (I) ; when 04 or 0-8% NaOH is used, yields are smaller. CH2Ph-OH yields p-benzylphenol ; CH2PlrCH 2-OH XI. A historical review, summed up in favour of the or CHPhMc’OH gives a-phenyl-a-p-hyrdroxyphenyl- structures : NRjNCl -> NRjN-OH -> NRiN-OK ethane, m.p. 64° (40) (dehydration of the former aRIN-OH (see Part IX ). ’ On this view, “ (I) ” presumably^ preceding addition of the PhOH) ; oididiazotates ” of Hantzsch) should be renamed CPhMcEt-OH affords $-phenyl-$-])-hydroxyplienyl- diazotates,” and “ (H) ” (“ syrediazotates ” of butane, b.p. 145—148°/2-5 mm., also prepared hantzsch) be renamed “ diazoniates.” The very small (method : A., 1935, 79) from PhOH and (3-phenyl-A^- depressions of f.p. of aq. NaOH caused by diazonium butene; CPhMePr^OH yields B -ph cnyl-B-p- hydroxy - fdts (A., 1895, i, 661) support the view that slightly plienyl-y-methylbutane, b.p. 157—-160°/3 mm., also nvdrolysed diazotates are formed, and are in contrast prepared from the appropriate phenylpentene. The to the great depressions now observed with methyl- nos. quoted in parentheses are the PhOH-cocffs. Pyndinium and o-tolyltrimethylammonium iodides. (using Stapli. aureus). II. B. *11 aq. solution of benzeneazoxycarbonamide (III) Reduction of fsosafrole with sodium and A-, 1922, i, 1071) [but not anhyd. (Ill)] reacts with ethyl alcoh ol. Iv. O no and M. I moto (J. Chem. r to form a substance, m.p. 102— 103°, decomposed Soc. Japan, 1934, 55, 991— 1001).— A mixture of )' boding H20. (Ill) heated in H20 with Br, and m- and p-CGH4Pr-OH is jiroduced. Addition of , edwith S02, yields an insol. substance, m.p. 222°, active C increases the yield. Ch. Abs. (r) m.p. 142° (decomp, to a substance, m.p. ' A which couples with (3-C10H7-OH and is regarded Phenols of anthracene oil. O. K r u b e r (Ber., As t>enzenmzoxycarboxylic acid, Ph-N20-C02H, together 1936, 69, [B], 107— 114).— The liquid products witti a substance, m.p. 75°. The action of NaOH on obtained by centrifuging a crude pheuanthrene NPh:N(0)-C0-NH2^ NPh-N:NH:0 fraction, b.p. 320—340°, after extraction with NaOH i 1 h;N-OH —> NPhjN’ ONa. (I) treated with aq. and distillation of the extracted matter in vac., yielded r-,.,00!'0' H2S04, or with PC15, does not give PhN 02 p-hyrdroxydiphenyl, m.p. 163°. Similar treatment Xpu/r,v>TUlcl be exPe°fced if (I) were of crude C10H 8 press-cake yielded [3-C10H 7-OH and i i as suggested by Angeli (A., 1917, a diphenol, C18HI80 2, m.p. 135°, b.p. 341°/755 mm. ’ 41slJ> ut only, after prolonged action, PhOH. [Me2 ether, b.p. 200—201°/15 mm., m.p. 85°; di- TS. . E - W - W ‘ phenylurethane, m.p. 199—200°; compound, j • , duplication of phenols with l-chloro-2 :4- C42H380 4N2, m.p. 192— 193°, with CO(NPIPh)2]. trobenzene. R. W . B o s t and F. N i c h o l s o n Separation of the phenols of the anthracene oil frac is. Amer. Chem. Soc., 1935, 57, 2368— 2369)?—Aryl tion, b.p. 340—370°, is rendered difficult by the pre \L>ri \lmtJ°Pbenyl ethers are prepared by heating sence of complex, non-phenolie substances with feebly7 C H nnvA01 moL in 5 c-c- of H2°) with 1:2:4- acidic properties; it is best effected by repeated t D i o ' 2)2 (0-01 moL in 30 °.c. of 95% EtOH). alternate extraction with NaOH and distillation of m b 0Ao°Wlng are described: Ph, m.p. 69°; 0-, the extracted matter, whereby the complex materials A an‘! m’ ’ m -P- 74°, -folyl; p-tolyl, m.p. are extensively decomposed. Distillation of the > hymyl m.p. 67°; o-anisyl, m.p. 97°; a- phenolic fraction over Zn dust or a Mo contact affords 10 T’ m'P- 1-8 ; P-C10H-, m.p. 95°; p-rliphentylyl, diphenylene oxide and fluorene. Further fraction- 330 BRITISH CHEMICAL ABSTRACTS.— A. XV (i-k) ation and prolonged keeping of the individual 129).— CHPhPr-OH (H phthalate, m.p. 90— 91°) is fractions in PhMe at 0° causes the separation of a resolved through the quinidine salt, m.p. 168—169°, solid material which cannot he separated into its of the d-H phthalate, m.p. 53— 54°, [a]5461 —11-5° in components by crystallisation. When treated with EtoO, into the d-form, b.p. 115°/14 mm., m.p. 49°, NaOH and Me2S04 it yields a mixture of ethers, Ms-uu +32-2° in CGH6, and afterwards through the non-separable by crystallisation, from which 2- strychnine salt, m.p. 184— 185° (decomp.), of the methoxydiphenylene oxide (I), m.p. 98°, is isolated Z-H phthalate, m.p. 52—53°, [a]546x — 11° in Et20, after partial oxidation with Na2Cr20 7 in AcOH at into the Z-form, m.p. 48— 49°, [a]54G, —53-5°, [a]5S!)3 70°. Treatment of (I) with NH2Ph,HCl at 250° affords —45-9° in CGHG (cf. Levonc and Marker, A., 1932, 2-hydroxydiphenylcne oxide, b.p. 348°/75S mm., m.p. 1027). Vals. for other solvents and XX are given, 142— 143° (phenylurethane, m.p. 173°). The syn II. B.. thesis of (I) from 2-aminodiphenylcne oxide is re epfafZoCholesterol, a new isomeride of chole corded. Treatment of the mother-liquors from (I) s te r o l. E. A. E v a n s , jun., and R. Schoenheimer with NH20H,HC1 and BaC03 leads to the isolation (J. Amer. Chem. Soc., 1936, 58, 182).—Reduction of of 2-methoxyfluorenoneoxime, m.p. 174° after softening, cholestenone with Al(OPr+, gives epiallocholesterol (I), whence 2-methoxyfluorenone, m.p. 78°. Separation m.p. 84°, [a]?,4 +120-8° in CGH 6 (acetate, m.p. 82-5°), of the crude methylated product into its components and an isomeride [pptd. by digitonin whereas (I) is can also be effected by Na at 180— 200° but is com not]. (I) is reduced (catalytically) to a mixture of plicated by many by-reactions. H. W. epidihydrocholesterol and epicoprosterol, indicating that (I) contains C3*OH trans to C10,M o; an intense Phenyl ether series. IV. 4 : 4 '-Dithioldiphenyl Rosenheim reaction also indicates that the double ether and related compounds. C. M. Sijter and linking is between C1 and C5. (I) is dehydrated by P. II. Scrutchfield (J. Amer. Chern. Soc., 1936, dil. HC1 in 95% EtOH to a hydrocarbon, C27H44, m.p. 58, 54—55).—Reduction (SnCl,, AcOH-HCl) of (p- 79°, [a]j,3 —118-2° in CgHg, the absorption max. (244, S 0 2C1-CG1I4)20 (A „ 1931, 616) gives 4 : 4 '-dithiol- 235, and 229 mg) of which differ from those of chole- diphenyl ether, m.p. 103— 104° (Me2 ether, m.p. 81—- sterilene (Heilbron et al., A., 1928, 219). II. B. 81-5°), converted by CH2C1-C02K into the 4 :4 '- dithioglycollic acid, m.p. 165— 166° (chloride, converted Androsterone and related sterols. R. E. by A1C13 into a red tar), which could not be cyclised M a r k e r , F . C. W hitm ore, and 0 . K am .m (J. Amer. by oleum or C1S03H to a thionaphthen derivative. Chem. Soc., 1935, 57,2358— 2360).— a-Cholestyl chlor ide (I), m.p. 112°, is prepared (a) by reduction (H?, (+ )- and (—)-y-Phenyl-a-methylallyl alcohols. Pt02, AcOH) of cliolesteryl chloride, (6) from epi- J. K e n y o n , S. M. P a r t r id g e, and II. P h illips cholestanol (II) and PC15, and (c) from 3-cholestanol (J.C.S., 1936, 85— 88).— CHPlnCH-CIlO and MgMeBr (III) and S0C12; Walden inversion occurs in (a) and give df-y-phenyl-a-methylallyl alcohol (I), b.p, 129— (c). (I) is hydrolysed (KOAc in valeric acid followed 131°/11 mm., m.p. 33° [p-nitrobenzoate, m.p. 58—59°; by EtOH-KOH) to (II). P-Cholestyl chloride, m.p. H phthalate (II), m.p. 92—93-5°, prepared by the 102— 103°, obtained from (II) and S0C12 or (III) and action of o-C6H4(C0)20 on (I) (in C5H5N) or the PCI5, is similarly hydrolysed to (III). Oxidation Grignard complex], which could not be separated (Cr03, AcOH) of (I) gives tz-chlorocholanic acid, m.p. (distillation; partial fusion; crystallisation) into cis- 174— 175°, and a-chloroandrosterone, m.p. 170— 1713 and fraws-forms. Recrystallisation (from EtOAc) of (Butenandt and Dannenbaum, A., 1935, 413; cf. the cinchonidine salt of (II) affords the cinchonidine Ruzicka et al., ibid., 1125). H. B. salt, m.p. 179° (decomp.), of (+)-y-phenyl-a-methyl- Alkaline halogenation. Bromination of sod allyl 11 phthalate (III), m.p. 68-5°, [a]s46i +44-71° ium benzoate. P. L. H ar r is and J. C. Smith in CS2, -15-4° in EtOH (vals. for many solvents and (J.C.S., 1936, 168; cf. A ., 1934, 405).— BzOH (61 g.) different XX given). Hydrolysis of (III) with aq. in aq. NaOBr [2 litres from NaOH (40 g.) and Br Na2C03 gives (I); 5iV-NaOH and subsequent crystall (80 g.)] at 35°/7 days gives approx. 5 g. each of 0-, isation from CH„CL,-light petroleum lead to the m- (I), and p-CGH4Br-C02H ; the results vary owing (-f)-alcohol (IV ),“ n ip . 61°, [c+% + 28;3° in CS2 to rapid decomp, of NaOBr. Use of 2 equivs. of (p-xcnylcarbamate, m.p. 179— 180°; p-nitrobenzoate, NaOH (i.e., NaOBz : N a O B r= l) almost inhibits brom m.p. 41°; acetate, b.p. 132— 133°/9 mm.), reduced ination. In agreement with Stark (A., 1910, i, 234)> (Adams) to (-)-C II2Ph-CH2-CHMe-OH (V) (phenyl- (I) is the main product from BzOH and HOBr in H20- carbamate, m.p. 47—48°) (J.C.S., 1914, 105, 1124). H. B. The recovered H phthalate [from (III)] gives the Syntheses in the anaesthetic group. I. G. brucine salt, decomp, about 110°, of (—)-y-phenyl-a- San n a (Annali Chim. Appl., 1935, 25, 638—64 3 )+ methylallyl H phthalate, m.p. 6S-5°, [a]M61 —-44-53° p-chloroacetamidobenzoate, m.p. 115°, is prepared bv in CS2, and thence (as above) the (—)-alcohol, m.p. treating amesthesine (I) in CGHG with CH2CbC0Cl, and 61°, [a]5481 —28° in CS2. Comparison of the rotatory is converted (NHMe2) into Et p-dimethylglycylamulo- powers of (IV), (V), (-)-CHMeEt-OH, and (+)- benzoate (II), m.p. 95° (hydrochloride, m.p. 193°) ani ClUICirCHMo-OH shows that introduction of Ph (NHEt2) into the corresponding Et2 compound (IH)> [as in (IV) and (V)] causes [i¥] to be approx. doubled; m.p. 115° (hydrochloride, m.p. 211). (II) and (IB) the introduction of the Aa-double linking doubles [¥ ] are more sol. than (I) in H20, and have anmstbetic and reverses the sign. H. B. properties, which are being examined. E. W. • Resolution of phenyl-n-propylcarbinol. J. Preparation of a-naphthoic acid. D. J. K en yon and S. M. P ar tr id g e (J.C.S., 1936, 128— and F . C. W h itm o re (J. Amer. Chem. Soc., 1935, 57, XV (k) ORGANIC CHEMISTRY. 331 2727).—a-C]0H7,C02Et, obtained in 70% yield from by Quadrat-i-Khuda (A., 1930, 471), but different a-C10H/MgBr and Et2C03, is hydrolysed to the acid from Winzer’s acid (loc. cit.), which is ds-3-acetyl- (yield > 90%). ' H. B. 1:2: 2-trimethylcy dopentane-l-carboxylic acid (IV) (semicarbazone, m.p. 218°, indefinite). With 2 mols. Synthesis of alkeines derived from O-phenyl- of MgMel (II) gives dimethyleampholide and 3- lactic and -mandelic acid. E. P ł a z e k , Z. R o d e - isopropenyl-1 : 2 : 2-trimethylcydopeniane- 1 -carboxylic wald, and D. K r z y ża n ia k (R ocz. Chem., 1935, 15, acid (V), the m.p., 68-5— 70-5°, of which (Komppa. 300—304).— 0 -Phenylmandelyl chloride, b.p. 135°/0-6 A., 1908, i, 353) is raised to 87— 88° b y repeated mm., yields the tropyl ester, b.p. 208°/l mm. (picrate, crystallisation, probably by conversion into the 3- m.p. 171°; picrolonale, m.p. 187°), with tropine, and impropylidene acid (VI) ; ozonolysis of (V) gives a $-dimethylaminoethyl O-phenylmandelale, b.p. 148— 3-acetyl-l : 2 : 2-trimethylcydopentane-l-carboxylic acid 150°/0-2 mm. (picrolonate, m.p. 141— 142°), with (semicarbazone, m.p. 220— 221°) not identical with XEt2-CH2-CH2-OH. KOPh and CHMeBr-C02Me (2 either (III) or (IV), whereas (VI) gives an indefinite hr.; 100"), followed by hydrolysis of the product oil with 03. The results of Houben et al. (A., 1908, with EtOH-KOH, yield 0 -phenyl-lactic acid (I), m.p. 539) on the interaction of CH2Ph-MgCl on (II) are 114°, the chloride, b.p. 115°/20 mm., of which affords confirmed and, in addition, are isolated an Et phenyl- thetropyl, b.p. 140— 150°/0-6 mm. (picrate, m.p. 175°; acetyltrimethylcydopentanecarboxylate, b.p. 217—218° picrolonate, m.p. 200— 202°), and ¡1 -dimethylaminoethyl [converted into the dicyclic compound (VII) by hydro- esters of (I), m.p. 75° (picrate, m.p. 113°; picrolonate, lysis], and an Et (1-phenyl-a-benzyl- m.p. 148°). R . T. CH2 c i i — ę o ethylidenelrimethylcydopenlanecarb - ¿Mc2 ĆHPh oxylate, b.p. 230—234°/9 mm. Dehalogenation of fi-bromo-acids. IV. (3- CMe-CO k (acid, m.p. 166— 167°). Santenic Bromophenylpyruvic acid. B. So bin and G. B. (VII.) Bachman (J. Amer. Chem. Soc., 1935, 57, 2458— anhydride (VIII) with MgMel gives 2460).— p-Bromophenylpyruvic acid (I), m.p. 103— 104° ds-3-acetyl-2 :3-dimtlhylcydopentanc-1 -carboxylic acid. (from CH2Ph-C0*C02fI and Br in CC14), is converted m.p. 63—65° (semicarbazone, m.p. 218°), not identical by boiling with H 20 or shaking with Ag20 in H 20 with cis-3-acetyl-l : 2-dimethylcydopentane-\- carb into CH2Ph-C02H (II) (yield 77 and 94%, respect oxylic acid, m.p. 95— 96° (semicarbazone, m.p. 219°), ively) ; the following reactions are considered to obtained by Winzer’s method. With 2 mols. of occur: CHBrPh-COCOJI-> C02+HBr+CHPh:c:0; MgMel (VIII) affords dimethylsantolide, b.p. 136— CHPh:C:0+H20 -> CH"2Ph-C02H. GII2Ph-C02Et is 138°/15 mm., and a trace of an unsaturated acid. similarly obtained in 36% yield from (I) and J. W . B. Ag20 in EtOH. (I) and aq. Na2C03 give benzoyl- Preparation of tetrachlorophthalic acid. J. S. carbinol (III) (by rearrangement of the intermediate Salkin d and M. B elikova (J. Appl. Chem. Russ., OH-CHPh-CHO); with aq. NaHC0 3, a mixture of 1935, 8 , 1210— 1213).— o-C6H4(CO)20 at 240— 250° (II) and (III) and a little of an acid, C^H^Oj, m.p. and Cl2 (in presence of 3% of Fe) yield tetrachloro 213—219° (Ac derivative, m.p. 162— 163°), result. phthalic acid in 90—95% yield. The product loses Tars (free from CHPhlCiO) are produced from (I) H 20 of crystallisation (1-5 mols.) at 100°, and is con and GH-N or NPhMe2. H. B. verted into the anhydride at 110° R. T. Lithium phthalate.— See this vol., 282. General reaction fo r the p rep aration of keto- ncids, unsaturated acids, and disubstituted lact Synthesis of hydrogenated phenanthrenes. ones. I I . G. Kom ppa and W . R o h rm a n n (Annalen, E. E. Gru ber and R. A dams (J. Amer. Chem. Soc., 1936, 521, 227—242).—apoCamphoric anhydride 1935, 57, 2555— 2556; cf. Barnett and Lawrence, (I) (1 mol.) and MgMel (1 mol.) at —15° (cf. A., A., 1935, 1243).— 1 :1 '-D ihydroxy-1: l'-dicycfohexyl 1934, 650) give, after esterification, Et ds-3-acetyl- (from cyc/ohexanone, Mg, and HgCl2 in C0H c) is dehydrated (10% H 2S04) to di-AI:1'-cycfohexene, b.p. 7.) \'^m^hylcyc\opentanc.-l-carboxylate, b.p. 122— 101—102°/5-5 mm., which with maleic anhydride mo ^ mm’’ IkoI^TocI as its semicarbazone, m.p. 14, 142-5°, not identical with the trans-ester [semi- in C8H 6 gives the anhydride, m.p. 122-5— 123-5°, wrbazone, m.p. 196— 200° (dccom p.); semicarbazone of dodecahydrophenanthrene- 9 : 10-dicarboxylic acid, w the free acid, m.p. 191° (deeomp.)] obtained by m.p. 242° (Maquenne block) (imide, m.p. 182— 183°), Winzer’s method (A., 1890, 1152) by the action of and with CH2ICH-GHO in C6HG at 50—60° affords tm.\a(C02E t)2 on (I) in C6H 6 to give malonyhpo- dodecahydrophenanthrene-3-aldehyde, b.p. 136— 137°./ ca,nphoric anhydride, m.p. 63-5— 64°, b.p. 216°/12 4 mm. (semicarbazone, m.p. 179— 180°). H. B. *mn., and subsequent hydrolysis with NaOEt-EtOH. Synthesis of l-methylcyclopentane-l : 3-di- ith 2 mols. of MgMel (I) affords dimethylapo- carboxylic acid (1 -methylnorcamphoric acid). Mmpholidc (45% yield), m.p. 102— 103°, and 3- N. J. T oivonen, A . J ohn, E. Sa in io , and T. K uusinen li0propylidene-2 : 2-dimethylcydopentane-T-carboxylic (Suomen Kem., 1935, 8 , B , 46— 47).— Et3 2-methyl- actj (35% yield), m.p. 103— 104° (gives 2 : 2-dimethyl- cyciopentanone-2 : 4 : 5-tricarboxylate with glycerol- cz/eiopentanone-3-carboxylic acid on ozonolysis). H 20 at 170— 200° affords Etz 2-methylcydopentanone- • inularly d-camphoric anhydride (II) with MgMel 2 : 4-dicarboxylate, b.p. 153— 156°/11 mm., which with 1 m°l-) gives Et ds-3-acetyl-2 : 2 : 3-trimethylcydo- K-IIg in EtOH-dil. H 2S04 gives Et2 2-methylcydo- pentane-1 -carboxylale, b.p. 133—135°/8 mm. (semi- pentan-l-ol-2 : i-dicarboxylale, b.p. 126— 128°/0-5 mm. f r m ZOne- m'P‘ IT7°), hydrolysed to the acid, + H 20 [acid, m.p. 172— 174°, converted by PIBr followed 76—78° (semicarbazone, m.p. 223—224°), by Zn in AcOH-HCl into cis- (cf. this vol., 339) and probably identical with the acid, m.p. 73°, obtained trans-1 -methylcydopentaned : 3-dicarboxylic acid, m.p. X Y (k, I) 332 BRITISH CHEMICAL ABSTRACTS.— A. 114— 115°, the former of which with PC15 and excess pound, m.p. 60°, together with (IV); AcCl reacts of Br gives the 3-Br-derivative, m.p. 136— 138°]. similarly, as do other substances. It is concluded h J. L. D. that the Perkin synthesis depends on the intermediate Condensation of bindone with a-halogeno- formation of acid—salt or anhydride—salt compounds carboxylic esters. G. W an ag (Ber., 1936, 69, [B], (which are decomposed by H20), on their stability 189—194; cf. A., 1935,623).—Bindone [(I) X = R = H ] at the temp, of reaction, and their solubility in the condenses with CH2Cl-C02Et in boiling EtOH con medium, and on the homogeneous presence in this taining K2C03 to Et bindonylacetate, [(I) X=H; of substances capable of absorbing H20. I he R=CH„-CO„Et], m.p. 109°, converted by Br in boiling formation of Ac and imide derivatives of aldehydes 2 CHClj into Et impedes the reaction. E. W. W. C«H v i> > C O bromobindonylacetale Removal of hydrogen and acid radicals from ^CXR/ (II) f(l)X=Br; R = organic compounds by bases. II. Removal of (J. Amer. Chem. Soc., 1935, 57, 2500—2503).—2- with either CHNa(C02Et)2 or CN-CHNa-C02Et and Ammovanillin is converted (Sandmeyer) into 2-iodo- complete hydrolysis of the products. Reduction of vanillin (I), m.p. 155— 156° [Ac derivative, m.p. hexahydroisophthalic anhydride with H2-Ni at 280— 70—72°; oxima (+ 0-5H 2O), softens ca. 122°, m.p. 290° affords the lactone, b.p. Ill—113°/8 mm fp (anhyd.) 142-5— 143-5° \ semicarbazone,m.p. 199—200°; -5 ° to -10°, of 3-hydroxymethylcyc/ohexane-l- g-nitroplienylhydrazone, m.p. 211— 212°; benzidine carboxylic acid, also obtained by the action of I at condensation prodwci, decomp. ca. 232— 233°], methyl- 150° on the Ag salt of (IV). dicyclo-[ 1:2:3]- ated (Me2S04, aq. KOH) to 2-iodo-2 : 4-dimethoxy- Octanone (V) (loc. cit.) [oxime, m.p. 66— 67°; semi- benzaldehyde, m.p. 82°. 5-Aminovanilhn (hydro- carbazone, m.p. 183— 183-5° (corr.), and not 189— chloride; slannichloride; ON-Ac,, m.p. 174— 176°, 190° as previously recorded] is best obtained by dis and ON-Rz2, m.p. 161— 162°, derivatives), prepared tillation of the Ca salt of (IV). Oxidation of (V) with by reduction (&nCJ2, cone. HC1, EtOH) of the N02- HN03 cat 50° gives cfs-hexahydroi«sophthalic acid, compound, similarly gives 5-iodovanillin, m.p. 179— and reduction (Na-EtOH) affords dicyclo-[l : 2 : 3J- 180° [Ac (II), m.p. 105— 106°, and Bz, m.p. 135-5— octanol, b.p. 200—205°, m.p. 170° (corr.) (phenylurelh- 136-5 , derivatives; oxime, m.p. 178— 179°; semi- ane, m.p. 133° (corr.)], the chloride, b.p. 73— 75°/14 carbazone, m.p. 205—205-5°; p-nitrophcnylhydrazone, mm., m.p. 43—45°, of which is reduced (Na-EtOH) m.p. 242— 243° (decomp.); benzidine condensation to dicyclo-[l : 2 : 3]-ockme, m.p. 133— 134°. product, m.p. 232° (decomp.); M e ether, m.p. 69— j . \y p 70°], which is identical with the iodovanillin of Carles P reparation of m -nitr oacetoph enon e. V. G. (A., 1872, 708). (II) or 5-iodo-4-acetoxy-Z-methoxy- M org a n and H. B. W a tso n (J.S.C.I., 1936, 55, bcnzylidene diacetate, m.p. 132— 133°, with fuming 29— 30t).—A method of nitration, using UN0.,— io^P3 ap < Sives derivative, m.p. 124— H2S0 4, is described, differing in some details from the 1-5 , of b-iodo-2-nitrovanillin, m.p. 146-—147° [oxime, procedure given in “ Organic Syntheses,” 1930, 10, m.p. 128 129 ; semicarbazone, m.p. 187— 188° 74, and leading to a better yield of a very pure product, (decomp.); p -nitrophenylhydrazone, (+0-5EtOH), The m.p. of m-nitroacetophenono is 79-5° (corr.). m.p. 228—230° (decomp.); benzidine condensation product], reduced [Fe(OH)2, aq. NH3] to 5-iodo-2- Synthesis of mixed acetones by means of minovanillin (III), m.p. 155°. (I) and I in AcOH- ethyl malonate. A. G ia c a lo n e [in part with F. NaOAc give 2 : 5-di-iodovanillin, m.p. 200° [Ac deriv- Russo] (Gazzetta, 1935, 6 5 ,1127— 1138).— Acyl chlor- ative, m.p. 127— 128°; oxime, m.p. 174-5— 175-5°; ides react with CHNa(C02E t)2 (I) to form acyl com- xmicarbazone, m.p. 235° (decomp.); p -nitrophenyl- pounds of type R-C0-CH(C02E t)2 (II), and acyl fojArazone, m.p. 252—253° (decomp.); benzidine derivatives of the enolie form" of these, viz., condensation product; M e ether, m.p. 94°], also pre- R-C02-CR:C(C02E t)2 (II). (II) and (III) with NH 2Ph, pared (Sandmeyer) from (III). II. B. NHPh-NH2, or NH2OH yield CH2(C02E t)2 and „ , R-CO-NHR'. BzCl and (I) give Et2 benzoylmalonate, synthesis of Reaction between (A) phenyl a3-dibromo-G- anthrene, m.p. 114— 115°, dehydrogenated (Pt-black phenylethyl ketone and azides, (B) phenyl ag-di- at 310— 320°) to 9-phenanthrol and dehydrated (ZnCl2 bromo-B-m-nitrophenylethyl ketone and sodium at 180°) to hexahydrophenanthrene, b.p. 125— 126°/ azide. V. A. K u zm in and N . I. Z e m l ia n sk i (Mem. 2-5 mm., which is similarly dehydrogenated to phen Inst. Cliem. Ukrain. Acad. Sci., 1935, 2 , 183— 190, anthrene. ai-Octahydrophenanthrene (A., 1933,1042) 191— 194).— (a ) NaN3 and CHPhBr-CHBr-COPh in is oxidised (Cr03, AcOH) to a mixture of (VIII) and aq. C0Me2 (12 hr. at 60— 65°) yield a Br-containing an isomcride ( ?) (oxime, m.p. 186-5— 187-5°). The oil, and a monoazide of Ph styryl ketone, m.p. 64— 65°, Grignard reagent from impure 1 - chior o - 2 - benzyleyclo- both decomposed by H 2S04 with evolution of N2. liexane, b.p. 85— 100°/0-2 mm. [from (III) and S0C1, (b ) w -N 0 2-C8H4*CHBr-CHBr-COPh and NaN3 inin NPhMe,], and C02 give cis- (IX), m.p. 86— 88°, aq. EtOH or COMe2 (12— 14 hr. at 65— 70°) afford a and trans- (X), m.p. 133— 134°, -2-benzylhexahydro- monoazide, m.p, 76—77° (decomp.) of Ph 3-nitro- benzoic acids. The Grignard reagent from l-5romo-2- styryl ketone. R. T. benzyloyclohexane, b.p. 120°/0-4 mm. [from (III) and PBr3 in cold CC14], with ClC02Et affords (after hydro New route to hydroaromatic ketones related lysis with aq. EtOH-KOH) (X), probably 4-benzyl- to anthracene and phenanthrene. J. W. Co o k , hexaliydrobenzoic acid, m.p. 140— 141° (the formation C. L. H e w e t t, and C. A. L aw ren ce (J.C.S., 1936, of which involves a migration), and 2 : 2'-dibenzyl- 71— 80).— 2-ChloroM/c/ohcxanol and CH2Ph-MgCl (I) dicyclohexyl, m.p. ISO—181° (cloudy; clear at lead (by ring-contraction) to cyclopentylbenzylcarb- 191°). o-CH2Ph-C6H 4-C02H is reduced by Na and inol, b.p. 120° (bath)/0-l mm., m.p. 30° (3 : 5-dinitro- amyl alcohol to (X) and by H 2 and PtO, in AcOH to benzoate, m.p. 100-5— 101-5°), oxidised (Cr03, AcOH) o -hexdhydrobenzylbenzoic acid, m.p. 95-5— 96-5° [oxid to phenylacetylcycZopentane (semicarbazone, m.p. ised (alkaline KMn04) to o-G0H 4(CO2H )2]. (X) with 117— 118°). cyc/oHexene oxide (II) and (I) give cold conc. H2S04, or its chloride with A1C13 in cold 2-benzylcycZohexanol (III), m.p. 76-5— 77-5° (3 : 5-di- CS2, leads to trans-hexahydroanthrone (XI), m.p. 109— nitrobenzoate, m.p. 133— 135°) (oxidised to 2-benzyl- 109-5° (oxime, m.p. 174-5— 175-5°) ; (IX ) similarly cycMiexanone), and a mixture (A ) of cis- and trans- gives cis -hexahydroanthrone (XII), m.p. 79—80° 2-chlorocycZohexanols. The Mg(CH2Ph)2 present in (cloudy; clear at 85°) (oxime, m.p. 150— 151°), and the Grignard reagent thus appears to be more reactive some (X I). Dehydrogenation (Pt-blaclc at 300°) of than the CH2Ph-MgCl [responsible for the production (XI) and (XII) affords anthracene. A mixture of of (A)] towards (II). 2-Phcnylc?/cZohexanol (IV), b.p. (XI) and (XII) is formed from either (IX) or (X) 153— 154°/16 mm., m.p. 56— 57° (lit. 54— 55°) (3 : 5- and conc. H 2S04 at 100°; interconversion of the dinitrobenzoate, m.p. 121— 121-5°), prepared from (II) ketones probably occurs through an intermediate and LiPh in Et20 and N2, is oxidised (Cr03, AcOH) enolic form. to S-benzovlvaleric acid and 2-phcnylcj/c/ohcxanone [By R . R obin son .] Contrary to the previous (V). The poor yield of (IV) from (II) and MgPhBr statement (A., 1934, 75), cyc/ohexene oxide and (Bedos, A., 1926, 508) is due to cycZopentylcarbinol CH2Ph-CH2-MgBr (X III) give cycZopentyl-p-phenyl- formation. 2-Bromoacetyl-Q: IQ-dihydrophenanthrene has m.p. ones. E. P. K o h le r, M. T is h l e r , and H. P otter 93-5—95°. 9 : 10-Dihydroanthracene is obtained in (J. Amer. Chem. Soc., 1935, 57, 2517— 2521).— The nearly quant, yield by reduction (H ,; Cu chromite; compound, [CHPh2• CII• CO• 6 6H 2Me3 ]MgBr (A), ob- ICO0) of anthracene. H. B. tainedfrom mesityl stju-yl ketone (I) and MgPhBr, with BzCl gives < 96% of yy-diphenyl- afford CH2PhBr and 10-bromo-9-bromomethylan- 1 : 2-dicarboxylic acid. Treatment of (I) with dil. thracene. The formation of (II) and MeCHO from KOH-EtOH at 15—20° gives the corresponding acid, 10-hydroxy- 10-ethylanthrone (III), m.p. 107° [from which passes with loss of C02 into cis-1 : 3-diketodeca (II) and MgEtBr in Et20-C BHB], and AcOH-conc. hydronaphthalene (III), m.p. 124— 125° (dioxime, m.p. II2S0 4 in 0 2 supports the view that 10-ethylidene- 152— 153°; methylenedi-cis-1 : 3-diketodecahydronaph- anthrone (IV), b.p. 245— 247°/20 mm. [obtained when tlialene, m.p. 147— 148°). Oxidation of (III) with (III) is distilled at atm. pressure in N2], reacts as NaOBr leads to cw-o-carboxyc?/c/ohexanoneacetic acid, 9-hydroxy-10-vinylanthracene. The ready oxidation m.p. 146°. (Ill) is isomerised to (II) by treatment with (0,) of (IV) to (II) and vinyl alcohol through the per boiling 20% KOH-EtOH. Hydrolysis of (I) with oxide, and the oxidative decomp, of (IV) to (II) and boiling 15% HC1 (cf. Ruzicka et al., A., 1931, 1302) C2H2 during attempted distillation at atm. pressure, followed by distillation of the product in vac. gives an are thus satisfactorily explained. Anthraphenone, acid, o-CBH?0Ac-CH2-CO,H or o-CH2Ac-CBH10-CO2H, which resembles an a(3-unsaturated ketone, is reduced m.p. 52— 53° {A Differentiation of sterols from other poly- 310—340°) of cinobufagin (I), C25(2fi)H32(34)0 B (cf. A., terpene alcohols. Structure of lanosterol and 1934, 412), gives a little of (probably) methylc?/cio- onocerol. H. S c h u lz e (Z. physiol. Chem., 1936, pentenophenanthrene. (I) and (probably) other bufa- 238, 35—53).— “ isoCholesterol ” (I) (modified prep.), gins appear to contain the same ring system as the m.p. 136— 137°, [a]n +61-9° in CHC13, or its acetate sterols and cardiac aglucones. H. B. with Se at 320— 335° gives 1:2: 8-trimethylphen- Carotenoids of purple bacteria. II. Rhodo- anthrene, a hydrocarbon, m.p. 212— 213°, and an violascene. P. K a r r e r and U. S olm ssen (Helv. alkali-sol. substance,, (?) a hydroxytrimethylphen- Chim. Acta, 1936, 19, 3— 5 ; cf. this vol., 2 48 ).- anthrene {Me ether, m.p. 179— 180°, b.p. 215— 230°/14 Rhodoviolascene is C42HB0O2. It contains 2 OMe and mm.), hut (I) is largely unchanged by Pt at 300°. absorbs 26 H when catalytically hydrogenated. It Onocerol (II) (modified prep.), C30H 50±2O2, dimorphic, affords COMe2 when treated with 0 3, and hence is m.p. 232° and 202°, [a]£ +5-04° in C5H 5N [diacetate probably a (OMe)2-derivative of lycopene (I) or (III), m.p. 224°, [a]!» + 2 8-3°; dibenzoate, m.p. 237— similar hydrocarbon. It appears to be optically 238°, [a]“ +21-5°; dichloroacetate, m.p. 238— 244°, inactive in C6H6. It does not react with NH 20H or [a]},9 + 1 1 4 °; di-3 : 5-dinitrobenzoate, m.p. 291° (de give a H2-derivative by short treatment with Zn- comp.), [«][[ +19-3°; dianisate, m.p. 232— 234°, A cO H -C 5H 5N. The bacteria contain also rhodo- [a]];2 + 9 °; all [a] are in CHC13], gives no PhCHO on vibrene, but rhodopurpurin is possibly identical ozonisation (cf. lit.) and does not resemble CHgiCHPh or neoergosterol in absorption spectrum, reacts with with (I). H. W. 2 mols. of B z 0 2H, and is difficultly reducible. (Ill), Preparation and reactions of tertiary tetra- however, readily absorbs 2H (Pt0 2 in AcOH). With hydrofurylcarbinols. A. L. B o u n c e , R. H. Ward- Se at 300—320° (II) gives 1:2:5: 6-C10H 4Me4. (I) lo w , and R . C o n n o r (J. Amer. Chem. Soc., 1935, 57, and (II) thus do not contain a q/cZopentanophen- 25511—2559).—Reduction (H 2 at 100— 130 atm., antlirene skeleton (the criterion of sterols), but are Raney Ni, 150°) of Et furoate (I) gives 93-3% of Et poly terpenoid. R- S. C. tetrahydrofuroate (II), b.p. 18S—190°/740 mm., Lignin. XI. Pine wood and thiol acids. B. which with MgPhBr affords dijrhenyl-2-tetrahydro- H o lm b e r g (Ber., 1936, 69, \E], 115— 119; cf. A., furylcarbinol (III), m.p. 79— 80°, dehydrated (anhvd. 1935, 1502).— The treatment of pine wood with thiol- M gS04) to 2-benzhydrylidenetetrahydrofuran (IV), b.p. acetic, a-thiolpropionic, a-thiolisobutyric, thiolsuc- 195°/10 mm., m.p. 107-5— 108-5° [ozonolysis products, cinic, and a-thiol-a-methyjsuccinic acid is described, COPh2 and y-butyrolactone (V)]. Prolonged treat but it is difficult to find a theoretical basis for the ment of (III) with MgPhBr (3 equivs.) in xylene does interpretation of the results. The change appears to not cause ring fission; hydrolysis and removal of the proceed in two stages, during the first of which the xylene gives (IV). 2-Tetrahydrofuryl-diethyl-, bp. lignin reacts with the SH-acid giving acids contain 200—203°/740 mm., and -di-n-butyl- (VI), b.p. 151— ing S which in the subsequent stage become sol. in 152°/24 mm., 251—252°/740 mm., -carbinoh, best H20 or alkali. H. W. prepared from (II) and MgRBr, are also obtained by Action of ethylene oxide on wood and lignin. reduction of 2-furyl-diethyl-, b.p. 92—95°/14 mm., II. N. I. N ik itin and T. I. Kulneva (J. Appl. and -di-n-butyl-, b.p. 128— 131°/14 mm., -carbind, Chem. Russ., 1935, 8,1176— 11 S3).— Willstiitter lignin respectively [from (I) and MgRBr], Dehydration treated with 18% NaOH and (CH2)20 (I) (2 hr. at (MgS04-K 0II) of (VI) gives an inseparable mixture. 70°, or 2 days' at room temp.) yields amorphous (V) is obtained in 10% yield by reduction (H2 at hydroxyethyl-lignin (II), containing 38-76% of OEt-f- 90—130 atm., Cu-Cr-BaO catalyst, 250°) of Et OMe, and 5-18% of acetylatable OH. (I) is eliminated succinate. (V) and N2H4,H20 give a little succin- from (II) by HI at 135— 140°, but not by hydrolysis hydrazide and (mainly) y-hydroxybutyrhydrazide, m.p- with 5% H„S04 (5 hr. at the b.p.), which, however, 89— 90°. H. B. transforms 21-6% of (I) into a H 20-sol., non-reducing Dicarboxylic acid esters of tetrahydrofurfuryl product. A product apparently identical with (II) alcohol. J. N. B o r g lin (Ind. Eng. Ghem., 1936, is obtained from wood by treatment successively with 28, 35— 36).—Tetrahydrofurfuryl alcohol reacts (48 NaOH and (I), followed by hydrolysis with 5% hr.; 170— 190°) with the calc, amoun tof terpinene, HoS04. The hygroscopieity and swelling capacity of maleic, maleic, or phthalic anhydride to form the (II) are > those of lignin. R. T. corresponding acid ester or di-ester. F. N. W. Elemic acid from elemi resin. VIII. fi-Elem- on ic acid. M. M. Mladenovi6 and I. B erk eS Production of furfuraldehyde from xylose (Monatsh., 1935, 67, 36— 41; cf. A., 1935, 495).— solutions by means of hydrochloric acid-sodiuxn p-Elemonic acid (I), m.p. 220-5° [modified prep, from chloride systems. E. I. F u lm e r, L. M. C h r i s t e n cc-elemolic acid (II); oxime, m.p. 218°, hydrolysed to sen , R . M. H ix o n , and R . L. F o s t e r (J. Physical (I) by HN02], gives (Pd-C in AcOH) a H4-acid (III), Chem., 1936, 40, 133— 141).— Xylose-HCl-NaCl mix m.p. 244° [oxime, m.p. 245°, hydrolysed to (III); tures were refluxed with PhMe and the furfuraldehvde also obtained by hydrogenation of crude (II)], and (I) yields determined from the d of the resulting (I)" is identical with S-elcmic acid (A., 1932, 749). PhMe solutions. The yield of (I) diminishes as the R . S. C. concn. of xylose increases, being twice as great for Toad poisons. VIII. Dehydrogenation of 4% as for 60% xylose. It increases with increasing cinobufagin. H. J e n s e n (J. Amer. Chem. Soc., concn. of NaCl, i.e., it is a linear function of the pm 1935, 57, 2733— 2734).— Dehydrogenation (Se at or of the activity coeff. of the acid. M. S. B. XVII (a, b) ORGANIC CHEMISTRY. 341 Terpene furoates. J. N. Borglin (Ind. Eng. 49— 50°, 2 : 3-di-o-, m.p. 105-7— 106-2° (corr.), -in., Chem., 1936, 28, 31— 32).— Borneol and fenchyl m.p. 84-2° (corr.), and -p-, m.p. 56—57-2° (corr.), alcohol heated (40 hr. ; 160°) with furoic acid give, -lolyl-, 2 : 3-di-p-chtorophenyl-, m.p. 152— 153° (corr.), respectively, bornyl, b.p. 275°/760 mm., and fenchyl 2 : 3-di-p-anisyl-, m.p. 79— 80-2° (corr.), 2 : 3-di-a- furoatc, b.p. 275°/760 mm., hydrogenated (Pt02) to naphthyl-, b.p. 255—258°/3—4 mm., 2 : 3-dixenyl-, fenchyl tetrahydrofuroate. E. N. W. m.p. 144-5— 146° (corr.), and 2 : 3-dibenzyl-, m.p. Orientation in the dibenzfuran series. W. G. 62-2° (corr.), -dioxans are prepared from 2 : 3-dichloro- Bywater, E. W . Sm ith , G. E. B r o w n , and H. dioxan (I) and MgRX. The main product from Gilman (Proc. Iowa Acad. Sci., 1934, 41, 166).— (I) and MgMeBr, MgEtBr, or MgBuBr is p-dioxen f1LT ,p U 1 Sulphonation and chlorination take place at position (ii). o < CH|_ CH2> 0 , b.p. 94-2°/749-9 mm. [ozono- 2, nitration at position 3, whilst metals attack in position 4. Rules governing the position of entry of lysisproducts, HC02HandC2H4(0 H)2]; smallamounts a second substituent are given. Sulphonation of of the 2 : 3-dialkyld“ioxans (Et2, b.p." 164— 175°/747-9 dibenzfuran-2-sulphonic acid yields the -2 : 8-disul- rum.; Bu2, b.p. 120— 122°/16— 17 m m.; not charac phonic acid ; nitration of 2 -bromo- and bromination terised) are also produced. (II) and Hal in CC14 of 3-nitro-dibenzfuran give the same 7-bromo-3-nitro- at 0 ° give (I) and 2 : 3-dibromodioxan, m.p. 69— 70° dibenzfuran. Bromination of 3-acetamidodibenzfuran (softens at 64°). (I) and HC1 at 0° afford chlorodioxan welds 2 - bromo-3 - a ?ninodibenzfuran. Ch. A bs. (r) (III), b.p. 62—63°/14 mm., which is unstable even Constituents of Matteucia orientalis- II. C on at room temp.; in presence of a little BiCl2, a poly- mcridc of (II) results. (Ill) and MgPhBr give stitution of demethoxymatteucinol. S. F ttjise phenyldioxan, m.p. 45— 46°. Chlorination of dioxan and T. N ishi (J. Chem. Soc. Japan, 1934, 55, 1020— (IV) to (I) is considered to occur thus : (IV) -> (III) -> 1023, 1024— 1027; cf. A., 1935, 91).— II. Condens ation of dimethylphloroglucinol with cinnamoyl chlor (II) - » (I)- H. B. ide affords 5 : 1-dihydroxy-G : 8-dimethylJlavanone, m.p. Dimorphism of rotenone. E. L. G ooden and 202-7—203°; although the m.p. is lowered about 1° C. M. Sm ith (J. Amer. Chem. Soc., 1935, 57, 2616— on admixture with demethoxymatteucinol, thé ident 2618).—Rotenone exists in two enantiotropic forms, ity of all other properties leads to the conclusion m.p. 163° (stable) and approx. 180° (unstable); that they are identical. Ch. A bs. (r) optical data are given. H. B. General method for synthesis of flavonol de 6 : 7-Benzoylene-j3(V-benzofurans from 1 : 5-di- rivatives. T. Oy'amada (J. Chem. Soc. Japan, 1934, aroylanthraquinones. R. Scholl and S. H ass p, 1256—1261).—Elavonols are formed when o- (Ber., 1936, 69, [E], 194— 197).— 1 : 5-Di-m-xyloyl- hvdroxyehalkones are treated with H20, in the pre anthraquinone is transformed by Na2S20 4 in boiling sence of dil. alkali. Several examples are given. 80— 85% EtOH in absence of air into 9-hydroxy- Mlioxyflavone has m.p. 114°. Ch. Abs. (r) 1 : 5-di-m-xyloylanthr-10-one, m.p. 230° in a preheated bath (pyridinium salt; ji-bronwbenzoate, m.p. 288°), Preparation of hom ogeneous anthocyanins by which in indifferent media or when subjected to cnromatog-raphic analysis. P. K arrer and F. M. CBH3Me, pressure passes into an equili awy^ (Helv- Cllim- Acta> 1936> 19> 25—28).— brium mixture with 1 : 5-di- j, y'3- activated by cautious treatment with tap- 40 0 " m-xyloylanthraquinol. It is 29, is a suitable adsorbent for anthocyanins. converted by boiling AcOH nice the slightly basic material partly converts or conc. H,S0 4 at 15—20° e oxonium salt into colour base, carbinol base, into 2-m-xylyl-G : 7-6'-m- pnenolbetaine, a given pigment does not necessarily xyloylobenzoylene - ¡3(3' - benzo - pro uce a homogeneous zone. Pæonin, obtained j ii furan (I), m.p. 193°, which to Willstâtter et al. (A., 1915, i, 288), is (I.) 0 ■C-C6H3Me2 is not reduced by Na2S20,, nf-i! contain cyanin; the colour of a solution and NaOH and suffers fission of the furan ring with I ? l)ure material and FeCL in EtOII is unchanged hot C5H 5N-NaOH. H W. addition of H ,0 . H. W° Tetrahydroxydibenzothianthrendiqriinone ; of cotton flowers. II.—See this vol., chemistry of naphthazarin. K. B rass, R. P elu - ger, and K. H onsberg (Ber., 1936, 69, [B], 80— 87).— Sethis °1 arjuna- I. Arjunin.— The interaction of Ha2S (1-5 mols.) with dibromo- naphthazarin (I) does not proceed as smoothly as with 2 : 3-dichloro-a-naphthaquinone, but gives m îanal^ ic chlortoation of dioxan. J. J. K ucera N aJt Na3, and Nas derivatives converted by dil. 57 o-ijf Caepentek (J- Amer. Chem. Soc., 1935, acid into tetrahydroxydibenzothiardhrendiquinonc (II; litflà o AT- —dioxan and Cl, in presence of a R =S), m.p. > 300°, best obtained from (I) and Na2S derh-it \ at 90° S‘ve 9C>'6% of the 2 : 3-Cl2- (1 mol.) at 200°. (II) cannot be acetylated, but is nf , *. iTC’ c“ ‘°rinated further (in absence or presence ot catalyst) at 145° to 8 3 -8 5 % of a mixture of s- reduced and then benzoylated to octabenzoyldibenzo- thiantliren, m.p. 283°. It is not attacked by cold “ ' ^ aU(I 2-methylpyridine, whereas 5-aminopyridine-3-carb- Br from which a homogeneous material could not be oxylic acid is unaffected. 4 -Chloropicolinic acid and isolated. 2 : 3-Dibromonapkthazarin is best obtained 4 -chloro-2-aminopyridine are resistant to irradiation, Me whilst pyridine-2: 3-dicarboxydic acid and -3-carb- oxy'diethylamide are completely unchanged. The OH 0 behaviour of -CHO in 5 : 6-dichloropyridine-3- and 4 : 6-dichloropyridine-2-aldehyde is uncertain. 4-Iodo- pyridine-2-carboxylic acid yields I formed by photo oxidation of primarily-formed H I. Et2 2 : 6-dimethvl- nyridine-3 : 5-dicarboxvlate is rapidly hydrolysed. 1J ‘ H. W. A lkylated ben zen eazoam inopyridin es.— Sec B., by the action of a slight excess of Br on naphthazarin 1936, 124. in AcOH; it does not react with GTI2N2 or Me2S04, Aldehydes of the indole series.— See B., 1936, hut is transformed by £>-C6H 4Me-S 0 3Me and anhyd. 140. Na„C03 in o-C6H4Cl2 at 170° into (III) Under Condensation of indolealdehydes with hippuric similar conditions naphthazarin affords the 31 e2 ether, acid. E. R e s t e l l i (Anal. Asoc. Quim. Argentina, m.p. 160°. Reasons are advanced for assigning 1935, 23, 58— 62).— Indolc-3-aklehyde and hippuric the above constitution to (III) and for considering acid, when heated with NaOAc in addition to Ac20, its reduction product to be 2 :3-dibromo-l . 4- give' 2-plienijlA-{V-acetylindolylidene)oxazolone, m.p. dihydroxy-5 : 8-dimetlioxynaphthalenc. II. W. 205° (2’-Me derivative, m.p. 185°). E. R. G. Syntheses by means of magnesylpyrroles. Catalytic decomposition of ethyl propyl ketone Series II. X X I. B. O d d o and G. A cuto (Gaz- phenylhydrazone. A. E. A r b u s o v and I. A. zetta, 1935, 65, 1029— 1036).— Mg 2 : 5-dimethyl- Z a itz e v (Trans. Butlerov Inst. Chem. Tech. Kazan, pyrryl bromide in Et20 with AcCl yields 3-acetyl-l - 5- 1934, No. 1, 33— 38; cf. A., 1932, 1236).— A substance, dimethylpyrrole, m.p“ 89° [.semicarbazone, m.p. 234° C12H 15N, b p 167°/15 mm. (picrate, m.p. 144°), is (decomp.)]. The 3-propionyl, m.p. 102-5° [semt- obtained, which may be either 2 : 3-diethyl- or carbazone, m.p. 197° (decomp.)], 3-butyryl, m.p. 00 , 2-methyl-3-propyl-indole. Ch. A bs. (r) and '3-benzoyl, m.p. 132°, compounds are similarly pre pared. With C 02Et-C0Cl, Et 2 : 5-di?nethylpyrryl-‘3- Quinolone-acids from oxindole derivatives. glyoxylate, m.p. 83-5°, is obtained, hydrolysed to the E. Z r ik e and H. G. L in d w all (J. Amer. Chem. Soc., acid, m.p. 196— 197° (decomp.) (NHt , Pb", and other 1936, 58, 49— 50).— Isatin (I) and CH2Ph-C02Et m salts); this gives, when heated, an aldehyde, and, with E tO H -N H Et2 at room temp, for 5 days give 3-hydr- EtO H -N H 3 at 120°, 2 : a-dimethylpyrryl-3-ghyoxaniide, oxy-3-a-carbethoxybenzyloxindole, m.p. 154— 156°, con m.p. 225° (decomp.). U. W. W. verted by warm 1% NaOH into (1) and by conc. HI - EtOH into 2-keto-3-phenyl-l : 2-dihydroquinoline-4- Occurrence of piperidine in black pepper.— carboxylic acid. 3-(Dicyanomethylene)oxindole (ID See this vol., 395. (Walter, A., 1902, i, 373) is reduced (aq. Na2S20 4) to Action of ultra-violet light on pyridine. VI. '3-(dicyanomethyl)oxindole, m.p. 183— 185° (darkens Reactions of photopyridine and behaviour of about 160°), which is unstable in hot solvents and pyridine derivatives in the region of ultra-violet is converted by 10% NaOH (or acid) into 2-keto- radiations. II. F r b y ta g (Ber., 1935, 69, [ip , 32— 1 • 2 • 3 : 4-tetrahydroquinoline-4- carboxylic acia 40; cf. A., 1934, 303).— Dil. alkaline K M n04 is un (III). CN-CH2-CO-NH2 and (I) in EtOH-piperidme suitable for the detection of photopyridine [NII4 salt afford 3 -{cyanoformamidoinethylene)oxindole, m .p. 248— of enoiglutacondialdehyde (I)], since irradiation of 250°; this and (II) are hydrolysed (conc. HCl) to a Ho0 causes formation of H 202. The applicability of dibasic acid, C11H 70 5N, m.p. >340° (Ag2 salt; ^ dimedon (I), l-phenyl-3-methylpyrazol-5-one (II), and ester, m.p. 150— 151°), also formed from Et4 oxindole- indole (III) has therefore been tested with the Na salt 3 : 3-dimalonate (A., 1935, 758) and 10% ' of (I); coloured derivatives are obtained which could which is reduced (Zn, AcOH or Na-Hg, H 20 ) to (B )■ not be completely purified. Anaisthesin (IV), how H. B. ever, yields glutacondiancestheside, m.p. about 154— Amino-compounds of the quinoline series.— 155°. “ The effect of irradiation of G5H 5N, 2-, 3-, and See B., 1936, 92. 4-methyl-, 2 : 4 - and 2 : 6-dimethyl-, 2:4:6-tri- Preparation of 4-alkyl- and 4 -aryl-quinolines- methyl-, and 2-benzvl-pyridine in presence of (I), (II), (III),-'and (IV), respectively, is tabulated, whereby it J. K e n n e r and F. S. S tath am (Ber., 1936, 69, I J> appears that Me in position 3 hinders the photo- 16_18).—The following % yields of 4 -arylqumohne reaction. Several C3H 5N derivatives become coloured are obtained from the requisite arylamme and L - yellow to yellowish-brown in I120 or EtOH, but do ketone (cf. Blaise et a l, A., 1907, i, 241) w i t h o u t and not give an aldehydic reaction. Substances with with PhNOo (1 mol.), As,Os (0-5 mol.), SnCl4,SH2u halogen and carbalkoxy-groups become hydrolysed (1 mol.). and"FeCl3,6H20 (2 mols.) as oxidising agen - and give halogen ions. 5-Bromo-3-aminopyridine 4 -phenyl (10, - , - , 52-6, - ) ; p-tolyl- (7, 9, 14, 3 6 j becomes very rapidly discoloured with elimination of 44-6); 2-methoxy-5-methvlphenyl- (5, — , - 7. • ' ' B r; since discoloration commences at the boundary7 _), and p-naphthyl- (-, - , - , 41, - ) -q»“ 0^ of solution and air a photo-oxidative attack on the The respective % yields of 4 -alkylqumohnes NH, appears to occur. This applies also to 5-amino- PhNO., (1 mol.), SnCl4 (1 mol.), SnCl4,8H20 (1 mo1-). XVII (c) ORGANIC CHEMISTRY. 343 and FeCl3,6H20 (2 mols.) as oxidants are as follows : Synthesis of 5-amino-2 : 8-dialkoxy-10-alkyl- Me- (28, 21, 40, 35— 40); Et- (20, — , 40, — ); Pr“- (25, - , 40, — ); Bu“- (28, - , 40, — ). acridinium iodides. VII. Synthesis of 5-amino- 2 : 8 - dialkoxy - 1 0 - alkylacridinium oxalates. CH2Ci,CH2,COCl, and A1C13 in CS2 afford VIII. Synthesis of 5-amino-2 : 8-dialkoxy-10- V-chloroethyl 2-naphthyl ketone, m.p. 83°, converted bv alkylacridinium derivatives and 5 -( 2 ' : 8 '- d i - K0H at 280° into 2-C10H 7-CO2H and by NHPh-NH, alkoxy-At'-alkylacridonamino )-2 : 8 -dialk oxy-10- in warm EtOH into 1-phenyl-3- [i-maphthylpyrazoline, m.p. 181— 182°. The picrates, m.p. 200° (decomp.), f^ yl^ C^ dinium derivatives. IX. Synthesis of 205° (decomp.), and 185— 189° (decomp.), of 4-ethyl-, (2 . 8 -dialkoxy-lO'-alkyl-lO'-suhstituted-acrid- ine)-5 : 5'-ethylenediamino-2 : 8 -d ia lk o x y -1 0 - 4-n-propyl-, and 4-?i-butyl-quinoline, respectively, are described. j j 'yy alkylacridinium derivatives. K. I sh ih ar a (J. Ghem. hoc. Japan, 1934, 55, 945— 958, 1028— 1039 Tetrahydrocarbazoles with substituents in the 040— 1050, 1185— 1206, 1277— 1294: cf. A., 1935’ 7-position. S. G. P. P l a n t and (Miss) K. M. 1132).— V. The following 5-anilino-, 5-o-, -m-, and Rogers (J.C.S., 1936, 40— 41).— 9-Acetyltetrahydro- -p-toluidino-, and 5-p-pAfiweiidijio-derivsitives of sub carbazole (I), AcBr, and A1C13 give 7 : 9-diacetyitetra- stituted -acridinium hydroxides have been prepared hydrocarbazole, m.p. 110°, hydrolysed to 7-acetyltetra- by hydrolysis of the chlorides : 2 : 8-dimelhoxy-lG- hydrocarbazole (II), m.p. 206—208°, which is dehydro methyl-, m.p. 148— 149°, 133— 134°, 137— 138°, 133— genated (S) to 2-acetylcarbazole and reduced (Zn-Hg) 134°, 180°; 2 : 8-dimethozy-10-ethyl-, m.p. 145— 146° to 1-ethylhexahydrocarbazole, m.p. 44— 46°. (I) and 157-158°, 165-166°, 167-168°, 154-155°; 2: 8- BzCl afford 1-benzoyl-Q-acetyl-, m.p. 126°, hydrolysed diethoxy-10-methyl-, m.p. 164— 165°, 131— 132° 172__ to ¡-benzoyl-, m.p. 165°, which is also obtained from 173, 158 159, 167— 168°; 2 : 8-diethoxy-lQ-ethyl-, t y)-dibenzoyl-telrahydrocarbazole, m.p. 121°. 9-Benz- m.p. 156°, 138— 139°, 176°, 174— 175°, 171°. mjl-l-acelyltetrahydrocarbazole, m.p. 149°, hydrolysed VI. The -acridinium iodide derivatives (as above) to (II), is similarly obtained. F. R. S. are obtained from the hydroxides and AeOH-KI : Chemotherapeutic studies in the acridine 2 : 8-dimethoxy-10-methyl-, m.p. 237—238° 236 237° series. I. 2 : 6 - and 2 : 8 -Diaminoacridines. 2^3 244°, 253— 254°, 238°; 2 : 8-dimethoxy-10-ethyl- A. Albert and W . H. L innell (J.C.S., 1936, 88— 93). m.p. 249°, 224— 225°, 243— 245°, 230— 231°, 227— ~Aa2-ehloro-4-nitrobenzoatc, m-N02-C6H4-NH2, and 228°; 2 : 8-diethoxy-10-methyl-, m.p. 252—253° i>48° ya yield 5 : 5'-dinitrodiphenylamine-2-carboxylic acid 263°, 257°, 251°; 2 : 8-diethoxy-10-ethyl-, m.p.’ 255°’ U), m.p. 263° (Ag salt), reduced (SnCl2-HCl) to 3 : 3'- 248°, 262°, 274°, 234— 235°. wmmhphenylamine, m.p. 94-5— 95° (Ac2 derivative, VII. Similarly the corresponding 20 oxalates are It-i, ), also obtained by reduction of 3 : 3'-dinitro- prepared from the hydroxides and H 2C20 4 in A cO H : y^ujlarnine, m.p. 186-5°. Ring-closure of (I) respective m.p., in the order given above, are • 932°’ Reids a mixture of 5-chloro-2 : 6- (II), m.p. 200—203° 214— 215°, 220—221°, 214— 215°, 180°; 206— 207°’ iPnjKipally), and - 2 : 8-dinitroacridine (III), with 200— 201°, 204— 205°, 184— 185°, 209°; 231— 239°’ tffrn antl 2 : B-dinitroacridone. (II) is hydrolysed 210— 211°, 212— 213°, 224— 226°, 202— 203°- 2 1 9 ° ’ VJ> to 2 ; 6-dinitroacridone, reduced to the 2 : 6- 234— 235°, 212— 214°, 212°, 218— 219°. |-'ti2)2-compound (-¡-0-5H2O), m.p. 306°, which with V III. 5-Amino-2 : 8-dimetJioxy-lO-methylacridinium gives 2 : G-diaminoacridine, m.p. 213— 216° chloride (I), m.p. 324— 325°, is prepared from the 5-Gl-compound with aq. NH3. The correspondum ITTW1^- 2 : B-Diaminoacridine, obtained from t ),tonnsdibenzylidene, m.p. approx. 370° (decomp.), hydroxide, m.p. 74— 78°, iodide, m.p. 339— 340° and 3.# at30ve 350°, and Bz2 derivatives, m.p. above oxalate, m.p. 252— 253°, are described. (I), with AcOH, yields 2 : 8-dimethoxy-5-(2' : 8'-dimethoxy BA' - in F- R‘ S- methylacridonamino) -1 0 - methylacridinium chloride, K m iydr,0Xyacridone and “ acridol." II. A. m.p. 269— 270°. The following are prepared similarly: 202 m i ' Bh9samle (Ber., 1936, 69, [£], 1 9 7 - 5-amino-2 : 8-dimethoxy-10-ethylacridtnium chloride in OH A b 867).—Oxidation of acridine (I) m.p. 282—283° (hydroxide, m.p. 140— 142°; iodide, with6 “6 , Bz02H affords acridine 10-oxide, identical m.p.^ 294 , oxalate, m.p. 190°); 2:8 -dimethoxy- 1914 ini« ” ^oc' Tanasescu et al., A., 5 -(2' : 8' - dimetlioxy - N' - ethylacridonamino) -10 - ethyl - heatment { L- hmstedt’ A -’ 1935’ 1251 )• Similar acridinium iodide, m.p. 295°; o-amino-2 : 8-diethoxy- acrid;**in • 6-methoxyacridine gives 5-methoxy- 10-methylacridinium chloride, m.p. 311— 312° (hydr B R S « * p i; ™:I>- 158" («Iso + 1H.O), oxide, m.p. 153— 154°; iodide, m.p. 312°; oxalate methviof 1(lentical with the Me ether obtained by m.p. 228°); 2 : 8-diethoxy-5-(2' : 8'-diethoxy-X' - «V. 1 PnfL1 of, 16-liydroxyacridone (III) (Kliegl, loc. methylacridonamino) -10 - methylacridinium chloride treated wifh f ' ? 1()-hydroxyacridone when m.p. 287— 288° (iodide, m.p. 288—290°); o-amino- seated. with kll nruXI LI and T nponmnncm j af olmuf flao enmn temn and decompose at about the same 2 : 8-diethoxy-10-elhylacridinium chloride, m.p. 294__ basic anH r HaP and bufc (IX) is pronouncedly 295° (hydroxide, m.p. 149— 150°; iodide, m.p. 303°; (HD , dissolves readily in 2A-HC1 at 15— 20V oxalate, m.p. 237— 238°); 2 : 8-diethoxy-5-(2‘ : S'-di- tteinfl“ onJeric> ,tbe free compound passing under ethoxy-'N'-ethylacridonamino)-10-ethylacridinium chlor °f alkali into 5-hydroxyacridine 10-oxide. ide, m.p. 218° (iodide, m.p. 269°). IX. 5-Chloro-2 : 8-dimethoxy-10-methylacridinium with v a r i n ° xy". O-alkylacridinium derivatives chloride with (CH2-NH2)2 yields (10'-hydroxy-2’ : 8'- 5-carbon a f f ^ds of amino-groups on the dimethoxy - 10' - methylacridino) -5:5'- ethylenediamino - dialkoxv rn 1 SyntBesis of 5-amino-2 : 8- 2 : 8-dimethoxy-lO-methylacridinium hydroxide, m.p. -\y-4U-alkylacridiniurn hydroxides. VI. 230° (tetravicrate, m.p. 231— 232°); this with AcOH XVII (C, e) 344 BRITISH CHEMICAL ABSTRACTS.— A. affords (W-chloro-2’ : 8'-dimethoxy-10'-rnelhylacridino)- C H ,0, MeCHO, PhCHO, o-Cr,H4Me-CHO, and o- 5 ■ O' - etliylenediacetamido-2 : 8 - dimethoxy -1.0 - methyl - OMe-CGH4-CHO gives di - (iV - phenyl ^ N ' - piperazyl) ■ acridinium chloride, m.p. 250°. The 10'-chloro-chlor methane, m.p. 123— 124° (also formed using CH,I2), ide, m.p. 231— 232°, 10'-iodo-iodide, m.p. 282— 283°, -ethane, m.p. 121— 123°, -phenylmethane, m.p. 125— and W-oxalato-oxalate, m.p. 233—234°, are obtained 126°, -o-fnlylmethane, m.p. 144— 144-5°, and -o-anisyl- similarly. The following are described : (10'-hydroxy- methane, m.p. 135— 136°, respectively. H. B. 2' : 8' - dimethoxy -10' - ethylacridino) -5:5'- ethylenedi - Synthesis of 6-amino-4-ethylpyrimidine. W. T. amino-2 \8-dimethoxy-\0-ethylacridinium hydroxide, Ca ld w el l and W . M. Z ie g le r (J. Amer. Chem. Soc., m,p. 218__220°, and the derived 10'-chloro-chloride:, 1936, 58, 78—79).— 6-Hydroxy-2-ethylthiol-4-ethyl- m.p. 253°, 10'-iodo-iodide, m.p. 271— 272°, and 10'- pyrimidine [best prepared from E t G 0 • 0 H 2 • C 0 2E t and oxalato-oxalate, m.p. 235°; (10'-hydroxy-21 : 8’-dieth- SEt-C(NH)-NH2,HBrinMeOH-KOH at 0°] is hydro oxy-W-methylacridino)-5 : 5 '- ethyknedidmino-2 : S-di- lysed to 4-cthyluracil, m.p. 204— 205°, converted by ethoxy-\0-methylacridinium hydroxide, m.p. 236— 238°, POC1, into 2 : O-dichloro-4-ethylpyrimidine, b.p. 90— and the derived 10'-chloro-chloride, m.p. 267—268°, 95°/4 mm., 103— 107°/7 mm., which with red P and 10'-iodo-iodide, m.p. 290°, and 10 -oxalcito-oxalate, m.p. H I (b.p. 127°) gives 0-hydroxy-4 - ethylpyrimidm 253°; [W-hydroxy-2' : 8'-diclhoxy-lO'-cthylacridino)- hydriodide, m.p. 170-5— 171-5° (sinters at 160°). This 5 ; 5'-ethylenediamino-2 : 8-diethoxiy-lO-ethylacridinium with P0C13 affords G-chloro-4-ethylpyrimidine, b.p. hydroxide, m.p. 204— 206°, and the derived 10'-chloro- 193°, which with E tO H -N H 3 at 150° gives Q-amiwj- chloride m.p. 241— 242°, and 10'-oxalato-oxalate, m.p. ethylj)yri7nidine(-{- 3H20), m.p. 47*5— 48°, m.p. (anhyd.) 249—250°. Ch- Abs- (r) 87.5— 88° (jncrate, m.p. 204— 205°; hydrochloride, m.p. 198— 199°; aurichloride, m.p. 150— 151°). H. B. Action of alkalis and alkali salts on antipyrine. L. E. H a r r is and E. D. T e b o w (J. Amer. Pharm. Reaction products of aromatic amidines with Assoc., 1935, 24, 1069— 1070).— The immiscible liquid diketones, dialdehydes, and their monoximes. obtained on the addition of antipyrine to conc. solu J. B. E k e l e y and J. L. E lliott (J. Amer. Chem. tions of alkalis or alkali salts is apparently an Soc., 1936, 58, 163— 164).— The following 5-hydroxy- isomeride. E. H. S. 2-phenyl-4-arylpyrimidines are prepared (cf. A., 193c, 1133) from N H yCPIlN H (I), (CHO)2, and the appro Derivatives of 1 : 3-diaryl-5-pyrazolones and priate ArCIIO "in aq. EtOH-KOII at room tempi of 1 : l'-diaryl-3 :3'-arylene-5 : 5'-bispyrazolones. 4-o-carboxyphenyl, m.p. 259—260°; 4-0-, m.p. '-Ml, — See B., 1936, 92. and -p-, m.p. 305— 306°, -clilorophenyl; 4-2' : 4 -, m.p. Alkylerlyoxalidines . H. C. C h itw o o d and E. E. 248— 249°, -2' : 5'-, m.p. 268— 269°, and -3' : 4'-, m.p. R e id (J. Amer. Chem. Soc., 1935, 57, 2424— 2426).— 259— 260°, -dimethoxyphenyl; 4-p-dimethykmno- 2-Methylglyoxalidino (I), m.p. 105° (205°), obtained phenyl, m.p. 277— 278°, 4-p-phenetyl, m.p. 292-213C in 68% yield when (•CH2-NHAc)2 is heated with Mg 4-m-hydroxyphenyl, m.p. 265—265-5°; 4-dibromo-- powder at 270°, is hydrolvsed (aq. alkali) to hydroxyphenyl, m.p. 311°; 4-o-hydroxybenzyl, ^ (•CH2-NH2)„. 2-Ethyl-, m.p. 38-1° (137-1°), 2-propyl-, 287—288°; 4-5'-nitro-2'-hydroxyphenyl, m.p. > 3W . m.p. 35-3° (129°), 2-butyl-, m.p. 41° (125-8°), 2-amyl-, 4-p-cumyl, m.p. 246—247°; 4-G'-methoxy-n\-tolyl,W- m.p. 33-8° (128-4°), 2-hexyl-, m.p. 46-2°, 2-heptyl-, 253—254°; 4-3' : 4'-metliylenedioxyphenyl, m.p. 2m m.p. 60° (104-8°), 2-octvl-, m.p. 52-1°, 2-nonyl-, m.p. 287°; 4-m-tolyl, m.p. 237— 238°. The follo*®g 71-4° (122°), 2-decyl-, m.p. 79-5° (82°), and 2-undecyl-, 5-hydroxy-2-m-tolyl-4-arylpyrimidines are sumlari) m.p. 79-8° (61-5°), -glyoxalidines are similarly obtained prepared from (CHO)2, r«-CfiH4Me-C(NH)-hH2 ( ( (in some cases Mg is replaced by Na) in 5-6— 49% and ArCHO : 4-2' : 4'-, m.p. 250—251° -2' : 5 -, m-P- yield from the appropriate (•CH2,NH*C0R)2. The 229—230°, and -3' : 4'-, m.p. 238—239°, -dunehoxf temp, given in parentheses are m.p. of the picrates; phenyl-, 4-p-phenetyl, m.p. 237— 238°; 4-p-crmyi, mP the aurichldrides^&ve analysed. The toxicity (towards 263—264°: 4-0-, m.p. 272— 273°, and -p-, m.p. Lupinus albus and animals) of the first 5 compounds 229°, -anisyl; 4-3' :4 '-methylenedioxyphenyl, m.p. decreases with increase in size of the alkyl group. 4-6'-methoxy-m-tolyl, m.p. 237-239° (I) and Br in CHC1, give (probably) the H-Br-deriv- quinone with (I), (II), and o-CGH4Me-C(XH)X 21 ative hydrobromide, hydrolysed (H20) to (I). hydrochlorides) in 50% alkali gives compound- H. B. U21RC21H 14UL\I2,14ON2, m.p. 277—z i l — x278°, io , G%H1gON2,e ,2u 1Gwx 2, m.p.“ ‘ ■w 726J- ,. Preparations of methyl p- (tymethyl-A'-hept- 270°, and C2,H 1BON2, m.p. 2 8 7 -5 - 2 8 8 ° , i-espectn^ enyl)amine.— Sec B., 1936, 124. (I) and (II) with CAcMciX-OH similarly affor compounds, C15H220 4N4, m.p. 105— 10/ > ., Piperazine. VIII. Condensation with alde C16H240 4N4, m .p. 94 96°, respectively, » " t t o hydes. W. T. F o r s e e , jun., and C. B. P o l l a r d (J. quinoneoxime (111 amyl alcohol) with (1), { >< Ainer. Chem. Soc., 1935, 57, 2363— 2364),—Piperazine p-CGH4Me-C(NH)-NH, (in CHCI3+ K O H ) gives ex (I) and ECHO in presence or absence of solvent give pounds, C21H 170 2N,, m.p. 186“, C22H1902i 3’ insol. products of the type ("X^q^jj^^X-CHR-),,; 165- 166° and 6 ^ 0 ^ m.p. 182-183°, : j e f k tively. A compound, Cp,H1G02N3, m.p. 1 „ g those where R =H , m.p. > 300° [also formed from described. ' ’ _ (I) and CHJJ, Eh, m.p. 270° (decomp.) [also formed from (I) and CHPhCl2|, o-OH*CGH4*, m.p. 210° (de Synthesis of nitrated 2 : 3-dihydr opyrim* M comp.), p-C6H4Me% m.p. 275° (decomp,), o-CgH 4C1-, ole. 0 . B rem er (Annalen, 1936, 521, 286—- J: With S0C12, 3-nitro-4-p-hydroxyethylainmop\n m.p. 240° (decomp.), and p-0Mc-GfH4-, m:p. 290° (decomp.), are described. W-Phenylpiperazine with gives the -4-^-chloroethylamino-coraponna, m.p- XVII (e) ORGANIC CHEMISTRY. 345 reduced (Na2S20 4) to 3-amino-4-$-chloroethylamino- enes and preparation of di-isatogens. P. Ruggli pyridine, m.p. 85— 80°. B-Nilro-i-ß-hydroxyethoxy- and E. W o lf e (Helv. Chim. Acta, 1936,19, 5— 15).— pyridine, m.p. 112— 113° [from 4-chloro-3-nitro- p-Cr,H4(CHO)2 and 2 : 4-C6H3Me(N02)2 in presence pyridine, Na and (-CH2-OH)2], similarly affords of piperidine at 160° give 2 : 4 : 2' : 4'-tetranitro-p- the -4-ß-chloroethoxy-componnd, m.p. 70— 71°, sinters distyrylbenzene, m.p. 294°, transformed by CI2 in 44°. 4-Chloro-3-nitropyridine, m.p. 74—75° (Jit. AcOH at 110° into the corresponding tetrachloride, m.p. 45°), is reduced (Na2S204) to the 3-AU/,-coni- m.p. (indef.) 92— 99°, which passes in boiling C5H 5N pound, m.p. 82°. 2-ChIoro-5-nitropyridine (I) and into 2 : 4 : 2' : 4'-tetranitro-p-dichlorostyrylbenzene (I), its 3-Br-derivative with NII2-CH2-CH2-0H in EtOII in.p. 248 . Protracted insolation of (I) suspended in at 100 give, respectively, o-nitro-2-fi-hydroxyethyl- C5H6N yields 6 : 6'-dinitro-2 : 2 '-p-phenylenedi-isato- aminopyridine (II), m.p. 131— 132° (hydrochloride, m.p. 182°), and its 3-Br-dorivative (III), m.p. 136°; yen, p - C BH4 ( qCCH3• N0 2)2, m.p. 294°, reduced 2-chloropyridine gives 2-$-hydroxyethylamino-, m.p. by NHPh-NH2 in EtOH at 100° to dinitro-p-phenyl- 65° (hydrochloride, m.p. 158-5°), converted by SO CL, enedi-indoxyl, isolated as the Ac,, derivative, gradual into 2-$-chloroethylamino-pyridine (IV) (hydrochloride, decomp. > 280°. Similarly, m-C6H4(CH0)2 gives m.p. 146°). (I) and (-CH2-OH),-Na give 5-m7ro-2-ß- - : 4 : 2 : 4 -tetranilro-m-distyrylbenzene, pi.p. 243°, nydroxyethoxy-, m.p. 113— 114°, converted (SOCl2) the tetrachloride, m.p. (indef.) 90— 108°, of which gives mto -2-ß-chloroethoxy-pyridine, m.p. 131— 132°, con 2:4:2': 4' -tetranitro - m - dichloroslyrylbenzene, m.p. verted by NHEt2 into 5-nitro-2-ß-diethylaminoethoxy- 215°, whence 6 : 6'-dinitro-2 : 2'-m-phenylenedi-isato- pyridine, b.p. 170°/3 mm. [reduced by SnCL and con ejen, m.p. 289° (decomp.), reduced to dinitro-m- densed with p-NMe2-C0H4-CHO to give the 5-p-di- phenylenedi-indoxyl (Ac2 derivative, m.p. 304°). wdhylaminobenzylideneamino-derivative, m.p. 163 - Under like conditions o-C6H4(CHO)2 undergoes one 164 (picrate, m.p. 131°)], also obtained from (I) sided condensation giving o-2' : 4 '-dinitrostyrylbenz- and NIt,t2• CH2• OH2• ONa in Et20. Similarly (I) aldehyde m.p. 186° (phcnijlhydrazone, m.p. 193°). and the appropriate base afford" o-nitro-2-fi-amino- p-CfiH,(CHO)2 and o-nitro-p-toluonitrilc give 2 : 2'- tmjlamino-, m.p. 123°, -2-$-(diethylamino)ethylamino-, dinitro-4 : i'-dicyano-p-distyrylbenzene, m.p. 350° (de Hydroxydiethylamino- (V), m.p. 59— 60°, and -2- comp.), whence tlie corresponding tetrachloride, m.p. wylamino-, m.p. 97° [converted by HBr to 2-ß- 2/8 , 2 : 2'-dinitro-4 : 4- -dicyano- p - dichlorostyryl- Dnmopropylamino- (VI)], -pyridine. (VI) is converted benzene, m.p. 296°, and (?) 6 : Q'-dicyano-2 : 2'-p- oy warming in H20 into 5-nitro-3-methyl-2 : 3-dihydro- phemjlenedi-isatogen, blackens > 300°. 2 : 2'-Di- Pjniiunazole, m.p. 185°. Gentle heat converts (IV) nitro-4 : 4 '-dicyano-m-distyrylbenzene, m.p. 298°, gives KOlt ■ dr0pyriminazoliuni chloride, converted by a tetrachloride, m.p. (indef.) 80— 100°, or cryst. m.p., , Y“ lnto 2 : 3-dihydropyriminazole, m.p. 64— 65° 248 , and thence 2 : 2'-dinitro-4 : 4'-dicyano-m-di- (pfrnfe, m.p. 213°), also obtained by the action of chlorostyrylbenzene, m.p. 268°, and 6 : 6'-dicyano-2 : 2'- 2 and alkali on 1-ß-hydroxyethylpyridoneimine m-phenylencdi-isatogen, decomp. about 300° after Munjanz, A., 1935, 627). SOC1., converts (II), darkening at 270°. o-2'-Nitro-4'-cyanoslyrylbenzalde- ?««’n (V) lnto> respectively, 5-nitro- (VII), m.p. hyde, m.p. 210°, and its phenylhydrazone, m.p. 182°, (decomp.) (chloride, not melting at 280°), 7- are described. H. W. b^ T t ni! ro^ ’ m-P- 222°'(decomp.) [also from (VII) Quaternary ammonium compounds of deriv ethul 9 r0 7° arld 5-nitro-8-hydroxy-1 - ÿ w : 44xhydropyriminazole. J. W . B. atives of the anthracene series [mainly pyrimid in es].— See B., 1936, 140. *Äphthoquinoxaline-2: 3-dicarboxylic acid. l readily absorbs 2H in AcOH (Pd-black), but 4H in Chem. Soc., 1935, 57, 2627— 2630; cf. A., 1933, O05iY-NaOH; it cannot be converted into or obtained 1174).—Alkylation (alkyl halide on Na salt in EtOH) from mesobilirubinogen (II). (II) with 02 in HC1 of 2-arylamino-4-thiazolidones [prepared (a) from gives mesobiliviolin and a little urobilin [reduced to NHAr-COCH2Cl and KCNS in EtOH, or (b) from (II) by Na-Hg]. (I) and H N 0 3 give (-CH2-C02H)2, NHAr-CS-NH2 and equimol. amounts of CH2Cl*C02Et but no mcthylethylmaleinimide which is readily so and CjH5N in EtOH] gives generally a mixture of a obtained from mesobilirubin (III) or glaucobilin (IV). little 2-arylimino-3-alkyl-4-thiazolidone (I) [the (I) and HI-AcOH at 100° give pyrrole bases but no 5-benzylidene derivatives of which are hydrolysed bilirubinic acid. With H Br-AcOH at 180° (I) gives (EtOH-conc. HC1) to NH2Ar and 2 :4-diketo-5- an unidentified porphyrin. With PhN2Cl (II) and benzylidene-3-alkyltctrahydrothiazoIes] and much (III) give the ester hydrochloride, m.p. 193°, of a dye, 2-Ar-alkylarylamino-4-thiazolidone (II) (the 5-benzyl- stercobilinogen gives an uncrystallisable dye, but (I) idene derivatives are hydrolysed to NHArAlk and does not react; (I) also does not react with PhCHO. 2 : 4-diketo-5-benzylidenetetrahydrothiazoles). Cer With conc. H2SO,, at 100° (I), (II), and (III) give (IV). tain exceptions are noted. (I) are also synthesised (I) is strongly lsevorotatory (hydrocliloride, [a]^m from CH2Cl-C02Et and NHAr-CS-NHAlk. The —1733°, [aJoSoo —1007° in AcOH), but is readily 3-aryl-2-ethylimino-4-thiazolidones of Beckurts and racemised by various reagents. (I) is probably as Frerich (A., 1916, i, 744) are (II). The following are shown. Opsopyrrole and p-CeH4Me-N2Gl give a described : (a) substituted thiocarbamides : p -cymyl-, monoazo-<%e, m.p. 238° JJiydrochloride, m.p. 208°; m.p. 152°; N-o-, m.p. 88°, and -p-, m.p. 112°, -ethoxy- hydrobromide, m.p. 185°; picrate, m.p. 182°' phenyl-, lü-^-cumyl-, m.p. 138°; N-o-, m.p. 11°, -m-, m.p. 112°, and -p-, m.p. 147°, -anisyl-, N -p-cymyl-, —7,R' R ' m.p. 126°, N-p-iodophenyl-, m.p. 147-5°, and N-2 : 4- c h 2r I C H = CH,R R= di-iodophenyl-, m.p. 164°, -N '-ethyl- ; N -¡p-cumyl-, > - \ / OH m.p. 179°, and N-p-iodophenyl-, m.p. 171°, -N '-methyl- ; NH HN 0H ~N-p-iodophcnyl-W-amyl-, m.p. 130°, and -W-benzyl-, R '= -[C H 2]3-C02H m.p. 149°; (6) substituted 4-thiazolidones : 2-p-ethoxy- R . S. C. anilo-3-ethyl-, m.p. 93° (5-benzylidene derivative, m.p. Preparation and tinctorial properties of benz- 135°); 2-o-ethoxyanilino-, m.p. 172°; 5-benzylidene oxazole dyes. V. J. M ikesica and M. T. B o g e r t derivative, m.p. 210°, of 2-N-ethyl-p-ethoxyaniliho-; (J. Amer. Chem. Soc., 1935, 57, 2513—2517).—A 2-1Ü-ethyl-o-ethoxyanilino-, m.p. 99° (5-benzylidene series of substantive cotton dyes are prepared from derivative, m.p. 164°); ‘¿-o-cthoxyanilo-'i-ethyl-, m.p. diazotised 4-phenyl-l-p-aminophenylbenzoxazole (I) 79° [5-benzylidene derivative, m.p. 113°); 2-ijj-cumyl- [and its S03H derivative (II)] and 4-amino-l : 6-di- imino-3-methyl-, m.p. 91° (5-benzylidene derivative, phenylbenzoxazole (III) (and its S 0 3H derivative) m.p. 136°), and -3-ethyl-, m.p. 77° (5-benzylidene deriv by coupling with a- and p-C10H7*OH, PhOH, ative, m.p. 141°); 5-benzylidene derivative, m.p. 180°, '?!'C6H4(OH)2, and a-C10H7*NH2; those prepared of 2-AT-ethyl-^-cumylamino-; 2-0-, m.p. 114°, -m-, from (I) are more substantive than those from (III). m.p. 65— 66°, and -p-, m.p. 83°, -anisylimino-3-ethyl- Tne_dyes resemble, but give lighter shades than, the (5-benzrylidene derivatives, m.p. 99°, 109°, and 125°, corresponding derivatives from dehydrothio-p-1oluidine respectively); the 5-benzylidene derivatives, m.p. 149°, O ') (A., 1927, 679). Absorption curves for “ ingrain 135°, and 198°, of 2-N-ethyl-o-, -m-, m.p. 112°, and red ’ [from (IV) and fi-C]0H7-OH] and “ oxazole red ” -p-anisidino-, respectively; 2-m-anisidino-, m.p. 165°; [from (II) and 3-C10H7-OH| are given; the former 2-p-cymylamino-, m.p. 174°; 2-lü-ethyl-p-cymylamino-, \t An w^er absorption. Oxidation (aq. EtOH- m.p. 85° (5-benzylidene derivative, m.p. 169°); \ , f-f at 0— 10°) of (I) gives pp'-di-(4-phenyl- 2-p-cymylimino-3-ethyl-, m.p. 64° (5-benzylidene deriv •benzoxazolyl)azobenzene, decomp. >300° [(S03Na)2 ative, m.p. 73°); 2-2': 4'-di-iodoanilino-, m.p. 233°; erivahre (V); (S03Na)4 derivative, prepared by 2-2' : 4'-di-iodoanilo-3-ethyl-, m.p. 173° (5-benzylidene similar oxidation of 4-phenyl-l-p-aminophenylbenz- derivative, m.p. 210—211°); 2-p-iodoanilino-, m.p. OMzoleclisulphonic acid]. Similar “ chloramine 226° ; 2-id-methyl-, m.p. 207°, -ethyl-, m.p. 116°, ,'elow dyes are prepared from l-p-aminophenyl-4- -amyl-, m.p. 116°, and -benzyl-, m.p. 176°, -p-iodo- niethylbenzoxazole [resembles (V)] and (III) [inferior anilino- (5-benzylidene derivatives, m.p. 246°, 231°, 0 (' )]• Pabrics dyed directly retain (after 5 years) a 202°, and 221°, respectively); 2-p-iodoanilo-3-methyl-, e(ter colour than those dyed by the “ ingrain ” m.p. 152°. -ethyl-, m.p. 103°, -amyl-, m.p. 57°, and Process. H. B. -benzyl-, m.p. 137° (5-benzylidene derivatives, m.p. 167°, 172°, 105°, and 162°, respectively); 2-anilino-3-amyl-, Pyridine and quinoline derivatives of dibenz- an oil (5-benzylidene derivative, m.p. 78°); 2-benzyl- ran and their physiological properties. W. H. imino-3-benzyl-, m.p. 74° (5-benzylidene derivative, l93f l ^ CKand (Proc. Iowa Accad. Sci., m.p. 109°); (c) miscellaneous : chloroacet-2-p-cymidide, 172).— The physiological properties of a m.p. 85°, and -2 : 4-di-iodoanilide, m.p. 153°; p-nitro- -ot amino- and substituted amino-dibenzfurans and benz-o-ph'enetidide, m.p. 155°; benzenesulplion-N-ethyl- eir nuclear reduction products have been studied. o-phenetidide, m.p. 61°, -Ts-ethyl-o-anisidide, m.p. , t, mai\v cases the NH2-eompounds undergo cyclis- 90°, and -N-methi/1-p-iodöänilide, m.p. 78°; N '-phenyl- n’ yrolding pyridinodlbenzfurans. Ch . A b s . (r) ’N-p-ethoxyphenyi-Hl-etkyl-, m.p. 93°, and N-p-toh/f- N '-o-ethoxyphenyl-, m.p. 172°, -carbamides; 2 : 4 -di- derivatives of aryl-suhstituted thiazol- keto-5-benzylidene-3-amyl-, m.p. 74°, and -3-benzyl-, J - A. D avis and F. B. D a in s (J. Amer. m.p. 134°, -telrahydrothiazoles. H. B. 34S BRITISH CHEMICAL ABSTRACTS.— A. XVII (/) Aneurine. II. Synthesis of .V-arylthiazolium giving l-imino-5-ethoxy-2-methylbenzthiazoline (HI), salts ; details in the constitution of aneurine m.p. 98°. l-Amino-5-ethoxybenzthiazole (III) is and thiochrome. A. R . T o d d , F. B ergel, and transformed by Me2S04 at 100° into l-amino-o-ethoxy- K arim ullah (Ber., 1936, 69, [I?], 217— 223).— 2-meihylbenzthiazolium methosulphate, m.p. 187— 189°, CH2PhBr and 2 : 4-dimethylthiazole at 100° give converted by NaOH into \-methylimino-~i-ethoxy-2- 3-benzyl-2 : 4-dimethylthiazolium bromide, m.p. 173°. methylbenzthiazoline, m.p. 86°. \-Amino-o-ethoxy-2- Addition of thioacetmethylamide to CH2CbC0Me at methylbenzihiazolium iodide, m.p. 245°, results from 80° yields 2 :3 : 4-trimethylihiazolium chloride, m.p. 235° (II) and HI or from (IV) and Mel in MeOH at 100°, (decomp.). Similarly thioacetanilide and CH2Cl-C0Me whilst the corresponding chloride, m.p. 308° (decomp.), at 100° afford 3-phenyl'-2 : 4-dimethylthiazolium chloride is obtained from (II) and boiling HC1. The presence (I), m.p. 184° (decomp. in sealed capillary; corre of NH in (III) is established by the isolation of sponding picrate, m.p. 115°). If reaction is effected at l-nitrosoimino-5-ethoxy-2-methylbenzthiazoline, which 15— 20°, S-acetonylthioacetanilide hydrochloride (II), evolves N2 quantitatively when boiled with xylene m.p. 112° [corresponding perchlorate, m.p. 130°, and gives 5-ethoxy-2-methylbenzthiazolone, m.p. 87°. unstable free base and its semicarbazone, m.p. 230° (III) is converted by boiling Ac20, BzCl, or valeric (decomp.)], is formed. It passes at 100° into (I) anhydride, respectively, into 1 -acetimido-, m.p. 172°, and is hydrolysed by boiling H20 or dil. acid to 1 -bènzimido-, m.p. 191°, and 1 -valerimido-, m.p. 119°, NHVPh, NHAcPh, and a substance (III), -5-ethoxy-2-methylbenzthiazoline, which essentially yield ( ?) SH*CH2,C(CH2),S,CH2,COMe [semicarbazone, salts with mineral acids. Bromo-l-amino-5-ethoxy-2- C?H13ON3S2, m.p. 213° (decomp.)]. 3-o-Tolyl-2 : 4- methylbenzthiazolium methosulphate is transformed by dimethylthiazolium chloride, perchlorate, m.p. 172°, Me2S04 and NaOH into bromo-l-methylimino-5- picrate, m.p. 150°, and iodide, m.p. 217— 218° (de ethoxy-2-methylbenzthiazoline, m.p. 158°, transformed comp.), are obtained analogously. S-Acetonylthio- by NaNOo in AcOH and subsequent treatment of the acet-o-toluidide hydrochloride, m.p. 125°, is more product with boiling xylene into bromo-5-ethoxy-2- stable than (II) ; its hydrolysis leads to o-CBH4Me,NH2 meihylbcnzthiazolone, m.p. 126°. The benzthiazolium CeH4Me-NHAc, and (III). o-N02-0fH4-NHAc is con hydroxides and benzthiazolines have identical ab verted by cautious treatment with P2S5 into o -nitro- sorption spectra in MeOH possibly owing to conversion thioacetanilide, m.p. 114°, whence 3-o-nitropKenyl- of the former into the latter. The absorption spectra 2 : 4-dimethylthiazolium perchlorate, m.p. 205°. Deter of 2-methylated benzthiazole, benzoxazole, ben?.- mination of 6'-alkyl by oxidation with Cr03 of thi- selenazole, and benziminazole are compared, p- azolium, pyrimidine, and allied compounds shows Chlorophenyl-thiolacetic and -selenolaeetic acid have that Williams’ pyrimidine compound from aneurine closely similar absorption spectra which differ con (IV) contains oniy one alkyl; (IV) and thiochrome siderably from that of p-chlorophenoxyacetic acid. • 8 each contains two alkyls, the H. IV. 7 N S higher val. indicated (Kuhn) Compounds for treatment of textiles [benz- for (IV) being observed with thiazoles].— See B., 1936, 92. A î*ï itfvr other compounds which lose \ / C f — CMe CMe quantitatively. Cyanine dye series. II. Carbocyanines with 4 - o-CfiH4(NH2)2 and CS(NH2)2 substituents in the three-carbon chain. L . G. S. V y yield thiobenziminazoline, m.p. B ro o ker and F. L . W h ite (J. Amer. Cliem. Soc., 295— 300°, converted by CH2Cl"COMe into 3-methyl- 1935, 57, 2480—-2488).— Substituted thiacarbocyaniiw thiazolo-2' : 3' : 2 : 1-glyoxaline (V), m.p. 164— 165°. iodides, cgh4<|^>c:ch-cr':ch-c<|^>c6h4, ! H. W . 1 - Amino - 5-ethoxy-2-methylbenzthiazolium are prepared from various ortho-esters (I), e.g., hydroxide and its derivatives. 0. B e iia g iiel and CR'(0Me)3 (R'=H , Me, Et, Pr, Bu, amyl, CH2Ph, E. Sch n eider (Ber., 1936, 69, [B], 88— 98).— OPh'CH,/, Pli) and 1-methylbenzthiazole alkiodides Repetition of the work of Hunter et al. (A., 1930, 1452) or alk-p-toluenesulphonates (followed by aq. KI) shows that p-ethoxyphenylthiocarbamide is trans in boiling C5H5N. The following are described: formed by an excess of Br in CIIC13 into bromo-1- 2 : 2 '-diallyl-, m.p. 264— 266° (decomp.); 2 : 2'-dt:n- amino-5-ethoxijbenzthiazole (I), m.p. 196°, and by propyl-, m.p. 296— 297° (decomp.) ; 2 : 2'-di-n-bulyl-, the calc, quantity into l-amino-5-ethoxybenzthiazole, m.p. 275— 277° (decomp.) ; S-methyl-2 : 2'-diallyl-! m.p. 162°. Treatment of (I) with Me2S04 yields the m.p. 267—268° (decomp.), -2 : 2'-di-n-propyl-, m.p- corresponding methosulphate, converted by NaOH 295—296° (decomp.), and -2 : 2'-di-n-butyl-, m.p. into bromo-l-irnino-5-ethoo:y-2-rnelhylbanzthiazoline, 236—237° (decomp.) ; 2 : 2'-dimethyl-3-ethyl-, m.p- m.p. 144°, also derived from as-p - ethoxyphenyl- 286—287° (decomp.) ; 2 : 8 : 2'-triethyl-, m.p. 236— meihylthiocarbamide, m.p. 139° (prepared from N- 237° (decomp.) ; 8-ethyl-2 : 2'-diallyl-, m.p. 214%' metbyl-p-phenetidine hydrochloride and NH4CNS), 216° (decomp.), -2 : 2'-di-n-pràpyl-, m.p. 248—2u0 and Br in CHC13. AC-Methyl-p-phefietidine and KCNS (decomp.), and -2 :2'-di-n-butyl-, m.p. -241—243 in 95% AcOH are transformed by Br in warm AcOH (decomp.); 2 : 2'-dimethyl-8-\\-propyl-, m.p. 26S—- into 1 -amino-o-ethoxy-2-melhylbenzthiazolium bromide, 269° (decomp.), -8-n-butyl-, m.p. 16S— 169° (deconip-)> decomp. 295°, whereas in MeOAc the corresponding -8-n-amyl-, m.p. 217— 219° (decomp.), -8-isoamyl; thiocyanate, m.p. 1S7°, is produced. Treatment of the m.p. 241—242° (decomp.), -8-benzyl-, m.p. 288— salts with cold Na2C03 affords 1 -amino-5-ethoxy-2- 289° (decomp.), -8-phenoxymethyl- {bromide), m.p- methylbenzthiazolium hydroxide (II), m.p. about 255— 257° (decomp.), and -8-phenyl-, m.p. 275— 64°, which readily loses H20 when kept over H2S04 277° (decomp.) ; 2 : 2'-diethijl-8-n-propyl-, m.p. 240— XVII (/) ORGANIC CHEMISTRY. 349 248° (decomp.), -8-n-butyl-, m.p. 233—234° (decomp.), as the condensing agent; EtOH-KOH (cf. Hamer, -8-n-amyl-, m.p. 237—238° (decomp.), -8-isoamyl-, A., 1928, 307) leads to a 3% yield. The following m.p. 219—220° (decomp.), -8-benzyl-, m.p. 242— are prepared in yields of 10— 87% usually in PraOH- 243° (decomp.), -8-phenoxymethyl-, m.p. 202—204° NEt3 : 2 : 1'-diethylselena-2'-cyanine iodide [A, R = (decomp.), and -8-phenyl-, m.p. 300— 301° (decomp.); Se), m.p. 280—282° (decomp.), from (I) and 1-methyl- 8-benzyl-, m.p. 225—227° (decomp.), and 8-plienoxy- benzselenazole ethiodide; 1 : 1'-diethyl-2-pyrido-2'- melhyl-, m.p. 211— 213° (decomp.), -2:2'-diallyl-. cyanine iodide (II), m.p. 237—239° (decomp.), from In the above series introduction of 8-Me (for II) (I) and 2-methylpyridine ethiodide (III) or from causes a shift in the absorption max. (in MeOH) 2-iodopyridine ethiodide (IV) and 2-methylquinoline of about 150 A. towards the blue; replacement of ethiodide (thus affording further evidence of the 8-Me by Et (or higher alkyl) causes a shift of about virtual tautomerism of the cyanine dyes); 1 : V-di- 50 A. back towards the red. The following substituted e thyl-2-pyr ¿do-4' - cyanine iodide, m.p. 194— 196° (de 5:6:5': 6'-dibenzthiacarbocyanine bromides are simi comp.), from (IV) and 4-methylquinoline ethiodide; larly prepared from (I) and 1 -methyl- (decomp.), 4-methyl-d : 1 '-diethyl-, m.p. 255—257° (de (I) in neutral solution yields the substance, comp.), and 4-phenyl-Z : 1 '-diethyl-, m.p. 247— 249° m.p. 118— 120°, [a]],3 — 10-8° in CHC13, whereas in (decomp.), -thiazolo-, and i-methylS : V-diethylselen- acid solution a compound, ^22^-35®4X) m.p. 134 , [a];; azolo-, m.p. 232— 233° (decomp.), -2'-pyridocyanine — 13-2° in CHC13 (hydrochloride), is produced. Since iodides are prepared from 2-iodopyridine ethiodide (I) does not give an ultra-violet absorption spectrum and the above S and Se salts. All the above dyes above 234— 313 mg the presence in it of an aromatic are sensitisers; absorption spectra are given. ring is excluded. The presence of a pyrrolidine ring H. B. is possible since in conjunction with I, Mel, or EtI it Sensitisation of photographic emulsions.—See is oxidised by air to a neutral substance, C22H290 4N, B., 1936, 125. m.p. 186°, which retains the lactone ring, readily gives the Ehrlich pyrrole reaction, and has a charac Manufacture of unsymmetrical heptacarbo- teristic ultra-violet absorption spectrum. Electrolytic cyanine and h exam ethine dyes.— See B., 1936, 93. reduction of (1) yields the di-deoxo-6ase, C22H3702N Catalysed photo-reduction of vat dyes.—See (perchlorate, m.p. 244— 245°; methiodide, m.p. 261— this vol., 300. 262°), which does not contain a lactone group; the Alkaloids from the seeds of Cassis absus, second replaced 0 is attributed to the presence of Linn. S. Sibdiqui and Z. Aiimed (Proc. Indian non-reactive CO. (I) is very stable towards H N03 and Acad. Sci., 1935, 2, A , 421— 425).— Kernels of theso Cr03 but is oxidised by KMn04-H 2S 0 4 to ¿-methyl- seeds extracted with MeOH-HCl give a product from succinic acid, m.p. 108— 109°, [a]£,0 —9-3° in CHC13, which the quaternary alkaloids chaksine (I) and iso- and by alkaline K M n04 to a substance, C1TH250:!K, chaksine (II) arc separated through their iodides. m.p. 134— 135° after softening at 130°. H. W. Chaksine iodide (III), m.p. 168° (decomp.), is con Conessine series. I. Isomérisation of cones- verted into the (impure) base, [a]D +32° in EtOII, sine and its nor-bases. S. S id d iq u i (Proc. Indian which absorbs C02 from the air to give chaksine II Acad. Sci., 1935, 2, A, 426— 437 ; cf. A., 1934, 787).— carbonate, C12H 2oON3'HCO3,0-5H2O, m.p. 167— 169° Conessine dissolved in cold cone. H 2S04, poured on (decomp.). Chaksine sulphate (IV), m.p. 316° (de to ice, and treated with NaOH, AcOH, and KI, gives, comp.), and picrate, m.p. 239— 240° (decomp.), are with oxidation products, the hydriodide, m.p. 325— prepared; the platinichloride, (C12H 20ON3,HCl)2PtCl6, 326° (decomp.), of isoconessine (I), C24H 40N2, b.p. 239— m.p. 232° (decomp.), loses HC1 at 120°. iso Chaksine 241 °/3 mm., [a]“ +97° in EtOH [hydrochlorife iodide gives (II); this is also obtained by treating (+ 2 H 20), m.p. 318° (decomp.), [«]* +72°; plalim- (IV) with Ba(OH)2, and its carbonate, (C12H 20ON3)2CO3, chloride, m.p. 271— 273° ; aurichloride, m.p. 293—295 m.p. 128° (decomp.), by heating chaksine H carbonate (decomp.) ; picrate, m.p. 240—242° (decomp.) ; hydro in EtOH. iso Chaksine chloride loses H20 at 90° to bromide (II), m.p. 318—322° (decomp.) ; dimethiodiac, form a product, m.p. 250— 252°; the picrate has m.p. m.p. 316— 318° (decomp.)]. (I) with Br in CHC13 or 184°; thc platinichloride, (C12H20ON3,HCl)2PtCl6, m.p. AcOH yields (II) and an oily product. With H3S0j, 172° (decomp.), is stable at 120°. (Ill) gives no isoconessimine similarly isomerises, to isowonsocon«- evidence of containing OMe or W-Me; (I) and (II) sine (III), C23H3gN2, [a]3? +101° in EtOH [hydriodide, appear to be quaternary bases, with a second N m.p. 289° (decomp.) : hydrochloride, m.p. 335° (de- feebly basic. (IV) is a general depressant (heart, comp.), [a]“ +72-80° in H20 ; picrate, m.p. 166 > respiration, nerves); lethal dose for frogs, 0-1 g. platinichloride, m.p. 290—292° (decomp.)]. (Ill) vit“ per kg. E. W. W. Mel gives an ill-defined product, m.p. 280— 300° ; with ; Alkaloid from Crolalaria spectabilis, R oth . CH20 -H C 0 2H followed by ICI it furnishes the hydr- . W . M. N e a l, L. L. R u s o ff, and C. F. A hm axx (J. iodide of (I). (Ill) in HC1 with NaN02 forms a Amer. Chem. Soe., 1935, 57, 2560— 2561).— The seeds Ar0-derivative (hydrochloride, m.p. 282— 284°). Con- are soaked in 5% aq. NH3 and the filtrate is extracted imine in H 2S 0 4 gives rise to isoconimine (IV), C22H36a«. with CHC13; monocrotaline (I), probably C16H260 6N, [a]“ +89° in EtOH {hydriodide, m.p. 332° (decomph m.p. 196— 197°, is thus obtained. (I) is the toxic carbonate, hydrochloride, m.p. 335— 336° (decomph principle of C. spectabilis', pharmacological data are- picrate, m.p. 135°; platinichloride, m.p. 285 -6 given. H. B. (decomp.); (NO)2-, m.p. 123— 125°, and Hc2, m-P- 139— 140° [bromination product, m.p. 185— 186 + ' j Alkaloid of Stemona sessilifolia. H. S c h ild comp.)], derivatives}. The Me2 derivative of (} (Ber., 1936, 69, [B], 74—80).—The isolation from (CH20 -H C 0 2H) is identical with (I). _ isoConessinc tS. sessilifolia is described of an alkaloid (I), m.p. is about three times as active (respiration of frog*' 86— 87°, b.p. about 220°/0-0006 nun., [a]}3 -47-1° in as conessine. m-r W v* ■ W. CHC13, analyses of which together with those of its perchlorate, m.p. 243°, and methiodide monohydrate (II), Alkaloids of Erythrophlceum (juineense. C- decomp. 230—233°, agree most closely with the D a l m a (Annali Chim. Appl., 1935, 25, 569 571). formula C^HjgC^N. (II) is transformed by AgCl into From the bark of the West African r e d - water tr the methochloride dihydrate, m.p. 169°, and by A g,0 were isolated cassaine, C24H 390 4N, m.p. 141 > W® into the betaine, C^jH^OjNjH^O, decomp. 227— 229°, — 103° in EtOH, cassaidine, C24H430 5N, m-P- . ’ which re-forms (il) when heated with HI. (I) is a norcassaidine, C23H410 5N, m.p. 131°, and omojui’ • tert. base which does not evolve CH4 with MgMel. C56Hgo09N2. Colour reactions are given. ^ ^ 2 0 are present in a lactone group, since it dissolves in 1 mol. of hot KOH. Further groups sensitive to Reduction in morphine series. VII. i/j-Codemi alkali are not present. Catalytic hydrogenation of one. R. E. L u tz .and L. Sm ai.l (J. Amer. t ' cl XVII (g, h) ORGANIC CHEMISTRY. 351 Soc., 1935, 57, 2651— 2656).— The alicyclic double racemate, m.p. 114— 116°, with de-A’ -methyldihydro- linking in i/r-codeinone (I) [hydrochloride ( + H 20 ) (II), codeinone (II), [a]],1 —4-00° in MeOH (Freund et al., m.p. 201— 203° (decomp.)] is considered to be between A., 1921, i, 125). Reduction (H2-P d -B a S 0 4 in C6 and C7 [as suggested by Gulland and Robinson 0-3% HC1) of (I) gives its i/,-derivative, m.p. 93— (A., 1926, 83)] since treatment with an excess of 91°, [«]» +50-00° in EtOH, which gives a racemate, semicarbazide gives (as with a(3-unsaturated ketones) m.p. 113— 116°, with the 7/,-derivative, m.p. 95— 98°, semicarbazinodihydro-^-codeinonesemicarbazone [a]},1 —50-5° in EtOH, of (II). Catalytic reduction (-¡-H20), m.p. 225—227° (uncorr.; decomp.). Con of thebaine in < Ar-HCl affords dihydrothebaine (III) densation of (I), which is prepared by oxidation and a little dihydrothebainone (IV); in 2-5./V-HC1 (method : Knorr and Horlein, A., 1907, i, 547) of (IV), dihydrococ]einone (V), and metathebainone (VI), 0-codeine or allo-^,-codeine, with PhCHO doet not are obtained, whereas in 5A-HC1 a 75% yield of (VI) indicate the •CHyCO group since codeine undergoes is obtained (Cahn, A., 1933,1061). (Ill) is hydrolysed the same reaction. Reduction (H2, PtO,, AcOH) of by cold 2A-HC1 to (V). The, mixture (A., 1930, 1600) (II) affords the non-phenolic dihydro-,¡¡-coaeinone. (Ill), of deipethoxydihydrosinomenine [(+)-dihydrothe- m.p. 113°, H i? + 3 7 ° in EtOH [jhydrochloride ( + H gO), bainone] [hydrobromide, m.p. 291° (decomp.); hydro m.p. 172— 173°; hydriodide, m.p. 250—255° (de chloride, m.p. 293° (decomp.)] and demethoxydi- comp.); H tartrate (?), m.p. 199— 200° (uncorr.); hydrosinomeninol [(+)-dihydrothebainol] is separated oxime, m.p. 244—245°], reduced (Na, EtOH) to by dissolution in HBr or HC1, salts of the former- dihydro-0-codeine-A (A., 1933, 170) and converted crystallising. 1 -Bromodemethoxydihydrosinomenine by Ac20-Na0Ac into de-kl-acetyldihydro-^-codeinone (oxime, m.p. 177— 178° : the m.p. 263° given in A., enol acetate, m.p. 191-5— 192°. Reduction (H2, P t0 2, 1930, 795, is that of the oxime hydrochloride) has EtOH) of (I) gives the phenolic tetrahydro-0-codein- been obtained in a form, m.p. 167°, [a]i> +78-67° in one (+0-511,0) (IV), m.p. 137— 138-5°, m.p. (anliyd.) CHC13, which gives a racemate, m.p. 190— 193°, with 170—171°, [«]» + 8° in EtOH [ihydrochloride (+ 2 H aO), 1-bromodihydrothebainone. J. W. B. m.p. 165— 166° (decomp.); hydriodide ( + H 20), m.p. New alkaloid of ergot. S. Sm ith and G. M. 154—155°; Ac derivative; oxime, m.p. 218—219° Timmis (Nature, 1936, 1 3 7 , 111).— Ergot contains an (lit. 137°)], which differs considerably from Hill’s alkaloid, probably CggHgjOgNj, decomp, approx. 228°, description (Diss., Frankfurt, 1925). (IV) does not Hmof +522° in CHClg. L. S. I . react with CH2N2; it is reduced, as is (I), by Na and EtOH in N2 to tetrahydro-0-codeine. Demethyl- Dim orphism of ergometrine. R. L. G r a n t and ation (48% HBr) of (III) gives dihydroisomorphinone S. Smith (Nature, 1936, 1 3 7 , 154).— A second modi (V), m.p. 198°, [«]» + 4 6 ° in EtOH. (I) and MgMel fication, m.p. 212° (decomp.), of ergometrine, m.p. 162— 163° (decomp.), has been cryst. in long needles afford the phenolic metliyldihydro-^-codeinone (VI), m.p. 213-5— 214-5°, which could not be reduced from COMe2. The form of low m.p. tends to pass (various methods); no oxime or semicarbazone could into the less fusible on keeping, and is the more sol. be prepared. (VI) may be formed by 1 : 2- or 1 : 4- Both forms have H ein +62-6°, [a]“ +42-2° in EtOH. addition involving fission of the •O* ring. All m.p. L. S. T. are corr. unless stated otherwise. Pharmacological Aconitine. I. Oxonitin and the oxidation of data for (III) and (V) are given. H. B. aconitine with nitric acid and chrom ic acid. A. L aw son (J.C.S., 1936, SO—83).— Oxonitin is oxidised Strychnos alkaloids. LXXXIX. Behaviour of (HNO3) with loss of OMe to an acidic compound, strychninonic acid towards barium peroxide. C3iH 350 14N3, m.p. 263° (decomp.). Aconitine (I) is H- Leuchs and W . D ie ls (Ber., 1936, 69, [7i], 47— oxidised (Cr03) to aconitoline, C30H37°9N > m-P- 220°, 48).—'Treatment of strvchninonic acid with Ba(OH)2 hydrolysed (NaOEt) with loss of BzOH to a base, HA at 85—90° gives the NH,-acid (I), CojIIjgOgN [hydrochloride (+ 3 H 20), m.p. 222°; Ac., hsHi804X2i m.p. 248—255°, [a]™ -18-8° in H20 derivative, m.p. 239°]. (I) with HN03 gives an acid, dnfn°perchlorate, m.p. 240—243° (decomp.) after C30H35O13N2, m.p. 268° (decomp.), containing NO, softening at 230°, [a]!,0 -1 7 -4 ° ( ± 8°); semiperchlor- hydrolysed with loss of BzOH and AcOH to a sub ?, J- (I) with NaOH-MeOH-Mel gives the product, stance, C22H 290 11N3, m.p. 201°, and with HC1 con + 2oQ|N2 (perchlorate, decomp. 262°), and a mixture verted into an amino-acid, C31H30O12N2,HCl,2H2O, of neutral products. H. W. m.p. 218° (decomp.). Aconitoline with HN03 yields Sfflomffline. XLIII. K. G o to and H. S h ish id o a nitroso-acid, C^HggO^Nj, m.p. 186° (decomp.), bull. Chem. Soc. Japan, 1935, 1 0 , 597— 600).— which with HC1 forms an NH2-acid, C29H310 I2N2, -bromodemethoxydihydrosinomeneine methiodide m.p. 250° (decomp.), hydrolysed (NaOEt) to an acid, (A., 1931, 1171) with hot 2% NaOH C22H3oOhN2,HC1,H20 , m.p. 218° (decomp.). Oxid OMe^SjR' affords 1 -bromode-'N-methylde.meth- ation of (I) with HN02 gives a substance, C31H40O12N2, m.p. 276° (decomp.). These results are in agreement oxydihydrosinomeneine (A ; R '= with the formula for (I) of Spath and Galinovsky (A., n/\ A Br), m.p. 130°, [a]],1 +7-00° in vR -l 11 MeOH (methiodide, m.p. 278— 279°), 1931, 1313). F- R- S. which gives a racemate, m.p. 148°, Arsenical derivatives of thym ol. V. B e l l a v i t a o;i with 1 -bromode-lH-methyldihydro- and M. Battistelli (Annali Chim. Appl., 1935, 25, (A.) codeinone, m.p. 132°, [a]” —8-00° 631— 634).— 2-Aminothymol is diazotised and con R=-[0H,|„-NH, *n MeOH. Similarly- de-N-methyl- verted by As20 3 in NaOH (Cu) into 2-hydroxy-Q-methyl- r>, " 2 2 dertiethoxydihydrosihomeneine(i){Aj 3-propylphenylarsinic acid (I), m.p. 189— 190' (de K -H ), m.p. 120°, [«]» +4-00° in MeOH, gives a comp.). (I) is resistant to reduction by H3P 0 2; with 352 BRITISH CHEMICAL ABSTRACTS.— A. XVII (A, i), XVIII Na2C03-K I -S 0 2 it- gives after 10 days 2-hydroxy-6- temp., but they differ from SH groups in that their methyl-'i-propylphenylarsinoxide, unaltered at 320°. activity depends on the concn. and time of exposure In EtOH with HC1 (or HBr) and S02, (I) yields to K 3Fe(CN)6. F. A. A. respectively 2^hychroxy-Q-methyl-3-jpropylphenyldi- Thiol and disulphide groups of proteins. II. chloro-, m.p. 60— 62°, and -dibromo-arsine, b.p. 140°/12 Relation between number of SH and S-S groups mm. With Br in AcOH, (I) forms 5-bromo-2-hydroxy- and quantity of insoluble protein in denaturation 6-methyl-3-propylphenylarsinic acid, m.p. 204— 205°; and in reversal of denaturation. III. Thiol the corresponding 5-/-compound, m.p. 195°, is groups of native proteins : haemoglobin and the obtained in alkaline solution using 0 -liY-I. (I) gives proteins of the crystalline lens. A. E. Mtrsky no colour with FeCl3. . E. W. W. anclM . L. A n son (J. Gen. Physiol., 1936, 1 9 , 427— Polymethylbenzenes. XIII. Mercuration. 438, *439—450).— I I . No -SH groups are detectable L. I. Smith and F. L. Taylor (J. Amer. Chcm. Soc., (see A ., 1935, 506) in native ovalbumin, but on heat- 1935, 57, 2370— 2372).— The hydrocarbons are heated coagulation as many are found as in the fully hydro with Hg(OAc), in MeOH-AcOH; the resulting lysed protein. The same no. of them appears when OAc-Hg- derivatives (in CHC13, EtOH, or EtOH- ovalbumin is denatured by ultra-violet radiation, or at CHC13) with aq. EtOH-HCl, -NaBr, and -Nal surfaces. The sol. fraction of partly heat-coagulated (<1 equiv.) give the HalHg-compounds. The follow ovalbumin shows no -SH. When serum-albumin is ing are described : pentamethylbcnzene (OAc-Hg-, denatured, S’S groups appear, but disappear when m.p. 180°, ClHi]•, m.p. 205°, and BrHg-, m.p. 195— denaturation is reversed. 196°, derivatives); durene (OAc-Hg-, m.p. 158— 159°, III. Native haemoglobin and 'the proteins of the ClHg-, m.p. 188— 189°, BrHg-, m.p. 174°, and IHg-, cryst. lens contain SH groups, the no. increasing with m.p. 161— 162°, derivatives); i.sodurene (OAc-Hg-, rise of pn from 6-8 to 9-5. On denaturation, more SH m.p. 108°, ClHg-, m.p. 174°, BrHg-, m.p. 160°, and groups appear; these latter are active at pK vais, so IHg-, m.p. 163— 164°, derivatives); prehnitenc low that those in the native proteins are barely (OAc-Hg-, m.p. 147°, ClHg-, m.p. 216— 217°, BrHg-, detectable, and thus may be differentiated from them. m.p. 213— 214°, and IHg-, m.p. 200°, derivatives); At p B 6 -8, K 3Fe(CN)6 oxidises the Fe-porphyrin of mesitylene (OAc-Hg- derivative, m.p. 102— 103°); hannoglobin without affecting the SH groups; at (j-.cumcne (5-OAc-Hg- derivative, m.p. 145—147°). 9 6 , the SH groups may be oxidised, by cystine, Hg(C6MeB)2, m.p. 278° (lit. 266°), and Hg diduryl, without affecting the Fe-porphyrin. F. A. A. m.p. 242— 243°, diisoduryl, m.p. 217— 218°, and Characterisation and determination of the diprehnityl, m.p. 200°, .are prepared from the appro hydrolysis products of elastin. Isolation of the priate IHg* derivative and Nal (4 mols.) in EtOH. monoamino-acids by a new technique. R- H. B. E n g e la n d (Bull. Soc. Chim. biol., 1935, 1 7 , 1790— Antiseptics. Mercury salts of alkylfluores- 1804).— NH2-acids are separated by fractional ppt-n. c e in s . A. N o v e l li (An. Farm. Bioquim., 1933, 4, of the hydrochlorides from MeOH solution. From 29— 35; Chem. Zentr., 1935, i, 3691).—-Mercuration elastin two NH 2-acids, C14H 220 4N 2 and C17H 3804N2, ROH of cVaCe^ 1;i 1diPr1°- are isolated as the Cu salt, C11H20O4N2Cu, and the pionyl-, diethyl-, di aurichloride, C17H 30O4N 2,2AuC14, respectively. A. L. propyl-, dibutyl-, and dihexyl - fluoresceins Determination of the m.p. of organic sub leads to IIg compounds s t a n c e s . F. F r a n c is and F. J. E. Collins (J.C.S., (I). The antiseptic 1936, 137— 142).— A description of apparatus for ■Hg-OH activity increases with setting point and m.p. determination. Setting point increasing length of gives more accurate experimental vais, for transition R OH temp, from solid to liquid. With the apparatus the side-chain, R. Presence of ICO in R diminishes antiseptic power. described, existence of metastable forms fusing within 1° of each other can be detected, transition temp- H. N. R. Action of radioactive substances on proteins.— recorded, and a judgment reached on the purity of See this vol., 301. the specimen. F. R. S. M ultivalent am ino-acids and peptides. VI.— Organic micro-analytical practice. C. W eY - See this vol., 379. ga n d and H. H e n n ig (Chem. Fabr., 1936, 9, 8— 10)--- The technique of methods of C, H, N, halogen, S, Influence of neutral salts on the optical rota and OMe-determination, asapplied to samples of tion of gelatin. I l l, IV .— See this vol., 288. 0-001— 0-01 g ., is detailed. J . W. S. Colloid chemistry of edestin. III.— See this vol., 288. Determination of carbon and nitrogen by the action of chrom ic acid under reduced pressure. Salting-out and peptisation of edestin by m ix C. N. A c iia r y a (Bioehem. J ., 1936, 3 0 , 241— 247).— tures of two salt solutions.— See this vol., 288. C and N are determined in org. material by oxidation Reducing groups of proteins. A. E. Mbrsky with Cr03 and H 2S04 and the C02 evolved is absorbed and M. L. A n son (J. Gen. Physiol., 1936, 19, 451— and weighed. Subsequent direct distillation of the 459).—Proteins contain, besides SH groups, others digest with alkali gives low vais, for N owing to the which will react with K 3Fe(CN)6, and are probably in formation of N 03' so that a preliminary reduction is the tyrosine and tryptophan units. Their activity is necessary. The disturbing influence of Cl is avoided enhanced by denaturation and by increase of pa and by addition of HgO. H. D. XVIII ORGANIC CHEMISTRY. 353 Analysis of organic compounds containing H h a ra . VI. Reaction of ascorbic acid and glut and D . H. Erlenmeyer and H. G a r t n e r (Helv. athione -with phospho-18-tungstic acid reagent. Chun. Acta, 1936, 19, 129— 144).— The customary VII. Modified phospho-18-tungstic acid method determination of H in org. compounds which of determining cysteine, cystine, and ascorbic contain H and D gives accurate results only when the acid in urine. K. S h in o h a r a and K. E. P a d is content of H is very high. In the general case a (J. Biol. Chem., 1936, 1 1 2 , 671— 682, 683— 696, differentiation between a H- and D-compound cannot 697— 708, 709— 721; cf. this vol., 60).— IV. Cysteine thus be effected or only very, inexactly. Generally, (I) and SH,CH2,C02H are allowed to react with a the differences in the % of C allow an approx. differ deficiency of HgCl2 and the excess is determined entiation between H- and D-compounds but for accur colorimetrically by phospho-18-tungstic acid (II). ate results a high % of C and H is necessary. Suitable II20 and a little cystine (III) are the chief impurities relationships exist in hydrocarbons particularly in in commercial (I). (Ill) does not interfere with the those of the paraffin series. A method is described determination of (I) by this method. in which the substance (0-05 to 0-15 g.) is burnt with V. ( I l l ) is reduced by NaHS03 and then de CuO and the water is collected in a tube cooled in termined colorimetrically by (II). NaHSOa alone solid C02-CC14-CHCI3. It is mixed with 10 c.c. of develops little colour; HgCl2 inhibits formation of standard H 20; the mixture is distilled and its d colour by (III). Various reducing agents, but not is determined. The sensitiveness is such that in a (I), interfere. mixture of isotopic benzenes, approx. PhD, it is just VI. Ascorbic acid (I V) is determined colorimetrically possible to discriminate between C8H 1.D95D 1.q05 and by (II), the colour being twice as intense as that due ^C-®5005®0-995' H. W. to equimolar amounts of (I). The colour is not affected under specified conditions by HgCI, or small Determination of organic sulphur by the liquid amounts of CI120. (I), (HI), and (IV) are thus ammonia-sodium method. P. J. S ow a, V. G. determined in the same solution by use of CH20, Arcadi, and J. A. N ie u w la n d (Ind. Eng. Chem. HgCI,, and (II). Oxidised (IV) gives no colour. [Anal.], 1936, 8 , 49—50).—0-1 g. of substance is Glutathione gives irregular results, probably due to dissolved in 175 c.c. of liquid NH 3 with the help if hydrolysis, and interferes with the methods. necessary of an inert solvent and Na is added until the VII. Modifications are necessary for determinations blue colour is permanent. The solution is evaporated in urine. Eresh normal urine contains 0— 0-9 mg. [2a c.c.), 3— 5 g. of NH4C1 are added, and the mixture of (I), 1-1— 4-8 mg. of (III), and 3-2— 26-8 mg. of is evaporated to dryness. The residue is taken up in (IV) per 100 c.c. R . S. C. HjO, oxidised with 2 g. of Na202, and the S pptd. as BaS04. The method is accurate and of general Determ ination of cystine by Sullivan’s m ethod : applicability. S. C. supposed cleavage of cystine from casein by dilute alkali. H. J. L e e (Austral. J. Exp. Biol., p-Bromobenzhydrazide as a reagent for the 1936, 1 3 , 229— 237).— Various factors may interfere identification of aldehydes and ketones. S. M. with the determination of cystine (I) by Sullivan’s King, Cheng-Heng Kao, Chung-Hsi: Kao, and method. The conclusion of Jones and Gersdorff (A., lb P. T. Sah (Sci. Rep. Nat. Tsing Hua Univ., 1935, 1934, 313) that treatment of casein by dil. alkali A, 3, 279—284).— p-Bromobenzhydrazide, m.p. 164° destroys some of the (I) is vitiated by their failure (prep, from p-C6H4Me-NH2 described), condenses to make allowance for the interfering effect of the with aldehydes and ketones in boiling 95% EtOH casein hydrolysate on the determination of (I). containing a few drops of glacial AcOH yielding p- W. O. K. WMnobmzoylhydrazones of the following substances : Titration of am ino-acids in glacial acetic acid M g ) , m.p. 192— 193°; EtCHO, m.p. 172— 173°; s o lu t io n . G. F. N a d e a u and L. E. B r a n c h e n (J. lr°CH0, m.p. 157— 158°, Bu“CHO, m.p. 153— 154°; Amer. Chem. Soc., 1935, 57, 1363— 1365).— NH2-acids hexaldehyde, m.p. 144— 145° ; u-heptaldchyde, m.p. (I) (in glacial AcOH) are determined by titration 121—125°; PhCHO, m.p. 242—243°; p-, m.p. 250— with OTAr-HC104 using crystal-violet, a-naphthol- f l > and m-, m.p. 217—218°, -N0 2-CfiH4-C H 0 ; benzein, or benzoylauramine as indicator; picric acid furfuraldehvde, m.p. 218—219°; CHPhiCH-CHO, does not interfere. (I) insol. in AcOH are determined m.p. 235—236°; COMe,, m.p. 198— 199°; Me hexyl by dissolution in an excess of OTAr-HC104 and back- Ketone, m.p. 131— 132°; COPliMe, m.p. 192— 193'°; titration with guanidine acetate. The results agree m.p. 212—213°; benzylidene- with potentiometric titration (in AcOH using chlor- acetophenone, m.p. 219— 220°; wi-N02-C6H4-C0Me, anil electrode). H. B. m.p 219—220°; COPh,, m.p. 160— 161°; lmvulic r n k m-P- 158— 159°; Et, m.p. 128— 129°, and Colorim etric determination of allantoin. G. 21°h, m.p. 123— 124°, kcvulate; CH2Ac-C02Et, M o u r o t (Bull. Soc. Chim. biol., 1935, 1 7 , 1845— m.p. 74—rjtf' Primary and sec. alcohols are oxidised 1850).—The method is a modification of that of Fosse and then identified by this method. H. W. (A., 1931, 976). The allantoic acid is hydrolysed to glvoxylic acid, which is determined colorimetrically Determination of thiol and disulphide com using NHPh-NH2. A. L. pounds, with special reference to cysteine and cystme. IV. Accurate determination of thiol Weydel reaction for xanthines. G. D enic^s compound3. Standardisation of cysteine hydro (Bull. Trav. Soc. Pharm. Bordeaux, 1934, 7 2 , 345— chloride . V . Cystine determination by sulphite 355; Chem. Zentr., 1935, i, 3162).— Colour reactions and phospho-18-tungstic acid reagent. K. S h in o- for caffeine, theobromine, theophylline, xanthine, and 354 BRITISH CHEMICAL ABSTRACTS. A. XVIII guanine are described; the underlying mechanism Spectrophotometric determination of chloro- and the influence of constitution are discussed. phyll a and t>, carotene, and xanthophyll.—See H. N. R . this vol., 396. Biochemistry. Effect of respiration of pure oxygen on meta on the rate in vitro. I. B in e t and I. K rasznai bolism. P. B ie lch o w sk y and S. T h a d d e a (Z. (Biochem. Z., 1936, 283, 190— 198).— Westergreen’s klin. Med., 120, 330— 340; Chem. Zentr., 1934, ii, method gives trustworthy results only if const, temp, 3399).— Blood-ketones in man, if high, are diminished, and p a are maintained in the tubes. In vitro the and pH is shifted towards the alkaline side as the rate of sedimentation of washed red blood corpuscles result of decreased alveolar C02 tension. The lactic and to a smaller extent that of blood is diminished acid curves obtained by injections of Na lactate and by addition of globulin. W. McC. adrenaline in man or the dog lie considerably lower “ Urea surcharge ” (Delaunay) of the erythro in 0 2 respiration. R. N. C. c y t e s o f Sipunculus : distribution of urea be Respiration of carbon dioxide in narcosis and tween erythrocytes and plasm a in the ccelomic in paralysis of the respiratory centre. H . F r a n - liquids charged with erythrocytes. M. F lo r k ix k en (Schmerz, Narkose, Ansesthesie, 1934, 7, 26— 36; (Compt. rend. Soc. Biol., 1936, 121, 158— 160).— Chem. Zentr., 1934, ii, 3646). R. N. C. The erythrocytes of the ccelomic liquid of Sijmncufas Simple valveless apparatus for determination are surcharged with urea, but not those of Echiurus, of gaseous metabolism in man. P. F oldes (Bio- Glycera, or Gapitella. R . N. C. chem. Z., 1935, 282, 303— 307).— The apparatus (cf. Effect of heparin on the permeability of the the similar apparatus for dogs, A., 1935, 238) is erythrocytes to adrenaline. M. K u c z a r o w (Klin. described. The error of duplicate experiments is W och., 1934, 13, 734— 735; Chem. Zentr., 1934, ±3%. P. W. C. ii, 3780— 3781). R . N. C. Respiratory characteristics of the blood of the Characteristics of the stability of corpuscular seal. 1,. Ir v in g , 0 . M. So l a n d t , I). Y. So l a n d t , glucose subjected to washing with physiological and K . C. F ish e r (J. Cell. Comp. Physiol., 1935, 6 , s o lu t io n . G. P a tr a s s i an d U . T e o d o r i (Boll. Soc. 393—403).—The capacity of the blood for C02 and ital. Biol, sperim., 1935, 10, 525— 526).— Repeated its buffering power are < those of human blood. 0 2 washing of erythrocytes with 0-9% NaCl reduces capacity vals. and dissociation curves are given. their glucose to a steady min., which in erythrocytes R. N. C. from diabetics is slightly > from normal subjects. Vapour pressure of the blood of arthropods R. N. C. from swift and still waters. II. M. Fox and Corpuscle resistance and bilirubinsemia in E. J. B a ld e s (J. Exp. Biol., 1935, 12, 174— 178).— young m amm als with trychophytia after slow No correlation was apparent between the v.p. of dosage with thallium acetate. I. G a t to and G. blood and the 0 2 consumption. Ch . A bs. (p) M e lo d ia (Pediatria, 40, 230—235; Chem. Zentr., Effect of oxygenation of the external medium 1934, ii, 3397).— Corpuscle resistance is increased and on the composition of blood in Scyllium canicula. bilirubinsemia diminished or abolished. R . N. C. E. A. P ora (Compt. rend. Soc. Biol., 1936,121, 194— Diurnal variations in concentration of red 196).— Total osmotic pressure, Na, Ca, proteins, org. blood cells and hsemoglobin. J. J. S h o r t (J- substances, and the alkaline reserve are increased, Lab. Clin. Med., 1935, 20, 708— 713). Ch. Abs. (p) whilst plasma-Cl falls; corpuscular Cl is unaffected. Mineral salts in serum and muscle increase simul Percentage of hsemoglobin com pared with the taneously, and H 20 passes from the blood to the volume of erythrocytes. Importance of this muscles. R. N. C. relation in correcting the Van Allen determin Variation of blood-p„ and blood-gas after ation of the volum e of platelets. K. K . N ygaar» injection of sodium silicate. K. D a ik o k u (Trans. and D. L. D u x b u r y (J. Lab. Clin. Med., 1935, 20, Soc. Path. Japon., 1934, 24, 72— 76).— Continuous 767— 772).— The hsemoglobin content expressed as injection caused a decrease in blood-p„ and -gas. g. per 100 c.c. is closely related to the vol. of erythro Ch. Abs. (p) cytes expressed as vol.-% of the sample. Tables for Regeneration of blood in fish following bleed intercalculation are given. Ch. Abs. (p) in g. L. B a u d in (Compt. rend. Soc. Biol., 1936, 0 1 .Y-Hydrochloric acid as diluent for com 121 330— 332). R. N. C. bined leucocyte and hsem oglobin determinations. Effects of extracts of pituitary gland on sedi C. A. P ons and W . P. B elk (J. Lab. Clin. Meek, mentation of red blood corpuscles of normal 1935, 20, 766— 767).— Blood diluted with O-lN-HCl and hypophysectomised dogs. T. I chijo (Sei-i- is suitable for white cell counts and for examination Kwai Med. J., 1934, 53, No. 6 , 123— 132).— Data in the Huden-Hausser hsemoglobinometer. obtained by Kowarski’s apparatus are given. Ch. Abs. (p) Ch. Abs. (p) B i r t h pains and the blood of the new-born- Determination of rate of sedimentation of Z. H o rvath , and C. H oll6 si (Ainer. J. Dis. Children, blood corpuscles. Effect of globulin solutions 1935, 49, 689— 694). Cii. A bs. (p) XIX (b) BIOCHEMISTRY. 355 Determination of haemoglobin in experimental human serum are bilirubin (I), carotene, and xantho- anaemia in rabbits. R. D am ade, L. Servantie, phyll. (I) in aq. EtOH is determined after treat and J. Ferville (Compt. rend. Soc. Biol., 1936, ment with SOgH-CjHyiSqCl. The pigments produced 121, 229—232).—The methods of Sahli and Auten- by ultra-violet irradiation of (I) are insol. in light rietli and of Wong are recommended. R . N. C. petroleum and cannot be diazotised. W. McC. Solutions of haemoglobin stabilised with time. New crystalline derivative of blood-pigments. I, W. D uce II. (Boll. Soc. ital. Biol, sperim., 1935, M- W a g e n a a r (Z. anal. Chem., 1935, 103, 417— 418). 10, 376—-379, 379— 382).— I. Solutions of haemo —The object to be tested for blood is moistened on a globin (I) after prolonged dialysis are coagulated by microscope slide with COMe2, and a drop of dil. boiling, and by 2A7'-NaCl, or EtOH, are coloured red mineral acid is added. Characteristic crystals of by slight acidification or alkalisation, and pptd. acetone-hsemin are produced with the dried residue by HNOg, AcOH, H g(N 03)2-HN03, and K,Fe(CN)G from 0-05 mg. of blood. J. S. A. (II). but not by CuS04, NiS04, AgN03, basic Pb acetate, or HgCl2. After prolonged storage at room Spectrophotometric investigation of cyano- temp, dialysed (I) is coagulated only by 217-NaCl, compounds of blood-pigments. S. Schonberger is coloured brown by acids and alkalis, and pptd. and P. B a lin t (Biochem. Z., 1936, 283, 210— 221; by all the above reagents except (II). cf. A., 1935, 999).— In the visible part of the spectrum II. The absorption bands of (I) in the red are dis the absorption curves of cyanomethfemoglobm (I), placed towards the red end by prolonged dialysis cyano-NH3-parahamiatin,cyano-C5H 5N-parahaematin, and storage. The absorption quotient falls. and cyanoh;cmatin are identical and exhibit a max. R. N. C. at 541 mg. In the ultra-violet (I) and cyanopara- Sulphur content of heemoglobin with special huematin (but not cyanohrematin) exhibit an intense reference to b lo o d -g r o u p s . G. B alassa (Biochem. well-defined band at 424 mg. The sp. extinctions in Z., 1936, 283, 222— 228).— In man the haemoglobin the visible are decreased 15% by increasing the (I) of the blood of some individuals contains 0-611% alkalinity. The results throw light on the constitu of S whilst that of others contains 0-662%, the corre tion of blood-pigments. W. McC. sponding F e: S ratios and min. mol. wts. being, Variations of osmotic pi'essure and of the size respectively, 4 : 13, 4 : 14, and 68,000, 34,000. The of hsemocyanin molecules during a long fast (in blood of individuals belonging to blood-groups A summer or hibernating) of varieties of H elix. and B contains the second, that of the blood of in A. R och e and J. R och e (Compt, rend., 1935, 201, dividuals belonging to blood-group O the first, kind of 1522— 1524; cf. A., 1934, 673).— The mol. size of W- W . MoC. hcemocyanin in H. pisana and H. pomatia is about Optical properties of acidified solutions of halved by fasting. This may be the mechanism for v f anfl CO-haemoglobin in blood. G. B a r k a n H20 retention within the animal. J. L. D. Z-, 1936, 2 8 3 , 241— 252; cf. A., 1930, Reticulo-endothelial origin of fibrinogen : j™ ’)■—Spectrophotometrie examination indicates comparative study of the fibrinogenetic action of at the darker colour of the solutions containing CO some carioclasics. P. Campellone (Boll. Soc. is due to a difference in the degree of dispersion. ital. Biol, sperim., 1935, 10, 497— 499). R. N. C. a , . W . McC. Analysis of the spectra of hsemoglobin deriv- Micro-Kjeldahl technique for determining 189SSi- D' L ' D rabk in (Amer. J. Med. Sei., 1935, fibrinogen. H. R. G a rb u tt and R. S. H u b b ard ’ '"A)■—Absorption curves are represented as (J. Lab. Clin. Med., 1935, 20, 758— 761).— Plasma ca h 10nS a no' i'ldividual bands. Oxy- (I), (0-5 c.c.) is mixed with 24 c.c. of 0-85% NaCl and ®)> cyano-, and two forms of met-hacmo- 0-5 c.c. of 2-5% CaCl2 solution. The clot is removed k .r'1 e certain bands in common. Their position centrifugally, washed with 0-05% CaCl2 solution, bclnISCf Sed: ^ le “-bands of (I) and (II) do not digested with the Folin-Wu mixture, and diluted to , ,JnS 1° this series and probably represent the union 10 c.c. N is determined by nesslerisation. oi hemoglobin with a gas. “ Ch . A b s. (p) Ch. Abs. (p) Protein and electrolyte contents of the plasma ^ phatic amino-content of the oxyhaemo- and transudates (serous effusions and sub anirnals. K. Gergely (Biochem. Z., cutaneous fluid). L. Antognetti (Pathologica, of h iP-9—232).—The average NH2-N contents 1935, 27, 182— 189).— A progressive and parallel H bog-, and ox-oxy hsemoglobin are, respec- decrease occurs in the [H’j and protein concn. in the a r i 1 '96~ 12'48- 13-14, and 13-28%. The vals. order erythrocytes, plasma, serous effusions, sub altered by repeated recrystallisation, cutaneous transudates. Variations in [HC03'J are in r),-« . . * W. McC. the reverse order. The Donnan membrane equi serum rer^lati°n of the pigments of human librium explains the facts. Ch. Abs. (p) F Vp„' - Sbllm ann, E. Szecs£:nyi-Nagy, and A, m - A\ (Biocbcm. Z „ 1936, 2 8 3 , 263—272; cf. Protein equilibrium of blood-serum in ana bv i ^pigments may be determined phylactic states. Aubry, Thiodet, and R ibebe a), jwrjr? advantage of their differing solubilities in (Compt. rend. Soc. Biol., 1935, 120, 1257— 1259).— by’ „1 ' anc’ light petroleum and may be separated Protein equilibrium is disturbed in anaphylactic excenH at? 8raphie adsorption on A1203. With the states, particularly urticaria, albumins remaining biliniliin'V?. vciry small amounts of non-diazotisable steady whilst globulins fall considerably. -like pigments the only pigments in normal R . N. C. XIX (6) 356 BRITISH CHEMICAL ABSTRACTS.— A. Protein, lipin, and total cholesterol content of 373).—There is a statistically significant correlation the serum of the normal cat. L. Blanchard between the adenine nucleotide and haemoglobin (Bull. Soc. Chim. biol., 1935, 17, 1677— 1692).— The contents of the erythrocytes. J. X. A. vals. for the serum-protein, -serine, -globulin, total Oxidised/reduced glutathione ratio in acute serum-lipins, and cholesterol of the normal cat are oxidosis. W. L ib b r e c h t and A. M a ssa rt (Compt. 73-44±8-64, 38-35±6-97, 34-7S±8-72, 8-63±l-92, and rend. Soc. Biol., 1935, 1 20, 1330).— The oxidised/ 1.Q3-CO-20 g. per 1000 g., respectively. These vals. reduced glutathione (I) ratio of rabbits’ blood is are of the same order as those for the dog and for increased by prolonged exposure to air or 0 2 in vitro, man. . A - L . but is reduced by exposure to pure 0 2 at high pres Influence of ingestion of colostrum on proteins sures in vivo; the state of (I) depends therefore on of the blood sera. I. P. E a r le (J. Agric. Res., 1935, oxidation in the tissues. R. N. C. 51, 479—490).—Sera of new-born foals, kids, pigs, Liver and glutathione. L. B in e t and G. W eller and lambs are deficient in euglobulin (I) and low in (Compt. rend., 1935, 201, 992— 993).— In fasting dogs, pseudoglobulin I (II). On ingestion of colostrum (I) total glutathione (I) (oxidised-/-reduced) in the blood and (II) increase rapidly. With foals the amounts from the portal vein is 9%, and in the suprahepatic of (I) and (II) absorbed are related to the quantity vein 44%, > in blood from the femoral artery. of colostrum ingested. E. P. During digestion, the figures are 51% and 27%, Determination of the tyrosine index of serum respectively, indicating that during fasting the blood polypeptides. R . L e f a u x (Bull. Soc. Chim. biol., absorbs (I) from the liver, and deposits (I) during 1935, 17, 1822— 1827).— The difference in colour digestion. F. A.A. intensity between the CC13*C02H and phosphotungstic Determination of glyoxalines in serum. A. acid filtrates of the material after treatment with S ch w artz and A. R ie o e r t (Compt. rend. Soc. Biol, conc. HN03 and aq. XaOH is measured. A. L. 1935,1 20, 1309— 1312).— The method of Loepcr dal. Polypeptidaemia in anaphylactic shock. M. is unsatisfactory. R- X- C. Polonovski, C. G ern ez, and J. D rie s s e n s (Compt. Does the blood contain acetylcholine? R- rend. Soc. Biol., 1936, 121, 37— 38) — Blood-poly- A mmon (Klin. Wocli., 1935, 14, 453— 456).—Acetyl peptides show no significant modification either in choline cannot be detected chemically or biologically anaphylactic shock or during sensitisation. in the blood. R- X. C. 1 J R.X. C. Arginine as the cause of the non-specificity oi Polypeptidaemia during anaphylactic shock. analytical methods for blood-guanidine. M. E. Maignon (Compt. rend. Soc. Biol., 1936, 121, Zappacosta (Diagnostica tec. lab. [Xapoli], 1934, 5, 225—226).—A reply to Polonovski, Gernez, and 919— 927).— Reagents for colorimetric tests give the Driessens (see above). R- X . C. same colour intensity with guanidine (I) as with Hyperazotaemia of neuro-central origin. P. equimol. quantities of arginine (II). (II), like (I).13 J e d lo w s k i (Boll. Soc. Ital. Biol, sperim., 1935, 10, adsorbed by C and 70% of it may be eluted with 615— 618). R .X .C . 0-02iY-HCl in EtOH. Ch . A bs. (?) Variation of residual nitrogen in blood after In dole. II. E ffect of indole on blood-sugari injection of sodium silicate solution. II. A ica- urea-nitrogen, and blood-amino-acids. ty bane (Trans. Soc. Path. Japon., 1934, 24, 76— SI).— Indolsemia provoked by ligaturing the hepatic Residual X increased after injection. peduncle : indican-indole index. E. M accHU Ch . A b s. (p) (Boll. Soc. ital. Biol, sperim., 1934, 9, 1314— 1315. , Influence of protein feeding on the nitrogenous 1935, 10, 528— 530).— II. Indole (I) temporarily in blood constituents in the dog. L. Sas (Biochem. creases blood-sugar in clogs, but scarcely affects non- Z., 1935, 282, 308—316).—The blood-residual-X is protein-X and XH 2-acids. greatly increased by protein feeding, due in the initial III. Ligature of the hepatic peduncle in the dog stages to increase in blood-urea. The polvpeptide-N after injection of (I) increases blood-(I) and reduce shows no characteristic changes. In animals receiving blood-indican. The liver is hence concerned in (m a N-free diet, blood-urea decreases, but residual X metabolism. The indican-(I) index is defined. remains unchanged. P. W. C. R. N. C- Blood- and urinary nitrogen of a lamelli- Blood-lipins, -calcium, and -potassium during branch mollusc (Anodonta cygnea). M. E lorK IN experimental excitation of the hypothalamus ,1" and G. B osson (Compt. rend. Soc. Biol., 1935, 120, d o g s ]. A. van Bogaert and L. v an M e e l (Compt 1308— 1369).— Total, protein-, and non-protein-X vals. rend. Soc. Biol., 1936, 121, 199— 201).— Blood-lip"« for blood and urine at different seasons are given. are temporarily depressed, the fall being alnios^ R„ N. C. exclusively due to decrease of fatty acids. Cholestero Non-protein-nitrogen content of blood of and unsaponifiable material are scarcely affected, t. healthy K orean adults. H. S. L e e (J. Chosen Med. sometimes shows a slight temporary rise, and h Assoc., 1934, 24, 1541— 1548).— In most cases, vals. slight fall. R-X. varied from 29 to 43 mg. per 100 c.c. of blood (mean Serum-lipins by a micro-gravimetric tech for 79 cases 36-ll±0-S 3). Ch . A b s. (p) nique. W. R. W ils o n and A. E. H an sen (J- h»°J- Adenine nucleotide content of human blood. Chem., 1936, 112, 457—468).—The inorg. P » “ ' II. C orrelation w ith haem oglobin. M. V. B u e l l wt., total acidity, and I val. of the fatty acids o (J. Biol. Chem., 1936, 112, 523— 530; cf. A., 1935, saponifiable fraction and the I val. of the unsapom XIX (6) BIOCHEMISTRY. 357. able fraction of the serum-lipins were determined in of EtOH from putrefying blood increases with rise 2-5—5 c.c. of serum. The mean total, unsaponifiable, of temp. B. N. C. and saponifiable lipins were 0-657, 0-260, and 0-362%, respectively. 81% of the lipin-P is found in the Organic phosphorus of the blood studied by saponifiable fraction. H. D. the method of prolonged spontaneous hydrolysis, Carotensemia. E. B o u n in and M. L é v in s o n (Z. in man and in some domestic animals. G. d e Vitaminforsch., 1935, 5, 12— 21).— Carotenaunia is T o n i (Arch. 1st. Biochim. Ital., 1935, 7, 303— 340).— associated with tuberculosis, diabetes, typhus, mal The autolysis curves at 37° of org. P in infantile and aria, metabolic disturbances, spleen and liver diseases, adult human and animal blood are described. The and in normal persons with a carotene-rich diet. The curves are essentially the same in laetating animals subnormal oxidation of carotenoids is related to the of all species. Autolysis is rapid during the first 24 concomitant hypocholesterolmmia. E. O. H. hr., but slackens very considerably afterwards. In the adult animals inorg. P is always < in the corre Blood-cholesterol in the carotid artery, venae sponding laetating animals, and the autolysis curves cavas, and portal vein. F. H. Shillito, E. H. show wide variations from each other. Autolysis is B idw ell, and K. B. Turner (J. Biol. Chem., 1936, most extensive in rabbit blood, moderate in human 112, 551—556).—The level of the blood-cholesterol (I) and horse blood, whilst sheep’s and cows’ bloods in these vessels was the same for a given animal, contain little or no org. P. p . N. C. whether the whole blood or serum was used, and whether or not cholesterol was administered pre Influence of pituitary body and preparations viously. Passage through the lungs had no effect on of other endocrine organs on inorganic salts of (I). Large doses of KI given for 2— 14 days pro the blood. S. N ish id a (Sei-i-Kwai Med. J., 1934,53, duced no variation in the distribution of (I). No. 6, 133— 175).— Hypophysectomy causes a de „ . . J. N. A. crease in blood-Cl* -Na, -K, and -Mg and an increase Variations in blood-cholesterol in man and in in -Ca. Pituitrin, antuitrin, and pituglandol produce animals. L. I. Putschinski and T. T. G lu h e n k i a reciprocal effect in normal clogs and restoration to (Bull. Soc. Chirn. biol., 1935, 17, 1836— 1844).— The normal levels in hypophysectomised animals. Oophor- cholesterol (1) content of (fasting) human blood over min, thyroxine, and adrenaline cause a decrease in a 24-hr. period varies between 50 and 130 mg. per Mg and K arid an increase in Ca. Insulin produces 100 g. (1.) of rabbit and dog blood varies likewise. no change in Mg in normal, but a decrease in that of - „ A. L. hypophysectomised, dogs. Ch. A bs. (p ) influence of a hyperthermal sulphuretted Blood, bile, and liver of animals with perma radioactive e n v iro n m e n t o n s o m e co n stitu e n ts of nent biliary fistulas. F. Cavazza (Pathologica, the blood. A. Krijanovsky (Compt. rend. Soc. 1935, 27, 241—250).—In dogs blood-Ca and alkaline Biol 1935, 120, 1236— 1238).— Blood-sugar, -N, reserve are lowered and blood-K increases. No -cholesterol, and plasma-Cl are depressed, whilst marked changes occur in Ca content of bile and corpuscular CL rises, in man in the Luchon radio- hepatic tissues. Ch . A bs. (p) raporarium. R K. q Blood-sugar of Cancer pagurus : nature of Effect of changes in the concentration of reducing substances and factors of variation of plasma-electrolytes on the concentration of ood-sugar. J. B o c h e and C. D u m a z e r t (Compt. electrolytes in the red blood cells of dogs, mon rend. Soc. Biol., 1935,120, 1225— 1227).— The hcemo- keys, and rabbits. H. Yannet, D. C. D a rro w , Jn'ph contains glucose (I) and non-fermentable M. K. C a ry (J. Biol. Chem., 1936, 112, 477—488).__ reducing substances pptd. by Cd(OH)2. The average In monkeys and rabbits changes in the plasma-Na, produced by intraperitoneal injection of aq. glucose nor i • contcilfc is ° '21 g- Per 1000; it is tem- i>o arily increased by removal from the aquarium, or NaCl, caused changes in erythrocyte-Na and -K is unaltered by insulin, adrenaline, or muscular due to shift of I120 alone, in the dog a certain ork- B. N. C. migration of cations occurred. H. D. Hypoglycmmia by conditioned reflex. C. C. Bromine in blood and spinal fluid ; its relation iovHOiL?n$ A- Budeanu (Compt. rend. Soc. Biol., to blood-iodine. U. C. B o n o r in o , M. S ch te in - r.,’ r¿l> 185— 186).— Babbits injected with 0 -9 % g a r t, and B. F e r r a m o la (Prensa med. Argentina, nf n i daily injections of insulin exhibit a fall 1934, Mar. 7).— Blood-Br varied from 0-6 to 3-6 01 bkod-sugar. B . N. C. mg. per 100 c.c. Br and I vary in a parallel manner, nnr^°U^ constancy °f phenolsemia in man in I : Br ranging between 70 and 170. Spinal fluid ]it,m f nd Pathological states. B. B a n ei, E. contains 0-2 mg. of Br per 100 c.c. Ch . A bs. (p) Id'}«’ 11- Marenzi (Compt. rendí Soc. Biol., Blood-chloride in healthy Koreans. M. S. Km tnflv i ? ’ — 359).— Free phenols (I) in nophro- (J. Chosen Med. Assoc., 1934, 24, 1537— 1540).— liiJot i ,od are > in normal blood, whilst eon- Vais, for Koreans who eat excessive amounts of c(.? <>c Phenols (II) are more variable. The Con salt fall within normal variations found in occidentals. ner; C‘] c « *n n°rm aí blood is > that of (II) over a Period of 28 hr. j> q Ch . A bs. (p) Effects of hydrochloric acid and sodium in^-f °* ^ c°1lo1 in the blood in putrefaction hydrogen carbonate administrations on distri 10't-,1-ioA N ic lo u x (Compt. rend. Soc. Biol., bution of blood-chlorine. N. M a tsu o k a and K. ’ ’ 1301— 1306).— The rate of disappearance D a ita (Trans. Soc. Path. Japon., 1934, 24, 82— 91).— XIX (b) 358 BRITISH CHEMICAL ABSTRACTS.— A. NaHCOg increases blood-Cl and decreases plasma-Cl. < in teleosteans. Blood-Cl in cephalopods is approx. Both vals. increase after administration of HC1. equiv. to Cl in the sea; in selachians it is half, and in C h . A b s . (p ) teleosteans a quarter, of the ceplialopod val. Proteins Metabolism of iodine. I. Blood-iodine. II. are high in cephalopods. R. N. C. Influence of ascorbic acid on blood-iodine. H. New antagonistic property of normal sera: L o h r (Arch. exp. Path. Pharm., 1936, 180, 332— the cercaricidal action. J. T. C u l b e r t s o n and 343, 344— 353).— I. Improvements in methods for S. B. T a l b o t (Science, 1935, 82, 525— 526).—Sera the micro-determination of I are described. The of manv animals have a definite cercaricidal action. blood-I (I) of healthy men and women is 20— 30 X L. S. T. 10'6% and is not influenced by sex or season; it is Investigations [on sera] in the ultra-violet. greatly increased by exercise (rowing) for 1 hr., re W . G r a u b n e r (Z. ges. exp. Med., 81, 1—5; Cliem. turning to normal after 1 hr. rest, but increasing Zentr., 1934, ii, 3397).— The absorption spectra of again after 24 hr. different human sera vary considerably, but no II. Ascorbic acid lowers the (I) of normal and significant deviation appears in any single serum. thyroidectomised dogs and antagonises the (I)- Pptn. with EtOI-I or dialysis shifts the spectrum increasing action of thyroxine. P. 0. H. about 10 mg towards the visible, but deproteinisation Diffusible calcium in the serum of laying and with Fe(OH)3 or large p a changes with II2S0., or NaOH are ineffective. The substance responsible n on -layin g hens. M. W . T a y l o r and W . C. R u s s e l l (J. Agric. Res., 1935, 51, 663—667).—No difference for the spectrum is not one of the known seriuu in the level of diffusible Ca was apparent. Non- constituents, and probably contains a CO or a C6He diffusible Ca was much higher in the laying condition. ring. Urine always shows a band between 260 A. G. P . and 280 mg; the max. is indefinite. The spectra Variability of non-hsemoglobin iron. T. G. of both sera and urine are probably due to the same substance, which is also present in cerebrospinal and K l u m p r (J. Clin. Invest., 1935, 14, 351— 355).— Non-hsemoglobin Fe varies widely and is a signi pathological fluids. R- N. C. ficant fraction of the total Fe. Ch. A b s . (p) Behaviour of calcium in the electrodialysis of Chemical and physico-chemical sexual dif blood-serum and its dialysate. G . P e r e t t i (Boll. Soc. ital. Biol, sperim., 1934, 9, 1333— 1336).—6* ferences in the blood of selachians. E. A. P o r a (Compt. rend. Soc. Biol., 1936, 121, 105—107).— transport is anodic with small currents and catbodic Corpuscular vol. and Cl, arid k in the blood of males with large currents in both serum and its dialysate; are > in females, whilst the alkaline reserve is less. this confirms the existence in serum of diffusible The osmotic pressure and inorg. salts in the male are non-ionisable Ca complexes. R. N. C. > in the female in Scyllium canicula, but less in C alciu m m eta b olism in the first phase of Raia undulata, whilst with blood-proteins and org. sub blood clotting. III. Mechanism of t h r o m b i n stances of the serum the reverse is the case. formation. H. S c h e u r i n g (Biochem. Z., 1935,283. R . N. C. 1— 11).— The mechanism of the earlier described Chemical and physico-chemical sexual differ (A., 1935, 1263) shift of Ca from the ionised to tne ences of the. blood of Labrus bergylta. E. A. negative Ca complex condition during thrompm P o r a (Compt. rend. Soc. Biol., 1936, 121, 102— formation is further investigated. The governing 105).— The osmotic pressure, k, blood-, serum-, reaction results from the affinity of Ca" for pro- and corpuscular Cl, serum-Na, and total inorg. thrombogen (I), the reaction conforming to the mas substances in the blood of the male are > in the law and the complex formed being identical wjj I female, whilst K, Ca, proteins, the alkaline reserve, thrombogen (II). The union of thrombokinase (m corpuscular vol., and org. substances are less. The with (II) also conforms to the mass law. Norma- fraction of the osmotic pressure duo to NaCl in the male dog serum contains Ca" corresponding with the (1) is > in the female. R . N. C. content, whilst (I) is present in about twice tie Action of indole on hydrsemia, chloraemia, and amount required by the (III) content. I5. W. b. glycsemia. G . F . d e G a e t a x i (Boll. Soc. ital. Biol, A ction in vitro of iron-vitamin-C complex®5 sperim., 1935, 10, 441— 443).— Injection of indole with different bases on the coagulation of blood- in guinea-pigs increases H 20 and depresses Cl in the F. A r l o e n g , A. M o r e l , and A. J o s s e r a n d (Compt blood; blood-sugar behaves variably. R. N. C. rend. Soc. Biol., 1936, 121, 39— 41).—-Na‘ ascorbate Blood-modifications from administration of restrains slightly the coagulation of blood in w r0- j indole. G. F. d e G a e t a n i (Boll. Soc. ital. Biol, Ferriscorbone complexes with inorg. and org. base sperim., 1935, 10, 439— 441). R . N. C. exhibit greater restraining action, Ca ferriscorbom being the least anticoagulant. With ferroscorbon» Composition of the blood of some marine in the time of coagulation is always > 1 hr. R- N. <-• vertebrates and vertebrates. E. A. P o r a (Compt. rend. Soc. Biol., 1936, 121, 291—293).—From the Influence of splenic fractions on blood co analytical data given, the osmotic pressure of poikil- agulation. I. Effect of splenectomy, splee osraotic marine animals is slightly > that of the diet, and spleen extract. S. B o k u , I- Hnui> an external medium, whilst that of homeosmotic animals K . Gon (J. Chosen Med. Assoc., 1935, 25, 48 1¡»)yj is less, k of the serum of poikilosmotic animals Splenectomy accelerates coagulation for 2 d a y s a differs from that of the external medium. The % subsequently delays it. Administration of spie 1 of the osmotic pressure due to NaCl in selachians is material restores normal conditions. Ch. AbS. [Pi XIX [b, c) BIOCHEMISTRY. 359 Mechanism of the action of anticoagulant sheep cells is inhibited by human group-sp. A- substances. H. G o ld ie (Compt. rend. Soc. Biol., antiserum. Differences between the acetylated and 1935, 120, 1181— 1185).—-The anticoagulant power deacetylated polysaccharides of Pneumococcus type I of compounds of the moranyl group corresponds are demonstrated by inhibition of hmmolysis, by exactly with, or is slightly > , the alexin-destroying complement fixation, and by inhibition of group-sp. power; these compounds therefore affect a coagulant isoagglutination tests. Destruction of potency of agent, probably prothrombin, the structure of which acetylated polysaccharides by faeces filtrates is“ not resembles that of alexin (I). Naphthalenesulphonates due to fission of Ac. Ch . A bs. (p) with high anticoagulant power exert only a feeble effect on (I). The incoagulable plasma exhibits Effect of various enzymes on toxin and ana variable characteristics as regards pptn. by acids, toxin . Y. A n azaw a (Sei-i-Kwai Med. J., 1934, 53, and contains “ protective colloids.” R. N. C. No. 10, 1—62).—Trypsin detoxicates diphtheric and tetanic toxins and destroys their antigenic property. Toxicity of ricin and body temperature. H. Anatoxins prepared by heating these toxins with Moriyama (Japan. J. Exp. Med., 1934, 12, 591— CH20 are not destroyed by trypsin. Neither diastase c00)- Cii. A bs. (p) nor lipase destroys the toxins or anatoxins. Ricin. II. H. M oriyam a (Japan J. Exp. Med., Cii. A bs. (p) 1934, 12, 437— 453).— Effects of various substances Antibody production through the cutaneous on the hajmagglutinating power of ricin are recorded. route. Y. H irose (Sei-i-Kwai Med. J., 1934, 53, The lyophiiic character of the protein is associated No. 6, 1—73).—The antibody for cholesterol was with the presence of a double linking, the loss of which produced in rabbits by smearing cholesterol or causes changes in colloidal state, toxicity, and dehydrated lanoline over the skin. Ch. A bs. (p) agglutinating power. Ch. A b s. (p) Antibody-forming accelerator in spleen. IV. Distribution of isoagglutinins in blood-serum Influence of spleen diet on hsemolysin and fractionated by electrophoresis. A . Gro n w all agglutinin formation. S. B o k u , I. H ir a i, and (Biochem. Z., 1935, 282, 257— 262).— Human serum K. Gon (J. Chosen Med. Assoc., 1934, 24, 1508— of individuals of blood group 0 is fractionated by 1518).— Splenectomy delays hsemolysin and agglutinin electrophoresis and the agglutinin titro, protein-N, formation. Oral administration of spleen counteracts and preeipitability with (NH4)2S04 are determined. this effect. Cir. A b s. (p) Isoagglutinin is distributed uniformly through the Chemical composition of pig’s stomach.—See tactions pptd. by 30% saturation with (NH4)2S04. B., 1936, 168. , . P. W. C. Antigemc properties of detoxicated Indian and Structure of protoplasm. W. Seifriz (Bot. African venoms : cross-reaction exerted by the Rev., 1935,1, 18—36). Ch. A b s. (p) respective antivenins. E. G r a s s e t and A. Zotr- Isoelectric point of mucoproteins. A. R o c h e texdyk (Trans. R oy. Soc. Trop. Med. Hyg., 1935, (Compt. rend. Soc. Biol., 1935, 120, 1229— 1231).— , 391—398; cf. A., 1934, 1022).— Venoms were The isoelectric point of the mucoprotein of tho rendered atoxic by 1% CH20 . The potency of these submaxillary of the ox is pn 2-70. R . N. C. preps, is compared with that of African viperine and Isoelectric point of mucoproteins. A. R o c h e colubnne venoms. Multivalent antivenins of colubrine (Compt. rend. Soc. Biol., 1936, 121, 71— 73).— The 'enomsmay be produced either by unmodified venoms isoelectric points of a no. of mucoproteins from by ana venoms. Ch . A b s . (p) invertebrate tissues are given. That of the vitreous T?*5! and- antigenic properties of S. African humour is about pn 3-0, whilst those of tho skin are , e vea°m s with special reference to m ulti- generally higher. R . N. C. ency of S . A f r ic a n a n t iv e n in . E . G r a s s e t , The myogen volume in relation to the volume C- "taTENDYK, and A. Schaaesma (Trans. Roy. of the muscle fibre. W. H aum ann and H. H. ml Med- 1935’ 28> 601— 612).— The W e b e r (Biochem. Z., 1935, 283, 146— 152).— The ion nC'V Borse antivenin can be titrated with myogen solution of mammalian muscle occupies j] 0n?s ,0^ the puff adder and Cape cobra. A sp. 35% of the vol. of the minced muscle and may -cuution is shown with these venoms and the amount to < 20% of the vol. of the intact muscle ® antrvenin. Ch . A b s. (p ) fibre. Close agreement was obtained by different a^riC'P^ reaction to phosphatides of tubercle methods in the determinations of the non-solvent \vl- pr°rsy b a c i lli. G- R- D u n c a n , C. C. V a n space for myogen. P. W. C. tin 7, E- S- M a r i e t t e , and E. P. K. F e n g e r Myoglobin. I. Solubility in concentrated ivf® / Tuberc., 1935, 31, 307— 322).— Human ammonium sulphate solutions. V. E. M o rg a n for atale (Anderson (Amer. Rev. Tuberc., 1935, 31, 542— 546).— Pro ism is extracted with MeOH under H2, BuQ0H is longed grinding of starch causes its transformation added, the MeOH removed, and the BuOH solution into erythrodextrin, and then into achroodextrin. treated with BzCl. Bz or Ac derivatives of luciferin Similarly, gelatin is changed to a H20-sol. peptone (I) are more stable to 0 2 than is (I) itself. Preps, of like compound incapable of forming a gel even at 0°. (I) 2000 times as active as the starting material are Tuberculoprotein (I) is decomposed by grinding into obtained, in yields up to 65% , by two benzoylations HjO-sol. protein, peptone, and polysaccharide. Boil followed by hydrolysis with IV-HCl. F. A. A. ing with dil. acid or treatment with 4% aq. NaOH Organic bases, especially spermine, in the produces the same change in (I). Ch. A bs. (p) m u scle o f higher animals. K . Y osh im u ra , Y. Factors affecting the affinity of the pulmonary Hiwatashi, and T. Sakam oto (J. Chem. Soc. Japan, proteins and their degradation products for the 1935, 56, 280— 288).— Vais, for creatine, hypoxanth- lu n g. P. MaSCHERPA (Boll. Soc. ital. Biol, sperim., ine, carnosine, creatinine, methylguanidine, carnitine, 1935, 10, 459— 461).—The proteins of the portion of and spermine are given for muscles of cattle, horse, the lung juice expelled by 400 atm. pressure are able pig, and hen. Ch. Abs. (p) to fix Co and convey it to the lungs, the effect being Antiansemic principle of liver. H. B. Sreerax- unaffected by tryptic digestion. The effect is not gach ar and M. Sreenivasaya (Current Sci., 1936, 4, shared by aq. lung extracts or the proteins of the 468— 472).—A review. juice expelled by 200 atm. pressure. R. N. C. Hsematin pigments of Actinia (actiniohaematin) Relation of protein coagulation to oxidation- and cytoclirome-b. J. R o c h e (Compt. rend. Soc. reduction potential. Y. N a k a m u r a (J. Agric. Chem. Biol., 1936, 121, 69— 71).— The muscle of Actinia is Soc. Japan, 1935, 11, 1101— 1104).— Treatment of rich in cytochrome-6 (I), but contains little or no ov- and serum-albumin by heat or ultra-violet irradi cytochrome-c (II). C5H5N extracts of (Il)-free ation and of milk by enzyme action lowers the muscles contain protohaomatin and the hsematin of potential, indicating a relation between coagulation (II), with traces of that of cytochrome-a. Hence (I) and hydrolysis. P. O. H. and (II) of Actinia contain the same prosthetic group. Hydrogen-ion dissociation curve of the crystal R. N. C. line albumin of the hen’s egg. R. A. Kekwiok Hsematin of cytochrome-c and nature of the and R. K. CANN a n (Biochem. J., 1936, 30, 227— 234). combination of hsematins with globins. I —The H‘ dissociation curve of ovalbumin has been R oche and M. T. B en even t (Compt. rend. Soc. Biol., constructed. The H*-combining capacity reaches a 1935, 120, 1227— 1229).— Hsematin-c (I), the pros max. of 30—32 equivs. per mol. just below pK 2. thetic group of cytochrome-cy (II), shows absorption Evidence of a max. dissociating capacity was observed bands at 614, 568, 535, 498, and 395 mg. C5H5X at p„ 8—9 (corresponding with a dissociation of 11 transforms it into a parahsematin (bands at 578 and equivs. of H' per mol.), but not at pa 11-5— 12-0. 538 mg), which is reduced to a hsemochromogen H. G. R. (bands at 550, 521, and 410 mg) identical with that Effect of formaldehyde on the hydrogen-ion formed from (II) by C^H5N. (I) and (II) are reduced dissociation curve of ovalbumin. R. A. K e k w ic k to the same porphyrin. (I) and natural globin w and R . Iv. Ca n n an (Biochem. J., 1936, 30, 235— 240). neutral or slightly alkaline solution form another —H' dissociation curves of ovalbumin (I) in presence parahsematii) (bands at 505 and 538 mg), whereas of CH20 indicate the presence of 16— 18 NH2 groups, other hsematins form mcthaomoglobins. The results other than a-NH2, which are identified with the suggest that hannoglobins and hsemochromogens are s-N H 2 of lysine. The action of HN02 on (I) indicates not formed by the action of the same group in the the presence of 19—20 NH2 groups per mol. and the haomatin mol. R. N. C. lvsine-N of the phosphotungstate ppt., 17— 18 mols. of lysine per mol. H. G. R. Contents of glutathione and vitamin-O in anti- anaemic liver preparations. F. G. K oser (Arch, Relations between some alkaloids and protein exp. Path. Pharm., 1936, 180, 183— 188).— Glut substances. P. M asc iierpa (Boll. Soc. ital. Biol, athione does not occur in several (commercial) liver sperim., 1935,10, 464— 467).—Brucine (I) and strych preps., whilst the vitamin-6' content varies consider nine in ovalbumin solutions form non-dialysable com ably. F. 0. H. plexes with the protein. They also form complexes with serum-proteins, the quantity of alkaloid fixed Glycogen in the central nervous system of by ox-serum being > by sheep serum. A method h u m an e m b ry o s. O. F u sejim a (Sei-i-Kwai Med. of determining (I) is described. R. N. C. J., 1934, 53, No. 9, 80— 93).— A histological study. Ch. Abs. (p) Electric cataphoresis of brucine and strych Laraacein from the scale of the insect Cero- nine in solutions of ovalbumin or in blood-serum plastes rubens, Maskell. R. K oyam a (J. Chem- from different animals. P. M asciierpa (Boll. Soc. Soc. Japan, 1935, 56, 365— 372).— The wax from ital. Biol, sperim., 1935, 10, 461— 464).— Brucine and insects grown on tea and on citrus trees had «« strychnine in the free state in solutions of ovalbumin 0-69694, 0-99208, m.p. 54— 56°, 55— 57°, sap. vat. or animal sera travel to the cathode, but when bound 152-8, 126-0, acid val. 22-9, 46-6, I val. 76-3, 130;o> to the protein they travel to the anode. R. N. C. respectively. From the wax were obtained, melissic, Bioluminescence. II. Partial purification of ceronielissic, CgaHggOa, m.p. 94°, ceroplastic, C.wH;pGr Cypridina lu ciferin . R. S. A n d er so n (J. Gen. m.p. 96—98°, and a resin acid, C22H;u02. The Physiol., 1935, 19, 301— 305).— The powdered organ unsaponifiable fraction contained ceromelissyl, cero- XIX (c, d) BIOCHEMISTRY. 361 plasyl, and melissyl alcohols, all of which are primary. Action of lipins on lacteal secretion and the The wax does not contain ceryl or ibotaceryl alcohols chemical composition of milk. I. Action of or the corresponding acids. Ch . A bs. (p) lecithin and cholesterol introduced by the Lipin composition and physiological activity parenteral route in the goat. II. Action of the in the ovaries of pregnant guinea-pigs. E. M. total lipins of egg-yolk introduced by the paren Boyd (J. Biol. Chcm., 1936,112, 591— 595).— Ovaries teral route in the goat. D. T o r r ts i (Boll. Soc. ital. from guinea-pigs at various stages of gestation showed Biol, sperim., 1935, 10, 443—445, 445— 447).— I. the same average phospholipin content of about 1-25% Lecithin (I) in small quantities increases, and in as those from non-pregnant controls at the pre- larger quantities reduces, body-wt. and lacteal secre ccstrous stage. Similarly there was no significant vari tion; small quantities increase total milk-lipins ation from the mean (0-30%) for the free cholesterol. (II) and cholesterol (III). Cholesteryl oleate (IV) There is no increase in physiological activity in the increases body-wt., (II), and (III) without affecting ovaries of gravid guinea-pigs. J. N. A. secretion. Mixtures of (I) and (IV) in small quantities increase body-wt., lacteal secretion/total, inorg., Liver-fat and blood determinations after and easein-P, (II), and (III), without affecting acid- adrenalectomy. J. F. B. B a r r e t t and A. T. W ils o n sol. and lecithin-P. Larger quantities reduce body- (J. Physiol., 1934, 81, 43— 45p).—In doubly adrenal- wt. slightly without affecting lacteal secretion or the ectomised cats increased blood viscosity causes an composition of the milk. increase in residual blood in the liver and a con II. Injection of egg-yolk lipins in well-fed animals sequent fall in the % of total solids. No correlation increases body-wt., lacteal secretion, total, inorg., is apparent between adrenalectomy and the amount and casein-P of the milk, (II), and (III); org. acid- and nature of liver-fat. Ch . A bs. (p) sol. P and kephalin-P are unaffected. In sparingly- Jaboty fat. Composition of mink fat. New fed animals body-wt. and lacteal secretion are di alcohols and h yd roca rb on s in sp e rm o il.— See B., minished, whilst small quantities also diminish (II) 1930, 158. and kephalin. A succession of small daily doses in Hexadecenol and tetradecenol in sperm head fluences favourably body-wt., lacteal secretion, (II), oil. H exadecenol in sp erm b lu b b er o il.— See this and the various P fractions in the milk. R. N. 0. vol., 311. Monohydroxypalmitic acid in butter fat. A. W. Tetradecenoic and dodecenoic acids in sperm B o s w o r th and G. E. H e lz (J. Biol. Chem., 1936, oil. I, II.— See this vol., 313. 112, 489— 492).— A monohydroxypalmitic acid, m.p. 16-5— 17-5°, [ Modifications of the thiocyanate concentration Micro-determination of trimethylamine in the of the nasal mucus and other secretions, in rela u rin e. G. M onasterio (Boll. Soc. ital. Biol, sperim., tion to stimulation of the trigeminum and the 1935, 10, 385— 386).— The urine is distilled with olfactorium. P. N icco lin i (Boll. Soc. ital. Biol, alkaline NaOCl, which decomposes all but the lert. sperim., 1935, 10, 431— 432).-—Stimulation of the bases. NMe3 is collected in 0-02Ar-H2S04 and excess olfactorium with eucalyptus oil increases CNS' of II2S04 determined with I. R. N. C. in the nasal and lachrymal secretions and the urine, Histidine in human urine. F. F oldes (Biochem. but not in the saliva. R. N. C. Z., 1936, 283, 199— 209).— The frequency of the Saliva. A. Ca st e l l a n i, M.D ou glas, P. R e d a e l l i, occurrence of histidine (I) in human urine increases and G. A m alfitano (J. Trop. Med. Hyg., 1935, as its d increases. (I) is detected more frequently 38, 81— 87).— A review. Cii. Abs. (p) in the urine of pregnant women than in that of non Presence of lactic acid in the saliva. R. pregnant, but a test for pregnancy cannot be based on this difference. No (I) could be detected in the V ladesco (Compt. rend. Soc. Biol., 1936, 121, 275— 276).—Lactic acid is always present. R. N. C. urine of non-pregnant animals (dog, horse, cow, elephant, giraffe, tiger, antelope). A method described Hcemolytic actions and surface tension of is more sensitive for the detection of (I) than is human and animal biles and cholates. S. Tsuji that of Kapeller-Adler (A., 1934, 1050). (Japan. Z. Mikrobiol. Path., 1934, 28, 1534— 1552).— W . McC. Among various biles examined those of carp and Renal innervation and reducing substances in toads had the greatest hoemolytic action and that of the urine. E. M a r t in i, A. B on sign or e, and F. chicken the highest surface tension. Ch . A b s. (p) P in otti (Boll. Soc. ital. Biol, sperim., 1935, 10, Action of post-pituitary extracts on gastric 474— 477).— The oxidised/reduced ascorbic acid ratio secretion. L. L a n g e ro n , M. P a g e t, and A. D an es in the urine of the dog is increased by congelation (Compt. rend. Soc. Biol., 1936,121. 33— 35). of the vagi, renal denervation, or injection of atropine. R. N. C. It is reduced by excitation of the congealed vagi or Gastric acidity and its significance. F. L. injection of eserine. R . N. C. A pf e r ly (Lancet, 1936, 230, 5— 9). L. S. T. Determination of ascorbic acid in urine by Urine of the normal cat. L. B la n c h a r d (Bull. titration. H. yon E u ler and D. B urstrom (Bio Soc. C t o . bio!., 1935, 17, 1693— 1706).— The vol., chem. Z., 1935, 283, 153— 157).— The ascorbic acid acidity, and urea, NH3, and Cl' content of the urine contents of the same samples of urine as determined of the cat are 37 c.c. per kg. wt. per day, 0-060 g. of by the Bezssonoff method (using molybdophospho- H, 84-10— 89-85, 1-88— 2-69, and 3-05—4-67 g. per tungstic acid) are always very much > results on 1000 g., respectively. The normal urine contains the same urines by the Tillmans method. albumin (0-5 g. per 1000 g.), and under certain P. W. C. conditions of feeding small amounts of lipins and Use of M ayer’s reagent for detection of quinine cholesterol. A. L. in alkaline urine. J. W. F ie ld and M. K a n d ia h Modifications of the urinary reaction following (Trans. R oy. Soc. Trop. Med. Hyg., 1935, 28, 385— 390).—-Addition of AcOH to the reagent ensures renal denervation. E. T r ia and B. Ca p a l d i (Boll. Soc. ital. Biol, sperim., 1935, 10, 502—504).—Renal pptn. of albumin (I), and of quinine (II) in clinically significant amounts. If (I) is present, urine and dcnervation induces a fall of the actual and potential reagent are boiled and filtered while hot. On cooling acidity of the urine, a slight rise in NH3, and a (II) is pptd. Ch . A bs. (p) considerable rise of combined C02, free C02 being scarcely affected. Conditions tend to return to Detection of acridine derivatives in urine. normal after 10—15 days. R. N. C. G. F e r r a r i (Diagnostica tec. lab. [Napoli], 1934, 5, 92S— 932).—The sample (5 c.c.) is treated with 1—2 Partition of nitrogenous constituents of urine drops of 20% aq. Na caffeine benzoate. An intense and its physiological significance. VII. Evolu green fluorescence or the enhanced intensity of an tion of specific endogenous nitrogen metabolism existing fluorescence indicates the presence of during protein inanition. G. M ourot (Bull. Soc. acridine derivatives. Cii. A bs. (p) China, biol., 1935, 17, 1741— 1789).— In the urine of rats undergoing protein starvation, the total X, Determination of urinary ketones for clinical after remaining nearly const, for some time, increases use. E. M a cch ta (Diagnostica tec. lab. [Napoli], before death. Whilst urinary creatinine, uric acid, and 1934, 5, 908— 918).— An application of the nitro- purine bases do not, the urea-, NIL-, and NH2-N, prusside reaction is described. Ch. Abs. (p) allantoin, and creatine losses do, follow the same Paraffin hydrocarbon from urine of pregnancy. course as that of the total N. A. L. W . F. H art and M. A. N orthup (J. Amer. Chern. Detection of leucine and tyrosine [in urine], Soc., 1935, 57, 2726—2727).—The material extracted F ischer and H. Str aller (Pharm. Ztg., 1936, by light petroleum from the adsórbate (fuller’s earth) 81, 38—39).—A method is given for detecting 0-01% from the acidified, aged urine is separated by warm of leucine (I) and tyrosine (II) in urine. In fresh MeOH into insol. heptacosane, m.p. 58— 59°, and urine containing sediment, (I) and (II) are in the (probably) sol. pentacosane, m.p. 52— 54°. H. B- sediment and not in solution. Control tests are Urinolysis in fat metabolism. F. J. J irka and advisable when the microscopic test is used. (I) C. S. Scu deri (J. Lab. Clin. Med., 1935, 20, 631— and (II) occur very rarely in urine. P. G. C. 633).—Intracystic fat occurs exclusively in the last XIX (e,f) BIOCHEMISTRY. 363 few drops of urine excreted. It may be determined (Compt. rend. Soc. Biol., 1936, 121, 22— 24).— Pan directly by centrifuging in a Babcock bottle. creatic Ca is 2— 5 times as great as hepatic Ca in Ch. A b s . (p) pathological states, which is probably the cause of Determination of glucose and chlorides in its rapid petrification. R. N. C. urines containing sodium formaldehydesulph- Blood and urinary phosphorus in various oxylate. E. H ug and R . II. b e M eio (Compt. rend. diseases. T. Ih io (J. Chosen Med. Assoc., 1935, Soc. Biol., 1936, 121, 370— 372).— Na formaldehyde- 25, 26— 40).— Data are recorded. Ch . A b s . (p) sulphoxylatc reduces A gN 03 and alkaline Cu solu tions, and must bo oxidised with H N 03 and K M n04 Carbon disulphide and adrenals (Addison’s before Cl' can be determined. Glucose can be deter disease). L. D evoto (Arch. Gewerbepath. mined polarimetrically, or by Cu after preliminary Gewcrbehyg., 1934, 5, 429— 432).— A ease is reported deproteinisation with H gS04-H 2S 04 and BaC03, and of Addison’s disease following prolonged work with removal of Hg with H 2S. R . N. C. CS2. R . N. C. Enteric coatings. II. Excretion studies with Prophylaxis of simple anaemia in infancy with iron and copper. Effect on haemoglobin, weight, sodium salicylate tablets. M. W r u b l e (J. Amor. Pharm. Assoc., 1935, 24, 1074— 1077).— The amounts and resistance to infection. S. J. U sh e r, P. N. of salicylate recovered from the urine by a modified M acD erm ot, and E. L ozinski (Amer. J. Dis. Chil Thoburn-Hanzlik method were approx. the same dren, 1935, 49, 642— 657).— Daily administration of whether coated or uncoated tablets of Na salicylate Fem glycerophosphate to infants increased the were administered. • E. H. S. average haemoglobin concn. at 1 year by 15%. Simultaneous administration of CuS04 enhanced the Approximate rapid determination of the bar effect, and increased gains in wt. and resistance to bital content of urine and drugs. H. Oettel infection. Ch. A b s . (p ) (Arch. Pharm., 1936, 274, 1— 10).— The barbital con tent of urine is determined within a few mg. by Glutathione and anaemia. G. C. D ogliotti and T. Castellani (Boll. Soc. ital. Biol, sperim., 1935,10, acidifying 10 c.c. with a few drops of 0 -lAr-HCl, extracting with 20 c.c. of CHC13, and adding small 521—523).—Total glutathione (I) in the blood is normal or slightly reduced in post-hsemorrhagio or amounts of 0-2% MeOH-Co(OAc)2 and 0-2% MeOII- LiOH to the extract. Barbitals are detected in urine acute infectious anaemia, whilst corpuscular (I) is immediately and several days after administration. normal or slightly raised. In other anaemias total R . S. C. (I) is generally normal, whilst corpuscular (I) is "Donaggio phenomenon” in the urine of raised; in polycythsomia corpuscular (I) is reduced. R . N. C. children affected with muscular dystrophy both Further evidence for the presence of a toxic at rest and after fatigue. E. Bozzi (Boll. Soc. ital. factor in pernicious anaemia. G. E. W a k e r l in Biol, sperim., 1935, 10, 586— 587). R . N. C. and H. D. Br u n er (Science, 1935, 82, 494— 495).— "Donaggio phenomenon” in the urine of The urine contains a thermolabile, comparatively horses in febrile conditions. P. R icci B it t i (Boll. toxic, reticulocyte-decreasing factor and a partly' 8oc. ital. Biol, sperim., 1935, 10, 561— 563). thermostable, relatively non-toxic, reticulocyte-stim R . N. C. ulating principle for the pigeon. Normal human " Donaggio reaction ” in the urine of fatigued urine contains the latter, but not the former. individuals. A. T orboli (Boll. Soc. ital. Biol, L. S. T. sperim., 1935,10, 548—550). R. N. C. Non-identity of lactoflavin and the “ extrinsic “ Inhibition p h e n o m e n a ” of Don a g g io. T. factor " in pernicious anaemia. C. A. A sh f o r d , ' n'ALT(Diagnostica tec. lab. [Napoli], 1935,6, 9— 20). L. K l e in , and J. F. W ilkin son (Biochem. J., 1936, Ch . A b s . (p) 30, 218—223).—Lactoflavin is not identical with Microdetermination of the p n of fluid in renal either the liver anti-pernicious anaemia principle or glomeruli and tubules. H. M ontgom ery and the “ extrinsic factor.” H. G. R. • A- Pierce (Amer. J. Med. Sci., 1934, 187, 735).— Effect of transfusion of heterogeneous formol- colorimetric method for 0 -2-c.c. samples and a ised blood in experimental acetylphenylhydr- ‘l.umhydrone electrode for 0-02 c.c. are described, azine anaemia in the rabbit. O. Malag u zzi- tais, for glomerular, proximal, and intermediate V al er i (Boll. Soc. ital. Biol, sperim., 1935, 10, 453— tubular fluids in Necturus are the same as that for 455). H N- °- Plasma. The p a decrease occurs in the distal tubule, Effect of heterogeneous formolised transfusion 111 which vals, are always < that of glomerular fluid in experimental anaemia from bleeding in the nd > that of the corresponding urine. ra b b it. O. M a l a g u z z i -V a l e r i (Boll. Soc. ital. Biol, Ch . A b s . (p) determination of total lipins and lipin parti sperim., 1935,1 0 , 546— 548). R - N. C. tion in faeces. H . C. T id w e l l and L. E. H olt, jun. Cholesterol content of plasma in arthritis. , ' Biol. Chem., 1936,1 1 2 , 605— 613).—A method for E. E. H artung and M. B eu ger (J. Lab. Clin. Med., erminitig the partition of lipins, unsaponifiable 1935, 20, 675— 681).— Plasma-cholesterol (I) de umtter, neutral fat, fatty acid, and soap in a single creased in rheumatoid and increased in osteo-arthritis. sample is described. .T. N. A. The ratio of free (I) : (I) esters is normal. Total (I) Calcium precipitation in the pancreas. M. of the blood and sedimentation rate are not related. Ch . A b s . {p) EPEE, A - L esure, E. B io y , and P. P e r r e a u 364 BRITISH CHEMICAL ABSTRACTS.— A. XIX (/) Cholesterol-induced atherosclerosis : preven The average concns. of oxidised and of reduced tion in rabbits by feeding an organic iodine glutathione (I) remain normal in cancer, but vals. compound. I. H. P a g e and W . G. B e r n h a r d (Arch. for reduced (I) in erythrocytes were slightly > Path., 1935, 19, 530— 536).— Administration of org. normal. Ch. Abs. (p) I compounds prevents atherosclerosis following feed Aminoethyl phosphate from tumours. E. L. ing of cholesterol (I) in olive oil. Persistent lipsamia O u th ou se (Biochem. J., 1936, 30, 197— 201).— also occurring under these conditions is more marked Bovine malignant tumours contain aminoethyl phos when I compounds are given. The lipanna differs phate (I) [Ba salt; brucine salt (one equiv. of brucine); from that occurring in nephrosis, in that total, free, jlavianate, m.p. 223°] identical with synthetic (I) and ester-(I) are increased relatively > are lipin-N, from aminoethanol (II) phosphate and P0C13. Hydro -NH2-N, or -P. ‘ Ch. A bs. (p) lysis of (I) with phosphatase gives (II) (flavianate, Separation of liver substances which are m.p. 198° and 212°). Probably the formula of (I) reticulocytogenic in the guinea-pig and thera is CH2<^3'2>PO -O H , at least at p a 5— 9. peutically active in experimental canine black tongue. Y. S u b a r r o w , B. M. J a co b s o n , and W. McC. C. H. F isk e (New England J. Med., 1935, 212, 663— Biodynamics of the pseudo-proteins. Chemo 664).—Approx. 50% of the activity of crude liver therapy of carcinoma by redox substances from extract was due to ¿-tyrosine. A second active sub osteocolla. 0. H u p p e rt (Wien. med. Woch., 1934, stance can be adsorbed on charcoal and eluted by 84, 624— 628; Chem. Zentr., 1934, ii, 3788).—A EtOH. Ch. Abs. (p) thiogelatin, an org. Fe-heavy-metal complex with Serum-proteins in cancer. W. Kopaczewski a synthetically-introduced thiazole-glyoxalinc group (Compt. rend., 1935, 201, 1229— 1231).— In cancer of the character of glutathione, prepared from serum-globulin and -albumin are < and myxo- osteocolla, has an inhibitory effect on growth of proteins > normal. The hydrophobic colloid con B. coli, and is thus a possible therapeutic agent for tent, and the physical condition of the colloid, are cancer. R. N. C. concerned in the acceleration of lactogelatinisation of Effect of brom ohexoic acid on rat sarcoma 39. cancerous sera. A. G. P. W. A. S b lle and M. B o d a n sk y (Amer. J. Cancer, 1935, 23, 2S9— 296).— No sp. inhibition of gro\rth Schubert-Dannmeyer test for cancer. E. R. was observed. C h . Abs. (p) H o lid a y and F. C. Sm ith (Amer. J. Cancer, 1935, 23, 339—342).—The method, based on changes in Enzymes in rabbit sarcoma. K . Mi yam a (Sei-i- serum-lipin in cancer, is not sufficiently trustworthy Kwai Med. J., 1934, 53, No. 6 , 105— 123).— Necrotic for clinical use. Ch. A bs. (p) and non-necrotic areas in rabbit sarcoma contain amylase and lipase, the latter being greater in necrotic Early diagnosis of carcinoma by exact chemi sections. The lipase is resistant to atoxyl and cal measurement. R . L in k s (Z. Krcbsforsch., quinine. Small amounts of trypsin and a pepsin 1934, 41, 166— 206; Chem. Zentr., 1934, ii, 37S7— like enzyme occur in both areas. C h . Abs. (p) 3788).—A formula is given for the diagnosis of carcinoma from serum-Iv and -Mg determinations. Dental caries. III. Rickets in relation to R. N. C. caries in deciduous and in permanent teeth. Inhibiting the development of tar-carcinoma A. F. H ess, II. A bram son and J. M. L ew is (Amer. in mice. J. R. D a v id s o n (Canad. Med. Assoc. J., J. Dis. Children, 1934, 47, 477— 487). C h . Abs. [p) 1935, 33, 364— 366).— A diet rich in vitamin-A (and Mottled enamel in Texas. H. T. D ea n , R. M. incidentally in ~BX and -A.,) increased the resistance D ix o n , and 0 . ConEN (U.S. Publ. Health Kept«., of mice to carcinogenic factors in tar. Ch. Abs. {p) 1935, 50, 424— 442).— A review. C h . Abs. (p) Carcinogenic action of 1 :2-benzpyrene. C. Calcium and phosphorus metabolism of chil Sannie, C. O b e r lin g , M. G u erin , and P. G u e rin dren with mottled enamel. E. M. L a n tz, M. C. (Compt. rend. Soc. Biol., 1935, 120, 1196— 1198). Smith, and R. M. L e v e r t o n (J. Home Econ., 1935, R . N. C. 27, 236—239).—The Ca and P metabolism is not Physiological validity of enzyme [amylase] de affected by feeding F. F probably causes mottled terminations in tumour tissue. F. H. S c h a r le s , enamel by a sp. effect, on the enamel-forming organ. P. R o b b , and W . T. S a lt e r (Amer. J. Cancer, 1935, C h . A b s . (p) 23, 322—327).—The method previously described Changes in teeth and bone in chronic fluoride (A., 1934, 1023) determines only the enzymic activity, poisoning. G. J. S u tr o (Arch. Path., 1935, 19- and not the effect of accelerators or inhibitors. 159— 173).— Changes in the enamel and bone matrix Ch. A bs. (jj) caused by feeding NaF are due to chemical disturbances Plasma and erythrocyte glutathione in human unrelated to the parathyroid glands. Ch. Abs. (p) cancer. J. W. Schoonover (Amer. J. Cancer, 1935, Glutathione and diabetes. G. C. D o g l i o t t i and 23, 315—321).—In cancer the ratio of oxidised O. M e lo n i (Boll. Soc. ital. Biol, sperim., 1995, glutathione (I) to reduced (I) is increased in plasma 10, 523—525).—Total glutathione (I) in the blood and lowered in erythrocytes. The quotient of the of diabetics is normal whether or not insulin (II) l,as ratio in plasma -f- the ratio in erythrocytes is > been administered. Corpuscular (I) is slightly > normal. C h . Abs. (p) normal in moderate diabetes, and slightly < normal Blood-glutathione in human cancer. J. W. after (I I ); it is also < normal in severe cases. Schoonover (Amer. J. Cancer, 1935,23, 311— 314).— R, N. C. XIX (/) BIOCHEMISTRY. 365 Diabetes mellitus, its differentiation into Significance of thiocyanate in hepatic coma. H. insulin-sensitive and insulin-insensitive types. In o u e (J. Chosen Med. Assoc., 1934, 24, 1355— 1365). H. P. Himswortii (Lancet, 1936, 230, 127— 130).— —The SCN' in blood and urine is lowered in hepatic One type appears to be caused by a deficiency of coma. Vals. were also low in rabbits with total insulin (I), and the other to lack of an unknown biliary obstruction and in dogs with Eck fistula. factor which sensitises the body to (I). L. S. T. Ch. A bs. (p) Effect of protein on carbohydrate tolerance of Pathological physiology of the liver. III. two patients having combined diabetes mellitus Impaired function in relation to nitrogen- and pernicious anaemia. N. Jolifee, H. Bran- containing substances. I. M a tsu o and K. I n o u y e daleone, and H. M ost (J. Clin. Invest., 1935, (Acta Schol. Med. Kioto, 1935, 17, 417— 432).— A 14, 357—365).—High-protein (II) diets reduced review. Ch. A bs. (p) carbohydrate (I) tolerance. Use of high-(I) diets Role of fats and cholesterol in the Henry counteracted the immediate effects of (II), but loss reaction. V. C h o rin e (Compt. rend. Soc. Biol., 1936, in tolerance was permanent and not affected by 121, 297— 300).—The intensity of the Henry reaction insulin. Ch. A bs. (p) is reduced by washing the serum with Et20 , which Absorption curve of glucose by the red cor reduces surface tension and removes fats and puscles of normal and diabetic subjects in vitro. cholesterol. The reaction is associated with protein G. Patrassi and U. T e o d o r i (Boll. Soc. ital. Biol, modifications in the serum, the role of fats and sperim., 1935, 10, 527— 528).— The absorption curves cholesterol being secondary. R. N. C. of the corpuscles are very similar in the two cases, Lipins and melano-flocculation (Henry re both rising to a steady max., the increases of the glu action). E. T re n s z (Compt. rend. Soc. Biol., 1935, cose contents being equal. II. N. C. 120, 1268— 1270).— The euglobulins of paludic sera Relations between bilirubinsemia and carbo that have been freed from fat by pptn. with COMe, hydrate metab olism . I. Bilirubinsemia in fast no longer give positive melano-flocculation reactions. ing and glucose-fed diabetics. E. S la v ic h (Boll. The isolated globulins also lose their melano-floccui- Soe. ital. Biol, sperim., 1935, 10, 531— 532).— Bili- ability when treated with COMe2; the reaction is rubin:emia in diabetics is considerably > normal. therefore dependent not on the protein part of the It is not affected by ingestion of glucose. R. N. C. globulin mol., but on associated lipins or other Effect of thyroidectomy in poisoning by COMe2-influeneed substances. R. N. C. diphtheria toxin. P. L o c a t e l l i (Boll. Soc. ital. Chemical factors of malaria-flocculation Kol. sperim., 1934, 9, 1317— 1318). R. N. C. (Henry reaction) in anophelian paludism. E. Influence of acute infection and artificial fever B enham ou and R. G ille (Compt. rend. Soc. Biol., on plasma-lipins. A. V. Stoesser and I. Mc- 1935, 120, 1259— 1261).— The three factors con Qcarrie (Amer. J. Dis. Children, 1935, 49, 658— trolling malaria-flocculation are euglobulin, serin, ''G).—Plasma-lipins decrease in acute febrile, but and cholesterol; the Henry reaction depends on their ¡wt in afebrile, disorders or induced fevers. Fever, ratio (the index of flocculability), but not on any of m itself, does not cause lipin changes. them separately. R. N. C. Cii. Abs. (2;) Melano-precipitation serological reaction in Experimental goitre: functional, chemical, malaria. E. D. W. G rieg , C. O. van Rooyen, and histological studies. C. A. H e llw ig (Arch, E. B. H e n d ry (Trans. Roy. Soc. Trop. Med. Hyg., lath., 1935, 19, 364— 371).— A Ca-rich diet induces 1934, 28, 175— 191).— The substitution of a colloidal goitres in rats. The I content of goitres is related to melanin (I) solution (prep, described) for the ox- at °I the diet. Colloid (I-rich) goitres have a choroid antigen (Henry) is suggested. In the course 1 fi -j %Toid function than do parenchymatous, of a benign tertian infection the blood-phospbolipin 00 oid-rich goitres. The latter induce the higher inversely oc the reacting titre with (I). blood-Ca vals. Ch. A bs. (p) Ch. A bs. (p) Etiology of enzootic bovine haematuria. I. Malaria and blackwater fever. I. Malaria. A■ L a t t a (Indian J. Vet. Sci., 1934, 4, 341— II. Blackwater fever. Haemoglobinsemia. III. /• Oral administration of Ca lactate or intra- New blood pigment in blackwater fever and injection of CaCl2 caused no appreciable other biochemical observations. N. H. F a ir le y 1 erence in coagulability of blood in affected cases. and R. J. B rom eield (Trans. Roy. Soc. Trop. Med. rum-Cawas not affected, but serum-P04"' increased. Hyg., 1933— 1934, 27, 289— 314).— I. Blood destruc w _ Ch. Abs. (p) tion in malaria is associated with hyperbilirubimemia, bn index and juandice of the new- urea increase, decrease in blood-cholesterol, and normal « ,» ■ • H ° l l 6si and Z. H o r v a t h (Amer. J. Dis. alkali reserve. Haemoglobimemia does not occur. birl ■ n> 1935, 49, 638— 641).— The haemoglobin Sp. treatment (quinine etc.) decreases plasma- n °u LS ^ ^10% in normal and < 100% in jaundiced bilirubin and -urea and increases blood-cholesterol. ne*bom- Ch. Abs. (p) II. In blackwater fever blood is brownish-red and iau 6j^irn"Pl10sPllat'ase in toxic and hcemolytic contains metluemoglobin (I). Washed red cells do uT“ “ ' A. R. A rm s tro n g and E. J. K in g (Canad. not contain (I). Variations in (I) and oxyhemoglobin (II) are recorded. (I) arises from (II) which has been 4031 J jtr 00' u ’’ 1935’ 3.2’ 379— 383; cf. A., 1935, but f • Phosphatase increased markedly in toxic, liberated from corpuscles after lysis. Drug-methiemo- 0 m haemolytic, jaundice. Ch. A bs. (p) globinaimia is intracorpuscular in origin and does not 366 BRITISH CHEMICAL ABSTRACTS. A. X IX (f) involve presence of (I) in plasma or excretion in vals. arc given. Changes in serum-protein level took urine. place slowly even during N retention. III. The pigment resembles but is not identical Ch. Abs. (p) with (I). The hsemolytic agent in blackwater fever Indican test on blood and urine in renal in arises from metabolic breakdown in chronic sub su fficien cy. S. H. P o la y e s and E. A. Eckert (J. tertian malarial infection, is pptd. by quinine, lysing Lab. Clin. Med., 1935, 20, 681— 688).— High blood- the corpuscle and converting the liberated (II) into indican (I) is always accompanied by high total non- (I), or the new pigment. Ch. A bs. (p) protein-N (II). In some cases of severe renal disease normal (I) occurs with high (II). A persistent Function of the liver in malaria. Overloading increase in (I), concomitant with a decrease in urinary with galactose and combined overloading with indican, indicates a fatal prognosis. Ch. Abs. (p) insulin-glucose-water. K. T s c h ilo v and I. M la d e n o v (Arch. Scliiffs- u. Tropen-Hyg., 1934, Influence of glycine on creatinuria in peripheral 38, 282— 287; Chem. Zentr., 1934, ii, 3405).— n eu ritis. M. J. C. A llis o n , H. H. H e n b t e ll, and Galactosuria following overloading with galactose II. E. Hxmavich (Amer. J. Med. Sci., 1934,188, 560— does not indicate liver injury. In some patients 564).—Ingestion of glycine markedly increased cre blood-sugar (I) is increased without sugar excretion. atinuria. Edestm and glutamic acid had no action. Combined administration of glucose and il20 after Ch. Abs. (p) insulin produces a disturbance of the liver function, Nutritional cedema in the dog. II. Hypo- with hypoglyciemia and an abnormal difference albuminsemia and the augmentation of tissue between (I) in the unaffected and hypoglycsemic fluid. A. A. W e e c h , E. G o e tts c h , and E. B. states. (I) is frequently delayed in reaching its R e e v e s (J. Exp. Med., 1935, 61, 717— 734).— Data max. R. X. C. relating to N metabolism and wt. changes indicate increasing retention of fluid during the pre-oedema Experimental chemotherapy in malaria. W. stage. A positive correlation between the duration K ikutii (Deut. med. W och., 1935, 61, 573— 577). of oedema and the protein content of the cedema R , N. C. fluid is not demonstrable. Ch. Abs. {}>) Chlorine metabolism in meningitis. A. P r u n e l e (Prensa med. Argentina, 1935, No. 2).— Polypeptidcemia in pellagra. P. Tomesco, Bacilliary meningitis is usually followed by decreased N. G. Io n e s c o , and P. Constantenesco (Compt. Cl' in spinal fluid; glucose content is lowered and rend. Soc. Biol., 1936, 121, 190—192).—Polypeptid- fibrin is present. Blood-NaCl is correspondingly icmia is increased in pellagra, particularly in the decreased. Ch. A bs. (p) more pronounced visceral forms. R. X. C. Behaviour of hepatic lipins in experimental Diagnostic and prognostic significance of the rabies. R. M a c c o lin i (Boll. Soc. ital. Biol, spcrim., creatine-creatinine metabolism in various myo 1935, 1 0 , 5S0— 583).— Hepatic lipins are > normal pathies before and after amino-acid therapy. in the rabbit. R . N. C. H. H. B e a r d , C. J. T r ip o li, and J. E. A n d e s (Amer. J. Med. Sci., 1934, 188, 706—712).— Clinical im Action of the lung on polypeptides : applic* provement is associated with increased creatine ation to the study of scalds. L. B in e t and M- excretion (50—200% > that of control period) B u r n s te in (Compt. rend. Soc. Biol., 1936, 121, provided this increased creatinuria soon disappears 287—289).—Perfusion of blood through an isolated or returns to the control level. Creatinuria probably scalded lung causes an increase in the polypeptide has an exogenous origin from the NII2-acids of the content of the blood, which is reduced b y subsequent diet. Ch. A bs. (p) perfusion through a normal lung. R. N. C. Thiocyanate ions in blood and urine of nephri Chemotherapy of schistosomiasis. M. IvHAiU* tic cases. H. I n o u e and M. Y a m a sh ita (J. Chosen (J. Egypt Med. Assoc., 1935,18, 284—295). Ch . A bs. (p)_ Med. Assoc., 1935, 25, 1— 13).— Blood-SCN' increases Experimental scurvy. XX. Leucocytes in and urinary SON' decreases in nephritis. A similar blood of guinea-pigs on a vitamin-C-free die*' retention of SON' occurs in experimental nephritis produced in rabbits by cantharidin, U, and HgCl2. XXII. Amounts of reducing substance and hydrolysed sugar in urine of guinea-pigs on a Ch. A bs. (p) Phenol contents of blood of nephritic and vitamin-C-free diet. J. S him ada. X X IV . Gas metabolism. Y. S o n e d a and Y . K a t o (Sei-i-KYm hepatic patients. D. Yanagihari (J. Chosen Med. Assoc., 1934, 24, 1562— 1570).— Vais, for free, Med. J., 1934, 53, No. 6, 105— 123, No. 10, 159- combined, and total PhOH in nephritic patients 171, 172— 186).— X X II. Scurvy does not affect the were < , and in hepatic patients > , normal. The reducing substances in urine. Partial inanition free PhOH in blood increases with the gravity of the causes a decrease in the amount and % of these disease. No relationship was apparent between substances. . . . , XXIV Diets free from vitamin-C c a u s e an uU“ 8 blood pressure and blood-PhOH. Ch. A bs. (p) decline (2 days), a return to normal (3 days), and fro111 An optimal diet in promoting nitrogen gain in the tenth scorbutic day7 till death a steady7 decline n eph rosis S. H. L iu and H. I. C hu (J. Clin. Invest., in gaseous metabolism. The 0 .2 intake of sem* 1935,14, 293—303).—In Bright’s disease of the neph starved guinea-pigs is reduced in abs. val., hut rotic type, N retention was favoured by increasing practically unchanged if calc, on a bod.y-wt; basis. the carbohydrate, fat, and N in the diet. Optimum 1 b Ch . A bs. (y) XIX (/,£/) BIOCHEMISTRY. 307 Complement fixation as related to resistance In fasting rabbits, distilled H20, orally administered, and allergy in experimental tuberculosis. A. B. has no sp.-dynamic action and during the fast that of B a k e r (Amer. Rev. Tuberc., 1935, 31, 54— 61). glucose (I) is very weak. The sp.-dynamic action .... Ch. Abs. (p) of glycine (II) gradually decreases and finally dis Gastric acidity in pulmonary tuberculosis. appears as fasting continues. The action of (II) I. Gray and J. M elnick (Amer. Rev. Tuberc., 1935 is weakened and curtailed by administration of 31, 460 465). Ch. A bs. (p) phloridzin. In both cases previous administration Vitamin therapy in intestinal tuberculosis. of (I) increases the action of (II). Hence the presence M. M. S tein bach and M. B. Rosenblatt (Amer. of (I) is essential for the development of the sp - ller. Tuberc., 1935, 31, 35—43).— High-vitamin dynamic action of (II). diets neither cured nor prevented intestinal tuber- II. Iho sp.-dynamic action of ¿-alanine, ¿-glutamic cu'os‘s- Ch. Abs. (p) acid, and ¿-aspartic acid is respectively > that of the Effect of applications of irradiated chole- corresponding d- and (¿¿-acids, the action of (¿¿-aspartic sterolised lanoline on the blood-cholesterol in acid being very weak. pulmonary tuberculosis. A. D u f o u r t and P. III. 1* or each NH2-acid there is an optimal amount Laroux (Compt. rend. Soc. Biol., 1936, 121, 43— which has the most powerful sp.-dynamic action, this being less powerful with larger or smaller amounts. 45>- R . N. C. There is no relation between the amount of NH2-acid Standardised tuberculin (purified protein de given or its NH2 content and the magnitude of the rivative) for uniformity in diagnosis and epi action. The action of urea is strong, but weaker than demiology. E. R. Long, F. B. Seibeet, and J. D. that of (II) and alanine. W. McC. • A r o x s e n (Tubercle, 1935,16, 304— 322). n i. . , . Cir. A bs. (p) Diffusion of nitrogenous compounds from Uid tuberculin, human tubercle bacillus pro frog muscles in Ringer's solution. W. O. F e n n tein, and trichloroacetic acid precipitate. G. A. (J. Cell. Comp. Physiol., 1935, 6 , 469-485).—Frog St e w a r t (Amer. J. Dis. Children, 1935, 4 9 , 625— muscles in Ringer’s solution at 22° lose about 5 2 ± 6 ori rin rianeous sensitivity to tuberculoprotein (by mg. of N per 100 g. of muscle in 5 hr., half the N lost oeljLOjH pptn.) differs with age. Cn. A b s . (p) being protein, and the remainder urea, creatine, and NH 2-acids. In solutions of varying [K‘j the loss hi ESect of reduced glutathione on the curative protein cc the gain in Cl', with a rrh’nt at about 50 mg. action of neosalvarsan in the nagana-infected of K per 100 g. Protein loss is increased by rise ,/r - C. Moncoeps and R . M. B o h n s t e d t of temp., asphyxia, and frequent renewal of the B -Dermatologie, 1934, 170, 26— 32; Cliem. solution; non-protein-N loss is increased by stimul ntr., 1934, ii, 3983).— Glutathione (I) increases the ation and asphyxia. Both N losses are reduced by HMence of trypanOsomes, and detoxifies neosalvar- previous perfusion of the muscle with Ringer’s solu f I *1 mice infected with T. nagana the action tion. During immersion in Ringer’s solution p n y ) ls weakened by small quantities of (I) (sub- falls in the muscles and rises in the solution, owing to (in‘ravenous)bUfc StrenSthened bX IarS° V ^ itities loss of K’ and gain of Cl' by the muscle. Ringer’s solution as a medium for muscle is abnormal. a^i!dy °f gastric acid secretion by fractional R . N. C. yscs m cases of gastric and duodenal ulcers. Water balance of a marine mammal, the seal. ■ 1)elfin° (Pathologica, 1935, 27, 261— 268).— L. I r v in g , K . C. F ish e r, and F. C. M cIn to s h (J. with'V reprosenting changes of titratable acidity Cell. Comp. Physiol., 1935, 6 , 387— 391). R , N. C. Barak1?16-0^ ex4lac^on °f the gastric secretion are Mechanism by which the acidity of an acid ation ' 10 111 norniaI cases but not in cases of ulcer- H i ll, ' Ch. Abs. (p) meal is reduced in the stomach. F. C. L. C. H e n rich , and C. M. W tlh e lm j (Surg. Gynecol. regulation of basal metabolism. L. Obstet., 1935, 60, 966— 96S).— The mechanism in Basalmffu (,0rvosi Hetilap, 1935, 79, 311— 314).— cludes neutralisation and the regurgitation of duodenal inr rm l i 13 not mfluenced by agents affect- fluids. The two factors may be determined by use > ¡Qii/ G 'a centres. Narcotics cause a change of phenolphthalein. In dogs vals. were 35 and 65%, g Cii. A bs. (p) respectively. Ch. A bs. (p) 411 eEildren of normal and Metabolism of injured tissue, (a) W. F le is c h - -creatinivf lntelligence. Blood-cholesterol and mann. (b) H. D e u c k e e y (Naturwiss., 1936, 24, 15; Dis. C’hn?e vabl,es- II- Rothbaet (Amer. J. cf. this vol., 102).—The results of Druckrey are in was armnr61* I 672—688).—No correlation harmony with previous work, e.g., that by Fleisch- gence iiiAi’' between metabolic rates and intelli- g C Iuotlents. ^ c h . A bs. (p) mann on the metabolism of leucocytes. W. O. K. E acti°n of amino-acids. I. Metabolism of injured tissue. II. D e u c k e e y of glycijj^ ueose on the specific-dynamic action (Arch. exp. Path. Pharm., 1936, 180, 231— 250; cf. this vol., 102). F. 0 . H. fic-dvnarr.i„ . • ect °I con figu ra tion on speci fic-dynamic ac. .lon- 111 • Dependence of speci- Tissue metabolism. VIII. Effect of fumar- Kasai n on a m in o-g rou p content. Y. ate and succinate on tumour respiration. E. z -. 1936 5 »« Y S 1* and T - IhJKiwAKE (Biochem. B o y la n ij and M. E. B o y la n d (Biochem. J., 1936, 283, 159-168, 169-173, 174-179).-!. 30, 224— 226).— Respiration of tumour tissue, like 368 BRITISH CHEMICAL ABSTRACTS. A. X IX (g) that of muscle, kidney, and liver, is increased by Nutritive value of canavanine. M. K i t a g a w a succinate or fumarate and decreased by malonate. and M. W a d a (J. Agric. Chem. Soc. Japan, 1935,11, H. G. OR. 1083— 1088).— Dietary experiments on rats failed to Exhaustion of the respiratory capacity in vitro elucidate the growth-promoting action of canavanine of som e tissu es. G. D om in i and P. P e r u zzi (Boll. (cf. Ogawa, A., 1934, 1391). F. 0. H. Soc. ital. Biol, sperim., 1935, 10, 493— 496). Nutritive value of mustard oil. B. B. B k a h - R. N. C. m a c h a r i (Indian Med. Gaz., 1934, 62, 327— 329).— Respiration in vitro of some tissues in relation The oil contains no vitamin-A and tends to inactivate to the growth-curve of the organism. P . P e r u z z i -A in other foods. It has a nutritive val. similar to (Boll. Hoc. ital. Biol, sperim., 1935, 10, 489— 493).— that of other fats provided the -A supply is adequate. 0 2 consumption by surviving muscle, spleen, and Ch. A b s . (p) liver sections of the albino rat rises to a max. during Comparison between the nutritive value of the period when body-wt. has reached 40—60 g., and some legumes and some cereals. V. Z a g a m i and then falls to a steady val. R. N. C. V. F a m i a n i (Arch. ital. Biol., 8 8 , 119— 127; Chem. Utilisation of oxygen by Mya arena ria. L. Zentr., 1935, i, 3301). G. II. F. V an D am (J. Exp. Biol., 1935, 12,-S6—94).—'The 0 2 Nutritive value of alcohol-extracted animal utilisation coeff. is normally 3— 10% , but increases tissues, and supplements required for growth temporarily to 25% after a period of anaerobiosis. and lactation. W. H. S e e g e r s and H. A . M attill C n . A b s . ( p ) (Proc. Iowa Acad. Sci., 1934, 41, 173— 174).—Ex Anoxybiosis of the embryo of lia n a fusca in tracted tissues (beef heart, kidney, round, and liver) different stages of development. I. L a t i n i r - produced inferior growth in rats to that obtained , V e t u l a n i (Bull. Acad. Polonaise, 1935, B, 273— 278). with whole tissues. The deficiency was supplied by —The effect of anaerobic conditions on C02 produc the EtOH-extraet of liver. C h . A b s . (p) tion by the embryo varies with the stage of develop Determination of digestibility coefficients. I ment. The mechanism of these effects is examined. Method and computation for directly obtaining A. G. P. coefficients of individual nutrients in a mixed Respiratory quotients during embryonic de ration . M. C a r b e r y , I. C h a t t e r j e e , and M. 4- B o e l l velopment (Orthoptera). E. J. (J. Cell. H y e (Indian J. Vet. Sci., 1934, 4, 295—340).- Comp. Physiol., 1935, 6 , 369— 385).— Bound C 0 2 in Methods utilising graphical and multiple regression eggs of Melanoplus differentialis increases during equations are described. C h . A b s . [p) development. The 0 2 consumption curve reaches a Nutritional investigation of the porgy. IV. max. in 20 days at 25°. In diapause, respiration is Fractionation of porgy meat. Y. H a t a k o s h i (J- maintained at a min. level, but afterwards it increases Chem. Soc. Japan, 1935, 56, 221— 229).— Max. dis steadily. The R.Q. shows that fat is the chief solution of protein from ground meat was obtained metabolite oxidised during development; it decreases with O-lIV-NaCl or 0-02A7-NaOH. Ch. Abs. (?) slowly in later stages and is probably converted into chitin. R. N. C. “ Disequilibriating ” effect of fructose. B. L e c o q (Compt. rend. Soc. Biol., 1936, 121, 226— Photodynamically-induced oxygen consump 228).— Fructose (I) causes disequilibrium when present tion in muscle and nerve. A. J. K o s m a n and R. S. in the diet to 80—84% of the total carbohydrates. L i l l i e (J. Cell. Comp. Physiol., 1935, 6 , 505— 515).— The disequilibrium is not so accentuated as with Exposure of eosin-stained muscle and nerve to visible galactose or lactose. Equilibrium is established with light increases 0 2 consumption by 135— 183% and 35% of (I), and with 66% if yeast is added to the 133— 144%, respectively. The increase is unaffected diet. R- X. C. by Ca", Na salt solutions, CN', or boiling. Ovalbumin Metabolism of the lung-fish. II. Effect of stained with eosin consumes 0 2 in presence of light; feeding meat on metabolic rate. H. W. S mith glucose-eosin solutions, either alone or in presence of (J. Cell. Comp. Physiol., 1935, 6 , 335— 349).—Lung- adsorbents, do not. Irradiated fat-free muscle ex fish fed with meat exhibit a rise of 0 2 consumption, tracts but not protein-free extracts consume 0 2. The photodynamic effect in skeletal muscle is possibly and fasting causes a logarithmic decrease. ^ ^ associated with the membrane proteins. R. N. C. Organic matter in dissolved and c o llo id a l Energy sources in ontogenesis. VIII. Re form as food for Daphnia magna. S. S. Glfi® spiratory quotient of developing gastropod eggs. and G. L. C l a r k e (Physiol. Zool., 1935, 8 , 127—13d- E. B a l d w in (J. Exp. Biol., 1935, 12, 27— 35).— — The animals require colloidal nutrients. Throughout development the R.Q. was 105. Fat C h . A b s . (?) synthesis is indicated. The increase in C02 content Nutrition : vegetable proteins. L. B . Mendeh of the eggs coincides with the formation of true and H. B. V i c k e r y (Carnegie Inst. Wash. Y earbook, shell. Synthetic fat is probably not derived from 1934, 3 3 , 289—295).—In synthetic rations for rats protein. Uric acid is synthesised by the embryo in P-metabolism trials casein may be replaced during the later period of development. lactalbumin or, less satisfactorily, partly purih C h . A b s . (p) ovalbumin. Highly purified vitamin-A2 PrePs- :!rC Nutrition and national health. (S i r ) R . M c - obtained from liver, protein-free milk, or yeast ' C a r r i s o n (Roy. Soc. Arts., 1936, 56 pp.).— Cantor extraction with 5% HC1, adsorption on activate Lectures. fuller’s earth, and elution with NH3 or CjHs1 ' XIX (g) BIOCHEMISTRY. 369 Yellow solutions showing green fluorescence (especially acid. A. W h i t e (J. Biol. Chem., 1936, 112, 503— in ultra-violet light) are produced. A yeast con 509).—Rats fed on a diet low in cystine (I) and con stituent other than -B1 or -B2 is required for satis taining cholic acid (II) lost wt., but addition of either factory growth of rats. The cystine content of l-(I) or df-methionine (III) caused resumption of hemoglobin (Cu1 mercaptide method) is : horse 0-41, growth. Taurine and Na2S04 were ineffective. The sheep 0-61, dog 1-16%. Histidine was completely deficiency in (I) and (III)“ produced by (II) may be pptd. from protein hydrolysates by HgCl2. In addi due to the demand for taurine for the synthesis of tion to nicotine, green tobacco leaves contain N- taurocholic acid, or to a direct detoxication of (II) methylpyrrolidine and nornicotine, but no sol. qua by (I) and (III). J. N. A. ternary bases other than volatile alkaloids. Influence of feeding amino-acids and other Ch . A bs. (p) compounds on the excretion of creatine and Influence of protein on longevity. C. Y. Chen creatinine. M. B odansky (J. Biol. Chem., 1936, (Nat. Peiping Univ. Coll. Agric. Nutrition Bull., 1935, 112, 615—624).—Comparatively' large doses of argin B, 2, 12—21).—-On a 9% protein level the life span ine, aspartic acid, glutamic acid, cystine, histidine, of rats was shortest on a beef diet and the longest on tyrosine, choline, betaine, sarcosine, and salts of a mixed cereal diet containing maize protein 2, casein guanidine had no effect on the excretion of creatine or soya-bean protein 1. Cii. A bs. (p) (I) and creatinine in rats. Gly'cine, guanidinoacetic Protein metabolism and oxidation processes acid, and to a smaller extent, alanine increased the in experimental scurvy. I I I . Urea and creat output of (I). 30—80% of (I) given in doses of inine excretions in experimental scurvy and the 35— 120 mg. was recovered in the urine within 48 hr. eSect of iron. L. D. Kaschevnik and I. B. Frid- J. N. A. lakd (Biochem. Z., 1935, 2 8 2 , 265— 268) .— The Resorption of bile acids in the small intestine. urinary creatinine in guinea-pigs increases during E. F r o lic h e r (Biochem. Z., 1936, 283, 273— 279).— the devolopment of scurvy and also by addition In the small intestine of rats taurochlolic acid is of Fe to the diets. Addition of Fe, however, does more readily' absorbed than are cholic and glyco- not affect urea excretion. P. W. C. cholic acid. The absorption of the acids is more rapid Histochemical studies of the development of in the lower than in the upper part of the intestine. fish. I. Vitellogenesis in the gudgeon (G obio The differences are not due to variations in pn (5'9, ¡hiviatilis) and the carp (Cypritms carpio). B. 7-8) or to excretion of bile acids by the upper part hoxoPACKA (Bull. Acad. Polonaise, 1935, B, 163— of the intestinal mucous membrane. W. McC. -)• Appropriate histological technique is decribed Indican. IV. Absorption of indoles and and the stages of formation of vitellin during the indican synthesis in the body. V. Excretion of growth of the oocyte are examined. A. G. P. indican by bile. H. I n o u e (J. Chosen Med. Assoc., Synthesis of creatinephosphoric acid in organ 1934, 24, 1519— 1536 ; 25, 121— 135).— IV. In rab extracts a n d in liv in g s p e r m a t o z o a . I. T orres bits and dogs absorption of indoles can be greater 7 p a - 1' Z'’ 1935, 283> 128— 133).— The transfer in the small than in the large intestine. Some ot PO/" from phosphopyruvic acid (I) to creatine absorbed indole passes into blood by the lymphatics. occurs in many organ extracts, most rapidly in Symthesis of indican (I) occurs in liver and lungs but « a n d next in extract of testicles, the activity not in kidneys or intestines. Emulsions from liver in the latter ease being related to the sperm content, and lungs synthesise (I) in vitro (optimum p u 6-8— n mg sperms on addition of (I) and creatine show 9-0). a cous'deral)le synthesis of creatinephosphoric acid. V. Normal bile contains 0-06— 0-12 mg. of (I) per Tln. . P. W. C. 100 c.c., vals. being close to those in blood at the time , at10n of tryptophan administered sub- of excretion. Ch. A b s . (p ) neously. V. Du Vigneattd, R. R. Sealocic, Formation of xanthurenic acid : experiments VAiv E tten (J. Biol. Chem., 1936, 1 1 2 , 451— on m an. F. M. C h i a n c o n e (Boll. Soc. ital. Biol, thn V16W A lcock’s contention (A., 1934, 1392) sperim., 1935, 10, 578— 580).— Administration of in ill » 1 * - (1) produces no growth response kynurenine (I) to a healthy' man produces the diazo- ..J. 1'deficient animals, earher work indicating the reaction in the urine, but none of the other reactions Thp1^' 1933, 89) was repeated and confirmed, of xanthurenic acid. (I) is present in the urine, woo (lscrepancies remained when A lcock’s technique and is probahlv responsible for the diazo-reaction. "as used exactly. H. Dl R. N. C. suunf^*3^ ^ °1 tryptophan derivatives for Phosphatide metabolism and the influence of C p e4nentlng diets deficient in tryptophan. thyreoidin. L. P a s t e r n a k and I. H. P a g e (Bio Sei i J ;R(' an Choline and dietary production of fatty livers. fats of the uterine liquid and embryonal tissues are C. H. B e s t , H. J. C h a n n o n , and J. H. R i d o u t (J. < that of the maternal liver, which hence must under Physio)., 1934, 81, 409— 421).— Fatty liver caused by go a saturation process in order to be utilised by the high-fat diet is due to an increase in the neutral fat foetus. R. N. C. fraction. That caused by cholesterol is due to ex cessive amounts of cholesteryl esters with an in Nutritive effect of plant gums on formation of crease in neutral fat. The phosphatide (I) content fat and glycogen. H. I w a t a (Bui. Sci. Fak. of both types of fatty liver is inversely oc the total Terkult. Kjusu, 1933, 5, 352— 366).—Feeding gum lipin content. Choline prevents the occurrence of arabic or starch to rabbits did not increase glycogen both types of fatty liver, and increases the % of formation. Blood-protein-N and haemoglobin were (I) in the livers without disproportionate increases unchanged but -total sugar increased somewhat. Ch. A b s . (p) in lecithin and sphingomyelin. C h . A b s . (p) Influence of acid-base equilibrium on the Physiology of lipins and sterols under com glycogen content of the liver. S. K u m a j iu e a plete and protein inanition. S. V a l l a (Bull. Soc. (Trans. Soc. Path. Japan, 1934, 24, 2— 5).—Acidosis Chim. biol., 1935, 17, 1715— 1740).— A comparison decreases, and alkalosis increases, liver-glycogen. is made of the lipin and sterol content of normal mice Cii. A b s . (p) and animals undergoing complete and protein G lycogen ic fu n ction of the liver in the chicken starvation. Although the length of life under protein embryo. A. G u e l i n -S c h e d r i n a (Compt. rend. starvation is > that under complete starvation, Soc. Biol., 1936, 121, 144— 146).— Insulin does not the continuous carbohydrate intake in the first case cause the premature appearance of liver-glycogen (I) does not prevent the complete utilisation of the fatty in the developing chick embryo ; (I) appears at a later reserves. Fasting increases both cholesterol and stage than the pancreas. R. N. C. total N of the animals. A. L. Glycogen metabolism of the organiser in Fat metabolism. I. Effect of ingestion of amphibian gastrula. C. P. R a v e n (Proc. K. Akad. olive oil on lipin contents of rabbit tissues. II. Wetensch. Amsterdam, 1935, 38, 1107— 1109).— Effect on lipin contents of splenectomised rabbit When pieces of ectoderm were inserted in the dorsal tissues. III. Effect on sulphur distribution in lips of the blastospore of the embryo, there was a rabbit tissues. Y. S o n e d a (Sci-i-Kwai Med. J., definite decrease of glycogen (I) in those cells which 1934, 53, No. 8, 49— 65, 66— 87, 88— 91).— I. Daily had involuted. This loss of (I) is closely connected administration of 10 c.c. of olive oil increased the with the involution. J. N. A. fat acid (I) and lecithin (II) contents of spleen and Initial transformations of glycogenolysis : adrenals, and the cholesterol (III) hi spleen arid function of hexose monophosphoric ester. P. (slightly) in kidneys. Other organs were unaffected. O s t e r n and J. A. G u t i i k e (Compt. rend. Soc. Biol., II. Splenectomy lowered the (I), (II), and (III) 1936, 121, 282— 285).— Glycogen is first broken in all organs. Administration of olive oil markedly down to hexose monophosphate, which then reacts increased the (I) of the lungs, decreased the (III) : (I) with adenosinetriphosphoric acid to form hexose and (III) : (II) ratios of the kidneys, and increased diphosphate. R. N. C. the (II) : (I) ratio in the heart. III. Feeding of olive oil caused a considerable Utilisation of d-mannoheptulose (d-manno- increase in liver-S, and a slight increase hi S of all ketoheptose) by adult rabbits. J. H. R oe and other organs except lungs (decrease) and kidneys C. S. H u d s o n (J. Biol. Chem., 1936,112, 443—449).— (no change). C h . A b s . (p )~ Rabbits fed with d-mannoketoheptose (I) showed Combustion of odd-numbered fatty acids in an increased blood-sugar which was not accounted for by the blood-(I) ; (I) is converted into a reducing the anim al org a n ism . S. S k r a u p and E. S t r i e c k (Verh. Ges. Verdauungs- u. Stoffwechselkrankh., substance fermentable by yeast. The conversion 1934, 132— 136; Chem. Zentr., 1934, ii, 3784).— does not occur in the liver, but during the process Saturated Cn and CKi fatty acids are not oxidised of intestinal absorption. Insulin accelerates the in the body of the dog when administered alone, oxidation of the reducing substance forined from (I)- but the oxidation is catalysed by small quantities H. D- of unsaturated fats which are not themselves oxidised. Hydrolysis, oxidation, and energy changes in dogs. IV. Absorption of fructose by the organs R. N. C. Central regulation of fat metabolism in the of d og s in vivo. M. W ierzuchowski and H. F i s z e l (Biochem. Z., 1935, 283, 30— 44).—Further epidermis. A. P e r u t z , B. L u s t i g , and A. E. K l e i n (Arch. Dermatol. Syphilis, 1934, 170, 511— 520; work on the utilisation of fructose (I) is described Chem. Zentr., 1934, ii, 3784).— Destruction of the mid (cf. A., 1935, 1017, 1542). The absorption velocities brain followed by prolonged feeding with fatty of (I) by the organs of the dog are, in mg. per g. per hr., substances hi rabbits increases hair-fat and blood-(3- for liver 21, organs of the portal system 3-5, motor hydroxybutyric acid, blood-ketones being unaffected. system 0-4, muscle only 0-8, organs of the head Fat excretion by the skin is therefore probably regul 0-39, other organs 2-0. Simultaneously glucose is ated by a central mechanism. R. N. C. being formed by the liver and is being absorbed by the organs of the head with a velocity of 1*3, of Fat metabolism in the course of gestation of the portal system 1-0 , motor system 0-02, other organs Trygon violacea. G. S t o l f i (Boll. Soc. ital. Biol, 0-32. One fifth of the (I) absorbed is returned by sperim., 1934, 9, 1315— 1316).— The I vals. of the the liver to the blood as lactic acid. The organs of XIX (g, h) BIOCHEMISTRY. 371 the head and portal system do not appear to give phosphate in the urine. Excreted P is not unduly lactic acid in this way. The glucose-forming power high if the intake of CaC03 is adequate. Pullets of the liver is unchanged during the introduction of receiving 5% of CaC03 in the ration produced eggs inositol, dSTa lactate, and MeCHO. P. W. 0. with a higher P content than when the CaC03 was Chief method of lactic acid form ation inm uscle. omitted. A. G. P. 0. Meyerhof and W . K iesslin g (Biochem. Renal threshold of potassium. H. Griffo n 1935, 283, 83— 113).— Lactic acid (I) arises in muscle (Compt. rend. Soc. Biol., 1936, 1 2 1 , 47— 49).— chiefly by the oxidation of 1 mol. of triosephosphoric Theoretical. R. N. C. acid to phosphoglyceric acid with simultaneous Aluminium in nutrition. H. H. K eil and V. E. reduction of 1 mol. of A cC 02H to (I). This reaction N elson (Proc. Iowa Acad. Sci., 1934, 41, 161— proceeds much more rapidly than does the earlier 164).— Of the salts examined the order of toxicity described reaction in which a-glycerophosphoric was A1(OH)(OAc)2 < K alum and A1(N03)3 < A1C13. acid + AcC02H gavo 2 mols. of (I). The stages of Ch. Abs. (p) ' the new reaction can be separated using NaF and Influence of lungs on salt metabolism. S. CH2rC 02H in the same way as with alcoholic ferment R yü (J. Chosen Med. Assoc., 1934, 24, 1404— ation. A complete scheme of the intermediate 1410).— Blood-Cl in the right heart of the rabbit is reactions in muscle is given, and it is seen that in > , and the plasma-Cl < , the corresponding amounts muscle AcC02H is the biological equiv. of MeCHO in the left. Passage of C02 into arterial blood and (I) of EtOH of alcoholic fermentation. P04"' increases plasma-Cl and decreases corpuscular Cl. changes involve the muscle-adenylic acid system. Reverse effects occur in venous blood. Lungs The scheme is in close agreement with the require not only remove Cl from blood but regulate Cl ments of the Harden-Young equation. P. W. C. distribution by the gaseous exchange. Ch . A b s. (p) Effect of hydrazine on the production of Probable nervous mechanism of the increase ketonic substances in the phloridzin-intoxicated of the reducing power of the aqueous humour Gre e n b e rg animal. M. M. (J. Biol. Chem., 1936, under the action of Hght. A. B onsignore (Boll. 112, 431—436).—Phloridzinised rats, treated with Soc. ital. Biol, sperim., 1935, 10, 505— 509).— The NjH4, showed a decreased excretion of ketones which increased ascorbic acid content is probably due to was not due to kidney retention, decreased deamin parasympathetic action. R. N. C. ation of NH2-acids, or increased glucose or protein metabolism. H. D. Insolation and acidosis. G. h i Macco (Boll. Soc. Ital. Biol, sperim., 1935, 10, 437— 438).— Comparison of the tendencies of different Administration of HC1 to rabbits delays death from animal species to ketonuria and ammoniuria. insolation. R. N. C. E.P.Tebroine and H. T rimbach (Arch. int. Physiol., 1934, 39, 377— 416; Chem. Zentr., 1934, ii, 3980).— Increase of cell permeability by mitogenetic Ketonuria in milk-fed animals is higher in those of irradiation. (Chemical detection of the mito smaller body-wt., but is independent of the amount genetic effect.) I. R. B ach romejev (Biochem. Z., of food ingested per kg. The ratio (COMe2 + 1935, 282, 297— 302).— The small amounts of inorg. tHAc-C02H)/p-hydroxybutyric acid in the excreta P, phosphatide, phosphatase, sugar, and catalase m generally 30 : 70, but is less for the cat and hedge separated from surviving mouse liver into Ringer’s hog. XH3 excretion differs greatly with the species, solution are very largely increased when the liver is and is independent of the type or quantity of the previously subjected to mitogenetic irradiation for food- ' R . N. C. \ hr. ' P. W. C. Acetaldehyde in muscular work and avita- Role of the reticulo-endothelial system in the punosis-i{. H. H a n d o v s k y (Compt. rend. Soc. fixation of radiothorium. K . Schachowitch , Biol., 1935, 120, 1357— 1358).— Blood-MeCHO is D. K . Jo w an owitsch, and M. W isciinitschewa not modified in the dog by muscular work. Injection (Glas Srpske kralewske Akad., 1933, 78. 65— 73; ot MeCHO in vitamin-A-deficient pigeons delays Chem. Zentr., 1934, ii, 3401). R . N. C. death- R .N .C . Radioactive effect of potassium on the vegetat- Fate of alcohol in the corpse of an alcoholised ative n ervous system . O. M erck (Strahlenther., marrunal: formation of alcohol in non-alcohol- 1934, 50, 471— 475; Chem. Zentr., 1934, ii, 3786). ised control animals. M. N ic lo h x (Compt. rend. R. C. N. Biol., 1935, 120, 1306— 1309).— The rate of Influence of changes in the medium on the isappearance of EtOH from the corpse of an alco- development of eggs of Jiothriocephaius seörpii (Müller 1776). S. M a r k o w s k i (Bull. Acad. Polon Ptrht mouse increases with temp. Formation of OH occurs in non-alcoliolised control animals; aise, 1935, B , 49— 58).— Eggs are not susceptible e rate of formation increases with temp., but to any but oxtreme changes in salt concn. in the a " a-vs Hses to a max. and then falls. The highest medium. Light intensity is a more important max. occurs at 15— 18°. R. N. C. factor. A. G. P. Mineral metabolism of puHets. II. R, H. Behaviour of the water-flea, Daphnia pulex, m S L ( J - Af?ric- Sci., 1936, 26, 85— 100; cf. A., de Geer, in media of different hydrogen-ion of D. pulex in a culture is restricted but the parth- improved by treatment with thyroxine (I). Ripe enogenetic increase of the survivors is not affected. sperm and eggs are unaffected. (I) causes a tem A. G. P. porary rise in the 0 2 consumption of unripe eggs. Embryonic and larval development in Succit- C h . A b s . (p) lina (Rhizocephala) in media of changed osmotic Interpretation of the [physiological] action of con dition . M. R a m u lt (Bull. Acad. Polonaise, some preparations of bromine. I. S i m o n (Boll. 1935, B , 87— 109).— Effects of hypo- and hyper Soc. ital. Biol, sperim., 1935, 10, 382— 383).— tonic solutions on the various stages of development Injection of dibromocholesterol in olive oil in rabbits are examined. A. G. P. causes a deposition of Br in the blood, liver, kidney, Water exchange and fatigue : effect of inges and adipose tissue, but not in the brain. tion of water on tachycardia and hyperpncea R. N. C. fro m w o rk . G. d i M a cco (Boll. Soc. ital. Biol, Effect of cupric, manganous, and ferric chlor sperim., 1935, 10, 436—-137). R . N. C. ides on cardiac explants in tissue culture. D. C. Electromotive force in biological systems. H etiierington and M. E. Sinrr (Biol. Bull., 1935, IV. Effect of carbon monoxide on the electro 6 8 , 215—230).—Low concns. of the salts produced stimulatory and higher concns. toxic effects. A motive force of frog skin. A. B. T a y lo r and E. J. combination of the three chlorides was very toxic. B o e l l (Proc. Iowa*Acad. Sci., 1934, 41, 316— 317; cf. A., 1934, 327).— The e.m.f. of frog skin is depressed C h . A b s . (p) The combination of iron and copper and their by CO in C 0 -0 2 mixtures. The effect is not due to relation to blood-formation and to general decreased [0 2]. No additional change occurs in darkness. Aeration causes a return to normal metabolism, and the connexion between their effects and the crystallin e state of the metals. (and sometimes > normal) vals. Cn. A bs. (p) S. O d a (Z. ges. exp. Med., 1932, 84, 719— 727; Chem. Sensitisation of animals with simple chemical Zentr., 1935, i, 3154).— Active Fe20 3 (Siderac) (I) compounds. K. Landsteiner and J. J a cob s causes no polycythsemia in normal animals, but (Proc. Soc. Exp. Biol. Med., 1934, 31, 790, 1079).— produces changes in the urinary C/N ratio. Cu- Positive effects on guinea-pigs are obtained with a albumin compounds or Cu glycerophosphate cause no. of substances. The mechanism of the action is polycythcemia, are efficacious in experimental anaemia, discussed. Ch. A bs. (p) and affect the urinary ratio. Mixtures of (I) and Harmful effect of certain chemicals on the Cu compounds have the greatest effect on blood uterus of the rat. F. E. D ’A m ou r and N. R iv e n and C/N ratio, but cryst. combinations of Cu and (Amer. J. Obstet. Gynecol., 1935, 29, 503— 509). (I) have no effect on blood formation. G. H. Id Ch . A b s . (p) Therapeutic action of iron. L. J. W itts (Lancet, Toxic action of heavy metal salts on the three- 1936, 230, 1— 5).—Factors affecting the require spined stickleback (Gastrosteus acullatus). ment, absorption, and utilisation of Fe are discussed. J. R . E. J o n e s (J. Exp. Biol., 1935,12, 165— 173).— Absorption of Fe from food or drugs cc the ease Toxic effects of the salts are largely due to the cations, with which Fe" ions are liberated. Fe is a nutrient although anions have some influence, e.g., S 04" > and not a stimulant for blood-forming organs. N 0 3' or Cl'. Difference in toxicity is closely related L. S.T. to difference in electrical conductivity. Mercurial (novurit) suppository as a diuretic Ch. A bs. (p) for cardiac oedema. J. P a r k in s o n and W. A. R. Mammalian organism and action of metallic T hom son (Lancet, 1936, 230, 16—19). L. S. T. salts. L. E. W a lbu m (Z. Immunitats., 1934, 82, 399— 419). R. N. C. Action of potassium on formation of lactic acid Influence of neutral salts on the photodynamic and b rea k d ow n of ph osph agen in the isolated stim ulation of m u scle. R. S. L i t t l e , M. A. muscle of the frog. D. N a c h m a n s o h n , J. W a j z e r , H in rich s, and A. J. K osm an (J. Cell. Comp. Physiol., and A. M a r n a y (Compt. rend. Soc. Biol., 1936,121, 1935, 6 , 487—501).—Pure Na salts in solution 141— 142).— Excess of K* accelerates lactic acid sensitise eosin-stained muscles to stimulation by formation and phosphagen breakdown in the isolated light, the efficiencies of the anions being C l'< B r '< muscle in anaerobiosis. R. N. C. N 0 3'< F . Stained muscles irradiated in Ringer’s Physiological and pharmacological action of solution are sensitised to subsequent stimulation by su lp h u r. F. M. C h i a n c o n e (Boll. Soc. ital. Biol, Na salts; staining alone has a depressant action. sperim., 1933, 8 , 1511— 1513).— S injected sub- Ca" inhibits the photodynamic response, which is cutaneously in dogs in aq. EtOH-glycerol solution more sensitive to Ca” than to Na'. 0 2 is essential increases the resistance of the erythrocytes, and also to photodvnamic response. R. N. C. augments the alkaline reserve of the plasma, thus Effect of iodine on the sexual organs and growth favouring the 0 2-fixing power of haemoglobin and in the rat. A. L epschu tz and E. M o r a le s (Compt. increasing the buffering power of the blood. The rend. Soc. Biol., 1936, 121, 337— 340). R . N. C. intracellular oxidation-reduction processes are main Iodine compounds and fertilisation. IX. tained and accelerated. R. N. C. Fertilisation in the starfish, Asterias rubens, L. Action of Viterbo sulphurous water on ger G. S. C a r t e r (J. Exp. Biol., 1935, 12, 108— 118; mination and on the activity of the epithelium of cf. A., 1932, 1285).— Immature starfish sperm is frog’s oesophagus. A. R o s s i n i (Annali Chim. Apph, activated and the fertilisability of unripe eggs is 1935, 25, 541— 557).—The S02-containing H20 (ana- XIX (h) BIOCHEMISTRY. 373 lyses given), after a brief initial retardation, acceler Relation between the chemical constitution ates the germination and growth of wheat and lentil and pharmacological action of phenylhydrazine when compared with controls in normal H20 or derivatives. W. F. von Oettingen and W . Knop’s solution. The movements of ciliated epi Deichm ann-Gruebler (J. Ind. H y g , 1936, 18, 1— thelial cells are depressed and finally (1— 2 hr.) 16).—Attempts to preserve the antipyretic action of arrested. F. 0 . H. NHPlrNH 2 while decreasing its toxicity have been Action of some natural mineral waters on the unsuccessful. Substitution of one or more H by alkyl, isolated heart. G. Guidi (Boll. Soc. ital. Biol, aryl, alkoxy, or acyl decreases toxicity, which depends sperim., 1935, 10 , 432— 434). R . N. C. largely on the solubility in H20 and the ease of hydrolysis. Introduction of Bu, GH|Ph, or CHO Action of hydrocyanic acid on carbon dioxide assimilation and respiration of Stichiococcus yields compounds which have no effect on blood pressure, respiration, etc. because of their stability bacillaris. F. v a n d e r Paauw (Planta, 1934, 24, at high temp. P. G. M. 353—360).—Small amounts of HCN accelerate assim ilation and respiration under conditions of high or Action of indole on the dehydrogenating power low light intensity. The inhibitory effect of larger of tissues. G. F. d e G a e t a n i (Boll. Soc. ital. Biol, dosages of HCN is more marked in high light intensity. sperim, 1934, 9, 1291— 1294).— The dehydrogenating A. G. P. processes are generally diminished; blood-sugar is Fixation of propyl bromide in the blood and raised. R . N. C. brain of the guinea-pig, after preliminary ad Action of diketopiperazines on fibroblasts ministration of different poisons of the central cultivated in vitro. R. T r u h a u t and D. O d i e t t e nervous system . M. T i e e e n e a u and D. B r o u n (Compt. rend. Soc. B iol, 1935, 120, 1198— 1201).— (Compt. rend. Soc. Biol., 1935, 120, 1169— 1170).— Growth is stimulated by 2 : 5-diketopipcrazine, and The Pr“Br-fbdng capacity of the brain is reduced by to a smaller extent by glycine. R. N. C. hypnotics (chloralose, soneryl, urethane), but in A lk ylglyoxalid in es.— See this vol., 344. creased by stimulants such as caffeine. R. N. C. Mercury salts of alkylfluoresceins.—See this Pharmacology of bromoacetic acid. H. vol., 352. Ieeund (Arch. exp. Path. Pharm., 1936, 180, 199— 208).—The mechanism of the sp. actions of Action of E-dinitrophenol (1:2:6) on respir CHjBrCOjH on carbohydrate metabolism of animals atory exchange and temperature of homceo- and bacteria and of the toxic action on ascarides th erm ic anim als. G. S a r z a n a and D. E l i a (Boll. (the muscular contraction of which is compared with Soc. ital. Biol, sperim, 1935, 10, 545— 546).— 2 :6 - that due to santonin) is discussed. F. 0. H. Dinitroplienol increases 0 2 consumption in pigeons and rats by about 100%. R. N. C. Elimination of sodium formaldehydesulphoxyl- ate by the lddneys. E. H ug (Compt. rend. Soc. Pharmacology of the vegetative nervous Biol, 1936, 121 , 365— 367).—The kidneys of the dog system. IV. Point of attack of 2 :4-dinitro- have a concentrating capacity of 2— 2 -5 % for the phenol. B. d e B i a s i o (Boll. Soc. ital. Biol, sperim, compound. The greater part is excreted in 2— 3 hr. 1935, 1 0 , 383— 385). R. N. C. after injection. R . N. C. Action of phenylglyoxal on the vasomotor Pharmacology of tetraethylammonium phos innervation of the kidney. E. M a r t i n i and G. phate. I . S i m o n (Arch. i n t . Pharmacodyn. Tlidr, F r a n c h i (Boll. Soc. ital. Biol, sperim, 1935, 10, 1934,47,75—95; Chem. Zentr, 1934, ii, 3981). 473—474). R. N. C. B.N.C. Vagal central action of phenylglyoxal. E, p-u-Alkylcholine chlorides and their acetyl M a r t i n i (Boll. Soc. ital. Biol, sperim, 1933, 8,1709— esters.—gee this vol., 319. 1710).—BzCHO acts similarly to AcCHO, but is Influence of the water vapour content of an effective in smaller concns. R. N. C. orou s gas on the olfactory sense. H. W o e r d e - Urinary sulphate determinations as a measure 2 * fArch. Necrland. Physiol, 1935, 20, 591— 595).— of benzene exposure. W . P. Y a n t , H. H. S c h r e n k , . intensity of the odour of fsoamyl acetate when R. R. S a y e r s , A. A. H o r v a t h , and W. II. R e i n h a r t mixed with damp air is > when mixed with dry' air. (J. Ind. H y g , 1936, 18, 69— 88).— A marked decrease J. N. A. in the % of inorg. S04" in the urine occurs many . Relations between simple odorous and odorous weeks before symptoms of anaemia etc. P. G. M. irritant stim uli and thiocyan ate con cen tration in we nasal mucus. P. N i c c o l i n i (Boll. Soc. ital. Proliferation-stimulating action of 1 : 2 : 5 : 6- fa°l. sperim, 1935, 10, 429— 431).— The [CNS'] of dibenzanthracene on Obelia genicutata. S. P. e mucus is increased by non-irritant and decreased R e i m a n n and F. S. H a m m e t t (Amer. J. Cancer, °y irritant odours. R . N. C. 1935, 20, 343—349).—Hydranth development was stimulated in sea-H20 cultures containing this com Organic effects of hydrazine derivatives. pound. " Ch. Abs. (jj) ‘V. 0. Hueper (J. Ind. H y g , 1936, 18, 17— 36).— e tour derivatives examined produced lesions of Hypoglycaemic action of methylene-blue. G. cj 10 sam° type and in the same site, differing only in Piotrowski (Compt. rend. Soc. B iol, 1935, 120, egree. «-Ethyl-[i-propylacraldehj’dehydrazone was 1215__1216).— Methylene-blue does not reduce normal e most toxic. Destruction of erythrocytes and blood-sugar in rabbits, but apparently reduces hyper- leucocytes occurred in all cases. P. G. M. glycsemia caused by adrenaline or glucose. R. N. C. c c 374 BRITISH CHEMICAL ABSTRACTS.— A. XIX (h) Secretion in tissue cultures. I. Inhibition of Effect of specific substances of the body on phenol-red accumulation in the chick kidney. blood pressure in man. III. Action of lacarnol, R . Ch am bers, L. V. B e c k , and M. B e l k in . II. myoston, padutin, “ fourth substance " (Lange), Effect of sodium iodoacetate on the chick kidney. and eutonone on intravenous application. H. J. L. V. B eck and R. Cham bers (J. Cell. Comp. Physiol., W olf and H. A. H einsen (Z. klin. Med., 1934, 127. 1935, 6 , 425—439, 441—455). R. N. C. 1— 14; Chem. Zentr., 1934, ii, 3787). R. N. C. Influence of pyocyanine on respiration of sea- ( A ) Antagonistic action of lipins to the toxic urchin's eggs. J. R u n n strom (Biol. Bull., 1935, 6 8 , a ction of bile salt. (B) E ffect of thyroid gland 327— 334).— Pyocyanine (I) increases the respiration preparation on formation of gastric ulcer by bile of the eggs, the effect being further increased by salts, and antagonistic action of cholesteryl HCN in unfertilised, but decreased in fertilised, eggs, oleate. (C) Relationship between toxicity of bile The block in division of the egg caused by HCN is salts and their antagoniser. K. Isrni (Sei-i-Kwai not removed by (I). The rate of respiration in Med. J., 1934, 53, No. 9, 94— 191, 192— 198, 199— presence of (I) is > that in the presence of methylene- 211).—( a ) Susceptibility to bile salt (I) toxicity in blue. Neither the Fe-containing enzyme nor the the male is > in the female starfish. The effect is dehydrase-substrate system acts as a limiting factor antagonised by cholesteryl oleate (II) or phospho- for the oxidation rate in the unfertilised or newly lipin, but not by free cholesterol, oleic acid, castor or fertilised egg. Ch . A b s . (p) olive oil, glucose, Na K tartrate, Na citrate or lactate. (b ) Hyperthyroidic guinea-pigs are more susceptible Action of acetylcholine on energy exchange. to gastric ulcer formation by (I). (II) antagonises V. B asun ti (Minerva med., 1935, i, 486— 489).— Sub the thyroid effect. cutaneous injection of acetylcholine (0-2 c.c.) during (c) When (I) and diphtheria toxin are simul fasting produces a slight but inconst, increase in taneously injected into guinea-pigs the antagonistic respiratory exchange and a definite const, increase in ratio of (II) : (I) is 1 : 0’8. Ch . A bs. (p) the sp. dynamic effect of foods. Ch . A b s . (p) Influence of cell constituents of the pancreas Acetyl-fi-methylcholine (mecholine). Action on the external secretion of the pancreas. I. on blood pressure, skin temperature, and the Influence of parenteral introduction of pancreas heart as exhibited by electrocardiograms of cell constituents into dogs with complete pan hypertensive patients. I. H. P age (Amer. J. Med. creatic fistulas. II. Influence of cell con Sci., 1935, 189, 55— 64). Ch . A b s . (p) stituents of other organs. III. Influence of Developmental growth and the amino-acids. purified extracts of pancreas and other organs. II. /-T ryp top h a n . F. S. H am mett and M. L. IV. Mechanism of hypersection and nature of E llio tt. III. d -A rgin in e. F. S. H ammett and the exciting agent. K. T a b u c h i (Japan. J. Exp. N. Chatalbash (Protoplasma, 1935, 23, 457— 465, Med., 1934, 12, 411— 418, 419— 421, 423— 425, 427— 492—502).—II. Effects of various concns. of l- 435).— Pancreatic cell constituents and their purified tryptophan (I) on the development of Obelia arc extracts stimulate strongly the external secretion of recorded. The chief function of (I) is that of re the pancreas, independently of simultaneous secretion tarding catabolic activity, hence its indispensability of gastric juice and bile. Secretion is not inhibited for wt. maintenance. In developmental growth (I) by atropine. The mechanism of stimulation differs is a sp. determining participant in processes concerned from that of insulin and histamine and is effected by in differentiation or organisation and in the prep, of a hormone acting by way of the blood stream on the the tissue reaction basis for new growth initiation. acinar cells. Ch . A bs. (p) III. The function of arginine (II) in growth is not Action of some amines related to adrenaline: the regulation of any particular metabolic activity, methoxyphenylmethoxyethylamines. G. K- but participation in preparatory processes essential E lphick and J. A. G unn (J. Physiol., 1934, 81, for organisation of the tissue reaction basis for new 422— 433).— The physiological effects of p-methoxy-, growth initiation. The possible significance of (II) in 3 : 4-dimetlioxy-, and 3:4: 5-trimethoxy-phenyl-?- malignancy is discussed. A. G. P. methoxyethylamines are compared with corresponding Highly active pressor substance from cerebral compounds lacking OMe. Addition of OMe to the ventricular fluid of human beings. I. H . P age side-chain diminishes the activity. Ch . A bs. (p) (Science, 1935, 82, 550).— Intravenous injection into Importance of cholesterol in the action of cats of extract of human cerebral ventricular fluid calcium on heart muscle. S. M e n tl, J. K a r a s e k , from malignant hypertension cases produces a sharp and V. K r u t a (Arch. int. Physiol., 1934, 40, 158—- rise in arterial pressure. Similar extracts prepared 172; Chem. Zentr., 1935, i, 3158).— The heart of from plasma produce a slower but more prolonged cholesterol-treated frogs reacts normally to Ca and rise. L. S. T. adrenaline, although the isolated heart is abnormally Vasoconstrictive substance in blood. M. E no- sensitive in presence of cholesterol. The right moto (J. Chosen Med. Assoc., 1935, 25, 14— 25).— auricle of cholesterol-fed guinea-pigs is more sensitive The amount of vasoconstrictive substances is in and contains more cholesterol than normal. creased in pulmonary tuberculosis, typhoid, nephritic G. H. F. and hepatic cases. The substance is not destroyed Action of creatine on the double electric curve by 02, H,, or C02, nor by heating at 60° for 30 min. of fatigue in man. G. B o rgatti (Boll. Soc. ital. It is destroyed at 100°. Ch . A b s. (p) Biol, sperim., 1935,10, 609—611). R. N. C. XIX (h) BIOCHEMISTRY. 375 Variations of the dehydroascorbic/ascorbic convulsions started. Simultaneous injection with acid ratio in the liver and adrenals after ad (I) was non-toxic. Ch . A b s. (p ) ministration of parasympatheticotropic sub Cardiazol as a reviver in anim al experim ents. stances. F. Copello (Boll. Soc. ital. Biol, sperim., M. H. F ischer and H. L owenbach (Klin. Woch., 1935, 10, 509— 515).— The ratio is decreased by 1934, 13, 1401; Chem. Zentr., 1934, ii, 3983). parasympathetic excitants, and increased by para lysers, in the liver, but is not affected by either in the R . N. C. adrenals. R. N. C. Carioclasic crisis in the reticulo-endothelial system and endogenous uric acid exchange. G. Theory of narcosis. N. V. L a z a re v (Biochem. D omini (Boll. Soc. ital. Biol, sperim., 1934, 9, 1297— Z., 1935, 283, 158).— Claim of priority in respect of 1300).— Carioclasic substances do not affect blood- the work of Meyer and Hemmi (À., 1935, 893). or urinary uric acid in the dog, but allantoin excretion P. W. C. is increased. R. N. C. Effects of chloral hydrate on maternal and Comparison of the effect of guanidine, syn- fœtal organisms. R. E. C a m p b ell (Amer. J. thalin, and " anticoman ” on the m uscle of cold Obstet. Gynecol., 1934, 28, 83— 88).— Chloral hydrate blooded animals. R. R ittm a n n and J. Magerl depresses respiration and urinary output. (Arch. Verdauungskr., 1935, 57, 9— 14; Chem. Cii. A bs. (p) Zentr., 1935, i, 3158).—The fatigue induced in frog Carbohydrate metabolism under barbiturate sartorius muscle, indicated by the acceleration in narcosis. M. G. M u linos (Arch. int. Pharmaeo- rate of production of lactic acid, gives the order : dvn. Ther., 1934, 47, 111— 112; Chem. Zentr., 1934, synthalin > guanidine > “ anticoman ” > “ anti ii, 3403).—Blood-sugar (I) in rabbits and dogs is coman ’’-(-pancreatic enzyme prep. > “ anticoman ” raised by amytal, pernocton (II), nembutal (III), tablets. G. H. F. and dial. (II) anaesthesia does not affect the action of subcutaneously-injected glucose, adrenaline, or Action of ricin on the isolated heart of the rab insulin on (I). Oral administration of glucose to b i t . R. Attim onelli (Boll. Soc. ital. Biol, sperim., anæsthetised rabbits raises (I) to only 00% of the val. 1933, 8 , 1524— 1528). R. N. C. reached in unanæsthetised animals. The urine of Action of thevetin, acardiac glucoside, and its (Hl)-ansesthetised cats contains a reducing substance clinical application. H. L. Arnold, W. S. M id d le that is not glucose. R. N. C. to n , and K. K. C hen (Amer. J. Med. Sci., 1935, Constitution and hypnotic action : bromo- 189, 193—206).—Thevetin from “ be-still ” nuts ethyl- and diethyl-barbituric acid. L. D onatelli (Thevetia neriifolia) has a digitalis-like action with (Arch. Farm, sperim., 1935, 40, 497— 516).— The potency and toxicity approx. 1 /7 of that of ouabain. Xa salt of 5-bromo-5-ethyl- (I) has a stronger hypnotic Cii. A b s . (p) action than that of 5 : 5-diethyl-barbituric acid (II), Mechanism and course of chemotherapeutic and is very toxic. In restricting the respiration, a c t io n . F. A xm a ciier (Arch. exp. Path. Pharm., diminishing the amplitude and the frequency of the 1936, 180, 142— 166).— The action of various chemo cardiac function, and in vasodilatory action the effect therapeutic substances is ascribed to purely physical °f (I) is much > that of (II). E. P. processes, e.g., changes in permeability and surface action, resulting in exclusion of nutritive substances Effect of oxygen in the prevention of liver from the cell and in inhibition of eell-enzymes. necrosis produced by volatile antiseptics. S. The action of germanin (I) on the fermentation of îoldschmidt, I. S. R a v d in , and B. L ucké (Amer. cell macerates does not depend on adsorption-in- • : Med- Sci., 1935, 189, 155— 156).— In CHCJ3 or activation of zvmasc, but is possibly related to the mriyl ether anæsthesia, 0 , decreases subsequent presence of -S03H in (I); that of Sb preps, is due to necrosis. Ch . A b s. (p) inhibition or destruction of carboxylase. The mech Local anaesthetics with vasopressor action. anism of curative processes is discussed. F. 0. H. ■ Esters^ of arylethanolamines. G. A. A xles M ode of action of chemotherapeutics in spiro- nnd R., K Knoefel (Arch. int. Pharmacodyn. chsete and protozoan infections. E. S in g e r 1934, 47, 96— 110; Chem. Zentr., 1934, (Med. Klinik, 1935, 31, 380— 389). R. N. C. n’ 34w)- R .N . C. New antipyretic: i.sopropylantipyrine. G. Effects of drugs on the autonomic nervous Orestano (Boll. Soc. ital. Biol, sperim., 1935, 10, and on protein metabolism in normal 470—473). R- N- C. a hypopbysectomised dogs. Y . TAiazAKi (Sei- Pharmacology of chenopodium oil. II. M. ê r Med' J -’ 1934’ 5 3 > N o - n > 98— 117).— In- A ia zzi-M ancini and L. D ovatelli (Boll. Soc. ital. mc,10,n oserine increased protein and intermediate e a holism. The effect was reversed by adminis- Biol, sperim., 1934, 9, 1306— 1307). R. hi. C. a mn of nicotine or atropine. Ch. A bs. (p). Theosan and its combinations. F. Eckhardt (Wien. med. Woch., 1934, 84, 1059; Chem. Zentr.. Action of decametbylenediguanidine bitar- 1934, ii, 3787). R - K C- j ,°.n blood-sugar. B. L. M ontas (Illinois Med. sto i —dosages of 12 mg. administered by Mechanism of the action of ephedrine on gaseous exchange. G. O re s ta n o (Boll. Soc. ital. .sun’Ina t^11^6 cause<4 a temporary increase of blood- arufr'i Larger amounts (24 mg.) caused convulsions Biol, sperim., 1935, 10, 467—469).— The action of death even when glucose (I) was given after ephedrine on gaseous metabolism is similar to that of 376 BRITISH CHEMICAL ABSTRACTS. A. XIX (h) adrenaline, and is effective in the same species, the Influence of quinine derivatives on the iodine effect persisting longer. R. N. C. contents of endocrine organs. II. A. Ohta (Sei-i-Kwai Med. J., 1934, 53, No. 11, 78—97).— Octaverine, a new spasmolytic. P. E l l in g e r , W. K oschara, and H. Se eg e r (Arch. int. Pharmaco- Quinine hydrochloride (10 c.c. of 10% solution per dyn. Thér., 1934, 48, 50— 62; Chem. Zentr., 1934, ii, kg.) increased the I content of thyroid, adrenals, 3402).— Octaverine, a derivative of phenyKsoquinoline, liver, ovaries, and testicles, and lowered that of is less toxic and is less rapidly absorbed and detoxic blood, thymus, spleen, pituitary, and pancreas. ated than papaverine. R. N. C. Both cinchonine hydrochloride and 2-hydroquinine produced smaller increases in I in thyroid, adrenals, Action of bulbocapnine on the frog’s heart. and testicle; the former lowered that of spleen, and E. M. Ohian cone and U. Porn (Boll. Soc. ital. Biol, the latter that of spleen and liver. Optoquin caused sperim., 1935, 1 0 , 573— 575). R . N. C. no changes (cf. A., 1935,1396). Ch . A bs. (p) Action of bulbocapnine on isolated frog muscle. Action of quinic and phenylcinchoninic acids Ciiia n c o n é U. Popi'i and F. M. (Boll. Soc. ital. Biol, on metabolism. E. B eccari (Boll. Soc. ital. Biol, sperim., 1935, 10, 570— 573). R. N. C. sperim., 1935, 10, 402— 405).— Injection of quinic Action of cocaine on fish. R . d e Marco (Boll. (I) and phenylcinchoninic acids (II) in healthy human Soc. ital. Biol, sperim., 1933, 8 , 1488— 1490). subjects increases uric acid excretion. (I) produces R . N. C. a negative and (II) a positive balance of N and P. Pharmacology of physostigmine. C. R . L in e - The urinary urea-/total N ratio is reduced by (I) g a r , J. M. D il l e , and T. K o ppa n y i (Science, 1935, through an increase of non-urea-N excretion, whilst 82, 497). L. S. T. the variations produced by (II) are due to variations New active principle in ergot : effects on of urea. The azoturic coeff. is reduced by both acids. uterine mobility. M. E. D a v is , F. L. A d a ir , G. R . N. C. R ogers, M. S. K h ar asch , and R . R . L egau lt (Amer. Alkaloids from the seeds of Cassis absus, J. Obstet. Gynecol., 1935, 29, 155— 167).— A yellow, L inn.— See this vol., 350. stable, non-alkaloidal fraction is isolated. It provokes Isomerisation of conessine and its nor-bases.— the characteristic uterine response. Ch . A b s . (p) See this vol., 350. Physiological action of ergometrinine and of V ariable action of co b ra ven om s standardised ergometrine. R. H am et (Compt. rend. Soc. Biol., for therapeutic use. P. Simomin and J. Bríos 1935, 120, 1208— 1212).— The activity of ergo (Compt. rend. Soc. Biol., 1935,120, 1253— 1255). metrinine in the dog is the smaller. R . N. C. R . N. C. Effect of morphine and of heroin on blood- Ultra-violet absorption spectra of snake sugar and respiration in rabbits. H. G y o k t i (J. venoms. H. F. H o l d e n and C. G. Sette r (Austral. Chosen Med. Assoc., 1935, 25, 222— 226).— Blood- J. Exp. Biol., 1936, 13, 223—228).—The venoms of sugar is increased by injection of morphine hydro many snakes exhibit an ultra-violet absorption band chloride (0-05 g. per kg.), reaching a max. in 2— 3 hr., at about 280 nig, but no correlation exists between and regaining normal in 6-—7 hr. Heroin hydro the toxicity of the venom and the position or intensity chloride produces similar but smaller changes. of the band. W. 0. K. Ch . A b s . (p) Carbon tetrachloride intoxication. A. Nassas Antagonism between nicotine and some and M. Salah (J. Egypt. Med. Assoc., 1935, 18. quaternary hexamethylenetetramine iodides. 207— 214).— Poisoning by CC14 used as an anthelmintic Curare poisons. J. Ga u tr e le t and N . H a l pe r n is not related to the amount used or to Ca deficiency, (Arch. int. Pharmacodyn. Thér., 1934, 47, 4— 44; but is due to constitutional intolerance. Chem. Zentr., 1934, ii, 3402). R . N. C. Ch. Abs. (p) Effect of nicotine on sex and sexual hormone. Arrow poisons. C. G. Sa n tesson (Skand. Y . C. L ee (Trans. Soc. Path. Japon, 1934, 24, 446— Arch. Physiol., 1934, 70, 102— 125; Chem. Zentr., 449).—Luteo-hormone had a marked antidotic 1935, i, 3310).— An arrow poison of central African action to nicotine. Ch . A b s . (p) pigmies is of the digitalis-strophanthus type. In Action of pilocarpine and acetylcholine, intro vestigation of two Celebes arrow poisons points to duced into a Vella loop, on enteric secretion. G. their glucosidic nature, one of them possibly being Sa rzan a (Boll. Soc. ital. Biol, sperim., 1935, 10, derived from Antiaris toxicaría, Lesch. H. N. R- 542—544). R! N. C. Physiology of the treatment of barbiturate Action of pilocarpine on formation of lactic poisoning. R. Massiere and G. B eaumoxt acid and breakdown of phosphagen in the isol (Presse Médi, 1935, 43, 4— 7 ; Chem. Zentr., 1935, i, ated frog's muscle at rest. ~ D. N a c h m a n so h n , 3310).— The efficacy of strychnine as an antidote for J. W a j z e r , and R . L ippm an n (Compt. rend. Soc. barbiturate poisoning is not due to antagonism, but Biol., 1936, 121, 139— 141).— Pilocarpine accelerates is an adsorption effect analogous to the toxin- both lactic acid formation and phosphagen breakdown antitoxin reaction. H. N. B. in the isolated muscle in anaërobiosis. R. N. C. Toxicity of methyl alcohol. S. K ajiztika (J- Tolerance of cells cultivated in vitro to the Soc. Chem. Ind. Japan, 1935, 38, 746— 747b).— action of quinine dichloride. L. P il a t i (Boll. Soc. MeOH stimulates the mucous membranes locally, but ital. Biol, sperim., 1935, 10, 414—416). R. N. G. is not highly toxic. On a diet containing 10% MeOB, XIX (h, i) BIOCHEMISTEY. 377 rats show a turbidity of the urine arid an increased supplemented by the skin reaction with Na2S, is excretion of H C02H. H. G. R. best. H. N. R. Cause of the toxicity of methyl alcohol. I. Action of electromagnetic waves on enzyme Sdion (Boll. Soc. ital. Biol, sperim., 1935, 8 , 1376— systems. A. d e P. F orjaz (Biochem. Z., 1935, 283, 1379).—The toxic effect of MeOH is considered to be 53—58).—Electromagnetic waves have no effect due to MeOH itself, no oxidation to CH20 or HC02H on the activity of fumarase, but increase the activity occurring in the body. R. N. 0. of the phosphatase of takadiastase by 20%. Distribution of arsenic a few hours after P. W. C. ingestion of small amounts. G. Yitte (Bull. S o-called “ blood-group enzyme " content of Trav. Soc. Pharin. Bordeaux, 1934, 72, 357— 358; saliva. O. Sievees (Klin. Woch., 1934, 13, 1640— Chem. Zentr., 1935, i, 3159).— The distribution of As 1641; Chem. Zentr., 1935, i, 3148).— The power of in the viscera with and without simultaneous dosing saliva to destroy blood-group characteristics is greatest with Na2S04 has been investigated. J. S. A. when collected during starvation. G. H. F. Effect of Fowler's solution on animals. E. Enzymic reactions in heavy water. D. L. Fox Bobeets and W . M. D aw son (Illinois Agric. Exp. (J. Cell. Comp. Physiol., 1935, 6 , 405—424).— Cata- Sta. Bull., 1935, No. 413, 187— 202).— The practice lase, amylase, and emulsin show no loss of activity of feeding Fowler’s solution to animals for show in D 20 at the same temp, and pa as controls in H 20 . purposes diminishes respiratory activity and repro The activity of amylase appears to be increased in ductive functions. In treated animals As may be conc. D,0. “ R. N. C. detected in the urine, faeces, and hair. A. G. P. Enzymic hydrolysis of glucosides in heavy Increase in toxicity for mice of solutions of water. K. F. B onhoeffee and F. Sa l zee (Natur- neoarsphenamine on exposure to air. R. W ie n wiss., 1935, 23, 867).— Glucosides with high affinities (Quart. J. Pharin., 1935, 8 , 631— 641).— The toxicity for emulsin (e.g., saiicin) are hydrolysed more slowly to rats of a solution of neoarsphenamine increased by in D20 than in H20 , whilst for those with low affinities 17-5 and 23% after exposure to air for 15 and 25 min., (e.g., methylglucoside) the reverse is the case. D20 respectively, bub this increase was prevented if the retards the hydrolysis of the enzyme-substrate com solution was protected by a layer of liquid paraffin. plex, but may also increase the affinity of the enzyme W. 0. K. for its substrate, in which case the higher concn. of the Toxicity of sodium cyanide and the efficiency enzyme-substrate complex may compensate for the °f the nitrite-thiosulphate combination as a retardation of the hydrolysis, leading to an increase remedy for poisoned animals. A. B. Cl a w so n , in the rate of reaction. E. A. H. R. «• P. Couch, and H. B u n yea (J. Washington Acad. ml, 1935, 25, 357— 361).— NaCN is less toxic than Hydrogen-transporting co-enzyme, its com hCX or HCN, whilst the two latter are similar, position and mode of action. O. W a r b u r g , W. the ratio min. toxic/min. lethal doses is 1 : 2 for KCN Ch ristia n , and A. G riese (Biochem. Z., 1935, and HCN, and 1 : 1-25 for NaCN. Intraperitoneal 282, 157—205),—The co-enzyme (I) from red blood nijection of 1 g. of N aN 02 and 2 g. of Na2S20 3 in cells, which is designated the H-transporting enzyme, ii,0 1-5— 4 min. after the NaCN effected recovery was purified until its catalytic activity could not be Jh 4 out of 7 cases. P. G. M. further increased. The purest prep. (12-9% N, 12-3% P) was readily sol. in H 20 , did not crystallise, Use of sodium tetrathionate in cyanide poison- and on hydrolysis yielded 1 mol. each of adenine and K Meneghetti (Boll. Soc. ital. Biol. sperim., nicotinamide together with 3 mols. of H3P 0 4 and 2 35, 10, 386—391).—-A criticism of the method of mols. of pentose. Assuming that these are united Aunsicchio and de Nito (cf. A., 1935, 1276). with the loss of 6H20, (I) is C21H 280 17N -P3. The T R . N. C. H2 transportase of heart-muscle is probably, and that ¿fatmeht of cyanide poisoning of sheep and of yeast is certainly, identical with (I). (I) cannot ,L „e' H- Bunyea (J. Amer. Vet. Med. Assoc., replace cozymase (II) in yeast fermentation nor can v 656—661).—Injections of methylene-blue, (II) replace (I) in oxidation experiments. (I) is nf inn/6’ Ka>N02, and Na2S20 3 had some val. 10 c.c. however, probably closely related to (II). (I) is 200/ y ^ aH0 2 followed immediately by 20 c.c. of active only in association with certain proteins, /o ha2S203 was preferable to either alone, which are called intermediate enzymes (III). Hexose- m . . Ch. Abs. (p) phosphoric acid (IV) in presence of traces of (I) + ac^ and soaps are not antidotes for (III)-f-Warburg’s yellow enzyme (V) is oxidised to 40 T^vf^'r ®ELLECCI (Arch. Farm, sperim., 1935, hexosephosphonic acid (VI), (V) being reduced and, lptli i i 633).—If intraveneous injection of the min. in presence of atm. 0 2, reoxidised. (IV) is also oxid . ■ ,a ,l.os® HgCla is followed by injection of tannic ised by an equiv. amount of (I) in presence of a • j ' or Ha oleate (II) death is not prevented; (III), giving (VI) + (I)-H2, the latter then being able m S Ictarded by small, accelerated by large, doses of to react with (V) to give free (I)-f (V)-H2. This then W or (II). If HgCl2 is given per os, (I) or (II) (per reacts with atm. 0 2 giving H 20 2+(V). (I) can be deaf™11111 lar§e excess retards but does not prevent hydrogenated reversibly by Na2S20 4 and irreversibly E. P. by Pt+3H2. In the latter reaction the C5H 5N Diagnosis of lead poisoning in children. M. is converted” into a piperidine ring and (I) loses its (Klin. Woch., 1934, 13, 1646— 1647; activity. The reversible hydrogenation of (I) is a • Zentr., 1935, i, 3320).— X -R ay examination, partial hydrogenation of the C5H5N ring. P. W. C. 378 BRITISH CHEMICAL ABSTRACTS.— A. XIX (*) Destruction of hydrogen transporting co mandelic acid by the extract is more rapid, but not enzyme by ultra-violet light. 0. W a r b u r g and so complete. W. McC. W. C h ristia n (Biochem. Z., 1935, 282, 221— 223).— Complete enzymic hydrolysis of chondroitin- When 0-001 mg. of co-enzyme (I) in 1 c.c. of H 20 and mucoitin-sulphuric acid. C. N e u b e rg and is irradiated in a quartz vessel at a distance of 30 W . C a h ill (Atti R. Accad. Lincei, 1935, [vi], 22, cm., the activity of (I) is lost in 15 min. Irradiation 149— 155).— Enzyme preps, from B. fluorescent in a glass vessel or of more cone, solutions (1 mg. per hydrolyse chondroitinsulphuric acid to glycuronic c.c.) in quartz vessels does not result in detectable acid (I), chondrosamine, AcOH, and H 2S04 and loss in 15 min. Using dil. solutions, the time for mucoitinsulphuric acid to (I), glucosamine, AcOH. lialf-destruetion of (I) increases rapidly with the X, and H 2S04. F. 0. H. being 520 times as great at 283 m(i as at 186 mp. P. W . C. Glucosulphatase. XII. Purification of the Constitution of the prosthetic group of catalase. enzym e and the effects of phosph ate, sulphate, K . G. S te r n (J. Biol. Chem., 1936, 112, 661— 669; and fluoride on the enzyme action. T. Sob a and cf. A., 1935, 127S).— Catalase (I) solutions from F. E gam i (J. Chem. Soc. Japan, 1934, 55, 1164— horse liver after an AL>0 3 gel adsorption were further 1168).— Activity of the enzyme is inhibited by conc. by C0Me2-C 0 2 treatment. The (I) solution P04"' and F' in concns. > 0-00054/ (cf. A., 1935, is then sufficiently conc. to allow the cleavage of 659). Cii . A bs. (p) (I) by the acid-COMe2 treatment used for respiratory Pancreatic lipase. I. II. Influence of various hsem pigments, which ppts. the protein. On removal compounds on the hydrolytic activity. S. S. of the C0Me2 the prosthetic group of (I) is pptd. W e in s te in and A. M. W y n n e (J. Biol. Chem., The identity of this prosthetic group with the 1936, 112, 641— 648, 649— 660).— I. The rate of protohamiatm of haemoglobin is established by the hydrolysis of glycerides and alkyl esters of fatty prep, from it of a mesoporphyrin Mc2 ester and acids by pancreatic lipase (I) is investigated. The by its conversion into the haemoglobin of the same initial rate of hydrolysis of triglycerides decreases species by the substitution of native globin for the in the order tripropionin (II), tributyrin, trihexoin, enzyme-protcin. E. A. H. R. triacetin, trivalerin. The initial rates of acid form Nutritive value of pentosans. V. Digestion ation from mono-, ay-di-, and tri-acetin are in the by intestinal enzymes. H. Iw a ta (J. Agric. Chem. ratio 1 : 2 : 2-66, indicating that the ester linking on Soc. Japan, 1935, 1 1 , 1024— 1027).— Xylanase occurs the (i-C is more slowly hydrolysed than the two end in rabbit’s and pig’s intestine to an extent < that of linkings. The rate of hydrolysis of the alkyl esters co-existing amylase. Optimum temp, and pB are of the fatty acids increases with the length of the 38° and 6 , respectively. F. 0. H. C chain of the acid radical, but decreases with its length in the alkyl. With phosphate buffers the Action of lithium, sodium, and potassium initial rate of hydrolysis of (II) and of PrC02Me is bromides and iodides on the activity of the amyl greatest at p B 7-2, but in glycine buffers the optimum ase of the fowl's crop. VII, VIII. A. B e r n a r b i p H is 9-3. The initial velocity of hydrolysis oc (I) and M. A. S ch w a rz (Giorn. Biol. Appl. Ind. Cliim., concn. and (II) concn. (in the range 0-016— 0-16J/)- 1932, 2, 41— 52; Chem. Zentr., 1935, i, 3679).— The vals. did not accord with the Michaelis equation. LiBr>KBr>NaBr stimulates the amylase activity; II. Ketones and aldehydes markedly inhibit (I)- otherwise they behave similarly to the chlorides. The degree of inhibition depends on the time of LiI retarding action. Cysteine (II), CH20 , glucose, compounds, and not merely to differences in the fructose, and NaHS03 produced similar effects, but amounts. W . McC. cystine had no action. Lipase, inactivated by Physiology of digestion of plankton Crustacea?. oxidation, was not regenerated by addition of (I) I. Digestive enzymes of Daphnia. A. D. H asler and (II). Ch . A b s. (p) (Biol. Bull., 1935, 6 8 , 207—214).—The p a of the Inhibitory action of formaldehyde on the intestine of D. magna varied from 6-8 at the anterior activity of blood choline-esterase. E. Corteg- to 7-2 at the posterior end. Tryptic digestion of oiani, J. Gau tr elet, N. H a l pe r n , and A. Sereaty casein is indicated. Glycerol extracts of the in (Compt. rend. Soc. Biol., 1930, 121, 310— 318).— testine digested gelatin. Hog-pancreas extract gave a CH,0 inhibits the action of choline-esterase after a similar hydrolysis curve. Extracts of defatted D. latent period which oc the dilution of the CH20. pulex contained amylase and lipase. Ch. A bs. (p) The inhibition is probablv the result of alterations Multi valent amino-acids and peptides. VI. of pH. R . N. C. Action of proteolytic enzymes on synthetic sub Formation of acetylcholine in the body, and an s t r a t e s . J. P. Greenstein (J. Biol. Chem., 1936, investigation of the choline-esterase. I—III. 111, 517— 522; cf. this vol., 194).— Anhydro-Z-lysyl- F. H. Shaw (Austral. J. Exp. Biol., 1935, 13, 251— Z-glutamamide, [a]“ — 27-7°, is unaffected by pepsin, 260).—Stimulation of the lingual nerve of the dog trypsin, or papain-HCN (also without action on does not alter the choline content of the tongue. anhydro-eZZ-aminotricarballylic tetra-amide), which is Two esterases exist in serum, of which only one is inconclusive evidence against the existence of diketo- inhibited by eserine. In presence of pig’s serum, piperazine rings in proteins. Z-Lysy 1- Z-glutam am id e acetylcholine (I) is synthesised from choline and and -Z-histidine are hydrolysed by yeast peptidase, NaOAc. Neither this action nor the enzymic the former more slowly. Glycyl-dZ-aminotricarballylie synthesis of tributyrin is inhibited by eserine. The acid is slowly split by yeast autolysate and intestinal synthesis of (I) in the body is probably effected erepsin, but not by carboxypeptidase. R . S. C. through the synthetic action of tissue-esterase. Inhibition of enzymic proteolysis by oxidising W . 0 . K . agents. Nature of the action of potassium Enzymic histochemistry. I. Distribution of brom ate and analogous substances as im provers arginase activity in rabbit kidney. L. W e i l and of wheat flour. II. H. J o r g e n s e n (Bioehcm. Z., J. 0. E l y (J. Biol. Chem., 1936, 1 1 2 , 565— 577).— 1935, 283, 134— 145).— The inhibition of proteinases The micro-method of Linderstrom-Lang el al. (A., (I) in flour-H20 suspensions by K B r0 3 and the 1635, 1163) for determining arginase (I) activity is consequent decrease of solubility of fiour-N are greatly suitable for histo-enzymic studies if the solution is emphasised on adding yeast, due to the activation buffered at p u 9-5. A micro-(I) unit is defined. of (I) by the glutathione of the yeast (cf. B., 1935, (I) activity is present in the cortex only of rabbit 1115). P. W , C. Kidney, and runs parallel with the no. of proximal Action of enzyme extracts on soluble keratin. convoluted tubular cells. The medulla shows no P. G. Castellino (Arch. 1st. Biochim. Ital., 1935, (I) activity, and as addition of inactive medullary 7, 417—424).—Extract of rabbit’s skin is free from tissue to cortical tissue causes no inhibition of (i) enzymes hydrolysing sol. keratin [prepared by the activity in the latter, it is concluded that the in action of Na thioglycollate (A., 1934, 1238)] at p H 1-5, activity of the medulla is not due to inhibitors. 3, or 8, but contains a tryptic enzyme hydrolysing t v « . • E ' A ‘ H ’ R ‘ caseinogen. F. O. H. m o Slon °T aspartase. K. P. Jacobsohn and Enzymic synthesis from thyroid di-iodo- 9-, -EES- (Compt, rend. Soc. Biol., 1936, 121, tyrosiue peptone of an artificial protein which -•h—2o5).—Experiments described do not establish relieves myxoedema. W . T. S a lt e r and O. FI. e presence of aspartase in the vegetable tissues P e a rs o n (J. Biol. Chem., 1936, 112, 579— 589).— examined, nor the amination of fumaric acid as a A solution of di-iodotyrosine peptone (I) was prepared regular metabolic reaction in plants. R. N. C. by peptic digestion of thyroglobulin (II) of human V °*various salts on the aspartase system. origin, followed by removal of thyroxine (III). (I) : -6. Pereira and M. Soares (Compt. rend. Soc. was cone, and then subjected to a peptic synthesis, 10k 1936, 121, 255—258).—Synthesis of acid by with the formation of an artificial protein containing spartasc is accelerated by S04" and retarded by I, analogous in its properties to a true protein. 3 relative to Cl'. A toxyl does not affect the Clinically, in equiv. I dosage, it relieves myxoedema action in presence of P04'" buffer, but morphine as effectively as (II). The view is held that di- s rains it. P04"' buffer alone exerts a restraining iodotyrosine is the precursor of (III) and that a 010n> as does Na‘ in presence of Cl'. R. N. C. naturally occurring protease in the thyroid cells is possibly responsible for the synthesis. E. A. H. R. n>^ep^° hydrolysis of caseinogen. L. Utk in ( i°chem. Z., 1936, 283, 233— 240).— In the early Phosphatase content of blood-serum and of p hydrolysis the liberation, at p n 4-6, tissues in the rat following administration of sb °r^ compounds occurs in two (possibly more) v i t a m i n - /! a n d - 4 . P. D. Crimm and J. IV. S t r a y l r cnm r fined phases. The P : N ratio of the (J. Biol. Chem., 1936, 112, 511— 515).— The mean phosphatase (I) content of rat serum is about 20 thnt^0fmi!S Produced in the first phase differs from v • "those produced in the second, the difference times that of human serum. Toxic doses of viosterol ag due to differences in the composition of the (II) lead to a marked decrease of (I) activity in blood 380 BRITISH CHEMICAL ABSTBACTS. A. X IX ({) unci kidney, and a considerable increase in the small of 10-5 mol. per litre, half of the (III) is dissociated intestine. The effect of (II) on the high (I) content into (I)-[-(II). As a result of such dissociation, of bones is variable. Liver and spleen contain small a small amount of (II) can effect hydrogenation of amounts of (I) both before and after administration large amounts of (I). (II) therefore differs from the of (II). The decrease in serum-(I) with rats deficient carrier of the yellow enzyme (IV), since it is combined in vitamin-A (Ill) or with hypervitaminosis-A is with (IV), and the oxidational reaction requires there attributed to impaired nutrition rather to the presence fore a stoicheiometric amount of pigment. or absence of (III). E. A. H. It. P. W. C. Plasma-phosphatase in normal and rachitic Oxidation, phosphorylation, and fermentation by apozymase in presence of reversible oxido- children. 0. A n d e r se n (Jahrb. Kinderheilk., 1935, reduction systems. A. L e n ner strand and J. 144, 206— 221; Chem. Zentr., 1935, i, 3148).— R unnstrom (Biochem. Z., 1935, 2 8 3 , 12— 29).— Antirachitic treatment of rachitic children (technique of Kay) produces a diminution of plasma-phosphatase. Oxidation and phosphorylation are studied in a G. H. E. system containing apozymase, cozymase, hexose di phosphate, glucose, and either methylene-blue (I) Intestinal phosphatase. H. G. K. W estenbrink or pyocyanin (II), fermentation being inhibited by (Arch. Necrland. Physiol., 1935, 2 0 , 566—590).— The activity of a solution of intestinal phosphatase NaF. The system absorbs 0 2, but forms practically no C02. Although (I) and (II) belong to the same (I) is not oc its concn., and the rate of hydrolysis of Na glycerophosphate continually decreases with time potential range, the 0 2 absorption with (II) is three times that with (I) and moreover using a-naphthol-2- of reaction. This is not due to inhibition by H3P04 sulphonate-indophenol, which lias a much higher or glycerol, or to decreasing substrate concn. or to potential, the 0 2 absorption is < with (II). There is inactivation by the buffer of p a 8-8. The activity a definite connexion between oxidation and phos- of (I) oc concn. if it is previously kept in contact phorydation, 1 mol. of glucose being esterified with with the buffer for some hr. at 25°. In determining P04 for each mol. of phosphoglyceric acid produced (I) by the hydrolysis of H3P04 from a suitable sub strate, it is best to work in a medium containing Ca. by oxidation from triose phosphate. P. W. C. J. N. A. Formation of flavin enzyme systems in ger Determination of the phosphatase activity of minating seeds. H. v o n E u l e r and 0 . D a h l (Bio- whole blood, plasma, and serum. J. Ca y l a (Bull. chem. Z., 1935, 2 8 2 , 235— 241).— The total flavin Soe. Chim. biol., 1935, 17, 1707— 1714).— A modific (I) content of barley in the first 5 days of germination ation of the Mo colorimetric method for the deter is 3—7 times that of oats. The (I) synthesis is com mination of phosphatase (I) is described. In the pleted in barley by the 2nd day, but continues longer normal adult the (I) content is 15 units per litre of in oats. In extracts of germinated seeds, the ratio serum, 1 unit of (I) liberating 1 mg. of H3P04 from of non-dialysable to total (I) is 2 : 3, and is maintained 10% aq. Na [3-glycerophosphate at p a 7-6. A. L. fairly const, during germination. In peas (ungermin- ated) which contain considerable amounts of (I), Specific pyrophosphatase. E. B a u e r (Natur- almost all the (I) is in the non-dialysable form. wiss., 1935, 2 3 , 866—867).—Glycerol extracts of Tables summarise the accompanying increases in yeast retain their ability to act on pyrophosphate respiration during germination. P. W. C. after the a-glycerophosphatase activity has largely been destroyed by heat, indicating the separate Nicotinamide and luminoflavin. 0. W a r b u p o existence of a sp. pyrophosphatase. E. A. H. R. and W. C h r i s t i a n (Ber., 1936, 6 9 , [E], 228; cf. Kuhn et al., this vol., 227).— Nicotinamide has been Glycerophosphatase of the brain. F. Cedran- obtained previously from co-enzyme (I) and lumino golo (Boll. Soc. ital. Biol, sperim., 1935, 10, 374— flavin by irradiation of an alkaline flavin solution 376).—Brain-glycerophosphatase shows optimum obtained from milk. Since the yellow enzyme and activity at p n 5-32 and 9-16, with a max. in 0-00164/- (I) are universal components of cells, Kuhn’s discov glycerophosphate. Prolonged electrodialysis abolishes eries are not fundamentally new. H. W. the enzyme activity, which is restored by MgCl2. Fermentation velocity of hexosediphosphoric Activity is inhibited by NaF, CH2I*C02H, As20 3, acid and phosphate transfer to adenylic acid. P- and phloridzin. The enzyme shows a preference for O h l m e y e r (Biochem. Z., 1935, 2 8 3 , 114— 127).— a-glycerophosphate. R. N. C. Although muscle-adenylic acid (I) is not identical Mode of action of intermediate enzymes. E. with and cannot replace cozymasc in all its reactions, N e g e l e i n and E. H a a s (Biochem. Z., 1935, 2 8 2 , yet (I) has an activating role in some fermentation 206— 220).—In the reaction, co-enzyme (1)4-hexose- reactions. Thus hexose diphosphate in yeast macer phosphoric acid=(I)-H2+phosphohexonic acid, ation juice with added (I) is partly fermented and which occurs in presence of intermediate enzyme (II), partly converted into hexose monophosphate (H)> the velocity of hydrogenation can be determined whilst (I) is converted into adenyl pyrophosphate in terms of the rate of the resulting increase of ab (III), which is identical with muscle-(IH). The sorption in the ultra-violet at 345 mg. A study of higher is the concn. of (I) in this reaction, the greater the hydrogenation velocities with varying amounts is the max. velocity. The fermentation velocity of (I) and (II) shows that (II) functions not as a of (II) is also increased, but to a smaller extent by catalyst, but as the colloidal carrier of (I). (I) and addition of (I), and (III) is again formed. Addition (II) by a reversible reaction are converted into the of (III) has no effect on the velocity of fermentation H-transporting enzyme (III). At a concn. of (I) of the diphosphate. P. AV. C. XIX (j) BIOCHEMISTRY. 3S1 Action of extracts cf liver and other organs rises temporarily when reduction begins, afterwards on fermentation by yeast. J. D a d l e z and W. faffing rapidly to < the initial val. R. N. C. K oskowski (Biochem. Z., 1936, 2 8 3 , 292— 297; cf. Catalytic fermentation of some fructoholosides. Zipf et al., 1935, 253).— The stimulating effect on R. G uillemet (Compt. rend., 1935, 2 0 1 , 1517— fermentation by yeast of liver extract is > that of 1519).— Rafiinose, gentianose, stachyose, and levosin extract of other organs (spleen, stomach, lung, heart, are fermented by yeast juice to the extent of 100, muscle, kidney, brain, testes, uterus, mammary gland, 66, 50, and 30%, but in the absence of von Euler’s Z bonc-marrow, pituitary, thymus, adrenals). With factor fermentation is much reduced and levosin is liver and spleen extracts the action does not always not fermented. J. L. D. run parallel with the anti-ansemic effect. W. McC. Action of methyl and ethyl alcohol on en Mechanism of oxidation processes. XLIII. zymes. I. Action on beer yeast and on the Arrest of the respiration and fermentation pro cytoplasm of castor seeds. N. T. D eleano and cesses of yeast. H. W ie l a n d , K . R a u c h , and A. If. D . M ezincesco (Bull. Soc. Chim. biol., 1935, 1 7 , Thompson (Annalen, 1936, 5 2 1 , 214— 226).— The 1805— 1813).— Small quantities of MeOH and EtOH inhibiting action of variouspoisonson the fermentative increase slightly the rate of carbohydrate fermentation action (glucose) of “ impoverished ” yeast is generally by yeast, but larger amounts inhibit the reaction, smaller than that on the aerobic dehydrogenation MeOH being less toxic. The inhibition of lipase of EtOH at 30° and p a 6-8. 0-0002J/-KCN reduces action by MeOH and EtOH is almost the same, but the 0, consumption to 56%, but 30 times this con is more marked with olive oil than with castor oil centration is necessary to effect an equal retardation as substrate. A. L. of the fermentation process. Na2S is similar, but Yeast lipins. III. Lecithin and kephalin. NaCNO, which is more potent than KCN, inhibits L. F. Salisbu ry and R. J. A nderson (J. Biol. both processes to approx. the same extent; NaNn, Chem., 1936, 1 1 2 , 541— 550).— The mixed phos- which inhibits the dehydrogenation as effectively pholipins of yeast have been separated into lecithin ss does KCN, has actually a small accelerating (I) and kephalin (II). (I) was obtained free from influence on the fermentation, and is equally effective NHo-N and all the N of (II) was in the NH2-form. under 02 as under N2. The catalase activity is On hydrolysis (I) gave a mixture of fatty acids, inhibited by NaCNO>NaN3>KCN. The inhibiting 86% of which were liquid, optically active glycero- action of these poisons is largely removed by centri phosphoric acid (III), and choline, whilst (II) gave fuging the yeast with H20. The 02 consumption a similar mixture of acids, 84% of which were liquid, 111 the aerobic dehydrogenation of EtOH is greatly optically inactive (HI), and NHyCHyCIIyOH. The reduced if the [0 2] is only 2— 5% (cf., A.. 1932, 303). liquid component acids of both (I) and (n) gave a J. W. B. mixture of palmitic (IV) and stearic (V) acids on Effect of selen ium on cellu lar m eta b olism , catalytic reduction. The solid acids consisted only fete of oxygen uptake b y livin g yeast in p resence of (IV) and (V). Methods of prep, of- hydrolccithin of sodium selenite. V. R. Potter and C. A. and hydrokephalin arc given. E. A. H. R. Elvehjem (Biochem. J., 1936, 30, 189— 196).— The uptake in presence of glucose, fructose, and mannose Biological value of two Torulce from the cheese i» diminished by 80% when Na2Se03 (min. effective factory. G. G u it to n n e a u and H. Sim o n n et (Compt. concn. 0-0033.il/) is added. W ith lactate and pyru rend. Soc. Biol., 1935, 1 2 0 , 1166— 1168).— The vate as substrates, the diminution is < 10%. The antineuritic vals. of both Torulce are < that of oxidation by yeast of EtOH, AcOH, and possibly brewer’s yeast; the Torula with lactose-fermenting uecinic acid also appears to be diminished by Na2Se03. power is the more active of the two. R. N. C. le acti°n is in all cases most marked in the acid Yeast growth-promoting substances. N. zone and decreases rapidly at pn 7-0— 7-5. Se N ielsen (Compt. rend. Trav. Lab. Carlsberg, 1935, appears to act primarily as inhibitor of glycolysis. 2 1 , No. 7, 151— 183).— The effect of growth-promot ajAsOj (min. effective concn. 0-0014/) is more toxic ing substances (I) (bios) on yeast can be shown by ^dative systems than is Na2Se03. W . McC. the increase in dry wt. of cultures. The heavier is the inoculation the less is the relative increase in fW'C^?-n m~dinitrobenzene and its reduction growth. (I) can be quantitatively extracted from nyauves on the metabolism of Fleischmann’s yeast with boiling H20. The (I) content of yeast 1 2 1 9 , r . REAC’H (Compt. rend. Soc. Biol., 1936, cultures is determined by the (I) content of the culture .’ ') 248).—Respiration of liquid-cultured yeast medium. Yeast must contain more than a certain « increased considerably by to-N02-CgH4-NO (I) min. amount of (I) to grow on a (I)-free culture solid e6u y ky Wl-CGH4(N02)2 (II)> whilst that of medium. Most of the utilised (I) undergoes no great i l l . C'i , t t yeasfc ' s increased considerably by both chemical change, as it can be extracted again, but a to m u possibly through the reduction of (II) certain proportion is so transformed that it cannot n J ’er I tho organism. m -N 02-CGH4-NH-0H does be extracted. -X- H. R. not affect respiration. 4 R. N. C. Buffered and low oxygen content physiological of^Tu^°-n dinitrothiophen on the metabolism salt solu tion s. M. R a n d a ll and T. C. D o od y m«l ? C . atm’s yeast- p- Cr e a c ’h (Compt. (Biol. Bull., 1935,6 8 ,258—262).—Mn(OH)2 effectively removes 0 2 and buffers solutions from p a 7-0 to 9-0. thionl,, Bl01l> 1936> 1 2 1 , 248-250).-Dinitro- latenov11 1S ^ irreyersibly after a period of Its use is convenient in the culture of protozoa. } cc the concn. Respiration of the yeast Ch. Abs. (p) 382 BRITISH CHEMICAL ABSTRACTS.— A. XIX (j) Nature of crystals found in amoeba. R. H. increased progressively. In NOs' media (I) and (II) Luce and A. W . P o h l (Science, 1935, 82, 595— are produced from all sugars examined, except lactose. 596).—The most prominent cryst. inclusions have In no case was (II) formed in NH, media. n 1-66S, m.p. approx. 290°; they probably consist A. G. P. of Ca chlorophosphate. L. S. T. Assimilation of oxalic acid by Aspergillus Ultra-violet irradiated am oebae. W . A. B la ck niger. 1). B a c h and J. F o u r n i e r (Compt. rend., (Science, 1935, 8 2 , 495— 497).— A . proteus is negatively 1935, 2 0 1 , 982—984).—5-day-old cultures of this phototropic towards ultra-violet light. Irradiation organism consume H2C204; the amount diminishes appears to stop the digestion of food. L. S. T. with increasing p u, and is practically zero at p u >5-8. The acid ion as well as the neutral mol. appears to Infection with Trypanosoma equiperdum. be utilised. F. A. A. D. P b r l a (Arch. Path., 1935, 1 9 , 505— 523).— Infected but surviving rats acquired a secondary Proteolytic enzymes of Aspergillus niger. H. lisemolytic anaemia, and showed increased [Fe], O t a n i (Acta Schol. Med. Kioto, 1935, 1 7 , 317— without change in [Cu], in livers. [Fe] and [Cu] in 322).—Aq. or glycerol extracts of A . niger exhibit- the spleen declined. Ch. A b s. (p) digestive properties typical of pepsin, trypsin, and erepsin. Optimum digestion of fibrin occurs at p» Action of certain derivatives of copper on 7-1 or 2-0. C h . A b s . (p) Treponema cuniculi and Trypanosoma brucei. R . Sazerac and N. L arthe (Compt. rend. Soc. Mould enzymes splitting nucleic acid. H. Biol., 1935, 1 2 0 , 1179— 1181).— T. cuniculi lesions O t a n i (Acta Schol. Med. Kioto, 1935, 1 7 , 323— in the rabbit are cured by injections of Na2C!u(S20 4)2, 329).— Glycerol extracts of a no. of species of moulds but in the case of CuO they recur. T. brucei infection hydrolysed nucleic acid. Optimum p H vals. were in the rat is reduced temporarily by Cu20, electro- between 4-2 and 6-2. C h . A b s . (p) cuprol, or 1% CuS04. ' ' “R. N. C. A ction of m o u ld en zym es on benzene deriv Changes in the nucleus of Euglena gracilis, atives of amino-acids and dipeptides. H. O t a m Ehrbg., in chronic arsenical poisoning. S. B. (Acta Schol. Med. Kioto, 1935, 1 7 , 330— 333).—Mould R y b in s k y and L. M. Z h ykin a (Arch. Protistenk., enzymes readily decomposed benzoyl-dZ-leucylglycine. 1935, 8 5 , 334— 340).—-Chronic As20 3 poisoning results In general hippuric acid was more strongly attacked in an increase in the thymonucleic acid of the nucleus than benzoyldiglycine. Benzoyl- and benzylglycyl-dl- and changes in morphological characteristics. phenylalanine are not attacked. Ch. Abs. (p) A. G. P. Nutrient solution purification for removal of Relation of hydrogen-ion concentration to heavy metals in deficiency investigations with g ro w th of Chilom onas and Chlorogonium. J. B. Aspergillus niger. R. A. S t e i n b e r g (J. Agric. L o e f e r 8 5 , — — (Arch. Protistenk., 1935, 209 223). Res., i935, 5 1 , 413—424).— The solution is treated Total growth ranges of p H and optimum zones are with CaC03 and filtered while hot. Supplementary determined for Chilomonas paramecium, Chlorogonium use of C is unnecessary and lowers experimental euchlorum, and C. elongatum. NaOAc prevents precision. Extraction of spores of A . niger with growth of Chlorogonium below p u 5-4 and of Chilomonas aq. KHCOj partly removes Fe, Cu, and Mn. Sub below 8-5. A. G. P. sequent growth of treated spores leads to accentuated Influence of heat and storage on electro deficiency effects in respect of these metals. phoretic migration velocities of various micro organisms. K. P. Dozois and F. H atch el (J. Pharmacodynamic action of zinc in general Bact., 1935, 3 0 , 473— 477).-— Migration velocities metabolism. 0. K auffm an-Cosla and R. B r u i l increased with rising temp. > 60°. A. G. P. (Bull. Soc. Chim. biol., 1935, 17, 1828— 1835).—The Precision photometer for study of bacteria and absence of Zn from cultures of Aspergillus niger leads to a decrease in the synthesis of carbohydrates, other micro-organisms. H. M estre (J. Bact., 1935, 30, 335—358).—A “ densitometer ” used in lipins, and protein. A. L. conjunction with a photo-electric cell is described. Mould tissue. X. Phospholipins of Aspergillus A. G. P. sydow i. D. W. W o o l l e y , F. M. S t r o n g , W. H. Growth and survival of micro-organisms at P e t e r s o n , and E. A. P r i l l (J. Amer. Chem. Soc., sub-freezing temperatures. H. F . S m a r t (Science, 1935, 5 7 , 2589— 2591; cf. A., 1934, 697).—The 1935, 82, 525).— Many species of bacteria, yeasts, and phospholipins (0-4— 0-7% of mycelium), purified by moulds are able to survive in frozen fruit kept at repeated pptn. from Et20-solution with COMe,- —9-4° for 3 years; some of these showed slow growth consist of a mixture of lecithin and kephalin- at —8-9° in fresh cultures. L. S. T. Hydrolysis (5% H2S04) gives glycerophosphoriaacid, Carbohydrate metabolism of Aspergillus niger choline, cholamine [picrolonate, m.p. 222— 226° (de- is a function of the nitrogen source of the nutrient comp.)], oleic acid, and (probably) traces of palmitic, stearic, and a more unsaturated acid. H. B. m ed iu m . R . B o n n e t and J. J acqu ot (Compt. rend., 1935, 2 0 1 , 1213— 1215; cf. A., 1935, 1027).— Dissimilation of glucose by heteroferment- A. niger produces citric (I) and oxalic acid (II) when ative lactic acid bacteria. M. E. N e l s o n and C. H- N is supplied as peptone or NH2-acids. The wt. of W e r k m a n (J. Bact., 1935, 3 0 , 547— 557).— The end- mycelium and its (I) content remained practically products of fermentation of glucose by three hetero- const, during 4—20 days, but accumulation of (11) fermentative species were lactic acid, AcOII, Cu2> XIX (j) BIOCHEMISTRY. 383 EtOH, and glycerol. The amount of C 0 2 produced fructose, but not from glucose, mannose, or galactose. was equiv. to the E tO H +A cO H (mols.), and that of Morphological characteristics are given. F. O. H. glycerol to twice the AcOH (mols.). A tentative scheme representing these changes is presented. Anaerobic bacteria capable of fermenting w aste sulphite liq u or. A. M. P a r t a n s k y and B. S. A. G. P. Utilisation of amino-acids as com m on sources H e n r y (J. Bact., 1935, 3 0 , 559— 571).— Five new of carbon and nitrogen by soil bacteria : organ species of Clostridium are described, and their bio isms decomposing betaine and valine. H. chemical activities are recorded. A. G. P. H e i g e n e r (Zentr. Bakt. Par., 1935, II, 9 3 , 81— Production of d-lactic acid and of butyric acid. 113).—As simultaneous sources of N and C, valine — See B., 1936, 167. (I), betaine (II), and glycine were but poorly utilised A m ylase of Clostridium acetobutylicum. W. W. by soil bacteria; leucine, phenylalanine, alanine, and J ohnston and A. M. W yn n e (J. Bact., 1935, 3 0 , asparagine were rather more effective. Glutamic and 491—501).—The amylase shows optimum activity aspartic acid were very generally utilised. Organisms at p n 4-8—5-05. NaOAc retards its action in vitro, decomp. (I) and (II) were isolated and described but when added to the culture media increases the and their significance in humus formation is discussed. amount of amylase present in the nutrient at the end A. G. P. of the fermentation. P04"' and Cl' also retard Relation of oxidation-reduction potential to starch hydrolysis at p n 4-95. Temp, effects are growth of an aerobic micro-organism. W. B. examined. A. G. P. Wood, jun., M. L. W ood, and I. L. B a l d w in (J. Bact., 1935, 3 0 , 593— C02).— Reversible oxidation- Effect of synthetic surface-active materials on reduction indicators positive to, and including, bacterial growth. I. Effect of sodium di-sec.- inethylene-blue when in oxidised forms inhibit the butylnaphthalenesulphonate on growth of M yco growth of B. megatherium. Indicators negative to bacterium smeymatis. J. K atz and A. L ipsitz (J. this do not inhibit. Substances which are inhibitory Bact., 1935, 3 0 , 419— 422).— In concns. of 1 : 10,000 m the oxidised form are not bacteriostatic when the salt inhibits growth. In small proportions (to reduced. Bacteriostatic compounds affect growth 1 : 50,000) involution forms occur frequently. No only in the lag phase. Addition of inorg. reducing synergistic action was apparent between the salt agents to broth renders it more favourable to the and neutral acriflavine. A. G. P. growth of the organism. A. G. P. Existence in B. tumefaciens of an endotoxin capable of causing the formation of tumours in Effect of som e alk aloid s on soil m icr o -o r g a n plants. A. B o iv in , M. M a r b e , L. M esro- isms : nitrogen fixers. I. Effect on JB. radici- bean u , and P. J uster (Compt. rend., 1935, 2 0 1 , cola. G. M e zzadroli and L. So arzi (Giorn. Biol. 984— 986).— CClg’COaH extracts a “ complete” antigen Appl. Ind. Chim., 1934, 4, 162— 174; Chem. Zentr., (1) from B. tumefaciens (II), corresponding with 3% of 1935, i, 3679).— Development is stimulated by caffeine, the dry wt. of the bacteria. (I) is a solid, aq. solutions quinine, and strychnine, the effect in nutrient solution of which are not dialysable. In dil. AcOH at 100° it being > that in soil mixture. Glucose can serve as yields fatty acids and a slowly dialysable polysac a source of carbohydrate. R. N. C. charide (III) (“ residual antigen ” ). Both (I) and (III) (A) Action of radiation in the extreme ultra are pptd. specifically by serum from rabbits injected violet on Bacillus subtilis spores. (B) Inhibition with (II). (I) is toxic to mice, whilst (II) is non fV°vrth of B. subtilis by ultra-violet-irradiated toxic. (I) produces tumours in Helianthus annum carbohydrates. I. H. B l a n k and W. A r n o l d (J. stems similar to those produced by living (II). 193?> 30< 503— 506, 507— 511).— (a) Radiation F. A. A. action re°*0n — 140 my. has a marked germicidal Bactericidal action of organic acids towards Bang’s bacillus. E. Z im m erman (Zentr. Bakt. Par., (b) Radiations of 235-7 my. modify agar in a manner 1935, I, 215— 221).— Lactic, tartaric, citric, and vn'n'ievents the growth on it of B. subtilis. A non- (especially) formic acid have marked toxic action on fh v thermostable inhibitory agent, diffusible the bacillus. Lethal dosages are determined. ° y aoai', is formed. A similar inhibition is Possible chemotherapeutic uses of org. acids are dis • ,, oy irradiation of carbohvdrate solutions used cussed. A. G. P. »1 the prep. 0f media, A. G. P. Presence of hsemolysins in young cultures of cholera vibrios. W. D oorenbos (Compt. rend. decomposition of chitin. II. B u c h e- (Zentr. Bakt. Par., 1935, II, 9 3 , 12—24).— Soc. Biol., 1936, 1 2 1 , 128— 129). R. N. C. imi ASms decomp. chitin are isolated from soil Cultural requirements of bacteria. VI. na other sources. A. G. P. Diphtheria bacillus. J. H. M ueller. V II. Amino-acid requirements for the Park-Williams Urea-decomposing microflora of soils. I, See B., 1936, 114. N o. 8 strain of diphtheria. J. H. M ueller and I. K apnick (J. Bact., 1935, 3 0 , 513— 524, 525— 534).- / f^ f^ °l‘*°rming bacteria isolated from VI. Animal tissue extracts contain substances essential u i . ,?otatoes (Ipomcea edulis, M ak in o), to the growth of the organism. Considerable amounts Bull a (Mospyros kaki). Y . I w a s a i « of the active substance occur in the 95% EtOH 164— ’ So°' JaPan> 1935, 1 1 , 159— 164, filtrate of aq. liver extract (beef), and may be ad 1- Both strains produce mannitol from sorbed on C and eluted with acidified EtOH. The 384 BRITISH CHEMICAL ABSTRACTS.— A. X IX (j) filtrate from such C adsorptions also contains growth- Importance -of the electric charge in certain stimulating materials, including K and Mg. aspects of immunity. H. C. B r o w n and J. C. VII. This strain grows freely on media containing B room (Trans. Roy. Soc. Trop. Med. Hyg., 1935, only Z-cystine, ¿-glutamic acid, ¿¿-valine, ¿/-leucine, 28, 357— 376).— Leptospira arc lulled by colloidal ¿/-methionine, glycerol, inorg. salts, and liver “ elute.” Cu when suspended in immune but not when in normal The prep, of the latter is described. A. G. P. serum. Victoria-blue is toxic in both sera. If the charge on red cells is diminished, a hsemolytic serum Electrophoretic phenomena of bacteria. II. becomes inactive. Ch. Abs. (p) Electrophoretic velocities of virulent and non- viru len t C. diphtheria;. III. Electrophoretic Violet agar reaction as a differential char velocity in relation to growth, senescence, and acteristic of the Micrococcus catarrhalis group. death. C. W . B uggs and R . G. Gr e e n (J. Bact., G. II. Ch apm an (Stain Tech., 1936, 11, 25— 26).— 1935, 30, 447— 451, 453—463).— II. Although no The crystal-violet-agar reaction is useful in the strict line of demarcation was apparent, the average study of different strains of this group. P. G. M. velocity of all non-toxigenic strains is 18-8% > that of Cultural characteristics of Pasteurella tula- all toxigenic strains. reuse. C. M. D ow n s and G. C. B o n d (J. Bact, III. The velocity of cultures was approx. const, 1935, 30, 485—490). A. G. P. from 6 hr. to 10 days, and showed variable changes Effects of quinine derivatives in experimental after killing by heat, but not after treatment with Pneinnococcus studies. W . W . G. Maclachlax, PhOH, CH20, or HgCl2. Extraction of cultures II. H. P erm ar, J. M. J ohnston, and J. R . K enney with hot 70% EtOH lowered the velocities approx. (Amer. J. Med. S ci, 1934, 188, 699— 705).— Toxicity to those of cells killed in P 04"' buffer solution. of ethylapoquinine varies considerably, but decreased A. G. P. toxicity does not diminish its protective power. Metabolic activity of various colon group or Hydroxyethylerpoquinine is less toxic but has greater ganisms at different phases of the culture cycle. antipneumococcic power. Hydroxyethylhydrocu- G. M o on ey and C. E. A. W inslow (J. Bact., 1935, preine is the least toxic, and its protective action is < 30, 427— 440).—The presence of a fermentable sugar that of other derivatives. Ch. Abs. (p) (glucose) stimulates multiplication of E. coli and Salmonella gallinarium in aerated media, but tends A n aerobic su rface cu ltu res. II. Gaseous to inhibit that of S. pullorum. Production of CO, products of metabolism of organisms (yeast, per cell per hr. by organisms in the same period of Staphylococcus aureus, B. coli, B. prodigiosum) '• culture cycle is independent of species and culture aldehyde content and bactericidal action at a medium. Metabolic rates vary considerably with distance. W. B ach m an n and O g a it (Zentr. Bakt. the phase of the cycle. The period of physiological Par, 1935, I, 134, 281—288).—The inhibitory action youth in cultures is characterised by relatively larger (at a distance) of certain yeasts etc. on aerobic and cells and by greater metabolic activity per unit of anaerobic bacteria depends on the production of living matter concerned. A. G. P. appreciable amounts of MeCHO. A. G. P. Escherichia coli and three of its rou g h varian ts. Denaturation of staphylococcal proteins. A. P. K ru eg e r and V. C. N ichols (J. B a ct, 1935, 30, E. H. R en nebau m (J. Bact., 1935, 30, 625— 638).— As energy sources AcOH, lactic, and malic acids are 401— 409).— Antigens separated by ultrafiltration more readily utilised by the parent cell, whilst tar contain < 10% of the total bacterial protein in the taric, citric, and salicylic acids are preferentially denatured form. On heating, the native proteins utilised by one or more of the variants. A typical are denatured, become insol. at the isoelectric point, rough variant has less vigorous enzymes than the and show a considerable decrease in •SH. The de parent, in respect of glucose decomp. Injection of naturation process obeys the law of mass action. the normal strain into the ear vein of rabbits causes The facts are considered in relation to the prep, of a sudden increase in blood-sugar and death in a few vaccines and the preservation of active antigens. hr. Variants have no appreciable action. The fatal A. G. P- O rga n ism of E u ropean fo u l-b ro o d of bees. action of the normal form is probably due to a sol. exo-toxin which increases the permeablity of lung H. L. A. T a r r (Nature, 1936, 137, 151— 152).— capillaries. A. G. P. Photomicrographs of two kinds of Streptococcus apis, which differ only in that one rapidly liquefies gelatin “ Complete ” somatic antigen contained in and coagulates and peptonises the casein of milk, som e If. coli. A. Botvin, L. M e sro b e a n u , G. are reproduced. L. S. T. M a g h eru , and A. Magheru (Compt. rend. Soc. Donators and acceptors of hydrogen for Biol., 1935, 1 2 0 , 1276— 1279).— Eight strains of Streptococcus hcemolyticus. D. B a cii (Compt- B. coli examined fall into six serological types. The rend. Soc. B iol, 1936, 121, 215— 217).— Eructose, “ complete ” antigens contain 38—48-4% of sugar glucose, mannose, xylose, galactose, lactose, sucrose, and 9-9—20-7% of fatty acid (liberated by acid maltose, arabinose, glycerol, CHJCITOH, EtOH, hydrolysis); the chemical composition is not const, MeOH, Bu“OH, lactate, cysteine, fumarate,^ and for strains of the same type. R. N. C. pyruvate are active H donators; NaBrOa and NaI03 “ Residual ” antigen of B . coli. G. Magheru, are the only active H acceptors. R. N. C, A. M a g h eru , A. B otvin , and L. Mesrobeanu (Compt. Lipins of tubercle bacilli. XLI, XLII.—Sec this rend. Soc. Biol., 1935,120,1279— 1282). R. N. C. vol., 311, 314. xix 07 k) BIOCHEMISTRY. 385 Comparison of antigenic properties of defatted Production of a neurotropic strain of Rift tubercle bacilli and their derived proteins. C. H. Valley fever virus. R. D. Ma c k e n zie and G. M. Boissevain (Amer. Rev. Tuberc., 1935, 31, 547— F in d la y (Lancet, 1936, 230, 140— 141). L. S. T. 552).—The H 20-sol. proteins from ground or hydro lysed bacilli or from filtered culture media all have Action of sodium ricinoleate on rabies virus. H. V iolle and J. L ivon (Compt. rend. Soc! BioL, the same tuberculin activity. Guinea-pigs cannot 1936, 121, 100— 102).— Na ricinoleate injected with be rendered hypersensitive to 1% tuberculoprotein rabies virus in rabbits prevents the onset of rabies. by injection of 10— 100 mg. of any H 20-sol. protein R. N. C. or peptone derived from the bacillus. On. A b s . (p) Cultivation of the virus of St. Louis encephal Preparation of purified tuberculin. A. B oquet itis. J. T. Syverton and G. P. B e r r y (Science, and G. San dor (Compt. rend. Soc. Biol., 1936, 121, 1935, 82, 597). L. S. T. 99—100).—Tubercle bacilli filtrate is pptd. with Apparatus for determining the fermentative pliosphotungstic acid and H 2S04. The ppt. is col properties of aerobic and anaerobic micro lected by centrifuge, washed with 0-2W-H^SO4, organ ism s. A. P. St r u y k (Chem. Weekblad, 1936, and eluted with Ba(OH )2 solution; the residue is 33, 44—45). S. C. washed twice with H20 and the eluate and washings are combined and filtered. The stable filtrate contains Hormonal equilibrium and hormonal derange tuberculin. R . N. C. ment in the interferometric picture of the serum. A. Sohittenhelm, F. Ciirom etzka, and W. Spie k er Cultural characters of Trichomonas (T richo- (Z. ges. exp. Med.,. 1935, 95, 149— 167; Chem. mastix) colubrorum. R. Cailleatj (Compt. rend. Zentr., 1935, i, 3431). R , N. C. Soc. Biol., 1936, 121, 108— 110).— T. colubrorum Gaseous exchange after injection of adrenaline ferments glucose, galactose, fructose, maltose, sucrose, in cock s and ow ls. A. P agan o (BoH. Soc. ital. Biol, raffinose, and lactose with production of acid. speriin., 1935, 10, 540— 542).— Gaseous exchange, as Horse serum, but not rabbit serum, can replace whole in pigeons, is scarcely affected. R. N. C. blood or organs as nutrient. R . N. C. Adrenal cortex and carbohydrate metabolism, Nitrogen distribution in the protein of mouse S. T haddea (Z. ges. exp. Med., 1935, 95, 600— 626; typhoid b acillu s. H. Ot a n i (Acta Schol. Med. Chem. Zentr., 1935, i, 3299).— Adrenal cortex hormone Kioto, 1935, 17, 334—337).—-Data are given for injected into guinea-pigs causes increase of blood- the dry defatted bacilli and for the fraction pptd. sugar and of liver- and muscle-glycogen ; it counter from a conc. II2S 0 4 extract on dilution to 5%. acts the action of insulin. G. H. F. Ch . A b s . (p) Variation of the haemolytic power of the El Tor Modifications of the hypertensive action of vibrio. W. D oorenbos (Compt. rend. Soc. Biol., adrenaline by certain colloidal products. D. 1936, 121, 130— 132). R. N. C. B roun and A. B eaune (Compt. rend. Soc. Biol., 1935, 120, 1202— 1204).—The action of adrenaline Microbiological basis of chemotherapeutic in the dog is reduced by colloidal lipins, and by certain action. III. Fixation of therapeutically ad- colloidal metals and proteins. R. N. C. mmistered gold compounds by various recurrent Physiology of the autonomous nervous system. spirochcetes. N. v o n J an c s6 and E. N ovak VI. Action of adrenaline on the blood-calcium (¿entr.Bakt. Par., 1935,1 ,134, 159— 169).— Fixation of the dog with parathyroid insufficiency. F. of Au by Sp. obermeiri is reversible. Washing -with Mat h iè u and Z. M. B acq. VII. Phosphagen in serum removes the Au. Sp. usbekista?iica does not the muscle of the sympathectomised cat. W. L. absorb Au to any appreciable extent. A unimol. D ulière, Z. M. B acq, and L. B rouha (Arch. int. surface fixation by this organism is postulated. Physiol., 1934, 38, 160— 163, 164— 171; Chem. . A. G. P. Zentr., 1934, ii, 3401).— VI. Serum-Ca falls 10— 15 bacteriostatic and bactericidal studies of dyes min. after intravenous injection of adrenaline, which and allied compounds. S. A. P etrofe and W . S. therefore has only a secondary rôle in Ca regulation. wmp (J. Lab. Clin. Med., 1935, 20, 689— 698).— VII. P in the muscles affected is increased some zine, oxazine, thiazino, and basic CHPh3 dyes (I), time after sympathectomy, owing to the slackening j'uii-quinoline derivatives (II), and some alkaloids of the process of resynthesis. After 3—5 months 'iu e bactericidal and bacteriostatic effects on Gram- P metabolism in the resting state is scarcely affected, positive organisms. The order of activity for Gram- whilst in the muscle a compensating or adapting negative organisms was (II)> (I)> a crid in e dyes. process has taken place. R. N. C. „ Ch. A b s . (p) . tudy °I the relations between bacteria, ultra- Action of adrenaline and potassium on the ruses, bacteriophages, toxins, and enzymes, phosphagen of muscle poisoned with iodoacetic y means of the action of g on a crin e . C. L evaditi, acid. J. W a jze r , R. L eppmann, and A. M a r n a y j 12 -„ER> an d G- H ornhs (Bull. Acad, med., 1934, (Compt. rend. Soc. Biol., 1936, 121, 142— 144).— .. > 573-^586);—Gonacrine rapidly suppresses the Adrenaline scarcely affects phosphagen (I) in the ality, virulence, and sp. activity of b acteria, isolated CH2I*C02H-poisoned frog’s muscle in ac enophages, and ultraviruses (except that of anacTobiosis, no resynthesis occurring even when (I) po lomyclitis), but does not affect toxins or enzymes. is almost absent from the muscle. Excess of K' R .N . C. causes a breakdown of (I). R. N. C. 386 BRITISH CHEMICAL ABSTRACTS.— A. X IX (k) Influence of rapidity of intravenous injection A. L acoste, E. A u b e r tin , and R. Saric (Compt. of adrenaline on hyperglycsemic action. Y. rend. Soc. Biol., 1936, 1 2 1 , 239— 241).—The no. of Suganum a (Folia Pharmacol. Japon., 1935, 1 9 , islets of Langerhans and the insulin content are 412—416).—The longer was the time of injection increased. R. N. C. the stronger was the hyperglycajmic response (max. Modifications of the cardiovascular action of at 10— 30 min.). Ch. A bs. (p) acetylcholine by insulin. D. B r o u n and A. Decomposition of adrenaline in tissues. H. B eaune (Compt. rend. Soc. Biol., 1935, 1 2 0 , 1205— B laschko and H. Schlossmann (Nature, 1936, 1 3 7 , 1208).— The action is reinforced by insulin. 110).-—Rat-liver tissue accelerates the loss of adren R. N. C. aline (I) activity in presence of 02. The 0 2 uptake Effect on local glycæmia, in vivo, of parathyroid of liver tissue is not markedly influenced by (I), but hormone injected intravenously. J. Olmer, J. that of liver extracts is increased when (I) is added. P a illa s, and B. Sicnasi (Compt. rend. Soc. Biol., In presence of tissue extracts activity is approx. 1936, 1 2 1 , 78—80).—Intravenous injection of para halved after the uptake of one 0 and practically thormone (I) in a section of a limb that has been abolished after that of 2 0 per mol. of (I). L. S. T. ligatured off from the circulation does not affect Significance of the vegetative nervous system local blood-sugar ; the action of (I) is therefore not due to direct glycolytic influence exercised by muscle on the regulation of blood-sugar. E. F illa (Minerva med., 1935, I, 489— 494).— Insulin (I) or blood. R. N. C. injection with adrenaline is less effective in producing Effect of parathyroid extract on blood co hypoglycscmia than is (I) alone. Simultaneous agulation. R. B o n n y n s (Arch. Int. Physiol., injection of atropine and ginergin followed by (I) 1934, 4 0 , 189— 208).— Parathyroid extract (I) does has a greater effect than (I) alone. Ch . A bs. (p) not affect coagulation of re-calcified oxalated blood in vitro. The time of coagulation of such blood of Action on local glycaemia, in vivo, of insulin rabbits is reduced by intravenous injection of (I), injected intravenously. D. Olm er, J. Olm er, reaching its min. 45 min. after injection, and returning J. P aellas, and J. V ague (Compt. rend. Soe. Biol., to normal in 3 hr. The action takes place principally 1936, 1 2 1 , 76—78).—Injection of insulin in a section in the second phase of (I) action. Plasma-serozyme of a limb that has been ligatured off from the circul is increased, and also, very slightly, the fibrinogen ation causes a local fall of blood-sugar that varies and platelet contents of the blood, the p n and alkaline with the subject. The hypoglycsemic action of reserve being unaffected. R. N. C. insulin probably depends on direct glycannic and muscular glycolysis, but the hepatic factor is excluded. Action of hormones on the secretion of digest R. N. C. ive enzymes. Effect of (I) th yroid , (I I ) para State of functional reactivity of the endocrine thyroidectomy, (I I I ) insulin, on the composition pancreatic tissue in normal dogs subjected to of gastric juice. R. F e r r a r i (Boll. Soc. ital. Biol, prolonged biquotidian injection of insulin. E. sperim., 1934, 9 , 1320— 1322, 1323— 1325, 1325— A u b er tin , A. L acoste, and R. Saiiic (Compt. rend. 1328).— I. Thyroid preps, fed to dogs increase the Soc. Biol., 1936, 121, 241— 244).— The blood-sugar enzyme content of the gastric juice; thyroidectomy curve after glucose does not exhibit an abnormal reduces it, whilst subsequent administration of rise in animals subjected to prolonged insulin treat thyroid preps, restores it to the normal val. Total ment, but the post-hyperglycamhc fall is increased. acidity and free HC1 are unaffected. R . N. C. II. Parathyroidectomy increases the enzyme con Influence of insulin on the liver-glycogen level tent and free HC1, but does not affect total acidity. of frogs. E. Geiger [with H . H alm os] (Arch. exp. III. Insulin increases the enzyme content, total Path. Pharm., 1936, 1 8 0 , 251— 257).— Continuous acidity, and free HC1 as the blood-sugar falls, and electrical stimulation of the muscles in summer and vice versa; the rate of secretion is also increased. spring (but not winter) frogs diminishes the liver- Glucose increases enzyme content and free HC1 glycogen (I). Prior administration of insulin (II) slightly, but does not affect total acidity. inhibits this change. Administration of glucose R. N. C. causes production of (I) in all seasons, but the increase Rôle of cholesterol in thyroid-ovarian anta m (I) of summer frogs disappears after a few days gonism : ovarian and adrenal cholesterol in unless (II) is injected. Hence the seasonal variation thyroidectomisedand thyroxine-treated animals. in (I) is due to deprivation of (II), which inhibits C. I. P a rh on , C. P a riio n -Stefanescu, and I. glycogenolysis but does not influence (I) formation. Orn stein (Compt. rend. Soc. Biol., 1936, 1 2 1 , 187— F. 0 . H. 189).— Thyroidectomy in rabbits and guinea-pigs Direct action of glucose on secretion of insulin causes an increase in ovarian cholesterol (I), which is by the pancreas. V. G. F oglja and R. F e r n a n d e z slightly further increased in rabbits and decreased in (Compt. rend. Soc. Biol., 1936, 1 2 1 , 355— 358).— guinea-pigs by administration of excess of thyroxine Injection of glucose in a dog with a pancreatic graft (II). Adrenal (I) is decreased in guinea-pigs and on the neck causes an increase of insulin secretion increased in rabbits by both thyroidectomy and excess in the graft, independent of extrinsic innervation. of (II). (I) is- apparently concerned in thyroid- R . N. C. ovarian antagonism. R. N. C. Effect of repeated injections of insulin on the Influence of thyroxine on the oxygen con histological state of the endocrine pancreatic sumption of surviving tissue. W. H a a r m a n X tissue and its insulin content in the normal dog. (Arch. exp. Path. Pharm., 1936, 1 8 0 , 167— 182).— XIX (4) BIOCHEMISTRY. 387 The 0 2 consumption of surviving muscle or liver Effect of pituitary on protein metaboHsm. I. tissue is increased by addition of 10-17— 10~9% Pituitary preparations. II. Thyroid prepar (max. 10' 12— 10~14%) of thyroxine : higher concns. ations. I I I . Pancreatic preparations. IV. have an inhibitory action. F. 0. H. Adrenal preparation. V. Ovarian preparations. Influence of thyroxine on tissue respiration. Y . T okizaki (Sei-i-Kwai Med. J., 1934, 5 3 , No. 9, 212— 242, No. 10, 105— 117, 118— 129, 130— 139, A. R e u t e r (Z. ges. exp. Med., 1935, 95, 214— 21G; Chem. Zentr., 1935, i, 3300).— Thyroxine caused a 140— 148).— I. liypophyscctomy decreases protein rise in 0 2 consumption of isolated organs of rat and (I) metabolism and only the anterior pituitary cat (Warburg’s method) of 20—35%; the effect prep, can accelerate it. vanished after 1—2 hr. Results on isolated organs II. Injection of thyroxine accelerates (I) metabolism may not be comparable with those on living organisms. in normal and hypophysectomised dogs, the action being less in the latter. G. H. F. Pathogenesis of the histological alterations of III. Injection of insulin into normal animals in the myocardium with excessive administration creases all N fractions in urine, and the total, non- of synthetic th yroxin e. C. M a n z in i and E. protein-, NH3-, and creatinine-N in blood. Blood- Costantini (Boll. Soc. ital. Biol, sperim., 1935, 10, urea, -uric acid, -creatine, and -NH2-acid decline. 597-600). R. N. C. With hypophysectomised dogs all urinary N fractions increase, blood-uric acid increases, and all other N Mode of toxic action of excessive administra fractions together with H I0 3 decrease. tion of thyroxine on the liver. C. Ma n z in i and IV. Adrenaline increases (I) metabolism in normal E. Costantini (Boll. Soc. ital. Biol, sperim., 1935, and hypophysectomised animals. 10, 594—597). R . N. C. V. Ovarian prep, (oophormin) increases (I) metabol Histological lesions of the liver with excessive ism in normal > in hypophysectomised dogs. administration of thyroxine. C. M a n z in i and Ch. A bs. (p) Influence of pituitary preparations on non- E. Costantini (Boll. Soc. ital. Biol, sperim., 1935, 10, 591—594). R. N. C. protein-nitrogen and urea in blood, and iodic acid in serum, of normal and hypophysectomised Influencing of the thyroxine-catechin balance d ogs. Y. T o k iza k i (Sei-i-Kwai iMed. J., 1934, 53, of different types of blood by a growth-promoting No. 10, 149—158).—Pituitrin and pituglandol in principle. H. E u f in g er and J. B. G ottlieb (Klin. creased, but hypophorin decreased, the non-protein-N Woch., 1934, 13, 1204— 1205; Chem. Zentr., 1934, and urea in blood of normal and hypophysectomised >i, 3396).—The. effect of thyroxine (I) on Rana dogs. H I0 3 in serum increased in all cases. kmporaria when added to the aquarium-H20 is Ch. A bs. (p) restricted by addition of umbilical, retroplacental, Difference of response of the pituitary glands or pubertal blood, which contain an inhibitory and of male and female albino rats treated with the growth-promoting substance. Lactic and uric acids growth hormone. H. S. R u b in stein (Anat. Rec., increase the effect of (I), probably through shifting 1934, 61, 131— 140). R. N. C. of Ph. R. N. C. Significance of the pituitary in kidney disease. Occurrence of thyrotropic hormone in the H. M a r x (Klin. Woch., 1935, 1 4 , 367— 372; Chem. < ffa l nervous system and cerebrospinal fluid. Zentr., 1935, i, 3153). G. H. F. A. Schittenhelm and B. E isle r (Z. ges. exp. Med., 1935, 95, 121— 123; Chem. Zentr., 1935, i, 3434).— Stability of anterior pituitary extract in thyrotropic hormone occurs in the mid-brain and aqueous solution. I. W. R o w lan d s (Quart. J. cerebrospinal fluid of the cat. The mid-brain contains Pharm., 1935, 8 , 642— 645).— Aq. extracts of anterior 0 ]/3 of the pituitary content. R. N. C. pituitary preps, lost about 50% of their gonadotropic activity in 9 davs at room temp, and in about 1 year ., ^^snussion of thyrotropic hormone through at 0— 2°. ' W . 0 . K. e placenta and milk. A. Schittenhelm and E isler (Z. ges. exp. Med., 1935, 95, 124— 125; Migraine as a pituitary disease and its treat em.. Zentr., 1935, i, 3298).— Thyrotropic hormone ment with ovarian preparations. I. M u eller <(ministered to guinea-pigs, when pregnant or when (Med. Klinik, 1935, 3 1 , 448— 450).—The anterior "S y°ung, produced no change in the thyroids pituitary hormone content of the urine of women of the young. 6 q H_ F suffering from migraine is frequently > normal. Progynon exerts a curative effect. R. N. C. k ^^kyrotropic substance in blood and carbo- y ate m etabolism of the liver. A. L oeser Adrenalotropic action of the anterior pituitary. T i n CX])' Path- Pharm., 1936, 180, 325— 331).— K. J. A nselmino, L. H erold, and F. H offmann r,.,C. principle (I) antagonistic to the anterior (Klin. Woch., 1934, 1 3 , 1724).—The chrome-pig- w to a Z t thyrotropic hormone (A., 1935, 1543) mentability of the adrenal medulla is almost abolished ism * Ti i. ohocacteristic symptoms of hyperthyroid- and vacuole formation increased by injection of thni k Pat'c carbohydrate metabolism indicates anterior pituitary extract in rats or mice. The active , A changes (e.g., glycogenolysis) due to thyroxine principle is sensitive to acids and alkali, but compara infli. ^ ‘hdependently of the thyroid gland are not tively thermostable; it can be separated from the is dis n°e PPe Motion of (I) to thyroid activity corticotropic hormone by ultrafiltration through collodion, which retains it. R. N. C. 388 BRITISH CHEMICAL ABSTRACTS.— A. X IX (k) Influence of hormones of the anterior and Action of the male hormone (androsterone) posterior lobes of the pituitary, the thyroid, and injected into the chicken embryo : experimental the adrenals on the spontaneous creatinuria of production of intersexuals. E. W olff (Compt. endocrine disturbances. A. Schittekheliu and rend. Soc. Biol., 1935, 1 2 0 , 1312— 1314). F. B uiiler (Z. ges. exp. Med., 1935, 9 5 , 206— 213; R. N. C. Chem. Zentr., 1935, i, 3435).— Spontaneous creatinuria Interpretation of the results obtained by in males with gonadal insufficiency is abolished by injection of synthetic androsterone in the chicken prolan and orasthin, but not by prochormone. embryo. E. W olff (Compt. rend. Soc. Biol., 1935, Thyrotropic hormone and thyroxine induce creatinuria 1 2 0 , 1314— 1316). R. X. C. in myxcedema. Spontaneous creatinuria in Addison’s Influence of sex hormone on the spontaneous disease is abolished by small doses of cortical preps.; creatinuria of endocrine disturbances. A. Schit- its appearance is due to increased breakdown of te x h e lm and F. B u h le r (Z. ges. exp. Med., 1935, phosphagen in the muscles. R. N. C. 9 5 , 197— 205; Chem. Zentr., 1935, i, 3433).- Glyco-chloro-proteineemic curve in normal Spontaneous creatinuria in males with gonadal and diabetic individuals after injection of pos insufficiency is abolished by “ proviron,” but not if terior pituitary extract. G. d e l l ’ A cqu a (Boll. muscle metabolism has been disturbed by degener Soc. ital. Biol, sperim., 1935, 10, 423— 447).— ative muscle changes. Similar creatinuria in women Injection of the extract in normal subjects induces at the climacteric is abolished by “ progynon,” a short rise of blood-sugar (I) followed by a prolonged but not so uniformly. In certain cases creatinuria fall and recovery to normal. Proteins (II) show a is abolished also by the heterosexual hormone. fall followed by a recovery to almost normal; KaCI R. X. C. falls without recovering. In diabetics (I) shows a Response of immature rats to various gonado marked rise followed by a fall without recovery. tropic substances. R. D ea n e sl y (Quart. J. Pharm., (II) rise rapidly at first, fall to vals. < normal, and 1935, 8 , 651— 66S).— Various gonadotropic preps, then rise slowly to > the first max. XaCl rises were administered to male and female immature rats irregularly. R. N. C. and their resulting actions observed. A method of assay which employs 10 rats with an error of ± 10% is Determination of the excretion of prolan b y described. W. 0. K- mature and b y aged men. H. Sa e th re (Klin. W och., 1935, 14, 376— 378; Chem. Zentr., 1935, Relative activity of different gonadotropic i, 3153).—The urinary prolan excretion of healthy preparations on oestrous rabbits, p re g n a n t men is 25—30 mouse units per litre. In old age thero rabbits, and immature rats. I. W. R o w l a n d s may be some increase. G. H. F. (Quart. J. Pharm., 1935, 8 , 646— 650).— Extracts of pituitary gland (cow, horse) and urine of pregnancy Prepubertal reversal of the sex difference in have been assayed on oestrous, 15 days- and 25 davs- the gonadotropic hormone content of the pituit pregnant rabbits, and on immature rats. For ovul ary gland of the rat. H. M. Cl a r k (Anat. Rcc., ation, pregnant rabbits require more of all extracts 1934, 6 1 , 175— 192).— The prolan content of the tested than do oestrous rabbits. Horse pituitary pituitary in the immature female rat is > that in the and urine of pregnancy extracts are relatively equally male; at puberty the male gland is more potent. potent when tested on rabbits and rats, butox pituitary From 4 to 6 months the sex difference is negligible, is less potent in rats. W. 0. K. whilst at 7 months it is reversed. In the female the content rises sharply at 13—20 days, whilst in Physiology of the corpus luteum. IX. In* the male it increases gradually to a const, level at hibition of cestrin by progestin-containing ex puberty. R . N. C. tracts of the corpus luteum. W. M. A lley and R . IC. M e y e r (Anat. Rec., 1935, 6 1 , 427-439).- Sex difference in the change of potency of the Progestin inhibits cornifieation by cestrin and the anterior pituitary following bilateral castration oestrous smear. R. X. C. in newborn rats. II. M. Cl a r k (Anat. R cc., 1934, S tru ctu re of cestrin in alkaline solution. 61,193—202).— Prolan in the male pituitary increases K . P. B je r g aa rd and S. A. Schott (Quart. J. Pharin., on castration; it fluctuates in females. R. N. C. 1935, 8 , 669— 673).—In neutral or acid EtOH solu Is there an antagonism of sex hormones ? tion, the max. ultra-violet absorption of cestrin O. O. F e l l x e r (Z. ges. exp. Med., 1935, 9 5 , 373— occurs at 282 mg, whilst in alkaline solution it is at 377; Chem. Zentr., 1935, i, 3431— 3432).— Hormones 295 mg. The shift is probably associated with enol- are extracted from urine by boiling with CaO and pptn. isation of the keto-group. W. 0. K. with X a2C20 4, the hormones remaining in the filtrate. Biological activity of theelol. R. K. Meyeb, The masculin (I) content of pregnancy urine is > that L. C. M il l e r , and G. F. Cartlan d (J. Biol. Chem., of male urine, (I) probably originating from the 1936,112, 597— 604).—Theelol (I) has little biological placenta. The sox hormone antagonism hypothesis activity compared with international standard theeun is discarded in favour of one of synergism between (II) when determined by the vaginal smear method, the hormones and gonads. R. N. C. but it is 4 times as active when determined by the Physiology of A5-androstenediol. A. B u te- opening of the vagina of the immature rat. (Bj x a x d t (Naturwiss., 1936, 24, 16).— A5-Androstenediol is approx. 90 tunes as active as (I) when administer® in pure condition displays the activities of both in oil and 250 times when injected in aq. 10% EtOn testicular and follicular hormones. W. O. Iv. containing 0-5% Xa2C03. J. X. A. XIX (i, I) BIOCHEMISTRY. 389 Follicular hormone content of eclamptic blood. sperim., 1935, 1 0 , 538—540).—The melanophore W. Bickenbach and H. F rom m e (Klin. Woch., hormone inhibits, whilst prolan stimulates, these. 1935,1 4 , 496— 497).— The follicular hormone content R. N. C. of the blood of eclamptic women is > that of the blood Standardisation of the melanophore hormone. of pregnancy. R . N. C. M. A glialoro and U. Ciu lla (Boll. Soc. ital. Biol, sperim., 1935, 1 0 , 537— 538). R . N. C. Sexual hormones in domestic animals. K üst (Klin. Woch., 1934, 1 3 , 1782— 1784).— Pregnancy Villikinin in the human intestine. G. vo n is diagnosed in mares by the Aschheim-Zondek L u d a n y (Klin. Woch., 1935, 1 4 , 123— 124; Chem. serum reaction from the sixth week to the fifth month, Zentr., 1935, i, 3301; cf. A , 1934, 331).—Human and later by increased follicular hormone (I) excretion intestinal mucous membranewhen extracted with HC1, in the urine. (I) excretion is increased in the 23rd neutralised, and the extract injected intravenously week in cows, and after 31 months in goats; in the into fasting dogs caused great acceleration of the rate sow it reaches max. in the fourth week and at the end of contraction of villi. G. H. F. of pregnancy. (I) is present in the urine of mature Colour reactions of vitam in-4, -D, and -E, and boars. R . N. C. of som e sterols. S. U en o, Y. O ta, and Z. U e d a (J. Sexual hormones in domestic animals. S. Soc. Chem. Ind. Japan, 1935, 3 8 , 745— 744 b).— The colour reactions of these vitamins and of cholesterol, Kober (Klin. Woch., 1935, 1 4 , 381).— Excretion of follicular hormone in the urine of the pregnant mare ergosterol, and sitosterol, with fourteen new reagents appears before the 110th day, rises to a max. between (mainly PhOH -f- a second substance) are tabulated the 6th and 8th months, and then falls to a trace at and briefly discussed. J. W. B. the conclusion of pregnancy (cf. preceding abstract). Vitamin-4 storage of Macmrus nipestris. R. N. C. S. Schmidt-N ielsen , A. F lood , J. Sten e, and N. A. Artificial (hormonal) growth of the oviduct Sorensen (Kong. Norske Vid. Selsk. Forhandl., 1935, in female carp. K. E h r iia r d t and K . K ü h n 7, 174— 177 ; Cliem. Zentr., 1935, i, 3302).— Data (Endokrinol., 1934, 1 5 , 1 — 14; Chem. Zentr., 1935, for liver-fat and tintometer no. are given and i, 3433; cf. A., 1935, 413).-—-The oestrus hormone correlated. H. J. E. (I) is apparently not identical with the oviduct Vitam in-4 content of the liver and its variations. hormone (II); crude (I) affects the oviduct more A. Ciieva llie r and Y. Ciioron (Compt. rend. Soc. strongly than the cryst. product, whilst (II), although Biol., 1935, 1 2 0 , 1223— 1225).— Vitamin-4 (I) is resembling (I) in solubility, thermostability, and decreased in the liver and increased in the blood of absorbability on C, is difficult to elute from the the rabbit by anassthesia. In the guinea-pig, liver- adsórbate, and is destroyed by 15% NaOH or by (I) shows marked variations with the animal, whilst Ac0H. R . N. C. blood-(I) is practically const. R. N. C. Embryological interpretation of changes in Metabolism of rat liver in avitaminosis-4. duced by oestrogens in the male reproductive O. R osenthal (Arch. Neerland. Physiol., 1935, 2 0 , tract. S. Z u c k e rm an (Lancet, 1936, 230, 135— 539—551).—In about 2/3 of the avitaminotic rats 136)- L. S. T. examined, the energy of metabolism decreased considerably, and there was a slight decrease in Follicular and luteal hormones and their respiration. These effects appeared as often in fatty reaction on the an terior lobe of the pituitary. as in de-fatted livers. Fatty degeneration, probably , ; Clauberg and W . B reepohl (Klin. W och., 1935, 14,119—121; Chem. Zentr., 1935, i, 3298). as a result of the respiration disorder, is assumed. Changes in metabolism and fatty degeneration of the r i G- H- F- liver are secondary effects of the vitamin-4 deficiency. inhibitory effect of follicular hormone on the J. N. A. anterior lobe o f th e p itu ita r y g la n d . B. Z o n d e k Effect of standard diet on liver metabolism in (Lancet, 1936, 230, 10— 12). L. S. T. experimental avitaminosis-4 in rats. 0. R osen Biological determination of corpus luteum th al (Arch. Neerland. Physiol., 1935, 2 0 , 552— ?no-acts' ^ Co u r r ie r (Compt. renfl. Soc. Biol., 558).— The changes in metabolism and the histological I93o, 120, 1263— 1266). R . N. C. fatty degeneration of the liver are due to an unsp. diet deficiency. The importance of this in the . Antigonadotropic h orm on e in the pineal gland, problem of experimental avitaminosis-4 is discussed. ioo- A^nd o rgan s. P. E ngel (Z. ges. exp. Med., J. N. A. V 95> 441—4:57; Chem. Zentr., 1935, i, 3300).— Size and vitamin content of liver of various * n ^gonadotropic hormone (I) of pineal gland is anim als. S. Sch m id t-Nie lse n , A. F lood, and J. ■> anuardised by injecting into immature female rats Stene (Kong. Norske Vid. Selsk. Forhandl., 1934, » multaneously with standardised gonadotropic hor- 3 , 81— 84; Chem. Zentr., 1935, i, 2620).— Vitamin-4 of°m ° anferior pituitary (II). The amount contents of livers of warm-blooded animals are < of /Tn ■ e content is increased, especially in rats. In rats fed amply supplied with -BA, especially when growth is 011 (I)-rich diets, the free cholesterol of the skin and used as a criterion of potency. The improved the cholesteryl esters (II) of the liver and kidneys growth often obtained by adding large amounts of are increased. In guinea-pigs, the changes are -Bx to rats on a low -B 1 diet may be due to the ad indefinite, although the (II) content, the I val., and ditional effect of traces of -B4 present as an impurity. the neutral fats of the liver are increased. L. S. T. J. L. D. Objective method for fluorescence determin Fate of carotene injected into the circulation ation, with special application to the determin of the rat. J. C. D ru m m ond and R. J. M a c w a lt e r ation of vitamin-/},,. F. H. C o h e n (Acta Brev. (J. Physiol., 1934, 8 3 , 23G— 242).— Vitamin-A. and neerl. Physiol., 1935, 5, 18— 19; Chem. Zentr., fat distribution is fairly uniform in the three main 1935, i, 3306).— The apparatus previously described lobes of the liver. Carotene injected into the portal (A., 1935, 466) is applied to the determination of circulation is taken up uniformly by tho lobes, and vitamin-B2. H. N. R. tends to disappear after a few days, -A not increasing Effect of adenine fed to rats on a diet de simultaneously, but in some cases falling. Removal ficient in vitam in-/}4. T. Y. Lo (Nat. Peiping of one lobe may cause a fall in the -A of the other Univ. Coll. Agric. Nutrition Bull., 1934, B , 1, 40— lobes. R. X. C. 46).—Pure adenine from yeast does not serve as a Vitamin-/1 in the red corpuscles of the blood source of vitamin-/J4 for rats. Ch. Abs. (p) of vertebrates. A. M ag na n and II. G ir e r d Influence of som e food factors on pellagra-like 2 0 1 , (Compt. rend., 1935, 1219— 1221).— Vitamin-X symptoms in rats. F. J. G o r t e r (Z. Vitamin- occurs in certain of the red corpuscles of the blood forsch., 1936, 5, 1— 11).— The incidence and type of of the ray and is localised on the chondriome. pellagra-like disease in rats depend on the com A. G. P. position of the basal diet. There exists an anti- Determination of vitam in-/!. A. L. B a ch a - pellagrie growth-promoting factor other than flavin r a c h , J. C. D rum m ond, and R. A. M o r to n (Nature, and perhaps identical with vitamin-/},.. This factor 1936, 1 3 7 , 148— 149).—-A crit. discussion of tho three is separated from caseinogen by hydrolysis. Factors approved methods of standardisation which may causing dermatitis in rats arc discussed. F. 0. H. give three different results. L. S. T. Antiscorbutic activity of dehydroascorbic acid: Effects of vitam in-/} on female genital organs its storage and that of ascorbic acid by the of white rats. J. U e n o (Japan. J. Obstet. Gynecol., guinea-pig at different levels of intaie. F. W. 1934, 1 7 , 388— 411). Ch . A b s . (p) Fox and L. F. L e v y (Biochcm. J., 1936, 30, 211— 217).— The antiscorbutic val. of dehydroascorbic Deficiency of vitam in-/} and endocrine glands acid has been confirmed (Hirst et al., A., 1933, 1091). of female white rats. J. U e n o (Japan. J. Obstet. After reduction to ascorbic acid (I) it is stored in Gynecol., 1934, 17, 267— 278) Ch . A bs. (p) small amounts in the liver. Storage of (I) in the Effect of arginine and of liver and stomach liver is dependent on the level of intake, being small extracts on vitamin-/} deficiency in pigeons. at the min. protective dose and reaching an upper A. von J e n e y (Klin. W och., 1935, 1 4 , 379— 380; limit at higher levels. H. G. R- Chem. Zentr., 1935, i, 3155).— The length of life of Does vitamin-C affect the occurrence of pigeons on a vitamin-/}-freo diet was increased by norm al pigmentation ? F. T e n c h i o (Klin. Woch., administration of extracts from yeast, liver, or pig’s 1934,13, 1511— 1512; Chem. Zentr., 1934, ii, 3644- stomach, or of arginine. The -B complex appears 3645). R. N. C. to contain an antianremic factor resembling arginine. Reversibility of oxidation of ascorbic acid G. H. F. R . W u r m s e r and N. M a y e r (Compt. rend. Soc. Assay of vitamin-/}! by the '' beri-beri" Biol., 1936, 1 2 1 , 3—5).— Oxidation of ascorbic acid q u o t ie n t (Qb). G. A m a n tea (Atti R. Accad. Lincci, by 2 : G-dichlorophenol-indoplienol is as reversible as 1935, [vi], 2 2 , 173— 176).— Further details of the oxidation by I. R . N. C. technique are given (cf. A., 1934, 460, 706). F. 0 . H. Reversible oxidation of ascorbic acid by Vitamin-B! and -B2. J. F. F e a s t e r and V. E. norite charcoal. F. W . F ox an d L . F. L evy N e ls o n (Proc. Iowa Acad. Sci., 1934, 41, 149—- (Biochem. J., 1936, 30, 208— 210).— The C (and to a 152).—Autoclaved yeast supplies a factor, probably smaller extent other kinds) rapidly (10—15 min.) vitamin-B2, enhancing lactation in rats. converts ascorbic acid almost quantitatively into | Ch . A b s. {p) dehydroascorbic acid. With small amounts of C, Interrelationship of vitam ins. C. A. Elvehjem the effect oc the amount of C. Probably the oxid and A. A r n o ld (Nature, 1936, 137, 109— 110).— The ation results from direct transfer of 0 2 from the G cure of certain symptoms in experimental animals surface. W. McC- even with cryst. preps, of vitamin does not necessarily Biological oxidations. V. C o p p e r and hsenro- mean that the deficiency is due to a lack of the chromogens as catalysts for the oxidation of factor fed. Rats showing -/}4-deficiency may be ascorbic acid. Mechanism of the oxidation. relieved by administration of -B v The latter appears E. S. G. B a r r o n , R . H. D e M e i o , and F. K l e m p e r e r to relieve accompanying anorexia, and food con (J. Biol. Chem., 1936, 1 1 2 , 625— 640).—Ascorbic sumption increases to a level which supplies adequate acid (I) is not autoxidisable in solutions free from -R4. Synthetic diets used for -B1 studies must be Cu when the p a is < 7-6. Above p a 7-6 the rate of XIX (I) BIOCHEMISTRY. 391 autoxidation increases rapidly with the p n. KCN Sources of vitamin[-C]. XI—XVI.— See B, slightly accelerates the rate of 0 2 consumption. 1936, 121. In neutral and acid solution Cu" (alone of metallic Vitamin-D requirements in relation to the ions) catalyses the oxidation of (I) in concns. as low calcium and phosphorus content of the diet. as 0-046 mg. of Cu per litre. The 0 2 uptake is 1 A. Q u e r i d o (Arch. Neerland. Physiol., 1935, 2 0 , 0 per mol. of substrate. The optimum p a of the 487— 538; cf. A., 1935, 1431).— The daily require Cu-catalysed oxidation is 6-95. The hoemochromo- ment for rats varies between 0 and 1 x 10~° g. of gens of nicotine, C5H 5N, and pilocarpine can also calciferol. It is influenced by the salt level of the actas catalysts. O-OOlJf-KCN completely inhibits the ration, and diminishes with increase of the abs. concn. catalytic effect of Cu, and CO, by combining with of P. Influence of vitamin-D on the ash content of Cu2Cl2 and thus inhibiting its reoxidation to CuCl2, bone is seen only with diets having a Ca : P ratio of 4. also considerably retards the reaction. The low val. Unpreventable rickets produced by some diets can of 1-65 for the temp, coeff. suggests that the reoxidation be changed into a preventable form by preliminary of Cu2Cl2 is the reaction governing the rate of oxidation feeding with a diet rich in minerals. Rickets pro of (I). The oxidation product can be completely duced by a diet containing 0-2% of P and Ca : P=1 reduced by H2S up to p n 5-0, but above this the amount resembles the human form > that produced with a of (I) recovered gradually decreases until at p n 7-6 Ca : P ratio of 4. J. N. A. the oxidation is mainly irreversible. E. A. Ii. R. Evaluation of the relative toxic effects of large Diagnosis of vitam in-C subnutrition by urine doses of calciferol and the crystalline antirachitic analysis. M. A. A b b a s y , L . J. H a r r i s , S. N. R a y , preparation substance L. J. van N iekerk (Arch. and J. R. M arrack (Lancet, 1935, 2 2 9 , 1399— 1405). Neerland. Physiol., 1935, 2 0 , 559— 561).—The ratio —Data obtained by the method previously described of toxic to- antirachitic activity of the substance L (A., 1935, 417), together with its specificity, are dis of Rcerink and van Wijk is identical with that of cussed. The urinary excretion of vitamin-C by- calciferol. J. N. A. adults receiving graded doses of -C over long periods Anti-infective power of vitam in-H . G. S p a g n o l reaches levels a: the intake. Little variation occurs (Rev. sudamer. endocrinol., 1935, 1 8 , 163— 166).— between individual subjects; the same daily dose of -C Irradiated ergosterol prevented infection of rats with soon produces an almost identical rate of excretion. Salmonella typhimurium. Ch. A bs. (p) During fever, output falls, and an additional dose is needed to restore the original level. A diet appears Changes in com position of blood in rabbits by to be unduly low in -C whenever the daily excretion ir r a d ia t e d f o o d . A .Falaschini (Boll.Soc. Eustach., 15 < a titration val. of 10— 15 mg. per day per 10 1934, 3 2 , 1— 15; Chem. Zentr., 1934, ii, 3782—3783). stone body-wt., or when the standard dose of 700 R. N. C. ®g- produces no response on the second day. In Irradiation and growth. F. Rogozinski and England, the average daily excretion of normal Z. G low czynski (Bull. Acad. Polonaise, 1935, B , adults receiving small allowances of fruit or other 123— 136).— Ultra-violet irradiation had no apparent source of -C is approx. 20 mg. per day. L. S. T. influence on the growth, food utilisation, or bone composition of rats receiving a complete diet, but Effect of vitamin-C on the growth of plants. afforded marked protection when a rachitogenic diet S. von Hausen (Suomen Kem., 1935, 8 , B , 50; was used. A. G. P. c'f- A., 1935, 1036).— Removal of the cotyledons of Cereals and rickets. VI. Comparative voung pea seedlings reduces their ascorbic acid (I) rickets-producing properties of different cereals. content to a low val. and growth is almost completely B. H. T h o m a s and H. S t e e n b o c k (Biochem. J., 1936, retarded. Addition of (I) causes increased (approx. 3 0 , 177— 188; cf. Green et al., A., 1928, 333).— Rolled normal) growth; the (I) content of the treated plants oats, patent flour, whole wheat, polished rice, and 13 luuch > that of the untreated. J. L. D. yellow maize fed to rats as 75% of a low-Ca diet do •Antiscorbutic value of dandelion. I. S. K l e i n e r not differ as regards the severity of the rickets pro i n ^A,JBER (Science, 1935,82,552).— The ascorbic duced. W. McC. acid (I) content varies between 0-08 and 0-10 mg. per Hypervitaminosis-D. L. T h a t c h e r (Lancet, S- of fresh greens. Compared with the greens of 1936, 2 3 0 , 20— 22).—Young infants may have idio 0 er vegetables it is not a good source of (I). syncrasy to the vitamin-H (I) in cod-liver oil as well a L - S. T. as to artificially-prepared calciferol. The current Ascorbic acid content of plant tissue. L. tendency to increase the (I) potency of cod-liver oil 'Avdoin, A. Gir o u d , and C. P. L eblond (Bull, is deprecated. D. S. T. ‘-oc. Chim. biol., 1935, 1 7 , 1649— 1676).— Equal Vitamin-D content of calf, beef, lam b, and hog quantities of tissue containing chlorophyll and that liv e r s . G. M. D e v a n e y and H. E. M u n s e l l (J. ntaimng no chlorophyll of the carrot, turnip, Home Econ., 1935, 2 7 , 240— 241).— Ox and hog upers-grass, endive, lettuce, leek, and beetroot are livers have 0-5— 0-4, lamb 0-2, and calf liver < 0-1 tuninistered to guinea-pigs in addition to a diet international units per g. C h . A b s . (p) ntaming no vitamin-C. The chlorophyll tissue has much higher antiscorbutic val., as is shown by the Vitamin-D content of New Zealand fish oils : V‘ Cl*rves and the ascorbic acid content of the prophylactic method of biological assay. M. M. renal glands, the kidney, liver, and testicles. Cunningham (New Zealand J. Sci. Tech., 193o, 1 7 , 503 507 a A. L. __ ).__Vais, for no. of oils are recorded. 392 BRITISH CHEMICAL ABSTRACTS. A. XIX ( i;m ) That for groper-liver oil was exceptionally high. Modification of [plant] leaf structure by The trustworthiness of the prophylactic method of X - r a y s . Y . N o g u c h i (Plant Physiol., 1935, 10, assay is confirmed. A. G. P. 753— 762).—Localised modifications of cellular struc ture and of the distribution of chloroplasts follow V i t a m in -E. IV. Influence on fertility and exposure to X-rays. A. G. P. condition of the young-. L. S c h i o p p a (Z. Vitamin- forsch., 193G, 5, 22— 26).—Administration of large Theory of assimilation. H. G a e f r o n and K. doses of wheat-germ oil to doe rabbits increases their W o h l (Naturwiss., 1936, 2 4 , 81— 90, 103— 107).— fertility and body-wt. F. 0. H. A discussion. Chemical properties of vitamin-JS. H. S. Metabolism of certain Chlorella and allied O l c o t t (Proc. Iowa Acad. Sci., 1934, 41, 173; cf. f o r m s . T. D. B e c k w i t h (Publ. Univ. Calif. Biol. A., 1935, 1431).— The inactive product obtained by Sci., 1933,1, No. 1,1— 34).— Three among S examined bromination of vitamin-A concentrates is reactivated species of unicellular algae produced N 02' from N03'. by boiling with Zn and HC1 in MeOH. Catalytic None effected the reverse change, although several hydrogenation at 200°/200 atm. does not destroy -A. species grew well on N 0 2' media. As source of N C h . A b s . (p ) urea was generally unsuitable, asparagine had a Newly-discovered nutritional factor in milk. depressive action, peptone was favourable to some G. v o n W e n d t (Z. Volksernahr., 1935, 1 0 , 116— species, and in one case (NH4)2C03 was satisfactorily 118; Chcm. Zentr., 1935, i, 3686).— The milk of cows utilised. The end-products of N metabolism were fed with green food contains a nutritional factor that bases. Neither indole nor tryptophan was formed, stimulated growth and lacteal secretion in rats and Complete protein was not essential to these organisms. in a nursing woman. It is not stored hi the organism, In diffuse light only maltose and glucose favoured nor bound to the milk fat. It is stable to drying of proliferation. The end-products of carbohydrate the milk, but not to drying for hay of the grass fed metabolism were alkaline whether grown in darkness to the cows. R. N. C. or in light. The antigenic protein structure of Chlorella varies with the species. A. G. P. Relationships between the chem istry of chloro phyll and its function in photosynthesis. A. Phosphorus metabolism in leaves of per- S t o l l (Naturwiss., 1936, 24, 53—59).— A lecture. sistent-foliage plants, during yellowing. E. M i c h e l -D u r a n d (Compt. rend., 1935, 2 0 1 , 121a— Photosynthesis in Grimmia inontana. E. 1217; cf. A., 1935, 265).—Fractionation of the P M c K a y (Plant Physiol., 1935, 1 0 , 803— 809).— compounds of end-of-season green leaves and ol Photosynthesis begins within 10—20 min, of moisten yellowed leaves is recorded. Small amounts of ing the dry moss, and reaches equilibrium with phytin-P occurred in all green leaves. On yellowing respired C02 in 30 min. The reducing sugar contents this migrated completely in Algerian ivy and Avcuba of the plant increase from the beginning of photo (but not in cherry-Iaurel) before actual leaf-fall. synthesis and reach a steady level after 30 min. Other forms of P declined in varying proportions at A. G. P. this stage. A. G. P- Photochemical responses of wheat plan to spectral regions. E. J. L e a s e and W . E. T o t t i n g - Lipin metabolism in germinating mung bean. K a o h a m (J. Amer. Chem. Soc., 1935, 57, 2613— 2616).— H. C. (Biocliem. J., 1936, 3 0 , 202— 207).— During Elimination of XX < 390 or 520 mg from artificial germination the N and ash contents of the whole sunlight decreases the assimilation of N03' (I) and bean (Phaseolus aureus) remain const., the amounts of conserves carbohydrates in young wheat plants. Et20 and EtOH extracts increase, the chief constitu The chlorophyll and SH-compounds in the tissue also ents of the cotyledon are gradually transferred to the decrease; these appear to influence the reducing germinating portion, the sterols increase, and the power of the press sap. Increased assimilation of (I) phosphatides decrease. The total fatty acids first is accompanied by a reduction in the pentosans. decrease and then increase. In the cotyledon the Most of the compositional effects in the tissue are amount of fatty acids remains const., but the amount associated with variations in the proportion of blue- in the growing portion increases. The degree of violet light. Reduction of (I) to N02' is, however, saturation of the fatty acids in the sprouting portion associated with long ultra-violet radiation. H. B. increases. W. McC. Histological variations in Cosmos in relation Effect of an atm osphere enriched in oxygen on development of plants. M o l u a r d (Compt- to photoperiodism. 0 . B i d d u l p h (Bot. Gaz., M. 1162 D ry 1935, 9 7 , 139— 155).— Short-day treatment of C. rend., 1935,201,1160— ).— matter production sulphureus causes rapid initiation of flower primordia by radish plants decreased with rising [0 2] (20—80% (7 days). Transition of foliar to flower primordia of the atm., probably as a result of chlorophyll is accompanied by marked accumulation of carbo injury. A . niger was similarly affected, but to a hydrates and protein in the growing tip, and by hydro relatively smaller extent. In a current of 0 2, conidia lysis o f these at the base of the stem. The glutathione produced after exhaustion of sugar in the medium content of the tip shows diurnal variations during were coloured brick-red. A. G. P- the short-day treatment, but remains permanently high Structure of the walls of higher plants. D- B- from the time of the actual anatomical change from A n d e r s o n (Bot. Rev., 1935, 1, 52— 76).— A review. vegetative to flower primordia. Flower-bud formation C h . A b s . (p) is associated with somewhat higher asparagine and Physiological characteristics of frost-resistant lower NH4‘„contents in the stem tip. A. G. P. winter grains. M. T . T i m o f e e v (Bull. Appl- XIX (m) BIOCHEMISTRY. 393 U.S.S.R., 1934, Ser. A, No. 9, 17—24).—The signi gradient due to streamline flow in tubes. Move ficance of the proteins, the p a of the sap, and other ment of solutes in the H20 stream of the xylem may physicochemical properties, in addition to the sugar be considerably more rapid than that indicated by and H20 contents, is emphasised. Ch. A bs. (p) transpiration data. A. G. P. Distribution of plant constituents in capillary Temperature regulation of the dry matter form. II. Fluorescence of chlorophyll. A. production in marine algse as a plasmatic Ktihn and G. Schafer (Pharm. Zentr., 193G, 77, adjustment. H. L ampb (Protoplasma, 1935, 23, 33—35).—With capillary formation, the green zone 534—578).—Respiration rates and the assimilation/ of chlorophyll (e.g., from tinctures) as viewed by respiration quotient of several species of marine algse daylight becomes black or red by filtered ultra are examined in relation to temp, and seasonal changes violet light. This is duo to presence of essential and to the distribution of species. A. G. P. or fatty oils. p . O. H. Influence of the carbohydrate-nitrogen rela Cause of co ld -r e s is ta n c e in p la n t s . W . K essler tion on nodule production by red clover. C. E. (Planta, 1935, 24, 312— 352).— No causal relationship Georgi (J. Agric. Res., 1935, 51, 597— 612).— The exists between cold-resistance and the osmotic pressure inhibitory action on nodulation of combined-N or [H‘] of the cell sap. The winter resting period feeding of clover plants is partly counteracted by of the plant is associated with changes in the con increasing carbohydrate synthesis, e.g., by C0 2- dition of the plasma resulting in increased viscosity and enriclnnent. The inhibitory influence is associated hydration of the colloids and probably with greater with increased conen. of sol. carbohydrates, and d of the plasma. ' A. G. P. decreased % of N and concn. of inorg. N in the sap. Course of stone cell form ation in pear fruits. A. G. P. W. W. Smith (Plant Physiol., 1935, 1 0 , 587— 611).— Possible structure of chlorophyll granules in Changes in the lignin, cellulose, reducing substances, the plastid. J. G. W a k k ie (Proc. Iv. Akad. and H20-j alkali-, and EtOH-extractives during the Wetensch. Amsterdam, 1935, 38, 1082— 1086).— development of the fruit are recorded. The decrease Additional support is given for the granular model in the % of lignoccllulose (I) during growth of certain of the plastid. Anisotropic colloidal chlorophyll (I) varieties of apple and pear is due not to a decline models were made, which fluoresced in a hydrophilic (n ahs. amounts present, but to a relatively rapid environment by association with a “ carrier-mol.” increase in EtOH-extractives. There is no evidence Owing to the low concn. of (I) the models did not of a breakdown of (I) to simpler substances. Sugars possess the required band spectrum. The results we probably elaborated to form lignified tissue. are in agreement with data for the diffusion of (I) in Hemkellulose disappears during storage of fruit paraffin and MeOH. J. N. A. and probably serves as a source of respirable matter. Formation of cell-wall substance [in plants]. A. G. P. »A . K iesel and R. J atzin a (Planta, 1935, 24, 308— usmotic pressure and water content of prairie 311).— Both H 20- and EtOH-sol. galaeturonic acids rn S‘ L’ A ' S to d d a r t (Plant Physiol., 1935, 1 0 , occur on the cell wall. The EtOH-sol. form is probably i OSO).—The osmotic pressure of plant saps is stored within the cell. A transition into EtOH- characteristic of environment, i.e., the resultant of insol. and probably into H20-insol. forms in the cell soil forces which supply H20 and transpiration wall is indicated. A. G. P. enects. A close inverse relationship is established Slime flux [of trees]. E. F. G u ba (10th Nat. • (pvcc'u the osmotic pressure and H20 contents of Shade Tree Conf. Proc. Ann. Meet., 1934, 56— 60).— ™ plants. The osmotic pressure in new was > that in old tissue. A. G. P. Exudates from heartwood of shade trees become gritty through deposition of CaC03 dissolved from ^°mParison of the plasmolytic and cryoscopic cell walls. Exudates are alkaline and favour growth n?a ♦ ior determining osmotic values in of numerous organisms. Exudates from wounds in 579— Bühjianh (Protoplasma, 1935, 23, inner bark or sapwood are usually acid and rich in hv t —^-PProPriate technique is described. The sugars, proteins, and starch : many contain BzOH, ° methods yield comparable results. Extensive H 2C204, cinnamic acid, and traces of MeCHO and • pcnniental data are recorded and discussed. PhCHO. Ch . A b s. (p) Digitalis lanata and D. purpurea : co m n W * eZak*e anB freezable water equilibrium in parative biological investigation. E. B erto- atn tissues as influenced by sub-zero temper- nasco (Giorn. Farm. Chim. Sci. aff., 1934, 83, 421— 10 7qi‘ A' G r e a t h o u s e (Plant Physiol., 1935, 424; Chem. Zentr., 1935, i, 3690). R- N. C. f ’ ' A ~, ®)-—The conception that normally “ un- at 711 ^ G a® in plant tissues does actually freeze Plant pigments and reproduction. R. H. hard iLte Iow fcemP- ( - 1 8 ° to - 20°) applies to R oberts and N. L ivingston (Science, 1935, 82, tn . ei.'C t not to unhardened clover-root tissue or 596).—With apple leaves, no correlation between 10 potato tubers. A. G. P. fruitfulness and the carotenoid pigments could be detected (cf. A., 1934, 1045). L. S. 1. in*tir0£tIn^ne tl°w and the m ovem ent of solutes 1 R JfansPiration stream. R. C. M cL e a n and Assimilation and respiration of Mediterranean 7S0 — °^NGS. (Plant Physiol,, 1935, 10, 773— macchia plants in rainy and dry seasons. H. exnj„. the diffusion of solutes in plants may be vo n G uttenberg and H. B uhr (Planta, 1935, 24, ned by consideration of the radical velocity 163— 265).— Daily and seasonal changes in assimil XIX (rn) 394 BRITISH CHEMICAL ABSTRACTS. A. ation and respiration rates and in the starch and sugar Action of sulphurous mineral waters on contents of leaves are recorded. The influence of germination and plant development. P. T estoni temp., light conditions, and H ,0 supply is examined. (Annali Chim. Appl., 1935, 2 5 , 558— 563).—Mineral A. G. P. H 20 (analyses given) of Tivoli and Telese produces Gaseous exchange in aquatic plants during more rapid germination and growth of wheat and photosynthesis. F. G 6r s k i (Bull. Acad. Polonaise, lentil than does normal II20 . F. 0. H. 1935, B , 177— 198).— Factors affecting the results of Growth and seasonal changes in composition the “ bubble ” method are examined. Most of the of oak leaves. A. W. Sam pson and R. Sajhsoh 0 2 produced (70%) diffuses in the H,0, the balance (Plant Physiol., 1935, 1 0 , 739— 751).— Protein (I) escaping in bubbles. Relatively less LN passes from and fibre accumulate in the leaves at an early stage the H20 into the intercellular spaces at higher rates of growth. Assimilation of N ceases for a considerable of assimilation, since the rate of diffusion is slow. period during active leaf expansion. Fibre production The size of the plant has little influence on the relative proceeds, only very slowly. Resorption of (I) of amounts of gases evolved. A. G. P. older leaves occurs in the late growth stage. The E t20-extractives increase steadily throughout growth. Kinetics of an intracellular system for respir Accumulation of N-free extractives varies with the ation and bioelectricpotential at flux equilibrium. location. Rates of intake of Ca, Si, K , and P varied G. Marsii (Plant Physiol., 1935, 10, 681— 697).— individually with advancing growth. A. G. P. Mathematical. A. G. P. Formation of ethylene by plant tissues and its Absorption and accumulation of potassium significance in the ripening of fruit. R. Gane (J. bromide by Elodea as related to respiration. Pomology, 1935,1 3 , 351— 358).— Ripe apples generate R . S. R oseneels (Protoplasma, 1935, 23, 503— gaseous products which produce cpinastic effects 519).— In Elodea tissue immersed in aq. KBr, artifici on petioles and leaves of plants and abnormal growth ally induced changes in respiration rate were paralleled of seedlings similar to those produced by C2H4. by similar changes in Br' absorption. The mechanism Esters evolved by ripe apples do not affect seedlings. of these effects is discussed. A. G. P. C2H 4 is isolated” from the “ active substance ” of Hormones in relation to root formation on apples (cf. A., 1935, 265). A. G. P. stem cuttings. W. C. Cooper (Plant Physiol., 1935, E ffects of ethylene on p la n t-g row th hormone. 10, 789—794).—Application of (3-indolylacetic acid H . D. Mic h e n er (Science, 1935, 8 2 , 551— 552).— to leafy or leafless cuttings of lemon and other species Experiments in which C2H4 acts on plant growth in stimulates root formation. The hormone is trans a mamier different from heteroauxin are described. located in the phloem. A. G. P. Action of C2H 4 on growth may be explained, not as direct effects of C2H4 alone, but as effects of C2H4 on Chemical nature of some growth hormones as a growth hormone. L- S. I- determined by the diffusion method. A. N. J.» H kyn (Proc. K. Akad. Wetensch. Amsterdam, 1935, Germination experiments with peas in heavy w a ter. J. B r u n and L. T r o n sta d (Kongl. Norske 3 8 , 1074— 1081).— The growth hormone from root tips of Vicia faba is identical with auxin, and the Vid. Selsk. Forh., 1935, 7 , 171— 173; Chem. Zentr., latter is probably present in the regenerated tip of 1935, i, 3242).— Germination occurred in H20 con the coleoptile of A vena. The hormone obtained taining > 40% D 20 , but was inhibited at higher from the sporangiopliore of Phycomyces nitens is concns. Algal growth occurred up to 94% D 20- J. S. A. probably [J-indolylacetic acid. J. N. A. Effect of the pyrrole nucleus on the formation Follicular and other hormones and plant of chlorophyll. G. P olacci, B. O d d o , and M- grow th . M. A. H. T in c k e r and S. E. J acobs (Ann. Gallotti (Boll. Soc. ital. Biol, sperim., 1935, 10, Appl. Biol., 1935, 22, 619—629).—Administration of 565— 567).— Growth of algoe and formation of chloro ketohydroxycestrin and theelol to plants, by the roots, phyll are not opposed by Mg pyrrole-2-carboxyiate. by injection, or by application to cut surfaces failed to produce any growth response or acceleration of Influence of sulphur deficiency on the meta flowering. Auxin stimulated the growth of Bacterium b o lism of soya bean. S. V. E a to n (Bot. Gaz., 193o, auxinophilum (nov. sp.) isolated from gelatin cultures 9 7 , 68— 100).—External symptoms of S deficiency of greenhouse .cuttings.- A. G. P. resemble those of N, P, or Iv deficiency in many re spects, and are probably the immediate effect o Influence of ovarian hormone on plant develop inferior assimilation of N 03' within the plant. Stem m en t. G. T eodoro and R. Z am petti (Arch. 1st. elongation is only slightly reduced by S deficiency, Biochim. Ital., 1935, 7, 425— 440).— The cryst. largely because of the ability of the soya bean o hormone tends to inhibit germination of some plants, break down and re-utilise protein. Plants lacking but stimulates the subsequent growth especially of S produce harder stems. Cell-wall thickness is more tho roots (e.g., with Lens esculenla). Variations closely related to the accumulation of starch an occur with different plants and also with different hemicellulose (I) than to that of total carbohydrates. culture media. F. O. H. (I) probably acts as a reserve material. S-deficien Effect of artificial wind on growth and trans plants contain much sol. org. N, but have a ovv piration in Helianthus animus. E. V. M ar tin sugar content. Proteolysis is active but resyntnes and F. E. Clem ents (Plant Physiol., 1935, 10, is incomplete through inadequacy of the S supply- ^ 613— 636). A. G. P. A. G. f • XIX (m, n) BIOCHEMISTRY. 395 Biochemical modifications in phytopathology : to 4-021, which indicates that the S or P content carbohydrate substances of the leaf oîAmpelopsis depends on the physiological requirements of the veitcliii, H ort. R. S a l g u e s (Compt. rend. Soc. plant. The capacity to “ fix ” S, probably present Biol., 1935, 120, 1212— 1214).— Sol. polysaccharides in org. combination, is more variable than for P. in the healthy leaf increase during the iate summer . J. L. D. and fall in autumn, whilst insol. polysaccharides Constituents of Orthosiphon stamineus, B enth. fall rapidly in summer and more slowly in autumn. R. D ietzel and E. Schmidt (Arch. Pharm., 1936, In the leaf affected with Phyllosticta allescheri, Syd., 274, 10—16).—Cold and hot aq. extracts of O. the changes are similar but retarded. R . N. C stamineus are treated with urease at p n 7-2 and the Effect of titanous chloride on the formation of C02 (modified Barcroft method) and NH3 liberated chlorophyll in Xea m ays. 0. L. Inm an, G. B a r determined. 100 g. of air-dried drug contain 14 mg. c l a y , and M. H u b b a r d (Plant Physiol., 1935, 10, of free and a further 26 mg. of combined urea. 821—822).—In chlorophyll formation Ti cannot R. S. C. replace Fe. Addition of Fe to nutrient media Occurrence of piperidine in black pepper. increases root formation. A. G. P. E. Spath and G. E nglaender (Ber., 1935, 6 8 , 171], Calcium deficiency effects on Pisum sativum. 2218— 2221).— Distillation of a mixture of finely D. Day (Plant Physiol., 1935, 10, 811— 816).— In divided black pepper and MgO with steam in vac. at sufficient supplies of Ca are associated with shorter 35° affords an alkaline distillate which after neutralis and less succulent growth, high % of dry matter in ation with HC1 gives a mixture of NH,jCl and piperi the tops and low % in the roots, and low Ca content dine hydrochloride separable by CHC13. Under theso in the whole plant. A. G. P. conditions piperine is not hydrolysed. Since similar Serological studies of plant viruses. J. M. results are obtained with an aq. extract of pepper free from piperine the presence of piperidine (0-0086%) Bikkeland (Ann. Appl. Biol., 1935, 22, 719— 727).— Precipitin reactions with plant viruses cultivated in as such or as a simplo salt is established. The serologically unrelated hosts show that the virus is, in presence of 3-methylpyrroline could not bo confirmed. itself, antigenic. Viruses of cucumber mosaic, tobacco H. W. Odoriferous constituent of Periploca grteca, nngspot, and tobacco mosaic are serologically dis L. T. S o la c o lu , A. M a v ro d in , a n d G. H errm a n n tinct, whereas tobacco mosaic, aucuba mosaic, and probably tomato streak virus are indistinguishable. (J. Pharm. Chim., 1935, [viii], 22, 548— 556).— T h e bark contains 2-hydroxy-4-methoxybenzaIdeliyde, A. G. P. which is distributed fairly widely in the Asdepiadacece. Properties of virus causing degeneration diseases of beet. G. V k rplan ck e (Sucrerie beUc, J. L. D. Acids contained in the wood of Liboced ru s 1935, 54, 118— 127, 142— 151, 162— 168; Chem. form osan a, Florin. VII. N. I c h ik a w a (J. Chem. -¿entr., 1935, i, 3210).— The properties of the virus Soc. Japan, 1934,55,1124-— 1133).— Oxidation experi causing yellowing and mosaic diseases of beet leaves, ments with dihydroshonanic acid indicate the presence and its resistance towards temp, and chemical agents, of the 3-carboxy-6-methylene-A4-cycfohexyl grouping are reviewed. The virus in purified solutions is more sensitive than that in the juice. J. S. A. in shonanic acid. Ch . A b s. (r) ° Chlorosis of horten sia (Hydrangea hortensis) B ark o f Terminalia arjuna, Bedd. I. Isol ation of arjunin. R. R. Agarwal and S. D u t t m relation to iron .— See B., 1936, 165. (Proc. Acad. Sci. Agra and Oudh, 1934— 1935, 5, Effects of fuel oil on plants. G. D . F u l l e r and 50— 54).— C6H 6 extracts arjunin, C2bIL ,O m, m.p. 820V ’ m DBETTETl (Plant Physiol., 1935, 10, 817— 192° (decomp.) [Pb, Ag, and Na salts; J c 2 and with injures plants when brought into contact Bz2 derivatives, m.p. 103° and 207°, respectively; titv u’ edect. becoming fatal when the quan- (AYl2)5-derivative, m.p. 118°], from the bark. The ~ re es,a level crit. for each species. Penetration substance is sol. in NaHC03 and gives many colour „ ” or may V°t occur, but if oil enters the root it reactions. J. L. D. ‘ 11 ars principally in the primary xylem. A. G. P. Lichen substan ces. L X II.— See this vol., 314. rnit!!tin^Ca^ con*position of grasses in pure Colouring matter of flowers of Kerria japónica, ¡930 169 ^ different staoes oi growth.—See B., DC . T. I to u g h , H. S uginom e, and K. U eno (J. Chem. Soc. Japan, 1934, 55, 1101— 1105).— In the c°ntent of plants and water. B. K. colouring wax the palmitate with smaller amounts l,io,SKI fnd K- Cr- K unasciieva (Trav. lab. of the oleate of lutein was the chief constituent. The R Cad‘ Sci' U-S.S.R., 1935, 3, 31— 41).— Ch. Abs. (p) 10-120/ C(S terît of Plants varied from 0-89 to 20-5 X Pigments of cotton flowers. II. Uppam as the r r °n contained 10 times as much Ra (Gossypium herbaceum). K. N ee la k a n ta m , YeastSCa I2? fr°m which they were obtained, T. R. Sesh adri, and R. H. R. R ao (Proc. Indian ontained amounts of the same order. Acad. Sci., 1935, 2, A , 490— 496).— Petals of G. Corrma Ch. A bs. (p) herbaceum from Coimbatore, South India, differ from of nlar,? lve sulphur and p h osp h oru s content those (from North India ?) studied by A. G. Perkin and T «1 gr0Wn “ the same soil. G. B e r t r a n d (A., 1916, i, 280) in containing gossypitrin and 1 '4 5 3 );1 S 1 b F ^ (Compt. rend., 1935, 201, 1449— quercitin (instead of Moquercitm), and a new jlavonol grown nr,a /, ratl° ln 1M foliage of many plants monoglucoside, m.p. 247— 249°, with small quantities under the same conditions varies from 0-377 of gossypetin (cf. A., 1929, 326). E. W . W . 394 BRITISH CHEMICAL ABSTRACTS. A. X IX (m) ation and respiration rates and in the starch and sugar Action of sulphurous mineral waters on contents of leaves are recorded. The influence of germination and plant development. P. T estoni temp., light conditions, and H20 supply is examined. (Annali Chiin. Appl., 1935, 2 5 , 558— 563).—Mineral A. G. P. H.,0 (analyses given) of Tivoli and Tclcse produces Gaseous exchange in aquatic plants during more rapid germination and growth of wheat and photosynthesis. F. G 6r s k i (Bull. Acad. Polonaise, lentil than does normal H20. F. 0. H. 1935, B , 177— 198).— Factors affecting the results of Growth and seasonal changes in composition the “ bubble ” method are examined. Most of the of oak leaves. A. W. Sam pson and R. Sajhsoh 0 2 produced (70%) diffuses in the H20, the balance (Plant .Physiol., 1935, 10, 739— 751).— Protein (I) escaping in bubbles. .Relatively less N passes from and fibre accumulate in the leaves at an early stage the H20 into the intercellular spaces at higher rates of growth. Assimilation of N ceases for a considerable of assimilation, since the rate of diffusion is slow. period during active leaf expansion. Fibre production The size of the plant has little influence on the relative proceeds, only very slowly. Resorption of (I) of amounts of gases evolved. A. G. P. older leaves occurs in the late growth stage. The Kinetics of an intracellular system for respir Et20-extractives increase steadily throughout growth. ation and bioelectric potential at flux equilibrium. Accumulation of N-free extractives varies with the G. Marsh (Plant Physiol., 1935, 10, 681— 697).— location. Rates of intake of Ca, Si, K , and P varied Mathematical. A. G. P. individually with advancing growth. A. G. P. Absorption and accumulation of potassium Formation of ethylene by plant tissues and its bromide by E lodea as related to respiration. significance in the ripening of fruit. R. Gane (J. Pomology, 1935,13, 351— 358).— Ripe apples generate R . S. R osenkels (Protoplasma, 1935, 23, 503— 519).— In Elodea tissue immersed in aq. KBr, artifici gaseous products which produce cpinastic effects ally induced changes in respiration rate were paralleled on petioles and leaves of plants and abnormal growth by similar changes in Br' absorption. The mechanism of seedlings similar to those produced by C,H4. of these effects is discussed. A. G. P. Esters evolved by ripe apples do not affect seedlings. C2H4 is isolated from the “ active substance ” of Hormones in relation to root formation on apples (cf. A., 1935, 265). A. G. P. stem cuttings. W. C. Cooper (Plant Physiol., 1935, E ffects of ethylene on p la n t-g row th hormone. 10, 789— 794).—Application of [1-indolylacetic acid H. D. M ich e n er (Science, 1935, 8 2 , 551— 552).— to leafy or leafless cuttings of lemon and other species Experiments in which G2H4 acts on plant growth in stimulates root formation. The hormone is trans a manner different from heteroauxin are described. located in the phloem. A. G. P. Action of C2H4 on growth may be explained, not as Chemical nature of some growth hormones as direct effects of C2H4 alone, but as effects of C2H4 on determined by the diffusion method. A. N. a growth hormone. L. S. T. H kyn (Proc. K . Akad. Wetensch. Amsterdam, 1935, Germination experiments with peas in heavy 3 8 , 1074— 1081).— The growth hormone from root w a ter. J. B r u n and L. T r o n sta d (Kongl. Norske tips of Vicia faba is identical with auxin, and the Vid. Selsk. Forh., 1935, 7 , 171— 173; Chem. Zentr., latter is probably present in the regenerated tip of 1935, i, 3242).— Germination occurred in H20 con the colcoptile of Avena. The hormone obtained taining >• 40% D,0, but was inhibited at higher from the sporangiophore of Phycomyces nitens is concns. Algal growth occurred up to 94% DoO. probably fi-indolylacetic acid. J. X. A. J.S.A. Effect of the pyrrole nucleus on the formation Follicular and other hormones and plant of ch lorop h yll. G. P olacci, B. O d d o , and M. g ro w th . M. A. H. T in c k e r and S. E. J acobs (Ann. Gallotti (Boll. Soc. ital. Biol, sperim., 1935, 10, Appl. Biol., 1935, 22, 619—629).—Administration of 565— 567).— Growth of algos and formation of chloro ketohydroxycestrin and theelol to plants, by the roots, phyll are not opposed by Mg pyrrole-2-carboxylate. ky injection, or by application to cut surfaces failed R.N.G to produce any growth response or acceleration of Influence of su lp h u r d eficien cy on the meta flowering. Auxin stimulated the growth of Bacterium b o lism of soya bean. S. V. E a to n (Bot. Gaz., 1935, auxinophilum («or. &p.) isolated from gelatin cultures 9 7 , 6 8 — 100).—External symptoms of S deficiency of greenhouse cuttings. A. G. P. resemble those of N, P, or K deficiency in many re Influence of ovarian hormone on plant develop spects, and are probably the immediate effect of m en t. G. T eoboro and R . Z am petti (Arch. 1st. inferior assimilation of NOs' within the plant. Stem Biochim. Ital., 1935, 7, 425— 440).— The cryst. elongation is only slightly reduced by S deficiency, hormone tends to inhibit germination of some plants, largely because of the ability of the soya bean to but stimulates the subsequent growth especially of break down and re-utilise protein. Plants lacking the roots (e.g., with Lens esculetila). Variations S produce harder stems. Cell-wall thickness is raore occur with different plants and also with different closely related to the accumulation of starch and culture media. F. O. H. hemicellulose (I) than to that of total carbohydrates. (I) probably acts as a reserve material. S-deficient Effect of artificial wind on growth and trans plants contain much sol. org. N, but have a low piration in IleUanthus at mint s. E. V. M arti n sugar content. Proteolysis is active but resynthesis and F. E, Clem ents (Plant Physiol., 1935, 10, is incomplete through inadequacy of the S supply^ 6 13-636). A.G.P.