BRITISH CHEMICAL ABSTRACTS
A.-PURE CHEMISTRY
JANUARY, 1936.
General, Physical, and Inorganic Chemistry. Intensity of the hydrogen a- and (i-lines as the low- and high-pressure absorption bands of 0 2 determined by the frequency of the electrical at XX 2400—2800 A. are compared and discussed. field in electrodeless discharge. 0 . St u h l m a n , H. J. E. jun., and M. S. M cCa y (Physical Rev., 1934, [ii], Far ultra-violet absorption spectrum of 45, 750— 751; cf. A., 1935, 799). L. S. T. oxygen. W. C. P rice and G. Collins (Physical Rev., 1935, [ii], 48, 714— 719).—The speotrum was Striation of the positive column in the glow photographed under high dispersion in the region discharge of hydrogen. H. H. P a u l (Z. Physik, 1300— 650 A., and frequencies of the vibrational 1935, 97, 330— 354).— Probe measurements in the progressions are tabulated. The bands are explained positive column suggest that striations are duo to as going to the various excited states of 0 2+ as limits. an electric double laj-er formed by positive and Results support Mulliken’s assignment of the visible negative ions; this explains the increasing diffi 0 2+ bands to the transition 42g~ -> 4n u. The distances culty of obtaining striations with increasing purity of these states of 0 2+ from the ground state of 0 2 of H, A.B.D.C. are 18-2 and 16-1 volts. N. M. B. Reproducibility of the relative energy dis Influence of an electric field on the absorption tribution of the continuous H 2 spectrum emitted spectrum of sodium. N. T. Ze and W. W. Po by a hydrogen discharge tube. V. E. Gonsalves (Compt. rend., 1935, 201, 716— 718).—The no. of (Phvsica, 1935, 2, 1003— 1015).—The H discharge members of the principal series observed decreases tube may be used as an ultra-violet standard. The with increasing field strength. Certain of the for intensity of the total emission between 1850 and 3200 bidden >S—D and S—S transitions were observed. A. is const, between 3-0 and 3-4 mm. if the current H. J. E. is const. The relative energy distribution is inde Nuclear moment of aluminium. F. W. B r o w n pendent of the current between 150 and 250 m. amp. and R. K. Cook (Physical Rev., 1934, [ii], 45, 731).— if the pressure is const., and does not change in the A tentative val. of 4-8 for the g(I) factor has been region 1— 3-5 mm. for currents between 150 and 250 calc. L. S. T. m. amp. T. G. P. New absorption spectrum of diatomic sulphur Nuclear moments of lithium, potassium, and vapour in the Schumann region. K . W ie l a n d , sodium. M. Fox and I. I. R a b i (Physical Rev., W. M e h r li, and E. M iesc h er (Helv. phys. Acta, 1935, [ii], 48, 746—751).—The at. beam method 1934, 7, 843— 849; Chem. Zentr., 1935, i, 1978).— of “ zero moments ” gave, for the hyperfine structure Data are given for two band systems between 1600 separations of the normal 2Si state of Li, K, and Na, and 1870 A., both originating from the S2 mol. the vals. 0-0268±0-0003, 0-0154±0-0002, and The heat of dissociation of S2 in the 3£ state is 1-68 0-0596^0-0006 cm.-1, respectively. The calc, nuclear volts. J. S. A. magneticmoments are Li7 3-20, K39 0-397, and Na23 2 -08 Deep terms in the isoelectronic sequence VI nuclear magnetons. The nuclear spin was 3/2 for L i; to Cu vii. P. G. K r u g e r and (Miss) H. T. Gilr o y a higher resolution arrangement gave an upper limit (Phvsical Rev., 1935, [ii], 48, 720— 721; cf. A., of 5/2 for the spin of the K 41 nucleus, and 2/2, or 1932, 208).—The 3d= «£5/2 and 3d44p«P« terms of this greater, for LiG, the magnetic moment of the nucleus sequence have been identified by the use of const, being of the order of that of the deuteron. second differences in the radiated frequencies from N. M. B. terms involving an electron transition to the ground Vacuum arc spectra of rubidium and lithium. state. _ N. M . B. S. D a tta and P. G. B ose (Z. Phvsik, 1935, 97 , 321— 329). ' A. B. D. C. New terms in the spectrum of Fe II. J. C. D o bb ie (Proc. Roy. Soc., 1935, A, 151, 703— 726).— Rotation structure of the b'x band system of An analysis of the spectrum of Fe II between ¿327 the nitrogen molecule in the Schumann region. and 9000 A. has resulted in the discovery of numerous V. M. T schulanovski (Compt. rend. Acad. Sci. new terms, many of which belong to the doublet U.R.S.S., 1935, 3, 155— 156; cf. A., 1934, 575, system; >900 lines, not previously classified, have 935).—A preliminary report of new data. J. W . S. been accounted for by the new terms. A fairly Ultra-violet absorption spectrum of oxygen. close approximation to Russell-Saunders coupling L. H erm an and (Mm e .) R. H er m an (Compt. rend., is found in the spectrum. The separations between 1935, 201, 714—716; cf. A., 1934, 828).— Data for the terms of higher and lower multiplicity derived 1 2 BRITISH CHEMICAL ABSTRACTS. A. from the same parent terms are nearly all large and positive ions is a negligible factor in producing compared with the intervals between the levels of luminosity. L. S. T. these terms. L. L. B. Intensification by drying of Hg lines in a Absolnte intensity of the zinc resonance line mercury-hydrogen discharge. H. B e c k (Z. 2139 Â. and life of 2lP i state of zinc. W. Bil- Physik, 1935, 97, 382— 389).—Protons are most likely LETER (Hclv. phys. Acta, 1934, 7, 841— 842 ; Chem. the source of increased intensity of the Hg lines on Zentr., 1935, i, 1979— 1980).— The abs. intensity drying of the Hg-H2 mixture. A. B. D. C. is calc. as/(2139) = 1-17, and the life of the 21jP1 state Determination of the absorption coefficient, as l-78xl0~9 sec. J. S. A. Ii (x0), of the mercury resonance line, 2536-5 À., Ionisation potentials of Ge v, As vi, Se vu, by the resonance scattering method. G. P. B a l in (Physikal. Z. Sovietunion, 1935, 8, 93— 99).— Sb vi, and Te v u . P. G. K r u g e r and W. E. Shoupp (Physical Rev., 1934, [ii], 45, 759).—Radiations The theory of the method of Goos and Meyer (A., represented by d10bS0— 3P1°, 1P1°, 3D1° have 1926, 334) for determining absorption coeffs. by been found in the above. Term vais, of the d10 1S0 resonance scattering is discussed and extended. terms are given and ionisation potentials are 93, If the density of the saturated vapour used is not 127, 166, 107, and 137 volts, respectively. L. S. T. too great, the vais, of K (Xq) are in good agreement witli those obtained by other methods. A. J. M. Influence of pressure on the discharge radi Paschen-Back effect with Bellevue electro ation of cadmium vapour. V. A. F a b r ik a n t and magnet supplied with supplementary coils. P. A. S. K a n e l (Compt. rend. Acad. Sci., U.R.S.S., Ja c q u in o t and T. B e llin g (Compt. rend., 1935, 1935, 3, 257—258).— Preliminary notice. W. R. A. 201, 778—779).—The effect has been studied with Hyperfine structure and the gross structure the Hg lines 5789— 5790 and 5770 Â., and a field of analysis of the spectrum of doubly-ionised anti 65,800 gauss. Displacements and doubling agree mony. J. S. B a d a m i (Nature, 1935, 136, 836). with theory. R. S. B. L. S. T. o Line absorption of thallium doublet = 3519-29 Ultra-violet fluorescence spectra of iodine Â. during thermal excitation of the metastable vapour. F . D tjschinsky and P. P r in g sh e im 62P3/2 level. F. M ü ller (Helv. phys. Acta, 1934, 7, (Pliysica, 1935, 2, 923—932).—The fluorescence 813— 840 ; Chem. Zentr., 1935, i, 1979).—Determin bands at 3400 Â. (Oldenberg, A., 1924, ii, 579) ation of the line absorption as a function of the T1 occurring in I vapour in presence of N2 have been pressure confirms the application of the Maxwell- studied. I in presence of He gives a different spectru m Boltzmann partition law to metastable states. in the same region, which is also obtained with N2 J. S. A. at higher temp. The bands may also be obtained Term values in the spectrum of lead v. as a sensitised fluorescence in presence of Hg, accom G. K. S ciioepfle (Physical Rev., 1934, [ii], 45, panied by H gl bands. Modification of the usual 747).— 65 terms, involving approx. 200 lines, have now energy level system of I is necessary if the bands been established. L. S. T. are to be explained by transference. The 4400 Â. band of Hgl has been investigated. T. G. P. Absorption spectrum of lead vapour in the Schum ann region. N. V. K r e m e n e v s k i (Compt. Hyperfine structure and nuclear magnetic rend. Acad. Sei., U.R.S.S., 1935, 3, 251— 252).— m om ent of Cs I. L. P. Gr a n a t h and R. K. The absorption spectrum of Pb vapour was examined S tranathajî (Physical Rev., 1935, [ii], 48, 725— between 2200 and 1350 Ä. and between 420° and 1070° ; 731).—The hyperfine structure of the lines XX 8761, the results are discussed. W. R. A. 4593, 4555, 3889, and 3877 of the arc spectrum of Cs was observed. The interval factors for the Determination of the temperatures of gases 62
At. wt. of germanium. I. Analysis of ger no. of tho last electron added in the building up of the manium tetrabromide. 0. H onigscjimid, K. successive elements. L. S. T. W entersberger, and F. W it t n e r (Z. anorg. Chem., Radioactive fluctuations. A. E. R u a r k and L. 1935, 225, 81—89; cf. A., 1934, 1053).—The mean of D evo l (Physical Rev., 1935, [ii], 48, 772).— Mathe 10 analyses of GeBr4 by nephelometric titration with matical. Expressions arc found for the fluctuations AgN03 gives Ge 72-588±0-008, anwater, and flesh. J. S. R ogers (Brit. an approx. abundance ratio Si28: Si29: Si30= J. Radiol, 1934, [ii], 7, 176— 186; Chem. Zentr., 89-6:6-2:4-2. The abundance of Si29 and Si30 relative 1935, i, 2133).—The absorption lias been determined to Si28 is slightly > that estimated by Aston. An at. photographically, and conclusions have been reached wt. > the accepted val. is obtained. L. S. T. as to gypsum thicknesses for protection from y-rays, and radiation intensities for penetration of varying Isotopes of nickel. J. d e Gie r and P. Z eem an (Proc. K. Akad. Wetensch. Amsterdam, 1935, 38, flesh thicknesses. J. S. A. 810—813).—Ni64 has been detected by the parabola y-Ray emission of various targets under bom method, but Ni61 (Aston, A., 1935, 802) was not found. bardment by deuterium ions. L. R. H a f s t a d , The abundance figures are Ni58 68-1%, Ni00 27-2%, M. A. T u v e , and C. F. B r o w n (Physical Rev., 1934, Ni82 3-8%, and Hi«4 0-9%. R. S. [ii], 45, 746—747).—Powerful y-ray emission from Interference-spectroscopic examination of the Be, C, and CaF2 bombarded by deuteronsis described. gold hydride band spectrum in search of the There is faint or doubtful emission from Si02 and Al, isotope effect due to the suspected gold isotopes. but none from Ag. L. S. T. S. I m a n ish i (Sci. Papers Inst. Phys. Chem. Res. Experiments with neutrons slowed down at Tokyo, 1935, 28, 129— 134).—No evidence for the different temperatures. C. H. W kstcott and H. existence of Au199 could be obtained. This is in N iewodniczanski (Proc. Camb. Phil. Soc., 1935, agreement with Dempster (A., 1935, 677). R. S. 31, 617— 624).—Neutrons were slowed down by Periodic classification of the rare earths. H. paraffin wax at the temp, of liquid N2 and liquid H2. The absorption produced by certain substances Y ag o d a (J. Amer. Chem. Soc., 1935, 57, 2329— 2330).—The tendency of the rare earths to form stable increased as the temp, was lowered. The no. of tervalent compounds is said to mask the fact that the transformations also increased, the increase depending on the thickness of the paraffin layer. When liquid properties of these elements in other valency states H2 was substituted for paraffin similar effects were are a periodic function of at. no. Examples are given. E. S. H. produced. W. R. A. New periodic table. P. v a n R ysselberghe (J. Disintegration by slowneutrons. J. C h a d w ic k Chem. Educ., 1935, 12, 474— 475).—The new table and M. G o ld h aber (Proc. Camb. Phil. Soo., 1935, emphasises the importance of the azimuthal quantum 31, 612— 616).—Details of work (A., 1935, 277) arc 6 BRITISH CHEMICAL ABSTRACTS. A. 1 (e), ( /) given and a different interpretation of the results 4Be8+ 0n1, the neutrons (5% of the disintegrations) observed with B. The reaction between B and slow being nearly homogeneous, with a max. energy of neutrons is B10- ^ 1 -> Li7+H e4. The disintegration 13-3+0-5 m.e.v. The calc, mass of 4Be8 is 0-3+0-75 process with nitrogen is N14+7i1 -> B11+H e 4. No m.e.v. > that of two a-particles. N. M. B. increase was found for H, D, He, Be, C, 0 , F, Ne, Na, Mg, Al, Cl, A, Ca, Ni, Cu, Zn, In, and U. W . R. A. Transmutation of deuterium by deuterons. K. D. A lexopoulogs (Naturwiss., 1935, 23, 817).— Excitation, of secondary y-rays by neutrons. Experiments are described which indicate that no I. General ; phenomena in paraffin. II. y-radiation is emitted in the nuclear reaction between Measurements with iron, copper, cadmium, deuterons. A. J. M. and lead. R. F l e is c h m a n n (Z. Physik, 1935, 97, 242— 264, 265— 267).—Nuclear y-rays have been Disintegration of lithium by lithium ions. V. excited by slow neutrons in H, Fe, Cu, Cd, and Pb, P e t u h o v , C. Sin e l n ik o v , and A. W a l th e r (Physikal. and absorption of the y-rays by paraffin, Al, and Z. Sovietunion, 1935, 8, 212— 214).—The excitation Pb has been determined. The mass of the neutron function and abs. yield of the transmutation 3Li®+ is 1-0083. A. B. D. C. 3LiG ->- 32He4 are > vals. predicted by Gamow’s Absorption and detection of slow neutrons. formula. The contrary result of Whitmer and Pool (Physical Rev., 1935, [ii], 47, 795) is probably due to D. P. M it c h e l l , J. R. D u n n in g , E. Se g r è , and G. B. protons in the ionic beam. T. G. P. P eg ram (Physical Rev., 1935, [ii], 48, 774— 775; cf. A., 1935, 1441).—The disintegrations of B and Li Artificial radioactivity. II. D. v a n d e r were examined in terms of the absorption observed V e e n (Chem. Weekblad, 1935, 32, 667— 671).—A in B, Li, and Cd. Absorption-transmission curves further review (see A., 1934, 826). show slight departure from the exponential. N. M. B. Synthesis of radio-elements with deuterons Scattering of slow neutrons by iron and other accelerated by an impulse generator. F. J oliot, L a za r d , Sa v e l substances. D. B u d n it z k i and I. K u rtsc h ato v A. and P. (Compt. rend., 1935, 201, (Physikal. Z. Sovietunion, 1935, 8, 170— 178).— 826— 828).— Preliminary results for the conversion The free paths of slow neutrons in C, Fe, Cu, and Pb 6C12-f 1D2= 7N13+ 0?i1 are recorded. Production of have been found by using their reflexion, and are com 7N13 becomes measurable -with accelerating voltages pared with vais, obtained by Dunning et. al. (Physical > 0-95x10® volts. H. J. E. Rev., 1935, [ii], 47, 416) for fast and slow neutrons. Induced radioactivity by bombarding mag In calculating paths the selective sensitivity of the nesium with a-particles. C. D. E llis and W. J. indicator and the absorption of neutrons by H20 H en d e r so n (Nature, 1935, 136, 755).— In addition must be considered. T. G. P." to Al28 (3-ray period 137 sec.) two other radioactive Absorption of slow neutrons by iron. I. K a r a , bodies, probably Al29 and Si27, emitting [3-rays with L. R osenkevitsch , C. Sin e l n ik o v , and A. W alth er a period of approx. 11 min. and positrons with a (Physikal. Z. Sovietunion, 1935, 8, 215— 218).— period of 5— 7 min., respectively, are produced. Absorption in Fe and Cu is < recorded by Fermi Relative yields indicate that Mg25 has a strong (A., 1935, 910). T. G. P. resonance level for a-particles of energy < 5-4x10® volts, and that Mg24 and/or Mg26 have one for a- Selective absorption of neutrons. I. K a r a , L. particles of energies between 5-4 and 6-1x10® volts. R osenkevitsch , C. Sin e l n ik o v , and A. W alth er (Physikal. Z. Sovietunion, 1935, 8, 219— 222; cf. L. S. T. preceding abstract).—Absorption of neutrons by Cu Radio-elements produced by neutrons. P. is independent of the change in concn. of B203 in P r e is w e r k and H . vo n H a l b a n (Compt. rend., H20 surrounding the indicator. This is explained 1935, 201, 722— 724).—The induced activities of by the selective absorption of B. The average half-periods 97 and 4 min. observed on bombarding vais, of sensitivity increase in the order B, Ag, Cu. T1 with neutrons are attributed to 81T1204 and 81T120®, The cross-section for absorption decreases rapidly respectively. No activity was observed on irradiating with increased velocity of neutrons. T. G. P. Bi with neutrons. P gave a product of half-period 15+1-5 days, attributed to 15P32. H. J. E. Evaluation of the accuracy of Bethe and Peierls' formula concerning the decomposition of the Radioactivity of some rare-earths induced by deuteron with y-radiation. V . J. M amasachlisov neutron bombardment. (Si r ) J. 0. M cL e n n a n (Physikal. Z. Sovietunion, 1935, 8, 206— 207 ; cf. and W. H. R a n n (Nature, 1935, 136, 831— S32; A., 1935, 279). T. G. P. cf. A., 1935, 1049, 1050).— Bombardment of rare- Disintegration of lithium by deuterons. T. W. earth oxides or oxalates by retarded neutrons from a B e-f Ra source gave the following vals. for the half- B o n n er and W. M. B r u b a k e r (Physical Rev., 1935, [ii], 48, 742—746; cf. A., 1935, 1Ô49).—The energy periods : Nd 35+5 min., Gd 6-4+0-3 In-., Dy 2-5+0-1 distribution of the neutrons from the disintegration hr., Er 5-8+0 2 min., 2-7+0-2 hr.. Ho 2-6 hr., anctLu of Li by 0-S5 m.e.v. deuterons was determined by 3-6+0-4 hr. L. S. T. the method of recoil protons in a high-pressure Nature of the high-energy particles of pene cloud chamber. Results indicate that the neutrons trating radiation and the status of ionisation come from the reactions gL F +jH 2 -> 22He4+ 0?i1, and radiation formulae. E. J. W illia m s (Physical the neutrons (95% of the disintegrations) having a Rev., 1934, [ii], 45. 729— 730).—A discussion. continuous energy distribution; and gLi’ + jH 2-> L. S. T. I (f-h), II (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 7
Alterations of intensity of cosmic radiation Permutation degeneration in vector models of on the Hafelekar (2300 m etres). V. F. H ess, atoms. M. M a r k o v (Compt. rend. Acad. Sci., H. T. Gr a zia d e i, and R. Stein m a u r e r (Sitzungsber. U.R.S.S., 1935, 3, 103— 104).—From the general Akad. Wiss. Wien, 1934, Ila, 143, 313—338; Helv. permutation theory identities of the kind derived by phys. Acta, 1934, 7, 669—670; Chem. Zentr., 1935, Van Vleck for two equiv. p electrons arise for other i, 2134). J. S. A. kinds of electrons. W. R. A. Frequency and intensity of cosmic-ray bursts Calculation of the self-consistent field with from lead. H. G eiger and 0. Z eiller (Z. Physik, exchange for lithium. V. A. F ock and M. I. 1935, 97, 300— 311). A. B. D. C. P etrashen (Compt. rend. Acad. Sei. U.R.S.S., 1935, 3, 295— 296).—The difference between the observed Shower production in small thicknesses of and calc, term vals. for Li largely disappears when the lead and other elements. J. E. M organ and W. M. self-consistent field method is used with quantum N ielsen (Physical Rev., 1935, [ii], 48, 773—774).— exchange instead of without it. The use of wave The increase in counting rate, for dual and triple functions of the generalised self-consistent field gives coincident discharge of the counters, as a function the intensity of the principal line of each series with of Pb thickness is examined. N. M. B. great precision. A. J. M.
System of masses of light atoms deduced from Electromagnetic field theory. T. L e w is (Phil. nuclear reactions alone. L. I s a k o v (Compt. rend. Mag., 1935, [vii], 20, 1000— 1025).—Theoretical. Acad. Sci. U.R.S.S., 1935, 3, 301— 304).— 19 equations Pure field theory based on Maxwell’s equations of nuclear reactions of light nuclei have been collected, and the principle of least action leads to a satisfactory together with their uncertainties. Solution of these theory of the electron. T. G. P. equations by the method of least squares, the indi vidual equations being weighted according to then.’ y-Transformation of electromagnetic fields. uncertainties, gives a system of at. mass vals. for W. H. W atson (Physical Rev., 1935, [ii], 48, 776; H1 to Ben. Vals. for Hi, H2, He1, Li«, and Li7 cf. Schrödinger, A., 1935, 912).—Mathematical. are in good agreement with mass-spectrograph N. M. B. Elements of the quantum theory. V. B. The vals. corr. for the error in the ratio He : 0 (1-8 parts in 10,000). It is shown that Be8 should be radio rigid rotator (concluded). S. D ü sh m a n (J. Chem. active, although direct observation of its activity is Educ., 1935,12, 485--191; cf. A., 1935, 1298). diffieult. A. J. M. L. S. T. Collision problems and the conservation laws. Nuclear theory. K . N a k a b a y a s i (Z. Physik, (A) J. L. Sy n g e , (b) B. H offm ann (Physical Rev., 1935, 97, 211—220).— Mass defects and nuclear 1934, [ii], 45, 500—501, 734— 735).—Theoretical. radii are calc. A. B. D. C. L. S. T. Pair production by magnetic multipole radi Ultra-violet radiation of chemical reactions. 0. V ikto rin (Chem. Listy, 1935, 29, 245— 249).— ation. J. C. Jae g e r (Proc. Camb. Phil. Soc., 1935, 31, 609—611).—Pair production by magnetic multi Ultra-violet radiation is shown by means of an A1 pole radiation has been calc, for dipoles, quadripoles, or Cul photocathode to accompany the reactions and octopoles. The probability of pair production of oxidation .of pyrogallol by atm. 0 2, of K2C204 decreases with the order of the multipole. W. R. A. by Br, of EtOH by Cr03, of glucose by KMn04, of Na2S204 in alkaline media, and of Al at the anode, Neutrino theory of light. III. R. De L. and of neutralisation of H N 03 by NaOH. R. T. K ronig (Physica, 1935, 2, 968—980; cf. A., 1935, Variation of spectra of detonations with the 1187).— Characteristics of neutrino-fields in relation nature of the surrounding gas. A. Mic h e l -L £ v y to radiation-fields are deduced. T. G. P. and H . M u raour (Compt. rend., 1935, 201, 828— Properties of ultimate particles. G. W atag h in 830).—With C(N02)4+PhMe in A, Kr, 0 2, C02, air, (Ann. Acad. Brasil. Sci., 1935, 7, 273—276).—Modern and Cl2 continuous emission predominated. In views on the constitution of matter are discussed and N,, He, and H2 bands were observed. The luminosity the development of the conception of the electron, is attributed to excitation of the surrounding gas by positron, photon, etc. is traced historically. the shock wave. H. J. E. D. R. D. Colour of sm oky quartz. N. M. M oh ler (Physi Evidence for a resonance level in the B10 cal Rev., 1934, [ii], 45, 743).—Absorption spectra nucleus. E. P ollard (Physical Rev., 1934, [ii] 45, (200—700 mjj.) of smoky quartz before and after 555— 556). L. S. T. decoloration by heat and recoloration by exposure Atomic frequencies in alkali metals. B. N. to Ra, and the spectra of irradiated clear cryst. Sen (Gazzetta, 1935, 65, 907— 908; cf. A., 1934, and fused specimens, support the view that the colour 719).—The calc. at. frequencies (v) of the alkali of smoky quartz is due to radioactive action. metals (except Li) are in good agreement with ex L. S. T. perimental and other calc. vals. Since these elements The 4502 A. band of NH. R. W. L u n t, R. W. B. have marked photo-electric properties, it seems likely P ea rse , and E. C. W. Smith (Proc. Roy. Soc., that the discrepancy in the calc. val. of v for S and 1935, A, 151, 602— 609; cf. A., 1935, 679, 912).— Se is due to the existence of allotropic forms and not to A new band at 4502 Ä., degraded to the red, has been their photo-electric property, which in the case of observed in the spectrum of a hollow-cathode dis S is very weak. O. J. W. charge in streaming NH3. The band arises from a s BBinSH CHEMICAL ABSTRACTS.— A. 11(a)
UI -4- 1X transition. The rotational consts. for the a 2n —2S transition degrading to the red, has been new level bave been calc. L. L. B. photographed. L. S. T. Beryllium deuteride spectra. P. G. K o ontz Photo-dissociation of polyatomic molecules in (Physical Rev., 1935, [ii], 48, 707—713).—The spectra the Schumann ultra-violet. A. T e r e k ix and H. of the BeD green bands at 4990 A. and the ultra Neujmex (J. Chem. Physics, 1935, 3, 436— 437).— violet BeD+ bands at 2200—3100 A. were photo Threshold energies of dissociation were obtained for graphed. Rotational analyses of the former and rota the vapours of FL>0, MeOH, EtOH, HCO»H, AcOH, tional and vibrational analyses of the latter are tabu MeCN, NH3, and 1. N. M. B . lated. The electronic isotope shift in the ultra Spectrum, fluorescence, and photochemical violet is 0-8 cm /1 Rotational consts. are evaluated, decomposition of acraldéhyde. H. W. T hom pson and the slight discrepancy between the ratio of the and J. W. L ix x e t t (J.C.S., 1935, 1452— 1459).— Be consts. for the deuterides and hydrides and the Absorption by the vapour was observed at XX 3800— ratio of the reduced masses is discussed. N. M. B. 2900 and < 2320 A. In the first region there were Fine structure of the C b a n d s of ca lciu m sharp bands, degraded to the red, and max. absorption deuteride. B. Gr u n d s t r o m (Z. Physik, 1935, 9 7 , was at approx. 3450 A. The bands at < 2320 A. 171— 176). A. B. D. C. were narrow and diffuse. No fluorescence was ob /: Band system of calcium hydride. W. W. served on irradiating with XX 3800— 3000 A. The Wat.sox and R; L. W e b e r (Physical Rev., 1935, photochemical decomp. (XX 3665, 3135 A.) yielded [ii], 48, 732— 734).—The E band system of CaH polymerised C2H3-CHO, CO, and small amounts of at 4900 A. is the A r=0 sequence of a 2n -> 2£ tran C2H2. The quantum yield for the decomp. (X 3665 Â.) sition, the lower state being the normal 22 + state. was approx. Iff2. That for the polymerisation was Frequency assignments and calc. mol. consts. are 2-3. Both vais, increased with decreasing X. tabulated. There is evidence of strong interaction H. J. E. between the E state and other near CaH states. Influence of temperature on methyl iodide N. M. B. absorption spectrum in [cjuartz] ultra-violet. A. Dissociation energy of carbon monoxide. F. H en r ic i and H. Gr ie n e is e n (Z. phvsikal. Chem., B hONS (Nature, 1935, 136, 796, and Physica, 1935, 1935, B, 30, 1—39; cf. A., 1933, 445).—Numerous 11 , 1108— 1113).—The structure of the fourth positive new bands have been observed, particularly at higher group in the spectrum of CO confirms the val. 8-41 temp. The electron transition responsible for the volts for dissociation energy (cf. A., 1934, 828). B bands is either in the CT linking or in a non-linking L. S. T. I electron shell (cf. A., 1935, 562). Most of these Vibrational analysis of the hafnium oxide bands may be accounted for by assuming vibrational frequencies of 525, jl 880, and 1237 cm.-1 in the band spectrum. R. W. S h a w and II. C. K e tch a m (Physical Rev., 1934, [ii], 45, 753).—Approx. 100 ground state and 508, jl 780, 1090, and jl 1250 cm.-1 bands arising from the IlfO mol. have been observed in the excited electronic state. A resolution of in the region >.6350—3330 A. in an arc flame. No various bands, observed at higher temp., is inter rotational structure has been observed. L. S. T. preted as removal of a degeneracy. Several bands exhibit exceptional weakening with rise of temp, Ultra-violet band spectrum of N20 3. E. H. and apparently represent transitions to a new electron M el v in and 0. R. W ulf (Physical Rev., 1934, [ii], term, 49,220 cm.-1, the probability of transition to 45, 751— 752).—Mixtures of NO and small amounts which varies with temp. In this term the frequencies of N 0 2 give a group of bands in the near ultra-violet have become 495, j . 805, and 985 cm.-1 R. C. probably due to N203. A process of dissociation of the N203 mol. in the region 2400—2200 A. is in Optical absorption of substituted benzenes. dicated. L. S. T. E. Ste u r e r (Z. physikal. Chem., 1935, B, 30, 157— 158).—The absorption curves of fcum enc, mesitylene, Emission spectrum of the selenium oxide SeO. and p-xylene have been determined and the results L. B locii, E. B loch, and C. S. P u w (Compt. rend., compared with those of Conrad-Billrotli (A., 1935, 1935, 201, 824—825; cf. A., 1935, 1443).—The 913). R. C. spectrum of a high-frequency discharge in Se02 vapour has a no. of bands at XX 3800— 2880 A., Optical absorption of porphyrins. III. A. degraded to the red, attributed to SeO. The funda Ste r n and H. W e n d e r le in (Z. physikal. Chem., mental vibrational frequencies of SeO in the normal 1935, 174, 321— 334; cf. A., 1935, 1444).— The and excited state were 908-9 and 533-4 cm.-1, respec absorption curves of two chloroporphyrin-e5 Me2 tively ; energy of dissociation 5-31 e.v. H. J. E. esters accord with the structure previously suggested (A., 1933, 402). The curve of 4-de-ethyldeoxy- Spectra of SeO and Se02. R . K . A s u n d i, M. phylloerythrin Me! ester exhibits only a small shift J a n -K h a n , and R. Sam u e l (Nature, 1935, 136, towards the blue compared with that of the corre 642— 643; cf. A., 1935, 1188).—The emission bands sponding porphin with Et substituted in the im of SeO and the absorption bands of Se02 have been position. Absorption curves of derivatives of the analysed. The energy of dissociation of unexcited chlorophyll-5 series reveal regularities similar to those SeO is 4-17 volts. L. S. T. observed in the a series. The effect on the light Vibrational analysis of BaCl and BeCl bands. absorption of the hydrogenation of the vinyl group A. E. Par k e r (Physical Rev., 1934, [ii], 45. 752; in methvlphœophorbide-a and -b has been examined. cf. A., 1934, 1153).—A band system due to BeCl, R. C. 11(a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 9
Determination of ionisation by ultra-violet spectra to 15 g has been studied for pure rubber, spectrophotometry : its validity and application gutta-percha hydrocarbon, balata hydrocarbon, poly- to the measurement of the strength of very weak indene, polystyrene, indene, styrene, Cellophane, bases. L. A. F l e xse r , L. P. H am m e tt , and A. pokeweed pith, onion skin, moonwort-soed septum, D in g w a l l (J. Amer. Chem. Soc., 1935, 57, 2103— cotton-seed wing, chitin, pith of feathers, fish bladder, 2115).—Ultra-violet absorption spectra of BzOH, dragon-fly wing, bat-wing, ovalbumin, egg membrane, 2 : 4-CgH3(N02)2-0H, NH2P1i, COPh2, antkraquinone, gelatin, polyvinyl acetate and chloroacetate, glyptal CH^PlrCOoH, and p-N 0,,CGH4-C02H in different resin, shellac, paraffin oil, sperm oil, linseed oil, solvents have been determined. The technique of CC14, (CH0C1)2i PhEt, PhCl, o-CGH4Cl2, EtOAc, ionisation determination by this method is described PraBr, Bu“Br, and C2HC15. J. W. S. and discussed. The strengths of the very weak bases Origin of the wing accompanying the Rayleigh COPko, BzOH, and CH2P1vCO„H have been measured. line in liqpiids. S. C. Sir k a r (Nature, 1935, 136, E. S. H. 759—769).—The changes in intensity of the wings Interpretation of vibration spectrum of organic which accompany the dissolution of CGHG, C10Hg, or molecules with the aid of the isotopy effect. E. Ph20 in cycfohexane do not support the hypothesis B artholome and H. Sachsse (Z. pliysikal. Cliem., of Gross and Vuks (A., 1935, 914). L. S. T. 1935, B, 30, 40—52).—The magnitude of the change in a frequency when in a H compound D is substituted Determination of degree of depolarisation of for H is a measure of the participation of the sub light scattered by molecules. H. V o lkm an n stituted atom in that particular mol. vibration. In (Aiin. Physik, 1935, [v], 24,457— 484).—An apparatus numerous cases substitution reduces the symmetry is described by which the degree of depolarisation of the original mol., resulting in a resolution of (A) of light scattered in CH4, 1I2, C02, and N20 has vibrations which are degenerate in the II compound; been determined. The accuracy of former determin from the resolution the degree of degeneracy and hence ations is discussed. A for CH4 is 0, indicating the symmetry character of the original frequency tetrahedral symmetry. The influence of the Raman may be deduced. Comparison of the infra-red effect on A for CHt is <0-001. A for C02 is 0-0724i absorption spectra of MeOH and MeOD has made it 0-003; for H2, 0-009±0-001; for N20, 0-102±0-004. possible to identify the normal vibrations; in an A. J. M. appreciable proportion of the mols. there is no freo Rotational Raman spectrum of nitrous oxide. rotation of the OH relative to the Me. The 827 cm.-1 D. B e n d er (Physical Rev., 1934, [ii], 45, 732).— band of C2HG is a degenerate cr-vibration, and 1465 Comparison of the rotational Raman spectra of N20 and 1495 cm.-1 are cr-bands. The identification of the and C02 shows no resolution of N20, the mol. of which normal vibrations of C,HG is largely completed. is asymmetric. L. S. T. R. C. Raman effect in fuming sulphuric acid. J. Infra-red spectrum of heavy water. E. F. Ch e d in (Compt. rend., 1935, 201, 724—726).—Vais, B a r k er and W. W. Sleator (J. Chem. Physics, are recorded for oleum with 10—68% of S03, and 1935, 3, 660—663).—The absorption bands v2 and for H2S04. Oleums rich in S03 have no Raman v3 for DoO and v2 and v4 for HDO have been located lines in common with H2S04. This is attributed in water vapour containing 90 and 40% of D. v3 for to formation of H2S207. H. J. E. HDO is masked by the corresponding band for H20. Raman spectrum of sodium nitrate, sodium The fine structure of the v2 bands agrees approx. with acetate, and acetic acid. E. R. L a ir d and D. A. that calc, from mol. dimensions. F. L. U. F r a n k lin (Physical Rev., 1934, [ii], 45, 738).—The Infra-red absorption spectrum of methyl Raman one-line spectrum for NaN03 solutions deuteride. N. Gin sb d r g and E. F. B a r k e r (J. has been re-examined. The slight change in A Chem. Physics, 1935, 3, 668—674; cf. A., 1934, between dil. and conc. solutions and the marked change 716).—The six fundamental vibrational frequencies in X for the crystals and the appearance of other of MeD have been observed and the fine structure of lines in the solid have been confirmed. With solu the bands resolved. Moments of inertia and inter- tions of NaOAc, there is no difference in appearance nuclear distances are calc. F. L. U. or position of the five lines found. The solid gives Infra-red absorption of cyanides and thio- a strong continuous background with faint lines in cyanates. W. G o r d y and D. W illiam s (J. Chem. approx. the same positions as solutions. All lines, Physics, 1935, 3, 664—667; cf. A., 1934, 1288).— except one, are different from those found for AcOH, The absorption of MeCN, CH2Ph-CN, MeCNS, in which the no. and position of the lines change and aq. solutions of IICN and of some simple and com markedly from the glacial acid to a 28% solution. plex metal cyanides shows in all cases a character L. S. T. istic band in the region 4-3S—4-90 p. Slight Raman spectrum of arsenic trichloride. D. M. variations in the position are attributed to changes Y ost and T. F. A nderson (J. Chem. Physics, 1935, in the vibrational energy of the bound CN groups. 3, 754).—It is pointed out, with reference to a paper An additional band shown by highly ionised cyanide by Brodski and Sack (A., 1935, 1189), that central solutions is attributed to CN'. F. L. U. forces alone do not suffice for the treatment of mols. Infra-red absorption spectra of plant and of the AsC13 type. F. L. U. animal tissue and of various other substances. Raman spectra of oxalic acid. J. H. Hibben R. S tair and W. W. Coblentz (J. Res. Nat. Bur. (J. Chem. Physics, 1935, 3, 675—679).—Raman Stand., 1935,15,295— 316).—The infra-red absorption spectra of H2C204, H2C204,2H20, and of aq. and 10 BRITISH CHEMICAL ABSTRACTS. A.
BtOH solutions have been determined. The results substituents tend to increase the dissociation const, indicate that in the anhyd. acid and aq. solutions of BzOH. A. J. M. the two •CO.JL groups behave differently, whilst in Raman effect and organic chemistry : hsopro- EtOH they behave similarly. Shifts due to CIO pylacetylene, isopropylethylene, and some of oscillations are either absent or are far weaker in their derivatives. B. Gr e d y (Bull. Soc. chim., the dihydrato. Chemical interpretations are suggested. 1935, [v], 2, 1951— 1958).—Raman lines are recorded F. L. U. for CPr^iCH, CHPr^ICH2, and some of theirderivatives. Raman spectrum of the isomeric chloronitro- Lines characteristic of the double and triple linkings benzenes. R. M anzoni-Ansidei (Gazzetta, 1935, are found in all the substances. The influence 65, S71— 877).— Raman hues are recorded for o-, of substituted Cl or Br on the double linking frequency mi-, and p-CfiH.,ChN02. The vals. of the frequency at about 1600 cm.-1 is confirmed. 0. J. W. characteristic of the NO» group are : o- 152S, m- 1535, p- 1548 cm.-1 Measurements of other workers Raman eSect and organic chemistry. Raman are discussed. 0. J. W. spectra of the ethylenic compounds CH2:CHR. M. B ourguel and L. P ia u x (Bull. Soc. chim., 1935, Raman effect. XLV. Raman spectrum of [v], 2, 1958— 1969).—Measurements are recorded organic substances. Poly-substituted benzenes. for > 20 substances of the type GH2;CHR (R = a VII. K . W. F. K o h lr a u sc h and G. P. Y p s il a n t i. variety of atoms and radicals). These all have five XLVI. Poly-substituted benzenes. VIII. A. W. characteristic frequencies, each of which may vary R eitz and G. P. Y p s il a e t i, XLVII. Aromatic within narrow limits. For butene the vais, are : polycarboxylic acids. A. P ongratz and R. Se k a . 1295, 1417, 1642, 3004, and 3083 cm.-1 The various XLVIII. Nuclear-substituted etbyl benzoates. radicals R are classified according to their influence K. W. F. K ohlrausch and W. Stockm air (Monatsh., on the 1600 frequency. In derivatives of the type 1935. 66, 2S5—298, 299—306, 307—315, 316—326).— CH,ICH‘CH,R' this frequency is const, at 1642 cm.-1 XLV. The Raman spectra of o-, »«-, and p- 0. J. W. CBH4BrNH», o- and p-CGH4Br-OH, o-, m-, and Raman spectra of methyldiethylcarbinol, p-CgHjBrCN, p-C.H4BrF, o-, »?-, and p-CBH4Br», benzyldimethylcarbinol, and the corresponding p-C6H4Brl, p-C6H4F-X 11». p-C8H4FI, and p-CBH4F-OH olefmes. J. Sa v a r d (Compt. rend., 1935, 201, have been determined. Three lines found in the 833—835; cf. A., 1935, 681).— Data are recorded and Raman spectrum of these substances occur also in compared. H. J. E. that of C611,, and the degrees of depolarisation of these Polarisation of Raman radiation. F. H e i d e x - lines are almost, identical with the corresponding reich (Z. Physik, 1935, 97, 277— 299).— The method ones for CBHB. Only the line 1156 cm.-1 occurs in o-, of circular polarisation (cf. Hanle, A., 1933, 114) has m-. and jp-di-derivatives, in mono-derivatives, and in been applied to Raman displacements of C2H»C12 CeHe itself. The lines 615, 999, and 1020 cm.-1 (cis and irans), C»C14, C»C16, cyc/ohexane (I), and occur independently of the substituent in mono- Ac»0. Pure rotation broadening should be shown by substituted derivatives, but in the di-derivatives 634 inverted circular polarisation, as do PhMe, C6H6, (corresponding with 615) occurs only in the spectrum AcOH, and Ac»0 ; EtOH, H»0, and (I) do not give of p-eompounds, 994 only in that of »«-compounds, inverted polarisation, and indicate that all broadening and 1037 only in that of o-eompounds. The special due to liquids is not rotation broadening. Sirkars characteristics of the spectra of p-eompounds are polarisation dispersion (cf. A., 1934, 942) could not be discussed. observed. A. B. D. C. XL\ 1. The Raman spectra of compounds of the Depolarisation in. the Raman spectra of halo- typo CsH4X*0Me [X = N H 2 (o, h i , and p), OH (o, h i , and p), Me (o, hi, and p). F (p), Cl (o and p), Br (o and genated derivatives of ethyl acetate. H. C. )')■ 1 (o> and p), CX (p)] have been determined. Ch e x g (J. Chim. phys., 1935, 32, 541— 54S; cf. All ¿»-derivatives show lines at 634, 1169, and 1590 A.. 1934. 1056).— Raman spectra of AcOH. EtOAc, cm.-1 CH2Cl‘CO»Et, CHCl»-CO»Et, and CCl3-CO»Et have been measured, and the fundamental frequencies XLY1I. The Raman spectra of h i - and p- CBH4(CG2X)2 (X=Mo, Et), 1:2:3- and 1:3:5- of C*CO»Et, CH»CI, CHC1», and CC13 ascertained. CsHs(CO»Me)3 have been determined. The positions Various depolarised lines are fully discussed in of the double linkings in the nucleus with respect relation to the irroupincs in the molecules. to the substituent groups cannot be found by a T. G. P. study of the constitutive effects of substituents on Intensity and polarisation of R a m a n radiation the frequencies of the nucleus. from liquids. A. Y. R ao (Z. Physik, 1935, 97, XL\ 111. The Raman spectra of compounds of 154— 157).—The relative intensity and polarisation of the type CBH4X-C02Et ( X - X H 2, OH, Cl, Br, XO». Q branches of the different Raman fines of C6H6, o. «», and p in each case) have been determined. CC14. CHC1S, and AsCls have been determined; the The effect of X on the inner vibrations of the XO» total depolarisation obtained from the Raman lines and C02R groups is discussed. The effect is strongest is an appreciable fraction of the depolarisation of ir> the <>-position, and the characteristic frequencies the total scattered radiation. A. B. D. C. of the XO» and CO groups arc increased by the intro Raman effect of organic molecules. Vibration duction of further substituents, the increase being the spectra of acrylonitrile and ethylene oxide. B. greater the higher is the substituent in the series OH, T imm and R. M kcke (Z. Physik." 1935, 97. 221— NR». Me. Cl. Br, CO»R, XO». i.e., in the order in which -24).— Frequencies are given for C»HS-CX and II (fi-c) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 11
(CH,)20, and are classed as valency frequencies of Role of oxidation-reduction potential and the vinyl groups, ring frequencies, and CH frequencies. acidity in quenching of fluorescence in solutions. A. B. D. C. K. W eb er (Z. physikal. Chem., 1935, B, 30, 69—83). Relation between the ultra-violet absorption —For quinine sulphate and scsculin the logarithm spectrum and the Raman spectrum of pyridine. of the concn., k, of halogen ion which halves the V. H e n r i and P. A ngenot (Compt. rend., 1935, fluorescence intensity increases linearly as the re- 201, 895— 896).—Fundamental frequencies of 600, duction-oxidation potential, E, of the halogen ion 857, 993, 1031, and 1159 cm.-1 have been observed becomes increasingly negative, whilst for fluorescein in the ultra-violet absorption spectrum of the vapour and uranino the relation between k and E is more of C5H5N (I) at various pressures. The frequencies complex, k rises with [H‘], Following Schneider correspond with those of the Raman spectrum of (A., 1935, 681) and assuming quenching by halogen (I) and C6H6, since CH and N have nearly the same ions to be a sensitised photo-oxidation, a reaction mass. For the higher electronic level the frequency mechanism is postulated which leads to quenching 542 cm.-1 lias been observed. Ultra-violet light of formulae agreeing with experiment. These latter X < 2750 A. falling on (I) is photochemically active yield quantitatively the observed relation between and causes predissociation. R. S. B. k and E, so that from k the differences between Application of the Raman effect to the cis- the E vals. of the halogens may be derived. For the trans isomerism of methylct/cfohexanols. J. quenching of the fluorescence of the above substances Tabuteaij (Compt. rend., 1935, 201, 897— 898).— by cations there is no connexion between k and E, The Raman spectra of cis- and trans-o-, m-, and p- suggesting that oxidation-reduction reactions play methylcycZohexanol differ most for frequencies 300— no part. R. C. 900 cm.-1 The spectra of the cis-alcohols and Photochemical reactions connected with the -acetates have many lines in common, but with the quenching of fluorescence of dyes by ferrous ions fraws-compounds the no. of common lines is much in solution. J. W eiss (Nature, 1935, 136, 794— less. The distinction between cis- and trans-iso- 795; cf. A., 1935,1211).— Irradiation of different dyes, merides decreases in the order o, m, p, and is < with e.g., methylene-blue, thionine, brilliant-eresyl-blue, the borneols and myrtanols owing to the relatively etc., in acid FeS04 with the visible radiation of a small mass of the Me. R. S. B. strong C arc produces bleaching or a change in colour, Stability of the Lenard light centres in zinc due to the formation of lcuco-dyes, which is irreversible sulphide. N. R ie h l (Ann. Physik, 1935, [v], 24, when the F c"' is pptd. by hydrolysis. With the 536—542).—An investigation has been made to dis above dyes the process is completely reversible in cover whether the Lenard light centres change spontan the dark, the Fe"' being reduced by the leuco-dye. eously in the course of time, depending on the history The direct, unsensitised photochemical process is of the phosphor. ZnS phosphors which have been kept obtained by irradiating 0-5il/-FeSO4 in II2S04 with in the dark for some years show a decreased sensitivity light from a strong Hg arc, H2 being formed when to a-ray phosphorescence and probably also to ordinary 0 2 is excluded. The bearing of these results on light phosphorescence, showing that spontaneous biological problems is discussed. L. S. T. changes in the lattice or light centres have taken place. Dependence of fluorescence spectra on the vis X-Ray analysis shows that the ageing is not due to a cosity of the solvent. A. Ja b l o n s k i (Physikal. Z. change of the wurtzite lattice into the Zn-blende Sovietunion, 1935, 8, 105— 108).—The results of lattice. The aged phosphor can be partly regenerated Tumermann (A., 1935, 807) are not inconsistent with by prolonged heating at 500°. The thermodynamic those of Jablonski (A., 1932, 213). A. J. M. instability of the light centres may be due to the rapid cooling of the phosphor when first prepared, the equili Photoluminescence. F. Ob e r h a u se r and R. brium being frozen, for minerals which have cooled Cabr er a (Anal. Fac. Filos. Univ. Chile, 1934, 1, comparatively slowly show but feeble phosphorescence. 28— 44; cf. A, 1929, 793).— Org. acids containing The existence of phosphorescent minerals indicates a trace of fluorescein exhibit fluorescence and phos that the capacity to phosphoresce is not completely phorescence when exposed to light sources. lost by ageing. A. J. M. F. R. G. Diffusion in the bulb of a mercury rectifier. Luminescent properties of zinc sulphide in D. R. K a n a sk o v (Physikal Z. SoVtetunion, 1935, relation to A'-rays. L . L e v y and D. W . W est 8, 119— 135).—The dark space in a Hg rectifier has (Brit. J. Radiol., 1935, 8, 184— 185).—The afterglow been examined with a Langmuir probe. Linear and latent fluorescence of “ Fluorazure ” ZnS intensi relations exist between (a) log random electron current fying screens becomes very feeble if a trace of Ni is or (b) log concn. of electrons, or (c) the potential, at a added before firing the powder. A screen made from point along the axis of the tube and the distance of ZnS and CdS is superior to one from CdW04. the point from the cathode. T. G. P. Ch . A b s. (e) Polarised fluorescence of organic compounds. Bulk and superficial conductivities of cuprous S. M. M it r a (Z. Physik, 1935, 9 7 , 138— 153).— oxide. L. D u b ar (Compt. rend., 1935, 201, 883— Variation in polarisation of fluorescence radiation 885).—Using conductors of different surface the bulk from succinylfluorescin and eosin •with temp., viscosity, and superficial conductivities (a, to) of Cu20 have been and concn. of solution, and X of the exciting radiation determined in dry air at 15-8°; a = l-6 1 x l0 -8 mho is given for the solvents glycerol, castor oil, sugar cm./cm.2 and to=21-7xl0'8 mho cm./cm. a is solutions, collodion, and gelatin. A. B. D. C. unaffected by H20 vapour, but to decreases owing to 12 BRITISH CHEMICAL ABSTRACTS. A. adsorption, to is greatly reduced by the action of Dipole moments of certain organic compounds. dil. H3P0 4. R. S. B. J. N. P e a rc e and L. F. B e rh e n k e (Proc. Iowa Investigations on electrets. A. Ge m a n t (Phil. Acad. Sci., 1934, 41, 141— 142).—The dielectric Mag., 1935, [viij, 20, 929— 952).—The main results consts. of p-CGH4Br-CHO, p -CGH4Me • CH 0, p- of Eguchi (A., 1925, ii, 462) have been verified. OH-CcH4*CHO, and p-anisaldehyde in dioxan at Electrets prepared by allowing substances to solidify 25° gave dipole moments 2-20, 3-27, 4-18, and 3-70 X in a field of 5— 10 kv. per cm. are the electrical 10-18, respectively. The angle between the CHO analogues of permanent magnets. The field on moment and the line through the 1 :4 C atoms of their free surface may be utilised provided they are the C0H„ nucleus was 51°. Those between the nearly short-circuited and kept dry. The charge is directions of the OH and CHO group moments were acquired either by ionic space charges (heterocharge) 50°, 49°, respectively. Ch . A bs. (e) or by the orientation of dipole mols. (homocliarge) Structure of antipyrine [and pyramidone] in which may be accompanied by a secondary piezo aqueous solution. G. D e v o to (Atti R. Accad. electric effect. Acidic substances yield ions producing Lincei, 1935, 21, 819—820).—The dielectric consts. heterocharge, whilst non-dissociating dipoles, chiefly of aq. antipyrine (I) and pyramidone (II) of various esters, yield homocharge. For mixtures an additive concns. have been determined at 25° (X 90 cm.). law is valid. T. G. P. de/dc=1-5 for (I) and —6-7 for (II), indicating that Elimination of peculiarities in the dielectric polar structures for these compounds are untenable. behaviour of water vapour. J. D. St r a n a t h a n D. R. D. (Physical Rev., 1934, [ii], 45, 741).—The breaks in Transitions in camphor and chemically re the pressure-(X—1) curves for H20 vapour have been lated compounds. I. Dipole rotation in crys eliminated by using a brass condenser, and quartz talline solids. W. A. Y a g e r and S. O. M o r g a n . or Pyrex insulators, and by exercising a strict control II. Vibration of atomic groups. A. H. W h ite on the rate at which the vapour enters the condenser. and S. 0. M o rg an (J. Amer. Chem. Soc., 1935, 57, The electric moment of the H„0 mol. is 1-83 XlO-18. 2071—2078, 2078—2086).—I. Determination of the L. S. T. dielectric properties of d- and JZ-camphor, d-camphoric Dipole moments and structure of quinoline anhydride, bomeol, woborneol, and bomyl chloride derivatives.— See A., 1935, 1506. shows that these compounds undergo transitions Physical methods in chemistry. IV. Dipole in the solid state. Above the transition temp, measurement and its application to chemistry. the dielectric const, of the solid is that normally P. C. H en r iq u ez and L . J. N. v a n d e r H hlst expected of the polar substance in the liquid state; (Chem. Weekblad, 1935, 32, 636—645).—The calcul below the transition temp, the dielectric const, ation of at., electronic, and orientation polarisation has a low val., approx. equal to n2. This behaviour and the relationships between dipole moment and is explained by the rotation of dipoles in the solid. structure are discussed. D. R. D. II. An increase of about 18 g.-cal./° C./mol. Configuration of the mercuric halides. W. J. in the sp. heat of d-camphor at the transition at —30° has been observed; it is assumed that energetic Curran and H. H. W e n zk e (J. Amer. Chem. Soc., 1935, 57, 2162—2163).—Electric moments of HgPh2, intramol. vibration arises. The total polarisation HgCl2, HgBr2, and Hgl2 have been determined. behaviour of d-camphor in dil. solution is explained The vals. are < those calc, from solubility data. by assuming that at room temp, dipole moment is The configuration of these compounds is not linear. < and at. polarisation > was formerly supposed, and that at. polarisation begins to decline with falling E. S. H. Dipole measurements with isomeric plato- temp, below —10°, when the transition to the more rigid mols. begins. Similar transitions, observed in com plexes. K. A. Je n s e n (Z. anorg. Chem., 1935, 225,97— 114).—Determinations of the dipolemoments crystals of cycZohexane derivatives, appear to be of compounds [PtX^SR,,),,] (X=C1, Br, I, NO,, due to transformations from the rigid to the pliable N 03, and R = E t, Pra, Pr8, Bua, BlA CHMeEt, forms of the mols. forming the crystals. E. S. H. CH2Ph) give 2-2—2-5 X Kb18 e.s. unit for the a- Calculation of dipole interaction. R. P. B e l l compounds and about 9xl0 -18 (Cl, Br) or 13xl0-18 (Trans. Faraday Soc., 1935, 31, 1557— 1560).— The (NO,, N 03) for the (3-compounds. The results in method proposed by Martin (A., 1934, 1063) for dicate that the a-compounds are trans- and the [3 calculating dipole interaction is shown to be valid cis-isomerides. Cryoscopic measurements in C6H„ for sufficiently small vals. of the dipole moment. show both the a- and ^-chlorides to have simple F. L. U. mols., the latter being associated in conc. solutions. Reactivity and dipole moment. E. H e r t e l No interconversion of the a- and (3-forms occurs in and E. D um ont (Z. physikal. Chem., 1935, B, 30, C6H6, but it does in the case of [PtCl2(Et2Sc),]. 139— 148; cf. A., 1935, 1232).— Measurement of “F. L. U. the dipole moments of p-substituted derivatives of Dipole moments of ethyl and isoamyl borates NPhMe2 and the corresponding substitution products and triphenyl phosphate. E. G. Co w l e y and of CGHG has shown that the effect of a substituent J. R. P a r tington (Nature, 1935, 136, 643).—The on the reactivity of a functional group (NMe2) runs vals. obtained in C6H6 at 20° are 0-75, 0-81, and parallel with its contribution to the dipole moment of 2-79 D, respectively. P 2m and PE are 50-5 and 38-63, the compound. It is suggested in explanation that 94-3 and 80-20, 252-5 and 87-41 c.c., respectively. the group moment of a substituent is the result chiefly L. S. T. of a considerable dissymmetry in the distribution II (O-ff) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 13
of charge about the point of attachment to the ring, symmetrical lattices, for which there are insufficient and that the reactivity of a functional group is de electrons for twofold occupation of each linking, termined by the state of the nuclear C to which it can be formed only at high temp., when free rotation is attached, this in its turn being a function of the within the lattice is possible. J. S. A. states of the other C atoms of the ring. R. C. Planar configuration of quadricovalent nickel, Index of refraction of HC1 from 1 to 10 a. R. palladium, and platinum : dithio-oxalate deriv R ollefson and A. H. R ollefson (J. Cliem. Physics, atives. E. G. Cox, W. W a r d l a w , and K. C. 1935, 3, 434).—Dispersion measurements over 1— 10 W ebster (J.C.S., 1935, 1475— 1480).—The three ¡a show that the dispersion curve is matched best sails KatM^COS)*] (Mlr=N i, Pt, and Pd) have been by using the vals. 1-00 Xl0~10 and 1-18 xlO -18 e.s.u. prepared, and are shown to be isomorphous. The for the effective charge of the rotator-vibrator and four valencies to the metal atom are co-planar in the electric moment of the rotator, respectively. each case. The crystals are monoclinic; 4 mols. in N. M. B. unit cell; space-group A'2fa (C,%). The principal Double refraction of chitin tendons. J. M. interat. distances were Ni-S 2-30, Pd-S 2-44, D ie h l and G. v a n I ter so n , jun. (Kolloid-Z., 1935, Pt-S 2-44, C-S 1-83, K -0 2-57— 3-0, K -S 3-73 73, 142— 140).—When chitin is immersed in glycerol- (min.) A. Crystallographic and X-ray data are quinoline mixtures its double refraction changes from given. ‘ II. J. E. positive to negative as wof the liquid mixture increases. Electronic: structures of molecules. XIV. E. S. H. Linear triatomic molecules, especially carbon Maximum rotations of carboxylic acids con dioxide. R. S. M u l l ik e n (J. Chem. Physics, 1935, taining a phenylethyl group.—See this vol., 70. 3, 720—739; cf. A., 1935, 1188).—Electron con Optical rotatory power of solutions in an figurations of a no. of triat. linear mols. are given, electric field. J. K tjnz and A. M cL e a n (Nature, and ionisation potentials of C02, CS2, N20, and HgCl2 1935, 136, 795—796).— Changes in optical rotatory are interpreted in relation to these. An explanation power are observed when solutions of 2-Z-menthyl of the triangular form of N 02 is given. F. L. U. H 3-nitrophthalate in C8H0 or PhMe are placed in “ Most probable" locations of the valency an electric field. This behaviour is distinct from the electrons in the carbon atom. W. P. D a v e y Kerr effect and is attributed to the electric moment (Physical Rev., 1934, [ii], 45, 763).—Theoretical. induced in the solvent mols. by the electric field. L. S. T. Anomalous effects are obtained with the 2-Et ester. Deuterium. II, III. D. LIacGil l a v r y (Chem. L. S. T. Weekblad, 1935, 32, 650—655, 679—684; cf. A., Magnetic birefringence in solutions of para 1935, 1185).—A further review. magnetic salts of rare earths. S. W . Ch in - c iia lk a r (Phil. Mag., 1935, [vii], 20, 856—858; cf. Deuterium and X-ray absorption. D. K. A., 1932, 677).—The results of Haenny (cf. ibid., 909) F roman (Physical Rev., 1934, [ii], 4 5 , 731).—The are reduced to the same equiv. concn., and the presence of D2 in ordinary H2 does not account for connexion between the birefringence arid the orbital the peculiarity in its absorption of X-rays in the range moment of the ion is discussed. N. M. B. 0-5—0-6 A. L. S. T. Temperature variation of the electro-optical Sputtering of metals by incidence of slow ions Kerr effect of nitrobenzene at its transition and measurement of sputtering swelling values. point. W. H erzog (Z. Physik, 1935, 9 7 , 233—241). H. LiiDER (Z. Physik, 1935, 9 7 , 15S— 170).—Degree — No discontinuity was observed at the Wolfke- of sputtering by positive ions of energies of 40 volts Mazur transition point (cf. A., 1932, 329). and upwards was determined from the resistance of A. B. D. C. the sputtered wire. Swelling val. or min. energy Magneto-optics. C. G. D a r w in (Proc. Roy. of sputtering was determined for A + ions incident Soc., 1935, A, 151, 512— 539).—Theoretical. A on Ni, Cu, Fe, and W, for K +, Cs+, and Li+ incident formal method suitable for the discussion of magneto- on W, and for Cs+ on Cu. A. B. D. C. optics, irrespective of the underlying at. theory, is Molecular ions from heated salts of some of developed. The magneto-optic effects of material the alkali m etals. L. L. B a r n e s (Physical Rev., of any at. character are discussed. The formulae 1934, [ii], 4 5 , 751).—At temp, just < m.p., KC1 give are applied to test the experimental results of the an ion of mass K2Cl+, and K2S04 one of massK3S04+. Kerr effect. L. L. B. Salts of other alkali metals give similar ions. Discussion of experiments on the time-lag in L. S. T. the magneto-optic effect. G. F. H ull (Physical Periodic system of energy coefficients. A. E. Rev., 1934, [ii], 45, 738). L. S. T. F ersm an (Compt. rend. Acad. Sci. U.R.S.S., 1935, 3, 173— 176; cf. A., 1935, 1305).—The VEK vals. Affinity in Hume-Rothery phases. U . D e h - lin g e r (Metallwirts., 1935, 14, 145— 149; Chem. (energy of unit valency of an ion) for a large no. of Zentr., 1935, i, 2130).—Theoretical. The affinity in ions are tabulated according to the periodic classi Hume-Rothery phases is explained by the attribution fication, and correlated. J. W. S. of a definite lattice linking to each valency electron. Solution of variation problems in quantum The energy levels are calc, from Bloch’s wave mechanics. A. S chuchovicki (Compt. rend. Acad. theory of metallic electrons, where X must be an In Sci. U.R.S.S., 1935, 3, 161— 164).—Mathematical. tegral sub-multiple of the lattice spacing. Highly J. W. S. 14 BRITISH CHEMICAL ABSTRACTS.— A. II (g), III (a)
Temperatures and heat effects of genotypic (J. Chinese Chem. Soc., 1935, 3, 301— 307).—The transformation of alkali salts of long-chain fatty fundamental frequencies assigned by Kistiakowski acids. P. A. T h iessen and J. v o n K l e n o k [with et al. (A., 1934, 30, 145) are criticised. The restoring H. G ookowiack and J, Sta u ff] (Z. physikal. Ohem., force consts. of linkings in the mols. HCN, C1CN, 1035, 174, 335—358; cf. A., 1933, 1004, 1011).— BrCN, (CN)2, and C2H2 have been calc, from the The temp, at which the heat effect, Q, corresponding fundamental frequencies of tho valency vibrations. with genotypic transformation sets in has been deter All tho cyanides have the same type of CN linking. mined. The dielectrio const.-temp. curve is dis The frequencies have been re-assigned on the basis continuous at the transformation point. For a of the above calculations, the selection rule for infra single crystal of Na stearate on heating up through red and Raman spectra, and heats of formation of 49° tho double refraction undergoes an abrupt linkings. A. J. M. irreversible change in sign. Q increases with the Quantum-mechanical discussion of orient chain length and also runs parallel with tho radius ation of substituents in aromatic molecules. of tho cation. Abovo the transformation tomp. G. W. W h e la n d and L. P a u l in g (J. Amer. Chem. the sp. heat rises discontinuously. R. 0. Soc., 1935, 5 7 , 20S6—2095).—Using the method Kinetic interpretation of internal effects. V. of mol. orbitals, the charge distribution in aromatic N jec.ovan (Z. Physik, 1935, 97, 390—394).— Rotation mols. undergoing substitution is discussed quantita and vibration of elastic mol. of an ideal gas effectively tively, taking into consideration the inductive effect, docreaso tho radius of tho mol. and so liborato the resonance effect, and the polarising effect of the energy. This hypothesis is applied to thermal attacking group. With reasonable vals. for the para dissociation, ionisation, and gas degeneracy. meters involved, the calc, charge distributions for A. B. D. C. several aromatic compounds are in qual. agreement Movement of a heavy drop in the acoustic with experimental results regarding position and rate field. S. V. G orbatsch ev and A. B. Se v e r n y of substitution. E. S. H. (Kolloid-Z., 1935, 73, 146— 154).—Theoretical. Effect of surface tension on flow from Poncelet E. S. H. apertures. H. L a u f f e r (Forsch. Ing., 1934, 5, A, Relation between internuclear distances and 266—274; Chem. Zentr., 1935, i, 1987).—Theoretical. force constants of molecules and its application Contrary to accepted views, the flow from small to polyatomic molecules. R. M. B a d g e r (J. apertures at low pressure is augmented by the in Ohem. Physics, 1935,3,710— 714; cf. A., 1934,477).— fluence of surface tension. J. S. A. The relation between internuclear distances and force consts. found for diat. mols. persists in polyat. Aluminium alkoxides and their parachors. mols. This fact provides a method whereby inter R. A. R obinson and D. A. P e a k (J. Physical Chem., nuclear distances in the latter can be calc, from vibra 1935, 39 , 1125— 1133).— Surface tension and density tional data alone. F. L. U. data and parachor vals. are given for Al acetyl- acetonate (I), imp. 192°, aluminoethyl acetoacetate (IX), Mean free paths of molecules and wave imp. 78— 79°, Al diethylmalonate (III), m.p. 95—96°, m echanics. J. A. EiIdridge (Proc. Iowa Acad. Cr acetylacetomite, m.p. 212°, [Al(OEt)3\, m.p. Sci., 1934, 41, 257).—Direct determinations of the 146— 15i°, [A/(OPr“)3]4, m.p. 106— 108°, [Al(OPr%]A, mean free path of H2, X2, and 0 3 yield vals. for the m.p. 118?, [AifOBu“).]*, m.p. 102— 106°, [Al(OBufi)3\i; effective cross-section of*the mol. which are 4— 5 m.p. 20S— 210°, sec.-[Ai(DBa)3]4, b.p. 174— 176“/5 times those based on viscosity data; theoretical factor mm., Sb(Otit)3, b.p. 99-5°/13 mm. Assuming singlet should be > 2. ' Ch . A b s . (e) linkings in (1), (11), and (III), tho mean parachor of Electrostatic interaction in atoms. R. F. Al is 39-5. The parachor deficiencies which occur B ach er and S. G oudsm it (Physical Rev., 1934, [ii], in the alkoxides may be accounted for by an 8- 45,767). ‘ L .S .T . membered ring in which the O are attached to Al Vibrations and internal rotation of a chain of by singlet linkings. R. S. four atoms. L. S. K asse l and C. W. M ontgom ery The parachor as a function of density and (Physical Rev., 1934, [ii], 45, 766).—The dynamical molecular volume of a substance in its different behaviour of a chain of four equal atoms with tetra chemical states. I. R. M orozov (J. Gen. Chem. hedral bond angles has been studied in an attempt Russ., 1935. 5, 1020— 1023).—The parachor is calc, to classify the infra-red and Raman spectra of the from P = ( F - f F 1)(2ciF4/F)i , where V is the sum of higher hydrocarbons. Extra Raman lines observed the vols. of the constituent atoms, Vx is the mol. by Kohlrauseh and the tendency of long-chain vol. of the substance, and d is the density. R. T. hydrocarbons to exist in a linear form are explained. Investigations on diffusion of cathode rays by L. S. T. means of the cloud chamber. I. G u n th e r (Ann. Hydrocarbon linking additivity. V . D eitz (J. Physik, 1935, [v], 24, 377— 392).—The directional Chem. Physics, 1935, 3, 436).— Corrections previously distribution of cathode rays after passing various proposed for obtaining linking additivity (cf. A., thickness of matter was particularly studied. The L935, 2S4) are tested with the help of experimental results suggest that the passage of rays through matter data (cf. Kistiakowsky, ibid., 825) on the heats of is a combination of absorption and diffusion processes. hydrogenation of some olefines. N. M. B. J. W. S. Fundamental frequencies of the cyanogen Absorption of short-wave-length X-rays. W. V. m olecule. S. C. W oo, T. K. Liu, and T. C. Ch u M a y n e o r d and J. E. R oberts (Nature, 1935, 136, I l l (a, b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 15
793).—For elements up to Ca the mean absorption Res. Japan, 1935, 14, 1105—1112).—Intensities of per electron for X-rays of X 59 X is in agreement X-rays reflected from a strained quartz plate have with the Klein-Nishina formula. The photo-electric been measured. The distribution of intensity depends absorption coeff. per electron varies according to on the distribution of strain. R. S. (at. no.)3. L. S. T. Relation between amorphous and crystalline Widths of X-ray hands in solids. J. R e h n e r , scattering and its application to crystal analysis. jun. (Physical Rev., 1934, [ii], 45, 735).—Theoretical N. S. Gingrich and B. E. W ar r en (Physical Rev., (cf. A., 1934,576). L. S. T. 1934, [ii], 45, 762—763).—An expression for the X-Ray and magnetic measurements of KC1 average radial distribution of atoms about any one powders in relation to lattice distortion and atom, expressed as a series over the no. of lines in photochemical coloration. Q. W. B r in d l e y , the powder pattern, is given. Intcrat. distances F. W. Spiers, and F. E. II o are (Phil. Mag., 1935, can be obtained directly without determining a [vii], 20, 1041— 1054).— Comparisons of high-ordcr complete structure. L. S. T. spectra of finely-ground and pptd. KC1 show that the Structure of layer lattices. W. L otmar (Z. greater photo-coloration of the former, which has Krist., 1935, 91, 187— 191).—To explain the ob been attributed to flaws and cracks (Smekal), is not served broadening of (hkl) reflexions in layer lattices due to lattice distortion. The question of extinction as compared with the (hkO) and (OOl), a particular is considered in detail. Grinding reduces the dia distortion is suggested which leaves the (hlcO) planes magnetic susceptibility of KC1 only from 39-3 X10*6 undisturbed. B. W. R. to 38-8 xlO -8, confirming the above conclusion. T. G. P. Alternating axes and symmetry symbols in Examination of electro-deposited nickel coat crystallography. J. D. H. D o n n a y (J. Washington ings by X-ray diffraction. W . A . W ood (Phil. Acad. Sci., 1935, 25, 476—488).—A discussion of the Mag., 1935, [vii], 20, 964— 971).—Specimens of use and nomenclature of the alternating axis, regarded electro-deposited Ni differing in hardness and initial as a single symmetry operation, in point- and space- brightness have been examined. Brightness is group theory. The international point-group symbols associated with the selective orientation of the metal arc tabulated with the other notations in use. grains, and hardness with the degree of diffusion B. W. It. of the X-ray diffraction spectra. The grain size has Advantages of employing four-index notation been estimated from the broadening of the spectral for crystals of rhombohedral symmetry. H. lines for a series of deposits of known hardness. U ngem acH (Z. Krist., 1935,91,97— 113).—The reasons T. G. P. for preferring the Bravais to the Miller system for X-Ray examination of lattice distortion in crystallographic calculation and description are given. copper and nickel powders. G. W. B r in d l e y B. W. R. and F. W. Spiers (Phil. Mag., 1935, [vii], 20, 882— Growth of metal crystals in metal vapour. 893; cf. A., 1935, 150).—Thescattering factors IV. M. Str a u m a n is (Z. physikal. Chem., 1935, for Cu Ka. radiation of finelyfiled Cu and Ni are B, 30, 132— 138; cf. A., 1934, 946).—Experiments < those of chemically prepared powders. The have been made on the sublimation of To and So diminution increases with the order of the spectrum. in II2 and the equilibrium crystal forms determined. The average displacements due to lattice distortion The results do not wholly agree with Stranski’s caused by filing are 0-106 A. for Cu and 0-083 A. for theory of homopolar crystal growth. R. C. Ni, and are explicable if distortion is a random dis X-Ray diffraction in solutions. J. A. Prins placement of atoms from the points of the undistorted and R. F o n t e yn e (Physica, 1935, 2, 1016— 1028; lattice. Scattering factors for the (200) reflexions cf. A., 1935, 931).— “ Superarrangement ” of the indicate, however, that distortion is not entirely cations is present with ThCL, U 02C12, La(N03)3, random. T. G. P. Cd(N03)2, Zn(N03)2, Ni(N03)2, ZnCl2, Znf2, aind Discontinuous variation in the diffusion of NiCl2; it is probable with the multivalcnt anions of X-rays with the angle of diffusion. J. L a v a l Na2W04, Na2Mo04, H2PtCl6, HIO,„ HC10,„ and H2S04. (Compt. rend., 1935, 201, 889— 891).—For a beam of No such arrangement is found in univalent cations. X-rays of X incident at an angle
Dimorphism of trinitroresorcinol, bromo- Crystal structure of potassium persulphate, benzhydrazine, and benzaldehyde-p-nitrophenyl- K 2S20 8. R. C. K e e n (Z. Krist., 1935, 9 1 , 129— hydrazone. R. F ischer and A. K ofler (Mikro- 135).— The cell is triclinic, a0 5-10, b0 6-83, c0 5-40 A., chem., 1935, 19, 38— 46).—The following stable a 106° 54', (3 90° 10', y 102° 35', space-group C\. At. (s) and metastable (ms) forms are obtained on parameters are found from intensity measurements. vac. sublimation. Trinitroresorcinol: (s), m.p. 177°, B. W. R. monoclinic prisms of high optic axial angle; (ms), Crystallography of the copper-pyridine-sac- m.p. 165-5°, trigonal prisms, uniaxial and optically charin complex. J. B e in t e m a , P. T erpstra, and negative. “ Bromobenzhydrazine ” : (s), m.p. 165°, J. J. d e V rieze (Pharm. Weekblad, 1935, 7 2 , 1287— rectangular monoclinic prisms with high double 1294).— Cu(C5H5N,H20,CtH503NS)2 (A., 1933, 732) refraction; (ms) monoclinic plates, m.p. 159°. forms rhombic bipyramidal crystals with 4 mols. in Benzaldehyde-p-nitrophenylhydrazone : (s), stout the unit cell of dimensions a 9-50, b 21-57, c 13-16 A., monoclinic rods, m.p. 261°; (ms), thin ill-formed space-group VI0. Full crystallographic data are monoclinic crystals, m.p. 234— 236°. J. S. A. given and the orientation of the constituent mols. is discussed. D. R. D. Silicon disulpbide, a fibrous inorganic com pound with chain molecules. E. Zin t l and K. Structure of natural wollastonite. M. B arnicic L oosen (Z. physikal. Chem., 1935, 17 4 , 301— 311).— (Naturwiss., 1935, 23 , 770—771).—X-Ray methods In respect of the character of the constituent units give monoclinic symmetry for wollastonite (a 15-33, of its lattice SiS2 is intermediate between the mols. b 7-28, c 7-07 A.; a=y==90°, ¡3 95°24'30"). The of the mol. lattice of C02 and the three-dimensional unit cell contains 12 (Ca0,Si02). It does not possess macromols. of Si02 in quartz. It forms on sublim a chain structure, but has Si309 rings. A. J. M. ation flexible fibres, which consist of one-dimensional Crystal structure of hexagonal silver iodide. macromols. oriented parallel to each other. The L. H elmh olz (J. Chem. Physics, 1935,3, 740—747).— crystals are rhombic and the probable space-group is Hexagonal Agl has been examined by powder, Laue, V f. R. C. and oscillation methods. At —180° the structure Orthonitric acid, H 3N 0 4. E. Z in t l and W. is essentially that of wurtzite with the ideal parameter H a u c k e (Z. physikal. Chem., 1935, 17 4 , 312— 316).— val., whilst at room temp, the Ag atoms appear to Comparison of the powder diagram of HN03,H20 be distributed at random among four positions with those of the five low-pressure modifications of tetrahedrally surrounding the ideal position. On the NH4N03 and that of H3P04 makes it appear not basis of these structures an explanation of some of improbable that HN03,H,0 is orthonitric acid. the peculiarities of Agl is offered. F. L. U. R. C. Crystal structure of silver azide. M. B assier e Crystal growth of the alkali halides. Z. (Compt. rend., 1935, 2 0 1 , 735— 737).—The crystals G yuiai (Z. Krist., 1935, 9 1 , 142— 153).—Crystallis are ortliorhombic (a 5-58, b 5-93, c 6-04, all rh 0 03 A .; ation from conc. solution, vapour, and melt of NaCl 4 mols. in unit cell; space-group F“ ). The crystal and KC1 is studied microscopically, and the chief is built up from Ag and N3 ions. The N3 group is directions of growth from the nucleus are described. linear, the N -N distance being l-18±0-04 A., as in B. W. R. other azides. H. J. E. Crystal structure of [Rh(NH3)5Cl]Cl2. C. D. Molecular structure of di-iodoethane. Iodine W est (Z. Krist., 1935, 9 1 , 181— 186).—This typical bond resonance and molecular structure of di- member of the isomorphous ortliorhombic pentam- io do ethylene. Molecular packing in their crystal mines [R(NH3)5X]Y 2 has a0 13-32, b0 6-7-1, c0 10-42 A., lattices. H. P. K lug (J. Chem. Physics, 1935, 3, space-group i’“ . The 16 necessary parameters are 747— 753).—Distances between the I atoms of (CH2I)2 determined, and the structure is compared with and of s-ira«s-C2H2I2 in mol. models predicted that of the hexammines R(NH3)6Y2. B. W. R. theoretically agree well with these distances within Structure of green basic cobalt bromide. W. the crystal cells as given by X-ray data (A., 1935, F eitk n ec h t and W. L otmar (Z. Krist., 1935, 91, 1195). These models, in conjunction with Mack’s 136— 141).—The three isomorphous basic compounds, concept of the at. domain radius in crystals, lead basic Zn bromide III, green Co bromide and iodide, to a picture of mol. packing which agrees with observed are investigated by X-rays. The existence of physical properties of the crystals. F. L. U. regular layers of pure hydroxide groups at intervals of Molecular map of resorcinol. J. M. R obertson 8-2 A. is established; the intervening material is (Nature, 1935, 1 3 6 , 755—756).—The electron density randomly arranged, and its origin and relations are map obtained by a quant. X-ray analysis of resorcinol discussed. B. W. R. (I) is reproduced. The complete structure is described. Crystal structure of nickel sulphate hepta- OH belonging to adjacent (I) mols. approach to within hydrate, NiS04,7H20. C. A. B eevers and C. M. 2-66 A., indicating the existence of a strong (OH) Sch wartz (Z. Ivrist., 1935, 9 1 , 157— 169).—The linking or secondary valency force between mols. at. parameters of the ortliorhombic variety have been L. S. T. determined, using Patterson’s method for the location Crystal structure of pyrene. J. D iiar and A. C. of Ni and S and a double Fourier analysis for the Gu h a (Z. Krist., 1935, 9 1 , 123— 128).—Pyrene is remaining parameters. 6 H20 surround Ni forming monoclinic prismatic, a0 13-74, b0 9-22, c0 8-45 A., an almost octahedral group. The structure is com (3 1021°, 4 mols. in cell, space-group C^. Tentative pared with that of NiS04,6H20. B. W. R. mol. orientations are suggested. B. W. R. in (M GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 17
An orthorhombic crystalline modification of films are rings. Stretched films gave points generally 1 :2 :5 :6-dibenzanthracene. K. S. K r is h n a n explicable on Susich’s X-ray structure (A., 1928, and S. B anerjee (Z. Krist., 1935, 91, 170— 172).— 1186), but certain modifications are necessary. This substance is normally monoclinic; an ortho Unstretched chloroprene gave spots of an ortho rhombic bipyramidal form occurs occasionally when rhombic u n it: a, 10-93, b 8-23 A. (for crepe a 12-23, cryst. from EtOAc. M.p. and d are nearly the same b 8-3 A.). No spots were obtained with Na-butadiene as for the normal form. B. W. R. rubber. T. G. P. Magnetic anisotropy and crystal structure of Permanent polarisation of Rochelle salt. H. 1 :2 :5 :6-dibenzanthracene. K. S. K r is h n a n M ü ller (Physical Rev., 1934, [ii], 45, 736; cf. A., and S. B an er jee (Z. Krist., 1935, 91, 173— 180).— 1935, 288). L. S. T. Measurement of the anisotropy and the absolute susceptibility for very small crystals (0 02 mg.) is Dielectric properties of Rochelle salt. J. E. F orbes and H. M ü ller (Physical Rev., 1934, [ii], described. Measurements on botli monoclinic and 45, 736—737; cf. A., 1935, 228). L. S. T. orthorhombic dibenzanthracene enable the directions of the lengths of the mols. and the angles of tilt of the Magnetisation of imperfect crystals. F. B it mol. planes to be determined. B. W. R. ter (Physical Rev., 1934, [ii], 45, 742; cf. A., 1934, Thread diagram for polyvinyl alcohol. E. 945). L. S. T. H alle and W. H ofm ann (Naturwiss., 1935, 23, Dependence of internal friction on magnetis 770).—Polyvinyl alcohol gives a typical thread diagram ation in iron. W. T. Cooiie (Physical Rev., 1934, similar to that of a natural fibre; identity period in [ii], 45, 742). L. S. T. the direction of the thread axis is 2-57±6-02 A. It Approach to the theoretical magnetisation is composed of crystallites which readily arrange curve. T. D. Y e n s e n (Physical Rev., 1934, [ii], themselves parallel on stretching, especially when 45, 743).—The curves reproduced for Fe, Fe-Si warmed. " A. J. M. and Fe-Ni alloys show that the approach to the theo X-Ray structure investigations on elastic retical curves, based on the Langevin-Weiss theory, tissue with special reference to extension and depends not only on lattice orientation, but also shrinkage. H. K o lpak (Kolloid-Z., 1935, 73, on purity of material. L. S. T. 129— 142).—The results previously reported (A., Separation of magnetic viscosity and eddy- 1934, 244) are confirmed and extended, and discussed current lag. A. V. M it k e v it sc h (Compt. rend. in relation to current theories of valency chain struc Acad. Sei. U.S.S.R., 1935, 3, 209— 211).—Eddy- tures. E. S. H. current lags can be detected through the sp. influence Electron diffraction b y gases.' L. R. M a x w e l l , of previous changes in magnetic induction. C. W. G. S. B. H e n d r ick s, and V. M.M o sley (J. Chem. Rotatory power of quartz for rays perpendicu Physics, 1935, 3, 699—709; cf. A., 1934, 17, 835).— lar to the optic axis and its dispersion between The O O -C valency angle in 4 : 4'-di-iododiphenyl 2537 and 5780 A. G. B r u h a t and L. W e i l (Compt. ether has been found to be 118±3° by the electron rend., 1935, 201, 887— 889).—The ratio of the rotatory diffraction method. This is > the O valency angle for . powers of quartz for rays perpendicular and parallel simpler mols. such as F20, C120, and Me20. By the to the optic axis is (mean) O-Sd^O-Ol. The dispersion same method P and As mols. have been shown to is the same for both rays. R. S. B. have regular tetrahedral structure, the at. separations being respectively 2-21 and 2-44 A. F. L. U. Quantum mechanical investigation of the cohesive forces of metallic copper. K. F uchs Electron diffraction pattern from the natural (Proc. Roy. Soc., 1935, A, 151, 585— 602).—The wave (111) face of diamond. R. B e e c h in g (Phil. Mag., 1935, [vii], 20, S41—855).—Intensity measurements functions and energies of the 4s electrons of Cu have been calc, by a method analogous to that used by on the pattern were made, relative intensities of the Wigner and Seitz for Na (A., 1933, 660). The right main spots were determined, and tolerances in the Bragg angles were compared with the widths of the order of magnitude is obtained for the lattice const, and for the heat of vaporisation, but to obtain the corresponding Kikuchi lines (cf. A., 1935, 570). correct compressibility, the interaction between the The inner potential was measured, and various ions in the lattice due to the overlapping of the closed qual. observations were made. A case where a spot shells must be considered. For Cu, the face-centred has been partly suppressed by Kikuchi lines is recorded. N. M. B. structure will have lower energy than the body- centred, but for Na the two structures have almost “ Extra " electron diffraction rings. (A) L. H. equal energies. Thus the calculations show why Ger m e r . (B) G. I. F inch (Nature, 1935, 136, 832).— Cu has a close-packed structure, but fail to show why (a ) Calculations show that the exit face theory (A., Na should have one cubic structure rather than the 1935, 287) of the origin of these rings is untenable. other. L. L. B. (b) Germer’s calculations agree with the view that Effect of photochemical colouring on the ex the “ extra ” rings are due to surface contamination tension and strength limits of single crystals of {ibid., 1452). L. S. T. rock-salt. M. N. P odaschevski (Physikal. Z. Electron diffraction in rubber films. K. I. Sovietunion, 1935, 8, 81— 92).—The extension and K rilov (Physikal. Z. Sovietunion, 1935, 8, 136— strength limits of single NaCl crystals are increased 152).—The diffraction patterns from crepe rubber by photochemical coloration, the result being the 18 BRITISH CHEMICAL ABSTRACTS.— A. Ill (e,/), IV [b) same whether the coloration is produced by X-rays Change in resistance of single crystals of bis or ultra-violet light. A. J. M. muth in a magnetic field at low temperatures. W. J. de H aas , J. W. B lom , and L. S ch u b n ik o v Plastic properties of silver chloride and sod (Physica, 1935, 2, 907— 914; cf. A., 1930, 1102, ium chloride single crystals. A. V. St e p a n o v 1353).—The influence of magnetic fields (4000—22,000 (Physikal. Z. Sovietunion, 1935, 8, 25— 40).—The gauss) on the resistance of Bi single crystals is greater plastic properties of single crystals of AgCl and NaCl at 1-35° and 4-22° abs. than at 14-15° abs. are compared to show that they are connected with T. G. P. the polarisation effect of the lattice. Single crystals Magneto-resistance of bismuth films at low of AgCl show a high degree of plasticity and metallic temperature. C. T. L a n e (Physical Rev., 1934, properties in general. AgCl which has been ex [ii], 45, 733—744).—The magneto-resistance of films posed to light is not so plastic. The elastic limit 0-1— 4 ji thick has been measured at —180° and 20°. along the cubic axis of a crystal tempered at 350° There is a change in direction of the [A if-180./A li20.] - was 70 g. per sq. mm. Deformation on extension is thickness curve at a thickness < 1 ¡i, and the magneto- similar to that of a metal belonging to the cubic system. resistance approaches temp, independence as the The elastic limits for crystals of AgCl and NaCl are similar. The deformation work for NaCl is > for film thickness approaches zero. L. S. T. AgCl. At room temp. AgCl is more plastic than Resistance of single crystals of gallium in a NaCl. A. J. M. magnetic field. III. W. J. d e H a a s and J. W. Tension coefficient of [electrical] resistance of B lom (Physica, 1935, 2, 952— 958; cf. A., 1934, the single hexagonal crystals, zinc and cad 588).— Change of resistance of single crystals of Ga with the pseudo-tetragonal axis parallel to the m ium . M. A l l e n (Physical Rev., 1934, [ii], 45,757). L. S. T. length of the wire in a magnetic field perpendicular to Allotropy of calcium. M. C. N e u b e r g b r (Z. the wire has been measured at liquid He temp. At Eloktrochem., 1935, 41, 790).—Published work is 1-35° and 4-22° abs. the influence of the magnetic considered. E. S. H. field is independent of temp., but > at liquid H2 temp. T. G. P. Thermodynamics of stationary systems. I. Electrical resistance of tantalum wires charged The thermo-element. II. The diffusion ele with hydrogen. A. Sie v e r ts and H. B r u n in g (Z. ment. B. B r u zs (Proc. Roy. Soc., 1935, A, 151, physikal. Chem., 1935, 174, 365— 369).—For H , 640— 651, 651— 665).—I. A quant, application of the pressures, p, up to ~ 1 atm., the amount sorbed first and second laws of thermodynamics to stationary by Ta at 500° and 600° is cc a/p ; at 400° there are systems is connected with an introduction of certain deviations from this relation. The resulting increase arbitrary assumptions, of which two are distinguished. in resistance is at 500° and 600° cc \/p, whilst at 400° The first is the “ non-interaction ” assumption of this is approx. Comparison of these results with Kolvin, leading to the well-known relations connecting similar data for the system Pd-H 2 indicates that the the Seebeck, Peltier, and Thomson coeffs. The sorption has not involved the formation of a new second postulates the existence of a const, ratio phase. B. C. between the Joule and the polarisation effects, and leads to a new relationship between the Seebeck coeff. Electrical conductance of colloidal solutions and the thermal and electrical conductivities of the at high frequencies. H. J. Curtis and H. F rtcke material. (Physical Rev., 1935, [ii], 48, 775; cf. ibid., 47, 974).— II. The above treatment of the thermo-element is Suspensions of powdered glass and kaolin, and colloidal extended to the problem of the diffusion element, and A1203, V205, starch, and. gelatin showed a marked it is shown that a close correspondence exists between increase in conductance at frequencies > 16,000 kc. thermo- and diffusion element. The problem of per sec. The phenomenon is attributed to a form of the diffusion element reduces to a knowledge of the Debye-Ealkenhagen effect. N. M. B. diffusion and electrical conductivities. L. L. B. Diamagnetism of the tervalent bismuth ion. Influence of a magnetic field on the high-fre S; S. B h atn ag ar and B. S. B a h l (Current Sci., 1935, quency conductivity of an ionised medium. E. V. 4, 234).—The val. calc, for B i"‘ is in agreement with A ppleto n and D. B. B oohariwalla (Proc. Physical the experimental val. (A., 1935, 1453). From Kido’s Soc., 1935, 47, 107-4—1084; cf. ibid., 1932, 44, 246).— work the predicted difference between the diamagnet The relation between the transverse high-frequency ism of Bi and B i'" should be of the order of 12-87, conductivity and the pressure of ionised air under the as is obtained. W. R. A. influence of an imposed magnetic field was investigated. Theory of dispersion of magnetic permeability The pressure for max. conductivity varies with field in ferro-magnetic bodies. L. L a n d a u and E. intensity. The relation of results to ionospheric L ifschitz (Physikal. L. Sovietunion, 1935, 8, 153—• conductivity is discussed. N. M. B. 169).—The distribution of magnetic moments in a Change in resistance of bismuth single crystals ferromagnetic crystal is investigated. The crystal at the m .p. J. H. S c h r o e d e r (Proc. Iowa Acad. consists of elementary layers magnetised to saturation. Sci., 1934, 41, 254).—Measurements of resistance T. G. P. for various crystal orientations are recorded up to Ionic diamagnetism in the solid state and in temp. > the m.p. The change from solid to liquid did solution. H. F a h l e n b r a c h (Ann. Physik, 1935, not occur suddenly at the m.p., but began 1-5° < and [v], 24, 485— 488).—The results of Frivold et al. continued 1-5° > m.p. Ch . A bs. (e) (A., 1935, 1197) on the susceptibility of solutions may IV (6, d) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 19
be explained by the work of Cabrera et ad. (A., 1933, than in air and is diminished by addition of H20 766, 1002, 1233). The results of Flordahl et al. vapour. J. W. S.” (A., 1935, 1197) are also discussed. A. J. M. Collision excitation of intramolecular vibra Magnetic moment of the manganic ion. L. C. tions in gases and gas mixtures studied by Jackson (Proe. Physical Soc., 1935, 47, 1029— 1031). sound dispersion measurements. III. Mea —The magnetic susceptibility of Mnm acetylacetone surements with nitrous oxide. A. E u c k e n and was measured for a powdered specimen in the range H. Jaaoks (Z. physikal. Chem., 1935, B, 30, 85— 292— 16-9° abs. The law x (T + 5-5)=const, is 112; cf. A., 1935, 155).—From determinations of obeyed down to about 75° abs., below which the sus the X of ultrasonic waves in pure N20 and mixtures ceptibility increases more rapidly. The calc, mag of N20 with foreign gases the variation of collision neton no. of the Mn+++ ion is 4-98, in agreement with efficiency with temp, and pressure at —60° to 200° the Bose-Stoner theory. N. M. B. and 0-3— 1 atm. has been measured. The deactivation of N20 mols. by either N20 or NH3 mols. occurs by Diamagnetic study of structure. F. W. Gr a y binary collisions. The difference between physical and J. H. Cru ic k sh an k (Trans. Faraday Soc., 1935, and chemical collision excitation of mol. vibration 31, 1491— 1510).— A new method of treating at. is discussed in relation to the collision efficiency in and mol. diamagnetic data is described, whereby presence of H2, D2, and He. Measurements have been deviations of the observed diamagnetism of mols. made with C02 mixed with a little H20 to determine from that calc, from the diamagnetism of free atoms the effect of H20 on the vibrational excitation of C02. may be used to establish the modes of linking of The reported dispersion of the rotational heat of atoms in mols. Details are worked out for CGHG, H2 in the ultrasonic region (A., 1934, 588) could not C10H8, -C02H, H20, and H202. F. L. U. be confirmed (cf. ibid., 950). R. C. Effect of crystalline fields on the magnetic Experiments at very low temperatures ob susceptibilities of Sm+++ and Eu+++, and the tained by the magnetic method. II. New heat capacity of S m ++ + . (Miss) A. F r a n k (Physi superconductors. N. K urti and F. Sim on (Proc. cal Rev., 1935, [ii], 48, 765—771; cf. A., 1932, 217).— Roy. Soc., 1935, A, 151, 610—623; cf. A., 1935, Mathematical. The temp, variation of the para 290).—The experimental technique of cooling down magnetic susceptibility of Sm+ + + is calc, on the as additional substances with the paramagnetic salts sumption that the ion is subject to a cryst. field which by applying the magnetic method (loc. cit.) is dis can be represented by a potential expression. Eu cussed. The measurement of the magnetic behaviour behaves, in contrast, like the free ion even in presence of a metal can be used to detect superconductivity, of a cryst. field. The contribution to the heat capacity and to find the transition point and the threshold of Sm+++ at various temp, due to the excited levels vals. . Cd, Zr, and Hf become superconducting in is calc. Results are compared with available ex the new temp, region, the normal transition points perimental data. N .M .B . • being 0-54°, 0-70°, and 0-35° abs. Au, Cu, Bi, Mg, Magnetic susceptibility of mixtures of oxides and Ge did not become superconducting down to of the rare earths : mixtures of neodymium with 0 05° abs. L. L . B. praseodymium and of neodymium with samar ium [oxides]. I . L. M azza (Atti R. Accad. Lincei, Theory of anomalies in specific heats. L. 1935, [vi], 21, 813— 818).—The mixtures of the oxides L a n d a u (Physikal. Z. Sovietunion, 1935, 8,113— 118). were obtained by calcining the co-pptd. oxalates. T. G. P. In the system Sm203-N d203, the magnetic susceptibi Characteristic point of pure substances. F. lity follows the simple additive law. In the system Mich aud (J. Chim. phys., 1935, 32, 527— 540).— PrG0n -N d 203, this could not be established, but the The characteristic point of a solid body is defined as deviations are attributed to mutual reduction and the point of contact of the tangent passing through oxidation of these oxides during the calcining. For the origin to the curve giving at. or mol. heat capacity Nd203 k=3-10x 10~7; for Sm203, 6-1 xlO -6; and for as a function of abs. temp. The co-ordinates of this PrGOn , 1-56 xlO -7. D. R. D. point define the characteristic temp, and characteristic heat capacity. The point with tho same abscissa Propagation of elastic waves in ice. I. M. on the curve at. or mol. entropy/abs. temp, is the E w in g , A. P. Cr a r y , and A. M. T h o r n e , jun. II. characteristic entropy. The characteristic point plays A. P. Cr a r y and M. E w in g (Physical Rev., 1934, a part in comparisons of heat properties of solids [ii], 45, 749). L. S. T. analogous to that of the crit. point in comparisons of Propagation of sound and supersonic waves in thermo-elastic properties of fluids. The curves ¿’/temp, for certain substances are approx. super- gases. H. L. Sa x t o n (Physical Rev., 1934, [ii], 45, 749).—The derivation of equations for velocity and posable by a simple translation of the co-ordinates. the absorption const, is outlined. L. S. T. The characteristic entropies of pure substances of the same atomicity are approx. equal amongst Vibrations of air and carbon dioxide in closed themselves, diat. and triat. mols. having twice and bulb resonators. K. V oeokler (Ann. Physik, three times the characteristic entropy of a normal 1935, [v], 24, 361—376).— The frequency of vibration metal. A more rigorous comparison is effected by is in accord with the theory of Rayleigh and Thiesen, plotting log heat capacity/entropy. Such curves and the damping is of the order oi magnitude pre are a criterion of the existence of alio tropic changes. dicted by the theory. The damping is less in C02 Anomalies are discussed. T. G. P. 20 BRITISH CHEMICAL ABSTRACTS.— A. IV (d,f)
Specific heats of solid substances at higher A o y a m a and E. K a n d a (Bull. Chem. Soc. Japan, temperatures. XX. Molecular heats of the 1935, 10, 472— 481).—Existing vals. for the b.p. alloys of palladium and antimony in comparison of 0 2 and N2 and the sublimation point of C02 are with the sum of the atomic heats of the free ele confirmed by means of the H thermometer described. ments. XXI. Molecular heats of the compound Temp, are determined to within ¿0-036° at 0° and PtSb2 in comparison with the sum of the atomic ±0-025° at -200°. J. G. A. G. heats" of the free composing elements. XXII. Melting curve of oxygen to 170 kg. per sq. cm- Molecular heats of the supposed binary com J. H. C. L ism a n and W. H. K eesom (Physica, 1935, pounds of copper and palladium. T. J. P oppema 2, 901— 906; cf. A., 1935, 1197).—Points on the and F. M. J aeger (Proc. K. Akad. Wetenscli. Amster melting curve of 0 2 have been determined up to dam., 1935, 38, 822— 833, 833—836, 836—841; cf. 167-7 kg. per sq. cm. and 56-25° abs. Extrapolation A., 1935, 924).—X X . The sp. heats of Sb measured gives the triple point 54-32(5)° abs. The density under different conditions are not quite const., but of solid y -0 2 at the triple point calc, from Clapeyron’s no transformation point could be observed at 414°. equation is 1-37(2). T. G. P. At. heat data between 100° and 600° arc tabulated and sp. heats of PdSb, PdSb2, and Pd3Sb over a range Polarisation effects in thallous fluoride. E. of temp, are given. The difference between the mol. H ayeic (Z: anorg. Chem., 1935, 225, 47— 48).— T1F heats G'v and the sum of the at. heats £ is small, but has b.p. 655°±10°, d f 8-36. Attempts to prepare increases with rise of temp, and % of Pd. The change a subfluoride analogous to Ag2F were unsuccessful. P-Pd3Sb -> a-Pd3Sb — 4800 g.-cal. per g. occurs at 950°. F. L. U. X X I. Sp. heat data are given for PtSb2 up to 600°. Transition points of hexachloroethane. E. H. C'„ — £ increases from —8% of C'v at 200° to —19% W ie b e n g a (Z. anorg. Chem., 1935, 225, 38— 42).— at 600°. Transition temp, of C2C16, determined both thermally X X II. Alloys of the composition CuPd and Cu3Pd and dilatometrically, are : rhombic — triclinic 43-6°, have been prepared and the sp. heats determined triclinic — cubic 71-1°. The transition reported at up to 900°. C'p—S is small, and it is concluded, 125° does not occur. The rates of transformation, in conjunction with X-ray measurements, that the although slow, are finite except at the actual transition alloys are chiefly composed of solid solutions. temp. F. L. U. R. S. New form of thermodynamic diagrams. K. Specific heat of AgoHgl,, in relation to the P a v l o v and A. P iv o v a r o v a (Chimstr., 1935, 7, crystal structure. J. A. A. K etelaa r (Z. physikal. 33—37).—A graphical method is described. Ckem., 1935, B, 30, 53— 60; cf. A., 1934, 1056).— Ch . A b s . (e) The sp. heat has been measured at 20— 100°. From Influence of the degree of dispersion on 37° it rises anomalously, and immediately below the physico-chemical constants. IV. E. Co h e n and transition point at 50° reaches three times the normal J. J. A. B le k k in g ii (Proc. K. Akad. Wetenscli. val., to which it falls discontinuously at transition. Amsterdam, 1935, 38, 842— 849).— Crystals of KCl The heat of transition is 0-32 for the homogeneous, of 0-1, 0-5, and 5 mm. mean cross-section have been and 113 g.-cal. per g. for the heterogeneous, part. prepared. d=T9S91 ±0-0004 in each case. R. S. The explanation of the sp. heat anomaly is that with rise in temp, even below the transition point there is International Bureau of Physico-Chemical increasing misplacing of the metal atoms (cf. ibid., Standards. VII. Physical constants of twenty 947). An “ averaged structure ” may be interpreted organic compounds. J. T im m er m an s and (Mm e .) either as a statistical distribution of the atoms over H ennatjt-R oland (J. Chim. phys., 1935, 32, 501— the available lattice points or as the result of repeated 526; cf. A., 1934, 480).—The following data for twinning (cf. ibid., 16); X-ray examination affords b.p./760 mm., f.p., and d]0 have been determined : no means of decision. With a-Ag2HgI4, however, ii-CjH!, 36-10°, -129-1°, 0-63114; w-CvH1G 98-35°, the high electrical conductivity and considerable -9 0 °, 0-68785; (CHvOH)o 197-85°, -12-6°, 1-11710, heat of transition |3 a decide for the former alter glycerol — , “ — , 1-26443; Et2S 92-10°, native. R. C. -103-3°, 0-84102; HCO-NH2 — , 2-55°, 1-13756; Specific heat of iron nitrides. S. S ato h (Sci. PhF 84-85°, -41-9°, 1-03091, CHJPhCl 179-35°, Papers Inst. Phys. Chem. Res. Tokyo, 1935, 28, -39-2°, 1-10426; CH„Ph-OH 205-45°, -15-3°, 135— 139; cf. A., 1933, 27).—The sp. heat of a series 1-04927; anisole 153-80°, -37-5°, 0-99858; COPhMe of Fe-N alloys is a max. at 9-7% N. This is discussed 202-00°. 19-6°, 1-03236. The data include the re in relation to the Fe-N equilibrium diagram. R. S. lations between b.p. and pressure, coeffs. of dilatation, Evaporation as mechanical subdivision to refractive indices, viscosity coeffs., and surface tensions. The crit. solution temp, of w-C5H10 in P1iN 0 2 is 24-5°. m olecules. P. V. Z olotarev (Trans. Inst. Chem. Tech. Ivanovo, 1935, 50— 53).— Mathematical. The Earlier data are tabulated. T. G. P. heat of evaporation of a given substance is shown to Isotherms of methane between 0° and 150° and be oc the work expended in breaking it down to its densities 19 and 53 Amagat (pressures between constituent mols. Formulae are derived for calculat 20 and 80 atm.). A. Mic h els and G. W. N e d e r - ing Avogadro’s const, for different types of mols., bragt (Physica, 1935, 2, 1000— 1002; cf. A., 1934, and for solids and liquids. R. T. 837).—Isotherms, of pure methane (b.p. const, to Determination of fixed points at low temper 0-03°) have been determined at 25° intervals between atures with a hydrogen thermometer. S. 0° and 150°. T. G. P. IV (/, h) GENERAL, PHYSICAL, AND INOHGANIC CHEMISTRY. 21
Acetylmethylcarbinol. J. R. P o u n d and A. M. Cs (28-8°) 1-900 c.c. per g.-atom. These vals, were W ilson (J. Physical Chem., 1935, 39,1135— 1138).— obtained by measuring the increased upthrust of a The v.p. of acetoin between 0° and the b.p. (144°) given wt. of metal at the m.p. in petroleum or has been determined and the polymerisation has vaseline oil by means of a hydrostatic balance. The been studied by measurement of n and d. Crystall- vals, for Rb and Cs were confirmed by measurements ographic and thermal data relating to the polymeride of the m.p. at pressures from 1 to 135 atm. The are given. R. S. change in vol. on fusion of elements in relation to their Difference in vapour pressures of ortho- and position in the periodic classification is discussed. poro-deuterium. P. G. B r ic k w e d d e , R. B. S cott, 0. J. W. Aggregative states. An empirical law. E. I. and H. S. T a ylo r (J. Chem. Physics, 1935, 3, 653— 660; cf. A., 1934, 1164).—The differences in v.p. A ciiu m o v (J. Gen. Chem. Russ., 1935, 5, 843— S47).— of the mixture of ortho- and para-T>2 in equilibrium The empirical expression ¡3(Tb—T^)—C, where p is at 20-4° abs. and of the normal mixture have been the coeff. of expansion of a liquid between the m.p. determined between 15° and 20-4 abs. The speed of Tk and the b.p. Tb, and G is a const., is shown to hold the uncatalysed change for normal liquid D2 is about for a no. of org. liquids. R. T. 0-001 of that for H2. F. L. U. Thermal expansion of cast and rolled zinc. H. G. J ones (Proc. Physical Soc., 1935, 47, 1117— Vapour pressures of neon of different isotopic 1128).—Data tabulated and plotted for steady and compositions. W. H . K eesom and J. H a a n t je s continuously rising temp, show marked differences (Proc. K. Akad. Wetensch. Amsterdam, 1935, 38, 810).—The differences in v.p. of Ne of five different in the coefi's. for cast and rolled Zn. On rolling, the random orientation of crystals in the cast Zn isotopic compositions (at. wt. 20-043—21-157) have been determined. At const, temp., v.p. is a linear is broken up, and most of the long axes are set function of at. wt. The divergence between the perpendicular to the plane of rolling, but no change is theoretical and observed dependence on temp, of produced in the vol. coeff. For small crystals the continuous expansion is small, but increases with the l°g P20A°g P'x f°r solid state is attributed to a difference between the potential energy of Ne20 and size of the crystals. Discontinuities in the continuous expansion are traced to the long axis. N. M. B. Ne22 and to variation in the zero-point energy. It is concluded, from data for the liquid state, that the Linear thermal expansion of sodium tungstate sp. heat of Ne20 is > that of Ne22. The triple point between 20° and 600°. J. B. A u st in and R. H. H. of Ne22 is 0-134° > that of Ne20 and the melting P ie r c e , jun. (J. Chem. Physics, 1935, 3, 683—686; heat of Ne22 is the greater by 1-18 g.-cal. per mol. cf. A., 1933, 342).—The results, obtained by an R. S. interiorometric method, show that at atm. pressure Measurement of v.p. of mercury from absorp Na2W04 is trimorphous. The transition III — II tion of resonance radiation. H. v o n H alb a n , jun. occurs at 585°, and II — I at a slightly lower temp., (Helv. Pliys. Acta, 1934, 7, 856—875; Chem. Zentr., II being stable over a very short range. F. L. U. 1935, i, 1980).—The v.p. of Hg at —18° and —53-4° Thermal stability of the lower atmosphere. is calc, from abs. measurements of the absorption A. L. H ales (Proc. ltoy. Soc., 1935, A , 151, 624— of the 2537 A. resonance line by saturated Hg vapour 640).—Mathematical. Equations for the conduction at those temp. The accuracy is independent of the of heat by turbulence, and for the stability of a v.p. and unaffected by other gases at pressures below compressible fluid when the hotter fluid is below, those causing broadening of the absorption line. are deduced. Super-adiabatic lapse rates are possible J. S. A. in limited regions of the atm. L. L. B. Vapour pressure of metals and their velocity of vaporisation in a vacuum. J. A. M. van Thermal conductivity law in moving media. Derivation of a molecular kinetic theory of L iem pt (Rec. trav. chim., 1935, 54, 847— 852).— Formula} are derived relating the velocity of sublim thermal conductivity with an investigation of ation in a vac., v.p., and heat of sublimation with the the limits of the Fourier method. M. L an g (Ann. at. wt., m.p., and at. vol. of the metal and the temp. Pliysik, 1935, [v], 24, 393— 408).—Theoretical. The equations agree with experiment. J. W. S. A. J. M. Viscosity of liquid phosphorus. A. N. Cam p Vapour pressure of zinc, lead, cadmium, bell and S. K atz (J. Amer. Chem. Soc., 1935, 57, cuprous, and silver chlorides. D. N . T a r a se n k o v 2051—2055).—Viscosity has been determined between and P. A. K oshm jakov (J. Gen. Chem. Russ., 1935, 20° and 140°. There is evidence of association in 5, 830— 835).—The v.p. have been determined at liquid P below 45°, but no evidence of a change of 516—728°/7-4—723 mm. for ZnCl2, at 650—942°/ viscosity when heated P is suddenly chilled. 4-5—692 mm. for PbCl2, at 618—952°/3—722 mm. E. S. H. for CdCl2, at 632— 1070°/3—216 mm. for Cu2Cl2, Viscosity of liquid methane and ethylene in and at 882— 1120°/3-7— 59 mm. for AgCl. R. T. relation to temperature. N. S. R u d e n k o and Variation of the volume of elements in the act L. V. S ch u bn iko v (Physikal. Z. Sovietunion, 1935, 8, 179— 184).—Measurements have been made be of fusion. I. L. L o sa n a (Gazzetta, 1935, 65, 851—864).—The change in vol. in passing from the tween 90° and 111° abs. for G'H4 and between 110° solid to the liquid state of the alkali metals is found to and 169° abs. for C2H4. T. G. P. be (m.p. given in parentheses) : Li (180-2°) 0-184, Complex viscosity. A. G e m a n t (Trans. Faradav Na (97-7°) 0-512, K (62-1°) 1-072, Rb (38-8°) 1-472, Soc., 1935, 31, 1582— 1590; cf. A., 1935, 1065).— BRITISH CHEMICAL ABSTRACTS. A. IV (h), V (a)
Maxwell’s theory of the behaviour of materials 347). The data for •/) are used to test the validity of exhibiting both viscosity and plasticity is generalised several equations connecting -t) with concn. and developed so as to take account of mol. vibrations. E. S. H. The theory is applied to dielectric losses due to dipole Viscosity of sugar and dextrin solutions con rotation. F. L. U. taining salts. J. H. C. M e r c k e l (Kolloid-Z., 1935, 73, 171— 174).—The influence of Nal, NaBr, NaCNS, Definition and correction of diffusion con NaCl, NaBr03, N aI03, and NaF on the viscosity of stants of gases. J. K u u s in e n (Ann. Physik, 1935, sucrose or dextrin solutions is in the order of their [v], 24, 445—440).—The work of Trautz and Muller lyotropic nos. E. S. H. (A., 1935, 575) is criticised on the ground that a false interpretation of Fick’s law was used. The S-Shaped viscosity curves. M. U sa n o v itsc h Maxwell-Chapman method leads to results identical (J. Gen. Chem. Russ., 1935, 5, 996—1001).— S-Shaped with those obtained by the correct use of Fick’s viscosity-composition curves are obtained in binary law. A. J. M. systems of which one component is associated when this forms an unassociated compound with the other Definitions of diffusion constants. J. K u u s i component. The rule is exemplified by the systems n e n (Ann. Physik, 1935, [v], 24, 447—456).— A PhN02-H2S04 and AsCl3-Et20. R. T. general definition of the diffusion const, of a binary mixture is derived. A. J. M. Concentrated solutions. I. Conductivity, Criticism of certain researches on the physico viscosity, and density of fused NH4Ag(NOa)2 chemical analysis of binary systems. V . F . U st- and of its concentrated solutions. M. S. S k an avi- Grigorieva S c h te rn in K atschkintzev (J. Gen. Chem. Russ., 1935, 5, 892— and E. B. (J. Gen. Chem. 898).—The experimental data given by Terpugov Russ., 1935, 5, 799—806).—The conductivity k of (A., 1933, 354; 1934, 1167) for the systems Et20 - the fused salt rises abruptly at 113°, and then con AsCl3 and -H,SO.}, by Usanovitsch et al. (A., 1934, tinues to increase at a slower rate with rising tem p.; 1167) for Et20-SbBr;i, and by Pushin et al. (A., 1932, 7) falls linearly over the same range. Up to 10% 1197) for C5Hr)N-AcOH do not confirm the conclusions H20 has little effect on k at 100°, but further addition reached by the authors relative to the existence of of H20 leads to a rapid rise in ic to a max. in 75% compounds. In general, systems which exhibit solutions. At 25° a well-defined max. val. of k is deviations from the additive rule for certain properties found for 60% solutions. Composition-d and —/j may follow it for others, and, in particular, max. curves are given for numerous aq. systems at 25°. and min. on curves which represent temp coeffs. of R. T. various properties cannot be accepted as evidence Conductivity and viscosity in the systems of compound formation. R. T. (A) sulphuric acid-nitrobenzene, (B) nitrobenz ene-acetic acid, (c) sulphuric acid-acetic acid. Association and molecular polarisation. V. M. U sanovitsch (J. Gen. Chem. Russ., 1935, 5, 701— Simultaneous formation of double and triple 708, 709—711, 712—718).— (a ) [with G. K ozm ina complexes in dipole association. I. Sa k u r a d a and V. T artakovskaja ]. The conductivity curves (Bull. Inst. Phys. Chem. Res. Japan, 1935,14,1120— (0—30°) have a well-defined min., suggestive of the 1126; cf. A., 1935, 927).—The equilibrium consts. compound 2PhN02,H2S04. The temp, coeff. of con for double and triple dipole association can be calc, ductivity curves have 2 max. and a min., corresponding from dielectric data, and it is concluded that such with 2:1, 1:1, and 1 :2 compounds of PhNO, complexes exist simultaneously in the mixtures and II2S04. The ^-composition curves do not possess CCl4-PhCl, CClj-PliBr, C0H14-PhNO2, and C0Ha- max. or min. quinoline. The heats of association have been calc, (b ) [-with A. T enenbatjm]. The system (20— 80°) from the variation of the equilibrium consts. with is non-conducting, and the composition curves do not temp. R. S. suggest compound formation. The formation of electrolytic solutions when two non-electrolytes are Simultaneous formation of double and triple mixed is ascribed exclusively to compound formation. complexes in dipole association. E. H e r tel and (c) [with A. Naumova]. The temp, coeff. of E. D um ont (Z. physikal. Chem., 1935, B, 30, 149— conductivity-composition curves (0— 30°) suggest 151).— Polemical against Sakurada (A,, 1935, 927). 1 : 1 and 1 :2 compounds. R. T. R. C. Viscosity of sulphuric acid [solutions]. S. D. Viscosity coefficients in the system fused KC1- B e sk o v and O. A. Slizkovskaja (Chimstr., 1935, M gC l2. S. K ar p a tsc h e v and A. Strom berg (J. 7, 32— 33).—Vais, for H2S04 (d 1-38— 1-84) between Gen. Chem. Russ., 1935, 5, 625— 630).—The viscosity 5° and 90° aro recorded. The 7) of H2S04-H 20 isotherms (550— 650°) suggest the compound mixtures does not follow the additive law. MgCl2,2KCl. R. T. Ch . A b s . (e) Viscosity of solutions of salts in methyl alcohol. Chemical composition and optical properties G. J ones and H. J. F o r n w a lt (J. Amer. Chem. Soc., of solutions. I. Quaternary system KCl-NaCl- 1935, 57, 2041—2045).—Determinations of d and rt MgCl2-H20 at 15°. E. I. A oh u m o v and M. P. at 25° have been carried out for solutions of KC1, G o lovkov (J. Gen. Chem. Russ., 1935,5,500— 509).— KBr, I d , and NH4C1 ovor a wide concn. rango in Composition-?!, curves for the above system are of the MoOH. Tho results for d can bo expressed by an same general shape as are those connecting com equation of the form suggested by Root (A., 1933, position with other physical properties. R. T. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 23
Equilibria in liquid mixtures and solutions. hardness increase is less. The elasticity of the alloy IV. B . p. and composition of vapour of solutions with 15% of Be equals that of steel. H. J. E. of carbonyl chloride in dichloroethane and Structure of zinc-cadmium eutectic. M. xylene. V. A. K ir e e v , S. I. K a p l a n , and V. N. Straum anis and N. B rakes (Z. physikal. Chem., Z lobin (J. Appl. Chem. Russ., 1935, 8, 949—951).— 1935, B, 30, 117— 131; cf. A., 1912, ii, 744).—The B.p. and composition of the vapour phase at the b.p. eutectic consists of comparatively coarse fibres which have been determined for 0—35% C0C12 in xylene grow into the melt perpendicularly to the surface of and in C2H4CI2. R. T. cooling and are built up of alternating parallel Fugacity of salts present in boiling solutions. crystal leaflets of Zn and Cd, running lengthwise. P. Z olotarev and J. Ob u d o v sk a ja (Trans. Inst. These leaflets, which are somewhat crumpled, are Chem. Tech. Ivanovo, 1935, 54— 55).—The salt so arranged in the fibres that their wide basal faces content of river-H20 falls from 134-6 to 3-4 mg. per are in contact and the digonal axes of the first position litre after one distillation; the same salts are present make an angle of 0—5° with the fibre axis. The in the distillate as were originally present. The leaflets are thinner the more rapid is the cooling. phenomenon is ascribed to sputtering at the heated It is inferred that the structure of eutectics is deter walls of the vessol abovo the surface of the liquid, mined primarily by the crystallophysical properties leading to the formation of an aerosol of the salts. of the components, surface tension playing a part R. T. only in exceptional circumstances. R. C. Röntgen analysis of ß-phases of Cu-Be and Binary systems of alkali metals. I. C. G oria Al-Zn alloys at high temperatures. G. P. Kosso- (Gazzetta, 1935, 65, 865—870).—The system R b-K lapov and A. K. T r apesn ik o v (Metallwirt., 1935, shows limited solubility in the solid state and a eutectic 14, 45— 46; Chem. Zentr., 1935, i, 2243).—The ß- at 34° with 15 at.-% K. In the Rb-Na system there phaso of a Cu-Be alloy (7-2% Be) exists above 620°, is a eutectic at —5-2° with 92 at.-% Rb, but no solid with a random-distributed body-centred lattice, a solutions or compounds are formed. 0. J. W. 2-79 Ä. The a-phaso has the Cu lattice, and the Electrical resistance of wires of palladium- y-phase at room temp, a CsCl structure, a (570°) 2-72 A. silver and palladium-gold alloys charged with Al-Zn alloy with 40% of A1 exhibits the Zn and A1 hydrogen. A. Sie v e r ts and H. H a g e n (Z. physikal. lattices at room temp., and a single face-centred Chem., 1935, 174, 247—261).—The pressure-concn. y-phase at 410°. J. S. A. (p-c) isotherms for alloys with 5 and 10% Ag are X-Ray studies on the systems tin-antimony similar to those for pure P d ; at 155° there is a hyst and tin-arsenic. G. H ägg and A. G. H y b in e t t e eresis loop and at 200° an approx. flat portion on the (Phil. Mag., 1935, [vii], 20, 913—929).—The homo isotherm, but no hysteresis. Tho isotherms for alloys geneous phase extending from 45 to 55 at.-% Sb has with 20—50% Ag are all parabolic. Up to 30 at.-% a deformed NaCl structure. The unit cell at the Sn Ag the prcssure-resistance (p-R) isotherms are similar limit is a rhombohedron with r 6-117 A., a 89-70°, to those of Pd, but for a given c and p the increase and vol. 228-9 A.3 With increasing Sb content the in R caused by tho H is the smaller the larger is the vol. and deformation increase until r is 6-138 A., a proportion of Ag. For alloys with 30 and 40% Ag 89-18°, and vol. 231-2 A.3 As is insol. in the Sn phase. . AR is negative over a certain range of temp, and p, Two intermediate phases of narrow range exist at whilst for 50% AS rises again. Pd-Au alloys behave Sn3As2 and SnS. The Laue symmetry of the former similarly to Pd-Ag alloys of the same at. composition, is D3d. The unit cell is a rhombohedron with r but both the H absorption and AR for tho Ag allo3Ts 12-23 A. and a 19-22°. The structure probably are for the Au alloys at the same temp, and p. corresponds with the ideal formula S^Asg, where R. C. some As is replaced by Sn. The probable space- Resistance thermometry below 10° abs. J. D. group is Dh- The phase at SnAs has the NaCl B a b b itt and K. Mendelssohn (Phil. Mag., 1935, structure with lattice const. 5-716 A. As dissolves [vii], 20, 1025— 1041).—Tho resistances of phosphor- 21 at.-% Sn, which increases the rhombohedral bronze -wires have been measured at low temp. edge and diminishes the angle of the As phase. The superconductive component responsible for the T. G. P. temp, dependency below 7° abs. is Sn-P, transition Alloys of rhodium with copper. O. E. Z v j a - point 8-9° abs. A binary alloy of definite composition g in tzev and B. K. B r u n o v sk i (Ann. Inst. Platine, properly treated is suitable for low-temp. thermo 1935, No. 12, 37— 66).— Cu-Rh alloys are easily metry, e.g., 5% Pb-Ag. T. G. P. oxidised in air. With 0—20 at.-% Rh they are homo Experiments on a superconductive alloy in a geneous and have the structure of Cu. From 90— magnetic field. J. M. C. J o n k e r and W. J. d e 100 at.-% Rh they have the Rh structure. Between BLaas (Physica, 1935, 2, 935— 942).—Resistance these limits there are two phases, except where the may be detected by studying the dying-out of the compounds Cu2Rh2 and CuRh., (both with a face- persisting current in a ring composed in part of Pb centred cubic structure) exist. There is also a partial wire and in part of thfe alloy, when the latter is placed change of structure at Cu3Rh. Ch . A b s . (e) in a longitudinal magnetic field. Tho magnetic Modulus of elasticity of copper-beryllium transition curve of a 64-8% Tl-Pb alloy has been alloys. L. G uillet fils (Compt. rend., 1935, 201, studied. In a magnetic field slightly > the pene 960—962).—The modulus of elasticity and Rockwell tration val. there is no resistance > 5 x 10~n ohm. hardness increase linearly with [Be] up to approx. The magnetio threshold depends on the measuring 18 and 12% Be, respectively. For [Be] > 12% the current. T. G. P. 24 BRITISH CHEMICAL ABSTRACTS.— A. V (a, b)
Intermetallic compounds. W. K lem m (Angew. -piperidine have been constructed at 0—80°. The Chem., 1935, 48, 713).—A review in which the general systems H20-C 5H5N and -piperidine appear to differences between intermetallic and salt-like com have a high lower crit. miscibility temp. R. T. pounds are discussed. R. S. B. Physico-chemical properties of certain aque- New methods and results for the detection of ous systems containing amines, and capable of intermetallic compounds. G. Gr u b e (Angew. stratification. R. V. M er zlin (J. Gen. Chem. Chem., 1935, 48, 714— 719).—-A review of experi Russ., 1935, 5, 886—891).—The composition-d and mental methods, including the study of magnetic -surface tension (a) and c-temp. curves have been susceptibility (yj. For Pd-Mn below 500° / rises determined for the systems H20-p-eollidine and rapidly with increasing % of Mn. The classification -N Et3; the composition--/) curve for the latter of compounds is discussed. R. S. B. suggests a 1 :1 compound. The data suggest form Structure of intermetallic phases. G. H agg ation of thermolabile compounds in both systems. (Angew. Chem., 1935, 48, 720—723).—A review R. T. of structural relations from the viewpoint of the Viscosity of binary systems at critical zones. position of the constituents in the periodic table. R. V. M erzlin (J. Gen. Chem. Russ., 1935, 5, 899— R. S.B . 903).— Binary liquid systems exhibit irrational max. Energy and space problems in the formation in the -/¡-composition curves at the lower crit. temp, of intermetallic compounds. W. B iltz (Angew. zone; at the upper crit. temp, two types of curve Chem., 1935, 48, 729—734).—A lecture. E. S. H. are possible, (a) in which the curves exhibit a negative deviation from additivity, due to dissociation of Magnetism and chemical linking in inter associated complexes, and (6) in which electrolytic metallic phases. E. V ogt (Angew. Chem., 1935, dissociation of the complexes is superimposed on this 48, 734— 740).— A crit. discussion of published effect. R. T. work. E. S. H. Theory of transition of metallic mixed phases. Mutual solubility and surface tension. II. III. Diagrams of state for partly ordered Surface tension and dipole moment. V. K. Sementsciienko and T. N. Iv a n o v a (J. Gen. Chem. mixed phases. G. B o relius (Aim. Physik, 1935, [v], 24, 4S9—506).—Theoretical. The theory pre Russ., 1935, 5, 807— 813).—The surface tension, a, viously put forward (A., 1934, 724, 1166) is applied of H20, nicotine (I), and PhN02 (II) at 25° is depressed to alloys in which the constituents are not in stoicheio- by PrCO-NH2 (III), PrCl, PrCIIO (IV), PrCN, metrical proportions. The general thermodynamic PrOH, and PrC02H (V), to an extent which increases theory underlying the equilibria in binary alloys is with the concn. In the case of H20 no obvious considered. The zero-point entropy and zero-point connexion exists between surface activity and dipole energy are discussed as measures of the at. ordering. moment, p ; in (I) and (II) it rises with increasing A. J. M. p. for substances not containing N, and falls for those Effect of thermal agitation on atomic arrange containing N. The crit. temp, of miscibility of (I) ment in alloys. II. W. L. B ragg and E. J. with HoO is raised by (III) and (V), is unaffected by PrOH, and lowered by the remaining substances, W illiam s (Proc. Roy. Soc., 1935, A, 151, 540— 566).—Theoretical. The treatment given previously to an extent which increases linearly with the concn. (A., 1934, 954) for the order-disorder transformation The val. of a at 70° at a H20-(I) interface rises with in alloys, and a recent extension of it by Bethe (A., increasing concn. of PrCl, (IV), and PrCN, but is 1935, 1193), are compared with the formal methods practically unaffected by PrOH, and is lowered by of Borelius, Gorsky, and Delilinger (A., 1928, 822, (III) and (V). R. T. 1078; 1933,896). The energy contents of the alloys Homogenisation by means of amines of certain CuZn and Cu3Au as deduced theoretically are compared aqueous amine systems with an upper critical with those found experimentally by Sykes (A., 1935, temperature of stratification. R. V. M er zlin 576). Expressions are given for the dependence of and V. F. U st-K atschkintzev (J. Gen. Chem. Russ., temp, on composition. L. L. B. 1935, 5, 904—919).— Phase diagrams have been Solid solutions with a varying number of constructed for the systems H20-NHPh-NH2 (I)- atoms in the unit cell. G. H agg (Z. Krist., 1935, piperidine (II), -C ,H 5N, -NH./CH2Ph (III), and 91, 114— 122).— “ Interstitial solution” is suggested -N H 2Ph, and for H20-N H 2Ph-(II), -C 5H5N, and to describe those solid solutions formed by adding or -(III), at 0—50°. No connexion is apparent between subtracting one kind of atom A in a given lattice B. the dipole moment, dissociation coeff., or dielectric For stability, a rigid skeleton lattice B and small const, of the amines and their homogenising action substituent atoms A are desirable. The interstitial at any arbitrarily fixed temp. Within the temp, solutions can be classified according to the means range studied the homogenising action rises in whereby electrical neutrality is maintained. Valency the series (I)< (III)< C 5H5N< (II), but falls with change in one kind of atom maty make an interstitial rise of temp, for C5H5N and (III), and rises for solution possible. The electrical conductivity of (II); the principle of corresponding temp, should be such lattices is discussed. B. W. R. taken into account in comparing the activity of a Separation of binary liquid mixtures into two series of homogenisers. R. T. layers. R. V. M er zlin and V. F. U st-K atsc h - Solubility of ammonium oxalate in water. k in tze v (J. Gen. Chem. Russ., 1935, 5, 771— 778).— A. E. H il l and E. F. D istler (J. Amer. Chem. Soc., Phase diagrams for KCl-H20-N E t3, -C 5H5N, and 1935, 57, 2203—2204).—Data are recorded for the V (6, c) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 25
range 0— 100°. The solid phase throughout is the results, considered in relation to Almquist’s equation monohydrate. E. S. H. (A., 1934, 22), suggest that AcOH forms double Solubility of sodium cyanide in water and in mois. in Pr^20. R. S. aqueous sodium hydroxide. Y. A. K ir e e v and Equilibria and surface phenomena in the L. I. V agranskaja (J. Gen. Chem. Russ., 1935, 5, system water-formic acid-phenol. V. I. N este 963—966).—The solubility of NaCN at 0°, 25°, and r o v a , N. N. P e t in , and K. V. T optschieva (J. Gen. 40° falls linearly with increasing [NaOH]. R. T. Chem. Russ., 1935, 5, 848— 861).—The partition coeff. Solubility of cobaltous nitrate in aqueous of HC02H (I) between H20 and PliOH at 20° rises nitric acid, and the transition point of with increasing concn. to l-075ilf, and then falls to Co(N03)2,6H20 to Co(N03)2,3H20. A. V a l d m a n T507i)/-(I), at which concn. the system becomes and L. L. K latsch ko-G urvitsch (J. Gen. Chem. homogeneous. The conductivity of the PhOH layer Russ., 1935, 5, 791—794).—Aq. Co(N03)2 saturated rises uninterruptedly to the crit. point, whilst that at 80° solidifies on cooling to 25°, to yield 39-5% of of the aq. layer rises to a max., and then falls with trihj'drate (I) and 60-5% of hexahydrate (II). (I) increasing [HC02H]. The dissociation coeff. of (I) alone can be prepared by cooling to 56°, and (II) alone rises with increasing [HC02H] in the PhOH, but by saturating at 56° and cooling. The transition remains const, in the aq. layer. The surface tension point of (II) to (I) falls from 54° in absence of IIN03 at the air-H ,0 interface remains const., but that at to 42° in presence of 30% of HN03. R. T. the H20-P h0H interface rises linearly with in creasing [HC02H] to the crit. point. R. T. Determination of solubility of the complex K2SiFG under various conditions. A. A. V a ssi- Solubility of deuterium and hydrogen in solid lie v and N. N. M ar tian o v (Z. anal. Chem., 1935, palladium . A. Sieverts and G. Z aff (Z. physikal. 103, 103— 106).—The solubility of K 2SiF6 in H20 Chem., 1935, 174, 359—364).—The solubilities have at 17° has been determined titrimetrically. The been determined at 300— 1100°. The ratio of the solubility is lower in 50% aq. EtOH, and is further solubility of D to that of H is 0-67 at 300° and 0-91 decreased in presence of 2% of KC1. J. S. A. at 1000° and approaches 1 at higher temp. The solubility of either at a given temp, is oc \/(gas Solubility of phosphoric acid. A. E. Mako- pressure). R. C. v e t zk i and M. A. Ostrohmov (Trans. Kirov Inst. Chem. Tech. Kazan, 1935, No. 3, 103— 106).—The Colloid-chemical phenomena in metals. I. best solvents for separating Il3P0 4 from its aq. Gases in aluminium. J. A. K ljatsc h k o (Kolloid- solutions are isoamyl alcohol and fusel oil. H3P04 Z., 1935, 73, 226—236).—Mainly a discussion of is almost insol. in CHC13, CC14, liquid SO,, PhMe, published work. The vol. of gas liberated from Al xylene, benzine, kerosene, and turpentine. and duralumin when heated at different temp, and Cn. A b s . (e) the proportion of H2 contained therein have been Solubility of 6-nitro-3-methylbenzoic acid in measured. E. S. H. benzene, toluene, and water. A. Giac alo n e Accommodation coefficient of hydrogen on (Gazzetta, 1935, 65, 844— 850).—The solubility of iron. H. H. R o w l e y and W. V. E v a n s (J. Amer. 6 : 3-NO2-C0H3Mc'CO2H (I) has been measured in Chem. Soc., 1935, 57, 2059—2064).—The accommoda C6Hg and in PhMe between 10° and 80° and in H20 tion coeff. is 0-31 at 450—350° abs. and increases between 10° and 100°. In the first two solvents the steadily with falling temp, to 0-55 at 120° abs. Com influence of temp, is given by S = K x 2"10, where parison with other work suggests that the exchange K is a const. (I) crystallises from CGHG in two forms, of energy between H2 gas mols. and an adsorbed of which only one is stable at higher temp. The layer of H2 is measured in each case. An attempt to solubility in H20 is very small up to 50°, but increases remove this adsorbed layer reduces the accom rapidly above 60° due to formation of hydrates. modation coeff. to 018 at 350° abs. E. S. H. O. J. W. Sorption of gases by minerals. V. [Extra- Solubility of several compounds of the man- Japanese zeolites.] VI. J. Sa m esh im a and N. nose series in alcohols. E. W. U pso n , E. A. M orita (Bull. Chem. Soc. Japan, 1935, 10, 485—490, F lu e v o g , and W. D. A lbert (J. Physical Chem., 490— 494).—V. The rate of absorption of NH3 and 1935, 39, 1079— 1094).—The solubilities of Z-rhamnose C02 at 1 atm. by the dehydrated minerals has been (I), a-(Z-mannose (II), (3-cZ-mannose (III), (Z-mannono-y- determined at 25°. Thomsonite, scolecite, epistilbite, lactone (IV), d-mannono-8-lactono (V), a-methyl- and phillipsite absorb large vols. of NH3, probably (7-mannoside, and d-mannitol (VI) in MeOH, EtOH, forming compounds, but only very small quantities CH2:CH-CH2-OH, IVOH, Pri*OH, Bu“OH, ik v o h , of C02 are absorbed; the absorption depends on the BuvOH, and sec.-BuOH have been determined at temp, of dehydration. different temp. (I) is the most sol. and (VI) the least VI. Sepiolite absorbs large vols. of NH3 and C02, sol. in all cases. (II) is more sol. than (III), whilst and belongs to the Si02 gel class. Asbestos, acid (IV) is almost twice as sol. as (V). R. S. clay, and bentonite absorb large vols. of NH3, but Solute as liquid. W. D. B ancroft (Science, only very small quantities of C02. Talc, serpentine, 1935, 82, 388—389).—A discussion. L. S. T. and vivianite absorb only very small quantities of Equilibrium distribution of acetic acid between NH3 and C02. J. G. A. G. fsopropyl ether and water. A. A. Smith and Adsorption of alkali metals on metal surfaces. J. C. E lg in (J. Physical Chem., 1935, 39, 1149— VI. Selective photo-electric effect. J. H. de 1153).—Distribution data are given for 20°. The B oer and C. F. V een em an s (Physica, 1935, 2, 915— 26 BRITISH CHEMICAL ABSTRACTS. A.
922; cf. A., 1935, 929).—The photo-electric emission has been studied at 20°. Absorption during drop of a cathode has been measured at increasing vals, of formation is negligible compared with that during the covering fraction for XX > 3600 Á. and 2537 A. time of fall. G/G„=6
75 g. of Fe203 per litre, obey the mixture law. The Imbibition of organic solvents by Yamagata val. of x for Fe203 does not vary appreciably with the imbibing clay. M. U t id a (J. Soc. Chem. Ind. length of dialysis, but decreases with increasing age Japan, 1935, 3 8 , 513—514b).—The quantity of org. of the sol, the decrease being faster at higher temp. solvent imbibed is < for H20, but no systematic 0. J. W. relation applies. The relative -q of the system clay Osmotic pressure and mol. wt. of cellulose sol-H20-EtO H is infinite near the max. point of the acetate. A. D ob r y (Bull. Soc. chim., 1935, [v], 2, system H ,0-E t0H . R. S. B. 1882— 1884).—From the limiting val. of the osmotic Imbibition of electrolyte solution by Yama pressure at zero concn. in various solvents the mol. gata imbibing clay. M. U t id a (J. Soc. Chem. wt. of cellulose acetate is found to be 66,500. Ind. Japan, 1935, 3 8 , 514b).—The swelling of clay 0. J. W. in aq. HC1, NaOII, and NaCl is compared with -q for Viscosity of solutions of cellulose in cupram- the systems clay sol-electrolyte. A base exchange monium. 0. K r a t k y and G. Saito (Cellulosechem., occurs, as with zeolites, the reaction velocity in 1935, 1 6 , 85— 90).— Data are recorded for t\ of 0T, creasing rapidly with concn. of electrolyte. 0-25, and 0-5% solutions of modified celluloses R. S. B. regenerated from alkali-cellulose aged in air, and these Structure viscosity of lyophilic sols. I. Gel are approx. expressed by the equation qsp/c—A-\-Bc, atin sol. N. P e sk o v and S. A v e rb u c h (Kolloid-Z., in which A and B are consts. The term Be is regarded 1935, 7 3 , 182— 191).—A viscosimeter for use with as due to mechanical interaction of the long chain lyophilic sols is described. The deviations from the mois, or micelles with each other. The ratio length/ Hagen-Poiseuille law shown by gelatin sols are width of the particles calc, on this hypothesis agrees traced to the inner structure and orientation of the approx. with that calc, from Staudinger’s equation. particles. The influence of acids and alkalis on -q is A. G. ascribed to the electro-viscous effect, the increase in Dissolution of cellulose nitrate. I—III. T. dispersity, the possible increase in swelling power, T omonart (J. Soc. Chem. Ind. Japan, 1935, 38 , and the change in the form of the micelles. Deviations 517— 528b ; cf. A., 1934, 637).—The solubility of from the law disappear at 34° in 2% electrodialysed various types of cellulose nitrate in org. solvents and gelatin, and at 30° when acids or bases are added to in aq. HNO;i-f H2S04, and the relative r, for solutions, give p a < 3-5 or > 5-5. E. S. H. have been determined at 0— 25°. Dissolution of di- and tri-nitrates in aq. H N 03+ H 2S04 is hindered Silicic acid gels. V. Determination of the by the presence of an unknown constituent. hydrogen-ion concentration of gel mixtures. It. S. B. C. B. H urd and R. L. Grtffeth (J. Physical Chem., Action of alcohols on organosols (especially 1935, 39, 1155— 1159; cf. A., 1934, 730).—The polystyrene, caoutchouc, and cellulose acetate). quinhydrone (I) method can be used for the deter H. E rbring and K. Sa k u r a d a (Kolloid-Z., 1935, mination of the pn of Si02 gels. The vals. obtained 7 3 , 191—201).—The pptg. effects of a homologous are < 7 and const, during setting, whilst the time of series of alcohols increases with increasing mol. setting is unaffected by the presence of (I). R. S. polarisation, except for organosols of paraffin and Cryolysis, diffusion, and particle size. II. caoutchouc, where the reverse effect is observed, and Investigations with myosin. F. E. M. L a n g e and polystyrene in COMeEt, in which thé pptg. val. is F. F. NoRb (Biochem. Z., 1935, 2 8 1 , 444— 446).— independent of mol. polarisation. In general the A table shows the diffusion coeffs. for myosin (un concn. of alcohol required for pptn. increases with frozen) at temp, down to —79°. The decrease of increasing viscosity of the system. By addition of these coeffs. with chilling points to an irreversible alcohols to polystyrene in CfiH- a liquid-liquid system aggregating action. P. W. C. is formed at first. E. S. H. Ideal and real protein solutions. G. E t t is c h Coagulation of organosols of cellulose nitrate and R. H avem ann (Z. physikal. Chem., 1935, 1 7 4 , by electrolytes. II. S. P a p k o v and M. T sc h v e l - 199—221).—If a homodisperse quartz suspension is e v a (Kolloid-Z., 1935, 7 3 , 202— 203; cf. A., 1935, allowed to sediment in presence of a protein the in 1319).—The coagulation of sols of cellulose nitrate in crease in the sedimented vol. compared with the val. C0Me2 by II20 in presence and in absence of electro in absence of the protein is a max. at the isoelectric lytes has been studied. The stability of the sols Pn (I)- Tbis is a more precise method for the location cannot be traced to the charge on the particles ; the of / than mere observation of the sedimented vol. existence of such a charge is doubtful. E. S. H. alone. For ovalbumin and serum-albumin the val. of I so obtained falls with increasing protein concn., Variation of flocculation threshold in starch c, when the latter is > a certain val. It follows sols. H. K o b er and F. D ittm ar (Kolloid-Z., 1935, therefore that at the higher c the mean valency of 7 3 , 219— 226).— Capillary-active substances, such as the protein mol. (cf. A., 1934, 36) is a function of c. sulphonated fatty acids, have very little influence on Cataphoresis measurements show that at concns. the coagulation of starch sols except in presence of > 0-5% I of ovalbumin is not const, at p n 4‘93, but salts, when small concns. cause turbidity or floccul moves to lower p n with rising c. These observations ation according to the concns. of electrolyte and sol. are attributed to electrical interaction between the The effect also varies with the degree of hydrolysis of isoelectric protein mols. in the more cone, (non the starch which occurs dining prep, of the sol. ideal) solutions. In such solutions the mols. behave E. S. H. as polypoles, and at I the NH3‘ and C02' groups of V(e), VI (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 29
different mois, approach as close as possible. This Equilibrium studies on the exchange reaction theory accounts for the above phenomena and also between acetylene and heavy water. L. H. for the effect of neutral salts on I. R. C. R e yer so n and B. Gillespie (J. Amer. Chem. Soc., Diffusion of colouring matters in gelatin and 1935, 57, 2250— 2251).—Average vals. of K x for the morphology of their reactions with electrolytes. reaction C2H2+H D O = C 2HD -fH 20 are 0-365, 0-45, S. V e il (Bull. Soc. chim., 1935, [v], 2 , 1830— 1832).— and 0-51 at 0°, 25°, and 100°, respectively. E. S. H. The use of characteristic diffusion figures in gelatin Second dissociation constant of carbonic acid. (cf. A., 1934, 1172) for the purpose of qual. analysis Y. K auko and V. M antere (Suomen Kem., 1935, is extended to the case of colouring matters. 8, B, 34; cf. A., 1935, 823).—Extrapolation of 0. J. W. measurements in dil. solution gives if 2=5 -0 x HH1 Diffusion in gelatin and rhythmic precipitation "at 18°. R. S. of magnesium hydroxide. G. A m m o n and R. Peculiar behaviour of aqueous carbonic acid. A mmon (Kolloid-Z„ 1935, 73, 204— 219).—The form Y. K auko (Suomen Kem., 1935, 8, B, 39— 41).— ation of periodic structures of Mg(OH)2 in gelatin by Recorded vals. for the dissociation consts. of H2C03 interaction of aq. NH3 and MgCl2 has been studied are discussed. The author’s val. for the second in relation to the diffusion coeffs. of the two reagents, const, is 5-3±0-3x 10'11 at 25°. A slow change the ratio of the distances between successive rings, occurs in the solution. R. S. B. and the viscosity of the gelatin. The results of other investigators are discussed in the light of these results. Relative strengths of acids in u-butyl alcohol. E. S. H. L . A. W ooten and L. P. H ammett (J. Amer. Chem. Quinone-gelatin gels. J. B uch holcz (Kolloid- Soc., 1935, 57, 2289—2296).—The relative strengths Z., 1935, 73, 237).—The phenomenon previously of 33 carboxylic and phenolic acids have been deter reported has been observed with tolu-, naphtha-, mined by the potentiomctric method. The effect and anthra-quinone. E. S. H. of a substituent on variation in relative strength Lyophilic colloids. XXV. Coacervation. II. with changing medium is that to be expected from Complex coacervation of the system gum arabic- the electric moment of the substituent and the dielectric const, of the medium, when the substituent gelatin. H. G. B. d e J ong and W. A. L. D e k k e r (Kolloid-Beih., 1935, 43, 143—212; cf. A., 1935, is introduced into the mol. at some distance from C02li. 821).— Determinations of i), turbidity, and electro Some other influence is preponderant when substitu phoretic velocity have been carried out. Neutral tion is adjacent to C02H. E. S. H. salts inhibit coacervation ; a valency influence, Existence of boric acid complexes with one but not a lyotropic influence, is noted. Coacervation and with two molecules of a diol in aqueous is still observed in very dil. solutions. The composition solutions. J. B o e s e k e n and N. V er m a a s, and (in relations for optimum coacervation vary with pn- part) W. H . Z a a y e r , and J. L. L eefers (Rec. trav. The behaviour of the coacervate droplets in the electric chim., 1935, 54, 853—860).—From the equations field is described. E. S. H. representing the equilibria involved in the titration Phenomena of electrofiltration in the electro of diols with K B 02 (cf. A., 1932, 1204), and the evalu ation of K 1 (2-5 X 10*6 at 18° for mannitol; 3-7 x 1(H lysis of gels. J. Sw y n g e d a u w (Compt. rend., 1935, 201, 821— 823 ; cf. A., 1934, 961).— A discussion. at 18-5° for sorbitol) and K 2 (1-10 and 2-11 x l(H , H. J. E. respectively), it is possible to calculate the concn. of Generalised thermodynamic notation. H. A. C. all the components present in solution. Rotatory McK ay (J. Chem. Physics, 1935, 3, 715— 719) dispersions, in close agreement with the experimental F. L. U. vals., are calc. The rotatory dispersion curve for a Quantity parameter, intensity parameter, and solution containing an excess of borate is different stable equilibrium. M. P l a n c k (Physica, 1935, 2, from that containing an excess of mannitol. A pre 1029— 1032).—Polemical, (cf. A., 1935, 1076). liminary analysis of the system NaB02-sorbitol T. G. P. indicates that the system is less simple. J. W. B. Displacement of equilibrium and the laws of Activity of chloride ions in some solutions of moderation [i.e., of Le Chatelier and van't Hoff]. complex chlorides of cobalt and chromium D. Maturo (Rev. Fac. Quim. Ind. Agric., 1934, 3, (III). M. Ch a telet and F. K ertksz (Compt. rend., 109— 118).— Mathematical. D. R. D. 1935, 201, 817— 819).— Electrode potential measure Reversible thermo-elastic systems. General ments with AgCl electrodes are recorded for aq. ised coefficients. D. M a tu ro (Rev. Fac. Quim. KC1, BaCL, [CoC1(NH3)5]C12, [CoH20(NH3)5]C13, and Ind. Agric., 1934, 3, 119— 130).—Mathematical. [CrCl(NH3)JCl2 (0-0002— 1 molar). For the two D. R. D. Co salts there is only one ionised Cl. For the Cr Osmotic equilibrium and real solutions. D. salt the ionisation of the second Cl increases with M aturo (Rev. Fac. Quim. Ind. Agric., 1934, 3, 131— dilution. H. J. E. 146).—Theoretical. A rigid thermodynamic treat Amphoteric hydrated oxides, solutions of their ment of equilibria across a semi-permeable membrane. hydrolysing salts, and their compounds of high D. R. D. mol. wt. XXX. Iso- and hetero-polytungstic Partial molal quantities in an infinitely dilute acids, especially the mechanism of formation of solution. I. R. K ritschevski and J. S. K a sa r - arseno- and phospho-tungstic acids. G. Ja n d e r n o v sk i (J. Amer. Chem. Soc., 1935,57, 2171— 2172).— and H. B an th ien (Z. anorg. Chem., 1935, 225, 162— Theoretical. E. S. H. 172 ; cf. A., 1934, 1319).—In aq. solutions containing 30 BRITISH CHEMICAL ABSTRACTS.— A. VI (a, b)
WO.," and P 0 4"' (or As04"') increasing [H‘] leads to form an unbroken series of solid solutions, the f.p. the successive formation of hexatungstic acids, of which is a linear function of the composition. and hetero-acids in which P(As) : W = 1 : 6, I : 12, Separation by means of fractional crystallisation is or 2 :18. The systems have been studied by the therefore impossible. F. L. U. diffusion method. P. L. U. Thermal analysis of the system P0C13-S 0 2C12. Test of mass law on concentrated molten G. P. L utsc h in sk i and A. I. L ichatscheva (Z. anorg. solutions by potential measurements. L. H o l u b , Chem., 1935, 225, 175— 176).—The m.p.-composition F. N e u b e r t, and F. S a u e r w a l d (Z. physikal. Chem., diagram of P0C13+ S 0 2C12 is of the simple eutectic 1935, 174, 161— 198).— Equilibrium consts. and type. The eutectic point is at —73-8° and 25T activities have been determined by potentiometric mol.-% of P0C13. F. L. U. measurements for the systems Ph-Sn-Ch, Pb-Cl2, Thermal analysis of the system argon-boron Cd-Pb-Cl2, Cd-Cl2, Pb-Ag-Clo, Pb-Ag-Bra, Pb-Ag- trifluoride. Compounds with the inert gases I,, Tl-Cd-Cl2, Tl-Pb-Cl2, and Cd-Sn-Cl2. The of the atmosphere. H. S. B ooth and K. S. W il l equilibrium consts. determined directly with cells son (J. Amer. Chem. Soc., 1935, 57, 2273—2280).— of the Daniell typo differ from the vais. calc, from F.p.-composition curves show maxima at ratios of activities, indicating that activities cannot generally 1 atom of A to 1, 2, 3, 6, 8, and 16 mols. of BF3, be determined electrochcmically owing to irreversi indicating that compounds are formed. The com bility of the necessary electrodes. The Lorenz- pounds are unstable and decompose above their van Laar mass law (A., 1926, 355) fails completely m .p.; A,2BF3 appears to be the most stable. The in almost every case. There are large deviations influence of pressure on f.p. suggests the equilibrium from the ideal mass law, and in some cases where the A+xBF3^=A,xBF3 or A,xBF3+yBF3^==A,(x-)- const, has approx. the correct val. this is due to the j/)BF3. E. S. H. accidental compensation of opposed deviations from Critical phenomena of the system argon-boron ideality on the part of the substances involved. It trifluoride. H. S. B o oth and K . S. W illso n (J. has not been possible to determine at what concns. Amer. Chem. Soc., 1935, 57, 2280—2284).—Retro there is ideality of behaviour of the mois, and ions. grade condensation and immiscibility are observed. In attempting to determine the mol. state of reactants The compounds formed in this system (cf. preceding from the constancy of the appropriate mass law abstract) are completely dissociated in the crit. temp, quotients it is found that quotients which are most region and scarcely affect the results. E. S. H. nearly const, do not always correspond with the most probable reaction ; both simple and associated mois, Dissociation of ferrous carbonate.' J. K r u s - or ions may bo present simultaneously. R. C. tin so n s (Z. anorg. Chem., 1935, 225, 93—96).— Physical chemistry of lipins. III.—See A., Dissociation pressures of FeCOs have been determined 1935, 1523. over the range 250— 290°. The calc, heat of dissocia tion is 20-9 kg.-cal. F. L. U. Thermodynamical calculations of solubilities of nitrogen and hydrogen in water at high Dissociation of NiS. D. N. T a r a s e n k o v and A. V. B ogoslovskaja (J. Gen. Chem. Russ., 1935, pressures. I. R. K ritschevski and J. S. K a s a r - 5, 836— 838).—NiS gradually loses S when heated in k o v s k i (J. Amer. Chem. Soc., 1935, 57, 2168— 2171). — A thermodynamic equation, which allows the N2 at 700°, and the v.p. gradually diminishes as the calculation of the solubility of slightly sol. gases in composition of the product approaches that of Ni3S2. solvents with small v.p., is given. The equation is This suggests that the NiS ordinarily prepared from verified for N2 and H2 in H20 at 0— 100° and pressures Ni and S is a solid solution of S in some other sulphide. up to 1000 atm. Partial mol. vols, of N2 and II2 R. T. in aq. solution are calc. E. S. H. Direct determination of zinc vapour concen tration in the thermal reduction of zinc oxide. Deliquescence and efflorescence. A. D a m ie n s O. D o n y -H(cnault and C. D ecr o ly (Compt. rend., (Bull. Soc. chim., 1935, [v], 2, 1893— 1901 ; cf. A., 1935, 201, 726— 728).—The [Zn] in the vapour phase 1934, 490).—It is suggested that the terms “ de has been determined by allowing the gas in the liquescent ” and “ efflorescent ” should be replaced reduction vessel (at 920—1075°) to expand into a by “ critical hygrométrie state ” defined by 100p/P, second evacuated vessel, cooling the latter, and where p and P are the v.p. of the system and the v.p. determining its Zn content. H. J. E. of H20, respectively. Hygrométrie data recorded in various parts of France during several years are Solubility product constant of calcium carbon discussed. O. J. W. ate in sea-water. R. R e y e ll e and R. H. F le m in g (Proc. 5th Pacific Sci. Cong., 1933, 3, 2089—2092).— Determination of critical hygrométrie states. The solubility product of CaC03 in sea-II20 is 2-37 X M. D lesnis (Bull. Soc. chim., 1935, [v], 2,1901— 1907 ; 10-6. The activity coeff. of Ca" for normal salinity cf. preceding abstract).— The aq. v.p. of various is 0-225. Sea-H20 is approx. saturated with CaC03. saturated salt solutions and solid salt hydrates has Ch . A b s . (e) been measured at 20° and 25°. The “ crit. hygro Equilibrium in the system H20-M gBr2. F. H. métrie states ” are recorded. 0. J. W. Getm an (Rec. trav. chim., 1935, 54, 866—872).— Fusion curves of mixtures of water and Solubility data are recorded for —42-7° to 100° deuterium oxide. Solution equilibrium in the and extrapolated to 172-4°, the m.p. of MgBr2,6H,0. system water-deuterium oxide. M. D e zelic (Z. F.-p. data for MgBr2 solutions are also given. The anorg. Chem., 1935, 225, 173— 174).—H„0 and D„0 only hydrates formed are MgBr2,6H20 and VI (b, c), VII (a, c) GENEBAL, PHYSICAL, AND INOBGANIC CHEMISTBY. 31
MgBr2,10H2O, the transition temp, being 0-S3°. H ’ and OH' should approximate to Na' in mobility, and The eutectic temp, for MgBr2,10H2O, ice, and solution an interpretation of the proton transference is offered is —42-7°. Attempts to obtain MgBr2,4H,0 by on the basis of the tetrahedral structure of H20, heating MgCl2,6H20 were unsuccessful. J. W. S. H30 ’, and OH'. H30 has one potential “ hole ” System alkali oxide-CaO-Al20 3-S i0 2-C 02. V. and 3 protons, H20 2 holes and 2 protons, OH' Stable equilibria in the system Na20-S i0 2-C 0 2 3 holes and one proton, so that in a sense OH' is the and pressures of C02 in the reaction between mirror image of H30 ’ . The effect of a field on the K 2COs and K 2Si0 3. C. K bo g eb and E. F in g as ions does not require further assumptions. (Z. anorg. Cliem., 1935, 225, 1—23; cf. A., 1935, A. J. M. 935).—The reaction of Na2C03 with Na2Si20 5, Electrolysis of copper in rock-salt. S. A. Na2Si30 7, and NaGSi207 and mixtures of these has A b zibisc h ev (Compt. rend. Acad. Sci. U.R.S.S., been studied by measuring the pressure (p) of C02 1935, 3, 157— 160; cf. A., 1935, 39).—Data recorded over the systems at various temp. (t). C02 is ab previously are corr. and discussed. Cu diffuses sorbed only when the ratio Na20/S i0 2 > 0-5. p-t readily in either NaCl or KC1, although the ionic diagrams are given for this system and for the system radii of K ' and Cu” are very different. Aiu also K 20-S i0 2-C 0 2. Thermal data relating to the form diffuses readily in KC1 or NaCl. J. W. S. ation of several Na silicates are calc. Dissociation Thermodynamics of the electric cell in hetero pressures of cryst. and fused Na2C03 and K 2C03 geneous system s. D. M a tu b o (Rev. Fac. Quim. have been determined. F. L. U. Ind. Agric., 1934, 3, 159— 167).—Mathematical. Double decomposition in absence of a solvent. D. R. D. The concentration cell and Nernst’s formula. XXVIII. V. P. R adischtsciiev (J. Gen. Chcm. Russ., 1935, 5, 455— 490).—Equilibrium data are D. M a tu b o (Rev. Fac. Quim. Ind. Agric., 1934, 3, recorded for the system NaCl-NaBr-Nal-KCl-KBr- 168— 176).—The equations already deduced (cf. KI, which is treated as a combination of 9 binary, preceding abstract) are applied to the study of the 2 ternary, and 4 quaternary systems. The solid contact potential between a metal and a solution phases are binary, ternary, and quaternary solid of one of its salts. D. R. D. solutions. R. T. Potentials of cells in liquid ammonia solutions. Heat capacity and free energy of formation Thermodynamic constants of the amminocad- mium chlorides and of cadmium chloride. C. S. of naphthalene. J. N. P eabce and W. B. T a n n e b (Proc. Iowa Acad. Sci., 1934, 41, 123— 120).—The Ga b n e b , E. W. Gb e e n , and D. M. Y ost (J. Amer. heat capacity of CinH8 has been measured from liquid Chem. Sop., 1935, 57, 2055—2058).— E.m.f. of the air temp, to 298-1° abs.; vals. for changes in heat cells Zn(amalgam, N2)|ZnCl2,6NH3(s), NH4C1 in content, entropy, and free energy accompanying its NH3(1), CdCl2,6NH3(s)|Cd(amalgam, N2) have been formation from its elements are calc. Ch. Abs. (e) determined at 25°. When Zn and Cd are present as pure metals E?iM.2 =0-3605 volt. The standard free Difference in the heats of formation of the two energies, heat contents, and virtual entropies of CdCl2 isomerides of butane. Estimate of the heat of and CdCl2,a;NH3 (where x = l, 2, 4, 6, 10) have been form ation of tetramethylmethane. F. D. R o ssin i calc. . E. S. H. (J. Chem. Physics, 1935, 3, 438; cf. A., 1934, 966, 1071).— Computed vals. (kg.-cal. per mol.) Becquerel cells. G. A t h a n a s iu (Ann. Physique, are : w-C4H10 (gas) -> fso-C4H10 (gas), —1-63 ± 0-15; 1935, [xi], 4, 377— 449; cf. A., 1925, ii, 1067).— n-C5H12(gas) -> CMe, (gas), —4 -9 ± l-0 ; 5C (graphite)-f- For cells with Ag-AgI and Hg-Hg2I2 electrodes the 6H „->CM e4, -4 0 -7 ± 1 -2 ; 5C (diamond) + 6H, -> positive photo-voltaic effect is increased by the H CMe„, -4 1 -S ± l-2 . N. M. B. ions of the electrolyte, and may be destroyed or re versed by the OH ions. 'This is explained by assuming Ionic migration as a molecular-kinetic prob that the electrolyte is a “ receiver ” of products lem . A. M a g n u s (Z. physikal. Chem., 1935, 174, liberated in the photo-chemical reaction. Lowering 262—26S).—Regarding the solvent, not as a continu of temp, increases the photo-voltaic effect; this is ous medium, but as a system the mol. motions of explained by regarding the electrode as the seat of which are controlled by the laws of the kinetic theory two opposing reactions, a photo-chemical, on which of gases, the steady mobility of ions is accounted for temp, has little effect, and a purely thermal inverse by supposing that between two collisions with reaction. Ag-AgI electrodes show sensitivity max. solvent mols. the ion is accelerated in the direction at 0-4225 and. 0-30 g, coinciding with the absorption of the electric field, then slowed down again by the max. of A gl; 0-4225 ¡a coincides with the photo next collision. From known ionic mobilities the conductivity max. of Agl. For Hg-Hg2I2 electrodes mean free paths can be calc., and prove, especially the max. is at 0-400 ¡j ., and the sensitivity threshold for small and doubly-charged ions, to be the calc, at 0-530—0-540 g. The Cu-CuO electrode sensitivity mol.-kinetic vals. and independent of temp., a ranges from 1 (x, in the infra-red, to a max. at 0-400 ¡a. discrepancy which is attributed to attraction between Ag electrodes covered with a thick cryst. layer of the ions and the H20 dipoles. R. C. Ag2S show a sensitivity max. at 1-35— 1-4 ¡x, coin Mobility of the hydrogen and hydroxyl ions in ciding with the photo-conductivity max.; this is also aqueous solution. I. G. W a n n ie b (Ann. Physik, the case for Cu electrodes covered with Cu20 by 1935, [v], 24, 543—544).—The explanation of the thermal and by electrical deposition. The sensitivity high mobilities of H' and OH' on the basis of a proton max. is at 0-480 ¡a, and the photo-voltaic and photo- transfer from one H20 mol. to the next is discussed. cryst. effects are compared. Results, in general, D 32 BRITISH CHEMICAL ABSTRACTS.— A. VII (c), VIII (a) support 'the theoretical explanations previously re K u l e v (J. Gen. Chem. Russ., 1935, 5, 1007— 1015).— ported. N. M. B. The e.m.f. between Na and Pt electrodes in C6H 6 Polarographic studies with the dropping mer solutions of ketones, keto-acids, aldehydes (except cury cathode. LV. Influence of air on solu MeCIIO), nitriles (except MeCN), amines, Cr,H5N, cycZohexanone, and mesitylene oxide is greatly in tions of salvarsan derivatives. R. B rdrSk a (Coll. Czech. Chem. Comm., 1935, 7, 457— 466; cf. A., 1934, creased in presence of Nal, whilst that of carboxylic 1241).—Traces of toxic oxidation products (I) present acids, esters (including nitrates), alcohols, unsaturated in neosalvarsan (II), syntharsan (III), and myo- hydrocarbons, pyrrole, and nitromethane is un salvarsan (IV) may be determined electro-polari- affected ; PhN02 and fsoamyl nitrite occupy an inter metrically. (II) is most sensitive to oxidation and mediate position. R. T. has been studied most fully. Using an atm. of II2 Explosion regions. XXVI. Shape of explo and a dropping Hg cathode it is shown that (II), sion regions and their diameters. W. P. J oris- (III), and (IV) are not electro-reduced in presence sen (Rec. trav. chim., 1935, 54, 888— 892; cf. A., •of NaCl, LiCl, and LiN03, but waves appear in the 1933, 469, 573, 790).—Theoretical. J. W. S. polarograms, due to electro-reducible (IV) (present Heavy hydrogen. V. Elementary reactions even in the purest specimens). Solutions which have of light and heavy hydrogen. Thermal conver been oxidised by 0 2, and from which dissolved 0 2 sion of ortho-deuterium and the interaction of has been expelled by H2, give more pronounced waves hydrogen and deuterium. VI. Ratio of the ■owing to increased concn. of (I); the latter may he determined from the height of the waves. (Ill) magnetic moment of the proton to the magnetic gives smaller waves than corresponding solutions of moment of the deuteron. A. F a r k a s and L. (II) owing to its greater purity, but is otherwise F a r k a s (Proc. Roy. Soc., 1935, A, 152,124—151,152— similar; (IV) is more slowly oxidised than (II). 157).—V. In the temp, range 850— 1000° abs. and at In presence of LiCl, Na' gives a wave of the polaro pressures 3—74 mm. the reconversion of ortho-D2 grams at —2-0 volt, owing to the diffusion current (i) and the interaction of H2 and D2 (ii) proceed in associated with the deposition of Na, and the % of Na the homogeneous gas phase according to the mechan can be determined from the height of this wave. isms : (i) D -f o-D2 =5=2= p-D.,-f D and (ii) D -f H2 R. S. B. HD-f II, H-f D2 HD-f D. Reaction (i) proceeds Electrode polarisation in separation of metal 2-4 times, and reaction (ii) 1-5 times, more slowly than the reconversion of para-H at the same temp, and from solutions of complex cyanides. 0. E ssin 2 pressure. In (i) this is mainly due to the different and A. Ma t a n ze v (Z. physikal. Chem., 1935, 174, 384— 394).— Analysis of Glasstone’s experimental collision frequency and concn. of D atoms. The data (A., 1929, 654; 1930, 864) has shown that the difference in the energies of activation involved in existence of concn. polarisation caused by accumul the reactions D -f D, D »-fD and H -f H2 Il2— ation of CN' at the cathode leads in several cases H is only 510 g.-cal., hut in (ii), the different reaction to relations between polarisation and c.d. which are rate is due to the fact that the energy of activation analogous to the equation for IT overvoltage. For for the partial reaction H -f D2 ==s= H D -f D is about the discharge of Hg from cyanide solutions, this 1-7 kg.-cal. > that for D -f H, H D -fH . This demonstrates the existence of chemical polarisation, behaviour is explained by assuming that the activated supposedly due to delayed discharge in the sense of complexes HHH, DHH, HDD, and DDD possess Volmer’s theory of overvoltage. In the separation zero-point energies similar to the mols. H2, HD, and of Cu there is no chemical polarisation, but rather a D2. A scheme for the energy levels involved in these depolarising action. For the separation of Ag and interchanges is worked out. Cd the experimental data are indecisive. R. C. VI. From a comparison of the velocity coeffs. of the ortho-para H , and D2 conversions, in the presence Organic depolarisers. W. E. H u n t e r and of 0 2, using the theory of Kalckar and Teller (A., L. F. Stone (J. Physical Chem., 1935, 3 9 , 1139— 1934, 940), the ratio of the magnetic moment of the 1147).—The single potentials of a no. of depolarisers proton to that of the deuteron is found to be 3-96— have been measured against Pt, Au, Ag, Sn, and 0-11. L. L. B. Ni cathodes. A general interpretation in terms of the electron affinity of depolarisers and the work Mechanism of the chain reaction in oxygen- function of electrodes is advanced. R. S. hydrogen mixtures. M. P rettre (Compt. rend., 1935,201,728—730; cf. A., 1935, 827).—The activ Acid-base titration in alcohol-water mixtures. ation energy of the H2- 0 2 reaction in reaction vessels III. Titration of alkaloids and alkaloid salts.— coated with KC1 is 95,000±6000 g.-cal. The reaction See this vol., 91. kinetics under these conditions are consistent with Electrometric control of displacement reac the Haber chain mechanism. H. J. E. tions. (Ml l e .) S. V e il (Convpt. rend., 1935, 201, Explosion of mixtures of combustible gases 885— 887).—The e.m.f. produced by Pt and Zn with air by nuclear drops of water and other when in contact and immersed in 0-2iV-CuSO4 de nuclei and by X-rays. V. Experimental con creases rapidly from the Volta p.d. to a min., then ditions required for ignition of hydrogen-air rises to a max., and oscillates. R. S. B. mixtures and nuclei. VI. Nuclear drop-igni- Determination of activity of unsaturated tion temperatures of ethylene-air mixtures pass organic compounds from the e.m.f. of their ing through a silica combustion tube ; relation reaction with sodium. B. V. T r o n o v and L. P. between wall and gas temperature and effect on V III (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 33
ignition temperatures of the central thermo given by £ = l-2 6 x l0 14e-3T>000‘sr sec.-1 Comparison couple sheath. VII. Effect of a variety of of the rates and activation energies of PraNC2 and nuclei, mainly mineral dusts, to ignite and Pr^NO., shows that there is no appreciable variation explode a mixture of hydrogen and air ; excep due to chemical configuration. L. L. B. tional efficacy of Ni2Os dust to ignite mixtures of air with hydrogen, ethylene, or methane. Thermal decomposition of triethylamine. R. 0. King and G. M ole (J. Inst. Petroleum Tech., H. A. T a ylo r and E. E. J cter eo ck (J. Physical 1935, 21, S3S—S45, S45—S53, S53—859; cf. A., Chem., 1935, 39, 1103— 1110; cf. A., 1932, 1002).— 1934,1074).—V. An apparatus for direct measurement Tho decomp, is unimol. at high pressures between of the steam-forming activities (from dry H.> and air) of 450° and 500° and tends to become bimol. at lower various combustion-tube surfaces, e.g., Cr-Ni steel, Ni pressures. In the initial stages, the energy of activ steel, and SiO.,, is described. The over-all steam-form ation is approx. 50,000 g.-cal. A sevenfold increase ing effect varies in a particular tube with the variety, of surfaco and additions of N2 and NH3 art' without temp., and distribution of surface oxide, and steam effect, but marked differences occur when fl2 is added. is not formed at a const, rate until the oxide attains It is suggested that tho intermediate products aro equilibrium with the H, in the existing conditions. Et4N> and C4H10, which ultimately yield CH4 and N„. Self- (T,) and nuclear-ignition temp. (Tn) wero deter R. S. “ mined in the same apparatus. T, varies with surfaco Mechanism of slow oxidation of propane. activity, and it is concluded that self-ignition occurs R. N. P ease (J. Amer. Chem. Soc., 1935, 57, 2296— in the boundary layer adjacent to the hot surface. 2299).—At 300°, with mixtures containing 10—30% VI. The wall tomp. in the Ni-steel tubo was of 0 2, the primary products aro MeOH, MeCHO, 16— 30° > the temp, indicated by a central thermo CO, and H20. Tho results aro interpreted in terms of couple, and the differences were always 2— 5° greater Rico’s radical-cliain theory, on tho assumption that when the tube was coated with oxide. Experiments OMo and Pr are the chain carriers. Similar mechan showed that the surface of the thermocouple sheath isms may apply to tho oxidation of CH4 and CaH». was without effect on T, of C2H4-air mixtures. E. S. H. Ignition in this mixture may begin in the gaseous Thermal decomposition of nitromethane. mixture apart from a free surface. Ts diminishes on H. A. T a y l o r and V. V. V e sse lo v sk y (J. Physical changing from the active steel surfaco to the relatively Chem., 1935, 39, 1095— 1101; cf. A., 1931, 175).— inactive Si02 surface and the rango of inflammability The reaction is unimol. in its early stages and has increases to a remarkablo extent. Nuclear ignition an energj- of activation of 61,000 g.-cal. Tho gaseous is obtainable when ignition from the surface is pre and solid products have been analysed and the inter vented by steam dilution of the adjacent layer of mediate formation of MeNO is postulated. Increase gaseous mixture, the effect then being obtained on of surfaco affects tho later stages of tho reaction, the surface of the nuclei in the gaseous stream. Tho additions of He, N2, NO, and C02 aro without effect, effect is obtained when oxidation nuclei reach a suitablo whilst 0 2 reacts. 1\. S. concn., or it may be induced by providing nuclear Induction period in gaseous thermal explo centres, e.g., H ,0 or dust. sions. O. K . R ic e , A. O. A l l e n , and H. C. Ca m p VII. Added nuclei such as compounds of Fc, Pb, bell (J. Amer. Chem. Soc., 1935, 57, 2212— 2222).— Zn, Ni, and Cr all proved effective to explodo a mix When tho differential equation connecting temp, ture of II2 and air, Ni203 having an exceptional with time in an oxothcrmio gas reaction is integrated, igniting effect; T„ was as low as 430° for Ni203, a sudden rise of temp., corresponding with an ex compared with 640—690° for other nuclei, for a 40% plosion, is indicated abovo a definite pressure. An H2 mixture supplied to a Cr-Ni steel tube at 300 c.c. approx. method for calculating the induction period per min. In a Si02 tube for Ha-air, the min. T, under in thermal explosions has been obtained from such given conditions was 566° compared with Tn 395°. curves, and applied to explosions of Mo2N2 and EtN3. Ni203 has a smaller igniting effect on C2H4-air Approx. heats of dccoinp. of thcso compounds havo mixtures than on H2-air, the max. igniting effect been obtained. E. S. II. occurring when the [C2H4] is about 50% > is required for combining proportions. For CH4-air, using Temperature coefficients in the acid hydration Ni203, Tn is about 75° < Tn and the min. Tn is obtained of sodium pyrophosphate. S. J. K ik iil and E. when the [CHJ is 50% < is required for combining Cl a u sse n , jun. (J. Amer. Chem. Soc., 1935, 57, proportions. C. C. 2284—2289).—Tho rate of conversion of Na4P20 7 Ignition of firedamp by compression.—See B., into Na;jP04 in HC1 solution has been determined at 1935, 1124. 30—90° and an empirical equation developed. Temp, coeffs. for 15° intervals have been calc. E. S. II. Homogeneous unimolecular decomposition of gaseous alkyl nitrites. IV. Decomposition of Kinetics of the permanganate-oxalate reaction. isopropyl nitrite. E. W. R. Steacie and G. T. I. Effect of various salts on the rate of reaction. Sh a w (Proc. Roy. Soc, 1935, A, 151, 685—693).— R. W. F essen d en and B. C. R edm on (J. Amer. The thermal decomp, of Pr^N02 between 170° and 210° Chem. Soc., 1935, 57, 2246— 2249).— A negativo is homogeneous and of the first order. The main salt effect has been found in this reaction. Zn", Cd", reaction is Pr0NO2=NO+0-5COMe2+0-5Pri,OH, and AT", which show apparent positive effects, analogous to those of the other alkyl nitrites investi form complex oxalates and thus dccreaso [C204"]. gated (cf. A., 1934, 847, 1312). The reaction rato is E. S. H. 34 BRITISH CHEMICAL ABSTRACTS. A. VIII {a, b)
Oxidation under pressure of ferrous sulphate with respect to (I); the reaction is retarded by H ’ , in neutral and acid solution. G. A g d e and F. and unaffected by neutral salts, whilst Cl' acts cata- Schimmel (Z. anorg. Chem., 1935, 225, 29— 32).— lytically in acid solutions only, so that in presence The influence of temp., [FeS04], and pressure of 0 2 of HC1 the velocity of reaction —d[HOCl]/di= on the oxidation of aq. FeS04 has been determined. (&'[H']+&"w)[HOCl][erotonic acid][Cl'], where n is the Under suitable conditions the oxidation is nearly dissociation const, of (II). The temp, coeff. of the complete. A part of the product is in the form of reaction in presence of HC1 is 1-62 per 10°. The order insol. basic salt, unless the required amount of free of the reaction varies greatly with changes in the H2S04 is added. The presence of the latter does not concn. of the substrates and in the pn of the medium. affect the extent or the rate of oxidation. F. L. U. The reaction in acid media is supposed to consist Kinetics of the reaction between permanganate of addition of the complex HOCl.HCl to the •C1C-, followed by regrouping and elimination of HC1, and m anganous ions. M. J. P olissar (J. Physical Chem., 1935, 39, 1057— 1066).—The reaction between whilst in alkaline media, in which 0C1' is the catalyst, Mn" and Mn04' has been studied visually and by the complex ion HOCl,OCl' is assumed to react a semi-quant. H2C204-I method. It is autocata- directly with (II). R. T. lytic, catalysis being due to the Mn02 formed. The Time course of the heat effects in rapid chem rate increases with the concn. of reactants, but dimin ical changes.—See this vol., 91. ishes with increasing acidity. Mn02 prepared in Oxidation of haemoglobin to methaemoglobin neutral solution is more effective than that prepared by oxygen. II.— See this vol., 92. in acid solution, probably owing to its greater dis persion. Determinations of Mn02 by the H2C204 Kinetics of displacement of silver from silver method may be carried out only at low [Mn*’]. The nitrate solutions by metallic lead. S. K k z y z a n - course of the reaction is altered by addition of S04" sk i (Z. anorg. Chem., 1935, 225, 151— 161).—The re or F', which form complex manganic ions, whilst action is of zero order for initial concns. within the sunlight has no appreciable effect. P . S. limits 0-125— ltV-AgNOg. The temp, coeff. of the velocity is of the same order as that of the diffusion Hydrolysis velocity of ketimines : steric hin coeff. F. L. U. drance effect. J. B. Cu l b e r tso n , W. R e y n o l d s , and C. M a in (Proc. Iowa Acad. Sci., 1934, 41, 170— Dust explosions. A. A. v a n d er D u sse n (Rec. 171).—Data are recorded for the rates of hydrolysis trav. cliim., 1935, 54, 873—884).—The quantities of of 2:6-, 2 : 5-, 2 : 4-, and 3 : 5-dimethyldiphcnyl Al-S mixture, coal, or anthracene dust required to ketimine hydrochlorides. Ch . A b s . (e) be suspended in unit vol. of air to cause explosion on ignition have been measured. The effects of Hydrolysis of phenyl furyl ketimine : relative non-combustible powders in suppressing such ex negativity effect. J. B. C ulber tson and L. H in e s plosions follow the order K 2S04>(N H 4)2S04> stone (Proc. Iowa Acad. Sci., 1934, 41, 172).—Data for dust>fuller’s earth. J. W. S. the rate of hydrolysis at 0° and 25° are recorded. The rule that the ketimine salts are more resistant Corrosion of iron.—See B., 1935, 1145. to hydrolysis the more negative are the radicals Sensitised explosions. I. Hydrogen-oxygen attached to the CINH is supported. Cir. A b s . (e) reaction catalysed by nitrogen peroxide. S. G. Velocity of decomposition of diazo-compounds F oord and R. G. W. N orrisii (Proc. Rov. Soc., in water. XVIII. E. Yam am oto (J. Soc. Chem. 1935, A , 152, 196—220; cf. A., 1933, 236).—The Ind. Japan, 1935, 38, 528— 532b ; cf. A., 1935, region of ignition, which occurs between narrow limits 1082).—The velocity coeffs. for the decomp, of 4 : 4'- of concn. of catalyst, is bounded by regions of slow tetrazo-, 2 : 2'-dimethyl-, 2 : 2'-dimethoxy-, and reaction, the velocity of which is increased by light 2 : 2'-disulpho-4 : 4'-tetrazo-diphenyl chloride at 30° which generates O atoms from the N0.2. There is are respectively 1-31, 10-3, 0-0483 (extrapolated) no distinction in the mode of generation of the slow and 2-42 x 10”4. The temp, coeffs. have been and explosive reactions; both intervene sharply at determined. R. S. B. the end of an induction period, during which the no. Reaction rate of acetic anhydride and water. of chains grows at first slowly and then rapidly to a crit. val. The induction periods are reduced by E. Iv. P l y l e r and E. S. B arr (J. Chem. Physics, 1935, 3, 679— 682 ; cf. A., 1934, 829).—By measuring irradiation to < 1 sec. over nearly the whole range the intensity of infra-red absorption bands character of catalytic effect of N 02. The data support the istic of AcOH and Ac20, reaction velocities of view that the branching initially exceeds the extinction Ac20 + H 20 -4- AcOH have been determined. The of chains over the whole region of catalysis, and that reaction is approx. unimol. at all concns. studied, an equilibrium concn. of chains is ultimately imposed and the velocity coeff. decreases with time. An ex on the slow reaction by the self-neutralisation of tended application of the method is suggested. chains, and by an increase in their extinction due to F. L. U. products of reaction. The process becomes adiabatic Kinetics of addition of hypochlorous acid to when the no. of chains exceeds a crit. val. N 02 double linkings. I. Crotonic acid. E. A. Schi- exercises a triple role in affecting the origin, branching, l o v and N. P. K a n ja e v (Trans. Inst. Chem. Tech. and extinction of chains. L. L. B. Ivanovo, 1935, 19—46).—The reaction of addition Oxidation of carbon monoxide catalysed by of HOC1 (I) to crotonic acid (II), or its anion, is one nitrogen dioxide. R. H. Crist and O. C. R o e h l in g of the first order with respect to (II), and of the second (J. Amer. Chem. Soc., 1935, 57, 2196—2203; cf. A., VIII (b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 35
1934, 1314).—The rate is first order with respect to Active nitrogen of long duration, law of 0 , at high concns. of N 02, and at low concns. it is decay and of increased brightness on com oc [0,] and [CO]2. “ E. S. H. pression. (Lo r d ) R a y l e ig h (Proc. Roy. Soc., 1935, A, 151, 567— 584).—The catalytic destruction of Aqueous solutions of stannic chloride. III. active N2 caused by the walls of the vessel is reduced Autocatalytic character of the flocculation. J. to a min. by coating the walls with H2S04 or HPOs. G uéron (Bull. Soc. chim., 1935, [v], 2, 1993— 1998; Using H P03 and a large bulb, the glow remains cf. A., 1934, 960).—The curves previously given for visible for > 6 hr. A photometric examination over the rate of hydrolysis of aq. SnCl4 solutions can be a wide intensity range of the decay of the glow at represented satisfactorily by an equation of the const, vol., using (a) a bulb coated with Apiezon oil autocatalytic type. The bearing of this on the struc (considerable wall activity), and (b) a bulb coated ture of the colloidal particles formed during the with 11P03, shows that for (a) the decay proceeds flocculation is discussed. 0. J. W. according to an exponential law, being apparently Thermal decomposition of sugars and its a first order reaction, whilst for (6) the data indicate catalytic acceleration.—See this vol., 56. a reaction of the second, or possibly the third, order. The increase of luminosity under compression has been Influence of pectin on inversion of sucrose. studied photometrically; the intrinsic brightness S. B erlingozzi and M. T esto n i (Annali Chim. oc (concn.)2. This indicates a bimol. reaction in which Appl., 1935, 25, 489— 496).—The presence of pectin the excess of neutral N2 mols. have no part. lowers the velocity of inversion of sucrose (I) in aq. L. L. B. citric acid, the effect being max. at 35° and tending Chlorination of propane. II. The hetero to decrease with rise in temp. For the same temp., geneous reaction. L. H. R e ye r so n and S. Y uster inhibition with high concns. of (I) is > that with low (J. Physical Chem., 1935, 39, 1111— 1123; cf. A., concns. E. 0. H. 1935, 1082).—The reaction in presence of A1203, Effect of salts on the velocity of inversion of Cu, and CuCl2 catalysts deposited on Si02 gel has sucrose at 25°. J. N. P earce and M. T homas been investigated and the energies of activation have (Proc. Iowa Acad. Sci., 1934, 41, 139).—For equal been determined. A1203 gave some H20, but good molal concns. of different salts the velocity coeff. results were obtained with CuCl2. The amount of increased in the order KCl
Electrolytic separation factor of hydrogen 1934, 1186).—The electrode processes occurring in isotopes under various experimental conditions. presence of fused alkali and carbonate electrolytes A. E u ck en and K. B r atzlek (Z. physikal. Chera., are discussed. R. S. 1935,174, 273—290).—Separation factors, S, varying Electro-deposition of nickel from nickel chlor from 2-7 to 17 have been observed. Using cathodes ide solutions.— See B., 1935, 1147. of Pt, Au, Ag, Cu, Pb, graphite, and Hg no relation between the material or overvoltago of the cathode Nickel-plating of aluminium.—See B., 1935, and S' could be detected. After anodic polarisation 1147. of the cathode, unless this is Hg, S is for some time Electric currents flowing over rusting iron. abnormally high, which suggests that the max. U. R. E van s (Nature, 1935, 1 3 6 , 792— 793).—An separation will be obtained by electrolysis with a.c., arrangement for investigating currents flowing over or botter, commutated d.c. This effect appears to bo an Fe surface in contact with 0-01JV-NaHC03 during due not only to electrolytic liberation of 0, but to rusting is described. Intense anodic action occurs sorption of 0 by the cathode from the solution or air, immediately around a scratched line where rusting is forming a surface oxide; probably the catalytic power rapid, while cathodic areas are free from attack. of the surfaco for the union of H atoms to H2 mols. is L. S. T. in this way increased, so that very rapid removal of Electrodeposition of tin alloys from alkaline the II atoms liberated is achieved. Small amounts stannate baths.— See B., 1935, 1098. of a-naphthoquinoline doprcss S considerably (cf. A., 1935, 309), possibly owing to the formation of Chemical reactions in rarified gases under intermediate reduction products the H and D atoms the influence of electric discharges. P. J o u b o is of which aro able to equilibrate tliemsolves with the (Bull. Soc. chim., 1935, [v], 2, 2035—2052).— A solvent. For a given eloctrodo motal S, if it is already lecture. largo, rises with the c.d. There is no direct connexion Chemical reaction in the electric discharge. between S and the slope of the logarithmio c .d - I. Chemical effects of impulse discharges. potential curve. R. C. E. J. B. W il l e y (Proc. Roy. Soc., 1935, A, 152, Efficiency of separation of hydrogen and 158— 171).— Wrede’s results for N2 (A., 1930, 394) deuterium by electrolysis. T. II. O d d ie (Proo. may be confirmed by chemical means and by simpler Physical Soc.„ 1935, 47, 10G0— 1067).—A method is apparatus. The controlled impulse discharge is described, taking account of evaporation and spraying far superior, as regards both abs. and power yields, lossos, for determining the efficiency a of concn. of to a.c. and d.c. discharges. Some probable conse DaO by oloctrolysis of H20-D 20 mixtures, a is quences of the action of an impulse discharge on independent of the [H*l of the electrolyte and the a gas are discussed. It is considered that, if the break nature of the electrodes, but increasos with rising down period is not too short compared with the e.d. a—4-0fi;0-2 for c.d. 0-6, and 4-6±0T for c.d. total duration of the discharge, and if the develop 2 amp. per sq. cm., in agreement with theory. ment of the positive column does not lead to a de N. M. B. struction of products first formed in this induction Electrolytic separation of lithium isotopes. period, the total effects may approximate to those A. E ucken. and K . B ratzlek (Z. physikal. Chem., found in cathodic reactions. L. L. B. 1935, 174, 269—272).—Experiments in which aq. Effect of light on periodic reactions. V. K. Li2S04 was electrolysed with a flowing Hg cathode, N ik if o r o v (J. Chim. phys., 1935, 32, 585— 587).— and the Li sot free reconverted into Li2S04, and again Wave equations yield the correct order for the ratio electrolysed and so on five times gave finally a between the distances apart of Liesegang rings in the specimen of Li the at. wt, of which differed from that presence and absence of light in the reaction of ordinary Li by an amount within the limit of ex 2AgN03+KX'r20 7= Ag,Cr20 -4-2KN03 (Kofman, A., perimental error. The separation factor, S, was at 1934,346). “ “ T. G. P. most 1-070. Bell’s calculation of S (A., 1934, 73S) is criticised. R. C. Separation of the mercury isotopes by a Kinetics of formation of anode films on metals. photochemical method. K . Zuber (Nature, 1935, II. Films of lead chloride on lead. L. J. K urtz 136, 796).—A partial separation of Hg200 and Hg202 (Compt. rend. Acad. Sci. U.R.S.S., 1935, 3, 305— from ordinary Hg has been effected by irradiation 30S; cf. A., 1935, 10S3).—When 0-5AT-HCl saturated of Hg vapour in a magnetic field with the Hg resonance with PbCL is eloctrolysed with a Pb anode, the latter line 2537 A. L. S. T. is first covered with “ islands ” of cryst. PbCL,, Question of further maxima of the density which later spread over the whole surface and in curves of photographic emulsions after the crease in thickness. The electrical conductivity of appearance of solarisation. H. B orst (Phot. Ind., the PbCl2 film increases with increase of c.d., as for 1935, 33, 1056, 1058).—With some plates (e.g., Agfa AgCl and AgBr films. PbCL films have very small Normal), but not with others (e.g., Perutz Ortho- porosity. The kinetics of the growth of PbCl2 films chromatic), second and third max. can be shown to are studied in the same way as for AgCl films, but the occur in the density curve, after the first solarisation, polarisation curves show some differences owing to on prolonged exposure (to Uviol or Nitrapliot lamp). the greater porosity of the AgCl films. A. J . M. Measurement of the densities of the direct blackening Reaction mechanism at a graphite anode. V. produced (not developed), by red light, shows similar Sihvonen (Suomen Kem., 1935, 8, B , 35; cf. A., variations, but these densities are always much < Yin (d) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 37
those obtained by development, and cannot therefore Reaction between ethylene and chlorine in be concerned with the causes of the recurring max. presence of chlorine acceptors. Photochlorin J. L. ation of ethylene. T. D. S te w a r t and B. W e id e n - Mechanism of the desensitisation of photo raum (J. Amer. Chem. Soc., 1935, 5 7 , 2036— 2040).— graphic plates. II. M. Blau and H. Wambacher The rate of photochlorination of C21I4 oc [Cl2] at (Z. wiss. Phot., 1935, 34, 253—266; cf. A., 1935, const, light intensity and is independent of [C2H4]. 177, 1331).—About 300 experiments were made to In H2-C12-C2H4 mixtures, illuminated or in the examine the relation of the density curves obtained dark, practically no 112 reacts, although the C21I4- from desensitised emulsions (Agfa Contrast) to the 0 2 C1.2 reaction goes to completion. The reaction of content of the surrounding atm., and also to the C2H4 with Cl2 in C2li4Cl2 solution is very rapid and concn. of the dcsensitiser. Graphs are given showing involves < 10% of the Cl2 in substitution; in pcntane the relation between various factors, e.g., intensity solution 37—73% of Cl2 is used for substitution, of light against concn. of desensitiser, for const, the amount increasing as the C2ll4 : Cl2 ratio increases. density production. Previous results are substanti E. S. H. ated, that desensitisation is dependent on the presence Photobromination of tetrachloroethylene and of 0 2, without which there is no residual efTect; the of chloroform with special reference to the dye acts as 0 2 carrier for reoxidation of nascent Ag. effects of oxygen. J. W i lla r d and F. D a n ie ls Other theories are discussed in detail. Solarisation, (J. Amer. Chem. Soc., 1935, 5 7 , 2240—2245).—Photo unobtainable in desensitised plates at atm. pressure, bromination of C2C14 is inhibited by the reaction appears on exposure in vac. Similarly, increased product, and depends little on [C2CI4] ; the temp, densities were obtainable in emulsions bathed in effect is small. Small amounts of 0 2 accelerate the KBr or K I solutions, when exposed in vac.; bathing reaction, but large amounts almost completely inhibit in NaN02 or Na salicylate was, however, not affected it, probably because of a competing Br-sensitised by the presence or absence of 0 2. J. L. photo-oxidation. C1ICI3 and Br react at 25° when Law of blackening of the photographic plate. illuminated with X 2650 A. in presence, but not in absence, of O,. The mechanism is discussed. H. Iy ie n l e (Naturwiss., 1935, 23, 762— 767).—The failure of the photographic reciprocity law is examined E. S. H. Catalysis of acetylene polymerisation in ultra particularly in connexion with intermittent illumin violet light by mercury vapour. (A) F. T o u l . ation. For each emulsion there is a lower-frequency limit of illumination, independent of intensity, above (B) W. K em u la (Coll. Czech. Chem. Comm., 1935, which the Talbot law holds. The curves expressing 7, 491— 492, 493— 494).— (a) Polemical against deviations from the reciprocity law are parallel for Kemula (cf. A., 1935, 1208). (b) A reply. R. S. B. all XX at all temp, investigated. A. J. M. Primary process in the photochemical and Photographic photometry. H. K ie n le (Natur thermal decomposition of azomethane. F. P a ta t wiss., 1935, 2 3 , 759—762).—Theoretical discussion. (Naturwiss., 1935, 2 3 , 801).—The photochemical The assignation of a scale to intensities of blackening dccomp. of Mc2N2 under various pressures at temp, produced on a photographic pla te can be of val. from 20° to 266° by light of X 366 mg has a zero only when the method of determining the intensities temp, cocff. in respect of the quantum yield. The is stated. The different effect on the plate of inter primary process is Me2Na->2M o+N2 and the existence mittent and continuous illumination when the same of a chain reaction involving the interaction of Me total quantity of light falls on the plate is discussed. with Me2N2 is excluded. W. O. K. A. J. M. Heterogeneous reaction kinetics. Effect of Photochemical decomposition of methylamine light exposure on the kinetics of thermal decom and ethylamine. H. .J. E mulous and L. J. J olley position of silver oxalate. A. F. B en to n and (J.C.S., 1935, 1612— 1617; cf. A., 1931, 1251).— G. L. Cunningham (J. Amer. Chem. Soc., 1935, The absorption spectra of N ll2Me and NH2Et are 5 7 , 2227—2234).—Exposure to light, especially on the short-X side of approx. 244 and 237 mg, XX < 520 mg, accelerates the subsequent thermal respectively, and the frequency differences between reaction; the effect is relatively less at higher decomp, tho bands lead to the frequencies 670 and 726 cm.-1, temp. Contact with 0 2 during exposure results respectively, which are probably characteristic of in initial poisoning. In the earlier stages of thermal the excited *NH2. The bands of long X have fine decomp., the extent of reaction at any time, t, approx. structure. In tho light of the Hg lamp and the Al cc tm, where m is 3-5 for unexposed samples, but is spark, the chief products from NII2Me are II2, NH3, progressively less with increasing exposure. and a liquid, with small quantities of CH4 and N2. E. S. II. Similarly, NH2Et gives tho same gaseous products Change of sodium nitroprusside into Prussian- and small quantities of C2H„ and C2II4. " Photo blue. E. Justin-Mueller (Bull. Soc. chim., 1935, oxidation of NH2Me affords chiefly NI13 and a liquid, [v], 2 , 1932— 1936).—When exposed to sunlight in an and smaller quantities of CO, N2, H2, and CII4. In open vessel an aq. solution of Na nitroprusside (I) each case, < 0-7 mol. is decomposed per quantum is decomposed giving NaN02, HCN, and Na2Fc2(CN)„. absorbed. J. G. A. G. The last named, in presence of NaOH, is converted Photochemical decomposition of nitrosoiso- into Prussian-blue. When (I) is exposed to sunlight propylacetono and p-nitroso-[k-dimethylhexane. in a closed vessel NO is evolved. The structure of K. \). Anderson, C. J. Crum pler, and D. L. IIammick (I) is discussed. 0. J. W. (J.C.S., 1935, 1679— 1684; cf. A., 1903, i, 322; 1935, 38 BRITISH CHEMICAL ABSTRACTS.— A. V III (d, e), IX
307).— The quantum efficiency of the decomp, of the H a a n tje s (Proc. K. Akad. Wetensch. Amsterdam, monomeric forms of nitrosoisopropylacetone (I) and 1935, 3 8 , 809).—Ne of at. wt. 21-157 has been pre P-nitroso-(3s-dimethylhexane (II) in CGH6 solution is pared after 14 rectifications. R. S. approx. unity in light of X 6400— 7100 A. (I) and Influence of hydrogen-ion concentration on (II) give H2N202 and its decomp, products; (I) oxidation and reduction reactions. A. K. B abk o also yields mesityl oxide and (II) affords, probably, (Z. anal. Chem., 1935, 1 0 3 , 98— 103).—In oxidation- (k-dimethyl-A^-hexene. The reaction probably pro reduction reactions not directly involving H\ but ceeds by the primary elimination of HONn involving compounds of multivalent ions with 0, J. G. A. G. H' lowers the stability of the compounds, and raises Primary photochemical reactions. VIII. the oxidation-reduction potential e. Expressions Quantum yield of the • photolysis of methyl for the influence of [H‘] on e are derived. J. S. A. »-butyl ketone. B. M. B loch and R. G. W. N or- rish (J.C.S., 1935, 1638— 1642; cf. A., 1934, 852).— Change of isotopic composition of water by In light of X 2480-—2770 A., the quantum efficiency, distillation. J. H o r iu ti and G. Okam oto (Bull. y, of the decomp, of COMeBu (I) at 760 mm. and 127° Chem. Soc. Japan, 1935, 1 0 , 503—505).—The % of by the primary processes (I) -> CO-f CH3-f-C4H9 D in the distillate is < that in the original liquid and (I) -> C3H6+COMe2 is approx. 0 03 and 0-27, when H20 containing 2-6% of D is distilled between respectively, y for condensation or polymerisation - 7 ° and 22°. J. G. A. G. is approx. 0-04. The absorption spectrum is diffuse Purification of water and its p a value. S. B. and fluorescence was not observed. It is probable E l l i s and S. J. K i e h l (J. Amer. Chem. Soc., 1935, that the energy of a considerable proportion of the 5 7 , 2145— 2149).—Technique for purifying H20 is excited mols. which do not decompose is degraded critically discussed. The purest H20, collected in by an internal redistribution process. J. G. A. G. Ag vessels, had p ti 7-01 at 27-5°, as determined by the Products and processes of ionisation in methyl glass electrode. E. S. H. chloride as determined by a mass spectrometer. Action of alkali hydroxide solutions on ultra- S. H. B a u e r and T. R. H ogness (J. Chem. Physics, marine-blue. K. Leschewski and E. P od sch u s 1935, 3, 687— 692).—The following ions, in order of (Z. anorg. Chem., 1935, 2 2 5 , 43— 46; cf. A., 1934, decreasing intensity, are generated as primary 1318).— Aq. LiOH (1— 2-5N) when boiled with ultra products in the decomp, of MeCl by electrons: marine-blue (I) decolorises it and yields a cryst. MeCl+, Mer, CC1+, CH,+, Cl’ , HCL, CH+, C ', H +. product (II) containing no S. KOH is relatively Appearance potentials for MeCl+, Me+, and Cl+ are inactive, but at a concn. of 7-5N removes all S on respectively 11-0, 14-7, and 26 volts. Experimental prolonged boiling, giving a cryst. product having a details are given. F. L. U. lattice different from that of (I) or (II). In both cases Inversion of sucrose solutions in tropical sun the Na of (I) is almost completely exchanged for Li light. N. A. Y a j n ik , D. N. G o y l e , and M. L. or K. F. L. U. W ad iie r a (Z. anorg. Chem., 1935, 225, 24— 28).— Hydrolysis of solutions of cupric sulphate. Aq. sucrose solutions contained in Jena glass vessels O. B in d e r (Compt. rend., 1935, 2 0 1 , 893— 894).— undergo inversion when exposed to tropical sunlight The slow hydrolysis of CuS04 has been studied by in the absence of acid. When acid (0-25N) is present boiling solutions for 0-25— 12 hr., and determining the rate of inversion is increased by sunlight. These the change in acidity by the glass electrode and the experiments confirm Dhar’s observations (A., 1922, composition of the ppt. by X-rays and analysis. ii, 39). F. L. U. Hydrolysis increases with the time of boiling and the Photochemical oxidation of haemoglobin.—See change in acidity increases with concn. (c). Insol. this vol., 92. solid phases are 4Cu0,S03,4H20 (c < 0-06 mol. per Action of radon on polymethylenes : eyelo- litre) and 3Cu0,S03,2H20 (c > 0 06). R. S. B. pentane and eyeiopentene. G. B. H eisig (J. Physi Substitution of copper and silver by silver. cal Chem., 1935, 39,1067— 1073; cf.A., 1932, 918).— A. P. S e r g eev and A. A. K oshuchovski (J. Appl. V.-p. data are given for cyclo-pentane and -pentene Chem. Russ., 1935, 8, 1073— 1075).—A ppt. of Cu is and the —31JN vals. for the Rn polymerisation are obtained on the surface of Ag foil (I) when the latter 1-7 and 4-5, respectively. —M/N is inversely oc is immersed in aq. CuS04 containing excess of KC1 A(H2+C H 4)100/—AHC and increases above 2 with or NaCl. When (I) is wrapped up in filter-paper a negative heat of formation. R. S. moistened in H20, and the packet is placed on conc. Decomposition of ozone by the action of aq. AgN03, crystals of Ag deposit on the filter-paper; a-particles. P. C. Capron and R. C lo e te n s (Bull. the system acts as a concn. cell, in which Ag is Soc. cKim. Belg., 1935, 4 4 , 441— 466).—M/I data for dissolved from the foil, and pptd. at the boundary C2H2 have been used to calculate 31/1 vals. in the between conc. and dil. AgN03. R. T. decomp, of 0 3 (3— 20 mm. in about 700 mm. 0 2). Electrometric and analytical evidence for the It is shown graphically that the velocity of decomp, composition of precipitated basic copper per oc [03] and increases with the radiation intensity. chlorate. R. A. B eeb e and S. Goldwasser (J. Considering 0 3 ions alone, the ionic yield is approx. Physical Chem., 1935, 39 , 1075— 1078; cf. A., 1932. const, for a given intensity. R. S. 243).—The composition of Cu{Cl0i)2,QCu0,xH20 Separation by rectification of neon into its has been determined electrometrically and by direct isotopic components. W. H. K eesom and J. analysis. R. S. IX GENERAL, PHYSICAL, AND INOEGANIC CHEMISTRY. 39
Preparation of sulphur and magnesium sul [with B. S. H opkins] (J. Amer. Chem. Soc., 1935, phate from sulphur dioxide and magnesia. II. 57,2185— 21S6).—Amalgams of Ce, Nd, “ didymium,” H . H ag is a w a (Bull. Inst. Phys. Chem. Res. Japan, and Y t have been prepared by the action of Na 1935, 14, 1161— 1176).—The velocity of absorption amalgam on conc. alcoholic solutions of their chlorides. of dil. S02 by aq. Mg(OH)2 has been studied. When The metals (except Yt) can be obtained free from Hg cone. aq. Mg(HS03)2 is heated with MgO (+ S ) in a by heating the amalgams in vac. E. S. H. sealed tube at 130— 140°, the reaction 3Mg(HS03)2+ Production of rare-earth metals by thermal Mg0=4MgS04+3H 20-)-2S is complete. R. S. decomposition of their amalgams. L. F. Au- Preparation and properties of mono-, di-, and d r ie t h (Metallwirts., 1935, 14, 3—5; Chem. Zentr., tri-calcium phosphates. H. W. E. La r so n (Ind. 1935, i, 2145— 2146).—Amalgams of Ce, La, Nd, Eng. Chem. [Anal.], 1935, 7, 401— 106).— Sm, and Y are made by electrolysis of EtOH solutions CaH4(P04)2,H20, Ca2H,(P04)2,4H20, and of the anhyd. chlorides with an Hg cathode. The Ca3(P04)2,H20 have been prepared. Their solu amalgam is conc. in vac. at 250°, and Hg is removed bilities, pn of the solutions, n, and behaviour on heating completely by heating the residue at >1000°. Cru have been determined. E. S. H. cibles lined with pure rare-earth oxides, grading Reactions of phosphates with soils. II. outwards into A1203, must be used. Ce is cubic Action of lime on monocalcium phosphate in face-centred, a 5-14 A .; La and Nd are hexagonal presence of anhydrous calcium sulphate. J. with a 3-75, 3-65, c 6-06, 5-88 A., respectively. Clarens and H. Margulis (Bull. Soc. chim., 1935, j . S. A. [v], 2, 19S0— 1985; cf. B., 1934, 642).—When solu Action of Clerici's solution on gypsum. G. tions of H3P04 and Ca(OH)2 are mixed in presence Peh rm an n (Zentr. Min;, 1935, A, 54—55; Chem. of anhyd. CaS04 pptn. of CaHP04 first takes place. Zentr., 1935, i, 2146—2147).— Clerici’s solution With further addition of Ca(OH)2 the CaHP04 is attacks gypsum (I) and deposits T12S04, thereby converted into Ca3(P04)2. 0. J. W. making the apparent d of (I) too high. J. S. A. Decomposition of barium sulphate by chlor Preparation of carbon suboxide. A. K lem enc, ine.—See B., 1935, 1141. R. W eciisberg , and G. W a g n e r (Monatsh., 1935, 66, 337— 344).— Pure C30 2 may be obtained by the Cadminitrites of univalent metals. A. F er dehydration of CH2(C02H)2, and from diacetyltartaric r a r i, A. B a r o n i, and C. Colla (Gazzetta, 1935, anhydride, and subsequent fractionation of the pro 65, 797—809; cf. following abstract).—The prep, ducts. A. J. M. of KCd(N02)3 and of the compounds MCd(N02)3 (M =Rb, Cs, Tl, NH4) is described. They crystallise Preparation of pure carbon monoxide. G. in the monometric system, 1 mol. per unit cell, and M e y e r , R. A. H e n k e s , and A. Slooff (Rec. trav. have, in the order given, a 5-325, 5-375, 5-390, 5-340, chim., 1935, 54, 797— 799).— CO cannot be freed 5-355 A., and dcaic. 3-183, 3-509, 4-063, 4-958, 2-902, completely from H2 by fractional distillation. Pure respectively. Arguments in favour of the structure CO is obtained by decoinp. of Ni(CO)4 at 200°, and M2Cd[Cd(N02)6] are given, but, as with the Hg a laboratory apparatus for this purpose is described. compounds, the cationic Cd cannot bo replaced by J. W. S. other metals. O. J. W. Silicates. III. Behaviour of talc on heating with MgO and Mg, Co, and Mn chlorides. E. Mercurinitrites of univalent metals. A. F er T hilo (Z. anorg. Chem., 1935, 225, 49—63; cf. A., r a r i and C. Colla (Gazzetta, 1935, 65, 789— 797).— 1933, 794).—Experiments are described showing that, The prep, of the compounds MHg(N02)3 (M=Rb, Cs, although the chemical composition and cryst. Tl) is described. The corresponding Iv and NH4 structure of pyrophyllite and talc are closely analogous, compounds could not be obtained. These double the latter behaves quite differently towards MgO nitrites crystallise in the monometric system with and anhyd. MgCl2, CoCl2, and MnCi, when heated with 1 mol. per unit cell. For the Rb, Cs, and Tl compounds them. An explanation based on the respective a=5-540, 5-475, 5-385 A., and dcaic.=4-35, 4-77, 5-77, lattice structures is offered. F. L. U. respectively. The Hg and M are at the corners and centre of the cube, but the position of the N 02 Form ation of “ persilicate.” H. Drrz (Z. anorg. is uncertain. It seems probable that the formulae Chem., 1935, 225, 90—92).—Comments on a paper by of these substances should be doubled, viz., Krauss and Oettner (A., 1935, 833). F. L. U. M2Hg[Hg(N02)6]. The Hg outside the complex Carbides of lead and silver. E. M on tig n ie cannot, however, be replaced by any other metal. (Bull. Soc. chim., 1935, [v], 2, 1807— 1809).—PbC2 O. J. W. is obtained by adding CaC2 to a solution of Pb(OAc), Mercury powder. A. Ga l a t z k y (Bull. Soc. in MeOH. It is stable at room temp., but is easily chim., 1935, [v], 2, 1801— 1807).—Very finely-divided hydrolysed, and in acid solution evolves C2H2. Hg powder is prepared by reducing HgO suspended in Pb cyanide could not be prepared. Org. Ag salts H20 with N2H4 and other reducing agents. The grey do not give Ag2C2 when strongly heated. 0. J. W. powder has an appreciable v.p., forms an amalgam Attempted concentration of the heavy nitrogen by simple contact with Au or Sn, and is readily isotope. M. H. W a h l , J. F. H u f fm a n , and J. A. dissolved by 25% HN03. It is probably a mixture H ip p l e , jun. (J. Chem. Physics, 1935, 3, 434—435).— of Hg with small amounts of HgO. O. J. W. A study of the isotopic reaction N15H3+ N 14H4OH — Rare earths. . XLV. Preparation of rare- N14H3+ N 15H4OH showed that the distribution of earth amalgams b y displacement. D. H. W est N15 was slightly favoured in the NH4OH mol. The 40 BRITISH CHEMICAL ABSTRACTS. A. IX ratio of the v.p. of N14H3 and N15H3, determined Isotopic exchange reactions with iodine. F. by fractional distillation of anhyd. NH3, was 1-0052^ J uliusburger , B. T o p l e y , and J. W e iss (J. Chem. 0-0013. N .M .B . Physics, 1935, 3, 437^138; cf. A., 1935, 1328).— The reaction RX+I-=RI+X~ (R=alkyl, X=I) Corrosive action of solutions of ammonium was examined for two series of aliphatic I compounds nitrate in liquid ammonia on metals.—See B., by dissolving activated Na+I~ in alcohol-H20, 1935, 1091. thereby obtaining radio-I ions in solution, adding the Action of hydrogen sulphide on hydrogen alkyl iodide, removing the partly activated org. sulphite solutions. J. Ja n ick is (Z. anorg. Chem., iodide by pptn. with H20, and, after conversion into 1935, 2 2 5 , 177— 203; ef. A., 1931, 1255).—The pro Agl, making Geiger-Miiller counter measurements. ducts of the action of H,S on aq. KH S03 at pn 5-1— Exchanges > 5 0 % were found. The upper limit 2-3 are S203", S„0G" ( » = 2— 5), S, and H\ At first of the activation energy for the interchange reaction S203" and S30 G" are chiefly formed. The production M e l + r in EtOII is 16-5 kg.-cal. N. M. B. of higher polythionates is favoured by increase of X-Ray investigation of method of preparing [H‘] or of [S203"], but there is no evidence that spongy iron by reducing haematite with gases. S30 G" takes part in it. The occurrence of the reaction V. P. K a san zev (Z. pliysikal. Chem., 1935, 1 7 4 , H2S62+2H S203' -> S50 G''+ 2 H 20 is supported by the 370—383).— X-Ray examination of the products of above observations and by the qual. detection of reduction with H2 shows them to consist of a mechan H2S02 in the reaction mixture. S40 G and S30 G ical mixture of a-Fe, FeO, Fe304, and Fe203; no are successive degradation products of S50 G" accord solid solutions are present. The length of edge of ing to : S50 G"+ H S 0 3' -> S40 g” + S 203"+ H - ; the primary fine crystals of a-Fe lias been measured. S40 g"+ H S 0 3' -> s3o c" + s 2o3" + h -. f . l . u . At 700° the reduction of Fe203 to Fe304 is more rapid Reaction of sulphur dioxide with water under than the subsequent stages of reduction. After reduction is 82-5% complete the product is mainly pressure.— See B., 1935, 1091. a-Fe with a small residue of Fe30 4. R. C. Hydrogen sulphites. III. Reduction of sod Ageing and stability towards light of ferrous ium hydrogen sulphite by zinc amalgam. II. oxide hydrates in presence and absence of alkali T. M u rook a (Bull. Inst. Phys. Chem. Res. Japan, nitrates. O. B a u d is c h (Ber., 1935, 68, [B], 2046— 1935, 1 4 , 1154— 1160).— Reduction of HS03' by the 2049).— Colourless FeO hydrate is obtained by gradual amalgam method can be carried out in the presence addition of alkali to FeCl2 and allowing to age under of H2S03 or H2S04. The yield decreases as the temp, H20 during |—several hr. The suspension when rises, and the best result is obtained when the quantity agitated with 0 2 gives a-Fe,03 which probably con of amalgam is 1-2 times the theoretical. The solid tains y-Fe203 on account of the magnetic properties. remaining after reduction has the approx. composition Ageing occurs very rapidly. Pptn. of Fe(OH)2 3ZnS03,Na2S03+Z n (0H )2. R. S. in presence of air and nitrates causes almost immediate Thermal decomposition of Cr04,3NH3. W. F. reduction of the latter to nitrites. It is probable E h r et and A. Gr een sto ne (J. Amer. Chem. Soc., that H20 eliminated from the primary Fe(OH)2 1935, 57, 2330—2331).— Cr04,3NH3 does not lose yields active H under the experimental conditions, NH3 in vac. at room temp., but at 120±10° a vigorous H20 -> H + 0H(H202) and corresponding with pro reaction occurs and a solid residue, CrOs,NH3, is duction of the latter compounds the oxidation formed. The presence of small amounts of impurities of suitable org. compounds (lactic acid, uracil, has a marked influence on the rate of decomp.; thymine) occurs concurrently in the system. Neither the reaction does not occur in the dark. Cr03,NH3 reduction nor oxidation is observed with aged Fe11 has d 2-073; it is stable in air, but hydrolysed by H20. hydrates. Even after very long periods in the dark E. S. H. nitrates are not reduced by Fe11 salts in the complete Formation of masked complexes in normal absence of 0 2. At. O, liberated from nitrates by and basic solutions of chromium and aluminium light energy, has a powerful oxidising action and the salts. A. KU n tze l, C. R ie ss, and G. K o n ig feld nitrite thus produced reacts momentarily with excess- (Collegium, 1935, 484—502; cf. B., 1935, 818).— of F e " ; according to the pn of the medium, further Cr acido-complexes are formed with both sulphates and complete reduction of the O-N compounds and chlorides, but analogous A1 complexes are not ensues. H. W. formed. Conductivity measurements show that A1 Action of alkali sulphides on sodium nitro- sulphato-complexes are not present in aq. A12(S04)3 prusside. E. Justin-Mueller (J. Pharm. Chim., which has been boiled and cooled again, but arc formed 1935, [viii], 2 2 , 496— 503).—The violet colour is due in aq. Cr2(S04)3. The hydrolysis of Cr salts occurs to the formation of an intermediate compound, in three successive stages, but that of A1 salts is in Na2(CN)3Fe(SNO)2, which rapidly decomposes into one stage. Masking occurs on adding a neutral Na(NO)S groups and Na2Fe2(CN)G; these partly salt containing an anion common to both aq. Cr recombine to give Fe2S4(NO)2Na, and the residual and A1 salts; the rate of masking is greater in A1 Na2Fe2(CN)G is transformed into Fe[Fe2(CN)G] and salts, but the masked Cr salts are more stable. Both finally into Prussian-blue. E. H. S. basic A1 and Cr salts form complexes; the change is complete in A1 salts, but in Cr salts the degree of New group of complex compounds. Com formation diminishes as the Cr salt is more aged. pounds with a complex anion, the central ion of D. W. which is a complex cation. Ill. Complex phos- IX , X GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 41
phato-anions with complex cobalt cations as Electro-capillary method of qualitative an central ions. H. B r in t zin g e r and H. Ossw ald alysis. S. I. D ijatsohkovski (J. Gen. Chem. Russ., (Z. anorg. Chem., 1935, 225, 33—37; cf. A., 1935, 1935,5,728—730).—Theoretical aspects of electrolysis 1091).—Determination of the ionic wt. by measuring of solutions on filter-paper are discussed. R. T. the rate of diffusion of complex Co cations in 3N- Analysis of anions. S. M. Puzevskaja (J. Gen. K 2HP04 indicates the existence of the following Chem. Russ., 1935, 5 , 498—499).—The procedure complex anions (X = H P 0 4") : proposed by Birulia (A., 1933, 1260) is not feasible. r [Co(NH3)6]X 4] - ; [ [Co(NH3)5(H20)]X 4F ; R. T. [ [Co(NH3)4(H20)2]X 4]5- ; [ [Co(NH3)-Cl]X4]ft- ; Application of the glass electrode to unbuffered [ [Co(NH3)cN03]X 4]6- ; [ [Co(NH3)4F2]X4]7- ; systems. S. B. E l l i s and S. J. K i e h l (J. Amer. [ [Co(NH3)4S04]X 4]7- ; [ [Co(NH3)4S203]X4]7- ; Chem. Soc., 1935, 57 , 2139—2144).— General tech [ [Co2 en,]X4f ; [ [Co2(NH3) ln02]X4]i- ; nique for Ph determination in unbuffered solutions is [ [Co2(NH3)10(H2O)18O2]X 4]3- ; [Co(NH3)4(C03)X]i-. described. The method has been applied to very F. L. U. pure H20 and to some very dil. salt solutions. Mixed nickelnitrites of uni- and bi-valent E. S. H. metals. II. A. F errari and C. Colla (Gazzetta, Application of bimetallic electrodes to titration 1935, 65, 809—818; cf. A., 1935, 717).—The prep, of acids or alkalis. J. A. B o ltu n o v and M. A. of the triple nitrites MI2Cd[Ni(NO2)0] (J\F= V orsin a (J. Gen. Chem. Russ., 1935, 5, 519—528).— Tl, K) is described. These are isomorphous with The bimetallic electrodes Pt-Ni, -Sb, -Co, -Pd, K2Pb[Ni(N02)(!] and have a 10-37 and 10-28 Â., Pd-Ni, and Ni-Hg2Cl2 may be used repeatedly respectively. When M1 is Rb, Cs, or NH4, the triple without inactivation for the titration of weak or nitrites with the general formula given above could strong acids (< 0-001N), and of alkalis, Pfc-W, not be obtained, as there is a great tendency to form -Mo, -Ta, W -Ni, and C-Sb are less suitable, as they solid solutions between nickelnitrites and cadmium- have to be reactivated after each determination, whilst nitrites, with a 10-58,10-81, and 10-41 Â., respectively. Pb-Fe, -Cu, -C, -Al, -P b, and -Sn electrodes do not O. J. W. give trustworthy results under any conditions. Red and green forms of Magnus’ salt. H. D. K. R. T. D r e w and H. J. T ress (J.C.S., 1935, 1586— 1588).— Determination of small quantities of water by When the red form of Magnus’ salt, [Pt(NH3)4]PtCl4 Crism er’s m ethod. L. d e B r o u c k e r e and A. (I), is treated with AgN03 followed by K 2PdCl4, Glllet (Bull. Soe. chirn. Belg., 1935,44, 473—503).— [Pt(NH3)4]PdC]4 is pptd., whereas the red triammine Crit. solution temp, (c.s.t.) have been determined plato salt, [Pt(NH3)3]2PtCl4 (II), of Peyrone and for the mixtures MeOH-CS2, MeOH-EtOH-CS2, Cleve gives the quite different chlorotriammino- MeOH-u-CGH14, and MeOH-cycfohexane. Inter platinous palladochloride, [Pt(NH3)3Cl]2PdCl4. Con action occurs between MeOH and CS2 at high temp., trary to Cox et al. (A., 1933, 41), (II) could not be resulting in a progressive shift of the c.s.t., but this converted into a green form, and (I) and (II) are not may be avoided by addition of EtOH, which lowers identical. Earlier work (A., 1906, ii, 2S9) was con the c.s.t. Ac.s.t. oc the concn. of H ,0 added, and small firmed, but some H2PtCl4 solutions gave the red form quantities can be determined by this means. The of (I) even in the presence of much HC1, which usually combustion analysis of an org. compound is given as favours the green isomeride. The red and green an example. R. S. forms of (I) may be electro-isomerides. J. G. A. G. Asymmetric platinum atom. VII.—See this Titrimetric determination of water and alco vol., 84. hols by their acid-catalysed reactions with acetic Microchemical spectral analysis in high- anhydride in organic media. G. T o e n n ie s and frequency spark. A. Schleicher and N. B r e c h t- M. E l l i o t t (J. Amer. Chem. Soc., 1935, 5 7 , 2136— B e rg e n (Z. anal. Chem., 1935,1 0 3 , 198; cf. A., 1935, 2139).— General technique and scope of the method 947).—Supplemental details are recorded. J. S. A. are described. The error in concns. of about 1% is < ± 1 % ; the lower limit of response is < 0-001%. Quantitative analysis of solutions by spectro- E. S. H. graphic means. O. S. D u e f e n d a c k , F. H. W il e y , Chromyl chloride test for chloride. L. M a r and J. S. Ow e n s (Ind. Eng. Chem. [Anal.], 1935, tin i (Annafi Chim. Appl., 1935, 2 5 , 528— 530).— 7, 410— 413).— An uncondensed spark in air between A positive reaction -with H2S04-K 2Cr20 7 may be due a suitable solid electrode and the solution is photo to either Cl' or F'. The vapour is absorbed in dil. graphed and, from measurements of the relative alkali, Cr04" confirmed as Pb salt, and Cl' or F' intensities of chosen spectral fines, the analysis for identified by the usual tests (CaCl2, AgN03, etc.) metals is made by comparison with previously con with due consideration to the presence of I or Br. structed reference curves. The method has been F. 0. H. applied to the determination of Na, K, Mg, and Ca Determination of fluorine in soluble and in in dil., mixed solutions of their salts. The error is soluble fluorides by its separation as K2SiFG about 2%. E. S. H. and subsequent titration of the complex. A. A. Solubility of precipitates in acids. A. K. V a ssilie v [with N. N. Martianov] (Z. anal. Chem., B abko (Z. anal. Chem., 1935, 1 0 3 , 190— 196).— 1935, 1 0 3 , 107— 113).—Sol. fluorides are dissolved A general expression is given for the solubility of in H20 and an equal vol. of aq. Na2Si03 (0-01 g. of ppts. with varying acid concn., with or without the Si02 ’per c.c.)+KCl is added, and then acidified with presence of excess of precipitant. J. S. A. 50% HC1 (Me-orange). The solution is made 50% 42 BRITISH CHEMICAL ABSTRACTS. A. X with respect to EtOH. Pptd. K2SiF6 is collected, 528).—The sample (0-1 g. in 50 c.c. H20) is boiled for dissolved in C02-free H20, and titrated with 0-1A7- 10 min. with 16% H2S04 (10 c.c.) and 0-lAr-KMnO4 NaOH (phenolphthalein). The loss due to solubility (50 c.c.). The ppt. of Mn oxides is dissolved by addition of K2SiEg is calc, from the vol. of solution and wash of excess (25 c.c.) of 0-lA-H 2C2O4 and the solution liquid. Insol. fluorides are fused with Si02+N aK C 03, is re-titrated with 0-lAr-KMnO4. The difficulty of and extracted with about 10% aq. (NH4)C03. F' in dehydrating NaH2P0 2,H20 is demonstrated. an aliquot part of the solution is determined as above. F. 0. H. J. S. A. Determination of small concentrations of Examination of therapeutic oxygen.—See B., arsine in air. B. A. Raschkovan (J. Gen. Chem. 1935, 1117. Russ., 1935, 5, 675—689).—H2S04 and H2Mo04 Determination of sulphur in soluble sulphides afford colourless sulphomolybd.ic acid (I), which is by photometric titration. S. IIir a x o (J. Soc. unstable when [H2S04]/[M o03] < 30, and yields Mo- Chem. Ind. Japan, 1935, 38, 598—601b).—The sol. blue when SnCl2 is added. Addition of H3As03 sulphide is neutralised with HC1 and titrated in pre causes formation of arsenomotybdic acid (II), which sence of gum arabic with 0-01 and 0'001iV-Pb(N03)2 is in equilibrium with (I) and H2S04; when [H2S04]/ and HgCl2, the end-point being determined photo [Mo03] >75, (II) is not formed, and no coloration metrically? BiCl3 may be similarly used in slightly results with SnCl2. The following procedure, based acid solution. The method is trustworthy in presence on the above considerations, is proposed for determin of reducing agents (sulphite, thiosulpliate) which ation of A sH 3 (<2x 10“8 g.) in air : the sample of air preclude the use of the I method. R. S. B. is shaken with 10—20 c.c. of 65% H N 03, and a known vol. of the acid is evaporated to dryness after 24 hr. Determination of sulphuric acid in presence The residue is dissolved in a known vol. of H20, and of ferric salts. M. I. Gar ber and I. V. S tjrikov 1 c.c. of the solution is shaken with 1 c.c. of a solution (Trans. Butlerov Inst. Chem. Tech. Kazan, 1934, containing 3-4 g. of (NH4)2Mo04 and 3 c.c. of conc. No. 2, 35— 40).—Lunge’s method (A., 1905, ii, 350) H2S04 per 100 c.c. 15 min. later, the mixture is shaken was superior to those of Allen and Bishop (A., 1913, with 0-05 c.c. of aq. SnCl2 (prepared by dissolving ii, 722) and of Küster and Thiel (A., 1900, ii, 242). 25 g. of Sn in 30 c.c. of conc. HC1, adding a further Ch . A b s . (e) 20 c.c. of HC1, and diluting to 1 litre), and the color Determination of carbon disulphide and hydro ation is compared with that of a standard solution. gen sulphide in air.—See B., 1935, 1087. R. T. Potassium thiocyanate as a primary standard Determination of small amounts of boron by substance. I. M. K oltiioff and J. J. L inc.a x e (J. means of quinalizarin. G. S. Sm it h (Analyst, Amer. Chem. Soc., 1935, 57, 2126— 2131).—The 1935, 60, 735— 739).—A difference in colour produced side reactions occurring in the pptn. of Ag‘ solutions by equal amounts of quinalizarin with 1 c.c. of test with KCNS have beeninvestigated. KCNS is a suitable solution+9 c.c. of H2S04‘, and 10 c.c. of solution of standard for work of ordinary accuracy (±0-1% ). 9 : 1 H2SO,„ indicates the presence of H3B03, and may The solubility product of AgCNS at 24° in 0-05JV- be matched against a standard solution of H3B0 3. K N 03 is 3-2 x Kb12. E. S. H. The method is suitable for determining 1— 40 X10~G g. Stability of standard potassium thiocyanate of B. Al-Si alloys may be dissolved in 10% NaOll, solutions. E. N. T a r a n (J. Gen. Chem. Russ., 1935, the solution after acidification being examined for 5, 602—604).—The titre of OJiV-KCNS rises, during B as above. J. S. A. 8 months of storage, to a greater extent (+1-5% ) in Determination of carbon monoxide in admix presence of air and diffused light than in their absence ture with hydrogen and methane. G. M e y e r (-f-0-63%). The variations are ascribed to develop and A. Slooef (Rec. trav. chim., 1935, 54, 800— ment of micro-organisms. R. T. 803).— CO in a mixture of CO, H2, and CH4 may be Kjeldahl method. IV. Metallic catalysts and oxidised to C02 by passage over I20 5 at 120— 130°, metallic interferences. R. A. Osborne and J. B. the C02 being retained by a liquid-air trap during W il k ie (J. Assoc. Off. Agric. Chem., 1935,18, 604— measurement of the decrease of vol. Combustion 609; cf. A., 1934, 857).— Hg is the most satisfactory of a second sample with CuO completes the analysis. catalyst, but it must be pptd. as HgS before distill J. W. S. ation of NH3. Te, Ti, Fe, and Cu are also satis Dependence of the detection of carbon mon factory. Se, Mo, V, W, and Ag are satisfactory in oxide with palladium salt solutions on various ordinary amounts ( < 0-003 g.-mol. per g. of material) additions. W. D a lle r (Z. anal. Chem., 1935, 103, or under less violent conditions of digestion. Pt and 83— 88).—The presence of excess of acid or of chlorides larger amounts of Se, V, and Mn04' interfere. Mixed hinders the deposition of P d ; salts of weak acids, catalysts are not recommended for the digestion of e.g., NaOAc, favour the action. Solutions of Na2PdCl4 samples of flour. E. C. S. containing excess of Na2S03 are somewhat slowly Micro-determination of phosphorus. A. D. reduced by CO but not by H2, and may be used for the B r a u n (Trud. Vseso. Inst. Exp. Med., 1934, 1, analysis of CO-H2 mixtures. CH4 reduces Pd solutions No. 3, 171—174).—The Fiske-Subbarow method at 100°, or at 50° in presence of NaOAc. J. S. A. was modified by replacing the mixture of sulphite Determination of the C 02 pressure of natural and H sulphite by 30% CH20. Ch. A b s . (e) waters. A. P e k k a r in e n (Suomen Kem., 1935, 8, Oxidative determination of hypophosphite. B, 34— 35).— If a stream of air containing a known L. M a r t in i (Annali Chim. Appl., 1935, 25, 525— % of C02 is passed through dil. NaHC03 and the solu- X GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 43
tion is then shaken with a known vol. of air, the % Spectrographic micro-determination of zinc [in of C02 taken up is equal to that of the first air. This plant m aterial]. L. H. R ogers (Ind. Eng. Chem. principle has been applied to the determination [Anal.], 1935, 7,421— 422).—The method is applicable of free C02 in natural H20. R. S. when the concn. of Zn is 0-1—0 005%. Fe interferes in eonens. of about 1 %, but a procedure for making Electro-analytical determination of alkalis. allowance is suggested. E. S. H. K. A bresch (Angew. Chem., 1935, 48, 683—685; cf. B., 1935, 1059).—K and Na are separated by the Quantitative separation of lead from other perchlorate or platinichloride method, and are then cations by the chromate method. Z. K ar ao g la- each determined by the polarographic method (cf. n o v and M. Micitov (Z. anal. Chem., 1935,103, 113— B., 1933, 944; A., 1933, 1024). K and Na can be 119).—Pb is quantitatively pptd. as PbCr04 by determined in this manner conveniently and rapidly (NPI4)2Cr04 in HN03 solution, and may be so separated in solutions containing also Fe, Al, Ca, Mg, etc. from Cu, Ni, Ag, Ca, Ba, Mn, Zn, Cd, Sr, Fe‘", or Al. A. B.M. J. S. A. Application of spectrum analysis to deter Separation of lead from copper, cobalt, nickel, mination of alkalis and alkaline earths. V. and cadmium by carbon dioxide in pyridine Direct photometric determination of alkali solution. A. JIl e k , J. K ot’a , and J. V r e St ’al m etals. W. H. Ja n s e n , J. H e y e s , and C. R ichter (Chem. Listy, 1935, 29, 299—304).—The solution of (Z. physikal. Chem., 1935,174,291— 300; cf. A „ 1935, nitrates, containing alkali metals and > 0-2 g. of 185).—The liquid under examination is fed into a Cu, is made alkaline with 10% aq. C5H5N, the vol. compressed air-C2H2 flame and the principal strong is made up to 100 c.c., C02 is passed for 5 min., 2 c.c. line of the element to be determined, picked out of aq. NH3 are added, and C02 is passed for a further by a monochromator, falls on a photo-electric cell. 40 min. The ppt. of PbC03 is collected, washed with The magnitude of the photo-electric current, which is aq.-alcoholic C3H5N-NH3 mixture saturated with measured by allowing it to charge a Lindemann electro C02, ignited, and weighed as PbO ; Cu is determined meter, is within certain limits of concn. of the element eleetrolytically in the filtrate. Pb is separated from in the flame a linear function of the concn., which Ni and Co similarly, except that NH3 is omitted from is therefore determined by interpolation of data the solutions. A similar method cannot be applied obtained with solutions of known concn. The ex to separation of Pb from Cd. R. T. perimental error is ± 5 % . R. C. Use of eerie sulphate in determining cuprous J. Lawrence Smith fusion [method]. M. 0. oxide obtained by reducing sugars on Fehling’s Steg em a n E nglis L a m a r , W. M. H a z e l , and W. J. O’L e a r y (Ind. Eng. solution. R. A. and D. T. Chem. [Anal.], 1935, 7, 429— 431).—Modified pro (Trans. Illinois State Acad. Sci., 1934, 27, 75—76).— cedure is recommended. E. S. H. Cu20 is treated with excess of Ce(S04)2 and the latter titrated back with standard FeS04 (o-phenanthroline Determination of calcium phosphates. H. as internal indicator). The results are better than T rapp (J. pr. Chem., 1935, [ii], 144,93— 105).— Ca in those by the KMn04 and K 2Cr20 7 methods. CaHP04,2H20 can be determined (max. error, Ch. A bs. (e) -fO’17% to —0-18%) by dissolving the sample (0-7 Determination of mercury in mercuric cyan —0-1 g.) in 30 c.c. of 30% AcOH+1 c.c. of HC1 ide. E. Ca tte l a in (J. Pharm. Chim., 1935, [viii], (d 1-19) at 100°, diluting to 400 c.c., and adding 4 g. 22, 454— 456).—Hg(CN)2 acidified with HCI affords of (NH4)2C20 4 to the boiling solution. The ppt. HgS quantitatively when boiled with Na2S20 3. is ignited, treated with (NH4)2C03, and weighed as Traces of S are removed with Na2S03 and the residue CaCO.,. Similar results are obtained by dissolving is weighed. J. L. D. CaHP04,2H20 in HCI, diluting with H20 to 250 c.c., adding NH3 until the solution is red to phenol- Volumetric determination of mercuric chloride phthalein, and then 25 c.c. of 10% NH3. The by means of lead sulphide. N. A. T a n a n a e v and mixture is heated for several hr. on the water-bath, V. D. P onom arev (J. Appl. Chem. Russ., 1935, 8, 1076— 1078).—25 ml. of approx. 0-lAr-HgCl are kept overnight, and the pptd. Ca (P0 is -washed 2 3 4)2 boiled during 15 min. -with 25 ml. of an aq. suspension with H20 and weighed. Difficulties in the alkalimetric of freshly pptd. PbS, the solution is filtered, the determination, 3CaHP04,2H20+ 2N a0H = C a3(P04)2 -f-Na2H P04, by use of excess of 0- LY-NaOH and filtrate-]--washings are boiled, and titrated -with back-titration with acid are due to the tenacious 0-lAI-Na2CO3 (phenolphthalein); the HgCl2 content is calc, according to the reaction HgCl2+PbS -> occlusion of alkali by the ppt.; the optimum conditions HgS-rPbCl2. The mean error is —0-4%. R. T. are defined. Under suitable conditions, pptn. of PoOj by Mo04' is quant, and the ratio Mo03 : P20 5 Analytical reactions for detecting salts of is const. Variations are due to the ignition, whereby cerium and other elements with methylene-blue. reduction to ill-defined lower oxides readily occurs. L. P a sser in i and L. Michelotti (Gazzetta, 1935, Repeated alternate treatment with NH3 and ignition 65, 824— 832).— Complex compounds with charac of the blue residues leads to its complete dissolution teristic colours are formed when an aq. solution with the exception of a residue containing Fe20 3, A120 3, of methylene-blue is added to solutions containing CaO, and P20 5. The proportion of the blue matter the following ions : Ce"", Hg", PtCl6", Au’", Ir"", in the residue varies with the conditions of ignition; Pd", Mo04", Fe(CN)6"', Fe(CN)G"", CNS', Cr20 7". it is richer in P20 5 than the portion sol. in NH3. With many other ions no characteristic colours are H. W. formed. The intense scarlet coloration formed with 44 BRITISH CHEMICAL ABSTRACTS.— A. X
Ce"" salts can be used for detecting this element in either by Na2C03 or by conversion into a complex presence of all other elements of the third analytical fluoride. Removal of Fe by means of pptd. CaC03 group, including Fo and Cr. The composition of leaves the sensitivity of the Co test unimpaired, so many of the coloured ppts. is given. 0. J. W. that 1-5 mg. of Co per litre can be detected in presence of 15 g. of Fe. F. L. U. Colour reactions of rare-earth metals with pyrogallol and gallic acid. II. F. M. S ohem - Analysis of iron and nickel present together. ja k in and T. V. V asciiedtschenko (J. Gen. Chem. J. IIanus and J. VofiiisEK (Chem. Listy, 1935, 29, Russ., 1935, 5, 667— 674; cf. A., 1934, 621).— The 288—295).— When N i: Fe < 1 : 40, a single pptn. of phenomena observed when solutions of Ce(N03)3, NH3, Fe suffices [acetate, succinate, and (CH2)„N4 pro and pyrogallol or gallic acid (I) arc mixed are repre cedures], whilst when N i: Fe > 1 : 40 a double pptn. sented on triaxial diagrams. A colorimetric method is necessary for the first two methods, but does not for CeHi determination, based on the diagrams, give complete separation in the third method. The consists in placing 4 c.c. of O-OOlif-(I) in a Nessler amount of Ni carried down with the Fe ppt. may be cylinder, adding 4 c.c. of 0-0001—0-0002il/-Cem , reduced by adding AcOH to 0-OliV and NH4C1 to 1%. and 2 c.c. of 0-1j1/-NH3 containing 1% of Na2S03, The fraction of the Ni pptg. together with Fe is const, filling the remaining space with Et.,0, and comparing for a given N i: Fe, irrespective of the vols. of solutions the intensity of coloration with that of a standard taken. R. T. solution after
however, is applicable to the determination of -£ Use of a: [heated] bar in determining m.p. 6 X 10-6 g. of Ti. R. T. R. D olique (J. Pharm. Chim., 1935, [viii], 2 2 , 441— 451).—The temp, gradients along bars of different Colorimetric determination of titanium in metals heated at one end and with different cross- presence of bromine compounds. G. P. Lut- sectional areas are studied and the method is applied schtnski and A. I. L ichatscheva (Z. anal. Chem., to the determination of m.p. J. L. D. 1935, 103, 196— 198).—A high [H2S04] and a largo excess of H20 2 are added to the Ti solution, liberating Colour temperatures of the Hefner and acetyl Br quantitatively. Br is extracted with CHC13, and Ti ene flames. A. R. P earson and B. P leasance in the aq. layer determined from the yellow coloration (Proc. Physical Soc., 1935, 47, 1032— 1041).—The remaining. J. S. A. colour of the “ cylindrical ” C2H2 flame depends on gas pressure, rate of consumption, and height of Detection of vanadium. E. I. K retsoii (J. Appl. flame. In view of discordant data for photometric Chem. Russ., 1935, 8, 1092— 1094).— 5— 100 mg. of purposes, results for various burners and conditions powdered salt or alloy are mixed with 0'05— 0-1 g. are given. The colour temp, for C2H2 flames is of wood C and 0 2 —0-5 g. of anhyd. A1CI3, and the approx. 2380—2520°, and for the Hefner flame 1910° mixturo is gently heated for 1—2 sec. in a test-tube abs. N. M. B. having a plug of glass-wool moistened with 75% H 2SO,j inserted at about 7 cm. from the bottom, Simple thermo-regulator. II. P. B lo xam (J. when an orange coloration indicates V (< 0-01 mg. Sci. Instr., 1935,12, 361— 363).—A bimetallic instru as V20 5). Other elements not giving coloured ment with a general accuracy of ¿ 2—3° is described. chlorides volatile at < 150° do not interfere. R. T. It is suitable for temp, up to 300°. C. W. G. Persulphate method of determining vanadium. Semi-automatic potentiometer for thermal analysis. R. J. M. P a y n e (J. Sci. Instr., 1935, 12, L . N. M on jak ov a (Rept. Cent. Inst. Mot., 1934, 348—355).—A mechanically-driven potentiometer is No. 16, 197— 199).— Factors affecting the method [e.gr., the rate of reduction of V with Mohr’s salt, combined with an inverse-rate recorder. G. W. G. and the time for oxidation of excess of Mohr’s salt with Determination of the b.p. of small quantities (NH4)2S2Os], and its application for determining of substances. R. D olique (Bull. Soc. chim., 1935, V in high-V steel were studied. Ch. A bs. (c) [v], 2, 1832— 1847).—A differential Hg manometer Possibility of determining bismuth as basic is described, which can be used for measuring v.p. and b.p. with only a few drops of liquid. The appara carbonate. F. H ech t and R . R eissner (Z. anal. Chem., 1935, 103, 186— 189).— Bi, in solution as tus can bo made suitable for the fractional distillation nitrate only, is treated at room temp, with the min. of small amounts of liquid, and can bo used for dis excess of aq. (NH,t)2C03. The liquid is heated to tinguishing a pure liquid from an a/.eotropic mixture. boiling, and the ppt. of (Bi0)2C03 is washed and dried 0. J. W. Precision determination of lattice constants. at 100°. The method may be applied to micro- analytical determinations. J. S. A. E. R. J ette and F . F oote (J. Chem. Physics, 1935, 3, 605— 616).—Theoretical and experimental con Micro-electrolytic determination of bismuth ditions necessary for the precise determination of and lead, and their separation by graded poten lattico consts. are discussed with reference to sym tial. A. J. L in d s e y (Analyst, 1935, 60, 744— 746).— metrical focussing cameras. Methods for the evalu Bi is deposited at 60—70° from dil. HN03 solution ation of standard errors and fiduciary limits of results at a potential of 0-8 volt, in presence of N2H4,H20 from one film and from a set of films are dovelopod. as depolariser. Pb is deposited anodically as P b02 X-Ray targets of alloys have been used to obtain a from dil. HNOs at 90— 100°, at a potential of < 1 volt. larger no. and better distribution of lines. The For the separation of Bi and Pb, Bi is first deposited influence of the no. of Miller indices of diffraction as above. The solution and washings are treated lines on the vals. of lattice consts. in non-cubic systems with an excess of N a0H +N a20 2, and are finally is shown. The importance of the method of prop, acidified with HN03. P b02 is deposited at a potential of the samples is emphasised. Lattice consts. of of 1-2 volts, and is preferably rcdissolved and re- pure Al, Ni, Ag, Au, Si, Fe, Mo, W, Mg, Zn, Cd, Sb, deposited from 20% HN03. J. S. A. Bi, and Sn have been measured. T. G. P. Determination of bismuth with [a-]naphtho- New technique for obtaining X-ray powder quinoline. F. H ech t and R . R eissn er (Z. anal. patterns. R. A. St e p h e n and R. J. B arnes Chem., 1935,103, 88—98).—To a solution containing (Nature, 1935, 136, 793—794).—In the method Bi as Bi2(S04),-)-3% free H2S04, 2-5% aq. a-naphtho- described a flat specimen such as is met with in quinoline sulphate (I) and some H2S03 are added and metallurgical practice is used, the intensity of each then an excess of KI. Ci3H9N,IIBii4,H20 is pptd., line can bo easily calc., and the sharpness controlled, and is collected on a glass filter. The ppt. is washed and the time of exposure is lessened in certain cases. twice with a solution of (I)-(-KI (3 c.c. for 10 mg. Bi), L. S. T. followed by > 6 c.c. of H20. The ppt. is dried at Variable-temperature X-ray powder camera. room temp., and the Bi calc, as if from C13H9N,HBiI4. W. H. B arnes and W. F. H ampton (Rev. Sci. Instr.. V ols. of solution and wash liquid must be rigidly 1935, [ii], 6, 342—344).—Temp, between —60° and adhered to, to ensure compensation between H20 0° are obtained in the camora by circulating through in the ppt. and loss of C13H9N,HI during washing. it a suitable liquid precooled in a separate bath. J. S. A. C.W . G. 46 BRITISH CHEMICAL ABSTRACTS. A. XI
Two-crystal spectrometer for X-rays of wave 1934, 16, 169— 178; Chem. Zentr., 1935, i, 2141).— length 0 -0 3 0 < ). < 0 -2 1 5 A. T. It. K u y k e n d a l l A magnetic balance, especially suited for measurement and M. T. J ones (Rev. Sci. Instr., 1935, [ii], 6, on paramagnetic substances, is described. Conditions 356—361).—Transmission and reflexion through the necessary for abs. measurements on ferromagnetic body of the crystals are empoyed instead of reflexion material have been investigated. J. S. A. from the surface. Specially designed induction coils Accurate measurement of volumes, and accur and a cascade Coolidge tube for a source of short-X ate titration. R. G o ltz (J. Gen. Chem. Russ., 1935, X-rays are described. C. W. G. 5, 779— 782).—A burette adapted for the accurate Trichromatic colorimeter. R. D o n a ld so n delivery of liquids is described, and conditions for (Proc. Physical Soc., 1935, 47, 1068— 1073).—A prep., standardisation, and storage of standard solu simplified instrument for use with a.c. or d.c. is tions are specified. R. T. described. The integrating properties of a diffusing Absorber for titrimetric determination of sphere are employed to effect the mixture of the three traces of admixtures to gases. V. G. G u r evitsc h instrumental stimuli; means are described for (J. Appl. Chem. Russ., 1935, 8, 1107— 1109).— A obtaining linearity of the scales. N. M. B. wash-bottle for the absorption of traces of admixtures Universal colorimeter-nephelometer. A. A. to gases is described. R. T. M aliq in (J. Appl. Chem. Russ., 1935, 8, 1.110— 1115). Kjeldahl flasks and other apparatus of arsenic- —A double-wedge colorimeter, also adapted to free glass. G. L ockem ann (Z. anal. Chem., 1935, ncphelometry, is described. R. T. 103, 81— 82).—The use of apparatus of special Jena Optical system of the disappearing-filament As-free glass (cf. A., 1935,948) is discussed. J. S. A. pyrom eter. F. A. Cu n n o l d (Proc. Roy. Soc., 1935, Pyknometer. G. A. F e s t e r (Rev. Fac. Quim. A, 1 5 2 , 64— 80).—Reflexion at tho round filament is Ind. Agric., 1934, 3, 177).—The apparatus consists negligible in tho usual typo of disappoaring-filament of a tap-funnel attached to a narrow U-tube with a pyrometer. Perfect disappearance of tho filament is bulb on tho other limb and a graduation mark above not essential for tho attainment of max. accuracy. the bulb. The liquid is run in through the tap until Tho aperturo limits suggested by previous workers tho meniscus reaches the mark, and the excess in the may bo considerably widened, enabling pyrometers funnel is washed out before weighing. D. R. D. transmitting much more light to be constructed. L. L. B. Absorption and titration flask for carbon Construction and use of a quartz quarter dioxide determination. R. G a r d n e r (Ind. Eng. Chem. [Anal.], 1935, 7, 437— 438).— A modification of wave. G. B r u h a t and L. W eil (Compt. rend’., 1935, Thomas’ absorption unit (B., 1933, 574) is proposed. 2 0 1 , 719—721). H. J. E. E. S. H. Bism uth electrode. D. N. M e h ta and S. K. K. Continuous distilling apparatus. F. M. S c h e r tz J a tk a r (J. Indian Inst. Sci., 1935, 18a , 109— 113).— (Ind. Eng. Chem. [Anal.], 1935, 7, 441).—The Tho Bi electrode can be used for pu 5-0— 7-4. apparatus is suitable for liquids with b.p. 20— 100°, C. W. G. and minimises risk of fire. E. S. II. Glass electrodes. P. L. V a r n e y (Science, 1935, Glass water-stills. B. S ie d e (Chem.-Ztg., 1935, 8 2 , 396— 397),—A double-shank electrode is described. L. S. T. 59, 925).—Modern resistance glasses enable satis factory stills to be constructed. The simple all Micro-hydrogen electrode. J. L o b e r in g (Z. anal. Chem., 1935, 103, ISO—183).—An electrode for glass apparatus without rubber or ground joints use with < 0-1 c.c. of liquid is described. J. S. A. illustrated compares favourably with metal stills for efficiency. G. H. C. Unpolarisable electrodes to carry action cur rents.—See A., 1935, 1552. Molecular still. W. H. St r a in and W. M. A l l e n (Ind. Eng. Chem. [Anal.], 1935, 7, 443).—Apparatus, Application of controlled potential to micro accommodating 1—2 g. of substance, suitable for chemical electrolytic analysis. A. J. L in d s e y the purification of biological products is described. and H. J. S. Sa n d (Analyst, 1935, 60, 739— 743).— E.S.H. Apparatus and procedure are described. J. S. A. Automatic cut-off for electric stills. M. R. A. Sound-proof box for electrically driven labor R ao and B. S. R ao (Ind. Eng. Chem. [Anal.], 1935, atory centrifuges. X. P ollard (Analyst, 1935, 60, 7,377). E.S.H. 752— 753). J. S. A. Automatic still cut-oS. A. H. H ale and F. D. Image errors of the electron microscope. W. Tuem m ler (Ind. Eng. Chem. [Anal.], 1935. 7, 441). G la s e r (Z. Physik, 1935, 9 7 ,177— 201).— Comma and E. S. H. spherical aberration errors are discussed theoretically. A ll-glass valve. J. W i ll a r d (J. Amer. Chem. A. B. D. C.' Soc., 1935, 57, 2328—2329). E. S. H. [Mechanical] relay for spark counters of the Superiority of a Knudsen type vacuum gauge Greinacher type. H. T e ic h m a n n (Nature, 1935, for large metal systems with organic vapour 136, 871— S72). L. S. T. pumps, its design and operation. J. W. M. Magnetic properties of natural and artificial DuMond and W . M. P ic k e ls , jun. (Rev. Sci. Instr., iron-oxygen compounds. I. Magnetic measure 1935, [ii], 6, 362— 370).—A discussion of the advant ments on powder samples. W. L uyken and L. ages and disadvantages of different tvpes of gauge. K r a e b e r (Mitt. Kaiser-Wilh. Inst. Eisenforsch., C. W. G. XI GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY.
Use of the Pirani gauge in finding vacuum glyoxime, mixtures of A1 and Fe (or of Al, Fe, and leaks. T. It. C u yken d all (ltcv. Sci. Instr., 1935, Ti) hydroxides, NaCl and KC1 (1 : 1), MgNH4P0.1, [ii], 6, 371—372).—Gauges may be made from C- graphite ash, MgNll.,AsO.,, Na*SQ4, MnNIi4P0.,. filnuicnt lamps. Leaks are shown by the gauge CaC03, a mixture of K2820 7, A120 3, and Fe20 3 (the if a stream of illuminating gas is played over the surface loss in wt. was — that of a Pt vessel used under similar of the apparatus. ' C. W. G. conditions), CaC20 4, and BaS04. A. L. R. Precision oil gauge. S. Palkin (Ind. Eng. Diacolation and filtration under pressure. C. C'hem. [Anal.], 1935, 7, 434— 435).—The gaugo is R ohm ann and J. II. E ulers (Plmrm. Ztg., 1938) suitable for measuring pressures < 4 0 mm. with a 80, 1190— 1197).— -A laboratory apparatus for main precision of about 0-033 mm. Tig. E. S. II. taining const, pressures 4-1 atm. for a const, delivery Design of pressure control assembly. S. Pa l of 1 c.c. per min. from the diacolator or filter over a k in (Ind. Eng. Clicm. [Anal.], 1935, 7, 430).—The period of 80 hr. is described. E. 11. 8. apparatus previously described (A., 1934, 1195) is Determination of the v.p. of compounds of modified. E. S. II. m otals. D. N. Tarasenkov, A. N. Grigorovitsch, Sampling apparatus for cliemical-climato- and A. V. Bogoslovskaja (J. Gen. Chem. lluss., logical and technical investigations. H. Ca u e r 1938) 5, 924—933).—Jcllinck’s method (A., 1929, (Z. anal. Cliem., 1935,103, 100—180).— Portable and 1202) is preferred to that of Volmer (ibid., 1220). permanent installations of pump, flow meter, air Tho b.-p. method gives trustworthy results for salts filter, and absorption tubes for air sampling aro de of high v.p., On condition that no decomp, occurs. scribed, and their uses indicated. J. S. A. Johnston’s static method (A., 1908, ii, 358) is in par ticular convenient for determination of dissociation Cataphoresis chamber for measurement of pressure when one of tho products is a gas. R. T. the cataphoretic migration velocity of micro scopic particles. R. ITa v e m a n n (Biochcm. Z., Stirring air within desiccators. F, J. Z in k 1935, 281, 402— 407).—The usual methods for (Ind. Eng. Chem. [Anal.], 1935, 7, 442-443).—Small determination of £-potential and the thcoroticnl fans mounted on pivots inside tho desiccator are requirements for microscopic measurement of cata caused to rotate by a series of mechanically moved phoresis in suspensions with the help of a closed cham permanent magnets passing near the outside. ber are discussed. Tho setting up of a stiitablo E. S. 11. chamber is described. P. W. C. Reflux condenser for use with Erlenmeyer Laboratory apparatus for ammonia synthesis. flasks. J. W. Olson and 0. E. B lass (Ind. Eng. Chem. [Anal.], 1935, 7, 444). E. S. II. V. F. P o stnikov (Trans. Inst. Chem. Tech. Ivanovo, 1935, GG—67).—Apparatus for tho study of catalytic Liquid absorption tube. W. I). T u r n er (Ind. NH3 synthesis at 500°/100 atm. is described. R. T. Eng. Chem. [Anal.], 1935, 7, 444). E. S. H. Precise method of measuring viscosity of solu Carbon dioxide from “ dry ice.” W. S. Idb tions of organic substances. A. v a n d e r W y k (Ind. Eng. Chem. [Anal.], 1935, 7, 442).—Solid CO., and Iv. II. M e y e r (J. Chim. phys., 1935, 32, 549— is a convenient source of gaseous C02 for uso in the 563).—With the object of determining viscosities determination of N by the micro-Dumas method. of dil. solutions of org. substances the errors in Ubbo- A suitable apparatus is described. E. S. II. lohde’s method have been examined in detail, and Continuous production of distilled water free necessary precautions and corrections ascertained from carbon dioxide and ammonia. F. G. so that t] may be found in the range 0-015—0-050 Stra ub (Ind. Eng. Chem, [Anal.], 1935, 7, 433— with an accuracy of 4 x 10 g./cm. sec. T. G. P. -4 434).— Tho apparatus described gives a distillate Structure-capillary viscosim eter. V. Z. D a n e s having a conductivity of 0-5—0-3x10-® mho and p,r (Kolloid-Z., 1935, 73, 17-4—181).—An overflow capill 6-8. E. S, H. ary viscosimeter with a very wide range of working Calculation of AD in a crystal growth process. pressures is described. Results are given for II20 M. Gordon (Ind. Eng. Chem. [Anal.], 1935, 7, 386— and some aq. solutions. E. S. H. 387).—‘Mathematical. E. S. H. Durability of quartz glass ignition vessels. Decantation of crystalline suspensions. I. M. A. B esborodov and T. A. L ad e (J. Soc. Glass General theory. II. Characteristic functions. Tech., 1935, 19, 217— 220t ).—Measurements of tho G. B ozza (Atti R. Accad. Lincoi, 1935, [vi], 21, 097— loss in wt. of transparent fused Si02 vessels when used for the ignition of various ppts. encountered in quant, 700, 752—755).— Mathematical. O. J. W. analysis showed that, after three successive heatings, Decantation of suspensions of crystals. III. the corrosion was greatest with PbS04 (especially Continuous cylindrical decanting apparatus. G. marked), ZnNH4P04, ZnC03, and Sn02. Little or B ozza (Atti R. Accad. Lincoi, 1935, 21, 809—813).— no loss in wt. was caused by the following, for the Theoretical, Formuke correlating rate of flow, ignition of which fused Si02 vessels are recommended : efficiency, tho dimensions of tho apparatus, concn. K N 03, K2PtCl6, MgSOj, HC1 (conc.), Ni dimethyl- of suspended matter, etc. are evolved. D. R. D.
E 48 BRITISH CHEMICAL ABSTRACTS.— A. XIII
Geochemistry.
Reduced thickness of the atmospheric ozone R. H. F lem in g (Proc. 5th Pacific Sei. Cong., 1933, [layer] during Polar winter. D. B a r b ie r , D. 3, 2085— 2088).—The surface layer had 150 mg. of Ch a l o n g e , and E. V a ssy (Compt. rend., 1935, 201, org. N and 30 mg. of NH3-N per cu.m., N 02' and 787— 789).— The quantity of 0 3 in the atm. has been N 03' being absent. The [NH3] was const, to a depth studied spectroscopically at Abisko (Swedish Lapland) of 70 m. N 03' was found at 40 m. and below. and compared with charts of air movements. In- Ch . Abs. (e) ci eased reduced thickness of 0 3 coincided with an Abnormal density of water from the deep invasion of Arctic air, which is richer in 0 3 than that portions of Lake Baikal. J. M e n d e l e e v (Compt. of lower latitudes. The method permits the study rend. Acad. Sei. U.R.S.S., 1935, 3, 105— 10S).—-The ol displacements of large masses of stratospheric air. d of samples of H20 from different depths of the lake Since air coming from regions to the north of the increase with increasing depth of the sample. Com aurora zone is rich in 0 3 the origin of the latter is parative vals. for the sample before and after distill problematical. It. S. B. ation show an almost const, diminution of d on distill Visual spectroscopic study of atmospheric ation. W. R. A. ozone. J. Ga u z it (Ann. Physique, 1935, [xi], 4, Sulphur bacteria in the 11 pink ’ ’ waters of 450— 532).—A simple spectrophotometer is described the Surakhani oilfields and their significance for the estimation of the abundance of atm. 0 3 by in the geochemistry of water. V. T. M a lisc h e k observation of the Chappuis bands when the sun is a and A. A. M a l ia n c (Compt. rend. Acad. Sei. U.S.S.R., few degrees below the horizon, by the study of the 1935, 3, 221— 224).— Bacterial oxidation and re 0 3 absorption bands in the ultra-violet from ob duction are discussed. C. W. G. servations of the blue sky, and by lunar spectrophoto Occurrence of selenium in the Colorado River metry. Results of 156 measurements over 15 months and some of its tributaries. K. T. W illiam s and show a max of 0 3 in Mareh-April, and a min. in II. G. B y e r s (Ind. Eng. Chem. [Anal.], 1935, 7, 431— August-September. The distribution of 0 3 in a 432).— The Se content has been determined and its horizontal stratum was examined. Assuming the origins are traced. E. S. H. “ thin layer ” hypotheses, the estimated height of this layer is 20—50 km., with an average val. of 33 km. Boron content of sea-water of the North N. M. B. Atlantic Coast. N. W. R a k e s t r a w and H. E. Emanation content of air from the soil and M a h n c k e (Ind. Eng. Chem. [Anal.], 1935, 7, 425).— underground tectonics. (Foundation of geo The variation with locality and depth has been physical investigations on the basis of eman investigated. E. S. H. ation measurements in air from soil.) H. Coastal ground water at Yumigahama, Tot- I sr ael-K oh ler and E. B e c k e r (Naturwiss., 1935, tori. Y. T o y o iia r a (Mem. Coll. Sei. Kyoto, 1935, 23, 818).—It is assumed that Pick’s law of diffusion A , 18, 295—309).— A theory based on hydrodynamical governs the distribution of Rn in the air derived from considerations holds good for the actual sea-shore as the upper layers of soil. Three cases are possible : well as for models. C. W. G. (a) the emanation originates completely in the sur Geochemical characteristics of protocrystall- rounding earth, (b) an active layer at a certain depth isation. A. E. F er.sm an (Compt. rend. Acad. Sei. is covered by weaker and inactive layers, (c) the U.S.S.R., 1935, 3, 21&—220).—Theoretical. sources of Rn are tectonic clefts covered with weakly C. W. G. active sedimentary layers. In the normal case the Granite of Schärding [Upper Austria]. G. Rn content of the air increases rapidly with depth H o r n in g er (Tsch. Min. Petr. Mitt., 1935, 47, 26—79). and reaches a const, concn. at a depth of about 5 m. —A description is given of the rock, with chemical In other cases the concn. varies exponentially with analyses. L. J. S. the depth. A. J. M. Baryte from Kitzbühel, Tyrol. H. L e itm e ie r Daruvar thermal spring. S. M iiio lic (Bull. (Tsch. Min. Petr. Mitt., 1935, 47, 1—25).— White Soc. Chim. Yougoslav., 1935, 6, 121— 129).—The sparry baryte occurring as veins in dolomite has analytical data do not differ from those obtained in long been mined at this locality. The dolomite-rock 1S39. R. T. contains BaO 0-15% (sol. in HC1 and presumably as Ansh-Bulat sulphate lake, and the possibilities carbonate) near the veins and 0 08% at some distance of its exploitation. A. B. Z d a n o v s k i and D. I. from them, but there is no evidence that the baryte R jabtschikov (J. Appl. Chem. Russ., 1935, 8, 981— was accumulated by lateral secretion from the rock. 993).— The II.>0 contains 17-4% of solutes, chiefly At one place the mineral is violet-coloured, but this Na2S04 6-9," MgS04 2-5, and NaCl 7-6%. quickly fades on exposure to light, and is restored by Na2SO.1,10H2O crystallises out over the range 16° exposure to Ra. L. J. S. to —5°, and the mother-liquors yield 80 kg. of NaCl Wollastonite and parawollastonite. M. A. P e a per ton when conc. at 25° and then cooled to —10°. cock (Amer. J. Sei., 1935, [v], 30, 495—529).— The final filtrates can be further conc. for the prep, Measurements of wollastonite crystals from Crestmore, of MgCL, and Br. R. T. California, show them to be triclinic, whilst crystals Distribution of nitrogen compounds in the sea from the limestone blocks of Monte Somma, Vesuvius, near Southern California. E. G. M oberg and are mostly monoclinic, but some are triclinic and others XIII GEOCHEMISTRY. 49
consist of an intergrowth of the two kinds. In both Batopilas, native Ag is associated with safflorite, kinds the angles and cleavages in the prism-zone rammelsbergite, arsenopyrite (I), galena (II), and parallel to the 6-axis are identical, and the optical sphalerite (III). All the evidence indicates a primary characters are the same, except that in the triclinic origin for the Ag. The probable order of deposition crystals the extinction is 2 i°to the 6-axis. The name is (i) sulphides, including pyrite, (II), and (III), wollastonite is reserved for the more common triclinic (ii) Ni and Co arsenides and (I), and (iii) Ag minerals form, and the monoclinic form is called parawollas- and Ag. At Bullard’s Peak, native Ag is associated tonite. A third modification of CaSi03 is pseudo- with a Ni-skutterudite in a manner similar to that of wollastonite. L. J. S. Ag and arsenides in the Cobalt district of Ontario. “ Ferrosilite ” as a natural mineral. N. L. Primary origin of the Ag, and centrifugal replace ment of the arsenide by Ag, arc indicated. L. S. T. B o w e n (Amer. J. Sci., 1935, [v], 3 0 , 481^194).— “ Ferrosilite,” FeSi03 (A., 1932,92G), has been asserted Monazite from West Portland Township, to have no real existence (A., 1932, 997; 1933, 1120; Quebec. I. H. S. Sp e n c e . II. O. B. M u e n c h 1935, 447). Minute acicular crystals found in the (Amer. Min., 1935, 2 0 , 724— 732).— I. The waste lithophysse of an obsidian from Lake Naivasha are dump of a felspar quarry at 45° 45' 30” N, 75° 36' 30” monoclinic with a prism angle of 90° 50', a 1-763, W contained tourmaline, euxenite, monazite, allanite (3 only slightly greater, y 1-794, c : y=34|°, 2 7 very (?), titanite-f ilmenite, fergusonite (?), cyrtolite, small, suggesting a monoclinic pyroxene. From these muscovite, tengerite, and specularite. data it is further concluded (by extrapolation in the II. Analysis of the monazite by Fenner’s method systems CaSi03-FeSi03 and MgSi03-FeSi03) that gave Th 3-44, and Pb 0-068%; U, by emanation the crystals have the composition FeSi03, and the method, 0-054%. The Pb-U ratio is 0-053, giving mineral is named clinoferrosilite. The systems a val. of 388—391 X 10° years for the age of the mineral. CaSi03-FeSi03 and MgSi03-FeSi03 are now discussed The % of Pb obtained by a micro-analysis (A., 1935, afresh. Similar crystals were also found in lithophysal 1216) is less (0-032—0-05%) than that obtained obsidians from Iceland, Wyoming, and California; above by macro-methods. L. S. T. analyses of the obsidians are given. L. J. S. Piedmontite from Los Angeles County, Cali Composition of tectites. F. L o e w in s o n -L ess- fornia. R. R. Sim onson (Amer. Min., 1935, 20, in g (Compt. rend. Acad. Sci. U.R.S.S., 1935, 3, 181— 737—738).—Piedmontite occurs as small euhedral 185; cf. A., 1931, 60, 1028, 1146).—There are no crystals in quartz-sericite-biotite schist and in eruptive rocks analogous to tectites, although many quartzite from this locality. L. S. T. of the latter have acidity coeffs. and monobasic : di Radioactivity of ferro-manganese formations basic oxide ratios similar to rocks of terrestrial origin. in seas and lakes of the U.S.S.R. L. M. K u r b a J. W. S. tov (Nature, 1935, 1 3 6 , 871).—-The Ra content of Synthesis of pyrophyllite. It. Sc h w a rz and G. Fe-Mn bottom deposits of these lakes or seas varies T r ageser (Z. anorg. Chem., 1935, 225, 142— 150).— from l-2 x l0 -10% (Caspian Sea) to 31-8 x l(h10% In the synthesis of pyrophyllite (I) from orthoclase (Black Sea); it is much < in deep-water concretions or anorthite (A., 1935, 110i) montmorillonite is not of the Pacific Ocean (47-6— 146-6 X 10~10%). Small formed. The natural occurrence of kaolin or (I) concretions are more radioactive than large ones, arising from felspars may serve as a geological thermo and the surface layer is more active than the centre. meter, since (I) is not formed below 400°. F. L. U. The Th-X content is small. L. S. T. Structural relationship of glauconite and mica. Crystallised melanterite from Pfaffenreuth, J. W . Gr u n e r (Amer. Min., 1935, 2 0 , 699—713).— Bavaria. F. M ac h a t sc h k i (Zentr. Min., 1935, A, X-Ray investigation (data given) of 8 glauconites 53—54; Chem. Zentr., 1935, i, 2148).—Native subjected to various treatments shows that glaucon melanterite crystals, of octahedral habit, have been ite (I) is a mica in structure. The average vals. found; a : 6 : c=l-180 : 1 : 1-534, ¡3=104° 23'. from 6 specimens for the consts. are a0 5-24, 60 9-07, J. S. A. c0 20-03 A., ¡3 95° 00'. (I) is as stable as biotite at Maxixe beryl. K. Sciilossmacher and H. K lan g temp, as high as 750°. It can absorb T1 ions, (Zentr. Min., 1935, A, 37— 44; Chem. Zentr., 1935, which probably replace K" to > 25%. The high i, 2147).—Structure and characteristics of the stone Si02 and H20 content of (I) is apparently due to the are discussed. The blue pleochroic colour is rapidly environment in which it is formed. Excess of sol. lost on exposure to light. J. S. A. Si02 over sol. A120 3 gives rise to a S i: A1 ratio in the Osmiridium. III. X-Ray analysis. 0. E. (Si,Al) jO10 tetrahedral layer > in mica, and may even Z v jag in tzev and B . Iv. B ru n o vsk i (Ann. Inst. cause substitution of a few Si for Fe’" or A1 in Platine, 1935, No. 12, 5— 15; cf. A., 1932, 1107).— approx. the positions having a covalency of 6. In Natural osmiridium has a fibrous structure, probably comparison with a muscovite (I) may occasionally due to partial recrystallisation. Ch. A b s . (e) have vacant positions in its structure, and a suitable Gypsum crystals from Alfalfa County, Okla formula is (OH)6_10K „(M g,F c” Cah^FciH.Al.Si);™ hom a. C. A. M erritt (Amer. Min., 1935, 2 0 , 674). Probably one half of the H20 L. S. T. given in analyses is adsorbed. L. S. T. Method for removing iron oxide coatings from Primary native silver ores at Batopilas, minerals. M. D rosdoee and E. T ruog (Amer. Mexico, and Bullard’s Peak, New Mexico. P. Min., 1935, 20, 669—673).—The mineral is suspended K r ieg er (Amer. Min., 1935, 20, 715—723).—At in H20, treated with H2S, and then with 0-05X-HC1. 50 BEITISH CHEMICAL ABSTRACTS.— A. XTTT
Silicates and apatite are practically unaffected. Combined water in clay substance. O. K o e r - The action of H2S on hmmatite, limonite, goethite, n e r , K. P u k a l l , and H. Sa lm an g (Z. anorg. Chem., biotite, basalt, granite, and certain Fe-coated minerals 1935, 225, 69—72; cf. A., 1930, 720).—Isothermal is also described. L. S. T. dehydration of a very pure Zettlitz kaolin, extending over periods up to 1-5 years, shows that, contrary Augelite from Mono County, California. D. M. to the usual belief, the composition of the clay mol. L em m on (Amer. Min., 1935, 20, 664— 668).-—Augelite, is Al 0 ,2Si0 ,l-5H 0 , the remaining II20 being basic A1 phosphate, d 2-67, hardness 5, occurs as a 2 3 2 2 adsorbed. Dehydration proceeds by way of the hydrothermal mineral deposited from solutions which mono- and hemi-hydrates. F. L. U. acted on the andalusite (I) deposit subsequent to the formation of (I), corundum, diaspore, topaz, Minerals of Franklin and Sterling Hill, New etc. It is directly associated with lazulite, rutile, Jersey. C. P a l a c h e (U.S. Geol. Surv., 1935, Prof. barite, pyrophyllito, muscovite, alunitc, and quartz. Paper 180, 1— 135).—Detailed descriptions are given Other occurrences arc briefly described. L. S. T. of 148 minerals from this unique mineral locality; 30 of these minerals have not been found elsewhere. Pseudo-brookite. C. P a l a c h e (Amer. Min., 1935, 20, 660— 663; cf. ibid., 1934, 19, 16).-—Pseudo- In addition to details from the lit., many new crystall- ograpliic and optical data and some new chemical brookite from Thomas Mts., Utah, has [F. A. G o n y e e ] Fe20 3 60-57, T i02 38-12, and MgO 1-26, total 99-95%, analyses are given. Two new species are established : indicating an excess of approx. 4% of T i02 over that liydrohetaerolite, 2Zn0,2Mn20 3,H20, tetragonal (?), as required by Fe2Ti05. L. S. T. distinct from hetaerolite (Zn0,Mn20 3) ; and magnes ium chlorophoenicite, (MgMn)3As20 8,7(Mg,Mn)(0H)2, Mineralogical classification of igneous rocks : monoclinic, differing from chlorophoenicite in con comparison of recent proposals. S. J. S h a n d taining Mg in place of Zn. The primary ore is a (J. Gcol., 1935,43, 609—617).—Various classifications granular mixture of franklinite (43%), willemite based on texture, colour, degree of saturation with (26%), calcite (25%), zincite (1%), with tephroite Si02, composition of the felspar developed in a rock, and other silicates (5%). It is suggested that and the ratio of AL20 3 to bases are compared and dis hydroxides of Mn and Fe and liemimorphite were cussed. L. S. T. first formed by the metasomatic replacement of Mixing and unmixing of silicate rock magmas. limestone, and that this deposit was altered by regional G. Linck (Cliem. Erde, 1935, 1 0 , 126— 128).—A metamorphism in pre-Cambrian times, and further criticism (cf. Grigoriev, Zontr. Min., 1935, 242). alterations by later intrusions of pegmatites giving L. J. S. the complex variety of minerals. L . J. S. Lias clay from Dobbertin [Mecklenburg]. Heavy minerals of the 11 Erinpura ’ ’ granite F. K. S chlünz (Chcm. Erde, 1935, 10, 116—125).— and microgranite of Danta state (N. Gujrat). Chemical analyses and microscopical examination N. L. Sh a r m a and S. P u r k a y a st h a (Proc. Indian wcro mado of the fractions of the clay > g arid 1 Acad. Sci., 1935, 11, B, 369— 376).— Comparative < 1 g. X-Ray patterns show the latter to be mainly mineralogical data are recorded and discussed. halloysite. L. J. S. A. G. P. Minerals of lead slags. W. F a b e r (Cliem. Erde, Pre-Cambrian rocks of the Lake Superior 1935, 10, 67— 115).— Chemical analyses and optical Region. C. K. L e it h , R. J. L u n d , and A. L e it h determinations are given of several fractions separated (U.S. Geol. Surv., 1935, Prof. Paper 184, 1—34).— by heavy liquids from a Pb slag from the Harz. The correlation of the rocks in relation to their Tire minerals identified include a-colsian, willemite, geological age is discussed. The extensive deposits fayalite, magnetite, Zn-blende, and wurtzite. The of banded jaspery Fe ores were probably derived from diagrams of the systems CaO-FcO-Si02 and the weathering of volcanic rocks with chemical y-Ca.,Si04-MgoSi04-ZnoSi04-Fe.,Si04 are discussed. (or organic-algal) pptn. from solution and subsequent L. J. S. concn. by oxidation and leaching of Si02 by percolating Recent and fossil red earth (terra rossa) form surface waters. “ L. J. S. ation. E. B l a n c r and E. v o n Oldershausen (Cliem. Erde, 1935, 10, 1—66).—Analyses are given Dark inclusions in a tonalite of Southern of soils and of the underlying limestone from which they California. C. S. H u r l b u t , jun. (Amer. Min., 1935, are derived in the district of the southern Frankenalb 20, 609— 630).— Dark inclusions in a quartz diorite, in the Altmiild valley in Bavaria. L. J. S. known as the Bonsall tonalite (analysis given), are described. Plagioclase, hornblende, and biotite make Structure of dickite and other clay minerals. up the bulk of the inclusions and are always present, C. J. K sa n d a and T. F. W. B arth (Amer. Min., whilst quartz, orthoclase, and pyroxene are sometimes 1935, 20, 631— 637).— X-Ray measurements of dickite found in small amounts. The inclusions and the from Schuylkill Co., Pa., give a0 5-145, 60 8-882, tonalite are mineralogically similar, but the former Cq 14-337, p 96° 45', dcaic. 2-618, with four mols. of are xenoliths of older rock (gabbro) and owe their Al2Si20 R(0H )4 per unit cell; space-group or C*. present condition to reaction with the tonalite magma. A test for piezo-electricity gave a negative result, L. S. T. making the latter improbable. Gruner’s structure Paragenesis of the mineral assemblage at is, in the main, confirmed, but a certain difference Crestmore, Riverside County, California. J. W. renders proposed structures of kaolinite, nacrite, D a l y (Amer. Min., 1935, 20, 638— 659).—The geology halloysite, and vcriniculite uncertain. L. S. T. of the district, the rocks, and the minerals are X III, X IV (a) ORGANIC CHEMISTRY. 51 described. The mode of formation of the latter is Conversion of plant substances into fossil discussed, and the contact metamorphic minerals are coals.—See B., 1935, 1122. grouped under the rocks to which they owe their Origin of petroleum. G. A. F e s t e r and J. origin. L. S. T. C ru ee la s (Rev. Fac. Quim. Ind. Agric., 1934, 3, Radiometric prospecting of a [volcanic] flow 76— 108).—The following theory is put forward, of rhyolite. E . R o th e and (Mme.) A. IIAe (Compt. based on numerous analyses of relevant materials. rend., 1935, 201, 892— 893).—The deposit at Welsch- Marine flora and fauna suffer decomp, in tropical bruch has been delimited radiometrically. climates, evolving gases (including H2S) and leaving R. S. B. mainly fatty material, which by further decomp, is Occurrence of vanadium in fossil coals. V. converted into petroleum. In colder climates, the Silbermintz (Compt. rend. Acad. Sci. U.R.S.S., cellulose and lignin do not decompose completely 1935, 3, 117— 120).— 800 samples of coal of different and coal etc. are produced. This theory is supported types and origins were considered. Analyses for V by the geographical distribution of petroleum and coal. were made on 500 samples. Most samples show very The presence of colloidal V sulphides in South American slight content of V20 6 in the ash, but certain specimens petroleums is explained by the presence of vanadates contained up to 8-79% V20 5. Most coals high in (derived from the local igneous rocks) in the H20 , V205 are of the clarain-vitrain typo and often have the H2S causing pptn. of tho V. Analyses and other a lignite structure. Tho origin of V in coal appears to data concerning South American raphaelites and depond principally on local conditions. W. R. A. petroleum are given. D. R. D.
Organic Chemistry.
Free radicals. E. D arm ois (Bull. Soc. chim., Hydrogenation catalysis. II. Technique.— 1935, [v], 2, 2053— 2067).— A lecture. See this vol., 35. Thermal decomposition of nitromethane.— Oxidation of y- and (3-methyl-A8-pentene by See this vol., 33. selenium dioxide. A. Guxllemonat (Compt. rend., Thermal decomposition of hexane at high 1935, 201, 904—906; cf. A., 1935, 852).—y-Methyl- pressures. J. N. P e a rc e and J. W. New som e A-8-pentene with Se02 in AcOH gives y-metliyl- (Proc." Iowa Acad. Sci., 1934, 41, 139— 140).— A8-penten-8-ol (cf. A., 1910, i, 454) and [3-methyl- Between 460° and 490°/14,000— 15,000 lb. the gaseous A8-pentene gives ^-methyl-^-pcnten-a-ol, b.p. 61— product consists of 25% CH4, 47% C2H6, 15% 63°/14 mm. (Ac derivative, b.p. 61— 63°/12 mm.). C3Hg, and 7% C4H10; at 460° it contains 2-1% H2, J. L. D. 1-4% C2H4, 1-5% C3H8, and 2-1% C4H8. At 497° Kinetics and mechanism of thermal trans both H2 and C2H2 have disappeared and the C3H 8, formations of unsaturated hydrocarbons. Poly C4H 10, C3Hg, and C4H 8 have fallen to 5-5%, 4-0%, merisation of Aay-butadiene at atmospheric pres 0-04%, and 0-16%, respectively. At this temp, sure. V. G. Moor, N. V. Strigaleva, and L. V. abundant formation of C begins and the proportion Schilaeva (J. Gen. Chem. Russ., 1935, 5, 818—829). of CH4 increases. The liquid product contained —C4H 5 yields chiefly C8H12, b.p. 130°, when heated cycloparaffins, CGH6, substituted benzenes, and higher at 400°, whilst at higher temp. (450—700°) fractions unsaturated compounds. Ch. Abs. (r) of higher and of lower b.p. are obtained. The velocity of the reaction 2C4H 6->C8H12 varies with temp, Polymerisation of ethylene under high pres according to log K = —6400/Y-4-'7-32^0-04; the sures and in presence of phosphoric acid. V. N. energy of activation is 28 kg.-cal. per mol. R. T. I patiev and H. P in es (Ind. Eng. Chem., 1935, 27, 1364— 1369).—The gaseous products of polymeris Oxidation with selenium dioxide. Y. R. ation of C2H4 under pressure in presence of H3P04 at Naves and (Mme.) INI. G. I golen (Bull. Inst. Pin, 1935, 250°, 280°, 300°, and 330° contain chiefly C2H4 and iso- 234— 238).—A review of its various applications. C4H]q (2-5% of the total product at 250° and 18-8% J. L. I). at 330°), produced by hydrogenation of Aa- and A8- Acetylene series. VI. Oxidation of acetyl- C4H8. The liquid products b.jp. < 60° aro paraffins; enic hydrocarbons with permanganate. V. N. olefines are present in all fractions, naphthenes occur Rrestinski and M. K. Ivelbovskaja (J. Gen. Chem. in fractions b.p. > 110°, and fractions b.p. > 250° Russ., 1935, 5, 871— 876).— C2H2 and dil. aq. KMn04 are mainly aromatic, the proportions of tho lower at 0° afford HC02H (I) and traces of H2C20 4, CPh-CH paraffinoid and higher aromatic fractions increasing gives BzOH, C02, and traces of (I), CMe-CEt gives with rise of temp, of polymerisation. The thermal C02, AcOH, and EtC02H, and CBffilCH gives polymerisation of C2H4 in absence of H3P 04 gives BuyC02II, C02, and (I). Neutral intermediate oxid rise almost exclusively to olefines and naphthenes and ation products were not found in any case. R. T. aromatic compounds are absent. At 180° C2H4 and Atomic equilibria in hydrocarbon molecules H3P 04 give (OH)2POOEt, which decomposes at of the CH-C-CHaR series. E. F. Zeberg (J. Gen. higher temp, with the formation of olefines and naphth Chem. Russ., 1935, 5, 1016— 1019).— aP-Dibromo- enes. The latter are subsequently hydrogenated to y-phenylpropano and KOH at 100—120°, with or paraffins and dehydrogenated to aromatics, respec without EtOH, afford CPhiCMe and traces of tively. There is no evidence of cracking. S. C. CH2Ph*CH:CH2. R. T. 52 BRITISH CHEMICAL ABSTRACTS. A. X IV (O)
Action of acetylene on acetyl chloride. A. Preparation of pure sorbitol and sorbose and Cornillot and R. A lq u ie r (Compt. rend., 1935, the influence of this ketose on the conductivity 201, 857— 838).— Condensation of AcCl with C2H2 of boric acid. J. B o e se k e n and J. L. L e e fe r s in presence of A1CI3 at 15° affords Me fi-chlorovinyl (Rec. trav. chim., 1935, 54, 861— 865).— Details ketone (I), b.p. 40°/20 mm. [semicarbazone, m.p. are given for the prep, of an efficient Ni-Co-Cr 180° (decomp.)], which probably has a cts-configur- catalyst and its use in the reduction of glucose in ation and rapidly decomposes, even in the dark, 96% EtOH with H 2 at 150°/150 atm., to give cryst. with evolution of HG'l to an amorphous mass. With sorbitol. An improved oxidation of sorbitol to boiling NaOH-EtOH (I) gives a 20—25% yield of sorbose using Acetobacter suboxydans is described, C6H3A c3. J- W. B. oxidation being complete in 3-5 days instead of 4— 6 weeks, necessary with B. xylinum. Addition of Use of copper to increase the yield of ethyl 0Til/-H3BO3 to 0-llf-sorbose causes a much greater bromide. P. H e n d r ix s o n (Proe. Iowa Acad. Sei., increase in conductivity than does similar addition 1934, 41, 105).—Addition of Cu to the reaction to fructose. J. W. B. mixturo of EtOH, H2S04, HaO, and NaBr increases the yield of EtBr from 57% to S0%. The effect is Fluorination of halogenomethyl ethers. I. due to the liberation of S02, which reduces any free Fluorination of trichlorodimethyl ether. H. S. Br to HBr. ” Ch . A bs. (r) B o o th and Pi E. Burchfield (J. Amer. Chem. Soc., 1935, 57, 2069).—Treatment of CClyOMe with Photochlorination of ethylene.—See this vol., SbE3 without a catalyst yields Me chlorodifluoromethyl 37. ether, b.p. 55-3°, m.p. —105-1°, and Me trifluorometliyl Chlorination of propane.— See this vol., 35. ether, b.p. 30-1°, m.p. —96-2°. These compounds are only slowly hydrolysed by II20. E. S. H. Mechanism of slow oxidation of propane.— See this vol., 33. aS- and as-Oxido-compounds. Synthesis of as-oxidodecane. A. E r a n k e , A. K r o u p a , and 0. Photobromination of tetrachloroethylene and S chmid (Monatsh., 1935, 66, 406— 432).— Et liexoyl- of ch loroform .— See this vol., 37. acetate (improved prep, from technical Me heptinene- Isotopic exchange reactions with iodine.—See earboxylate) is converted by the successive action this vol., 40. of Na-fEtOH and CH2(CH2Br)2 followed by heating of the product under diminished pressure into Aluirunium alkoxides and their parachors. anhydrodecan-oL-ol-z-one (I), which readily adds H20 — See this vol., 14. giving decan-a-ol-z-one (II), m.p. 24-5—25-3°, b.p. Synthesis of octadecyl alcohols with branched 144— 14S°/11 mm. (distillable only in complete chain. 0. B r u n n e r and G. W ie d e m a n n (Monatsh., absence of acidic or halogenic impurities), which does 1935, 66, 438— 442).—CHEt(C02Et)2 is converted not reduce Fehling’s solution or NH3-A g20, is little by myristyl iodide in presence of Na and PhMc into changed when heated at 100°, and according to Et» ethylletradecylnialonate, b.p. 132— 136°/14 mm., optical evidence has the open structure hydrolysed and decarboxylatcd to a-cthylpalmitic C5H 12-CO-[CH2]3-CH2-OH. Oxidation of (II) with acid, b.p. 215— 220°/10 mm. (amide, m.p. I l l — 112 °), Cr03 in AcOH affords S-ketodecoic acid, m.p. 56-3°, the Et ester, b.p. 198— 203°/12 mm., of which is and s-keto-ii-decyl S-ketodecoate, m.p. 52°, probably reduced by Na and Bu°OH in light petroleum to formed through the semiacetal, since the direct $-ethylhexadccyl alcohol, m.p. 15° (non-cryst. phenyl- esterification of acid by alcohol is somewhat difficult. urethane; 4'-chlorodvphenylcarbamate, m.p. 105— 106°), (II) is unchanged by Al-Hg or Na-Hg in EtOH- Analogously, Et., n-bulyldodecylmalonate, b.p. 22V— H20, but is reduced by Na in 96% EtOH to decane- 226°/l mm., affords successively a-butylmyristic as-diol (III), m.p. 23— 24°, b.p. 155-5— 157°/11 mm. acid, b.p. 214— 219°/10 mm. (Et ester, b.p. 1S9— Hydrogenation (Pt sponge in Et20) of (I) leads to 192°/10 m m .; amide, m.p. 109— 110°), and. (5-n- ae-oxidodecane (IV), b.p. 198-5— 200-5°/747 mm., butyltetradecyl alcohol, b.p. 125— 130°/high vac., m.p. which is transformed successively into az-dibromo- 1° (non-cryst. phenylurethane; 4'-chlorodiphenyl- n-decane, b.p. 150— 151-5°/10 mm., az-dicyano-n- carbamate, m.p. 102— 103°). Et2 hexyldecylmalonate, decane, b.p. 187— 193°/9 mm., and non-cryst. a-n- b.p. 222—225°/12 mm., yields successively a- amylpimelic acid (diamide, m.p. 161-5° after softening at hexyl-lauric acid, b.p. 218—222°/12 mm. (Et ester, 160°); indications of the presence of isomeric diamides, b.p. 195— 19S°/12 mm.; amide, m.p. 110— 1110), and hence of a8-oxide in the initial material, are not and fi-hexyldodecyl alcohol, b.p. 120°/high vac., f.p. observed. Elimination of HaO from (III) by H2S0,t —7-5° (non-cryst. phenylurethane', 4-chlorodiphenyl- occurs at a noticeable rate with boiling 30% acid, carbamate, m.p. 77— 78°). Et., dioctylmaloiw.te, b.p. and then leads mainly to an unsaturated alcohol, 220—225°/15 mm., affords a-octyldecoic acid, b.p. C10H20O, b.p. 228— 231°/1 atm., with smaller amounts 212—218°/13 mm. (Et ester, b.p. 195— 197°/12 m m .; of an oxide essentially (IV). Interaction of amide, m.p. 122-5— 123-5°), and fi-octyldecyl alcohol, Br-[CH2],;-Br with CH2Ac-C02Et appears to lead b.p. 110 — 120°/high vac., f.p. —8° (non-cryst. phenyl- mainly to the cryst. diketone Ac-[CH2]8-Ac. Treat uretham; 4'-chlorodiphenylcarbainate, m.p. 96°). ment of dry NaOBz with Br-[CH2]0-Br at 200° affords 11. W. Z-bromohexyl benzoate (V), b.p. 1S7— 190°/9 mm., Existence of boric acid complexes with one and a.L,-dibenzoyloxy-n-hexane, m.p. 55-5— 56° after and two molecules of a diol in aqueous solution. softening at 55°. (V) and CH2Ac-C02Et in boiling — See this vol., 29. EtOH containing NaOEt afford a product which X IV (a, b) ORGANIC CHEMISTRY. 53
after successive acid and alkaline hydrolysis gives Addition of hydrogen bromide to triple and nonan-a-ol-Q-one, m.p. 23—23-5°. When heated with double linkings. Undecynoic, undecenoic, and H3PO4 the ketol gives only complex substances of tK-epoxyundecoic acids. P. L. H arris and J. C. uncertain constitution, whereas (II) readily yields (VI). Sm ith (J.C.S., 1935, 1572— 1576).—The reaction H. W. between A‘-undecinenoic acid and HBr is sensitive Constitution of adenylpyrophosphoric and to “ oxidants.” In the presence of Bz02H (I) (modi adenosinediphosphoric acid. K. L o h m a n n (Bio- fied prep.) at 0° during 3 hr. /c-broinouiidecenoie chem. Z., 1935, 2 8 2 , 120— 123).—Examination of the acid (II) is formed, whilst in the presence of NHPh2 electro-titration curve of adenosinediphosphoric acid the reaction is slower and the i-Br-acid (III) results” (I) before and after hydrolysis indicates that it is Undecenoic acid (IV) and (I) (in Iigroin at 30° during adenylic acid (II) esterified with 1 H3P04 and that 24 hr.) yield iK-epoxyundecoic acid (V), m.p. 45-5° adenylpyrophosphoric acid (III) is (II) esterified (after 10 days m.p. 50°), which reacts with HBr in air, with 2 H3P 04. Constitutional formulæ, based on forming mixed bromohydrins, m.p. 49—53°. In these and other deductions, arc given for (I) and (III). Iigroin solution (IV) and HBr in air yield (III); The NH2 of the adenine residue is free in (I) and (III). in presence of (I) (0° during 15 min.) or (V) the product W. McC. is (II). None of the catalysts is effective in absence Introduction of chlorine into nitromethane- of mol. 0 2. F. N. W. disulphonic acid. H. J. B a c k e r (Rec. trav. chim., 1935, 54 , 899—904).—The following salts of nitro- p-Xenylamine as new reagent for the identi methanedisulphonic acid (A., 1931, 64) are described, fication of fatty acids and fatty acid derivatives. crystallographic data (by T er tstr a) being given for Synthesis of the p-xenylamides [p-phenylanil- some of these: dibrucine-\- 10H2O, Pa2+ 2H ,0, K 3, ides] of oleic and elaidic acid and their bromo- Tl3, and Ba3. All salts of type M02NiC(S03Mj2 derivatives. W. K im u r a and M. N ih a y a s h i (Bcr., are explosive. The action of Cl2 on K 0 2N!C(S03K )2 1935, 68, [R], 2028—2034).—The p-phenylanilides in H20 gives K chloronitromcthanedisulphonatc (I), are obtained by heating the requisite acid with whence the strychnine, brucine+4:ll20, Ba yi-CGH4Ph-NH2 (prep, from Ph2 described) in a vac. -f-3H20, decomp. 150°, Tl, Ag-y 2H20, and Ca+3H20, or through the acid chlorides and their derivatives salts of cliloronilroinctlianedisulphonic acid+4H20 by bromination of the anilides or through the chlorides and +2HoO, m.p. 95-5° (explosive decomp.) (prep, of the Br-acids. Their m.p. are 34—61° > those from Ba salt), are obtained. (I) and aq. K2S03 of the corresponding p-phenylphenacyl esters. The affords Knitromelhanedisulplionatc thus : (I)+ K 2S03+ following are described : ole*, m.p. 120°, elaid-, H20 -> (S03K)2CH-N02+ KC1+ KHS04. J. W. B'. m.p. 134— 135°, oleodibromostear-, m.p. 87-5°, and c\oA(\odibrom.ostcar-p-pIienylanilide, m.p. 133-5°. Influence of an element or of a negative group II. W. on the relative mobilities of alkyl radicals in Preparation in a high state of purity of long- their chloroformâtes. P. C a rré and H. P asse- chain compounds. I. Oleic acid. L. K effler d o uet (Compt. rend., 1935, 2 0 1 , 898—900).—The and J. H. M cL e a n (J.S.C.I., 1935, 5 4 , 362— 367t ).— effect of introducing Cl or Ph into the alkyl of alkyl The Pb salt method fails to remove the final 3—4% chloroformâtes is to diminish the temp, of thermal of saturated impurities in oleic acid, even when pre decomp. (cf. A., 1935, 1105), i.e., to increase the mobi pared from high-grade olive oil and a large excess of lity of alkyl (cf. A., 1933, 806 ; 1934, 509). The Pra Pb(OAc)2 is used. The higher unsaturated impurities ester has a lower mobility than the allyl ester, but can be completely removed by 10—12 recrystallisations the p-phenylpropyl ester has a higher mobility than of the Li salts from 5 vols. of 80% EtOH; the final the cinnamyl ester. The suggestion that the tendency 3— 4% of saturated impurities can then be removed, to migration is the greater the more electropositive within 0-2 or 0-3%, by repeated fractional distillation is the migrating group is abandoned. J. L. D. under much reduced pressure. Oleic esters which Condensation of carboxylic compounds with had “ aged ” by keeping for long periods have also substances capable of forming organo-metallic been purified by repeated fractional distillation, compounds or tautomerides thereof under the but the pure products were highly susceptible to influence of alkali metals and of their water- rancidity changes, as were also the samples known decomposable derivatives. G. V. T sc h elin c ev to contain highly saturated impurities. Improve (J. Gen. Chem. Russ., 1935, 5, 562—569).—Theoreti ments in fractional distillation of fatty esters are cal. Ester condensation reactions consist of the steps : described E t0A c+C H 2Na-C02Et=^0Na-CMc(0Et)-C02E t^±: Oleic acid. T. P. H il d it c h (Chem. and Ind., CH.Ac-COoEt+NaOEt ^ ONa-CMe:CH-CO,Et+ 1935, 1009).—A reply to Keffler et al. (see above). EtÔH. R. T. J. W. B. Addition of hydrogen bromide to allylacetic Unsaturated acids of natural oils. TV. The highly unsaturated acid of Telfairia Occidentalis. acid. M. S. K har asc h and M. C. M cN ab (Chem. and Ind., 1935, 989—990; cf. A., 1933, 805).—A E. H. F ar m e r and E. S. Pa ic e . V. a- and p- criticism of the views of ¿instead et al. (A., 1935, Licanic acids. W. B. B r o w n and E. H. F arm er 195). J. W. B. (J.C.S., 1935, 1630— 1632, 1632— Io33).—IV. T. occidentalis oil (7 months old) on saponification gives Addition of hydrogen bromide to olefinic acids. a mixture of fatty acids from which (3-elseostearie R. P. L in s t e a d and H. N. R y d o n (Chem. and Ind., acid (10% yield) is obtained. Freshly extracted 1935, 1009).—A reply to thé above. J. W. B. (light petroleum) kernels give an oil containing 54 BRITISH CHEMICAL ABSTRACTS. A. X IV (b, c) a- but no ¡3-eleeostearic acid, although after irradiation Oxidation of di-a-hydroxystearic acid and its (12 hr. in presence of S) the p-acid only is found. significance as regards the structure of cere- V. Technical oiticica fat (1; or the kernel fat of bronic acid. (A) E. K l e n k and F. D it t . (B) Licana rigida normally yields a-licanic acid (semi P. A. L e v e n e and P. S. Y a n g (J. Biol. Chem., 1935, carbazone, m.p. 110— 111°; Me ester) on saponi 749— 750, 751).— (a ) dZ-a-Hydroxystearic acid and fication, but after irradiation (8 hr. in presence of I or KMnO.j in COMe2 give other acids as well as margaric. S) isolicanic acid, m.p. 99-5° (semicarbazone, m.p. The conclusions of Levene et al. (A., 1933, 1276) 138°), is formed. The fatty acids from (I) contain concerning cerebronic acid are thus invalidated. stearic (1-4%) and palmitic acids (about 1%) (b ) The above result is admitted, but the con F. N. W. clusions are upheld. R. S. C. Polymerisation of methyl esters of higher Condensation of a-aldehydo-aS-dicarboxylic unsaturated fatty acids. XVI. Polymerisation esters with esters of a-halogeno-substituted of methyl stearolate. K . K in o (Sci. Papers Inst. acids. M. N. S chtschukina and N. A. P r e o - Phys. Cliem. Res. Tokyo, 1935, 28, 140— 145).— b r ash en ski (Ber., 1935, 68, [B], 1991— 1998).— Me stearolate heated in H2 at 280—290° slowly The condensation is considered to consist of an polymerises to a bimol. 'product, which is not de O-alkylation of the ICH’OH form of the aldehydo- polymerised when catalytically hydrogenated. succinic ester. Condensation of CH2ChC02Et with E. W. W. NaOEt and Et, a-aldehydo-p-ethylsuccinate (I) or Oxidation products of the unsaturated acids directly with the Na derivative of (I) obtained from of linseed oil. L. C. A. N u n n and I. S. M ac le a n G02Et-CHEt-ClI2-C02Et and HC02Et gives Et., (Biochem. J., 1935, 29, 2742—2745; cf. A., 1935,
“ Bukuryo,” sclerotia of Pachyma Hoelen, (V) contain only one type of structure, that of (III), Rumph. I. Chemical structure of p-pachy- from which a straight chain leads to the poly man, the polysaccharide obtained from “ Buk saccharide, which is thus an extrapolation of (V), uryo,” and its determination. K. T a k e d a (Mem. is as follows. Methylcellobiose (VI) is hydrolysed to Tottori Agric. Coll., 1935, 3, 1— 123).— Extraction of 1 mol. of tri- (VII) and 1 mol. of tetra- (VIII) -methyl- “ Bukuryo ” with EtOH-NaOH yielded fi-pachyman glucose. Methylcellotriose (IX) yields 2 mols. of (I), (C6H10O5)„, no m.p., but darkening at 230—235°, (VII) and 1 mol. of (VIII), whereas methyleellotetraose H d +24-78° in 5% NaOH, mol. wt. probably < gives 3 mols. of (VII) and 1 mol. of (VTII), and methyl- that of starch [trinitrate, m.p. 195— 199°, [x];,° —63-63° cellulose many mols. of (VII) and one of (VIII). (VII), in C5H5N-EtOAc (3:2); triacetate (II), decomp. 255— (VIII), (III), (VI), and (IX) have been completely 258°, [aft0 -68-75° in CHC13; Me, ether (III), m.p. synthesised and their structure has been elucidated. 265—268°, [a]" -11-25° in C5H5N-C0Hc]. Hydro [J/] from (III) onwards changes almost additively lysis of (I) with dil. or conc. H2S04 or dil. HC1 yielded by the val. of one intermediate section for (I), of two glucose (IV), whilst takadiastase gave (IV) and a sections for (II), and so on. [Af] of this intermediate disaccharide (osazone, m.p. 177°) similar to, but not section is nearly [Af] of the unit of (IV). The yield identical with, gentiobiose. Hydrolysis with of (III) leads to the conclusion that the biose union H2C20.j or conc. IICl produced (IV) and an unstable alone is constitution-chemically and configuratively disaccharide, C12H220 11, m.p. 110° [a]™ +76-7° in present in (IV). The course of the hydrolysis of H20 (osazone, m.p. 167°), insol. in 95% EtOH, which (I), (II), and (iV) can be adequately explained by the on keeping decomposes to (IV). Neither fructose nor hypothesis that all unions are of a single type, that of mannose was found in the hydrolytic products. (III). Evaluation of the graphs obtained polari Acetolysis of (I) using ZnCl2 yielded (II) and hiose metrically shows that all unions are sterieally similar. octa-acetate, m.p. 80—82°, [a]™ +36-10° in CHC13, II. W. +25-3° in C6H g; hydrolysis of this yielded only (II). Action of ethylene oxide on cellulose. I. N. I. Acetolysis with IIC104 gave p-tetra-acetylglycuronic N ik it in and T. I. R u d n e v a (J. Appl. Chem. Russ., acid, and with H2S04 [using (II)], glucose a-penta- 1935, 8 , 1023— 1032).—Bleached cotton-wool (I) acctate, m.p. 109— 111°, was obtained. Hydrolysis of and (CH2)20 at 50° afford a product containing (III) with 5% HC1 gave a 90% .yield of 2 : 3 : 6-tri- 1 0H-CH2-CH2-0- (II) per 32 C6H10O5 units; the methylglucose, and with 1 % MeOH-HCl, a 93% proportion rises to 1 : 4—8 in presence of dil. alkalis, yield of 2 : 3 : 6-trimethylmethylglucoside. 2 : 3 : 4 - and attains a max. of 1:1-5 in presence o f . 18% Trimethylglucose was not detected. It is concluded NaOH or 35% ICOH (50— 60°; 15 min.). The pro that in the structure of (I), many a- and p-gluco- ducts are much more readily hydrolysed and acetyl- furanoses (1 : 4) are linked, commencing with the a, ated than is (I), but the velocity of benzoylation is at the first and fifth C. Two methods, the “ alcohol ” not affected; they yield highly viscous solutions in and the “ enzyme,” for the determination of (I) in NaOH, the viscosity rising with the no. of (II) intro “ Bukuryo ” are described. J. N. A. duced. R. T.
“ Bukuryo,” sclerotia of Pachynui Hoelen, Celluloid formation. II. Effect of reaction Rumph. VII. Production of tetra-acetylglycur- medium on heterogeneous changes occurring onic acid by acetolysis of p-pachyman in the in the fibrous state. M. W a d a n o , K. H e s s , and presence of perchloric acid. K. T a k e d a (J. C. T r o g u s. III. Catalysed reactions in the Agric. Chem. Soc. Japan, 1934, 10, 1010— 1013).— fibrous state. Heterogeneous catalysis with a Two acetates were obtained: (a), m.p. 83—86°, [aft0 solid substrate and liquid catalyst. M. W a d a n o , +9-56° in CHC13, +8-47° in C6H G, (b) C14H 18Ou , C. T r o gus, and K. H e ss . IV. Production of m.p. 103— 107°, [aft0 +65-6° in CrH6, +66-2° in celluloid from cellulose nitrate and I- or di CHC13, +60-9° in MeOH. (b) is probably tetra- camphor. K. H ess, C. T r o gus, and M. W ad an o acetylglycuronic acid and hydrolysis gave a syrup (Z. pliysikal. Chem., 1935, B, 30, 159— 182, 183— which yielded an osazone, ClsH20O5N4, m.p. 167— 174°. 231, 232—235; cf. A., 1932, 568).—II. The reaction J. N. A. between cellulose nitrate (I) and camphor in presence Hydrolysis of cellulose and its oligosacchar of aliphatic alcohols as solvents is complete at such ides. K. F r e u b e n b e p .g and G. B lo n q u ist (Ber., low camphor concns. that it can be effected at room 1935, 68, [B], 2070—2082).—New data are recorded temp. The X-ray diagrams and analysis of the solid for [A/] for cellotriose (I) and cellotetraose (II) and phase show the existence of two new compounds, the velocities of hydrolysis of cellobiose (III), (I), (II), camphor-cellulose nitrate II (II) and camphor- and cellulose (IV) are measured in 51% H2S04, the cellulose nitrate III (III), in addition to the camphor- changes being followed polarimetrically and by cellulose nitrate I (IV) previously observed. It iodometric determination of liberated -CHO. The seems probable that (III) corresponds with hydro- hypothesis that from (I) onwards each unit with a cellulose and (II) and (IV) correspond with natural terminal union reacts according to k, with all other cellulose. The camphor concn. at which reaction unions according to kn, is a suitable basis for calcul starts to proceed into the interior of the micelles ation, but is an approximation, and it appears increases with the size of the alkyl radical. The fact probable that the hydrolysis of (IV) and its oligo that the nature of the reaction product and the re saccharides (V) is precisely similar to the fission of lation between the amount of camphor taken up and the polj'peptides of glycine and, in a measure, to the the camphor concn. vary with the solvent is possibly cracking of hydrocarbons. The evidence that the due to the first stage of the reaction being formation of X IV (f,g) 58 BRITISH CHEMICAL ABSTRACTS.— A. a double compound between the solvent and (I). pared by the reduction (Sn-HCl) of yyy-trichloro-a- Aromatic hydrocarbons promote the reaction of nitro-(3-hydroxypropane. Similarly yyS-trichloro-a- (I) with camphor in varying degrees. amino-P-hydroxy-w-pentane, m.p. 141° (darkening) III. The reaction of (I) with camphor in benzine [hydrochloride (II), m.p. about 231° (decomp.); solution in presence of ketones and alcohols has been oxalate, m.p. 232° (decomp.); sulphate, m.p. 235— studied. The effect of these substances on the concn. 240° (decomp.); Ac derivative, m.p. 109°; Ac2 of camphor required for complete reaction is due to derivative, m.p. 136°], is obtained from the corre catalysis, and the varying fine structure of the pro sponding N 02-compound. (I) with KCN yields duct is determined by processes which are super yyy-trichloro-[i-liydroxy-i\-prop>ylcarbamide, m.p. 175°, imposed on the sorption of camphor. COMe2 and and (II) similarly yields yy8-trichloro-$-hydroxy-n- cyc/ohexanone are better catalysts than alcohols. amylcarbamide, m.p. 175°. F. N. W. For a camphor concn., c, of 30% the amount taken Introduction of halogen or thiocyanate into up passes through a max. with increasing COMe2 organic compounds by means of dichloropenta- concn., 0, whilst for const. G the amount of camphor methylenetetram ine. M. V. L ichoscherstov and taken up rises towards a limit with increase in c. T. D. A ldosciiin (J. Gen. Chem. Russ., 1935, 5, When c is moderate and G small the product is (IV). 981—985).—The reaction (CH2) 5N4C1.>+ 2M X -f 2HR-> (II) is obtained when G is > 1% . If G is > 1 0 % and 2RX+2MC1+ (CH2)5N,jH2 (M=K, Na; X=halogen c = 5—20%, the product is camphor-cellulose nitrate or CNS; R =aryl radical) is of general application, IV, which contains COMe2. The formation of the and affords high yields of relatively pure products in various compounds of camphor and (I) is irreversible, cases in which the ordinary methods do not do so and it is in general impossible to transform one (nitrophenols). R. T. into another. The catalytic action of COMe2 is attributed to its relatively rapid reaction with (I) (A) Action of A7-sulphuric acid and Ar-sodium to give a compound which reacts with camphor hydroxide on glycine. (B) Interaction of glycine giving camphor-celluloso nitrate and re-forming and glycylglycine with nicotine. I. S. Jait- COMe2. With increasing G the swelling of the (I) sch nikov (J. Gen. Chem. Russ., 1935, 5, 967—969, fibres passes through a max., then through a min. 970—971).— (a ) Formol-titratable N diminishes im EtOH and MeOH act similarly to COMe2 as catalysts. mediately after addition of glycine (I) to IV-H2S04, The presence of H20 favours the formation of (II). to attain a min. val. after 3 days, and then rises to IV. The optical isomerides of camphor are identical a const, val. after 30 days at room temp. JV-NaOH in their behaviour towards (I). R. C. exerts a similar action, the min. val. being attained after 28 days. The phenomena are ascribed to trans Reaction mechanism : action of fused sod- ient formation of anhydride, peptide, or polymeride. amide on mono-, di-, and tri-methylamines. (b ) (I) and glycylglycine combine with nicotine H. S. Fry and W. V. Culp (Rec. trav. chim., 1935, 54, 838—846).—Analogy with the reaction RHn+«N aOH in presence of CH20. R. T. R(ONa)n-f- wH2 (A., 1928, 615) suggests the re Determination of the sum of glycine and action RHn+«NaNH 2->R(NHNa)„+?!.H2. Sum serine. S. R apoport (Biochem. Z., 1935, 281, mation of the expected reaction stages leads to the 30— 36).—The sum of the amounts of these acids equation NH2Me+NaNH2 -> NaCN-f NH3+ 2H 2 for (e.g., in protein hydrolysates) is determined, after the interaction between NH2Me and fused NaNH2 removal of dicarboxylic NH2-acids, by deamination (in excess) at 250°. Determination of the NH2Me with NaN02 and oxidation (to H2C204) of the pro used (liberated from XH2Me,HCl by dropwise addi duct with 0-1N alkaline KMn04. The results are tion of lOJV-NaOH), NaCN (Volhard), NH3 (absorbed slightly > those obtained by other methods except in an excess of 6W-H2S04), and H2 (no other gaseous with caseinogen, ivith which the vals. are much higher. products formed), gives 94% agreement with this At 120° in 5 hr. serine (I) is converted by H I+P into equation. Similarly the mechanism NHMe2 + alanine (II), which is then determined by the method 2NaNH2 -> 2NaCN+NH3-f4H 2 is verified to the of Kendall et al. (A., 1931, 246), but this procedure extent of 97%, but the derived NMe3+3NaNH2-> gives inaccurate results when preformed (II) is present. 3NaCN+NH3+ 6H 2 is invalid, since NMe, docs not Glyceric acid is colorimetrically determined with the react with fused NaNH2, It is suggested that the help of the blue colour produced on addition of conc. initial stage NMeR2+NaNH2 -> [NHMeR./NHNal -> H2S04andnaphthoresorcinol,andhence (I) and glycine NHMeNa+ XHIt, occurs with NH2Me (R2= H 2, K b= can be separately determined in sericin, the vals. 5-Ox 1(H) and NFIMe2 (R2=MeH, Ab=5-4x 1 (H), being 8-71 and 1-69%, respectively. W. McC. but not with the more weakly basic KMe, (R ,=M e„ Carbamido-acid and hydantoin of arginine. X b= 5 -9 xK H ). J .W . B. W. R. B oon and W. R obson (Biochem. J., 1935, Thermal decomposition of triethylamine.— 29, 2573— 2575).—Arginine on warming in aq. See this vol., 33. solution with KCNO gave carbamidoarginine, m.p. Trichlorohydroxy-aliphatic amines. F. D. 172°, passing in warm acid solution into arginine- Ch a t t a w a y and P. W itherington (J.C.S., 1935, hydantoin, m.p. 100°. H. D. 1623— 1624).—yyy-Trichloro- a- amino - p - hydroxy - Conversion of arginine into citrulline. K. propane, m.p. 123° [oxalate, m.p. 220° (decomp.); Dirr and H. Spath (Z. physiol. Chem., 1935, 237, sulphate., m.p. 255° (decomp); Ac derivative, m.p. 121— 130; cf. A., 1934, 993).—The hydrochloride 154°; Ac2 derivative, m.p. 99°], is obtained from the (1H20), m.p. 155° (decomp.), [a&° +13-0°, of arginine- hydrochloride (I), m.p. 235° (decomp.), which is pre amide (I) [pierate, m.p. 220° (decomp.)] obtained from XIV (g) ORGANIC CHEMISTRY. 59
the Me ester in MeOH and NH3, and the hydrochloride and solvent; the underlying reasons are fully dis (1H20), decomp. 260°, of a-monobenzoylarginine- cussed. Absorption of Br in some measure, however, amide (II) yield no citrulline (III) on hydrolysis and invariably goes hand in hand with occurrence of a are not attacked by arginase (IV). Together with (I) colour with FeCl3. CN-CHyCOoMc gives a red colour arginine-diketopiperazine, decomp. 316°, is obtained. with FeCl3 and immediately decolorises Br in MeOH, Dibenzoylarginine Me ester hydrochloride has m.p. but not in CHC13. With CH2N2 in Et20 at —50° 171°. (I) and (II) yield the Bz3 derivative of (I), it yields two substances, m.p. 76° and 97— 98°, m.p. 245°, which gives a 10% yield of the corre (A . Me-OOMe Me-C'OMc ,R . sponding Bz3 derivative (V), m.p. 220°, of (II) on ( > CN-C-C02Me C02Me-C-CN 1 J hydrolysis with conc. HC1 at room temp., a substance, m.p. 178°, probably an inactive form of (V), being probably A and B, since the former passes into the produced (sometimes) at the same time. Hot acid latter when heated for some time at 130° and each hydrolysis of (V) gives BzOII, NH3, ornithine, and forms the same compound with NH3. The enimine or proline, but no (III) or CO(NH2)2. CH2N2 with a- ester OH groups do not participate in the change, p- benzoylcitrulline gives the Me ester, decomp, about Toluenesulphonylacetonitrile (I), m.p. 147— 148°, does 120°, and NH3 converts the ester into the corre not react with Br or FeCl3; in absence of catalyst it sponding amide (VI), m.p. about 140°. Benzoylation does not react with CH2N2, but after liberal addition of of (VI) gives (V). It seems that in the biological con MeOH it slowly affords a-p-toluenesulphonylpropio- version of arginine (VII) into (III) by deimidase and nitrile, m.p. 60° (corresponding amide, m.p. 168°), and (IV) the attack on the guanidine residue must be the compound ^ ^ > C - C H 2-SO2-C0H4Me, m.p. 162°. preceded by blocking of the C02H. W. McC. Its acidity is therefore due solely to CH,. Me p-toluene- Preparation of ornithine, ornithuric acid, and sulphonylcyanoacetate, m.p. 79— 80°, from the Na de a-benzoylornithine. v W . R . B o on and W . R obson rivative of (I) and CICOoMe, shows marked reaction (Biochem. J., 1935, 29, 2684—2688).—Improved with FeCl3 and decolorisation of Br; with CHgN, it methods (yields in brackets) for the prep, of the follow yields the substance CBH4Me,S02,C(CN)IC!NMe, m.p. ing are described : ornithuric acid (I) [68-5%] from 125— 127°, and Me a-cyano-oL-p-toluenesulphonylprop- arginine hydrochloride and [nearly theoretical] from ionate, m.p. 101°. The solid substance is therefore carbamido-arginine (II); ornithine hydrochloride C„H4Me-S02-CH(CN)-C02Mc, and passes in solution [nearly theoretical] from (II); and benzoylomithine completely or preponderatingly into the enimine [76%] from (I). J. N. A. form. a-Cyano-oL-p-tolucnesulphonylacctonc, m.p. 122— 123°, from the Na derivative of (I) and AcCl Relationships between acidity and tautomer- in cold EtaO, gives a moderate FeCl3 reaction, and ism. IV. Effect of the cyano-group. F. A r n d t , immediately decolorises Br in EtOH or CHC13. H. Scholz, and E. Frobel (Annalen, 1935, 521, In solution in Et20 it is converted exclusively into 95— 121).—The behaviour of a series of CN-compounds the enol ether, CGH4Mc-S02-C(CN):CMe-OMe, m.p. 124°, towards FeCl3, Br, and CH2N2 shows that the acidify whereas the solid when treated with CH2N2-E t20 ing action of CN exceeds that of any other simple . affords also a-acetyl-oL-p-toluenesulphonylprojnoiiitrile, C-containing substituent and approximates to that of m.p. 150— 151°. AVMetliylation is not observed. The •S02\ CN shows electromeric action in the form of solid substance is CGH,Mc-SO,-CfIAc-CN and is partly “ enotropic effect ” and as conjugation partner; enolised but not eniminised in solution. CH2(CN)2 in both respects it is considerably inferior to keto-CO, does not react ■with Br or FeCl3 or with CH2N2 in but superior to ester CO. CH-CN can therefore pass presence of MeOH. p-Toluenesulphonylmalononitrile, into CICINH, but a conjugation partner is necessary, m.p. 101— 102° after softening at 93°, from the Na which, as always, must not precede CN in the sequence compound of (I) and CNBr, gives considerable FeCl3 of electromeric activity. A second CN, ester CO, or, reaction and immediately decolorises Br in EtOH or in certain circumstances, NO, can function as con CHC13. With CH2N2 at —50° it yields small amounts jugation partner for the eniminisation of CN. In of p-toluenesulphonylmethylmalononitrile, m.p. 103°, addition, the prototropic expenditure of energy must whereas under the customary conditions some N- be greatly decreased by strong acidification of the methylation is observed. Hence the solid is central CII to render eniminisation possible. Hence CcH4Mc-S02-CH(CN)2 and becomes eniminised in solu it does not occur with CN-CH2-C02Et or CH2(CN)2. tion. Me dicyanoacetale, m.p. 65°, gives strong FeCl3 In combination with keto-CO, CN behaves essentially reaction and decolorises Br. With CH2N2 at —50° as conjugation partner. The enimine group behaves it gives a non-cryst. product with 6-3% NMe and towards FeCl3, Br, and CH2N, similarly to the enol 12 0% OMe (of which 10-9% is present as C02Me). group and can, if it occurs, have a more or less con cax-Dicyanoacetone, m.p. 141°, from CHNa(CN)2 and siderable share of the empirical activity of the corre AcCl [p-nitrophenylhydrazone, m.p. 144° (decomp.)], sponding dissolved compound. With regard to gives a, marked FeCl3 reaction and immediately acidifying action (inductive effort) and electromeric decolorises a little Br. O-Methylation predominates effect the sequences of substituents are, respectively, with CHgN,, but some iV-methylation is observed. N 02 > SO,OR > SO,R > CN > CO,R > CHiO > CRIO An ethereal solution of CH(CN)3 gives an intense and ch:o>cr:o>on>co 2r > n o 2. FeCl3 reaction and absorbs much Br. The product Application of the Br titration method to the follow formed with CH2N2 gives about half the calc. N ile val., ing compounds gives variable and non-reproducible showing that NH is formed and resembles enolic OH results which frequently depend greatly on temp. in behaviour towards FeCl3. H. W. 60 BRITISH CHEMICAL ABSTRACTS.— A. X IV (£7-0
Determination of thiol and disulphide com Dicyanodiam ide. F. Ch a s te l l a in (Helv. Chim. pounds, with special reference to cysteine and Acta, 1935, 1 8 , 1287— 1302).—Hydrolysis of dicyano cystine. III. Reaction between thiol com diamide (I) with a slight excess of acid at 50—S0° pounds and mercuric chloride. K . S iiin o h a r a gives a quant, yield of guanylcarbamide (II), but with (J. Biol. Chein., 1035, 111, 435—442).— Cysteine or insufficient acid further hydrolysis to NH!C(NH2)2 SH-CH.-COoH reacts rapidly with HgCl2 at pa 5, giving occurs. Hydrolysis of (I) with 1% NaOH at 100° a niercaptide of the type Hg(S,R*C02H)2, followed by a has been quantitatively studied by determination of slow reaction giving CO.,RdPS,Hg,S\R,C02,HgCl. the NH, evolved (cf. B., 1926, 505), C0(NH2) (Fosse), F. A. A. NIlyCN (Pcrotti), and unchanged (I). The increase Optical rotatory dispersion in the carbo in the NH3 evolved is rapid during the first 2 hr. and hydrate group. VI. Amide rotation rule. T. L. thereafter becomes linear with time. The amount H arris, E. L. H ir st, and C. E. W ood (J.O.S., 1935, of NII3 evolved is equally dependent on the concn. 1658— 1002; cf. A., 1935, 568).—The rotatory of (I) and of NaOH, and is the same whether the mol. dispersion of rf-dimethoxysuccinamide, d-dimethoxy- ratio (I)/NaOH (r) is a or 1 ¡a. The CO(NH2)2 formed succinmethylamide, and I-2 : 3 : 5-trimethylarabon- [only slightly increased by excess of NaOH, but amidc (all obeying the amide rule) is controlled greatly increased by increasing the mol. proportion by the induced dissymmetry, and can be represented of (I)] increases to a max. at about 3 hr. and then by a one-term Drudc-Natanson equation. Similar decreases linearly with time. The sum NII3-N-f- examination of 4 : G-dimothylmannonamido, which CO(NH2)2-N increases to a const, val. for any obeys the amide rule in EtOH but not in H20, particular val. of r, and this const, val. itself increases shows that special stereochemical arrangements of from 16-5% of total N when r = 5 to 60% when r=0-5, tho substituent groups may give rise to an induced and then remains approx. const, to ?-=0-2. The activity opposite in sign to that of the normal amide. initial stage is the depolymerisation of (I) to NHyGN, Data for various 7.X for tho above compounds and for which reaches max. concn. after < 1 hr., and dis Me d-dirnethoxy succinate, b.p. 120°/12 mm., with H20 appears after 5 hr. (r= l), and no (I) could be detected and EtOH as solvents are given. F. N. W. after 9 hr. During the first ten hr. only CO(NH2)2 is hydrolysed, hydrolysis of melamine [formed from Action of magnesium phenyl bromide on a- (I) and NH.yCN] to (finally) (HCNO), requiring brom obutyrdim ethylam ide. S. P. Ti (Bull. Soc. more drastic conditions. No (II), NHyCONH-CN, chim., 1935, [v], 2, 1799— 1800; cf. A., 1931,1279).— or NH(C0*NH2)2 could be detected in the alkaline Tho reaction products of MgPhBr and a-bromo- hydrolysis. These and earlier results are discussed butyrdimethylamide, b.p. 123— 124°/17 mm., are and it is concluded that (I) is tautomeric, butyrdimethylamide, crotondimethylamide (impure), b.p. about 200°, and a littlo COPhlV and {i-dimethyl- NH:C<^§>C:NH — NH:C(NH2)-NH-CN, existing amino-ixoi-diphenylbutanol, m.p. 58° [picrate, m.p. solely as the former in alkaline and neutral solution 155°; perchlorate, m.p. 1S2°; He derivative (pierate, and probably in the solid state, and as the latter in m.p. 138°)]. H. G. M. acid solution. J. W. B. Reactions of sulphuryl diamide (sulphamide). Photochemical and thermal decomposition of F. 0. W ood (Nature, 1935, 13 6 , 837).—Dixanthyl azomethane.— See this vol., 37. sulphamide, m.p. 182— 184°, is obtained bv adding a solution of xanthhydrol (I) in EtOH to one of sulph Iron-cyanogen compounds. VI. Action of amide in aq. AcOH. Condensation products have oxalates on the blue iron-cyanogen compounds. also been obtained with (I) and p-NH2-G'JH,-S02-NH„ M. Kohn (Monatsh., 1935, 66, 393—405; cf. A., m.p. 209°, m-CeH4(S02-NH,)2, nip. 170°,' and 1924, i, 21).—Sol. and ordinary Prussian-blue (I) p-C6H4Me*S02*NH2, m.p. 198°. These general re dissolve completely in K 2C20 4 with formation of actions can be used for the determination of sulph- K3F2(C20 4)3 and K 4Fe(CN)G; Turnbull’s blue (II) is amides and sulphonamides. L. S. T. mainly but not completely sol., leaving a residue of white Fe2Fe(CN)G. The action of H20 2 on a mixture Determination of glutamine in presence of of 3FeS044~2K;jFe(CN)6[ - (II)], whereby complete asparagine. H. B. V ic k e r y , G. W. P uch er, H. E. reaction should lead to OH-FerafFe^FeiCN),,].,, Cl a r k , A. C. Ch ib x a ll, and R . G. W estall (Biochem. or on a mixture of 2FeS04-|-K4Fe(CN)G which J., 1935, 29, 2710—2720).—The amide group is similarly should give (OH)2FeUI2[Fe(CN)G] gives in completely hydrolysed when glutamine (I) is heated each case blue preps, of insol. basic (I), which are at 100° for 2 hr. at pH 6-5. The increase in NEh-N converted by K2C20 4 into Fe(OH)s in theoretical that occurs gives the amount of (I) NH2-N in the amount, K4Fe(CN)G, and K 3Fe1II(C„Ol)3. Oxidation extract of the plant tissue. The decrease'in NH.,-N of a mixture of FeS04 and K 4Fe(CN)“6 by H 2Oa affords of an extract on hydrolysis under these conditions is a basic (I), colloidallv sol. in H ,0, which when a valuable qual. criterion of the presence of (I). treated with K2C20 4 gives K3Fem (C20 4)3, K 4Fe(CN)G, Interference from asparagine is negligible, for it and considerably more Fe(0H)3 than is expected from requires heating for 3 hr. at 100° with AT-H,SO-, theory, since the unused K4Fe(CN)G is oxidised to whilst tho effect of CO(NH2)2 and allantoin can be K 3Le(CN)G and the OH' thus liberated is consumed by easily detected. Data on the stability of (I) with the blue ppt. For this reason basic (I) results from regard to temp, and pH are given. The chief products sol. (I) by the action of H20 2 in presence of excess of hydrolysis of (I) at essentially neutral reaction are K 4Fe(CN)G. Basic (I) is not formed in appreciable NH3 and pyrrolidonecarboxylic acid. J. X. A. amount from sol. (I) under the influence of H20 2. X IV (i, I, m), X V (a) ORGANIC CHEMISTRY. 61
(I) is transformed by KHC20 4 into a colloidal, blue dihydroresorcinol in EtOAc with an active Pt catalyst. solution and, if large amounts of KHC20 4 are used, The d, n, and rj of these compounds are recorded. also converted into H4Fe(CN)G and K3Fe(C20 4)3, H. G. M. whereby pale yellowish-green solutions which are Constituents of the unsaponifiable fraction of sensitive to light result. H. W. wheat-germ oil. Vitamin-/?.—See A., 1935, 1551.
Dihydroxides of tertiary arsines, arsonium The hydrocarbon C6D G. H. E r l e n m e y e r and H. L obeck (Helv. Chim. Acta, 1935, 18, 1464— 1466). derivatives, and their salts. G. A. R a z u v a e v , —Distillation of dry C0(CO2)GCa3 with Ca(OD)2 (from V. S. M a l in o v sk i, and D. A. G o d in a (J. Gen. Chem. Russ., 1935, 5, 721— 1727).—AsMe, in Et20 and HN03 Ca and D20) gives pure CGDG, b.p. 79-4°/760 mm., yield the mononitrate, m.p. 127°, of AsMe3(OH)2; m.p. 6-8° (cf. Wilson, A., 1935, 1198). J. W. B. the free hydroxide readily eliminates I1 20 to yield Fluorinated chlorobenzenes. H. S. B o o th , AsMe30. AsMe4I affords AsMe^NOv m.p. 268— H. M. E ls e y , and P. E. Burchfield (J. Amcr. Chem. 270°, with AgN03, and AsMe^OH with AgOH. The Soc., 1935, 57, 2064— 2065),—Tho prop, of m- following compounds have been prepared analogously : chlorojluorohenzene, b.p. 127-6°/700 mm., m.p. < AsPhMe20, m.p. 157— 161°, OH-AsPhMe2*NO,, m.p. —78°, and 2 : 4 : G-lrichlorofluorobcnzene, b.p. 208-4°/ 149— 150°, AsPhMe3*0H, m.p. 106— 116° (nitrate, 760 nun., m.p. 11-2°, is described. V.p. of theso m.p. 195— 196°), AsPh2Me(OH)2 (nitrate, m.p. 106— compounds at 0— 130° have been measured. 107°), AsPh2Me2I, m.p. 211— 213°, AsPh„Me2-OH, E. S. II. m.p. 120— 135° (nitrate, m.p. 149— 151°), AsPhAle-NO.,, Iodoxy-group and its relations. I. Ma s s o n , m.p. 100°, (AsPh3-OH)2SO, m.p. 195°, AsR2Me, h.p. E. R a c e , and (in part) F. E. P ou n d er (J.C.S., 1935, 170°/20 mm., AsR2Me2I, m.p. 186— 187°, AsR2Me-OH 1669— 1679).— PhI02 (I) (modified prep.) is not (nitrate, m.p. 147°) (R=cyclohexyl). R. T. identical with diphenyliodonium periodate, m.p. 129° (decomp.) ; it is quantitatively nitrated (methods Preparation of germanium alkyl or phenyl described)tom-IO2
GflIL and Pi^OlI. in presence of A1C1, afford PhPrP 1- and 2-sulphonic acids. R. L a n t z (Bull. Soc. and CJLRrA, b.p. 205- 210°; with PliMe the product cliim., 1935, [v], 2, 1913— 1932).—Under closely is p-G(ill.,M(‘lV , and with Bu^OH, PliBufl and defined conditions l-C10H /SO nH (I) is brominated with GAI.Molhif* arc obtained. The reaction is ltOH loss of S03H to an insol. substance wliich is deter -|-AiCl.. -> AlCh-Olt (I)+HC1; (I)-t-OaHB -> PhR mined by OrO.,-oxidation (cf. B., 1932, 590), whilst -l-AlClUm. ' R. T. 2-0jqH7*S03H (II) is brominated without loss of SOsH and remains sol., thus permitting the determin Influence of structure on the polymerisation ation of (I) and (II) in mixtures. H. G. M. of substituted styrenes. P. P. Souorigin and N. V. ScaionifiiNA (J. Gen. Ohem. Russ., 1035, 5, Substitution in polycyclic systems. I. Nitra 555—561).—Tho polymoride of o-tolylethylene is more tion of fluorene and 9-bromofluorene. S. V. elastic limn is that of styrene, whilst thoso of m- and A nantakrishnan and E. D. H ughes (J.C.S., 1935, p-tolyl- and 1-naphthyl-othylono are loss so. R. T. 1007— 1000).—Nitration of fluoreno (cf. A., 1930, 1125) yiolds 2 : 5- and 2 : 7-dinitrofluorene, m.p. Optical rotation of phenylethylmethyloctyl- 205—300° (docomp.) (lit. 269° and 331°). Mild methane [a-phenyl-y-methylundecane]. P. A. nitration (HN03 in Ac20 ; 1 hr.; 0°) of 9-bromo- Levene and S. A. H arris (J. Biol. Chom., 1935, fluorono (I) gives 0"-broino-2-nitrofluorcne (I I ); 111, 735—73S).— bCfl.Ph'CHyOHMe'CHyMgBr and more vigorous treatment (2 hr. at 0°, followed by ( U ll3-pllO giyo o.-phenyl-y-methylundecan-z-ol, b.p. 15 hr. at room temp.) gives 9-bromo-2 :5 - (III), .183- 181°/5 nun., [a];? —2-61°, convorted by cold m.p. 199°, and -2 : 7-dinitrofiuorene (IV), m.p. 255° 111 into the iodide, which, when hydrogenated (Raney (decomp.). Nitration of (I) in AcOH yields (IV) Ni) in ligroin-MeOlI-NaOll, affords a-phenyl-y- and 7-bromo-2-nitrofluorenone (?), whilst oxidation methylundecane, b.p. 1-13—1-15°/2 nun., [ajif5 —1-12°, (Na Cr 0 in AcOH) of (II), (III), and (IV) gives and theneo (IL-Pt0a; AoOlI-EtOAo) a-cyclohcxyl-y- 2 2 7 2-rutro-,2:5- and 2 : 7-dinitro-fluorenone, respectively. methyluiidecanc, b.p. 1-17 °/3 nun., [a]$ —O-Jhi0. (Ill) and (IV) are also obtained bv nitration (HNOs in Tho contribution of C0H11 to [Ji] is much < that of Prfl in this series, [a] are max. vals. for tho homo Ac,0) of ( II). F. N. W. geneous liquids. R. S. C. Influence of poles and polar linkings on the course pursued by elimination reactions. Laws of substitution in the sulphonation of XXIII. Stable derivatives of the tercovalent naphthalene and its derivatives. V. N. Uecmtzev carbon compound of Ingold and Jessop. E. D. (J. Gen. Chem. Russ., 1035, 5, G53—COO).—Substitu H ughes and K. I. K u r iy a n (J.C.S., 1935, 1609— tion takes place according to tho same laws as for 1611).— 9-Bromo-2-nitrofluorene with Me„S in MeNOa CeHe, on the assumption that C US exists in three 10 yields 2-nitrojluorenyl-G-dimethylsulphcmium bromide tautomeric forms, containing two aromatic nuclei, (I), m.p. 130° (decomp.). (I) or the corresponding or one aromatic mid one hvdroaromatic nucleus. picrate, m.p. 185° (decomp.), with alkali in H 0, R. T. 2 EtOH, or COMe, yields dimethylsulphonium 9-2- Nitration of 1-ethylnaphthalene. G. Levy (Compt. rend., 1035, 201, 000—002).— l-C10H7Et nitrojluorenylidide, m.p. 300°, which decomposes in when nitrated (ef. A., 1033, 57) gives an inseparable boiling MeN0 3 solution forming 2 : 2'-dinitrobisdi- mixture of isomerides, reduced (Fe-AcOH) to 1- plieuylene-ethylene (II), with liberation of Me.,S. cthybx-tiaphlhylumine, an oil (Ac derivative, m.p. (II) is oxidised (Xa2Gr20 7-A c0H ) to 2-nitrofluorenone. 118-5°; hydrochloride), tho sulphate of which with Nitration [HN03 {d 1-5) at —15°] of fluorenyl-9- 1 % H2S0 4 at 200° gives 1 -ethvl-x-naphthol (cf. dimethylsulphomum picrate yields 2 :1 -dinitrojiuor- A., 1933,12S7). ‘ J. L. D. enyl-9-dimethylsulphoniu/ii picrate (III), m.p. ISO0 (decomp.), converted by aq. alkali into dimethyl Methylethylnaphthalenes. III. Synthesis of sulphonium 9-2 : 7-dinitrofluorenylidide, which with 2-methy 1- 6-ethylnaphthalene. O. Bru reek and IlBr-COMe., yields 2 : 7-dinilrojluorenyl-d-dimethyl- F . Grok (Monatsh., 1035,66,133— 437).—Application sulphonium bromide (IV), m.p. about 230°, and when of Reformatski’s method to p-C6H4Et-CHO and boiled in MeNOa gives 2 : 2' : 7 : 7'-tetranilrobisdi- I HMeBrCOaEt leads to Et u-methyl-p-eihylcinnamate, phenylene-ethylene (V), m.p. >300°. (Ill) when re- b.p. 150— 160°/11 mm., reduced by Xa and EtOH tluxed Avith HBr-AcOH (30 ruin.) gives 9-bromo-2 : 7- to y-p - ethyl phenyl-?, - melhylpropa nol'{I), b.p. 110°/10 dinitrofluorene (VI), whilst (IV) with Cr03-AcOH mm. (I) is transformed successively into y-p-ethyl- yields 2 : 7-dinitrofiuorenone and when heated alone phenyl-^-nuthyl-n-propyl bromide, b.p. I l l — 112°/10 forms (VI) with liberation of Me2S. (V) is oxidised mm., and the corresponding nitrile, which is hydrolvsed to 2 : 7-dinitrofluorenone. Me2Se" and 9-bromotiuor- by boiling 10 % KOH-EtOH to y-p-ethylphenyl-3- ene in MeN02 give fluorenyl-d-dimethylselenoniuin mclhyl-n-bulyric acid, b.p. 185— 1S7°/10 mm. The bromide, m.p. 131— 135° (corresponding picrate, m.p. acid and cone. H2S0 4 at 100° afford ■i-keio-2-methyl-Q- 113°). F .N .W . eihyl-l : 2 : 3 : ■i-tetrahydronaphthalenc, b.p. 113— 118°/ II mm, reduced (Clemmensen) to 2-methyl-G-ethyl- Compounds related to the sterols, bile acids, 1 : 2 : 3 : i-ietralujdronaphthaleme, b.p. 140—115°/i0 and cestrus-producing hormones. VII. A. mm., dehydrogenated by S at 270—300° to 2-methyl-G- Co h en , J. W. Cook, and C. L. H e w it t (J.C.S., 1935, ethybiaphihalene, b.p. 115— 150°/11 mm. (picrate, 1633— 1637).—2-JIethyl-l-allyl-2 :1 - dihydropkenan- m.p. 10Q—101° ; styphnate, m.p. 138— 130°). H. W. threne (I) {picrate, m.p. 75— 76°) is obtained from CH2.OH*CH2*MgBr and l-keto-2-methyl-l : 2 : 3 : 1* Sulphonation of naphthalene. I. Determin tetrahydrophenanthrene (II) (modified prep.). 2- ation of the relative proportions of naphthalene- Methyl-l-u-propylphenanthrene, m.p. 65° [picrate, m.p- X V (b, c) ORGANIC CHEMISTRY. 03
121-5— 122°; s-C8H3(N02)3 complex, m.p. 131°], Nitrobenzaldchyde-wi-tolylhydrazone with Br-AcOH is obtained from (I) either by heating with Se (320°, affords a-bromo-m-nitrobenzaldehydc-4 : G-dibromo-m- 15 hr.) or by heating in saturated HCl-AcOH solution lolylhydrazone, m.p. 191°, alsoobtained by bromination (100°, 1 hr.). 2MMethyl-1 -Av-butehyl-3 : 4-dihydro- of (I) and (II). a-Bromobenzaldehyde-, m.p. 122°, phenanthrene,b.p.155— 160°/0-3mm. (picrate,m.p. 77— and a.-bromo-o-nitrobenzaldchyde-i : G-dibromo-m-tolyl- 78°), contaminated with 2-methyl-3 : 4-dihydrophen- hydrazonc (III), m.p. 151°, were similarly prepared. anthreno results from the interaction of (II) and a-Bromo-p-nitrobenzaldehyde-4 : 6-dibromo-m-tolyl- CH2ICH-CH2-CH2"MgBr, and when cyclised with hydrazone when wanned with Et0H.-H20-N H 3 H2S04-A c0H (1 : 20) (100°, 2-25 hr.) yields principally yields p-nitrobenzenyl-4 : G-dibromo-m-tolylhydrazidine, metliylhexahydrochrysene. l-($-5-Telralylethyl)cyc\o- m.p. 207°. The corresponding m-AT0 2-compound, simi- hexanol, b.p. 175— 180°/0-4 mm. (3 : 5-dinitrobenzoate, larly prepared, has m.p. m.p. 124— 125°), obtained by the interaction of Me 155°. (Ill) when warmed cycfohexanone and Mg ¡3-5-tetralylethyI chloride, ,, with just sufficient yields l-($-5'-tetralylethiyl)-A1-cyc\ohexene (III), b.p. 5 = > N- 0 1 EtOIl for dissolution 140— 150°/0-05 mm., when heated with KHSO,, Br yields 3-kcto-l : 3-endo- (160— 170°, 1 hr.). (Ill) when cyclised with AIC13 4' : 6' - dibromo - in - tolyl - (0°, 7-5 hr.) gives a mixture of dodecahydrochrysene, imino-1 : 2-dihydro-l : 2-benzisodiazolc \-oxide (IV), which is partly hydrogenated (300—310°, 14 hr., Se) which explodes at 126°. II. G. M. to s-octahydrochrysene, m.p. 136— 138° (picrate, m.p. Synthesis and chemical properties of a-ethyl- 139— 140°), and a hydrocarbon, b.p. 123— 130°, enic carbimides, R-CHICR'-NICiO. J. Hocii which is dehydrogenated (Pt-black; 300—320°, (Compt. rend., 1935, 201, 733—735).—iV-Carbethoxy- 3 hr.) to 4 : 5-benzhydrindene-l-spirocyclohexane, m.p. ketimines (A., 1935, 1483) under reduced pressure 56— 57° {picrate, m.p. 125— 126°). F. N. W. in presence of kieselguhr at 400° afford carbimides. The alleged dihydrophenylbenzamidine. A. The following are prepared: 8-Av-heptenyl-, b.p. K irssan o v and I. I vastch en ko (Bull. Soc. chim., 55—56°/17 mm., A1:2-eyc\ohexenyl- (I), b.p. 61— 1935, [v], 2, 1914— 1950).— Contrary to the views 63°/18 mm., 2-methyl-A1 ■ --cyclohexenyl-, b.p. 73— of Bemthsen et al. (A., 1880, 639) no dihydrophcnyl- 74°/18 mm., a-phenylvinyl-, b.p. 99°/25 ram., and benzamidine (I) is obtained when phenylbenzamidine a.-phenyl-A,‘-propenyl-carbimidc, b.p. 110— 112°/18 (II) (improved prep.) is reduced by Na-IIg, the only mm. They decolorise Br rapidly and with NH2Ph products being PhCHO, NH2Ph, NHPh-CH2Ph, in anhyd. Et20 afford phenylcarbamidcs, m.p. 102°, CH2Ph-NH2, and unchanged (II). The product re 197°, 170°, 142°, and 185°, respectively, which are garded by Bemthsen as (I) is considered to be purified easily decomposed by dil. HC1 into ketones and (II). (I) has therefore never been prepared. NHPh-CO-NH2. (I) with NH3 gives A1 :2-cyclo- H. G. M. hexenylcarbamide, m.p. 144°, with N2H4, hydrazine-a[3- Reactivity of halogen compounds. Ill, IV.— dicarboxydicyc\ohexenylamide, m.p. 186°, and with See A., 1935, 1465. NHPhMe, X-cyclohexenyl-'is' -phenyhnethylcarbamide, Derivatives of 6-bromo- and 4 : 6-dibromo-m- m.p. 8?°. With EtOH, Pr^OH,' and PhOH, (I) affords Et, b.p. 148— 149°/26 mm., Pr», b.p. 147 toluidine. G. D. P a r k e s and E. d ’A. B u r n e y (J.C.S., 1935, 1619— 1621).—The following m-toluid- 148°/23 mm., and Ph Al:2-cyc\ohexcnylcarbamale, ides, prepared by suitable modifications of ordinary m.p. 106— 107°, respectively, and with CPh2!NH, methods, are described : o'-, m.p. 146°, m'-, m.p. 114°, lE-eyd.ohexenyl-'E'-diphenylmethylenemrbamidc, m.p. and p'-nitrobenz-, m.p. 148°; benz-6-bromo-, m.p. 119°. J .L .D . 123° (lit. 98°); o'-, m.p. 163°, m'-, m.p. 185-5°, Rearrangement of thiocyanates into thiocarb- and p'-nitrobenz-G-bromo-, m.p. 258°; benz-4 :6 - im ides. E. B er g m a n n (J.C.S., 1935, 1361— 1362). dibromo-, m.p. 131°; o'-, m.p. 203°, m'-, m.p. 207°, If the change CH2:CH-CH2-SCN -> CH2:CH-CH2-N:G:S and p '-nitrobenz-4 : G-dibromo-, m.p. 182-5°. 6- proceeds by attachment of N to terminal 0 and Bromo-, m.p. 191°, and 4 : 6-dibromo-m-/oly¿carbamide, rupture between CH2 and S, cinnamyl tliiocyanale (I), m.p. 218°, are obtained from the appropriate toluidine, m.p. 68° (prepared from CHPhICH-CH2Br and KCNO, and warm 0-5M-HC1. CO(NH2)2 when heated KSCN), should when heated in vac. give with excess of the appropriate base yields s-bis-G- CHPh(NCS)’CH!CH2; actually cinnamyllhiocarbimide bromo-, m.p. 276°, and G-bis-4 : G-dibromo-m-tolyl- (II), b.p. 162°/12 mm., is formed. The structure of carbamide, m.p. 297°. 6-Bromo-, m.p. 143°, and 4 : 6- (I) is proved by hydrogenation to y-phenylpropyl dibromo-m-tolueneazo-{i-naphlhol, m.p. 193°, were pre thiocyanale, b.p. 180°/30 mm., also obtained from pared from the appropriate diazotised base and CH2Ph-[CH2]2-Br (III) and XH4SCN; that of (II) ¡3-C10H7-OH-2Ar-NaOH. The following were prepared by reaction with NH2Ph to form s-phenylcinnamyl- from the appropriate aldehyde and 6-bromo-wi-tolyl- thiocarbamide, m.p. 119°, also obtained from NPh.'CIS hydrazine hydrochloride obtained by reduction of and CH2Ph;CH'CH2*NH2 (IV ); and that of (IV) diazotised 6-bromo-wi-toluidine with SnCi2-HCl : confirmed by hydrogenating the phthalimide, from benzaldehyde-, m.p. 154°; o-, m.p. 175-5°, m- (I), which it is prepared, to phthalo-y-phenylpropylimide, m.p. 188°, and p-nitrobenzaldehyde-G-bromo-m-tolyl- m.p. 61°, also obtained from (III), and thus excluding hydrazone, m.p. 171-5°. The following were prepared the alternative structure NH»,CHPh-CHlCH2. by similar methods: benzaldehyde-, m.p. 109°; E. W. W. o-, m.p. ISO0, m- (II), m.p. 204°, and p-nitrobenzalde- Substitution in arylsulphon-1- and -2-naphth- hyde-4 : G-dibromo-m-tolylhydrazone, m.p. 221°. m- alides. It. Co n s d e n and J. K e n y o n . (J.C.S., 1935, 64 BRITISH CHEMICAL ABSTRACTS.— A. X V (C)
1591— 1596).—m - Nitrobenzencsulphon -1 - naphthalide the diazotisation of the 6-NH2-compound is best (I), m.p. 162— 164° [obtained from a-C10H7-NH2 and effected in HBr. (I) is reduced (SnCl2) to dl-b-bromo- mi-N0.,,CcH4,S02C1 (II)], is nitrated (a) by AcOH- 6'-amino-2 : 2’-dimethyldiphenyl (II), m.p. 77-—-78°, conc. IlNOg giving 2 : 4-dinitro-l-m-nitrobenzene- which is resolved by d-tartaric acid into the 1- (III), sulphon-naphlhalide, m.p. 185— 1S8° [hydrolysed by m.p. 77— 78°, [a]20 -5-32°, and d-, m.p. 77— 78°, cone. H2SO., to 1 : 2 : 4-C10H5(NH2)(NO2)2], and (b) [a];,0 + 5 04°, forms. (II) is converted into dl-, m.p. by ice-cold fuming HN03, and (c) by AcOH-fuming 109— 110°,and (III) into 1-, m.p. 109— 110°, [«]» -6 -2 °, HN03 on the water-bath giving the 2 : 4 : 5-(N02)3- -6 : 6'-dibromo-2 : 2'-dimethyldiphenyl. E. W. W. derivative, m.p. 215° (decomp.) (C5H5N salt, m.p. Alkylated ethylenediamine derivatives. TV. 170—175°), also obtained from o-nitro-l-m-nilro- Reaction between aß-bis(benzylideneamino)- benzenemlphon-naphthalide, m.p. 208—210°, and etbane, phenylcarbimide, and water. J. v a n AcOH-HNOg. (I) when refluxed with CHClg-Br A lph en (Ree. trav. chim., 1935, 54, 885— 887; cf. gives i.bromo-l-m-nitrobenzenesulphon-naphthalide, A., 1935, 1118).—Interaction of equimol. proportions m.p. 174— 176° (hydrolysed by II2S04 to 4 :1 - of PhNCO and (•GH2vN;CHPh)2 (I) in moist Et20 C10HfBr-NH2), and in C5H-N with Br gives the affords s-phenyl-ß-benzylideneaminoethylcarbamide 2 : 4-2?r2-derivative, m.p. 232—233°, also obtained (II), hydrolysed by dil. HC1 to ß-(y-phenylcarbamido)- from 2 :4 : l-C10H5Br2-NH2 (improved prep.) arid (II). cthylamine (Bz derivative, m.p. 210°), and reduced 4-Nitro-l-p-toluenesulphon-naphthalide with Br in (Na-EtOH) to the hydrochloride of benzyl-$-(y-phenyl- C5H5N (but not CHClg) yields its 2-Br-derivative, carbamido)elhylamine (Bz derivative, m.p. 160°). m.p. 193— 195°, hydrolysed to 2 : 4 : 1- With an excess of PhNCO (I) gives 2-keto-3 : 4- C10H5Br(NO2)vNH2. p-Toluenesulphon-1 -naphthalide diphenyl-\-$-(y-phenylcarbamido)ethyl-l : 3-dmzcyclo- with AcOH-conc. HN03 affords its 2 : 4-(N02)2- and 2-iV02-derivative, m.p. 154°, hydrolysed to butane, NPh<^Q^>N-C 2H4-NH-CO-NHPh, m.p. 1 : 2-C10H e(NHa)-NO2. Nitration of 2 : 4-dinitro-a- 208°. (decomp.) [also by action of PhNCO on (II)], naphthol with fuming HN03 (with or without AcOH) hydrolysed by boiling dil. HC1 to PhCHO and yields the 2 :4 :5 - and 2 : 4 : 7-(N02)3-derivatives NHPh-CO-NHR, and reduced (Na-EtOH) to in the ratio of about 5 :2 . p-Toluenesulphon-2- NHPh-CO-NHR-CH2Ph (R =-C 2H 4-NH-CO-NHPh). naphthalidc (III) with Br-CHC13 yields its 1 -Br- J. W. B. derivative. 1 : 3 : 2-C10H5Br2*NH2 when refluxed Preparation of in- and p-phenylene diethyl- (2 hr.) with EtOH-conc. HC1 granulated Sn affords amine and benzohexamethyleneimine from the 3-bromo-$-naphthylamine, m.p. 173° (Ac derivative, three phenylenediacetonitriles. P. R u g g l i, B. B. m.p. 177°), the p-loluenesuljihonyl derivative, m.p. B u ssem aker, W. M ü ller, and A. Sta u b (Helv. 127— 129°, of which is nitrated in AcOH to 3-bromo- Chim. Acta, 1935, 18, 1388— 1395).— Reduction of \-nitro-2-p-toluenesul2ihon-naphtlialide, m.p. 237— m- and p-plienylenediacetonitrile, in EtOH saturated 239° (decomp.), also obtained from the appropriate with NH3, with H2-N i at 90— 100°/70 atm. affords, nitro-compound with C H N-Br, reduced (Sn-HCl 5 5 respectively, m- [dihydrochloride + H 0, m.p. 300— or Zn-AcOH) to 3-bromo-2-p-iolucnesulphomyl-\ : 2- 2 302° (block); plalinichloride, m.p. 242° (decomp.); naphthylenediamine, m.p. 185°, and hydrolysed (ice- j 8z 2 derivative, m.p. 181°], and p-phenylene-$$'- cold H S04) to 3-bromo-l-nilro-?j-naphthylamine (IV), 2 diethylamine, b.p. 130°/3 mm., m.p. 36° (dihydro m.p. 105° (Ac derivative, m.p. 136°). This with chloride) plalinichloride; pier ale, decomp. 246°; Ac2, boiling A-NaOH affords 3-bromo-l-nitro-$-naphthol, m.p. 131° (decomp.). (IV) is reduced with Sn-HCl m.p. 210°, and Bz2, m.p. 225°, derivatives). Similar reduction of o-phenylenediacetonitrile gives s-homo- to 3-6romo-l : 2-naphthylenediamine, m.p. 85°, which with benzil in hot EtOII gives a quinoxalinc derivative, tetrahydroisoquinoline (von Braun el al., A., 1926, m.p. 195— 199°. 1: 6-Dinitro-2-p-toluenesulphon- 178) (Bz, m.p. 100°, and Ac, m.p. 70°, derivatives). naphthalido with Br-C5H5N gives its 3-Br-derivative, A mechanism is suggested. J. W. B. m.p. 228— 231° (decomp.), hydrolysed to 3-bromo- Interaction between aromatic diamines and 1 : d>-dinitro-$-naphthylamine, m.p. 238—241° [Ac ethyl acetoacetate. 0. G. B a c k e b e r g (J.C.S., derivative, m.p. 273—277° (decomp.)]. (Ill) in 1935, 1568— 1570).—Primary aromatic diamines with CgHgN with I, IC1, or IC13 affords l-iodo-2-p-foiwene- CH2Ac-C02Et (I) yield ß-phenylaminocrotonic esters sulphon-naphthalide, m.p. 126— 127°, from which the and no acetoacetarylides. m-C6H4(NH2)2 when base could not be obtained owing to its instability heated with (I) on the water-bath (2 hr.), or when (cf. J.C.S., 1885, 47, 520), and which when warmed heated to 200° and rapidly poured into boiling (I), with Ac0H -N aN02 during 3 hr. affords the corre yields Et m-pheiiylenebis-fi-aminocrotonate. These sponding l-N 02-derivative. The following were reactants, however, when heated under seal gave obtained by similar methods: 3-iodo-2-p-toluene- 5- or 7-amino-2-hydroxylepidme (cf. A., 1898, i, sulplionamidodiphenyl, m.p. 114— 115°; 3-iorfo-4- 450). m-Aminoacetanilide and (I) when heated p-toluenesulphonamidodiphenyl, m.p. 109— 115°; 2- on the water-bath yield Et $-3-aeetamidophenylamino- iodo--p-toluenesulphon--p-toluidide, m.p. 127— 123°. crotonate, m.p. 92°. p-C6H4(NH2)2 when heated to H. G. M. 200° and poured into boiling (1 ), or when heated Ditolyl series. IV. Separation of dZ-6-brom o- with (I) on the water-bath (2 hr.) or at 150° (4 hr.) 6'-am ino-2 : 2 '-dimethyldipb.enyl into its optical [but not at 170° (4 hr.)], yields Et -p-phenylenebis- antipodes. A . A n g eletti [in part with C. Mig - $-aminocrotonate, m.p. 135° (cf. A., 1887, 247) (insol. liard i] (Gazzetta, 1935, 65, 819— S23).—-For the in N a 0 H -H ,0 ; gives dark red coloration with FeClg- prep, of 6-bromo-6'-nitro-2 : 2'-dimethyldiphenyl (I), EtOH). By similar methods p-C6H4(NH2)-NHAc X Y (c-e) ORGANIC CHEMISTRY. 65
and (I) yield Et ji-i-acetamidophenylaminocrolonate, Co 1-benzeneazo-^-naphthoxide, m.p. 221°; Cu, m.p. m.p. 185° (hydrolysed by boiling MeOH), but when 237°, Ni, m.p. 293° (olive-green; gives brown solutions heated under seal at 140° for 5 hr. affords some in CGH6, PhMe, and CHC13), and Co 2-benzeneazo-a- p-CGH4(NHAc)2. Dianisidine when refluxed with (I) in naplithoxide, m.p. 199°. No metallic derivatives MeOH yields Et 3 : 3'-dimethoxydiphanylencA : 4'-bis- could be obtained from p-hydroxyazo-compounds, fi-aminocrotonale, m.p. 132— 134°. Similarly tolidine as chelation is impossible. H. G. M. and (I) afford Et 3 : 3'-dimethyldiphcnylene-i : 4'- bis-^-aminocrotonale, m.p. 129— 130°, whilst benzidine Azo-dyes and their intermediates. XVI. Re and (I) give a little Et diphenylene-i : i'-bis-B-amino- actions of tetrazo-compounds of the benzene crotonate, m.p. 99-5— 100°. and mainly a double com and naphthalene series. peW-Disazo-dyes. III. pound (NH2-O6H4-C0H4-NHX).2,NHX-C0H4-C6H4-NHX P. R ugglt and E. Caspar (Hclv. Chim. Acta, 1935, (X = iCMe;0H,CO2Et), m.p. 134° (cf. A., 1899, i, 18, 1414— 1420).—??i-Xylylene-4 : 6-diamine hydro 366), which, although readily dissociated, could not chloride (improved prep.) with NaN02-HBF4 at —10° be separated into its components, and with CcH0- gives the bisdvazonium borojluoride, which couples A c20 gave Et A-acetamidodiphenylA'-^¡-aminocrotonate, with 6 : 2-Cj0HgBr-OH in NaOAc-AcOH to give m.p. 201°, readily hydrolysed to monoacetylbenzidine. m-xylene-d : (i-bisazo-6'-bromo-fi-naphthol, is converted H. G. M. by CuS04-KCN at 0° into 4 : 6-dimethylisophthalo- Reduction of azoxy-compounds in relation to dinitrile, and by SITGHyCO.JI into the unstable that of diazonium derivatives. D. E ig ia v i and bisazo-compound, CLH2Me2(N!N• S• CII2• CO2H )2, which C. A lb a n e se (Gazzetta, 1935, 6 5 , 773—788).— decomposes in H20 to give m-xylylene-4 : 6-dithio- NaHSn02 reacts at once -with p-CGH4Me'N2-0H and glycollic acid. Similarly 1 : 8-C10H0(NH2)2 affords p-OMe^CgHpNyOH, but KHSnOo only very slowly its bisdiazonium borojluoride, which couples with with the o-isomerides, or with 2 :4 :5 - CGH2Mc3• N2■ 0II. (I) to give naphthylene-l : 3-bisazo-C-bromo-^-naphthol. NaHSnOo reduces dimethylaminoazoxybenzene slowly J. W. B. to dimethylaminoazobenzene, and pp'-dihydroxy- Chromium compounds from salicylic acid- azoxybenzene to azophenol. Azoxybenzene, and azo-dyes and from o-methoxybenzoic acid. K. the a-and [3-forms of itsp-NH2-,p-Br-,p-OH-,p-C02H-, B rass and W. W ittenberger (Bcr., 1935, 68, [B], p-Me, p-OEt-, and oo'-Me2 derivatives, are reduced 1905—1912).— Introduction of Cr into salicylic acid- . by NaHSn02 with varying ease to azo-compounds. azo-dyes can be effected by Cr alum, but not Na3As03 does not reduce a- or p-benzeneazoxyphonol; by K 2Cr20 7 unless a reducing agent such as these are, however, reduced by FeS04, as is p- OITCHMe-C02H is present. The azo-dyes from OH’C8H4-N2-Ph, which gives NH2Ph and p- o-OH-CcH,-C02H and m-N02-C6H4-NH2 (I), NH2Ph, NH2'C6H,pOH. A new test for small amounts of o-C6H4Me-NH2, and benzidine, respectively, are fsodiazo-compounds in solution is to dip filter-paper converted into the corresponding lakes by heating into the latter, to which AcOH and (3-C10H7*OH or their solutions, after neutralisation with NaOH, with i?-salt are added; the paper removed and exposed Cr alum (Cr:: dye : Na : : 1 : 1 :1). In the lakes, to the air develops a red stain. This reaction is dye: Cr: H20 = 2 :1 :2. They are stable at 130°, andCr given only very slowly by phenylnitroamine; the can be removed from them by boiling AcOH, leaving last, and its NO-derivative, are reduced to fsodiazo- the homogeneous dye acid. H20 cannot be directly compounds fairly rapidly by NaHSn02, but only determined in them with accuracy, and attempts very slowly by Na3As03. E. W. W. to displace it by NH3 lead to adducts in which 2NH3 is very firmly retained. These and the lakes are there The azo-group as a chelating group. I. fore formulated according to A and B, respectively : Metallic derivatives of o-hydroxyazo-compounds. (Miss) M. E lk in s and L. H u n t e r (J.C.S., 1935, H20 h 2o 1598— 1600).—The following Cu11, Ni, and Co111 NHo H ,0 H20 salts of some o-monohydroxyazo-compounds are described. They are insol. in H20, sparingly sol. -0 — Cr— 0<^ ^ V - O —Cr- -O. in polar solvents, readily sol. in non-polar solvents, - and are chelated. They have > 0 "COnH COoH \ i the annexed structure, in which (A.) (B.) y \ /i M the arrangement of the aryl Repetition of the work of Morgan et al. (A., 1924, \ / O |\ groups about the azo-group is i, 1359) shows that (I) prepared under their conditions trans. Decomp, of the metallic contains unchanged dye, after removal of which the complexes by cold acid always regenerates the original residue has the same composition as that obtained azo-compound, and this supports the view that all by the authors’ method. Méthylation of (I) is not stable azo-compounds are trans. Cu, m.p. 230°, Ni, effected with Me2S04 or éthylation with EtBr, and m.p. 216°, and Co 3-benzeneazo-p-tolyloxide, m.p. 202° ; coupling of o-OMc-C6H4-C02H with ?w-N02-C6H4-N2G1 Cu, m.p. 242°, Ni, m.p. 242—243°, and Co 3-p'- does not lead to the methylated dye. In a simpler case lolueneazo-p-tolyloxide, m.p. 200—201° ; Cu, m.p. 221°, the action of Cr alum on o-OMe-CGH4-C02H aff ords the Ni, m.p. 214° (impure), and Co 3-nï-tolueneazo-p-tolyl- compound 0H >Cr(0-C0-CGH4-0Me)2,H2Ô, suggesting oxide, m.p. 187° ; Cu, m.p. 243°, Ni, decomp. 295— 310° the analogous structure 0H ,Cr(0'C0,CgHp0H)2,H20 (impure), and Co 2 : ‘i-bisbenzeneazophenoxide, m.p. for Barbieri’s chromisalicylic acid. Similar structures 180— 185°; Cu, m.p. 295°, Ni, m.p. 290° (dark green; can be assigned to the lakes, but their difficult solu gives brown solutions in C6H6, PhMe, and CHC13), and bility in alkali is hard to explain. H. W. X V [e, g, i) G6 BRITISH CHEMICAL ABSTRACTS.— A.
Oxidation of hydrohalides of phenylhydrazine and PhOMe afford chiefly o- and p-C0H4Pr^-OMe, in presence of copper salts. A. B. B r u k e v and together with C0H3Pr^-OMe and (I). R. T. L. S. Soborovski (J. Gen. Chem. Russ., 1935, 5, 1024— 1028).—NHPh-NHo in aq. HC1 and CuCl2 Action of isobutylene on phenyl methyl ethers, form the compound NHPh*NH2,HCl,CuGl, decomp, and the structure of fei-f.-butylphenyl methyl at 150°, converted by excess of Cu11 or by atm. 0 2 ethers. B. M. D u b in in (Compt. rend. Acad. Sci. into PliCl and N2. When F is taken in place of Cl U.R.S.S., 1935, 3, 263—266).—The substance ob in the above reaction the sole products are C„HG and tained from isobutylene and p-CGH,Me-OMe (A., Nr R. t . 1933, 60) is 3-ter<.-butyl-p-tolyl Me ether, since it is also obtained from BuH3r and 1 : 4 : 3- Aryldiazonium chloride-heavy metal chloride CGH3Me(OMe)-MgBr (cf. A., 1894, i, 449). Nitration double salts and the preparation of organo-tin affords the 5-iY02-derivative, m.p. 93-5°, and then compounds through diazo-compounds. A. N. 1:3:5: 4-CGH2Me(N02)2-0Me by elimination of the N esm ejanov, K . A. K ozesch kov, and V. A. K limova Buy. The Bin groups in the Bu>'1 (I) and B u l, (II) [with, in part, N. K . Girr] (Bcr., 1935, 68, [B], derivatives of 1 : 3-CGH4(OMe)2 are given the 4 and 1877— 1883).—The synthesis of organo-mercury sub 4 :6 positions, respectively, since nitration of (I) stances from diazonium compounds (A., 1929, 711) affords i-nitro-G-tert.-butylresorcinol Me2 ctlier (III), is an example of a general reaction, (RN2C1)„,XC1,+ m.p. 99— 100°, and then 4 : 6 : 1 : 3-CGH2(N02)2(0Me)2; 2m/pM,f,'= R mX("’Cl„ _ m+ mN2+2?» /pM'r'Cl,,. Double (II) also affords (III). The blue colour pro&uced in salts aro obtained by mixing cold solutions of the heavy the prep, of (III) from (I), but not from (II), is due metal chloride (ZnCl2, CdCU, SnCl.,, PbCl4, PtCl4, to the presence of a free position p to an OMe in (I) TlClj, BiCl3, FeCl3, AuC13) in HC1 (d= 119) and the (cf. A., 1920, i, 37; 1921, i, 240; 1922, i, 135). requisite aryldiazonium chloride (Pin, o-, m-, and p- P. G. C. C0H4Mc-, p-OH-CgHp, p-OMe^CgHp, o-, m-, and p- Compounds of bivalent carbon. XI. Carbon CGH4Cb, p-C0H1Bi-, p-CGH4I% o-, m-, and p- monoxide acetal fission of esters and amides of N 02-CGH4-) in about 52V-HC1. For details the original diphenoxyacetic acid during chemical reactions. must bo consulted. Decomp, of (RN2Cl)2SnCi4 is XII. Thermal carbon monoxide acetal fission effected by its gradual addition to a well-stirred of diphenoxyacetic acid and its derivatives. suspension of the metallic powder in the solvent heated XIII. Diphenoxymethyl chloride (formyl chlor at the requisite temp. The best solvent is usually ide diphenyl acetal) and its transformation into EtOAc at its b.p. Sn powder is more effective than tetraphenoxyethylene (dicarbon monoxide tetra- Zn dust or Cu powder. The solo organo-metallic phenyl acetal). H. Sc h e ib l e r and M. D e p n e r product is SnR2Cl2 except when R = o - C 02Me • C CH, •. (Ber., 1935, 68, [B], 2136— 2143, 2144— 2151, Small yields of PbPh3Cl and PbPh20 are obtained 2151— 2153).— XI. Ph diplienoxyacetate, m.p. 95°, by decomp, of (RN2Cl)2PbCl4. H. W. could not be obtained by heating CH(OPh)2-CO-NH2 Action of bromine on 2- and4-nitro-a-naphthyl- with PhOH or CH(0Ph)2-C02Et with PhOAc, but amines. R. Co n sh e n and J. K e n y o n (J.C.S., 1935, is readily prepared by the successive action of S0C12 1596— 1597).—4 : l-NO2*C10H G-NH2 (I) with Br in and PhOH on the acid in Et20 -C 5H5N. It is con CHC13 yields 2 : 4-dibromo-l-naphthalenediazo- verted bv excess of NaOEt in boiling C6H 6 into perbromide (II), decomp. 128— 136° according to HC02Et," CH(0Ph)2*C02Et, and C(OPh)2:C(OEt)2, rate of heating, but no HBr. (II) is converted into whereas CH(0Ph)2-C02Et and KOPh in boiling C6H G 1:2: 4-C10H5Br3 when heated, treated with C5H-N, afford HC02Et and Rafter treatment of the non or boiled with Ae20 or AcOH, and was also obtained volatile portion with H ,0) HC02H and PhOH, from diazotised 2:4: l-C10H5Br2-NH, and HBr-Br whilst in boiling EtOH the products are HC02H ancl (cf. J.C.S., 18S3, 43, 4). (1) when heated (watcr-bath, CH(OPh)„-CO„H. The change is therefore : 30 min.) with Br-AcOH yields a little (II), but CH(OPh)“-CO;Et+KOPh -> chiefly 4:2: l-NO2-O10H.Br-NH2 (Ac derivative, CH(OPh),-C(OEt)(OPh)-OK -> C(OPh)„+ m.p. 235— 236°), which with Br in CHC13 or CHC1,- OEt-CH(OPh)-OK (I); (I) -> HCO.,Et-f KOPh; AcOH yields (II). 2 : l-NO2-C10H G-NH2 with Br C(OPh)2-> PhOH+HC02Ph -> 2Ph0H +H C 02H. in AcOH or CIIC13 yields 2:4: l-NO2-C10H-Br*NH., The CO acetal fission is also observed during the action (J.C.S., 1910, 97, 1709), which with excess of Bi- of NEtvMgBr on CH(0Ph)2*C02Et, whereby a neutral yields (II). o- and p-N02-C6H4*NH2 with Br yield product, b.p. S5°/15 mm., possibly Ph Et2 orthoformate, Br-derivatives and no diazo-perbromides. H. G. M. and, probably, CH(OPh)2*CO-NEt2 are obtained. Higher yields of these compounds are obtained Alkylation of phenols. I. Tzukervanik and Z. when the reaction product is heated with EtOH N azarova (J. Gen. Chem. Russ., 1935, 5, 767—770).— at 150°. whereby PhOEt is also produced. Amylene hydrate, PliOH, and A1CU in light petroleum CH(0Ph)2-C02Ph is much more stable than the Et yield a mixture of amylphenol and CrHn Ph. PhOH ester, but in CrH(, at 150° gives HC02H and PhOH and BuyOH yield chiefly C6H4Buv-OH, together with (? HC02Ph). Only elimination of PhOH is observed PhBuy and C6H4Buv2, in amounts increasing with the by the action of KEt„-MgBr on diphenoxyacetdiethyl- relative amount of A*1C13 present. PhOH and BiVOH amide,m.p. 137° [from CH(0Ph).,-C02Et andNHEt,in under similar conditions yield chiefly C6H4Bus-OBu®, EtOH at 100°]. b.p. 230°, together with CGH4Bu^bH and PhBus ; XII. CH(0Ph)2-C02H passes at 120° into CO, C02, PhOH and 1VOH give similarlv CsH,Prs-OIV, HCO.,Ph, Ph2C03, and, probably, diphenoxymaleic b.p. 232°, C6II4Pr3-OH (I), and PhBr^, whilst Pr^OH anhydride, m.p. 153°; CO acetal fission has only a XV(z,j) ORGANIC CHEMISTRY. 67
subordinate part in the change. CH(0Ph)2*C02Et the NO-form in CGHG and hi the quinoneoxime form is comparatively thermostable, but the following in EtOH, whereas its 3-Cl-derivative (II) is always in thermolabile derivatives have been examined. Di- the NO-form and is highly chelated, being sparingly phenoxyacetyl chloride (II), obtained by cautious sol. in H20 and readily sol. in CGHG. The following treatment of the acid with SOCl2 in C6H G, passes at salts of (I) (X=C 7Hg0 3N) and (II) (Y = C 7H50 3NC1) 170— 180° into CO and CHCl(OPh)2, probably with are described; they are sol. in org. solvents (CGHG intermediate production of C(OPh)2 and HCOC1. and CHC13) andprobably are co-ordination compounds: Acetic diplienoxyacctic anhydride [attempted prep, HgX2, m.p. 201°; HgY, ; A1XC1, ; A1YC12; SnXCL, from (II) and AgOAc or from AcCl and m.p. 147°; SnYCl3; Fe"(OH)X2 ; “ FeX3 ; Fe(OH)Y,; CH(0Ph)2-C02Ag] is decomposed in Et20 into FeY3 ; CoX3 ; CoY3 ; NiX2 ; NiY2 ; and the following AcOH and C(OPh)2!CO. (II) and NaN3 in CGHG double compounds with salicylaldéhyde (= S ) : NaX,S ; give NaCl, C(OPh)2:CO, and N3H. CH(0Ph)2-C02Ph NaY,S ; KX,S ; and ICY,S. The following salts is produced by the action of Ag20 (II) in CGHG, are insol. in org. solvents and probably are PhOH, resulting from hvdrolysis, reacting with normal salts (non-eo-ordinated) : NaX ; NaY ; ICX ; C(OPh)2:CO or unchanged CH(OP1i)2-COC1. ICY; AgX ; AgY; ZnX2; ZnY2; CdX2; CdY2 ; C(OPh)2:CO does not appear to be formed intermedi PbX2 ; PbY2 ; MnX2 ; MbY2 ; U 02X 2"; U 02Y 2. ately by the action of CH^OPh^COCl on PhOH in The Ag and Hg salts of 2-nitroso-3-ethoxyphenol presence of C3H5N. Elimination of HC1 from described by ICietaibl (A., 1899, i, 343) are really those CH(OPh)2-COCl occurs under the influence of p- of 2-nitroso-5-ethoxyphenol. Wool mordanted with OH,CGH,'N!NPh, whereby the compound C12H u ON2Cl Fe11 salts is dyed bluish-green with nitrosophenol separates and, on exposure to moisture, solutions : the colour lake is decolorised by acids, CH(0Ph)2-C02H is formed, presumably from restored byNH 3, and destroyed by SnCl2 H. G. M. C(OPh)2!CO. Triphenylmethyl diphenoxyacetate, m.p. Dimorphism of trinitroresorcinol, bromo- 112°, from CH(0Ph)2-C02Ag and CPh3Cl in anhyd. benzylhydrazine, and benzaldehyde-p-nitro- Et20, decomposes at i60°/high vac. into C02, CHPh3, phenylhydrazine.—See this vol., 16. and C(OPh)2. X III. Treatment of CHCl(OPh with CNaPh Diaryls and their derivatives. IV. Oxidation )2 3 of (3-naphthol-6-sulphonic acid and : -dihydr- in Et20 under N leads to CHPh and aafifi-tetraphen- 2 6 2 3 oxynaphthalene. V. Optical activity of 2 : 2'- oxyethylene (dicarbon monoxide Ph acetal), m.p. 4 dihydroxy : '-dinaphthylsulphonic acids. I. S. 168°, which readily reduces alkaline KMnO,, unites -1 1 J ofee (J. Gen. Chem. Russ., 1935, 5, 877— 885, energetically with Br in CHC13, and is converted by 950—955).— IV [with S. G. K u zn etzo v], 2 : 2'- 30% HBr in AcOH into CH(0Ph)2-C02Ph. H. W. Dihydroxy-1 : l'-dinaphtliyl-6 : 6'-disulphonic acid (I), Ester enolates and keten acetals. XIX. Di- obtained in 90% yield from Na P-naplithol-6-sulphonate phenylketen diphenyl acetal, and phenyl diphenyl- and aq. FcCl3 (20—25°; 20 days), yields 2 :2 '- vinyl ether. H. Sc h e ib l e r and M. D ep n e r (Ber., dihydroxy-1 : l'-dinaphthyl when heated with H2SO. 1935, 68, [5], 2154—2157).—CH(0Ph)2-C02Et is (170— 180° ; 12 hr.), and 2 : 6 : 2' : 6'-tetrahydroxy- transformed by MgPhBr in Et20 into a.-hydroxy-$$- 1 : 1'-dinaphthyl (II), m.p. 318— 320°, when heated dijrfienoxy-aoL-diphenylrlhane (hydroxydiphenijlacetalde- with KOH (320— 330°; 15 min.). (II) may also hyde Ph2 acetal) (I), m.p. 103°, converted by SOCl2 in be obtained from dil. aq. 2 : 6-C10H G(OH)2 and FeCl3 Et20-C 5H5N into
Mg, CH2PhI, and EtCHO afford p-phenylbutyl alcohol, m.p. 156-5— 157° (cf. lit.)]. In each case only the b.p. 124— 127°/25 mm. [benzoate, m.p. 115— 116°), Ph has migrated during the deamination. H. G. M. which with HBr in Et20 yields the bromide, b.p. Action of magnesium phenyl bromide on d- 1120/15 mm. " ‘ R- T. dibenzoylglyceraldehyde. Formation of a single diastereoisomeride : a-d-dibenzoylphenylgly- Semipinacolic deamination of p-amino-p-tolyl- cerol. M. T if f e n e a u , I. S. X e u b e r g -R a b i n o - and -a-anisyl-a-phenylpropanol. Exclusive v it c h , and II. Ca h n m an n (Bull. Soc. chim., 1935, preferential migration of phenyl. M. T if - [v], 2, 1866— 1871).— d-Dibenzoylglyceraldehyde and f e n e a u , J. L e v y , and E. D itz (Bull. Soc. chim., 1935, MgPhBr (1 mol.) give a single d-dibenzoylphenyl- [v], 2, 1871— 1876).—Treatment of the a- and 3- glycerol (lœvorotatory), which with BzCl and C5H5X forms of p-CGH.1Me*CPh(OH),CHMe,NH2 in AcOH gives solely lævorotatory a-d-tribenzoylphenylglycerol, with NaN02-H 20 yields p-tolyl
A. K lin g and M. R o u il l y (Compt. rend., 1935, 201, Ozonisation of (III) or (IV) in CHC13 followed by 782— 784; cf. A., 1934, 216).— Cholesterol in warm reductive or oxidative fission of the ozonide yields a CHC1 reacts with C0C1 to give a chlorocarbonate 3 2 H2C Me CH*C H (I), m.p. 114°. ClC02Me does not react; 9 17 C1C0 CH C1, C1C0 CHC12, and C1C0 CC give a 2 2 2 2 )3 ?H2 highly unstable product, cholesteryl dichloromethyl Oïl! ÔH. /Ho carbonate, m.p. 85°, and cholesteryl CCl3 carbonate, QH, CH/\ ç ‘ m.p. 107°,respectively. COjO-CClg)^ similarly V " ' affords (I) (cf. A., 1920, i, 805). This reaction may OH-CH^O' /CH (A.) account for the toxicity of these substances when £ h 2 inhaled. J. L. D. Hydrogenation under the action of selenium. ketone, C^H^O (semicarbazone, m.p. 225°; oxime, I. Action of selenium on cholesterol at 230°. m.p. 129-5°). Hydrolysis of (I) gives a-calciferol- -, tt C. D orée and V. A. P etrov H,C Me CH*C9H 19 (J.C.S., 1935, 1391— (A.) ( \|/ % 1393).—After 10 hr., chole CH, OIL, h 2 II.. sterol is partly converted C H Y ^ N- f/'Y T H - -C O $ CH ¥2 CH 1 by Se at 230° into chole- stanone (I) (semicarbazone, / ^ ' “ > 0 (BO N H / ^ m.p. 234—238°), with small Oh“h\X H— Y-CH /k / quantities of cholestanol maleic acid, m.p. 146— 147° (decomp.), dohydrogenatcd ' and cholestenone ; after 25 by Pd-C at 330—340° to C10H 8, and |J-C10H 7?CO2H, hr., 10 % of (I) is formed. and by Se at 280— 325° to 2 : 3-C10H0Me2. The With NHPh-NH2 in AcOH, structures A and B are therefore assigned to calciferol (I) forms a telrahydrocarbazolc derivative, m.p. and the H2-adduct, respectively. H. W. 180— 181° (picrate, m.p. 209—210°), which from ease of formation and surface film area probably has the Reaction of carboxylic acid chlorides with angular structure (A). E. W. W . metallic hydrides. 0. Neunhoeffer and F. N e rd e l (J. pr. Chem., 1935, [ii], 144, 63— 66; cf. Sitostanol and stigmastanol. B. E. B en g tsso n (Z. physiol. Chem., 1935, 237, 46— 51).—The pro Wolil et al., A., 1912, i, 161).—Freshly prepared bability of the identity of ordinary dihydrositosterol CuH is red to chocolate-brown, and even when with tetrahydrostigmasterol is advanced. “ Ordin moist with Et20 cannot be handled without some ary” and y-sitostane can be differentiated by their danger, whereas the aged product is black and almost mixed m.p. with stigmastane. Fucostanol is not non-dangerous. Its complete purification from com identical with stigmastanol (cf. A., 1934, 1347). pounds of P is extremely difficult. Interaction of F. 0. H. CuH and BzCl in presence of Et20 in an inert atm. Phytosterol of wheat-germ oil.—See A., 1935, affords EtOBz in widety varying yield, but no 1551. PhCHO. Since in presence of C0H 0 or cyc/ohcxane in place of Et20 there is 110 formation of EtOBz, Constitution of vitamin-/!2. A. W in d a u s and its production must be ascribed to fission of Et20. W. T h ie le (Annalen, 1935, 521, 160— 175).—Treat Reaction between CuH and acid chloride is accom ment of caleiferyl acetate with maleic anhydride in panied by evolution of H2. Since the amount thus boiling C6H6 affords an adduct, m.p. (indef.) 189— liberated + that evolved on subsequent addition of 196°, hydrolysed and then converted by CH2N2 HC1 equals the total H present, it follows that none into tx-calciferyl acetate Me2 maleate (I), m.p. 141°, is expended in reduction. Since CuH is very sensitive Mï? +170-8° in CHC13, which absorbs 2 O when titrated to Cl', the BzCl used is first shaken with CaC03 and with BzOoH. The filtrates from (I) when treated a trace of C5HSN is added to accelerate the change; with KOH-MeOH give a sparingly sol. K salt, from under these conditions CuH is almost completely which AcOH liberates ^-calciferol-maleic acid (II), stable to BzCl, and evolution of II2 does not occur m.p. 196° (decomp.), the Me ester, m.p. 67— 68°, until HC1 is added. CaH2 and LiH are more stable of which is converted by Ac20 into p-caleiferyl acetate than CuH. AcCl, CHPhiCH COCl, and adipyl chlorido jl/e2 maleate, m.p. 94-4)5°, [ceg? —158-3° in CHCI3, behave similarly to BzCl. ' II. W. which absorbs 3 O from BzO,H. The adducts can be distilled in a vac. without decomp. Hydro Nitration of henzoic and toluic acids. A. genation (Pd in C0Me2) of (I) gives the //¡¡-derivative Giac alo n e (Gazzetta, 1935, 65, 840— 844).—Nitr (III), m.p. 112°, [ajp1 +167-8° in CHC13, which ation at 0— 5° of m-toluic acid (20 g.) with K N 03 in absorbs 1-16— 1-33 0 and is further reduced (Pt in H2S04 gives 4-nitro- (12 g.) and 2-nitro- (6 g.) without AcOH) to the //¡-compound. Similarly (II) gives a 6-nitro-m-toluie acid. Similar nitration of BzOH //¡¡-derivative, m.p. 193° (decomp.) [$-diliydrocalci- and of o- and p-toluic acid gives products more readily feryl acetate Me2 maleate (IV), m.p. 86— 86-5°, [a]},9 purified than those obtained in the usual manner. —144-7° in CHC13, which absorbs 2 O from Bz02H], E. W. W. and a non-crvst. //.¡-derivative, converted by acétyl Effect of substituents on organic reactions.— ation and méthylation into §-telrahydrocalciferyl See A., 1935, 1465. acetate Me2 maleate, m.p. 122°, [a]},9 —51-5° in CHC13, Electrolytic preparation of anthranilic acid. which absorbs Br but is only slowly attacked by 0 3. J. W. Sh ip le y and J. M. Ca lh o u n (Canad. J. Res., X V (k) 70 BRITISH CHEMICAL ABSTRACTS. A,
1935, 13, B, 123— 132).—o-N02-CfiH4-C02H is re mm. (the acid, m.p. 123°, loses C02 in vac. at 170 to duced electrolytically (92% yield) in Et0H -H 2S04 give $-tetrahydronaphthylpropionic acid, m.p. 127°), with a Pb cathode to the NH2-acid. The effects of the Na derivative of which affords (cf. A., 1935, 975) varying temp., c.d., electrolyte composition, and an allyl derivative, b.p. 189— 190°/2 mm. [acid, an oil, quantity of current have been measured and optimum which loses C02 in vac. at 170— 180° to give (3-/efra- conditions determined. The C00H is not reduced. hydronaphthyl-cL-allylpropionic acid (I), an oil], F. R. S. (i) with A c0H -H 2S04 at 50° gives a lactone, b.p. Novocaine oxide. W. K e il (Arch. exp. Path. 187°/2 mm., and i-viethyloctahydroplienanthrenc-2- Pharm., 1935, 179, 125— 426).—Novocaine (I) with carboxylic acid, m.p. 148— 149°, which with Se- at H.,02 for 48 hr. yields novocaine oxide (II), C12H220 4N2, 300— 350° gives 4-methylphenanthrene, m.p. 116° a genalkaloid ” (isolated as picrate, m.p. 172°). (cf. A., 1931, 1282; 1932, 608). J. L. D. In its anaesthetic actions on the rabbit’s cornea and Addition of halogens to unsaturated acids and human skin, (II) has respectively 50 and 25% of the esters. V. Bromination ofm-methoxycinnamic activity of (I). F. 0. H. acid and its ethyl ester. J. I. J o n es and T. C. Hydrolysis of phenylalanine.—See A., 1935, J am es (J.C.S., 1935, 1600— 1604).— m-Methoxy- cinnamic acid (I) when brominated in AcOH in the 1465. dark (cf. A., 1928, 519), in boiling AcOH in sunlight, Maximum rotations of carboxylic acids con or in CC14 or CHC13 at 0° in the dark, affords 6-bromo-3- taining a phenylethyl group. P. A. L e v e n e and methoxycinnamic acid (II), and when brominated S. A. H arris (J. Biol. Chem., 1935, 111, 725—733).— in boiling MeOH in sunlight, or MeOH in the cold and The max. [dI]D of CH2Ph-CH2-GHMeEt is determined dark, yields the Me ester of (II). (I) when treated and that of related compounds calc. In the series, with Br and dry CC14 at the b.p. in bright sunlight CH2Ph,CH2-CHMe-[CH2]„>C02H, there is periodic yields a{i-dibromo-\i-3-methoxyphanylpropionic acid fluctuation of [il/] as n increases from 0 to 3. y- (III), m.p. 167°, also obtained, but less readily, when Phenyl-a-methylbutyric acid, resolved by the cin- (I) is brominated in CC14 in the cold in sunlight, or in chonidine salt in C0Me2, has [a]“ —28-75°. a-Phenyl- boiling CS2. Bromination of (I) in boiling CHC13 y-methylpentane, from (a) the alcohol and cold in sunlight gives a mixture consisting mainly of (II). HI, followed by H2-Raney Ni in 10% NaOH-MeOH, (Ill) is unaffected by boiling EtOH, and is oxidised or (b) ¿-C5HU-Mgl3r and PhCHO, has [a]“ —5-52°. by KMn04 to m-0Me-CGH4-C02H (IV). Bromination Ç-Phényl-S-methylhexoic acid, b.p. 152— 154° (or 162°)/ of the Et ester of (I) in AcOH or CHC13 in the cold and 1 mm., [a]p15 —1-60°, is obtained from (a) dark gives only the Et ester of (II), but in CC14 in CH„Ph-CH2-CHMe-[CH2]2-MgBr and CO„, or (b) strong sunlight gives the Et ester, m.p. 58°, of (III). CH.2Ph-CH2-CHMc-CH2P»r and CH2(C02Et)2” and leads (II) in boiling CC14 with Br in strong sunlight yields to the Et ester, b.p. 122°/5 mm., [a]“ —3-71°, and u$-dibro7no-$-Q-bromo-3-methoxyphenylpropionic acid, Z,-j)henyl-8-methylhexan-2-ol, b.p. 155°/10 mm., [a]” m.p. 163°, also obtained by bromination of (III). -5-27°. CH2Ph-CH2-CHMe-[CH2]3-MgBr and C02 (III) with KOH-EtOH affords a-bromo-m-methoxy- give Ç-iohenyl-S-mcthyïheptoic acid, b.p. 172°/2-5 mm., cinnamic acid (V), m.p. 122° (A., 1934, 72), and a- [a]“ —3-27°. Hydrogenation (Pt02) in AcOH affords bromo-m-methoxy&llocinnamie acid, m.p. 91°, separated e-cyclohexyl-y-methylhexoic acid, b.p. 180°/10 mm., by means of their Ba salts and also obtained by re [a]'o —1-18°, and Ç-cyclohexyl-ü-methylhcptoic acid, moval of HBr from the ester of (III). The aWo-acid, b.p. 136— 140°/0-3 mm., [a%5 —1-41°. [a] are max. when kept in the solid state or in CC14 solution, vais, for the homogeneous liquids. R. S. C. in strong sunlight, or when heated during several Catalytic hydrogenation of ethyl cinnamate hr. at 150°, is converted into (V). (V) when boded under pressure. S. P. L agerev (J. Gen. Chem. with KOH-EtOH during 4 hr. yields m-methoxy- Russ., 1935, 5, 517—518).—Et cinnamate yields phenylpropiolic acid, m.p. 109°, which with K 2C03- CH2Ph-CH2-C02Et, but not S-phenylbutyl alcohol, I-K I-H 20 affords x$-di-iodo-n\-methoxycinnamic acid, when heated with H2 (12 hr. ; 250°/220 atm.) in pre m.p. 142°, and is hydrogenated (colloidal Pd “ pro sence of Cr-Cu catalyst in an Fe autoclave. R. T. tected ” by Na protalbate) to m-methoxyaWocinnamic acid (VI), m.p. 109— 110°, converted on long exposure Steric factor in organic chemical reactions. to sunlight into (I). (VI) with CHC13-B r in the cold I. Influence of estérification on mode of addi and dark affords 6-bromo-3-melhoxya,\\ocinna7nic acid, tion of bromine to p-phenylpropiolic acid. P. R. m.p. 133°, oxidised by KMn04 to (IV). H. G. M. A y y a r (J. Indian Inst. Sci., 1935,18, A, 123— 127).— Addition of Br to CPhiC-C02H (I) at 0° in the dark Preparation of fluorinated arylamides [of affords cis- and
81— 82°). (I), Mg, and EtBr give fr-a-hydroxy-*- It is considered therefore that monomeric E-truxillic eihyl-n-propyl-2c : 4(-diphenylcyclobutane-l’-carboxylic anhydride cannot exist. Interaction of MgMel and acid, m.p. 216— 2179 (Me ester, m.p. 141°); c-a- 3 COoH CMeo-OH hydroxy-a-cthyl-n-propyl-2c : i ’-diphcnylcyclobutane-1'- carboxylic acid has m.p. 151° (Me ester, m.p. 97— H 0 2C / | / H0„C 98°). Treatment of (II), (III), or (V) with AcOIi Ph ! / Ph at 210° yields 3-isopropylidene-2c : M-diphenyl- I (X.) (XII.) cyclobutane-l'-carboxylic acid (VI), m.p. 143— 144° Ph Ph Ph Ph 0 —CMe2 I ] Bz Ph Bz ?!CMeo H 02C Br Bz H 0 2C -K(VI.) Ph Ph Ph (VII.) (XIII.) (XV.) Ph Ph (sparingly sol. Na salt), best obtained by passing IlCl rapidly through a solution of (II) in boiling (XI) gives comparatively very large quantities of .cone; HC1. It is thus established that there is no e-lelramethyltruxilldiol, m.p. 146°, and 3c-a-hydroxy- alteration in the spatial distribution of the other isopropyl-21: i ’-diphenylcyclobutane-M-carboxylic acid groups around tho cyclobutane ring. Bromination (XII), m.p. 145° (Ca salt), which gives CHPh:CH-C02H of (VI) in CHC13 affords a single, saturated bromo- and a non-cryst., non-hydrolysable substance of lactone [probably (VII)], m.p. 157— 15S°, which high b.p. when its dehydration is attempted by the is not debrominated in acid or neutral solution, methods used for the y-acid (see above). Un but with Zn and AcOH or Al-Hg yields small amounts expectedly, treatment of (XI) with MgPhBr leads to of (VI) and is .converted by red P and HI (d 1-5) (X) and l c : 3c-dibenzoyl-2‘ : ‘i’-diphenylcyclobutane into a Br-freo lactone, m.p. 101— 162°, probably (XIII), m.p. 207—208°, which passes when heated with formed by ring fission, and an acid, C20H21O2I, m.p. KOH-EtOH and NH2OH, but not with K O H - 210—2 11° (Na salt); treatment of it with alkali EtOH only, into an isomeric truxillketone, m.p. 222°; gives a CO-acid, an unsaturated acid, and a OH- both ketones yield Ph styryl ketone when cautiously laotone of unexplained structure. Treatment of distilled under atm. pressure. the diol with AcOH at 210° yields 1 ; 3-dnsopropylid- Treatment of y-truxillic anhydride (XIV) with ene-2c : i ’-diphenylcyclobutane, b.p. 202° /ll mm., A1C13 in C6H(. at 100° gives 3c-benzoyl-2i:; 4'-diphenyl- ozonised to (?) iaopropylidcnediphcnylcyclobutayione, cycZobutane-P-carboxylic acid (XV), m.p. 227° [spar m.p. 106— 109°. Proof that the acid (VI) contains ingly sol. Na and NHi salts; phenylhydrazone, m.p. a somicyclie double linking is aiVordcd by the pro 100° (much decomp, with production of lactam); duction of COMe2 after ozonisation. The ozonide Me, m.p. 169°, and Et, m.p. 162°, ester], which is decomposes very rapidly in CHC13, AcOH, or EtOAc, depolymerised when heated or treated with cone. and when treated with alkali gives phenylbenzyl- H2S04 to CHPh:CH-C02H and CHPhiCHBz. The succinic acid (VIII), m.p. 183— 1S4° (ilie, ester, m.p. corresponding chloride, m.p. 150— 152°, is transformed 125°). If ozonisation is effected in EtOAc and the by AlClj and CGHG into much non-cryst. matter and product is immediately catalytically hydrogenated, a substance, m.p. 92—93°. The behaviour of (XIV) diphenylcyclobutanonecarboxylic acid (IX), m.p. 98° towards A1C13 and CGHG depends greatly on the quality (Me ester, m.p. 72°; p-nitrophenylhydrazone, m.p. of the A1C13, temp., and duration of action. With 184°), is almost quantitatively obtained; it appears somewhat weathered A1C13, a truxillketone, m.p. 77— unsaturated towards KMn04 and reduces ammoniacal 7S°, and a substance (Cu H G02)„, m.p. 195° (possibly Ag solution, but does not give the Angeli-Rimini Stobbe’s truxillketone D), are obtained in small yield. test or colour fuehsin-H2S03. If the ozonide is X X . Treatment of y-truxillic acid with HC1 and kept overnight, it yields an isomeric acid, m.p. 141— cold MeOH gives the Me H ester (very sparingly 142° (Me ester, m.p. 64°), stable in hot CGH6 or AcOH, sol. Na salt), converted by S0C12 hi boiling CGHG into but readily transformed by boiling H ,0 or aq. media, the corresponding chloride, m.p. about 86°, which is or by dissolution in cold Xa2C03 or~XH3 and pptn. transformed by A1C13 in CS2 into Me y-truxonate. with acid, into (IX). Reduction of (IX) with a large The latter is hydrolysed by KOH-EtOH to y-truxonic excess of Zn and HC1 leads to 2 : i-diphenylcyclo- acid (XVI), m.p. 152° (Me ester, m.p. 127— 128°; butane-l-carboxylic acid, m.p. I l l — 112 ° (anilide, oxirne, m.p. 207°; amide, m.p. 236—237°; phenyl m.p. 165— 166°). hydrazone, m.p. 225°). Me H x-truxillate, m.p. 195° X IX . e-Truxillic acid (X) is converted by boiling (very sparingly sol. Ha salt), is similarly transformed A c20 into the polymeric e-anhydride, transformed by through the chloride into Me cn-truxonote, m.p. 1S6°, warm NH2Pli into a mixture of (X), its diauilide, hydrolysed by alkali to (XVI), but by boiling AcOH and anilic acid. Repeated distillation of (X) under containing a little H2S04 and H20 to a-truxonic acid 0-4 mm. yields peri- and y-truxillic anhydride, thus (XVII), m.p. 216° (sparingly sol. Na, Ca, and NHi affording the first instance of a change of the s-con- salts; phenylhydrazone, m.p. 239°), converted by SOCl2 figuration. Me H s-truxillate (XI), m.p. 131° (Na and in CgH6, and thence by A1C13 in CS2, into a-truxone. Ca salts), obtained by the action of HNO, on Me pen-Truxillic anhydride, m.p. 287°, is best obtained s-truxillanilate or by half-hydrolysis of Me2 s-truxillate, by heating the y-anliydride under X 2 at about 280°, passes when heated into MeCl and CHPhiCH-COoH. and converting the crude product by XH 3-EtOH into X V (Je) ORGANIC CHEMISTRY. pcri-truxillamic acid (XVIII), m.p. 256-5° (decomp, lysed by KOH-MeOH to fi-phenyl-oL-benzyl-lcevulic acid, in sealed capillary) (NH4 salt), which is boiled in m.p. 120— 121° (Me ester, m.p. 81— 82°), transformed by NHP1tNH2 in AcOH into 2 : 5-dipihenylA-benzyl- CO ,co G-methylpyridazin-3-one, m.p. 148— 149°, and oxidised by NaOBr to (I). The change is therefore H,C„ 110,0 C02H-CH(CH2Ph)-CHPh-C02H -> Ph Ph C02H-CH(CH2Ph)-CPhAc-C02H ■> (XVI.) (xvil.) COoII C02H-CH(CH2Ph),CHPhAe -> (III). This view is supported by tho observation that whereas ,C0 Ph CH2Ph• CIl2-C0 2H is stable towards boiling Ac20 / containing NaOAc, CH2Ph-C02H is converted into HAY h 4cg, H 0 ,0 CH2Ph-COMe in very good yield. H. W. Oxidation of bisphenylpyruvic [a-lxydroxy-y- (XXII.) keto-p-phenyl-a-benzylglutaric] acid. J. Ja r - (X XI.) COoII rousse (Compt. rend., 1935, 201, 676—677).— AcOH or treated with H N 02 in AcOII. It is trans Bisphenylpyruvic acid with KMn04 in alkali at 0° formed by CH2N2 in C2H4(OH)2 into Me II peri- affords xy-diketo-pS-diphenylvaleric acid, which easily truxillamale, m.p. 197— 198°, which with H N02 in loses C02 to give p-keto-a.y-dij)henylbzttaldehyde, AcOH affords homogeneous Me H peri-truxillate. m.p. 114° [semicarbazone, m.p. 200° (decomp.)], Treatment of (XVIII) with cone. X II,'a t 110° gives oxidised by I in presence of Na2C03 to a substance, unimol. pen-truxillimide, m.p. 237°, and epitruxill- m.p. 190° (decomp.). J. L. D. 6-amic acid (XIX), m.p. 263°, whereas with boiling Lichen substances. LIX. Non-existence of 10% NaOH it yields epitruxillic acid, m.p. 286°. y-collatolic acid. LX. Microphyllic acid and With CH2N3 in MeOH (X IX ) gives Me cpitruxill-a- its fission products. LXI. Olivetoric acid. amale, m.p. 228°, transformed by H N02 in AcOH into III. Y. A s a h in a and E. E u z ik a w a (Ber., 1935, Me H epitruxillate, m.p. 204-5°, identical with that 68, [B], 2020—2021, 2022—2025, 2020—2028).— obtained by half-hydrolysis of Me2 epitruxillate. L IX (cf. A., 1933, 713).— a-Collatolic acid (I) in The isomeric b-ester (XX), m.p. 141° (sparingly sol. moderately cone. NaHC03 solution is slowly converted Na salt), is obtained by saturating a suspension of tho into |3-collatolic acid (II). (II) is not a natural pro epf-acid in MeOH at 20° with HC1. (XX) is converted duct, but is formed during the alkaline hydrolysis of by SOCl2 and thence by the Friedel-Crafts reaction Mo a-collatolatc. Me $-collatolate, m.p. 75°, is into Me epilruxonale, m.p. 106—107, smoothly formed by the restricted action of CH2N2 on (II), hydrolysed by KOH-MeOH to epilruxonic acid whereas prolonged action gives the Me ester Mez (XXI), m.p. 160° [oxime, m.p. 260° (decomp.)], ether (III), m.p. 114°, also obtained similarly from (I). peri-Truxonic acid (XXII), m.p. 221— 224° [phenyl- y-Collatolic acid is (II) more or less contaminated hydrazone, m.p. 189° (indef.)], is obtained among with (I), since homogeneous (II) can be isolated other products by the action of A1C13 in CS2 on peri- therefrom by crystallisation from C0H0, and treat truxillic anhydride and is converted through the ment of it with an excess of CH2N2 gives (III). (II) chloride into pexi-lruxone, m.p. 194°, transformed by has therefore structure A. NHPh-NH, in AcOH into the monophenylhydrazone, ÇH— m.p. 217°, and by NIIPh*NH2 in N2 at 150— 160° into the diphcnylJiydrazone, m.p. about 280° (decomp.). (A.) Its isomérisation into a-truxone by cone. HC1 at 180° OH OMe! could not be established definitely. H. W. IC02H CH -C0-C IIj Phenylbenzylsuccinic acids. R. Stoerm er and 2 5 H. S tro h (Ber., 1935, 68, [B], 2112— 2116).—Et3 LX (cf. A., 1935, 490). Micropli3dlic acid (IV), a - phenyl - (3 - benzylethane - a¡3(3 - tricarboxylate,' b.p. m.p. 116°, is transformed by boiling HC02H into 232°/3 mm., m.p. 48°, from CHPhBr-C02Et and olivetonide (V) and olivetonide p-Mo ether (VI). CH2Ph-CH(C02Et)2, is hydrolysed by 18% HC1 at (IV) and Ac20 containing a little cone. H2S04 afford 180— 190°~ to phenylbenzylsuccinic acid (I), m.p. anhydrodiacetylmicrophyllic acid, m.p. 98°. Hydro 176° (Me ester, m.p. 89—90°), whereas hydrolysis lysis of (IV) with 11% NaOH gives (VI) and olivetonic with AcOH and 50% H2S04 at 120° leads to the acid (VII), m.p. 159— 160° (Me ester, m.p. 85—86°), isomeric phenylbenzylsuccinic acid (II), m.p. 183— also obtained by the action of KOH on (V). (IV) is 184° (Me ester, m.p. 125°, identical with that obtained decomposed by excess of CH2N2, but treatment with by degradation of diphenylcyc/obutanonecarboxylic Ag20 and Mel gives Me microphyllale Me2 ether acid obtained from a- or y-truxillic acid (preceding (VIII), m.p. 89—90°, hydrolysed by boiling 95% abstract). Short treatment of (II) with boiling HC02H to olivetonide Me2 ether, m.p. 94° [also ob AcCl leads to the corresponding anhydride, m.p. 92°, tained by treatment of (VI) with Ag20 and Mel], whereas (I) with warm AcCl affords a non-cryst. and olivetonide o-Me ether, m.p. 146— 147°, converted mixture of anhydrides converted by H20 into a by CH2N2 into (VIII). The following derivatives mixture of (I) and (II). Boiling Ac20 containing of (V) and (VII) are described : p-acetylolivetonide, NaOAc converts either acid into phenylbenzylangelica- m.p. 55°, and its o-Me ether, m.p. 84°, obtained by means of Ag20 and M el; diacetylolivetonide, m.p. lactonc (III), ^H2Ph CPh’GMe'^®’ m-P- hydro- 59°; o-acetylolivetonide p-Me ether, m.p. 60—61°; 74 BRITISH CHEMICAL ABSTRACTS. A. XV (Jj-m) olivetonic acid p-, in.p. 94—95°, and o-Me etlier, m.p. and
If the nitration products of these carbamates are the dihydrocholesterol (alio or trans) or the copro heated to 50° before pouring on ice, substances, m.p. sterol (cis) series. Treatment of coprostanone with 200° and 135°, respectively (from the Me ester), Br in AcOH containing traces of HBr gives 4-bromo- and m.p. 153° and 113° (Et ester), are obtained. coprostanone, m.p. 110 — 1 1 1 °, converted by boiling Nitration of N-i-acetylphenyl-N'-ethy¿carbamide, m.p. anhyd. C5H5N into cholestenone, m.p. 79—80° 157° [from (II) and EtNCO in dry CGHr> at 100°] (yield 30%). Under similar conditions, cholestanone with HN03 (d 1-45) at 0° affords 1A-(2-nitroA-acctyl)- affords 2-bromocholastanone, m.p. 169— 170° (ap N'-nitro-W-ethylcarbamide, parently not homogeneous), largely resinified by C0H4Ac(NO2),NH'CO-NEt,NO2 (VII), m.p. 91°, where boiling quinoline and transformed by boiling anhyd. as HN03 (d 1-52) gives the corresponding 2 : G-NO.r C5H5N into a compound, m.p. > 300°. It is converted nilroamine (VIII), m.p. 120° (dccomp.), converted by by AcOH-KOAc at 200° into A1 :2-chole.sten-2-one, the appropriate ROH, respectively, into carbamates. m.p. I l l — 112 °, [a][? —32-1° in EtOII (oxime, m.p. Hydrolysis of (VII) with boiling aq. COMe2, of (III) 146— 147°). H. W. or (V) with conc. H ,S0 at 100°, or of (I) with boiling 4 Substituted unsaturated cyclic ketones. A. GiV-HCl, affords 3-nitro-4-aminoacetophcnone (VIII), Cohen and J. W. Cook (J.C.S., 1935, 1570— 1572).— the 3 : 5-(iV02)2-derivative, m.p. 176° (Ac derivative, Unsaturated cyclic ketones are obtained byelimination m.p. 222°; cf. above), being obtained similarly from of HC1 from nitrosochloridcs and hydrolysis of the (IV) or (VI). Bromination of p-C6H4Ac-NHAc gives resulting oximes. l-P-Phenylethyl-A1-Ci/cfohexene the 3-Br-compound, hydrolysed by 6xY-HCl to the nitrosochloride, m.p. 139— 140° (lit. 118— 119°), hydrochloride, decomp. <100° (Raiford et al., A., when boiled with C H 5N for 2-5 hr. yields 2-fi-phenyl- 1928, 303, give m.p. 155— 156°), of 3-bromo-4-amino- 5 ethyl-A2-cyc\ohexe?wneoxime, m.p. 118— 120°, hydro acetophenone, but with Br-AcOH at 100° the co-Br- lysed by boiling 6xV-H2S04 to the ketone, b.p. 125— compound is obtained. p-C0H4Ac-NH2 with 130°/0-7 mm. (semicarbazone, m.p. 188— 190°). CH Br-COCl-AcOH-NaOAc at 0° gives p-bromo- 2 Similarly\-(^-Y-naphtliylethyl)-A1-eyc\opentene nilroso- acetamidoacetophenone, m.p. 157°. With IIN03 (d chloride, m.p. 108— 110° (obtained from the cyclo- 1-52) at —10° to —15°, 3-bromo-4-acetamidoaceto- penteno, AcOH, Et.,0, amyl nitrite, and IICl), when phenone gives its 5-AT0 2-derivative, m.p. 203°, boiled with C H5N for 5 min. affords 2-(p-l'-naphthyl- hydrolysed (conc. H2S04 or 61V-IICI in presence of 5 ethyl)-A2-cyc\opentenoneoxime, m.p. 106-5— 107-5°, EtOlI) to S-bromo-b-nitroA-aminoacelophenone, m.p. hydrolysed to the ketone, b.p. 165— 167°/0-3 mm. 181°, also obtained by the action of Br-AcOH on (semicarbazone, m.p. 226—227°), which gave no (VIII). The structures of these derivatives are ccstrous response when injected into ovariectomised confirmed by elimination of the N1I2 group after mice. All attempts to cyclise these ketones failed. diazotisation, to give known COPhMe derivatives. H. G. M. J. W. B. Benzanthrone derivatives. III. Autoxidis- Derivatives of p-aminoacetophenone. C. W. able dihydrobenzanthrone. E. Clar (Ber., 1935, R aad sveld (Rec. trav. chim., 1935, 54, 827— 832).— Condensation of p-C„H4Ac-NH2 (I) with the appro 68, [B], 2066—2070; cf. A., 1932, 1134).—Benz- priate carbimide affords p-acetylphenylcarbamide, anthrone (I) is reduced by Zn dust in boiling AcOH m.p. 183° (lit., m.p. 148°), s-p-acetylphenylphenyl-, to dihydrobenzanthrone (II), m.p. 150— 152° when m.p. 195°, and s-Y>-acetylphenyl-a-naphtkyl-carbamide, rapidly heated under CO, in a sealed capillary, which m.p. 209°. With PhNCS a substance, m.p. 195° is very sensitive to air, adds 2 0 in xylene, immediately (not the thiocarbamide), is obtained. Condensation decolorises 2 Br, and becomes disproportioned by of (I) with the appropriate aromatic compound strong acids or weak bases or when heated at 150° to containing reactive Cl affords p-(2 : 4-dinitroanilino)-, (I) and 9-hydroxy-l : 10-trimethylenephenanthrene. m.p. 192° (lit., m.p. 185°),p-(2 : 4 : 6-trinitroanilino-), Oxidation is accelerated by light and occurs most and p-(2-A-dinitro-aL-Tidphthylamino)-, m.p. 162°, -acelo- rapidly in AcOH, but then requires only 1-6 0. phenone. With CO(NH2)2 at 200—215° (I) gives a A peroxide could not be isolated, but the solutions substance, decomp. 280° (block), and, with CS2- retain peroxidic properties. Apparently in xylene EtOH-KOlI, a yellow substance, m.p. 230—235°. the active 0 is imparted to the hydrocarbon and does The following ketazines (with N2H4,H2S04) and not further affect unaltered (II), whereas in AcOH phenylhydrazones are prepared: the Icetazine of H20 2 is formed which transforms (II) into (I). (II) 3-nitro-4-amino-, m.p. 350° (phenylhydrazone, m.p. gives an acetate, m.p, 159— 161° in sealed capillary 135—-138°); 3-nitro-4-acctamido-, m.p. 270° (phenyl filled with C02. The intermediate occurrence of hydrazone, m.p. 160°); 3 : 5-dinitro-4-amino-, m.p. an orange colour during the reduction of (1 ) indicates 345° (phenylhydrazone, m.p. 245°); 3-bromo-4-acet- the possible formation of a IIr derivative similar to amido-, m.p. 80°; 5-bromo-3-nitro-4-amino-, m.p. that, m.p. 120— 125° in sealed tube under C02, 315° (phenylhydrazone, m.p. 80°); and 5-bromo- obtained by mixing equimol. amounts of (I) and (1 1 ) in hot AcOH under C02. Bz-1 -Brornodihydrobenz- 3-nitro-4-acetamido-, m.p. > 350°, -acetophenone. anthrone has m.p. 167° (decomp.). H. W. J. W. B. Bromination of cholestanone and copro- Condensation of phthalic anhydride with s- stanone ; A1:2-cholesten-3-one. A. B ttte n a n d t octahydrophenanthrene. E. b e B. B a r n e t t , N. F. and A. W olff (Ber., 1935, 68, [/J], 2091— 2094).— G o o d w a y , and C. A. L aw r en c e (J.C.S., 1935,1684).— The action of 1 mol. of Br on 3-keto-compounds of the s-Octahydrophenanthrene and o-C6H4(CO)20 with sterol group results preferentially in substitution A1C13 in C2H2C14 yield o-l : 2 : 3 : 4 : 5 : 6 : 7 : 8- at C2 or C4 according as the initial ketone belongs to octahydrophenanthroylbenzoic acid (I), m.p. 200°. 76 BRITISH CHEMICAL ABSTRACTS.— A. X V (m)
Similarly the corresponding 4 ': 5'-dichloro-octahydro- ester (III), m.p. 60°]. y-Hydroxij-y-G-methoxy-1- phenanthroylbenzoic acid, m.p. 276° (decomp.), is naplithyl-n-butyric acid and the corresponding lactone, obtained from 4 : 5-dichIorophthalic anhydride, but m.p. 114°, are obtained as by-products. Hydrogen the product from ¡5 : 0-dichlorophthalic anhydride ation of (III) in AcOI-I (Pt or Pd) and hydrolysis of could not bo crystallised. (I) when heated (water- the product gives y-6-methoxy-\-naphthyl-n-butyric bath) during 15 hr. with activated Zn dust, NaOH, acid, m.p. 149°, cyclised by SnCl4 at 105° to 1-methoxy- and NH;,-HoO yields to-1 :2:3:4:5:6:7: 8-octa- l-lceto-l : 2 : 3 : 4-telrahydrophenanthrene, m.p. 101°, hydrophenanthryl-Q-toluic acid, m.p. 192°, cyclised by which with HBr (d 1-48) in boiling AcOH yields cold, eono. H2SO,, to octahydro-] : 2 : 3 : 4-dibenz- (I), m.p. 232° (slight decomp.) (Bz derivative, m.p. anihrone (11), m.p. 200°, converted by Ac20-C 5HsN 212°). Et succinaldeliydalc seinicarbazone has m.p. into octahydro-1 : 2 : 3 : 4-dibenzanthranyl acetate, m.p. 133°. H. W. 214°, (II) is oxidised by boiling CrOa-AcOH -H 20 Manufacture of polynuclear cyclic ketones.— to octahydro-] : 2 : 3 : 4-dibcnzanthraquinone (III), m.p. See B., 1935, 1133. 234°, and when boiled (3 hr.) with activated Zn dust, EtOH, 1120, and KOH is reduced to octahydro- Sex hormone. VIII. Preparation of testo 1 : 2 : 3 : l-dibcnzanthraccnc, m.p. 129°. Attempts to sterone by use of mixed esters. L. R u z ic iia , A. dohydrogcnato this with So, and (III) with Br, failed W e t t s t e in , and H. K a g i. IX. irons-A'-Dehydro- to yield any pure products. H. G. M. androsterone and the preparation of trans-A5- dehydroandrosterone from stigmasterol. L. Carvacrol. V. Benzyl ethers of acylated R u z ic k a , W. Eisc h e r , and J. M e y e r . X . P re methyl/.sopropylphenols. II. John and P. Beetz paration of 17-methyltestosterone and other (J. pr. Chom., 1935, 144, 49—53).—The following androstene and androstane derivatives. Re ethers aro obtained in about 85% yield by the action lationship between chemical constitution and of 0H2PhCl or p-NO.yCj.ir.j'CiUGl on the K salt of male hormone activity. L. R u z ic k a , M. W. the requisito phenol: p-acetothymyl CHJPh, m.p. G oldberg, and H. R . R osenberg (Helv. Chim. 711’, and p-XOyC^IlpCH,,, m.p. 104°, ether; p-propio- Acta, 1935, 18, 1478— 1482, 1483— 1487, 1487— thymyl CH.,Ph, m.p. 64°, and p-j\r0.rC\JIpCII2, m.p. 1498).— VIII. With BzCl-C5H5N frans-A5-androstene- IIP", ether-, p-butyrothymyl CIl.,Vh, m.p. 475, and 3 : 17-diol 3-monoacetate (A., 1935, 1371) gives its p-NOpC^HpCIIa, m.p. 91°, ether; p-isovalerothymyl 11 -benzoate, m.p. ISO—182°, hydrolysed by KOH- CUtPb, m.p. 40°, and p-NO^-CJIpCH.,, m.p. 84°, MeOH at room temp, to the -3 : ll-diol 11-mono- ether-, p-benzoylthymyl p-NO.,:C0lIpCII.,~ ether, m.p. benzoate, m.p. 220-5—222°. Addition of Br-AcOH, 91°; p-acetocarvacryl CUJPh, m.p. 64°, and p- followed by oxidation with CrOa-90% AcOH, and X().,'G\HpVH2, m.p. 114°, ether-, p-propiocarvacryl p-XO.eC'tJlpCil., ether, m.p. 128°. Glyceryl ay-di- debromination of the product with NaI-EtOH-C6H6 acetothymyl ether, m.p. 109°, from p-acetothymol, and 2% Na2S03 gives the 17-monobenzoate, m.p. 194— 196° (corr.), of 17-hydroxy-A4-androsten-3-one SH’OU2(CliaCl)2, and KOH-KtOlI, and glyceryl ay-di- o-nitro-p-acetylthymyl ether, m.p. 95°, are described. (testosterone), which is obtained by hydrolysis with 2% KOH-MeOH. H. W. Action of organo-magnesium compounds on IX . irons-A5-Dehydroandrosterone (I) (A., 1935, 1125) in Et20 with EtOH saturated with HC1 at 0° adiponitrile. A. Comp Ark (Bull. Soc. chim. Belg., 1935, ^ 44, 523—526).—Adiponitrile with MgEtBr gives its hydrochloride, m.p. 156— 157°, converted by and Et.,0 yields C2H6, l-imino-2-cyanocyciopentane, KOAc-EtOH into tcaws-^-dehydroandrosterone, m.p. and decane-yQ-dione; with MgPhBr it gives 12S-5— 130° [rather less active than (I)]. Oxidation COPh’[GH«L-COPh and a little Ph2, and with of stigmasteryl acetate (hydrobromide, m.p. 160-5— CH2Ph-MgBr it gives mO-diphenyloctane-^n-dione, m.p. 161-5°) by bromination, Cr03, and debromination 72° (disemicarbazone, m.p. 210°). H. G. M. (as for cholesteryl acetate) also gives (I). Stigmasterol with an excess of HCl-Et20 gives its hydrochloride 7-Hydroxy-l-keto-l : 2 : 3 : 4-tetrahydrophen- (*4c derivative, m.p. 1S3— lS3-5°). anthrene. A. Butenandt and G. Schramm (Ber., X. (I) (seinicarbazone, m.p. 267°) with MgMel 1935,68, [B], 2083—2091).—Unlike 1-keto-l : 2 : 3 : 4- or MgEtl affords, respectively, trans-E5-ll-methyl- tetrahydrophenanthrene, 1-hydro.vy-l-keto-l : 2 : 3 : 4- (II), m.p. 204°, and -17-ethyl-androstene-3 : ll-diol, tetrahydrophenanthrene (I) is physiologically inactive m.p. 173°. (II) is converted by bromination, oxid according to the Alten-Doisy method. 1 :6- ation with Cr03, and debromination with Zn into HH2*C10H(.'SOgll is heated with KOH at 250— 310° 11 -hydroxy-11 -methyl-X^-androsten-S -one (17 - methyl- and the product is treated with cold Ac.,0. thus giving testosterene), m.p. 163— 164°. Oxidation of methvl- 1 :6-NHA0‘C10H,*OH, m.p. 214°, in 36% \-iekh androstanediol (A., 1935, 1125) with Cr03-A c0H , It is converted by Me2SO,-NaOH into 1 : 6- gives 17-hydroxy-11 -methylandrostan-3-one, m.p. 192— XHAcCjpHyOMe, m.p. 140°, hydrolysed by HCl- 193° (seinicarbazone, m.p. 235— 236°). Reduction EtOII to 6-methoxy-x-naphthylamine (II), m.p. 74° of ¿rans-androstenone (3-hydroxyietioaZiocholan-17- [hydrochloride, m.p. 205—220° (decomp.), whence one) (III) (seinicarbazone, m.p. 282—2S3°) with ti-methoxy-x-naphthonitrile, m.p. 79°]. Treatment of H2-P t0 2 in AcOH and hydrolysis (some acetate (II) in the usual manner but at the lowest possible formed) gives tr-Mis-androstanedl : ll-diol, m.p. 168° temp, gives 1 : 6-CwHsI-OMe (in 55% yield), the (-4c._> derivative, m.p. 127— 128°). With MgMel or Cu'ignard compound from which is transformed bv MgEtl (III) gives, respectively, trans-17-methyl-, CH0-0H2-CH,-C02Et or CHO-CH.,*CH,-CO.JHgI into m.p. 211— 212°, and -17-ethyl-androstane-Z : 17-diol y-Q-methoxy-1 -naphthylbutenoic acid, ni.p. 156° [Me (IV), m.p. 204— 205°. Oxidation of (IV) with Cr03- X V (m) ORGANIC CHEMISTRY. 77
AcOH affords 17-hydroxy-17-ethylandrostan-3-one, m.p. oxime, m.p. 143° (uncorr.)] (cf. A., 1935, 1125, 1242). 137— 13S°. Androsterone and MgEtl afford cis-17- (II) has no sp. progesterone activity, whilst the cock’s- ethylandrostane-3 : 17-diol, m.p. 143— 144°. The re comb test indicates a ratio of activities for (I), (II), and lationship between physiological activity (on the androstanediol (A., 1935, 1033) of 1:3:9 (cf. A., basis of both the cock’s comb and rat tests) and (a) 1935, 1285). (II), unlike related compounds, is more the cis- or trails-configuration, or the presence of a active by the “ capon unit ” than the “ mouse unit.” double linking at C5, or (b) the nature and configur The physiological activity of (II) appears to be especi ation of substituents at C3 and C17, for these and other ally of a “ male ” character; its relation to other sex known androstane derivatives, is summarised and hormones and its possible conversion into testosterone discussed. J. W. B. (A., 1935, 1370) and, by loss of CH4, into oestrone Sexual hormones and related substances. V. are discussed. F. O. H. ep/Dihydrocinchol and its oxidation to 3-epi- Testosterone. Conversion of dehydroandro hydroxyætion JJocholan-17-one (androsterone). sterone into androstenediol and testosterone. W. D irsciierl (Z. physiol. Chem., 1935, 237, 52— Preparation of testosterone from cholesterol. A. 56).— Oxidation of dihydroeinchol (I) (from hydrolysis B u t e n a n d t and G. H anisch (Z. physiol. Chem., of acetyldiliydrocinchol ; A., 1935, 1242) by Cr03 1935, 237, 89— 97).—Testosterone (I) (A., 1935, yields diliydrocinchone, m.p. 163° (all m.p. corr.), 1033) is identical with A4-androsten-17-ol-3-one [“Id -f 42° in CHC13, which on reduction (Pt-H2) (ibid., 1370), and hence can be synthesised from affords ejtidihydrocinchol (II), m.p. 206°, [a]j) +26° cholesterol. Growth of cocks’ combs indicates that in CHC13 [obtained directly from (I) by reduction the ratio of activities of (I), androstanediol, and with NaOEt at 215° and subsequent isolation as androsterone is approx. 6:2:1. (I) has also a digitonide]. Oxidation of the Ac derivative, m.p. much greater action on the genital organs of male 90°, [a]o4 +28-4° to +29-4° in CHC1S, of (II) with Cr03 rats. F. 0. H. yields 3-epiacetoxyætioaZZocholan-Î7-one, the semi- Catalytic hydrogenation of progesterone. A. carbazone, m.p. 284— 285°, of which is converted by B u t e n a n d t and G. F leisch er (Ber., 1935, 68, [B], AcOII-HCl followed by hydrolysis into 3-epihydroxy- 2094— 2097).—Hydrogenation of progesterone (Pt02 ætioa//ocholan-17-one (cf. ibid. ; A., 1934, 1221). in AcOH) gives a mixture of diols (I) oxidised by F. 0. H. Cr03 in AcOH to aZZopregnandione and pregnan- Dehydroandrosterone. A. B u t e n a n d t , H. dione. Similar reduction of pregnen-3-ol-20-one D a n n e n b a u m , G. H an isc h , and H. Kunszus (Z. affords (I) almost exclusively'. In acid solution, physiol. Chem., 1935, 237, 57— 74).— Dehydroandro therefore, the compounds behave as expected from sterone (I) (A., 1935, 413, 1125) [benzoate, m.p. 250° their constitutions. Contrary to Slotta et al. (A., (all m.p. uncorr.) ; acetate, m.p. 16S— 169°, [a]},3 1935, 128), there is no evidence of the production +3-9° in EtOH; oxime, m.p. 188— 191°; semicarb- of a new diketone, m.p. 188°. H. W. azone, decomp. 262—264°] exists in polymorphic modifications, e.g., m.p. 137— 138° and 1S0°, the latter New members of the androsterone group. A. showing marked depression on irradiation by arc B u t e n a n d t , Iv . T sch er n in g , and G. H an isc h (Ber., or sun-light. All forms have [a]},8 + 10-9°+0-7° in 1935, 68, [B], 2097— 2102).— isoAndrosterone (I) EtOH. (I) is separated from the CHCl3-sol. unsaponi- is reduced by Na and PraOH or by Al-Hg to iso- fiable matter of men’s urine by pptn. with digitonin; androstanediol (II) [s\\ocetiocholane-3 : \l-diol], m.p. this yields a cryst. mixture from which cholesterol 164°, [a]jJ +4-2° (diacetate,m.p. 123— 124°), which does and, by means of the semicarbazone, (I) are isolated. not yield a sparingly sol., additive compound Treatment of (I) with MeOH-HCl, pptn. by digitonin, with digitonin and which somewhat exceeds (I) in etc. affords the chloroketone, C19H270C1 (A., 1935,413), physiological activity, iso Androstanediol diacetate also prepared by treating (I) with S0C12 in presence is partly hydrolysed and the monoacetate is oxidised of dry CaCO, and Et20. Hydrogenation (Pd-CaC03) by Cr03 to androstan-17-ol-3-one acetate, the semi of (I) in MeOH yields fsoandrosterone (A., 1935, carbazone of which is hydrolysed to androstan-Yi-ol 1033). Cholesteryl acetate in AcOH treated with Br d-one (III) [alloaitiocholan-ll-ol-3-one], m.p. 178°, followed by Cr03 yields, on debromination etc., [“]“ +32-4° in EtOH (acetate, m.p. 157°; oxime, 2-78% of (I) and 3-hydroxy-A5:6-cholenic acid, m.p. 209°), also obtained, together with (II), by hydro m.p. 224° (cf. A., 1935, 1125) (3-OAc-acid, m.p. 181°, genation (Pd sponge in -Et20) of testosterone (IV). and its Me ester, m.p. 156— 157°). Similarly 3- Physiologically (III) is more active than androsterone. hydroxy-A5-bisnorcholenic acid (A., 1933, Î290) Reduction of (IV) with Al(OPr®)3 affords Ai:5-andro- was prepared from stigmasterol. Both (I) and stene-3 : 17-diol, m.p. 155-5°, which gives a yellow its acetate have approx. J the activity of androsterone colour with C(N02)4, a violet colour with CC13-C02H, by the cock’s-comb assay; the benzoate is much and an additive compound with digitonin; it has less active than (I). F. O. H. little physiological activity. H. W. Androstenedione. Genesis of reproductory Examination of products obtained in the pre hormones. A. B u t e n a n d t and H. K u d szu s (Z. paration of ketones by the Friedel-Crafts reac physiol. Chem., 1935, 237, 75— 88).— Dehydro tion from acid chlorides and ethers of phenols. androsterone (I) (cf. preceding abstract) with Br and Synthesis of ketones of the naphthalene series. Cr03 yields a product which on debromination (Zn) P. E. Popov (J. Gen. Chem. Russ., 1935, 5, 986— affords A4-androstene-3 : 17-dione (II), m.p. 173— 992).— a-C10H7,OMe and AcCl in CS2 with A1C13 174°, [a]Jf +185°, absorption max. at 235 mg \di- afford chiefly7 l-methoxy-4-acetydnaphthalene, to- 78 BRITISH CHEMICAL ABSTRACTS. A. X V (m, n)
gcther with 2 : 4-diacetyl-u-nxvphthol, m.p. 139— 140°, part,H.KoBs] (J. pr. Chem., 1935, [ii],144,54— 62).— also obtained from 4-acetyl-a-naphthol as above. The main product of the oxidation of trimethyl- Under analogous conditions, a-C10H/O E t and BzCl deoxybrazilin is the colourless trimethylbrazilone, yield chiefly l-ethoxy-4-benzoylnaphthalene, together but small amounts of a red quinone (I), C17H140 5, with 4-benzoyl-, m.p. 164— 165°, and 2 : 4-dibenzoyl- m.p. 241° (yellow Ac derivative, m.p. 158— 160°; cc-naphlhol, m.p. 138—139°. 2-Acetyl-a-naphthol and violet monoxime), are also produced. The colour, BzCl with A1C13 afford 4-benzoyl-2-acetyl-
methyl-1 : ±-naphthaquinone, m.p. 146°, whilst 1- The a-position of the OH is thus proved. (VI), benzoyl-2:6-dimethylnaphthalene, m.p. 83—84° (whence b.p. 123— 124°/10 mm. (p-CGHiBrCO-CH2 ester, 5-benzoyl-2 : 6-dimethyl-1 : i-naphthaquinone, m.p. m.p. 74— 75°), is synthesised from NaOMe and Me 169°), is obtained from 2 : 6-C10H6Me2, BzCl, and a-bromo-z-methyl-n-hexoate, b.p. 88—90°/10 mm., A1C13 in CS2. obtained by Br and red P at 100°; when mixed with [With A. K e ller .] 1 : 1 ': 4 : 4'-Tetraliydroxy-2 : 2'- other acids, it cannot be detected by conversion into dinaphthyl and the corresponding diquinone in (VII) by distillation with Cu, but the Pb02-H 3P04 AcOH give the quinhydronc, C20H12O4, decomp, method is effective. about 200°. " H. W. (Ill), m.p. 99°, sublimes at 120— 140°/0-001 mm. (2 active H ; Ac2 derivative, m.p. 99— 101°), gives Constitution of alkannin, shikonin, and alkan- only 0-23 mol. of COMe2 (Kuhn-Roth), with Ae20-Zn nan. H. Brockmann (Annalen, 1935, 521, 1— 47). gives 1:4:5:8-telra-acetoxy-2-8-methyl-ii-amyhiaph- Alkannin (I) is Z-2-a-hydroxy-8-methyl-Av-pentenyl- ihalene, m.p. 170°, and with SnCl2 the 1 : 4 : 5 : S- naphthazarin; shikonin (II) is the ¿-form, mixed (0 //)4-compound, m.p. 65—66° [oxidised by air to with 20% of the di-form, which is named shikalkin. (III) (only)]; with KMn04 it gives z-methyl-n-hexoic (I), m.p. 148°, [a]*°38 -1 6 7 ° in CGHG, -2 2 6 ° in CHC13 acid {p-C0HiBr-CO-GH2 ester, m.p. 75°). With acids (3 activo H; Bz2 derivative, m.p. 174— 175°), best other than HC1 or with 2X-NaOH at 100° (I) yields extracted from the roots of Alkanna tincloria by ligroin, anhydroalkannin \2-8-methyl-AaY-pentadienylnaphth- contains < 0-1% of alkannan (III) [2-isoAea:?/Z- azarin], m.p. 155°, sublimes at 140— 145°/0-001 mm. naphthazarin], m.p. 97— 98°, [a] 0°, from which it is [gives 0-85 mol. of COMe2 (Kuhn-Roth); 2 active separated by adsorption from CGHG by ldeselguhr. H], which is hydrogenated (Pt02) in AcOH to (III). (I) is decomposed by long heating in Ac20, but can With SnCl4 in C6H6 or CHC1, (I) gives cycloalkannin be crystallised therefrom, and with Ac20-N a0A c [1:4: 6-trihydroxy-8 : 8-dimethyl-5 : 6 : 7 : 8-tetrahydro- (short heating) or Ac20-C 5H5N gives the Ac3 deriv anthraquinone] (VIII), m.p. 79—80°, sublimes at ative (IV), m.p. 132°, [a]=»38 -1 1 0 ° in C6H6. With 140— 145°/0 001 mm., [a]§»38 -59-2° in CGH8. Zn-Ac20 it gives a substance, C20II2lO8, m.p. 147°, (II), obtained by ligroin from the roots of Litlio- [a] 0°, probably a mixture. (I) sublimes unchanged at spermum crythrorhizon, has m.p. 143°, [a]]]33 -f-135° 140— 150°/0 001 mm., but at 200°/760 mm. gives in CcHg, gives a product, m.p. 146— 147°, only after H20 and 5-methylquinizarin, m.p. 246—247°, which sublimation and repeated crystallisation, is identical is readily obtained from diacetylnaphthazarin by with (I) in absorption spectrum, is hydrogenated as is condensation with piperylene in EtOH at 100° and (I), gives the inactive Me ether, and with SnCl2 aerial oxidation of the product in 2Ar-NaOH. When affords the impure isomeride [cycloshikonin], m.p. distilled with Zn dust, (I) gives 1- and 2-methyl- 79— 80°, [a]&8 +51-2° in CGHG, of (VIII). The anthracene and ClnHg [which last proves the two-ring racemate of (VIII) has m.p. 86°. The relationship of structure of (I)]. With KMn04 in aq. alkali or C0Me2 (I) and (II) is proved by mixed m.p. determinations, (I) gives only AcOH and maleic acid, and with which show a racemate, m.p. 148°, to be a stable 0 3 in AcOH a product oxidised by KMn04 to 0-8 mol. compound. Absorption spectra and changes of of COMe2, which is obtained to the same extent from colour with pa are recorded. (I) and (II) have lower (I) by the Kuhn-Roth method, proving the presence oxidation potentials than naphthazarin, in spite of of CMe,! in (I). (IV) and 0 3 in CHC13 give a little the a-OH in the side chain, showing that they exist 3 : 6-dihydroxyphthalic acid, establishing the naphth- mainly in 5 : 8-dihydroxy-2-alkyl-l : 4-quinone form azarin grouping in (I). (I) and 10% HCl-MeOH at with relatively little, if any, of the 6-alkyl form. room temp. (15— 18 hr.) yield 2-a.-methoxy-8-methyl- M.p. are corr. R. S. C. tA-pentenylnaphthazarin [Me ether of (I)] (V), m.p. 105°, sublimes at 140— 150°/0 001 mm. (2 active H ); Some examples of substitution addition in the complete racemisation occurs in this reaction, indic anthraquinone series. C. Ma r s c h a l k (Bull. Soc. ating the a-position of the aliphatic OH, which is chim., 1935, [v], 2, 1809— 1830).—Na quinizarin-2- confirmed by the sparing solubility of (I) in aq. sulphonate (I), Na2C03, KCN, and H20 at 90° (30 Na2C03. The dl-a-Et, m.p. 83°, and Pra ether, min.) yield a dicyano-leuco-compound oxidised by m.p. 57—58°, are similarly prepared. Hydrogen (NH4)2S20o to 1 : 4-dihydroxy-2 : 2-dicyanoanthra- ation of (I) is very rapid at first [1 m ol.; formation of quinone (II), m.p. > 300°, also obtained, but less the quinol, which is very rapidly oxidised by air to readily, from quinizarin and conc. KCN. (II) on (I)], then slower (further 2 mols.), and thereafter hydrolysis with 90% H2S04 yields the anhydride of still slower. The second stage in the reduction 1 : 4 - dihydroxyanthraquinone - 2 : 3- dicarboxylic acid (Pt02) in AcOH or other solvents gives (III) and other (+ H 20) (III), readily obtained from the anhydride products. Intermediate reduction products could not and by oxidation of 1 : 4-dihydroxy-2 : 3-dimethyl- be isolated. Hydrogenation of (V) is similar; ab anthraquinone with H2S04-H 3B03-N aN 02 at 140— sorption of 3 mols. gives (III), but at the 2 mol. 150° (8 hr.). This establishes the constitution of stage some dihydroalkannin Me ether [2-u-methoxy-§- (III). (I) and NaOH-KCN at room temp, yield methyl-n-amylnaphthazarin], m.p. 50— 51°, is obtained. 1 : i-dihydroxy-2-cyanoanihraquinone (IV), m.p. 228— This ether with KMn04 gives a-methoxy-s-mcthyl-n- 229°, hydrolysed to the corresponding amide, m.p. hexoic acid (VI), the presence of which in the products > 300°, and acid (V). (IV) and Na2S03-H 20 at 80° is proved by formation of 8-methylvaleraldehyde yield 1 : 4-dihydroxy-3-cyanoanthraquinone-2-sul- (VII) (2 : i-dinilrophenylhydrazone, m.p. 95°) there phonic acid (VI), also obtained from (I), Na2C03- from by distillation with P b02 and dil. H3P04. KCN-H20, and air, and desulphonated to (IV) by G 80 BRITISH CHEMICAL ABSTRACT'S.— A. X V (n, o), X V I treatment with Na2S204 followed by oxidation. (II) is derived by treatment with Zn dust in boiling Both (IV) and (VI) with alkalino KCN give (II). AcOH. H. W. (ITT) is decarboxylated to (V) (a) when heated with Snitter's camphenilene. G. Gr a t to n and J. L. H S .r H B at 200°, (b) when boiled with aq. NaOH, 2 0 3 03 Sim onsen (J.C.S., 1935, 1621— 1623).— By elimination and (c) when treated below 4° during 1 hr. with of HCl from camphenilyl chloride, a hydrocarbon Na2C03-Na2S204-H 20 followed by oxidation with closely agreeing in physical properties with santene NaOII-air. Prolonged boiling with NaOH and treat and Snitter’s hydrocarbon (A., 1933, 1300) has been ment with excess of Na2S204 at room temp, results in obtained. Oxidation (03) shows it to be not homo the loss of both C02H. "(V), its amide and Et ester geneous and to consist mainly of santene, giving with KCN each yield products hydrolysed to (III), acidic products, CH20, a ketone, C8II120 [2 :4- and Na quinizarin-2 : (5-disulphonate and KCN give dinitrophenylhydrazone (I), m.p. 114— 115°], and a a product which contains both S and N. Similarly hydrocarbon, CflH14, m.p. 42° (opocyclene). (I) 1 - am ¡no - 4 - hydroxyanthraquinone - 2 - sulphonie acid differs from methylnorcamphor-2 : 4-dinitrophenyl- and the corresponding -3-sulplionic acid with KCN- Jiydrazone, m.p. 116—117°. Snitter’s hydrocarbon Na2C03-H 20 at 90—95° afford 1 -aminoA-hydroxy- is probably mainly apoev clone. F. R. S. 2 : 3-dicyanoanthraquinone, m.p. < 300°, oxidised by H2S04-M n02 to (II), and hydrolysed by II2S04 Transition in camphor and chemically related at 140— 150° to X-aminoA-hydroxyanthraquinone- com pounds.—See this vol., 12. 2 : 3-dicarboxylic acid (anhydride). No reaction occurs Caryophyllenes. III. G. R. R a m a g e and J. L. wi t h 1 -amino-4 - methoxyanthraquinono - 2 - sulphonie Sim onsen (J.C.S., 1935, 1581— 1584).— Ozonolysis of acid. cj/cioPontadienc reacts with (I) (with loss of fS-caryophyllene nitrosite in EtOAc-CCl4 gives CH20 S031I), (IV), (V), quinizarin, and naphthazarin in and the a-dinitro-ketone, C14H220 5N2, m.p. 161-5°, aq. alkalino sol., but not in org. solvents. Those [a]54G1 —33-6° in CHC13 (plienylsemicarbazone, decomp. aro not considered to be normal “ diene ” reactions. 224° ; 2 : •i-dinitrophenylhydrazone, decomp. 225°), The colours and colour reactions of the foregoing and in AcOH forms an isomeric ^-dinitro-ketone, products aro described. H. G. M. decomp. 155°, easily converted into the a-form. Kinetics of sulphonation [of anthraquinone ]. The a-ketone and C5H5N yield a nitro-ketone, m.p. — See A., 1935, 1465. 69°, [a]54q4 —114° inCHCLj (semicarbazone, m.p. 186— Turpentine oil. I. Laricinolic acid. F. T rost 187°), oxidised (03) to a diketo-monocarboxylic acid, (Annali Chim. Appl., 1935, 25, 496—504).—From C14H2104, of which the Me ester, b.p. 194— 195°/ laricinolic acid (I), m.p. 140— 147° (block), [agj 15 mm. (bis-2 : i-dinitrophenylhydrazone, decomp. —48-5° in EtOH (from larch turpentine) (A., 1900, i, 108— 110°), is identical with that obtained by Semmler 680), were prepared: Me ester; retene, m.p. 124° and Mayer (A., 1912, i, 120). The constitution of (picrate, m.p. 99°), by dehydrogonation by Se (A., the caryophyllenes is discussed. F. R. S. 1928, 51); rotonequinone, m.p. 196— 197° (A., 1885, Constituents of natural phenolic resins. III. 905); the abietic acid, m.p. 160— 164°, of Steele Synthesis of dehydro-11 sulphite-liquors lactone ’ ’ (A,, 1922, i, 739); various isomerides formed during dimethyl ether and some observations on the distillation and by treatment with AcOH and HC1; structure of podophyllotoxin. R . D . H a w o r t h , the additive compound, m.p. 213-5— 215° of Me ester T. R ich ardson, and G. Sh e l d r ic k (J.C.S., 1935, and maleic anhydride (A., 1932, 1254) and the derived 1576— 1581).—Et 3-(3 : -i-dimethoxybenzoyl)pmpionate, anhydride-carboxvlic acid, m.p. 227—228° (ibid.). m.p. 57— 58°, with HC02Et gives Et p-(3 : 4-dimethoxy- The relation of (I) (for which the name “ laricinic benzoyl)-$-hydroxymethylenepropionate, m.p. 114— 116°, acid ” is proposed) to abietic acids is discussed. and with Et2C204 forms Et fi-(3 : i-dimethoxybenzoyl)- F. O. H. bfi-crotonolactone-y-carboxylate, m.p. 154— 156°, Synthesis of di-piperitone (df-M-p-menthen- neither ester giving well-defined reduction products. 3-one). J. W a l k e r (J.C.S., 1935, 1585— 1586).— [i-3 : 4 - Dimethoxybenzoyl - a - (3' : 4 '-dimethoxybenzyl- Me P-chloroethyl ketone, Et a-isopropylacctoacctate, idene)-$-methylenepropionic acid, m.p. 157— 158°, ob and NaOEt give Et A*-p-menthen-3-oneA-carboxylate, tained from the corresponding -propionic acid and b.p. 155— 105o/16 mm., hydrolysed (MeOH-KOH) aq. CH20, is converted (MeOH-HCl) into the lactone to rfZ-piperitone, identical (oxime) with the racemised of the -3-c/iloromethylpropionic acid, m.p. 183— 184° natural product. F. R. S. (which with MeOH gives the lactone of the -{i-methoxy- Synthesis of di-fenchone. G. Komppa and A. melliylpropionic acid, m.p. 145°), and Me 6:7- Klami (Ber., 1935, 68, [B], 2001—2003).—dl- dimethoxy-1 -(3' : 4 '-dimethoxyphenyl)-2 -chloromethyl- Camphenonic acid is converted by S0C12 into dl- naphthalene-2-carboxylOte, m.p. 176— 177°, the corre camphenonyl chloride, b.p. 135— 137°/9 mm., m.p. sponding^ acid (I), m.p. 244— 245°, being cyclised 33°, transformed by H, in xylene containing Pd- to 4 ': 5 ': 6 :7 -telramethoxybenzo-3 : 4-flitorene-l-carb- BaS04 at 150° into l-ketofenchone (I), b.p. 127— oxylic acid, m.p. 303—305° (Me ester, m.p. 202— 204°). 128°/18 mm. (monosemicarbazone., m.p. 238°; mon- (I) or its Me ester and NaOH give the lactone of oxime, m.p. 102— 103°), which readily passes into a 6 : 7 -dimethoxy-l-(3' : 4' - dimethoxy phenyl)-2 -hydroxy- polymcride, m.p. 240°. Reduction of (I) in AcOH niethylnaphthalene-Z-carboxylic acid (dehydro- containing P t02-FeS04 gives dZ-fenchone (II) and sulphite-liquors lactone ” Me., ether), m.p. 215— co-hydroxyfenchone (III)," b.p. 134— 135717 mm. 216°. (oxime, m.p. 140°). (Ill) and PC15 in CHC13 afford The Na salt of [}-(3 : 4 : o-trimethoxybenzoyl)prop- to-chlorofenclmie, b.p. 121— 123°/18 mm., from which ionic acid, m.p. 121—122°, obtained from Et 3 : 4 : 0- XVI, X V II (a) ORGANIC CHEMISTRY. 81
trimethoxybenzoylacetate, CH2Bi"C02Et, and C20H22O9N2, sintering at 128°, which readily adsorbs NaOEt, with piperonal and AcaO forms the y -lactone org. vapours. Attempts at elucidating the structure of (3-(3 : 4 : 5-triniethoxybcnzoyl)-a.-(3' : 4'-methylene- of (IV) were not successful. R. T. dioxybcnzylidcne)-propionic acid, m.p. 161— 162°, Sanguisorbigenin. T. M a tsu k a w a (J. Pharm. hydrolysed to the acid, m.p. 183— 184°, which is Soc. Japan, 1934, 5 4 , 965—979; cf. Ivodako and Abe, converted into the -^-methylene-propionic acid, m.p. A., 1934, 175).—Pure sanguisorbigenin (I), C30H4fiO3 169°— 170°. A similar scries of reactions leads to [:monoacetate (II), m.p. 324°], has m.p. 275—276°, 6 : 7 -methylenedioxy-1 - (3' : 4' : 5' -trimethoxy phenyl) - and contains one double linking. (I), with AcOH- 2-chloromethylnaphthalene-3-carboxylic acid, m.p. > HC1, yields acetylsanguisorbigenin lactone, decomp. 300°, and the lactone of the -2-hydroxymethylnaphthalcne- 323°, which is hydrolysed to the parent lactone, 3-carboxylic acid (II), m.p. 288— 289°. (II) differs m.p. 301°. (II) and Cr03 afford (3- or 8-hydroxy- from the lactone obtained from dehvdroanhydro- acetylsanguisorbigenin lactone, decomp. 268° (acetate, picropodopliyllin (III), and this is evidence in favour m.p. 287°), which contains a teri.-OH. When heated, of the Borsche-Spath formula for podophyllotoxin. (I) yields sanguisorbigenol, m.p. 206° (acetate, m.p. Oxidation (KMnOJ of (II) gives 6 : 7-methylenedioxy - 185— 186°), a triterpene alcohol. When oxidised with l-(3' : 4' : 5' - trimcthoxyphcnyl)naphthalene- 2 : 3 : di- Cr03, (I) yields sanguisorbigenone, m.p. 159° and 229° carboxylic acid (anhydride, m.p. 299—300°; Me2 (double m.p.) (monoxime, decomp. 281°). The il/e ester, m.p. 206—207°), identical with the oxidation ester (III), m.p. 207— 209°, of (I) yields sanguisorbi product of (III). F. R. S. genone Me ester, m.p. 216° (monoxime, decomp. Complete deoxidation of resins by catalytic 243°), on oxidation; hence the OH is sec. (1) is not hydrogenation. II. I. W a t e r m a n , J. F. Cl a u s e n , hydrogenated with Pt-black. Methylation of (II) and A. J. Tullenebs (Rec. trav. chim., 1935, 5 4 , or acetylation of (III) affords acetylsanguisorbigenin 701— 710).— Brown colophony resin, consisting chiefly Me ester, m.p. 243— 245°. Ch. A b s. (r) of abietic acid (I), is complete^ freed from 0 when Toad poisons. I. Dehydrogenation of cino- heated to about 400° with H2 (initial pressure about bufagin by selenium. R. T sch esch e and H. A. 100 kg. per sq. cm.) in presence of a Mo or Ni catalyst. O ffe (Ber., 1935, 68, j®], 1998— 2000; cf. A., 1932, The temp, at which H2 is mainly absorbed depends 397).—Dehydrogenation of cinobufagin (improved on the nature of the catalyst. The products are method of isolation from Ch’an Su) with Se at 270— stable, partly aromatic, and free from defines even 330° gives very small amounts of methylcyctopenteno- when a low initial H2 pressure (10 kg. per sq. cm.) is phenanthrene, thus proving the poison to have the used. Two compounds, CJ9H34 and C20H3(., closely ring system of the sterols and bile acids. H. W. related to (I) (C20H30O2) in structure have been iso Constituents of red sandalwood. Homoptero- lated. They were examined by the method of carpin. H. L e o n iia r d t and E. O e ch ler (Arch. Waterman et al. (B., 1932, 536). H. G. M. Pliarm., 1935, 2 7 3 ,447— 452).— 1 -Dihydrohomoptero- Resinic acids of Pinus sylvestris resin. I, II. carpin (modified prep.), m.p. 153— 154°, [a]],0 —5-8° P. S. Pischtschimuka (J. Gen. Chem. Russ., 1935, (2 : ‘i-dinitrophenylhydrazone, decomp. 292°), with 5, 738—751, 752—763).— I. The chief, if not only, Cr03-A c0H or B z02II gives diliydrohomopterocarpone acidic constituent of the fresh resin is CjgHgj-COjjH (I), C17H160 5, m.p. 178-5° [2 : i-dinitro-, decomp. (I), m.p. 138°, the following salts of which are 258°, and p-nitro-phenylhydrazone, decomp. 148°; described : MgR2, CaR2, BaR2, PbR2, m.p. 190°, oxime, decomp. 225° (2 : i-dinitrophenylhydrazone, CuR2, HgR2, NaR,3HR, CaR2,2HR, m.p. 160°, decomp. 199°)]. (I) is a 1 : 4-quinone and with BaR2,2HR, m.p. 158° (R = C19H29*C02). The acid Zn-Ac20-NaOAc yields a quinol diacetate, m.p. 122— from a 14-year-old sample of resin crystallised in 123°, sol. only in hot NaOH. R. S. C. hexagonal plates, [ocjjf —30-36° in EtOH, which passed M anchurian kaoliang.—See this vol., 124. at 118° into lentiform crystals, m.p. 157°. [a]D (in Acetylation of lignin. F. K om arov and G. EtOII) of (I) changes from —61-7° to +42-5° when Fil im o n o v a (J. Appl. Chem. Russ., 1935, 8, 1033— it is heated at 120° in C02, and again changes to 1042).— > 5-6— 6-6% of the OH-groups of sulphate -32-7° at 145°. In xylene solution at 130° [a]D lignin (I) are acetylated by treatment with Ac20 in approaches zero after 5 hr., and attains a max. val. C5H5N, or with Ac20 in AcOH in presence of cata of +40° after 24 hr., falling to +30-8° after 48 hr., lysts (H2S04, ZnCLj, H3P04) (18—20°; 90 min.); whilst at 200° and 250° [a]„ tends to a const, val. in absence of catalysts the latter reaction takes place of +10°. The I val. of (I) corresponds with the pre only at the b.p. of the mixture. Decomp, of (I), or sence of two ethylenic linkings. (I) is readily oxid elimination of Me groups, does not occur during the ised by atm. 0 2, but not by H N 03. It is suggested above reactions. The products are sparingly sol. that abietic acid has the structure (II), readily chang in org. solvents. R. T. ing to (III). Hydrogenation of furfur aldehyde. I. G. M e / \ _ _ _ CMe2 Me R oberti (Annali Chim. Appl., 1935, 2 5 , 530—540).— Reduction of furfuraldehyde to furfuryl alcohol (I) at > 200° and under pressures of H2 of approx. 100 C02H atm. with Ni, Cu, and Cu chromite (II) catalysts was • (II-) investigated. With (II), an almost quant, formation II. (I) and 33% HN03 or (I) in ligroin and cone. of (I) occurs, but (II) rapidly loses its catalytic activity H N 03 at 50— 60° yield a dibasic acid (IV), (cf. A., 1934, 1225). The influence of reagents 82 BRITISH CHEMICAL ABSTRACTS. A. X V II (a, d)
(e.g., CaO, AcOH) on the above hydrogenation cata measured with the apparatus previously described lysts is discussed. F. 0. H. (cf. A., 1935, 598): dioxan (0-3); 2 : 3-dichloro- (I) (1-6), 2:3:5: 6-tetrachloro-, m.p. 60° (0), m.p. Hydrolysis of phenyl furyl ketimine.—See this 100° (1-85°), m.p. 144° (1-05), and 2 : 2 : 3 : 5 : 5 : 6- vol., 34. hexachloro-dioxan (0); thioxan (0-47); selenoxan y-Tetrahydropyranaldehyde. V. P relog and (0-30); cis-, m.p. 111° (1-9), and tvms-naphthadioxan, E . Cerkovnikov (Coll. Czech. Chem. Comm., 1935, 7, 430— 435).—Catalytic reduction (poisoned Pd) of the S h 2'o -c h -o -c h 2> m;P- 1360 (°‘72)- These lasfc two chloride of y-tetrahydropyrancarboxylic acid (I) isomerides were obtained from (I) and glycol (II), and affords y-tetraliydropyranaldehyde (II), b.p. 74—77°/ from glyoxal and (II), and correspond with the cis- 11 mm. (phenylhydrazone, in.p. 93— 94°; 2:4- and frans-decalins. The configuration of these com dinitrophenylhydrazane, m.p. 163°; semicarbazone, pounds is discussed (cf. A., 1935, 15). H. G. M. m.p. 191°), also obtained by heating the mixed Ba salts of (I) and HC02H. On keeping, (II) deposits a Uneqfual reactivity towards organometallic trimeride, m.p. 221°, depolymerised by heat. Con compounds of the carbonyl group in -succin- densation of (II) with rhodanine affords the substance, methylimide and in IV-methylpyrrolidone. R. CgHjjOoNSa, m.p. 254°, converted by aq. NaOH L u kes and K. Sm olek (Coll. Czech. Chem. Comm., into {iA-tclrahydropyranyl-a-tMonpropionic acid, 1935, 7, 476— 481; cf. A., 1929, 576, 935; 1930, 1296).—iSuccinmethylimide with CH2PlrMgCl in cold o< c ÎÎ2'c h 2> c h 'Gh 2'c s ‘c o ^h , m-P-151— 152°- dry C8H6-E t20 rapidly gives 2-benzyl-l-methyl-5- 2 2 P. G. C. pyrrolone, whereas iV-methylpyrrolidone with MgEtBr Condensation of benzoin with quinol. 0. gives 1 : 2-dimethyl-A2-pyrroline only after many D ischendorfer (Monatsh., 1935, 66, 201—217).— hr. The difference is explained in terms of the The alkali-sol. product obtained by Japp et al. (J.C.S., polarities of the mol. groupings. J. L. D. 1899, 7 5 , 1035) by condensation of benzoin (I) with Action of Grignard reagent on the amido- resorcinol (II) in H2S04 is proved to be 5-hydroxy- group. VIII. Action of organo-magnesium 2 : 3-diphenylcoumarone, new m.p. 163°, since its compounds on ethyl l-methyl-2-pyrrolone-5- Bz derivative, m.p. 122°, is oxidised (Cr03) to 2 : 5- acetate. R. L u k e s and J. P r e u c il (Coll. Czech. dibenzoyloxybenzophenone, m.p. 118°, which is hydro Chem. Comm., 1935, 7, 482^190; cf. A., 1932, lysed to 2-benzoylquinol. The alkali-insol. product, 521).—Et l-methyl-2-pyrrolone-5-acetate (I) with obtained by using excess of (I), is s-tetraphenyl- MeMgl in C6H6-E t20 gives Et 1 : 2-dimethylpyrrole- 1 : 2 : 4 : 5-p-difuranobenzene (III) (cf. A., 1933, 5-acetate, b.p. 135— 136°/20 mm. [the acid, m.p. 1302), new m.p. 281° (cf. loc. cit.). (Ill) is oxidised 119-5° (decomp.), is decarboxylated to give 1:2:5- (Cr03) to the Bzi derivative, m.p. 220—221°, of 2 : 5- trimethylpyrrole]. Similarly, with Mg n-hexyl dibenzoylquinol, m.p. 203° (Ac,, derivative, m.p. 209°), bromide and MgPhBr, (I) yields Et l-methyl-2- different from the compound to which Bogert and hexylpyrrole-5-acetate, b.p. 184— 185°/21 mm. (acid, Howells (A., 1930, 477) incorrectly ascribe this struc m.p. 89—91°, which when heated gives 5-hexyl- ture (cf. this vol., 78). With Br in C6H0 at 100°, 1 : 2-dimethylpyrrole, b.p. 171— 172°/71 mm.), and (III) yields a meso-Pr2-derivative, m.p. 384— 388°, Et 2-plienyl-\-methylpyrrole-5-acetate, b.p. 208—210°/ Ph Ph 18 mm. [acid, m.p. 157° (decomp.), decarboxylated to 5-phenyl-l : 2-dimethylpyrrole, m.p. 50— 51°], re spectively. In no case was a diketone isolated (cf. A., 1932, 621). MgRX does not attack the •C02Et because this is probably in close electronic association (HI.) (IV.) with N. J. L. D. which is also obtained from (I) and 2 : 5-dibromoquinol Basic properties of pyrroles. P. P r atesi in H2S04, and is oxidised (Cr03 in PhN02-A c0H ) to (Gazzetta, 1935, 65, 658—668).—-When pyrroles form the Bz2 derivative, m.p. 317°, of 3 : G-dibromo-2 : 5- salts, the using of the unshared N electrons converts dibenzoylquinol, m.p. 288° (decomp.). The position the aromatic into a conjugated olefinic structure, of Br is confirmed by oxidation (KMn04-NaOH), the stability of which is increased by substituents. which gives BzOH, without the Br-acids which would Thus 2:3: 4-trimethylpyrrole forms a hydrochloride result from a bromophenyl compound. A third and a ferrocyanide', 2 : 4-dimeth}d-3-ethylpyrrole product from (I) and (II), recovered from the mother - can be recovered from HC1 solution (as can 2:3:5- liquors, is ad-tetraphenyl-1: 2 : 4 : 5-p-difurano- trimethyl-4-ethylpyrrole), and forms a ferrocyanide; benzene (IV) (cf. A., 1933, 1302), m.p. 264— 265°; these salts are monomeric. The ferrocyanide of 1- this is oxidised (Cr03) to the Bz2 derivative, m.p. methyl-2 : 5-diethylpyrrole is contaminated with that 276°, of 2 : 3-dibenzoylquinol, m.p. 188°, which with of a polymeride. 2-Methvlpyrrole is polymerised by N2H4,H20 yields 5 : S-dihydroxy-1 : i-dijAmiylphlhal- HC1 and H4Fe(CN)6. “ E. W. W. azine, m.p. 315° (decomp.). E. W. W. Molecular compounds of pyrrole. M. D e z e l i 6 Configuration of dioxan and the cts- and trans- (Annalen, 1935, 520, 290— 300).—Mixed m.-p. curves naphthadioxans. J. B o e s e k e n , F. T e l l e g e x , and of the binary mixtures of various pyrrole derivatives P. H. H enriquez (Bee. trav. chim., 1935, 54, 733— (A) and acidic compounds (B) show the existence 739).—The dipole moments, given in parentheses in of the following compounds. Et 3-acetyl-2 : 4-di- Debye units, of the following compounds have been methylpyrrole-5-carboxylate gives compounds with X V II (d) ORGANIC CHEMISTRY. 83
CH2C1-C02H, m.p. 85-3°, PhOH, m.p. 93°, picric acid, 2-o-hydroxybenzylaminopyridine, m.p. 105° (picrate, m.p. 97-8°, all of type AB, salicylic acid, AB, m.p. m.p. 185— 186°), thus proving the structure of the 107°, and AB2, m.p. 113°, o-, m.p. 108-5°, m-, m.p. amide. Similar reduction of 2-pyridylphthalimide 139°, and p-C6H4(OH)2, m.p. 153°, all of type AB2. causes fission. R. S. C. No compounds are formed with AcOH, BzOH, or succinic acid. Et 2 : 4-dimethylpyrrole-5-carboxylate Hydroxy quinolines. I. Iodo-derivatives of 8- gives a compound AB2, m.p. 100°, with picric acid hydroxyquinoline. E. Pir r o n e and A. Ch e r u b in o (initial polymerisation to B2), but not with (Gazzetta, 1935, 6 5 , 743—754).—An extended account CH2C1-C02H, BzOH, PhOH, salicylic acid, or o-, of work previously published (A., 1934, 418). 5-Iodo- m-, or p-C6H4(OH)2. Et 3-aldehydo-2 : 4-dimethyl- 8-hydroxyquinoline (I), new m.p. 125— 127° (picrate, pyrrole-5-carboxylate gives compounds with new m.p. 170— 172°; sulphate, new m.p. 209—211°; CH2ChC02H, m.p. 74-5°, salicyhc acid, m.p. 135°, 1-MeI derivative, new m.p. 134— 137°; chloroacetate, picric acid, m.p. 97°, and o-, m.p. 114°, and m- m.p. 157— 158°; Co salt), when prepared in aq. C6H4(OH)2, m.p. 111°, all of type AB, and of type EtOH, using I and KI, is accompanied by 5:7- AB2 with p-CGH4(OH)2, m.p. 142° : no compound di-iodo-8-hydroxyquinoline, m.p. 185— 187°. Using with BzOH. Et 4-aldehydo-2: 5-dimethylpyrrole- I in EtOH in presence of NaOAc, only (I) is formed. 3-carboxylate gives compounds with salicylic acid, E. W. W. Absorption spectra in relation to the con AB, m.p. 111-5°, and A B 2, m.p. 111°, and m-, m.p. stitution of derivatives of isatin and carbostyril. 98°, and p-C6H4(0H )2, m.p. 117-5° (type AB), but not R. G. A u l t , E. L. H ir st, and R. A. M orton (J.C.S., with o-CgH4(OH)2. Constitutions are briefly dis cussed. J. W. B. 1935, 1653— 1657).—Absorption spectra of isatin (I) and derivatives have been measured under rigidly Yellow coloration produced by ultra-violet controlled conditions, and show that (I) and its light on mixtures of pyridine with sugars, O- and X-ethers all possess similar spectra. There is monohydric alcohols, and acetone. R . Ca n t ie n i sufficient difference between the spectra of the lactam (Helv. Chim. Acta, 1935, 18, 1420— 1427).—The and lactim derivatives in the hydroxyquinoline relative effects of various concns. of the above-named series to permit the use of absorption spectra in substances on (a) the velocity of formation of the yel structural determinations. (I) and CH2N2 yield low colour, and (b) the fading of this yellow colour, 3-hydroxy-, m.p. 360°, and 3-methoxy-quinoline, produced by ultra-violet irradiation of C5H5N have m.p. 191°. N - Methylisatin and CH2N2 give been investigated quantitatively by colorimetric 3-melhoxy-1 -methylquinoline, m.p. 42°, and O-methyl- comparison with 1 vol.-% solutions of C5H5N in H20. isatin forms 3 - hydroxy - 2 - methoxyquinoline, m.p. The main conclusions are as follows : glucose, galac 83— 84°. F. R. S. tose, sucrose, and lactose accelerate colour formation and retard fading, but their effect is < that of fructose. p-Dimethylaminobenzylidenequinaldine. Ac Pure MeOH is almost without influence on colour tion of chromophoric and auxochrome groups. formation, but has a greater retarding action on fading H. R u p e , H. H a g e n b a c h , and A. Co llin (Helv. than has fructose. Pure EtOH retards colour form Chim. Acta, 1935, 1 8 , 1395— 1413).—The following ation, but the colour is more stable in EtOH than in salts of 2-p-dimethylaminostyrylquinoline (I), m.p. MeOH. COMe2 has a powerful inhibiting effect on 183-5— 184-5° (Noelting et al., A., 1906, i, 886; colour formation. J. W. B. Pfeiffer et al., A., 1925, i, 411, give m.p. 177— 179°), are prepared pure : colourless dihydrochloride; 4-B rom opyridine. J. P. W ib a u t , J. Ov e r h o ff, bluish-violet monohydrochloride, m.p. 239—240°; and H. G eldof (Rec. trav. chim., 1935, 54, 807— almost colourless diperchlorate; reddish-violet mono 812).— 4-Hydroxypyridine with POBr3 and PBrs perchlorate, m.p. 229— 230° (decomp.), and mono- at 130— 140° affords (together with some 2:4:6- picrate, m.p. 167— 168°. With Mel in MeOH at 100° tribromopyridine) 4-bromopxyridine (I), b.p. 27-5— (I) gives a mixture of a pale yellow methiodide, 30°/0-4 mm., f.p. 0— 1°, also obtained by the action C9HGN-CH!CH-C6H4-NMe3I (II), decomp. 250—251°, of NaN02-conc. HBr on 4-nitroaminopyridine (Koenigs synthesised by condensation of p-aldehydophenyllri- et al., A., 1924, i, 989), and characterised as its melhylammonium iodide, m.p. 144° (decomp.), and picrate, sinters 135— 140°, m.p. 223° (decomp.), quinaldine in EtOH-piperidine, and a bluish-red mercurichloride, darkens 130— 140°, decomp. > 270°, methiodide, NMe2-C6H4-CH:CH-C9H6NMeI (IH), m.p. and platinichloride. (I) is very unstable and is 253—254° (decomp.), synthesised from quinaldine converted in the dark at 0°, and even in Et20 solution, methiodide and p-NMc2-CnH4-CIIO (IV). With 1 into a yellowish-brown substance which may be mol. of Me2S04 in H20 (I) gives red 2-p-dimethyl- 4 - bromo - N - 4' - pyridylpyridinium bromide (plalini - aminostyrylquinoline methosulphate, m.p. 242—243° chloride, decomp. > 325°; platinibromide\ mercuri (decomp.), of type (III), synthesised from ‘¿-methyl chloride, m.p. approx. 221°). When heated with quinoline methosulphate, m.p. 223—224° (decomp.), aq. NH3 (d 0-9) at 200°, (I) is converted into 4-amino- and (IV), whereas condensation of p-dimethylamino- pyridine. J. W. B. benzaldehyde methosulphate, m.p. 154°, and quinaldine 2-Aminopyridine series. III. 2-Salicoyl- give the colourless ¡3-2-quinolylstyryltrimetkylammonium amidopyridine and its electrolytic reduction to methosulphate, m.p. 201-5— 202-5° (decomp.), of type 2-o-hydroxybenzylaminopyridine. K. F e ist , W. (II). With 2 mols. of Me2S04 (I) gives its colourless A w e , and W. V olksen (Arch. Pharm., 1935, 273, dimethosulphate, m.p. 252— 253° (decomp.). Thus 476—478; cf. A., 1935, 92).—Electrolytic reduction salts of type (II) and the bis-quaternary salts are of 2-salicoylamidopyridine in E t0H -H 2S04 gives colourless, and those of type (III)- are coloured. X V II (d, e) 84 BRITISH CHEMICAL ABSTRACTS. A.
Reduction of (I) with H2—Ni in EtOAc-EtOH first give 5'-nitro-2'-methoxydiphenylaminc-2-carboxylic acid saturates the ethylenic linking and yields, finally, (VI), m.p. 234°, from which i-nitro-l-methoxyacridone 2-$-p-dimethylaminophemylethyl-l : 2 : 3 : i-tetrahydro- (VII), m.p. 281°. (decomp.), may be prepared by quinoline, m.p. 68—68-5° (dihydrochloride, m.p. 210 heating with conc. H2S04 or with P0C13. On 211°; diperchlorate, m.p. 157— 15S°; dimethiodide, chlorination, (VII) yields the corresponding 5-chloro- m.p. 158— 159°; NO-, m.p. 90-5—91°, and Bz, m.p. acridine (VIII), m.p. 173° (hydrochloride), also obtained 120-5— 121-5°, derivatives). With MgPhBr in Et20 directly from (VI) and excess of P0C13. 4-Chloro- (I) affords a 1 : 4-adduct, 2-(fi-p-dirnelhylaminophenyl- d'-methoxydiphenylaminc-2-carboxylic acid, m.p. 189°, $-phcnylethylidene)-1 : 2-dihydroquinoline (V), m.p. prepared from 3 : 6-dichlorobenzoic acid, p-anisidine, 125° [dihydrochloride; diperchlorate, m.p. 192— 194° KOH, and CuO in glycerol (140°; 10 hr.), affords (decomp.); methiod- similarly 1-chloro-l-methoxyacridone, m.p. > 300° ide, m.p. 125— 126° and 1 : 5-dichloro-l-methoxyacridine (IX), m.p. 205— L Jl J:CH-CHPh-C6H4-NMe3I (decomp.); NO-de- 206° (hydrochloride). The hydrochlorides of (IV) and v / rivative, m.p. 195— (IX) are hydrolysed when boiled with dil. HC1, under Aale2I 196° (decomp.); N- which conditions those of (V) and (VIII) are converted methyl dimethiodide (annexed formula), m.p. 206—20S° into the corresponding acridones. The above ob (decomp.); and N-methyl diperchlorate, m.p. 216— servations do not support the view that acridol is 217° (decomp.)], and a substance, m.p. 194-5° [per an intermediate stage in the conversion of mesochloro- chlorate, m.p. 207—208°; dimethiodide, m.p. 196— acridines into acridones. R. T. 197° (decomp.)], which is not isomeric with (V), and gives no NO- or Bz derivative. The relationship Antimalarial drugs. Syntheses in the acrid of colour to constitution is discussed. J. W. B. ine series. J. C. F e l d m a n and E. L. K opeliovitscii (Arch. Pharm., 1935, 273, 4S8— 495).— 2 : 5- Reaction products of indoles with diazo-esters. CgHgCl^COaH (prepared from o-C6H4Me-N02by way of R. W . J ackson and R. H. M an sk e (Canad. J. Res., 5-chloro-o-toluidine and 2 : 5-C6H3MeCl2) with p- 1935, 13, B, 170— 174).—Addition of CHN2-CO,Et OMe-CfiH4-NH2, K 2C03, and a little Cu in iso-C5H11*OH and indole gives, after hydrolysis, indolyl-3-acetic at 130— 135° gives o-chloro-2-p-anisylaminobenzoic acid (I), and indylene-1 : 3-diacetic acid, m.p. 242°, acid, m.p. 185— 186°, converted by P0C13 at 100— hydrolysed to 3-methylindolyl-l -acetic acid, m.p. 123° into 5 : l-dichloro-3-methoxyacridine, m.p. 203— 178° . Indole and Et2 diazosuccinate similarly form 204°, which with NH2-CHMe-[CH2]3-NEt2 yields 7- indolyl-3-succinic acid, m.p. 199°. No substitution chloro-5-^-diethylaniino-rj.-methyl-n-butylamino-, m.p. occurs in position 2. Hydrolysis of Et2 p-cyano- 221— 222°, and with NH2-[CH2]3,NEt2 7-chloro-5-y- propionacetal to the acid, and further hydrolysis diethylaminopropyl-3-meihoxyacridine dihydrochloride, (HC1) to the semialdehyde of succinic acid, followed m.p. 246—247°. C8H3MeCl2 with Cl2-F e gives a by condensation with NIlPh-NH., and treatment mixture, m.p. 80— Sl°, C6H2MeCI3, converted by with H2SOj, leads by the Fischer synthesis to (I). HN03 into a mixture of 2:4:6- and 2:4:5- E. R. S. CgHoClyCC^H (I). (I) leads to 4 : 5-dichloro-2-p- Colour and constitution of indole derivatives. anisylaminobenzoic acid, m.p. 233— 234°, 5:7:8- C. T offoli (Gazzetta, 1935, 6 5 , 647— 658).— trichloro-3-methoxyacridine, m.p. 192— 193°, and 7 : 8- Theoretical. The colour, and changes of colour on dichloro-5 - 8 - diethylamino - a. - methylbutylaminoacridine salt-formation, of various indoles, e.g., o-3-(2-methyl- dihydrochloride, m.p. 236—237°. The three acridine indolyl)phenyl 3-(2-methylindolyl) ketone (A., 1934, 1110), and act-3 : 3'-di-indolyl- and -3-indolyl-3'- bases are less effective antimalarials than is acrichine indolidene-ethano (ibid., 1113), are discussed on the (atebrine). R. S. C. basis of the Bonino model for pyrrole (A., 1933, S86), 3 - Phenyl -1 - (3 - phenylethylpyr azol - 5 - one. E. and of Burawoy’s theories (A., 1931, 144, 544; 1932, V otoCe k and 0. W ich terle (Coll. Czech. Chem. 791). Salt-formation disturbs the aromatic character Comm., 1935, 7, 388— 391).— 3-Phenyl-\-$-phenyl- of indoles, and introduces chromophoric conjugated ethylpyrazol-5-one (I), m.p. 145-5° (methiodide, m.p. systems. E. W. W. 174— 175°), is obtained from CH2Ph-CH2-NH-NH2 and Preparation and properties of mesochloro- C0Ph-CH2-C02Et. (I) with NaN02-HCl affords a AO- acridine and acridone, and their derivatives. derivative, m.p. 138— 139°, converted by Zn-AcOII into N. S. D rozdov and N. S. L eznova (J. Gen. Chem. Russ., 1935, 5, 690—700).—Mesochloroacridine (I) the compound RH'NIR [ R = CH2Ph-CH2-N<^^Q.^J yields acridone (II), together with the hydrochloride m.p. 165°, and an AH,-derivative (not isolated) of (I). (III) of a double salt of (I) and (II), when boiled with P. G. C. dil. HC1; (III) readily decomposes in aq. NH3 or Asymmetric platinum atom. • VII. A new boiling H20 to yield (II). 4'-Methoxydiphenylamine- type of optically active compound. H. R e ih l e n , -2-carboxylic acid and excess of P0C13 in xylene yield G. Se ip e l , and E. W ein b r e n n e r (Annalen, 1935, 5-chloro-3-melhoxyacridine (IV), m.p. 154°, the hydro 520, 256—269).—Dichloro-Z-phenylethylenediamine- chloride of which is obtained by boiling with dil. platinum (I) (A., 1935,1132) boiled with 2 :2'-dipyridyl HC1; with a limited amount of P0C13 the product affords dipyridyl -1 -phenylethylenediamineplatinum is 3-methoxyacridone. 5-Chloro -1 - nitro - 7 - methoxy - chloride (II) +2H20 and +3H20, [J/],> +90° (platino- acridine (V), m.p. 226°, and its hydrochloride are pre chloride), which is a racemate of the active Pt centre pared analogously. o-C6H4Cl-C02H, 4-nitro-2-amino- [denoted by (±)P t], With dil. H N 03-N aN 03 it anisole, KOH, and CuO in iso-C5Hn *OH (140°; 10 hr.) gives the ( i ) P t nitrate, partly separated by shaking X V II (e) ORGANIC CHEMISTRY. 85 with II20 at 10— 15° into the less sol., stable (+ )P t 4 : 5-diamino-3-methyluracil (II), dhsobarbituric acid nitrate (III), [M]D +115°, [APtJo +25°, whereas the (III) and its oxidised form (IV), diuracilpyridazine, mother-liquor affords only the racemate from the the azine [A), m.p. 268—269° [from (II) by heating readily raeemised ( — )Pt salt. With 1 mol. of Na c/-bromocamphor---sulphonate (IV) in H20, (II) CO N gives the ( ± )Pt d-bromoayjiphor-n-sulphonate chloride +3H 20, [M\d +363° (273°+90°), but the gelatinous (+ )P t di-d-bro)7iocamphor-n-sulpho7iate, [ili]u +622°, obtained by evaporation of (II) with 2 mols. of (IV), MeN N slowly affords crystals of the (+ )P t d-bromocamphor- 7z-sulpho?iate chloride (V) +3H20, [M]D +392°, [ APt]D +25° to 29°, converted by dil. H N 03-N aN03 in C02 at 190—200° for 45 min. with Bz2], the azine into (III). The mother-liquor of (V) with (iV) gives (B), m.p. > 330° [from (II) by boiling in AcOH for the ( —)Pt di-d-bromocamphor-T.-sulphonale + 2 H 20, 20— 30 min. with phenanthraquinone], dioxindole (V), [d/]n +604°, [APt]D —32°. o-Phenanthroline (VI) and acridine has been examined, pn-fluorescence with K2PtCl4 in hot H20 affords dichloro-o-phenan- curves being given for (I)— (V). W. McC. throlineplatinum, converted by Z-NH2-CHPh-CH2,NH2 Crystalline hypoxanthine. H. St e u d e l (Z. into o-phenanthroline-\-phenylethylenediamineplatinum physiol. Chem., 1935, 236, 228—229).—Pure cryst. chloride + 2 H 20, [4/]d +121° [also from (I) and (VI)] xanthine (I) (prisms) is obtained from the sulphate (nitrate, [d/]D +119°; platinochloride; di-d-bromo- after conversion into the compound with NH3, and camphor-T.-sulphonale +2H20, [il/]D +666° ±10°). pure cryst. hypoxanthine (II) (rhombic plates) from Similarly dichloroethylenediamineplatinum with (I) the hydrochloride, in both cases by treatment with affords 1 - phenylethylenediamine - ethylenediamine - NaOAc. The cryst. form attributed by Horbaczewsld platinum, chloride, partly separated by crystallisation (A., 1898, i, 50) to (I) is that of (II). W. McC. into fractions of [il/]D +134° and +120°, whence Flavin syntheses. VIII. Synthesis of 6- are obtained the iodide, [J/]D +139° and +110-5° methyl-9-l-(i-ribityl).soalloxazine and other syn (pure, [M\d +125°, the ¿-compound, [il/]» —125°, thetic investigations in the flavin series. P. also being obtained), perchlorate, [M]x> +110° and K arr er and F. M. Strong (Helv. Chim. Acta, + 142°, and iodide perchlorate, [J/]D +142°. Thus 1935, 18, 1343— 1351).— 4-Nitro-m-toluidine (im 'A . .D | proved prep.) with ClC02Et in CIIC13 gives its in the spirans of type ;Pt>; either the four B- carbethoxy-derivative, m.p. 51—52°, reduced (H2- Pt02) to 3-carbethoxyamino-p-toluidine, m.p. 120°, N are not in the same plane as the Pt, or the four Pt—N converted successively by usual methods (cf. A., 1934, linkings are not equiv. All [il/]D vals. are in H20. 1134) into 2-carbethoxyamino-p-tolyl-d-ribamine, m.p. J. W. B. Preparation of 2 : 2'-diquinolyl by catalytic 153°, and G-77iethyl-d-d-riboflavin (I), m.p. 282°, Md —84-6° in 0-05Ar-NaOH. 6-Nitro-2: 4-dimethyl- debydrogenation of quinoline. J. P. W ib a u t , aniline (by hydrolysis of its Ac derivative, m~p. H. D. T. W il l in k , jun., and W . E. N ie u w e n h u is (Rec. trav. chim., 1935, 54, 804— 807).— Dehvdrogen- 176-5°; lit., m.p. 172°) with ClC02Et gives a poor ation of quinoline (I) by heating at 325—335° with a yield of its carbethoxy-derivative, m.p. 135° (lit., 125—126°), which is best obtained by the action of Ni-Al203 catalyst affords 2 : 2'-diquinolyl [15% yield, conc. II2S04 calc, on (I) consumed]. Very poor yields are also -HN03 (d 1-40) at on Et 2 :4 - obtained using 0-5% of an I rfitalyst, but with 2-0% I dimethylphenylcarbamate, and is reduced (H2-Pt) complete decomp, results. J. W. B. to the 6-N //2-compound, m.p. 99--5°, from which 2 -carbèthoxjjamino - 3 : 5 -dimethylphenyl-d -ribamme, Decolonisation of indigotin by alkyl- and aryl- m.p. 139°, is obtained. Alkaline hydrolysis of this sulphinic acids. M. B a zle n and F. Scholtz (Ber., gives only l-d-ribityl-2-hydroxy-i : 6-di7>iethylbenzi7>iin- 1935, 68, [B], 2045).—Indigotin becomes decolorised azole, m.p. 248°. (I) exhibits good growth-promoting when heated at 180° in glycerol with the Zn or Na salts efficiency in 10—20X 10~6 g. daily doses. J. W. B. of MeS02H, EtS02H, PhS02H, 1- or 2-C10H7-SO2H ; the free acids cannot be used, since they become de Synthesis of lactoflavins. P. K ar r e r , B. B eck composed at temp, below that at which reducing e r , F. B e n z , P. F r e i, H. Salo m o n , arid K. Schöfp action is developed. The colour returns when (Helv. Chim. Acta, 1935, 18, 1435— 1448).—In part the solution is cooled and shaken with air. p- a historical résumé of flavin syntheses. Details are C6H4Me*S02H, o-NH2-CGH4-S02H, benzanthrone-Bs-l- given for the prep, of d-ribose (I) (270 g.) from d- sulphinic acid, and anthraquinone-2-sulphinic acid arabinose (3 kg.) by the method used by Austin behave similarly. H. W. et al. (A., 1934, 759) for Z-ribose. The production of NH2-C6H2Me2-NH-CH2-[CH-OH]3-CH2-OH by catalytic Manufacture of conversion products of Ar- reduction of NO/CgHaMeg'NiCHdCH-OHJj-CH^OH nitroamines etc. [benztriazoles].—See B., 1935, (Kuhn et al., A., 1935, 1382) is disputed, since these 1132. authors describe the condensation of 5-nitro-4-amino- Fluorescence of derivatives of pyrimidine, o-xylenc only with Z-arabinose and not with cZ-ribose. purine, and pyrimidazine. H. v o n E u l e r , K. M. The synthesis of 6 : 7-dimethyl-9-
trimethyl-i-ethylpyrromethane hydrobromide, m.p. 214° CjHjN-AcOH give the Cu salt, C39H3303N4Cu. (decomp.), from (I) and 3-acetyl-2 : 4-dimethylpyrrole, Benzoylpyrroporphyrin oxime has m.p. 224°, but of i'-benzoyl-3 : 3' : 4 : 5 : 5'-pentamethylpyrromethehe reaction is not observed with the acid and p- hydrobromide, m.p. 224° (decomp.), from (II) and N 02-C(;H4-NH-NH„ or NH2-CO-NH-NH2. Reduction 2 : 3 : 4-trimethylpyrrole-5-aldehyde, of 4'-benzoyl- of (VI) gives a-liydroxybenzylpyrroporphyrin, m.p. 3 : 3 ': 5 : o'-tetmmethyl-i-ethylpyrromethene hydro- > 300°, which gives minimal amounts of new por bromide (III), m.p. 211° (decomp.), from 2 :4-dimethyl- phyrins with boifing Ac20 or (EtCO)20 and pyrrorhodin 3-ethylpyrrole-5-aldehyde and (II), of i'-benzoyl- when treated with conc. H2S04 at 100°. Reduction 3 : 3' : 5 : 5'-telramethyljjyrromethene hydrobromide, of bcnzoylpyrrohajmin with Na and isoamyl alcohol m.p. 189° (decomp.) (corresponding 4-Br-derivative is described. H. W. which becomes discoloured at about 210°), and of Porphyrins. XXXV. Synthesis of porphin. 4' - benzoyl - 3 : 3' : 5' - trimethyl - 4 - (3 - carboxyethylpiyrro - methene hydrobromide, m.p. 204° (decomp.) (corre H. F ischer and W. Gleim (Annalen, 1935, 521, 157— sponding 5-Br-derivative, which has no defined m.p.). 160).— Slow addition of pyrrole-2-aldehyde in EtOH If (II) is heated with 95% HC02H and 48% HBr is then added, 4 : 4'-dibenzoyl-3 : 3' : 5 : 5'-tctramethyl- pyrrometliene hydrobromide (IV), decomp. 225°, is obtained, also prepared in AcOH or from Et 3- aldehydo-2 : 4-dimethylpyrrole-o-carboxylate and (II). 4 : 4 '-Dibenzoyl-3 : 3' : 5 : 5 '-tetramethylpyrromethene, m.p. 209°, is very stable. Addition of an intimate mixture of (III), 5 : 5'-dibromo-4 : 4'-dimethyl-3 : 3'- di-P-carboxyethylpyrromethene hydrobromide, and to boiling HC02H followed by protracted ebullition Et,7 nMe Mer -,Bz of the mixture gives very'small amount of porphin -CH-- (I), which darkens above 360° and blackens at 400°, \ t \ v and, in dioxan, closely resembles spectroscopically NH deoxosetioporphyrin. The Cu and Fe salts have been N \H, examined spectroscopically. II. W. NH N / Optical absorption of porphyrins. III.—See ,/\_ -CH- this vol., 8. Mo1! or (A.) YYR 1= 1 Me Fluorescence spectra of chlorophyll pigments. (-CH2-C02H)o to boiling (-CH2-C02H) gives, after — See this vol., 125. treatment of the product with CH2N2, small amounts of i-benzoyl-2 : 3 : 5 : 8-tetramethyl-X-ethyl-G : 7-cZi-P- Optical activity of haemoglobin and its deriv carbmnethoxyethylporphin (cf. A ; R=-[CH2]2-C02H), atives.—See this vol., 92. m.p. 263° (corr.), and mesoporphyrin 13, thus establish Mechanism of oxidation of o-toluenesulphon- ing the formation of cryptopyrrolemethene as inter amide to saccharin. 0. J. M a g id so n and I. G. mediate product. Analogous treatment of (IV) Z ilberg (J. Gen. Chem. Russ., 1935, 5, 920—923).— and 5 : 5'-dibromo-4 : 4'-dimethyl-3 : 3'-di-(3-carboxy- o-CGH4Me-S02'NH2 (I) in Ac20 and Cr03 at —5° ethylpyrromethene hydrobromide leads to 1 :4 - to 30° yield o-C6H4Me-S02-NHAc, m.p. 132— 134°, dibenzoyl-2 : 3 : 5 : 8-tetramethyl-G : l-di-\i-carbomethoxy- a substance (II), m.p. 174— 176° (probably ethrylporphin [dibenzoyldeideroporphyrin Me2 ether 13] 0Ac-CH2-CßH4-S02*NHAc), and a substance (III), B z.t Me -,Bz m.p. 103— 105°; in presence of H2S04 acetsaccharin -CIR is obtained in addition to the above products. (II) and (HI) yield saccharin (IV) when oxidised with NH KMn04, and (II) is probably an intermediate in the H A CH oxidation of (I) to (IV). R. T. N N Fission of ketosulphidocarboxylic acids, II. -CH= A- Aryl selenohalides. VI. 0. B eh a g e l and W- M e l= J R (B.) r Y jMc M ü l le r (Ber., 1935, 68, [B], 2164— 216G; cf. A., (cf. B: R = '[C H 2]2-C02Me), m.p. 252° (corr.), which 1935, 1237, 1257).— 3-Keto-2 : 3-dihydro-l : 4-benzo- with Fe(OAc)2 and NaCl in boiling AcOH affords the compound C4GH40OGN4FeCl, m.p. about 290°; pro selenazine (I), CGH4<^ ^ | • (X)2’ m-P- 1^2°, obtained by ducts, m.p. 183-5° (corr.) and 257° (corr.), respectively, reduction of o-nitrophenylselenolaeetic acid, is con are also obtained in the synthesis, which gives poor verted by Br in CHC13 into 1 \ \-dibromo-3-keto-2 : 3- yields. Dibenzoyldeutero-porphyrin 5 is described. dihydro-l : ‘i-benzoselenazine (II), m.p. 211°, which Treatment of pyrrohsemin ester with Bz20 and loses HBr in boiling PhMe giving 2-bromo-3-keto-2 : 3- SnBr, at 70° leads to benzoylpyrroporphyrin Me ester 5 dihydro-1 : i-benzoselenazine (III), m.p. 213—214°. (V), m.p. 313° (corr.), less readily obtained by use of Analogously 1 : l-dichloro-3-keto-2 : 3-dihydro-l : 4- SnCl4; the corresponding free acid (VI) has m.p. benzoselenazine (IV), m.p. 222°, affords 2-chloro-3- > 320°. Treatment of (V) with AcOH, Fe(OAc)2, keto -2 :3 - dihydro -1 :4 - benzoselenazine, m.p. 228°. and NaCl in boiling CHC13 affords benzoylpyrrohmmin Boiling H20 transforms (II) or (IV) into the corre Me ester, C39H3803N4FeCl. (V) and Cu(OAc), in sponding oxide, m.p. (indef.) 160°. (Ill) condenses X V II (/, g) 88 BRITISH CHEMICAL ABSTRACTS.— A. with SH-CH2-C02H in feebly acid solution to the m.p. 148— 149° (or, + 1 II20, m.p. about 100°), [a]i, —118-7° in CHC13 (hydrochloride, m.p. 151— acid, E I^oe>CH-S-CH2-C02H, m.p. 209-210°, 152°; sparingly sol. oxalate, m.p. 211—212°; methiod hydrolysed by alkali to (I), H2S, and H2C204. ide, m.p. 199—200°), which contains NMe, 2 OMe, and OH. (I) is transformed by Mel and NaOMe Amidation with sodium and potassium amides in boiling MeOH into O-methylarmepavine methiodide, on a- and a'-aminoanabasine. IV. Nitration of m.p. 120— 122°. Treatment of (I) in CHC13 a'-aminoanabasine. M. M. K atzn e lso n and M. I. with ClC02Et and NaOH gives an optically inactive K abatsciinik (Corapt. rend. Acad. Sei. U.R.S.S., oil, indicating that (I) may be a tetrahydrofsoquinoline 1935, 3, 1G9— 172).—2-(2'-Amino-5'-pyridyl)piper- derivative. H. W. idine (I), m.p. 109° (a'-aminoanabasine; A., 1935, Alkaloid of chin-shih-hu. K. K. Ch e n and H. L. 223), with 11N03 fd l-4)-H2S04 at 0° affords the 2'- Chen (J. Biol. Chom., 1935, 111, 653— 658).— Chin- nitroamine isolated as its sulphate-]-H20 and anhyd. shih-hu from Szechuan contains 0-52% of alkaloids, (II), m.p. 233° (decomp.), converted by heating with mainly dendrobinc (modified isolation), ClnH2502N, conc. I-I2S04 at 70—80° into 2-(3'-nitro-2'-amino-5'- m.p. 135°, [a]“ —52° in EtOH [hydrochloride, m.p. pyridyl)piperidine, m.p. 178-5— 179°, also obtained, 193°, [a]o —40-3°; hydrobromide, m.p. 259— together with a substance, C10H9O6Nj, m.p. 70°, 259-5°, [a]3D° —34-3°; hydriodide, m.p. 284— 284-5°, by nitration of (1) at 70—90°. Diazotisation of (I) [a%° —29°; nitrate, m.p. 19S-5— 199°, [a%3'5 —30-2°; affords the corresponding 2'-OH-dcrivative (Na salt) sulphate, m.p. 178°, [a]^f —36-7°; oxalate, m.p. 137— isolated only as its picrate, m.p. 241' (decomp.), 138°, [a]^5 —50-8°; picrate, m.p. 210° (decomp.); also obtained by heating (II) with Ac20 and sub flavianate, decomp. 212°; methiodide, m.p. 246°, sequent hydrolysis with boiling 5% aq. NaOH. [a]'o —28-8° in EtOH; aurichloride, m.p. 183— 184°; [Noto: the m.p. of the 3'- and 5'-pyridyl compounds platinichloride, m.p. 283°. [a] are in H20]. The (loc. cit.) should be interchanged; that of the former Kweichow variety con tarns another alkaloid, but is 89-5—90°.] J- W. B. no dendrobine. M.p. are corr. R. S. C. Cactus alkaloids. XV. Separation of the Alkaloid from Trichodesma incanmn Anhalonium bases. E. Sbath and F. B eck e D.C. I. G. Menschikov and V. Rubinstein (Ber., (Monatsh., 1935, 66, 327— 336).—Mescal buttons 1935, 68, [B], 2039—2044).— Percolation of the dried are extracted with pure EtOH at room temp, and, plant with 95% EtOH containing 1% of NH3, removal after removal of solvent, the extract is dissolved of the solvent, and extraction of the residue with dil. in H20, treated with excess of KOH, and exhaustively HC1 followed by treatment of the acid solution with extracted with pure Et20. The extract is shaken with NH3 and CHC13 yields trichodesmine (I), C18H270gN, conc. KOH. The combined alkaline solutions are m.p. 160— 161° (decomp.), [a]D +3S° in EtOH neutralised, rendered slightly alkaline with K2C03, [methiodide, m.p. 202° (decomp.)], which does not and extracted with Et20, thus giving all the phenolic react with cold H N 02, and hence contains tert.- alkaloids with small amounts of non-basic compounds. N. Hydrolysis of (I) with 10% NaOH at 100° From them anhalamine is first separated as the hydro affords COMeBu3, r-lactic acid, and trichodesmidine chloride. The free bases are isolated from the mother - (II), C8H1302N, m.p. 117— 11S-50, [a]D +50° in liquors from this salt, distilled in a high vac., and MeOH (picrate, m.p. 142— 143-5°), not identical with pellotine is pptd. as the hydrochloride from their heliotridine. Hydrogenation of (II) readily affords solution in EtOH-Et20. The residual mixture of the saturated liydroxijtrichodesmidane (III), C8H15ON, bases give a cryst. perchlorate which is not homo m.p. 92—94° [picrate, m.p. 211-5— 212-5° (decomp.)]. geneous. Treatment of the bases with Et20 separates Treatment of (III) with conc. H2S04 at 165— 170° them into the sparingly sol. anhalonidine and an- and subsequent hydrogenation (Adams) of the pro haliiline [N - methylanhalamine]. From the non- duct leads to heliotridane. Heliotridine and (II) phenolic bases the bulk of the mescaline is first separ have therefore the same skeleton, and are differentiated ated as the sulphate from H ,0 ; from the mother- from one another by the position of OH and possibly liquors anhalonine is isolated as the sparingly sol. of the double Unking. (I) is a complex ester of (II) hydrochloride. Anhalinino [O-Methylanhalamine] is and r-lactic acid and either CHPr'3Ac• C02H or iso- also isolated, whilst the final mothcr-liquors afford valcrylaeetic acid. The distribution of acid residues lophophorine, separated as the picrate. H. W. in the mol. cannot yet be established; since (I) does Alkaloids of Papuver types. I. Alkaloids of not give a colour with FeCl3 it is probable that lactic P. arnieniactnn and P. orientate. R. K o n o valo va, acid esterifies the enolic OH of the tautomeric form S. Ju n u sso v , and A. Orekhov (Ber., 1935, 68, [B], of the P-CO-acid. H. W. 2158—2163).—Percolation with C2H4C12 of the air- Sinomenine. XLIV. Tuduranine, a new alk dried foliage of P. orientale which has been moistened aloid from Sinotneniuin acutum. K. Goto with 10% NH3 leads to the isolation of thebaine and (Annalen, 1935, 5 2 1 , 175— 184).—The mother-liquors oripavine, C18H2103N, m.p. 200—201°, [a]D -211-8° from the extraction of sinomenine give the sparingly in CHC13 (hydrochloride, m.p. 244—245°; methiodide, sol. tuduranine hydrochloride (I), C18H1903N,HC1, m.p- m.p. 207—20S°), which dissolves in 10% NaOH 286° (deeomp.), [a]“ 5 -1 4 8 ° in H20+ M e0 H , from giving a cryst. Na salt. It appears to be which the poorly cryst. tuduranine (II), m.p. about C1?H 120(NMe)(OMe)• OH. The presence of isothe- 125° after softening at 105°, is isolated. (II) contains baine could not be detected. Similar treatment of 2 OMe, but no CH202I, is freely sol. in alkali, but gives P. armeniacum yields annepavine (I), C19H2303N, a feeble FeCl3 or diazo-reaction. The presence of X V II (g) ORGANIC CHEMISTRY. 89
1 OHis established by the isolation of diacetyltuduraninc, methylate it by K 0Ii-p-C GH4Me-S03Me lead to m.p. 170°, [a]},4 —321-71° in MeOH, which does not carboxyiso-V-columbin, m.p. 194— 195° (decomp.). combine with Mel, and is hydrolysed to N-acetyl- H. W. tiiduraninc, m.p. 277°, [a]}? —395-24° in MeOH-CHCln, Alkaloids of Duboisia Hoptcoodii.— See this whence Id-acetyltuduranine Me ether, m.p. 189°, [a]Jf vol., 125. -400-17° in CHClg. (II) and Mel in MeOH afford !N-methyltuduranine methiodide (III), m.p. 224°. (II) Alkaloids of European Lycopodium species.— gives a characteristic, fuchsin-red colour with See this vol., 125. CH20-H ,S 04. Spectroscopically, (I) is closely Influence of air on solutions of salvarsan similar to morphothebaine Me2 ether (III). The derivatives.—Sec this vol., 32. Hofmann degradation of lA-mcthyUuduranine Me ether methiodide, m.p. 219°, however, affords successively Arsenical derivatives of carbazole. S. SI. de-N-dimcthyltuduranine Mo ether (methiodide, m.p. Soherlin and A. J. B erlin (J. Gen. Chem. Russ., 279°) and trimethoxyvinylphenanthrenc, m.p. 93-5°, 1935, 5, 938—942).— Diazotised 3-aminocarbazole and with NMe3; the positions of the 3 OMe in the ether do Nn3As03 in presence of CuS04-NH3 yield carbazyl- not therefore coincide with those in (III) or isothebaine S-arsinic acid, which yields carbazyl-3-dichloroarsine Me ether. (I) is transformed by NaOH and Et2S04 (I), m.p. 150°, when treated with S02 in cone. HC1- followed by K I into ~N-ethyltaduranine Et ether EtOH at room temp, in presence of I, and carbazole ethiodide, m.p. 238°, [a]},0 -112-47° in CHC13 (with and A sC13 in the boiling solution. (I) and aq. NH3 some N-diethyltuduranine Et ether ethiodide, m.p. afford carbazyl-3-arsinous acid, m.p. 267—269°. 163— 164°), converted by the successive action of R. T. NaOH and EtI into de-N-diethyltuduranine Et ether Action of alkyl iodides on heterocyclic organic ethiodide, m.p. 164°, [a]D ± 0 ° arsenic compounds. I. V. S. M a l in o v s k i (J. (corresponding hydriodide, m.p. Gen. Chem. Russ., 1935, 5, 510— 514).—The Cl of 163— 164°), whence dimethoxy- 5-chloro- and 5-chloro-10-acetyl-5 : 10-dihydrophen- OMe ethoxyvinylphenanthrene, m .p. 148° arsazine, chlorophenoxarsinc, and diphenylenecliloro- OMe-l after softening at 110°, and NEt3. arsine in replaced by I when the compounds are heated OH The Hofmann degradationof (lit) with Mel, EtI, or fso-CjHuI in sealed tubes, products gives de-N -dimethyltuduranine containing Asv not being formed. 5 : 10-I)ihydro- (methiodide, m.p. 259°), whence phenarsazine oxide and Mel (6 hr.; 90°) afford an (A.) a compound, C18Hlc0 3, m.p. 292— unidentified product, C14H,5NAsI2, m.p. 138— 142°, 294°. Oxidation of (II) with containing Asv, whilst EtI and iso-C5Hu I yield KMn04 gives very small amounts of an acid, m.p. about 5-iodo-5 : 10-dihydrophenarsazine. 5 -Acetyl-5 : 10- 263°, but no hemipinic or raetahemipinic acid. The dihydrophenarsazine and Mel give 5-methyl-5 : 10- structure A is therefore assigned to (tl). H. W. dihydrophenarsazine methiodide. R. T. Sinomenine. XLII. (+)- and (-)-Bromo- Hydroxy-derivatives of 5-alkyl (aryl )-5 : 10- thebenone. K. G oto, M. Og a w a , and J. Saito dihydrophenarsazine. II. Synthesis and pro (Bull. Chem. Soc. Japan, 1935, 10, 481— 482; cf. perties of monohydroxy-5-R -5-R '-5 :10-di- A., 1935, 1138).—Dihydrode-iV-methyldemethoxy- hydrophenarsazine. III. Synthesis of deriv diliydrosinomenine (I) and Br-AcOH give the atives of the betaine type. G. A. R a z u v a ie v and (+ ) -1 -Hr-derivative (it), m.p. 192°, [a]}/ +61-6° in CHC13 ¡hydrobromide, m.p. 257° (decomp.); meth V. S. M alin o vsk i (J. Gen. Chem. Russ., 1935, 5, 570—574, 575— 579).—II [with A. F. Siitgatsch and iodide, m.p. 273°]. Tho'-methiodide of (I) and 25% Z. I. A zarch]. The methiodides of 5-alkyl (aryl)- KOH give (-)-l-bromothebenone (III), m.p. 70°, [a]],7 dihydrophenarsazincs yield the following hydroxides —22-67° in CHC13. 1-Bromodemethoxydihydro- sinomenine methiodide and 15% NaOH give 1- and nitrates with AgOH and AgN03, respectively: monohydroxide of 5 : 5-dimethyl-, m.p. 242° [nitrate brainode - N - methyldemethoxydihydrosinomenine (IV), (I), m.p. 258°; V 0 2-derivative (II)], of 5-plienyl- m.p. 200—201°, [a]" -8-67° in CHC13, the methiodide, 5-methyl-, m.p. 202— 204° [nitrate, m.p. 210°; N 02- decomp. 243°, of which with 11% NaOH affords derivative (III), m.p. 120— 124°], and of 5-methyl- (—)-l-bromodehydrothebenone (V), m.p. 145°, [a]],7 5-isoamyl-5 : 10-dihydrophenarsazine, m.p. not given -186-8° in CHC13. (—)-Dehydrosinomenine and (nitrate, m.p. 191— 193°). Attempts to reduce the Br-AcOH yield (-)-is o -9- or -10-bromodehydrothe- N 02 of (II) and (III) resulted in its elimination. benone (VI), m.p. 125— 133°, [a]” -113-3° in CHC13. I ll [with S. E. A r k in a ]. 5-Methyl-5 : 10-dihydro The stereoisomerides are prepared from thebainone phenarsazine and CH2C1-C02H in C8HG at 90° yield and admixture gives the dl-6a^es, (II), m.p. 175— 177°, 5-chloro-5-methyl-5 : 10-dihydrophenarsazinoacetic acid (III), m.p. 191— 193°, (IV), m.p. 189— 192°, (V), m.p. (IV), m.p. 237—238° [Et ester (V), m.p. 198°; nitrate, 159— 162°, and (VI), m.p. 156— 158°. R. S. C. m.p. 179°; plalinichloride, m.p. 138— 140°; picrate, Bitter principles of the Colom bo root. III. m.p. 199°]; the analogous 5-Et derivative, m.p. K . F e is t , E. K u n tz, and R. B rach vogel (Annalen, 201—204° (nitrate, m.p. 170°), is obtained similarly. 1935, 521, 184— 188; cf. A., 1935, 1245).—The (IV) or (V) afford an anhydride (VI), m.p. 199— 203°, discrepancies between the -authors’ observations and of the betaine type, when heated with aq. NaOH. those of Wessely et al. (ibid., 1432) are due to the use The dinitro-derivative of (VI), m.p. 163— 165° by the latter of insufficiently purified material. obtained from (IV) and HNOa, yields (VI) when Columbin is very sensitive to alkali, and attempts to reduced with Fe(OH)2 in aq. NaOH. R. T. X V II (/, g) 88 BRITISH CHEMICAL ABSTRACTS. A. with SH-CHvC02H in feebly acid solution to the m.p. 148— 149° (or, + 1H 20, m.p. about 100°), [a]D —118-7° in CHC13 (hydrochloride, m.p. 151— acid, m.p. 209— 210°, 152°; sparingly sol. oxalate, m.p. 211—212°; methiod hydrolysed by alkali to (I), H2S, and H2C204. ide, m.p. 199— 200°), which contains NMe, 2 OMe, and OH. (I) is transformed by Mel and NaOMe Amidation with sodium and potassium amides in boiling MeOH into O-methylarmcpavine methiodide, on a- and a'-aminoanabasine. IV. Nitration of m.p. 120— 122°. Treatment of (I) in CHC13 a'-aminoanabasine. M. M. K a tzn e lso n and M. I. with ClC02Et and NaOH gives an optically inactive K abatschnik (Compt. rend. Acad. Sci. U.R.S.S., oil, indicating that (I) may be a tetrahydroisoquinoline 1935, 3, 169— 172).—2-(2'-Amino-5'-pyridyl)piper- derivative. H. W. idino (I), m.p. 109° (a'-aminoanabasine; A., 1935, Alkaloid of chin-shih-bu. K. K. Ch e n and H. L. 223), with HNOj (d l-4)-H2S04 at 0° affords the 2'- Ch e n (J. Biol. Chem., 1935, 111, 653— 658).— Chin- nitroamine isolated as its sulphate+ H 20 and anliyd. shih-hu from Szechuan contains 0-52% of alkaloids, (II), m.p. 233° (decomp.), converted by heating with mainly dendrobine (modified isolation), C^H^OoN, cone. H2S04 at 70—80° into 2-(Z'-nitro-2'-amino-5'- m.p. 135°, [a%9 —52° in EtOH [hydrochloride, m.p. pyridyl)piperidine, m.p. 178-5— 179°, also obtained, 193°, [a]?,0 —40-3°; hydrobromide, m.p. 259— together with a substance, CjoHgOgNg, m.p. 70°, 259-5°, [a%° —34-3°; hydriodide, m.p. 284— 284-5°, by nitration of (I) at 70—90°. Diazotisation of (I) [a]™ —29°; nitrate, m.p. 198-5— 199°, [a]??'5 —30-2°; affords the corresponding 2'-OH-derivative [Na salt) sulphate, m.p. 178°, [a]^ —36-7°; oxalate, m.p. 137— isolated only as its picrale, m.p. 241° (decomp.), 138°, [ag?-* —50-8°; picrate, m.p. 210° (decomp.); also obtained by heating (II) with Ac20 and sub jlavianate, dccomp. 212°; methiodide, m.p. 246°, sequent hydrolysis with boiling 5% aq. NaOH. [a%9 —28-8° in EtOH; aurichloride, m.p. 183— 184°; [Note: the m.p. of the 3'- and 5'-pyridyl compounds platinichloride, m.p. 283°. [a] are in H20]. The (foe. cit.) should be interchanged; that of the former Kweichow variety contains another alkaloid, but is 89-5—90°.] J. W. B. no dendrobine. M.p. are corr. R . S. C. Cactus alkaloids. XV. Separation of the Alkaloid from Trichodesma incannm Anhalonimn bases. E. Spath and F. Becke D.C. I. G. M en sch ikov and V. R u b in s t e in (Ber., (Monatsh., 1935, 66, 327—336).—Mescal buttons 1935, 68, [B], 2039—2044).—Percolation of the dried are extracted with pure EtOH at room temp, and, plant with 95% EtOH containing 1% of NH3, removal after removal of solvent, the extract is dissolved of the solvent, and extraction of the residue -with dil. in H20, treated with excess of KOH, and exhaustively HC1 followed by treatment of the acid solution with extracted with pure Et20. The extract is shaken with NH3 and CHC13 yields irichodesmine (I), C18H270 6N, cone. KOH. The combined alkaline solutions are m.p. 160— 161° (decomp.), [a]D + 38° in EtOH neutralised, rendered slightly alkaline with K2C03, [methiodide, m.p. 202° (decomp.)], which does not and extracted with Et20, thus giving all the phenolic react with cold H N 02, and lienee contains tert.- alkaloids with small amounts of non-basic compounds. N. Hydrolysis of (I) with 10% NaOH at 100° From them anhalamine is first separated as the hydro affords COMeBu®, r-lactic acid, and trichodesmidine chloride. The frco bases are isolated from the mother- (II), C8H1302N, m.p. 117— 118-5°, [a]D +50° in liquors from this salt, distilled in a high vac., and MeOH (picrate, m.p. 142— 143-5°), not identical with pellotine is pptd. as the hydrochloride from their lieliotridine. Hydrogenation of (II) readily affords solution in EtOH-Et20. The residual mixture of the saturated hydroxytrichodesmidane (III), C8H15ON, bases give a cryst. perchlorate which is not homo m.p. 92—94° [picrate, m.p. 211-5— 212-5° (decomp.)]. geneous. Treatment of the bases with Et,0 separates Treatment of (III) with cone. H2S04 at 165— 170° them into the sparingly sol. anhalonidine and an- and subsequent hydrogenation (Adams) of the pro halidine [N- methylanhalaminc]. From the non- duct leads to heliotridane. Heliotridine and (II) phenolic bases the bulk of the mescaline is first separ have therefore the same skeleton, and are differentiated ated as the sulphate from H20 ; from the mother - from one another by the position of OH and possibly liquors anhalonine is isolated" as the sparingly sol. of the double linking. (1) is a complex ester of (II) hydrochloride. Anhalinino [O-methylanhalamine] is and r-lactic acid and either CHPr+\c-C02H or iso- also isolated, whilst the final mother-liquors afford valerylacetic acid. The distribution of acid residues lopliophorine, separated as the picrate. H. W. in the mol. cannot yet be established; since (I) does Alkaloids of Paparor types. I. Alkaloids of not give a colour with FeCl3 it is probable that lactic 1*. armeniacuni and P. orientate. R. K o n o v a lo v a , acid esterifies the enolic OH of the tautomeric form S. Juxussov, and A. Or ekh ov (Ber., 1935, 68, [5], of the p-CO-acid. H. W. 215S— 2163).—Percolation with C2H4C12 of the air- Sinomenine. XL,IV. Tuduranine, a new alk dried foliage of P. orientate which has been moistened aloid from Sinotnenium acutum. K. G oto with 10% NH3 leads to the isolation of thebaine and (Annalen, 1935, 521, 175— 184).—The mother-liquors oripanne, C1SH2103N, m.p. 200—201°, [a]„ —211-8° from the extraction of sinomenine give the sparingly in CHCl.j (hydrochloride. m.p. 244—245°: methiodide, sol. tuduranine hydrochloride (I), C18H190 3N,HC1, m.p. m.p. 207—20S°), which dissolves in 10% XaOH 286° (deeomp.), [a]**5 -14S ° in H „0+M cOH , from giving a cryst. Xa salt. It appears to be which the poorly cryst. tuduranine' (II), m.p. about CigH120(NMe)(OMe)*OH. The presence of isothe- 125° after softening at 105°, is isolated. (II) contains baine could not be detected. Similar treatment of 2 OMe. but no CH20,'., is freely sol. in alkali, but gives P. anneniacum yields artncpavine (I), CjgH^OgN, a feeble FeCl3 or diazo-reaction. The presence of X V II (g) ORGANIC CHEMISTRY. S9
1 OHis established by theisolation of diacetyltuduranine, methylate it by K 0 H-p-CfiH4Me-S0 3Me lead to m.p. 170°, [a]c —321-71° in MeOH, which does not carboxyiso-X-columbin, m.p. 194— 195° (decomp.). combine with Mel, and is hydrolysed to N-acetyl- H. W. tuduranine, m.p. 277°, [a]]? —395-24° in MeOH-CHCl3, Alkaloids of Duboisia Hoptcoodii«—See this whence N-acetyltuduranine Me ether, m.p. 1S9°, [a]“ vol., 125. -400-17° in CHC13. (II) and Mel in McOH afford -methyltuduranine methiodide (III), m.p. 224°. (II) Alkaloids of European Lycopodium species.— gives a characteristic, fuchsin-red colour with See this vol., 125. CH20 -H 2S04. Spectroscopically, (I) is closely Influence of air on solutions of salvarsan similar to morphothcbaine Me ether (III). The 2 derivatives.—See this vol., 32. Hofmann degradation of 'iA-methyltuduranine Me ether methiodide, m.p. 219°, however, affords successively Arsenical derivatives of carbazole. S. M. de-iV-dimethyltuduranine Me ether (methiodide, m.p. Scherlin and A. J. B erlin (J. Gen. Chem. Russ., 279°) and trimethoxyvinylphenanthrene, m.p. 93-5°, 1935, 5, 938—942).—Diazotised 3-aminocarbazole and with NMe3; the positions of the 3 OMe in the ether do Na3As03 in presence of CuS04-NH., yield carbazyl- not therefore coincide with those in (III) or isothebaine 3-arsinic acid, which yields carbazyl-3-dichloroarsinc Me ether. (I) is transformed by NaOH and Et2S04 (I), m.p. 150°, when treated with S02 in conc. HC1- followed by KI into N-ethyltuduranine Et ether EtOH at room temp, in presence of I, and carbazole ethiodide, m.p. 23S°, [a]],5 —112-47° in CHC1S (with and A sC13 in the boiling solution. (I) and aq. NII3 some N-diethyltuduranine Et ether ethiodide, m.p. afford ca rbaz i/l-3-nr si no us acid, m.p. 267—269°. 163— 164°), converted by the successive action of R. T. NaOH and Etl into dc-iA-diethyltuduranine Et ether Action of alkyl iodides on heterocyclic organic ethiodide, m.p. 164°, [a]D ¿ 0 ° arsenic compounds. I. V. S. M a l in o y s k i (J. (corresponding hydriodide, m.p. Gen. Chem. Russ., 1935, 5, 510—514).—The Cl of 163— 164°), whence dimethoxy- 5-chloro- and 5-chloro-10-acetyl-5 : 10-dihydrophen- OMe e th oxyvinylphenanthrene, m. p. 148 ° arsazine, chlorophenoxarsinc, and diphenylenechloro- OMe after softening at 110°, and NEt3. arsine in replaced by I when tho compounds arc heated OH VNH The Hofmann degradation of (lit) with Mol, Etl, or tso-CgHjjI in sealed tubes, products JH2 gives do - N -dimethyltuduranine containing Asv not being formed. 5 : 10-l)ihydro- (methiodide, m.p. 259°), whence phenarsazine oxide and Mel (6 hr.; 90°) afford an a compound, C18HiC0;,,m.p.292— unidentified product, C14H ir>NAsT2, m.p. 138— 142°, 294°. Oxidation of (II) with containing Asv, whilst Etl and" »so-C5Hu I yield KMn04 gives very small amounts of an acid, m.p. about 5-iodo-5 : 10-dihydrophenarsazine. 5- A cetyl-5: 10 - 263°, but no hemipinic or metohemipinic acid. The dihydrophenarsazine and Mel give 5-methyl-5 : 10- structure A is therefore assigned to (II). H. W. dihydrophenarsazine methiodide. 11. T. Sinomenine. XLII. (+)- and (-)-Bromo- Hydroxy-derivatives of 5-alkyl(aryl)-5 : 10- thebenone. K. G oto, M. Og a w a , and J. Saito dihydrophenarsazine. II. Synthesis and pro (Bull. Chem. Soc. Japan, 1935, 10, 4S1— 482; cf. perties of monohydroxy-5-R -5-R '-5 :10-di A., 1935, 1138).—Dihydrodc-iY-methyldemethoxj'- hydrophenarsazine. III. Synthesis of deriv dihydrosinomenine (I) and Br-AcOH give the atives of the betaine type. G. A. R a z u v a ie v and (- f j- 1 -/Ir-derivative (II), m.p. 192°, [x]],7 +61-6° in V. S. Ma lin o v sk i (J. Gen. Chem. Russ., 1935, 5, CHCI3 [hydrobromide, m.p. 257° (decomp.); meth 570— 574, 575— 579).— II [with A. F. S hioatsch and iodide, m.p. 273°]. Tho'-methiodide of (I) and 25% Z. I. A zarch], The methiodides of 5-alkvl(aryl)- KOH give (—)-l-bromothebenonc (III), m.p. 70°, [a ]],7 dihydrophenarsazines yield the following hydroxides —22-67° in CHCI . 1 - Bromodemethoxydihydro - 3 and nitrates with AgOH and AgN03, respectively : sinomenine methiodide and 15% NaOH give 1- monohydroxide of 5 : 5-dimethyl-, m.p. 242° [nitrate bromode - N - methyl-demethoxydihydrosinomenine (IV), (I), m.p. 258°; jV02-derivative (II)], of 5-phcnyl- m.p. 200— 201°, [a —8-67° in CHC13, the methiodide, ]],7 5-methyl-, m.p. 202—204° [nitrate, m.p. 210°; NO„- decomp. 243°, of which with 11% NaOH affords derivative (III), m.p. 120— 124°], and of 5-methyl- (—)-l-bromodehydrothebenone (V), m.p. 145°, [a]],7 5-\&oamyl-5 : 10-dihydrophenarsazine, m.p. not given — 186-8° in CHCI . (—)-Dehydrosinomenine and 3 (nitrate, m.p. 191— 193°). Attempts to reduce the Br-AcOH yield ( —)-jso-9- or -10-bromodehydrothe- NOo of (II) and (III) resulted in its elimination. benone (VI), m.p. 125— 133°, [a]],7 -113-3° in CHC13. I ll [with S. E. A r k in a ], 5-Methyl-5 : 10-dihydro The stereoisomerides are prepared from thebainone phenarsazine and CHoC1-C02H in C H at 90° yield and admixture gives the dl- ases, (II), m.p. 175— 177°, 6 6 6 5-chloro-5-mcthyl-5 : 10-dihydroj)hcnarsazinoacctic acid (III), m.p. 191— 193°, (IV), m.p. 189— 192°, (V), m.p. (IV), m.p. 237—238° [Et ester (V), m.p. 198°; nitrate, 159— 162°, and (VI), m.p. 156— 158°. R. S. C. m.p. 179°; plalitlichloride, m.p. 138— 140°; picrate, Bitter principles of the Colom bo root. III. m.p. 199°]; the analogous 5-Et derivative, m.p. K . F e ist , E. K tjntz, and R. B rach vogel (Annalen, 201—204° (nitrate, m.p. 170°), is obtained similarly. 1935, 521, 184— 188; cf. A., 1935, 1245).—The (IV) or (V) afford an anhydride (VI), m.p. 199— 203°, discrepancies between the authors’ observations and of the betaine type, when heated with aq. NaOH. those of Wessely et al. (ibid., 1432) are due to the use The dtmiro-derivative of (VI), m.p. 163— 165° by the latter of insufficiently purified material. obtained from (IV) and HN03, yields (VI) when Columbin is very sensitive to alkali, and attempts to reduced with Fe(OH)2 in aq. NaOH. R. T. X V II (g, i), X V III 00 BRITISH CHEMICAL ABSTRACTS.— A.
Ilolmvlourof «-toluidfno with mercuric acetate. Chemical groups of proteins which possess I,, Vv.i'
Formaldehyde, alcohol, and acetone titrations. Spectrographic determination of phenol.—See Addendum . G. M. R ic h a r d s o n (Rroc. Roy. Soc., this vol., 126. 1935, B, 119, 85— 86; cf. A., 1934, 634).—In the titration of substances containing several acidic or Photo-electric determination of salicylic acid. basic groups the initial and end-points must be clearly P. F. B ech (Dansk Tidsskr. Farm., 1935, 9, 289— defined. E. A. H. R. 302).—The depth of colour of the Fe-salicylic acid complex in aq. solution is measured photo-electrically Determination of reducing sugars.—See this with a previously calibrated apparatus. Improve vol., 126. ments in the author’s earlier method are described Potentiometric determination of polypeptides (Farm. Tidende, 1933, 446). The effects of excess of and amino-acids. E. W. B a l s o n , G. A. E a r - salicylic acid and EtOH and of varying pa have been w ic k e r , and A. L a w so n (Biochem. J., 1935, 29, investigated. Reproducible results are obtainable 2700—2704).—Titration of mixtures of NH2-acids so long as F e"‘ is in excess, [EtOH] > 8%, and and polypeptides is carried out in 90% aq. EtOH: the pn < 2-2. M. H. M. A. degree of separation is discussed. As the pn of the end-point for some mixtures varies over a range of Acid-base titration in alcohol-water mixtures. 2 units depending on the proportions of the con III. Titration of alkaloids and alkaloid salts. stituents, a potentiometric titration is used with a H. B ag g esg aar d -R asm ussen and F. R eimers special method of differential plotting. J. N. A. (Dansk Tidsskr. Farm., 1935, 9, 253—28S; cf. A., 1934, 160).—The acidity consts. PK for narcotine, Determination of benzene by the Pulfrich step- papaverine, strychnine, morphine, codeine, brucine, photom eter.— See this vol., 126. cocaine, procaine, quinine, emetine, cinchonine, atro Determination of toluidines in aqueous solu pine, and ephedrine in 50% and 75% aq. EtOH have tion. D. Cism a r u (Bui. Soc. Chim. Romania, 1934, been determined colorimetrically andelectrometrically, 16, [A], 37— 41).— Aq. o-, to-, or p-toluidine, CuS04, and the variation of PK with [EtOH] is compared with and (MiY-NH.jGNS give quantitatively salts, that of indicator end-points. Most alkaloids lie [CuB,](SCN)2. The base is determined by filtration on the border of practicable titration in 50% EtOH, and titration of the excess of NH.CNS in the filtrate. but titration of alkaloid salts with bases is more R. S. C. accurate in aq. EtOH than in H20. J. A. S.
Biochemistry. Gravimetric method for determining oxygen the same in whole and laked blood and in purified consumption in man. J. P . H e ttw e r (J. Lab. (I) solutions. Q increases with increasing p B, due Clin. Med., 1935, 20, 499— 506). Ch. A b s. (p) partly to the difference between the Q for ionised (I) and that for non-ionised (I), and partly to secondary Respiration apparatus for small animals. S. ionic reactions. H. D. Belak and A. It.lenyi (Biochem. Z., 1935, 281, 27—29). W. McC. Time course of heat effects in rapid chemical Oxygen saturation of human arterial blood. changes. I. Apparatus and methods. II. K. M atth es (Arch. exp. Path. Pharm., 1935, 179, Reactions of haemoglobin with oxygen and car ■>98—711).— Continuous photo-electric recording bon m onoxide. J. B. B a t e m a n and F. J. W. (cf. A., 1934, 1377) indicates variations in arterial R oughton (Biochem. J., 1935, 29, 2622—-2638). 0 2 saturation during inspiration of 0 2-ricli air, The earlier apparatus for measuring the heat effects hyperventilation, respiratory failure, speaking, in rapid chemical changes (A., 1930, 426) is modified singing, etc. During the respiratory pause there is so that the method will follow to within 1—2% the a fall in 0 2 saturation, the rate of which is a function time course of the heat effects over a period of 0—0-01 of alveolar vol. The exact respiratory vol. being sec. in wrhich the total temp, change is < 0 01°. known, determinations of this rate for resting men The method is applied to the reaction of hajmoglobin during a series of respiratory pauses give the vol. of (I) with 0 2 and CO. With 0 2 the liberation of heat residual air and total capacity of the lungs. Tension, is complete within 0 008 sec., and with CO in approx. consumption, and velocity of transport of 0 2 during 005 sec. The half-reaction times for (I) with O, relaxation after heavy work are discussed. and CO were 0-002 and 0 010 sec., respectively, in ™ F - °- H‘ ordinary solutions of (I); in the intact corpuscles the Thermochemistry of the oxygen-bsemoglobin times were 0-007 and 0-016 sec., respectively. The reaction. I. Direct measurements of the heat reaction rates as determined in this way agree with of reaction under various conditions. F. J. W. those obtained by Millikan’s optical technique (A., R oughton (Biochem. J., 1935, 29 , 2604— 2621).— 1934, 383). It is concluded that the primary com The heat of reaction (Q) of haemoglobin (I) with 0 2 bination of (I) with 0 2 or CO is not followed by any is measured by shaking the solution of (I) with 0 2 secondary reactions of appreciable heat effect. in one Thermos flask and determining the temp, difference between this and another flask containing Action of some guanidine derivatives on con the same amount of fluid. Q is independent of the stituents of blood. K. T ach tbana (Folia Pharm degree of 0 2 saturation of the blood, and is practically acol. Japon., 1935, 19, 365— 376).—Decamethylene-, X IX (b) 92 BRITISH CHEMICAL ABSTRACTS. A. pentamethylone-, and cyciohexyl-guanidine had no The ratio of concns. at 1 cm. distance apart varied effect on red cells in rabbits, but increased pseudo- between 1-004 and 1-019. The osmotic pressures eosinopliile and blood platelets when low concns. of the (I) solutions are calc., correcting for variation were used. Higher concns. hindered leucocyte form in concn. with height in the sac; estimates of the mol. ation. Cii. Abs. (p) wts. of the (I) obtained from the three sources are comparable with those obtained by Svedberg (A., Normal hematological standards. E. E . Os 1933, 171). H. D. good (Arch. Int. Med., 1935, 56, 849—863).—From examinations of > 500 healthy persons of both sexes State of phenol added to blood. G. B ar ac and of ages between 4 and 30, average vals. have been (Compt. rend. Soc. Biol., 1935, 120, 522— 523).— obtained for the erythrocyte, reticulocyte, and PhOH can be recovered completely from blood by leucocyte counts, the hemoglobin content and coeff., deproteinisation with CC13-C02H, and is therefore cell vol., vol. coeff., the colour, vol., and saturation not destroyed by the red corpuscles. It is distributed indices, and sedimentation rate. H. G. R. equally between the plasma and the corpuscles. Plasma-PhOH is not partly bound to the lipins, Oxidation of haemoglobin to methaemoglobin since it is separated completely from these by ultra by oxygen. II. Relation between rate of oxid filtration. R- N- G ation and partial pressure of oxygen. J. B rook s (Proc. Roy. Soc., 1935, B, 118, 560—577).—The rate Plasma-lipins of normal men at difierent of oxidation of hemoglobin (I) to methemoglobin ages. I. H. P a g e , E. K ir k , W. H. L e w s , jun., at pa 5-69 and 30° is unimol. with respect to the W. R. T hompson, and D. D. V a n Sl y k e (J. Biol. (I) concn. With varying 0 2 partial pressures (p) Chem., 1935, 111, 613—639).— Free and ester chole the rate is a max. at p —20 mm., being oc the reduced sterol, neutral fat, and total lipins were determined (I) concn. and to pl(\-\-bp). The rate-determining in the plasma, and frequency distribution curves were step is not the selective action of 0 2 with any of the plotted. The individual vals. and their relative intermediate compounds of (I) and 0 2, and the effect magnitudes showed no dependence on the ago of the of 0 2 appears to be threefold: (i) the determination subject. There is an approx. reciprocal relationship of the concn. of the other reactant, (ii) oxidation of between the amounts of cholesteryl esters and neutral compounds containing Fe", (iii) an inhibiting effect fats in the lipin mixtures. The vals. are compared on the oxidation. There is evidence of the presence with those obtained by other workers. II. I). of another inhibitor. F. A. A. Influence of harmine on blood-sugar picture Photochemical oxidation of haemoglobin. F. G. in rabbits. K. T a c h ib a n a (Folia Pharmacol. L en n o x (Austral. J. Exp. Biol., 1935, 13, 193— Japon., 1935, 19, 346—354).— Harmine (2— 50 mg. 196).—The photochemical conversion of Haemoglobin per kg.) causes a marked hyperglyccemia. This action into methaemoglobin is accelerated by K I and NH4I. is inhibited by ergotamine, yohimbine, or by double Free I is without effect either in presence or absence splanchnicotomy, is increased by small doses of pilo of KI. W. 0. K. carpine, and is opposed by insulin. Ci i . A b s . (p) Optical activity of haemoglobin and of deriv Residual carbon of blood in relation to sensit atives : sulphur content. S. Sim onovits and G. isation and anaphylactic shock. F. D ie h l (Arch, B alassa (Biochem. Z., 1935, 281, 186— 197; cf. exp. Path. Pharm., 1935,179, 670—677).—The total A., 1931, 857).—Horse-blood luemoglobin (I) exists blood-residual C compounds (I) (i.e., not pptd. by, in two forms containing, respectively, 0-43 and 0-49% e.g., phosphotungstic acid) increase on sensitisation of S, the CO compounds of these having [a]^so +11-6° of dogs by injection of horse-serum. This increase and 4-12-3° in H ,0, respectively (in 0-1% aq. NaHC03 is restricted to the “ known ” (I) [e.g., sugar (II), the val. is independent of the concn.). Horse lactic acid (III), total phenols, and NH2-N, urea-N, oxyluemoglobin (II) once cryst. has [a]=°00 about and glyoxaline derivatives], the “ unknown ” (I) 4-14-4° and [a]'$80 about 4-12-4° inH 20 (1%), the vals. remaining unchanged. The marked increase in (I) decreasing as the dilution increases. Repeated produced by subsequent anaphylactic shock is mainly recrystallisation causes these vals. to decrease and restricted to unknown (I). The changes in (II), (III), the max. absorption of the transmitted light to in and hydrolysable reducing substances indicate that crease. CO-(I) from cattle has [a]i$80 4-7-9° in H20 carbohydrate metabolism is involved. F. O. H. (1%). Horse-(I) once cryst. and reduced with Na2S.,04 has [a]$20 about +28-3° in H ,0 (5%). Blood modifications provoked by subcutane The S content of (II) is not altered by recrystallisation. ous injection of glucose. G. D e l r u e and P. W. McC. H ollebeke (Compt. rend. Soc. Biol., 1935, 120, Osmotic equilibria of hsemocyanin in a gravit 529—530).—Subcutaneous injection of glucose in the ational field. J. R o ch e, A . R och e, G. S. A d a ir , rabbit increases total proteins; the increase of and M. E. A d air (Biochem. J., 1935, 29, 2576— globulins is > that of serines, and the serine-globulin 2587).—Hamiocyanin (I), prepared from the blood ratio falls. Cl and total bases show decreases of the of Helix pomatia, Carcinus moenas, and Octopus same order. Creatine and P O /" are increased. vulgaris, is placed in J//15-phosphate buffer solution R. N. C. in a collodion sac, and the pressure attained at equili Precipitation of serum-proteins with chloro brium with a similar buffer solution measured. form . A. Gr ó n w a l l (Biochem. Z., 1935, 282, 85— Samples of the solution are withdrawn from different 87).—The extent of pptn. of proteins from human depths and protein is determined refractometrically. serum by mixtures (3 :1 ) of CHC13 and C5Hlt-0H X IX (b) BIOCHEMISTRY. 93
varies greatly with [H‘], max. being observed at (I) contracts the uneserinised muscle, and this action pH 4-3, 6-5, 8-4— 8-7, and 9-4. W. McC. is not inhibited by atropine or destroyed by treating Form of the micelles of the stroma-proteins. the blood or urine with NaOH. Types of blood in G. Boehm (Biochem. Z., 1935, 282, 32— 4G; cf. A., which corpuscular K > serum-K show a (Il)-like 1932, 121).—A method for separating the proteins action when hsemolysed. R. N. C. of the stroma of red blood-corpuscles (calf) from the Total and reduced glutathione compared with haemoglobin is described. The product is sol. in oxygen content and capacity in the blood of salt solutions of pa 6-5— 7-1. The solutions exhibit pregnant and non-pregnant women. F. W. streaming double refraction and contain thread-like O berst and E. B. W oods (Proc. Iowa Acad. Sci., micelles (length-width ratio several thousand to 1). 1934, 41, 166— 167).—No relationship was apparent Since the space requirements of the micelles are very between the 0 2 content and 0 2 capacity of blood and great, concns. > 3— 4% cannot be obtained without the concn. of total or reduced glutathione (I). Vais, production of gels. It follows that the stroma- were similar in pregnant and non-pregnant women. protein of the erythrocytes is not conc. in a membrane, Added (I) disappeared more rapidly from blood than but extends throughout their interior. W. McC. from H20 at 38°. Disappearance from blood was Blood-amino-nitrogen in health and disease. accelerated by NaF. Ch . A b s. (p) A . Sim on and B. Z em plén (Arch. exp. Path. Pharm., Azotsemia and chloraemia in vitro. J. L o ise- 1935, 179, 712—716).—The NH2-N contents of le u r (Compt. rend. Soc. Biol., 1935, 120, 605— whole blood, corpuscles, and plasma (before and after 608).—Addition of urea (I) to blood in vitro causes a haemolysis) of 21 normal and 44 diseased persons are movement of Cl from the corpuscles to the plasma tabulated and discussed. P. O. H. oc the (I) added. Glycylglycine causes a movement of Cl into the corpuscles. R. N. C. Significance of post-operative rises in blood- non-protein-nitrogen. H. A. D er o w (New Eng Azotsemia and chlorsemia in course of histo land J. Med., 1935, 212, 509—511).—In patients lysis. J. L o iseleu r (Compt. rend. Soc. Biol., 1935, with normal renal function the increases may result 120, 675—678).—The corpuscular/plasma-Cl ratio from an oliguria, increased destruction of body- in the blood depends on p n, and is also influenced protein, or post-renal anuria. Ch . A b s . (p) by the release of N compounds into the blood-stream from cell histolysis. It is inversely oc the urea-N/ State of combination of residual nitrogen [in total residual N ratio, and consequently falls on in blood-serum] in experimental uranium poison jection of peptone. Total blood-Cl falls in azotsemia, ing. M. Ja c o b y (Biochem. Z., 1935, 281, 198— 199; the fall being oc the no. of mols. of N compounds. cf. A., 1934, 558).—In rabbits the proportion of R. N. C. urea-N in the residual N of blood-serum increases Blood-iodine ; a new chemical method. D. R. following subcutaneous administration of U 02(N03),. M cCdllagh (Cleveland Clin. Quart., 1935, 2, No. 1, W. McC. " 15-—37).— Variations in blood-I under varying con True and apparent creatine and creatinine of ditions are examined by the author’s method (A., blood and urine. H. B o h n , A. F r ie d s a m , and 1934, 1397). Ch . A b s . (p) F. H ah n (Zentr. inn. Med., 1935, No. 22, 465— 473).— For determination of true creatine (I) alone, hydrolysis Effect of age on the plasma-calcium content of the blood filtrate or urine must take place at a of m en. E. K ir k , W. H. L e w is , jun., and W. R. moderate temp. (60°) in presence of HC1. The true T hompson (J. Biol. Chem., 1935, 111, 641— 642).— val. for blood-(I) in health is about 33% of the usually The plasma-Ca of normal adult men was independent accepted val. In high blood pressure associated of their ages. H. D. with paleness, the true blood-(I) is reduced. The Iron in the blood. Comparison of values for resultsof Linneweh(Klin. Woch., 1934,13, 589) indicate haemoglobin determined by the Newcomer that preformed blood-creatinine is not entirely method and calculated from the iron content. composed of pseudo-creatinine. N u t r . A b s. (?«) H. W. J osephs (Bull. Johns Hopkins Hosp., 1934, Does creatinine occur in normal blood? F. 56, 50—56).— Calc. vals. were the higher in most cases. Ch . A b s . (p) L in n e w e h (Klin. Woch., 1935, 14, 293—294).— Creatinine (I) can be detected in normal blood, Spectrographic micro-method for detection of extracted, and purified by adsorption on Lloyd’s pathological lead in peripheral blood. H . B l u m - reagent. (I) excretion is therefore probably due to berg and T. F. McN. S cott (Bull. Johns Hopkins the removal of (I) from the blood by the kidneys, Hosp., 1935, 56, 32—36).— A pathological finding rather than to formation from creatine (II). The is indicated when the Pb line 2833 A. is detectable adsórbate from blood contains no substance that on the plate without the use of a lens. 0-1 c.c. of ¡nterferes with (I) determination, since Et20 extraction blood is examined. Ch . A b s . (p) does not reduce the (I) val., and supplementary (I) Blood chemistry of swine. II. Blood changes is not formed from (II) during the process. following ingestion of glucose. D. F. E v e l e th R. N. C. and M. W. E veleth (J. Biol. Chem., 1935, 111, Occurrence of acetylcholine in blood. R. 753—756; cf. A., 1934, 543).—Feeding of glucose A mmon (Klin. Woch., 1934, 13, 1472).—The acetyl to fasting swine increases the serum-Mg and H2C204, choline-like effect of blood or urine, with or without and decreases the inorg. P 04"' and Ca. Ingestion eserine (I), on leech-muscle is not considered to be due of H20 alone decreases the serum-sugar, Ca, Mg, to acetylcholine (II), since luemolysed blood without H2C204, and inorg. P 04"'. J. N. A. X IX (6) 94 BRITISH CHEMICAL ABSTRACTS.— A.
Sodium, potassium, calcium, and inorganic 1935, 179, 743—747).—The blood is introduced into phosphate of blood during prolonged fasting. a capillary tube, kept at const, temp., and the course I). T orrisi (Arch. Fisiol., 1935, 34, 259).—In the of coagulation followed by its movements in response serum of dogs and rabbits, during prolonged fasting, to unilateral pressure. Rabbits’ blood (ear) gave there is a progressive decrease in Na to < 21% of vals. of 3—3-5 min. for the initiation and 4— 5 inin. normal. The other elements show irregular and minor for the completion of coagulation. F. 0. H. changes. N u tr. A b s. (m) Absence of correlation between lacto-gelific- Distribution of different fractions of acid- ation and protein disequilibrium of blood- soluble phosphorus in the blood of dogs during serum . G. L efrou and L. A u ffret (Compt. rend. intermediary metabolism, as observed on an Soc. Biol., 1935,120, 614—616).—There is no evidence empty stomach after introduction of glucose and of correlation between the time of lacto-gelification radon. A. A. A r apova (Aim. Roentgenol. Radiol. and the degree of protein disequilibrium. R. N. C. U.S.S.R., 1934, 13, 338— 351).—Fractions of ortho- and pyro-phosphates and sol. and insol. phosphoric Haemostatic effect of ascorbic acid in haemat- esters occur in blood-vessels. No creatininephos- uria. A. K o r a k y i and A. B e n t s ä t h (Orvosi Heti- phoric acid is found in blood. The sol. ester fraction lap, 1935, 79, 378— 379).—In some, but not in all, (I) is the most changed in its passage through organs, cases the haemostatic action was accompanied by and also after introduction of glucose. Introduction changes in composition of protein fractions in blood- of Rn increases (I) in arterial blood and in eliminations plasma. Ch . A b s . (p) of the kidney. Ch . A b s. (p) Effect of Röntgen rays on the appearance of Conductivity of blood in the wave-length complement-fixing bodies in the blood. I. P. region 6—25 m . F. Gr a u l (Ann. Physik, 1935, [v], M ischtschenko and M. M. F om enko (Ann. Roent 24, 326—348).—The conductivity of ox, pig, and genol. Radiol. U.S.S.R., 1934, 13, 327— 336).— human blood shows no change with frequency between Complement-fixing bodies appeared in blood following XX 6 and 20 m .; at 20—25 m. it decreases, but the X-irradiation. Ch . A b s . (p) effect is detectable only with centrifuged blood. ‘ * Serum sickness ' ’ in rabbits following the Its variation at 13-6 m. with time of centrifuging and intravenous injection of various foreign sera: with the low-frequency conductivity is in accord with relation to precipitins. D. K horazo (J. Immunol., theory. ' “ J. W. S. 1933, 25, 113— 120).—No differences in the rate of Effect of pressure on the hydrogen-ion con precipitin formation or disappearance of injected centration of blood : use of glass electrodes. antigen from the blood could be associated with A. T h iel and H. Gemsa (Biochem. Z., 1935, 282, “ serum sickness.” Ch . A b s . (p) 146— 156).—At 37°, no change in the p n of cattle blood occurred when it was subjected to N2 pressures Precipitin reaction between type III pneumo up to 100 atm. W. McC. coccus polysaccharide and homologous anti body. II. Conditions for quantitative precipit Amphibian metamorphosis. X. Hydrogen- ation of antibody in horse sera. III. Theory ion concentration of the blood of anuran larvae of the reaction mechanism. M. H eidelberger during_ involution. 0. M. He lit (Biol. Bull., 1932, and F. E. K e n d a ll (J. Exp. Med., 1935, 61, 559— 63, 405— 418).—Blood-pu shows a steady decline 562; cf. A., 1930,1608).—II. The customary immuno (7-50-> 7-18) in progressive stages of metamorphosis. logical procedure (2 hr. at 37° and overnight in oil) Ch . A b s. (p) does not permit establishment of equilibrium, or max. Calcium salts and blood coagulation. J. pptn. of antibody-N. Analysis should be carried Matusevich (Semana med., 1935, 1, 1021— 1024).— out at 0° and materials kept cold for < 24 hr. Oral administration of CaCl2 has no action, but The chemical method for determining antibody is an Ca lactate-f-NH4Cl shows a considerable effect with accurate measure and does not include non-sp. a max. after 8 days. Injected CaCl2+Ca gluconate protein. is effective in 2— 4 hr., with a return to normal after III. Antibody solutions and sera probably contain 24 hr. Ch. Abs. (p) > one antibody reactive with S III. The reaction Acceleration of blood coagulation by acidic between the sp. polysaccharide and homologous substances, especially pectin. 0. R iesser [with antibody is represented as a bimol. reaction, followed A. N agel] (Arch. exp. Path. Pharm., 1935, 179, by a series of competing bimol. reactions dependent 74S—760).— Oral and parenteral administration of on the relative proportions of the components. pectin (I) to rabbits accelerates the rate of coagulation, Ch . A b s . (p) the effect persisting for 4— 5 hr. Galacturonic and Anaphylactogenic properties of milk. Im- lactic acids, AcOH, and, in small intravenous doses, munochemistry of the purified proteins and HC1 have a similar action. Intramuscular injection antigenic changes resulting from heat and of the neutral salts, in-vitro addition of the acids, or acidification. B. R a t n e r and H. L. Gr u e h l injection of (I)-aetivated blood [in which (I) is not (Amer. J, Dis. Children, 1935, 49, 287— 306).— Casein detectable] into other animals has no effect. The and lactalbumin fractions of milk-proteins retain mechanism of the phenomenon is discussed. antigenic characteristics after drying, acidification, F. 0. H. superheating, or evaporation. The whey fraction Determination of velocity of blood coagulation. shows a marked loss of antigenic properties after 0. R iesser and A. N ag el (Arch. exp. Path. Pharm;, evaporation or superheating. Loss of antigenic X IX (b, c) BIOCHEMISTRY. 95
properties of heated milk is due to coagulation of lipin contents of various organs. S. H ongo whey proteins. Ch . A b s . (p) (Sei-i-Kwai Med. J., 1934, 53, No. 5,1— 22, 23—28).— Anaphylactogenic properties of malted sugars I. On a dry-wt. basis organs of scorbutic guinea- and maize-syrup. B. R a t n e r and H. L. Gr u e h l pigs contained more lecithin (I) (notably in testicles, (Amer. J. Dis. Children, 1935, 49, 307— 317).— muscle, and kidney, but not liver and lungs) and more Allergy to carbohydrate food is due to added protein free cholesterol (II) (especially lungs, intestine, constituents rather than to the carbohydrate itself. and kidneys) than normal animals. Intestine and Malt extracts and the barley-malts from which they kidneys have more total (II). The ratio of (I) : (II) are derived are highly anaphylactogenic and react in intestine, kidney, and muscle is smaller in scorbutic specifically with hordein. Maize-syrups and pure animals. “ dextrimaltose ” sugars are not anaphylactogenic. II. Increased oxidation in rabbits injected with Addition of wheat germ or dried milk to non-anaphyl- thyroideum is generally associated with a decrease in actogenic converts them into active substances. fat acids (III) and other lipins in various organs. Ch. Abs. (p ) In muscle (III) increased. In liver there is an increase Protein reaction for the more definite identi in unidentified unsaponifiable substance without fication of blood-stains. V. Tuma (Chem. Listy, change in other lipins. Removal of thyroid increases 1935, 29, 313— 316).—Agglutination and pptn. re (III) (except in the spleen) and other lipins without actions serve to distinguish dried human from animal affecting the ratios in the various organs. blood-stains, and to determine the serological group Ch. A bs. (p) to which the blood belongs. R. T. Eel oil. I. Fatty acids. T. O no (J. Agric. Chem. Soc. Japan, 1935, 11, 773—780).—The oil Test for occult blood, especially in urine. contains myristic, palmitic, and stearic acid, a satur W. J. Sto n e and G. T. B u r k e (J. Amer. Med. Assoc., ated acid, m.p. 57— 58°, probably the unsaturated 1934, 102, 1549— 1550).—The sediment from 15 c.c. acids, C14H2602, CjgHgoO.,, CjgH^Oo, G4gH2202 of centrifuged urine is treated with 2 drops of a 1% (iso-acid), C1sHor0 2, C,nH,202, C22H„,Oa, and possibly solution of tolidine in MeOH and 3 drops of a 1 :1 C10H2602, C20H;0O2, and CI6H2402 fh o Carr-Price mixture of AcOII and H20 2. A greenish-blue reaction is negative and is very weak even with the colour lasting 1 min. develops in the presence of liver extract. W. McC. 100 blood-cells per c.c. of sediment. Ch . A b s . (p) Renal threshold for glucose in man. J. W. Determination of calcium and phosphate con Sh errill and E. M. MacK a y (Arch. Int. Med., tent of bones. C. K. D eisc h e r and W. M. M cN abb 1935, 56, 877—883).—The average vals. found for (Analyst, 1935, 60, 750—751).— Ca is pptd. as diabetics and normal persons were 149 and 128 mg. CaC204, which is titrated with KMn04. P is pptd. per 100. c.c., respectively. It is suggested that the as NH4 phosphomolybdate, which is dissolved in “ normal val.” is misleading and a normal average excess of standard NaOH. The excess of NaOPI is should not be given. H. G. R. titrated with HC1. J. S. A. Distribution of glycogen in the regions of the Fluorine content of bones and teeth. R . K l e - amphibian gastrula; micro-determination of m e n t (Ber., 1935, 68, \B], 2012— 2019).—Examination of the bones and teeth of many animals leads to the glycogen. N. G. H e a t l e y (Biochem. J., 1935, 29, following mean vals. for F in the inorg. matter : 2568—2572).—Tissue is fixed in EtOH and digested land mammals, 0-05%; sea mammals, 0-55%; with K O H ; glycogen (I) is pptd. with EtOH, hydro land birds, 0-11%; sea birds, 0-32%; fresh-H,0 lysed with acid, and the sugars formed are determined fish, 0-03%; sea-H20 fish, 0-43%. The differences by the Linderstrom-Lang method (A., 1931, 1455). between land and sea animals are attributed to During gastrulation of the embryo of Triton alpestris the F content of sea-H20 exceeding that of fresh the quantities of (I) are in the order : dorsal ecto H20. F replaces OH in the hydroxyapatite (I) of derm > ventral ectoderm > yolk endoderm. During bones and teeth with formation of mixed crystals invagination there is a loss of approx. 35% of (I) to a greater extent with sea than with land animals; in the invaginating cells. H. D. this is still more marked in fossil bones. The hardness Effects of repeated injections of glucose on of tooth enamel is explained by a small content of the muscle-glycogen of the frog under normal org. matter which causes a greater development of conditions. A. M oschtni (Compt. rend. Soc. Biol., the crystallites of (I). F is probably without bio 1935,120, 531— 533).—Repeated injections of glucose logical significance. H. W. (I) increase muscle-glycogen (II), the increase de Lipin content of the jelly of Wharton. E. M. pending on the total amount of (I) given when (II) B o y d (J. Biol. Chem., 1935, 111, 667— 669).—The is low, but when (II) reaches high vals. the increases mean lipin content of the jelly is 0-209%, which is < produced by further doses of (I) are smaller, until a that of any other body-tissue. This agrees with steady max. is attained. R. N. C. Bloor’s hypothesis that tissues of low physiological Effects of repeated injections of glucose on activity have a low lipin content. E. A. H. R. the muscle-glycogen of the frog, in different Lipins. I. Amounts of lecithin, total and free experimental states. A. M o sc h in i (Compt. rend. cholesterol, and cholesteryl ester in the organs Soc. Biol., 1935, 120, 533—535).— Glucose (I) in of guinea-pigs fed on a vitamin-C-free diet and creases' muscle-glycogen (II) in frogs with muscles the ratio among these lipins. II. Relationship atrophied by prolonged fasting, to the same extent as between oxidation in the animal body and the in normal frogs. Section of the sciatic nerve has no it 96 BRITISH CHEMICAL ABSTRACTS. A. X IX (c) immediate effect, but when degeneration of the foot Cryolysis, diffusion, and particle size. II. muscles sets in, the amount of glycogen taken up is Investigations with m yosin.—See this vol., 28. decreased. (II) falls after pancreatectomy, but (I) Polysaccharoproteins. VI. State of glycogen injections still cause deposition and mask this effect. in muscle. II. E. M. M is t k o v s k i, A. St il l e r , R. N. C. and A. Z ism a n (Biochem. Z., 1935, 281, 231— 237; (A) Determination of fermentable carbohydr cf. A., 1935, 1004).—Part of the glycogen (I) in the ates in rabbit liver. (B) Isolation of a reducing press-juice of rabbit, dog, and frog muscle exists dextrin. C. B. P urves (Quart. J. Exp. Physiol., irreversibly bound to myosin (II) and globulin-X 1935, 24, 383—389, 391—395).— (a ) The fermentable (III). The amylase present degrades added (I) carbohydrate in liver could not be accounted for (at < the expected rate), but not the native bound (by 25%) as glycogen and free sugar. The presence (I), which also resists attack by ptyalin (IV). When of a polysaccharide insol. in 90% EtOH, sol. in the bound (I) is removed by alkaline hydrolysis it is 32% EtOH, and destroyed during the glycogen attacked at the usual rate by amylase. The rate of determination, is postulated. hydrolysis of (I) by (IV) is reduced [extent of re (b ) The fermentable carbohydrate isolated was production oc concn. of (II)] by adding (II), but appears bably a mixture of dextrins containing free Cu-re- to be increased by adding (III). W. McC. ducing groups. Ch . A b s . (p) Protamines. VI. (i) Acid hydrolysis of sal- Colorimetric and iodometric determination of m ine. M. Y a m a g a w a and T. N is h iz a w a (J. Imp. glutathione. K. U h len bro o ck (Z. physiol. Chem., Fisheries Inst. Japan, 1934, 30, 97— 115).—-Salmine 1935, 236, 192—196; cf. A., 1935, 793; Fujita et prepared from Oncorhyncus kela is identical with that al., ibid., 772).—For deproteinisation sulphosalicylic from Rhine salmon. All (NH2)r acids are liberated acid is much better than H P03 and KCN should be by hydrolysis with 4iV-H2S0.1 for 8 hr., leaving a replaced by Na2C03 in the method of Bierich et al. residue of di- and tri-arginide. Ch. A b s . (p) (A., 1933, 523), the apparatus of Lange (ibid., 44) Nature of the substance in fish meat which being used for measurement of the colour. Solutions gives formaldehyde-like reactions. II. Squid should contain, per 100 c.c., 4-5— 100 mg. of reduced (Lolic/o bleekeri, Keferstein) from Hokkaido. glutathione (if < 4-5 mg. present larger vol. to be used). Y. H attori and T. H aselbe (J. Pharm. Soc. Japan, Results agree well with those obtained by titration with I for heart, muscle, lung, blood, brain, spinal 1934, 54, 1081— 1090).—The substance is identified cord, and spleen, but not for liver, kidney, and thymus. as NMe30. Ch . A b s . (p) The last two contain substances which rapidly attack Nuclein metabolism. VI. Constitution of the SH-compounds, and hence, with these organs, the nucleic acids. K. M a k in o (Z. physiol. Chem., 1935, colorimetric method cannot be applied. W. McC. 236, 201— 207; cf. A., 1935, 1003).—Samples of yeast-nucleic acid (I) differ greatly in regard to the Bound water and phase equilibria in protein ease with which they are degraded by alkali, there systems : ovalbumin and muscle. T. M oran being no relation between age of sample and ease of (Proc. Roy. Soc., 1935, B, 118, 548— 559).—The hydrolysis. The reaction of purified nucleosides with bound H20 of native (I) and denatured (II) ovalbumin H3B03 indicates that the deoxyribosides from thymus- at various temp. < 0° is dependent on the activity of nucleic acid (II) have the furan ring structure, and H20. The chemically bound H20 is approx. 0-26 g. consequent changes are made in the proposed structural per g. of protein for both (I) and (II), and for (I) the formulae for (I) and (II). The criticisms of Klein more loosely held H20 is > for (II) at the higher et al. (ibid., 510) are refuted. W. McC. activities. The bound H20 of muscle at intermediate and high H ,0 activities is approx. 0-40 g. per g. of Adenine nucleotide in tissues. II. In heart dry solid. The eutectic temp, of muscle is about muscle. K. L o h m a n n and P. S c h u ste r (Biochem. -37-5°. F. A. A. Z., 1935, 282, 104— 108; cf. A., 1934, 1020).— Most of the adenine nucleotide (I) of rapidly removed Annelid muscle. I. Taurine in Audoninia calves’ hearts occurs as adenylpyrophosphoric acid. spirabranchus, M oore. A. C. K urtz and J. M. A small amount of (I) is isolated as adenosinediphos- L uck (J. Biol. Chem., 1935, 111, 577—584).— 3% phoric acid and adenylic acid. W. McC. of taurine (I) was found in the muscle of A. spira branchus, Moore, traces were found in Nereis brandti, Pigments of hair. H. Z w ic k y and F. A l m a s y and none in Glycera rugesa, Lumbricus sp., Urechis (Biochem. Z., 1935, 281, 103— 110).— Spectrophoto- caupc, and Phoronopsis liarmeri. The possible function metric examination of alkaline extracts of white, of (I) in maintaining the osmotic pressure of the muscle red, and black horse- and mule-hair indicate that, is discussed. H. D. whilst two different pigments occur in the black hair (from different horses), one of them is indistinguish Selenium in proteins from toxic foodstuffs. able from that which occurs in the red hair and in the III. Removal of selenium from toxic protein hair from the darker parts of dappled horses. hydrolysates. E. P. Pa in t e r and K. W. F r a n k e W. McC. (J. Biol. Chem., 1935, 111, 643— 651).—The nature Pigments of the bull-frog retina. G. W a ld of the So complex in toxic proteins is investigated. (Nature, 1935, 136, 832— 833).—The substances and When the toxic proteins are hydrolysed, the Se may processes found in the retina and pigment epithelium be extracted with BuOH. All the Se is completely of Rana catesbiana are identical with those in species pptd. by HgCl2, but only partly by phosphotungstic of frogs previously examined (A., 1934, 913). The acid and by Cu and Ag salts. H. D. retina contains varying amounts of retinene (I) and X IX (c, d) BIOCHEMISTRY. 97
vitamin-X (II). With SbCl3, (I) yields a sharp non-toxic to cows, and when introduced into their absorption band at 662— 666 mjr and not at 655 nqr. diet provokes an increase in Ca in the milk; its with Dark-adapted retinas contain only a trace of (II), which drawal causes Ca to return to normal. The coagul can be extracted in the dark by benzine without ation reaction with EtOH becomes positive when injury to the visual purple. Light bleaches the latter Ca is high. Milk that is coagulated by EtOH is not to visual yellow, after which benzine extracts a large coagulated by boiling when the normal % of Ca in amount of (I). Destruction of the visual purple in the ash is increased by 4-6. R. N. C. the dark with CHC13 also liberates (I). Visual Effect of electrolytes on the synthesis of yellow thus appears to be simply free (I) (cf. be. cit.). lactose. D. Mic h l in and T. F etissova (Biochem. The (I) of bleached retinas is converted quantitatively Z., 1935, 2 8 2 , 26—31; cf. A., 1934, 1033).— The into (II) by a thermal process in approx. 1 hr. in light synthesis of lactose (I) in mammary gland is reversed or in darkness at 25°. In the isolated retina, (II) when hydration of the tissue occurs. Added electro- is the final product of the bleaching and fading re lytes (CaCl2 > LiCl, NaCI) check hydration and actions, but in the intact eye (II) is resynthesised prevent shifting of the equilibrium, hence increasing to visual purple, thus completing the visual cycle. the .amount of (I) produced or preventing reversal of L. S. T. the reaction. K2S04 acts in the same way, but Carotenoids of Itana esculenta. 0. B r u n n e r NH4CNS and sometimes KC1 check the synthesis. and R. S te in (Biochem. Z., 1935, 2 8 2 , 47—50).— The synthesis is inhibited at pa 9-5, but not at 4-8. The liver, skin, fat glands, and ovaries contain W. McC. (3-carotene (I) and esterified lutein (II); the ovaries Mineral constituents in fresh and canned contain also free (II). About half of the total (I) m ilk. A. J. H erm an o and S. Clar avall (Philip and (II) occurs in the ovaries and about 25% in the pine J. Sei., 1935, 57, 323—328).—Ca, P, Fe, fat, liver. In liver, skin, and ovaries the contents of protein, and lactose have been determined in fresh (I) and (II) are about equal, but the (II) content of and canned samples of carabao’s, goat’s, and cow’s the fat glands is much < the (I) content. milk. H. G. R. W. McC. Cow’s milk in Manchuria and Mongolia. TV. Visual purple. 0. B r u n n e r , E. B a r o n i, and Non-protein nitrogenous substance. M. S u giu ra W. R le in a u (Z. physiol. Chem., 1935, 2 3 6 , 257— (J. Orient. Med., 1935, 2 2 , 60).—Total N, non-protein- 262).— [3-Carotene, obtained from the retina by N, and protein in the milk from Manchu Mongol extraction with MeOH, is adsorbed by A1203. The cows were < in milk from Japan, America, and light-absorption curve of the adsorbed material is Europe. Free NH3 and urea showed considerable similar, especially in the long-wave zone, to that of variations, but the uric acid and purine bases were the visual purple. The retina contains no xantho- const. Nutr. Abs. (m) phyll. W. McC. Methylene-blue reduction test: its efficiency Accumulation of acid dyes in the silkworm and interpretation under Philippine conditions. by different tissues according to the route of J. B. U ichanco (Philippine J. Sci., 1935, 57, 295— application. P. P. Grasse and L. L esperon 319).—The test has been compared with the standard (Compt. rend., 1935, 2 0 1 , 618— 620).— Certain cells plate method on samples of carabao milk and is of the silkworm are stained by Congo-red, trypan- recommended for use with slight modification to suit blue, trypan-red, and NH4 carminate, but the results local conditions. H. G. R. depend on whether the dyes are injected or administered orally. W. 0. K. Determination of amylase in milk. M. M a n i- c a t id e , B r atescu , and M. P opa (Compt. rend. Soc. Progress of lactation in relation to the milk Biol., 1935, 1 2 0 , 657— 658).—Human colostrum yield and the butter-fat percentage of milk pro contains 1024—2048 Wolgemuth units of amylase duced by cows of the Shorthorn type. C. D. (I) per e.c., normal milk, 250 units (average). Cow's’ Ox l e y (J. Dairy Res., 1935, 6, 113— 120).—The milk contains scarcely any (I). (I) is destroj'ed by standard error of the mean of observations of milk boiling or pasteurisation. R. N. C. yields and % of butter-fat in milking records is determined. The time lag between the period of Extractives of peripheral lymph. S. A sa k u m a max. yield and min. % of butter-fat is discussed. (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, A. G. P. No. 4, 136— 137).—Et20-sol. matter in lymph from Influence of diet on the antirachitic potency the popliteal gland and of blood-serum from leg veins of rabbits averaged 285-8 and 244-6 mg. per 100 g. of co w ’s m ilk. B. H. T hom as and C. Y. Ca n n o n (Iowa Agric. Exp. Sta. Rept. on Agric. Res., 1934, of fluid, respectively. Ch . A b s . (p) 49).—Irradiated dried moulds may be used as a Hydrogen-ion concentration of peripheral supplement to rations for increasing the vitamin-D lym ph. M. A r a k i and G. H 5 jo (Arb. dritt. Abt. content of milk. The response is most marked Anat. Inst. Univ. Kyoto, D, 1934, No. 4,132— 134).— during the first few days of feeding and subsequently The pH of lymph from the popliteal gland of rabbits declines. The efficiency of transfer of -D from diet (7-90) was low-ered by injection of strychnine and to milk is very low. Ch . A b s . (p) increased by that of veratrine. Ch . A b s. (p) Effect of diet on the milk : chemical modific Carbon dioxide content of lymph under differ ation and sensitisation to the alcohol test. L. ent conditions. G. H ojO (Arb. dritt. Abt. Anat. E ch enique and B. Suar ez (Compt. rend. Soc. Biol., Inst. Univ. Kyoto, D, 1934, No. 4, 140— 144).— 1935, 1 2 0 , 570—572).—Xanthium cavanilliense is Lymph-C02 increased when rabbits were fastened 98 BRITISH CHEMICAL ABSTRACTS.— A. X IX {d) immovably. Vals. for efferent lymph from the 80—89, 152—160).—I. Injection is immediately popliteal gland were similar for both sides; those for followed by an increase in wt. and in Ca and P contents thoracic duct and intestinal lymph were markedly in the lymph gland. < that in the legs. Intravenous injection of KCN II. The Ag content of the gland increased rapidly and injection of pilocarpine hydrochloride by the ear to a max. and subsequently declined. Ag is soon vein lowered the CO, content. Adrenaline had no resorbed in the lymph passage, but part remains stored action. " Ch . A b s . (p) in the gland. Carbon dioxide content of peripheral lymph III. Injected starch was detected in the gland up .to 4 hr. after treatment. Resorption was complete of rabbits. K. T su ji (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 135).—Average vals. in 5-5—6-0 hr. Reducing substances in glands after for efferent and afferent lymph were 44-33 and 46-64 hydrolysis reached a max. soon after injection. The max. for reducing substances before hydrolysis was c.c. per 100 parts (?), respectively. Ch. A b s . (p) reached somewhat later. Ch. A b s. (21) Sulphates in lymph. I. II. Sulphates in peripheral lymph after intravenous injection of Lymph obtained by the ‘1 Brunnenlymph ’' acpieous phenol solution. S. M a s u d a (Arb. dritt. method of Watanabe. Y. I w a k i (Arb. dritt. Abt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 22— Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 7— 14).— 24, 25—28).—I. Small amounts of SO.," occur in Physical and chemical properties of the lymph are serous fluids, chyle, and blood. Onty ethereal S04 examined. Incoming lymph has the same physical (I) occurs in lymph. The (I) content in peripheral properties as that from lymph glands. lymph is > that of chyle, and, in turn, > in blood. Ch . A b s . (ji) II. Injection causes an increase in (I) content of the Decomposition of atropine in the peripheral lymph. Ch. A b s . (p) lymph of the rabbit. S. K ir iy a m a (Arb. dritt. Lactic acid in peripheral lymph. Y. HCjo Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 68— (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, 79).—Decomp, of atropine sulphate by lymph occurs No. 4, 115— 121).—Average vals. for efferent and at room temp! and at 37°, but not at low temp. afferent lymph were 0-795 and 0-673 mg. per 100 c.c., Outflowing lymph was more active than inflowing respectively. Vals. wore decreased by injection of lymph. Ch . A b s . (p) aq. NaF, Nal, or CH2I-C02H. Ch . A b s . [p) Alteration of lymph after death of animal. Lipase of peripheral lymph. Iv. I sh in o (Arb. Y. I w a k i (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, D, 1934, No. 4, 99— 111).—Physical and chemical 48—52).—The lipase occurs in the inflowing and out changes during 2 hr. after death are recorded. flowing lymph of the popliteal gland, there being Ch. A b s. (¡j) usually more in the outflow. It is not affected by Lymph in experimental pneumonia. J. S. neutral salts or by weakly acid or alkaline media. D a w s , jun., and A. J. D elario (J. Lab. Clin. Med., Ch . A b s. (p) 1935, 2 0 , 460— 467).—The increase in lactic acid (I) Total protein, globulin, and albumin fractions content of lymph and the decrease in C02 content of peripheral lymph. B. N a k a d a (Arb. dritt. tend to compensate for the loss of Cl'. The increase Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 112— in (I) is the more important factor. The 0 2 tension HI)-—Vals. per 100 c.c. of lymph were: total protein, of lymph is > doubled by 0 2 therapy. 2123 mg. in efferent and 1890 mg. in afferent lymph, Ch . A b s . (p) globulin, 757 and 715, albumin, 1689 and 1599 Relationship between sugar and urea contents mg., respectively. Ch . A b s. (p) of the blood and spinal fluid. J. N. C u m in g s Autolysis of lymph. I. Reducing power. M and E. A. Carm ich ael (Brain, 1934, 5 7 , 338—347).— Levels of sugar and urea in lumbar fluid do not rise F u k u o ka (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 92—93).—The reducing power in association with the normal rise in the blood. varied with the individual rabbit, reached a max. on Only in abnormal conditions does the ventricular the 2nd day of autolysis, and subsequently declined. fluid-sugar increase with a rise in blood-sugar. Ch. Abs. {p) Ch . A b s . (p) Fibrin content of lymph. B. N a k a d a (Arb. Proteolytic power of saliva. I. Proteolysis dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, in saliva. II. Action of human saliva on pro 63—64).—Average vals. were 276-7 mg. of fibrin per teins. P. F a n t l and J. W e ih m a n k (Biochem. Z., 100 c.c. of efferent, and 261-1 mg. for afferent, lymph. 1935, 2 8 1 , 37—41, 42—48).—I. The portion of human saliva which does not pass through filters Ch . A b s' (p) Non-protein-nitrogen of vascular lymph. S. contains enzymes which degrade the proteins of the Asakuma (Arb. dritt. Abt. Anat. Inst. Univ. Kyoto, saliva. The amount of enzymes present varies greatly D, 1934, No. 4, 46— 47).—The average non-protein-N from person to person, but remains almost const, content of lymph was 0-504 and of blood-serum in the individual. 0-513%. C h . Abs. (p) H- Proteins (hen’s egg, fibrin from human and horse blood) denatured by boiling or by pptn. at room temp, Resorption in the lymph passage. I. Re are not attacked by the enzymes of the saliva. sorption of yatoconin by subcutaneous applic 0 . W .M cC. ation. II. Resorption of colloidal silver. III. Significance of iron and copper in human Resorption of starch. M. K o sa k a (Arb. dritt. bile. E. S. J u d d and T. J. D ry (J. Lab. Clin. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 15—21 Med., 1935, 2 0 , 609—615).—The Fe content of liver X IX (d-f) BIOCHEMISTRY. 99
ranged from 0-031 to 1-68 and that of Cu from 0-063 yellow when fresh, but extracts from urines of the first to 1-07 mg. per 100 g. Cu is normally excreted by period of lipuria are decolorised by light; those from liver. Fe is secreted in bile and resorbed from the the second period are unaffected. The fat is free intestine: Ch. Abs. (p) from N and P, and the acid contained in it is chiefly Microchemical study of human biliary calculi. oleic acid. R. N. C. T. W. H a y (J. Biol. Chem., 1935, 111, 689—697).— Biochemistry of allantoin. I. Effect of leuco- There is no essential difference in chemical composition lysis on allantoin excretion. II. Amounts of ehole between cholesterol-pigmont-Ca stones and allantoin in urine of various animals. III. sterol-pigment stones. E. A. H. R. Effect of thyroxine ingestion on allantoin Concentration function of the gall-bladder : excretion. T. Miy a h a r a (Sei-i-Kwai Med. J., 1934, biliary glutathione. G. B altac ean o and C. V a s i- 5 3 , No. 8, 9—27, 28—41, 43— 48).—I. When a l iu (Compt. rend. Soc. Biol., 1935,1 2 0 , 666—668).— leucopenia is produced in rabbits by injection of a The concn. of the glutathione in the vesical bile is phagolytic serum of goat, excretion of allantoin (I), > in the hepatic bile. R. N. C. uric acid (II), and total N (III) is increased. The ratios of (II) : (III) and of (I) : (III) also increase, Bile acids. XLVII. C21H3GO10N2.—See this vol., whilst the uricolytic index is unchanged. The chief 74. end-product of purine metabolism is (I) with (II) Constituent of bile pigm ent. X IV .—See this as intermediary. vol., 86. II. Data are given for rabbit, guinea-pig, dog, pig, Gastric secretion. VI. Action of pilocarpine ox, rat, sheep, goat, and horse. on the secretion of a transplanted gastric pouch III. Injection of thyroxine (IV) increases the without Auerbach's plexus. E. K le i n (Arch. excretion of (III) and (I) and decreases that of (II). Surgery, 1935, 3 0 , 277— 283).—Pilocarpine hydro The uricolytic index is increased. (IV) increases chloride (I) in 7-mg. doses stimulates secretion of the oxidation of (II) to (I). Ch. A b s. (p) free acid. Smaller doses stimulate, pepsin secretion Action of colloidal substances on crystallis only. Atropine (1 mg.) inhibits secretion caused by ation, with reference to the problem of stone (I) but not that produced by histamine. C h . A b s . (p) formation. S. v o n K ( it h y (Magyar orvosi Arch., Copper content of urine of normal children. 1934, 3 5 , 289—297; Chem. Zentr., 1935, i, 2209).— A. Ross and I. M. R a b in o -w itch (J. Biol. Chem., Urine and bile are to be considered as supersaturated 1935, 111, 803— 805).— Cu is a const, constituent of solutions, in which normally crystallisation or con- urine and the amounts found ranged between 0-04 and crement formation should begin, but the colloidal 0-52 mg. per litre. J. N. A. or surface-active substances of high mol. wt. exert Detection of dinitrophenol and its derivatives a protective action. Model experiments with Pbl2 indicate the mechanism of this action of the colloids in urine. A. M e y e r and H. D r u t e l (Bull. Soc. Chim. biol., 1935, 1 7 , 1455— 1461).—Interference by to be by selective adsorption in stages. R. N. C. skatole, which, like 2 : 4-dinitrophenol (I), gives a Determination of lead in excreta and tissues. pink coloration in the Meyer test for (I), may be R. A. K e h o e (Amer. J. Clin. Path., 1935,5,13— 20).— avoided by using Hg(NO,)2 as defecating agent and Methods of prep, and ashing of samples are discussed extracting (I) with Et20 before reducing with Zn in and analytical methods are compared. For Pb in AcOII. A. L. tissues spectrographic methods are the most satis Urinary diastase. F. E c k a r d t (Deut. Arch, factory. Ch . A b s. (p) klin. Med., 1935,1 7 7 , 517—526).— Diastase, expressed Effect of external factors on perspiratio in- as g. of starch hydrolysed by 1000 c.c. of urine at sensibilis. A. v a n H a r r e v e l d , B. W. Gr u t - 37° in 3 hr., ranged from < 8 to > 600 (in adolescents t e r in k , and A. K. M. N oyons (Biochem. Z., 1935, 10— 40, in old age < 8 to 20); the mean val. for all 2 8 1 , 1—26).— In man the phenomenon is practically ages is about 20. The val. was uninfluenced by sex, unaffected by a ± 3 5 % change in the humidity and but varied inversely with food consumption. Vais, a change of temp, within the range 20—28-5° or by in many different types of disease are given. changes in the thickness of the clothing. Only after N u t r . A b s. (m) attainment of equilibrium are trustworthy results Variations in urinary reducing substances of obtained. The val. varies greatly in the individual two normal dogs maintained on bread diets. at different times with const, atm. conditions. E. P. Latjg and T. P. Nash, jun. (J. Nutrition, 1935, W. McC. 1 0 , 81— 92; cf. A., 1935, 513).—Significant variations Changes in hydration of serum-colloids as a in the total, fermentable, non-fermentable, and general feature of a disease. K. Schulhof hydrolysable reducing substances of urine are corre (Trans. Illinois State Acad. Sci., 1934, 2 7 , 80).— lated -with particular bread diets. A. G. P. Measurements of n and vj of serum are utilised to Lipuria in dogs experimentally deprived of assess the vol. occupied per g. of protein. their dorso-lumbosacral marrow. H. H e r m a n n , Ch . A b s. (p) J. D e c h au m e, and J. V ia l (Compt. rend. Soc. Biol., Azotaemia and elevation of the alkaline reserve 1935, 120, 648—649).—Removal of the dorso-lumbo- in course of anuria. R. H u g u e n in , R. T r u h a u t , sacral marrow induces an immediate increase in fat and C. Sa n n i6 (Compt. rend. Soc. Biol., 1935, 120, excretion, which disappears after 3—5 weeks, reappears 717—719).—Blood-urea (I) is increased and the alkaline after 3 months, and then persists. Et20 extracts are reserve is lowered in anuria. NaHC03 increases the 100 BRITISH CHEMICAL ABSTRACTS. A. X IX (/) alkaline reserve without affecting (I). Total Cl and results obtained in the treatment of cancers by in the corpuscular/plasma-Cl ratio fall. R. N. C. jections of mixed complex Fe and Ca salts of ascorbic acid are better than when Fe-Na salts are used (cf. Influence of 3 : 5-di-iodotyrosine on experi A., 1935, 1401). J. L. D. mental arteriosclerosis. A . O g a t a , S. Sa n o , and K. Mitsui (J. Pharm. Soc. Japan, 1934, 54, 248— Experimental tumours produced by decreased 272).—The lipin content of blood was increased by doses of coal tar. General action of the carcino feeding lanoline (I). Substitution of 3 : 5-di-iodotyro genic agent. L. M. Sc h a b a d (Acta Cancrologica, sine (II) hastened the restoration to normal lipin 1934, 1, 56—77).—The carcinogenicity of tar is due levels. The ratio of Et20 extract to body-wt. for to a general rather than to a local action. mice fed with (I) indicates the decrease in wt. following Ch . A b s . (p) administration of (II) to result from a decline in lipin Effect of certain polycyclic hydrocarbons on content. Ch . A b s. (p) the growth of the Jensen rat sarcoma. A. H a d d o w (Nature, 1935, 136, 868—869).— Intra- Proteins of cancerous cells. C. A c h ar d and M. peritoneal injections of colloidal preps, of 1 : 2 : 5 : 6- P iettre (Cornpt. rend., 1935, 201, 751—753; cf. A., 1935, 376).—Renal sarcomas of the ox and horse dibenzanthracene, 1 : 2-benzpyrene, 5 : 6-cyclo- contain lipins (1-38—2-95%, largely cholesterol), pcnteno-1 : 2-benzanthracene, and 1 : 2-benzanthra- globulins (2-6— 4-2%) from which amides (048— ccne, but not anthracene and phenanthrene, produce 0'67%) are isolated, and albumins (0-5— 0-7%), marked inhibition of growth of the implanted tumour which, although exhibiting the general properties in rats. Carcinogenic substances, like X-rays, may of serum-albumins, possess a much smaller mol. thus act primarily by producing a certain type of (cf. A., 1933, 730). The residue insol. in HaO affords inhibition in the activity of the normal cell. myxoprotein. J. L. D. L. S. T. The Costa reaction (200 cases). R. H. K am p- Heavy water and tumour growth. W. H. m e ie r (J. Lab. Clin. Med., 1935, 20, 531— 538).— W oglom and L. A. W eber (J. Amer. Med. Assoc., The ppt. formed in blood-serum by addition of 1934, 102, 1289— 1290).—D.,0 had no effect on procaine, Na citrate, and CH20 occurred in 70% mouse sarcoma. Ch . A b s . (p) of cases with pulmonary tuberculosis and in 90% Phosphorus in the blood-plasma of hens of cases with malignant tumour. None appeared suffering from sarcoma. F. P e n tim a lli and G. in syphilis. Ch . A b s . (p) S chmidt (Biochem. Z., 1935, 282, 62—73).— The Calcium and inorganic phosphorus of blood- amounts of total, lipoid, and acid-sol. P in the plasma serum in dental caries. C. G. K e r l e y , E. J. of hens suffering from Rous sarcoma are > those in L o r e n ze , and E. R. G o d f r e y (J. Pediat., 1935, 6, healthy hen plasma (30% increase in total P). The 665—666).— Serum-Ca and -inorg. P were within plasma of the diseased (but not that of the healthy) normal limits. N u t r . A b s . (m) hens contains protein-P possibly derived from the tumours, although plasma from the muscles, but Secretion of urine in diabetic coma. R. A. not that from the tumours, loses acid-sol. P. M cCance and R. D. L a w r e n c e (Quart. J. Med., W. McC. 1935, 4, 53—79).—In diabetic coma there may occur Anomalous crystallisation of sodium chloride disorganisation of renal function involving retention in normal and in sarcomatous blood-serum. of urea, creatinine, and probably uric acid, of ketones, V . K tlian (Acta Cancrologica, 1934, 1, 22—28).— if present, and of sugar, if above the threshold. Urine After dilution of serum with 0 -9 % NaCl and sub may become acid (pa 5); excretion of NH3 and salt is sequent evaporation, the form of crystallisation of normal. Ch . A b s . (p) NaCl from samples from sarcomatous chicken differed Hsemochromatosis. I. Iron and sulphur con from that from normal samples. Ch . A b s . (p) tent of the tissues. II. Results of spectro- Enzymes in uterine cancer. II. Lipase and graphic examination with special reference to lecithinase. III. Esterase. IV. Invertase. V. copper and calcium. H. R aslvge and J. H. Antitrypsin. K. N a k a h o r i (Japan. J. Obstet. S h e l d o n (Quart. J. Med., 1935, 4, 121— 129).— Gynecol., 1934,17,419— 445; cf. A., 1935,514).—The I. In 5 patients with hsemochromatosis there was a distribution of the enzymes in human uterine cancer uniform increase in the Fe content, distributed over tissues, lymphatic glands, mucosa, and muscular all the tissues except the blood, brain, and colon. layers of the uterus is examined. Ch . A b s. (p) Organs such as the liver, pancreas, and salivary Influence of magnesium on growth of glands may have 50— 100-fold increase. Enormous carcinoma, sarcoma, and melanoma in animals. deposits occurred also in the lymph glands, thyroid, K. Suigura and S. R. B en ed ic t (Amer. J. Cancer, pituitary, choroid plexuses, and heart. The somatic 1935, 23, 300— 310).—Effects of varying levels of muscles contain nearly as much Fe as the liver. dietary Mg on the growths are examined. Neoplasms The total Fe (calc.) of “the body is 25—50 g. There as well as normal tissue require definite amounts of was no general increase in S content. The "moderate Mg for growth. Ch . A b s. (p) increase in S in the alimentary canal, omentum, pancreas, and adrenal glands is probably related to Effect of intravenous injections of complex deposits of hsemofuscin. soluble salts of iron and ascorbic acid on II. Spectrograpliic examination showed a two- or tumours. F. Arloing, A. Morel, and A. Josser- three-fold increase in Cu in the liver and all tissues a n d (Compt. rend., 1935, 201, 745— 747).— Clinical except the kidney, small intestine, and omentum. X IX (/, g) BIOCHEMISTRY. 101
An increase in Ca was general, but most evident in duced in rats by feedings an excess of K and Na the liver, thyroid, striated muscles, and pancreas. phosphates or H3P0 4. Removal of excess of P 0 4"' Disturbance in the Na and K metabolism may have does not restore normal structure. Ch . A bs. (p) occurred, the concn. of these elements in the tissues Comparison of “ yeast ” milk and irradiated usually deviating in reverse directions from the normal. milk in the treatment of infantile rickets. E. T. The low Mn content of the liver is probably significant. W y m a n n , R. C. E l e y , J. W. M. B u n k e r , and R. No unusual elements were encountered. H arris (New England J. Med., 1935, 212, 257— Nutr. Abs. (m) 262).—The two milks are equally effective. Alkalosis, a clinical problem. C. T. W a y and Ch . Abs. (p) E. M u n t w y l e r (Ann. Intern. Med., 1935, 8, 818— Nitrogen balance and oxidation process in 824).—In cases of hypertension and renal disease experimental scurvy. II. Effect of reduced with a slight or no increase in non-protein-N, the acid- iron. L. D. K a s c h e v n ik , S. A . E id m a n n , and base balance of blood may change with a tendency J. B. F r ie d l a n d (Biochem. Z., 1935, 282, 56— 61; towards a lower Cl content. Administration of alkali cf. A., 1935, 888).—In guinea-pigs, daily oral adminis should be controlled by blood acid-base analyses. tration of 10 mg. of reduced Fe prior to the onset of Ch. A b s . (p) scurvy caused increase in N metabolism, stimulated Role of pressor substances in arterial hyper subsequent urinary N excretion when scurvy had set tension. R. B. Capps, E. B. F e r r is, jun., F. H. L. in, and tended to decrease the O : N ratio. The Fe T a y l o r , and S. W eiss (Arch. Int. Med., 1935, 56, caused retention and deposition of fat during the 864— 876).— In hypertension the urinary pressor course of the disease, but had no effect on the excretion substance is > the normal, and appears to be a 1120- of protein degradation products, there being retention sol. substance, acting centrally. COMe2 extraction of these when scurvy was developing and increased does not completely separate the pressor and depressor excretion when the disease was fully established. substances, but this fraction contains more pressor Subsequently, while the animals fasted, there was and less depressor material than the EtOH fraction. N retention. W. McC. H. G. R, Calcium metabolism in idiopathic hypopara Correlation of mineral metabolism and the thyroidism. A. G o e r n e r and G. Sa m u e l s e n (J. vegetative nervous system in thyroid disease. Amer. Med. Assoc., 1934, 102, 1001— 1002).—The J. K l e in (Ann. Int. Med., 1935, 8, 778—804). positive Ca balance in hypoparathyroidism was Ch . A bs. (p) reduced by parathyroid extract. The increased Interpretation of abnormal glucose-tolerance excretion was by the urine. Ch. A b s . (p) curves occurring in toxaemia in terms of liver Goitre prophylaxis with iodised salt. R. D. function. S. S o s k in , M. D. A l lw e iss, and I. A. Mir s k y (Arch. Int. Med., 1935, 56, 927— 934).— M cCl u r e (Science, 1935, 82, 370—371). L. S. T. Toxaemias cause abnormal glucose-tolerance curves M alaria in Panam a -with reference to control through an interference with the homeostatic mechan with atebrin and plasmoquin. W. H. W. K omp ism of the liver. H. G. R. and H. C. Cl a r k (Amer. J. Trop. Med., 1935, 15, 131— 154; cf. A., 1935, 1149).—Atebrin and plasmo Amino-acid content of the blood of the rabbit quin administered simultaneously enhance the toxic in tuberculous infection of the Yersin type. action of the latter. When given separately the E. S. P anayotoboulo (Compt. rend. Soc. Biol., desired effect is obtained with less toxicity. 1935, 120, 604— 605).—NH2-acids increase steadily Ch . A b s . (p) until death. The increases are of the same order for Muscle chemistry in myasthenia gravis, avian and bovine infections. R. N. C. pseudohypertrophic muscular dystrophy, and Tyrosine index of serum-polypeptides in the myotonia. S. N e v in (Brain, 1934, 57, 239— rabbit in the course of tuberculous infection of 254).— The P 0 4"' content of pathological muscle the Yersin type. E. S. P anayotopoulo (Compt. under various conditions is examined. A method for rend. Soc. Biol., 1935, 120, 695—696).—The tyrosine determining the partition of acid-sol. P between index increases steadily from the time of inoculation H3P0 4, creatinephosphoric and adenosinetriphos- until death. R. N. C. phoric acids is described. Sol. carbohydrate phos Whooping-cough : diagnostic significance of phates are determined by difference. Ch . A b s . (p) blood counts. N . D. B egg and M. F. C oveney Calcium and inorganic phosphorus in the (Lancet, 1935, 229, 1113— 1114). L. S. T. blood-serum of emotionally unbalanced children. Mathematical physics in metabolising systems C. G. K e r l e y , E. J. L o r e n ze , jun., and E. R. G od with reference to lung cells. N. R a s h e v s k y f r e y (N.Y. State J. Med., 1935, 35, 571— 572).— (Physics, 1935, 6, 117— 119; cf. A., 1935, 1073).— Of 90 children 81 showed normal Ca vals. and 83 Previous results are applied to glucose oxidation and normal inorg. P vals. Exaggerated nervous symptoms glycolysis. The relative rates of the two reactions, were not more severe in children with low Ca vals. when occurring simultaneously, determine whether than in those with normal Ca and P vals. the system will divide spontaneously or not. Rapidly- N u t r . A b s . (m) dividing cancer cells show abnormally high rates of Renal damage following ingestion of a diet glycolysis. Ch . A b s . (p) containing an excess of inorganic phosphate. E. N. M a c k a y and J. Ol iv e r (J. Exp. Med., 1935, Metabolism in children doing muscular work. 61, 319—333).—Permanent renal lesions were pro I. Effect of racing on urinary constituents in 102 BRITISH CHEMICAL ABSTRACTS. A. X IX (g) boys. I. Nakagawa and K . Kawam o (Amer. J. superior to pork. With 30% beef protein rats re Dis. Children, 1935, 49, 594—602).—Following a produced freely. Ch . A b s . (p) 1200-m. race some albuminuria and increased acidity Supplementary values of animal protein con occurred. NH3, creatine, and creatinine concns. centrates in chick rations. H. J. A l m q u ist , were practically unchanged. P increased and total N E. L. R. St o k st a d , and E. R. H a lbr o o k (J. Nutrition, decreased temporarily. The ratios, total N : urine 1935,10, 193—211).— Vals. of various meat products vol., total P : urine vol., creatine : total N, and as protein (I) supplements are determined. The NH3 : total N, were all increased. Ch . A bs. (p) cystine, tryptophan, and H2S contents of (I) feeds Metabolism of injured tissue. H. D r u c k r e y do not afford a basis for predicting their nutrient (Naturwiss., 1935,23,796—799).—Mechanical trauma, vals. Determinations of intact (I) (Cu ppt.), (I) such as that sustained by cells in thin sections of tissue, decomp, products (phosphotungstic acid ppt.), un- produces a marked immediate rise in their metabolism digestible (I) (pepsin-HCl), and hot H20-sol. (I), followed by a slow fall. The role of tissue damage in to which are assigned the relative nutrient vals. producing the observed results of 0 2 deficiency and 100, 40, 0, and 40, respectively, permit the determin also its possible significance in tumour metabolism ation of nutrient vals. of (I) concentrates which are discussed. W. 0. K. agree closely with biological trials. A. G. P. Insect metabolism at temperatures below 0°. Is linoleic acid essential in the nutrition of I. V. K osiiantschikov (Compt. rend. Acad. Sci. rats ? E. B e c k e r (Z. Vitaminforsch., 1935, 4, U.R.S.S., 1935, 3, 373—376).—The R.Q. of larvie 241—249).—Without small amounts of linoleic acid of Pyrausta mibilalis, Hb., and of Loxostege sticti- (I) rats fail to maintain normal growth and develop calis, L., indicate that metabolism at 0° is mainly a deficiency disease, which can be cured by daily concerned with carbohydrate, but at —6° and 20° doses of 5 mg. of walnut oil containing 2— 3 mg. of fats and proteins become important. A. G. P. (I). The growth curves of rats run parallel with the amount of (I) in the oil. It is not known which iso- Biological cell oxidation. A. B ertho (Chem.- meride of (I) is responsible for the action. J. N. A. Ztg., 1935, 59, 953—957).—A review. “ Bukuryo," sclerotia of Pachynia Iloelen, Metabolic oxidation and radiation. M. Copi- Rumph. V. Nutritive value of pachyman. K. sarow (Protoplasma, 1934, 21, 73—80).—Blood, T a k e d a (J. Agric. Chem. Soc. Japan, 1934, 10, urine, tissue extracts, and yeast exposed to atm. 685— 690).—Pachyman is not easily digested, and its 0 2 in the dark at 37° emit ultra-violet radiations. nutritive val. resembles that of cellulose. Neither The effect is abolished by heat; in the case of yeast it nor “ Bukuryo ” can be used as a substitute for it is also destroyed by H202, KMn04, KCN, or CO, cereals. J. N. A. but not by C02 or N2. No radiation is given off by pure cholesterol, calciferol, ascorbic acid, alkaloids, Biochemistry of fermented soya-bean paste or synthetic adrenaline. The radiation is associated (“ miso"). III. Effect of cystine on the with the chemical function of respiratory enzymes; nutritive value of miso-protein given as supple motabolic products radiate only in presence of the ment to rice. I. Iw a m u r a (Bull. Agric. Chem. Soc. enzymes. ’ R.. N. C. Japan, 1935, 11, 128— 134).—The nutritive val. of the miso-protein, when used as a supplement to Infant feeding and nutrition. S. Friedman a rice diet for albino rats, is increased by addition (Amer. J. Dis. Children, 1935, 49, 152— 190, 460— of cystine (I). For young rats the optimum amount 473).—A review. Ch.. A b s . (p) of (I) is about 0-1% (>0-5% is harmful), but for adult Effect of low calorific diets and resultant loss rats 0-5% is favourable. W. McC. in weight on plasma-cholesterol in the obese. Substitution of dithioethylamine (cystine- C. A. P o in d e x t e r and M. B ruger (Arch. Int. Med., amine) for cystine in the diet of the white rat. 1935, 56, SS4—890).—Plasma-cholesterol (I) in H. H. M itch ell (J. Biol. Chem., 1935, 111, 699— complicated or uncomplicated obesity is not altered 705).—Addition of cystineamine (I) to a cystine- primarily by reduction in wt. on a low-calorific diet; deficient diet depresses the growth of the animal and but an increase is noted in some cases due to the impairs appetite. There is therefore no evidence that “ starvation effect.” Some high vals. of (I) show (I) can replace cystine in a diet. E. A. H. R. a decrease due to secondary changes. H. G. R. Protein requirements of chicks. J. D. Growth, reproduction, lactation, longevity, M cCo n a c h ie , W. R. Gr a h a m , jun.,and H. D. B r a n io n and haemoglobin formation in albino rats on (Sci. Agric., 1935, 15, 754— 764).— Optimum levels meat diets contrasted with their response on the of protein feeding are determined for chicks of various Steenbock stock diet and on the Sherman milk ages. The efficiency of food utilisation declines with diet. P. M. N elson and P. P. Sw a n s o n (Iowa age. Mortality decreases as the proportion of pro Agric. Exp. Sta. Rept. on Agric. Res., 1933,116; 1934, tein fed approaches the optimum. High and low 144—-145).—As a N source dried beef muscle was protein intakes tend to modify the contour and tex superior to cereal or milk proteins. Neither pork ture of feathers, although the optimum protein nor beef nniscle at a level of 15% protein was adequate requirement for correct feather development is not for maintenance of body-wt., reproduction, and lact necessarily the same as that for growth. Slipped ation. Pork at 15 and 30% protein levels and beef tendons are not directly due to higli-protein feeding. at the 15% level fed to female rats allowed no repro .The occurrence of “ crow heads ” is a dietary rather duction beyond the second generation. Beef was than a genetic factor. A. G. P. X IX (g) BIOCHEMISTRY. 103
. Effect of protein and amino-acid metabolism Digestion of foods. V. Synthetic fats. S. on the urea and xylose clearance. R . F. P itts Suzuki (J. Agric. Chem. Soc. Japan, 1935,11,1— 10; (J. Nutrition, 1935, 9, 657— 666).— Post-absorptive cf. A., 1934, 920, 1027).— Comparison is made of clearances of urea and xylose on a basal diet are low triacetin (I), tributyrin (II), trioctoin, and tridecoin and not greatly affected by feeding the diet. Intro fed at the rates of 2 and 12% with a fat-free polished duction of meat into the diet produces a gradual and rice ration. At the lower level differences between prolonged post-prandial rise in both clearances. the real and apparent digestion coeffs. were con When meat feeding is prolonged, post-absorptive siderable, but there was little influence on the digestion clearances are raised without obliteration of the post of other food constituents. At the 12% level fats prandial effect. Similar effects are produced by retarded protein digestion. Except for (I) and (II), feeding casein, by administration of thyroxine to the lower acid compounds were the more digestible dogs on a basal diet or of phloridzin to fasting dogs, and had the higher nutrient vals. Ch . A b s . (p) or by replacement of part of the carbohydrate of the Fat metabolism. VII. [3-Oxidation of normal basal ration with glycine. The primary effect of saturated dicarboxylic acids administered per protein on renal function results from the action of os. P. E. V e r k a d e , J. v a n d e r L e e , A. J. S. v a n NH2-acids or OH-acids produced in the course of A l p h e n , and M. E lzas (Proc. K. Akad. Wetensch. their metabolism on glomerular activity. A. G. P. Amsterdam, 1935, 38, 943—948).—After administra Effects of varying amounts of animal protein tion to dogs of the Na salts of sebacic (I) or unde- fed to white Leghorn pullets. I. Influence of canedicarboxylic (II) acids, the urine was found to low-, medium-, and high-protein diets on the contain (I), suberic, and adipic acids or (II), azelaic, weight and number of eggs. C. C. R h o d e s, and pimelic acids, respectively. The ratios in which L. H. B a r t e l , and P. E. F. J ooste (Empire J. Exp. these acids are found varies, but (I) or (II) always Agric., 1935, 215— 228).— Comparison is made of the occurs in a greater amount. H. G. R. food consumption with different rations and varying levels of protein content. Differences in the ratio Carbohydrate metabolism in the guinea-pig. of carbohydrate to protein consumed were apparent, F. G o ttd e n k e r (Biochem. Z., 1935,281,128—139).— but there was a definite tendency for birds to balance In autumn the blood-sugar is greatly (up to 250%) the ration to a common nutritive ratio. The amount increased by fasting, but in the same animal, in winter, of protein consumed produced little significant fasting causes only slight increase or even decrease, effect on the body-wt. of the birds or on egg size, the difference not being due to the change in temp, but was directly related to the average no. of eggs of the surroundings. Oral administration of over per bird. A. G. P. doses of glucose causes hyperglycsemia, which reaches its max. within - 0-5— 1-0 hr., then decreases in in Effect of feeding vegetable protein on copul tensity, and finally attains a val. < that first reached. ation and fertilisation in the fowl. T. Hatano Overdoses of adrenaline cause increases of 250— (Bull. Agric. Chem. Soc. Japan, 1935,11,125— 128).— 300% in blood-sugar. Hypoglycsemic convulsions Vegetable (soya-bean) is more effective than animal are produced by overdoses of insulin, but the blood- (fish-meal) protein. W. McC. sugar level is only slightly lowered or even raised, Utilisation of meat by human subjects. II. there being no accompanying increase in the content Nitrogen and phosphorus of round and liver of of reducing substances other than sugar. W. McC. beef. Z. L o ng and M. S. P it t m a n . III. Nitrogen Nutritive value of lactose in man. A. E. and phosphorus of beef heart. B. L . K u n e r t h , K o e h le r , I. R app, and E. H il l (J. Nutrition, 1935, I. M. Ch it w o o d , and M. S. P ittm an (J. Nutrition, 1935, 9, 677— 683, 685—690).— II. The N of round of 9, 715— 723).— In normal adults ingestion of 1-5 g. beef was as effectively utilised as that of fiver. A of lactose per kg. had no appreciable effect on blood- higher proportional utilisation of fiver-P is indicated. sugar (I) levels. A similar ingestion of starch (II) III. Utilisation of the N and P of beef-heart was produced an increase in (I) which was nearly as great not appreciably different from that of round. as that produced by glucose (HI). The total hyper- A. G. P. glycajmia after (II) was > that after (III). In these “ Continuing ” metabolism of nitrogen in individuals lactose produced a slight and in diabetics a marked rise in (I). A. G. P. animals. H. B orsook and G. L. K e ig h l e y (Proc. Roy. Soc., 1935, B, 118, 488—521).—The continuing Xylan. H. I w a t a (Bull. Imp. Coll. Agric. Morioka, N metabolism (!) is defined as the N already present 1935, No. 21, 120 pp.).— Xylanase was not present in the tissues metabolised on any one day, and is in the saliva, pancreas, or bile of higher animals, and distinct from “ wear-and-tcar ” metabolism. For only in small amounts in the intestines. Decomp, of man in N equilibrium at a level of 10— 11 g. of urinary xylan (I) in the intestines into xylose (II) and small N per day, (I) constitutes > 50% of total urinary N. quantities of org. acids by micro-organisms was very S excretion is lowered, but only by about 50%, when active and several new species were isolated; these a normal diet is interrupted either by a day of N also hydrolyse starch, dextrin, inulin, and several starvation or a day on which N is ingested in the form carbohydrates, but do not affect xylose. The diges of compounds low in S ; the lowering persists for a tion velocity of (I) was < that of starch, but was short period after restoration of the original diet. increased by mild treatment "with alkali. On feeding NH3 may serve as precursor of urinary uric acid in (I) there was little change in the blood constituents man. NH2-acids do not stimulate either (I) or endo and no increase in the urinary excretion of (II), but a genous N metabolism. F. A. A. protein-sparing action was observed. Both glycogen 104 BRITISH CHEMICAL ABSTRACTS:— A. X IX for) and fat accumulation were nearly equiv. to that due Minerals for dairy cattle. J. C. K n o tt (Proc. to starch. The total calorific val. of (I) was 4167— 7th Ann. State Coll. Washington Inst. Dairying, 1934, 4184 and the assimilation 61-6%. H. G. R. 120— 124).—The occurrence and functions of Na, K, Mg, S, Cu, Fe, F, Zn, Mn, I, Ca, and P in dairy cows Influence of calcium on carbohydrate meta are discussed. Ch . A b s . (p) bolism . T. H a r a d a (Bull. Chem. Soc. Japan, 1935, 10, 494—503).—Injection of Ca lactate into albino Mineral requirements of milk production. rabbits decreases the hyperglyciemia and glycosuria Annual cycle of mineral and nitrogen meta caused by simultaneous injection of glucose, but bolism of the milch cow as affected by lucerne does not alter the effect of adrenaline on the blood- hay, timothy hay, bone flour, and ground lime sugar. R. S. C. stone. E. B. F orbes [with A. B l a c k , W. W. B r a m a n , D. E. H. F r e a r , O. J. K a h l e n b u r g , Hydrolysis, oxidation, and energy exchanges F. J. M cCl u r e , R. W. Sw if t , and L e R. V oris] in the dog. III. Absorption and assimilation (Penn. Agric. Exp. Sta. Bull., 1935, No. 319, 152 pp.). of hexoses in the organs during intravenous —Monthly determinations of balances of N, Ca, Mg, administration of galactose, maltose, and glucose. P, Na, K, and Cl resulting from the different rations M. W ierzuchowski and H. F iszel (Biochem. Z., are recorded and discussed. A. G. P. 1935, 282, 124— 145; cf. A., 1935, 522).—The absorption from and delivery to the blood of the Chemical reactions in muscle. X. P. Ostern carbohydrates by various organs are studied. As and T. B a r a n o w sk i (Biochem. Z., 1935, 281, 157— regards rate and extent of absorption of glucose (I) 167 ; cf. A., 1935, 1150).—In dialysed and non- and galactose (II), the organs form the series liver > dialysed extracts of autolysed skeletal muscle [free portal vein organs > organs of the head > motor from adenosinetriphosphoric acid (I) and adenylic system. The liver plays little part in absorption of acid (II)] phosphoglyceric acid and (II) successively maltose (III), the other groups of organs exhibiting added are converted into (I) [yield 40% calc, on (I)]. absorptions equal to those shown with (I). As In heart extracts (horse) the products are diadenosine- regards extent of absorption of (I) from the liver, the pentaphosphoric acid and a substance (possibly a order is organs of the head > portal vein organs > nucleotidephosphoric acid) yielding a Ba salt insol. motor system, the amounts of lactic acid (IV) simul in dil HC1. Extracts of rabbit heart contain free taneously produced by those absorbing organs corre (II), very little phosphocreatine, and half as much sponding respectively with 14— 17, 96— 164, and adenosinepolyphosphoric acid and total phosphate 40—60% of the amount of (I) injected. 5— 15% of as does skeletal muscle. The direct transfer of phos the injected and absorbed (I) or (II) is given up by phate [from phosphopyruvic acid to (II) and from these organs as (IV) to the blood. Absorption of (I) to creatine] is accelerated by Mg", which only injected (I) by these organs is at first slight, whilst slightly affects liberation of free phosphate. In urinary (I) excretion increases but later becomes heart the transfer of phosphate is the same as in more pronounced. The (I) consumption of the skeletal muscle, but (II) is here more stable and more organs during injection of (II) is about the same as it slowly deaminated by enzymes. W. McC. is during fasts. During (II) injection the liver ceases to give out (I), about 40% of the (II) absorbed by the Fission of adenylpyrophosphoric and arginine- organs being subsequently utilised or excreted in the phosphoric acid in crab muscle. K . L o h m a n n urine. Amytal narcosis has no effect on the assimil (Biochem. Z., 1935, 282, 109— 119; cf. A., 1934, ation of carbohydrates. Loss of blood and laparotomy 1033, 1034).— Only one of the readily eliminated have no effect on assimilation of (II), but they inter HsPO., residues is removed from adenylpyrophosphoric fere slightly with that of fructose (V) and considerably acid (1) by washed crab muscle and dialysed extract with that of (I) and (III). Of the intravenously of the muscle. On addition of Mg" the adenosine- injected carbohydrates tested (V) is the best utilised diphosphoric acid (II) produced is converted into during the narcosis. W. McC. adenylic acid (III). Hence dephosphorylation of (I) is a two-stage process (as in vertebrate muscle), Effect of sulphur administration on carbo different enzymes being involved. In the dialysed hydrate metabolism. T. Y o sh ik a w a (Sei-i-kwai extract argininephosphoric acid (IV) is hydrolysed Med. J., 1934, 53, No. 6, 74— 84).—Administration only if (I) or (il) is present because the extract, in of S by rubbing S-ointment on rabbit’s ears, by mouth, presence of (IV), cannot convert (III) into (II) or (I), or intravenously produced no appreciable change in whilst (II) is easily rephosphorylated. Crab muscle blood-sugar. Ch. Abs. (j>) contains no adenylic acid deaminase. W. McC. Chief sulphur compounds in nutrition. H. B. Production, of kynurenic acid from tryptophan L e w is (J. Nutrition, 1935, 10, 99— 116).—A review. nn r> *?^ole *^erivatives . L . C. B a u g u e s s and A. G. P. V- V I g tlÎ (Pl'oc. Iowa Acad. Sci., 1934, 41, 174— Calcium, phosphorus, and nitrogen retention J : When administered to rabbits Z-tryptophan- of children. Effects of acid- and base-forming amides (free amide, mono- and di-ethyl-amides, diets. N. J. D avis (Amer. J. Dis. Children, 1935, anilide, and ethylanilide) were as readily converted 49, 611—624).—The total Ca output was similar on kynurenic acid (I) as was Z-tryptophan (II). acid- and base-forming diets. Acid diet led to de substituted carboxylic acid derivatives were not creased ficcal P and slightly increased urinary P. converted P-3-Indolylpyruvic and cZZ-p-3-indolyI- Basic diets induced greater N retention and higher lactic acids, but not ¡3-3-indolylacrylic or a-oximino- NH3 excretion. Ch . A bs. (p) (3-3-indolylpropionic acids, were also converted into X IX (g, h) BIOCHEMISTRY. 105
(I), bub iii amounts < those from (II) derivatives. equal ionisations in air produced by X - and y-rays Indole derivatives are probably not intermediates in are not equally effective in killing fruit-fly eggs. the conversion of (II) into (I). Ch . A bs. (p) The therapeutic efficacy of high-voltage X- and y- Transformation of urobilinogen in the liver. rays cannot be predicted by the usual biological and physical tests. L. S. T. K. F e l ix and H. M oebus (Z. physiol. Chem., 1935, 236, 230—230).—Fresh liver pulp (pig) attacks Action of solar (ultra-violet) rays on the skin urobilinogen (p„ optimum at 7-1) in presence of 0 2 and the formation of cholesterol. A. H. R offo causing cessation of power to react to the aldehyde (Compt. rend., 1935, 201, 566— 568).—The ratio of test. Boiled liver pulp has no such effect. the cholesterol (I) content of the skin of the cheek to W. McC. that of the abdomen is in adults 3-42, in infants 1-4, Absorption of salicylic acid after intra and in the fcetus 1-1. Skin exposed to sunlight or muscular injection. Absorption by the bladder. ultra-violet light in vivo or in vitro increases in (I) W. B ltjme and F. W. F isch er (Arch. exp. Path. content. J. L. D. Pharm., 1935, 179, 646—654).— Following intra Radio-hsemolysis and cholesterol. B. S. L e v in muscular injection of 10 c.c. of 2-5% Na salicylate and C. P iffau lt (Compt. rend. Soc. Biol., 1935, into rabbits, salicylic acid (I) appears in the blood 120, 712—714).—The resistance of guinea-pigS’ after 1—2 min. and in the urine after approx. 30 corpuscles to X-rays is increased by injection or min. The rate of excretion is fairly const., 70% of ingestion of cholesterol. R. N. C. the administered (I) being excreted within 24 hr. Fats and a theory of pharmacodynamic actions The blood-(I) attains a max. within 1 hr. and returns of alkali and alkaline-earth ions. J. W ajzer and to zero in 6—7 hr. Absorption into the blood after L. L apicque (Compt. rend. Soc. Biol., 1935, 120, intramuscular injection is > that after rectal or 707— 710).— K ' and Na’ decrease, and Ca" increases, subcutaneous administration. (I) is absorbed by a between II20 and oils, by the formation of a unimol. inflamed (EtOH), but not by normal, bladder mucosa. layer of soap at the interface. The effect is unaltered F. O. H. by aliphatic amines. R. N. C. Absorption of intrapleurally and intraperitone- ally injected salicylic acid. W. B l u m e and K. Salt requirements and space orientation of the P l u m (Arch. exp. Path. Pharm., 1935, 179, 655— littoral isopod Ligia in Berm uda. T. C. B arn es 661).—Following intrapleural and intraperitoneal (Biol. Bull., 1932, 63, 496—504).—Toxicity of cations injection of Na salicylate into rabbits, salicylic acid in sea-H20 to L. bandiniana decreases in the order (I) appears in the blood after 3— 10 and 1—2-5 min. K, Mg, Ca, Na. K exerts a sp. paralysing action (max. being attained after 1 and 0-5 hr.) and in the on gill movements. Ch . A bs. {p) urine after 40 and 26 min., the total excretion being Difference in action of ter- and quinque-valent 77 and 59%, respectively. With both routes, max. arsenic compounds on the explanted spleen from excretion occurs after | hr. and falls to zero in approx. chick embryo. H. O k a d a (Folia Pharmacol. 7 hr. At max. excretion, the blood-(I) indicates a Japon., 1935, 19, 271— 282).—The growth of spleen- ratio of absorption by buccal mucosa, stomach- tissue is increased by low concns. of Na3As03 (I), intestine, rectal mucosa, pleural cavity, muscle, and Na3As04 (II), atoxvl (III), and neoarsphenamine abdominal cavity of 3 : 6 : 8 : 10 : 12 : 14. F. O. H. (IV). Tissue is killed by high concns. Potency Relationship between dielectric polarisation decreases in the order (I), (IV), (II), (III). h and pharmacological action. K. W. R o s e n m u n d C . Abs. (p) (Angew. Chem., 1935, 48, 701— 705; cf. A., 1934, Influence of bromine on the growth and meta 652).—The anthelmintic properties of different phen morphosis of the larvse of Bufo vulgaris. V. olic lactones are not related to surface activity, F a m ia n i (Atti R . Accad. Lincei, 1935, [vi], 21, 821— action on membrane permeability, or action on the 824).—Toad tadpoles fed on egg-yolk to which a swelling of proteins, but to the polarity of the mols., trace of Br-H20 had been added grew more rapidly as varied by the relative positions of substituents in than controls fed on unbrominated yolk. Meta the CgHg ring. F. A. A. morphosis commenced earlier, but the tadpoles died during metamorphosis; the liver and intestines had Relation of cell types in leucaemia to sensitivity developed to the adult state, the legs had appeared to radium. R. Isaacs (Folia Hematol., 1934, 52, early, but were stunted, and the respiratory system 414— 425).—Within 24 hr. of application of X-rays had failed to develop. D. R- D. or Ra, metabolic rates rise, showing increased 0 2 utilisation, and chemical changes associated with Differential biological reaction of cobaltous compounds and of some cobaltic complexes cell growth are accentuated. Ch . A bs. (p) (cobaltiam m ines). J. M. le G off (Compt. rend., Action and haemolytic dose of X-rays. A. 1935, 201, 531—532).—The human organism can R ogoziński and B. S. L e v in (Compt. rend., 1935, differentiate between subcutaneously injected Co11 201, 798—799).—The dose required for complete and Com , and between Co and N in complexes. ha2molysis is increased if irradiation is carried out R. N. C. in several stages, probably as a result of the formation New toxicant occurring naturally in certain of antilytic substances. J. L. D. samples of plant foodstuffs. IX. Toxic effects Ionisation in air and the biological effects of of orally ingested selenium. K. W. F r a n k e and y-rays. G. F a il l a (Physical Rev., 1934, [ii], 45, V . R . P otter. X. Effect of feeding toxic food 564).— Contrary to the conclusions of Packard, stuffs in varying amounts and for different time 106 BRITISH CHEMICAL ABSTRACTS. A. X IX (Ä)
periods. K. W. F r a n k e (J. Nutrition, 1935, 10, rend. Soc. Biol., 1935, 1 2 0 , 650—651).—The temp, 213—221, 223—231).—IX. Symptoms of poisoning rise in pigeons given cryogenin and (N 02)2CGH3*0H produced by Na2Se03 are practically identical with (I) is < in those given (I) only. R. N. C. those shown by the natural toxicant. [Pharmacology of] phenanthrene derivatives. X. Effects of feeding toxic grain are examined. V. Homologous acids and aldehydes and some A. G. P. of their derivatives. N. B. E d d y (J. Pliarm. Exp. Mechanism of the action of sulphur and mud Ther., 1935, 5 5 , 354^364; cf. A., 1933, 858).— The baths. L. Sch m idt (Orvosi Hetilap, 1935, 79, action on cats of phenanthrenecarboxylic and (3-(3- 318— 319).— Absorption of chemical components of plienanthryl)propionic acids, their Me esters, amides, mineral waters is probable. The S of therapeutic ketone and alcohol derivatives, and some position- muds is in steady circulation, but in dynamic equili isomerides of these compounds are compared. Effec brium, part being oxidised and part reduced. tiveness is greater in the higher homologues; that of Ch. A b s . (p) the alcohols is > that of ketones. The amides and Dietary depigmentation of young black and Me esters are less active than the acids. 3-derivatives pied rats, promoted by rapid growth, prevented are more active than the 2- or 9-derivatives. Of the and cured by ingestion of copper. F. J. Gorter compounds studied, Me phenanthrene-3-, m.p. 95°, (Z. Vitaminforsch., 1935, 4, 277—293; cf. A., 1935, and -9-carboxylate, m.p. 116°; phenantlirene-3-carboxy- 1148).—The curative effect of yeast on depigmentation dimethylamide, m.p. 120-5— 121°, -2-carboxylamide, is due to its Cu content and not to its anti-pellagra m.p. 242—243°, -3-, m.p. 79—S0°, and -9-aldehyde, property. Depigmentation in young growing rats m.p. 100-5— 101°; $-3-phenanthrylpropionic acid, is prevented by adding CuS04 to the diet, the daily m.p. 154-5— 155° (Me ester, m.p. 61— 62°; amide, preventive dose of Cu being 0-02—0-12 mg., and the m.p. 161— 162°); 3-, m.p. 100— 103-5, and 9-hydroxy- curative dose 0-07—0-24 mg. Other metals are methyl-, m.p. 149— 149-5°; 3-, m.p. 72°, 2-, m.p. 143°, ineffective. Cu in cereals appears to be more available and 9-acetyl-, m.p. 74-5°, 3-propionyl-phenanthrene, than Cu in proteins. J. N. A. m.p. 53—54°; phenanthryl-3-, m.p. 83—83-5°, and -2- Feeding and thyroid function. I. Effect of methylcarbinol, m.p. 134-5— 135-5°, are now. H. D. cyanides on the function and histological Pharmacology of some hydroxyphenoxyethyl- picture of the rat thyroid. F. B r u m a n and L. alkylamines. D. B o vet, A. Sim o n , and J. D r u e y B erm an (Z. ges. exp. Med., 1935, 9 5 , 724—728; (Compt. rend. Soc. Biol., 1935, 1 2 0 , 690— Cliem. Zentr., 1935, i, 2202-—2203).—McCN given 691).—sec.-Hydroxyphenoxyethylalkylamines exhibit daily does not alter basal metabolism in rats. The adrenolytic action, whilst the tert.-amines exhibit diminution of tissue oxidation due to MeCN is com nicotine-like action and resemble hordenine in having pensated by increased thyroxine secretion. a powerful gangliar nicotine-like action which is R. N. C. Effect of iodoacetate on post-mortem glyco- abolished by methylation of the OH. Certain of the feri.-amines exhibit both the above actions. genolysis in liver. H . R. N oltie (Quart. J. Exp. Physiol., 1935, 24, 377—382).—Iodoacetate did not R. N. C. prevent glycogcnolysis in rabbit liver incubated in Renal activity. VIII. Effect of xanthine and N2 at 38°, or the accumulation of sugar (although histidine fractions isolated from various organs exerting some inhibitory action), but caused the lactic of cows. IX. Effect of endocrine preparations acid content to remain stationary. Ch. Abs. (p) on renal activity. Y. M iz u n o (Sei-i-Kwai Med. J., 1933, 5 2 , No. 10,50—70,71— 90; cf. A., 1935, 258).— Effect of dinitrophenol on calcium and phos VIII. Xanthine fractions (especially from adrenals) phorus metabolism. C. L. R obbins (J. Nutrition, markedly accelerated renal activity in rabbits. The 1935, 10, 187— 191).—Increased basal metabolism histidine fraction is less effective. Arginine and lysine caused by administration of dinitrophenol was not fractions have no action. accompanied by any change in the excretion of Ca, IX . Injection of thyreoglandol caused marked P, or N. " A. G. P. acceleration. Pituitrin and adrenaline were non- Effects of moderate doses of dinitrophenol on effective. ch. A b s . (p) the energy exchange and nitrogen metabolism Effect of bile acids on sugar assimilation in of patients under conditions of restricted dietary. depancreatised dogs. T. H a s e g a w a (Arb. Med. M . L. T a in t e r , W . C. Cu t tin g , and E. H in es (J. Fak Okayama, 1935, 4, 453— 460).— Injection of Pliarm. Exp. Tlier., 1935, 55, 326— 353).—0-3— iSa cholate, with or without glucose, reduced hyper- 0-4 g. of 2 : 4-(N02),C6H3-0H (I) was given daily for 1—2 weeks to normal human subjects maintained glycremia and glucosuria in depancreatised dogs. on a low-calorific diet with only sufficient protein Ch . A b s . (p) •mfhience of bile acids on calcium m etabolism . to maintain N balance. (I) produced an increased VIII. Influence of bile acids and spleen extract loss in body-wt. associated with increased fat metabol on urinary calcium excretion. IX. Blood ism with the production of no ketones or acidosis. composition of normal and splenectomised There was no extra metabolism of carbohydrates or rabbits under the influence of bile acids and proteins; (I) was not conjugated in the body as an spleen extract. M. Iw a d 6 (Arb. Med. Fak. Oka org. sulphate and no extra secretion of Cl' in the urine, faeces, or sweat occurred. H. D. yama, 1935, 4, 346—355, ' 356— 364).— VIII. In normal or splenectomised rabbits subcutaneous in- Antagonism of cryogenin and 2 : 4-dinitro- 1 ch°kdc (I) augments and spleen extract phenol. A. L e u lie r and G. B £ r u a r d (Compt. (II) decreases urinary Ca. X IX (h) BIOCHEMISTRY. 107
IX . Splenectomy is followed by hyporcalcaemia, Novocaine oxide.— See this vol., 70. which gradually disappears. Blood-Ca is lowered Influence of morphine on local anaesthesia of by (II) in normal rabbits > in splenectomised rabbits, the cornea through various local anaesthetics in Post-operative hypercalccemia is increased by (I) rabbits. K. A r im a (Folia Pharmacol. Japon., 1935, and lowered by (II). Spleen and liver are concerned 19, 283—286).— Small amounts of morphine which do in the regulation of blood-Ca. Ch. A b s . (p) not affect the sensitivity of the cornea increased Influence of fractionated liver extract on blood and lengthened the action of cocaine, tutocaine, and composition of normal dogs. M. I w a d O (Arb. pantocaine. Ch . A b s . (p) Med. Fak. Okayama, 1935, 4, 438— 444).—The factor Morphine and ether hyperglycaemia in hypo- in aq. liver extracts which causes hypcrcalcsemia is physectomised dogs. E. d i B. d e Sa b e l l i and sol. in EtOH and slightly less sol. in Et20 (cf. preceding E. J. d i B en ed etto (Compt. rend. Soc. Biol., 1935, abstract). ” Ch . A b s . (p) 120, 738—739).—Hyperglycemia from morphine Blood composition of normal and splenectom in hypophysectomised dogs is > in normal dogs, ised rabbits under the influence of liver extracts whilst that from Et20 is less. R. N. C. from normal and splenectomised rabbits, spleen [Pharmacology of] morphine, codeine, and extracts, and bile salts. M. I w a d 6 (Arb. Med. their derivatives. X. Deoxymorphine-C, de- Fak. Okayama, 1935, 4, 424— 437).— Subcutaneous oxycodeine-C, and their hydrogenated deriv injection of Na cholate increases blood-Ca (I). atives. X. B. E d d y and H. A. H ow es (J. Pharm. Splenectomy removes a factor from the liver which is Exp. Ther., 1935, 55, 257—267; cf. A., 1935, 7S0).— capable of increasing (I). Ch . A b s . [p) Reduction of the alcoholic OH in members of the Barbiturates. XI. Methods of barbital re morphine and codeine series increases the analgesic search. C. R. L in e g a r , J. M. D il l e , and T. K op- and depressor effects and decreases the emetic effect. p a n y i (J. Amer. Pharm. Assoc., 1935, 24, 847— 852). Of the compounds formed, tetrahydrodeoxymorphinc, -—Prior to determination of barbiturates (I), highly m.p. 260°, [a]£4 —45-5° in EtOH, is new. H. D. pigmented urines are cleared by Na2Mo04-H 2S04 or Effects of morphine and its derivatives on Cu S 04-N a2W0 4-H 2S04. Extraction of urines or intestinal movements. IV. Dihydro-^-codeine cleared filtrates by CRC13 indicates that excreted (I) and dihydroa f io-^codeine. H. K r u e g e r , II. are present as acids even in alkaline urines. Following H o w e s , and H. Ga y (J. Pharm. Exp. Ther., 1935, pptn. of blood with Na2W04-H2S04 (Folin'-Wu), 55, 288— 318).—The quantities of morphine, 0-07% Sch m itt, and P. Gran ett (J. Agric. Res., 1935, 51, MoCHO and 0-02% H20 2 is less effective anaesthetic- 349—354).— Anabasine sulphate was more toxic ally than pure Et20. EtOH acts merely as a diluent. to a no. of insects than was nicotine, but when used H. D. as a stomach poison for grasshoppers and silk-worm cycfoPropane anaesthesia: post-operative larvae was much inferior. A. G. P. morbidity in 2200 cases. E. R. Sc h m id t and R. M. W aters (Anesthesia and Analgesia, 1935, Effect of nicotinism in the albino ra.t. C. S. d4, 1—3).— Respiratory, nausea, and emetic after Sm it h , S. R o sen feld , jun., and L. J. Sacks (J. effects of cyclopropane and EtaO were < those of Pharm. Exp. Ther., 1935, 55, 274^-287).— Injection C2H4 and N20 (with C02 absorption), but circulatory of 0-005—0-0075 mg. of nicotine per g. of body-wt. complications were slightly greater. Ch . A b s . (p) in. rats decreased their voluntary muscular activity 108 BRITISH CHEMICAL ABSTRACTS. A. X IX (A) and their fat contents; it had no influence on the Toxicity of optically active and inactive di- growth curves or oestrus cycles. H. D. hydrodeguelins. W. A. G er sd o r ff (J. Agric. Res., 1935, 51, 355— 361).—The order of toxicity to gold Balance of nicotine in the smoking of tobacco fish was rotenone > active dihydrodeguelin (I) > in cigarettes. A. K op erin a (Tabacn. Prom., 1934, deguelin > inactive (I), although the relative pro No. 5, 37— 10).— Of the nicotine (I) in tobacco, portional toxicity varied somewhat with the concns. 60% is burned during smoking, 27% escapes on examined. A. G. exhalation, and 12% is absorbed by the smoker. Absorption of (I) is through the lungs and not through Toxicity of methyl alcohol. A. B e n e d ic e n t i the stomach or saliva. Ch . A b s. (p) (Mem. R. Accad. Italia, 1935, 6, 601— 633).— In jection of MeOH into rabbits and dogs lowers the Use of rabbits in the assay of digitalis, stro- alkaline reserve of the blood. The toxic action is phanthus, and squill. G. N. R apson and S. W. F. not influenced by administration of cholesterol (I) U n derh ill (Quart. J. Pharm., 1935, 8 , 409—423).— or oils containing (I). Most animals tolerate 0'2— Application of the infusion method of assay (Gaddum, 0 4 vol.-% in the inspired air, but considerable vari A., 1932, 964) indicates that rabbits are less sensitive ations occur with different species and also with than cats to ouabain (I), strophanthus (II), or squill, animals of the same species. MeOH in air is deter but more sensitive than dogs or guinea-pigs to (I) mined by conversion into Me3B03 and subsequent and (II) ; to digitalis, rabbits are the most resistant decomp, in 0-lN-NaOH. Severe poisoning is followed of the four species. With strict adherence to con by accumulation of MeOH in blood, brain, etc. ditions characteristic for each drug, results from rab Normal combustion produces (non-toxic) traces of bits agree with those from cats. F. O. H. CO, CH20, and other reducing substances. In [Pharmacology of] samandarine and its dustrial hazards are discussed. F. O. H. derivatives and fission products. O. G essn er Mechanism of mercury diuresis. J. J. B e r e - and W. E sser (Arch. exp. Path. Pharm., 1935, tervtde and C. R e c h n ie w sk i (Prensa med. Argen 179 , 639—645).—The pharmacological action and tina, 1934, 21, No. 50— 51).— Novasural causes min. lethal dose of samandarine (I) and 9 deriv hydrsemia only when H20 is retained in the tissues. atives (A., 1935, 97) were determined in mice. The globulin content of blood is reduced. Samandarone approximates to (I) in its activity. Ch . A b s . (p) No correlation between constitution and pharma Influence of mercury on cultivated tissues. cological (especially convulsive) action is apparent. III. How will the action of mercury compounds F. 0. H. on cultures of fibroblast in vitro be influenced Pharmacological action of dendrobine, the by glucose ? K. H ir a siiim a (Folia Pharmacol. alkaloid of Chin-shih-hu. K . K . Ch e n and A. L. Japon., 1935, 19, 323—332).—The toxic action of Chen (J. Pharm. Exp. Ther., 1935, 5 5 , 319—325).— 1X 10-®Jl/-HgCl2 is decreased by raising the glucose Dendrobine produces moderate hyperglycæmia, di concn. in fibroblast culture media 0-01M > that in minishes cardiac activity in large doses, lowers blood normal media. Cultures in such media show normal pressure, suppresses respiration, inhibits isolated resistance to HgCl2. Ch . A b s . (p) rabbit’s intestine, and contracts the guinea-pig’s uterus. H. D. Repeated injections of a thio-derivative of gold : Yolk-sac vessels of the chick embryo. IV, V. T. tolerance and localisation. A. L e u l ie r and G. N akano (Folia Pharmacol Japon., 1935, 19, 293— B eruard (Compt. rend. Soc. Biol., 1935, 120, 651— 299, 300—305; cf. A., 1935, 893). Ch. A bs. (p) 654).—Sr aurothiopropanolsulphonate (I) is less toxic than the corresponding Na and Ca salts to guinea- Comparative actions of sympathomimetic pigs, and diffuses less readily through the organs on compounds : bronchodilator actions in experi account of its low solubility; it is excreted less rapidly mental bronchial spasm of parasympathetic in the urine. The Au storage in the kidneys, spleen, origin. J. R . Pe d d e n , M. L. T a in t e r , and W . M liver, and other organs produced by repeated in Cameron (J. Pharm. Exp. Ther., 1935, 55, 242— jections of (I) is not much > that produced by the 2 5 6 ; cf. A., 1934, 1134).— Of fourteen amines tried, more sol. salts. R. N. C. the most effective in producing bronchial dilation in dogs treated with arecoline were adrenaline, Has glucose any influence on the arsphenamine arterenol, and epininc; activity appeared to be action on cultivated tissue ? H. O k a d a (Folia associated with the pyrocatechol nucleus. H. D. Pharmacol. Japon., 1935, 19, 287— 292).— Combin ation of glucose and neo- or myo-arsphenamine Action on the gaseous metabolism of poisons causes better growth in spleen-tissue cultures than for the vegetative nervous system. F. Péter arsenicals alone. Ch . A b s . (p) (Biochem. Z., 1935, 281, 111— 120).—Subcutaneous administration of ergotaminę increases the basal Cyanide antidotes. P. J. H a n z l ik and A. P. metabolic rate of fasting male rats at 28° (max. 42%) R ichardson (J. Amer. Med. Assoc., 1934, 102, and its effects last 5— 6 hr. ; atropine (II) slightly 1140— 1745).—Intravenous injection of methylene- reduces the rate, and Na luminal (III) does not blue is recommended. A mixture of NaNOs and affect it. (I)-f-(III) cause increase, (II) + (III) slight Na2S203 is also effective. Ch . A b s . (p) increase, and (I) + (II) and (I) + (II) + (III) have no Antidote for acute mercury poisoning. S. M. effect. W. McC. R o senthal (J. Amer. Med. Assoc., 1934,102, 1273— X IX (A, i) BIOCHEMISTRY. 109
1276).— Oral or intravenous administration of Na genation of EtOH. The activation is due to the formaldehydesulphoxylate proved satisfactory. binding of heavy metals, since, when these are as Ch . A b s. completely removed as possible, the effects of reduced Influence of chronic fluorine toxicosis in (I) and KCN are < usual and the inhibition caused laying hens on the fluorine content of the egg and by added CuS04 is counteracted by addition of its relation to the lipin content of the egg-yolk. reduced (I) or KCN [< about 10 mols. of reduced P. H. P h il l ip s , J. G. H a l p in , and E. B. H a r t (J. (I) or KCN per mol. of CuSOJ. Cysteine (II) does Nutrition, 1935, 10, 93— 98).—Addition of F-con- not accelerate the dehydrogenation and even taining rock phosphate to hen’s rations increases counteracts the effect of reduced (I), probably because the F content of egg-yolks. Within the yolk the heavy-metal compounds of (II) catalyse oxidation additional F occurs mainly in the COMe2-insol. of reduced (I). W. McC. fraction of the fatty matter, possibly in combination Dehydrogenase of lactic acid. T. W a g n e r - with complex lipins. Ingestion of F by means of J a u r e g g and E. F. M ö l l e r (Z. physiol. Chem., 1935, mineral phosphate did not reduce egg size. 236, 216—221; cf. Adler ct al., A., 1935, 1276).— A. G. P. The yellow (flavin) enzyme of yeast plays no part in Oxidation-reduction catalysis in the living cell. the aerobic enzymic conversion of lactic acid into P. J o y e t -L a v e r g n e (Protoplasma, 1935, 23, 50— AcC02H. W. McC. 69).—Published work is discussed in support of the Enzymes of liver. III. Aldehydrase. IV. concept that vitamin-M and glutathione act as com plementary constituents of a catalytic system con Alcohol-dehydrase. L. R e ic h e l and H. K o h l e trolling intracellular oxidation-reduction processes (Z. physiol. Chem., 1935, 236, 145— 157, 158— 167; cf. A., 1934, 807; Battelli et al., A., 1910, ii, 980).— located on the surface of the chondriome. A. G. P. III. Dry preps, of the aldehydrase (I) (from pig liver), Catalase in lymphocytes. K. F ukuchi (Arb. which retain their activity almost unchanged for > dritt. Abt. Anat. Inst. Univ. Kyoto, D, 1934, No. 4, 1 year, have optimal effect at pa 7-5—7-8, are destroyed 65— 67).— The catalase activity of lymphocytes from at 69°, and cease to act after 2 hr. The action is the popliteal gland of rabbits is determined. greatly (> 50%) diminished by KCN, probably Ch . A b s . (p) because of cyanohydrin production, and decreases Iron. IX. Catalase and “ readily eliminated " as the concn. of substrate increases. Benzoquinone iron of blood. G.'Barkan (Z. physiol. Chem., 1935, (II) in high concn. inhibits anaerobic dismutation 236, 197— 200).—Since the catalase (I) is not affected by (I), methylene-blue (III) in high concn. increases by CO under conditions in which elimination of Fe it, and the oxidation product (IV) of adrenaline has is greatly restricted, it follows that (I) is not identical no effect. Cytochrome and indophenol-oxidase with the “ readily eliminated ” blood-Fe. accompany (I), which acts only if they are present. W. McC. In fresh liver, in presence or absence of 0 2 the action Cytochrome-c. IV. K. Zeile (Z. physiol. Chem., of (I) is slight, most of the EtCHO being consumed 1935, 236, 212—215; cf. A., 1934, 109; Theorell, in other ways. A., 1935, 1277).—The mol. wt. (18,000) and hsemin IV. Alcohol-dehydrase (from frog-liver) does not act content (3-5%) of the smallest unit of the cytochrome in absence of 0 2, converts PmOH (optimum at p a (I) are determined, taking advantage of the non 6-7—7-3) into EtCHO, no EtC02H being produced, adsorption of reduced (I) on kaolin. The isoelectric retains its activity for 6—8 weeks in a vac., but loses point of (I) is at p a 8-2. W. McC. it in a few days in air, is destroyed at 47-5° (pa 7-8), Tyrosinase action on mono- and di-hydric is not affected by KCN, and ceases to act after 80 substrates. M. G r a u b a r d and J. M. N e l so n (J. min. The extent of action decreases as the concn. Biol. Chem., 1935, 111, 757— 770).—pn-activity of substrate increases. (II), (HI), and (IV) act as curves for p-cresol (I) with various preps, of tyrosinase intermediate H acceptors in the process and increase (II) are given. The system (I)—(II) proceeds differ the extent of dehydrogenation, but ascorbic acid ently from the system pyrocateehol (III)-(II), for diminishes it. The extent of dehydrogenation is in the former (II) is not inactivated, whilst in the latter also increased by preps, from spleen (calf). it is inactivated very quickly and addition of NH2Ph W. McC. produces very little change. With (I) the rate of Cabbage-am ylase. B. A. R u b in and V. E. reaction oc concn. of (II), whilst with (III) the total T r u p p (Compt. rend. Acad. Sei. U.R.S.S., 1935, 3, O uptake depends on the pa and amount of (II). 229— 232).—In addition to amylase (I) an enzyme Neither NH2Ph nor NaHS03 inhibits the reaction, cytase (II) exists, capable of hydrolysing cellulose to but there may be prolonged induction periods. It reducing sugar. In “ Amager,” a late variety, the is concluded that (II) consists of only one enzyme leaves are richest in (II), whilst in “ No. 1 ” the stalks and that it acts like a peroxidase. J. N. A. have a higher (II) content. The (I) content is const, Activation by glutathione of the enzymic de during storage for 6 months, whilst (II) gradually hydrogenation of alcohol. T. W agner-Jauregg decreases. and E. F. Moller (Z. physiol. Chem., 1935, 236, Reversible inhibition of ß-malt-amylase by 222—227).—Reduced (but not oxidised) glutathione ascorbic acid and related compounds. C. S. (I), and also KCN [action > that of (I)], Na2S, a- H a n e s (Biochem. J., 1935, 29, 2588—2603). Ihe amino-3-naphthol-4-sulphonic acid, and thioglycollic degree of inactivation of ß-malt-amylase (I) by ascor acid (but not pyrophosphate) in presence of dialysed bic acid (II), dihydroxymaleic acid (III), andreductone extract of washed yeast activate the enzymic dehydro (IV) increases with the time of treatment. With low 110 BRITISH CHEMICAL ABSTRACTS.— A. X IX (i)
concns. of (II) regeneration of activity occurs after reaction, and displace the curve of reaction rate 10 min. treatment; the regeneration is more rapid against time so that the amount of enzyme present with (III) and (IV), and is correlated in all cases appears to be increased. A. L. with decreases in the I vals, of the inhibitor-enzyme Purification of choline-esterase. E. Stedman mixtures. (I) stabilises (II) against oxidation, whilst and (Mr s .) E. Stedmah (Bioehem. J., 1935, 29, 2563— it accelerates the oxidation of (III) and (IV), thus 2567; cf. A., 1933, 1081).—Preps, of choline-esterase, explaining the difference in inhibiting powers of .these 50 to 100 times as active as serum, may be pre three. Preliminary oxidation of the inhibitors, or the pared from the latter by fractional pptn. with addition of a no. of reducing substances such as HCN, (NH4)2S04 and AcOH and adsorption on A1203 or reverses the inhibition. CuS04 causes increased in Fe(OH)3 from acid solution using aq. NH3 and hibition. It is concluded that the sp. effect of (I) M/3-phosphate buffer at pa S as eluents. These lies in its dienol group as opposed to its reducing preps, do not attack PrC02Me. H. D. powers. H. D. a- and (3-Amylase in ripening wheat grain. Action of magnesium on the aspartase system. P. S. U g r ü m o v (Bioehem. Z., 1935, 282, 74—78; K. P. J a c o b so h n and F. B. P e r e ir a (Compt. rend. cf. Purr, A., 1934, 934; Stenstam et al., ibid., 1258).— Soc. Biol., 1935, 120, 551— 554).—Addition of Mg" During the early stages of the ripening, (3-amylase, to the aspartase system displaces the equilibrium which is predominantly a saccharifying agent, and in favour of fumaric acid formation, K f showing a a-amylase (I), which produces dextrin, are present. considerable decrease. R. N. C. (I) becomes inactive at the “ milky ” stage and cannot Enzymes of snake venom. I. Activation of be detected during subsequent ripening or in resting dipeptidase by the venom of the snake Tri- wheat, but it reappears during germination. meresunts niucrosqtiarriatus. Y. T s u c h iy a (J. W. McC. Agric. Cliem. Soc. Japan, 1935, 11, 720— 730).— Effect of potassium cyanide on amylase The dipeptidases of extract of dried tortoise liver activity. J. 0. P a g e and D . T . E n g l is (Trans. and of fresh or dried intestinal mucous membrane Illinois State Acad. Sci., 1934, 27, 74).—The rate of of the pig are activated by the venom, the effect saccharification by barley amylase is unaffected by being pronounced with respect to hydrolysis of KCN at pa 4-56. At pa 7-0 KCN increases the rate leucylglyeine, slight with respect to that of valyl- until it approximates to that at pa 4-56. glycine, and absent with respect to that of glycyl- Ch. A b s. (p) and alanyl-glycine when the tortoise liver extract Conversion of rutin into a brown pigment by is used. The p„-activity curve exhibits max. tobacco enzymes. C. N e u b e r g and M. K o b e l within a certain [H'] zone. The activating power (Naturwiss., 1935, 23, 800—SOI).—The enzymes decreases with time and the amount of venom re of the tobacco leaf convert rutin (quercetinrhamno- quired for max. activation cc the amount of enzyme glucoside) into a dark brown H20-sol. product which used. W. McC. on hydrolysis yields a H20-insol. aglucone. The reaction, which apparently consists in the oxidation Enzymic proteolysis. V I. Structure of prot of the rutin, is accelerated by the presence of 0-03% am ines. II. Clupein. E. W aldschmidt-Leitz and E. K o f r a n y i (Z. physiol. Chem., 1935, 236, H202. W. O.K. 181— 191; cf. A., 1931, 984).— Clupean is hydrolysed Enzymes of pectin. III. Complete direct by activated trypsin, 4 peptide linkings being broken hydrolysis of pectolic acid to d-galacturonic acid [no arginine (I) produced] and the product yields two by pectolase. F. E hrlich, R. Guttmann, and R. fractions separated by pptn. Avith aq. EtOH. The H a e n s e l (Bioehem. Z., 1935, 281, 93— 102; cf. A., less sol. (N : NH2 ratio 9) forms 73% of the product 1933, 491).—Crude material obtained from pectin by and is a mixture of tripeptides containing 2 (I) heating with HC1 and washing with HaO and EtOH residues and 1 (NH2)4-acid residue. The more sol. is rapidly (3—4 days) converted by pectolase into (N : NH^ 5) forms 27 % and is a mixture of dipeptides pure cryst. d-a-galacturonic acid in 87% yield. containing 1 (I) and 1 (NH2)1-acid residue. The re The conversion of purified material is much slower sults of acid and enzymic (aminopolypeptidase, (2 months) and is incomplete except at pH 6— 4. arginase, carboxypolypeptidase, dipeptidase) hydro W. McC. lysis of these fractions indicate the structure of clu Cellobiase activity of the bovine rumen. C. pein (mol. wt. 2021), Avhich is a chain of 10 (I), 4 Antoniani (Biochim. Terap. sper., 1935, 22, 48).— (NH2)4-acid, and 1 proline residues, the position of Neither the mucosa of the rumen nor aq. extracts the latter alone being uncertain, although only 3 made by prolonged maceration in presence of PhMe positions are possible. W. McC. at 37° hydrolyse cellobiose, although the presence of Proteolytic enzymes. V III. Proteolytic cellobiase (I) is readily demonstrated in expressed system s of papain. M. B e r g m a h n and W. F. Ross fluid. Possibly (I) is of alimentary origin. (J. Biol. Chem., 1935, 111, 659— 666).—The enzymic N u t r . A b s . (m) homogeneity and the activation processes of papain Retarding action of formaldehyde, acetalde- (I) are investigated. Substrates such as hippuryl- hyde, and acetone on the enzymic hydrolysis of amide (II) and carbobenzyloxydiglycylglycine are sucrose. A . Ch a u d in (Bull. Soc. Chim. biol., 1935, acted on by (I) only after activation by HCN, H2S, 17, 1346— 1350).—The effect of CH20, MeCHO, and and thioglucose. (I) inactivated by oxidising agents COMe2 on the hydrolysis of sucrose by invertase, (H202, I) has its proteinase but not its polypeptidase like that of alkalis, MeOH, and EtOH, is to retard the (III) action reactivated by the above activators, X IX (i,j) BIOCHEMISTRY. Ill so that (I) must contain two different proteolytic optimum p a val. for the reaction at low substrate enzymes. NHPlvNH, completely inhibits the split concn., and the other the actual hydrolytic activity, ting of (II) by HCN-activated (I), but the hydrolysis which at high concn., when the enzyme surface is of gelatin is only slightly affected. Excess of I saturated, controls the pa optimum. This interpret added to HCN-activated (I) destroys both enzymes, ation is applied to corresponding observations made but small amounts inhibit (III) only. The results with laccase and urease. A. L. are in accord with the presence of a CHO group in Inhibitory effect of pbloridzin on an enzymic (III). E. A. H. R. dismutation. H. K a l c k a r (Nature, 1935, 136, Enzymic amylolysis. V. Amylophosphatase 872— 873).—The dismutative conversion of triose- of barley. E. W a l d s c h m id t -L e it z and K. M a y e r phosphoric acid into phosphoglyceric acid and glycero- (Z. physiol. Chem., 1935, 236, 168— 180; cf. A., 1934, phosphoric acid is prevented or markedly inhibited 449).— Barley and malt extracts contain an enzyme, by approx. O-OEY-phloridzin (I). The velocity of amylophosphatase (I), which eliminates all bound conversion of hexose diphosphate into dihydroxy- H3P0 4 from starch paste, and the accompanying acetone phosphate (II), and of (II) into glyceraldehyde decrease in viscosity oc the amount of H3P0 4 elim phosphate, is not affected by this concn. of (I). inated. The degradation (optimal at pn 5-6) results L. S. T. in the production of reducing substances apparently Yeast zymin. I. Effect of some electrolytes consisting of chains of about 36 glucose residues. on carbon dioxide production. II. Effect of (I), which is not activated by amylokinase from malt, ethanol on the production of carbon dioxide. is purified and freed from accompanying enzymes III. Effect of some electrolytes, and of ethanol, by selective adsorption on A1203 and kaolin. Kidney- on the phosphate content during fermentation. phosphatase behaves very similarly towards starch H. E. St a v e l e y , L. M. Ch r is t e n s e n , and E. I. paste, but at p a 5-6 its action is very much slower. F u l m e r (J. Biol. Chem., 1935, 111, 771— 783, 785— W. McC. 790, 791— 802).— I. The optimum p a for the pro Phosphatase of the prostate gland. W. duction of CO, by zymin (I) is 5-8— 6-2, and (I) is K u t sc h e r and H. W o l b e r g s (Z. physiol. Chem., most active when prepared from yeast which has been 1935,236, 237—240; cf. A., 1935,1268).— The human kept for several days at refrigerator temp. NH4C1, prostate gland and seminal fluid contain large MgS04, NaCl, and KC1 increase the initial max. amounts of a phosphatase (I) not identical with urinary rate of C02 formation by (I), whilst NH4C1 (most phosphatase. (I), which'is destroyed in 5 min. at active), MgS04, NaCl, and CaCl2 increase the steady 60°, exhibits specificity as regards its action on const, rate of C02. NH4C1 and MgS04 increase the phosphates, a- and (3-glycerophosphates being readily rate of CO, formation in presence of added inorg. attacked, hexose diphosphate and pyrophosphate P 04"', but the effect of the two salts is not additive. only slightly affected. W. McC. II. Production of C02 by dried yeast, yeast juice, Glycerophosphatase activity of the tissue of living yeast, and (I) is increasingly lowered by EtOH in the order named. 1-86% of EtOH reduces the animals in avitaminosis-A. L. E m e r iq u e (Bull. Soc. Chim. biol., 1935, 17, 1372— 1377).—The phos activity of (I) 50%, whereas 14% is necessary to phatase (I) content of the kidneys and liver of rats reduce the activity of dried yeast 50%. Inorg. suffering from vitamin-A deficiency is the same as that P 04"' does not decrease the sensitivity of (I) towards in normal animals. In the lung, however, (I) is > EtOH. NH4C1 in presence of EtOH increases the normal. A . L . rate of CO, production to > that observed in absence of EtOH. " Combining power of taka-diastase towards III. The optimum p H for disappearance of inorg. glycerophosphates. J. Co u r t o is (Bull. Soc. Chim. P 04"' from a (I) fermentation mixture is 6-2— 6-4. biol., 1935, 17, 1340-—1345).—The reaction coeffs. Electrolytes markedly decrease the time which for the rates of hydrolysis of a- and (3-glycerophos elapses before P 0 4"' attains a min. val., and the effects phates by taka-diastase increase regularly with of the cations are in the order NH4> Mg> Na> K > increasing amounts of enzyme up to a certain point and Ca. EtOH in low concn. increases the time required thereafter both remain const., the amount of diastase for esterification and the min. steady state val. at this point being the same in both cases. This of P 04"', but the latter is decreased if NH4C1, KC1, behaviour is explained by the affinities of the enzyme or NaCl be present also. For compounds of the type for both substrates being the same, but the rates of R'NH3C1, the influence of R in decreasing the time hydrolysis different. A. L. necessary for inorg. P O /" to reach a min. val. is Comparative hydrolysis of a- and (3-glycero- C6H1105>H>Me. J. N. A. phosphoric acids by vegetable phosphatases. Fermentation of carbohydrates. G. M a l y o t h II. Taka-diastase. J. Co u r t o is (Bull. Soc. Chim. and E. S o m m e r f e l d (Biochem. Z., 1935, 281, 49— biol., 1935, 17, 1318— 1339; cf. A., 1935, 122).— 79).—The effect of changes in amount of enzyme, I he vals. of the optimum pa for the hydrolysis of vol. of H ,0, and amount of sugar and of addition of a- and (3-glycerophosphoric acids increase with the KH2P04 with and without nutrient media on the rate substrate concn., the displacement being greater and results of fermentation of glucose by yeast has for the (3- than the a-compound. This behaviour is been measured (error usually > 4% ) in a modification the result of two simultaneous reactions, one involving of the micro-apparatus of Krogh. When cell-free the affinity of the enzyme for the substrate which press juice is used, 100% fermentation is recorded, the increases with acidity and on which depends the deficit with living yeast being due to sugar con-
V? 112 BRITISH CHEMICAL ABSTRACTS. A. X IX (j) sumption for building up the cells, to undetected inhibit production of lactic acid (I) by B. aèrogenes gaseous exchanges, and to related causes. With and those < 0-024/ inhibit production of (I) in rabbit living yeast, alone or in nutrient media, the ferment muscle pulp, but addition of glycogen to the pulp ation is accelerated by KH2P04, especially when the prevents the inhibition. W. McC. proportion of yeast is small. When the juice is Determination of oxygen consumption of used, KH2P04 with nutrient medium causes acceler yeast. G. N e u m a n n (Biochem. Z., 1935, 281, 181— ation > that found with living yeast. The apparatus 185).— Spectroscopic examination of a standard may also be used to measure the fermentation of oxyliæmoglobin (I) solution (saturated with 0 2) polysaccharides (e.g., hydrolysis of maltose by to which a known amount of yeast has been added leucocytes from horse blood). W. McC. (with exclusion of 0 2) permits determination of the Chemical reactions during alcoholic ferment time required for the yeast to reduce (I) and hence ation. I. Production and hydrolysis of adenos- of the 02 consumption of the yeast. If the time of inetriphosphoric acid and their connexion with reaction is suitably chosen, the vol. of 0 2 consumed hydrolysis of sugar. C. L utwak-Mann and T. by 1 mg. of yeast is about 17 c.c. with dil. and 22 c.c. Mann. II. Theoretical considerations. J. K. with conc. (I) solutions. W. McC. Parnas, C. Lutwak-Mann, and T. Mann (Biochem. Determination of phosphorus in yeast by the Z., 1935, 281, 140— 156, 168— 174).—I. Fresh bottom bomb calorimeter. R . A i r o l d i (Annali Chim. yeast contains appreciable amounts and Lebedev Appl., 1935, 25, 523— 525).— Application of the extract only small amounts of adenylic acid (I) and method of Garelli and Carli (A., 1933, 621, 1179) to adenosinetriphosphoric acid (II). The extract con yeast is described. F. O. H. tains an enzyme which converts (II) into (I), but no Influence of buffer on sugar consumption and enzyme which produces NH3 and inorg. phosphate acid production by Aspergillus. V. B o lc a to from (I). During alcoholic fermentation with yeast (Annali Chim. Appl., 1935, 25, 515— 523).— Pro or extract (I) is converted into (II), phosphate being duction of acid by Aspergillus grown in aq. sucrose transferred to (I) from liexosediphosphoric acid (III) is increased by the presence of citrate buffer, due to when the extract is used and otherwise from phospho- both buffering action and diminished rate of carbo glyceric (IV) and pliosphopyruvic acid (V) with hydrate consumption. Utilisation of the citric acid accompanying production of AcC02H. In the first case the process is not affected by NaF, in the second produced is unaffected. F. 0. II. it is completely inhibited. (II) added to the extract Chemistry of mould - tissue. VIII. Innate in presence of glucose yields (III) and (I), but no factors influencing growth and sterol production dephosphorylation of (II) occurs if (III) is present. of Aspergillus fischeri. P. R. W e n c k , W. H. It is concluded that when fermentable substances P e t e r s o n , and H. C. G r e e n e . IX. Cultural are added to (II) fructosediphosphoric acid is produced, factors influencing growth and sterol production and that the transformation of (IV) and (V) into of A. fischeri. P. R. W e n c k , W. H. P e t e r s o n , AcCOoH provides the occasion for a transformation of and E. B. F r e d (Zentr. Bakt. Par., 1935, II, 92, 324— (II) additional to that which occurs during the first 330, 330— 338; cf. A., 1935, 535).—VHI. Growth phase of fermentation by yeast. and sterol (I) production varied with the strain used. II. The above (and other) results indicate that (I) IX . With a no. of C sources the amount of mycelium and (II) act as phosphate carriers during alcoholic produced and its (I) content were inversely related. fermentation much in the same way as they do in Urea was the best N source in CaC03-free media, muscle. W . McC. whereas NH4N03 was superior in the presence of CaC03. The % of (I) in mycelium increased with the Effect of cholesterol and insulin on fermentation glucose concn. in the medium, with the glucose : urea by yeast. S. H e r m a n n [with R . N e ig e r ] (Biochem. Z., 1935, 281, 121— 127).—The fermenting power of ratio (optimum 40 : 1), and with temp, (optimum 37°). living yeast is specifically restricted by cholesterol With prolonged incubation, production of (I) increased (I) sols which, however, accelerate fermentation by even after autolysis of mycelium set in. Aeration autolysed yeast. Some samples of insulin (II) influenced the rate of fermentation, but not of (I) accelerate fermentation by living yeast, but this formation. The max. % of (I) was obtained in low- acceleration is checked by (I) sols. Fermentation urea media at p s 2-0. A. G. P. by autolysed yeast is not accelerated by (II). The Production of dimethylpyruvic and pyruvic sensitivity of yeast to poisoning with H2S04 and sali acids by Aspergillus niger. T. H i d a (J. Shanghai cylic acid is increased by washing with light petroleum. Sci. List., 1935, IV, 1, 201—214).— The mycelium The acceleration of fermentation caused by cozymase of A. niger, when transferred to a medium of p n 7, (III) is checked by (I) sols. Apparently the samples containing glucose or sucrose 5%, Na2S03 5%, NH4C1 of (II) contain a thermostable (not destroyed in 30 1%, KH2P04 2%, produces Pr^C0-C02H (I) and min. at 100°) substance which is not (III). AcCO,H (II). (I) was synthesised by the interaction W. McC. of Et2C204, Pr^Br, and Mg in Et20. The Mg com Effect of vitamin-C on fermentation by yeast pound on decomp, with H20 affords the Et ester of (I). and on lactic acid production in B. aèrogenes NH," favours the production of (I) and inhibits that cultures and muscle pulp. K. Zipe and M. of (II). J. H. B. Thurah (Biochem. Z., 1935, 282, 51— 55).—Alcoholic Effect of thymol on progress of rabbit moni fermentation by yeast is not inliibited by ascorbic liasis. W. D. St o v a l l , S. B. P e s s in , and L. A lm o n acid in concns. of 1 :10°— 1 :125. Concns."< 0-0044/ (J. Lab. Clin. Med., 1935, 20, 572— 582).— Thymol X IX (j) BIOCHEMISTRY. 113
(I) inhibits growth of Monilia in cultures, hut has no NH4C1 media, and produces indole from trypsin- effect on the progress of infection in rabbits. (I) peptone-H20. A. G. is completely absorbed and can be recovered from Toxin formation by bacteria. I. Stimul urine, blood, or liver, but not in appreciable amounts atory and inhibitory substances in peptones. P. from fasces. Ch . A b s . (p) S t a d l e r and I. M e is s n e r (Zentr. Bakt. Par., 1935, Effect of certain nitrogen compounds on I, 134, 102— 109).—The influence of peptones on grow th of Chlorogonium and Chilomoiias. J. B. toxin production by B. botulinus varied with their L o e f e r (Arch. Protistenk., 1935, 85, 74— 86).— source and method of prep., and was dependent on Cliilomonas cannot utilise NH2-acids, whereas the presence of certain chemical substances. Decomp, Chlorogonium produces markedly increased growth, products of animal proteins have an inhibitory action. notably with aspartic acid. Neither species can A. G. P. use amide-N. A. G. P. Metabolism of Bact. coli. Production of Alcohol- and carbohydrate-oxidising bacteria biogenic amines. P. St a d l e r and E. N e u s isolated from fruits, and a new classification of (Zentr. Bakt. Par., 1935, I, 134, 110— 114).—Some oxidising bacteria. II. T. A s a i (J. Agric. Chem. strains of B. coli converted tyrosine into tyramine, Soc. Japan, 1934, 10,1124— 1136 ; 1935,10, 50— 60; others produced OH-acids by deamination. cf. A., 1934, 1036).— Organisms are grouped according A. G. P. to the optimum temp, for multiplication. The Influence of lithium chloride on Bact. coli. II. optimum pa for production of gluconic acid is < K. R ic h t e r (Zentr. Bakt. Par., 1935, II, 92, 249— that for multiplication. Peptone and glucose are 256).—Addition of LiCl2 to agar media lowered the the best sources of N and C, respectively. dry-matter production, sugar fermentation, and re Ch . A b s . (p) spiration rates of cultures. A. G. P. Deamination of alanine by bacteria. E . A u b e l Acid and gas formation by members of the and P. E g a m i (Compt. rend. Soc. Biol., 1935, 120, coli-aero genes intermediate groups in the 684— 685).— “ Resting ” bacteria in aerobiosis con presence of certain sugar alcohols and their vert alanine into AcC02H more readily in presence anhydrides. K . P. Dozois, F . H a c h t e l , C. J. of N 03', which is reduced, or of NH2OH. The Ca r r , and J. C. K r a n t z , jun. (J. Bact., 1935, 3 0 ,1S9— process is therefore probably a dehydrogenation; 192).—Dulcitol and mannitol are fermented by many the action of catalase on the H20 formed, which would organisms of the group, but the anhydrides arc not otherwise destroy the AcC02H, is partly inhibited. utilised. A. G. P. R. N. C. Amino-acids necessary for growth of Cl. sporo- Mechanism of non-symbiotic fixation of atmo f/enes. P. F il d e s and G. M. R ic h a r d s o n (Brit. J. spheric nitrogen. T. R. B h a s k a r a n and V. Exp. Path., 1935, 16, 326—335).— Growth occurs Subrahmanyan (Current Sci., 1935, 4, 234— 235).— in a medium containing NH2-acids as N source, In cultures of soil organisms glucose decomp, was the indispensable NH2-acids being tryptophan, tyro rapid during the first 4 days. During this period sine, phenylalanine, arginine, and leucine; histidine, C02 and org. acids were produced and approx. J of cystine, methionine, and valine are also probably the expected amount of N was fixed. Of this much indispensable. R. N. C. was in a H20-sol. form. Subsequently (4— 8 days) org. acids were destroyed, mucilage was formed, Gonococcal polysaccharides. S. M u t e r m il c h and N was fixed. Formation of mucilage and N and A. G r im b e r g (Compt. rend. Soc. Biol., 1935, fixation are related, but not proportional. A. G. P. 120, 587— 589).—A polysaccharide with the properties of a hapten is isolated from Gonococci by dissolving Occurrence of Azotobacter at high temper in Na taurocholate, acidification with AcOH, .filtra atures. J. Sin g h and A. H u s s a in (Current Sci., tion, neutralisation with NaOH, and evaporation in 1935, 4, 235— 236).—Azotobacter survive in a vac.; proteins are coagulated by heating to 100° vegetative condition at 45°. A. G. P. and removed by filtration, and the polysaccharide is Can Azotobacter cliroococcum synthesise repeatedly pptd. with EtOH in alternately acid and vitamin-D ? J. E. G r e a v e s (J. Bact., 1935, 30, alkaline solutions. The final product is protein- 143—148).—When grown on synthetic media A. free, and yields a reducing sugar on hydrolysis. It cliroococcum can synthesise ergosterol, which is trans fixes the antigonococcal antibody. R. N. C. formed into vitamin-D by irradiation. A. G. P. Interrelationship between the amount of V- Occurrence of a strain of Azotobacter chroococ factor and the amount of air necessary for cum which does not ferment mannitol. N. R. grow th of Hmmophiltts influenza:, type b, in Smith (J. Bact., 1935, 30, 323—328).—The organism certain media. M. P it t m a n (J. Bact., 1935, 30, is widely distributed in soils. A. G. P. 148-—161).— Growth of the organism in certain media Bacterium acidi lactici, Hueppe, and its containing small amounts of 7-factor is initiated only systematic classification on the basis of its pro if the culture is well aerated. With more F-factor perties. G. P r a n g e (Zentr. Bakt. Par., 1935, II, less air is necessary. A. G. P. 92, 305— 324).— Comparison is made of the bio Biochemistry of Bacillus mesentericus htjdro- chemical activities of various organisms of the coli- lyticus. S. H e r m a n n and P. N e u s c h u l (Biochem. aerogenes group and of B. acidi lactici. The latter does Z., 1935, 281, 219— 230).— The bacillus, obtained not ferment sucrose, raffinose, dextrin, starch, from carrots, grows very poorly or not at all anaerobic inulin, dulcitol, or inositol, fails to grow in citrate— ally, liquefies gelatin, and coagulates milk (clots X IX (j) 114 BRITISH CHEMICAL ABSTRACTS. A. later liquefied). It grows best in media (e.g., veget and sorbitol with both forms of N and raffinose and ables or suspensions containing them) containing erythritol (VIII) on NH4‘ media were inferior to (I). org. N (no growth if no org. N) and cellulose or liemi- As measured by total 0 2 consumption NH4 was more cellulose. Growth on bouillon or peptone solutions readily utilised than N 03'. For R. japonicum, (V) is not accompanied by production of H2S or indole. was the best energy source, (I), (IV), and xylose were Acid production is very small; no gas is evolved and equally effective, whereas (II), (VI), (VII), (III), and no reducing substances (Fehling) are produced except (VIII) were utilised little or not at all. N 03' was from starch, which, like sugars (glucose, fructose, more effective than NH4\ A. G. P. sucrose, galactose, maltose, lactose), is hydrolysed. Factors influencing the respiration of Rhizo The bacillus and enzymes obtained from it have bium. D. W. T h o r n e and R. H. W a l k e r (Proc. powerful softening action on vegetables, the con Iowa Acad. Sci., 1934, 4 1 , 63—70).— Stimulation of nective tissue being destroyed. W. McC. R. meliloti by certain substances (yeast and legume .Relation of micro-organisms to carotenoids extracts) is attributable to their nutrient content. and vitamuwl. II. Production of carotenoids The assumption that there is a co-enzyme of respir b y Mycobacterium phlei. M. A. I n g r a h a m and ation is not substantiated. C h . A b s . (p) H. S t e e n b o c k (Biocliem. J., 1935, 29, 2553—2562).— Oxidation of glucose by Rhizobium meliloti. On a medium containing asparagine (I), glucose (II), O. R. N e a l and R. H. W a l k e r (Proc. Iowa Acad. K2HP04, MgS04, and Na and Fem citrates M. phlei Sci., 1934, 4 1 , 167— 168),—In media containing produced less pigment than when [IC] and [HP04"] M /540—M /180 concns. of glucose the 0 2 consumption were lowered, or when glycols and alcohols replaced of R. meliloti increased rapidly for 4— 8 hr. and sub (II); at normal pa replacing (I) with NH4‘, CO(NH2)2, sequently declined to a low and fairly const, level, and peptones was without influence on pigmentation. the total consumption being approx. -J of that required Increasing the [Fe"‘] prevents pigmentation; excess for complete oxidation. The proportion of glucose-C of (I) causes autolysis, and on media containing converted into C02 in the presence of NH4'-N was glycerol or low concn. of (II), (I) is attacked by the < that in the presence of N 03'-N. C h . A b s . (p) bacteria. C2H4, Na‘ , Li', Ca", Mg", and Se, the redox potential, the light intensity, and temp, were without Inhibition of growth of Bacillus subtilis on a effect on pigmentation. By separating the pigments modified extract agar by X-irradiation of the from light petroleum on an adsorption column the m edium . I. H. B l a n k and H. K e r s t e n (J. Bact., presence of a- and ¡3-carotene, kryptoxanthin, and 1935, 3 0 , 21— 32).—The action of soft A-rays on esters of lutein, zeaxanthin, and azafrin wras estab agar produces a diffusible, non-volatile substance lished. H. D. which is toxic to B. subtilis. A. G. P. Solubility of Pneumococcus in saponin. III. Metabolism of spirochsetes in vitro. G. Saponinlysis reaction as a means of differenti S c h e e f (Zentr. Bakt. Par., 1935, I, 1 3 4 , 35— 43).— ating Pneumococcus and Streptococcus. S. J. In 4 species examined no 0 2 consumption was apparent. K lein (J. Bact., 1935, 3 0 , 43— IS; cf. A., 1933, Production of C02 occurs only in carbonate media 1207). A. G. P. and results from the action of lactic acid formed from sugars. A. G. P. Kinetics of the attack on glucose and lactic acid by small concentrations of bacteria ; concept of Evolution of dehydrogenases of Staphylococcus minimum active concentrations. P . C h a i x aureus during grow th. D. B a c h (Compt. rend. (Compt. rend., 1935, 20 1 , 626— 628).— Of three Soc. Biol., 1935,1 2 0 , 673—674).—The dehydrogenase species of propionic bacteria, one exhibited a threshold content of the cultures falls as their age increases; concn. below which it decomposed neither glucose the nature of the H donator does not affect the rate nor lactic acid, the second a threshold for short but of decrease. R. N. C. not for long periods of incubation, and the third a Hydrogen donators for Staj)hylococcus aureus. threshold for glucose, but for lactic acid only some retardation of decomp. W. 0. K. D. B a c h (Compt. rend. Soc. Biol., 1935, 1 2 0 , 608— 610).—The active H donators include most carbo Physiology of Rhizobium. III. Respiration hydrates and related substances and eight org. acids. and growth as influenced by the reaction of the EtOH and BuOH are the only active alcohols, and m edium . D. W. T h o r n e and R. H. W a l k e r . IV. cysteine and glutamic acid the only active NH2- Utilisation of carbonaceous materials. 0. R. acids; the activities of these are very feeble. Simple N e a l and R. H. W a l k e r (J. Bact., 1935, 30, 33— 42, aldehydes, ketones, and natural bases are inactive. 173— 1S7; cf. A., 1933, 638, 752).—III. Growth of R. N. C. R. meliloti and R. japonicum reached max. at p u Staphylococcus toxins and anti-toxins. A. T. 7-0, 6-7— 6-9, decreasing to zero at 4-6— 4-9, 4-2 and G l e n n y and M. F. S t e v e n s (J. Path. Bact., 1935, 9-6, 9-5, respectively. The optimum pa for respiration 4 0 , 201—210).—Certain strains produce two toxins was > that for growth in both cases. for which there are corresponding antibodies. IV. No significant differences in the rate and ex C h . A b s . (p) tent of 0 2 consumption by R. meliloti were apparent Differentiation of Streptococcus pyogenes in media containing glucose (I), mannitol (II), or from man and animals by the sorbitol-trehalose sucrose (III). Galactose (IV) and arabinose (V) were test. F. C. M i n e t t (J. Path. Bact., 1935, 4 0 , 357— more effectively utilised than (I) on N 03' and on NH4‘ 364).—Trehalose is usually fermented by human, and media. Maltose (VI), lactose (VII), inositol, dulcitol, sorbitol by bovine, strains. Ch . A b s . (p) X IX (j, k) BIOCHEMISTRY. 115
Toxic fraction of scarlatinal streptococci. Influence of various metallic compounds on C. A. G r e e n (Quart. J. Med., 1935, 4, 93— 115).— the growth of bacteria. W. H a a s e (Med. Klin., All strains produced a heat-labile exotoxin. Broth 1934, 30, 1585— 1587; Chem. Zentr., 1935, i, 2199).— filtrates also contained an acid-insol. toxic fraction The germicidal action of Cu, brass, Sn, Al, and Ag similar to that from an alkaline extract of washed foil was relatively small compared with that of bacterial bodies. It was species-sp. Ch. A bs. (p) Simanit (Ag202,Mn02) or Euthagen (Ag salt of thiocellobiose). A. G. P. Differences in effect of mercuric phenyl chloride on different races of bacteriophage and Effect of hormones on alcohol metabolism. similarity in effect on a phage and its homo E. M. P. W i d m a r k (Biochem. Z., 1935, 282, 79— 84; logous organism . N. R. G o l d s m i t h (J. Bact., cf. A., 1934, 213; 1935, 655).—In dogs, adminis 1935, 30, 237— 242).— Lysis by bacteriophages of tration of pituitrin, adrenaline, and thyroxine has no Staphylococcus or of Escherichia coli was not affected effect on the metabolism of EtOH, but that of insulin by HgPhCl (1 : 20,000—80,000) in a contact period (I) greatly increases slow rates of EtOH metabolism of 30 min. After 6 weeks’ contact the Staphylococcus until the max. attainable under normal conditions is phage was destroyed, but that of E. coli remained reached; high rates are not affected. The naturally unaffected. Toxicity of the antiseptic to the sp. phage occurring differences in the rates are partly dependent is paralleled by that to the homologous organism. on the (I) content of the organism. The effect of A. G. P. (I) is not counteracted by giving sucrose. Stimulation of bacterial growth rate by ger- W. McC. m anic m ethyl oxide. P. L. Ca r p e n t e r , McD. Adrenaline content of adrenals of splenectom- F u l t o n , and C. A. S t u a r t (J. Bact., 1935, 30, 137— ised dogs. S. T s u j io k a (Arb. Med. Fak. Okayama, 142).— As compared with nutrient broth cultures 1935, 4, 445— 452).— The abs. content of adrenaline those in germanic Mo oxide broth are inhibited and the amount per g. of gland increase until the 15th during the lag phase, stimulated during the early day after splenectomy and subsequently decline to logarithmic phase, and show a premature period of normal (30th day). Ch. A bs. (p) decline. A. G. P. Adrenal cortex. I. Fractionation of hormone concentrates. J. J. P e i f e n e r , O . W i n t e r s t e i 'n e r , Action of sulphurous acid on bactericidal and H. M. V a r s . II. Isolation of several physio pow er of blood. H. C r e m e r (Z. Unters. Lcbcnsm., logically inactive crystalline compounds from 1935, 20, 315—317).— Prolonged administration of active extracts. O. W intersteiner and J. J. small amounts of H2S03 to rabbits markedly decreases P f i f f n e r (J. Biol. Chem., 1935, 111, 585— 597, the power of the blood to destroy staphylococci. 599—612).—I. The cortical hormone preps, were E. C. S. Bactericidal principle in excretions of surgical assayed by an earlier method (A., 1934, 566). Preps, maggots, which destroys important etiological from ox glands (ibid., 1267) were purified by alter nate dissolution in H20 and Et20 and contained agents of pyogenic infections. S . W . S i .m m o n s (J. Bact., 1935, 30, 253—267).—The active bacter 100—200 dog units per m g.; these preps, gave phenyl- icidal principle (not a bacteriophage) isolated from hydrazones in cold aq. AcOH. More active preps, excreta of surgical maggots is heat-stable and retains which did not reduce alkaline AgN03 were obtained its activity longer in a desiccated condition than in by using CGHG in place of Et20 in the alternate solution. A. G. P. dissolution procedure. By fractionation of these preps, one containing 400 dog units per mg. was Therapeutic application of phenylmercuric obtained; this absorbed at 236 mg, was pptd. by salts. Use of basic phenylmercuric nitrate in NHPlrNHj, but no insol. NaHS03, semicarbazide, gynaecology. L. H. B i s k i n d (Lancet, 1935, 229, oxime, or dimedon derivatives were obtained. 1049— 1052). L. S. T. II. Four physiologically inactive compounds were separated from the most active preps.: C20H34O5 Antiseptic action of certain metals. V . J e n s e n or C21H3G05, m.p. 214°, C21H320 5 (I), m.p. 210— and A. J e n s e n (Zentr. Bakt. Par., 1935, I, 134, 214°, C24H4G07, m.p. 126-128“! and one with un 86—96).— The efficiency of Ag-Hg, Ag, Ag20, and determined empirical formula, m.p. 236—239°. (I) AgCl as urinary disinfectants is examined. A. G. P. reduces Benedict’s solution and alkaline AgN03 Microbiological basis of chemotherapeutic and is possibly identical with the life maintenance action. II. Microscopical detection of thera hormone of Kendall, but the absence of physiological peutically applied gold in spirochaetes, trypano- activity is stressed. Leucylproline anhydride was somes, and bacteria by ultracrystallisation. also separated. H. D. N. v o n J a n c s 6 and E. N o v a k (Zentr. Bakt. Par., Physico-chemical state of the adrenal hormone 1935, I, 134, 76—86).— Themethod is based on the in the blood. D. B r o u n and H. S c h e i n e r (Compt. absorption of injected Au by spirochaetes in rats or rend., 1935, 201, 794— 795).—Minced adrenal cap mice. Spirochaetes are removed centrifugally from sules give up their adrenaline (I) to serum (II), a blood sample. From a smear on a slide org. distilled H20 (III), or H20 at pa 3-5-40 (IV). matter is removed by gentle ignition and the remaining (Ill) and (IV) when injected into atropinised dogs minute Au crystals serve as nuclei for crystal formation under chloralose anaesthesia affect the blood pressure from a “ developing” solution of AuCl3-K 3Fe(CN)G. as does (I); (II) produces a much more prolonged, The Au “ picture ” is examined microscopically. but less abrupt, rise in arterial pressure and there is A. G. P. no apncea. The (I) in (III) and (IV) is completely 116 BRITISH CHEMICAL ABSTRACTS.— A. X IX (jfe) ultrafilter able, but in (II), practically not at all. in normal and hypophysectomised dogs induces a Extraction of (II) with Et20 or CgH6, or acidification fall of blood-Ca and an increase of plasma-P04. to pa 3-5—4-0, or dilution with H ,0, or treatment with Ca is restored to normal by parathormone, but de Ca", renders the (I) completely ultrafilterable. The pressed still further by anterior pituitary extract. hormone is probably bound to the protein-lipin com The Ca depression is due to parathyroid lesions plexes of the blood. J. L. D. following pancreatectomy. R. N. C. Action of adrenaline on liver suspensions. E. Use of mice in the standardisation of para G e ig e r (Biochem. Z., 1935,281, 86—92 ; cf. A., 1932, thyroid hormone. Effect of parathyroid on 188).—The sedimentation of the material pptd. from rachitic rats examined by the “ line” test. colloidal liver preps, (frog) by CC13*C02H is specific F. J. D y e r (Quart. J. Pharm., 1935, 8, 513— 524).— ally accelerated (thyroxine, insulin, histamine, ergot- The Mg-Ca antagonism method of Simon (A., 1935, amine, ephedrine, morphine, and atropine in equiv. 539) is applied by using at least 20 mice in each group, concns. have no effect) by added adrenaline (I) (concn. administering 1-7— 1-8 mg. of MgS04,7H20 per g. 10-°— 1(H6), although degradation of glycogen (II) body-wt., and recording the max. no. of mice affected and sugar production are unaffected. The effect 20— 60 min. after injection of Mg. The % obtained appears after < 5 min., reaches its max. after about for parathyroid prep, and control are then referred 20 min., and then becomes less pronounced. In the to a standard curve. Parathyroid preps, supplement absence of (II) or at pa outside the range 5-5—-7-5, the calcification produced by vitamin-/) as indicated or if the diastatic activity of the preps, is destroyed by the “ line ” test (A., 1928,1288), but the test when by heating for 1 hr. at 48—50°, there is no effect, but used for parathyroid alone is insensitive and non-sp. sedimentation is more rapid when (II) is absent. F. O. H. Added (I) has no effect on the extent of degradaton Influence of temperature on the secretion of or on production of simplexes. Possibly (I) alters the thyrotropic hormone. G. K u s c h i n s k y (Arch, physical state of (II), reducing its power as a protective exp. Path. Pliarm., 1935, 179, 726— 737).— Exposure colloid. W. McC. of rats to cold (4°) is accompanied by normal activity Influence of peripheral lymph on the blood- of the thyroid gland (indicated histologically) for sugar fluctuation due to adrenaline. H. A r a k i 10 days, after which the activity markedly increases. (Arb. dritt. Abt. Anat. Inst. Univ. Tokyo, D, 1934, At 38—40°, the gland is normal for the first few days, No. 4, 145—151).— Blood-sugar fluctuations were inactive at the 14th, and, in some cases, again active greatly suppressed when adrenaline-lymph mixtures after 26— 33 days. These changes are correlated were stored (notably at 37° for 24 hr.) prior to injection. with those in thyrotropic activity of the pituitary Lymph alone caused very little fluctuation. gland and the presence of an inhibitory factor. Ch . A b s. (p) F. 0. H. [Slow] continuous injection of adrenaline : Thyroid standardisation and dosage. R. F. [absence of] effect on blood-urea, -cholesterol, C o r r a n , J. P r it c h a r d , and F. E. R y m i l l (Quart. and -calcium. A. B a u d o u i n , H. B é n a r d , J. J. Pharm., 1935, 8, 331— 336).—Variations in total L e w i n , and J. S a l l e t (Compt. rend. Soc. Biol., and thyroxine (I)-I contents of fresh and of dried 1935,120, 629—631). R. N. C. defatted glands invalidate any correlation between “ thyroid B.P. 1932 ” and preps, expressed as fresh Influence of oxidation-reduction system on or dried gland. The relative activities of U.S.P. X adrenaline action. III. K. T e r a i and H. I c h i t - and B.P. 1932 thyroid preps, are approx. 74±12 : 100. s u b o (Folia Pharmacol. Japon., 1935, 1 9 , 306— Following hydrolysis, direct determination of I on 322; cf. A., 1935, 1172).—Injection of NaHSO„ the aeid-insol. [(I)-containing] ppt. affords a check instead of quinol into rabbits produced the quinol- for the B.P. 1932 method for (I) in thyroid preps. effect on adrenaline action. Ch . A b s . (p) F. O. H. Inactivation of adrenaline by acetaldehyde Role of the thyroid in the process of plumage verified on several plain-muscle organs. A. M. development in chicks. I. N. L e k t o r s k y and B a p t is t a (Compt. rend. Soc. Biol., 1935, 1 2 0 , 547— N. A. K u s m in a (Biol. Zentr., 1935, 55, 16—29).— 550).—The inactivation of adrenaline by MeCHO is The thyroid hormone shows no preferential effect on confirmed on the Lôwen-Trendelenburg vascular plumage development. R. N. G. prep., the isolated rabbit intestine, the enucleated frog’s eye, and the bronchial muscle of the cat or dog. Influence of thyroxine on the hypoglycaemic R. N. C. action of cholic acid. H. ELo s a k a (Arb. Med. Fak. Inactivation of adrenaline by methylglyoxal, Okayama, 1935, 4, 370—378).—Thyroxine does not glyceraldehyde, and acetaldehyde. J. T. Rico alter the blood-sugar level of normal rabbits, but lowers the capacity of Na cholate to produce a hypo- and A. M. B a p t i s t a (Compt. rend. Soc. Biol., 1935, 120, 545—546).—Adrenaline is inactivated as regards glycsemia when injected simultaneously. its pressor effect in decerebrate dogs by AcCHO, Ch. A b s . (p) glyceraldehyde, and MeCHO, but not by AcC02H Preparation of prolactin. R. W. B a t e s and O. or phosphoglyceric acid. The inactivation is not R i d d l e (J. Pharm. Exp. Tlier., 1935, 55, 365— 371).— opposed by ascorbic acid. R. N. C. Prolactin. (I) free from follicle-stimulating (II) and thyrotropic hormone (III) is prepared by extraction Hypocalcæmia of depancreatised dogs. R. of the anterior lobe with 60— 70% aq. EtOH at pn G e r s c h m a n and A. D. M a r e n z i (Compt. rend. Soc. 9— 10 and pptn. of (I) at higher EtOH concns. (I) is Biol., 1935, 120, 737—738).—Total pancreatectomy separated from (II) and (III) by pptn. from aq. X IX (k, I) BIOCHEMISTRY. 117 solution with H2S04 and is further purified by dis exp. Path. Pharm., 1935, 179, 717— 721, 722— 725).— solution in aq. EtOH and repeated pptn. with NaCl (a) Administration to rats of anterior pituitary-like at pa 6. Preps, so obtained have a potency of 5— prep, from pregnancy urine (prolan) (I) inhibits 10 units per mg. and may be boiled at p n 8 for 1 hr. formation and ripening of follicles and promotes without loss of potency. H. D. lutéinisation in the ovaries. (6) (I) enlarges the lipin- Diabetogenic anterior pituitary action inde containing cells of rats’ testes. F. O. H. pendent of the adrenals. B. A. II o u s s a y and L. F. (Estrogenic activity of cow’s urine during L e l o ir (Compt. rend. Soc. Biol., 1935, 120, 670— pregnancy. M. M. 0. B a r r i e , J. B. E. P a t t e r s o n , 672).—Adrenaline produces a transitory hyper- and S. W. F. U n d e r h i l l (Quart. J. Pharm., 1935, glycsemia, but neither it nor cortin is diabetogenic. 8, 424— 428).— Only small amounts of œstrin ( < 50 Anterior pituitary extract (I) produces diabetic international units per litre) are excreted by cows liyperglycsemia in hypophysectomised, pancreatect- during the first 23 weeks of pregnancy ; after this omised, and adrenalectomised toads, and in adreno- period the level increases to 700 units per litre at the medullectomised dogs, together with glycosuria; 30th week, 4000 at the 34tli, and 17,000 at the 37th. splanchnic section or sympathectomy does not in During the final weeks, the content varies probably hibit the action. The hyperglycsemia produced in due to variations in the concn. of urine. F. O. H. partly adrenalectomised dogs persists after complete Action of oestrin on mammary secretion. adrenalectomy only if (I) administration is continued; J. W. R o b s o n (Quart. J. Exp. Physiol., 1935, 24, the diabetogenic action of (I) is therefore independent 337— 344).— In lactating mice cryst. ketohydroxy- of the adrenals. It. N. C. cestrin temporarily inhibits mammary secretion Effect of hypophysectomy on pregnancy and according to the dosage and method of administration. lacteal secretion in the hitch. B. A. H o u s s a y C h . A b s . (p ) (Compt. rend. Soc. Biol., 1935, 120, 496— 497).— Hormone of the corpus luteum. E. F e l s Hypophysectomy results in abortion in pregnant, (Compt. rend. Soc. Biol., 1935, 120, 730—731).— A and cessation of secretion in lactating, bitches. mixture of luteosterone-G and -D, or of either -with The anterior pituitary is the necessary part of the pregnandione, is more potent than either separately. gland; the effects are not induced by removal of the R. N. C. posterior lobe only, and are abolished by anterior Dehydroandrosterone.— See this vol., 77. pituitary extract. R. N. C. Androstendione.— See this vol., 77. Lacteal secretion provoked by anterior pituit Testosterone.—See this vol., 77. ary extract in the dog. B. A. H o u s s a y (Compt. rend. Soc. Biol., 1935, 120, 502—503). R. N. C. Sexual hormones, and related substances. V.— See this vol., 77. Lacteal secretion through the action of anterior pituitary extract in male guinea-pigs. Sex hormones. VIII—X. See.this vol., 76. J. L. S a r d i (Compt. rend. Soc. Biol., 1935,120, 503— Recent progress in the study of v i t a m i n s . P . 504). R. N. C. K a r r e r (Chim. et Ind., 1935, 34, 1027— 1035).— Glutathione in the tissues of the hypophysec A review. tomised dog : evidence for a pituitary-thyroid International vitamin standards. E. M. N e l and pituitary-testicular association. L. B i n e t , s o n (J. Assoc. Off. Agric. Chem., 1935, 18, 610— L. e 3 d p in o v , and G.W e l l e r (Compt. rend. Soc. 611).—The standards adopted by the International Biol., 1935, 120, 589—590).—Hypophysectomy pro Conference on Vitamin Standards (1935) are discussed. duces a fall of total glutathione (I) of blood < that of E. C. S. reduced (I). The red cell count is only slightly Aseptic culture of insects in vitamin research. reduced. (I) is normal in the adrenals, spleen, E. G. v a n ’t H o o g (Z. Vitaminforsch., 1935, 4 , 300— pancreas, and cardiac muscle, and only reduced (I) 324).— Symbiont-free, aseptic cultures of Drosophila falls in skeletal muscle. Both total and reduced melanogastcr can be obtained from ova sterilised by (I) fall considerably in the liver, thyroid, and testicle, EtOH and chloramine-T, provided that the synthetic the falls being similar to those noted by Marenzi in food complies with certain requirements. D. the toad. The results favour a biochemical associa vielanogaster requires traces of vitamin-Bj and -B2 tion between the pituitary and the thyroid and and other H20-sol. yeast factors together with a very testicle. R. N. C. small amount of fat or unsaponifiable fraction, and Influence of extract of posterior lobe of the absence of -B1 or -B2 can be determined easily pituitary gland on urine- and blood-inorganic with these cultures. The insect does not require vitamin-A, -D, or -E. J. N. A. phosphate. G. D o d e r o (Arch. Farm, sperim., 1935, 60, 422— 429).—Subcutaneous or intravenous Vitamin-A, -C, and Ji2. Constitution and injection of posterior pituitary extracts into rabbits constitution specificity of action. P. K a r r e r increases the serum-inorg. P 04" ' ; the urinary level (Monatsh., 1935, 66, 367— 392).—The development tends to decrease. The phenomena are apparently of the chemistry of these compounds and the con independent of changes in renal function. nexion between constitution and physiological action F. 0. H. are discussed. H. W. Influence of luteinising substance on (a) func Sterol content and vitamin value of avocado tion of the lipin-containing cells of ovaries, oil. R. C. R o b b in s and L . N. B j x g e r (Hawaii (6) testes. G. Iy u s c h i n s k y and Tang-su (Arch. Agric. Exp. Sta, Rept. [1933], 1934, 23—24).— 118 BRITISH CHEMICAL ABSTRACTS. A. X IX (Z)
Sterols are isolated from the expressed oil. The oil III. The harmful effect of NaBOg and Bz202 is also contains vitamin-A and possesses strongly counteracted by simultaneous administration of -A, antirachitic properties. Ch . A b s . (p) but not by -B. E. C. S. Influence of experimental technique during the Vitamin-yl and -B of maize. E. T a k a i i a s h i preliminary period in vitamin-A determinations and G. M a s u d a (J. Agric. Chem. Soc. Japan, 1935, on the response of the test animal to supple 11, 741—749).—There is a close relationship between mentary feeding of the vitamin. P. M. N e l s o n vitamin-A content and the yellow pigment of the and P. P. S w a n s o n (Iowa Agric. Exp. Sta. Rept. on endosperms, but the colour of the pericarp has no Agric. Res., 1933, 116— 117; 1934, 145).—Vitamin-A significance. As regards vitamin-B content, neither supplements must be fed to the rats separately. colour has any significance. One out of 5 kinds of The influence of the body-wt. at the end of the Japanese maize had a high -A content, but the -B depletion period is shown. Females are more content was much the same in all the kinds. Pigeons responsive to -A than are males. Ch. Abs. (p) required < 60% of whole corn in the diet for normal State of combination of vitamin-yl in liver oils. growth. W. McC. L. R eti (Compt. rend. Soc. Biol., 1935, 1 2 0 , 577— Occurrence of vitamin-B in organs. J. B. 580).—Extraction with MeOH of unsaponified liver B r o d i e and F. L. M a c l e o d (J. Nutrition, 1935, 10, oils dissolved in light petroleum removes none of the 179— 186).—The -B content of organs decreased in vitamin-A ; if the unsaponifiable matter is extracted the order liver, heart, brain, muscle. Only traces in the same way, the whole of the -A is removed. occur in blood, spleen, and lungs. The feeding of -A is therefore present in the oil as an ester of a higher normal tissues to -B-deficient rats did not increase the fatty acid, and its formation in the liver from carotene survival period except in those receiving brain. The is followed by estérification. R. N. C. amount of -R in the body of the rat may be changed, Detection of vitamin-/l by the Rosenthal- within limits, by varying the dietary level of the Erdélyi test. H. W i l l s t a e d t (Z. Vitaminforsch., vitamin. A. G. P.
1935, 4 , 272—276).—The test has no advantages over B-Avitaminosis in rats. E.K o d i c e k and J. that of Carr and Price. Carotenoids do not give J o a c h im . (Z. Vitaminforsch, 1935, 4 , 250—255).— the rose-red to reddish-violet coloration, but inter No hyperglycemia could be observed in rats showing ference can be caused by sterols. J. N. A. the typical nervous symptoms of R-avitaminosis, and Vitamin-yl and carotene content of human the blood-cholesterol was normal. The hyperglyce m ilk. W. N e u w e i l e r (Z. Vitaminforsch., 1935, 4, mia in vitamin-Rj deficiency in pigeons may be due 259—271).—The vitamin-A content of human milk to an increase in non-sugar reducing substances. varies from 25 to 300 rat units per 100 c.c. It is J. N. A. independent of the age of the mother, the no. of Vitamin-/} in relation to carbohydrates, pro children, and daily vol. of milk, and is higher after teins, and fats in food. R. L e c o q (Bull. Soc. sci. suckling. Colostrum contains more -A than milk. Hyg. Aliment., 1934, 278—331; Chem. Zentr., Large doses of -A or of carotene (I) increase the -A 1935, i, 2205—2206).—The rate of assimilation content of milk. (I) is present to the extent of 0-005— of carbohydrate, protein, and fat is influenced by 0-400 mg. per 100 c.c. J. N. A. the supply of vitamin-B. The -R requirement is Vitamin-yl and carotenoids in the frog. C. greatest with high-carbohydrate rations. Fats and R a n d (Biochem. Z., 1935, 281, 200—205).—The proteins tend to lower the proportion of -R necessary. liver and fat glands and to a smaller extent the other A. G. P. parts (skin, ovary, eggs, testicles, kidney, lung, Crystalline vitamin-TV. Injection method fallopian tubes) of the frog (summer and winter) of assay. M. A m m e r m a n and R. E. W a t e r m a n . contain carotene accompanied by varying amounts V, VI. Effect of graduated doses on growing of xanthophyll. The liver also contains vitamin-A. rats and on pigeons. R. E. W a t e r m a n and M. W. McC. A m m e r m a n (J. Nutrition, 1935, 10, 25— 33, 35—44, Increase in length in rats receiving vitamin-yl. 161— 166).—IV. Appropriate technique is described. M. M a l m b e r g (Biochem. Z., 1935, 281, 215—218; V. The stimulative effect of the vitamin increases cf. Orr et al., A., 1934,1040).—In young rats receiving up to and probably beyond dosages of 160x10-6 g., a diet free from vitamin-A the length of the tail is an amount which is 80— 160 times that necessary increased by administration of 0-02 mg. of -A daily. for maintenance of life. Administration of thyroxine checks the increase. VI. The min. dose of vitamin-Bj hydrochloride W. McC. to cure polyneuritis was 4 x 10~° g. Larger amounts Physiological action of substances used in up to 160 X 10~® g. increased the wt. of depleted treatment of flour. II. Action on vitamin of pigeons, but failed to bring birds to normal wt. Results flour and on the animal organism fed exclusively are discussed in relation to -Rs. A. G. P. on bread. III. Effect of oxidising substances Physiological action of vitamin-B,. H. G. K. used in treatment of flour on vitamin of flour. W e s t e n b r i n k (Arch. Neerland. Physiol., 1935, 20, S. v on V itéz (Z. Unters. Lebensm., 1935, 7 0 , 258— "161 484; cf. A., 1934, 568).—In pigeons on a diet 265, 265—269; cf. A., 1935, 529).— I. The harmful free from carbohydrate and vitamin-Rj onset of effect of the oxidising substance is due to destruction polyneuritis is not delayed by increasing the fat of carotene and vitamin-A. NaBO- is more harmful content of the diet. Probably the disease is caused than (NH4),S208. by chronic poisoning with carbohydrate or with X IX (I) BIOCHEMISTRY. 119 a degradation product or products of carbohydrate 1 2 0 , 633— 635).—A guinea-pig requires 30 mg. of resulting from the absence of -Bv W. McC. ascorbic acid (I) daily to maintain an adrenal (I) Vitamin-/^ in grapes and grape products. C. content > 1 mg. per g.-wt., and considerable quantities V a c c a (Quad. Nutrizione, 1934— 1935, 1, 424— 432). to maintain the normal (I) content. R. N. C. Tests on pigeons show that the berry of the grape, Ascorbic acid in lens and aqueous humour. as opposed to the seed, is wholly or almost devoid V, D e m o l e and H. K. M u l l e r (Biochem. Z., 1935, of vitamin-i^. N utr. Abs. ( m ) 28 1 , 80— 85).—Fresh aq. humour (from the eyes of Vitamin content of beer. A. S c h e u n e r t and cattle) exhibits pronounced antiscorbutic action M. S c h i e b l i c h (Z. Vitaminforsch, 1935, 4 , 294— (3 c.c. of humour equiv. to 5 mg. of ascorbic acid) 299).—Beer contains very small amounts of vitamins when injected subcutaneously into guinea-pigs re of the B group only. Dark beer contains 3 inter ceiving a diet free from vitamin-C. A prep, from the national units of -B1 and 7-4 biological units of -B2 lenses behaves similarly. In the humour the activity per 100 c.c. If extracts of -By and -B2 are added to corresponds with 100%, in the lens with 50%, of the the beer after manufacture, no loss of vitamins reducing power (dichlorophenol-indophenol). occurs during storage. Possibly yeast withdraws W. McC. tho vitamins from beer during manufacture. Ascorbic acid content of blood and cerebro J. N. A. spinal fluid. F. P l a u t and M. B u l o w (Z. physiol. Nutritive value of fungi. II. Vitamin-/!), -/i2, Cliem., 1935, 2 3 6 , 241— 256; cf. A., 1935, 1036).— and -J34 content of mycelium of Aspergillus In human and rabbit cerebrospinal fluid the vitamin-C syclowi. III. Growth of rats on supplemented exists entirely in the reduced form, but in the blood and unsupplemented mould proteins. H. J. most of the -G occurs in the oxidised form. The G o r c ic a , W. H. P e t e r s o n , and H. S t e e n b o c k (J. variations which occur in the amount of -G in blood Nutrition, 1935, 9, 691— 700, 701— 714; cf. A., .1934, (caused, e.g., by diet changes) concern the reduced 220).— II. When fed at a 10% level in a vitamin-2^- part only and are not parallel to accompanying deficient diet the mycelium protected chicks from variations in the -G content of the fluid. Oral polyneuritis and produced good growth. Pellagra administration of moderate amounts of -G increases was prevented by additions of 1% of mycelium to a the -G content of the fluid and slightly increases that -jB2-deficient ration, although 3% was necessary for of blood. With large doses there are large increases good growth. At a 30% level in an otherwise -By in both. -G introduced into the blood is transported deficient ration the mould prevented the onset of in reduced form, is not oxidised by blood in vitro or paralysis. in vivo, and disappears rapidly. Oxidised -G is not III. Proteins of A. sydowi produced little growth reduced by the fluid in vitro or in vivo but is more in rats and failed to sustain life for > 7— 9 weeks. rapidly absorbed than is reduced -G. In rabbits, Growth was resumed by supplementing mould-protein injected -G can pass from blood into fluid and con with casein, egg-white, or yeast-protein. Still better versely but under physiological conditions the passage results were obtained with proteins of whole wheat from fluid to blood is in some way controlled. In the or of maize-gluten feed. No improvement was ob fluid -G persists much longer than it does in blood. tained by use of gelatin, cystine (I), histidine, tyrosine There is no evidence that the -C of the fluid is reduced (II), or a (I)-(II) mixture. A. G. P. in the nervous system or that this system produces reduced -C. ” W. McC. Flavin syntheses. VIII.—See this vol., 85. Comparison of the vitamin-C (ascorbic acid) Preparation and nutritional value of hepato- content of the cerebrospinal fluid and of the flavin. F. J. S t a r e (J. Biol. Chem., 1935, 1 1 1 , 567— urine in hypervitaminosis-C. F. P l a u t and M. 575).— Hepatoflavin (I) does not prevent dermatitis B u l o w (Naturwiss., 1935, 2 3 , 771).—The vitamin-C in vitamin-A2-deficient rats and chicks, whilst a content of the cerebrospinal fluid can be used for fraction of the liver extract not adsorbed by fuller’s diagnosis of vitamin-G-subnutrition in the same way earth does. Proper growth appears to depend on as the urinary content (cf. A., 1935, 417), the results the presence of both these factors in the diet. The by the two methods giving close agreement. prep, of (I) is modified by pptn. from EtOH with hot P. W. C. Ba(OH)2, pH fractionation of the Ag ppt., and extrac Ascorbic acid in glands. Isolation from the tion of the Ag ppt. with hot AcOH-|-H2S. H. D. pituitary. J. R. M e n d i v e and V. D e u l o f e u (Z. Modification of the Sherman method of study physiol. Chem., 1935, 236, 208—211).—As regards ing the multiple nature of vitamins, with an their content of the acid (I) organs of Argentinian application to vitamin-/!2. T. S. H a m il t o n and cattle form the series: pituitary, corpus luteum, H. H. M it c h e l l (J. Nutrition, 1935,1 0 , 117— 128).— adrenals > thymus, spleen, > testicles, pancreas, The precision of assay methods is much increased thyroid gland > follicular fluid, the val. varying by careful control of the intake of the basal diet as from 1-9 to < 0-2 g. per kg. (I) was isolated from well as of the vitamin supplement. The technique the pituitary, but from the corpus luteum only described disclosed no evidence of the multiple 4 - benzeneazo -3-1- threoglyceryl -1 - phenylpyrazolone nature of vitamin-B2. A. G. P. could be isolated. W. McC. Realisation of the normal ascorbic acid con Distribution of vitamin-C in lower organisms. tent in the organism responsive to deficiency. G . B o u r n e and R. A l l e n (Austral. J. Exp. Biol., A. G i r o u d , C. P. L e b l o n d , R . R atsimamanoa , and 1935, 1 3 , 165— 174).—Unicellular animals and plants, M. R a b in o w ic z (Compt. rend. Soc. Biol., 1935, algae, and fungi contain granules which stain with X IX (I) 120 BRITISH CHEMICAL ABSTRACTS. A. the AcOH-AgNOs reagent and therefore presumably following modification of the method of Tillmans contain reduced vitamin-C. W. 0. K. et al. (A., 1932, 310, 658) removes the reducing activity of most foreign substances in extracts of vitamin-C. Vitamin-C in fresh apples and in apple powder. The material is boiled with 5% AcOH (C02 stream), M. P ochino (La Pediat. med. prat., 1935, 10, 16).— cooled, neutralised (pH 5-0) with CaC03, and pptd. Administration of fresh apples to guinea-pigs receiving with Pb(OAc)2. After filtration the extract is BezssonofF’s scorbutic diet prevented appearance acidified -with AcOH to pn 3-0 and titrated with 2 : 6- of symptoms of scurvy, but did not permit normal dichlorophenol-indophenol to a slight pink (C02 development, whilst administration of apple powder stream). Good agreement -with biological assays is only delayed onset of the symptoms. obtained. J. W. B. N h t r . A b s . (m) (A) Effect of sulphitising on the preservation of Determination of ascorbic acid by titration. vitamin-C. B. I. Ja n o v s k a j a . (b ) Antiscorbutic B. A h m ad (Nature, 1935, 1 3 6 , 797).— Boiling before activity of “ marmelad ” jelly, enriched, after extraction with CC13-C02H increases the ascorbic four months' storage, with vitamin-C by addition acid val. for Darjeeling cabbage. The results support of a concentrate of infusion of pine needles. N. the views of McHenry et al. (A., 1935, 903) as opposed Jaru sso va. (c ) Antiscorbutic properties of pine to those of van Eekelen (ibid., 1176). L. S. T. needles. V. Effect produced on the vitamin-C Value of the chemical titration method in content of pine needles when cut pine branches determining the vitamin-C potency of certain are kept for a short time. N. E. S iiepilevskaja . foodstuffs. N. B. G u e r r a n t , R. A. R a s m u s s e n , (d ) Antiscorbutic properties of sulphitised dried and R. A. D utcher (J. Nutrition, 1935, 9, 667— cabbage. Antiscorbutic turnip preparation. 675).—Titration of ascorbic acid with 2 : 6-dichloro- S. N. Matzko (Problems of Nutrition, Moscow, 1935, phenol-indoplienol gives approx. results suitable as 4, No. 2, 51—54, 54—55, 56—58, 59—60, 61— 64).— preliminary data for biological assays of vitamin-C (a ) The process of sulphitising black-currant juice potency. The accuracy of the method varies with for storage seemed to preserve the vitamin-0 (I) the nature of the test material. A. G. P. activity, which was lost in untreated, stored juice. (b ) Four months’ storage at room temp, of a jam Influence of vitamin-C level on resistance to enriched with (I) concentrate from pine needles diphtheria toxin. I. Changes in body-weight caused very little destruction of (I). and duration of life. C. G. K in g and M. L. M e n t e n (c) Infusions in very dil. HC1 of fresh pine needles II. Production of diffuse hyperplastic arterio and of needles from a bough that had been kept sclerosis and degeneration in various organs. indoors for 10 days were almost equal in their M. L. M e n t e n and C. G. K in g (J. Nutrition, 1935, antiscorbutic acitvity. 1 0 , 129—140, 141—153).—I. A wide zone of vita (d ) Tho expressed juice from cooked, dried white min-C deficiency exists without the appearance of cabbage, which had been sulphitised for storage, scurvy, but in which physiological processes are protected guinea-pigs from scurvy in a min. dose subnormal and sensitivity to bacterial toxins is equiv. to 6 g. of original dry cabbage, so that in 1 kg. increased. A. G. P. of dried cabbage there were about 160 “ units ” of Reactions of animals susceptible to deficiency (I). Juice of a damaged white “ semi-table ” turnip to increasing doses of ascorbic acid. A. Ger o u d , gave fairly good protection from scurvy in guinea- R . R atsimamanga, A. B a r a t t e , and F. S y l v a pigs. N u t r . A b s . (m) (Compt. rend. Soc. Biol., 1935, 1 2 0 , 701— 703).— Ascorbic acid in sprouted oats. R . B ogart Vascular lesions and dental mobility decrease and and J. S. H ughes (J. Nutrition, 1935,1 0 , 157— 160). haemoglobin increases steadily as the quantity of —The vitamin-C content of sprouting oats increased ascorbic acid administered increases. R. N. C. to a max. at the tenth day. Yals. were similar whether sprouting was in light or in darkness. Fractionation studies on pro-vitamin-D. E. M. K och andF. C. K och (Science, 1935, 82, 394— 395).— A. G. P. Vitamin-C (ascorbic acid) content of the “ Cholesterol W” and heated purified cholesterol (I) are superior to viosterol or purified, unheated (I) paprika product “ Vitapric.” E. B ecker (Z. Yitaminforsch., 1935, 4, 255— 259).—Vitapric con in preventing leg weakness in rats and chicks. The tains about 0-45% of ascorbic acid (cf. B., 1935,1116), pro-vitamin-D of heated (I) separates readily in and increases the resistance of animals not only to crystallisation from EtOH. L. S. T. scurvy, but also to other diseases. J. N. A. Antirachitic efficiency of irradiated milk, Reducing power of vitamin-C in urine in yeast milk, cod-liver oil, and irradiated chole H a m a n St e e n b o c k health and disease. (a) T. B a u m a n n , (b ) W. v o n sterol. R. W. and H. (Proc. Amer. Inst. Nutrition, J. Nutrition, 1935, 9, No. 6, D rigalski (Z. Yitaminforsch., 1935, 4, 354—356, Suppl. 7).—When fed to chicks on a rat unit basis, 356— 357).— (a ) Von Drigalski’s method of iodometric titration (A., 1935, 793) for the determination of cod-liver oil, irradiated milk, and irradiated cholesterol ascorbic acid (I) in urine is untrustworthy. showed 10— 15 times the antirachitic potency of milk from cows fed on irradiated yeast. (b ) The method is upheld. J. N. A. ... . Nutr. Abs. (m) Chemical method for determining vitamin-C. Sensitivity of rachitic rats for vitamin-1) . V. A. D eviatn in and V. M. D oroschenko (Compt. J. v a n N ie k e r k (Arch. Neerland. Physiol., 1935, rend. Acad. Sci. U.R.S.S., 1935, 3, 177— ISO).—The 2 0 , 477— 4S0).—The sensitivity of the rat stock X IX (I, m) BIOCHEMISTRY. 121
fell to about 50% of the initial val. from 1929 to 1932, the concn. of the solution, and the nature of the inorg. but no seasonal variations were noted. H. G. R. N salts in solutions of which the roots are placed. Relationship of the vitamin-D intake of the hen R. N. C. Root exudation and root types in sugar cane. to the antirachitic potency of eggs produced. H. E v a n s (Mauritius Dept. Agric. Sugar Cane Res. N. B. G u e r r a n t , E. K o h l e r , J. E. H u n t e r , and Sta. Bull., 1934, 5, 13).—Mineral analyses of exudates R. R. M u r p h y (J. Nutrition, 1935, 10, 167— 178).— from cut roots of various parts of the rooting system The antirachitic potency of eggs depends on the are recorded. Ch. A b s . (p) vitamin-D intake of the hen. The transfer of -D from diet to egg is of low efficiency, and is more com Catadyn process for sterile cultures of higher plete from cod-liver oil than from viosterol. plants. F. C. G e r r e t s e n (Planta, 1935, 23, 593— A. G. P. 603).—The root system of the plant is protected from Constitution of vitamin-Z)2.—See this vol., 69. infection by means of a cork layer containing a catadyn (Ag)-infusorial earth prep. A. G. P. Sitostanol and stigm astanol.— See this vol., 69. Regulation of protein exchange and the con Differences in age of cells of some water plants dition of proteolytic enzymes in plants. K. in relation to their reducing powers. M . L i l i e n - P a e c h (Planta, 1935, 24, 78— 129).—Anaerobic s t e r n (Protoplasma, 1935, 33, 86— 92).—Differences decomp, of protein in plant cells does not depend in reducing power of laminae and midribs of leaves on deprivation of 0 2, but is influenced by injury to the of varying age and under varying conditions of assimil cell by prolonged anaerobiosis. In acid leaves ation are examined by means of methylene-blue and death of cells in 0 2 deficiency is not caused by increas thionine. A. G. P. ing proteolysis. In wilting petals the “ explosive ” Permeability studies of Valonia osmometers. decomp, of protein is a post-mortal process resulting Behaviour with neutral salt solutions. P. K o r n - from destruction of protoplasts. Synthesis or hydro m a n n (Protoplasma, 1935, 23, 34— 49).— With a lysis of protein in intact cells is controlled by the Valonia cell-membrane osmometer, K citrate, tartrate, relative amounts of active carbohydrate (monose) phosphate, sulphate, and acetate solutions caused and sol. N (NH3) present. A. G. P. a withdrawal of fluid at rates which declined in the Nitrogen fixation by germinating legume seeds order of substances named. K N 03 and KC1 caused wthout co-operation of nodule bacteria. K. an intake of fluid. In isotonic solutions the order G i r t s c h a n o v (Zentr. Bakt. Par., 1935, II, 92, 349— of intake of fluid was LiCl>NaCl>KCl. The 363).— In the absence of nodule organisms germin phenomena are explained by differences in the ating seeds of yellow lupin were unable to utilise degree of swelling of the internal and external sides atm. N9 even under the influenco of certain stimulants. of the membrane induced by the various salts. A. G. P. A. G. P Apparent assimilation of nitrogen by germin Dry matter production [by plants] in nitrogen ating peas. E. M. S m y t h and P. W. W i l s o n (Bio- and potassium deficiency. D. M ü l l e r and P. chem. Z., 1935, 282, 1—25; cf. Vita, A., 1932, L a r s e n (Planta, 1935, 23, 501— 517).— In H20- 436, 1180; Orcutt et al. A., 1934, 1273).—Apparent cultures of Sinapis alba respiration losses were sub increases in the N content of peas germinating hi stantially the same for plants in normal and deficient presence of stimulants (salts, alkaloids) or H20 are media. Assimilation intensity was lower in deficient due to inaccuracies in analytical methods. The plants, the difference between these and normal Kjeldahl method and its modifications yield untrust plants declining with light intensity. The com worthy results, and the Dumas method is recom pensation point was the same in normal and deficient mended. There is no evidence that direct assimilation plants. Lowered assimilation is not due to reduced of elementary N2 occurs. • W. McC. opening of stomata or smaller chlorophyll contents, but to “ protoplasmic factors.” The wt. of dry Role of asparagine and glutamine in the higher matter produced in stems and roots per unit leaf plants. G. S c h w a b (Planta, 1935, 24, 160— 162).— area was the same for completely manured and K- Asparagine (I) and glutamine (II) are present simul deficient plants, but was approx. doubled in N- taneously in plants. Increased “ amide” in germin deficient plants. A. G. P. ating seedlings or that induced by shading plants or supplying NH4 salts involves increases in (I) and Heat-resistance o f plants. I . S a p p e r (Planta, (II) in normal proportions. The (II) content of roots 1935, 23, 518—556).— Starved plants have a decreased of Aspidium filix declines with the total sol. N during heat-resistance, although small differences in C the summer months. Protein exchange in plants nutrition have only a slight effect. Deficiency of is discussed in relation to org. acid and carbohydrate nutrient salts causing increased osmotic pressure contents. Plant extracts contain enzymes sp. for (I) may increase the resistance. Heavy excess of and (II). Yeast extracts contain only (I) and can nutrients lowers resistance. The latter is controlled only effect the fission of (I). A. G. P. by sp. structural characteristics of the protoplasm Variation of saponins during germination and and merely modified by the H20 content. A. G. P. development in some species of grasses. T. Absorbing power of roots. P. M a z e , P. J. S o l a c o l u and E. W e l l e s (Compt. rend. Soc. Biol., M a z e , jun., and R. A n x i o n n a z (Compt. rend. Soc. 1935, 120, 662—664).—Saponin accumulates in the Biol., 1935, 120, 693— 695).—The absorbing power seeds when they reach maturity; it is then used up varies with the N compounds in the nutritive solution, partly in germination and partly in growth until the 122 BKITISH CHEMICAL ABSTRACTS.— A. X IX (771) appearance of the fifth leaf, after which it has dis diseased growth. Many elements, e.g., Al, Si, Na, appeared entirely. R. N. C. Cl, are utilised by particular groups of plants in con siderable amounts, but it is difficult to say that they Influence of partial pressure of carbon dioxide are essential to the life of the plant. Other elements, on photosynthetic efficiency. B. N . S i n g h and although not essential to life, stimulate the growth K. K u m a r (Proc. Indian Acad. Sci., 1935,1, B, 909— of the plant. The functions of the various elements 927).—The rate of photosynthesis in radish leaves are discussed and it is pointed out that all the in increases with rising [C02] to a stationary stage dispensable elements lie on a line drawn in the periodic followed by a decline as the proportion of C02 is table from A through C to A. P. W. C. further increased. With increasing light intensity the C02-photosynthesis curves show a steeper rising Effect of humic acid on assimilation in plants. phase and earlier evidence of toxic effects. The curves A. V. B lagovestschenski and A. A. P rosorovskaja are discussed in relation to those obtained by earlier (Biochem. Z., 1935, 282, 99— 103; cf. A., 1935, observers. A. G. P. 265).— Humic acid (I) stimulates plant growth by Oxygen intake of oily and starchy seeds. E. increasing the permeability of the tissues and so facilitating osmosis. NH4N03 enabled to penetrate R e u iil (Proc. K. Akad. Wetensch. Amsterdam, 1935, 38, 879—886).—In the early stages of germin the cells by (I) has no effect on the synthesis of proteins ation Brassica seeds absorb 0 2 at a normal rate with there. W. McC. decreasing 0 2 tension until it reaches 3%, whereas Vegetable growth-substances. F. K ogl (Natur linseed shows a retarded rate almost immediately wiss., 1935, 23, 839—843).—A lecture. and buckwheat shows intermediate vals. During Physiological analysis of the growth substance. the later stages this behaviour is reversed. H. G. R. A. J. H a a g e n S m it and F. W. W e n t (Proc. Iv. Akad. Energy of growth. XIV. Effect of zinc and Wetensch.1 Amsterdam, 1935, 38, 852— 857).—The manganese salts at toxic concentrations on the cell-elongation and polar transport properties of a energy output during germination. G. B o y series of org. substances have been examined. Some, (Bull. Soc. Chim. biol., 1935, 17, 1414— 1426).— which have only growth-stimulating properties, The energy output of rice seeds (heat of combustion do not exhibit polar transport and do not give the of the cotyledon/difference between the heats of A vena bending test nor the bud-inhibition of the combustion of the original and the germinated seeds) auxins. aZZoCinnamic acid has the greatest cell- grown in the dark in aq. solutions of Mn and Zn salts elongation power, comparable with that of 3-indoIyl- is < that of seeds grown in H ,0. With Mn the de acetic acid, whereas cinnamic acid has none. crease oc the concn.; with Zn the toxic action is H. G. R, not so marked, and is the same at a concn. of 2 as at Analysis of the activity of two growth-pro 4 g. of Zn per litre. A. L. moting substances in plant tissues. K. V. T h i- Possible association of vitamin-,4 with nutri mann (Proc. K. Akad. Wetensch. Amsterdam, tional conditions in plants. E. S. H a b e r , P. M. 1935, 38, 896—912).—Both indene-3-acetic acid N e l s o n , and P. P. S w a n s o n (Iowa Agric. Exp. Sta. and coumaryl-l-acetic acid show biological activity, Rept. Agric. Res., 1933, 134— 135; 1934, 163).— although the latter does not produce any Avena Poorly nourished plants were deficient in chloro curvature, but they lack the property of being readily phyll and in vitamin-A. The ability of plants to transported in the plant. It appears that cell- translocate -A is indicated. Ch . A b s . (p) elongation, root-formation, root-growth inhibition, and bud-inhibition arise from one primary reaction Effect of concentration of neutral salts on in the cell. H. G. R. seedling growth. J. P o r t (Acta Comment. Univ. Tartu., 1932, A, 23, No. 1, 166 pp.).—Growth was Lambertella corni-niaris, vonHohnel, a brown influenced by salt solutions absorbed by paper on spotted parasitic discomycete. T. H. H a r r is o n which seeds were sprouted. Concns. of < 0-liV and A. F. E l -H e l a l y (Trans. Brit. Mycol. Soc., inhibited the swelling of seed colloids and produced 1935, 19, 199—213).— Growth characteristics of the seedlings showing < normal growth and H20 con fungus are examined in relation to p u of the medium. tent. In wheat, diastatic activity was less in solu C h . A b s . (p) tions of higher concn. The effect of salts on growth Xyloporosis—the new citrus disease. I. decreased in the order SCN', N 03', Cl', Br', P 04"', R e ic h e r t and J. P e r l b e r g e r (Hadar, 1934, 163— S04" and Li’, NH4‘, Ba", Ca", K ‘, Na\ Mg", in 0-1JV 167, 172, 193—202).—Fruit from diseased trees con concn. With concns. of 0 01—0-001A salt effects tained less total solids, higher total and reducing were sp. for different species. The favourable action sugars and total acids than healthy fruit. of anions on root growth was in the reverse order C h . A b s . (p) of the lyotropic series. 0-0001N solutions of Li", NH4’, Biochemical modifications and phytopatho and Ba" were particularly beneficial to growth, logy- Officinal oil of lavender from plants probably because of increased imbibition of H20. parasitised with Sejitoria lavandulai, D esm . R. C h . A b s . (p) S a l g u e s (Compt. rend. Soc. Biol., 1935, 120, 703— Elements indispensable for plant nutrition. A. 704). Ihe infection reduces the quantity of oil and F r e y -W y s s l in g (Naturwiss., 1935, 23, 767— 769).— its terpene alcohol content, and increases d and the For the higher plants C, N, P, S, O, H, K, Mg, Ca, and cineole content of the essence. R. N. C. Fe appear to be essential. In addition, the absence Toxicity of magnesium towards higher plants. of Mn, B, Cu, and Zn often leads to deficient and D. R a b i n o v i t z -S e r e n i (Bull. Staz. Pat. veget., X IX (m, n) BIOCHEMISTRY. 123
1933,13, 346—366; JBied. Zentr., 1935, A, 5, 517).— isolating (II), which must contain an Ac group and Plants in solutions containing 1% of MgS04 showed not a formyl group (semi-acetal). J. W. B. loss of chlorophyll, restricted growth, and browning. South American drugs. I. Bixol, a new Enzyme processes are concerned. Low [Mg"] alcohol from the oil of Bixa Orellana. II. stimulated and higher concns. retarded eatalase Chemical composition of Canavalid oblusifolia. activity. Oxidase activity was favoured at all concns. M. B achstez and G. Ca v a l l in i (Chimica e l’lnd., examined. Respiration was increased by 0-1% and 1935, 17, 650—651, 652).— I. The unsaponifiable retarded by 1% solution of Mg” . A. G. P. matter (2-5%) of annatto-seed oil was submitted to Toxins of wilting [in plants]. 0. K. E l b i d i n a chromatographic analysis, using A1203, which ad (Compt. rend. Acad. Sci. U.S.S.R., 1935, 3, 360— sorbed ergosterol and vitamin-D (positive reactions 364).—The toxin produced by the Fusarium which in the Rosenheim and Briickner tests). The non causes wilting of potatoes is NH3. A. G. P. adsorbed portion was distilled in vac., yielding 0-58% (calc, on the seed) of bixol, C18H30O, h.p. 176°/2 mm., Action of potassium oxalate on the living a pale green oil, probably protoplasts of Allium cepa. R. E ich berger CMe2:[CH-CH2-CMe:]3CH-CH2-CH2-OH, oxidised to (Planta, 1935, 23, 479— 485).— Sections of A. cepa, the corresponding aldehyde, b.p. 175— 180°/6 mm. after 10— 15 min. treatment with aq. K2C204 (I), show (semicarbazonc, m.p. 96—97°). normal urea-plasmolysis only in the central area. II. Ouari seeds contain 10-42% H20, 2-50% ash, Injury to plasma by (I) is counteracted by treatment 0-65% fatty matter, 4-25% N, 26-5% proteins (93-5% with CaCl,, K citrate, K N 03, NaCl, or (NH4)2S04, or sol. in HCl-[-pepsin), 53-77% starch, 0-106% lecithin- by^ prolonged washing with H20. No sp. action of phosphoric acid (calc, as P20 5). They contain no Ca" in this respect was apparent. A. G. P. HCN or alkaloids and are not toxic to rabbits. Occurrence of lime in edible Mormordica. D. R. D. H . L . C h a k r a v a r t y (Current Sci., 1935, 4 , 239— “ Bukuryo,” sclerotia of Pachyma Jloelen, 240).—Cystoliths in various Indian species are Rumph. III. Chemical constituents. Iv. described. A. G. P. T a k e d a (Trans. Tottori Soc. Agric. Sci., 1934, 5, 62—73).— “ Bukuryo ” contains approx. 93% of a Iodine of seaweeds. III. E. M a s u d a and K. carbohydrate, pachyman (I), and also gum, chitin, N i s h i d a (J. Pharm. Soc. Japan, 1934, 5 4 , 243— protein, adenine, histidine, d-glucose, sterol, lecithin, 245; cf. A., 1934, 336).— Of the total I in Laminaria and fat, Cl, S, P, Ca, Fe, Mg, Mn, K, Si, Na, enzymes japonica, Aresch, an average of 48% occurs in org. which decompose fat and (I), and traces of pepsin and forms. L. ocfiotensis contains 65% of sol. I as org. trypsin. J. N. A. compounds. Warming causes a gradual transition to inorg. forms. In Ecklonia cava I is present as Arabogalactan of Siberian larch. N. I. N ik it in iodoammonium salts or I salts of amines and not as and I. A. So lo viev (J. Appl. Chem. Russ., 1935, 8, K I or Nal. C h . A b s . (p) 1016— 1022).—The arabogalactan (I) (1 mol.) with 12 mols. of NaOH and 13 of Me2S04 yields a product Chemical composition of saltbushes from the in which all the available OH-groups (20) are methyl Salm on Gum s area. L. J. H. T e a k l e (J. Dept. ated. (I), CH2PhCl, and NaOH (80°; 16 hr.) afford Agric. W. Austral., 1935, 12, 188— 189).—Complete the dibenzyl ether, and (I), BzCl, and NaOH (with analyses of Atriplex prostratum and A. halimoidcs cooling) give the Bzx ester. The mol. wt. of (I) cannot are given. Both specimens are high in Na20 and Cl, be determined cryoscopically, as the depression of but low in P20 5. N utr. Abs. ( m ) f .p. is not oc concn.; the I val. method gives a mol. . Saltbush. Its mineral composition. M. S. wt. corresponding with [C5H8O4(C6H10O5)6]2. B e n j a m i n (Agric. Gaz. N.S.W., 1935, 4 6 , 309—310). R. T. — Ghenopodium triangulare and Atriplex semibaccatum Lignin in straw and deciduous trees. R. S. were analysed. < 54-06% of the sol. ash in the latter H ilbert [with E . L it t m a n n , O. P e t e r s, H. H e ll - was NaCl. N u t r . A b s . (m ) w a g e , and 0. L issn er ] (Cellulosechem., 1935, 16, 92— 96).—The action of 72% H2S04 at room temp, Phytin of seeds of Eleusine coracana (besna), on various sugars produces insol. residues (I) which Sorghum eetiopicum (dura), Eragrostis Teff closely resemble lignin (II). Pentoses and fructose (teff), and Pennisetum spicatum (bultuc). R. are especially sensitive, but aldohexoses (particularly M o n t u o r i (Ateneo parmense, 1934, 6, 89).—The ash, glucose and galactose) are very stable. The amount P, and phytin contents of the seeds are recorded. of (I) formed decreases rapidly with fall in N u t r . A b s . (m ) reaction temp. The amount of (II) similarly formed Formation of acetic acid from ginkgo wood from straw also decreases from 41-66% at 60° to 2— 3% (Ginkgo biloba). Y. C. T a n g , Y. W. W a n g , and at -—10°, and dilution of the filtrate affords a carbo H. L. W a n g (Cellulosechem., 1935, 16, 90— 92).— hydrate material of composition 2C6H10O5 — H20. The Ac content of 4 samples of the wood (I) of different Thus the acid-sol. products are not (II) but carbo age and habitat is const, (mean 1-18%). The lignin- hydrate. Treatment of straw with alkali effects dis freed portion (II) (68-74%) (ash content 0-58, 0-64, solution of 20—30% (mainly hexoses) and dilution then 0-41, and 0-38%) contains 1-70% Ac, in close agree ppts. a substance with the composition of a partly ment with the val. (1-72%) calc, from that of (I) and methylated cellulose anhydride (pentosan content the loss resulting from isolation of (II). Thus no increased from 24 to 29% ; OMe reduced from elimination of AcOH occurs during the process of 4 to 3-1%), which is acetylated in presence of 8% X I X (») 124 BRITISH CHEMICAL ABSTRACTS.— A.
H2S04 to a substance (83% yield) of composition the conditions specified with regard to [CaCl2], dura tion [C, 49-5, H 6 0, OAc 61-6, OMe 1-3 (? 3-1), pentosans of boiling, and fineness of grinding are adhered to. 13%] closely resembling that of cellulose triacetate. The method is more trustworthy than that of enzymic Since tbe OMe content is the same as that of the original hydrolysis. The applications of the method are dis straw, this group is present not in lignin hut in the cussed. F- C. S. carbohydrate of which straw is composed. Treat Aromatic substances in maple sugar. J. Risi ment of the wood (III) of deciduous trees with HC1 and A. L a b r ie (Canad. J. Res., 1935, B, 13, 175— at —10° affords a residue (12%) of composition inter 184).—The aromatic substances in the syrup and sugar mediate between that of (III) and (II). The H20- of the maple contain vanillin (I), vanillic acid (II), pptd. material is also a cellulose anhydride. With and a resinous part, which is hydrolysed to guaiacol HC1 (d 1-19) at room temp, the C and H content (III) by emulsin. The bark contains an enzyme of tho residue is the same as that of (III), but the OMe (acerase) which hydrolyses coniferin and amygdalin; content, and lignin formed, are higher. Hence the the sap also contains an enzyme. The wood contains higher methylated portions are less readily attacked. a little coniferin, which may be the parent substance The ground-substance is a cellulose anhydride which of (I). The odour is due to presence of liadromal, readily loses H20 intramolecularly to give (II). which, during heating of the sap, is decomposed into J. W. B. (I), (II), and (III). Hadromal may bo synthesised New constituent of beechwood. E. W e d e from (I), (III), and sucrose. E. R. S. k in d and 0. M ü ller (Naturwiss., 1935, 23, 833— Constituents of tbe sap of sugar maple (Acer 834).—MeOH extraction of beech, eucalyptus, alder, saccliam m , M arsh). G. H. F i n d l a y and J. F. cherry, and, to a smaller extent, oak and hornbeam, Sn ell (Canad. J. Res., 1935, 13, B, 269— 275).— but not of pine and ash, yields a substance (I) (C The development of the maple flavour from its pre 57-1, H 4'3, OMe 4-8%) giving an intense red-violet cursor in sap, during boiling, is not due to oxidative colour with conc. acids. (I), which is separated changes. No individual constituent of various maple admixed with a less sol. substance converted into (I) extracts examined was capable of imparting the by hot aq. alkali, readily forms a Ac4 derivative flavour to sugar syrups. A. G. P. which does not give the colour reaction. F. 0. H. Biochemistry of amygdalin. A. V ie h o e v e r Leaf starch : isolation and properties. H. A. and H. M ack (Amer. J. Pharm., 1935, 107, 397— Spoehr and H. W. Mil n e r (J. Biol. Chem., 1935, 450).—The physiological properties of amygdalin 111, 679—687).—Depletion of starch (I) in leaves (the commercial product contains 2HaO) and of its does not occur on drying if the leaves have been frozen hydrolytic products are discussed. J. L. D. or treated with CHC13. To prepare (I) the leaves are dried, ground, the pigments extracted with EtOH and Manchurian kaoliang (Andropogon sorghum, light petroleum, polyuronides etc. are extracted Brot.). S. H irao (J. Agric. Chem. Soc. Japan, with cold H20, and (I) with hot H20, from which, 1935, 11, 921—924).—Three cryst. substances have after cooling, it is separated by centrifuging. If a been isolated from the hot aq. extract of kaoliang: (I) solution is frozen for some time and then allowed (1) yellow, m.p. 249—250°, a quercetin monoglucoside, to thaw, (I) is pptd. in a fibrous mass (rétrogradation). probably quercimeritrin; (2) long white Tieedles, Cooling for 3 days at —80° ppts. (I) completely, but m.p. 240—242°, probably a new flavanonol; (3) short 90—95% pptn. can be obtained if the solution is white crystals, m.p. 98— 100°, similar to pyrocatechol. cooled only to —8°. Retrograded (I) dissolves in H. G. R. H20, biit if thoroughly dried, it is more sparingly sol. Action of Nuphar luteum on the heart. M. Determinations of the amounts of (I) were made on B u l a je w s k i (Wiad. Farm., 1935, 62, 15— 18, 29— the basis of the reducing power of the solution after 32, 43—47 , 57—62).—EtOH extracts of blossoms of acid hydrolysis with an accuracy of ±1% . d-Glucoso N. luteum contain a cryst. glucoside, nijmphalin (I), is the chief product of hydrolysis. The apparent which exerts a toxic action on the animal heart. lower reducing power of retrograded (I) is due to its (I) has m.p. 40° (approx.) and gives a purple colour slower rate of hydrolysis. The leaves of Nicotiana with a-CjoH/OH and H2S04. Hydrolysis yields tabacum give the highest yield. E. A. H. R. Cu-reducing substances. (I) is present in flowers Detection of hydroxylamine in autolysed green and seeds but not in roots. Ch. A b s . (p) leaves. M. L em o ig n e, P. M o n g u illo n , and R. Ascorbic acid (vitamin-C) content of some D e s v e a u x (Compt, rend., 1935, 201, 1067— 1069).— Indian plant materials. M. D a m o d a r a n and M. By modification of Blom’s reaction NH2OH has been Srintv as a n (Proc. Indian Acad. Sci., 1935, 11, B, detected in the juice of leaves allowed to autolyse for 377— 386).—Data obtained by the Tillmans-Harris several days (1— 3 mg. per kg. of original leaves), but method are recorded. A. G. P. is absent from the juice of fresh leaves. W. O. K. Constituents of red sandal wood. Homoptero- Determination of starch in plants with special carpin.—See this vol., 81. reference to woody plants. J. T. S u lliv a n (J. Pigments of cotton flowers. I. Cambodia Assoc. Off. Agric. Chem., 1935, 18, 621—636).— (Gossypium hirsutum). K. Neelakantam, The starch is extracted with slightly alkaline aq. R. H. R. R ao, and T. R. S esh ad ri (Proc. Indian CaCl2, pptd. •with EtOH, redissolved in HaO, and Acad. Sci., 1935, 1, 887— 890).—The presence is pptd. with I in aq. K I in presence of (NH4)2S04. established of quercetin and quercimeritrin in pro The starch is then hydrolysed and glucose determined portions which varied with variety, locality, and season. by Cu reduction. A single extraction is sufficient if A. G. P. X IX (n, o) BIOCHEMISTRY. 125
Fluorescence spectra of chlorophyll pigments. Odorous substances of green tea. VI. Con C. D hkre and A. R a f f y (Bull. Soc. Chim. biol., 1935, stituents of tea oil. S. T a k e i, Y . Sa k a t o , and M. 17, 1385— 1413).— The bands in the fluorescence Oho (Bull. Inst. Phys. Chem. Res. Japan, 1935, 14, spectra of a-chlorophyll in hexane, Eb20, COMe2, 1262— 1274).—From tea-leaf oil were isolated EtOH, MeOH, CGHG, cyclohexanol, CHC13, and CS„ CHMeEt-CHO, w-hexyl, benzyl, and benzyl- and have axes at 663,663-5,666,666-5,667,666-5,668,670“ phenyl-ethyl alcohols, PhOH, cresol, AcOH, and and 676-5 mg, respectively, the corresponding val. héxoic acid. No ester with an odour characteristic for ¡3-chlorophyll in Et20 being 646-2 mjj.. The bands of that of the oil was isolated (cf. A., 1934, 571). in the fluorescence spectrum of the leaves of Pelar E. O. H. gonium zonale {in vivo) occur at 738 and 686, whilst Agar-agar of Black Sea phyllophora. V. E. with an Et20 extract of the leaves the vals. are Opotzki and L. A. B o r tn ik (Ukrain. Chem. J., 1935, 732-5 and 672 mp, respectively. The fluorescence 10, 331— 335).—The washed dried agar-agar contains bands of a- and (3-phytylphaaophorbide in CS2 have H20 19, protein 5-5, Ac 9-8, org. and total S (as S03) axes at 679 and 663-5 mp, respectively. A. L. 10-7 and 14-6, galactosans 42-5, pentosans 0-64, Phlobaphen and durasantalin in the colouring methylpentosans 0-16, ash 11-73% (S03 3-93, SiO, matter of Manchurian kaoliang (Andvopogon 1-81, Fe203+ A l203 2-01, CaO 2-52, M g0+N a20 - f K 20 1-46%). Japanese agar differs chiefly in its sorghum ). K. O k a n o and I. O h a r a (J. Agric. Chem. Soc. Japan, 1935, 11, 767— 772).—The Et20- lower protein (1-32%), org. S (4-35%), and ash con insol. fraction of the colouring matter of the hulls tent (3-98%). The hardness of the gels of Black Sea contains phlobaphen (I) (43% of the whole colouring agar is considerably < that of Japanese agar, and the matter) and the C0Me2-insol. fraction contains m.p. and setting points are lower. R. T. durasantalin (II) (red dura) (35%). The colouring Bitter principles of the Colombo root. III.— matter (2%) of the seed coats also contains (I) See this vol., 89. (82%) and (II) (15%). The coats contain 3% of Alkaloid of Chin-shih-hu.— See this vol., 88. Ho0 -sol. tannin but no apigenin (cf. Perkin, J.C.S., Chemistry and pharmacology of the alkaloids 1910, 97, 220). " W. McC. of Dnboisia Iloptcoodii. C. S. H ic k s and II. Le Carotenoids and some lipins of Ipomoea M e ssu r ie r (Austral. J. Exp. Biol., 1935, 13, 175— reptans (L.), Pair. M. I s h u (J. Soc. Trop. Agric. 188).—The leaves contain an alkaloid, C9HI2N„ b.p. [Nettai Nogoku Kwaishi], 1933, 5, No. 2 , 192— 197).— 266—26S°, [a]«5 +38-6° (picrate, m.p. 186— 188°; Analyses of the vegetable are given. (3-Carotene, picrolonate, m.p. 252—253°), which yields nicotinic xanthophyll, and a trace of taraxanthin were separ acid on oxidation with KMn04 and is probably ated. Lipins detected included n-hentriacontane, d-nornicotine (cf. A., 1932, 177). W. O. K. sitosterol and its glucoside, and a higher alcohol, m.p. Alkaloids of European Lgcopodium species. 267°. Ch. Abs. (p) J. M u s z y ń s k i (Arch. Pharm., 1935, 273, 452— 457).— Daturic acid. R. W. Clar k (J. Amer. Pharm. L. Selago, annotinum, inundatum, complanatum, and Assoc., 1935, 24, 843—847).— Solid fatty acids were clavatum, L., contain solid, non-volatile (amorphous prepared from the oil of Datura stramonium seeds. salts) and volatile, H20-sol. alkaloids (cryst., hygro Attempts to separate them by fractional crystallis scopic salts). The latter, named selagine, annotine, ation from EtOH, pptn. of Mg salts, and vac. dis inundatine, complanatine, and clavatine, respectively, tillation of the Me esters failed. The occurrence and confer poisonous properties on the plants. R. S. C. identity of heptadecoic acid are discussed. E. 0. H. Distribution of alkaloids in Ephedra sinica (M a-Huang). M. T arlé (J. Chinese Chem. Soc., Apple- and pear-seed oils. J. P e it z k e r and 1935, 3, 377— 380).—In the young herb the total R. J u n g k u n z (Z. Unters. Lebcnsm., 1935, 70, amount of ephedrine alkaloids (I) is almost evenly 255— 257).—Air-dried apple- and pear-seeds contained distributed between the pith and the rest of the stem, 19-23 and 21-44%, respectively, of their dry wt. but in the ripe plant the former contains much > the of oil, which had refractometer val. (40°) 62-9 and latter. The percentage of ¿-ephedrine in (I) is nearly 62-0, acidity 4-1° and 9-7°, acid val. 2-3 and 5-4, the same in early summer (56-45%) as in the autumn ester val. 185-4 and 184-1, sap. val. 187-7 and 189-5, (57-7%). ‘ H. G. M. I val. (Hanus) 122-4 and 124-1, Reichertr-Meissl val. 0-22 and 0-33, Polenske val. 0-4 and 0-33, un- Histochemical detection of sodium in plants. saponifiable matter 1-10 and 1-03%, phytosterol M. St e in e r (Ber. deut. Bot. Ges., 1935, 53, 720— (min.) 0-36 and 0-2S%, m.p. of phytosteryl acetate 732).—An adaptation of the uranyl Zn acetate method 122° and 119°, respectively. The fatty acids (95-8 is described. Other plant substances do not interfere. and 95-7%) had refractometer val. 48-4 and 47-7, A. G. P. neutralisation val. 196-5 and 196-8, mean mol. wt. Spectrographic micro-determination of zinc 285-5 and 285-1, solid fatty acids (Bertram) 7-2 and [in plant m aterial],—See this vol., 43. 10-3%, (Grossfeld) 4-9 and 6-0%, and ¿sooleic acid Method of making latent finger-prints visible. 0-62 and 0-45%, respectively. Each oil gave positive M. W a g e n a a r (Pharm. Weekblad, 1935, 72, 1265— Bellier, Bellier-Kreis, and H N 03 tests, and the apple- 1271).—The latent finger-print is developed by treat seed oil a positive Kreis test. The latter oil was clear ment with I vapour and permanent impressions yellow, and had a bitter almond flavour, the pear- are taken from the developed stain on paper coated seed oil egg-yellow, and had a slightly acid taste. with a prep, consisting of 1 g. of rice starch, 2 g. of E. C. S. KI, and 0-3 g. of thymol in 20 c.c. of H20. S. C. X IX (o) 126 BRITISH CHEMICAL ABSTRACTS.— A.
Impregnation of the nervous system with g. of carotene is the smallest amount detectable by the silver. J. S ze p s e n w o l (Compt. rend. Soc. Biol., yellow residue obtained on evaporation of light 1935, 120, 689—690).—Larva) of batrachians are petroleum solutions. A. L. impregnated with Ag by means of a 10% solution Infra-red absorption spectra of plant and of CH20 in 4% HC1 or HC02H as fixer, followed by animal tissue etc.—See this vol., 9. AkNCL solutions of gradually increasing concn. Iodine value as a biological constant. Rapid R. N. C. micro-determination by means of bromine Deproteinisation of blood and urine by copper vapour. H. W o l l s c h it t (Arch. exp. Path. Pharm., ferrocyanide. R. V la d e sc o (Compt. rend. Soc. 1935, 179, 260—265).—The material (0-1— 5-0 mg.) Biol., 1935, 120, 664—665; cf. A., 1935, 1044).— is exposed to Br vapour for 15—180 min. and then Deproteinisation of blood and urine by Cu2Fe(CN)6 heated at 100° to const, wt. The increase in wt. X 160/ removes uric acid and NH2-acids in the ppt. Urea, wt. taken is the I val. Vais, for common fats and creatine, and creatinine may be determined in the fatty acids agree with theoretical vals., but the filtrate if excess of Cu is first removed with H2S, as it indicated nos. of double linkings of some carotenoids interferes with the determination of the latter two (crocetin, methylbixin) and unsaturated esters are substances with Na picrate. Deproteinisation by < the known vals. The method differentiates various this method is preferable to the older methods body fats. F. O. H. in diabetic urines. R. N. C. Determination of carbon in biological fluids. Determination of benzene by the Pulfrich step- F. L a h e r s o n and K. V o it (Biochem. Z., 1935, 280, photometer. L. v o n S ze6 s£ n y i -N a g y (Biochem. 276—285).—The fluid is burned in air or 0 2 in an Z., 1935, 281, 178— ISO; cf. Janovsky, A., 1891, electrically heated combustion furnace and the C02 685).—The C0He is separated from the acidified produced is passed into aq. Ba(OH)2. Excess of material (biological) by distillation into a cooled 0-01V-HC1 is added and the solution is titrated with nitration mixture. The C0H4(NO2)2 obtained is O-OUV-NaOH using Tashiro’s mixed indicator (Amer. dissolved in COMe2, made alkaline with 33% aq. J. Physiol., 1920, 60, 519). 0-002 mg. of C can be NaOH, and shaken. The intensity of the violet determined. W. McC. colour in the COMe2 is measured. About 70% of the C6Hfi is thus determined. W. McC. Calcium determination in biological material. Spectrographic determination of phenol in C. C. W a n g (J. Biol. Chem., 1935, 111, 443—453).— Use of a washing solution, for CaC20 4 ppts., con different media. G. B a r a c (Compt. rend. Soc. Biol., 1935, 120, 520—522).—PhOH is determined sisting of 2% aq. NH3 in equal parts of H20, EtOH, in aq. solution, and in plasma and whole blood after and Et20 prevents loss by flotation and dissolution. deproteinisation with H2W04, by extracting with Et20 Treatment with CC13-C02H and C allows direct Ca and spectroscopic examination of the extract in the determinations to bo made on urines. F. A. A. Jobin-Yvon quartz spectrograph; PhOH shows three Determination of mercury in viscera. C. narrow bands at 267, 274, and 280-7 mu, the mol. N e w c o m b , S. R. N a i d u , and K. S. V a r a d a c h a r extinction eoeff. in Et„0 for the third of these being (Analyst, 1935, 60, 732—735).—-The' org. matter is 2400. " R . N. C. destroyed by heating with H N 03+ H 2S04, and the Sugar determination by the ferricyanide solution is distilled in a current of air until H2S04 electrode. P. A. Sc h a f f e r and R. D. W il l ia m s (J. fumes appear. Distillation is continued in a stream Biol. Chem., 1935, 111, 707—723).—Reducing sugars of air charged with HC1, HgCl2 distilling over. Hg may be determined by the ferri-ferro-cyanide elec in both distillates is pptd. as HgS, which is dissolved trode. Vais, are unaffected by pn change, by the in Br-H20 and repptd. Separation is quant, from products of the sugar oxidation, or by changes in other heavy metals, including As™, which is oxidised the vol. of the solution about the electrode. The to Asv. J. S. A. method can be adapted for determinations with 20 cu. Micro-determination of phosphoric acid in mm. of blood. As no supplementary reagents are tissue. L. T h iv o l l e (Bull. Soc. Chim. biol., 1935, used, side reactions are avoided. ” E. A. H. R. 17, 1427— 1450).— Cone. H N 03 containing Cu(N03)2 Rapid method for the determination of reduc is used for the mineralisation of the material. The ing sugars. G. I. Solomos (Bull. Soc. Chim. biol., aq. solution of the phosphomolybdate ppt. is reduced 1935, 17, 146o— 1469).—The solution containing with Zn, added to aq. Na phosphomolybdate, and the reducing sugar is added from a burette to a known titrated with KMn04 using benzidine as indicator. amount of 0-4% K3Fe(CN)6 in AT-NaOH until the red- A. L. colour disappears. The method is applied to blood, Micro-determination of sulphur in biological urine, and milk. A. L. m aterial. L. R e v o l and M. F e r r a n d (Bull. Soc. Determination of glutamine in presence of Chim. biol., 1935, 17, 1451— 1454).— Losses in the asparagine.—See this vol., 60. determination of S in org. compounds due to the escape of traces of S02 are avoided by passing Determination of carotenoids in blood, tissue, the vapour from the H N 03-H 202 treatment of the and fluids in clinical practice. P. R a t c h e v s k y material through aq. Br which is finally added to the (Bull. Soc. Chim. biol., 1935, 17, 1187— 1193).— main solution. The S04" is pptd. with benzidine. The method is based on the observation that 0-03 X1CH5 A. L.