BRITISH CHEMICAL ABSTRACTS
_ ' A.-PURE CHEMISTRY |
DECEMBER, 1935.
General, Physical, and Inorganic Chemistry. Slight correction to the Rydberg constant for 1000 A. have been photographed and arranged into hydrogen (H1). R. C. Williams and R. C. Gibbs three progressions for wliich formuła; are given. (Physical Rev., 1934, [ii], 45, 491). L. S. T. They are due to normal O. Otlier bands at shorter T riplet 3p complex of the hydrogen molecule. XX and between 1210 and 1000 A. liave also been G. H. D ieke (Physical Rev., 1935, [ii], 48, CIO—614; measured. L. S. T. cf. this vol., 917).—M any peculiarities in the Fulcher Oxygen in the sun’s chromosphere. T. R oyds bands of H2 can be explained by the interaction of (Naturę, 1935, 136, 606—607).—The observed infra- the ?yjM\ with tlie 3f>?£ level (cf. following abstract). red O emission lines 7771, 7774, and 7775 show th at N.' M. B. 02 is a normal and probably abundant constituent of 3p3I, -> 2s3L bands of HD and D2. G. H. the sun’s chromosphere. L. S. T. D ieke (Physical Rev., 1935, [ii], 48, 606—609; cf. New emission spectrum of sulphur in the this yoL, 555).—Fuli data for the system in the photographic infra-red. M. D k sib an t and J. extreme red and near infra-red are tabulated, and D uchesne (Compt. rend., 1935, 201, 597—598).— the band consts. are calc. N. M. B. Bands at 6650—7765 A., degraded to the violet, and Vibration and rotation spectrum of the mole attributed to S2, are described. H. J. E. cule HD. G. C. W ick (Atti R. Accad. Lincei, 1935, [vi], 21, 708—714).—Theoretical and mathematical. Deepest terms in ions of the isoelectronic O. J. W. secjuence Ai—Mn v m . P. G. K r u g e r and S. G. Anomalies in the Zeeman effect of helium. W eissberg (Physical Rev., 1935, [ii], 48, 659—663).— L. E. K insler and W. V. Houston (Physical Rev., Radiations corresponding with the energy difFerences 1934, [ii], 45, 134). L. S. T. bet^-een the terms 3pa 1S0—3]f>4cSsP
G riv et-M ey er (Compfc. rend., 1935, 201, 658—660). loss of activity, and after 5 cycles 50% of the actm ty —Lea’s results were not confirraed (cf. A., 1934, 235). remains, indicating that the valencies are uneąual. The increase in the no. of particles is attributed to J. W. S. the action of neutrons on Al used in the construction Proton source for atomie disintegration of the counter. H. J. E. experiments. S. N. Van Voorhis, J. B. H. Kuper, and G. P. H a rn w e ll (Physical Rev., 1934, [ii], p-Radioactivity of neutrons. L. M otz and J. 45, 492—493).—A focussed beam of ions of 20—50 S chw inger (Physical Rev., 1935, [ii], 48, 704—705; microamp. consisting mainly of protons has been cf. Konopinski, this vol., 1048).—Mathematical. obtained from a modified Lamar-Luhr low-voltage N. M. B. arc (A., 1934, 1052). L. S. T. Neutron-like particles accompanying p-ray em ission. G. H. D enison (Physical Rev., 1934, Detection of nuclear disintegration products. [ii], 45, 557).—An attempt to detect such particles H. A. Barton and D. W. M ueller (Physical Rev., emitted simultaneously with (3-rays failed \vith Ra-Z) 1934, [ii], 45, 650—651).—An arrangement for detect- and -E, KG1, and RbCl. L. S. T. ing disintegration products by means of tracks in a photographic emulsion is described. L. S. T. Possible models of an electrostatic neutron. Disintegration of Li® by protons and deutons. H. Margenatj (Physical Rev., 1934, [ii], 45, 559).— T. Y. Wu and G. E. Uhlenbeck (Physical Rev., Theoretical. L. S. T. 1934, [ii], 45, 553—554; cf. A., 1934, 343).—Bom- Scattering of slow neutrons. A. C. G. M itc h e ll bardment of ordinary Li by protons gives, in addition and E. J. M urpiiy (Physical Rev., 1935, [ii], 48, to the 8-4-cm. group, two groups of a-particles with f)53—656).—IJsing the radioactm ty produced in a ranges of 6-5 and 11*5 mm. The 6-5-mm. group Ag foil as a detector of neutrons, curves for the % may be ascribed to 3Li®. Bombardment of 3Li® with scattering of slow neutrons as a function of thickness deutons gives a-particles of 13-2 cm. rangę and protons by Fe, Cu, Pb, Sn, and Hg were obtained. The calc. of 30 cm. rangę; the latter are explained by assuming relative cross-sections for scattering are 9-9, 7-7, 7-2, the reaction 3Li6+ 1H2 -> 3Li7+ 1H1. L. S. T. 3-8, and 4-4, respectively. N. M. B. Transmutation of lithium by deutons and its Velocity of slow neutrons by mechanical bearing on the mass of the neutron. C. C. velocity selector. J. R. Dunning, G. B. Pegram, L a u ritse n and H. R. C ran e (Physical Rev., 1934, G. A. Fink, D. P. M itchell, and E. Segre (Physical [ii], 45, 550—552).—Experiments showing th at Rev., 1935, [ii], 48, 704; cf. this vol., 1186).—A curve -rays are not produced in the disintegration of Li is obtained showing the decrease in no. of slow y deutons are described. Hence, previous calcul- neutrons from a Rn-Be source detected after passing ations of the mass of the neutron are not invalidated through a Cd-duraluminium two-shutter system as by this assumption. The val. given for this mass is the speed of the sectors changed. N. M. B. 1-0068. L. S. T. y-Rays due to absorption of slow neutrons. Artificial radioactivity produced by deuton F. R a s e tti (Z. Physik, 1935, 97, 64—69).—Results bombardment. M. C. H e n d e rso n , M. S. Living- are given for energy associated with y-rays emitted sto n , and E. O. L aw ren ce (Physical Rev., 1934, from Cl, Co, Y, Ag, Cd, Ir, and Hg. A. B. D. C. [ii], 45 , 428—429).—W ith the possible exception of C, no radioactmty was induced in Ca and in the Slow neutrons. P. Lukirsky and T. Zarewa elements from Li to Cl (Ne and S not included) by (Naturę, 1935, 136, 681-—682).—The increased radio- bombardment with 1-5 X10® volt protons. With activity induced in Ag irradiated by slow neutrons 3 X10® volt deutons, each element emitted both on cooling the paraffin was to the temp. of liąuid air y-radiation and ionising particles, presumably posi- has been confirmed (cf. this vol., 802). W ith thick trons, of approx. electronic mass. The half-lives layers of wax, however, no temp. effect is observed of the radioelements produced in the following owing to loss of neutrons by absorption in the wax. targets were: CaF2 40 sec., CaCl2 13 min., B203, Absorption increases with a decrease in velocity of Na phosphate, Li2C03, and NH4N03, approx. 2 thermal neutrons. The calc. effective cross-section min., Al 3 min., Mg 9 min., Bo 9 min. and possibly of neutrons is approx. 10~24 cm.2 L. S. T. 3 min., and C 12 min. L. S. T. Application of radioactive bromine to the Further experiments with artificially-pro- investigation of the jnechanism of chemical duced radioactive substances. H. R. Crane and reactions. S. R ogin sk y and N. G o fstein C. C. L a u rits e n (Physical Rev., 1934, [ii], 45, 497— (Physikal. Z. Sovietunion, 1935, 7, 672—676).— 498).—When bombarded by protons, C and B203 Org. Br linked to C shows scarcely any interchange show an activity which decays at the same rate as with radioactive Br in Br2, HBr, KBr, or CuBr2. that produced by deutons (see below). The intensities Passage of radioactive Br vapour over heated aq. are approx. 10 and 20%, respectively, of those pro KBr, or dissolution and subseąuent evaporation of duced by deutons. Alternative reactions are dis- radioactive Br from aq. KBr, leads to complete dis- cussed. After deuton bombardment of B203 the tribution of the activity. At high temp. HgBr2 and active materiał appears to be a gas which rapidly AlBr3 show complete interchange of Br with the diffuses from the target. It is concluded that most vapour phase. Heating of CuBr2 containing radio- of the C11, assumed to be the radio-element formed, active Br, to form CuBr, followed by re-conversion exists in the target as CO or CO, and little, if any, into CuBr2 in non-radioactive Br causes < theoretical as C. L. S: T. 1442 BRITISH CHEMICAL ABSTRACTS.'— A.
Disintegration of boron by deutons and by 48, 641—648).—A survey co-ordinating available data protons. C. C. Lauritsen and H. R. Grane and thoory. N. M. B. (Physical Rev„ 1934, [ii], 45, 493-^195; cf. A., 1934, Effect of primary cosmic-ray energy on burst 579).—The radiation obtained from B bombarded production. W. F. G. Sw ann and D. B. Cowie with a mixed beam of deutons and protons has been (Physical Rev., 1935, [ii], 48, 649—652).—The in analysed. In addition to neutrons there is a large tensity of burst-production was much greator for component of y-radiation of energy 1-6 Xl06 e.v. vertical rays than for rays limited to a direction of The y-rays are probably associated with the same 45°, in agreement with the corresponding inerease transformation which produces the neutrons. This with altitude as compared with ray intensity. is assumed to be Bn +H 2 -> C12+w1+y> and the N. M. B. yal. l-6xlOG e.v. probably corresponds with an ex- Diurnal variation of cosmic-ray intensity and citation level in C12. L. S. T. N ova H ercu lis. J . B a rn ó th y and M. F o rró y-Rays from carbon bombarded by deutons. (Naturę, 1935, 136, 680—681). L. S. T. C. C. Lauritsen and H. R. Crane (Physical Rev., Positive and negative ions in tbe primary 1934, [ii], 45, 345—346; cf. A., 1934, 579). cosm ic radiation. H. J. W alkę (Naturę, 1935,136, L. S. T. 681).—Since equal nos. of positive and negative ions Radioactivity from carbon and boron oxide probably occur in the cosmic rays, the observed east- bombarded with deutons and tbe conversion of west asymmetry of cosmic radiation must bo explained positrons into radiation. H. R. Crane and C. C. in terms other than those of an unbalanced positive L a u ritse n (Physical Rev., 1934, [ii], 45, 430—432).— component. L. S. T. Additional data (cf. A., 1934, 579) are recorded and Vertical intensity of cosmic rays by tbreefold evidence for the assumption that the y-rays originate coincidences in tbe stratosphere. E. Regener from the annihilation of positrons together with and G. Peotzer (Naturę, 1935,136, 718—719). electrons is advanced. C appears to be transformed L. S. T. by deutons in two ways : 8C12 + iH 2-> GC13+ 1H1-f-y, Neutrons of high energy from cosmic-ray J p + iH 2-* .Ni3-j-oWi and 7Ni3-> 0C13 + (+e). The bursts in aluminium. G. L. L o c h e r (Physical nrst process is 10 times as freąuent as the second. Rev., 1934, [ii], 45, 235; cf. A., 1934, 235). With B the supposed transformations are L. S. T. sBio + ^ - y e C ^ + o # and GC“ -> 5B> H (+ e). Secondary photons in cosmic-ray showers. L. S.T . C. I). Anderson and S. H. Neddermeyer (Physical Investigation of nuclear disruption of alumin Rev„ 1934, [ii], 45, 295). L. S. T. ium by tbe photographic metbod. M. Blau and H. Wambacher (Sitzungsber. Akad. Wiss. Wien, Possible explanation of the frequency dis- 1934, H a, 143 , 401—410; Chern. Zentr., 1935, i, tribution of the size of Hoffmann Stosse. C. G. 1658).—Investigation by the photographic method M ontgom ery (Physical Rov., 1934, [ii], 45, 294). confirmed the presence of particie groups found by L. S. T. Chadwick and Constable, and revealed a new group Further geographic studies of cosmic rays. of rangę 35—50 cm. J. S. A. A. H. Compton, J. M. Benade, and P. G. Ledig (Physical Rev., 1934, [ii], 4o, 294—295). L. S. T. Secondary emission from elements of medium mol. wt. under action of radiation from Po+Be. Comparison of absorption coefficients of Z. O llan o (Ric. sci. Próg. tec. Econ. naz., 1934, diSerent elements for cosmic rays. J. C. 2, 374— 376; Chem. Zentr., 1935, i, 1821).—Heavy S te a rn s and C. H ed b erg (Physical Rev., 1934, [ii], elements, except Sn and Sb, have a relatiyęly lower 45, 294).—The cosmic-ray energy absorbed by 6 in. absorption per mol. than light elements toward of Al, Cu, Pb, and Zn, respectively, has been deter- radiation from Po+Be. Sn emits soft radiation of mined. “ L. S. T. great energy. J. S. A. Hypothesis of the instability of the deuton. G. N. Lewis, M. S. Livingston, M. C. H en d erso n , Nuclear evolution of iron, cobalt, and nickel. and E. O. L aw rence (Physical Rev., 1934, [ii], 45, H. J . W a lk ę (Phil. Mag., 1935, [yii], 20, 738—739; 497).—An alternative explanation for previous results cf. this yol., 427).—The isotopes 2«Fe5S iind 20Fe511 are (A., 1934, 471) is discussed. L. S. T. missing, and 20Fe67 and 28Ni58 are stable. The schemes proposed are : ,6Fe53-> 27Co58-> p-y 28Ni5S, and Excitation and disintegration of protons and „6FeM ^ 3 -> 27Co59. N .M .B . the neutret. R. M. L a n g e r (Physical Rev., 1934, [ii], 45, 495— 496).—Theoretical. L. S. T. Atomie fragment of short rangę from heavy inert gases. H. Pettersson and J. Schintl- Emission of fast particles. K. C. K ar (Current meister (Sitzungsber. Akad. Wiss. Wien, 1934, Sci., 1935, 4, 154— 155).—A modification of the wajye- H a, 143, 385—399; Chem. Zentr., 1935, i, 1657— statistical formuła for the emission of fast particles 165S).—Investigation of very short-range particles from radioactive elements is proposed. W. R. A. by means of a tube electrometer reveals the presence Collisions of very fast heavy particles. W. of such particles in addition to elastically scattered B rau n b e k (Z. Physik, 1935, 96, 600—606).—Theoret a-particles from Xe and Kr but not from Ni or I. ical. A. B. D. C. J. S. A. Theory of elementary particles. II. Electro- Corpuscular theory of primary cosmic radi magnetic whirls and elementary particles. N. S. ation. W. F. G. Sw ann (Physical Rev., 1935, [ii], Jap o lsk y (Phil. Mag., 1935, [vii], 20, 641—706; cf. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1443 ibid., 417).—Mathematical. It is suggested that the Japan, 1935, 56, 213—220).—Solutions of complex elementary particles electrons, protons, positrons, salts of Co, Ni, and Cr in liquid NHS show absorption light ąuanta, etc. can be considered as “ whirls ” or bands similar to those in aq. solution. Ch. Abs (e) certain systems of Maxwell electromagnetic waves. Ultra-violet absorption and colour centre In this way the quantum and relativity relationships, formation of alkali halide crystals. E. R e x e r the de Broglie formuła, and gravitation can be (Physikal. Z., 1935, 36, 602).—Pressure-deformation explained on classical electrodynamics. The theory of pure KBr with 800 g. per sq. mm. raises the ab leads to a proton-electron mass ratio agreeing with sorption coeff. at 203 m^ from 0-250 to 0-750 ram .-1 experiment. N. M. B. A. B .D .C . Ionising effects of meteors. A. M. S k e lle tt Spectra of strontium hydride. W. R. Frede- (Proc. Inst. Radio Eng., 1935, 23, 132— 149).—A rickson, M. E. Hogan, jun., and W. W. Watson meteor of average velocity has sufficient velocity to (Physical Rev., 1935, [ii], 48, 602—606).—Fuli cause ionisation of atm. gases by impact. data and quantum analyses of the SrH band systems, Ch . Abs. (e) photographed at high dispersion, are reported. Nuclear energies of aluminium and beryllium. N. M. B. H. A. W ilson (Physical Rev., 1934, [ii], 45, 430).— Emission band spectrum of the OD molecule. Bombardment data for Al and Be indicate that the Y. O ta (Mem. Fac. Sci. Agric. Taihoku, 1935, 15, nuclei of the atoms of the elements liave possible 181—191).—The spectrum excited by an electrical energies equal to 3-85?i or 3-85w-)-a const., where n is discharge through H20 vapour containing 65% of 0 or an integer. L. S. T. combined D was photographed, and fuli data for the Energy levels of inert gas configurations. (0,0) OD band of the 2S+ -> 2n transition are C. L. B a rtb e r g e r (Physical Rev., 1935, [ii], 48, tabulated. From the relative intensity of lines in 682—683).—A morę accurate calculation of the energy the P v P 2, Qv and Q2 branches the naturę of the levels for the configuration n'p5np is made (cf. abnormal rotation of the excited OD mol. is discussed Shortley, A., 1933, 1226; this vol., 556), taking in comparison with the corresponding OH band. account of the electrostatic interaction between N. M. B. groups. N. M. B. Absorption spectra of iodine solutions and the Values of Planck’s constant. K. Shiba (Buli. influence of the solvent. O. J. W alker (Trans. Inst. Phys. Chem. Res. Japan, 1935, 14, 897—908).— Faraday Soc., 1935, 31, 1432—1438).—The mol. The most probable vals. of e, e/m, and h are recalc. extinction coeff. for violet solutions of I in eight chlorinated hydrocarbons has been measured. In to be (cf. A., 1933, 884) (4-8032±0-02% ) X 1 O, 1, 2. . . (I) have ofcher bands at shorter XX, which Two new bands of C02 in the photographic are similar to bands of Ph2 in position and structure infra-red. G. Herzberg and H. Verleger and are attributed to the Ph groups; the height of the (Physical Rev., 1935, [ii], 48, 706).—New bands at max. do not vary with the no. of GIC linkings. The 1-2031 and 1-2178 n, showing.flne structure, have spectra of diphenylacetylenes differ in type from those been photographed. Results agree with the predic- of (I). Fundamentally the spectra of the porphyrins tions of Adel (cf. A., 1933, 661, 885). N. M. B. are similar to those of the aliphatic pplyęnes, but Rotation spectra of ammonia and ND3. R. B. on these bands other vibrations are superimposed. Barnes, W. S. Benedict, and C. M. Lewis (Physical VI. The absorption and fluorescence spectra of the Rev., 1934, [ii], 45, 347; cf. this vol., 806). L. S. T. diphenylpolyenes, Plr[CH;CH]„-Pli, are in the relation Absorption spectra, in the near infra-red, of of object to mirror image in respect of the position, amines and amides. Use of the phenomenon of but not of the height, of the bands. With increase “ dissimulation ” in studying amphoteric ions. in n the fluorescence bands shift more than the Influence of neighbouring groups. (Mme.) M. absorption bands and the heights of the max. fali. At —196° the positions of the fluorescence bands are Freym ann and P. Rumpf (Compt. rend., 1935, 201, given by v (cm.4 )= v 0—1550W/'— 1160ł'2”, wherę 606—608; cf. this yol.j 563).—The NH absorption v0 is the position of the band of shortest X and i’,", band at approx. 1-04 ll is not obseryed in a 20% aq. ł’2"= 0 , 1, 2, 3. . . The band separations 1550 and solution of glycine, or in saturated aq. taurine, but 1160 cm.-1 correspond with the strongest lines in is obseryed in solutions of the Na and Li salts, the Raman spectra and represent freąuencies of the respectiyely. 75-CfiH4Me-S0 2-NH2 does not show the CIO linlcing. The yariation of fluorescence with band, but its Na derivative does. N has a co-ordin- concn., solyent, temp., and state of aggregation ation no. of 4 when the band is not observed. Data agrees with the theory of ąuenching collisions (cf. for the position of this NH band in yarious amides A., 1925, ii, 474). The fluorescence of dodecapenta- are recorded. The structure of these compounds is enoic acid and iSomethylbixin proves that ring closure discussed. H. J. E. is not essential for fluorescence; they have almost Absorption of simple substituted hydro the same fluorescence spectra. R. C. carbons in the near infra-red. I. Influence of state of aggregation. (Gas-liquid comparison.) Optical absorption of porphyrins. II. A. R. M ecke and O. V ierlin g (Z. Physik, 1935, 96, Stern and H. W enderlein (Z. physikal. Chem., 559—570).—Absorption spectra of the third CH over- 1935, 174, 81—103; cf. this vol., 10).—Absorption tone were obtained for MeCl, MeBr, EtCl, vinyl in dioxan solution has been determined. Comparison chloride, and (CH2)20 in the gas and liąuid phases, of the absorption spectra of porphyrins with those and data are summarised for w-C0H14, cyclo-hexane of the corresponding chlorins supports the view that and -hexanol, C6H6, and dioxan. Condensation to in the latter the porphin framework has changed into the liąuid state always lowers the freąuency of a dihydroporphin (cf. ibid., 871). Substances with yibration in a series of overtones by the amount Av, a structure based on dihydroporphin, such as chlorins, where Av/v is a const. Closure of a ring also decreases pyroph;eophorbide-a, and methyłph;oophorbide-«, the frequency, as does an increase in ring size. have very similar yisible absorption spectra. Uropor- A. B. D. C. phyrin Petry, uroporphyrin Pteria, and Me8 Infra-red spectrum of hexadeuterobenzene 1 :3 :5 : 7-tetramethylporphin-2 : 4 : 6 8-tetrasuccin- and the structure of benzene. W. R. Anc.us, ate are spectroscopically identical. The absorption C. R. Bailey, C. K. Ingold, A. H. Leckie, C. G. curve of luemin solution has been determined. Raisin, J. W. Thompson, and C. L. W ilson (Naturę, R. C. 1935, 136, 680; cf. this vol., 914).—The principal Absorption spectra of tervalent halides dis- frequencies of the infra-red spectra of C6D6 and CGHG solved in ether and their dissociation products. are compared. The new measurements ’ for C6D6 S. K a to and F. Someno (Sci. Papers Inst. Phys. agree, on the whole, with those of Barnes and Brattain Chem. Res. Tokyo, 1935, 28, 95—111).—The ab (tliis vol., 1189). Coincidences between certain fre sorption spectra in rangę 2000—7000 A. of solutions ąuencies of the Raman and infra-red spectra of C6H6 of trihalides of As, Sb, Bi, Fe, and Tl in Et20, and of and of C6D6, which led to the rejection of the piane the yapours of As, Sb, and Bi trihalides, have been hexagonally symmetrical C0H6 model, are nów re- determined. The Raman spectra of AsC13, AsBr3, garded as accidental; the model is retained. and SbCl3 in Et20 are similar to the spectra with the L. S. T. liąuid salts, but differ from those with the crystals. Structure and interpretation of the infra-red Photo-dissociation with light from a Hg-vapour absorption spectra of crystals. R. B. Barnes, lamp or C arc has been studied chemically, the pro R. R. B rattain, and F. Seitz (Physical Rev., 1935, ducts being lower halides or metal, exeept with [ii], 48, 582—602).—A detailed investigation of the Asl3 (As203), Sbl3 (SbOI), and Bil3 (BiOI). The mols. absorption spectrum of MgO in the near infra-red is of salt in Et20 are in the ground state, but are deformed reported; the fundamental absorption is accompanied by the solvent. R. S. B. by much secondary structure. Results are inter- preted on the basis of a ąuantum-mechanical treat- Ultra-violet absorption spectra of certain ment of anharmonic potential forces, and show that compounds derived from living cells. F. F. the absorption spectra of a MgO-type cubic crystal Heyroth and J. R. Loofbottrow (Physical Rev., should have a very complicated secondary structure. 1934, [ii], 45, 126; cf. A., 1934, 1112). L. S. T. NIM . B. GENERAL, PHYSICAL, AND INORGANIC OHEMISTRY. 1445 Infra-red absorption byRochelle salt crystals. 667—669).—The Raman shifts observed for D20 were J. V alasek (Physical Rev., 1934, [ii], 45, 654—655).— 170, 350, approx. 500, 1207, 2389, and 2509 cm.-1, Optical measurements indicate that the unusually the corresponding vals. for H 20 being 176, 500, 700, large e of these crystals is not due to the polarisation 1659, 3221, and 3435 cm.-1 H. J. E. of the H 20 mols. L. S. T. Constitution of water in solutions of non- Rayleigh scattering, in crystals. F. Matossi electrolytes. I. Acetone. C. S. S. R ao (Phil. (Z. Physik, 1935, 96, 698).—Corrections (cf. this vol., Mag., 1935, [vii], 20, 587—594; cf. this vol., 295).— 146). A. B. D. C. The intensity distribution along the Raman H20 band Doppler effect in light scattering in liquids. was investigated in solutions of 0, 25, 50, and 75% II. Polarisation of the transversely scattered C0Me2. The band becomes sharper with inereasing radiations. B. V. R. R ao (Proc. Indian Acad. Sci., concn. of dissolved substance; the intensity max. 1935, 2, A, 236—241; cf. this vol., 1053).—For light does not shift with change of concn. as in the case of scattered transversely by CC14, PhMc, and CS2, the strong and weak electrolytes; the smaller frequency two Doppler components are completely polarised, branch of the intensity curve shifts and changes in and the central component is almost completely shape with inereasing concn. of COMe2. Results polarised. N. M. B. indicate a preponderance of double H20 mols. and double hydrates over the other types, especially at Bibliography of the Raman effect. III. S. C. high concns. of the dissolved substance. N. M. B. Sirkar and D. Cjiakravarty (Indian J. Physics, 1935, 9, 553—622; cf. A., 1933, 445).—A complete Molecular clustering in binary liquid mix- list of papers classified under subject hcadings, tures. R. S. Krishnan (Proc. Indian Acad. Sci., authórś, and substances studied is given. 1935, 2, A, 221—231; cf. this vol., 11).—A com- N. M. B. parative study of the intensity, by the photo-electric Intensity of Raman effect. A. Carelli (Rend. method, and the depolarisation of light scattered Accad. Sci. Napoli, 1933, [iv], 3, 156—160; Chem. transversely by mixtures of PhOH and H20 in Zentr., 1935, i, 1827).—The ratio of intensity of the different proportions and at different temp. was made. Ram an line of CC14, Av 1550 cm.-1, to its first over- The lowest vals. for the depolarisations of light tone is 1 : 10. An explanation is advanced. unpolarised, and perpendicularly and horizontally J . S. A. polarised, were found with the crit. composition mixture (34% PhOH) at the crit. solution temp. Raman spectrum of (a ) deuterium and (B) hydrogen deuteride. S. B hag av an tam (Proc. The intensity of scattering inereases considerably Indian Acad. Sci., 1935, 2, A, 303—309, 310—312).— for the 34% mixture as the crit. temp. is approached. (a) Using the X 4358 Hg line as incident radiation, The tendency for the formation of, and size of, and 17 atm. pressure, rotation lines ±179-5, ±297-4, clusters depend on the temp. and composition of the 415-2, 530-8, and 643-5 cm.-1, and a vibration line of mixture. These phenomena are most pronounced for shift 2992-7 were observed. Results agree w ith avail- the crit. mixture at the crit. temp. The relation able mol. const. data. Relative rotational intensities of results to anomalies of viscosity, magnetic agree with a nucleus of one unit spin and obeying birefringence, etc. is examined. N. M. B. the Bose-Einstein statistics. Intensity distribution Raman spectrum of phosphorus. C. S. Ven- agrees qualitatively with the theory of rotational kateswaran (Proc. Indian Acad. Sci., 1935, 2, A, Raman scattering in diat. mols. 260—264).—Data for solid, liquid, vapour, and solu (b) W ith X 435S, HD showed a spectrum contain- tion in CS2 are given. Only smali changes in frequency ing 267, 442, and 618 cm.-1, arising respectively from are found in passing from one state to another, the rotational transitions 0 -> 2, 1 -> 3, and 2 -> 4, indicating the non-polar character of the mol. In and agreeing with calc. vals. The anti-Stokes line all cases a strong fluorescence band extends from due to the transition 2 -> 0 was found. Alternating 6230 to 6550 A. N. M. B. intensities were not observed, and the line correspond- Raman spectra of heavy and light phosphine. ing with 1 -> 3 is the most intense. N. M. B. M. de Hemptinne and J. M. Delfosse (Buli. Acad. Raman spectrum of heavy water. R. A nan- roy. Belg., 1935, [v], 21, 793—799).—The Raman thakrishnan (Proc. Indian Acad. Sci., 1935, 2, A, spectra of PH3 and PD3 in the liquid and solid state 291—302).—The spectrum shows a strong band with have been investigated. Liquid PD3 gave lines three imperfectly resolved components of frequency 1664, 807, and 740 cm.-1 The most intense lines are : shifts 2363, 2515, and 2662 cm.-1, and a sharp band PH 3 (liq.) 2306, (gas) 2327; PD3 (liq.) 1664, (gas) ■with frequency shift 1235 cm.-1 with a feeble com- 1684; PH D 2, 1825; PDH2 1755 cm.-1 A. J. M. panion a t about 1110 cm.-1, and a strong low-fre- Raman spectrum of nitrogen pentoxide. J. quency band 175 cm."1 Comparison of H20 and Chedin (Compt. rend., 1935, 201, 552—554).— DaO spectra shows many similarities. The valency Raman spectra of N205 in HN03, H2S04, CC14, angles and force consts. do not alter much in passing and CHC13 are recorded. T. G. P. from H20 to D20. The triple structure of the prin- Raman spectrum and constitution of fuming cipal band indicates polymerisation similarly to H20. sulphuric acid. N. G. P ai (Phil. Mag., 1935, The low-frequcncy band is connected with the naturę [vii], 20, 616—623).—Raman data obtained for four of the liquid state. N. M. B. concns. of fuming H2S04 indicate that at Iow concn. Raman spectrum of liquid heavy water. E. all the S03 mols. go into combination, forming B a u e r and M. M agat (Compt. rend., 1935, 201, H2S207, and the H2S04 lines weaken in intensity; 1446 BRITISH CHEMICAL ABSTRACTS.— A. at higher concn. much free S03 and S20 6 are present; Raman spectra of solutions of pyrogallol, in 71% acid t.heir relative proportions are approx. gallic acid, and tannin. E. Briner, S. Eried, and as in a S03-S20 6 mixture in eąuilibrium; in S0% B. Susz (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., acid a smali concn. of free H„S04 mols. exists. 178—180).—Ram an freąuencies of pyrogallol and N. M. B. of gallic acid in EtOH solution and of tannin in aq. Influence of intermolecular action on the solution are recorded. S. J. G. Raman effect for licpiids. W. Buchheim Coloration of compounds of different elements (Physikal. Z., 1935, 36, 694—711).—The theoretical by cathode rays. H. Nagaoka and T. Mishima effect of an electric field on Raman scattering is (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1935, considercd. The Raman lines should inerease in 28, 77—94).—The intensity of the coloration pro- width with inereasing field strength, owing to alter- duced when cathode rays of 0—104 volts impinge ation of mol. yibrations by the effect on the electron on yarious metallic salts has been determined. charge cloud. A displacement of the lines is also It is inferred that the colours are due to dissociation to be expected. Lines forbidden by mol. symmetry of mols. near the surface, the metallic atoms pro- may appear on application of a field. The widening duced being protected by a surface layer of undissoci- of the lines due to infra-red active yibrations byelectro- ated salt. R. S. B. dynamic interaction is considered. The yariątion in intensity of the Raman spectrum of a substance Phosphorescent beryllium nitride. S. S ato h on mixing with anotlier was investigated in the follow- (Buli. Inst. Phys. Chem. Res. Japan, 1935,14, 920— irig cases : CGHG mixed with C6H14 and with CHC13; 924).—Phosphorescent Be3N2, activated by Al, gives CCl.j in COMe2 mixed with CGH6; CHC13 in C0H0 a cathode-ray spectrum with a continuous band at mixed with C6H14. A. J. M. 4200—1900A., m as. at 4650 A. R. S. B. Fluorescence in cycJohexane. R. Padmana- Raman spectra of methyl deuteride. G. E. bhan (Proc. Indian Acad. Sci., 1935,2, A, 209—212).— MacWood and H. C. Urey (J. Chem. Physics, Using an improved continuous distillation apparatus, 1935, 3, 650—651).—Vibrational frequencies of pure c?/c/ohexanc has no fluorescence; th a t reported MeD in the Raman spectra have been measured. by Haberl (cf. this vol., 11) is due to photochemical They are higher (max. +30 cm.4 ) than those calc. decomp. in which the region XX 2400—2600 is active. by Dennison and Johnston (Physical Rev., 1935, N. M. B. [ii], 47, 93). No rotational structure was observed. Comparison of efiect of ordinary and rjeno- T. G. P. alkaloids on the fluorescence of uranine solu Raman spectrum of neopentyl deuteride. tions. C. Achard, A. Boutaric, and J. Bouckaru D. H. Rank, E. R. Bordner, and K. D. Larsen (Compt. rend., 1935, 201, 629—631).:—The ge.no- (Physical Rev., 1934, [ii], 45, 566).—The results alkaloids (e.g., ge?io-strychnine hydrobromide) do not show that the vibrational degeneracy of the neo- inhibit the fluorescence of aq. uranhie in the same pentane mol. is partly removed by the substitution of way as the normał alkaloid. H. J. E. a D for a H. The C—D vibration becomes evident Spray electrification of liquids. S. Chapman through the appearance of a lilie at 2179 cm r1 (Physical Rev., 1934, [ii], 45, 135—136).—D ata L. S. T. correlating drop size, sign and magnitude of the charge, Raman spectra of dioxan and tetralin. C. S. y, and e are given for H20, glycerol, NH2Ph, PhN02, Venkateswaran (Proc. Indian Acad. Sci., 1935, and “ ameroil.” In generał, larger drops (4—5 X10*4 2, A, 279—290).—Fuli data, obtained with the cm. radius) have the greater charges, and the greater filters used, are tabulated. The spectrum of dioxan is e the higher is the charge val. L. S. T. consists of 24 lines, 14 being new, and closely resembles th at of cj/c?ohexane. Tetralin gave 11 new lines. Contact potential difference between clean Results are discussed with reference to mol. structure. and oxygenated tungsten. A. L. Reimann (Phil. N. M. B. Mag., 1935, [vii], 20, 594—607).—The contact p.d. Raman spectra of cis- and f»«/ts-decalins. at room temp. between slightly electronegativcly S. K. K. J a t k a r (Indian J. Physics, 1935, 9, 545— contaminated W and W when 02-covered, for most 551).—Using a sample containing 36% of cis-form effectively raising the work function was 1-70 yolts. prepared by fractional distillation, and a sample The calc. p.d. a t 1500° abs. between clean W and W containing mostly frans-form prepared by keeping less effectively 0 2-covered than above is 1-75 volts. ordinary decalin in contact with A1C13 for 24 hr., Loss of electronegativeness of oxygenated W by Raman data are tabulated, and results are discussed evaporation of 0 2 was detected at 1300° abs., and in relation to mol. structure. N. M. B. beyond this the rate of evaporation inereased rapidly with rise of temp. A clean W surface oxygenated when Chemical reactivity and Raman spectra of hot or cold showed no difference in electronegativeness the eugenols, yanillins, and safroles, and of or volatility of 02- The most complete 02-covering piperonal, estragol, and anethole. B. Susz, E. (of the degrees of covering stable in vac.) most effect- Perrottet, and E. Briner (Arch. Sci. phys. nat., ively raises the work function. N. M. B. 1935, [v], 17, Suppl., 133—134).—The oxidation of Photo-electric properties and electrical resist- the above compounds by 03 has been studied and ance of metallic films. D. R oller and D. Wool- their Raman spectra have been determined. Ali show d rid g e (Physical Rev., 1934, [ii], 45, 119—120).—As the characteristic freąuencies of the C6H6 nucleus, the average thickness of a Cd film decreases, the and CIO and CIC linkings where present. S. J. G. electrical resistivity inereases from the val. charac- GENERAL, PHYSICAL, AND INORGANIO CHEMISTRY. 1447 teristic of tlie metal in bulk at first slowly and then due to deformation rather than association. (I) exists moro rapidly, until just beyond a crit. thickness it largely as a zwitterion in all the solvents; in C6H6 rapidly approaches an infinite val. L. S. T. its dipole moment is 3 times that of (II). The Photosensitive layers of the photo-electric electrostriction of the solvent produced by betaines conductive thallium celi. (Miss) C. Asai (Buli. in H20 is < that produced by similar NH2-acids; Inst. Phys. Chem. Res. Japan, 1935, 14, 797—832).— the electrostriction in solvents of Iow dielectric const. Heating of a film of Tl in air yields T120, T1203, etc. is much > in H 20. E. S. H. Distillation of T12S gives the amorphous or cryst. Electric moments of organie compounds. form according to conditions of distillation, the formor J. N. Pearce and L. F. Berhenke (J. Physical being converted into the latter by annoaling. The Chem., 1935, 39, 1005— 1010).—The dielectric consts. photo-electric sensitmty is high when T120 and Tl and d of dii. solutions of ^-bromo-, y»-hydroxy-, and are disseminated in cryst. T12S, so the conductivity jj-methoxy-benzaldehyde, jj-tolualdehyde, p-ethyl- is explicable on the impurity theory of semi- hexan-a-ol, a-ethylhexaldohyde, tri-, di-, and mono- conductors. J. W. S. hydroxyetliylamine in C6H6 and dioxan have been Spectral photo-electric poly-selectivity of determined at 25°. The total polarisation and dipole various surface layers. W. Kluge (Z. Physik, moments have been calc. E. S. H. 1935, 96, 691—697).—Decrease in sensitivity due to Constitution of [alkyl] polysulphides. I and adsorption of 02 has been studied at XX from 200 to II. S. Bezzi (Gazzetta, 1935, 65, 693—703, 704— 1100 mjj. for the layers Ag-Cs20-Cs, Cu-Cs20-Cs, 723).—I. Measurements of d, b.p., refractive index, and Cs. A. B. D. C. and of mol. wt. in C6H6 have been made for Et, Pr, Dielectric loss in electrolytic barrier layers Bu, and isohexoyl mercaptides, sulphides, disulphides, at high field intensities to 107 volts per cm. A. and tetrasulphides. The at. refraction of S inereases G untiier-S cholze and H. B e t/ (Z. Physik, 1935, 96, from 7-95 in the mercaptides to 8-76 in the tetra 686—690).—The loss angle for A120 3 is 0-02, and for sulphides. Ta20 5 is 0-075, both at 50 cycles; its variation with II. Viseosity measurements for the above-men- time of measurement, formation voltage, field in- tioned substances are recorded. The viscosity of the tensity, time of formation, age, and frequency is also pure substances is a function of the mol. wt., and is given. A. B. D. C. independent of the constitution. From the viscosities of dii. solutions of these substances in CHC13 and in Measurement of the variation of the dielectric Et20 it is shown that the length of the mol. is the constant of water with extent of adsorption. same (for a given alkyl radical) in the mono-, di-, G. H. A rgue and O. Maass (Canad. J. Res., 1935, and tetra-sulphides, and that, therefore, ehains of S 13, B, 156—166).—Apparatus and techniąue for atoms are not present. O. J. W. determining the dielectric const. of cellulose contain- ing various amounts of adsorbed H20 aro deseribed. Behaviour [rotation] of benzylamine tartrate Dielectric consts. of the adsorbed H20 have been in acetic acid. E. Darmois and I. Peyches (Buli. calc. for the concn. rangę 0—18%. The dielectric Soc. chiin., 1935, [v], 2 , 1656— 1668).—[a] was deter const. of H 20 initially adsorbed is > 0-25 of th at of mined, using Hg lines, for benzylamine tartrate (I) liąuid H20, but inereases with inereasing amount of and tartaric acid (II) at different conens. in AcOH. adsorption until it approximates to that of liąuid [a] for the tartrate ion is independent of concn. for H20 as the fibrę becomes saturated. E. S. H. (II), but inereases linearly with the (concn.)1'3 for (I). The effect of the addition of H20 on the val. Structure of the naphthalene nucleus. N. of [a] is discussed. Vals. of electrical conductmty N akata (Buli. Chem. Soc. Japan, 1935,10, 318—323; for solutions of (I) and NMe4 tartrate in AcOH and cf. A., 1931, 1281).—Dipole moments of a no. of with added H20 are also given. F. R. G. C10HS derivatives are givon. Only the a-positions appear to be aromatic, and centroasymmetry is Anomalous rotatory dispersion of i-p-pinene. indicated. R. S. I. R. Padmanabhan and S. K. K. Jatkar (J. Indian Chem. Soc., 1935, 12, 518—526).—Tests on Dipole moment of tetralin. M. A. G. R au and samples of purified p-pinene indicate that the anomaly S. S. R ao (Proc. Indian Acad. Sci., 1925, 2, A, 232— in rotatory dispersion at about 2800 A. is duo to a 235).—The val. as measured in C6H6 as solvent is 0-4—0-5x10-18. N. M. B. closely associated impurity which is difficult to remove. The anomaly in the ultra-violet region is a Physical chemistry of betaines and related characteristic of (3-pinene. This is confirmed by the substances. I. Dielectric constants and ap- Raman spectra of the fractions on distillation. As parent molal volume. J. T. Edsall and J. there is no evidence of absorption in the region of Wyman, jun. (J. Amer. Chem. Soc., 1935, 57, 1964— anomaly, the latter is not due to a Cotton effect, but 1975).—D ata are recorded for betaines and for jV-di- is attributable to a superposition effect caused by a methylanthranilic acid (I) and its Me ester (II) in second rotation of opposite sign and different dis H20, EtOH, C6Hg, and their mixtures. Approx. persion. This second rotation is not due to induced dipole moments have been calc. for the relatiyely dissymmetry of the semicyclic double linking, because rigid benzbetaines. In solvents of Iow dielectric camphene, of similar structure, has normal dispersion. const., the dielectric inerements (and probably the J . W. S. moments) of all the betaines studied are much < Magneto-optical rotation of uranyl salts. S. S. their vals.. in H20 , an effect which. appears to be Bhatnagar, P. L. Kapur, . and. N. R. Verma (J. 1448 BRITISH CHEMICAL ABSTRACTS.----A. Indian Chem. Soc., 1935, 12, 514—518).—The mol. (Pliysikal. Z., 1935, 36, 600—602).—Assuming the rotation of U02", determined from the magneto- C-H eąuilibrium separation 1-01 A. and the C-C optical rotations of U 02(N03)2 and U 02C12 solutions, 1-226 A., together with two observed valency and is about —8, whereas the val. from measurements on deformation frecjuencies for C2H2, frequenci.es are U02S04 solutions is about —11, the diffcrence being calc. for C2HD, and C2D2. Similar calculations are . attributed to the formation of eomplexes between made for C2H4C12 and “C2H4Br2, and compared with U02" and H,S04. J. W. S. Raman displacements. A. B. D. C. Magnetic double refractionand light scattering Analytical representation of the potentials of in fused nitrates. V. N. Thatte (Proc. Indian diatomic molecules and their determination Acad. Sci., 1935, 2, A, 244—248; cf. A., 1934, 942).— from spectroscopic data. I. General theory. Data for Zn(N03)2 and Cd(N03)2 are given. The II. Application to CdH and N2. E. A. Hyl- calc. magnetic and optical anisotropies of the N03 le r a a s (Z. Physik, 1935, 96, 643—660, 661—668).— aro -the same as for the N03 in HN03 and in cryst. I. A generał expression for the potential-nuclear nitrates. N. M. B. separation curve is given; it includes those of Morse Influence of substituents in bases and anions and of Rosen and Morse as particular cases, and is on the co-ordination number of a metal. VII. determined from D, b»e, and rotation consts. An Influence of electric moment on the number of energy formuła for vibrational levels is deduced. m olecules of base fixed by a salt. A. A blov (Buli. II. The above formuła is applied to the 2£-state of Soc. chim., [v], 2 , 1724— 1736; cf. A., 1934, 755).— CdH and gives excellent reproduction of Rydberg’s If the dipole moment of a negatiye group sub- curve (cf. A., 1932, 104). It also gives improved stituted in the p-position in NH2Ph is >1-5 X 10~18 results for the DS-state of N2. A. B. D. C. it increases the no. of mols. of base co-ordinated by Potential curve for diatomic homopolar mole (CCl3-C02)2Ni and (CHCl2,C02)2Ni, whilst the same cules. Application to CdH and N2. E. A. group in the o-position has the reverse effect. The H ylłeraas (Physikal., 1935, 36, 599—600).—Pre- results are discussed with reference to the electro- liminary notes (cf. preceding abstract). static theory of valency. J. W. S. A. B. D. C. Concentration of H3 and O18 in heavy water. (C-C)diam. linking energy. H. Gershinowitz (J. W. B le a k n e y and A. J. G ould (Physical Rev., 1934, Physical Chem., 1935, 39, 1041).—A criticism (cf. [ii], 45, 281—282).—Results obtained with heavy this vol., 1058). E. S. H. water containing 70—98% D show that the ratio Moments of inertia and the shape of the H3 : D is < 1 in 105. Hence, in ordinary H2 the ratio ethylene molecule. R. M. Badger (Physical Rev., H3 : H1 is probably < 1 in 5 X 108. In 0 2 obtained by 1934, [ii], 45, 648).—Available spectroscopical data electrolysis of ncarly pure D20 yielding 98% D2, agree with a piane symmetrical structure, and the no increase in the ratio O18 : O1® was detected. moments of inertia calc. are 33-2 Xl0~40, 27-5 X 10*40, L. S. T. and 5-70 X 10“10 g. cm.2, respeciively, in the ground H3 in heavy hydrogen. W. W. Lozier, P. T. state. Yals. for the C-C and C-H distances and for Smith, and W. B leak n e y (Physical Rev., 1934, the angle between the Cdi linkings consistent with [ii], 45, 655).—Measurements with a more sensitive these moments are 1-37 A., 1-04 A., and 126°, re- apparatus give an abundance ratio H3 : D of 5 :10® spectively. L. S. T. in 99% D2 obtained by electrolysis of D20. The ratio •l3 ; D in natura! H is probably > 1 : 109. Periodic unequal potential minima and torsion L. S. T. oscillation of molecules. T. Y. W u (Physical Rcv., Stable hydrogen isotope of mass three. M. A. 1934, [ii], 45, 66—67).—The torsion oscillation of Tuve, L. R. Hafstad, and O. Dahl (Physical Rev., mols. of the cis- and irans-forms of C2H2C12 is dis 1934, [ii], 45, 840—S41).—Rangę measurements cussed. L. S. T. indicating H3 nuclei from stable H3 atoms present Suggested improvements of Morse’s rule. in the order of 1 in 10G in 9S% D2 are described. C. H. D. Clark and J. L. Stoves (Naturę, 1935, L. S. T. 136,682).—The modification of Morse’s rule previously Wandering of adsorbed atoms along the suggested (A., 1934, 833) gives better approximations surface of solid bodies. A. G e h rts (Z. tech. Phys., to experimental vals. than those of other workers 1934, 15, 456—401; Chem. Zentr., 1935, i, 1344).— (cf. this vol., 685). L. S. T. Activation and deactivation processes are interpreted Potential energy curves and structure of the in terms of Volmer’s conception of atom wandering. alkaline-earth oxides. P. C. Mahanti (Indian J. S. A. J. Physics, 1935, 9, 517—536).—Curves for the Affmity factors in molecular collisions. A. different electronic states of BeO, MgO, BaO, CaO, E ucken (Oesterr. Chem.-Ztg., 1935, 38, 162—166).— and SrO are drawn according to Morse’s function. A lecture. E. L. U. The electronic configuration, dissociation energy, Calculation of vibrational isotope effect in and the products of dissociation in each state are polyatomic molecules by a perturbation method. discussed, and similarities in the spectra of the different E. B. W ilson, jun. (Physical Rev., 1934, [ii], 45, members are traced. N. M. B. 427).—Mathematical. L. S. T. Extra negative term in the incoherent part Proper vibrations of heavy acetylene and of the diffuse scattering of X-rays from neon- ethylene halides. Y. M orino and S. Mizushima like crystals. G. E. M. Ja u n c e y and J . H. Deming GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1449 (Physical Rev., 1935, [ii], 48, 577—581; cf. A., 1934, of ice from the surface of supercooled H20 into the 1148).—Mcasuremcnts of the scattering vals. of air-free space above is discussed. T. G. P. NaF, MgO, and SiC at 295° abs. lcad to results in Sub-boundaries in a crystal grown by the good agreement with the Waller-Hartree theory of Bridgman method. W. II. G eorge (Naturę, 1935, the extra negative term, and give ©yidence for the 136, 392).—A photomicrograph of a single crystal operation of the Pauli exclusion principle on the outer of Cu grown by the Bridgman method and etclied shell electrons. N. M. B. with HN03 suggests that the crystal has broken down Stress analysis by Ar-ray diffraction. C. S. into a large no. of smaller ones, the outlines of which B a b r e tt and M. G ensam er (Physical Rev., 1934, appear as curved lines. The markings are similar [ii], 45, 563).—Mąthematical. L. S. T. to the “ sub-boundary ” or “ vcined ” structures observed in many metals. L. S. T. Selective A'-ray diffraction from artificially stratified metal films deposited by evaporation. Polymorphism from viewpoint of Rontgen J. W. M. D uMond and J. P. Youtz (Physical Rev., investigation II. Polymorphism and atomie 1935, [ii], 48, 703).—Stratified films deposited on structure of elements. Polymorphism of in- glass consisting of 100 layers of Au alternating with organic compounds. H. Stintzing (Ergeb. tech. 100 layers of Cu, and giving selective X-rav diffraction Rontgen., 1934, 4, 113—129; Chem. Zentr., 1935, of Mo K radiation in the first order, have been j, 1814— 1815).—Elements with crystal lattices otlier produced. The total thickness is approx. 10,000 A. than cubic face- or body-centred, or hexagonal close- and the “ grating const.” 100 A. N. M. B. packed, and particularly those with lattices of Iow co-ordination no., are especially prone to poly Ultra-soft Rontgen radiation and lattice bind- morphism. Only elements for which log d/(n — 1) is ing forces. H. Broili, R. Glocker, and H. < that for the inert gases exhibit polymorphism (cl— K iessig (Ergeb. Tech. Rontgen., 1934, 4, 94—99; interat. lattice distance and »—1= principal ąuantum Chem. Zentr., 1935, i, 1500).—The Ko. line of graphite no. of the highest filled electron sliell). Polymorph differs from that of diamond in the distribution of ism in inorg. compounds is a constitutive property, intensity amongst its 4 components. The difference and occurs only when one element is highly poly- is attributed to the lattice forces, four homopolar morphic, especially with O or S. J. S. A. linkings being present in diamond, and three homo polar and one very loose quasi-metallic linking in Stereochemistry of solid substances. W. graphite. SiC resembles diamond, but the C line of Biltz (Ber., 1935, 68, [.4], 91—108).—A lecture. Be Carbide shows a typical heteropolar linking. The H. W. structure of the Be line indicates complete mobility Large artificial crystals of graphite. K. S. of the conductivity electrons (electron gas state). K rish n a n (Physical Rev., 1934, [ii], 45, 115).—The J. S. A. crystal flakes composing the large artificial crystals Precipitation-hardening and secondary struc prepared by Goetz et al. are not necessarily parallel ture. K. H. M oore (Physical Rev., 1934, [ii], 45, to one another (cf. A., 1933, 1128). L. S. T. 296).—A preliminary report on the use of polarised Production of ‘‘colloidal single crystals.” liglit in investigating a possible connexion between A. G oetz (Physical Rev., 1934, [ii], 45, 282—283).— pptn.-hardening and the secondary or mosaic structure A reply to criticism (see above). L. S. T. of crystals, with special reference to a Cu-Be (2-5% Be) alloy. L. S. T. Attempts to produce relief patterns by the direct electrograpbic effect. E. W ilcox and P. H. Bitter’s powder patterns. K. J. S ixtits C a rr (Physical Rev., 1934, [ii], 45, 286).—Partial (Physical Rev., 1934, [ii], 45, 565).—Three different success in producing relief patterns by taking advant- types are distinguished in the Bitter powder patterns age of the direct electrographic effect, i.e. the partial (A., 1932, 1077) of single crystals of Si-Fe (3-5% Si). inactivity in metallic surfaces towards corrosive The different directions of the patterns can be vapours produced by exposure to cathode rays, is explained by the present theory of the magnetisation described. L. S. T. process. L. S. T. JY-Ray determ ination of the chem ical com pos- Molecular field of litjuids. J. W eigle (Arch. ition of oxide-coated cathodes. W. P. Jesse Sci. phys. nat., 1935, [v], 17, Suppl., 105— 107).— (Physical Rev., 1934, [ii], 45, 563; cf. A., 1933,345).— Mathematical. An expression is derived on the The changes which occur on heating mixtures of assumption that a liquid has a pseudo-cryst. structure, BaC03+SrC03 coated on a Ni ribbon cathode have one mol. being imagined fixed and the others arranged been followed by means of X-ray photographs. At somewhat as in a crystal lattice blurred by thermal 800°, the mixed carbonates are converted into the agitation. S. J. G. individual oxides, and at 960° a slow transformation Crystallisation of melts. III. J. Meyer and into a solid solution, BaO-SrO, occurs. L. S. T. W. P f o f f (Z. anorg. Chem., 1935, 224, 305—314; Structure and physical properties oi thin cf. this vol., S il).—Supercooling of H 20 and C6H 6 films of metal on solid surfaces. E. N. ba C. is shown to depend on the presence of nuclei, the Andrade and J. G. Martindale (Phil. Trans., naturę of the surface of the containing yessel, and 1935, A, 235, 79—100).—Uniform and reproducible purity. Distilled H20, filtered through collodion films of Ag and Au (30—100 atoms thick) have been into a ąuartz vessel and covered with paraffin, was obtained by slow cathodic sputtering on a cooled kept liąuid at —33°. The growth of single crystals surface. With films of 50 atoms thickness the first 1450 BRITISH CHEMICAL ABSTRACTS.----A. stago of crystallisation, observed at 230° for Ag and 2-717 A. and c/ Lattice constants and m.p. of berzeliites. W. of humic acid is compared with those of lignin, B ubeck (Geol. Fóren. Stockholm, 1934, 56, 525—530; coal, and graphite. The genetic relation of these Chem. Zentr., 1935, i, 1677).— a varied with the Mn substances is discussed. E. S. H. content from 12-35 A. with 2-3% MnO to 12-46 A. with 19-4% Mn. Corresponding m.p. were 1090° and Structure of seed-globulins.—See this vol., 1433. 1180°, respectively. Vegard’s rule is not obcyed. Process of stretching of highly polymerised J. S. A. substances. H. Mark (Ergeb. tech. Róntgen., Atomie arrangement in vitreous silica and 1934, 4, 75—79; Chem. Zentr., 1935, i, 1852).— germanium dioxide. B. E. W arren (Physical On tho basis that long-chain polymerides exhibit Rev., 1934, [ii], 45, 292).-—The at. arrangement in mobility corresponding with all the clegrees of freedom the two glasses is the same : eaeh cation is tetra- of oscillation and rotation present, and that in a hedrally surrounded by 4 O and eaeh O is shared swollen gel the polymeride chains, or bundles thereof, between two tetrahedral groups. The orientation are slowly oriented on deformation, a quant. statistical about the direction of linking is random, and the theory of elastic extension is derived. In the most resulting network non-repeating, distinguishing the probable orientation, the chain length is < total yitreous from the eryst. state. The interat. distances length of the constituent units, corresponding with in the glass and crystal are equal. L. S. T. bent chains. Alteration of the most probable state Orientation of the oxalate group in oxalic acid involves work of extension or compression. and some of its salts. S. B. H e n d ric k s (Z. K rist., J . S. A. 1935, 91, 48—64).—Lattice consts. and optical pro- Electron diffraetion by highly polymerised perties are determined for a and [3 anhyd. H2C204, substances. H. Mark and J. J. T rillat (Ergeb. and for several Na, Rb, and K oxalates; complete tech. Rontgen, 1933, 4, 69—74; Chem. Zentr., structure determinations are made for the acids, 1935, i, 1852).—Thin films (10^ to 10-6 cm.) of K 2C204,H20, Rb2C204,H20, KHC204, and RbHC20 4. unstretched caoutchouc gave an “ amorphous ” The C204 group has coplanar atoms, and when perfect diagram which changed to that of an orthogonal cleavage occurs it is in planes not cutting C204 groups lattice, periods 8-1 and 12-4 A., on 100% extension, or O-H-O linkings. B. W. R. in agreement with X-ray results. Cellulose acetate and nitrate give diffraetion rings when fresh due to Structure of cyanuric triazide. E. W. H ughes smali crystallites of sizo 30—60 A. On ageing, (J. Chem. Physics, 1935, 3, 650).—A reply to Knaggs growth of crystallites occurs. For the nitrate, (this vol., 434). T. G. P. periods a 4-7, b 7-1, c 5-0 A. were obtained. J . S. A. Structure of benzil. K. Banerjee and K. L. New interference phenomenon on the passage Sinha (Sci. and Cult., 1935,1, 301).—Rotation photo- graphs show 3 mols. per unit celi, confirming a hexa- of rapid electrons through crystals. F. K irc h - gonal basie lattice; space-group D f. Reflexion n e r and H. L assen (Ann. Physik, 1935, [v], 24,113— intensity measurements indicate that the mol. has 123).—When rapid electrons fali on very thin Ag its two C6 rings in parallel planes. N. M. B. layers (approx. 10-® cm.) the interference spots at the edges of the zero principal max. resolve themselyes Crystal structure of ergotamine. H. B ra s s e u r into cross-like patterns, which are due to a surface (Buli. Soc. Chim. biol., 1935, 17, 1462— 1464).— lattice effect. The same effect is obtained with By means of the polarising microscope and the X-ray reflexion photographs, and it is deduced that the inter- diffraetion method ergotamine eryst. from aq. ference is due to very smali Ag crystals with exactly COMe2 is shown to be monoclinic, with negative parallel orientation, on the surface. A. J. M. birefringence. Lattice dimensions are a 20-30,6 18-65, c 10-11 A., p 90°. A. L. Crystal structure and electron configuration of transition and univalent metals. U. Deh- .Y-Ray examination of the transformation of lin g e r (Z. Physik, 1935, 96, 620—633).—The sodium cellulose by the action of carbon di- crystal structures of transition metals are arranged su lp h id e.—See this vol., 1486. symmetrically about the column Cr, Mo, W ; only X-Ray examination of the effect of removing the last three metals have cube-centred lattices, the non-cellulosic constituents f rom vegetable fibres. others having cubic or hexagonal lattices of closest W. T. Astbury, R. D. Preston, and A. G. Norman spherical packing. The structures of the transition (Naturę, 1935, 136, 391—392).—JC-Ray examination metals are therefore due to a gradual building up of of the effect of the progressive removal of the xylan (I) the df-shell, all having only ono s outer electron. The of cellulose fibres from Manila hemp rcveals no funda- exception of ferromagnetic Fc is due to preponderance mental change; only a more perfect state of crystallis- of spin valency over orbital valency to produce the ation is indicated, supporting the view that the cube-centred lattice at Iow temp. A. B. D. C. incorporation of (I) is a kind of mixed crystallisation. Electron-optical observation of transform- Removal of lignin and enerusting hemicelluloses ations of iron between 500° and 1000°. E. clarifies the X-ray photograph and leads to improved B ru c h e and W. K n e c h t (Z. tech. Phys., 1934, definition through a sharpening of the crystallite 15, 461—463; Chem. Zentr., 1935, i, 1336).—The orientation. L. S. T. electron emission a t 1050° was employed (cf. A., 1934, Structure of humic acid and its relation to 859), using Fe specimens annealed a t 1050°, heat- lignin and coal. J. Sedletzki and B. Brunovski treated a t temp. between 500° and 1000°, and then (Kolloid-Z., 1935, 73, 90—91).—The X-ray diagram rapidly reheated to 1050°. Structural changes were 1452 BRITISH CHEMICAL ABSTRACTS.----A. observed between 665° and 725°, and between 615° intensity of magnetisation of soft Fe and Ni under and 665°. J. S. A. const. magnetie field is examined. Ni exhibits Intensity of diffraction of electrons by ZnO. negative hysteresis under the influence of an alternat H. J. Y e arian (Physical Rev., 1935, [ii], 48, 631— ing circular field but not with an alternating longi 639).—Electron diffraction patterns of ZnO powder tudinal field. W. R. A. were obtained in the rangę 10—80 kv. The intensity Validity of Becker’s relation for initial perme- distribution shows marked deviations from that of ability of highly strained nickel wires. G. the corresponding X-ray pattern. Numerous con- S c h a rff (Z. Physik, 1935, 97, 73—82).—Temp. siderations fail to explain the anomaly. Agreement variation of initial permeability of Ni under load between experimental and calc. curves for the scatter confirms Becker’s theory of magnetisation (A., 1930, ing factor is obtained by assuming a distortion of 844). ‘ A. B. D. C. the electron cloud (M shell of the Zn and L shell of Negative Matteucci effect. E. E n g le r t (Z. the O) resulting in a different parameter for the Physik, 1935, 97, 83—93).—Results are given for distances Zn nucleus—O nucleus, and Zn electrons—O wires of Ni and of Fe-Ni (92: 8%). A. B. D. C. electrons. An expression for the structure factor Displacement of the Curie point by tension. is found. N. M. B. E. E n g le r t (Z. Physik, 1935, 97, 94—96).—No such Diffraction of electrons by metals and organie effect could be found (cf. Ray-Chaudhuri, A.. 1931, polymerides. J. J. Trillat and H. Motz (Ann. 1216). ' A. B. D. C. Physiąue, 1935, [xi], 4, 273—304).—The electron Interior magnetie field in iron. L. Alyarez diffraction patterns obtained with cellulose nitrate (Physical Rev„ 1935, [ii], 45, 225—226, 566).—D ata and acetate, polyoxymothylenes, synthetic resins, obtained from the passage of fi-rays from Ra-C rubber, etc. are closely similar and are attributable through Fe after focussing in a magnetie field disagree to tlifio. oriented surface fllms of fatty matcrials (fatty with the classical theory of magnetisation. acids, waxes, or paraffins). The same phenomenon L. S. T. with metallic surfaces is due to the presence of long Comparison of theoretical and measured Hall alipliatic mols. oriented perpendicular to the surface. coefficients. K. K. Smith and N. A. Hedenburg J. W. S. (Physical Rev., 1934, [ii], 45, 122). L. S. T. “ Extra " rings in electron diffraction patterns. G. I. Finch and A. G. Quarrell New substance with the electrical properties (Naturę, 1935,136, 720).—The spacings of oxtrarings of Rochelle salt. G. Busch and P. Scherrer due to grease are found to be independent of the (Naturwiss., 1935, 23, 737).—KH2P04 shows a vari- naturo of the metal, confirming the results of Mark ation of dielectric const., e, with temp. similar to et al. (this vol., 813). Measurements recorded for Na K tartrate (I), although e is < for (I). The Au show that the rings obtained by heating a metal principal dielectric const-., e^, inereases with decrease in a gas depend on the metal, the gas, and the naturę of temp. attaining a max. of 155 at —130°. Lilce of the heat-treatment. Amalgamation also produces (I) it has two Curie points ( — 130° and —195°). cxtra ring systems which have spacings dependent Qual. investigation of the piezo-electric activity on the metal. L. S. T. shows that this varies with temp. in an analogous manner to e. X -Ray analysis indicates no structural Electronic structures of molecules. XIII. change at the upper Curie point. A. J. M. Diborane and related molecules. R. S. M ul- lik e n (J. Chem. Physics, 1935, 3, 635—645; cf. Dielectric anomalies of Rochelle salt. H. this vol., 1306).—B2H 6 is shown to have 11 low-energy S tau b (Naturwiss.. 1935, 23, 728—733).—A review. electron states within an energy rangę of 1-5 volts, A. J . M. belonging to three electron configurations, in generał Further studies on the double refraction of agreement with the suggestions of Sidgwick et al. interfacial layers of the normal aliphatic acids. (A., 1931, 1356). The three H atoms in each BH3 A. K ing (Physical Rev., 1934, [ii], 45, 562).— are held by two [ 595—598).—Cooling curves, electrical resistance, Iow temp. The calc. magnetic moments correspond thermal expansion, and X-ray data all show the with one unbalanced electron in each of the substances. presence of two allotropic forms of Ca. The a-p (I) and (II) are entirely, and (III) is preponderantly, transition hes near 300°, and the (3-y near 450°. monomeric both in the solid state and in solution at A. B. D. C. all temp., whilst (IV) may bo slightly associated at Syntaxy and polytypy. H. U ngem ach (Z. K rist., Iow temp. F. L. U. 1935, 91, 1—22).—Special forms of polymorphism are discussed in relation to coąuimbite, carborundum, Magneto-chemical investigations of organie parisite, and other minerals. B. W. R. substances. V. Magnetic behaviour of por- phyrexide and porphyrindin. VI. Determin- Pressure effect of electrical resistance of ation of the degree of dissociation of hexa-aryl m etals. N. K. Saha (Indian J. Physics, 1935, 9, substituted ethanes. E. M uller and (Frl.) I. 623—635).—The pressure coeff. of electrical resistance M u lle r-R o d lo ff (Annalen, 1935, 521, 81—89, and the change in resistance at different pressures 89—94; cf. prcceding abstract).—V. Porphyrexide are calc. on the rigid ionic model of Nordheim, using shows the expected (2-condition) magnetic beliaviour. a screened Coulombian form of potential. Good Porphyrindin is a mixturo of dia- and para-magnetic agreement is found for metals having Iow compress- mols., the former being favoured by lower temp., ibility. Results are compared with those of Kroll probably by change of using Fermi’s statistical form of ionic potential. QMe2—NOv n .w to c^ c -n :]^. The sp. resistances of Au, Ag, Cu, Na, K, and Li T _C(NH)-NH>ujn‘ ]2 10 [Ć(NH)-NH- are calc. using the two forms of potential on tho rigid VI. Free radicals should have a paramagnetic ionic model. Results on Fcrmi’s potential are less susceptibility, - / m o i , , -f-2-1270 X10-6 at 20°. Differences consistent. For the highly compressible alkali metals are due to incomplete dissociation, the degree of which neither form is satisfactory. N. M. B. can be calc. The method is applicable only for highly dissociated compounds or for high concns. of those Diamagnetism of the tervalent bismuth ion. slightly dissociated, e.g., for C2Phfi at > 4%. C2Ph6 S. S. B h a tn a g a r and B. S. B a h l (Current Sci., 1935, is found to be 2-1% dissociated at 20° in 4% solution, 4,153—154).—Experimental vals. for the diamagnetic the lieat of dissociation being —11-6 + 1-7 g.-cal. susceptibihties of 10 salts of Bi'" are recorded. R. S. C. From known vals. for the susceptibihties of the anions Change of magnetic susceptibility of metals the val. 41-24 for Bi’" is obtained, compared with 43-8 during melting and allotropic transformation. calc. from theory. W. R. A. K . H onda and Y. Shimizu (Naturę, 1935, 136, Magneto-chemical investigations. XVII. 393).—New measurements, in a vac., of the change Magnetic behaviour of chalcogenides of bi- in magnetic susceptibility during the melting of valent chromium. H. Haraldsen and E. Kow Sn, Cu, Ag, and Au, and the allotropic change of a ls k i (Z. anorg. Chem., 1935, 224, 329—336; cf. Sn, are recorded. L. S. T. Henkel et al., this vol., 436).—The susceptibihties of Diamagnetism of copper. S. R. R ao (Proc. CrS, CrSe, and CrTe have been measured. CrS and Indian Acad. Sci., 1935, 2, A, 249—259; cf. this vol., CrSe are paramagnetic between 90° and 600°. CrTe 19).—Colloidal Cu was prepared in vac. by an electrical is ferromagnetic bekw 70°. The results confirm method in a dispersing medium of CGH6 or PrOH. the presence of at. linkings between the metallic ions The diamagnetic susceptibility, determined by a (A., 1934, 1294) in certain compounds of the trans sensitive Curie method, was 0-080 for mass Cu, and ition elements. T. G. P. inereased as the size of the particles was reduced, Diamagnetism of alkyl acetates. D. B. Wood- the crit. diameter below which large changes occurred b rid g e (Physical Rev., 1935, [ii], 48, 672—682).— being 0-8 p.. The conclusions of Honda (cf. this yol., Susceptibility measurements on the first five primary 287) are confirmed. The thickness of the surface alkyl acetates and on MeOH for the rangę 5—70° layer is approx. 300 A., and its diamagnetic suscept show very slight variation of susceptibility with ibility 0-200. The density of the surface layer is temp. and indicate increasing temp. dependence for 8-404 as against 8-943 for mass metal. N. M. B. higher members of the series. The mol. susceptibihty of CH2 is additive, in agreement with Pascal’s law. Magnetic anisotropy of crystals of Sn, and of The magnetic properties of NiCl, solutions are dis Sn with added Sb, Cd, or Ga. H. J. H oge cussed. “ N. M. B. (Physical Rev., 1935, [ii], 48, 615— 619).—The principal magnetic susceptibihties of single crystals Magneto-chemical investigations of organie of white (tetragonal) Sn, grown by the travelhng substances. IV. Magnetic behaviour of free furnace method, were measured. Relative to the radicals. E. Muller, I. Muller-Rodloff, and tetragonal axis the susceptibihties per unit yol. were : W. Bijnge (Annalen, 1935, 520, 235—255; cf. this kx 0-197 X l0-G and &n 0-176 X 10~fl. The ratio vol., 689, 1116).—Susceptibihties of the following k±fku is strongly influenced by the addition of traces paramagnetic substances have been determined at of certain elements; for pure Sn the val. is 1-120, temp. down to —183°; C18H210 2N2 (I) (cf. A., 0-6% Sb gives 1-200, 0-76% Cd gives 0-923, and 0-89% 1932, 324); (p-0Me-C6H4)2N:0 (I I);' Ga gives 0-897. Tho relation between the change N Ph2*N:CfiH2(N 02)3 (IH ); C(C6H4Ph)3 (IV). in this ratio and the no. of valency electrons of the (I) and (II) obey Curie’s law exactly, whilst (II) shows added element is compared with data for Bi (cf. a slight, and (IV) a somewhat larger, deviation at Goetz, A., 1934, 353). N. M. B. 5 D 1454 BBITISH CHEMICAL ABSTRACTS.----A. Paramagnetism of metallic gadolinium above I-T diagram for methane. A. Eucken and its Curie point. F. Trom be (Compt. rend., 1935, W. B e rg e r (Z. ges. Kalte-Ind., 1934, 41, 145— 152; 201, 652—653).—Measurements of y are recorded Chem. Zentr., 1935, i, 1346).—The complete enthalpy- from 16° to 360°. The ferromagnetic and paramag- temp. diagram of CH4 is given between 110° and 290° netie Curie points are a t 16° and 29-5°, respectively. abs. C„ and the molar heat of evaporation are H. J. E. given as functions of T. J. S. A. Absolute temperature of the normal freezing Vapour pressure of deuterium. F. G. B rick- point of water. The i/,0-limiting- value. W. wedde, R. B. Scott, H. C. Urey, and M. H. W ahl Jac y n a (Z. Physik, 1935, 97, 107— 112).—This is (Physical Rev., 1934, [ii], 45, 565: cf. A., 1934. 1164). 273-22° abs. A. B. D. C. L. S. T. Anomaly in specific heat of lithium. G. W. Pressure-volume-temperature relations of the Panków and P. Scherrer (Helv. pliys. Acta, 1934, liquid, and the phase diagram of heavy water. 7, 644—647 ; Chem. Zentr., 1935, i, 1832).—Between P. W. B ridgm an (J. Chem. Physics, 1935, 3, 597— room temp. and —190° the energy supplied to Li 605).—Pressure-vol.-temp. relations of liquid D20 goes entirely to at. vibration, and not to a ąuantum and H 20 have been measured between —20° and 95° jump. The characteristic temp., 0, is given by three and up to 12,000 kg. per sq. cm., and the transition methods as 350—370°. J. S. A. parameters of the liquid and solid modifications of D20 in the rango —60° to 20° and up to 9000 kg. per Heat capacity, entropy, and free energy of sq. cm. An unstable modification IV of solid D20 sulphur vapour S2 between 100° and 5000° abs. occurs in the field of stability of V, which confirms the I. Godnev and A. S v e rd lin (Z. Physik, 1935, 97, existence of the corresponding modification in solid 124—130).—H eat capacity, entropy, and free energy H 20 (A., 1913, ii, 39). D20 and H 20 behave similarly, are deduced from spectroscopic data. A. B. D. C. and differ in the direction suggested by the greater Specific heats of liquid deuterium oxide. zero-point energy of H20 : the mol. vol. of D20 is > R. S. B row n, W. H. B arn es, and O. M aass (Canad. of H20 at the same temp. and pressure; the transition J. Res., 1935, 13, B, 167— 169).—The mean sp. heats lines of D,0 always run at higher temp. In detail over the ranges 4—26°, 26—45°, and 26—65° are the differences are irregular, and considerations other 1-018, 1-003, and 1-008, respectively. E. S. H. than zero-point energy are necessary for complete cxplanation. T. G. P. Anomaly of specific heat of Seignette salt. A. A. Rusteriiolz (Helv. phys. Acta, 1934, 7, 643— Baur and Brunner's measurements of vapour 644; Chem. Zentr., 1935, i, 1832).—The dielectric pressure of high-boiling metals. J. F isc h e r behaviour is abnormal below 25°, e being very high. (Helv. Chim. Acta, 1935, 18, 1028— 1029; cf. A., The yariation of mol. heat with temp. in that region 1934, 1301).—Baur and Brunner’s vals. for the b.p. resembles that of ferromagnetic substances, corre- of Pb and Ag disagree with accepted vals. Defects sponding with a work of electrification of 2-1 g.-cal. in the method are pointed out. H. J. E. per mol. J. S. A. Measurements of vapour pressure of high- Latent heat of vaporisation of water in the boiling metals. E. Baur and R. Brunner (Helv. pressurerangę 100—200 kg. per sq. cm. W. K och Chim. Acta, 1935,18, 1030; cf. preceding abstract).— (Forscli. Ing., 1934, A, 5, 257—259; Chem. Zentr., A reply. H. J. E. 1935, i, 1672).—The latent heat for H 20 between 100 Vapour pressure of barium. E. Rudberg and 200 atm. is given by r=59-5(374-ll—i)°-4 + and J. L em pert (J. Chem. Physics, 1935, 3, 627— 0-025(374-11 - t ) . “ J. S. A. 631; cf. this vol., 22).—The v.p. of Ba, determined Heat of vaporisation of water and specific between 525° and 750° by mol. effusion, gives log volume of saturated vapour up to 200 kg. per ^(mm.)=6-99—8980/T, and L=40-9 kg.-cal. per mol. sq. cm. (365°). M. Jakob and W. Fritz (Physikal. T. G. P. Z., 1935, 36, 651—659).—The heat of vaporisation Batio of the thermal coefficient of expansion of H20 has been determined calorimetrically up to to the specific heat at constant pressure for 202 kg. per sq. cm. pressure (365°). An empirical tungsten. W. J. Jac k so n (Physical Rev., 1934, formuła for the heat of vaporisation and sp. vol. [ii], 45, 285).—The ratio is const. for only a limited embodying these results and those of previous temp. rangę; above 200°, it inereases with rise of workers is deduced. A. J. M. temp. up to 500°, where the validity of the empirical relationships ceases. " L. S. T. Latent heat of condensation of metals. D. S. K o th a ri and N. K. S aha (Sci. and Cult., 1935, 1, Principal expansion coefficients of single 300—301).—The electron gas theory is extended to crystals of mercury. 4 D. M. H ill (Physical Rev., calculate the latent heat of fusion of metals. Results 1935, [ii], 48, 620—624).—Expansion coeffs. measured for Li, Na, K, Rb, Cs, Ag, Cu, Au, and Cd agree with at 5° intervals from —115° to —160°, and mean yals. esperimental data only in order of magnitude; those found from —160° to —190°, are tabulated and plotted. for Hg and Zn diverge widely. N. M. B. A recrystallisation process sets in between —115° and —110°. Relative to the trigonal axis, an is larger Expression of the second law of thermo- and inereases more rapidly with rise of temp. than a±. dynamics in terms of Clifford’s numbers. A. The vol. coeff. is given from the m.p. to —160°, M ercier (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., where the coeff. decreases rapidly with fali of temp. 112—113).—Mathematical. S. J. G. N. M. B. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1455 Thermal conductivity of carbonic acid. R. apparently causes a sheath of materiał to shear more Plank and 0. Walger (Forsch. Ing., 1934, A, easily than does the bulk of the materiał. E. S. H. 5, 289; Chem. Zentr., 1935, i, 1670).—Sellschop’s Mixed crystal formation with tin oxide. E. yal. (this vol., 574) is confirmed. J. S. A. H ay ek (Monatsh., 1935, 66, 197—200).—Pptn. of Thermal conductivity of yarious licpiids. R. SnO in presence of salts of Pb, ]\In, Fe, Zn, Cd, and P la n k (Z. ges. K alte-Ind., 1934, 41, 214; Chem. Ca gives mixed crystals, but Co, Ni, Mg, Sr, and Ba Zentr., 1935, i, 1506).—The yal. of Kardes (A., 1934, do not enter the SnO lattice. The mixed crystals 1300) for CÓ2 is too high, due to convection effects. have characteristie colours. Their homogeneity has Data for other liąuids are not so affected. J. S. A. been confirmed by X-ray photographs. SnO shows Thermal expansion of calcite. H. Saini (Arch. passivity. T. G. P. Sci. phys. nat., 1935, [v], 17, Suppl., 108—109).— Naturę of a solid solution. K. Honda (Metal Determinations of coeff. of expansion of the same Progr., 1934, 26, No. 3, 42—43).—Experimental vals. crystal of calcite by an optical interference method of d for a 4-5% Al-Ag alloy agree within 0-3% with and by an X-ray method agreed between 25° and the val. calc. from the displacement of the Ag lattice 100°. S. J. G. by Al in solid solution. Ch. Abs. (e). Density and compressibility of silicane and Ecpiilibrium diagram of the system mag- silicoethane. K. L. Ramaswamy and G. G. R ao nesium-lithium. P. Saldau and F. Schamray (Proc. Indian Acad. Sci., 1935, 2, A, 213—220).— (Z. anorg. Chem., 1935, 224, 3S8—398).—Thermal Using an apparatus for the simultaneous measure- analysis of Mg-Li mixtures, supported by micro- ments of density and approx. compressibilities, scopical obseryations, indicates the formation of vals. were obtained for SiH4 at room temp. and three solid solutions, the limits of which have been —79-8°, and for Si2HB at room tem p. The calc. established. The cotnpound LiMg2 (not Li2Mg5; mean mol. wts. are 32-13 and 62-74, respectively. cf. this vol., 591) melts without change. F. L. U. Corresponding at. wts. of Si are compared with those X-Ray study of aluminium-zinc alloys at of other authors. N. M. B. elevated temperatures. E. A. Owen and L. Variation of the yiscosity of gases with tem- Pickup (Phil. Mag., 1935, [vii], 20, 761—777; cf. A., perature over a large temperature rangę. A. B. 1934, 356).—Arrangements are described for ohtaining van Cleave and O. M aass (Canad. J. Res., 1935, rotation powder photographs of metals and alloys 13, B, 140— 148).—Data are rccorded for NH3, at high temp. in vac., with special reference to the C3H g, C2H4, and Me20 between 23° and —80°, with (3-phase in Al-Zn alloys which decomposes spon- a relative accuracy of 0-1%. The yalidity of different taneously below 270°. Eąuilibrium diagrams and viscosity-temp. relations has been tested with the accurate measurements of parameter vals., temp., present data; an empirical eąuation, which adeąuately and phase-boundaries aboye the eutectoid temp. are represents the results, is suggested, but it fails at given, and results compared with previous data. high temp. for all gases and at Iow temp. for H2, The y-phase parameter in the P+y region decreases air, and C2H4. The viscosity-temp. curyes for C02, with rising tem p .; the transformation temp. (272°), S02, NH3, Me20, and C3H6 show an inflexion point, and the (P+y)-y boundary are deriyed from the which is related to the polarity of the mol. and the thermal “ eśpansion ” curyes of the y-phase in certain crit. temp. E. S. H. alloys. N. M. B. Viscosity of air and the electronic charge. G. AT-Ray inyestigation of the system iron- K e lls tró m (Naturę, 1935, 136, 682—683).—For chromium-nitrogen. S. Eriksson (Jernkont. dry air -o20., determined by the rotating-cylinder Ann., 1934, 118, 530—543; Chem. Zentr., 1935, method, is (1820-0±3-0) X 10~7, corresponding with i, 2069—2070).—The existence of an intermediate t]23„=(1834-8± 3-0) x 10~7, a val. different from that a'-phase in the Fe-Cr system (approx. formuła used by Millikan in determining e. The new val. FeCr) is confirmed (cf. Wever, B., 1932, 469). In gives (4-818±0-012) X10'10 e.s.u. for e, the same the system Cr-N the hexagonal (3-phase has a “ super - yal. as calc. from X-ray measurements. L. S. T. structure,” the celi vol. of which is three times as Influence of a magnetic field on the coefficient large as that of the hexagonal close-packed lattice. of yiscosity of liąuids. H. S. Venkataramlah The upper and Iower limits of the region of homogeneity (Current Sci., 1935, 4, 156).—The results of experi- of the p-phase are 11-9% N (Cr2N) and 9-3% Ń, ments (in 1932) on the influence of a magnetic field respectiveły. Lattice dimensions are recorded. on the yiscosity of CeH e are published (cf. R aha et al., Results are given for the chief phases in the Fe-Cr-N this vol., 1198). W. R. A. diagram at 700° and 400°. H. J . E. Influence of the proximity of a solid wali on Metals and alloys. XV. AT-Ray analysis of the consistency of yiscous and plastic materials. lithium-zinc alloys. E. Zintl and A. Schneider. IV. R. K. S c h o fie ld and G. W. S. B la ir (J. XVI. Structure of platinum-thallium alloys. Physical Chem., 1935, 39, 973—981; cf. B., 1930, E. Zintl and A. H arder. XVII. X-Ray analysis 844; 1931, 825).—The rate of flow of an aq. pastę of lithiumamalgams. E. Zintl and A. Schneider of BaS04 through tubes of the same radius undcr the (Z. Elektrochem., 1935, 41, 764—767, 767—771, same pressure gradient is independent of the length 771—774; cf. this vol., 692).—XV. Examination of of the tube, but with tubes of different radii the velo- the phases existing at room temp. confirms the city gradient does not appear to depend only on the results obtained by thermal analysis and electrical shearing stress. The proximity of the tube wali conductiyity measurements (cf. A., 1934, 21). 1456 BRITISH CHEMICAL ABSTRACTS.— A. XVI. Pt dissolyes up to 1-5% of Tl -with widening either the hydride or the absorption hypothesis, of the space lattice. The solid solubility of Pt in Tl but resistance min. obseryed fayour the PdH hypo is very smali. The system includes the compound thesis. J. W. S. PtTl, the structure of which has been determined. Theory of superlattice structures in alloys. XVII. The results confirm the existence of the W. Httme-Rothery and H. M. Powell (Z. Krist., compounds LiHg3, LiHg2, LiHg, Li2Hg, and Li3Hg, 1935, 91, 23— 47).—Superlattices of yarious types the structurcs of which are discussed. E. S. H. are defined, which are intermediate between tlicrandom Irreversibility of iron-nickel alloys and their solid solution of A and B and the normal inter- eąnilibrium diagram. E. Sciieil (Arch. Eisen- metallic compound AmB„. The concept of “ zones ” hiittenw., 1935— 1936, 9,163—166).—The irreversible characterised by different distances between the atoms rangę of Ni steels has an appreciable width for the A and their nearest B neighbours is used to discuss temp. interyal in which place interchange of the atoms the stability and formation of different superlattices, takes place, and in this interyal the a-y transformation the lattices FeAl and CuAu being examined in detail. occurs throughout the irreversible rangę, provided B. W. R. that the time of annealing is sufficiently prolonged. Diffusion coefficients in alcohol-water mix- Transformation in the irreversiblc rangę reąuires tures. H. Mouquin and W. II. Cathcart (J. not only a change in the lattice structure, but also Amer. Chem. Soc., 1935, 5 7 ,1791— 1794).—Apparatus a diffusion of the Ni atoms to produce a y-phase which and technique are described, and results given for is richer in Ni than the still unconverted a; the crystal-yiolet. A break in the composition curve lirst occurs with great rapidity, but the second only occurs at 65% EtOH. E. S. H. very slowly. Measurements of the Acl, Ar 1, and Apparent volum.es and apparent compressi- Ar2 points of a 4-8% Ni steel after annealing ab bilities of solutes in solution. II. Concentrated 665—725° and of the resulting degreb of trans solutions of lithium chloride and bromide. formation shów that tho cc+y rangę in Fe alloys A. F. Scott and G. L. Bridger (J. Physical Chem., containing up to 10% Ni is probably bounded by 1935,3 9 ,1031— 1039; cf. this vol., 31).—Irregularities two curyed lines convex to the origin, one joining are discussed in the light of the data recorded and the points 900°, 0% N i; 725°, 4-8% N i; and 630°, previous moasurements. E. S. H. 10% Ni, and the other the points 900°, 0% N i; 600°, 4-8% Ni, and 520°, 10% Ni. A. R. P. Volume changes in mixtures of benzene and chloroform. G. Botecchia (Atti R. Ist. Veneto Alloys of palladium with manganese. A. T. Sci., Lettre Arti, 1934, 93, 567—572; Chem. Zentr., Grigoriey (Ann. Inst. Anal. pliys.-chim. U.S.S.R., 1935, i, 168S; cf. A., 1933, 1110).—The vol. inerease 1935, 7, 75—88; cf. A., 1933, 18).—Pd-M n alloys shows a max. a t 20 mol.-% CHC13. A pressure of (5—95% Pd), cast or tempered at 900° for 16 lir., 76 atm. is required to restore the vol. to tho sum of and at 300° for 7 days, form on cooling a continuous the vols. of the components. H. N. R. series of solid solutions. Alloys with 39-3—45% of Variation of yapour pressure of the isotopic Pd have a min. m.p. With fali in temp. the solid mixture of hydrogen with time at 20-38° abs. solution is converted into the compound PdMn. The thermal changes shown by alloys rich in Mn K. S te iste r (Physikal. Z., 1935, 36, 659—660).— The v.p. a t 20-38° abs. of samples rich in D2 decreases at 1040— 1089° and 730—797° are conditioned, respectively, by the Mn transformations y-> (3 with time. The results are discussed. A. J. M. and p a. ' Ch. Abs. (c) Critical data of light and heavy water and their density-temperature diagram. E. H. Riesen- Alloys of praseodymium and copper. G. f e ld and T. L. Chang (Z. physikal. Chem., 1935, C akneri (Met. i tal., 1934, 26, 869—871; Chem. B, 30, 61—68).—The crit. temp., tc, of mixtures Zentr., 1935, i, 1816).—The following compounds of H 20 and D ,0 can be calc. with considerable were found: PrCu6, m.p. 962°; PrCu4, transition exactness by the mixture rule, being given by tc— point S24°; PrCiL,, m.p. 841°; PrCu, transition point 563°. Eutectics occur a t 891°, 15% of P r; 374-2—2-7n, wliere n is the mol. fraction of D20. 792°, 45% P r; 472°, 82-5% Pr. The alloys are hard The crit. data for D20 are tc 371-5°, p c 218-6 atm., and brittle. J . S. A. dc 0-363 g. per c.c. H 20 and D20 have the same d at 49-5° (saturated yapour) and also a t 370-0° (liquid). X-Ray and electrical investigation of Pd-Ag-H R. C. alloys. G. R o s e n h a ll (Ann. Physik, 1935, [v], Mixed m.p. in eutropic series. H. D. K. Drew 24, 297—325).—Errors in deducing the [H] of Pd-H and J . K. L an d q u ist (J.C.S., 1935, 1480—1482).— alloys from the current passed during electrolysis of The series CPh4, SiPh4, GcPli.,, SnPh4, and PbPh4 show aq. KOH, using the Pd as cathode, are discussed. a continuous fali in m.p., viz., 285°, 237-5°, 233-4°, Addition of > 27% of Ag to the Pd leads to the 229-2°, and 227-8°, respectively. A m ixture con production of single-phase alloys at all [H]. The taining equimol. proportions of each has m.p. 220— resistance of such alloys decreases for about four 221°. The m.-p. depression of binary mixtures days after prep., this representing the time reąuired suggests a change in some function, possibly in the to reach ecjuilibrium. The Pd-Ag-H alloys have yalency angle, on passing from Ge to Sn. The m.-p. in all cases face-centred cubic lattices of which the depressions for binary mixtures of NPh3, PPh3, const. yaries with composition. The solubihty of AsPh3, SbPh3, and BiPhs indicate that N and Bi H2 in Pd-Ag alloys (30—100% Pd) shows a mas. diyerge from the other elements, and that only P only at pure Pd. X-Rav data can be explained on and As are compatible with one another. Austin!s GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1457 formuła for m.p. in org. homologous series (A., 1930, actual val. of the solubility varies with the smali 675) is inapplicablo to the eutropic series. J. W. S. amounts of H20 present even in carefully distilled Mutual solubility of heavy water and organie C0Me2. O. J. W. liquids in systems with a negative saturation Densities of adsorbed gases. I. Carbon di- curve. J. Timmermans and G. Poppe (Compt. oxide on charcoal. T. de Vries (J. Amer. Chem. rencl., 1935, 201, 608—610; cf. this vol., 1314).— Soc., 1935, 57, 1771— 1774).—He has been used as the Replaccmcnfc of H20 by D20 extends the region of displaced fluid to determine, before and after C02 non-miscibility of a H20-a-picoline mixture. With adsorption, the unoccupied vol. in a tube containing 33-2% of a-picoline the lower and upper crit. solution C at 30°. He does not penetrate the C02 layer when temp. are 92° and 112-5°, respectively. W ith in- d is > 0-09 mg. per ml. Polanyi’s theory gives d for creasing pressure these limits approacli one another, the adsorbed layer equal to the observed vals. if it the liąuids being miscible at all temp. for pressnres > is assumed that He penetrates the outer portion of 90 kg. per sq. cm. For D20-Buv0H mixtures a the adsorbed layer. E. S. H. smaller KC1 addition is needed to produce two phases Active charcoal. IX. Curves of sorption iso- than with H20. H. J. E. therms and their properties. X. Non-reduc- Ternary system jsoamyl alcohol-propyl ible sorption eqrdlibrium, hysteresis, drift, and alcohol-water. J. Coull and H. B. Hope (J. residual sorption. XI. Sorption and capillary Physical Cliem., 1935, 39, 967—971).—Miscibility, condensation ; their mechanism. O. K am ukę. d, and n have been determined at 25°. E. S. H. XII. Preparation of active charcoal by the zinc chloride process. Y. Imai. XIII. Velocity of Solubility of barium iodate in salt solutions. sorption of vapour in a dilute current of inert G. M acd o u g all and C. W. D avies (J.C.S., 1935, gas. S. Tamaru and Y. Imai (J. Chem. Soc.' Japan, 1416—1419).—Conductivity measurements on aq. 1935, 56, 114— 123, 124—132, 133—141, 142— 152, Ba(I03)2, and solubility measurements at 25° for 153—177).—IX. A summary of previous work. Ba(I03)2 in aq. KC1, K N 03, KC104, CaCl2, and KC103 X. Hysteresis and drift are different phenomena. solutions are recorded. The results, when corr. for The former can be observed at relatively high vals. of ionic association, are in aecord with the Debye- Y.p. Hiickel limiting formuła. The dissociation const. of XI. Org. substances, notably AcOH, are the more BaI03’ is 0-083, and that of BaC103‘, deduced from readily adsorbed by active C. The radius of the solubihty measurements of Ba(I03)2 in KC103, is about capillary is calc. 0-2. j . W. S. XII. Active C of good quality is obtained by Nitrates of neodymium and praseodymium dipping a specimen of Quercus glandulifera, in 30% and their solubilities in water. J. N. Friend aq. ZnCl2, treating with HC1 at 90° (16 lir.), and ignit- (J.C.S., 1935, 1430— 1432; cf. this vol., 928).— ing a t 700°. Nd(N03)3,6H20 exists in a- and (3-forms, the latter XIII. Relations between the amount of gas having m.p. 67-5°. The transition point is about absorbed, time of contact, and dilution are examined. 22°. Pr(N03)3,6H20, like the La and Nd salts, Ch . Abs. (p) is probably isodimorphous with Bi(N03)3,5H20, Adsorption of methane by coal. J. B. S u tto n and has m.p. 56°. The solubilities of Nd(N03)3,6H20 and E. C. H. Davies (J. Amer. Chem. Soc., 1935, 57, between 0° and the m.p. and of Pr(N03)3,6H20 1785— 1787).—The Freundlich equation is applicable between 15-8° and the m.p. aro recorded. The to the results obtained a t 10-94°, 17-77°, and 24-60°. solubilities of the Nd, Pr, and La salts are all too The calc. heats of adsorption are 4700—5200 g.-cal. close to permit good separation in neutral solution. per mol. for xjm vals. between 1-5 and 3-5. J. W. S. E. S. H. “ Salting-in ” of hydrogen peroxide by Sorption of dimethyl ether on alumina. J. electrolytes. M. H. Gorin (J. Amer. Chem. Soc., E d w ard s and O. M aass (Canad. J. Res., 1935, 13, 1935, 57, 1975—1978).—The solubility of H 20 2, as B, 133—139).—The investigations cover the ranges determined by its distribution between H20 ancl amyl 0-5—52 atm. and 25— 135°. No discontinuity in alcohol, is inereased in the aq. phase by addition sorption accompanies the transition of sorbate from of NaCl, N H 4C1, KC1, N aN 03, N H 4NÓ3, K N 03, vapour to gas at the crit. temp. With inereasing and NH4C104, but decreased by H 2S04. The apparent pressure the initially-formed unimol. layer is followed displacement of H20 of hydration by H,02 mols. by a multimol. layer; it is, however, unlikely that can be explained if the H202 mol. has a higher condensation to liquid occurs in the pores, except at dipole moment tlian that of H20 in the neighbourhood high pressures. The inerease in crit. temp. of such of the ion. A structure for H202, which would yield a liquid must be very great to account for the con- the necessary high dipole moment, is discussed. tinuous form of the isobars up to 135°. E. S. H. E. S. H. Heat of adsorption of gases on zinc oxide and Systems naphthalene-acetone and diphenyl- ZnO-Cr2Os at Iow pressures and room temper- acetone and the solubility of a third substance atures. W. E. Garner and F. J. Veal (J.C.S., in them . P. Spinoglio and G. R a y e n n a (Gaz- 1935, 1487— 1495; cf. A., 1931, 904).—The heats of zetta, 1935, 65, 668—678).—For a given sample of adsorption on oxidised or reduced surfaces of ZnO COMe2, the solubility of Cdl2 in C10H8-COMe2 and Zn0-Cr203 catalysts decrease as the surfaces and in Ph2-COMe2 mixtures of various concns. is become covered with gas, particularly with oxidised const. when referred to a fixed wt. of COMe2. The surfaces. The adsorption of CO and H2 on oxidised 1458 BRITISH CHEMICAL ABSTRACTS.----A. Zn0-Cr203 occurs irreyersibly, and with liberation Properties of thin layer of clay-water solution of 45 kg.-cal. per mol. The surface undergoes interposed between solid surfaces. H. Takó simultaneous reduction, the gases being adsorbed on (Buli. Inst. Phys. Chem. Res. Japan, 1935, 14, 909— the reduced areas with heats of 10—15 kg.-cal. per 919).—The coeff. of frietion between a rubber plate mol. 02 is also adsorbed on the reduced areas, (wetted with an aq. suspension of clay) and a piane a 2 : 1 C0-02 mixture being adsorbed completely surface decreases with concn. (c) of clay. With by oxidised Zn0-Cr203. CO, H2, C2H4, and C2H0 moving surfaces separated by a clay-H20 film the are adsorbed reversibly on tho reduced surface with resisting force is a min. for a velocity (V0) approx. lioats of 10—25 kg.-cal. per mol., but only when no cc c^/v) (•/) apparent yiscosity). r>vQ is approx.insensitive penetration of capillaries occurs can desorption be to the addition of CuS04 and A1C13, althougli r, in completed in a short time at room temp. The creases considerably. R. S. B. behaviour on desorption is discussed with reference Physical chemistry of flotation. VI. Ad to the energies of activation of the adsorption pro- sorption of amines by sulphide minerals. E. E. cess. I t is suggested th at the adsorption on the Wark and I. W. Wark (J. Physical Chem., 1935, reduced surface is chemisorption. J. W. S. 39, 1021— 1030; cf. B., 1935, 671).—The contact Kinetics of absorption of oxygen by pyro- angle between the minerał and aq. solutions of several catechol. M. A. J o s ly n and G. E. K. B ra n c h aminę hydrochlorides is the same (about 60°) for all (J. Amor. Chem. Soc., 1935, 57, 1779—1785).— the amines inyestigated. The Cu minerals respond The dependence of reaction rato on p H, pyrocatechol most readily and the ąuaternary NH., salts are most concn., partia! pressure of 02, temp., and surface readily adsorbed. Using hexylamine, sphalerite can has been studied in buffered and unbuffered solutions. be fioated away from galena. In a homologous The heats of activation in NaOH solutions and in series of amines the efficiency at a given concn. pliosphate bufFers liave been determined a t 20—35°. increases with inereasing no. of C atoms; the activity E. S. H. increases in the order primary, sec., tert. Contact Special cases of propagation of capillary action. tests are closely parallel to flotation tests in the same C. E. G uye (Helv. phys. Acta, 1934, 7, S50—855; solutions. The contact induced at certain minerał Chem. Zentr., 1935, i, 1987; cf. this vol., 581).— surfaces by some amines is prevented by addition Mathematical. J- S. A. of alkali or acid. E. S. H. Dimensions of soap molecules as supposedly Electro-osmosis with some ceramic dia- deduced from surface tension measurements. phragm s. A. Vasićek (Sborn. Skol. Tech. Brne, H. M. Cassel (J. Amer. Chem. Soc., 1935,57, 2009).— 1934, 8 , No. 32; Chem. Zentr., 1935, i, 1350).— A criticism (cf. du Noiiy, A., 1925, ii, 109). Electro-ósinotic properties of ceramic diaphragms E. S. H. in aq. KC1 liave been examined. Surface con Properties of detergent solutions. I. In duction and electro-osmosis take place in solutions fluence of hydrogen-ion concentration on the > 0-02—0-05i\r. Eleetrokinetic potential and surface surface tension of soap solutions. J. Pow ney conduction are dependent on the structure of the (Trans. Faraday Soc., 1935, 31, 1510—1521).— diaphragm. J. S. A. Surface tensions of Na and K laurate, myristate, Application of an empirical correction to the and oleate liave been measured at 20° in presence of Donnan effect in the determination of mol. wts. atm. C02 and of different concns. of added alkali. of proteins by osmotic pressure measurements. Tho effect of the latter is most marked with the laurate, D. R. B riggs (J. Physical Chem., 1935, 39, 983— and in all cases depends on soap concn. The results 995).—The relation between the obseryed osmotic arc discussed. F. L. U. pressure, Pa, and th at calc. on the basis of unequal Inter-pbase energies in systems of pure distribution of diffusible ions,Pc, is given by E (0-01—1-5 mol.). (II) oceurs entirely as single mols. Hydrous thoria hydrosols considered as poly- in dii. solution, but probably forms double mols. nuclear basie thorium complexes. A. W. at higher concn. Structures are proposed for single Thomas and C. B. Kremer (J. Amor. Chem. Soc., and double mols. (I) occurs entirely as single mols. 1935, 57, 1821— 1824).—The of Th(OH)4 sols is in dioxan solution, probably owing to association with raised by adding K salts. The effect is ascribed to solvent mols. On addition of an equiv. amount of displacement of co-ordinated OH groups by the anion H ,0 only incomplete formation of (II) occurs. of the added salt, the anion then becoming co- J. W. S. ordinately bound. The dialysed sols rapidly become Cryoscopic study of the total hydration of the more acid when kept at room temp., the rate inereasing ions of sodium bromide. (M lle.) O. H un at higher temp. The heated sols are less sensitive (Compt. rend., 1935, 201, 547—549; cf. A., 1933, to 2>h change on addition of salts. A polyolated or 46Ó).—The total hydration in N and in 0-5A7 solution oxolated structure of the micclle is assumed. corresponds with 12-9 and 15-3 mols. H20, respectively. E. S. H. T. G. P. Basic zirconium chloride hydrosols. A. W. Cryoscopic determination of the total hydr Thomas and H. S. Owens (J. Amer. Chem. Soc., ation of ions of sodium nitrate. F. Bourion and 1935, 57,1825— 1828).—T h e o f tho sols is raised on (M lle.) O. H un (Compt. rend., 1935, 201, 660—662; adding K salts by a process similar to tliat observed cf. A., 1934, 728).—H ydration corresponds with with Th(0H)4 sols (cf. preceding abstract). NaN03,9-3H20 and NaN03,ll-lH 20 in 1-0M and E.S.H. 0-5M solutions, respectively. H. J. E. Absorption spectra of metallic and organie colloidal solutions and the absorption of metal Effect of light on Brownian motion. R. film s. A. T. W illiam s (Compt. rond., 1935, 201, F u r th and O. Zimmermann (Ann. Physik, 1935, 665—667; cf. A., 1932, 691).—D ata are recorded for [v], 24, 183—208).—Unpolarised light of intensity colloidal solutions of Ag, Au, and Pt. The ultra- 0-00062—2-6 w att per sq. cm. has no effect on particie violet absorption band (2270—2820 A.) is independent size or Brownian motion, irrespective of the materiał, of tho method of preparing the colloid. The ab particie size, or X of light. The Brownian motion sorption spectra of colloidal solutions of org. mols. is the same in the direction of the light and per- resemble thoso of true solutions. H. J. E. pendicular to it. When linearly polarised light is used, the mean sąuare of the displacement in the Viscosity of titanium dioxide sol in presence direction of the magnetic vector of the light vibration of electrolytes. S. M. M eh ta and (Miss) O. is independent of the particie size and materiał, but Joseph (J. Indian Chem. Soc., 1935, 12, 552—559).— is 7—11% > in the direction of the electric yector The change of yiscosity of Ti02 sol. dialysed and or in the direction of propagation of the light. The diluted to different extents, on the addition of salts, effect disappears if the short-wave part of tho light has been studied by the method deseribed preyiously is filtered out. The results disagree with those of (A., 1932, 693). The yiscosity of the sol inereases Pospiśil (A., 1927, 823; 1930, 412), and a systematic with time, and the viscosity-time curves are periodic error in his work is suggested. A n explanation of or discontinuous in the slow region (cf. A., 1934, 1171). the effect is attempted on the basis of photo-electric The sp. conductivity and [H’] of the sol diminishes theory. A. J. M. on dilution and on dialysis, and the inereased rapidity of coagulation is attributable to decrease of peptising State of aggregation of colloids and calculation ions. Tho autocatalytic naturę of the coagulation of mol. wt. F. F. Nord and F. E. M. Lange process disappears as the sol is dialysed. J. W. S. (Naturwiss., 1935, 23, 722).—When solutions of lyophiJic and lyophobic colloids of concn. 10-6—5% Viscosimetric investigation of benzene solu are submitted to temp. < 0°, the particles are either tions of ethyl- and benzyl-cellulose. S. L ee and condensed or further dispersed according to the concn. I. Sakurada (J. Soc. Chem. Ind. Japan, 1935, Tho size of the particie depends on the previous 38, 436—438b).—Vals. are recorded for -/j3Pi/c (when physical treatment of the solution, and hence the mol. c = 0), the form and charge factor, and the sp. vol. wt. of a colloid has little cheraical significance. for solutions of ethyl- (I) and benzyl-cellulose (II) in A. J. M. C6H g a t 10—60°. ii/c for (I) is 0-885 at 20° and 0-74 Colloidal systems of three components. I. a t 50°, and for (II) is 1-2 at 10° and 0-77 at 60°. Colloidal behaviour of the critical mixture of A. G. three fluids. N. Sata and O. Kimura (Buli. Influence of gases on silver sols. T. I. T a y lo r Chem. Soc. Japan, 1935, 10, 409—420).—The crit. and W. H. Cone (J. Physical Chem., 1935, 39, 997— blue opalescence with 3-component mixtures of H20 1003).—The effect of 0 2, N2, H 2, CH4, and C2H4 on and yarious org. fluids has been studied at 30°. The the pptn. vals. (for NaN03), eloctrophoretic yelocities, system C6H6-H 20-Et0H or MeOH gives emulsoids and conductances of Ag sols has been investigated. with the greatest rangę of stabihty. When C5H12 The gases have a stabilising effect on those sols which or C6H 14 replaces CGHG, or when COMe2 replaces are on the border linę of stabihty and apparently EtOH, no opalescencc occurs. With CGH0-H2O- contain secondary particles. The electrophoretic EtOH at approx. 20—40° opalescence is.stable for measurements show ńo inerease in the ayerage an interyal of approx. 10°. Mixtures poor in H20 charge of the particles. E. S. H. aro stable at a lower temp. than those rich in H20. Properties of silver halides peptised by ultra- The disperse phase is rich, and the dispersion medium sonic waves in gelatin. H. W. D a n g ers (Z. poor, in C6HG. R. S. B. Physik, 1935, 97, 34—45).—Peptisation under yaried 1460 BRITISH CHEMICAL ABSTRACTS.— A. conditions has been studied, and it is shown that of unfused Pyrex particles and < the electro-osmotic this treatment can produce a max. colour-sensitivity. yelocity at a fused Pyrex surface. E. S. H. A.B.D.C. Thermal eąuilibrium between ethylene iodide, Comparative investigations on caramel and ethylene, and iodine. G. R. C u th b e rts o n and molasses colloids.—See this vol., 1485. G. B. K istiakow sky (J. Chem. Physics, 1935, 3, Helations between colloid and constitutive 631—634).—Results obtained between 50° and 125° changes of proteins. IV. Heat-coagulation and agree with the extrapolation of Mooney and Ludlam’s colloid structure of albumins. W. Pauli and data (A., 1929, 766) for lowcr temp., but disagree J. W eissbrod (Kolloid-Beih., 1935, 42, 429—462; with their high-temp, data. The heat of dissoeiation cf. this vol., 823).—Neutral salts raise the coagulation of C2H4I2 is 13-4+0-5 kg.-cal. per mol. The position temp. of serum albumin. The effect- is detectable of eąuilibrium is given by log K (atm.)=8T7—13,400/ at a concn. of 0-001JV, and varies with the anion 4-58T. T. G. P. according to the Hofmeister serics; SCN has the Exchange of heavy hydrogen atoms between greatest effect. Sucrose and CO(NH2)2 at high hydrogen and ammonia. K. W irtz (Naturwiss., concns. liaye a similar effect. The coagulation temp. 1935, 23, 721—722).— K for the reaction NH3-{- of ovalbumin is rąised by electrolytes only at Iow IID = N H 2D + H 2 is 1-9 a t 300°. A. J . M. concns. (< 0-001JV); at higher concns. the coagulation temp. is lowered. The order of effectiyeness of Fourth ionisation constant of ferrocyanic acid. different anions is that usually observed with posi- I. M. Kolthoff and W. J. Tomsicek (J. Physical tively-charged colloids; sucrose and CO(NH2)2 act Chem., 1935, 39, 955—958).—The val. 5-6 x 10"5 at as with serum albumin, but the effect of glycine is 25° has been deriyed from a study of the effect of similar to that of a neutral salt. Complex relations H" on the oxidation potential of a mixture of K4Fe(CN)6 are obscrved with mixed albumin sols. The mechan- and K3Fe(CN)6 at known ionic strengths. ism of these phenomena is discussed. E. S. H. E. S. H. Combination of bivalent manganese with Titration curves and dissoeiation constants certain proteins, amino-acids, and related com of i-ascorbic acid (vitamin-C) and diethyl di- pounds. 11. K. Main and C. L. A. Schmidt (J. Gen. hydroxymaleate.- W. D. Kumbler and T. C. Physiol., 1935, 19, 127— 147).—Partition, electro- D a n ie ls (J. Amer. Chem. Soc., 1935, 57, 1929— plioretic, and anomalous titration data show that 1930).—The results show that Z-ascorbic acid is Mn” forms complexes with H2S04, H3P0 4, nucleic and 1000 times as strong as E t, dihydroxymaleate. glycerophosphoric acids, with dicarboxylic, hydroxy- E. S. H. mono-, -di-, and -tri-carboxylic acids, dicarboxylic Interaction of amino-acids and salts. I. NH2-acids, and certain enol sulphonic acids; also with Zinc cbloride. II. Sodium chloride and certain proteins (casein, edestin, gelatin). thallous cbloride. N. R. Joseph (J. Biol. Chem., E. A. A. 1935, 111, 479—487, 489—499).—The addition of Lecithin as a dispersing agent for dibenz- yarious N H 2-acids decreases the activity coeffs. anthracene. H. D. B arn e s (Naturę, 1935, 136, of ZnCl2, T1C1, and NaCl in concn. cells without 756),—Two methods for obtaining colloidal dispersions hąuid junction. Comparison is made with results of dibenzanthracene using lecithin as dispersing obtained by other methods. These indicate that agent are described. L. S. T. “ salting-out ” forces of opposite sign are present, which become relatively greater with inerease in the Swelling of structured proteins.—See this vol., length of the liydrocarbon chain of the NH,-acid and 1522. the dielectric const. of the solvent. F. A. A. Electrophoresis of sterols.—See this yol., 1523. Association in the dissoeiation of simple Factors influencing electrophoretic mobilities straight-chain sulphonic acids in water. I. and apparent critical potentials. H. L. W hite Conductiyity. II. F.p. III. Electromotive and B. Monaghan (J. Physical Chem., 1935, 39, force. J. W. McBain and M. D. Betz. IV. Com 925—934).—In very dii. electrolyte solutions the parison of results, and so-called “ Hammarsten electrophoretic mobility of smali glass particles is effeets.” J. W. McBain (J. Amer. Chem. Soc., < the electro-osmotic mobility at a glass surface, 1935, 57, 1905—1909, 1909— 1912, 1913—1916, but at O-Olif the mobilities are identical. The same 1916—1920).—I. In very dii. solutions the straight- holds for gelatin surfaces. The effect is traccd to a chain sulphonic acids behave as simple, partly dis- retardation of the particles in very dii. solutions, sociated electrolytes. Conductiyity is at a min. in chiefly through polarisation of the double layer 0-05IV solutions and inereases greatly at higher by the applied field. The apparontly lower crit. concns. This is explained by the association of like potential obtained with electrolytes which coagulate ions to form ionic micelles, the equiv. conductiyity of in Iow concns., and kindred phenomena are explained. which in conc. solutions attains that of OH'. This E. S. H. effect predominates over the ordinary features of Comparison of the electrokinetic potentials interionic attraction. at fused and unfused glass surfaces. B. Mona- II. F.-p. data support the above results. ghan and H. L. WniTE (J. Physical Chem., 1935, III. E.m.f. data for sulphonic acids and their 39, 935—939).—The prep. of glass spheres 3 a or less mixtures with HC1 show that the ionic micelles of the in diameter is described. The electrophoretic velocity sulphonic acids cannot be regarded as equiv. to of Pyrex glass spheres in aq. KC1 is the same as that multiyalent ions in which the charges are conc. at GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1461 one point. The degree of dissociation of sulphonic and liquid solution. G. S c a tc h a rd and W. J. acids in conc. solution remains const. or tends to H am er (J. Amer. Chem. Soc., 1935, 57, 1809— increase. 1811).—Theoretical. Simple equations for tho change IV. The above results are discussed. The dis in chemical potentials on mixing are applied to the sociation of the colloidal electrolyte is about 50%. equilibria between solid and liquid solutions of the An explanation of the Hammarsten effect, based on Ag-Pd and Au-Pt systems. E. S. H. steric hindrance to close packing, is given. Vapour pressure and thermal dissociation E. S. H. of orthoboric acid. S. Bezzi (Gazzetta, 1935, 65, Thermodynamicproperties of methylbromide. 766—772; cf. A., 1933, 120).—The v.p. of H 3B0 3, S. S ugaw ara (J. Inst. Mech. Eng. Tokyo, 1935, measured at various temp. by a dynamie method, 38, 87—88). Ch. Abs. (e) is independent of the partial pressure of H20 in the Thermodynamic properties of uni-univalent transporting gas and equal to the v.p. of its saturated halide mixtures in aqueous solution. H. S. solutions. H3B03 is therefore volatile in steam on H a rn e d (J. Amer. Chem. Soc., 1935, 57, 1865— aecount of its own v.p., and not because it forms 1873).—E.m.f. of the cells H 2|HCl(0-01),NaCl(m)| volatile compounds with H20. The equilibriuni AgCl|Ag have been determined at 5° intervals from pressures of the system H3B03 IIB02+H20 0° to 60°. The results are considered in relation to have been determined. O. J. W. the law of linear variation of the logarithm of the Two compounds of titanium tetrachloride and activity coeff. a t const. ionic strength for such halide hydrogen chloride. A. Chretien and G. Varga mixtures. E. S. H. (Compt. rend., 1935, 201, 558—560).—Thermal Thermodynamics of ionised water in sodium analysis of the system TiCl4-HCl reveals TiCl4,6HCl, chloride solutions. H. S. H a rn e d and G. E. m.p. —86°, and TiCl4,2HCl, m.p. —30-8°, and the Mannweiler (J. Amer. Chem. Soc., 1935, 57, 1873— corresponding three eutectics. T. G. P. 1876).—Tlie ionic activity coeff. product of H 20 in System water-sulphuric acid-nickel sulphate. aq. NaCl has been calc. from e.m.f. measurements R. R ohm er (Compt. rend., 1935, 201, 672—674).— of the cells H 2|NaOH(0-01),NaCl(m)|AgCl|Ag and Equilibrium data at 25° and 50° aro recorded. In H 2|HCl(0-01),NaCl(m)|AgCl|Ag from 0° to 60°. The logarithm of the ionisation in alkaline halide solutions presence of H2S04, both NiS04,H20 (I) and NiS04 at a given concn. varies nearly linearly with the sum (II) may be prepared at 25°. NiS04,4H20, which is metastable, exists at 25° in contact with solutions of the reciprocal of the ionic radii. The total heat change for the ionisation of H20 and the relative containing < 43% of H 2S04. Above 84-8° only (I) and (II) occur as stable solid phases. H. J. E. partial mol. heat content of H‘ and OH' in aq. NaCl have been determined from 0° to 60°. E. S. H. Ternary system K2S04-(NH4)2S 04-H 20. E. Neutral salt action in non-aqueous solutions. B o v alin i and E. F ab ris (Gazzetta, 1935, 65, 617— 623).—The isotherms a t 0°, 35°, 50°, 70°, and 96-5° P. P. K ozakevitsch (Buli. Soc. chim., 1935, [v], have been studied. At all temp. tho salts form a 2, 1631— 1655).—The thermodynamic activity of C02, CC14, CHClą, N H E t2, C10H8, and camphor in continuous series of mixed crystals. 0. J. W. MeOH solution is increased by addition of salts Singular elements in the ternary system : to almost the same extent as in aq. solution. The lithium oxide-nitric anhydride-water. Effect distribution coeff. of these substances between vaseline of hydration. M. I. R avitsch (Ann. Inst. Anal. oil and MeOH is independent of their concn. but varies phys.-chim. U.S.S.R., 1935, 7, 235—244; cf. A., 1932, with the neutral salt concn. Setschenov’s equation 469).—Isotherms have been determined at 0°, 15°, holds for MeOH solutions of most metal halides 25°, 28-5°, 65°, and 130°. Ch . Abs. (e) except Li salts. The relative effects vary with the Singular fold in the ternary system : sodium naturę of the ions present and are discussed with chloride-platinum chloride-water. N. S. K tjr- refercnce to the action of undissociated mols. and the nakov and M. I. Ravitsch (Ann. Inst. Anal. phys.- structure of the solvent. The electrostatic effect of chim. U.S.S.R., 1935, 7, 225—233; cf. A., 1933, the ions extends probably only to a unimol. layer of 1013).—The singular points of the ice field and the MeOH mols. The anomalous behaviour of HgCl2 cryohydric lines are described. The results are com- and Cdi, in presence of camphor indicates the existence pared with other ternary systems. Na2PtCl6 behaves of compounds C10H16O,HgCl2 and Ci0H16O,CdI2. as a complex salt. Ch . Abs. (e) There is also evidence of complex formation between several salts and C10H8. J. W. S. SystemK2S 04-M gS04-CaS04. L. S. R am sd ell (Amer. Min., 1935, 20, 569—574).—Z-Ray examin- Application of equations for the chemical ation of fused mixtures of K2S04, MgS04, and CaS04 potentials to partially miscible solutions. G. show the existence of a continuous isomorphous series Scatchard and W. J. Hamer (J. Amer. Chem. Soc., with K2Mga(S04)3 (langbeinite) and K2Ca2(S04)3 1935, 57, 1805— 1809).—Equations for the free energy as end-members, no other compounds being formed. of mixing are computed from the mutual solubilities The lattice is a simple cube, 4 mols. per unit celi; of partly miscible substances; the vapour compositions the cube edge varies from 9-96 A. for the Mg to and pressures calc. from these equations agree satis- 10-37 A. for the Ca end-member. Polyhalito (I) factorily with experiment. E. S. H. calcined at approx. 475° for a short period gives a Application of eąuations for the chemical product of Iow d from which practically complete potentials to equilibria between solid solution extraction of K2S04 and MgS04 is obtained by hot 1462 BBITISH CHEMICAL ABSTBACTS.----A. H20. The CaSO., residue is rapidly converted into allows the varying magnitude of the effect with gypsuin by cold H20, but X-ray photographs show field strength to be rapidly determined. A. J. M. that it is norraal anhydrite. Calcination at higher temp. or for longer periods reduces the yiold. The Behaviour of oxygen electrodes in carbonate mechanism of dehydration of (I) is discussed. m elts. E. Baur and R. Brunner (Z. Elektro- L. S. T. chem., 1935, 41, 794—796).—The construction of Alkali aluminium silicates. X. System 0 2 electrodes for use at 450—1000° is described. ultramarine silicate-sulphur. E. Gruner and C.d.-p.d. curves covering this temp. rangc have been J. F o r s te r (Z. anorg. Chem., 1935, 224, 369—3S7; determined. E. S. H. cf. this vol., 1470).—Pressure-S content curves Oxidation potential of the system potass- representing the isothermal decomp. of blue and green ium ferrocyanide-potassium ferricyanide at ultram arine between 600° and 1050° have the same various ionic strengths. I. M. K o lth o f f and form as those of substances containing “ zeolitic ” W. J. Tomsicek (J. Physical Chem., 1935, 39, 945— H20. The residue left when all S has been expelled 954).—The normal electrode potential is 0-3560 volt by heat shows tlio lattice of nephelite. The con- at 25°. In very dii. solution the variation of potential stitution of ultramarine is discussed. F. L. U. with increasing ionic strength is > calc. on the basis Dissociation energy of carbon monoxide and of the simple Debye-Hiickel expression. For the the heat of sublimation of carbon. H. Less- same valencv type of salts the anion effect on the heim and R. Sam uel (Naturę, 1935, 136, 606).— potential is the same for different anions at the samo The vaL calc. for the heat of dissociation of CO is ionic strength. The cation effect of the alkaline- 10-45 v.e. (cf. this vol., 925), giving 155-7 kg.-cal. earth ions is > that of the alkali ions, which decreases per mol. for tho heat of sublimation of (ł-graphite in the order Ca > Rb > K = NEL > Na = Li. a t 25°. L. S. T. E. S. H. Heat oi dilution of cadmium chloride. (M lle. ) Junction potentials between solutions of M. Q uintin (Compt. rend., 1935, 201, 549—550).— sugars and potassium chloride. J. M. O rt and Calculations are made from prcvious data (this vol., M. H. R oepke (J. Physical Chem., 1935, 39, 941— 826). T. G. P. 943).—A saturated aq. KC1 bridge eliminates all significant liąuid junction potentials, even in the Free energy change that accompanies hydro- most conc. sugar solutions, if the sugar solution has genation of pyridine to piperidine. G. H. jhi > 10 and does not contain a large amount of ionised Burrows and L. A. King, jun. (J. Amer. Chem. Soc., decomp. products. E. S. H. 1935, 57, 1789—1791).—The eąuilibrium between C5H5N, C5Hn N, and H2 a t 150°, 170°, and 180° Electromotive forces due to the combination has been determined; the heat of reaction and of metal [electrodes] in gelatin and the import- accompanying free energy changcs have been calc. ance of the Volta effect in cells. S. Ve il (Compt. E. S. H. rend., 1935, 201, 551—552).—The p.d. between Conductivities of acids and other solutes in electrodes of Zn, Cd, Fe, Pb, Ni, and Cu and a P t pyridine. M. M. Davies (Trans. Faraday Soc., wire in gelatin have been measured with a ąuadrant 1935, 31, 1561— 1567).—Conductmties of HC10,„ electrometer (cf. this vol., 822). T. G. P. HN03, and HI in C5H5N at 25° liave been measured. The dissociation const. are, respectively, 7-55 X 10-1, Polarographic studies with the dropping 4-96 x l0 -5, and 5-9 X 10-4. Results obtained by mercury cathode. LII. Electro-reduction of addition of C5H5N to solutions of CPh3Cl and of benzaldehyde. M. T okuoka. LIII. Electro-re- CgH2C1(N02)3 in PhN 02 indicate the formation of duction of ferric-mannitol complexes in alkaline complexes with C5H5N. CfiH3(N02)3 behaves as a solutions. K. Komarak. LIV. Electro-reduc weak acid in C5H5N, whilst C0Me3(NO2)3 does not. tion of formaldehyde. F. G. J a h o d a (Coli. Czech. Chem. Comm., 1935, 7, 392—403, 404—414, 415— Conductance of non-aqueous solutions. I. 423).—LII. Polarographieally recorded current- Sodium triphenylboron and disodium tri-a- voltage curves show that the reduction occurs in naphthylboron in diethyl ether. H. E. Bent two stages, each of which recjuires one F per mol. and M. D orfm an (J. Amer. Chem. Soc., 1935, 57, of PhCHO. The first stage of reduction probably 1924—1927).—Equiv. conductances have been deter yields free radicals, -CIIPh-OH, which may sub- mined at 0° and 25° from 10*1 to 10-7 mol. per litre. seąuently form hydrobenzoin; the second stage leads The structure of B(C10H7-a)3 is discussed in the light to CHoPh-OH and does not involve the deposition of the results. E. S. H. of H’ or an alkali metal. As the j)n is increased, the potential for the first stage becomes morę negatire Transport number and valency of silver in and that for the second stage slightly more positive. silver amalgam. K. S ch w artz (Monatsh., 1935, The potentials coincide at >6 and decrease by 66, 218—219).—Ag in Ag amalgam is a bivalent anion approx. —0-025 volt per unit rise of p s t These for which transport no./concn.=4-0x 10-4 and dif- results are, in generał, independent of the type of fusion const.=1-0 X 10~5 cm. per sec. T. G. P. buffer solution used. The reduction potential is Cathode-ray oscillograph method of investig- approx. —1-5 volt, with respect to the i\T-Hg2Cl2 ating the Wien effect in electrolytes. W. H u te r electrode in neutral aq. MCI (M—Na, K, NMe4), (Ann. Physik, 1935, [v], 24, 253—272).—The oscillo- but is raised slightly by Sr", Ca", NH4', NH3Me\ graphic method clearly indicatcs the Wien effect, and NH2Me2’, and NHMe3", which also increase tlie GENERAL, PHYSICAL, AND ESTOKGANIC CHEMISTRY. 1463 diffusion current. Electro-reduction of BzOH in position and dissolution of gallium and their presence of NMe4‘ occurs at —2-3 volt. dependence on temperature near the m.p. O. LIII. Mannitol does not affect the current-voltage S te llin g (Z. Elektrochcm., 1935, 41, 779—789; curve obtained with slightly acid solutions of Fem, cf. this vol., 1325).—Further studies of the anodic but in alkaline solutions, especially in absence of and cathodic behaviour of Ga in dii. HC1 and NaOH 0 2, two saturation currents (“ waves ”) are observed. confirm that liquid Ga behaves as a nobler metal Glycerol, sucrose, lactic and citric acids give similar than solid Ga. E. S. H. results if added before the solution is madę alkaline. Electrode dispersion of noble metals. A. The “ wayes ” correspond with the successiye electro- V oet (Trans. Faraday Soc., 1935, 31, 1488—1491).— reductions : FeTII-org. mol. complex -> FeTI-org. Anodic disintegration of Au, Pt, and Pd is obseryed mol. complex -> Fe, and the ratio of the heights when acid, alkahne, or neutral solutions are electro- of the waves decreases from 1 : 2 to 1 : 1 as the alkali lysed at 100 volts and high c.d. It is always accom- is neutralised. The origin of the last phenomenon panied by periodicity of the current, and is not is discussed. The affinity of the Feln-mannitol due to the Wehnelt effect. An explanation based on complex is smali. the formation and disruption of an oxide layer is LIV. The saturation current, i, is a lincar function given. F. L. U. of [CH20] and the “ mol. reduction potential ” is — 1-50 volt. Reduction of 1 mol. of CH20 requires Passiyity of iron and steel in nitric acid solu 2F. i is increased in alkahne solutions and by tion. VII. Y. Yamamoto (Buli. Inst. Phys. Chem. rise of temp., indicating dissociation of poljanerisation Res. Jap an ’ 1935, 14, 925—964; cf. this vol., 827).— products. The max. of current-yoltage curves and The passiyation of Fe in conc. HN03 is more difficult i decrease with increasing age of CH20 solutions. to effect when the test piece has suffered interna! A t 90°, 7 x 10 8 g. of CH20 in 1 c.c. can be determined stress by twisting. R. S. B. polarographically to within 10% in presence of Quantum mechanics and kinetics of reactions other aliphatic aldehydes, ketones, esters, and org. in organie chemistry. C. N. Hinshelwood (Buli. acids. Minuto traces of CHo0 in coal gas are inferred. Soc. chim., 1935, [v], 2, 1786—1799).—A lccture. J. G.A. G. Electrolytic reduction potential of organie General method of statistics and its applic- compounds. -XXII. Mechanism of electrolytic ation to chemical energetics. G. A lla r d (Ann. reduction. I. Tachi (J. Agric. Chem. Soc. Japan, Physique, 1935, [xi], 4, 305—377).—M athematical. 1935, 11, 734—740).—Smali drops of H 20-insol. org. J. W. S. Kinetics of slow reactions and their entropy compounds placed on a Hg cathode having a smali surface at first bccome fiat owing to polarisation, changes. F. G. S oper (J.C.S., 1935, 1393—1395).— but further polarisation tends to restore the original On the hypothesis that the decomp. of the crit. form. The angles of contact between drop and Hg complex into the products and reagents cc the and the changes which these undergo when polaris relative thermodynamic probabilities of the three states, a factor representing the fraction of crit. ation occurs vary with the compound used and with the naturę of the dissolyed electrolyte. Camphor complexes which decompose to reaction products oil drops become flatter than do those of PhN02 has been introduced into the yelocity equation. and CC14. PhN02 drops become flatter in alkaline The modified equation is of correct thermodynamic than in acid media. W. McC. form, and reduces to k —Ze-EI,tT when the reaction is attended by an inerease of entropy, but gives General properties of electrodes of photo- grcatly diminislied rates when the entropy change is sensitive organie substances. (Miss) H. T. Nga negative. Existing data show that, with one cx- (J. Chim. phys., 1935, 32, 564—584).—Electrodes ception, the classification of reactions as “ normal ” were prepared by immersing Cu (or Pt) in collodion and “ slow ” is in generał agreement with that based and then in aq. solutions of yarious coloured sub on the sign of entropy change. The factor affects stances. The photo-potential (Ep) varies with the only slightly the existing agreement between obseryed naturo, and diminishes to a steady val. with increasing and calc. yelocities of reactions associated with smali concn., of the electrolyte. Oxidising or reducing decreases of entropy, e.g., 2HI -> I2+ H 2; NH4CN0 -> agents diminish Ej, irreyersibly. The temp. coeffs. CO(NH2)2. J . G. A. G. of the electrodes are generally negatiye; for pyro- Photographic investigation of flame move- nine it is positive, and for crystal-violet zero. The ments in gaseous explosions. VII. Pheno log. yariation of E p with hght intensity has been menon of spin in detonation. W. A. Bone, R. P. confirmed. The yariations of Ep (for different XX) F ra s e r, and W. H. W h e e le r (Phil. Trans., 1935, with the polarisation of the electrodes indicate that A, 235, 29—68; cf. A., 1932, 232).—The spiral track photo-electric and not electronie processcs play the formed by the rotation of the “ head ” of detonation major part. Ep bears no discernible relation to in the system moist 2C0+02 has been studied in photo-conductiyity, is sensibly zero in non-aq. relation to the influence of dimensions and shape solvents, and oc the % of H20 in aq. glycerol. The of the explosion tube and the addition of smali properties of org. and inorg. photo-electrodes are amounts of H2 or Fe(CO)5. Dmng the mixture with thus very similar. T. G. P. P20 5 incrcases the flame speed and stabilises the Dependence of the electrochemical properties spin. In a moist mixture the flame speed is reduced of an element on the state of aggregation. II. in passing through a powerful axial magnetic field, Polarisation relations in the electrolytic de- and hoth spin and detonation can be suppressed when 1464 BRITISH CHEMICAL ABSTRACTS.----A. the detonation traverses a sufficiently strong electric velocity coeff. by means of the transition state method field in a negative to positive direction. A new view indicates that the steric factor of bimol. association of the detonation wave is advanced. It is viewed reactions is related to the probability of the transition as two separable components, an intensively radiating state. The theoretical results are applied to the crack - flame-front with an invisible shock wave immediately ing of long-chain liydrocarbons. F. L. U. ahead of it; whether persistent spin is developed or not depends on the stability of their association. Velocity of oxidation of sulphides and sulph- E. S. H. oxides by peracetic acid. J. BSeseken and Ignition of gases. IX. Ignition by a heated (M lle.) E. A rria s (Rec. * trav. chim., 1935, 54, surface. Mixtures of niethane and air at re- 711—715).—The reaction between Ph2SO and A c02H duced pressures. C. A. N a y lo r and R. V. in AcOH is bimol. and its velocity coeff. inereases W h e e le r (J.C.S., 1935, 1426— 1430).—In generał, considerably with inereasing [Ac02H], possibly owing the upper ignition temp., T, of CH4-air mixtures to spontaneous decomp. of the Ac02H and an acceler- in a Si02 vessel rises as the proportion of CH4 is ating influence of the change of medium. The raised from 5-3 to 12-5%, but the variation of T oxidation of Ph,S by Ac02H occurs in two stages, with total pressure ( P = 263—760 mm.) is not uniform. the bimol. oxidation to Ph2S0 being complete in With > 10-7% of CH4, T decreases progressively as 3 min. and being followed by oxidation of the Ph2SO P inereases, but with less CH4, two pressure limits to Ph2S02. Oxidation of (p-CGH4Br)2S is similar, are found for each val. of T (cf. A., 1933,, 129). The but the velocity of reaction is less. The results are data do not conform to the Semcnov relation between compared with those for the oxidation of unsaturated T and P. The lag before ignition decreases as P liydrocarbons. J. W. S. is raised and as the % of CH4 is decreased. The results accord with earlier work (A., 1931, 1240) Decomposition of polythionate solutions. A. and an interpretation is suggested. J. G. A. G. Kurtenacker, A. Mcjtschin, and F. Stastny (Z. anorg. Chem., 1935, 224, 399—419; cf. A., 1934, Kinetics of the thermal decomposition of 160).—The different modes of decomp. of aq. solutions acraldehyde. H. W. Thompson and J. J. Frewing of K2Sn0 6 (n—3—6) are discussed. Velocities of (J.C.S., 1935, 1443— 1451).—The therm al decomp. decomp. have been measured, mostly at 50°, and the 0f 5—650 mm. of acraldehyde at 490—570° is essenti- influence of [H‘] has been studied. All the decomps. ally homogeneous and affords C4H8, C2H4, CO, C2H„, can be represented by a unimol. coeff'., except for CH4, and II2. The proportion of C4H8 inereases with tetra-, penta-, and hexa-thionates within the rangę inerease of initial pressure and decreases during the p a 4—9, where they may be markedly autocatalytic. course of a run. C2IIe, CH4, and H2 are also primary F. L. U. produets. The plot of the reciprocal of the period Critical inerement of ionic reactions. Influence of half change against the initial pressure, P0, is of dielectric constant and ionic strength. W. J. segmented and the reaction probably consists of Svirbely and J. C. W arner (J. Amer. Chem. Soc., several independent quasi-unimol. processes super- 1935, 57, 1883— 1886).—Assuming th at the rates of posed on a bimol. reaction. The energy of activation ionic reactions are functions only of temp., dielectric inereases with decrease of P 0. J. G. A. G. const., and ionic strength, eąuations are derived which Velocity of thermal decomposition of chloro- predict the influence of dielectric const. and ionic picrin. D. R adulescij and G. Zamfirescu (Buli. strength on crit. inerements. Experimental data for Soc. Chim. Romania, 1935, 17, 87—92).—The de the reaction between NH4' and CNO' in HzO and comp. is unimol. up to 160° and has a large temp. Et0H -H ,0 are in agreement with the theory. coeff. Photodecomp. is inliibited by the NOC1 E. S. H. produced, which absorbs the light. R. S. Mechanism and thermal effect of fulminic Diabatic reactions and primary chemilumines- acid polymerisation. K. Sennewald and L. cence. R. A. Ogg, jun., and M. Polanyi (Trans. B irckenbacii (Annalen, 1935, 520, 201—234; cf. A., Faraday Soc., 1935, 31, 1375— 1384; cf. this vol., 1934, 994).—The heat of polymerisation of fulminic 452).—An outline of the theory of ionogenic reactions acid (I) in 0-4iV aq. solution has been measured in and a list of its applications are given. Luminescence presence of H2S04 at various concns. When the accompanying a primary chemical change is described [H2S04] > 0-01A7 the heat produced is 20% > when as the iiwerse of predissociation. F. L. U. [H2S04] is > 015iV. In the latter case the reaction is bimol., whilst in the former it is of no simple order. Mechanism of ionic reactions. Heat of ionic These results, in conjunction with chemical observ- substitution reactions. R. A. Ogg, jun. (Trans. ations, indicate th at in neutral (< 0-01iV-acid) solu Faraday Soc., 1935, 31, 1385— 1392; cf. preceding tion cyano-oximinoacetohydroxamic acid is formed as abstract).—Estimates of the heat (H) involved in the finał, with metafulminuric acid as an intermediate, reactions between MeX (X=C1, Br, I) and a negative product. In acid (> 0-15iV) solution tlie primary ion other tlian halogen show that ionic interchange product is dicarbonyldioxime (II), a smali part of reactions having large positive H are characterised which combines with a mol. of (I) to form a trimeride, by smali energies of activation. Examples are given whilst a larger part undergoes polymerisation to iso- and discussed. F. L. U. cyanilic acid. The following [from (II) and aq. Steric factor of bimolecular association re halogen acid] are described : bromoglyozime, m.p. 173° actions. C. E. H. Bawn (Trans. Faraday Soc., (decomp.); iodoglyoxime, m.p. 163° (decomp.); also 1935, 31, 1536— 1547).—Consideration of the reaction bromogiyoxime a?i Reactivity of halogen compounds. III. Vel- solution. Mechanism of olefine formation in ocities of reaction, energies of activation, and such systems. W. T a y lo r (J.C.S., 1935, 1514— probability factors for the reaction between 1524; cf. this vol., 173).—Under the conditions of the 2 : 4-dinitrobromobenzene and aromatic prim- kinetie experiments at 25° and 55°, the reactions with ary amines. IV. Effect of addition of inactive EtOH-NaOH are : (i) CH2Br-CBr3 gives CHBrlCBr,, substances on the rate of reaction, energy of (ii) CH2BrC H B r2 gives CH2!CBr2, (iii) CMeBrs yields activation, and probability factor. A. Singh and NaOAc and 2-8% of bromo-olefine, (iv) CHMeBr2 D. H. Peacock (J.C.S., 1935, 1410— 1411, 1411— affords MeCHO and a very smali proportion of bromo- 1412).—III. Veloeity coeffs. of the reaction between olefine, (v) (CH2Br)2 gives 79-5% of CH2!CHBr and 1 : 2 : 4-CgH3Br(N 02)2 (I) and NH2Ph, m- and p- 18-5% of (•CH2'OH)2, and (vi) EtB r yields EtO H and toluidine in EtOH at 35° and 45° are > with 1:2 :4 - 1-3% of C2H4. The reactions with measurable rate CłBLCWNO,), (II), probably owinę to a higher prob are bimol.; the velocity increases with dilution of ability factor (J.C S , 1923,123, 3099). NaOH, is independent of the concn. of the bromo- IV. The rate of reaction of NH2Ph with (I) and (II) ethane, and is decreased by H20 and large proportions is retarded by added C6Hfi derivatives, but cycloh.exa.ne of NaBr. There is a elear distinetion between has no effect. The results negative an earlier liypo- (a) reactions involving OH substitution of Br and thesis (A., 1926, 691). J . G. A. G. (/;) those involving complete or nearly eomplete con- Influence of substituents on the additive re- version into olefine. In (a) two Br are displaced eitlier activity of ethylene derivatives. III. Addition simultaneously or consecutively at rates which are of b) one Br is of bromine in solution. S. V. A n a n ta k ris h n a n the same order of magnitude, whilst in ( displaced almost, if not quite, instantaneously and the and C. K. In g o ld (J.C.S., 1935, 1396— 1398; cf. this second is displaced relatively slowly. Existing vol., 1103).—Data are recorded concerning the effect of substituting Me, Ph, and CHO in C2H4 on the rate theories are criticised (A., 1933, 470; this vol., 452), and the data arc interpreted by a mechanism involving of addition of Br in CH2C12 solution. The rate is a primary mutual attraction of OH' and an initially increased with the no. of Me groups, in agreement with positively charged H, followed by simultaneous exten- the theory (A., 1931, 1267), but in eaeh case the 'CHO increases the rate, indicating an enforced reversal of sion and rupture of the C-H and C-Br linkings of the the anticipated functions of the reagent. two C of tho ethane mol., whereby H20, Br', and olefine aro formed. The eonsequences of tho theory J. G. A. G. Steric course of two diene syntheses.—See this are discussed. J. G. A. G. vol., 1500. Mechanism of, and constitutional factors con trolling, the hydrolysis of carboxylic esters. Hydrolysis of phenylalanine. E. B a u r and G. V II. eycłoPentanedicarboxylic esters. At- S c h in d le r (Biocliem. Z., 1935, 281, 238—248; cf. tempted check on the calculation of molecular A., 1934, 1314).—Results of experiments a t 110° con- dimensions. C. K. In g o ld and H. G. G. M oiir- firra those obtained at 80°. The umlateral equilibrium h en n (J.C.S., 1935,1482— 1486; cf. this vol., 1076).— follows the mass action law, the reaction being of tho From tho yeloeity coeffs. at 20° of the first and second first order. The val. for the heat of reaction deduced stages of the alkaline hydrolysis of Me2 cis- and Irans- from the shift of the eąuilibrium with temp. change l.:2 -an d -1 : 3-c2/cZopentanedicarboxylate, the dis- differs considerably from that deduced from calori- tanees between the C02H have been deduced on certain metric results, although there is qual. agreement. assumptions. In generał, the results conform moro W. McC. closely to the requirements of the mol. model when Velocity of hydrolysis of cyclic acetals. II. corr. for local dielectric effects in tho aq. medium. R. L e u tn e r (Monatsh., 1935, 66, 222—248; cf. A., The causes of the deviations are discussed. 1932, 932).—The veloeity of acid hydrolysis of the J. G. A. G. formal, acetal, and acetonal of ay-butylene glycol, and Constitution and reactivity. XIV. K inetics the formal and acetal of pinacone have been measured. of sulphonation with oleum and the properties The relative ease of rupture of the 6-ring of the ay- of fuming sulphuric acid of different concen- butylene glycol acetals of CH20, MeCHO, and COMe2 trations. K. Lauer and R. Oda (J. pr. Chem., is 1:4 x 103 : 7x10°. The relationship between hydro 1935, [ii], 144, 32—40).—Vals. of q and a x l 0 ~10 (cf. lysis and constitution is discussed. T. G. P. A., 1933, 69) for tho sulphonation of anthraquinone Aliphatic substitution and the Walden inver- using H2S04 with added SO:! are determined and sion. I. E. D. Hughes, F. Juliusburger, S. plotted against [S03]. The vals. of q and a X10"10 for M asterm an, B. T opley, and J . W eiss (J.C.S., 1935, sulphonation with S03 are 22,000 and 0-1, respectively. 1525— 1529).—The abs. rate in COMe2 solution of the These are < the vals. for sulphonation with H2S04 (cf. exchange of I between Nal and sec.-octyl iodide, deter this vol., 863). F. R. G. mined by means of the radioactive isotope of I, equals, Application of the law of mass action to the within the limits of experimental error of the measure synthesis of p-glucosides.—See this vol., 1485. ments of radioactivity (10%), the abs. rate of racemis- ation of cZ-sec.-octyl iodide by N al in COMe2 solution. Effect of substituents on organie reactions : The result confirms that in this reaction inversion is a quantitative relationship. G. N. B u r k h a r d t directly caused by substitution. J. G. A. G. (Naturę, 1935,136, 684).—-Using the logarithms of the dissociation consts. of various m- and p-substituted Kinetics of the interactions of sodium hydr- BzOH as an arbitrary reference series, linear relation- oxide with the bromoethanes in ethyl-alcoholic ships are obtained when the logarithms of the yeloeity 1466 BRITISH CHEMICAL ABSTRACTS.— A. coeffs. of a no. of side-chain reactions involvirig sub and peroxides. 1 part in 10,000 of 0 3 in air causes stances containing the same m- and ^-substituents are knocking in an internal-combustion engine by pro- plotted against them. Thus, a strałght line is obtained moting the formation of peroxides. S. J. G. for the alkaline hydrolysis of substituted EtOBz and Decomposition of chloral catalysed by nitric substituted NH2Bz, and the solvent hydrolysis of the benzyl chlorides, etc. The linear relationships are oxide. E. H. Y erhoek (Trans. Faraday Soc., 1935, discussed in terms of the transition state conception 31, 1521— 1526; cf. A., 1934, 1314).—The thermal of Evans and Polanyi. L. S. T. decomp. of both CC13*CH0 and CHC13 vapour is catalysed by NO. The catalysed reaction is of the Measurement of the velocity of rapid reac first order with CCl3-CHO, and approx. so with tions. M. Wygaerts and J. Eeckhout (Natuur- CHC13. The mechanism is discussed. F. L. U. wetensch. Tijds., 1935, 17, 163— 189).—The course of reactions in solution involving a change in absorption Decomposition of acetaldehyde catalysed by spectrum is followed by taking a photographic record nitrous oxide. F. H. Verhoek (Trans. Faraday of the galvanometer reading of a photo-electric celi Soc., 1935, 3 1 ,1527—1533; cf. preceding abstract).— registering the intensity of light of given X transmitted Study of the thermal decomp. of MeCHO yapour in by the solution. The decolorisation of malachite- presence of N20 indicates the occurrence of a reaction green by a large excess of NaOH (such that [NaOH] is between the MeCHO and N20 giving rise to a substance effectively const.) is unimol., with k 0-94 a t 19-85° and which acts as a catalyst or initiates a chain. In a 1 -6 at 29-65°. The decolorisation of reddened phenol- clean Si02 bulb the catalysed reaction is of the first phthalein by a large excess of NaOH is reversible, the order with respect to MeCHO. F. L. U. reaction in both directions being unimol., with hx Decomposition of acetaldehyde catalysed by M 4 x l0 -2 at 19-85° and 2-23xl0-2 a t 29-S0°, and k2 nitric oxide. F. H. Verhoek (Trans. Faraday 7-1 x 10'5 at 19-85° and 3-87xl0-‘‘ at 29-80°. The Soc., 1935, 31, 1533— 1536 ; cf. preceding abstract).— absorption spectra of m-N02-CGH1-CH2-N02 and its Na The decomp. of MeCHO catalysed by NO at 480° is salt (I) have been determined. The action of HC1 on approx. 3/2 order with respect to MeCHO, and the excess of (I) in 70% aq. EtOH at 13-9° is a bimol. rate oc [NO] when NO is in excess. An explanation reversible reaction (i.e., the velocity of both forward of the mechanism is offered. F. L. U. and back reactions cc the concn. of each reactant); ^=7-49, yt2=2-63. D. R. D. Catalytic decomposition of hydrogen peroxide in presence of mixtures of salts of manganese Corrosion of iron and steel.—See B., 1935, 1048. and copper. M. B o b telsk i and (Mme.) L. Bob- Atmospheric corrosion and tarnishing of tin. te lsk i-C h a jk in (Compt. rend., 1935, 201, 604— —See B., 1935, 996. 606).—The unimol. velocity coeff. inereases with inereasing [Cu"] to a max., and then diminishes. The Kinetics of the oxidation of metal filaments. max. val. inereases with the [Mn”]. Zn" and Cd" G. V alen si (Compt. rend., 1935, 201, 602—604; cf. this vol., 1328).—A generał expression is derived inerease the catalytic activity of Cu"-Mn" mixtures. from diffusion considerations for the rate of oxidation A mechanism, involving intermediate compound formation between Mn" or Cu" and H20 „ is suggested. of filaments of bivalent metals. The result accords with experimental vals. for Ni. H. J. E.' H. J. E. Catalytic decomposition of nitroamide in acid Kinetics of heterogeneous organie reactions : and salt solutions. C. A. M arlies and V. K. La reaction between benzyl chloride and solid silver M er (J. Amer. Chem. Soc., 1935, 57, 1812—1820).— nitrate. M. V. N a b ar and T. S. W h e e le r (Proc. The rate of decomp. has been measured in aq. acid Indian Acad. Sci., 1935, 2, A, 265—278).—The and salt solutions over a wide concn. rangę with an reaction, studied in the absence of solvents and error of about 1%. A negative primary salt effect, diluents, is independent of the amount of CH2PhCl which has been observed, is ascribed to the effect of (I), but cc the surface of AgN03 present. Results, the salt on the catalytic properties of H,0. Acid with particles of three different sizes, can be repro- catalysis has also been observed and a mechanism duced by the kinetic eąuation derived on the assump- proposed. D20 decreases the velocity of decomp., tion that the rate of reaction depends only on the sur whilst HgCl2 inereases it. ‘ E. S. H. face of AgN03. The velocity of th’e reaction is independent of the speed of shaking. H20 inhibits Conditions of formation of the chloride of the reaction; the effect of 0-18 wt.-% of (I) is marked, tervalent manganese in hydrochloric acid solu and this effect inereases with the amount of H20 tions, and its decomposition in presence of added. N. M. B. complex catalysts. M. Bobtelski and (Mlle.) R. Cohen (Compt. rend., 1935, 201, 662— 664).—The Rate of formation of fully-saturated glycerides catalytic activity of metals in the decomp. of MnCl3 during hydrogenation of different natural fats.— in presence of HC1 was in the order Ag1 > Ptlv> Pb11 > See B., 1935, 1053. Cu11. Inerease in [HC1] in presence of Cu11, Pb11, or Catalytic effect of ozone in the oxidation of P tIV inereases the rate of decomp. The temp. coeff. hydrocarbons. E. Briner and J. Carceller of the decomp. decreases with inereasing [HC1]. (Arcli. Sci. phys. nat., 1935, [v], 17, Suppl., 85— 86).— In presence of Ag1 it is independent of [HC1], and 0xidation of «-C4HJ0 by 0 2 is greatly aceelerated by approx. unity. H. J. E. smali amounts of 03 at < room temp. Products Catalytic polymerisation of gaseous olefines formed include aldehydes, acids, C0Me2, H2, C02, by liąuid phosphoric acid.—See B., 1935, 1035. GENERAL, PHYSICAL, AND INORGANTC CHEMISTRY. 1467 Physical chemistry of amino-acids, peptides, catalytic activity, and interna! and surface migration and related substances. V. Influence of amino- of the lattice units of the catalyst are considered. acids, carbamide, and alcohol on the velocity T. G. P. constants of chemical reactions. D. Straup and [Catalytic] synthesis of methane.—See B., 1935, E. J. Cohn (J. Amer. Chem. Soc., 1935, 57, 1794— 1035. 1800; cf. this vol., 695, 696).—The rate of reaction Adsorption and oxidation of succinic acid on of Na2S203 with alkyl iodides is increased by EtOH, carbon. B. Tamamushi and H. Umezawa (Z. Elek- slightty increased by CO(NH2)2, and decreased by trochem., 1935, 41, 761—764).—The catalytic activity ions or amino-acids. The rate of reaction between of different kinds of C in the oxidation of succinic Na2S203 and CH2Br-C02' is increased by salts, NH,- acid by 0 2 has been studied by gravimetric determin- acids, and CO(NH2)2, and but slightly influenced ation of fumaric acid, and compared with the ad- by EtOH. CO(NH2)2 and NH2-acids increase the sorptive power of the C. The influence of the re- dielectric const. of H20 in proportion to their concn., lativelv greater adsorption of fumaric acid is discussed. but this factor does not entirely explain the influence E. S. H. on reaction rate. An extension of Kirkwood’s Electrolytic preparation of deuterium from eąuation for the activity coeffs. of the NH2-acids heavy water. F. N o rlin g (Physikal. Z., 1935, 36, has been applied satisfactorily to the results. 711—713).—The apparatus is described. A. J. M. E. S. H. Catalytic decomposition of hydrogen peroxide Concentrating the hydrogen isotope D by on metals. J. W eiss (Trans. Faraday Soc., 1935, electrolysis of water. II. Production of heavy 31, 1547— 1557; cf. A., 1935, 174).—The initial water and its apparatus. Y. O ta (Mem. Fac. Sci. process in the catalytic decomp. of H202 by metals Agric. Taihoku, 1935, 15, 165—170). T. G. P. involves the transfer of an electron from the metal Hydrates of lithium perchlorate. K. N. M ocha- to the H202, with the conseąuent formation of free lo v (Trans. Butlerov Inst. Chem. Tech., 1934, No. radicals, thus : H202+e=0H +0H '. This leads to .1, 21—25).—LiC104 was prepared electrolytically the.initiation of chain reactions, 0H-j-H202= H 20 + from aq. LiClO., (c.d. 0-2 amp. per sq. cm .; temp. II02 and 02'+ H 202=0H ' + 0H + 02. The ease with <20°). LiC104,3H20 loses 2H20 at 98—100° and which the primary electron transfer occurs depends becomes anhyd. at 130—150?. Cii. Abs. (e) on the electronic work function of the metal, and if Electrolysis of aqueous solutions of alkali this is decreased by cathodic polarisation catalytic sulphates.—See B., 1935, 1000. decomp. becomes econsiderably greater, Hg and bright Pt, e.g., being effective catalysts under these Electrochemical anodic behaviour of alloys. conditions. The action of Ag, Pt, Au, Pd, and Zn W. J. M uller [with H. Freissler and E. Plettinger] on H202 has been studied in detail, and the observ- (Z. Elektrochem., 1935, 41, 774—778).—The anodic ations support the theory, which also provides a simple dissolution of Cu-Zn alloys in AT-HC1 and iV-H2S04 explanation of the action of poisons such as H2S and has been studied by determining the loss of wt. of KCN. F. L. U. the anodę and the amount of Cu dissolved from alloys of different compositions after the same time interval. Mechanism of sulphur dioxide oxidation in No Cu was dissolved from alloys containing <40% presence of vanadium catalysts.—See B., 1935, of Cu; with increasing Cu content the ratio of Cu to 991. Zn in solution approaches more and more to that in Effect of the ferromagnetic transformation the alloy. In HC1 Cu enters solution as Cu', in H,S04 on the catalytic power of nickel for the reaction as C u", E. S. H. 2 C 0 = C 0 24-C. J. A. Hedvall and F. Sandford Electrochemical behaviour of lead, lead-anti- (Z. physikal. Chem., 1935, B , 29, 455—463; cf. this mony, and lead-calcium alloys in storage cells. vol., 153).—The catalysis by Ni of the above reaction —See B., 1935, 1001. in and near the Curie interwal and the effect of im- Inorganic addition salts in the nickel-plating purities in Ni on the relation between its ferromagnet- ism and its catalysis of the reaction N2Ó=N2+0-502 solution.—See B., 1935, 998. have been studied. The yield curves exhibit changes Effect of oxidising agents on nickel deposi- in direction corresponding with the characteristic tion. II. Chromie acid. A. W. H o th e r s a ll and temp. of ferromagnetic transformation of the catalysts. R. A. F. Hammond (Trans. Faraday Soc., 1935, R. C. 3 1 , 1574—1582; cf. A., 1930, 1134).—The effeets Active oxides. CXII. Interaction between of Cr03 on cathode cfficiency, cathode potential, solid substances. G. F. Huttig [with T. Meyer, rate of gas discharge, and appearance of deposits H. Kittel, and S. Cassirer] (Z. anorg. Chem., in the deposition of Ni from a NiS04 bath containing 1935, 224, 225—252; cf., this vol., 1204).—The cata H3B03 and KC1 have been studied. The results lytic activity towards N20 decomp. of Cu0-Fe203 suggest that at Iow [Cr03] initial depolarisation and Cu0-Cr203, the magnetic susceptibility, bulk leads to pptn. of basie Ni compounds containing Cr, d. and colour of Fe203-Cr203, Fe203-Al203, Fe203- with resulting decrease of [Ni“], increased discharge S i02, Fe203-T i0 2, Cr20 3-T i0 2, Ct20 3-A120 3, and of H‘, and reduced cathode efficiency. At higher Cr20 3-S i0 2, and the rate of sorption of H 20 by [Cr03] chemical interaction with the cathode metal Mg0-Fe203, Be0-Fe203, Zn0-Fe203, Al203-Fe203, leads to the formation of a selectively permeable Zn0-Cr203, and Cu O-ALĄ have been measured and film and consequent complete inhibition of Ni de are discussed. The relationship between H20 sorption, position. F. L. U. 1468 BRITISH CHEMICAL ABSTRACTS.— A. Concentrated copper cyanide plating baths.— grains in the H-particle track was of the same order See B., 1935, 997. as that in an a-particle track. H. J. E. Copper plating of iron.—See B., 1935, 1050. Simple method for determining the colour Electrodeposition of zinc from acid solutions. temperature of flashlights. J. A. M. v a n Liempt and J. A. d e Y riend (Z. wiss. Phot., 1935, 34, 237— —See B., 1935, 1051. 240).—A colour chart (cf. Phot. Ind., 1930, 23, 629) Electrocłiemical purification of phosplioric was photographed by the flashlight on to panchrom- acid.—See B., 1935, 1042. atic plates, and the result compared with sources of Preparation of litharge by electrolysis.—See known colour temp. (C-filament, vac., gas-filled, and B., 1935, 1043. are lamps). The val. for “ Photoflux ” flashlight [Al-Mg alloy (5— 10% Mg) wire burning in pure 0 2], Preparation of potassium persulpbate by elec as also for Mg or Al foil burning in 0 2, was estimated trolysis.—See B., 1935, 1042. to be about 4000° abs. J. L. Electrolytic reduction of nitro-compounds.— Case of negative photocatalysis. J. M ilb a u e r See B., 1935, 984. (Phot. Korr., 1935, 71, 94—95).—The action of photo Inversion of solutions of sucrose in contact graphic desensitisers on the photochemical decomp. with regions traversed by an electric current. of “ Aktivin ” (Na £>-toluenesulpłioncliloroamide) in P. F a b re (Compt. rend. Soc. Biol., 1935, 120, 179— MeOH solution has been studied. Nile-blue, brilliant- 181).—Sucrose solution in both compartments of a green, Capri-blue, phenosafranine, fuchsin, and pina- Danieli celi vessel is iiwerted by passing an electric kryptol-green are negative catalysts. Malachite-green current througli the entire vessel. R. N. C. had 110 effect. Pinakrjrptol-yellow and methylene- Electrolytic preparation of nitrosonaphthols. blue are positive catalysts, oven in the darli. J. L. —Sec B., 1935, 1036. Free radicals in pliotodissociation of gaseous Photo-oxidation of hydrogen and deuterium metal alkyls. N. Prileshaeva and A. Terenin iodides. G. A. Cook and J. R. Bates (J. Amer. (Trans. Faraday Soc., 1935, 31, 1483—14S7; cf. A., Chem. Soc:, 1935, 57, 1775—1778).—The reaction 1935, 1052).-—The decomp. of COMe2, HgMe2, and of HI or DI with 02 at 0° under the influence of a PbEt4 vapours at Iow pressure by ultra-violet light low-voltage Hg-A lamp has been followed by pressure has been studied by photometric determination of the measurements and analysis of the products. The progressive thinning of films of Sb under attack by reaction between H and Ó3 is a 3-body process. The the free radicals produced. , F. L. U. results are: &„+Oi+M/&H + HI==(2-ll± 0-29)xl03 c.c. Primary photochemical reactions. VII. per mol.; &j,.j.Oj.i.jr/&i>.f:i)i=(3'P8±0'/5)x 10~^ c.c. Photochemical decomposition of ?sovaleralde- per mol.; fc,I + 0 +0lSfcD+0 +0 ^ -]'2x l 014 cm.2 mol.-2 hyde and di-n-propyl ketone. C. H. Bamford sec.-1 E. S. H. and R. G. W. N o rrish (J.C.S., 1935, 1504— 1511).— Use of the ortho-para-hydrogen conversion in The proportions of the products of decomp. in the fuli the detection of free radicals produced in photo- light of the Hg lamp correspond with the following dissociation. W. W est (J. Amer. Chem. Soc., 1935, primary processes: (i) Bu^CHO (I)-> iso-C4H10+CO 57, 1931— 1934).—Conversion is produced by Mel (47%) and (I) -> C3Hfi+MeCHO (53%) and (ii) COPr“2 (II) -> CgH14+CO (37%) and (II) -> C2II4+ or COMe2 vapour illuminated by radiation offreąuency in their continuous absorption regions, but not by COMePr (63%). The products containing ICO are propaldchyde or C6H6. The results indicate the further decomposed photochemically. Two types of primary photochemical change are distinguished in production of paramagnetic free radicals on illumin- ating Mel or COMe2. E. S. H. carbonyl compounds. In type (i) CO is eliminated and a saturated hydrocarbon is produced, and in Fhotolysis of azomethane. G. S. F orbes, L. J. type (ii) there is a rupture between the a- and [3-C of Heidt, and D. V. Sickman (J. Amer. Chem. Soc., the hydrocarbon chain, producing an olefine and a 1935, 57, 1935— 193S).—Quantum yields, independent of [Br'] or [I'] from 1-0—0-01 millimole electron diffraction. The film on Cu, formed at room per-litre. At higher [KI] free I is formed. No effect temp. and 100° in air, and a t 183° in 0 2 a t atm . was found with Cl'. H. J. E. pressure, consists of ordinary cubic-structure Cu20, Oxidation of ferrocyanide, arsenite, and selen- with a (111) piane parallel to the polislied metal ite ions by irradiation of their aqueous solutions surface; there was no indication of CuO. A Cu-Zn with X-rays. H. Fricke and E. J. H art (J. Chem. brass containing 70% Cu oxidised at temp. >183° Physics, 1935, 3, 596).—The [Fe(CN)fJ"" was acquires a Cu20 film; at 400° the film is ZnO. Al oxidisecl to [Fe(CN)0]'", an equiv. amount of H2 being brasses (22% Zn, 2% Al) show Cu20 after oxidation at liberated. The no. of equivs. oxidised was inde 183° for 10 m in.; at 400° ZnO is present. A120 3 was not pendent of concn. (0-1— 100 millimoles per 1000 c.c.) found. Mg and Mg alloys, oxidised a t 400°, acquire a and of p n (2-0—11-0). A s03"' and Se03" gave A s04"' film of cubic MgO. The orientation of oxide films on and Se04" togetlier with an equiv. amount of II,. polished surfaces is discussed; it is probable that the II. J. E. piane in the oxide having the highest density of metal Kinetic interpretation of the colouring of glass atoms per unit area tends to lie on the polished by A'-rays. R. Liyingston and C. E. Nurnberger surface. N. M. B. (J. Physical Chem., 1935, 39, 1011— 1019).—The rate Influence of temperature on the formation of of colouring of Pyrex glass by irradiation with hard additive compounds. M. Ragno and L. Vadala X-rays, and the distribution of relative absorption (Gazzetta, 1935, 65, 686—689; cf. this vol., 182).— of the coloured glass as a function of X for visible From solutions of Cu salts in C3H5N, which have been light, have been iiftrestigated. The analogous effeets kept at 70—80° for several hr., thero crystallise out of Rn are discussed. E. S. II. compounds which contain fewer mols. of C5H5N per Ring deposits on glass by positive-ray bom- mol. of Cu salt than the corresponding compounds bardm ent. B. DasannIcharya, V. T. Chiplon- which are obtained at lower temp. O. J. W. k a r, and L. G. S a tre (Naturę, 1935, 136, 642).— Reaction between calcium hydride and water. Brown rings are formed. L. S. T. H. Flood (Kong. Norske Vid. Selsk. For., 1934, 7, Chemical action of penetrating radium radi- 66—69; Chem. Zentr., 1935, i, 1516).—The prim ary ations. XX. Action on aqueous solutions of reaction between CaH2 and 11,0 is to give CaO, but glycerol, isobutyl and ethyl alcohols, and benzene. at Iow temp. < 2 mols. of H 2 per mol. of CaH2 is A. K a ila n (Sitzungsber. Akad. Wiśs. Wien, 1934, IIo, evolved, owing to the Iow v.p. of Ca(OH)2. Above 143, 163— 174; Chem. Zentr., 1935, i, 1968—1969). 350° reaction proceeds directly to CaO, and the —Prolonged action of Ra radiation, filtered through drying effect of CaH, is most intensive. J. S. A. 1 mm. of glass, on aq. glycerol and EtOH pro- Calcium chloroarsenate. C. M. Smith (J. Wash duced AcOII and some HC02H, + aldehyde. With ington Acad. Sci., 1935, 25, 435—436).—The com aq. Bu^OH, non-volatile acids resultcd. The effect pound (CaCl)2HA s04,2H.,0 has been prepared by is ascribed to H202 produced from the H20 by the addition of CaHAs04,H20 to aq. CaCl,. R. S. action of the radiation. Cr,HG was unaffected. Hydrates of monocalcium silicate. J. L e fo l J. S. A. (Compt. rend., 1935, 201, 669—672).—V.-p. and Preparation of deuterium.—See this vol., 1407. deliydration measurements proved the existence of the Concentration of heavy isotopes in cellulose. hvdrates Si02,l-2Ca0,2H,0 and Si0,,l-2Ca0,H,0. K. Okabe and T. Titani (Buli. Chem. Soc. Japan, H. J. E. 1935, 10, 465—466).—Purified H20 prepared by Formation of barium aluminates from barium burning filter-paper, cotton-wool, cedar wood, and carbonate and alumina in the solid state. G. bamboo is 6-3, 5-7, 4-5, and 4-4 p.p.m., respectively, G rube and G. H e in tz (Z. Elektrochem., 1935, 41, heavier than normal, owing to concn. of D. Purified 797—804).—At 900— 1050° the sole reaction product H20 from the skin, internal solid, and juice of a bam is Ba0,Al20 3, independently of which of the reagents is boo shoot is 4-4, 0-6, and 1-0 p.p.m., respectively, in exeess. At higher temp. 2Ba0,Al203 is formed; lieavier than normal; the concn. is not due to the the equilibrium conditions have been determined. rapid growth, but is a generał effect with carbo- E. S. H. hydrates. R. S. B. Complex salts of mercury cyanide. R. U zel Chemilununescence of 3-aminophthalhydraz- (Lekarn., 1934, 14, 335—343; Chem. Zentr., 1935, iae. L. H arris and A. S. Parker (J. Amer. Chem. i, 1353).—Salts of Cu, Ni, Zn, and Cd in aq. NH3 Soc., 1935, 57, 1939— 1942).— Under conditions of solution react with Hg(CN)2+excess of I', Br', CNS', max. light intensity the quantum efficiency of the or N3' to give complex salts of the generał type, oxidation of the Na salt of 3-aminophthalhydrazide is [M(NH3)4][(CN)2Hg<|>H g(CN )2], The fołlowing about 0-3%. There is evidcnce of compound form ation with H202. E. S. H. compounds were obtained : [Cu(NH3)4][Hg(CN),X],; Oxidation of metals. II. Copper, brass, [Cd(NH3)4][Hg(CN)2X]2; [Ni(NH3)4][Hg(CN)2X]3 (X aluminium-brass, aluminium-bronze, magnes- =1, Br, CNS, or N3); [Zn(NH3)4][Hg(CN)2Y]2 (Y =I, ium, and some magnesium alloys. G. D. P re s Br, or CNS). J . S. A. to n and L. L. B ircum shaw (Phil. Mag., 1935, [vii], Ammonium mercury sulphites. Potentio- 20, 706—720).—Investigations were made at temp. metric investigations. G. Spacu and C. Dragu- >400°, and the naturę, crystal structure, and le sc u (Z. anorg. Chem., 1935, 224, 273—279; cf. A., orientation of the oxide film were determined by 1932, 1216).—Potentiometric titration of aq. HgCl2 5 e 1470 BRITISH CHEMICAL ABSTRACTS.— A. with aq. (NH4)2S03 confirms the existence of df'° 2-317, and solubility in CHC13 (S ) 0-099 g. per (HgCl(S03)]NH4 and [Hg(S03)2](NH4)2, which were 100 g. Heating (I) for not too long a t 350—600° isolated as stable, cryst. compounds. The substance yields a cryst. yariety, d f'Cj 2-195, which has not been 3HgCl2,2(NH4)2S03, is probably a mixture. obtained pure, but is contaminated with a vitreous T. G. P. form which is the sole product when (I) is heated at Alkali aluminium silicates. IX. Silicate 450° for 3 weeks. This latter is the stable form, and component of ultramarine. E. Gru n er (Z. anorg. has d ? 9 2-737, S 0-0015 wt.-% . F. L. U. Chem., 1935, 224, 351—368; cf. this vol., 168).— Repeated fusion with KON completely removes S Formuła of sodium antimonate. L. A. V asi- from ultramarines (I). KCNS and K2SX are formed le v a (Trans. Butlerov Inst. Chem. Tech., 1934, No. in the earlier, and KCNS and IC2S in the later, fusions. 2, 41—49).—Dissociation vals. agree with Tomula’s The residue has the composition KAlSi04. The lattice results (A., 1922, ii, 74), showing the formuła to be of (I) with the ratio Ale : SiG remains unchanged, but NaSb03 and not Na2H2Sb207. Cu. Abs. (e) that of (I) with higher proportions of Si is modified by Reactions with oxygen. A. H. B elin fa n te the fusion. Jaeger’s determinations of the dimensions (Chem. Weekblad, 1935, 32, 611—615).—Theoretical. of the unit celi have been confirmed and extended. A The different types of reaction involving direct oxid- scheme showing relations between permutites, zeolites, ation by 02 are briefly reviewed. D. R. D. nephelite, and kaolin is given. F. L. U. Purification of gallium by fractional crystall- Reaction of sulphur with water at temper- isation of the metal. J. I. H offman and B. F. atures below 100°, and its geochemical signific- Scribner (J. Res. Nat. Bur. Stand., 1935, 15, 205— ance. E. Ch erbuliez and R. W eib el (Arch. Sci. 209).—If impure Ga is fractionally crystallised under phys. nat., 1935, [v], 17, Suppl., S7—88).—Ap- aq. HG1, Ag, Hg, In, Pb, and Sn are conc. in the molten preciable quantities of H2S and of S203" were de- residue, Cu and Tl remain about eąually divided be tected after boiling S with SO, buffered at p n 7-—6-1 tween crystals and residue, Zn is dissolved by the for 24lir. : 3S+2H20 ^ 2 H 2S+S02; S02+H20 ^= HC1, whilst Sb, Bi, Cr, Co, Cb, Au, Fe, Mn, Mo, Ni, H 2S0 3; H 2S0 3+ S ==±=H2S203. The presence of Os, Pd, Pt, Rd, Ru, and V concentrate in the crystals. H2S and S203" in minerał waters is explained in this It is impossible to separate Ga from > 0 001% Fe or way, tliese waters being huffered by H carbonates. Pt, from > 0 01% In or Pb, or from > 0-02% Sn S. J. G. by fractional crystallisation. J. W. S. Action of hydrogen sulphide on the chromates of hydrogen, ammonium, sodium, and potass- Mixed polyhalides of titanium. G. P. L ut- ium . M. A. Hamid, G. Singh, and H. B. Dunni- sch in sk i [with A. I. Lichatscheva] (Z. anorg. Clicm., cliff (J. Indian Chem. Soc., 1935, 12, 595— 600; 1935, 224, 420—426).—F.-p.-eomposition curveshave cf. A., 1932, 133).—In the action of H 2S on solutions been determined for mixtures of TiCl4 and Br. The of (NH4)2Cr20 7, of K 2Cr20 7, and of H 2Cr04 the form- existence of compounds, TiCl4Br (I) and TiCl4Br4 (II) ation of S04” is favoured by increased temp. at the is established. Eutcctics are formed from TiCl4 and expense of S203". Formation of S04" is suppressed (I), (I) and (II), and (II) and Br. Br is completely by an alkaline medium. Analyses of the products eliminated from (I) and (II) by the action of heat or of the reaction of H2S with (ŃH4)2Cr20 7 and with of HoO. F. L. U. (NH4)2Cr04 solutions under varying conditions are Extraction of germanium and gallium from recorded. O. J. W. germanite. I. Removal of germanium by dis- Action of hydrogen sulphide on insoluble tillation of germanous sulphide. W. C. J ohnson, chromates. I. Lead chromate and silver Ł. S. F oster, and C. A. Kraus. II. Acid extrac- chrom ate. H. B. D u n n ic liff and B. P rakash tion of germ anium . L. S. F oster, W. C. J ohnson, (J. Indian Chem. Soc., 1935, 12, 505—513).—Treat- and C. A. K raus (J. Amer. Chem. Soc., 1935, 57, ment of a suspension of PbCr04 with H2S leads to 1828— 1831, 1831—1835).—I. Finely-ground german- ite is heated in a stream of dry N2 at 800° to remove 90—95% attack with production of PbS~ Cr2(S04)3, Cr2(S203)3 (partly co-ordinated), and Cr(OH)3, to As.,S3 and S. N H 3 is passed over the residue at 825°, gę ther with some S, probably due to oxidation of when GeS2 is reduced to GeS, which distils and is collected. 99% of the original Ge is thus removed. H2S by atm. 02. • The reaction occurs much more rapidly at higher temp., but with less tendency II. Ga is obtained from the residue of the above to form Cr2(S203)3. No II2SO;i or thionic acids are process by boiling with HC1, pptg. sulphides of heavy formed. Ag2Cr04 under similar conditions yields metals, and separating Ga and Al from large ąuantities of Fe and Zn by boiling the solution with NH4HS03, Ag2S, Cr2(S04)3, Cr2(S03)3, Cr2(S203)3 and S. leaving Fe and Zn in solution. Al is separated as J . W. s. Preparation of phosphorescent substances. A1C13,6H20 from a HCl-saturated Et20-H 20 mixture in which Ga and traces of Fe remain dissolved. After IX. Ar-Ray luminophores. N. F. Sh iro y , T. E. removing the remaining Fe, Ga is pptd. as hydrated Getm an, and E. J. Matenko (J. Appl. Chem. Russ., oxide; the metal is obtained by electrolysis of a solu 1935, 8 , 848—863).—The X -ray luminescence of tion of the oxide in aq. KOH. E. S. H. the following rises in the order U02F,4NaF < U02F2,4KF < UO,F2,4NH4F < BaPt(CN)4 < Allotropy of phosphoric oxide. A. N. Camp Zn2Si04. Directions for the prep. of these substances b e l l and A. J. R. C am pbell (Trans. Faraday Soc., are given, and the theoretical aspect of the problem 1935, 31, 1567— 1574).—Amorphous P20 5 (I) has of J£-ray luminophores is discussed. R. T. GENERAL, PHYSICAL, AND INORGANIO CHEMISTRY. 1471 Triple sulphates containing water. B. Goss- Bromo-salts of tervalent iridium. (Mme.) M. n e r and J. B esslein (Zentr. Min., 1934, A, 358— D e l e p in e -Tard (Ann. Chim., 1935, [xi], 4, 282— 364; Chem. Zentr., 1935, i, 1352).—A series of 291; cf. this vol., 868).—The following compounds are sulphates analogóus to voltaite has been prepared, deseribed : KJIrBrJ^HaO ; K2[Ir(H20)Br]5],H20 ; having the generał formuła Fe"‘M"M'(S04)3,4H20, Rb3[IrBr6],H20 ; Rb2[Ir(H20)Br5]; Cs3[IrBrR],HoO; in which Fe is partly replaced by Al. The Zn K, Cs5Ir3Br14,2H20. " F. L. U. Co N H 4, Co Rb, and Mg Rb compounds are deseribed. Double ammines of platinum. G. Spacu and Mn forms with Li and Na compounds of type V. A rmeanu (Bul. Soc. ętiin^e Cluj, 1934, 7, 610— FeMn4M(S04)6,8H20, either with or without partia! 617; Chem. Zentr., 1935, i, 1354).—The following replacement of Fe by Al. J. S. A. compounds are deseribed : [Cu en2][Pt(SCN)G]; [Co(NH3)8][Pt(SCN)6]Cl; Effect of dehydrated product on the conrse of [Co(NH3)0]2[Pt(SeCN)G]3,6H 2O; dehydration. S. S kramoysky (Lekarn., 1934, 14, [Co en3]2[Pt(SeCN)G]3; [Ni en3][Pt(SeCN)6]. 317—322; Chem. Zentr., 1935, i, 1331).—CoSO^O J. S. A. and 7H20 dehydrate a t 60—80° to a product with Spectrum analysis. H. D in g le (Naturę, 1935, 1-5H20.~ Addition of dehydrated salt inereases the 136, 684— 685).—Definitions are discussed. rate of dehydration, and brings about initial form L. S. T. ation of tetrahydrate, which then deliydrates further. Sensitivity of chemical analysis with AVrays. J. S. A. I. Emission methods. II. Absorption methods. Complex ammines of tervalent metals. H. L. Mazza (Gazzetta, 1935, 65, 724—730, 730— B rintzin g er and H. Osswald (Z. anorg. Chem., 734).—I. The use of X-ray emission spectra in 1935, 224, 280—282; cf. this vol., 1091).—Mol. chemical analysis is discussed with particular reference Wts. of [Co(NH3)4(H20)2P +, [Co(NH3)4S20 3]+, to the rare-earth elements. In the K spectra it is [Co(NH3)4F21+, [Co en3F , [Cr(NH3)6]t, and possible to detect 1 : 1000, in the L spectra 1 : 25,000 [Ci'(NH3)4H20'Cl]21' have been determined by di- parts of an element in a mixture. With elements alysis. The triethylenediamine cobaltic ion is in the metalhc state the sensitivity can be extended dimeric; the remainder are normal. T. G. P. to 1 : 50,000. II. In absorption methods the sensitivity is Complex compounds of which the central ion greatly dependent on the at. no. of the element is [itself] a complex cation. II. Complex sul- which has to be detected. This practically limits phato- and oxalato-compounds with complex the method to the detection of heavy elements in cobalt cations as central ions. H. Br in tzin g er presence of lighter ones. O. J. W. and H. Osswald (Z. anorg. Chem., 1935, 224, 283— 288; cf. preceding abs.).—The following ions have Rapid determination of water in smali quan- been identified by mol. wt. determinations : tities of materiał. J. E rdos (Mikrochem., 1935, [[Co en3]2(S04)4]2-, [[Co(NH3]5N0 3](S04)4]«-, 18, 256—260).—The sample is distilled with xylene [[Co(NH3)4F2](S04)4]7-, [[Co(NH3)4S03](S04)4]7-, and the distillate centrifuged in a calibrated tube in [[Co(NH3)4S20 3](S04)4]7-, [[Co2(NH3)10O2](SO4)4]4-, which the H20 is measured. The % of H20 obtained [[Co2(NH3)10(H2O)1rO2](SO4)4]3-, [[Co en3]2(C20 4)4]2-, after suitable corrections is < that obtained by the [[Co(NH3)5N0 3](C20 4)4]6-, [[Co(NH3)4Ą](C20, drying method. R. S. [[Co(NH3)4S03](C20 4)4]7-, [[Co(NH3)4S20 3](C20 4)4]7-, Conductometric determination of water in [[Co2(NH3)10O2](C2O4)44-, acetone.—See B., 1935, 1036. [[Co2(NH3)10(H2O)18O2](C2O4)4] ^ p Determination of chloride with adsorption Composition and properties of precipitated indicators. F. H. C. K elly (J. Proc. Austral. Chem. nickel and cobalt sulphides. I. A. W. M id d l e - Inst., 1935, 2, 250—254).—A review. The addition of 1% starch solution as protective colloid is ad- ton and A. M. W ard (J.C.S., 1935, 1459—1466).— The ppts. obtained from aq. solutions of the salts Yantageous. J. S. A. by means of H2S in the absence of 0 2 are probably Determination of the chlorate content of Ni(SH)2, Co(SH)2, and Co(SH)3. In generał, the potassium and sodium chlorates.—See B., 1935, ratios óf combined S to metal in the ppts. dried in 990. N2 slightly exceed the vals. reąuired by the formulse Determination of residual chlorine [in water]. NiS, CoS, and Co2S3. The undried sulphides dissolve —See B., 1935, 1024. rapidly and extensively in 2A7-HC1 (but age to less sol. forms) and H2S is evolved, but Co"' changes a-Naphthoflavone as a reversible bromometric into Co", leading to partial oxidation and lower indicator. R. U zel (Coli. Czech. Chem. Comm., solubility. With aq. and C6HB solutions in presence 1935, 7, 380—387).—Colloidal a-naphthoflavone _ (I) of 0 2, the sulphide ppts. contain combined S exceed- forms reversibly an orange adsorption compound with ing the at. ratios corresponding with the simple free Br in solution. The indicator, 0-5—1 ml. of formuła) and, in generał, somewhat greater at. ratios 0-1% (I) in EtOH or AcOH added to 50—100 ml. of H and O. Drying removes H20 and H2S and may of solution, is used with KBr03 in determining, in cause further oxidation. The portions of these HC1 solution, As111, Sb111, Sb in tartar emetic, Sn11, sulphides sol. in acids afford S04", and only traces N2H4, NH2P1i, and NHPhAc after boiling with of H2S are produced. The dry sulphides are slowly 20**% aq. HC1, diluting and adding Br'. Fe11, Tl1, oxidised to sulphates in the air. J. G. A. G. finely-divided Hg, Hg1, PhOH, and saliejdie acid 1472 BRITISH CHEMICAL ABSTRACTS.----A. gave unsatisfactory results. When Br' is titrated so as to impart an oscillatory motion to the liąuid with AgN03 in presence of 1—2 drops of 0-lAT-KBr03 in the U, when a black ppt. is formed on the wali. and 1 c.c. of 0-1% (I), the end-pointis orange -> green. 4 KlO"4 mg. P and 6 x l0 -5 mg. PH3 can be detected Smali proportions of Cl' do not interfere. when a capillary of 0-83 mm. diameter is used. J. G. A. G. R. S. Micro-determination of iodine in common Elimination of phosphoric, oxalic, fluoride, salt.—Sec B., 1935, 990. silicate, and silicofluoride ions in group III. Determination of fluorine in potable waters.— S. Atjgusti (Annali Chim. Appli, 1935, 25, 448— Sec B„ 1935, 1024. 451).—The method is based on the pptn. of these anions as Pb salts by treating with Pb(OAc)2 in AcOH Colorimetric determination of dissolved oxy- solution. T. H. P. gen [in water].—See B., 1935, 1072. Determination of arsenie and phosphoric acids Determination of atmospheric ozone. Com- and iron in presence of one another. G. B ala- parison of spectrographic and chemical methods. nescu and V. I onescu (Buli. Soc. Chim. Romania, A. D auyillier (Compt. rend., 1935, 201, 679— 1935,17, 93—102).—The As is pptd. by H,S and P 0 4ł" 680).—The two methods gave approx. the same obtained as molybdate, whilst Fe"’ is determined mean vals. (4-1, 3-3 mg. of 0 3 per cu. m. of air, re- iodometrically after evaporation and treatment with spectively). H. J. E. HN03. As is obtained more accurately if titrated Determination of stibnite-sulphur in ores and iodometrically with the Fe"' and determined by m inerals.—See B., 1935, 1049. difference. R. S. Volumetric determination of sulphate and Step-photometric determination of silicie acid barium ions. Y. N. S kvortzov (Trans. Butlerov and its application to water and minerał water. Inst, Chem. Tech., 1934, No. 1, 164— 167).—S O /' R. Strohecker, R. Yaubel, and K. B r eitw ieser is titrated with BaCl2 in a buffered solution containing (Z. anal. Chem., 1935,103, 1—12).—50 c.c. of H 20 are Cr04". To determine Ba” an excess of standard treated with H2S04 and 2 c.c. of 10% aq. (NH4)2Mo04. HoS04 is added before titrating with BaCl2. The ycllow NH4 silicomolybdate (I) formed is de Ch .“Ab s. (e) termined by comparison with aq. picric acid (II) or Use of lead nitrate as precipitant in the titri- aq. K2Ct04 (III) in filtered blue light us}ng the step metric determination of certain ions. A. R inc;- pliotometer. Fe and PO,,"' must be removed by boji (Acta Acad. Aboensis, Matli. Phys., 1934, pptn. with Na2HP04+CaCl2+CaC03. Solutions of 8, No. 5, 142 pp.).—The potential of a Pt clectrode (I) with >10 mg. of Si per litre deviate from Bell’s in a solution of Pb2Fe(CN)6 containing a smali const. law. (II) and (III) behave similarly in the same region [Fe(CN)6]"' changes when an excess of Pb(N03)2 of colour intensity. At Iow [Si02], the intensity of is added. Using this electrode, S04" may be titrated Mo-blue formed by reduction of (I) is > corresponds in 0-025AT-Pb(N03)2 solutions in presence of moderate with [Si02]. J. S. A. amounts of neutral salts. In more dii. solutions, Micro-analysis of silicates. I. Determin or with large amounts of neutral salts, the end- ation of silicie acid. K. Schoklitsch (Mikrochem., point is improved by adding EtOH. Carbonate may 1935, 18, 144—153).—The indirect method, using be titrated with Pb(N03)2 by adding excess of pre H F (A., 1933, 687), has been adapted for micro- cipitant and titrating back, or by nsing hot solutions. determinations. Correction must be made for the S03" may be titrated at p n > 6. Cr04" cannot be loss of HP03 during the fusion. R. S. titrated. Tungstate and molybdate can be titrated in presence of a moderate concn. of neutral salt. Rapid test for silica in hydrogen peroxide Pb(N03)2 may be titrated with Na2C03 (phenol-red solutions.—See B., 1935, 1043. indicator). Oxalate may be titrated at an initial Sensitive test for non-metallic impurities in p a of 8—8-5 (phenol-red). For S04" the initial m etals.—See B., 1935, 1051. p a should be 9—9-5 (bromocresol-purple). The same Micro-determination of hydrogen cyanide. indicator is also used for S03" and Cr04". With M. T. F rancois and M. N. L affitte (Buli. Soc. Chim. tungstate the initial p a should be 8-5—9 (bromo- biol., 1935, 17, 1088—1096).—A method employing tliymol- or bromocresol-blue). Phenol-red is suitable “ picro-soda ” paper for the determination of 2 x 10-6— for molybdate. Ch. Ab s . (e) 1 X10-5 g. HCN is described. EtOH, oil, and starch Detection of the use of azides in the prepar- do not interfere. A. L. ation of electron tubes. H. F eitz (Mikrochem., Dipicrylamine as a micro-reagent for potass- 1935, 18, 162— 168; cf. this vol., 837).—The total N ium, rubidium, and cassium. C. J . van N ie u - content of the mirror gives an indication of the amount w enburg and T. yan der H oeck (Mikrochem., of azide used. A further test is the appearance 1935, 18, 175—178).—Cs can be distinguished from of'a permanent brown coloration when the mirror K and Rb by recrystallising the dipicrylaminate in is heated, owing to the presence of Ba etc. R. S. presence of glycerol. Photomicrographs are given. Detection of very smali amounts of phosphorus R. S. and phosphine. L. W olf, W . D usin g , and A. Gravimetric micro-determination of potass- Martos (Mikrochem., 1935, 18, 185—192).— Gas ium in presence of sodium by chloroplatinic acid. containing P or PH3 is passed through a capillary P. W en g er, C. Cimerman, and C. J . R zymowska tube inunersed in 1% AgNOs in aq. NH3 and having (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., 89—93).— the lower end turned up. The gas stream is adjusted Details are given for the determination of K" in GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1473 presence of 50 times as much Na' by converting into glass wool saturated with 20% KI. For the deter perchlorates and pptg. as K2PtClG. S. J. G. mination of Mg in biological materiał dry ashing in a mufiłe and the removal of Fe by the Alten method Triple nitrites of the rare earths and a new (A., 1933,1262) arerecommended. H. D. micro-test for cassium. H. C. Gos wami and P. B. Sarkar (J. Indian Chem. Soc., 1935,12, 608—610).— Determination of smali quantities of magnes By crystallising a mixture of aq. solutions of the rare- ium sulphate. M. Móller and G. Schlegel earth nitrate, NaN02, and CsN03, the following (Mikrochem., 1935, 18, 159—161).—The method of compounds have been prepared; Cs,CaCe(N02)G, repeated pptn. of MgS04 by Ba(OH)2 has been carried Cs2NaLa(N 02)G, Cs2NaPr(N 02)6, Cs2ŃaN d(N 02)6, out in an atin. of H2 using a special apparatus. Cs2NaSm(NÓ2)G, and Cs2NaGd(N02)G. A drop of R. S. a solution of Pr(N03)3 (3 g.) and NaN02 (10 g.) in Indirect volumetric determination of zinc. H20 (110 g.) yields octahedral crystals with a drop G. Spacu and C. G. Macarovici (Bul. Soc. ętiin^e of CsN03 solution. The test is not affected by Cluj, 1934, 8 , 129—139; Chem. Zentr., 1935, i, presence of K or Rb and its limit of sensitivity is 1422— 1423).—Zn is pptd. as [Zn(CNS)2(C5H 5N)4] 4 x 10~8 g. Cs. J. W. S. by addition of excess of 0-1iY-NH4CNŚ+C5H 5N. An aliquot part of the filtered solution is neutralised Determination of ammonium salts.—See B., (indicator: dinitrophenol), and excess of 0-lAr- 1935, 1043. AgN03 is added. The excess of Ag is then titrated Electrolytic determination of silver. F. F r ie d back with NII4CNS, using diphenylcarbazone as rich and S. R apoport (Mikrochein., 1935, 18, 227— indicator. J . S. A. 234).—Electrolysis is carried out in a micro-apparatus Micro-determination of zinc by anthranilic in presence of HoSO,, and tartaric acid, at 1-3—1-8 acid. C. Cimerman and P. W en g er (Arch. Sci. volts. " R.S. phys. nat., 1935, [v], 17, Suppl., 94—98).—To 2 c.c. Electrolytic drop analysis. I. Theoretical of solution a t p u 5-5—7 containing 1—3 mg. of Zn", principles. H. F ritz (Mikrochem., 1935,19, 6—16; freshly prepared Na anthranilate (I) is added drop- cf. A., 1929, 1414).—(a) Relatively noble metals wise, using 0-3 c.c. excess. After an intcrval the (e.g., Ag) in a drop of liquid may be detected by their ppt. is collected, washed once with 1—2 c.c. of 0-1% deposition on a strip of base metal {e.g., Cu). By (I) and 5 times with 1 c.c. of EtOH, dried a t 110°, absorption of the drop in filter-paper, the baser metals and weighed. An accuracy of ±0-3% is claimed. may then be detected as usual. (b) Electrolysis of Details of a second method are also given. a drop absorbed in filter-paper and carried on an S. J . G. insulating support avoids interference due to dis- Modification in the confirmatory test for zinc solution of the electrodes. J. S. A. ion. M. W. K elly and E. L. J ohnson (J. Chem. Educ., 1935, 12, 481—483).—Zn" ( be titrated with standard K2S04 solution, using (Buli. Soc. Chim. Romania, 1935,1 7 ,103— 105).—NH3 fluorescein as external indicator. The method can also must be removed by NaOH and the solution neutral- be applied to the determination of S04". O. J. W. ised with HN03 before titration. Aecurate results are Quantitative emission-spectrum analysis of obtained only when [Mo04"] > 0-002JV. R. S. lead and cadmium contained in zinc oxide.— Use of induced precipitation for detection of See B., 1935, 1043. smali amounts of titanium and zirconium. F. Identification of the copper ore minerals by F eig l and E. R ajmann (Mikrochem., 1935, 19, 60— means of X-ray powder diffraetion patterns. 63).—To a solution containing < 1 pt. of Ti in 50,000, a few drops of Zr solution are added, and Zr then pptd. A. W. W aldo (Amer. Min., 1935, 20, 575—597).— X-Ray data for 48 minerals are indexed in a form with H3As04. Ti is co-pptd. and may be detected which permits ready identification of the minerał from with H20 2 in the ppt. after dissolution in H2S04. The its X-ray diffraetion lines. L. S. T. sensitivity is lowered in presence of Fe, V, W, or Mo. Conversely, Ti may be added to a Zr solution, co- Determination of mercury. S. A ugusti (Gaz- pptg. Zr, which is detected with azoarsinie acid. zetta, 1935, 65, 689—693).—To a solution of the Hgu J. S. A. salt an ammoniacal solution of K2Cr04 is added, gm ng Determination of vanadium in the field. V. A. a ppt. of (Hg,N)2Cr04,2H20. When this is dissolved Silbermintz and K. P. F lorenzki (Mikrochem., 1935, in a solution of KI or of Na2S203, for every atom of 18, 154— 158).—A spot method depending on the Hg, 2 mols. of NaOH, which can be titrated with a oxidation of NH2P1i is used. HC1 and H 3P 0 4 are standard acid solution, are liberated. The complete added when Fe is present. R. S. determination reąuires 40—50 min. 0. J. W. Relation between sensitivity and mol. wt. Determination of mercury in iodinated organie (Weighting effect.) P. K rumholz and H. W atzek mercury compounds.—Sec B., 1935, 1068. (Mikrochem., 1935, 19, 55—59).—The sensitivity of Microchemicalcontributions. XII. L. R osen- cyclic N bases as preeipitants for HBiI4 is raised by tiialer (Mikrochem., 1935, 19, 17—22; cf. A., 1934, progressive weighting of tho ring system, by replace- 791).—Yellow, but not red, HgO reaets with NH3, aq. m ent of S by Se, or by conversion into the correspond NallSOg, and aq. KHS04. VanilUn gives charaeter- ing ethiodide. J. S. A. istic eryst. ppts. with Ba(0H)2 and MgS04+N’H4Cl. Micro-determination of bismuth as oxyiodide. Phenols give sensitive, in some cases eryst., orange to F. H echt and R. R eissner (Mikrochem., 1935, 18, red ppts. with p -diazonitroani 1 ine. Phloroglucinol and 283—288).—The method (A., 1928, 388) is inexact. pyrocatechol give characteristic ppts. with Zwikker’s R. S. Cu-C5H5N reagent. Prontosil gives characteristic Micro-analytical determination of platinum ppts. with [Co(N03)4(NH3)2]K, AgN03, HgN03, metals in simple and complex salts. J. Mey er Cu(OAc)2, and antliraquinone-l-sulphonic acid. and K. H oeiinb (Mikrochem., 1935, 19, 64—71).—P t J. S. A. may be determined by cautious ignition in air. Rh, Volumetric determination of aluminium, p a Ir, Ru, and Pd salts may be ashed in air and finally > 10. V. N. S kyortzoy (Trans. Butlerov Inst. reduced in H 2. Only with Pd is cooling in C02 Chem. Tech., 1934, No. 1, 156— 164).—Results in the essential. Os salts must not be lieated in air. Au determination of Al by titration with KOH with invariably gives losses due to volatilisation of Au malachite-green as indicator depend on the temp., halides. The method is applicable only in the absence concn. of indicator, concn. of solutions, and absence of other metals. J . S. A. of C02. The method is untrustworthy. Ch . Ab s. (e) Water thermostat. (Mme.) S. L allemand (Buli. Quantitative separation of metals byhydrogen Soc. Chim. biol., 1935,17, 1470— 1471).—An arrange sulphide. VIII. Separation of aluminium from ment for maintaining a water-bath at a temp. < that iron, nickel, and cobalt. H. K ató (J. Chem. Soc. of the room is described. A. L. Japan, 1935, 56, 210—212; cf. this vol., 719).— FeS, Temperature measurement with photo-elec- NiS, and CoS are pptd. with H2S at a suitable j?H, tric cells. H. J. Zetzmann (Arch. tech. Mess., 1934, basie Al acetate being pptd. from the filtrate by boiling 4, T, 116— 117; Chem. Zentr., 1935, i, 1420).—Temp. with NaOAc. Ch . Ab s. (e) and very rapid fluctuations of temp. above 550° may Spectrophotometric determination of man- be measured by determining photo-electrically the ganese in steel.—See B., 1935, 1047. intensity of some definite filtered spectral region of the Mixed perchloric and sulphuric acids. III. emitted tliermal radiation. J. S. A. Determination of chromium in chromie oxide. Errors in the measurement of temperatures G. F. Sm ith , L. D. McY ick ers, and V. R. Sulliyan with thermocouples.—See B., 1935, 1025. (J.S.C.I., 1935, 54, 369—372t; cf. A., 1934, 982).— Thermocouple vacuum calorimeter [for deter The oxidation of Cr20 3 by HC104 alone is incomplete mining heats of adsorption]. W. E. Garner and mńng to the production of a smali amount of H202. F. J . Veal (J.C.S., 1935, 1436— 1443).—The factors Rapid cooling minimises this and quant. results may affecting the trustworthiness of several designs of be obtained with a mixture of 1 vol. of aq. HC104 thermocouple calorimeters for determining heats of (72%)+2 vols. of aq. H2S04 (80%). R. S. adsorption of gases on oxides, whereby the adsorbent Conductometric titration of molybdate with is placed in a glass vessel surrounded by a high vac., silver nitrate. C. Candea and I. G. M urgulescu have been investigated. Total heats of slow and GENERAL, PHYSICAL, AND INORGANIO CHEMISTRY. 1475 rapid adsorption processes and differential heats of New method of focussing in X -ray spectro- slow adsorption processes are determined accurately, graphy. V. K unzl (Compt. rend., 1935, 201, 656— but untrustworthy data for differential heats of rapid 658). H. J. E. processes may be obtained owing to uneyen distribu- Photographic measurement of intensities of tion of gas throughout the adsorbent and Iow grain spectral lines. E. W. Muller (Z. Physik, 1935, conductiyity ih the absence of sufficiently high mobilty 97, 97— 106).—A subjective method applicable to of the adsorbed mols. in the capillaries. J. G. A. G. comparison of heterochromatic lines is described. A. B. D. C. New optical method for the determination of Compensating photo-electric colorimeter.— elastic constants of crystals. C. Sch a efer and See B., 1935, 1001. L. B ergmann (Atti R. Accad. Lincei, 1935, [vi], 21, 701—702).—Examples are given of the diffraction Variable layer photo-electric comparison figures obtained when a beam of monochromatic light photometer. New type of photo-electric colori is passed through rapidly oscillating crystals of ąuartz m eter. A. Goudsohm idt, jun., and W. H. S ummer- and other substances. From a study of these figures son (J. Biol. Chem., 1935, 111, 421—433).—The light the elastic consts. of the crystal may be calc. beams, after passing through the tubes of the colori O. J. W. meter, fali on two photo-electric cells, arranged to Simple process for absolute calibration of give a differential defłexion on a galvanometer, used photo-cells. H. T h eissin g (Physikał. Z., 1935, 36, as a nuli instrument. A sensitiyity of about 0-5% is 683—684).—The Hefner lamp, of which the spectra! attained. F. A. A. energy distribution closely follows Wien’s law, is used [Colorimetric technique.] R. Vladesco (Compt. to obtain a calibration curve. A. J. M. rend. Soc. Biol., 1935, 120, 221—223),—For colori metric determinations in complex solutions, equal Standardisation of photo-electric cells for the vols. of the unknown solution are introduced into both measurement of visible light. H. H. P oole and colorimeter yessels, a known yol. of the standard is W. R. G.A tkins (Phil. Trans., 1935, A, 235,1—27).— added to one, and the concn. of the unknown deter Representative types of vac. emission and rectifier mined by difference. R. N. C. photo-electric cells have been standardised in light Colour analysis and specification. J. R azek from (a) open solid C arc, (b) vac. sub-standard fila- (Paper Trade J., 1935, 101; T.A .P.P.I. Sect., 187— ment lamp at 2360° abs., (c) artificial “ mean noon 191).—A generał outline of the spectrophotometric sunlight ” derived from the latter by interposing method of colour analysis is given, and the method of special filters. The cells were also compared in mixed reduction to trilinear co-ordinates in accordance with daylight. Consts. relating to 19 such cells are the procedure suggested by the International Com- recorded. E. S. H. mittee on Illumination is described. The significance Modified photographic method for substances of dominant X, colorimetric purity, and relative of smali rotatory dispersion. R. P adm anabhan brightness is discussed. In the case of white samples, (J. Indian Chem. Soc., 1935, 12, 559—565).—The it is possible from the co-ordinates to calculate the usual method is unsatisfactory for substances of degreo of whiteness in accordance with Judd’s which the optical actmty does not vary very much formuła (B., 1935, 719). H. A. H. with X, but by determining the rotatory dispersion of Errors in colorimetric determinations. R. such a substance in a column whicli also contains D olique (Buli. Soc. Chim. biol., 1935, 17, 1304— another substance of normal dispersive power and 1317).—Errors in colorimetric determinations are high initial rotation, e.g., ąuartz plates, better results attributed to the effeets of eye-strain. These effeets can be obtained. Measurements for p-pinene are are reduced to a min. by systematic movements of recorded. J. W. S. the plungers alternating with periods of rest. A. L. Gaseous discharge tube designed as an in- Microscopical methods for determining re- tense source of continuous ultra-violet radi fractive index by immersion. C. P. Saylor (J. ation. R. H. Munch (J. Amer. Chem. Soc., 1935, Res. N at. Bur. Stand., 1935, 15, 277—294).—The 57, 1863— 1865).—A low-voltage H 2 discharge tube, sensitiyity of the criterion of match, which limits the reąuiring no H20 cooling, is described. E. S. H. immersion method of determining n, has been studied as a function of the method, objective aperture, and Rapid measurement of optical absorption for size and shape of particie. Objectiyes of Iow numerical smali light intensities. M. von A r d e n n e and aperture lead to greater sensitiyity. The effect of E. H aas (Z. physikal. Chem., 1935, 174, 115— 121).— birefringenee has also been studied" J. W. S. The current from a photo-electric celi creates a p.d. in a coupling resistance which is amplified to work a Mass spectrometer. S. H. Ba u er (J. Physical pointer galranometer. By using a carrier frequency Chem., 1935, 39, 959—965).—The principles of a of ~20 hertz, produced by periodic cutting off of the simple instrument are discussed. E. S. H. incident light, it is possible to use an a.c. amplifier. Measurement of dielectric constants. A. Light intensities as Iow as 7 X10-11 g.-cal. per sec. may B uchner (Z. tech. Phys., 1935, 16, 10— 12; Chem. be measured in 1 sec. with an accuracy of ± 1 % . The Zentr., 1935, i, 1828—1829).—A valye circuit for method is suitable for measuring the absorption of dielectric const. measurements which permits the light in living cells by the pigments involved in O simultaneous determination of dielectric losses is transfer. R. C. described. J , S. A. 1476 BRITISH CHEMICAL ABSTRACTS.----A. Simultaneous determination of dielectric con- Pregl micro-analysis. J. U nterzaucher (Mikro stants and conductivity of conductors at high chem., 1935, 18, 312—315).—A stopcock on the inlet fretjuency (two-phase bridge). H. Gross and I. tube of the Mariotte fiask allows the experiment to be H ausser (Ann. Physik, 1935, [v], 24, 127—160).— interrupted without interfcring with the adjustment Apparatus for a new bridge method which allows tho of the gas flow. Carius tubes can be opened with determination at higli freąuency of the magnitude and the blowpipe flame, thus avoiding contamination angle of loss of a resistance without the use of com- of the materiał by glass. R. S. pensating resistances is described. A. J. M. Analysis of smali volumes of gas by means of Camera for electron diffraction. R . Morgan the usual micro-analytical apparatus. W. E. and N. Smith (Rev. Sci. Instr., 1935, [ii], 6, 316— B ruce (Mikrochem., 1935, 18, 261—265).:—The 319).—Fuli constructional details are given. Pregl combustion trainhas beenadapted to the analysis C. W. G. of smali vols. of gas obtained from B. aertrycke in Transmission photographs of single crystals syntlietic citrate medium. R. S. with fast electrons, and their use in structure Compact vacuum gauge for measuring pres determination. G. A m inoff and B. Broome (Z. sures from 0-2 mm. to 0-0001 mm. of mercury. Krist., 1935, 91, 77—94).—Apparatus and technique C. T. K n ip p (Trans. Illinois State Acad. Sci., 1935, for obtaining diffraction photographs with thin 27, 127—128).—A smali McLeod gauge, requiring crystal flakcs and also with thicker specimens are 10 c.c. of Hg, and connected to the apparatus by a discussed. B. W. R. ground joint, is described. Ch. A b s . (e) Micro-cell for the measurement of electrolytic Improved method of extraction. C. A. Mar- conductivities. A. F in k and P. Gross (Mikro- LIES and V. K. L aMe r (J. Amer. Chem. Soc., 1935, chom., 1935, 18, 169—174).—A celi having a vol. 57, 2008).—Extraction of a H20-sol. substance, of 0-45—0-8 c.c. is described. The equiv. conductivity e.g., NH2*N02, by EtaO is more complete and rapid of DCI in D20 is 250. R- S. if tlie H20 is frozen in solid C02. R. S. C. Applicability of conductometric methods with Dynamie methods for determination of visual observation to titrations in presence of Young’s modulus. J. M. I de (Rev. Sci. Instr., much indifferent electrolyte. G. J a n d er and A. 1935, [ii], 6 , 296—298).—The specimen is set in E bert (Z. Elektrochem., 1935, 41, 790—794).— vibration by electric traction and the frequeney With good apparatus and techniąue, satisfactory determined by the use of a piezo-electric deteetor. results can be obtained when a 500-fold excess of C. W. G. foreign electrolyte is present. E. S. H. Hydrogenation apparatus for smali quantities of materiał. J. E rdos (Mikrochem., 1935, 18, Antimony electrode for p n measurement. A. 305—308).—H2 is admitted to the catalyst before H olmquist (Z. Elektrochem., 1935,41, 807).—Aclaim addition of 0-5— 1 c.c. of the solution. The vol. for priority (cf. this vol., 1218). E. S. H. change is measured in a gas burette. R. S. [Antimony electrode for p a measurement.] High-vacuum micro-desiccator. J. U n t e r - P. WuLFFand W. K ordatzki (Z. Elektrochem., 1935, zaucher (Mikrochem., 1935, 18, 315—318).—The 41,807).—A reply (cf. preceding abstract). E. S. H. boat is containedin a stoppered vessel in the desiecator. Micro-analytical notes. I. Methods of deal- Hygroscopic substances can be weighed without contact with the atm. R. S. ing with smali quantities of liquids and pre- cipitates. B. L. Clarke and H. W. H ermance New methods of determining mol. wt. K. (Mikrochem., 1935, 18, 289—298).—Yarious micro- R ast (Chem.-Ztg., 1935, 59, 853— 857).— A review, pipettes, a steam-jacketed capsule, and a micro- includmg micro-methods. R . S. B. distillation apparatus are described. The distillation Camphor as cryoscopic solvent and mol. wt. flask is Hat and contains sand to prevent frothing. determination by Rast’s method. C. F. Capello Sulphides are best pptd. in sealed tubes under pressure (Giorn. Farm. Chim., 1934, 83, 336—342, 345—347; by H,S produced from AcSH. R. S. Chem. Zentr., 1935, i, 1421).—The cryoscopic const. of camphor is taken as 400. ' J. S. A. Prevention of frothing in Arndt’s determin ation of nitrogen. W. Classen (Chcm.-Ztg., 1935, Micro-determination of mol. wt. M. af H all- 59, 857).—Froth produced on distilling nitratcs stróm (Ann. Acad. Sci. fenn., 1934, 41, A, No. 6 ; according to Arndt’s method may be removed by Chem. Zentr., 1935, i, 1421).—Isotonic solutions of adding sulphate, e.g., 0-5% of MgS04 to MgCl2 lye. the substance under examination and of a reference Distillation is rapid and the fiask is more easily substance are prepared by dropping solvent into an cleaned. R- S. B. evacuated desiecator within which the two solutes are in similai' open weighing bottles. The mol. wt. Improved screw plunger for use with mercury is calc. from the concns. of the solutions as deter piston micro-burettes. S. J. F olley and E. A. mined from their inerease in wt. J. S. A. R owsell (Mikrochem., 1935, 18, 303—304).-—A cotton-wool gland is fitted. R. S. Apparatus for the determination of mol. wt. by the camphor method. C. T ie d c k e (Mikro Simple mici-o-burette without stopcocks. K. chem., 1935, 18, 223—226).--T he H 2S04 bath is Schwarz (Mikrochem., 1935, 18, 309—311; cf. A., enclosed by a glass cap carrying the thermometer, 1933, 586).—Further details are given. R. S. stirrer, and a hook for the m.p. tube. R. S. GEOCHEMISTRY. 1477 Micro-filtration apparatus. H. Y a g o d a (Mikro Sealing metals to glass. A. W. H ull (Physical chem., 1935, 18, 299—302).—The use of a micro- Rev., 1934, [ii], 45, 285—286).—The differential filter of the Buchner type for the detection of Fe etc. thermal expansion between glass and metal has been is described. R. S. measured for the common sealing materials and for Fractional ultrafiltration. P. G r a b a r (Buli. some new alloys and glasses. A new alloy the ex- Soc. Chim. biol., 1935, 17, 1245— 1303).—A review pansion of which matches that of a particular glass from 0° to the softening point has been used to con- of recent work. firm the hypothesis that properly annealed seals will Fractional distillation of extremely smali be strain-free to exactly the clegree indicated by volumes of liquids. A. A. Benedetti-Pichler expansion data. L. S. T. and J. R. Rachele (Mikrochem., 1935, 19, 1—5).— Apparatus is described for the evaporation of 5—15 cu. Adolf von Baeyer, 1835—1917. J. R. P a rting - mm. of liąuid below its b.p., condensation taking place ton (Naturę, 1935, 136, 669—670).—Historical. on a cold point. J. S. A. L. S. T. Geochemistry. Helium content of the stratosphere. F. A. Travertine-depositing waters near Lexington, P aneth and E. Gluckauf (Naturę, 1935,136, 717— Virginia. E. Steidtm ann (Science, 1935, 82, 333— 718).—The % of He in the air of England remains 334).—These waters are supersaturated with practically const. (5-27—5:35 Xl0~6 c.c. per c.c.) up Ca(HC03)2 throughout the year, the excess ranging to a height of 18 km., but at 21 km. an 8% increase from approx. 6S to 76 p.p.m. of CaC03. The largcst has been observed. L. S. T. excess appears in wintcr. The annual rango of p a, temp., free C02, and other constituents are Proportion of heavy water in the water of recorded. The marked deposition of calcite (I) in crystallisation of minerals. E. H. R ie se n fe l d the summer is due mainly to a rise in temp., but and M. T obiank (Ber., 1935, 68, [B'\, 1962— 1969; adjustm ent is also hastened by aeration and close cf. A., 1934, 1327).—The enrichment in D20 of the contact of the H20 with (I). Travertine grows crystal water of rasorite, tincal, oarnallite, polyhalite, from the base of the plants upwards by addition of and gypsum is < that recorded by other authors (I) to (I), which may be a result of the catalytic for natural waters of differing origin. Since similar action of (I) on unstable CaCO, solutions. results have been recorded by other workers, enrich L. S. T. ment in D20 by crystallisation of salts and minerals [Electrical conductiyity of] salts dissolved in has never been observed. This is attributed to the waters of the Autonomous Sand/jak of Alex- rate of crystal formation being smali in comparison andretta. V. F rolow (Compt. rend., 1935, 201, with the rate of exchange reaction in the D20 content 613—615).—Conductiyity data are recorded. of the aq. and cryst. phase. The solubility of H. J. E. hydrated salts in D20 and that of salts containing Plate-like crystals of native silver from D20 of crystallisation in H20 are therefore not consts. “ Gottes Hiilfe in der Not ” mine, Kongsberg- at const. temp., but depend on the amount of salt feltet [Norway]. R. Storen (Tids. Kjemi, 1935, employed in determining the solubility and other 15, 124— 126).—Their occurrence (in a cavity), form, factors. Both must lie between the solubility of and habit are described. The crystals contain > hydrates in H20 and that of D20-containing com 3% Hg, whilst no tracę of this has been detected in pounds in D,0, both of which are true consts. the ordinary ZnS and PbS ores of the mine. It is H. W. concluded that the crystals represent a primary Occurrence of radium in north- and middle- deposition from magmatic H 20- M. H. M. A. German deep waters. O. H ahn and H. J. B orn (Naturwiss., 1935, 23, 739—740; cf., A., 1934, 505).— Genetic significance of biotite-pyroxenite and The high He content of sylvine indicates that it was hornblendite. D. L. R eynolds (Tsch. Min. Petr. deposited from H20 more highly radioacti\re than Mitt., 1935, 46, 447—490).—The biotite-pyroxenite sea-H20. The Ra content of H20 from oil-borings of the Newry igneous complex in Co. Down, Ireland, and elsewhere in the neighbourhood of the north is belieyed to represent the parent magma from German śalt deposits is > that of any previously which the other rocks (monzonite, syenite, diorite, investigated German H20. The Ra content increases granodiorite) have originated by its action on the with Ca content of the H20, and in the stronger surrounding sedimentary rocks. Emanations rich in Ra-containing H20, Li is present. A. J. M. alkalis first gave rise to a felspathisation of the sediments, which were then soaked with the highly Chemico-physical analysis of waters of Lurisia fluid magma. Similar occurrenees of biotite-pyr- and Mondovi. Presence of lithium in besi- oxenite or hornblendite in other regions are compared. maudite, quartziferous porphyry, of the same L. J. S. locality. L. F rancesconi and R. Bru n a (Annali Petrochemistry of the Middle Bohemian Chim. Appl., 1935, 25, 460—470).—These waters pluton. A. Orlov (Tsch. Min. Petr. Mitt., 1935, (cf. A., 1934, 273) are radio-active and contain 46, 416— 44G).—43 analyses (8 new) are tabulated of P20 5 and Li20 in appreciable amounts. T. H. P. rocks ranging from granite to gabbro from this 1478 BRITISH CHEMICAL ABSTRACTS.----A. plutonie complex (the so-called Middle Bohemian with the exception of minor ąuantities of “ sooty ” granite massif). The relation of the intrusion to chalcocite (III). Blue (III) and covellite (IV) the tectonics of the district is discussed. Differenti- replace an earlier chalcopyrite and bornite inter- ation of the magma took place both before and after growth, the latter being more susceptible to replace- the intrusion. L. J. S. ment. Deposition of (III) and (IV) has been followed Biogenic migration of rare elements. A. P. by a later sulphide replacement, represented chiefly Vinogradov (Trans. Internat. Soc. Soil Sci., Sov. by (I) and (II). Alunite is abundant throughout Sect., 1935, A, 64—69).—There appears to be a the ore body, and its close association with (I) and tendency towards the accumulation of elements of (II) indicates that they were carried and deposited uneyen at. no. in soil compared with the composition by acid solutions. L. S. T. of the earth’s crust. Elements which show greatest Grunerite from Rockport, Massachusetts, and biogenic migration are those which most easily form a series of synthetic fluor-amphiboles. N. L. sol. compounds. A. M. B owen and J . F. Sciiairer (Amer. Min., 1935, 20, Pyroxene group. A. N. W in c iiell (Amer. Min., 543—551).—The occurrence of grunerite (I), d 3-597, 1935, 20, 562—568).—Variations in optical properties a 1-686, p 1-709, y 1-729 (all ^0-002), as shells sur- and composition, expressed as mol. %, are dia- rounding fayalite from Rockport is deseribed. gramatically represented for the following series: This (I) provides the nearest approach to pure clinoenstatite (I)-diopside (II), (Il)-hedenbergite Fe7H2(Si03)8 yet encountered. The analysis is (III), (Ill)-clinohypersthene, MgSi03-FeSi03 mono- SiOo 47-54, A120 3 0-20, Fe„03 0-71, FeO 47-25, MnO clinic pyroxenes, and clinoenstenite-(li)-(III). 2-14“, MgO 0-04, CaO nonę, Na20 0-29, IC20 0-11, Minerals should no longer be regarded as compounds H ,0 1-55, F 0-01, total 99-84%. Regarded as an which can be expressecl by simple formulse, but as a end-member of the cummingtonite-grunerite series series varying in composition through a considerable the properties of this (I) aro compared with those of rangę. L. S. T. other members of the series. The optical properties of synthetic fluor-amphiboles, prepared from Genesis of the ore at the Flathead Mine, N.W. pyroxenes in closed tubes at atm. pressure in presence M ontana. P. J. Sh en o n (Econ. Geol., 1935, 30, of NaF, are also compared with those of Mg-Fe 585—603).—The ore minerals are dividcd into amphiboles and pyroxenes. The amphibole obtained liypogene and supergene sulphides and oxidation by this method is always more magnesian tlian the produets. The former include pyrite, galena, anti- pyroxcne from which it is produced, and in the inonial matildite, and smali amounts of enargite, typical discontinuous reaction series olivine, pyroxene, and the latter, argentite, smali amounts of covellite, amphibole the generał relation that each phase is and possibly marcasite. The associated gangue more magnesian than the member of the preceding minerals are mainly ąuartz, barite, clay minerals, phase with which it is in eąuilibriuin, appears to and alunite. The more common oxidation produets hokl. L. S. T. are anglesito, melanterite, siderotil, malachite, and a yeUow amorphous powder containing Pb, Sb, and Occurrence of narsarsukite in Montana. Bi. Two stages of mineralisation are deseribed, and W. A. P. Graham (Amer. Min., 1935, 20, 598— the genesis of tho deposit is discussed. L. S. T. 601).—Optical and chemical data for narsarsukite occurring at East Butte, Sweet Grass Hills, Montana, Red copper ore and plagihedral hemihedry. associated with ąuartz veins cutting a green syenite R. Schroeder (Zentr. Min., 1934, A, 353—358; are recorded and compared with similar data of the Chem. Zentr., 1935, i, 1354).—Crystals of red Cu ore same minerał from the type locality in Greenland. from Cornwall exhibited plagihedral hemihedry. Onlv riglit-handed forms were obscrved. L. S. T. Study of opaąue minerals by the method of J. S. A. imprints. Improvements in the technicjue of Copper ores of Kisenda (Belgian Congo). electrolytic attack. T. H iller (Arch. Sci. phys. II. Presence of two varieties of chalcocite. nat., 1935, [v], 17, Suppl., 119—122).—A piece of III. Presence of a hypogene covellite and a supergene covellite. M. Gysin (Arch. Sci. pliys. gelatined paper is pressed on the polished surface nat., 1935, [v], 17, Suppl., 82—85, 116—119).—The of the grain by a metal spatula, plate of a press, etc., varieties are deseribed and explanations of their which is connected to the negative pole of an 8-volt origin are ofFered. S. J. G. battery. The positive pole is connected to a needle touching the free part of the grain. The various Paragenesis of the Colorada copper sulphides, elements of the ore suffer anodic dissolution and are Cananea, Mexico. V. C. K elley (Econ. Geol., tested for in the gelatin by “ developing ” with suitable 1935, 30, 663—688).—The Colorada ore body is reagents. S. J . G. located within and along the contacts of a ąuartz porphyry stock which has been intruded into a series Examination of linnaeites of N. Rhodesia and of massive, fine-grained, volcanic rocks. The early Katanga by the method of imprints. T. H iller gangue minerals form an irregular, pegmatitic ring- (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., 122— dyke and the subseąuent sulphide mineralisation is 125).—The method deseribed above is applied to the localised within and along the pegmatite ring. The examination of certain linnaeites. S. J . G. ore minerals consist chiefly of Cu sulphides, molyb- Stainierite. II. L. de L e e n h e e r (Natuur- denite, and sulpho-salts of Cu, mainly luzonite (I) wetensch. Tijds., 1935, 17, 148— 156; cf. this vol., and tennantite (II). They are of hypogene origin 725).—Further data are given. D. R. D. 0RGANI0 CHEMISTRY. 1479 Schoepite and becquerelite. V. B il l ie t and Igneous assimilation and associated contact W. F. de J ong (Natuurwetensch. Tijds., 1935, 17, metamorphism in the Virginia mining district, 157—162).—Schoepite is 4U03,9H20 and has a New Mexico. S. G. L asky (Amer. Min., 1935, 20, 14-40, b 16-89, c 14-75 A., and cl 4-83. Becąuerelite 552—561).—The rocks consist mainly of basalt of is 2U03,3H,0 and has a 13-9, b 12-55, c 14-9 A., and probably Comanche age intruded by late Cretaceous cl 5-20. “ D. R. D. or early Tertiary porphyritic granodiorite (I). (I) Fluorescence experiments on natural sul- generally has a dark bor der which contains much phates. A. K ohler and H. L eitm eier (Zentr. augite as well as a more calcic plagioclase and more Min., 1934, A, 364—375; Chem. Zentr., 1935, i, magnetite than the main mass. The differences 1354).—Data are given for barytes, celestine, anhydr- are attributed to partial assimilation of the adjacent ite, anglesite, and other sulphates at room temp. basalt in accordance with Bowen’s reaction principle. and elevated temp. J . S. A. In addition, the basalt adjacent to the contact is metamorphosed to a rock mineralogically similar Zaratite : synthetic zaratite. M. F enoglio to the invading (I). L. S. T. (Period. Min., 1934, 5, 265—274; Chem. Zentr., 1934, i, 1851).—Materiał identical with zaratite in Some properties of opal. N. L. T aliaferro composition, properties, and crystal structure is (Amor. J. Sci., 1935, [v], 30, 450—474).—Vals. of obtained by the action of dii. aq. NiCl2 on MgC03,3H20 d and n for opals and opaline clierts show ranges d (nesquehonite). J. S. A. 1-983—2-111, n 1-441—1-456, H 20 4-75—2-70%, Orientation of mica microlitlis in plagioclases but they show no regular yariation with II20 ; when from eruptive rocks. C. A ndreatta (Period. plotted, they lie scattered between the theoretical Min., 1934, 5, 217—235; Chem. Zentr., 1935, i, curves for Śi02 glass+H20 and cristobałite+H20. 1851).—Tonalites, diorite, etc. freąuently show partial On slow dehydration at 120—350°, there is first an conversion of plagioclase crystals into preferentially increase in d and n up to a transition point (1-6—- oriented mica microliths. J . S. A. 2-8 mols. H20), after which they deerease, and in the completely dehydrated materiał cl and n are < Natural minerał gel from Vashegy. L. von in the original materiał. X-Ray powder płiotographs Zombory (Foldtani Kozlony, 1933, 63, 219—220; show faint patterns of high-temp. p-cristobalite, Chem. Zentr., 1935, i, 1851— 1852).—A minerał gel but no actual crystals are present. L. J. S. consisting essentially of mixed Fe and Al sulphates +Si02 and P20 5 is described. J. S. A. Conglomerates and grits of Kaldurga, Kadur Composition of sky-blue diopside from 1906 district, Mysore. C. S. P icha m u th u (Proc. Indian Vesuvius eruption. S. R estaino (Rend. Accad. Acad. Sci., 1935, 2, B, 254—279).—Geołogical charac- Sci. Napoli, 1934, [iv], 4, 32—35; Chem. Zentr., teristics are described. F. O. H. 1935, i, 1852).—The diopside has less S i02 and more Chemical analyses of Finnish rocks. L. Lokka CaO than corresponds with CaMg(Si03)2, -j-MnO, (Buli. Com. gćol. Fin., 1934, No. 105; Chem. Zentr., CuO, Fe203, A1203 etc. j. S. A. 1935, i, 1354).—A summary of published data. Minyulite, a new phosphate minerał from J . S. A. Dandaragan, W.A. E. S. Sim pson and C. R. De Geology of St. Kilda. A. M. Cockburn (Trans. Mesu r ier (J. Roy. Soc. W. Australia, 1932— 1933,19, Roy. Soc. Edin., 1935, 58, 511—547).—The rocks, 13—16).—The formuła is KA12(0H ,F )(P 04)2,3-5H20. all of them of igneous origin, are described with The occurrence and properties are described. chemical analyses of eucrite, gabbro, pitchstone, Ch . Ab s. (e) and basalt. L. J. S. Role of certain riparian plants in the form- ation of argillaceous concretions. J . R ousseau Geology of Raasay, Inner Hebrides. C. F. (Natural. Canad., 1935, 62, 99—105). Ch. Ab s. (e) D avidson (Trans. Roy. Soc. Edin., 1935, 58, 375— 407).—The igneous rocks of Tertiary age arc described Shungite. N. A. O rlov, V. A. U s p e n s k i, and with chemical analyses of gabbroid teschenite, I. N. Shachovtzev (Khim. Tverd. Topi., 1934, riebeckite-granophyre, peridotite, and andesitic pitch 5, 601—619).—Shungite, a natural eryst. C of very stone. L. J. S. Iow electrical resistance, contains H 20 7-76, ash 1-09, C 98-11, H 0-43, O + S 1-03%. An ash analysis is Rare elements in (A) coal ashes, (b ) Germ an given. Ch. Abs. (e) brown coal ashes.—See B., 1935, 978. Organie Chemistry. Evaluation of the structural theory of organie 328; cf. this vol., 1335).—D ata obtained for 17 com chemistry. II. J. K. Sen io r (J. Chem. Educ., pounds shew that the diffusion velocity of non- 1935, 12, 465—472; cf. this vol., 1305).—A lecture. ionised org. mols. depends on structure. T. G. P. L. S. T. Investigation of different types and isomerides Specific refraction in predicting the composi of non-dissociated organie compounds with the tion of saturated synthetic hydrocarbon mix- help of the dialysis method. H. B rin tzin g er and tures. H. I. W aterman and J. J . L een d e r t se H. G. B e ie r (Z. anorg. Chem., 1935, 224, 325— (Rec. trav. chim., 1935, 54, 725—727).—The sp. 1480 BRITISH CHEMICAL ABSTBACTS.— A. refraction givcs vals. for the C : H ratio of tho hydro- give smoothly e-dimetkylamino- (II), b.p. 133—135°/ genated polymerides of unsaturated hydrocarbons 752 mm., -diethylamino- (III), b.p. 166—167°/766 of Iow mol. wt. in good agreement with analytical mm., -N-piperidino- (IV), b.p. 207—209°/766 mm., vals. (cf. B., 1932, 536). H. G. M. and -dihcxylamino-pent-v.-en-y-ine.ne, b.p. 138— 140°/ Catalytic effect of ozone in the oxidation of 0-5 mm., which are stable and have characteristic hydrocarbons.—Sec this vol., 1466. odours. Hydrogenation of (III) and (IV) in EtOH (P t0 2) gives diethyl-w-amylamine and AT-?i-amyl- Influence of substituents on the addition re- piperidine, respectively. (II), (III), and (IV) add activity of ethylene derivatives. III.—See this HC1 in presence of aq. CuCl2 at 60° [less readily than vol., 1465. does (I)] to give y-cłiloro-e-dimethylaniino-, -e-diethyl- Addition of hydrogen sulphide to isoprene amino-, and -€-K-piperidino-Aay-pentadiene, which catalysed by ferrous sulphide. J. B o esek en and are fairly stable (do not give rubbery polymerides) N. v. d . L in d e (Rec. trav. chim., 1935, 54, 739— and with naphthaąuinone and (1CII-C0)20 give black, 744).—Isoprene and H2S when lieated to 96° under resinous additive compounds. (II) adds p- pressure in presence of Fe203 or FeS yield a mixture, CcH4Me-SH in ultra-violet light to give a-dimethyl- probably mainly li4hiol-B-metJiyl-Av-butcne (I), b.p. amiłio-e-ip-tolylthiol-AP-pentinene, b.p. 156—158°/0-5 67°/100 mm. (rod Hg salt; oxidised by I to a disulph- mm., adds MeOH in presence of NaOMe at 100° to ide, b.p. 87°/high vac.), and, probably, fiy-dithiol-[3- give a substance, C8H15ON, b.p. 69—71°/1 mm. methylbutane, b.p. 135°/20 mm. (I) rapidly adsorbs (destroyed by KMn04), and by exhaustive mofchyl- 30 when oxidised with Ac02H. Further oxidation to ation (Ag20 -H 20 a t 45°) gives a hydrocarbon, C5H4, H2S04 also occurs (cf. A., 1934, 1307). H. G. M. b.p. S0—90°, unstable to heat and 02. Physical Dimerisation of AaY-butadiene. S. L ebedey data are given. and S. Sebgienko (Compt. rend. Acad. Sci., U.R.S.S., XXIII. CH2:C:CH-CH2C1 and NaCN in hot MeOH 1935, 3, 79—82).—Thermal polymerisation of buta react with shift of the etliylenic linking to give a poor diene afFords a monocyclic product, probably vinyl- yield of ls.ay-pentadienonitńle (S-cyano-AaY-butadiene) A1-c?/ctohexeiie, which yields a trans-, m.p. 101-5— (V), b.p. 49—53°/30 mm., and 8-methoxy-A&-penteno- 102-5° and a cis-tetrabromide, m.p. 74-—75°, both of nitrile (VI), b.p. 65—67°/7 mm., (38- or yS-dimethoxy- which can be reconverted into the original dimeride. valeronitrile (VII), b.p. 70—73°/l mm., and a sub No open-chain dimerides are formed, and there is stance, C5H 12ON2, b.p. 131—134°/0-5 mm. Structures no tendency to further polymerisation, which brings are proved by the reactions described below. (V) the probabie mechanism of this reaction into line with conc. HCl-Et,0 at room temp. yields with tho polymerisation of isoprene and di/sopropenyl CH2:CH-CH:CH-C02H, m.p. 71° (Et ester, b.p. 65— (cf. A., 1922; i, 1043). J. L. D. 67°/30 m m .; polymerises slowly at 100° and does not add naphthaąuinone), with H2-P t02 in Ac20 gives Preparation of butadiene from s-dimethyl- 7i-C5Hn-NH2, with KMn04-K0H gives H2C204, ethylene. B. A. K azański and I. A. R afilzon and with HCl-EtOH affords by 1 :4-addition and (Sintet. Kauehuk, 1934, No. 1, 31—34).—3—4% hydrolysis Et S-chloro-A^-pentenoate, b.p. 72—74°/l of CHMelCHMe (I) is formed in the prep. of butadiene mm., oxidised by KMn04 to CH2C1-C02H. (VI) and (II) from EtOH. Addition of Cl2 to (I) affords KMnO., give 0Me-CH2-C02II. (VII), obtained also (•CHMeCl)2 (III), removal of 2HC1 from which in 23% yield from (VI) and NaOMe-MeOH at 60°, yields (II); the latter process is best carried. out by with H2S04 gives a dimethoxyvaleric acid, b.p. 119— passing (III) over BaCl2 a t 360—400° [30— 40% 122°/1 mm., hydrolj^sed by HBr to an unsaturated yield of (II)]. NiCl2 and A1203 are much less efficient lactone, b.p. 83—85°/3 mm., 226—228°/760 mm. as catalysts. Ch . Abs. (r) (solid polymeride, formed at 150°), which is hydrogen- Addition of methyl alcohol to dialkylacetyl- ated (Pt02) in EtOH to S-valerolactone fgives 8- enes. G. F. H e n n io n and J. A. N ieu w la n d (J. hydroxyvaleric hydrazide, m.p. 105° (błock)]. In Amer. Chem. Soc., 1935, 57, 2006—2007).—Acetyl- light at 40—50° (V) gives a rubbery polymeride, enes and OH-compounds react to produce successively resembling «-polychloroprene. In 3 weeks at room compounds of the types, CH2!CH-0R and CHMe(0R)2. temp. (V) gives 5% of an a -polymeride (VII), 14% Hg acetylides are not essential to the mechanism, of which is formed in 13 hr. at 100° with 42% of a sińce, in presence of a catalyst prepared from HgO, dimeride. (VIII) can be compounded and partly Et20,BF3, CC13-C02H, and MeOH, A^-octene, b.p. Tulcanised by heat. With hot NaOH (V) gives a 132—136° (from Mel and CjH^-C-CNa in liąuid brittle polymeride. Physical data are given. NH3), and MeOH give yy-dimethoxyoctane, b.p. 90— R. S. C. 92°/26 mm. (hydrolysed to C0Pro-C5Hn), and Kinetics of interactions of sodium hydroxide OMę*CH2-C:CMe gives similarly with bromoethanes.—See this vol., 1465. (OMe)2CMe,[CH2]2-OMe, b.p. 67—69°/30 mm. R. S. C. Isolation of crotonyl [bromide] and methyl- Acetylene polymerides and their derivatives. vinylcarbinyl bromide [y-bromo-A“-butene]. XXII. a-Dialkylaminomethyl-(3-vinylacetylenes. W . G. Y oung and S. W instein (J. Amer. Chem. XXIII. 8-Cyano-A“y-butadiene [Aay-pentadieno- Soc., 1935, 57, 2013).—CHMelCH-CHJBr or nitrile]. D. D. Coffman (J. Amer. Chem. Soc., CH2.CH*CHMe-OH with HBr and PBr,, gives mixtures 1935, 57, 1978— 1980, 1981— 1984; cf. A., 1934, of CHMe.CH*CH2Br, b.p. 107°/760 mm., 49°/93 mm., 990).—X XII. CH2:CHCiCH (I), paraformaldehyde, and CHa.CH• CHMeBr (I), b.p. 86-5°/760 min., which and the reąuisite .sec,-aminę in dioxan a t 100— 105° eąuilibrate in a few days at room temp., 1 hr. at 75°, 0RGANIC CHEMISTRY. 1481 and < 5 min. at 100° to a mixture containing 14% of 57, 1801— 1802).—All the isomeric Cj0-alcohols, (I). Distillation/760 mm. of a mixturo through a CHRR'-CH2*OH, are prepared by reduction of the column gives puro (I). Pliysical data are given. corresponding esters, prepared by the CH2(C02Et)2 R. S. C. synthesis. The following arc described, yields being Aliphatic substitution and Walden inversion. stated in parentheses : Et pentadecane-$-, b.p. 185— I.—See this vol., 1465. 187°/12 mm., - y , b.p. 191—199°/15 mm., -S-, b.p. Nitroso-compounds. III. Reactions of organo- 181—183°/14 mm., -e-, b.p. 180—185°/15 mm., metallic compounds with «-halogenonitroso- -K-, b.p. 180—182°/14 mm., -vj-, b.p. 181— 183°/14 mm., and -0-carboxylate, b.p. 182—183°/14 mm.; compounds. J. G. Aston and D. F. Me nar d . IV. Reaction of ethyl nitrite with isopropyl and cetyl alcohol, m.p. 49-3°; pentadecyl-(ł-, m.p. 12— 13°, b.p. 185—187°/15 mm. (66%), -y-, m.p. -0 -2 °, b.p. eyc/ohexyl ketones. J. G. Aston and M. G. May- 186—188°/15 mm. (53%), -8-, m.p. 5-5°, b.p. 181— berry (J. Amer. Chem. Soc., 1935, 57, 1920—1924, 184°/15 mm. (32%), -e-, m.p. —14-5 to —14°, b.p. 1888—1891; cf. A., 1934, 868).—III. CMe2Br-NO (I) (modified prep.; 90% pure) and CMe2Cl*NO (II) 181—183°/15 mm. (30%), m.p. -9 to - 8°, b.p. react with organo-metallic compounds by loss of 181—182715 mm. (33%), --/)-, m.p. -30 to -26°, halogen hydride to give ClIo-CMcNO (III) [leading b.p. 181—183°/15 mm. (27%), and -0-carbinol, to CMe2!Ń*0H (IV)] or by addition at tho NO. m.p. -25 to -18°, b.p. 181—182°/15 mm. (28%). (I) and“NH3-Et20 givc only NH4Br and (IV) [by n and d are given for the alcohols and their acetates. R. S. C. way of (III)]. (II) and ZnMe2 (1 mol.) give CH4 (1 mol.), (IV), COMe2, and NHMe-OH; the last two Velocity of hydrolysis of cyclic acetals.—See arise thus: (I)+ZnMe2-> CMe^l-NMe^OZnMe this vol., 1465. CH4+ C H 2:CMe*NMe,OZnCl > COMe2+NHMe-OH Benzyl ethers of ethylene glycol and glycerol. -{-ZnChOH, although at least some loss of HC1 occurs S. D antlov [with V. D riabchlitzin and O. Mano- prior to addition. (I) and ZnEt2 react similarly to china] (Rev. gen. Mat. piast., 1934, 10, 364—367; the extent of about 70%, giving COMe2 and NHEt*OH, Chem. Zentr., 1935, i, 1860).—Treatm ent of the Na2 but the formation of C2H4 shows 30% of reaction derivative of glycerol with CH2PhCl affords glyceryl thus : (I)+ZnEt2 -> C2H4+CMe2Br-NH-OZnEt -> benzyl, b.p. 173—175°/9 mm., and dibenzyl ether, C2HG+CMe2!N,OZnBr -> (IV). (I) and (II) react b.p. 214—216°/9 mm. Tliese are also obtained from with MgEtBr (2 mols.) as with ZnEt2, giving C2H0, glycerol (46 g.), Na OH (60 g.), and CH2PhCl (200 g.) C,H,„ COMe2, N H 2OH, and (IV), but formation of at 130°. Ethylene glycol mono-, b.p. 134— 135°/13-6 an excess of C2HG shows also some reaction thus : mm., and di-, b.p. 154°/2 mm. -benzyl ethers are pre (I)+MgEtBr -> (III)+MgBr2+C2Hfi. (II) and pared similarly. H. N. R. MgMeCl (1 mol.) react by addition a t the NO, Synthesis of glycerides by means of triphenyl- giving NHMe-OH. 2 mols. of MgMeCl give also methyl compounds. I. Mono-acid diglycer- replacement of the Cl, thus: (I)+2MgMeCl-> ides. P. E. Ver k a d e, J. yan d er L e e , and (Miss) CHMeEt-NMe-OMgCl->MgCl-OH+CHMeEt-NMe-OH, W. M eerburg (Rec. trav. chim., 1935, 54, 716— the resultant l$-methyl-N-sec.-butylhydroxylarnine, b.p. 724).—Glycerol a-CPh3 ether in ąuinoline and the 85—93°/115 mm. (hydrochloride, liygroscopic), heing reąuisite acid chloride in CHC13 yield the py-distearate identified by reduction by SnCl, to 'N-niethyl-sec.- (I) and Sy-dibenzoate in 82 and 84% yield, respectively bulylamine (hydrochloride, m.p. 242—244°; ozalate, (cf. A., 1933, 374). (I) with H Br~Et20 affords ay- m.p. 109—110°; also obtained from CMeEt!N*OH distearin in 82% yield. Details are given for the by reduction and methylation). (I) and MgMeCl determination of CPh3 as CPh3*OH in compounds react similarly, but lead also to a little N wethyl-N- which contain higher fatty acids. H. G. M. tert .-butylhydroxylamine [oxalate, m.p. 166— 167° Preparation of rf(— )-3-phosphoglyceric acid. (decomp.)]. (I) and MgPhBr givc 20% of CGH6 by loss of HBr. See this vol., 1418. IV. NO-O Etreacts with COPWl, or c?/ctohexyl ketone Simplexes of lecithin with polysaccharides. in presence of aq. or, better, dry HC1 or AcCl at the S. J. von P rzyeecki and R. Ma jjiin (Biochem. Z., «-CH2 or a-CH or both, but the relative amounts of 1935, 280, 413—415).—-The prep. is described of the two reactions cannot be correlated with tho struc sol. simplexes containing lecithin (I)-starch (II) ture of the second alkyl. The foliowing are incident- [about 50 mols. (I) to 1 mol. (II)], of (I)-glycogen and ally described: l-nitrosocyclohexyl Me, m.p. 114— of (I)-dextrin [about 4 mols. (I) to 1 mol. dextrin]. 115°, and Et ketone, m.p. 119-5—120°; o,yc\ohexyl P. W. C. cc-oximinoethyl, m.p. 78—7S-2°, and Bu& a-oximino- Partial synthesis of ribose nucleotides. II. isopropyl ketone, m.p. S9-2—90°; ethyliśoprópyl-, Muscle inosinic acid. P. A. L ev en e and R. S. m.p. 148-5—149°, and profyliśoprppyl-glyoxime, m.p. T ipson (J. Biol. Chem., 1935, 111, 313—323).— 140—140-3°. R, S. C. Inosine (modified prep. from adenosine; 100% yield), Chemical action of penetrating radium radi- [oc]f,7 —38-3°, with COMe2 and ZnCl2 gives the 2 :3- ations. XX.—See this vol., 1469. \sopropylidene derivative (I), m.p. 240—245° (decomp.) after softening a t 225°, [afj —69-2° in dry MeOH, Reactivity of atoms and groups in organie [a]j? —88° in CgHjjN, the structure of which is proved compounds. XVI—XVIII.—See this vol., 1206. by ready reaction of its 5-i>-CrIIi Me-S02 derivative, Isomeric branched hexadecanols. W. M. Cox, m.p. 185—186°, [a]n° +35-9° in C5H5N, with N al in jun., and E. E. R eid (J. Amer. Chem. Soc., 1935, COMe2. (I) and P0C13 in C5H5N at -40° to -10° 1482 BBITISH CHEMICAL ABSTRACTS.----A. give Ba 2 : S-isopropylideneinosiiic-o-phosphale, acid, b.p. 92°/l mm., [a]g* —1-26°. l-ccy-Dimethyl- -j-3-5H,0, hydrolysed by 0-05Y-HC1 to Ba inosine-5- raleric acid (obtained by the cinchonine salt in phosphate, + 7-5H ,0, [«]« -36-8° in 0-liY-HCl, COMe2 at -10°), b.p. 117°/17 mm., [a]?,1 -13-8°, identical with tho salt of natura! inosinic acid. gives the Et ester, b.p. 164°, [a]jf +1-5°, l-ps-dimcthyl- R. S. C. pentan-u-ol, b.p. 157°, [a]f? —1-1°, l-a-bromo-fio-di- Mechanism of reactions of diacyl peroxides methylpcnlane, b.p. 68°/30 mm., [a]^5 —0-44°, and with other organie substances and their thermal (38-dimethylhezoic acid, b.p. 91°/1 mm., [a]u —0-75°. decomposition. P. H. H ermans (Rec. trav. chim., [a] are for the homogeneous liąuids, but are not 1935, 54, 760—767).—A rcvie\v. Acyl peroxides necessarily max. R. S. C. when heated alone or with aromatic and aliphatic Tetradeuterostearic acid.—See this vol., 1407. hydrocarbons (or their substituted derivatives) react according to one or more of the following śchemes :' Fatty acids and glycerides of partly hydro- R-COOO-COR -> R-R+2C02 (a) and R-CO,R+CO, genated rape oil.—See B., 1935, 1054. (b), Pli-CO-O-O-CO-R-> R-CflH4-C0,H+C02 (c), Polymerisation of fatty oils. IX. Hydrogen- R-C0-0-0-C0-R+R'H -> R'-C0-0-0-C0“R+RH (d) ation of polymerised ethyl linolenate. X. Poly and R-CO‘O-O-CO-11 (decomp. to R*C02H+C 02) + merisation of ethyl linoleate. A. Steig er and J. R-R' (e). Thermal decomp. is represented by (a) van Loon (Rec. trav. chim., 1935, 54, 750—756, and (b). Purely aliphatic peroxides react mainly 756—759).—IX . Polymerisation of E t linolenate (I) according to (a), but mixed aliphatic and aromatic a t 300° in CO, is accompanied by the formation of peroxides react mainly according to (b) and (c), a compound, b.p. 95—100°/liigh vac. (30-7%), in- although, as with purely aromatic peroxides, all types capable of polymerisation and hydrogenated (Pd, H2, of reaction are possible according to the conditions. 1 atm., room temp.; Ni, H2, 50 atm., 170°) to a H. G. M. monocyclic acid Cj8H3102, slowly oxidised by cold, Iodo-fatty acids. I. Additive products of alkaline KMn04. A little stearic acid is also formed, lower unsaturated acids with hydriodic acid. probably from unclianged (I), during hydrogenation. E. Masuda and K. N ishida (J. Pharm. Soc. Japan, The main product from (I) is not completely hydro 1934,54,1091—1100).—Addition of H I to CH!OC()2H genated b}- Pd (H2, 1 atm., 15°) or by Ni (H,, 100 atm., afFords p-iodoacrylic acid (I), m.p. 147°, and pp- 170°). The resulting products have different I vals. di-iodopropionic acid (II), m.p. 87°. Addition of and aro oxidised by cold, alkaline KMn04 to products HI to CI;C-CO,H yields $(i{i-tri-iodopropio?iic acid considered to consist of unsaturated compounds. (III), m.p. 131°, pp-di-iodoacrylic acid, m.p. 133°, X. E t linoleate when heated (300°, 6— 14 hr.) and (II). Addition of HI to CI2!CH-C02H (IV) gives in CO, yields two main polymerisation products, (III), whilst CHI!CTCO,H and HI afford no I3-acid, b.p. < 100°/high vac. and b.p. > 150°/high vac. but only (II). (II) may also be obtained by the re (some decomp.). The proportion of the latter in duction of (IV) with HI. (II) with 10% NaOH yields ereases with inerease in the time of heating. The (I). Ch. Ab s. (r) sap. and I vals., n™, and mol. wt. of these fractions Vinylacetic fA^-butenoic] acid. C. Mannioh are given. H. G. M. (Arch. Pharm., 1935, 273, 415-417).—This acid Highly unsaturated acids in sardine oil. VII. is readily obtained in 65—75% yield from Separation of highly unsaturated C22-acids. CH2:CH-CH2-CN and conc. HC1 a t 100° (75 min.). VIII. Constitution of clupanodonic acid. Y. With 03 it gives only MeCHO, C02, and a little CH20 T oyama and T. T suchiya (Buli. Chem. Soc. Japan, and CH2(C02H),, and with Bz02H P-hydroxybutyro- 1935, 10, 433—440, 4*11—453).—VII. Fractionation lactone. W ith S0C12 a t 45°, followed by EtOH, or of the highly unsaturated acids by pptn. as Na salts by way of the Ag salt and E tl it gives the E t ester, from COMe, affords clupanodonic acid, a more highly b.p. 118—120°, which with 0 3 gives probably E t unsaturated fraction, chiefly docosahexaenoic acid, y-formylglutaconate. ' R. S. C. and a less’unsaturatcd fraction containing cetoleic acid, Configurative relationship of acids of the C22H,,02. Docosatetraenoic acid may be present. isopropyl and /sobutyl series to those of the VIII. Ozonotysis of amyl clupanodonate affords normal series. P. A. L ev en e and R. E. Ma rker EtCHO, MeCHO, C02, (-ĆH2-C02H)2, amyl H suc- (J. Biol. Chem., 1935, 111, 299—312).—Significant cinate, and lower fatty acids. Ozonolysis of di- differencesin[Jl/]f,5betweenPr“'[CH2]m-CHMe’[CHo],,*X bromoclupanodmic acid affords a Br-compound con- and Pr£'[CH2]m-CHMo-[CH2]n-X exist only if m —0 or 1. verted by debromination and subsequent hydrogen di-CHMePr^C02H, b.p. 9Ó°/16 mm., is resolved by ation into C6H13’C02H. This procedure applied to quinine to give the Z-form, [a]f? —18-9°. The cZ-acid, tetrabromo- and hexabromo-clupanodonic acids affords M +6-7°, gives the d -Et ester, b.p. 146°, [a]“ decoic and myristic acids, respectively. On tho above + 8-1°, and thence d-$-dimethylbutan-tx-ol, b.p. 142°, results clupanodonic acid is A>v-to-docosapentaenoic M d +1-9° (acetate, b.p. 147°, [ Manufacture of anhydrous glucose.—See B.; cf. this vol., 1195).-—The supposition that the C50 1935, 1064. ring of simple pyranose sugars is in a Sachse strainless Test of von Fellenberg’s titrimetric method form is without foundation, for it takes no account- for determination of sugar. T. von Fellenberg of the different radius and valency angle of O and and P. Dem ont (Mitt. Lebensm. Hyg., 1935, 2 6 ,168— assumes that the C valencies are directed towards 182; cf. A., 1921, ii, 136).—The tables previously the angles of a tetrahedron (cf. A., 1929, 383; given are incorrect for lactose and maltose, sińce the this vol., 810). AT-Ray evidence suggests that the specimens used were mixtures of the anhyd. substances C are nearly, although not ąuite, co-planar, and O is and their monohydrates. Correct data are now displaced (1—0-5 A.) out of their piane. Single given for the monohydrates and complete data for crystals of many of these sugars have a shortest axis the calcułation of mg. of glucose, iriyert sugar, of about 4-5 A., which is possible only in a direction sucrose, lactose hydrate, or maltose hydrate from almost perpendicular to the ring piane; the more c.c. of 0-lAr-I used are tabulated. E. C. S. highly methylated sugars have shorter axes (cf. A., 1931, 1219), and. the fact that configuration does not Determination of glucose in presence of di- alter this val. greatly for the pyranose sugars (the saccharides with Barfoed’s reagent. T. von furanose sugars also have as short or shorter axes) F e lle n b e rg (Mitt. Lebensm. Hyg., 1935, 26, 182— is additional evidence in favour of the “ flat ” struc 192).—The Cu20 formed by reduction of Barfoed’s ture for the ring. The assumption of a “ fiat ” ring reagent with glucose (I) is determined by the author’s permits the ready interpretation of the formation titrimetric method (cf. preceding abstract). The of benzyl idene and similar derivatives as compared reagent is only slightly reduced by sucrose, maltose, with analogous reactions in compounds generally and lactose. A table is given for calculating mg. of agreed to possess a Sachse configuration, e.g., cyclo- (I) from c.c. of 0-lA7-I used. The method is applied hexane derivatives, and in which there is at least to the examination of malt extract, starch syrup, as much strain as in the sugars. These considerations and malt bonbons. E. C. S. are applied in throwing light on the spatial configur- 2:3: 6-Trimethylglucose anhydride. K. ations of several sugars. a- and p-Glucose are found F keudenbeeg and E. B rau n (Ber., 1935. 68, [5], to have been assigned correct stereochemical struc- 1988).—Contrary to Hess et al. (this vol., 1109), tures. Data as to celi dimensions and space-groups the conversion of methylcellulose into 2:3:6- are recorded for many sugars. J. L. D. trimethylglucose anhydride (I) is reproducible pro- vided the initial materiał is insol. in H20. (I) cannot Ketone sugar series. V. Validity of Hudson’s be a derivative of idose, sińce it is hydrolysed to homo- rules of isorotation in the ketose group. Pre- geneous 2 : 3 : 6-trimethylglucose. H. W. paration of the true a-fructose<2 : 7>penta- acetate. E. Pacsu and F. B. Cramer (J. Amer. Methylation of glucosephenylosazone and its Chem. Soc., 1935, 57, 1944— 1946; cf. this formulation as a derivative of fructopyranose. vol., 735).—p-Acetochlorofructose<2 : 6> (p-frueto- (Mbs.) E. E. Percival and E. G. V. Percival (J.C.S., pyranosidyl chloride acetate) and NaOAc in boiling 1935, 1398—1402).—Glucosazone with Me2S04 in Ac20 give 71-2% of (3- and 28-8% of a-frudopyranose COMe2-E tO H a t 50° containing the theorctical amount penta-aceiate, m.p. 122—123°, [a]j,° +47-4° in CHC13 of 30% NaOH gives 5-methylglucosazonc (I), m.p. (hydrolysed by 0-lAr-NaOH to fructose), the first 116— 117°, [«]“ -4 9 ° to -1 2 ° in EtOH, which with pair of true a^-ketose isomerides of undoubted p-NO2,C0H4,CHO affords 5-m ethylglucosone, recon- structure. The [a] lead to «Ac 32,850 and 6fruct.ne. verted into the osazone with NHPh-NH2, and reduced — 14,350, and thence to [a]D +45-5° for a-methyl- (Zn-AcOH) to 5-methylfructose. (I) with 0-5% fructopyranose tetra-acetate [cf. 45-0° for Schlubach’s HCl-MeOH gradually forms a pyranoside (which product (A., 1928, 873)] and 51-3° for a-ethylfructo- supports the 5-Me structure), together with about pyranose tetra-acetate [cf. 51-6° for the author’s 15% of furanoside, which forms rapidly and then product (loc. cit.)\. Hudson’s rules, therefore, liold remains const. in amount and is probably a result in this series. The following are calc. : ff0Mc 30,850; of a side reaction; fructose yields a furanoside exclusively and rapidly. (I) when boiled with ®oeł 33,650; (ici 44,750; cip,- 63,350; on 17,750; all except aon are much > A x in the aldose series. MeOH-3%HCl gives 5-methylmethylfructopyranos- [a]D are predicted thus : acetates of a-fructopyranos- ide, which when methylated with Me2S04-NaÓH and idyl chloride +82-0°, fluoride + 8-0°, and bromide then twice with Mel-Ag20 gives a syrup, b.p. 110°/ + 119-2°: a-fructopyranose tetra-acetate +9-2°. 0-03 mm., hydrolysed (3% HC1) to 1 : 3 : 4 : 5- tetramethylfructose, and is converted through its R. S. C. Colour reaction for fructose. S. S u g a h a ra (J. osone (as above) into 3:4: 5-trimethylfrudose, [a]j,° Biocliem. Japan, 1935, 22, 85—91).—Treatm ent of —43° in MeOH, which with MeOH-HCl slowly dii. aq. fructose (I) with H2S04-Na2W04 at slighth7 affords a fructopyranoside (II), indicating substitution in position 5. (II) is furtlier methylated and then alkaline reactions produces a gi-een ppt. At suitable concns. {e.g., 0-015%), (I) but not glucose (II) gives hydrolysed to tetrametl^lfructopyranose, which shows that (I) probably contains a pyranose ring. J. L. D. a positive reaction. Uric acid, C0(CH2-0H)2, and adrenahne react similarly to (I) even after addition Crystalline structure of the sugars. II. of NaOH, when (I), (II), and arabinose give negative Methylated sugars and the conformation of the responses. The application of the reaction to pyranose ring. E. G. Cox, T. H. Goodwin, and deproteinised blood, uric acid-free urine, etc. is (Miss) A. 1. W agstaff (J.C.S., 1935, 1495— 1504; described. F. O. H . ORGANIC CHEMISTRY. 1485 Inversion of solutions of sucrose.—Sco this MeOH solutions (Bourąuelot et dl., A., 1913, i, 542, vol., 1468. 781) has ceased, further addition of glucose affords more (II), showing that a true eąuihbrium has been Test of Wein's grayimetric method for deter reached. The real cause is tho sp. action of (I) on mination of maltose. C. Zach (Mitt. Lebensm. P-glucose (III) and the decrease in the ratio (Cj) Hyg., 1935, 26, 192— 195; cf. Z. Anal. Chem., 1887, P-/total glucose as the [MeOH] inereases (A., 1934, 26, 255).—The method is slightly modified to bring 927). The yal. of i^= [(III)][M e0H ]/[(II)][H 20] is it into linę with the invert-sugar determination. independent of [MeOH] and is 0-149, the proportion The mg. of Cu20 corresponding with known wts. of of (III) being determined polarimetricahy. The maltose monohydrate are tabulated. E. C. S. inerease in TT,= [total glucose] [Me0H]/[(II)][H20 ]= Comparative investigations on caramel and KpjC-y, observed with inereasing [MeOH] (Euler molasses colloids. A. J oszt and S. Mo łin sk i et al., A., 1924, i, 1266) is due to diminution of C\ (Kolloid-Beih., 1935, 42, 367—383).—Three produets conseąuent on the displacement of tho eąuihbrium of caramelisation of sucrose have been isolated by (III) a-glucose towards the right. The strict dialysis and their properties (solubility, composition, application of the mass-action law is confirmed pentosan content, p u, electrotitration behaviour, by the const. vals. of Kp for the p-glucosides of surface tension, yiscosity, extinction coeff., colour, 0Et-CHo-CH2-0H (0-380) and of mannitol (0-051). and ease of coagulation) determined. Points of J. W. B. similarity of these produets with the colloids present Structure of cymarose. R. C. Elderfield (J. in molasses are discussed. E. S. H. Biol. Chem., 1935, 111, 527—535).—Partly a de- tailed account of work previously reported (this Structure of heterosides based on their ultra- vol., 848). Cymarose (I) is proved to be 3-methyl- violet absorption spectra. (Mm e.) R amart-Lucas digitoxóse. (I), Br, and Ba(OBz)2 in H20 give and J . R abatę (Buli. Soc. ehim., 1935, [v], 2, 1596— cymaroladone, b.p. 110—lll°/0-2 mm., [a]'£ —25° 1625).—Acetobromoglucose and phenols in ąuinoline in H20 (stable), leading to cymaronic acid phenyl- with freshly prepared Ag20 give the following: hydrazide, m.p. 154°, [a]f? + 2° in MeOH, and, by phenol-, m.p. 132— 134°, [a]B —60-8°, o-, m.p. 166°, Ag20-M el, 5-methylcymaro-\ : 4-lactone (II), b.p. 78— [a]D —68-3°, m-, m.p. 178°, [a]D —67-9°, and p- 80°/0-2 mm., [a]“ —36° in CHC13, which affords cresol-, m.p. 177°, [a]D —68-6°, guaiacol-, m.p. 152-5°, 5-methylcymaronic acid phenylliydrazide, m.p. 139°, [a]D —70-5°, and resorcinol-glucoside, m.p. 210°. [a]j,4 —6° in MeOH. Methylcymaropyranoside Piceoside and Cl2 in 5% Na2C03 yield chloropiceoside, (mixture; prep. by 0-25% HCl-MeOH), b.p. 54— m.p. 209-5°, which with emulsin gives glucose and 64°/0-2 mm., -with M el-Ag20 gives Me methylcymaro chloropiceolj 107-5°. Curves are given for the ab pyranoside, b.p.45—48°/0-2 mm., which with 0-lAT-HCl sorption spectra of these glucosides, together with a t 100° (10 min.) affords i-methylcymaro-1 : 5-lactone the curves for p-methyl-, benzyl-, amygdonitrile-, (III), b.p. 88—90°/0-2 mm., [a]£ +30° in CHC13 phenylethyl-, salicyl-, and cinnamyl-glucoside, (Ba salt), giving 4c-methylcymaronic acid phenyl- methylmannoside, aucuboside, amygdaloside, benzyl- hydrazide, m.p. 115—116°, [aft7 +17-5° in CHC13. galactoside, betuloside, arbutoside, methylarbutoside, (III) and conc. H N 03 a t 90—94° lead to ap-di- salicoside, coniferoside, helicoside, monotropitoside, methoxyglutardimethylamide, m.p. 173—174°, [a]^ lusitanicoside, geoside, populoside, and the corre —56° in H 20. The known position of the Me in sponding alcohols and phenols. The results are (III) proves that of the Me in (H). Me dimethyl- discussed. F. R. G. digitoziside, b.p. 43—46°/0-2 mm., from digitoxose Enzymie synthesis of a-glucosides. I. Vin t i- by OTAr-HCl-EtOH at room temp. (1 hr.) and LEsetr, C. N. I onescu, and A. K izyk (Buli. Soc. subseąuent methylation (Purdie), is shown by changes Chim. Romania, 1935, 17, 131— 136).—In tho of a during glucoside formation to be a mixture of presence of brewers’ yeast extract trimethylene furanose and pyranose forms. When hydrolysed glycol (I) and glucose afford trimethylene glycol-a- and oxidised, it yields (II). R. S. C. monoglucoside (II), m.p. 96°, [a]“ +137-48° (? in H20), obtained pure by Ba(OH)2-hydrolysis of its Hemicellulose from oat hulls. E. A n d erso n A c5 derivatiye, m.p. 84°, [a]i>° +112-62° in 95% EtOH, and P. W. K rznarich (J. Biol. Chem., 1935, 111, the isolation of which from the substrate is deseribed. 549—552).—A mixture of hemicelluloses is obtained The amount of (II) formed inereases with inerease from oat husks by extraction with aq. NaOH after in (I) concn. Mannitol-tx-monoglucosidc, m.p. 140°, removal of starch with hot H20. Hydrolysis with Mi? +S8-440, is similarly prepared. J. W. B. dii. H2S04 gives A'-Ray examination of the transformation of phenólsulphonate, m.p. 179-5—180-5° (corr.), toluene- sodium cellulose by the action of carbon disul- sulplwnate, m.p. 193-5—195° (corr.), and 2-naphthalene- phide. W. Schramek and F. K u ttn er (Kolloid- sulphonate, m.p. 227° after softening a t 224°. Boih., 1935, 42, 331—366).—The action of CS2 Leucine yields a toluenesulphonate, m.p. 153—153-5° gives a sol. product only when the eryst. component (corr.), and 2-naphthalenesulphonate, m.p. 202—203° of the fibrę is Na-cellulose I ; other Na-cellu- (corr.). The phenolsulphonate, m.p. 182—183° (corr.), loses give insol. or partly sol. produets. The CS2, and '2-naphthalenesulphonate., m.p. 157—-158° (corr.), aft-er adsorption bv the fibrę, reacts to form of (3-aminobutyric acid are described. H. W. SNa-CS-O(CęH9O4)(C6H10Os),,. E. S. H. Creatinephosphoric acid. K. £eile (Z. pliysiol. Ammonia-cellulose. K. H ess and C. T rogus Chem., 1935, 236, 263—272; cf. Fiske et dl., A., (Ber., 1935, 68, [5], 1986—1988).—Condensation 1929, 590).—When creatine is boiled with P0C13 of dry NH3 on cellulose at —77° to —80° and its a eryst. Ca salt very similar to but isomeric with subseąuent removal by evaporation causes a profound Ca salt of the natural acid is obtained. The synthetic alteration in the Y-ray diagram of the materiał. acid is more slowly hydrolysed than is the natural, The product is regarded as NH3-cellulose poor in and its hydrolysis is not accelerated by molybdate. NH3 or as a third modification of cellulose provisionally The titration curves of the acids are similar. Di- named cellulose III. If it is treated with H20, phenoxyphosphoryl cliloride (I) with CS(NH2)2 yields MeOH, or aq. NH3, the original Y-ray diagram is diphenoxyphosphoryllhiocarbamide, m.p. 149°, which, not restored. It does not appear to be the primary when warmed with HgO, gives the Hgu salt, m.p. 135°, product of the reaction, sińce the diagram depends of diphenoxyphosphorylcyanamide. Methylisothio- on the rate of evaporation of the NH3. H. W. carbamide (II) with (I) gives the corresponding salt, Mono- and tri-choline orthophosphates. E. L. m.p. 170°, of (II). W. McC. J ackson (J. Amer. Chem. Soc., 1935, 57, 1903— Synthesis of alkylamino-acids corresponding 1905).—Cholinę cliloride, H 3P0 4, and P20 5 lead to with chitosamic acid. E. Votoćek and R. L ukeś Ca cholinę diphosphate (I), N ^ e3 1934, 9, 663—672; Chem. Zentr., 1935, i, 1532).— sec. with H202 yields [Pt etn40H]Cl2,2H20 (VII) Ricinoleamides of varying properties are obtained by (yellow), dehydrated to a yellow anhyd. salt, recon- successive treatments of castor oil with EtOH-NH3; verted into (VII) in moist air. (VII) with HC1 the first reaeting fraction yields an amide of m.p. yields (I), and with HBr green needles, presumably 66-5—67°, [ 50°), also prepared from (I) and tert.-heptyl iodide, aminodiphenyl, or from (II) by diazotisation. With b.p. 64—66°/21 mm. (obtained from CEt3’OH and Br (1 mol.) in AcOH, (I) gives the. Ac., derivative, dry HI). A tracę of an unidentified aminę was also m.p. 228°, of 5-bromo-2 : 4'-diaminodiphenyl [hydro formed. (I), (III), and octylene (obtained from chloride, m.p. 253—255° (decomp.)], which gives rise sec.-octyl alcohol and II2S04) when heated under to 3-bromodiphenyl and to 2 : 5 : 4'-tribromodiphenyl, seal a t 210—240° (24 hr.) yield (II), an unidentified m.p. 76°. 4 : 2'-Dibromo-3-aminodiphenyl, m.p. 8S° primary aminę, and scc.-oclylaniline, b.p. 288—289° (Ac2 derivative, m.p. 118°), obtained from the N 0 2- (corr.)/751 mm., 150°/20 mm. ('p-toluensulphonyl compound, yields 2:3': 4'-tribromodiphenyl, m.p. derivative, m.p. 59°), also prepared from (1) and 91°. W ith Br (2 mols.) (I) forms the Ac2 derivative, sec.-octyl bromide. Similarly (I), (III), and CMe2!CMe2 m.p. 235°, of 5 : 3'-dibromo-2 : i'-diaminodiphenyl yield $-\>-aminophcnyl-$y-dimethylbulane, b.p. 138— (IV), m.p. 121°, which can bo converted into 3 :3'- 139°/23mm. (Ac derivativc, m.p. 118°; hydrochloride), dibromocliphenyl. 4 : 2'-Dichlom-3 : 5'-dibromodi- and an unidentified Sec. aminę. The relative yields phenyl, m.p. 100°, is obtained from either (III) or of primary and sec. amines depend on the experimental (IV), By diazotisation and treatment with KI, conditions; - excess of (I) and a smali amount of (IV) yields 5 : 3'-dibromo-2 : 4'-di-iododiphenyl, m.p. (III) favour the formation of an alkylaniline. 113°. E. W. W. H. G. M. Condensations between maleic anhydride and l-Chloro-3 :4-dinitrobenzene series. III. A. phenylhydrazones. G. L a P arola (Gazzetta, 1935, Mangini (Atti R. Accad. Lincei, 1935, [vi], 21, 65, 624—627).—Maleic anhydride (I) condenses with 759—763; cf. A., 1934, 177; this vol., 855).—Experi- phenylhydrazones in CGHfi at 70° to form benzylidene, ments on the reactivity of the 3-N02-group of m.p. 123—124°, -p-toluylidene, m.p. 107°, anisylidene, 1:3: 4-C6H,Cl(N02)2 with nitroanilines, toluidines, m.p. 136°, and salicylidene, m.p. 126°, derivatives of aminophenols, and aminobenzoic acids show: (1) maleic acid monophenylhydrazide, that substitution takes place relatively easily with CHR;N*NP1vC0'CH:CH'Ć02H. (I) does not react m- and p-C6H4Me-NH2, m- and ^-N H 2-C6H4*OH, with CHPh:N-NPhMe. ' E. W. W. and m- and j)-NH2-C6H4-G02H, but does not occur with the corresponding o-compounds; (2) that no Stereoisomerism of azoxybenzene [deriv- reaction occurs with the three nitroanilines, even in atives]. V. E. M uller and R. I llgen (Annalen, CjHjyOH after prolonged boiling. The following 1935,5 2 1 ,72—80; cf. A., 1933, 388).—CHPhMe-C02H were obtained : 5-clilaro-2-nitro-3'-melhyl-, m.p. 192— and fuming HN03 under defined conditions give~o- 193° (decomp.), 5-chloro-2-nitro-3'-hydroxy-, m.p. and ^-nitrohydratropic acid (I), m.p. 87°. (I) is 143—144° (decomp.), and 5-chloro-2-nilro-4‘-liydroxy- reduced by Zn dust in aq. NaHCÓ3-NH4Cl to p-hydr- dipheny laminę, m.p. 141— 142°; 5-chloro-2-nilro- oxylaminoatropic acid (II), m.p. 155— 158° after diphenylamine-Z'-, m.p. 240-5—241°, and -4='-carb- sintering at 95—96°, which with FeCl3 yields tho oxylic acid, m.p. 270—272° (decomp.). T. H. P. ip-NO-acid (III), m.p. 93°. (II) and (III) in MeOH give pp'-di-(a-carboxyethyl)azoxybenze‘>ie (IV), m.p. New derivatives of 2 :2/-dinitrobenzidine. III. 198°. Resolution of (I) by ąuinine gives the d- and D. P onte (Giorn. Farm. Chim., 1934, 83, 847—850; 1 -forms, m.p. S8-5° and 86-5°, [a]g> +10-9°, -11-2° Chem. Zentr., 1935, i, 1863; cf. this vol., 613).— in MeOH, and thence the d- and \-forms of (II), m.p. Partial reduction of 4 : 4'-di-iodo-2 : 2'-dinitrodi- 155— 158°, [a]j? +9-6° (V), -10-6° (VI) in MeOH, phenyl yields 4 : 4'-di-iodo-2-nitro-2'-aminodiphenyl, and of (III), m.p. 91°, and 92°, [aft2 +14-1° (VII), m.p. 155— 156°. 4 : 4'-[? 2 : 7-]Di-iodocarbazole, m.p. — 14° (VIII) in MeOH, respectively. (VI) and (VII) 265—266°, and a di-iododiphenylenciodonium iodide or (V) and (VIII) afford the dl-(-\- —)-form of (IV), are deseribed. H. N. R. m.p. 198°. The d -(+ + )-form of (IV), m.p. 198°, Diphenyl series. VI. Halogenation of 2:4'- Md +14-3° in MeOH, is obtained from (V) and (VII), diaminodiphenyl. V. B e lla v ita (Gazzetta, 1935, in conformity with the as-structure of the N.,0 group. 65, 632—646).—2 : 4'-Diaminodiphenyl (I) (1 mol.) R. S. C. treated in AcOH with Cl2 (1 mol.) yields the *lc2 deriv- New azo-derivatives of guaiacol. I. C. M. ative, m.p. 200°, of 5-chloro-2 : A.-diaminodiphenyl D an iel and W. A. F letcher (Trans. Kansas Acad. (hydrochloride, m.p. 255°), which is diazotised and con- Sci., 1934, 37, 119— 122).—The following are verted through 3-chlorodiplienyl into m-C6H4Cl*C02H, deseribed : 4-hydrozy-‘.i : 2'-dimethoxy-, m.p. 101-8°, and into 2:5: 4'-trichlorodiphenyl, m.p. 67°. 4 :~2'- ±-hydroxy-‘.ł-methoxjj-2'-ethoxy-, m.p. 113-9°, 4-hydr- Dichloro-3-aminodiphenyl, m.p. 44°, obtained by oxy-3-methoxy-4:'-ethoxy-, m.p. 95-1°, and In 4-bromo-2-benzeneazo-a-naphthylamine (I) and pliide, m.p. 228° [obtained when anthraquinone-l- its derivatives, the benzeneazo-gronping is unusually bromothiol (I) is heated (150°; 5—6 hr.) with excess stable. The following are prepared: 4-bromo-2-j)- of p-cresol (II) in PhCl], is oxidised by H202-Ac0H toluene-, m.p. 170° (phlhalimido-dcriva.tive, m.p. 220°), a t 100° to the sulphone, m.p. 220° (Me ether, m.p. and -2-p-bromóbenzene-, m.p. 149°, -azo-a-naphthyl- 225°), converted by 22V-NaOH a t 130° into 1 -anthra- amine; diphenyl-])])'-bis-(4-bromo-2-azo-a.-na,phthyl- guinonyl 'A-sulphino-y-tolyl etlier, m.p. 174°. l-Anthra- amine), m.p. 232°; 4-bromo- ąuinonyl 2-acetoxy-l-naphthyl sidphide, m.p. 20S°, is 1 - phthalimidonaphihalene,oxidised by H 20 2-A c0H at 100° to the sulphone, m.p. m.p. 220°. T heplithalimido- 264—265°, hydrolysed by hot H 2S04-E t0 II to 1'- derivative, m.p. 234°, from anthraquinonyl-2-hydroxy-\-naphthylsulplione, m.p. (I) is reduced (Zn in AcOH) 210°, which rearranges in the presence of 2iV-NaOH to 1 : 2-o-benzoylene-5 : 4- at the b.p. to \-antliraquinonyl l-sulphino-2-naphthyl ( ) (ap - 4' - bromonaphth)imin- ether, m.p. 160° (decomp.). This is converted by the azole (II), m.p. 246°. (I) forms N i, m.p. 280°, and Cu, usual method into 2 - a - anthraquinonyloxy-\-na ph thyl m.p. > 300°, co-ordination compounds; with PhCHO disidphide, m.p. 238°, and on oxidation with KMnÓ4 and MeCHO it yields 1 -anilino-2-phenyl-4: 5-(a(3-4'- followed by treatm ent with 20% H 2S04 a t 100° bromonaphth)iminazole (III), m.p. 195°, and the yields l-ańthraquinonyl 2-naphthyl ether, m.p. 170° -2-methyl analoguc, m.p. 202°. E. W. W. (lit. 180°), also obtained from l-chloroanthraquinone Preparation of some diazo-thioethers of thio- and p-C10H7-OK when heated a t 150° during 2 hr. (3-naphthol. J. T. Dukn, jun., and W. A. F letcheb 6-Bromo-P-naphthol and (I) w'hen heated a t 110° (Trans. Kansas Accad. Sci., 1934, 37, 123—126).— (4 hr.) yiold \-anthraquinonyl G-bromo-2-hydroxy-l- Diazonium chlorides and thiophenols afFord sulphides naphthyl sulpliide, m.p. 280—281°, the Ac derivative, of the type Ai-NiN-S-Ar. The following are dc- m.p. 240°, of which is oxidised by H202-Ac0H at scribed: diazobenzene, m.p. 59-5—60-5°, m-diazo- 100° to 1 '-anthraquinonyl-(S-bromo-2-acetoxy-\-naphthyl łoluene, m.p. 59—61° (decomp.), p - d i a zonaphthalcne, sulphone, m.p. 223°. This is hydrolysed (H2S04- m.p. 101— 102°, sulphodiazobenzenc (Na salt, m.p. > EtOH) to the corresponding OH-sulphone, which on 275°), and 4-sulpho-\-diazonaphthalene (Na salt, m.p. rearrangement yields \-antliraquinonyl l-sulj)hino-6- > 240°), 2-naphthyl sulphides; Na salt of p -sidpho- bromo-2-naphthyl ether, m.p. 170° (decomp.), reduced diazobenzene p -tólyl sulpliide, decomp. on warming. to 2-a.-anthraquinonyloxy-(]-bromo-\-naphthyl disul- Ch . Abs. (?•) phide, m.p. 283—284°. Acid hydrolysis of 1 -anthra- Acyl derivatives of o-anisidine. L. H. Am u n d quinonyl-$-acetoxyethylsulphone, m.p. 162—163° [ob se n and C. B. P ollabd (J. Amer. Chem. Soc., 1935, tained by oxidation of the corresponding sulpliide (III) 57, 2005—2006).—The following N -derivatives of with H 20 2-A c0H at 100°], yields 1 -antliraquinonyl-$- o-anisidine are prepared. EtCO, m.p. 33-5—34-5°; hydroxyethylsulphone, m.p. 198°, which on rearrange Pr“CO, m.p. 24-5—25-5°; BuaCO, m.p. 25-5—26-5°; ment with Na0H-Et0H-H20 at the b.p. yields a tsovaleryl, m.p. 49—49-5°; w-hexoyl, m.p. 33— sulphinic acid (IV) which is methylated to methyl- 33-5°; ?i-heptoyl. m.p. 42—43°; CH,Ph-CO, m.p. $-l-anthraquinonyloxyethylsulphone, m.p. 145—146°. 82-5—83°; Ph-[CH,]2-CO, m.p. 59r5—60°; m- \-Anthraquinonyl [i-acetoxyethyl sulphoxide, m.p. 168° C8H4Br-C0, m.p. 112-5—113°; ^-OMe-C0H,-CO, m.p. [also obtained by oxidation of (III)], is hydrolysed to 96-5—97-5°; Bz, m.p. 66—67° (lit. 59-5°); Ac, m.p. \-anthraquinonyl {i-hydroxyethyl sulphoxide, m.p. 220°, 85—35-5°; Bz2, m.p. 149-5—150°; and (EtCO)2, which rearranges rapidly with Na0H-Et0H-H20 at m.p. 62-5— 63-5°. o - Benz m ethylami dophenyl benzo- the b.p. yielding (IV) and di-([i-\-anthraquinonyloxy- ate has m.p. 114— 115°. R. S. C. ethyl) disulphide, m.p. 223°, also obtained by reduc tion of (IV). K 2-thiolbenzoate when heated with Amidines of the type of holocaine and deriv- CH2C1*CH2’0 H a t 100° (1 hr.) yields 2-carboxyphenyl atives. E. B ubeś and M. K u n d eba (Ćasopis Cesko- fi-hydroxyethyl suljMde, m.p. 127°, oxidised by H 20 2- slov. Lek., 1934, 14, 272—285; Chem. Zentr., 1935, H20 at 90° to the sulphoxide, m.p. 179°/ further i, 1368).—3 : 5-Dibromo-4-acetamidophenetole con- oxidised by H202-H 20 to the sulphone, m.p. 195°. denses (POCU) with p-phenetidine to jdeld N -3 : 5- The last two substances were recovered unchanged dibromo-Yi-phenetyl-^K-p-phenetylacetamidine (I), when heated (100°, 2 hr.) with Ar-NaOH. 2-Acet- m.p. 131—132° (hydrochloride; sulpliate; phosphate\ amido-2'-carboxydiphenylsulphone, m.p. 282°, and the tartrate; salicylate). (I) is also formed from acetyl- corresponding aminę were unaffected by 2A7-NaOH and 3 : 5-dibromo-/)-phcnetidine; with Ac20 and a t 100° during 3 hr. The following 4-hydroxy-m-tolyl EtOAc it yields 3 : 5-dibromoacetyl- and, with BzCl, sulphides were obtained by boiling the K salt of 3 : 5-dibromobenzoyl-p-phenetidine. Di-p-phenetyl- 4-hydroxy-m-tolylthiol with the appropriate bromo- acetamidine, m.p. 116— 117° (acetale; tartrate; sali compound in EtOH or Et0H-H20 : 4-carboxy-2- cylate, m.p. 176—178°), is formed in an analogous nitrophenyl (V), m.p. 215° [Na s a lt; Ac derivative, manner. H. N. R. m.p. 163°; the corresponding sulphone (VI), m.p. Rearrangement of o-hydroxysulphones. V. F. 265—266°]; 2-carboxyA-nitrophenyl (VII), m.p. 237° Galbbaith and S. Smiles (J.C.S., 1935, 1234— 1238: [Ac derivative, m.p. 230—231°; gives the laclone, cf. A., 1934, 647).—The rates of change of a series of m.p. 178°, with hot Ac20 ; the corresponding sulphone o-hydroxysulphones to ether-sulphinic acids and the (VIII), m.p. 245°J; 4-benzoyl-2-nitrophenyl, m.p. 165° behaviour of some anthraquinonyl sulphones in the [the corresponding sulphone (IX), m.p. 154°]; 2-benz- presence of alkali are in agreement with previous oyl-4-nitrophenyl, m.p. 139° [prepared from 2-bromo- eonclusions. \-Anthraquinonyl 4-hydroxy-m-tolyl sul- 5-nitrobenzophenone, m.p. 122°; the corresponding ORGANIC OHEMISTRY. 1491 sulphone (X), m.p. 209°]; 4-nitroplienyl [improved aminodiphenyl ether (IX) are rearranged respect- prep.; the corresponding sulphone, m.p. 162° (lit. ively to the Ac, m.p. 205°, and Bz derivatives, m.p. 158°)]. Rearrangement of (VI) gives a sulphinic acid, 172°, of 5-bromo-2' : 4'-dinitro-2-hydroxydiphenyl- converted without purification into 4- carboxy-2-nitro- amine (X) (p-toluenesulphonate, m.p. 211°), and are phenyl ‘i-methanesulphonyl-Tp-tolyl ether, m.p. 233°, and hydrolysed, with rearrangement, to (X). The o-, di-(Tp'-carboxy-o'-nitrophenoxy-m-tolyl) disulphide, m.p. m.p. 178° [also obtained from (X) and excess of (V)], 241°, by the usual methods, and degraded by succes- and m-nitrobenzoyl derivatives, m.p. 189°, of (IX) are sive treatm ent with HgCl2 and HC1 (ef. this vol., 485) rearranged respectiyely to the o- (XI), m.p. 202°, and to 4:-carboxy-2-nitrophenyl p-tolyl ether, m.p. 212° (Et m-nitrobenzoates, m.p. 183°, of (X). Tho foregoing ester, m.p. 78°), identical with the ether synthesised dcrivatives of (X) were also obtained directly from from (II) and 4-bromo-3-nitrobenzoic acid. Similarly (X). The Ac, m.p. 160°, o-, m.p. 200° [also obtained (VIII) yields a sulphinic acid, characterised as di- from 5-chloro-2' : 4'-dinitro-2-hydroxydiphenylamine (o'-carbpxy--p'-nitrophenoxy-m-tolyl) disulphide, m.p. (XII) and ęxcess of (V)], and m-nitrobenzoyl derivatives, 257°. This and the preceding disulphide are con- m.p. 197, of 4-chloro-2' : 4'-dinitro-2-aminodiphenyl verted by warm NaOH-EtOH into (VII) and (V), ether are rearranged respectiyely to the Ac, m.p. 207°, respectiyely (cf. A., 1932, 735). By similar methods o- (X III), m.p. 196°, and m-nitrobenzoyl derivatives, the crude sulphinic acid obtained by rearrangement m.p. 184°, of (XII). (XI) and (X III) were not of (X) yields 4:-nitro-2-benzoylphenyl p -tolyl ether, m.p. rearranged under any conditions. Attempts to 129°, also prepared from (II) and 2-bromo-5-nitro- prepare o-nitrobenzoyl derivatives of 2' : 4'-dinitro-2- benzophenone, and (IX) yields 2-nitroA-benzoylphenyl hydroxy-5-carboxydiphenylamine and the isoineric p -tolyl ether, m.p. 100°, identical with that synthesised 2-amino-4-carboxydiphenyl ether or of their dinitro- from (II) and 4-bromo-5-nitrobenzophenone. phenyl esters were unsuccessful. II. G. M. IV. 'N-Melhyl-p-toluenestdphon-o-anisidide, m.p. Rearrangement of o-aminophenyl ethers. III. 100° (obtained from jj-toluenesulphon-o-anisidide), is 2-Acylamidodiphenyl ethers. K. C. R oberts and hydrolysed by heating under seal with fuming HC1 C. G. M. d e W orms. IV. A7-Alphylphenoxazines. a t 170° (5 hr.) to o-methylaminophenol, which with K. C. R oberts and (Miss) H. B. Clark (J.C.S., 1935, (VII), NaOEt, and EtOH yields 2': 4'-dinitro-2-hydr- 1309—1312, 1312—1313; cf. this roi., 484).—III. oxy-Ń-methyldiphenylamine (XIV), m.p. 160°, and The rates of rearrangement of some aeylamidodi- 2' : 4:'-dinitro-2-methylaminodiphenyl ether, m.p. 182°, phenyl ethers, 1:3: 6-NHY,C0H3R -O-CcH3(NO2)2, to converted by C5H5N-H20-alkali, or by NaOH- 2-acyloxydiphenylamines E t0 H -H 20, a t 100° into 3 - nitro - Q-methylphenoxaz ine, (N 02)2C6H3*NH-C6H3R-0Y (I) (R = H , Me, I, Br, m.p. 182— 183° [also obtained from warm alkaline Cl; Y=Ac, Bz, o- and wi-N02-CgH4’CÓ, picryl; not solutions of (XIV)]. (II), (VII), and NaOEt in EtOH all combinations of R and Y have been studied) are in yield ON-6i.s-2 : i-dinitrophenyl-o-aininophcnol, m.p. generał agreement with the mechanism previously 176°, conyerted by C5H5N-Na0H-H20 into 3(?)- proposed. Those of the acetamido-ethers, however, 7iitro-Q-dinitrophenylphenoxazine, m.p. 230—233° (de appear to be anomalous. 2' : 4'-Dinitro-2-hydroxy- comp.), unaflected by boiling alkali. (IV) would not diphenylamine (II) [o-nitrobenzoate (III), m.p. 151°], condense with (VII) under conditions whicli precluded picryl chloride, and NaOAc or NaOEt yield an unstable rearrangement of the ether. H. G. M. picrate, decomp. 140—145°, converted by warm (3-Substituted ethylamines. II. Catalytic C5H 5N-H 20 into 2 : Ą-dinitro-~N-(2' : 4 '-dinitrophenyl)- hydrogenation of oximes. O. Schales (Ber., 1935, phenoxazine, decomp. 305—310°. 2 ': 4'-Dinitro-2- 68, [JS], 1943— 1945).—The production of sec. amines aminochphenyl ether (IV) with cokl Ac0H-Ac20- during the catalytic hydrogenation of oximes is H20 gives an Ac derivative, m.p. 146°, which is re ascribed to the intermediate formation of aldimine arranged to (I) (R=H, Y=Ac), and with (I) which condenses with the primary aminę. The 0-N0 2-C6H4-C0 Cl (V), COMe2, and anhyd. Na2C03 occurrence of (I) in appreciable amount is avoided gives the o-nitrobenzoyl derivative, m.p. 232°, which is by slowly adding the oxime in AcOH to the Adams rearranged to (III) in C5H5N. (IV) with excess of catalyst in Ac0H-H2S04. Under these conditions (V) yields (III). A similar rearrangement also occurs P-p-methoxyphenylethylamine and homopiperonyl- during picrylation. The picryl derivative, decomp. amine are obtained in 80% and 84% yield, respect 245—250°, of (IV) is obtained when 2-hydroxyphenyl- iyely, from the appropriate oxime. H. W. picrylamine (VI) is treated with C6H3Ć1(N02)2 (VII), EtOH, and NaOAc, and is converted by C5H5N-H20 Action of dieyanogen on phenols. G. H ahn (water-bath) into 1 :3-dinitrophenoxazine. (VI), (VII), and W. Leopold (Ber., 1935, 68, [JB], 1974— 1986).— and NaOEt-EtOH yield 2-nitro-N-picrylphenoxazine, Contrary to Machek (A., 1932, 1245; 1933, 709), m.p. 225—230°. i-Iodo-2’ : 4 '-dinitro-2-acetamidodi- the action of C2N2 on phenols invariably involves phenyl ether, m.p. 163°, is rearranged to S-iódć-2' : 4'- addition of the phenolic OH to the triple linking of dinitro-2-acetoxydiphenylamine, m.p. 200° [also ob- C2N2. Nuclear cyanisation is never obseryed. The tained from the corresponding hydroxyamine (VIII)], primary products are so unstable that isomerisation and hydrolysed, with rearrangement, to (VIII). cannot be attempted. Passage of C2N2 into aq. Similarly 4c-iodo-2' : 4'-dinitro-2-(o-?iitrobenzamido)di - pyrocatechol (I) causes separation of an unstable phenyl ether, m.p. 194° [also obtained from (VIII) and oil almost instantaneously transformed by dii. excess of (V)], is rearranged slowly to the o-nitrobenzo- HC1 into di-o-hydroxyphenyl di-imino-oxalate (II) ate, m.p. 174°, of (VIII). The Ac, m.p. 171°, and [•C(!NH),0*CbH4*0H]2, decomp. 220°, which passes Bz derivatives, m.p. 176°, of 4-bromo-2' : 4'-dinitro-2- when heated into pyrocatechyl carbonate, m.p. 1492 BRITISH CHEMICAL ABSTRACTS.----A. 120°, thus excluding the possibility of the presence of indenone-2'-hydrindane-1 : 3-dionc, m.p. 190-5— 191-5°. Machek’s “ 3-cyanopjTrocatechol.” The constitution This with MgPhBr yields successively l-liydroxy-l'- of (II) follows from its hydrolysis by boihng HC1- keło-l: 3 :3 '-triphenyl-2 :2'-di-indenyl, m.p. 244—245°, EtOH to (I) and (•CO-NH2)2, its solubility in NaOH, bis-2 : 2'-(I : %-diphenylinden-2>-ol), m.p. 292°, and and its ability to yield a Ac2 and a Bz2, m.p. 129— bis-2 : 2'-(l-chloro-l : 'd-diphenylindene), m.p. 237— 130°, derivative. Treatm ent of (II) with CH2N2 242° (unreactive to Zn and Hg, but giving a Na in C0 Mc2 affords di-o-anisyl di-imino-ozalate, m.p. derivative with 40% Na-Hg), identical with the pro- 164°, which is insol. in alkali and transformed by ducts of Eck and Marvel (preceding abstract). 4iV-ŃaOH into guaiacol and (•CO-NH2)2. The con R. S. C. stitution (0H-CcHj-0)2C(CN)-NH2 is assigned to Synthesis of pharmacologically important the oil. If C2N2 is passed into (I) in H 20 containing amines. X. Catalytic hydrogenation of co- H3BO3 (I) is pptd. witliout intermediate production nitrostyrenes to (3-arylethylamines. K . K in d l e r of oil. In presence of NaH2P0 4 the compound and E. B randt (Arch. Pharm., 1935, 273, 478— [•C(NH2)(0H)-0-C6H4-0H]2, m.p. 144“ (decomp.), 483; cf. A., 1934, 669).— Owing to compound-iorma.- is produced, the constitution of which is established tion with IŁSO,, the appropriate co-nitrostyrenes are by the formation of a Mc2 ether, m.p. 129— 130°, readily hydrogenated in Ac0H-H2S04 to good a A c4 derivative, m.p. 105°, and by its hydrolysis yields of tyramine, mescahne, homo-veratrylamine, to (I), NH4C1, and H2C204. The dependence of the -piperonylamine, and -myristicylamine. R. S. C. course of the reaction on tho p B of the solution is Synthesis of substances related to ster ols. discussed. The constitution [C6H4<^q^>C(NH2)-]2 IV. Derivatives of chrysene (contd.). H. J. is assigned to the product, decomp. 139°, obtained when Le w is, G. R. R amage, and R . R obinson (J.C.S., the reaction is conducted in MeOH. It is insol. 1935, 1412—1414).— fiy-Dianisyladipic acid-b, m.p. in dii. NaOH and unaffected by CH2N2. Warm 180° (Me ester, m.p. 67°, isolated from the Et20-sol. AcCl causes resinification. I t is hydrolysed to portion of the reduction products of Me 4-methoxy- (I), H2C20 4, (•CO,NH2)2j and occasionally o-liydroxy- cinnam ate; A., 1933, 828), is cyclised by A1C13 in phenyl oxalate. H. W. C2H2C14 to 2 : ll-diketo-5 : li-dimethozy-, m.p. 220°, New method for fission of methylenedioxy- reduced (Zn-Hg-conc. HC1) to 5 : 14:-dimethoxy- groups. L. H klfer and M. Mottier (Rev. Marques 1 : 2 : 9 ; 10 : 11 : 18-hexahydrochrysene-b, m.p. 140— Parfum. Savonn., 1934, 12, 362—364; Chem. Zentr., 141°. Reduction (Al-Hg in E t20) of Me 3-mełhoxy- 1935, i, 1862).—Safrole gives a blue colour with cinnamate affords mainly Me ę,-3-methoxyj)henyl- NaNH2, which disappears on heating, with production propionate, b.p. 146°/12 mm., and some Me $y-di-3- of tar and evolution of NH3. The reaction is moder- methoxyphenyladipate-&, m.p. 139-5°, hydrolysed to ated by using an indifferent solvent, propenylpyro- the acid, m.p. 247—248°, cyclised (90% H 2S04 at catechol (methylated to woeugenol and tsochayibetol) 100°) to 2 : 11-dikeło-G : 15-dimethoxy-,m.-p.&boxib350°, being formed; isosafrole is broken down similarly. reduced to 6 : 15-dimethoxy-l : 2 : 9 : 10 :11 :18-hexa- Pyrocatechol methylene ether and dihydrosafrole hydrochrysene-a, m.p. 159°. Condensation of piperonal similarly undergo fission to pyrocatechol and n- with MeOAc and Na affords Me 3 ; i-methylenedioxy- propylpyrocatechol, respectively. H. N. R. cinnamale, m.p. 133—134° [probably not identical with the ester, m.p. 68—69°, of Feuerstein et al. (A., Synthesis of bis-2 : 2'-(l ; 3-diphenylinden-3- 1901, i, 465)], reduction of which gives only Me ol). Rubrene problem. J. C. E ck and C. S. (3-3 : i-methylenedioxyphenylpro]ńonate, b.p. 165— M ary el (J. Amer. Chem. Soc., 1935, 57, 1898— 170°/13 mm., m.p. 34—35°. Similar reduction of 1900).—Bis-2 : 2'-(l : 3-diphenylinden-3-ol) (I) differs Me 3 ; 4-dimethoxycinnamate gives Me (3-3 : 4-di- from dihydroxydihydrorubrene. Bis-2 : 2'-(l : 3- methoxyphenylpropionate, b.p. 175—180°/12 mm., indandione) exists largely in the dienolic form, sińce m.p. 37°, and tho Me ester, m.p. 184°, of with MgPhBr it gives 65% of bis-2 : 2'-(l-phenylindan- (3y-(fi-3 : i-diinethoxyphenyladipic acid-a, m.p. 255°, 3-on-l-ol), forms, m.p. 345° (błock) and 358° (błock), cyclised to the 2 : ll-cZifceto-compound, m.p. 330° respectively, dehydrated by IvHS04 at 250° to bis- (decomp.), reduced to 5 : 6 : 13 : lŁ-tetramethozy- 2 : 2’-(l-phenylinden-3-one), m.p. 213—214°. W ith 1:2:9: 10 : 11 : lS-hexahydrochrysene-a, m.p. 204°. LiPh this gives (I), forms, m.p. 273° (błock), unstable, a's-Diketohexahydrochrysene with MgMel in CcH 6 and m.p. 293° (błock), stable, respectively, oxidised and aerial oxidation of the product affords 2 : 11- by K 2Cr20 7 to o-C6H4Bz2 (88% yield). (I) and dimethylchrysene, m.p. 237° [compound with 1:3:5- HCl-Efc,0 give bis-2 : 2'-(3-chloro-l : Z-diplienylin- C6H3(N02)3, m.p. 222°; styphnate, m.p. 207° (de denyl), m.p. 245—247° (błock), which does not give comp.)]. J. W. B. rubrene with Ag. (I) sublimes at 280°/0-3 mm. and could not be converted into an oxide. R. S. C. cycłoHexyl sulphite. W. Voss and W. Wachs Synthesis of bis-2 : 2'-(l ; 3-diphenylinden-3- (Ber., 1935, 68, [J3], 1939—1941).—Contrary to ol). C. F. K oelsch and H. J. R ich ter (J. Amer. Carre et al. (this vol., 480) repetition of the action of Chem. Soc., 1935, 57, 2010).—Diphenylmothyłone- S0C12 on cycZohexanol as described by Voss et al. succinic acid [from (-CH2-C02Et)2, COPh2, and NaOEt] (A., 1931, 462) affords cyclohexyl sulphite, b.p. 173— with H2S04 gives 3-phenylindenone-2-acetic acid, 173-5°/14-5 mm., the identity of which is confirmed m.p. 16(£—167°, which with o-C6H4(C0)2O and NaOAc by analysis, determination of mol. wt., ąuant. hydro yields 2' ~(Z' -phenylindenone)methylenepht}ialide, m.p. lysis, mol. refraction, and yiscosity. Carre’s results 173-5— 174°, converted by NaOMe into 2-3'-phenyl- are unexplained. H. W. 0RGANIC CHEMISTRY. 1493 Synthesis of ephedrine derivatives. V. B ru c k 108°. Reduction of chlorocholestan-6-one {ozime, ner and A. Kram u (Arch. Pharm., 1935, 273, 372— m.p. 178°; semicarbazone, m.p. 155°; p -nitrophenyl- 384).—Hydrochlorides of (3-hydroxylamino-a-aryl-?i- hydrazone, m.p. 207°) with N a-H g-E tO H affords propyl acetates (I) with aldehydes and alkali give isocholestan-G-one, m.p. 97° {ozime, m.p. 157°), nitrones before migi’ation of acyl occurs (inothod A). probably stereoisomeric with the known derivative, Sometimes the acyl is removed by hydrolysis, giving m.p. 98° (Windaus, A., 1920, i, 434), and by Clem the OH-nitrone, which is also obtained by hydrolysis mensen reduction gives an isocholesteryl chloride, of the (3-jV-acylhydroxylamino-a-aryl-?i-propyl alco- m.p. 110°. The presence of the suggested side-chain hols with dii. H2S04 and subseąuent condensation in (II) is indicated by the production (in smali yields) with the aldehyde and Na2C03 (method B). Nitrones of COMe2 and a solid ketone (menthol odour), which is are thus obtained by the methods given in parentheses not methylheptanone, by oxidation of sitosteryl from (3-hydroxylamino-a-3 : 4-dimethoxyphenyl-w- acetate with Cr03-Ac0H. J. W. B. propyl alcohol and PhCHO, m.p. 160° (A and B), Polyterpenoid naturę of the sterols. F. S. o-OH-CGH4-CHO, m.p. 148—150° (A and B), m- Spring (Chem. and Ind., 1935, 972—973).—A scheme N 0 2,CgH4,CH0, m.p. 174° (B ) [Ac dorivative, m.p. is proposed whereby the cholestane skeleton is built 196° (4)], and 3 : 4-C6H3(OMe)2-CHO, m.p. 148— up from six isoprene units by cyclisation and loss of 150° (A), and from p-hydroxylamino-a-3 : 4-methylene- three C. The ergosterol and stigmasterol structures dioxyphenyl-?i-propyl alcohol and PhCHO, m.p. 149° are derived by use of one or two C, respectively, of (B) [Ac derivative, m.p. 158—159° (i?)], o- another isoprene unit. Sterols with 30—32 C may OH-C6H4-CHO, m.p. 117— 118° (B) [Ac derivative, thus be expected in naturę. R. S. C. m.p. 146° (decomp.) (4)], ra-NO2*C6H4*CH0, m.p. 171° (B) [Ac derivative, m.p. 196° (4)], and piperonal Relationship between cholesterol and carotene [Ac derivative, m.p. 158—160° (.4)]. Reduction by structures. W. H. D. B ry a n t (Chem. and Ind., Cu-Zn and AcOH affords 3 : i-dimethozy-N-benzyl-, 1935, 907).—Formation of cholesterol by ring- m.p. 102— 103-5°, and -liomoveratryl-, m.p. 125—127°, closure is more probable from a- or p-carotene than and 3 : Ą-methylenedioxy-~N-benzyl-, m.p. 117-5— 119-5°, from sąualene (cf. Robinson, this vol., 209). and -homopiperonyl-norepliedrine, m.p. 123-5—125°. F. R. G. R. S. C. Sterol group. XXI. Lumisterol. I. M. H eil- Halogen derivatives of novocaine. II. 4- bron, F. S. Spring, and P. A. Stewart (J.C.S., Bromo-2-aminobenzoyldiethylaminoethanol. J. 1935, 1221— 1223).—B z02H titration and hydrogen- F re jk a and F. Y ym etal (Coli. Czech. Chem. Comm., ation of lumisterol (I) confirm that it is tetracyclic 1935, 7, 436—443).—2 : 4-NH2-CGH3Br-C02H, pre- with three ethylenic linkings. (I) with Bz02H in pared from p-CjH^r-NH-COMe or from o- CHC13 a t 0° yields lumistadienetriol monobcnzoate C6H4Me-N02 (the intermediate steps are described), (II), m.p. 185— 186°, [a]£ -68-0° in CHC13 (gives is converted into $-chloroethyl i-bromo-2-aminobenzo- carmine coloration, which changes to brown and then ate, m.p. 80—81°, which, with N H E t2, aiiords 4- to green, with SbCl3), hydrolysed by MeOH-KOH to bromo-2-aminobenzoyldiethylaminoeiImnol; the hydro- lumistadienetriol (lii), m.p. 180—181°, [a]j,° -8 -7 ° chloride, m.p. 160°, has local anaesthetic action. in CHC13 (A c2 dcrivative, m.p. 128— 130°, [<*]£ P. G. C. -4 8 -4 ° in COMe2, extremely sol. in the common Structure of sitosterol. M. V anghelovici and org. solvents). (I) is dehydrated by P0C13 and B. N. A ngelescu (Buli. Soc. Chim. Romania, 1935, CsH5N gmng lumistatetraene, m.p. 88—90°, [a]£4 17, 177—190).—When heated with citraconic anhydr- +298-9° in CHC13 (coloration, changing from crimson, ide cholesterol (I) and sitosterol (II) (following through purple, to green, with SbCl3 in CHC13), which formuła suggested) afford, respectively, cholesteryl, is not identical with Rygh’s ergostatetraene (A., 1930, 203). This proves th a t other changes apart CHMe-[CH2yCHEtPr0 from possible epimerisation occui- in the photo- chemical transformation of ergosterol (IV) into (I). Titration of (II) with Bz02H and (III) with Pb(OAc)4 indicates that (II) is not and (III) is an a-glycol. By analogy with similar known reactions with (IV) OHl it is concluded that (I) contains a A5:6-ethenoid linking. Lumisteryl acetate is dehydrogenated by m.p. 195° (iJf-dcriyatiye, m.p. 162°), and sitosteryl, Hg(OAc)2 in AcOH to dehydrolumisteryl acetate, m.p. m.p. 169°, citraconate. The following reactions, 142— 143°, [a]p° +126-4° in CHCL (cf. A., 1928, 424). similar in both series, show the identity of the H. G. M. structures of ring n in (I) and (II). With conc. Actiniasterol.—See this vol., 1398. HN03 sitosteryl chloride affords nitrodehydrosito- Colour standard for cholesterol determin- steryl chloride, m.p. 118°, reduced (Zn-AcOH) to ations.—See this vol., 1552. chlorositostan-G-one (III), C29H490C1 {ozime, m.p. 180°; semicarbazone, m.p. 207°; p -niłrophenyl- Physiologically active crystalline esters of hydrazone, m.p. 188°), reduced by N a-H g in boiling vitamin-yl.—See this vol., 1545. EtO H to sitostan-§-one, m.p. 77° (oxime, m.p. 173°). Optically active diphenylhydroxyethylamines Oxidation of (III) with fuming HNOs-AcOH affords and isohydrobenzoins. VII. The 1 :2-cyclo- a dibasic acid, C24H4904C1, m.p. 277°. Reduction hexanediols and related compounds. N. A. B. (Clemmensen) of (III) affords a chlorosiłostane, m.p. W ilson and J . R ead (J.C.S., 1935, 1269— 1273).— 1494 BEITISH CHEMICAL ABSTRACTS.----A. Methods for the separation of cis- (I) and dl-trans- nitrite, decomp. 190°, decomposed on attem pted 1 : 2-c?/cZohexanediol (II) are described. The following reduction (catalytic, or Na-EtOH). Crude 1 :2- derivatives of (II) have been prepared by adding the c)/c/ohexanediol monobenzoate is oxidised by appropriate acid chloride to (II) in C5H5N : mono- K 2Cr20 7-H 2S04-H 20 to 1 : 2-c?/c?ohexanolone benzo benzoate (III), m.p. 92—93°, b.p. 200—205°/35 m m .; ate, m.p. 85—86° (cf. A., 1913, i, 1201) (oxime, m.p. dibenzoate, m.p. 93°; cZi-m- m.p. 141—142°, and 120°). 1 : 2-cycZoHexanoloneoxime, m.p. 109°, when di-ip-nitrobenzoate, m.p. 149— 150° ; bis-3 : 5-dinitro- reduced by Na-EtOH yields only the known form of benzoate, m.p. 179°. 1 - (3' : 5' -Dinitrobenzoate) - 2 - (V). ’ H. G. M. benzoate prepared from (III) exists in two forms, m.p. Nitrones. A new transposition reaction. I. 105° and 132-5°, respectively : 1-p-, m.p. 131°, and V. B e lla v ita (Gazzetta, 1935, 65, 755—765).— l-m-nitrobenzoate-2-benzoate, m.p. 102°, were similarly N-Phenyl-o- (I), -m-, and -p- (II) -nitrobenzald- prepared. The mono- and the di-(Z-cainphor-10- oximes are converted by KCN in MeOH into Me o- sulphonate could not be recrystallised. The following (III), m-, and Tp-nitrobenzoate-N-phenylimides, m.p. derivativcs of (I) were similarly prepared : mono-, 74-5°, 76-5°, and 47°, respectiyely, the transposi b.p. 139—140°/0-5 mm. and di-benzoate, m.p. 63—64°, tion CHRiNPhIO -> [OH-CRiNPh] -> OMe-CRiNPh obtained as a mixture together with an unsaturated having occurred. In the formation of (III) from hydrocarbon; di-p-nitrobenzoate. m.p. 128—128-5°; (I), an intermediate substance, m.p. 103—105°, is bis-3 : 5-dinitrobenzoate, m.p. 169°; l-(3' : 5'-dinitro isolated by adding H20; with MeOH and KON it benzoate.)-, m.p. 102°, 1-p-nitrobenzoate-, m.p. 82°, and gives (III). When (II) is treated with KCN in EtOH, \-m.-nitrobenzoate-2-benzoate, m.p. 96—97°. Both the jEt p-nitrobenzoate-l^-phenylimide, m.p. 46°, is formed. cis- and the dl-trans-diols give an absorption edge in On hydrolysis, the imides give either the anilide of the ultra-yiolet region, the former being the less the acid, or anilinę and the ester (or acid). transparent. The Zrcms-monobenzoate is more E. W. W. rapidly esterified than the cis-isomeride (cf. this vol., (j-Alkoxyethyl p-aminohenzoates. H. V. Ash- 88). (II) with Z-menthoxyacetyl chloride and C5H5N BtnRN, A. R. C ollett, and C. L. Lazzell (J. Amer. yields d-, m.p. 126—127°, [a]1)'-3 2 -7 ° in EtOH, and Chem. Soc., 1935, 57, 1862—1863).—The appropriate 1-trans-l : 2-c}-clo/ie.xo?ie mono-\-menthoxyacetate, m.p. ethers, OH*[CH2]2-OR, afford §-propoxy-, b.p. 181-6— 64°, [a]n —91-7° in EtOH, hydrolysed, respectiyely, 182-6°, -isopropoxy-, b.p. 172—172-8°, -isobutoxy-, to the d- and l-trans-diol, m.p. 113—114°, [a]D +46-5° b.p. 184-8— 185-6°, -sec,-butoxy-, b.p. 183-5—184-5°, (cf. A., 1922, i, 651). l-trans-1 : 2-c?/c/oHexanediol and te rt,-butoxy-ethyl p-nitrobenzoate, b.p. 174-8— di-p-nitrobenzoate has m.p. 126-5°, [a]D —25-5° in 175-8°, hydrogenated (P t0 2; 45 lb. per sq. in.) CHC13, and the corresponding bis-3 : 5-dinitrobenzoate in EtOH in good yield to the corresponding ji-amino- has m.p. 160°, [a]D —83-0° in CHC13 (the corresponding benzoates, m.p. 44-5° (138-4°), m.p. 95-4° (156°), hexahydro-a-coumaranone, b.p. 137°/15 mm. Wlion 2 : 3-C6H 3Me2,C02H and another acid. Picrotindicarb- either this or A1-cycZohexenyl-l-aeetic acid is con- oxyhc acid with red P and I gives 64% of (I) and 30% densed with C6H 6 (A1C13), 2-phenylcyclohexyl-l-acetic of (II) (phenylliydrążone, m.p. 185°). (I) and 38% acid, m.p. 69—70°, b.p. 195—200°/8 mm. (chloride, KOH a t 280° give an acid, C13H 14(C02H)2, m.p. b.p. 168—171°/7 m m .; amide, m.p. 196— 197°), is 138° (Ag2 salt). (I) and KMn04 (30) give y-4- formed. E. W. W. carboxydimethylphthalide-3-n-butyric acid ( I I ; R = Diphenyl series. III. [Synthesis of] phen- C02H), m.p. 183°, affording a t 300—330° II20 , C02, anthrene [derivatives]. N. N. Chatterjee (J. and an a-tetralone derivative (IV), C14H 140 3, m.p. Indian Chem. Soc., 1935, 12, 591—594; cf. this vol., 147°, b.p. 228°/12 mm. [semicarbazone, m.p. 322° 1361).—E t w/cZohexanone-2-carboxylate, NaOEt, and (decomp.); phenylhydrążone, m.p. 184°; cmwie, m.p. CH2Ćl*C02Et give Et2 c.yc\oheocanone-2-carboxylate- 185° (decomp.)]. (IV) and hot HN03 (d 1-37) yield 2-acetate (I), b.p. 168—175°/11 mm., hydrolysed by fi-4:-carboxydimethylphthalide-3-2»vpio?iic acid (V), conc. HC1 to eyc\ohexanone-2-acetic acid, b.p. 163°/4 + I I 20, m.p. 235° (decomp.) (Ag2 salt), and dimetliyl- mm., the Et ester, b.p. 122°/5 mm., of which phthalide-2, : 4-dicarboxylic acid (VI), + H 20, decomp. with MgPhBr affords Et 2-hydroxy-2-cyćlohexyl- (slow heating) 293° or (rapid heating) 209—210° phenylacetate, b.p. 170—180°/8 mm. (corresponding (with formation of the anhydride, m.p. 293°) (/1<72 acid, m.p. 129°). W ith S this yields Et diphenylyl- salt). (V) at 240—270°/12 mm. affords the 1- 2-acetale, b.p. 165—175°/8 mm., which, when hydro hydrindone derivative, C13H 120 3, m.p. 187° [phenyl- lysed by KOH and heated with conc. H 2S04 at 100°, hydrazone, m.p. 210°; semicarbazone, m.p. 350° gives 9-hydroxyphenanthrene, m.p. 153° (picrate, (decomp.)], oxidised by HN03 to (VI). R. S. C. m.p. 1S5°). (I) and MgPhBr give Et 2-hydroxy-l- Synthesis of substances related to sterols. carbethoxy-2-cyclohexylphenylacetate (II), b.p. 180— VII. W. S. Rajpson, R. Robinson, and (in part) 190°/9 mm., and tho lactone, m.p. 97°, of 2-hydroxy-\- R. H ir t (J.C.S., 1935, 1533—1543).—Four hnes of carbethoxy-2-cyolohexylphenylacetic acid [also obtained synthesis are developed. (a) Reduction of E t 2- by keeping (II) over H 2S04; with hot KOH-EtOH methylc?/ctopentanone-2-carboxy]ate with Na-Hg (C02 gives the \-carboxy-lactone, m.p. 141°]. R. S. C. stream) is incomplete, but. dehydration of the OH- Stereoisomerism of 2 : 2'-disubstituted deriv- ester with P 20 5 in boihng C6H 6 and fractionation atives of diphenyl. III. A. Corbellini and C. affords Et l-methyl-A2-cyclopentene-l-carboxijlate (I), Viganó (Gazzetta, 1935, 65, 735—743).—E t II b.p. 70—71°/13 mm. (free acid, b.p. 110°/14 mm.), diphenate, Mg, and E tB r give 2-a-hydroxy-a.-ełhyl- reduced (Bouveault) to l-methyl-A2-cyclopentenyl- n-propyldiphenyl-2'-carboxylic acid (I), m.p. 92—93° methyl alcohol (II), b.p. 162—165°/760 mm. (p-nitro- (by pptn.) or 111° (from light petroleum) (Na salt), benzoate, m.p. 67°), converted by PC15 in ligroin at converted by Ac20 into tho corresponding lactone —5° into the impure chloride, b.p. 40—56°/18 mm., (II), m.p. 104°; 2 : 2'-di-x-hydroxy-a.-ethyl-n-propyl- which failed to give the reąuircd eondensation product diphenyl, m.p. 98—99°, is also formed. The sub with CHAcNa-C02E t. Dehydration of (II) with stances previously regarded as (I) and (II) (A., 1933, KHSO.j affords a hydrocarbon (probably a dihydro- 64) are a mixture of cis- and trans-, and either cis- toluene), b.p. 112—113°/760 mm. m-0H-CGH 4-CH0 or tTa.ns-2-x-ethylidene-n-propyldij)henyl-2'-carboxylic is readily reduced electrolytically to the alcohol, acid (III), respectiyely. (III) is obtained from (II) conyerted by Me2S 04 (in situ) into 3 : 3'-dimethoxy- and HC1 in EtOH; with I in CHC13 it gives 2-$-iodo- hydrobenzoin aa'-Jfe2 ether, m.p. 112—113°, and is converted through a.-hydroxy-a.-ethyl-n-j)ropyldiphenyl-2'-carboxylic acid wi-OMe-C6H4-CH2-OH (HI). (III) lactone, m.p. 111° (decomp.); a similar jBr-compound the chloride, nitrile, and ester into S-m-methoxy- is formed. Et H diphenate, Mg, and PraBr yield phenylethyl alcohol, tho iodide of which condcnses 2 - a -hydroxy - a - n -propyl - n - butyldiphenyl-2'-carboxylic with CHAcK-C02Et in PhMe to give Et p-m-methoxy- acid, m.p. 149° (lactone, m.p. 92°, hydrolysed to the phenylethylacetoacetate, b.p. lS0°/2 mm., hydrolysed acid, m.p. 158°). CH2PhCl yields 2-(u-hydroxy-fi- (cold aq. NaOH foUowed by hot 10% HC1) to y-m- phenyl-a.-benzylethyl)diphenyl-2'-carboxylic acid, m.p. methoxyphenylpropyl Me ketone, b.p. 168°/19 mm. (from lactone, m.p. 146°) 172°. Pr^Br, Bu°Br, BusBr, o- (semicarbazone, m.p. 109°), eondensation of which and p-C6H 4MeI, l-C 10H 7Br, and 2-Cł0H 7I give similar with (I) was unsuccessful. (b ) cł/c/oPentanone cyano- produets, which are, liowever, not purified. E. W. W. liydrin with SOC12-C 5H sN affords l-c?/a«o-A1-cyclo- pe-ntene, b.p. 69°/15 mm. Et /ra?«-q/cfopentane-l- Picrotoxin. XII. Degradation of picrotic carboxylate-2-cyanoacetate (Cook et all., A., 1934, acid, C1SH180 4, to the dibasic acids, C14H14Or> 1002 ) condenses with CH2Ph-CH2Br-K-PhMc to give and C12H10Og. P. Horrmann [with K. Thilo] Et a-cyano-cL-(tra,ns-2-carbethoxycyclopentyl)-y-phe7iyl- (Arch. Pharm., 1935, 273, 433—446; cf. A , 1922, i, butyrate, b.p. 195—200°/l mm., hydrolysed (conc. 161).—Previous evidence and the reactions deseribed HC1, then 25% KOH—EtOH) to a-ci/a7io-a-(trans- below indicate that picrotic acid (I) is (II; R=Me). 2-carboxy but with boiling Ac20-Na0Ac, tlie corresponding cis- c,i/cIohexane-2 : 6-dicarboxylate. P. C. Guha and compound, m.p. 155—156°, is obtained. These with N". K. S esh a d rib n g a r (Current Sci., 1935, 4, 158).— S0C12 afford, respectively, l-hydroxy-2-(tvnns-2'-carb- [CH2]3Br2 (I) and the Na derivative of C0(CH2-C02Et)2 oxyoyclopentyl)- (V), m.p. 162°, and \-liydroxy-2-(cis- (II) in CgHg at 140—150° form E t2 pę-dehydrohexan- 2'-carboxycyclopentyl)-3 : 4-dihydrona/phthalene lactone, ^-ol-|3-one-ay-dicarboxylate (J.C.S., 1887, 51, 739) m.p. 66° (cryst. data by Croweoot). (V) is reduced and a phloroglucinol lactone (J.C.S., 1897 , 71, 1110), by H2-l% Pd-SrCOg in EtOAc to 2-(2'-trans-carboxy- but (I) with the Mg derivative of (II) gives Et2 cyclo- cyclopeńtyl)-l : 2 : 3 : i-tetrahydrojiaphthalene, m.p. hexanone-2 : 6-dicarboxylate. E. W. W. 107°. E t cycZopentanone-2-carboxylate with PC15 in Mechanism of polymerisation reactions. IV. hgroin (b.p. 40—60°) affords E t 2-chloro-Al -cyc\o- a-Phenylbutadiene. E. B ergm ann (J.C.S., 1935, pentene-l-carboxylate, b.p. 95—98°/12 mm. (acid, 1359—1360).—E t sodiopropane-aay-tricarboxylato m.p. 115— 116°). (c) m-Benzyloxybenzaldchyde, m.p. in boihng CGHG with CHBrPh‘C02Et, followed by 54° (CH2PhCl-NaOEt on the OH-compound), with liydrolysis (18% MeOH-KOH) and decarboxylation NHBz-CH2-C02H and Ac20 a t 100° affords m-methoxy- a t 130° gives S-2)henyl-n-butane-a.yS-tricarboxylic acid, (? benzyloxy)benzylideneplienylisooxazolone, m.p. 129°, m.p. 163—165° (decomp.), which is different from the hydrolysed to the phenylpyruvic acid, converted by acid (I) obtained by oxidising the dimeride of a- H202-Na0H into m -benzyloxyphenylacetic acid, m.p. phenylbutadiene, as is tho apS-tricarboxylic acid (cf. 126°. The Na salt of this with 6-nitro-3-mothoxy- this vol., 976). (I) is identical with S-phenyl-n- benzaldehyde and Ac20 affords 2-nitro-5-methoxy- butane-a(3y-tricarboxylic acid (this vol., 977), so that 48).—Divanillin with Ac20 and a little H2S04 yields in Et20 in presence of HC1, except when some (HI) is the hem-acetate, m.p. 160°, and with Me2S04 in NaOH also present. gives diveratraldehyde, m.p. 138°, (dioxime, m.p. (II) and (III) in Et20 with NaOEt-EtOH yield 184°), which with MeN02 and KOH in MeOH yields benzophenoneoxime O-a.-phenyliminobenzyl ether (IV), bis-(3 : 4-dimetIioxy-oi-nitrostyrene), m.p. 206°, liydro- m.p. 72—76°, and 5—10% of benzophenoneoxime genated [Pd(OAe)2] to dihomoveratrylamine, an oil 'N-a.-phenyliminobenzyl ether, m.p. 178—179°, which (Ac2 derivative, m.p. 78°). 3 : 4-Methylenedioxy-u- yields (I) with conc. HC1, and (I) and (III) with nitrostyrene, 3 : 4-dimethoxynitrostyrene, and 3-nitro- Et20-HCl, but no benzoyl-s-diphenylbenzamidine (V) a-methoxy-a-3 :4-dimetlioxyphenylethane similarly with Et20-H2S04. The constitution of (IV) is give homopiperonylamine (•C0'C0.2Et derivative, confirmed by the oxidation by KMn04-Ac0H to m.p. 131°), homoveratrylamine, and a-methoxyhomo- CPh,:N-OBz. (IV) yields (I) with conc. HC1, and veratry]amine (cf. Kindler et al., this vol., 1362). (I) and (III) with Et20-HCl, and (V) with Et20- F. R. G. H2S04. The dry hydrochloride of (II) when heated Chemical reactivity and Raman spectra of abovc 130° yields (I) and s-diphenylbenzamidine. the eugenols, vanillins, and safroles, and of (II) when heated at 100° with picric acid and MeN02 piperonal, estragol, and anethole.—See this vol., in a sealed tube gave some (I), but no benz-iV-picryl- 1446. anilide, which would liave been expected had the change occurred through JY-phenylbenzimidopicryl Isomerides and derivatives of hexetone. R. ether. W e g le r and W. F ra n k (Arch. Pharm., 1935, 273, The following mechanism of the Beckmann change 408—414).—The d- and 1 -forms of hexetone (3-methyl- accounts for the foregoing observations. (a) A 5-isopropyl-A2-c?/cZohexenone) (I) have tho same primary slow rearrangement of (II) brought about by cardiac activity as dl-(I) (phenylhydrazone-Tp-sulphonic acids alone ; (b) a much more rapid change beginning acid, m.p. 228°, gives only oily alkaloidal salts). as soon as a tracę of (I) is formed by (a) and proceeding CHPhMcNIIo is readily resolved hy the H tartrate, as follows. (I) and HC1 yield (III) which condenses the i-salt crystallising from MeOH and the d-salt with (II) gmng (IV), which with HC1 forms the salt being purified by crystallising the salt from the mother-liąuors from H20. (I) is resolved by a- CPh2!N-0 -CPh!NHPh}Cl. This, by analogy with the phenylethylsemicarbazide to give forms, [a]j>0 —37-8° picryl ethers, rearranges to NPluCPh-O-CPhINHPhJCl and +37°, respectively. (I) and Grignard reagents which may rearrange further to (V) or be split by give hydrocarbons. (I) and H2-Pd-black in MeOH HC1 to (I) and (III). The (III) thus formed can give the saturated ketone, but with Pt-black the CO transform further ąuantities of (II). Attempts to pre- is also reduced to CH*OH, or in AcOH slowly to pare di-(a-phenyliminobenzyl) ether by' interaction CH2. (I) and OH-[CH2]2*NH2 give a Schiff’s base, of (III) and dry Ag20 failed, the only isolable pro- b.p. 125°/13—14 mm., stable to H2-Pd-C, but re ducts being (I) and (V). H. G. M. duced by H2-Pt-C to 3-methyl-5-isopropylcyc\o- hexyl-$-hydroxyetliylamine, b.p. 151°/15— 16 mm. (I) Preparation of o-nitrophenyl aryl ketones. and HCO-NHo give a base, hydrolysed by conc. HC1 M. Bojśtius and H. Romisch (Ber., 1935, 68, [5], to 3-metfiyl-5-isopropyl-A?-cyclohexeńylamine, b.p. 90°/ 1924— 1932).—o-Nitrophenyl aryl ketones can be ob 12 mm. [oxalate; resolved by (•CHPh,C02H)2], tained by the Friedel-Crafts method if FeCl3 in mol. which with pyridine-3-carboxyl cliloride gives the proportion is substituted for A1C13. C2H2C14 at amide, b.p. 230°/14 mm. R. S. C. 30—40° is the most suitable solvent, but smaller yields can be obtained in PhN02, CHC13, and C6H6; p-Bromophenacyl formate, a solid derivative CS2 and CC14 are unsuitable. In*addition to the ket of formie acid. C. D. Hurd and R. E. Christ ones, larger amounts of black, amorphous producte (J. Amer. Chem. Soc., 1935, 57, 2007).—Contrary to are obtained separable into portions sol. and insol. Judefind et al. (A., 1920, i, 480) this compound, in Na2C03, but from which a homógeneous materiał m.p. 140°, is readily prepared. R. S. C. could not be obtained by reduction, acetylation, Beckmann change. III. Rearrangement of or benzoylation. Distillation of them with Zn dust ketoxime hydrochlorides. A. W. Chapman (J.C.S., affords acridine. o-NO,,C6H4,COCl condenses with 1935,1223—1229; cf. A., 1934,1312).—The velocity of C6H6 in presence of C2H2C14 and FeCl3 to o-nitrobenzo- the rearrangement to NHPhBz (I) of CPh2:N*OH (II) plienone (I), m.p. 105° (yield 20%).' With mixtures in (-CH^ClJą in the presence of HC1 at 100° is smali at of FeCl3 and A1C13 containing 10% of the latter, first, but inereases with inereasing time to a val. (I) is not produced. The following o-nitrophenyl aryl which is nearly const. for the last two thirds of the ketemes are described; p -tolyl, m.p. 155° (yield 17— reaction. The time reąuired for a given amount of 14-6%); m-xylyl, m.p. 81-5° (yield 19-7—22-6%); change depends on the [HC1]. The initial slow period p -xylyl (II), m.p. 94° (yield 41-6—47-4%); mesityl, also occurs when the hydrochloride of (II) is used, m.p. 146° (yield 6-9%); j)-methoxyphenyl, m.p. 105° but is reduced by the addition of (I) and completely (yield 1-4%). (II) is reduced by Sn and conc. HC1 abolished by addition of a smali amount of to o-aminophenyl p -xylyl ketone, m.p. 88— 90° after CClPlnNPh (III) (A., 1931, S43). The change is softening a t 76—78°. H. W. inhibited by partial replacement of the (■CH2C1)2 Synthesis of suhstances related to the sterols. by EtOH, which prevents the formation of (IH)” II. General method for the synthesis of sub The presence of HC1 is essential to the progress of stituted ci/c/ohexenones. W. S. Rapson and R. the change. The rearrangement does not take place R obinson. III. Synthesis of certain ketohydro- ORGANIC CHEMISTRY. 1499 phenanthrene derivatives. R. Robinson and E. gives some y-xa-methoxyplienylbutyramide, m.p. 96— S c h little r (J.C.S., 1935,1285—1288, 1288— 1291).— 97°, and the corresponding butyronitrile, b.p. 164— II. CJ/cZoHexenones are obtained by dehydration of 170°/11 mm., hydrolysed by K0H-Me0H-H20 to (VII), m.p. 49—50°. Dehydration of l-allyl-2-methyl- diketones, e.g., CH3<^q_C^> C H 2 -> a/cZohexanol by P20 5 yields a dicyclic hydrocarbon, C10H 1G, b.p. 169— 170°, which absorbs 1 mol. of Bl CH<^q^_^^|^>C H 2. Sodioc?/ctohexanone (I) (from in cold CHC13. H. G. M. «yctohexanone, NaNH2, and E t20) and CHPhICH-COMe Vat dyes of the benzanthrone series. XI. (II) in Et20 yield 2-kdo-4-phemjl-A19-octalin, m.p. Formation and separation of isomeric dichloro- 91—92°, b.p. 175—185°/1 mm., hydrogenated (Pd- benzanthrones. XII. Constitution of the di- SrC03) to 2-keto-4-pJienyldecalin, m.p. 82—83° (2 : 4- chlorobenzanthrones. T. Maki and Y. Nagai (J. dinitrophenylliy drążone, m.p. 180°). Similarly (I) and Soc. Chem. Ind. Japan, 1935, 38, 487—489b, 489— acetylcyc/ohexenc (III) yield Q-keto-A10’-11-clodecahydro- 493b ; cf. A., 1933, 611).—X I. Benzanthrone (I) phenanthrene, m.p. 89°, b.p. 150—155°/1 mm. Tbe when treated with AcOH, C12, and Fe at 100° (68 Na derivative (IV) of l-keto-2-methyl-l : 2 : 3 : 4- min.) gives a 94% yield of a mixture of two dichloro- tetrahydronaphthalene, (II), and CcH6 yield 3-keto- benzanthrones, (II), m.p. 273-5—274-5° (corr.), and 1 -plienyl- 11 -methyl-2 : 3 : 4 : 9 : 10 : 11 -hexahydro- (III), m.p. 228° (corr.), separated by means of EtOH phenanthrena, m.p. 135°, b.p. 235—240°/l mm. and AcOH. A eutectic, m.p. 203-5—204-5° (corr.), l-Keto-6-methoxy-l : 2 : 3 : 4-tetrahydronaphthalene of (II) and (III) is also obtained. (V) (improved prep.) when refluxed with NaNH2 XII. Oxidation of 13-chlorobenzanthrone (IV) with and Et20 in a current of H2 and then treated with Cr03-Ac0H-H20 yields anthraquinone-l-carboxylic (III) yields 2-keto-10-methoxy- acid. Similarly, oxidation of (II) and (III) yields 2:3:4:5:6:7:8:14:15: W-decahydrochrysene, 6- and 8-chloroanthraquinone-l-carboxylic acid, re- m.p. 228—229°, hydrogenated (Pd-SrC03) to a spectively. The above eutectic gave only a mixturo saturated alcohol, C19H2g0 2, m.p. 151°. 1-Acetyl- of these acids. Since dichlorination of (I) proceeds cyelopentene, b.p. 75—78°/22 mm. (semicarbazone, through (IV), (II) and (III) are 6 : 13- and 8 : 13- m.p. 210—211°; obtained not ąuite pure by heating dichlorobenzanthrone, respectively. The fusion dia the product obtained from the interaction at —10° of gram of (II) and (III) is given. H. G. M. cyclopentene, anhyd. SnCl4, CS2, and AcCl, with NPhMe2 at 180° during 3 hr), with the Na derivative of Synthesis of benzoins. 2' : 4' : 6'-Trimethyl- (V) and E t20 yields Z-keto-1 -metlioxy-l: 2 :3 :9 :10:11- benzoin. R. C. Fuson, H. H. Weinstock, jun., liexaliydro-\ : 2-vyc\opentenophenanthrene, m.p. 196— and G. E. U lly o t (J. Amer. Chem. Soc., 1935, 57, 197°, hydrogenated (Pd-SrC03) in MeOH to a tetra- 1803— 1804).—Benzoins are obtained from a-keto- 7ii/^ro-derivative, C18H210 2, m.p. 167— 168°. An at- aldehydes, aromatic liydrocarbons, and A1C13. tempt to condense (IV) and (III) gave two forms 2' : 4' : 6'-Trimethylbenzoin [thus prepared from (cis- and trans-), m.p. 205—206° and 126—127°, mesitylglyoxal (I) and C8H G a t 10°], m.p. 102° of a dimeride (VI), (uretlmne, m.p. 158-5— 159°), is oxidised by air to PhCO-CO-CRHaMej (II), and with more (I) in C6H G at % < ^ h^ h°> ch-c% co- ^ I ; o5 ^ % °£ 50° gives (II) and [CfiH2Me3-CO,CH(OH),]2 (cf. A., (III). On oxidation by the Kuhn-Roth micro- 1934, 525). CGH2Me:i-CO”-CH2Bz and SeÓ2 in hot method (VI) gave 1 mol. of AcOH. dioxan give mesityl Ph trikełone (III), m.p. 90—91°, III. 5-Keto-8-m-melhoxy2)henyloctoic acid, m.p. and other products including a substance, m.p. 169— 69—70°, obtained by the method of G. M. Robinson 170°. (III) gives 3-2' : 4' : 6'-trimethylbenzoyl-2- (A., 1930, 742) from y-?w-methoxyphenylbutyryl plienyląuinazoline, m.p. 134—-134-5°, and with 10% chloride and Et sodio-a-acetylglutarate, is converted NaOH yields (II), C6H2Me3-C02H, and C02. into the Me ester, which is cyclised by Na0Et-Et20 R. S. C. to $-m-methoxyphenylethylcyclohexa?ie-2 : (j-dione, m.p. (A) Structures of bimolecular reduction pro about 150° (has pseudo-acidic character, but gives ducts of dibenzoylethylene. R. E. Lutz and F. S. negative Fe111 reaction in EtOH). This is dehydrated P alm er. (b) Reduction of unsaturated 1 : 4-di- by P20 5 in C6HG to \-lceto-l-methoxy-\ : 2 : 3 : 4 : 9 :10- ketones with zinc combinations. Formation of liezahydrophenanthrene, m.p. 75— 76°, b.p. 165— tbe cyclic bimolecular products. R. E. Lutz, 169°/0-23 mm. [2 : 4-dinilrophenylhydrazonc, m.p. 256° L. Love, jun., and F. S. Palmer. (c) Catalytic (decomp.), sinters at 253—254°], whicli has no hydrogenation of unsaturated 1 :4-diketones. oestrogenic properties, and absorbs 6H2 with an active R. E. Lutz and F. S. Palmer (J. Amer. Chem. Soc., Pt catalyst but only 2H2 with a Pd-black-BaS04 1935, 57, 1947—1952, 1953— 1957, 1957— 1961).— catalyst. It is reduced by Na-EtOH to \-liydroxy- (a) Reduction of (CHBz!)2 with Zn-AcOH or other 7 -methoxy-1:2:3:4:9:10:11: 12 -octahydrophen- reducing agents gives bimol. products, including anthrene (p-nitrobenzoate, m.p. 140°, sinters a t 125°). meso-“ bisdibenzoyletJiane-A ” (meao-yS-dibenzoiyl-XL,- An improved prep. of y - m- methóśyphenylbu tyr ic diphenyl-n-hexa-aX,-dio7ie) (I) and its less stable dl-B- acid (VII) (A., 1932, 1122) is described. E t fł-wi- isomeride (II), and three stereoisomcric 2:3:4- methoxyphenylpropionate, b.p. 145—-146°/10-5 mm., tribcnzxryl-\-phenylc,y<&opentan-\-óls [-A (III), -B (IV), is reduced by Na-EtOH to y-m-methoxyphenyl- and -C (V)], termed “ cyclobisdibenzoylethanes,” propyl alcohol (cf. this vol., 752), converted through the structures of which are proved by the following the corresponding chloride into the iodide, b.p. reactions. (I), m.p. 202°, obtained from (CH2Bz)2, 152—162°/11 mm., which with KCN-H20-Et0H (CHBz:)2, and NaOEt (62% yield), from (III) and 1500 BRITISH CHEMICAL ABSTRACTS.----A. cold NaOEt, or (IV) and 1 drop of CęH5N in hot OH-CPhlCH-CPhlCPh-OH. If, however, ZnBr2 is EtOH, is stable in boiling PhCl or EtOH and distils added, (XII) gives only (XV). Reduction of uncbanged at 240—250°/vac. (II), m.p. 168°, best (X1H) thus undoubtedly proceeds by way of prepared from (III) and hot C-H5N-EtOH or by OH-CPhICICPhBz and (XIII). dl- and meso- heating (III) at 200° [gives also (CHBz!)2 and (CH2Bz)2 (CHBrBz)?, but not (CHC1Bz)2 or (XIV), with Zn- in eąual amount], is also obtained from (V) and COMe, give much (III). (X) reacts with Zn- C5H3N-EtOH, showing that (III) and (V) are stereo- COMe2 only if ZnBr2 is added, but CH.BziCBrBz and isomeric a t C3 and 4. Since (I) is the raeso-form, (XIV; X=Br) are not affected, so that reduction of (IV) has the cis-configuration at C3 and 4, and (III) (CHBrBz)2 probably proceeds by way of (X). This and (V) the trans. (II) at 230—240° gives (I), (CH2Bz)2, is in harmony with the production of very little (in) and (CHBz:)2, and with cold NaOEt yields (I) only. if the concn. of (X) is kept Iow. (XI) with Zn-ZnBr2- (I) or (II) with H2S04-Ac20 affords 3 : 3'-bis-(2 : 5- COMe2 gives mainly unimol. products. Na2S204 in 60—65% EtOH with (X) gives mainly (ĆH2Bz)2, diphenylfuran) (VI), m.p. 195— 196° but deteriorated samples give bimol. products and the also obtained by AcĆl with some 2 : 5-diplienyl-Z : 4- additive compound (XVI), CH2Bz-CHBz-S03Na, m.p. diphenacylfuran (VII), m.p. 165°. (VI) with H N 0 3- 255—262° (converted by hot conc. HG1 into 2 : 5- AcOH a t 30—35° gives “ bis-1 : 2-dibenzoylethylene ” diphenylfuran), whilst in one case mainly (II) was (yS-dibenzoyl-aZ.-diphenylhezadiene-a.Z.-dione), m.p. formed. NaHS03 in 90% EtOH converts (X) into 214—218°, hydrogenated (Pt) in EtOAc to a littlc much (III) and some (IV), (V), (CH„Bz)2, and (XVI). (I) and other products, and reduced by Na.2S204 to (IV), m.p. 202—203°, or (V), m.p.“ 204—205°, with much (I) and b_y Zn-AcOH to substances, m.p. 160— NaOMe gives (I). 165° and 199—200°, respectively. (VII) and H N 03- (c) Catalytic hydrogenation with P t0 2 of (X) in AcOH give <ńs,-y'8-dibcnzoyl-u.‘Q-diphenyl-k.v-licxcne-aX,- EtOAc or dioxan, or with Raney Ni in decahydro- dione, m.p. 183—184°, reduced by Na2S.,04 in 70% naphthalene or 95% EtOH, gives mostly (CH2Bz)2, EtOH to a misture of (I) and (IV). (III), (IV), or but with Pt02 in other solvents much (III) and (V) with Ac20-H 2S04 at 90° gives 2:3: A-tribenzoyl-1 sometimes (I) and (II) are formed. Acid increases phenyl-t^-cyclopenlene (VIII), m.p. 182°, which with the amount of (CH2Bz)2 formed in EtOH. Hydro Oa in CHC13 yields a 1 : 2-pcrozide, m.p. 132—133° genation of (X) probably proceeds by a conjugate (clecomp.), which, when heated slowly to, 140°, mechanism, but is unique in that (XI) gives 45—50% gives (VIII), or rapidly BzOH and a substance, of (CH2Bz)2 and other similar ketones give mostly m.p. 217—219°, and which regenerates (VIII) with or only unimol. products. M.p. in (a), (b), and (c) KI-EtOH and is hydrolysed by 70% EtOH to are corr. R. S. C. 2:3: i-iribenzoyl-l-pkenylcyclopcyitana 1 : 2-ozide, Testicular hormone. L. R uzicka (J. Amer. m.p. 117— 119°. This oxide is unchanged by H 2S04- Chem. Soc., 1935, 57, 2011—2012).—Androstene- Ac20, but with cold NaOMe gives slowly a little 3 : 17-dione, androstane-3 : 17-dione and -diol are BzOH and much v$y-tribcnzoylpropanc. (fi-jihenacyl-aS- more active than androsterone. Androsten-3-ol- diphenyl-n-buta-aS-dione) (IX), m.p. 122°, which is 17-one with Na-EtOH gives androstene-3 : 17-diol obtained in 50—60% yield from (CHBz!)2 and (I), m.p. 175—178° (corr.), tho dibromide of which by CIIB z'. C B z • O Na in cold EtOH or from (CIIBz!)2 and partial oxidation and debromination gives androsten- COPhMe. (IX) is dehydrated by Ac20-H2S04 to 3-one-ll-ol, identical with testosterone, also obtained 3-phenacyl-2 : 5-diphenylfuran. The compound (A., from (I) by partial hydrolysis of the diacetate and 1891, 680), obtained from tricarballylic chloride oxidation of the acetate dibromide. R. S. C. and previously called (IX), is a- or {i-phenacyl-yy- diphenylbutyro-y-lactotie, sińce it gives only a mono- Constitution and preparation of the testicular phenylhydrazone and with KMn04 affords equal horm one. E. S. Wallis and E. Ferxholz (J. amounts of BzOH and COPh2. Amer. Chem. Soc., 1935, 57, 2012).—Concerning (b ) Zn reduction of irans-(ĆHBz!)2 (X) gives largepriority. R. S. C. yields of bimol. products, that of cjs-(CHBzI)2 (XI) Dideuterocoprostanone.—See this vol., 1408. only smali yields thereof, whilst only unimol. products result by Zn-AcOH (room temp.) reduction of cis- Two modifications of 4 : 2': 3' : 4': 6'-penta- and ćrans-(:CH-CO-C6H4Cl-p),, trans-(p- methoxycha!kone. G. Martinez (Rend. Semin. C6H4Me-CO-CH:)2, atives of a doubly unsaturated lactone, C23H 290 2(0 H)3, (HC1) of these esters or amides are obtained furyl Et of which one OH (that accessible to Ac20) is sec. and (VI) (semicarbazone, m.p. 189°), Pr?, b.p. 96°/20 mm. one is tert. and carries the Ac. Both probably have (semicarbazone, m.p. 90°), Pr®, b.p. 67°/33 mm., sterol structure. R. S. C. Bufi, b.p. 96°/16 mm. (semicarbazone, m.p. 174°), Bongkrekic acid.—See this vol., 1540. a-ethyl-n-propyl, b.p. 97°/17 mm. (semicarbazone, m.p. 162°), and cyclopropyl, b.p. 75°/23 mm. (semi Constitution of cuscutalein.—Sec this vol., 1550. carbazone, m.p. 167°), ketone. W ithM gRX compounds Bitter principle from Andrograpliis panicul- of the type C4H30-C0-CHR-C02Et (R=H or alkyl) a ta.—See this vol., 1549. regenerate the parent p-keto-estcr when the product Isolation of pyrethrin.—See this vol., 1550. is hydrolysed, but (V) affords Et \-(a.-hydroxy-u.- ethylfurfuryl)- (Bz derivative, b.p. 161°/12 mm.) and Derivatives of vitamin-/J.—See this vol., 1546. l-( CO(NH,), it yields a.-2-pyridylbutyramide, m.p. 125— an Ac derivative, m.p. 129°. Further (V) does not 126°. " R. S. C. react with EtI, whereas (VI) gives a eryst. ethiodide. (IH) is converted into 6-benzylideneamino-2-phenyl-5- Arylated pyridines. IX. W. Dilthey and H. styryl-l-ethylindoline ethiodide, decomp. 251°, con- Diericiis (J. pr. Chem., 1935, [ii], 144, 1—31; cf. A., 192G, 1254).—2 : 4 : 6-Triphenylpyrylium per- verted by dii. HC1 into G-atnino-2-phenyl-5-styryl-l- chlorate (A., 1916, i, 829) lieated with NH2Ph or ethylindoline ethiodide, m.p. 218°. Ring formation its appropriate derivative yields the following is not observed with the following substances: perchlorates; 1:2:4: 6-tetraphenylpyridinium, m.p. o-aminotolan, m.p. 89° (picrate, m.p. 85— 90°, decomp. 260°; 1-p-tolyl-, m.p. 243—244° [compound with 95°), obtained by reduction of o-nitrotolan with SnCl2 NH20H(+H20), m.p. 163°]; l-o-tolyl-, m.p. 254— in HCl-AcOH at 40°; o-aminostilbene; cis- and 255°; p -phenetyl-, m.p. 274°; o-anisyl-, m.p. 242— trans-2 : 2'-diaminostilbene; Et o-aminocinnamate 243°; p -anisyl-, m.p. 243° (iodide., m.p. 309—310°, (picrate, decomp. 145°) obtained by reduction of compound with NH2OH, m.p. 145— 146°); 1-p- o-N02-CGH4-CH;CH-C02Et by SnCl2 in AcOH-HCl, hydrozyplienyl-pyridinium (I), m.p. 245° [chloride, whereas H2 and Ni afford dihydrocarbostyril; 4- m.p. 380—381°; bromide, m.p. 382—383°; periodide, nitro-6-amino-l : 3-distyrylbenzene; G-amino - 4- acet- iodide, m.p. 340°; nitrate., m.p. 323—324° (decomp.); amido-1 : 3-distyrylbenzene, m.p. 218° [picrate, m.p. perhydrozide, m.p. 201° (decomp.); picrate, m.p. 214— 225° (decomp.); corresponding Ac2 derivative, m.p. 215°; Ac derivative, m.p. 288° ('periodide, m.p. 185°)]. 284°]; 2:4: 6-triamino-l : 3-distyrylbenzene; 4:6- (I) with KOH in MeOH yields a red base, m.p. diamino-3-styryl-l-o'-aminostyrylbenzene. Catalytic 197— 198°, [0 ;cf,H4:N-CPh:cH-cPh:cH-cPh:cph reduction of 2 : 4-dinitrostilbene leads to 2 : 4-di- aminostilbene, m.p. 115°, which gives an orange 1935, 1405— 1410).—Phenanthridones havc been pre phenylglyoxaline, m.p. 181° (Cu salt), from 2 : u- pared by oxidation (Na2Cr20 7-Ac0H) of 9-methyl- dihydroxyacetophenone, m.p. 65°; 4=(S)-2'-hydroxyr5'- phenanthridines and by the action of NaN3 on a methylphenylglyoxaline, m.p. 136— 137° (Cu salt), substituted fluorenone in H2S04, a method which from 2-hydroxy-5-methylbenzoylcarbinol, m.p. 76—77°; gives a mixture of isomerides. The following have 4:(5)--p-mcthoxyphe?iylglyoxaline, m.p. 137°; 4(5)-p- been obtained by the oxidation method: 9- and aceiamidophenylglyoxaline, m.p. 250—251° (Cu salt); 9-co-chloro-, 3-nitro-, m.p. >360°, and 3-brorm- 4(5)-p-aminoplienylglyoxaline (-j-0-5H2O), m.p. 97° phenanthridone, decomp. 302° (from 3-bromo-9-methyl- (Cu salt); 4(5)-p-carboxyphenylglyoxaline, m.p. 308° plienanthridine, m.p. 129-5—130°), which is conyerted [Cu salt; hydrochloride (+ 1 H 20), m.p. 338°]; 4(5)- by POBr3 into 3 : d-dibromophenanthridine, m.p. 170— methylglyoxaline from acetol acetate or COMe-CH2Cl; 171°. The following have been prepared from 2 : 4(5)-dimethylglyoxaline; 4(5)-hydroxymethylgly- fluorenones : phenanthridone, 2(or 7)-nitro~, decomp. oxahne from CO(CH2'OH)2; glyoxaline. H. W. about 340°, 2(or 7)-chloro-l(ov 2)-nitro-, m.p. 340°, Acetanilidoalkylbarbituric acids [alkyl-5- 2 : 7-dinitro-, m.p. > 340°, and 2(or 7)-amino-phenan- barbiturylacetanilides]. J. A. Timm (J. Amer. thridone, m.p. about 285° (by reduction and also Chem. Soc., 1935, 57, 1943— 1944).—NHPh-CO-CH2Cl directly from the fluorenone). The mixture of OH- (I) and 5-alkylbarbituric acids with NaOAc and KI compounds, from the NH2-derivatives, may be (not NaOAc alone) in aq. EtOH give 5-ethyl-, m.p. separated by crystallisation to give 2-hydroxy-, m.p. 243—247° (decomp.), -n-butyl-, m.p. 250—256° (de 341—343°, -acetoxy-, m.p. 273—274° (decomp.), and comp.), -isobutyl-, m.p. 250—255° (decomp.), -iso- -methoxy-phenanthridone, m.p. 251°, and 9-chloro-2- amyl-, m.p. 245—250° (decomp.), and -allyl-5-bar- methoxyphenanthridine, m.p. 137-5°, 1 -hydroxy-, m.p. 320-—322° (decomp.), -acetoxy-, m.p. 261—264° (de biturylacetanilide, CO<^ęQ>CR-CH2-CO-NHPh, comp.), and -methoxy-phenanthridone, m.p. 271—272°, m.p. 237—242° (decomp.). (I) and CNaEt(C02Et)2 and 9-chloro-2-methoxyphenanthridine, m.p. 107°. in EtOH at 100° give only ArAr'-diphenyldiketopiper- N E t2-CH„-CH2Cl and CH2Ac-C02Et give S-amino-a- azirie and (?) OEt-CH2-CO-NHPh. R. S. C. diethylaminopentane (I) (dipicrate, m.p. 134— 135°), which with 9-chlorophenanthridine condenses to Sulphur-containing barbiturate hypnotics. a-diethylamino-a-methylbutylamino - 9 - phenanthrid - D. L. Tabern and E. H. Vol-\to,er (J. Amer. Chem. ine, isolated as the dipicrate, m.p. 196—197°, and Soc., 1935, 57, 1961— 1963).—Contrary to Johnson converted into the sulphate. 3 : 9-Dibromoplienan- et dl. (A., 1911, i, 502) E t2 alkylmalonates, CS(NH2)2, thridine with NEfc2-CIi2-CTI2-NH2 followed by HC1 and Ń aO Et-EtO H at 100— 120° give 5-ethyl-5-iso- yield Z-br6mo-Q-^-diethylaminoethyldmińophenańthrid- prop?jl-, m.p. 192°, -n-butyl-, m.p. 144— 145°, -sec.- ine dihydrochloride (dipicrate, decomp. about 156°) butyl-, m.p. 163— 165°, -allyl-, m.p. 172— 173°, -P- and with (I) affords S-bromo-9-S-diethylamino-a- methylallyl-, m.p. 160—161°, -isoamyl-, m.p. 167— methylbutylaminophenanthridine dihydrochloride (di 169°, -a.-methylbutyl-, m.p. 158— 159°, -n-liexyl-, m.p. picrate, decomp. 217—218°). 9-Chloro-2-methoxy- 136—137°, -$-elhylbutyl-, m.p. 137— 138°, and -y- phenanthridine with N(CH2-CH2-NH2).! gives 9-P- chloro-AP-butenyl-, m.p. 128— 130°, 5-cyclohexyl-5- diethylaminoethylamino-2-methoxyphenanthridine di ethyl-, m.p. 205—207°, 5-phenyl-5-ethyl-, m.p. 215— hydrochloride [dipicrate, m.p. 207° (decomp.)], and with 217°, 5-methyl-5-fi-methylallyl-, m.p. 128— 130°, 5 : 5- (I) the d-8-diethylamino-a-methylbuthylamino-dihydro- diallyl-, m.p. 134°, 5-allyl-5-$-methylallyl-, m.p. 180— chloride (dipicrate, decomp. 192— 193°). Although 182°, 5-sqo.-butyl-5-allyl-, m.p. 142— 143°, 5-a-methyl- these nuclear-substituted meso-aminophenanthridines butyl-5-allyl-, m.p. 127— 129°, and o-benzyl-o-alhyl-2- resemble ąuinoline and acridine antimalarials in thiobarbituric acid, m.p. 140—150°. When injected type they possess no therapeutic val. F. R. S. intravenously into rabbits, many of these are power- Manufacture of acridinium compounds.—See ful hypnotics of very brief action with Iow toxicity. B., 1935, 1069. R, S. C. 5 :5-Diphenylbarbituric acid, 5-phenyl-5- Synthesis of glyoxaline derivatives. R. W ei- cyctohexylbarbituric acid, and 5-phenyl-5-c/ycto- denhagen and R. Herrmann (Ber., 1935, 68, [5], hexenylbarbituric acid. H. J. Morsman (Helv. 1953— 1961).—The synthesis of glyoxalines is more Chim. Acta, 1935, 18, 1254— 1264).—CPh2(COCl)2 (I) readily effected from ap-hydroxyketones or a(3- in Et20 is transformed by NH3 into diphenylmalon- hydroxyaldehydes than from aj3-diketones. Treat diamide, m.p. 243—244° (corr.), which ■with COCl2 ment of these with Cu-NH3 solution readily yields in PhMe a t 150° or with (C0C1)2 in boiling C6H B affords the ketones which in presence of an aldehyde aro 5 : 5-diphenylbarbituric acid (II), m.p. 298—299°, immediately condensed to the glyoxaline, usually also obtained from (I) and CO(NH2)2 at 100° or in pptd. at the Cu salt. The carbinols may be replaced boiling xylene. (II) is best prepared by the addition by their acetates and sometimes by the corresponding of 20% oleum to alloxan monohydrate in C6H6 at Cl-compounds. The yields may attain 90%. Thus 20°, heating tho mixture at 70—75°, and removing are obtained: 4(5)-phenylglyoxaline, m.p. 129— hy-products by the successive action of dii. NaOH and 130°, from CH2Bz-OH, CH20, Cu(OAc)2, and NH3; KMn04 in alkaline solution. Treatment of (II) with 4(5)-phenyl-2-mcthylglyoxaline, m.p. 161— 162°; 4(5)- excess of CH2N2 in Et20 gives 5 : 5-diphenyl-1 : 3- p)ienyl-2-ethylghyoxaline, m.p. 133° (Cu salt); 4(5)- dimethylbarbituric acid, m.p. 206—207° (corr.), also phenyl-2-\sopropylglyoxaline, m.p. 180° (Cu sa lt); obtained from (I) and CO(NHMe)2 in boiling xylene. 2 : 4(5)-diphenylglyoxaline, m.p. 193° (Cu salt; hydro 5-Phenylbarbituric acid is obtained from chloride monohydrate, m.p. 273°); 4(5)-2'-hydroxy- CHPh(CO*NH2)2 and (C0C1)2 in C8He a t 80°. 1508 BRITISH CHEMICAL ABSTRACTS.— A. CHPh(C02Me)2, cyc/ohexenyl bromide, and KOMe in vol., 1253).—VI. Piperazine (I) and its 1Y-PI1 deriv- C6Hg afford Me2phenylcyclohexenylinalonatc (III), m.p. ative are alkylated by CH20 or MeCHO in Zn-HCl. 79—80° (by-product, m.p. 204—205°), transformed H20-insol. aliphatic aldehydes rapidly effect alkylation by boiling KOH-MeOH into phmylcyclohezenylaeetic in hot HC02H, but aromatic aldehydes reąuire acid, m.p. 123— 123-5° (corresponding amide, m.p. several days. The following derivatives of (I) are 167— 168°). (III) and CO(NH2)2 in MeOH containing thus obtained : 'S-Ph-W-Me, b.p. 109—100°/5 mm., NaOMe at 105—108° give 5-phenyl-5-cyclphexenyl- T$-Ph-W-Et, b.p. 144—145°/10 mm., NN'-i!fe2, b.p. barbituric acid (IV), m.p. 209—210°, also obtained from 130— 135° [dihydrochloride, m.p. 263° (decomp.)], K 5-phenylbarbiturate and c;/c/ohexenyl bromide in m iU E ts, b.p. 174—177°, NN'-5m“2, b.p. 195-195-5°/ dioxan. Hydrogenation of (III) by Pt02 in MeOH 12 mm., NN'-(C/i’2P/ł)2, m.p. 92—93° (also obtained affords Me2 phenylcycloh&cylmalonate, m.p. S9—90°, from CH„PhCl), and NN'-di--p-methylbenzyl, m.p. whereas interaction of CHPh(C02Et)2 and cyclohex- 101— 102°. yl bromide yields unchanged materiał, CH2Ph-C02Et, VII. Anhyd. (I) and (CH2)20 in hot MeOH give and (IV). Similar hydrogenation of (IV) gives a 98% yield of 2V2V'-di-(3-hydroxyethylpiperazine, phenylcyclohexylbarbituric acid, m.p. 256° (corr.). m.p. 135— 135-5°, the di-p-nitrobenzoate, m.p. 158— (II) is only a feeble narcotic. H. W. 158-5°, of which is reduced (Fe) to the di-p-amino- Formation of “ triacetylacetic ester.” II. F. benzoate, m.p. 203—204° (tetrahydrochloride, eryśt., Seidel, W. Thier, A. Uber, and J. Dittmer (Ber., hygroscopic). R. S. C. 1935, 68, [5], 1913— 1924; cf. A., 1932, 931).— Naphthopyrazoles (benzindazoles). V. V esely , Evidence of the formation of CAc3'C02E t by the action A. Medvedeva, and E. M uller (Chem. Listy, of AcCl on Et sodioacetoacetate has been based on the 1935, 29, 259—263).—2 : l-C10H 8Me-NO2 in C2H2C14 formation of “ Et 4-acetyl-3 : 5-dimethylpyrazole-4- and Cl2 in presence of FeCl3 at 40—50° yield 8-chloro- carboxylate ” (I) when the product is treated with 1-nitro-2-methyhiaphthalena, m.p. 114°, reduced by N2H4. Since the substanee when heated above its Fe in AcOH to &-chloro-l-amino-2-viethylnaphthalene, m.p. passes into j3-5-hydroxy-3-methyl-4-pyrazolyl- m.p. 89° [N-/lc derivative (I), m.p. 214—215°], crotonolactone, m.p. 246°, and is hydrolysed by alkali which, when diazotised and treated with NaOH, to !3-5-hydroxy-3-methyl-4-pyrazolylcrotonic acid, affords 8'-chloronaphtho-V : 2' : 3 : 4-pyrazole, m.p. m.p. 154° (decomp.), it is now recognised as Et 159° (l-Ac derivative, m.p. 196°), also obtained by ,8-5-hydroxy-3-methyl-4-pyrazolylcrotonate (II). It treating (I) with HN02 in AcOH, and boiling a CGH6 arises from CHAc2-C02Et, which loses Ac under the solution of the iV.-N O - d eri vative so obtained. 4'- influence of N2H4; excess of N2H, reacts with Nitro-, m.p. 304—305° (1 -Ac derivative, m.p. 196— CH2Ac*C02Et thus produced, yielding 3-methyl- 197°), and 5'-bromo-naphtho-1' : 2': 3 : 4-pyrazole, m.p. pyrazol-5-one, which condenses with residua! 249—250° (l-Ac derivative, m.p. 168°), were prepared CH2Ac-C02Et to (II). During unsuccessful attempts analogously. l-Nitrosoacetamido-2-methyhiaphthalene,' to prepare (I) synthetically, the following observations m.p. 82° (decomp.), affords naphtlio-1' : 2' : 3 : 4- have been made. Et 3 : 5-diinethylpyrazole-4-carb- pyrazole, m.p. 158° (picrate, m.p. 193°; l-.de derivative, oxylate is converted by AcCl in C5H5N into Et 1- m.p. 108—109°), when boiled in C8H6 for 4 hr., whilst acetyl-3 : 5-dimethylpyrazole-4-carboxylate, m.p. 69°, 2-nitrosoacetamido-l-methylnaphthalene, m.p. 91°, in which the position of Ac is established by decarb- yields riaphtho-V : 2' : 4 : 3-pyrazole, m.p. 231° (picrate, oxylation of the corresponding acid, m.p. 164°, to m.p. 217—218°; l-A c derivative, m.p. 116-5°), 1-acetyl-d : 5-dimethylpyrazole, b.p. 70°/12 mm., also when similarly treated. R. T. obtained from 3 : 5-dimethylpyrrole (III) and AcCl Comparison of heterocyclic ring systems with in CjH5N or from NHa-NHAc and CH2Ac2 in boiling benzene. V. Benztriazole (azimidobenzene) EtOH. i-Benzoyl-3 : 5-dimethylpyrazole, b.p. 15S°/12 series. VI. Quinones of the tjuinoline and mm., is derived from (III) and BzCl in C0HgN or i\soquinoline series. VII. Isologu.es of anthra- from CH2Ac2 and NH2-NHBz in boiling EtOH. quinone containing one and two triazole rings. N2H4,H20 and CHAc3 in H20 afford -l-acetyl-3 : 5- L. F. Fieser and E. L. Martin (J. Amer. Chem. dimethylpyrazole, m.p. 128° [monohydrate, m.p. 121° (decomp.)], which with AcCl in C5H5N at 0° gives Soc., 1935, 57, 1835— 1839, 1840—1844, 1844— 1 : i-diacetyl-3 : 5-dimethylpyrazole, m.p. 50°. 3- 1849; cf. this vol., 1377).—V. E 0, 0-672 volt, for Methylpyrazol-5-one, m.p. 270°, is obtained from K benztriazole-4 : 5-quinone-7-sulphonate indicates th at the aromaticity of the triazole ring is intermediate N2H,j,H20 and E t isodehydracetate in boiling MeOH. l-Phenyl-3-methylpyrazoł-5-one, CH2Ac-C02Et, and between that of thiophen and C6HG. Benztriazole- NaOH in H 20 at 15— 20° yield Et $-5-hydroxy-l- ąuinones are difScult to prepare. ^-NHAc*C6H4-OAc phenyl-3-methyl-4;-pyrazolylcrolo7iate, m.p. 88°, which and H N 03 [d 1-5) at 0—5° give 3-nitro-4-acetamido- loses EtO H a t 70° and forms p-5-hydroxy-\-phenyl-'i- phenyl acetate, m.p. 144—145°, hydrogenated (Pt02) methylA-pyrazolylcrotonolactone, m.p. 132°. [1-5- in hot EtOH to a little 2: 2'-diacetamido-5:5'- Hy droży-1 -benzoyl - 3 - methyl - 4 -pyrazolylcrotonoktctone, acetozyhydrazobenzene (corresponding ctzo-compound, has m.p. 181°. H. W. decomp. 280—285°) and 75% of 2-acetamido-5-acetoxy- aniline (I), m.p. 178—179°, which yields 3 : 4-diacet- Piperazine. VI. Alkylation by means of amidophenol, m.p. 214—215° (lit. 205—207°), and aldehydes. W. T. Eorsee, jun., and C. B. Pollard. its acetate, m.p. 187— 188° (lit. 184— 185°). (I) VII. Procaine analogues. I. D. E. Adelson, and HN02 give 5-acetoxy-I-acetylbenztriazole, m.p. L. G. MacDowei.l, and C. B. P o llard (J. Amer. Chem. 125—126°, hydrolysed by HC1 to 5-hydroxybenz Soc., 1935, 57, 1788—1789, 1988— 1989; cf. this triazole, m.p. 234—235° (decomp.) [lit. 228° (decomp.); ORGANIO CHE.MISTRY. 1509 53% over-all yield from j>-NH2-CgH4-OH; hydro- Na2S204 to the corresponding (0//)2-compound [Ac2 chloride, decomp. about 225°; 4-p-, m.p. 224:—225°, derivative, m.p. 255° (decomp.)} allows reaction to form and 4-o-tolueneazo-, m.p. 243—244° (decomp.), N 0 2-, m.p. 262—203° (lit. 236°), and NO- (II) -derivatives]. O 4-Amino-5-hydroxybenztriazole, m.p. 216—217° (dc- eomp.), best (83%) obtained from (II) and aq. Na2S204 (dihydrochloride, decomp. 225°), in dii. solution gives a ąuinone, which, however, cannot be (V III.) isolated. (II) and NaHS03, followed by H2S04 at % :)\ / 40°, gives 4-amino-5-hydroxybenztriazole-l-sulphonic (VII), decomp. 240—245° (iV-Me derivative, m.p. 248— acid, cryst., which with Br-H20 readily gives a 250°). The Ac2 derivative, m.p. 253—254°, of 3 : 6- ąuinone, which could not be isolated; the resultant dichloro-2 : 5-diaminoquinone (improved prep.; 75% solution, however, with S02 yields K 4 : 5-dihydroxy- yield) with NH3-EtOH gives 3 : G-diami?io-2 : 5-diacet- benzlriazolc-7-sulphormle, cryst. o-NO./CgHfNH, with amidobenzoąmnonc, converted (onlyin hot AcOH) into Ac20-H 2S04 in C6Hg yields o-N02-CBH4-NHAc, p, Tyj-TT colourless bislriazolo-j)-benzoquinone, m.p. 92—93°, hydrogenated (P t0 2) in hot EtO H to a- / s (X) (Na salt, -fH20). The prep. o-NH2‘C6H4-NHAc (III), m.p. 132—133°, a little N------/ Y of IĆ 2 : 3-dihydroxynaphthalene- 2 : 2'-diacetamidoazobenzene, m.p. 270—271°, and Nn J------N 6 - sulphonate, 2 : 3-Cię)HG(OH)2, 2-methylbenziminazole. (III) leads to benztriazole, V r i a and -C10H g(NH2)2 is improred. m.p. 98—99° (>90% yield in each step; Ac deriv- x , . Hydrogenation (Pt0o) of 2:5- ative, m.p. 50—51°). Electrolytic reduction in (X’) C6H3(NHAc)2-N02 in hot EtOH conc. H3SÓ4 of 4-nitrobcnztriazole and its 1-Me deriv- affords 2 : 5-diacetamidoaniline, m.p. 236—237° (lit. ative, m.p. 181—182° (lit. 173°), gives 4-amino-7- 231—232°), converted into 5-aminobenztriazolc and hydroxy-bentriazole, decomp. about 225—230°, and thence by way of the PhN2-compound into 4 : 5-di- -1-methyltriazole (sulphate; Bz2 derivative, m.p. aminobenztriazole, the Ac derivative of which with 262—263°), which do not give ąuinones, but similar HNO, gives 1:2:3: 4-bistriazolobenzene, which did reduction of 7-nitro-l-metbylbenztriazole was un- not yield a quinone. R. S. C. successful. VI. The aromaticity of the ąuinoline and iso- Condensation of 4-aminotetrazole with carb- ąuinohne rings, as indicated by the E 0 of ąuinones, onyl compounds. E. Bures and F. Baesi (Casopis is about eąual, but < that of triazole or thiophen ćeskoslov. Lek., 1934, 14, 345—352; Chem. Zentr., rings. The generał validity of connecting E 0 and 1935, i, 1867).—4-Aminotetrazole (I) andMeCHO yield aromaticity of fused rings is discussed. Caution is 4:-ainino-l-methylmethenyltetrazole, ^^5?ll^^>N:CMe, necessary in interpreting the results. 5( ? 8)-Hydroxy- woąuinoline (IV) (from the a-S03H) gives a PhN2- m.p. 164—165°. (I), w th PhCHO and with cinnam- compound, reduced by SnCl2 to 8( ? o)-amino-5( ? 8)- aldehyde, similarly affords i-amino-l-benzenyl-, m.p. hydroxyisoquinoline dihydrochloride (V), cryst. Elec 120° (decomp.) and -1 -styrylcarbylamino-, m.p. 162— trolytic reduction in II2Ś04 of 5( ? 8)-nitroisoquinoline, 163°, -tetrazole, respectively; the last-named, with Br m.p. 104— 108°, gives 5( ? 8)-amino-8( la)-hydroxymo- in CHC13, yields 4-amino-l-dihromostyrylcarbylaniino- quinoline (VI) (sulphate; dihydrochloride; Bz2 deriv- tetrazole, m.p. 174— 175°. (I) condenses with COMe2 to ative, m.p. 223—224°), which with FeCl3 gives yield Ł-dimethylmethenyltctrazole, m.p. 187— 18S°. 5 : 8-dihydró\SÓquinoline hydrochloride, darkens at Aminoguanidine carbonate has m.p. 173°. H. N. R. about 260°, also obtained similarly from (V) and Rearrangement of allyl ethers in the purine from (IV) by Fe-reduction of the NO-derivative. series, with some remarks on the hydrogenation The A c2 derivative, m.p. 208—209°, of (VI) is partly of allyl ethers. E. Bergmann and H. Heimhold hydrolysed by cold 0-4% NaOH and then couples (J.C.S., 1935, 1365— 1367).—2 : 6-Dichloro-7-methyl- affording 5( ? 8)-acetamido-8( ? 5)-hydroxy-7(? 6)-p- purine (I) and Na allyloxide yield 2 : G-diallyloxy-7- sulphobenzeneazoisoąuinoline, reduced by Na2S204 to methylpurine, m.p. 111— 112°, which on hydrogen 7 (? 6)-amino-5( ? 8)-acetamido-8( ? 5)-hydroxyhoqui?ioli?ie ation gives heteroxanthine, and on heating is isomer- dihydrochloride, which with FeCl3 affords 5( ?8)-acet- ised to 1 : 2-diallyl-l-methylxanthine, m.p. 277—278°. amido\noquinoline-l : 8( ?5 : 6)-quinone hydrochloride. (I) and Na in A0-hexen-8-ol, after heating, form VII. lin - Naphthatriazole - 8 : 9-quinone (VII) is 1 : 3-di-(a-mothyl-A£-pcntenyl)-7-methy]xanthinc, b.p. strongly aeidic; its E0 differs from that of its 1-Me 215—225°/12 mm., from which the products of derivative and (VII) may thus be as shown. ozonolysis are EtC02H and EtCHO. Ph allyl ether q Naphthacene and “ 2 : 3-phthaloyl- gives on hydrogenation PhOPr but 2 : G-dipropoxy-l- ■^r phenanthrene” are probably (VIII) methylpurine, m.p. 92°, is not affected by Pd~H2. The / \ and (IX), respectiyely, on the isomerisation is due to migration of the allyl group theory th at max. aromaticity must from O to N. E. R. S. * (VII.) ®cŁieved. Inability to give the ^ vat test is connected with Iow E 0 Constitution of the purine nucleosides. III. rather than with absence of a true quinone ring, as in Potentiometric determination of the dissociation (IX). 3-Chloro-2-acetamidonaphthaquinoneand NH3 constants of methylated xanthines. A . G. Ogsto n in boiling PhN02 give 3-ami?io-2-acelamido-l : 4-naph- (J.C.S., 1935, 13?6— 1379).—Measurements of dis ihaąuinone, m.p. 233—234°, which does not give a sociation consts. indicate th at 3-, 7-, 9-methyl-, 1: 3-, triazole owing to its sparing solubility. Reduction by 1: 7-, and 1: 9-dimethyl-xanthines, and xanthosine 1510 BRITISH CHEMICAL ABSTRACTS.----A. are “ zwitterions,” xanthine, 1-methył- and 3:7- aUoxazine, m.p. 283°, [a]f>0 — 78°±S° in O-OSA-NaOH. dimethylxanthines are normal acids, whilst caffeine Similarly, ćZ-ribose and o-NH2-C6H4,NH,C02Et yield and isocafTeine are not acids. Structures aro assigned 2-carbethoxyaminophenyl-d-ribamine., m.p. 158°, [a] on the basis of these considerations. F. R. S. +0° in H20, hydrolysed and condensed to 9-d-l'- Degradation of flavins by light. P. K a r r e r ribityl\Boalloxazine, m.p. 283° (tetra-acetate, m.p. 237°). and H. F. Meerwein (Helv. Chim. Acta, 1935, 2-Carbethoxyamino-5-methylphenyl-d-ribamine, m.p. 18, 1126— 1130).—Photodegradation of Q-$-hydroxy-P- 150°, [a]j,° —14-2°+2°, affords 7-melhyl-(.)-d-l'-ribityliso- inethyl-n-propylisoallo.mzine (I) in H20 occurs much alloxazine, m.p. 285—286° (tetra-acetate, m.p. 215°). more slowly than that of lactofkwin, whereas in 75% H. W. MeOH the difference in the rates is less marked. Optical activity of lactoflavin.—See this vol., Preliminary dehydrogenation of [i-OH is not therefore 1521. essential to degradation, which can be initiated is Formation of porphyrins from pyrrole and some other unknown manner. NH2,GH2,C02Et is aldehydes. P. Rothemund (J. Amer. Chem. Soc., converted by MgMel into aminołrimethylcarbinol, 1935, 57, 2010—2011).—Pyrrole and dry CH20 or b.p. 53—57°/15 mm., which condenses with o- MeCHO in Me0H-Et20 with or without catalysts CgH4C1*N02 in boiling C5H 5N to o-nitro-$-hydroxy-$- give cryst. porphyrins. R. S. C. methyl-n-propylaniline. (I), m.p. 83°. (I) is hydrogen- Optical absorption of porphyrins.—See this ated (Pd-C in abs. EtOH) and the product is condensed vol., 1444. with alloxan to (I), decomp. 285°. H. W. Photochemical reaction of chlorophyll. E. Modified flavin synthesis. P. K a r r e r and II. F. B au r (Helv. Chim. Acta, 1935, 18, 1157—1160).—A M eerw ein (Helv. Chim. Acta, 1935, 18, 1130— film of chlorophyll (I) in collodion wlien exposed to 1134).—3 : 4-C6H3Me2-NH2 and Z-arabinose in boiling sunlight under air-free H,0 thi'Ough which C02 MeOH-HoO give 3: 4-dimethytphenyl-l-arabamine, is passed rapidly becomes yellow without apparent C6H3Me2-ŃH-CH2-[CH-OH]3-CH2-OH, m.p. 123°, production of CH20. Similar films containing also which couples with j)-N02,CGH4,N2Cl in aq. acid solu metliylene-blue (II) when exposed under H20 through tion to 0( i.)--p-nitrobenzeneazo-$ : 4-dimethylphenyl-l- which 0 2-free N2 and C02, respeetively, are passing arabamine, reduced (Zn dust and AcOH or H2-Ni- slowly exhibit incomplete blęaching of (I) with MeOII) to 9-l-l'-arabityl-6 : 7-dimethylisoalloxazine, l^ronounced formation of CH2Ó, which is therefore m.p. 299°. Similarly, 3 : i-dimethylphenyl-d-ribamine, produced from (I) and not from C02; the change m.p. 143°, is convcrted into 9-rf-l'-ribityl-6 :7- cannot be accomplished from (I) without aid. dimethyl?'soalloxazine, m.p. 280°. H. W. (II) does not function as photosensitiser, but as Methylalloxazines. P. K arrer and C. Musante redox agent, sińce it can be qualitatively replaced (Helv. Chim. Acta, 1935, 18, 1134—1140).—The by Fe", F e"’, or O. The course of the change is fluorescence colours of solutions of alloxazines in discussed. H. W. MeOH induced by ultra-violet light depend greatly Magnetic behaviour of porphyrexide and por- on substituents in the mol. Introduction of Me phyrindin.—See this vol., 1453. progreśsively displaces the fluorescence from violet through blue, greenish-blue, and yellow to yellow- Thiocarbonylsalicylamide (4-keto-2-thioketo- violet, wliereby Me ortho to the azine ring has greater 3 : 4-dihydro-l : 3-benzoxazine). I. T. UGAiand displacing influence than at 6 or 7. Ph behaves M. H ayasht (J. Pharm. Soc. Japan, 1935,55, 8—12).— similarly. 6-Nitro-2 : 4 : 5-trimethylaniline is re Salicylic acid and allylthiocarbimide yield thiocarbon- duced (Pt in EtOH) to the corresponding diamine, ylsalicylamide (I), C8H 50 2NS, m.p. 253°. Methylation which condenses with alloxan (I) to 5:7 :8(? 5:6: 8)- of (I) with CHoN, affords a substance, C9H70 2NS, trimelhylallozazine, decomp. >290°. 2-Nitro-3 : 4 : 5- m.p. 163°, whilst with alkaline H202 (I) yields a trimethylaniline similarly affords 6 :7 : 8( ? 5 : 6 : 7)- substance, C8H5ON, m.p. 227°. Methylation of triinethylalloxazine, whilst 5 : 6-dinitro-l : 2 : 3 : 4- carbonylsalicykmidc yields a substance, C„H70oN, tetramethylbenzene, m.p. 171°, is transformed into m.p. 149°. * Ch . A b s. (r) 5:6:7: 8-tetramethylaUoxazine, 2-Chloro-3-nitro - Crystalline vitamin-B1. X. Sulphite cleav- toluene and NH2-CH2-CH2-OH in boihng CcH.N age. III. Basic product. E. R. Buchman, R. R. afford non-cryst. 3-nitro-2-fl-hydroxyethylaminotolu- Williams, and J. C. Kerbsztesy. XI. Presence cne, reduced and then condensed with (I)' to S- of quaternary nitrogen. R. R. Williams and mcthyl-9-fi-hydroxyethylisoalloxazine, m.p. 294°, de- A. E. Ruehle. XII. Sulphur-containing moiety. graded by sunhght to S-methylalloxazine. 2:3- H. T. Clarke and S. Gurin. XIII. Ultra-violet Diaminotoluene and (I) give 8( ’ł5)-methylalloxazine. absorption of some derivatives of the basie H. W. cleavage product and their synthetic analogues. Synthetic flavins. P. K arrer, H. Salomon, K. A. E. R uehle (J. Amer. Chem. Soc., 1935, 57, 1849— Schotp, and F. Benz (Helv. Chim. Acta, 1935, 1851, 1856— 1860, 1876—1881, 1887—1888; cf. this 18, 1143—1146).—Condensation of <7-deoxyribose vol., 1385).—X. The basie cleavage product (I) is with 4-amino-5-carbethoxyamino-o-xylene in MeOH at probably C4H4NS-CH2-CH2-OH and the yitam in (II) 100° in presence of H2/25 atm. and Ni affords 2-carb- a quaternary salt thereof. (I) [picrolonate, m.p. 184° ethoxyam ino - 4 : 5 - dimethylphenyl - d - deoxyribamine, (decomp.); platinichloride, m.p. 181° (decomp.); C02Et-NH-C6H2Me2-NH-[CH2]2*[CH-0H]2-CH2-0H, picrale, m.p. 162—163°; aurichloride, a n o il; p -nitro- m.p. 115°, [a]p +21°4;20 in H 20, which is transformed benzoate, m.p. 131°; methiodide (IV), cryst., very by alłoxan into 6 : 7-dimethyl-Q-d-1'-deoxijribityliso- sensitive to alkalis (gives S")] does not give the pine- ORGANIC CIIEMISTEY. 1511 splinter reaction nor a colour with ^-S03H-C6H4-N2C1, and natural (I), (III), and (V) are confirmed by is stable to hot 20% NaOH, and does not give CHI3 absorption spectra. (V) closely resembles (I), skowing with NaOH-I. With HC1 at 145° it affords the the smali effect of replacement of OH by Cl. R. S. C. substance (III), CGH8NSC1 (hydrochloride), closely resembling it in ultra-violet absorption. With HN03 Thiazole derivatives from co-chloroacetopyro- a t 40° it gives W indaus’ acid (V), C5II50 2NS, de catechol. Z. H orii (J. Pharm. Soc. Japan, 1935, comp. 200—250° (Me ester, m.p. 74°). 55, 21—32).—o)-Chloroacetopyrocatechol (I) and XI. Electrometric titration shows that (II) and CS(NH2)2 (II) give 2-amino-4-(3' : 4'-dihydroxyphenyl)- (IV) have two basie centres, one very weak, the other thiazole hydrochloride, m.p. 235—236°. 2-Acetamido-, not quite as strong as a true ąuaternary salt; two m.p. 268°, and 2-allylamino-, m.p. 208—209°, equivs. of alkali are required for complete liberation -4-(3' : 4 '-dihydroxyplienyl)thiazole are similarly pre of these bases; after liberation of the strong basie pared from appropriately substituted (II). (I) and centre slow rearrangement occurs to a much weaker diphenylthiocarbamide afford 2-anilo-Z-phenylA- base. (I) behaves as an ordinary weak base. (3' : 4 '-dihydroxyphenyl)-2 : ‘i-thiazoline, m.p. 252— ■i-Methylthiazole ethiodide (VI) exactly resembles (II) 253°. The following are obtained from the appro and (IV), but 2 : 4-dimethylthiazole ethiodide behaves priate disubstituted (II) and (I) : 2-o-tolylimino-Z-o- as a true quaternary salt. Previous speculation as tolyl-, m.p. 130°; 2-m-tolylimino-3-m-tolyl-, m.p. to the naturę of (II) is thus confirmed. 226—227°; 2--p-tolylimi7io-3-])-tolyl-, m.p. 280°; and XII. (I), (III), and (V) are synthesised. The 2-])-hydroxyanilo-3-i')-hydroxyphenyl- (hydrochloride, neutralisation of an extra mol. of alkali by (II) and m.p. 198—200°), -4-(3' : 4 '-dihydroxyphenyl)-2 : 3- (IV) is due to reversible opening of the thiazole ring; thiazoline. Ch. Abs. (r) (VI) is similarly cleaved by alkali and its alkaline Derivatives of o-thioldiphenylamine. W. J. solution with air or I gives fj-K-formethylaminoallyl E vans and S. Smiles (J.C.S., 1935, 1263—1265).— disulphide, [HCO-NEt-CMeiCHS-],, m.p. 101— 102°. 2-o-Nitrophenyl-l-methylbenzthiazolonium iodide (I) The sulphite cleavage of (II) is a peculiarity due to (this vol., 485) when boiled with CH(OEt)3, Ac20, the pyrimidine portion, sińce synthetic thiazolium and C5H5N yields 2 - 2'-di-o-nitrophenylthiocarbo- salts are not thus cleaved. (I) is readily oxidised cyanine iodide, m.p. 269° (decomp.), whereby its by Br-H20 and reacts relatively slowly with structure as the salt of a pseudo-base is confirmed. Pb(ONa)2; with (II) the relative rates of reaction are 2-Nitro-2'-benzamidodiphenyl sulpliide when boiled reversed. Synthetic thiazoles and thiazolium salts with COMe, and NaOH-EtOH is rearranged to a show similar behaviour. The hydrochloride of (II) thiol, which with HI affords l-phenyl-2-o-nitrophenyl- gives a resinous additive product with KI,, whence thiazolinium iodide, m.p. 195°. Tho thiol is regener- it is recovered by H ,0-E t20 with unimpaired activity. ated by Na0H-H20 and is methylated in alkaline 4-Methylthiazole (VII) [modified prep. from HCS-NH2 solution (cf. ibid., 615). Similarly 2-nitro-2‘-cinnam- and CH2Cl-COMe (VIII)] (platinichloride, -B2,H2PtCl4, amidodiphenyl sulphide, m.p. 132°, is rearranged to a m.p. 198°) gives (VI), m.p. 144-5°. 2 : 4-Dimethyl- thiol, which on methylation yields 2-cinnamo-o- tliiazole (IX) (modified prep.) gives the ethiodide, nitrophenylamidophenyl Me sulphide, m.p. 170—171° m.p. 212° (decomp.). CHClAc-C02Et and HCS-NH, (decomp. by warm H I into MeSH), and with HI yields in E t,0 at 0—5° give Et i-methylthiazole-5-carboxylate, 2-o-nitrophenyl-l-slyrylthiazolinium iodide, m.p. 225° m.p. 28°, b.p. 140°/12 mm., which with NaOH- (decomp.). Rearrangement of 4-chloro-2-nitro-2'- EtOH yields the corresponding acid, sublimes at 255° acetamidodiphenyl sulphide (II) yields a thiol, (Me ester, m.p. 75°), identical with (V). which is rapidly converted into bis-2-aceto-~ę-cliloro-o- CHNaAc-C02Et and OEt-[CH2]2-Br in EtOH give nitrophenylamidophenyl disulphide, m.p. 187— 188°, Et a.-($-ethoxyethyl)acetoacetate, b.p. 85—90°/10 mm., and wrhen boiled with COMe2, EtOH, and NaOH which with SOC1, affords the a-67-ester, b.p. 115— yields Z-ćhlorothiodiphenylamine, m.p. 199° (also 118°/12 nim. This with hot 15% H2S04 and AcOH formed during the original rearrangement). 2 :4- (1 : 1) gives Me a.-chloro-y-ethoxypropyl ketone, b.p. Dinitro-2'-acetamidodiphenvl sulphide (III) when 72—730/12 mm., converted by HCS-NH2 into boiled with COMe2 and EtOH-NaOH yields 3-m/ro-N- 4:-methyl-5-$-ethoxyethyUhiazole, b.p. 235° (decomp.) acetylłhiodiphenylamine (IV), m.p. 146°, hydrolysed [platinichlorides, 7i,,2HCl,H2PtCl4, m.p. 154—155° by EtOH-NaOH to 3-nitrothiodiphenylamine, which (decomp.), and j3,,H2PtCl4, m.p. 144—145°; picrate, is also obtained when 4-nitrodiphenylamine-2-sulph- m.p. 112°]. Conc HĆ1 a t 150° thence affords 4-methyl- inic acid (V) (corresponding methylsulphone, m.p. 5-S-chbroethylthiazole hydrochloride, m.p. 127—128° 170—171°) is reduced by H I in warm H 20 containing (corresponding picrate, m.p. 139°), identical with H,S03. This proves that (IV) is formed from the (III), hydrolysed by H20 at 150° to ±-methyl-5-fi- corresponding thiol and not from (III) before re hydroxyethylthiazole (hydrochloride; picrate, m.p. 162— arrangement. No stable thiazolinium salts analogous 163°), identical with (I). NHPh-CSMe and (VIII) to (I) were obtained from the thiols derived from in EtOH give Z-phenyl-2 :4-dimethyllhiazolmm (II) and (III). The following substances are obtained platinichloride, m.p. 245° (decomp. from 240°), iodide, when (V) is warmed with the appropriate aldehyde m.p. 210°, and chloride, an oil. (VIII) and HCS-NHPh or ketone: 5-nitro-2-phenylbenzthiazoline S-dioxide, at 50° give 2,-phenyl-i-methylthiazolium iodide, m.p. m.p. 147°, and its \-methyl (VI), m.p. 150°, 1 : 1- 241°. dimethyl, m.p. 200°, and 1-p-hydroxyphenyl, m.p. XIII. The absorption spectra of (I), (VII), (IX), 220° (decomp.), derivatives. Attempts to convert and 2-hydroxy-4-methylthiazole are very similar, as (VI) by oxidation in acid media into salts analogous are those of (IV) and (VI). The identities of synthetic to (I) failed. H. G. M. 1512 BRITISH CHEMICAL ABSTRACTS.----A. Dithiazine rings. H. G. U n d e r w o o d and F. B. m.p. 114—114-5°; 5 - phenyl - 3 - p - bromophenyl - 2 - p - D ains (J. Amer. Chem. Soc., 1935, 57, 1769— 1771).— anisyl-, m.p. 132-5—133°; 5-phenyl-3-j)-bromophenyl Methylene halides and thiocarbamides give occasion- 2-piperonyl-, m.p. 138—139°; 3-phenyl-5-a-naphthyl-, (~łTT_ m.p. 71—71-5°; 3-phenyl-2-slyryl-5-«.-naphthyl-, m.p. ally methylene ethers, S<^Q^j^^>NPh, but usually 52—53-5°; 3 : 5-diplienyl-2-(2-hydroxyphenyl)-, m.p. X H R '-----Sx 51—52-5°; 3:5- diphemyl - 2 - (4 - hydrozy - 3 - methozy - 1:3: 5-dithiazans, So 5 3 /C!NR, the stab- phenyl)-, m.p. 132-5—133°; 5-phanyl-S-j)-bromophenyl- \C(NR)-NH/ 2-(2-hydrozyphenyl)-, m.p. 159-5—161°; 5-phenyl-3-\)- ility of whicli is greatly inereased if R is aromatie. bromophenyl - 2 - (4 - hydrozy - 3 - methozyplienyl) -, m.p. CH2I2 and CS(NH2)2 (I) in hot EtOH give 4 : 6-di- 152-5— 153°; 3 -phenyl - 2 - (2 - hydrozy phenyl) - 5 - a - imino-1 : 3 : 5-dithiazan, m.p. 202—209°, unstable naphthyl-, m.p. 72—73-5°; 3-phenyl-2-(4:-hydrozy-3- (hydriodide, eryst., stable), hitherto (J.C.S., 1916,109, methozyphenyl)-5-z-nap>hthyl-, m.p. 156-5—157°. 1255) assumed to be CH2[S-C(NH)-;S[H2]2. (I) and F. R. G. CHPhCl2 (II) at 150° give 4 : Q-di-imino-2-phcnyl- Fluorescent dehydrogenation product from 1:3:5-dithiazan, unstable to O-liY-alkali (hydro vitamin-131.—See this vol., 1286. chloride, m.p. 236°). NIIo-CS-NHPh (III) and CH2Br2 Ergometrine. H. W. D udley (Proc. Roy. Soc., at 120—130° give 4 : 6-dianilo-l : 3 : 5-dithiazan, m.p. 1935, B, 118, 478—484, and J. Amer. Chem. Soc., 107° (hydrobromide, m.p. 268°; with 15% KOH gives 1935, 57, 2009—2010).—Ergometrine, C19H2302N3, H 2S, PhNCS, and N H 2Ph ; 5- or 6-Bz derivative, m.p. 160— 161°, [a]j,5 -j-40-25° in EtOH, is identical m.p. 120—121°), the hydriodide, m.p. 263°, being with “ ergotocine ” of Kharasch and Legault (this similarly obtained with CH2I2; the structure of this vol., 872, 995) and with “ ergobasine ” of Stoli and base is proved by its prep. also from CH2Br2 and Burckhardt (ibid., 995). The hydrochloride, m.p. ■s'-diphenvldithiobiuret (IV). NHjs,CS*NH-C6H4Me (V) 245—246° (decomp.), [a]D +63° in H 20, and hydro at 130° gives 4 : 6-rfi-p-, m.p. 175° (hydrobromide, m.p. bromide, m.p. 236— 237° (decomp.), ozalate, m.p. 193° 283°), and -o-tolylimino-1 : 3 : 5-dithiazan, m.p. 174° (decomp.), [a]„ +55-4° in H20, and interconvertible (hydrobromide, m.p. 236°). (III) with CHMeBr2 at yellow, hydrated, m.p. 148° (decomp.), and red 160° givcs 4: Q-dianilo-2-methyl-l : 3 : 5-dithiazan, m.p. picrates, anhyd., m.p. 188— 189° (decomp.), are 181° (hydrobromide, m.p. 248°), and with (II) at 110— described. H. G. R. 150° gives 4 : ti-dianilo-2-phcnyl-l : 3 : 5-dithiazan, m.p. 145° (hydrochloride, m.p. 232°), also obtained Spectrographic absorption of ergometrine in from (IV) at 150°. (V) yields similarly 4 : 6-c/t-p- relation to the B .P . colour test. N. L. Allport tolylimino-2-phenyl-\: 3 :5-dithiazan hydrochloride., m.p. and S. K. Crew s (Quart. J. Pharm., 1935, 8, 447— 222°. CS(NHPh), and CH2I2 in EtOH give an impure 452).—Ergometrine (I), m.p. 164°, giving a colour base and NHPh-CS-OEt (cf. lit.). CS(NH-C6H4Me-p)2 test with ^-NM e^^Hj-CHO (II) (B., 1932, 1135) and CH2I2 in hot COMe2 give C6H4Me'NH„ equiv. to that produced by 1-78 times its wt. of CBH4Me-NCS, and the ether, C16H 16N2S, m.p. 1515. ergotoxine (III) base, has an extinction coeff., E\i 01"- NPh:C(SMe)-NH-CS-NHPh (VI) gives similarly the 1-85 at 316 m[x. In aq. tartaric acid solution, both 4-thiolmethylene ether, ClfiH 15N,S2, m.p. 125° (hydr (I) and (III) have a max. absorption band at 316 mu, iodide, m.p. 275°), and PhNCS, but (II) gives tri- whilst the colours due to (II) are spectroscopically phenyl- and tritolyl-guanidine. (IV) with CH2I2 identical. F. O. H. gives a dithiazan, but with CH2Br2 and NH3-EtOH- Ergostetrine. M. R. Thompson (J. Amer. Pharm. H20 it gives 2-anilotetrahydrothiazole-3-thioform- Assoc., 1935, 24, 748—753).—The prep. of the purc anil, m.p. 165°, hydrolysed by K O H -EtO H to alkaloid, m.p. 160—162-5° (decomp.), [aJJ? -}-50°±10° 2-anilinothiazolidine. (VI) and CH201-C02Et in EtOH in EtOH, colour reactions, and pharmacological pro give 3-phenxyl-\-thiazólidone-2 - thiolmethyl - 4> - thiocarb- perties are described. The identity of ergostetrine amide, m.p. 127°, the '.CHPh derivative, m.p. with ergometrine, ergotocine, and ergobasine is sug 157°, of which is hydrolysed to 5-benzylidene-3- gested. H. G. R. phenylthiazoledione. Phenylmethyldithiobiuret and CH2Ćl-C02Et or CH2C1-C0C1~C5H5N in COMe2 afford Optical rotation study of the new orally phenylmethyllhiazolidone-2-thiocarbamide, m.p. 222° efiective principle of ergot. E. C. K leid er er (J. ('.CHPh derivative, m.p. 274°, hydrolysed as above). Amer. Chem. Soc., 1935, 57, 2007—2008.)—The [a]D R. S. C. of ergotocine in H ,0 remains const. (+76*1°), but in Thiohydrazides as reagents for aldehydes. MeOH changes gradually (from + 40-2+ ° to 61-8° in H. W uyts and H. W achsmuth (J. Pharm. Chim., 95-5 hr.); that of its maleate changes both in H„0 1935, [vin], 22, 289—305; cf. A., 1934, 537).—The (+46-2° to +53-7° in 48 hr.) and MeOH f + 37-9° to appropriate aldehyde and thioacylhydrazine in EtOH +24-6° in 48 lir.). Only slight decrease in pharma with a little HC1 give the following substituted cological activity accompanies this change in [a]. 2 : 3-dihydro-l : 3 : i-thiodiazoles (thiodiazolines): 3 : 5- R. S. C. diphenyl-2-styryl-, m.p. 127-5—128°; 3:5 -diphenyl- Ergot alkaloids. VI. Lysergic acid. W. A. 2-'p-anisyl-, m.p. 130-5— 131°; 3 : 5-diphenyl-2-piper- Jacobs and L. C. C raig (J. Biol. Chem., 1935, 111, onyl-, m.p. 154— 154-5° : 3 : 5-diphenyl-2-(\-furyl)-, 455— 465; cf. this vol., 1137).—Formuła (I) for m.p. 111— 111-5°; 5-phenyl-3-~p-bromophenyl-, m.p. lysergic acid is discussed. Dihydrolysergic acid and 112-5— 113-5°; 5-phenyl-3-p - bromophenyl - 2 - methyl-, KOH in H 2 a t 295—300° give ? 2-methyl-3-ethylind- m.p. 93-5—94°; 2 : 5-diphenyl-3-j>-bromophe7iyl-, m.p. ole (picrate, m.p. 148—150°), a base (? a methyl- 142-5—143-5°; 5-phenyl-3-p - bromophenyl - 2 - styryl-, ethyleneindole), b.p. 145— 150°/0-2 mm., m.p. 68° ORGANIC CHEMISTRY. 1513 (picrate, decomp. 195—200°), E tC 02H, ? AcOH, a which does not yield any (II) (contrast Wright, loc. cit.). f,Tt base (I) (picrate, m.p. 165— (I) and Me ^-toluenesulplionate when heated at 100° 170°), an acid, m.p. 270° (45 min.), then at 110—120° (30 min.), and subseąuently / N ---- / ;'ę-C02H [probably gives (I) by de- treated with NaOH and steam yields 5-bromonarceine, l Jx UNMe carboxylation], and NH2Me m.p. 193° [hydrochloride, m.p. 241°; hydrobromide, m.p. 225°; picrate, m.p. 153°; platinichloride, m.p. £ ? ' S h 198° (decomp.); Me ester, m.p. 114°]. H. G. M. at 30° gives a methiodide, Cotarnine series. V. Condensation of cot m.p. 237°, witli the properties of an onium salt. arnine with aromatic nitroaldehydes. B. B. Dey 11. S. C. and (Miss) P. L. Kantam (J. Indian Chem. Soc., Dehydrogenation of nicotine in toluene as a 1935,12, 604—607).—Cotarnine and 0-N02,C6H4*CH0 solvent. A. A. Morton and D. H orvitz (J. Amer. in EtOH give \-o-nitrobcnzoyl-5-a.-liydroxy-o-nitro- Chem. Soc., 1935, 57, 1860—1861).—Nicotine and S, benzylhydrocotamine (I), m.p. 153° [hydrochloride, best in PhMe, give H2S (69%), thiodinicotyrine (18%), m.p. 172° (decomp.); hydrobromide-\-il20 , m.p. 177° and nicotyrine (2-5%). R. S. C. (decomp.); nitrate, m.p. 181° (decomp.); sulphate, m.p. 191—192° (decomp.); picrate, m.p. 175— 176°], Oxidation produets of vasicine with hydro- reduced by SnCl2 to the corresponding (iV7/2)2-base gen peroxide. T. P. Ghose, S. K risiin a, K. S. m.p. 122° (Ac2 derivative, m.p. 126°). 1-m-Nitro- Narang, and J. N. Ray (Current Sci., 1935,4, 158— be.nzoyl-n-rJ.-hydroxy-m-nitrobenzyl-, m.p. 146° [hydro 159).—Contrary to the view of Morris, Hanford, and chloride, m.p. 188° (decomp.); corresponding (NH2)2- Adams (this vol., 873) th at the product, m.p. 168°, compound, m.p. 113°], 1-2'-nitroA' : 5'-dimethoxy- obtained by the authors (A., 1933, 77) from H 20 2 and benzoyl-5-a.-hydroxy-2' - nitro -4' : 5 '-dimethoxybenzyl-, vasieine, is a mixture, it gives const. analytical vals., m.p. 168° [hydrochloride, m.p. 193° (decomp.)], and has a homogeneous appearance under the micro- and 1 - 6' - nitropiperonoyl - 5 - a - hydroxy - 6' -nitro - scope. It is now regarded as 4-hydroxy-2:3 : 2 ': 3'-bis- 3' : 4'-methylancdioxybenzyl-hydrocotarnine, m.p. 168° a-hydroxyirimeihylene-4i: 4 '-bisdihydroguinazolyl. [hydrobromide, m.p. 180° (decomp.)], are similarly E. W. W. obtained. 5-Bromocotarnine, however, condenses Cotarnine series. IV. 5-Bromonarcotine, 5- with only 1 mol. of aldehyde to give o-bromo-l-o- bromocotarnine, 5-bromohydrocotarnine, and nitrobenzoyl-, m.p. 120° after sintering [hydrobromide, 5-bromonarceine and their derivatives. B. B. m.p. 162° (decomp.)], and -6-nitropiperonoyl-hydro- Dey and T. K. Skinivasan (J. Indian Chem. Soc., cotarnine, m.p. 125° (hydrobromide, m.p. 172°), thus 1935, 12, 526—536).—Narcotine when treated with confirming Robinson’s formulation (A., 1924, i, 666) HBr, H20, Br, and subseąuently with H2S yields of (I) etc. The “ 1-cotamino-o-nitrophenyl ketone ” 5-bromonarcotine (I), m.p. 176°, [aft0 —95° in CHC13 of Ahluwahlia et al. (A., 1933, 960) was (I). (hydrochloride-\-H20, m.p. 120°; hydróbromide-\-II20, R. S. C. m.p. 168°; platinichloride; picrate, m.p. 197°, and Condensation of cotarnine and o-nitrobenz- methiodide, m.p. 220°), which with H B r-B r-H 20 aldehyde. K. N. K aul and G. S. Ahluwalia (J. .yields a perbromide hydrobromide, m.p. 220° (decomp.), Indian Chem. Soc., 1935, 12, 610).—The compound from which (I) is regenerated by H2S. (I) is oxidised formulated as “ 1-cotarnino-o-nitrophenyl ketone” by HN03-H 20 to 5-bromocotarnine (II), m.p. 135° (A., 1933, 960) is 5-o-nitrobenzoyl-l-a-hydroxy-o- [hydrochloride, m.p. 170° (decomp.); picrate, m.p. nitrobenzylhydrocotarnine. R. S. C. i71°; platinichloride; Bz derivative, m.p. 103°; oxime, m.p. 138°; oxime hydrochloride, m.p. 169°, Corynantheine. Raymond-Hamet (J. Pharm. and perbromide hydrobromide, m.p. 200° (decomp.)] Chim., 1935, [viii], 22, 306—325; cf. this yol., 894).— (cf. W right, J.C.S., 1877, 32, 525; Smali, “ Chemistry Corynantheine hydrochloride hydrolysed with KOH in of the Opium Alkaloids,” 1932, pp. 68, 70, and 9S), EtÓH gives corynantheic acid, C19H2,,N,,(0Me)-C02H, also obtained, but less conveniently, by bromination of [a]D -f7-53° in C5H5N. " ' F. R. G. cotarnine. (II) with PhNCO and CcH6 yields phenyl- Quinoidine. Occurrence of <*p/ąuinine and 5-bromocotaniomethylcarbamide, m.p. 160° (oxime, epiąuinidine in cinchona bark. W. Dirscherl m.p. 168—169°), and when heated with MeN02 at and H. T h ro n (Annalen, 1935, 521, 48—71).—A the b.p. yields anhydrobromocotarninonitromethane, C6HG extract of ąuinoidine (I), the s\Tup}' residue of m.p. 148° (hydrochloride, m.p. 166°). (II) when heated cinchona bark alkaloids after removal of the ąuinine with excess of Ac20 at the b.p. yields Ń-acetyl-5-bromo- (II) etc., deposits 4—5% of (II), and then yields with cotamidineacetic acid, m.p. 211° (Ag salt). (II) and KM n04-C r0 3 44% of ąuinic acid, absorbs 0-66 mol. Mel when heated under pressure yield 5-bromocotarno- of H2 when hydrogenated, and by the Hg(OAc)2 methine methiodide, m.p. 179°, which when steam- method yields 65% of vinyl bases. With H2S04 distilled with NaÓH vields 5-brornocotanwne, m.p. these last give amorphous quinoidotoxin, [aft1 +16-6° 104°, oxidised by KM n04, K 2C03. COMe2, and H 20 in Ar-HCl [yielding quinotoxin oxalate, m.p. 166— to o-bromocotarnolactone, m.p. 172°, further oxidised 167°, [aft0 (anhyd.) +25° in EtOII-CHCl3 (1 : 2)], and to 5-bromocotarnic acid [2-methoxy-3 : 4-methylenedi- thence its Bz and oximinobenzoyl derivatives, benzoyl- oxy-5-bromophthalic acid], m.p. 185° (anhydride, guinoidinonitrile, meroąuinoidine, acetylmeroąuinine, m.p. 225°). This establislies the constitution of (II). meroąuinine E t ester, and (3-collidine. The presence (II) is reduced by Na-Hg-A-HCl to 5-bromohydro of epiąuinine and epiąuinidine in the bark, thus cotarnine, m.p. 80° (hydrobromide, m.p. 242°), the indicated, is confirmed by their direct isolation as perbromide hydrobromide, m.p. 166° (decomp.), of benzoyl-d-tartrates, m.p. 160°', [aft7 —26-3° in EtOH, 1514 BRITISH CHEMICAL ABSTEACTS.— A. and m.p. 166—167°, [a]^1 4-1-9°, respectiyely, and by optically inactive), and d- (+5H20), m.p. 190°, partial benzoylation of (I). Benzoylquinotoxin has [a]is46i +105° in MeOH, and l-o-methyltubocurarine m.p. 113—114°, Mg5 +36° in EtOH. Toxins, if mełhine methiodide (+ 5 H ,0 ), m.p. 171— 172°, [a]M(ll present at all, constitute < 10% of (I). R. S. C. —57° in MeOH; a t the second stage of degradation, Constitution of matrine. XVII. H. K ondo, a N-free substanee, m.p. 198— 199°, is obtained. E. Octdlai, and K. T suda (Ber., 1935, 68, [JB], 1899— Similar methylation and degradation of ri-bebeerine 1904; cf. this vol., 766).—Catalytic dehydrogenation yields a series of substances identieal with those (Pd-asbestos a t 270—280°) of the base, C14H2GN2, obtained from tubocurarine: O -methylbebeerine- obtained by reduction of decarbonylmethylmatrinane mcthinc methiodide-A and -B, and d-O-methylbebeorine affords the base, C14H20N2, identieal with that methine methiodide (a monomethiodide, obtained by catalytic dehydrogenation of matrine. C4fH4n0GN2I,H20, has also been separated, m.p. Oxidation with KM n04 of the methohydroxide of 261°, [a]5461 +63° in 2\7-HCl), and a t the second stage, this base affords Pr“CO,H, showing the presence of 0-methylbebeerilcne, m.p. 198—199°. Probable struc- a Pr“ side-chain. Gon troi experiments with matrine tures are given and discussed for tubocurarine and methohydroxide do not give Pr“CO,H, so that the its derivatives. E. R. S. Pra cham is obtained by degradation of the lactam Alkaloids of Ciitisus caucasicus.—See this vol., ring which in matrine has the structure 1549. C H N/T c°-ęHMe or c H N/-N-CO-ęH2 J01- 1 -CH — CH, or i° 17 1-ĆH-CH2-CH2’ Preparation of asymmetric secondary aryl- arsinic acids. G. K. Kamai (Trans. Kirov. Inst. probably the former. Dihydro-a-matrinidinc (I) is Chem. Tech. Kazan, 1935, No. 3, 49—53).—B art’s therefore C10H17N ! considered in conjunction method (A., 1922, i, 1201) is superior to th at of with the production of pyridine-2:3-dicarboxylic Blicke and Smith (A., 1930, 99), whose phenyl-^3- acid by oxidation of the eompound, C12H14N2, ob tolylarsinic acid (I) probably contained unoxidised tained by degradation of (I) with CNBr and sub- tetra-arylarsine oxide. Pure (I) has m.p. 159— 160°; its prep. from PhAsO and p-C,;H4Mo-NoCl, seąuent oxidation, the struc- from ^-CGH4Me-AsO and PhN2Cl, and from MgPhBr 1 ture A or B can be assigned and ^-C^HjMe-AsO is described. Diazotised p- HNj to (I). Dehydro-a-matrinid- ine therefore has a 2-methvl- nitroaniline and PhAsO yield phenyl-p-nitrophcnyl- pyridine nucleus; in con- arsinic acid, m.p. 181° (NH4, Ba, Na, NH,Ph, firmation, it condenses with m.p. 162— 166°, and p-CcH4Me-NH2, m.p. 78—79°, salts). Ch. Abs. (r) PhCHO in presence of ZnCl2 a t 230—250° to benzylidene- Preparation of 3-nitro-4-hydroxyphenylarsinic dehydro-a-matrinidine, m.p. 106— 107°, hydrogenated acid from p-chloroaniline. V. A. Isjiailski and (P t0 2) to the benzyl eompound (platinichloride, decomp. A. M. Simonov (J. Pliarm. Chim., 1935, 22, [viii], 190°). If it be assumed th at displacement of a ring 337—357).—jj-Chlorophenylarsinic acid with KN03- does not take place during the formation of a-matrin- coąc. H 2S04 at 100° (cf. A., 1929, 5S4) gives 4-cliloro-3- idine the constitution of matrine (II) may be nitrophenylarsinic acid (I), which is converted by represented by C or D. 40% alkali at 85° into Z-nitroA-hydroxyphemjl- arsinic acid, also obtained by hydrolysis (25% NaOH CHMe-CO CHMe-CH, CH2 N CO CH a t 100°) of 2-nitrodiphenylamineA-ar sinic acid, pre pared by boiling the Na salt of (I) in H20 with V/ \ NH,Ph. J. L. D ¥ 9H 2 vCH v CH ĆH CH Stereochemistry of tervalent arsenie. II. Preparation of o-, m-, and p-phenylmethyl- h 2\ h \ h 2 arsinobenzoic acids and their attempted resolu c h 2 n H„ N CH2 tion into optically active components. G. W \ / “ Kamai (Ber., 1935, 68, [£], 1893— 1898; cf. this CH2 ^C H o CH, CH2 vol., 875).—Attempts to resolve the acids into (C.) (D.) their optically active components were unsuccessful. AsPhMel is converted by Mg and jj-CfiH4MeBr into (II) and lupanine are not stereoisomerides. On phenyl--p-tolylmethylarsine, b.p. 166—167°/8 mm. (com- oxidation lupanine methohydroxide giyes glutarie acid, pound, m.p. 59—60°, with CuBr), oxidised by K M n04 which is formed with certainty from its a-piperidone ring sińce it could not be obtained from sparteine but is in H 20 to phenyl-ip-carbozyjihenylmethylarsine oxide deriyed from tetraliydrocytisine. H. W. hydrochloride (I), m.p. 150—152° (decomp.), which with H 2S affords phenyl--p-carboxyphenylmethylarsine Curarealkaloids. I. Tubocurarine. H. K ing sulphide, m.p. 159— 160°. (I) is transformed by (J.C.S., 1935, 1381— 1389; cf. this vol., 655, 1138).— S02 in presence of I into p -phenylmethylarsinóbenzoic d-Tubocurarine chloride (+ 5 H 20), m.p. 274—275°, acid, AsPhMe-C6H4-C02H, m.p. 149— 151° (NH^, Ba, [a]s°6i +235° in H,0, is methylated to 0 -methyltubo- strychninę, m.p. 183—185°, [a]1^ —16-05° in CHC13, curarine iodide (+ 3 H 20), m.p. 267°, [a]5461 +178-2° ąuinine, m.p. 210—211°, [a]},6 —56-91° in CHC13, in H,0. Hofmann degradation of the iodide yields and non-eryst. brudne and dnehonine salts). The O-methyllubocurarinemethine methiodide A (+2-5H,0), following compounds are obtained similarly : phenyl- m.p. 234°, and B (+2-5H ,0), m.p. 230° (A and B ~are m-tolylmethylarsine, b.p. 165—166°/9 mm., (non- ClRGANIC CHEMISTRY. 1515 cryst. compound with CuBr), •phcnyl-m-carboxyplienyl- propionic acid). woStilbene gives rx-chloroniercuri-Q- methylarsine ozide hydrochloride, m.p. 148— 150° niellioxy-a.$-diphenylcthanc, m.p. 143°, but trans- (decomp.) (compound with HgCl2), phenyl-m-carboxy- stilbene does not react; this mercurial with a variety phenybnethylarsine sulphide, m.p. 134— 135°, and of reagents gives a mixture of isomeric stilbenes. m -phenylmethylarsinobenzoic acid, m.p. 92—93° (quin- Styrene affords Methods of chemical analysis by hydrogen dissolved in CHC13 and determined colorimetrically. ation. H. ter M e u len (Buli. Soc. chim., 1935, [v], CHMeAc-OH (I) is determined by oxidation to Ac2 2, 1692— 1694).—Methods are described for over- during distillation, the Ac, originally present being coming the difficulties observed by Gauthier (this subtracted from the total determined. The results vol., 506) in the determination of org. S, O, and N by are slightly Iow owing to escape of Ac2 in the C02. hydrogenation in presence of a catalyst. J. W. S. The detection of added Ac2 isdifficult, but addition may Determination of deuterium in organie com beinferred from the ratio of Ac2 to Ac2-j-(I). E. C. S. pounds.—See this vol., 1408. Micro-detection of liquid amines, especially Micro-volumetric determination of methoxyl. methylamine in presence of ammonia. A. von D. T. Gibson and T. H. Caulfield (J.C.S., 1935, W acek and H. L offler (Mikrochem., 1935, 18, 1419—1420).—Contrary to Viebock and Brecher 277—282; cf. A., 1934, 1278).—Methods of distin- (A., 1931, 246), the determination cannot be satis- guishing between NH3 and NH,Me are discussed factorily carried out on 1—5 mg. of materiał because and photomicrographs are given of the products the “ blank ” correction is signifieant and is inereased obtained with 1:2:4- and 1:4: 8-C10H 5(NO2)./OH, by time, temp., and dilution. Improvements in and 1:2:4: 5-C10H4(NO2)3-OH. R. S. teęhniąue are described. J. L. D. Microscopy of the amino-acids and their com Biochemical detection of organie compounds. pounds. I. Phosphotungstates and phospho- —See this vol„ 1416. molybdates. B. B ullock and P. L. K ir k . II. Structure and oxidation of nitrogenous sub Picrates and flavianates. B. L. Crosby and P. L. stances. C. N. Acharya (Naturę, 1935,136, 644).— K ir k (Mikrochem., 1935, 18, 129— 136, 137— 143).— When N compounds are oxidised by a mixture of Photomicrographs of the above salts of a no. of NH2- Cr03-f-H2S04, fuli recovery of N is obtained in the acids are given. toa;ether with n vals. of the flavianates. form of NH3 and N03' when the N are attached to R. S. different C. When two or more N are attached to Determination of creatinephosphoric acid.— the same C, liowever, a definite amount is lost either See this vol., 1521. as N2 or N20. The proportions of NH3 recovered [Analytical reactions of vanillin, phenols, and from typical groups are : -NH-CO-NH-, 2/3 of total N ; “ prontosil ” ].—Sec this vol., 1474. •N:CH-N:, 4/5; guanidine group, 4/11, and crcatine group, 2/3. NH,OH derivatives are almost ąuantit- Volumetric determination of camphor by the atively oxidised to N03', whilst in N2H4 derivatives hydroxylamine method. R. Va n d o n i and G. the N is almost completely lost as gas. Cl' present D esseigne (Buli. Soc. chim., 1935, [v], 2, 1685— as impurity and as hydroehlorides of bases tends to 1691).—Camphor, fenchone, menthone, carvone, and inerease the ratio N03' : NH3 and should be removed camphenilone are converted by NH2OH,HCl into by Ag2S04. L.S.T. their oximes and the liberated HC1 is titrated with Ar-Na2C03 (bromophenol-blue indicator). Experi- Colour reactions for tartaric, citric, and mental error is <1%. F. R. G. aconitic acids. O. F urth and H . H errm ann (Biochem. Z., 1935, 280, 448—457).—W ith Ac20 Determination of pyridine in presence of and C5HjN tartaric acid gives an emerald-green, nicotine. R. L. F ra tk in , L. P. J uravleva, and citric acid a carmine-red, and aconitic acid a violet A. G. B lankschtein (Sborn. Robot Chim. Otdela, 1935, colour whereas many of the aliphatic dibasic acids 88— 106).—The C5H5N is distilled off in presence of give no or only a brown colour. Tho reaction is excess of AcOH. The residue is made alkaline and very sensitive and using the fluorescence in ultra- the nicotine distilled in steam and determined as violet lięjht can detect 1() 6 g. of these acids. silicotungstate. The acid C5H5N distillate is mado P. W. C. alkaline, redistilled into dii. H2S04, pptd. with Determination of diacetyl and acetylmethyl- NH4CNS and CuS04, and the solution titrated with carbinol. C. R . B arnicoat (Analyst, 1935, 60, standard AgN03. The method is more accurate 653—662).—Ac2 is separated by distillation in C02, than th at of Mach and Sindlinger (A., 1924, ii, 357). and converted into Ni dimethylglyoxime, which is T. H. P. Biochemistry. Cerebral blood in conscious and narcotised Colloid osmotic pressure of the blood of sea- m en. D. L aszlo, H. U rban, and E. W eissenberg fish. P. Mey er (Compt. rend. Soc. Biol., 1935, 120, (Arch. exp. Path. Pharm., 1935,179,266—272).—The 303—305).—Vals. are given for the colloid osmotic difference in 0 2 content of arterial and venous blood of pressure of the blood of a no. of fish. Tliose of the brain supplyinman variesconsiderably,the average teleosteans are of the same order as for terrestrial being 3-7 vol.-% (during Et20 narcosis 2-23%). mammals, whilst those of selachians are of the order The difference in CO, content also diminishes (average of 3—6 cm. of H ,0 . Results for teleosteans do not vals. 4-6 and 3-9%, respeetively), giving R.Q. of support Krogh’s hypothesis. R. N. C. 1-3 before and 1-7 during narcosis. The effect is due toinhibition of metabolie oxidation and subseąuent Study by micro-incineration of the red cor- accumulation of acidie products. F. 0. H. puscles of the teleostean fish, Cichlasonui BIOCHEMISTRY. 1517 fa scetu m . A. P olicjard and P. R ojas (Compt. Absorption of carbon monoxide with reduced rend. Soc. Biol., 1935, 120, 366—367).—The nuclei haematin and pyridine-haemochromogen. L. E. on incineration yield a fine wliite ash. The peripheral Clifcorn, V. W. Meloche, and C. A. E lvehjem zone of the cytoplasm yields a coarse yellow ash, (J. Biol. Chem., 1935, 111, 399— 409).—The relative less abundant than that from amphibia, which con- rates of absorption of CO by alkaline (I) and acid tains Fe, whilst the inner region yields no ash. Tho reduced haematin (n), and by pyridine-hfemochrom- colour and character of the ash vary with the Fe ogen (III) at 25° havc been determined. (I) absorbs content. R . N. C. faster than (II). Excess of C5Hr,N expcls CO from CO-(ni). K for the system CO-(III) -> CO+(III) in Thickness of the wali of the red blood-corpuscle. a solution containing no excess of CSHSN is 1-24x10^. J . F. D a n ielli (J. Gen. Pliysiol., 1935,19, 19—22).— J. N. A. Max. vals. for the dielectric consts. of lipoid substances Effect of varying concentrations of oxyhaemo- in unimol. films are calc. from surface potential globin on its light absorption. G. B. R ay and measurements. These are in accordance with tho H. A. Blair (J. Biol. Cliem., 1935, 111, 371—378).— val. 3 assumed by Fricke for the erythrocyte cell- Oxyhaemoglobin in all concns. at X 540 and 560 mjz wall. F. A. A obeys Beer’s and Lambert’s laws, p a and salts in Haematopoietic action of phosphoric acid solution having no effect. At X 650 mu Beer’s law compounds of creatine and creatinine. V. is not obeyed, tłie absorption divcrging from the Suzuki, W. N akahara, and F. I ntjkai (Sci. Papers calc. val. a t 4 g. per 100 c.c., indicating th at mol. Inst. Phys. Chem. Res. Tokyo, 1935, 28, 1—9).— changes are taking place. J . N. A. The compound obtained by the interaction of creatine Modifications of blood composition under or creatinine with P20 5 and H P03 administered per os the influence of generał application of short to normal rabbits in 30 mg. daily doses gave a marked w aves. A. Compere (Compt. rend. Soc. Biol., incrcase in the erythrocyte count. A. L. 1935, 120, 237—240).—Sliort-wave application in the Haemoglobin metabolism and its disorders. dog causes diminution of the alkaline reserve and L. H eilm eyer (Zentr. inn. Med., 1934, 55, 818—S28; p u of the blood, and inerease of non-protein-N and Chem. Zentr., 1935, i, 1731— 1732).—Porphyrin elim- total protein. Total fixed bases, minerał acids, inated during hsematoporphyrinuria is not a decomp. and protein acidity are scarcely modified. Corpus- product of haemoglobin (I), but results from defective cular vol. is generally diminished. R. N. C. synthesis. The decomp. of blood-pigment follows Regulation of protein disequilibrium of hlood- the stages, bilirubin urobilin and stercobilin. Uro- serum under the influence of injections of serin : bilinogen is identical with mesobilirubinogen. A experiments on man. G. L efro u and P. B onnet secondary decomp. of (I) leads to formation of (Compt. rend. Soc. Biol., 1935, 120, 424— 427).— uroerythrin and urochromc B. A. G. P. Serin (I) injected into lepers exhibits feeble Haemoglobin studies. I. In rachitic chickens : anaphylactic properties. Serum-globulin and total effect of ultra-violet irradiation. G. H. Maughan albumin are decreased, whilst (I) and the (I)-globulin (Proc. Soc. Exp. Biol. Med., 1934, 32, 389—390).— ratio are inereased. (I) injections hence exert a Haemoglobin is Iow in th e blood of rachitic chickens, regulating effect on protein diseąuilibrium. R . N. C. but on ultra-violet irradiation inereases to vals. > Application of the differential determination those of normal Controls. R- N. C. of albumoses, polypeptides, and amino-acids, Escape of haemoglobin from the red celi during using ninhydrin, to blood. E. Ch erbu liez and haem olysis. E. P o n d er and D. Marsland (J. A. Mirim a n o ff (Arch. Sci. phys. nat., 1935, [v], Gen. Physiol., 1935, 19, 35—44).—Cinematograph 17, Suppl., 150—152).—After pptn. with various films of red blood-corpuscles losing haemoglobin under reagents the various fractions are determined with the influence of saponin (I) show that the permeability ninhydrin (A., 1933, 1181). H. G. R. is a function of the concn. of (I). In lysis by hypotonic Determination of the amino-acids of blood- solutions the permeability is nearly independent of serum with tyrosinase. A. Mirim anoff and E. the tonicity. F. A. A. P errottet (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., Volumetric determination of haemoglobin. 168—172).—The ninhydrin and tyrosinase methods S. R usznyak and E. B. H atz (Biocheni. Z., 1935, are compared. The former is more rapid, but the 280, 242—247).—DefTbrinated blood (1—2 c.c.) latter can be carried out without clarification. is saturated with CO (excess removed in N2) and the H. G. R. bound CO is liberated by the action of 32% aq. Modified Nessler's reagent for micro-deter K,Fe(CN)6 containing lactic acid. The liberated mination of urea in tungstic acid blood-filtrate. CO is then determined by Winkler’s method (B., 1934, J . F. B arrett (Biochem. J., 1935, 29, 2442—2445).— 557). W. McC. Addition of NaOCl to Nessler’s reagent prevents New haematological stain. I. Constituents its reduction by glucose, creatinine, etc., and allows direct colorimetric determination of urea in blood- and methods of use. D. M. K in g sley (Stain Tech., 1935,10,127—133).—A two-solution stain for generał filtrates. F. A. A. haematological use is described. When mixed it is Effect of thyroidectomy on the lipin, fatty acid, stable for 8 months and may be used for blood- cholesterol, and protein content of blood-serum. smears, fixed and frozen sections, and touch preps. C. I. P arhon and I. Ornstein (Buli. Soc. Chim. H. G. R . biol., 1935, 17, 1119— 1123).—Thyroidectomy in 5 h 1518 BRITISH CHEMICAL ABSTRACTS.----A. rabbits resulted in inereases in total lipins, fatty acids, of vagotomy on insulin secretion (cf. A., 1934, 1379; and cholesterol of the blood-serum. Little change this yoI., 378). F. O. H. was observed in the protein content. A. L. Level of carbonyl compounds in human blood. Determination of blood-sugar. I. Deprotein- R. E. J ohnson, A. P. Meik lejo h n , R. P assmore, isation with cadmium hydroxide. II. Iodo- and R. H. S. T hompson (Biochem. J., 1935, metric micro-determination of blood-sugar. 29, 2506—2509).—The amounts of total H S 03'- C. D umazert (Buli. Soc. Chim. biol., 1935, 17, 1163— binding substances in human blood fali within the 1170, 1171— 1177; cf. this vol., 642).—I. A raicro- limits 1-96—4-00 with an average of 2-81, expressed method employing deproteinisation with Cd(OH)2, as mg. of AcCOoH per 100 g. of blood. The followed by oxidation (Hagedorn-Jensen), for the IIS03'-binding capacity of blood from various cases determination of blood-sugar is described. 0-1 c.e. suffering from mental and physical diseases showed of blood is used and the error is 1—2%. By this no appreciable difference from that of normal blood. method, glucose in the blood-corpuscles of diabetics The latter may contain some CO-eompound other than is > that in the plasma. AcC02H, COMe2, or CH2Ac-C02H. J. N. A. II. Deproteinisation with Hg(OH)2 and Cd(OH)2 Blood-iodine values. H. D oering (Biochem. followed by iodometric determination of the aldoses Z., 1935, 280, 442—447).—The Iow blood-I vals. (A., 1934, 992) is employed. 1 c.c. of blood is used obtained by the Fellenberg method are correct, and the error is 3%. A. L. and there is no volatile I fraction which is lost on Modifications of the glycerol content of the ashing in an opon crucible. The high vals. obtained blood in glyeolysis in vitro. M. P olonovski, II. by ashing in a closcd system are incorrect, and aro W arembourg, and P. L amour (Compt. rend. Soc. due either to traces of Br and Cl beng incompletely Biol., 1935,120, 191— 192).—Glycerol (I) andglycero- removed or to traces of oxidants which liberate I from phosphoric acid inerease in blood during glyeolysis KI in acid solution remaining after ashing. P. W . C. in vitro at 37°. (I) falls after reaching 50% of the Iodine in blood. A. Sturm , K. P lo tn er, and calc. val., so that a (I)-destroying reaction begins in K. Maass (Biochem. Z., 1935, 280, 396—412).— the later stages of glyeolysis. (I) variations are not A generał discussion is given of the various methods oc the liydrolysis of blood-lipins; they are almost for determination of I in blood, the objections raised wholly responsible for the inerease of the residual to the author’s modification of the Fellenberg method chromie index, which is not affected bjr non-protein-N are refuted, and the interpretation of blood-I vals. variations. R. N. C. particularly in hyporiodsemia is discussed. P. W . C. Significance of phospboric esters in the course Occurrence of bromine in the normal of blood-glycolysis. II. Degradation of hexose organism . T. L eipert (Biochem. Z., 1935, monophosphate in hsemolysed blood. Z. D ische 280, 416—433).—The Br content of normal human (Biochem. Z., 1935, 280, 248—264; cf. this vol., blood is 0-160—0-4 mg. per 100 ml. and of plasma 0-18 104).—The degradation is preccded by a phosphoryl- —0-45 mg. per 100 ml. Br, unlike Cl, is retained ation, < two thirds of the phosphoric acid which in the erytlirocytes, and the distribution ratio is esterifies the monophosphate (I) being transferred therefore very variable, and is controlled by the from adenosinetriphosphoric acid. Decrease in the C02 tension of the blood. No evidence could be ratc of trans-estcrification oc the decrease in the concn. obtained of Br-protein complex formation, and no of (I). The aldo-form of (I) is probably only indirectly ultrafilterable org. Br could be detected, Br being involved, serving to provide nascent keto-form which present only in the ionised form. Br is excreted is phosphorylated much more rapidly than is the together with Cl, but the ratios of Cl to Br in plasma ordinary keto-form. There is no evidence of direct and urine are not identical. Br is constantly found conversion of (I) into 1 mol. of triose ester and 1 mol. together with Cl in intermediate metabolic processes, of triose. W. McC. and administration of tissue diuretics leads to elimin- ation of Br. Soon after birth, infants’ urine has a Gravimetric determination of fat and chole high C l: Br ratio (corresponding with the high blood sterol in blood. G. Gorbach and R. K a d n er ratio), and this diminishes during nutrition with (Mikrocliem., 1935, 18, 266— 271).—The sample is milk. P . W . C. extracted with ligroin in the micro-extractor (A., 1933, 139). Cholesterol in the extract is pptd. by Bromine content of the organism in mental digitonin and the fat obtained by difference. R. S. patients. T. L e iper t and O. W atzlawek (Biochem. Z., 1935, 280, 434— 441).—Tables summarise the Br Sulphur content of panereatie blood and of and Cl contents of the blood, the distribution of thoracic lympb. VI. Glucose injection in Br and Cl between erytlirocytes and plasma, the vagotomised dogs. S. K umami (J. Biochem. dependence of the Br and Cl index on the C02 tension, Japan, 1935, 22, 163— 179).—The S content of the the Br and Cl contents of the cerebrospinal fluid, thoracic lymph of vagotomised dogs varies consider- and the Br and Cl urinary excretion of mental patients. ably from hr. to hr., the average tendency being The Br in these cases is always wholly present as a gradual diminution. That of blood from the Br', and is in no way either ehemically or physically panereatie vein is not changed by injection of glucose, different from the normal condition. The preponder- whereas that of thoracic lymph slowly falls and then ance of cases of Iow Br val. is probably due to deficient returns to normal levels. The difference between these diet. No evidence was obtained for the existence of results and those in normal dogs is due to the influence a Br-containing pituitary secretion, the gland exereis- BIOCHEMISTRY. 1519 ing any effect on the Br content of the organism in a Active group of heparin. S. B ergstrom secondary way by regulation of the H20 content. (Naturwiss., 1935, 23, 706).—By the action of CISOgH in C5HjN on cellulose, ehitin, starch, glycogen, Volnmetric micro-determination of potassium gum arabie, yeast-nucleic acid, and chondroitin- in blood-serum. P. W en g e r , C. Cim erm an, and sulphuric acid, acid esters were obtained which pos- C. R zymowska (Arch. Sci. phys. nat., 1935, [v], sessed anticoagulating action of which the strongest, 17, Suppl., 140—143).—The method of Shohl and that derived from cellulose, had an activity < 1/10 Bennett (A., 1928, 1292) has been modified by incor- that of heparin. In contrast to natural heparin, porating a wet incineration (HC104 and HN03) the cellulose ester was markedly toxic to rabbits. and removal of NH4 salts with NaOH. H. G. R. W. O. K. Anticoagulant properties of the pyrogenic Isoelectric point of the erythrocyte membrane products of citric acid. A. L um iere and S. and hsemolysis by ammonium chloride. M. Sonnery (Compt. rend. Soc. Biol., 1935, 120, 213— R ocha e Silya (Compt. rend. Soc. Biol., 1935, 214).—The anticoagulant power of citric acid in 120, 174—176).-—Erythrocytes are not hamiolysed ereases as the successive C02H groups are neutralised; by 4% NH4C1 solution at p„ 8, the isoelectric point th at of Na salts of acids produced by heating is < th at of the celi membrane. Hacmolysis occurs with an of citric acid and decreases in tho order itaconic and unneutralised solution of NH.C1 at the same concn. aconitic > citraconic > mesaconic acid. Alkali R. N. C. citrates are more coagulant than heavy-metal citrates. Htemolysis by glucosides (saponin and solanin) R. N. C. and production of cholesterol in vivo. V. de Regulation of protein diseąuilibrium of blood- L avergne and P. K issel (Compt. rend. Soc. Biol., serum under the influence of injections of serin : 1935, 120, 149— 150).—Hsemolysis in guinea-pigs animal experiments. G. L kfrou and P. B onnet and rabbits by neutral or alkaline saponin (I) solutions (Compt. rend. Soc. Biol., 1935, 120, 342—343).— cause an inerease in plasma-cholesterol (II). Solanin Rabbits injected weekly with serin show neerotie and acid (I) solutions lower (II) by their pptg. action. areas at the point of inoculation after 7—9 injections R. N. C. in females, and later in males. The Arthus anaphyl- Follicular hormone and coagulation of blood. actic reactions are probably due to serin in the injected M. Saviano (Mem. R. Accad. Lincei, 1935, 6, 165— serum. R. N. C. 183).—Subcutaneous injection of folliculin (I) in Immunology and its connecting links with normal małe dogs lowers the time of coagulation of chemistry. L. E. d e n D ooren d e J ong (Chem. the blood, and inereases fibrinogen and blood-Ca, the Ca inerease occurring almost completely in the Weekblad, 1935, 32, 590—601).—A review. S. C. diffusible fraction. These effeets are not produced Production of immune serum by injection of by (I) added to normal blood in vitro. R. N. C. cholesterol adsorbed on kaolin. W. M utsaars (Compt. rend. Soc. Biol., 1935, 120, 263—266).— Index of flocculability of sera in flocculation Injection of rabbits with a suspension of pure chole and gelification reactions. E. B enhamou and sterol (I) adsorbed on pure kaolin produces an immune and R. G ille (Compt. rend. Soc. Biol., 1935, 120, serum the complement-fixing power of which with 430— 432).—Serum flocculation by H 20, melanin, (I) is > that of the serum obtained by injecting Fe albuminate, urea-stibamine, and sulpharsenol, (I) in combination with swine serum. Hence foreign and CH20-leuco- and lacto-gelification, are esplained proteins are not necessary to give (I) antigenic pro in terms of the index of flocculability. R. N. C. perties, which are considerably influenced by its Conditions of flocculation and gelification of physical state. R. N. C. pathological sera. E. B enham ou and R. Gille Characteristic chemical reaction of formol- (Compt. rend. Soc. Biol., 1935, 120 , 428— 429).— ised toxic filtrates. H. Go ld ie (Compt. rend. Flocculation or gelification of pathological sera Soc. Biol., 1935, 120, 313—316).—Diphtheria and occurs if euglobulin rises or serin or cholesterol falls tetanus antitoxins (I) give a red colour, stable for below certain limits. An “ index of flocculability ” some days, when heated to 100° with smali ąuantities is defined. R. N. C. of Na 8-amino-a-naphthol-3 : 6-disulphonate (II). The toxins (III) give the same reaction if treated with Abscess of fixation and serum reaction to smali ąuantities of CH20, but not with exicess. The resorcinol. P . B ordet (Compt. rend. Soc. Biol., reaction occurs in the cold with (I) from which the 1935, 120, 91—93).—The reaction of rab b ifs serum active principle has been pptd. with Na p-naphthyl- to m-CGH4(OH)2 is inereased during formation of an amine-3 : 6 : 8-trisulphonate and citric acid. (II) abscess or injection of turpentine; it retums to normal gives the same colour with H202, peptone containing when the abscess has been formed. R. N. C. traces of CH20 and NH3, or formolised broth, sug- Serum reaction to resorcinol, rate of corpus- gesting that the reaction with formolised (III) is cular sedimentation, and time of serum lacto- due to oxidisers formed by the action of CH20 on the gelification. P. B ordet (Compt. rend. Soc. Biol., NH2 of (III). (I) hence contain oxidising substances 1935,120, 93—95).—Turpentine or bacterial products that are non-sp. components of the formolised (III), that inerease the reaction of rabbifs serum to tri- which is active only after removal of the active C6H4(0H )2 also inerease the velocity of corpuscular principles by pptn. or destruction. R. N. C. sedimentation and reduce the time of serie lacto- Antigenic power of staphylococcal toxin and gelification. R. N. C. anatoxin : its resistance to heat. G. R amon and 1520 BRITISH CHEMICAL ABSTRACTS.— A. R. Richotj (Compt. rend. Soc. Biol., 1935,120, 291— II. Ganglion nodosum n. vagi has a higher 293).—Tlie antigenic power of the toxin is destroyed content of (I) than have ganglion coeliacus and the rapidly between 50° and 60°, whereas th at of the ganglion of the sympathetic trunk. For unsaturated anatoxin decreases slowly with rise of temp., only (II) and acid-sol. P the order is: g. coeliacus > g. disappearing completely a t 80°. R. N. C. of sympathetic trunk, much > g. nodosum n. vagi; Agglutination of Bacillns pullormn. A. Staub and for saturated ( I I ) : g. coeliacus (0-439) > g. (Compt. rend. Soc. Biol., 1935, 120, 341—342).— nodosum n. vagi and g. of sympathetic trunk. Agglutination is most intcnse at p a 7-5— 8. Old sera The total P contcnts are : g. coeliacus 1-777, g. of are more sensitive to p a than young sera. R. N. C. sympathetic trunk 0-939, g. nodosum n. vagi 0-836. The total N is equally distributed. The val. of Determination of ash content of the leg bones residual N exhibits considerable individual variations. of chicks with slipped tendon. T. T. Milby The proportion of creatine-N is very Iow especially (Poultry Sci., 1935, 14, 247—251).—Bones were in g. nodosum n. vagi. The dry residue vals. are : frced from flesh and stored in 95% EtOH. Samples g. coeliacus 24-4, g. of sympathetic trunk 21-1, g. were subscquently cruslied, wrapped in filter-paper, nodosum n. vagi 20-5. The ganglia of the sympathetic extracted with hot 95% EtOH, dried at 105°, and and parasympathetic nervous systems differ in bio- ashed at duli red heat. The desirability of making logical functions and in chemical composition. determinations at intervals during the course of E. P. expcriments on ealcification is emphasised. Vals. Creatine content of various parts of the brains for chicks having slipped tendon were not signifieantlj’ of vertebrate animals. A. V. P alladin and E. J. different from those for control hirds. The ash con- R aschba (Ukrain. Biochem. J., 1935, 7, No. 2, 51— tcnt of femurs from chicks receiving 3% of MgC03 71).—In the cow’s brain, the cerebellum contains in the ration was < that from chicks given a normal the largest amount of creatine, and then in decreasing ration, hut > that from rachitic chicks. A. G. P. amount the grey matter of tłie hemispheres, tlie Chemical topography of the brain. Chemical white matter of the same, and the corpus callosum. composition of the brains of normal and fasting The cerebella of rats, rabbits, and guinea-pigs con cats. H. Gorodisski (Ber. Ukrain. Biochem. Inst., tain most creatine, and the grey matter of the hemi 1928, 3, 125— 142).—In the brains of normal cats, spheres of these animals, as welł as th at of the cow, the total P contcnts of the different parts are in the contains the largest amount of total N and H„0. order : tract. optic. (I) > corp. genie. lat. (II) and J. ft. A. corp. quad. post. (III) > nuci. caudat. (IV) > grey Creatine content of different parts of the substanee of the cortical centres (motor, auditory, brains of vertebrates. II. A. V. P alladin and yisual). The distribution of P-containing lipins E. J. R aschba (Ukrain. Biochem. J., 1935, 7, Nos. follows that of total P, and the richer the parts are in 3— 4, 85— 116).—In the dog’s brain the creatine P-containing lipins, the greater is the proportion contents are in the order : cerebellum > cerebral of saturated, and the less of unsaturated, phosphatides. grey matter > white matter of hemispheres > The brains of fasting cats (5—24 clays’ hunger, mcdułla; in the cat: cerebral grey matter, cere 7—44% loss in wt.) show a diminution in total P of bellum > white matter of hemispheres, medulla; (I); the lipin-P (as % of total P) diminishes in all in hens: cerebellum > lobi optici, hemispheres. parts. The non-lipin-P iricreases in (II), (III), In the pigeon large indmdual variations occur, and the grey substanee of.the motor cortical centre. vals. for all parts of the brain lying within the same The content of saturated phosphatides diminishes limits. The creatine content of the total brains in nearly all parts, but most in (I) and least in (IV). of łizards, frogs, and toads is > in the brains of F. A. A. mammals and birds. H. D. Chemical composition of parts of the nervous Creatinephosphoric acid in the brains of system. I. Grey matter of parts of the central various animals. H. Gorodisski (Ber. Ukrain. nervous system of dogs. II. Vegetative nervous Biochem. Inst., 1928, 3, 109—114).—The acid is pre system of cows. A. V. P alla d in , E. J. R asohba, sent in the brain of yarious animals, the % being and R . M. H elman (Ukrain. Biochem. J., 1935, 8, greater in mammals (dog, cat, guinea-pig, rat) than No. 1, 5—26, 27—46).—I. As regards the amounts in birds (pigeon, drakę, cock, siskin). F. A. A. of cholesterol (I) and unsaturated phosphatides (II) the parts form the series : grey matter of the spinał Lecithin in brain when the diet contains cord > nucleus caudatus > cerebral cortex and cortex animal and plant lecithin. S. V. F omin (Ukrain. cerebelli. The amounts of saturated (II) and cere- Biochem. J., 1935, 8, No. 1,47—60).—Food containing brosides in the spinał cord are < in the otłier parts. lecithin (I) froiii soya bean or from egg-yolk, or brain For total N, the order is cerebral cortex > cortex (cow, rat) does not inerease the (I) content in the cerebelli and nucleus caudatus > spinał cord; as brain of rats. E. P. regards creatine, cortex cerebelli > nucleus caudatus Studies on osmotic equilibrium and on the > cerebral cortex > spinał cord. The quotients kinetics of osmosis in living cells by a diffrac- creatine-N: total N are: cortex cerebelli 4-20, tion method. B. L u ck e, M. G. L arrabee, and nucleus caudatus 3-94, spinał cord 3-42, cerebral H. K. H artline (J. Gen. Physiol., 1935,1 9 ,1— 17).— cortex 2-66. For amounts of dry residue, the order A diffraction method, permitting rapid measurement is : spinał cord > others. These results confirm the of the average yoIs. of large nos. of cells, is applied data of Abderhalden, Weil, et al. (I) is not a constituent to the unfertilised eggs of Arbacia punctulata. Good of highly differentiated nerye-cells. agreement with previous measurements by other BIOCHEMISTRY. 1521 methods is found for the permeabihty to H20 and to Influence of extirpation of the motor region (CH2-OH)2, and the relationship P (F —i>)=eonst. is of the cerebral cortex on chemical changes in found to hołd. F. A. A. m uscle. S. F omin and S. E pelbaum (Ukrain. Biochem. J., 1935, 7, No. 2, 39—50).—Extirpation Increased permeability to water of ageing of the motor region increases the creatincphosplioric unfertilised eggs (Arbacia punctulata). A. J. acid content of muscle, whilst the inorg. P is decreased, G oldforb (J. Gen. Physiol., 1935, 19, 149—165).— so that the total val. is unaltered. The proteolytic The rates of swelling of the unfertilised eggs, kept in processes in the motor cerebral cortex region undergo sea-H20 for various times after sliedding, and trans- no change. J. N. A. ferred to dii. sea-H20, are obseryed. These rates increase with age. This increase in permeability is Extractives of giant salamander muscle. F. not correlated with degree of injury. F. A. A. Y a m a s a k i (J. Biochem. Japan, 1935, 22, 5—8).— Data are givcn for the contents of glutathione, Effect of temperature on the glutathione creatine (I), creatinine (II), and total S in skeletal content of cold-blooded animals. L. Binet and muscle and of (I) and (II) in involuntary muscle G. W e l l e r (Compt. rend. Soc. Biol., 1935, 120, (heart, stornach, intestine). F. 0. H. 289—290).—Glutathione infrog’s muscles isunchanged by temp.; in frog’s liver and in Carassius auratus it Creatinephosphoric acid content of fish falls with rise of temp. R. N. C. m u scle. A. V. P alladin and R. R. Sigaloya (Ukrain. Biochem. J., 1935,7, No. 2, 29—37).—Muscle Distribution of glutathione in the organs of of Cyprinu-s carpus contained about 0-35% of creatine some marinę invertebrates. A. Mo n ie b (Compt. (I) and about 0-02% of creatinephosphoric acid (II) rend. Soc. Biol., 1935, 120, 456— 458).—The organs (expressed as P). With older fisli, the (I) content in descending order of glutathione (I) content are rises to 0-46%. Addition of dried blood to the H20 liver and hcpato-pancreas, genital organs, muscles. causes a very slight increase in (I). There is probably In all cases reduced (I) is > oxidised (I). R. N. C. no fundamental difference between fish and mammals Chemical investigation of the liver oil of as regards the (II) content of tlieir muscles. Barbus brachicei>halus. S. E pelbaum and D. J. N. A. Zuverkalov (Ber. Ukrain. Biochem. Inst., 1928, Determination of creatinephosphoric acid. 3, 167— 172).—The oil contains triglycerides of pal- I.T.S o r e n i (Ukrain. Biochem. J., 1935, 7, Nos. 3— 4, mitic, oleić, and stearic acids. The acids present 217—239).—The Fiske-Subbarow (A., 1926, 443) in the oil mostly have high mol. wt. and Iow I val. and Lohmann (A., 1928, 665) methods gave similar The oil giyes a colour test for vitamin-^l, approaching results with cat, dog, and rabbit muscle, whilst large in intensity those of the usual liver oils. F. A. A. differences occurred with those from rats and pigeons. H. D. Flavinphosphoric acid from liver. H. Influence of various diets on the amino-acids T h eo rell, P. K a rrer, K. Schopp, and P. F r e i in muscle. S. V. F omin and V. D em in (Ukrain. (Helv. Chim. Acta, 1935, 18, 1022— 1026).—Partial Biochem. J., 1935, 7, No. 2, 147—157).—The tyrosine separation of flavin (I) from flavinphosphoric acid content of rat muscle is fairly const. and is not (II) in liyer extracts is effected by repeated treat decreased by continuous protein staryation. The ment of the aq. solution with amyl alcohol. Further metabolism in the tissues is disturbed by a gelatin purification of (II) through the Ca and Hg salts and pea diet, and the amonnt of tyrosine is increased, leads to a product giving 42-8% of ash and, as judged whilst the proportion of tyrosine-N to total N remains by cataphoresis experiments and ability to give the normal. Complete starvation does not affect the yellow oxidation enzyme with proteins, containing tyrosine content of the muscle. J. N. A. about 25% of (II). The proportion of free (I) in liver is very smali. H. W. Influence of thyroidectomy on the amino-acid composition of muscle. S. V. F omin and I. E. Optical activity of lactoflavin. P . K a rrer and P ozner (Ukrain. Biochem. J., 1935, 7, No. 2, 159— H. F ritzsche (Helv. Chim. Acta, 1935, 18, 1026— 167).—Thyroidectomy increases the tyrosine (I) 1027).—Lactoflavin has [aft8 -106° ±4°, -103°±3°, in muscle, whilst the amount of tryptophan is un- -100°±4°, -96-6°±4°, and -90-0°±5° in 0-05IV- changed; after 40—51 days tho (I) returns to normal. NaOH (c=0-5, 0-3, 0-25, 0-15, and 0-1, respectively). The thyroid gland regulates the distribution of (I) H . W. in the organism. J. N. A. Hepatic chlorine in hyperthyroidised animals. C. 1. P arhon and M. Cahane (Compt. rend. Soc. Effect of diet on nitrogen and phosphorus Biol., 1935, 120, 52—53).—Liver-Clin guinea-pigs compounds of muscles during fatigue. I. and rabbits is generally increased by treatment with Effect on muscle-creatine and -phosphagen of thyroid powder or extract; occasionally it is dimin- albino rats. M. S. Misc h k is (Ukrain. Biochem. J., ished. R. N. C. 1935, 7, Nos. 3—4, 74— 83).—On a protein-free diet the phosphagen, creatine, and H20 contents of rats’ Comparative chemistry of muscle. I. T aka- muscles increase. Total N is unaffected. H. D. hashi (J. Biochem. Japan, 1935, 22, 1— 4).—The H20, P20 5> and S04 contents of various species of Influence of training on the change in the mammals, birds, reptiles, amphibia, fishes, molluscs, synthetic powers of muscle after work. B. M. and arthropoda are tabulated and discussed. K o l d a e y (Ukrain. Biochem. J., 1935, 7, Nos. 3— 4, F. O. H. 63—73).—Training diminishes to some extent the 1522 BBITISH CHEMICAL ABSTBACTS.— A. reduction in the power of the muscle to synthesise Swelling of structured proteins. Influence of hexosephosplioric acid due to fatigue. H. D. the reticular tissue on the swelling of collagen in water and hydrochloric acid. D. J. L loyd Influence of work and training on the oxid- ation-reduction potential of muscle-tissue. and R. H. Mabeiott (Proc. Roy. Soc., 1935, B, 118, 439—445).—Swelling of the collagen fibres from rats’ R. V. T schagovetz (Ukrain. Biochem. J., 1935, 7, tails is accompanied by rupture of the reticular slieath Nos. 3—4, 31-—62).—Fatigue makes the redox potential in rabbifs and frog’s muscle more positive; and rolling back to form rings. The reticular tissue training the muscle makes it more negative. H. D. of young rats is tougher and the swelling less. In HC1 of jJn < 2 this'tissue is weakened, and no differ Muscle activity and oxidation processes. II. ences were observed with age, but the swelling was Effect of training and fatigue on muscle-gluta- > would have been anticipatcd. H. G. R. thione. A. V. P alladin, S. E. B oesiikovski, and Mol. wt. and isoelectric point of thyroglobulin. L. I. P alladina (Ukrain. Biochem. J., 1935, 7, M. H eidelbebgee and K. O. P ed eesen (J. Gen. Nos. 3—4, 5— 14).—Training a rab b ifs muscle Physiol., 1935, 19, 95— 108; cf. this vol., 105).— prevents the decrease in reduced glutathione con- Pig thyroglobulin (I) has a mol. wt. of 650,000 as seąuent on fatigue. H. D. determined from the sedimentatioń const. and diffusion Effect of training and fatigue on the power of data, 700,000 from sedimentation eąuilibrium measure muscle tissue to reduce methylene-blue by the ments. Human (I) has a similar mol. wt. Native Thunberg method. A. V. P alladin and A. M. (I) has an isoelectric point at p a 4-58, denatured (I) K aschpue (Ukrain. Biochem. J., 1935, 7, Nos. 3—4, at_pu 5-0. The sp. vol. of (I) is 0-72. F. A. A. 15—30).—The reduction of methylene-blue (I) by Albumose and peptone content of the muscle fatigued rabbifs muscle is slower than normal; of horned cattle. I. A. SmoeodiNcev and N. N. a trained muscle reduces (I) more rapidly than normal. Keiloya (Buli. Soc. Chim. biol., 1935, 17, 1149— H. D. 1156).—Failure of erepsin to produce any inerease Physico-chemical constants of muscle-tissue. in tlie NH2-N of beef stored at 1—3° for 15 days III. Electrical conductivity and p H in the auto- indicates that 110 albumoses or peptones are formed. lysis of muscle-tissue of pigeons with avitamin- A. L. osis-Ii. S. V. F omin and D. N. Steashesko . IV. Acetylcholine in the tissues of invertebrates. S. V. F omin, Z. S. Geeschenoyitsch, and D. N. Z. M. B acq (Compt. rend. Soc. Biol., 1935, 120, Steashesko (Ukrain. Biochem. J., 1935, 7, Nos. 3—4, 243—245).—Acetylcholine is found in large ąuantities 117— 124, 125— 133).—III. The 'post-morlcm in in the tissues of the octopus, but only in traces or erease in k of the museles of pigeons in avitaminosis-B not at all in other invertebrates. Cholinergic nerves is < normal. probably exist in molluscs, worms, and echinoderms. IV. The k of the muscular tissue of mammals was R. N. C. 7-3—7-9 X 10~4 and th at of ampliibians and fishes Identification of acetylcholine extracted from 4-S—4-9 y lO -4 mho. H. D. the gangliar cells of the octopus. Z. M. B acq Physico-chemical constants of muscle-tissue. and F. Mazza (Compt. rend. Soc. Biol., 1935, 120, I. Influence of various foods on the conduct- 246—247).—Acetylcholine (I) is extracted from the ivity and p a of rat muscle. S. V. F omin and Z. S. ganglia of the central nervous system with CC13-C02H, Geeschenovitsch. II. Influence of training [by and after removal of Cu with H 2S, pptd. with electrical stimulation] on the variation of the Reinecke’s acid. The ppt. is dissolved in aq. COMe2, physical constants of muscle-tissue. S. V. S04 removed with BaCl2, and H2PtCl0 and picrie F omin, Z. S. Geeschenoyitsch, and V. D emin acid (II) are added to ppt. other impurities. After (Ukrain. Biochem. J., 1935, 7, No. 2, 133—140, removal of excess of (II) with E t20 and PhMe, (I) 141— 145).—I. Various protein foods produce very is pptd. by HAuC14 (III) and identified by its m.p. little change in the physico-chemical consts. of rat- and analysis of the Au salt. A further impure muscle tissue. A flesh diet causes a fali in [H'j, fraction can be pptd. by (III) from the mother- a bean diet gives a decrease of 12-4% in k, whilst a liąuor after evaporation. R. N. C. gelatin diet produces a rise of 7-13%. Colloidal condition of cholesterol, cholesteryl II. Training of the muscle causes a rise of 15-6% ester, and lecithin. X. Reducing action of in k and an inerease of S-44% in NH>-aeid-N. cholesterol sols. I. R emesoy and O. Sepalova J. N. A. (J. Biochem. Japan, 1935, 22, 71—83; cf. A., 1932, Phosphorus and nitrogen compounds in fish 632, 844).—Colloidal cholesterol (I) has a marked m uscle. E. V. L achno (Ukrain. Biochem. J., 1935, reducing action (5 and 10% sols correspond with 8, No. 1, 61—71).—There are no characteristic 0-063 and 0-108% aq. glucose, respectivelj') which differences between the creatinephosphoric acid (I), is dependent on concn. of (I), and is exerted in presence creatine (II), and total N contents of the museles of of serum or whole blood. Processes, e.g., pptn., certain vertebrate fishes {c.g., earp, cod, perch, filtration, etc., which influence the colloidal condition pike). They all contain (I) and their (II) content influence the reducing activity. Direct injection of is slightly < that of mammalian museles. The (I) sols into animals inereases the reducing action of total N is 2-79% (average), 5-77% of which is (II)-N. the blood; this is probably related to conversion of E. P. (I) into sugar by the liver. A correction for presence Heąt-coagulation and colloid structure of of (I) is necessary in glucose determinations in albumins.—See this vol., 1460. blood etc. containing (I). F. O. H. BIOCHEMISTRY. 1523 Electrophoresis of sterols. III. Cholesterol Determination of tissue-carbohydrates. N. R. surfaces. L. S. Moyer (J. Gen. Pliysiol., 1935, B latherw ick, P. J. B radshaw, M. E. E w ing, 19, 87—94).—Yarious cryst. forms of cholesterol (I) H. W. L ars on, and S. D. Sawy er (J. Biol. Chem.. have the same electrophoretic mobility. The mobility 1935, 111, 537—547).)—Various modifications of of (I) ground with ice at —10° decreases to one half, other authors’ methods of determining glycogen, reverting to the original val. on drying. The iso- lactic acid, and fermentable and non-fermcntable re electric point of (I), ground or unground, is near p a 3. ducing substances in muscle are deseribed in detail F. A. A. and applied to the determination of carbohydrates Biochemistry of the aphides of the terebinth. in fasting rats. Immediate freezing of the muscle J. T imon-Dayid and B. Gouzon (Compt. rend. Soc. to be examined is necessary. H. D. Biol., 1935, 120, 164— 166).—Analytical vals. are Accumulation of electrolytes. VIII. Ac- given for the common constituents. Lipins and cumulation of potassium chloride in models. glycogen are high, whilst H90 and total N are Iow. W. J. V. Osterhout and S. E. K amerling (J. Gen. R.N.O. Physiol., 1935, 19, 167— 178).—Models are deseribed Protective power of lipins.—See this vol., 1202. in which the accumulation of electrolytes, particularly Physical chemistry of lipins. III. Relations K‘, in living organisms is imitated. F. A. A. between the iodine value of monophosphatides Histochemical determination of potassium and their relations to neutral salts. M. Spie g e l- during the evolution of the ovocytes of the hen. Adolf (Biochem. J., 1935, 29, 2413—2415; cf. A., V. D. Marża and L. T. Chiosa (Compt. rend. Soc. 1932, 1089).—Sols of egg and brain lecithin and Biol., 1935, 120, 345—347).—K is high in the large kephalin variously treated show a parallelism between globules of the “ primordial vitellus,” the spherula of the decrease in I val. and the disappearance of the globules of the white vitellus, and the granules the anomalous effect of Br' on yiscosity. F. A. A. within the globules of the yellow vitellus. It is Iow in all other tissues, but rises slightly in the OYular Pigments of human fat. L. Zechm eister and membranes during the third period of vitellogenesis. P. T uzson (Buli. Soc. Clnm. biol., 1935, 17, 1110— The diffused enzymes of the cicatrula in the para- 1118).—Tłie distribution of carotene, lycopene, xan- blastic region modify the vitcllus globules consider- thophylls, and capsanthin in the fat from seyeral ably, and cause variations in their K content. pathological human tissues is determined by chromato- R. N. C. graphic analysis. A. L. Fixation of potassium by birds and fish. A. Crystal forms produced by the solidification L eu lier and F. P aulant (Buli. Soc. Chim. biol.. of fatty acids. M. O kra siń sk i (Wiad. farm., 1934, 1935, 17, 1124—1136).—The K content of the 61, 697—698; Chem. Zentr., 1935, i, 1952).—On embryo and the membrane of the eggs of the hen, cooling molten acids from cattle and horse fats, duch, pigeon, and guinea-fowl is 0-15—0-167%, the there are formed from numerous crystallisation corresponding val. for the turkey being somewhat centres groups of narrow polyliedra arranged similarly smaller. The K content of hen-egg yolk (0-090%) is to tissue cells. Each polygon consists of many crystals < th at of the others (0-110—0-156%). The inereases in forms characteristic of the acids present. in the wt. and K content of the chicken embryo run A. G. P. parallel during ineubation, 85% of the available K State of glycogen in the interior of the celi. being absorbed at the time of hatching. Growth I. Three-component system from clupein, and inerease in K content of trout fry also follow the nucleic acid, and glycogen or dextrin. S. J. same course. A. L. von P rzyeecki, W. Gied ro y c, and H. R afałowska Lactation. II. Technique for studying lact- (Biochem. Z., 1935, 280, 286—292).—If mixed in ation in rats. R. G. D aggs. III. Effects of appropriate proportions [smali amounts of nucleic yarious dietary principles on lactation in rats. acid (I) (from yeast or herring roe) or large excess of R. G. D aggs and R. L. T ombouman (J. Nutrition, glycogen (II)] clupein (III) (as sulphate), (I), and (II) 1935, 9, 575—580. 581—592).—A lactation-promoting combine in solution (pu 7-0—7-3) to produce three- factoi occurs in a variety of natural produets. Cystine component simplexes. Simplexes are also produced or glutathione acts as a mammary stimulant. with dextrin (IV) instead of (II), (IV) being united A. G. P. to the arginine residuc of (I). The affinity of (I) Dilatometric study of in vitro digestibility of for (III) is much > it is for (II). W. McC. m ilk s. K. B hagvat and M. Sreenivasaya (Proc. Indian Acad. Sci., 1935,2, B, 316—321).—Digestion of Carbohydrates of the albuminous gland of milk preps. and of caseinogen (I) by trypsin is readily liana esctilenta. F. N. Schulz and M. B ecker followed dilatometrically (A., 1934, 109, 450, 1137), (Biochem. Z., 1935, 280, 217—226; cf. A., 1900, the fali in the dilatometer being strictly cc liberation i, 478; 1934, 1251).—Dii. acid hydrolysis hberates of NH2-jSL The hydrolysis of (I) in milk does not from the dried gland 30—35% of reducing sugars differ from that of (I) in artifieial media. F. O. H. (calc. as glucose) consisting of eąuimol. amounts of galactose (I) and glucosamine. In the gland (I) Heterogeneity of casein. C. Groh and E. does not occur in the phosphorylated State. Accord- F altin (Math. nat. Anz. ung. Akad. Wiss., 1934, ing to the season of the year, 1—1-5% of polysacehar- 50, 457—466; Chem. Zentr., 1935, i, 1720—1721).— ide (almost entirely glycogen, only traces of galacto- Casein obtained from colostrum milk is sol. in 70% gen) is present. W. McC. aq. EtOH, particularly if this is slightly acidified. 1524 BRITISH CHEMICAL ABSTRACTS.— A. It resembles the Osborne-Wakeman albumin in chalaza, egg-white, shell-membranes, and shell have solubility, but its composition resembles that of been studied by cytological methods. H. G. R. ordinary casein. No essential and regular change Bile acids of Mugil cephalus, Linn. K. in the composition of casein is observed in the first W atan ab e (J. Biochem. Japan, 1935, 22, 119— stage of lactation. R. N. C. 121).—The prineipal acid is taurochenodeoxycholic Reductase and coreductase of milk. F. W yss- acid (A., 1925, i, 405). F. O. H. Chodat (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., Effect of grapę as compared with other fruit 166—167).—Dilution of milk inhibits the coreductase juices on urinary acidity and the excretion of which may be added in the form of yeast or meat organie acids. R. C. Clouse (J. Nutrition, 1935, extract to restorc the reducing action. H. G. R. 9, 593—610).—Bottled concord grapę and orange Standardisation of the methylene-blue reduc juices tend, in generał, to increase urinary p a, whereas tion test by the use of methylene-blue thio- appłe juice has the reverse effect. The C02-combining cyanate. H. R. T hornton and R. B. Sa n d in power of blood is inereased by feeding grapę and orango (Amer. J. Publ. Health, 1935, 25, 1114— 1117).—I t juices and decreased by apple. The inereased ex- is suggested that the thiocyanate be used, with 1 cretion of org. acids caused by grapę and orange part of dye to 300,000 parts of milk as the standard juices is not due entirely to unoxidised residues of concn. . H. G. R. fruit acids, but includes uric and citric acids. Org. Reductase-time of milk and the bacterial acids are concerned in the maintenance of the content. J. D. F ilu to (Chem. Weekblad, 1935, acid : base ratio of the body. A. G. P. 32, 601—602).—Examination of 426 samples shows Water exchange [in the organism]. IX. Vari- that there is no abs. parallelism between the no. of ations in diuresis and urinary p s in animals on bacteria present in milk and the time taken to de- acidogenic and alkalogenic diets. M. Sayiako colorise methylene-blue solution. Milk which de- (Atti R. Accad. Lincei, 1935, [vi], 21, 715—720).— colorises the reagent in < 2 hr. is unfit for human The greater is the diuresis produced in dogs or rabbits, consumption, although 3-8% of such samples con- the nearer approaches the urinary to the blóod-pa. tained 0-5—1x10® and 1*3% < 0 - 5 x l0 6 bacteria With alkalogenic diets, diuresis produces a p K < th at per c.c. S. C. of the blood; this is due to constancy of the C02 Ammonia content of human and cow’s milk. tension and diminution of HC03' in the urine. M. P olonovski and P. B oulanger (Buli. Soc. Chim. F. O. H. biol., 1935, 17, 117S—1183).—The increase in the Surface-active substances in urine. K. NH3 content of liuman and cow’s milk on keeping Y usawa (J. Biochem. Japan, 1935, 22, 49—70).— is mainly of bacterial origin, unlike that taking place Normal human urine has a 78-0—90-0 (average 83-2) in the blood. A. L. dynes per sq. cm .; it is lowest in summer, and higher a t p H 8—9 (NaOH) than n tp R 3—4 (HC1). Separation Ammonia content of the liquids of the internal of the constituents affecting a by dialysis, extraction media of some invertebrates. J. Sottterbicq with solvents, etc. indicate them to be fatty acid (Compt. rend. Soc. Biol., 1935, 120, 453— 455).— derivatives of indole, C„H6, and pyrrole, conjugated NH3 in the blood or secretions of inyertebrates is glycuronates, and ethereal sulphates. The effect of > in vertebrates; max. NH? occurs in carnirorous substances of these types on a and the influence of species such as Maja and Sepia. R. N. C. [H*J are tabulated and discussed. F. 0. H. Colloid osmotic pressure of the nutrient liąuids Excretion of the so-called synergistic gonado- of the marinę invertebrates. P. Me y e r (Compt. tropic factor of the anterior pituitary in the rend. Soc. Biol., 1935, 120, 305—307).—Vals. are urine of castrates. K. J. Anselmino and F. given for a no. of marinę inyertebrates. The colloid H offm astk (Klin. Woch., 1934, 13, 1471—1472; osmotic pressure of the internal medium inereases Chem. Zentr., 1934, ii, 3268).—The Evans syner with the species in genealogical order, suggesting a gistic gonadotropic factor is present in measurable relation with the generał organisation of the animal. quantities in the urine of castrates and women at the The tunicates are an exception to this rule, the colloid- menopause, and in smaller quantities in ox and gelding osmotic pressure being < that of crustacean internal urine. Methods of testing are described. R. N. C. media. R. N. C. Uroerythrin. M. W eiss (Deut. Arch. klin. Med., Application of the micro- significance of the minerał balance of foodstuffs, cells does not occur. Tumours are more sensitive notably the Ca/Mg ratio, is discussed. A. G. P. to irradiation than is normal tissue. W. McC. Synthetic hydrocarbons with carcinogenic Histological modifications at the surface of action. R. Sib o n i (Boli. Chim. farm., 1935, 74, the graft and the spleen in the course of regres- 709—720).—A review. sion of the Jensen sarcoma under the action of insulin. O. L ambret and J. D riessen s (Compt. Action of the serum of mice with tar cancer rend. Soc. Biol., 1935, 120, 188— 190).—Insulin on the fluorescent power of solutions of uranine. induces disappearanee of hepatic and muscular A. B outaric and J. B ouchard (Compt. rend. Soc. glycogen, and hyperplasia of the spleen, in rats where Biol., 1935, 120, 293).—No inhibition of the fluores the graft shows marked regression. R. N. C. cent power is produced by the cancerous sera. R. N. C. Variations of the fibrinogen content of the Existence in the liver of substances inhibitory blood in neoplasic affections. R. L oicq (Compt. to benzopyrene cancer of the white mouse. J. rend. Soc. Biol., 1935, 120, 253—255).—Blood- Ma isin , H. Yassiliadis, and A. Godenir (Compt. fibrinogen is increased in guinea-pigs with tumours rend. Soc. Biol., 1935, 120, 259—261).—The C0Me2- resulting from inoculation with the Murray liposar insol. fraction of Et20 extract of liver contains a coma and in patients with neoplasic tumours. substanee that inhibits the growth of experimental R.N. (ben/.opjTene) tumours and cancers in mice. The 11 Polypeptidasmia index ’ ’ in experimental inhibitory effect is increased by boiling, suggesting cancer in the guinea-pig, and in neoplasic that thermolabile activating substances are also tumours in man. R. L oicq (Compt. rend. Soc. contained in tlie extract. R. N. C. Biol., 1935, 120, 250—253).—The “ polypeptidsemia index ” represents the difference between the Kjeldahl Preparation of organie peroxides and per- N vals. of the CC13’C02H and phospliotungstic acid oxidogens. W. K och and J. Ma isin (Compt. rend. filtrates of the blood. It is increased in guinea- Soc. Biol., 1935, 120, 104— 106).—Acid peroxides are pigs with tumours resulting from inoculation with prepared by a modifieation of the method of D’Ans the Murray liposarcoma, but is scarcely affeeted in and Kneip, and ether peroxidcs by oxidation of the patients with neoplasic tumours in absence of cachexia ethers with 02 in presence of Pt. The name “ per- or infection. R. N. C. oxidogen ” is given to the unsaturated compounds prepared from fructose, paraldehj^de, MeCHO, and Action on an experimental tumour of intra- Et20 by slow dehydration over H2S04. Peroxides venous injections of ascorbic acid unassociated are decomposed by H20 into H202 and acids. Their with iron, or associated with copper. F. prophylactic effect in benzopyrene cancer in mice is Arloing, A. Morel, and A. J osserand (Compt. not simply due to 02 liberation; the most active rend. Soc. Biol., 1935, 120, 205—206).—Injection contain sufficient O for complete combustion to C02 of /-ascorbic acid in NaIIC03 solution in rabbits and H20, and in many cases can, in presence of the with experimental tumours causes hepatic, renal, corresponding acid, undergo intramol. rearrangement, and peritoneal lesions. The Cu-dehydroascorbic which liberates a considerable ąuantity of energy. acid complex causes rapid development of neoplasic R. N. C. lesions and visceral metastases, in sharp contrast Effect of organie peroxides on the prophylaxis with the Fe complexes. R. N. C. of experimental cancer in mice. W. K och and Action on experimental and human cancer of J. Maisin (Compt. rend. Soc. Biol., 1935, 120, 106— injections of combinations of iron and vitamin-C 108).—Diformaldehyde diperoxidc has a definite (ascorbic acid). F. Arloing, A. Morel, and A. prophylactic action on benzopyrene cancer. J osserand (Compt. rend. Soc. Biol., 1935, 120, 201—204).—In the reaction between Fe salts and Modifieation of the Weltmann reaction in ascorbic acid, (I), Fenl is partly reduced by (I) to Fe11, cancer : diminution of the coagulation band. which unites with (I) to form violet, strongly-reducing G. Carrikre, P. M artin, and J. D riessens (Compt. ferroscorbon (II), wliilst the unreduced Fe111 forms rend. Soc. Biol., 1935,120, 31—32).—The coagulation yellow, stable, non-reducing ferriscorbon (III) with band is diminished in the sera of most cases of cancer. dehydroascorbic acid. Perifocal reactions appear R. N. C. rapidly on injection of (II) in cases of cancer, but Production of lactic acid in irradiated and scarcely ever on injection of (III). (III) lends itself non-irradiated tumours. W. H aarmann (Bio more than (II) to use in prolongcd stabilisation chem. Z., 1935, 280, 173—183).—The capability of treatment. Both cause vaso-dilatation. R. N. C. extirpated human tumours to produce lactic acid (I) from added carbohydrates (II) [glucose (III), fructose, Hepatic function. II. In portal cirrhosis glycogen, Na hexosediphosphate] and AcCOoNa varies and congestive heart failure. A. Cantarow greatly with the kina of tumour, the (II) used and (Arch. Int. Med., 1935, 56, 521—529).—In cases of its concn., the naturę and amount of other (II) present, liver cirrhosis, the bromosulphonephthalein (I) test and the capability of the tumours anaerobically to of liver function did not run parallel with the concn. destroy (I). Almost always more (I) is produced from of serum-bilirubin (II), the latter being more closely (III) than from other (II). Irradiated tumours related to the degree of ascites. Similar observations hehave similarly, but in sonie cases the production of were made in four cases of Banti’s disease. In (I) by tliem is reduced, although destruction of the congestive heart failure tlie severity was more closely BIOCHEMISTRY. 1527 related to the retention of (I) than to the concn. of Chemotherapy of malaria. S. P. J ames (Naturę, (II). W. O. K. 1935, 136, 743—745). L. S. T. Importance of the 1 ‘ Takata reaction ’' for the Two cases of myxcedema treated with thyro- diagnosis of liver disease in its relation to tropic hormone. M. W achstein (Klin. Woch., galactose and bilirubin overloading. L. Sc h in - 1934,1 3 ,1434— 1436; Chem. Zentr., 1934, ii, 3269).— d el and E. Barth (Klin. Woch., 1934, 13, 1329— Basal exchange is scarcely or not at all affected even 1332; Chem. Zentr., 1934, ii, 328G).—The reaction by large ąuantities. R. N. C. is measured by the alterations in the flocculating Liver-arginase in myasthenia gravis. Origin effect of HgCl2 on the serum. It is positive in liver of creatine. A. T. Milhorat (J. Biol. Chem., 1935, disease, particularly cirrhosis. R. N. C. 111, 379—384).—The amount of arginase (I) in the Pancreatic diabetes in the dog deprived of its liver of a boy with myasthenia gravis was normal, sympathetic nervous system. J. T. L ew is and although large amounts of creatine had been excreted E. S. T tjrcatti (Compt. rend. Soc. Biol., 1935, in the urine. There is no evidence that the creatin- 120, 274—276).—Pancreatectomy in dogs that have uria occurring in m. gravis is related to a lack of been sympathectomised or deprived of the nervous liver-(I), and that an insufficient amount of (I) might tissue encircling the large vessels from the coeliac permit the preservation of the guanidine group in trunk to below the superior mesenteric artery results arginine, and the oxidation and conversion of the in diabetic symptoms similar to those appearing latter into creatine. J. N. A. in untreated animals. Blood-sugar rises similarly in botli cases, but the finał rise 24—48 hr. before Indicanssmia in nephritis. I. Gavrila and death, as well as the glycosuria, in the sympathectom Mihaileanu (Compt. rend. Soc. Biol., 1935, 120, ised animal is > in animals operated by the other 358—360).—Indicansemia in patients without renal method. R. N. C. lesions varies between 0-20 and 0-92 mg. per 1000. Indicansemia generally oc blood-N in acute nephritis Treatment of severe diabetic acidosis. Com- following scarlatina. In chronic nephritis it is const. parison of methods, with particular reference if blood-N is < 1 g. per 1000, but inereases with N to the use of sodium rfj-lactate. A. F . H art- above this level. It bears no relation to blood-Cl, mann (Arch. Int. Med., 1935, 56, 413—434).—Parent- albuminuria, or arterial pressure. R. N. C. eral administration of Na rfi-lactate to combat diabetic acidosis is advocated. W. 0. K. Role of cellular lysis (hsemolysis and leuco- lysis) in the cholesterol content of pleural Experimental diphtheric intoxication and effusions. V. d e L avergne and P. K issel (Compt. ascorbic acid of the adrenals. G. Mouriqtjand, rend. Soc. Biol., 1935,1 2 0 ,151—152).—Cholesterol (1) P. Sśdallian, and A. Cokur (Compt. rend. Soc. in pleural effusions is of local origin and is controlled Biol., 1935, 120, 216—217).—The AgN03 reaction by cellular lysis, depending on the no. and type of of the adrenals of guinea-pigs diminishes 18 hr. the destroyed cells. (I) is high in hsemorrhagic after the injection of diphtheria toxin. R. N. C. effusions, suggesting that hsemolysis takes place Disturbance of corpus luteum formation in more readily than leucolysis. In putrid pleurisy, avitaminosis-C and diphtheric intoxication. J. where leucocyte destruction is definite, (I) is > in yon Gagyi (Virchow’s Archiv, 1934, 293, 674— 681; hsemorrhagic pleurisy. R. N. C. Chem. Zentr., 1935, i, 1580).—A physiological relation- Inorganic constituents of the central nervous ship is indicated between ovaries and adrenals in system of rabbits with experimental rabies. respect of vitamin-C economy. A. G. P. N. W. R omenski (Ann. Inst. Pasteur, 1935, Suppl., Experimental azotsemia by injection of diph 181—190).—In experimental rabies, Na is decreased theria toxin in the guinea-pig. J . Ch a lier, M. and Ca inereased in the brain and marrow. Mg and J e u n e , and R. J . F ournier (Compt. rend. Soc. Biol., K are inereased in the latter. H. G. R. 1935, 120, 206—207).—Blood-urea begins to rise 6-9 Silicosis and anthracotic lungs. F. V. Tid e s - lir. after injection of diphtheria toxin, and continues WELIi (Refraet. J., 1934, 10, 185—1S6).—An attem pt to rise until cłeath; adrenaline secretion begins to to separate the “ actiye” Si02 producing silicosis fali at the same time. R. N. C. from the inactive form by a 2% KOH solution is Proteinases (cathepsin) in the tissues of the described. Ch. A bs. (e) infantile organism with dysentery and toxic Impregnation of the organism by dust. III. dyspepsia. B. Go ldstein and M. Guinzburg Partition of silica dust in the lungs. G. A nto in e (Ukrain. Biocliem. J., 1935,7, Nos. 3—4,147— 159).— (J. Pharm. Chim., 1935, [viii], 22, 412—430; cf. this The cathepsin per g. of dry matter is < normal in vol., 1396).—Determinations on roughly ehopped glycerol extracts of liver, kidney, and spleen of tissue are subject to wide variations (0-0099—0-033%), children who have died of toxic dyspepsia. H. D. but results on finely minced materiał do not vary > Composition of the ash of thyroid gland and 20%. There is a regular inerease in the Si02 content goitre. J. Stratjb (Endokrinol., 1934, 15, 15— of a lung with age, and the superior lobe has a larger 25; Chem. Zentr., 1935, i, 1577).—Glands from Hun- content than the other parts. The Si02 content of garian lowlands have less Ca and more K than those silicatesfrom different lungs is fairly const. (86—94%). of Switzerland. This is an effect rather than a cause The two lungs from the same individual give similar of the goitrous condition. A. G. P. results. P. G. M. 1528 BBITISH CHEMICAL ABSTRACTS.----A. Intestinał stasis in Iow minerał diets. E. C. Iow, of Fe definitely inadeąuate, and of S usually R obertson and M. E. D oyle (J. Nutrition, 1935, 9, negative. High storage of Ca, N, and Fe in early 553—567).—Stasis induced by low-mineral feeding is pregnancy proceeded independently of, and far in relieved by supplements of CaC03 and K2C03, but excess of, fcetal reąuirements when conditions were not by vitamin-jB. A. G. P. favourable for storage, and in such cases inereased retention in late pregnancy was not observed. Effect of traumatism on the distribution of chloride and sodium between the blood and A. G. P. Growth and development, with special refer- tissues and the acid-base etjuilibrium. H. ence to domestic animals. XXXV. Energetic Chabanier, C. L obo-On ell, A. de Gastro-Gal- efficiency of milk production and the influence hardo, and E. L eh r (Buli. Soc. Chim. biol., 1935, of body-weight thereon. S. B rody and R. C. 17, 1145—1148).—In the traum atised muscle the P rocter. XXXVI. Endogenous nitrogen and inerease in Cl' and Na over the normal val. is main- tained as long as 48 hr. In the blood, however, basal energy relationships during growth. U. S. whilst the corresponding vals. inerease up to 24 hr., Ashw orth (Missouri Agric. Exp. Sta. Res. Buli., 1935, No. 222,40 pp., No. 223, 20 pp.).—XXXV. The there is a subseąuent decrease to < normal; at the distribution of the total digestible nutrients in the diet same time, the alkaline reserve decreases for the first 24 hr. and then inereases. A. L. between milk production, maintenance, and live-wt. inerease is examined and a mathematical relationsliip Chemotherapy of tuberculosis. V. Ethyl established. Under customary conditions of observ- silicylricinoleate. E. H esse , G. Me issn e r , M. ation the gross efficiency of milk production decreased Seb elin , and H . Muller (Arch. exp. Path. Pharm., with body-wt., but if other related factors were const. 1935, 179, 296—309).—The ester (I) is absorbed to milk-production efficiency would probably be inde the extent of approx. 55% from the intestine (dog). pendent of body size. Retention of Si03" does not occur in mice. (I) is XXXVI. The ratio of endogenous urinary N to the excreted through the intestine after oral or sub- heat of basal metabolism inereases with advancing cutaneous, and through the kidneys after intra- age. Rats reeeiving a high-N diet excreted more N muscular administration. Favourable results (form per unit body-wt. than did those having a low-N diet. ation of new tissue and encapsulation) in tubercular Endogenous N approximates more closely to a log- rabbits follow continuous administration of (I). arithmic function of body-wt. than to a logarithmic F. O. H. function of basal heat production. More consistent- Chemistry of tubercular sputum. S. N aka- results are obtained by relating min. endogenous N yama (J. Biochem. Japan, 1935, 22, 35—40).—The to the initial body-wt. than to body-wt. attained at sputum (H20, 96-59%; fat, 0-68%; fat-free residue, the time of min. N excretion. A. G. P. 2-72%) yields on fractionation (with EtOH, Et20, Determination of basal metabolism by inter COMe2, etc.) cholesterol, phosphatide (?), a cryst. sub ferometrie gas analysis. M. B ourdeatt (J. stance, m.p. 136°, Ca, Mg, P, S, Cl, and protein (the Pharm. Chim., 1935, [viii], 22, 393—411).—The hydrolysate of which yields histidinc, arginine, apparatus and method described can be applied to tyrosine, and, in relatively high proportion, lysine). any mixture of three gases which have no action on The high P content is characteristic. F. O. H. the metal chamber employed, provided that one of Spectrographic investigation of gold distribu them can be easily eliminated. The results compare tion following gold therapy in men and animals. favourably with those obtained using Plantefol’s W. Geri.ach (Arch. exp. Path. Pharm., 1935, 179, precision eudiometer and the time taken for a deter 286—295).—Storage of Au occurs mainly in the liver, mination is 15 min. compared with 50 min. spleen, and, with greater variations, in the kidney of P. G. M. tubercular men and animals treated with solganal-B; ‘ ‘ Water intoxication ’ ’ and water diuresis in the diseased tissue (e.g., lungs) contains relatively adrenal insufficiency ; importance of the ad- smali amounts. Localisation of Au is, liowever, sig- renals in osmo-regulation. R. Rigler (Klin. nificantly influenced by calcification of the tissue. Woch., 1935, 14, 227—228).—H20 administered The histochemical method of Kurosu (A., 1928, 549) orally or 0-2% aq. NaCl injected intraperitoneally in is considered worthless (cf. B., 1932, 266). adrenaleetomised rabbits, rats, and mice is excreted F. O. H. less rapidly than in normal animals, even if good Action of magnesium in experimental ursemia. generał health is maintained. The adrenals must F. A mantea (Arch. Farm. sperini., 1935, 60, 353— therefore function as regulators of the osmotic 364).—With rabbits in which ureemia has been pro- condition of the body-fluids. R. N. C. duced by nephrectomy, hgature of the ureters, or Influence of calcium ions on energy metabol injection of U salts, administration of Mg salts ism of the mammalian heart. H. C. P eters, inereases the blood-urea, tho level retuming to normal C. E. R ea, and M. B. Yisscher (Proc. Soc. Exp. Biol. Within a few hr. This is due to liberation of urea from Med., 1934, 32, 268—271).—The mechanical energy the tissues. F. O. H. of contraction and total liberated energy of the Metabolism during pregnancy. C. N. Coons mammalian heart are inereased by Ca". R . N. C. [with A. T. Schiefelbusch, G. B. Marshall, and Depigmentation of the eggs of Cyprinus carpio. R. R. Coons] (Oklahoma Agric. Exp. Sta. Buli., 1935, T. B usnita and N. Gavrilescu (Compt. rend. Soc. No. 223, 113 pp.).—In balance studies retention of Biol., 1935,120, 224— 225).—The deposition of yellow Ca was high, that of P and Mg relatively lower, of N eggs instead of the normal green is associated with the BIOCHEMISTRY. 1529 retention of the green pigment of the bile by the of different tissues or between normal and tumour hepatic tissues; the pigmentation of the eggs is hence tissue of well-fed adult animals. E. A. A. related to the biliary function. R. N. C. Respiration of the brain. L. Crasnartj and N. Individuality in nutritive instincts and causes Gavrilescu (Compt. rend. Soc. Biol., 1935, 120, and effects of variations in the selection of food. 226—228).—Novarsenobenzene decreases respiration W. F. D ove (Amer. Naturalist, 1935, 69, 469—544).— of the brain, although it increases that of other tissues. The eenetics and physiology of nutritive instincts are It serves to distinguish in the brain between 0 2 con studied. " E. A. H. R. sumption in carbohydrate metabolism and in one or Influence of certain dietary constituents on more other undefined oxidative Systems co-existent the response of rats to gossypol ingestion. with carbohydrate metabolism. R. N. C. W. D. Gallup and R . R ed er (J. Agric. Res., 1935, Oxygen consumption in muscle activity in 51, 259—266).—A high protein intakc was favourable relation to fibrę length. P. W. Sm ith (Proc. Soc. to the detoxication of gossypol (I). Diets rich in Exp. Biol. Med., 1934, 32, 257—260).—O, consump lactose (20%) or acid diets containing much Ca, which tion in activity rises on extension to a max., after- were detrimental to growth in normal rats, had wards falling; resting 02 consumption rises with relatively smali effects on rats recemng (I). Alkahne inereasing rapidity, whilst the curve for total 02 diets high in Ca (1-2%) wero the most satisfactory for consumption is a straight line. R. N. C. nullifying the action of (I). A. G. P. [Digestion of] bread. W. H e u pt k e (Deut. Effects of common food ingredients on the med. Woch., 1934, 60, 1823—1827; Chem. Zentr., iodine content of hens' eggs. H. J. Almquist 1935, i, 1464).—Aleuronc-protein is digested by pepsin and J . W. Givens (Poultry Sci., 1935,14,183— 190).— and trypsin in a few hr. without destruction of the Use of marinę products (fish meal, oyster shell) in cell-wall. The protein of bran is easily digested. poultry rations provides > the I reąuirements of hens. High fsecal N following the feeding of brown bread is The I content of eggs is not closely related to that of not due to defective resorption, but is derived from the ration. A. G. P. the intestinal secretion. Of the dry matter of ffflees Effect of minerał supplements on the length 4—5% represents intestinal N. The val. of rye bread of the taił and wing feathers in white Leghorn is discussed. A. G. P. hens. W. A. H en d r ic k s (Poultry Sci., 1935, 14, Protein metabolism of the armadillo, Chaeto- 221-—227).—No effects of practical significance were phractus rillosus, Desmarest. B. B raier observed. A. G. P. (Compt. rend. Soc. Biol., 1935, 120, 361—362).— Synthetic diets for herbivora, with special Total protein catabolism in the fasting state is Iow reference to the toxicity of cod-liver oil. L. L. compared with those of the dog and rat. After a Madsen , C. M. McCay, and L. A. Maynard [with diet of meat the azoturic coeff. of the urme is raised G. K. D avis and J. C. W oooward] (Cornell Univ. from 65% to 75%; aliantom, representing 95—96% Agric. Exp. Sta. Mem., 1935, No. 178, 52 pp.).— of the purines, is unchanged. Creatinine is < in the Prolonged feeding of cod-liver oil caused degeneration fasting dog or rat. R. N. C. of skeletal and heart muscle, and fatty liver. Sub Biological value of the protein of dry diffusion stitution of a yitamin-^4 and -D concentrate lessened residues in the beet sugar industry. S. E. but did not prevent the injury, which was not entirely B orshkovski, I. S. Ono prien k o , and L. S. T scher- prevented by exclusion of cod-liver oil from the diet. kasova (Ukrain. Biochem. J., 1935, 7, Nos. 3—4, Other factors are probably involved. Vitamin-i? 177—198).—The biological val. of dry press-cake from (yeast) decreased the injury in goats. A. G. P. the beet industry is equal to that of clover hay and Synthetic diet for rabbits. R. P assmore (Bio is < that of caseinogen; it is increased by mixing chem. J., 1935, 29, 2469—2470).—A diet containing with these materials. washed Diophane enabled two out of three rabbits to Effect of starvation on aminogenetic and maintain wt. H. D. proteolytic processes in the cerebrum. A. V. Effects of glucose on the respiratory exchange P alladin and M. F. Guli (Ukrain. Biochem. J., 1935, of adrenalectomised dogs. A. Morales (Compt. 7, No. 2, 73—89).—The cerebra of dogs, rats, and rend. Soc. Biol., 1935, 120, 272—274).—The blood- pigeons showed large variations in the H20 content sugar curve falls a little after adrenalectomy and then and in the coeffs. of aminogenesis and proteolysis, as begins to rise; glucose (I) accelerates the rise, and the did also those of the starving animals. There is a curve returns to its initial level after 1 hr. The definite difference between the summer and winter increase due to (I) is increased 48 hr. after adrenal cerebral metabohsm of the pigeon. J. N. A. ectomy, and the normal level is not reached agam Nuclein metabolism. VII. Polynucleotidase. until after 5 hr. Basal metabolism and the R.Q. fali VIII. Bound and free purines in ox organs. progressively after adrenalectomy. (I) increases basal IX. Tissue-ammonia and nuclein metabolism. metabolism and R.Q. R. N. C. IC. Makino (J. Biochem. Japan, 1935, 22, 93—96, Respiratory quotients of normal and tumour 97—107, 109—118).—V II. Hydrolysis of yeast- or tissu e. K. A. C. E lliott and Z. B a ker (Biochem. thymus-nucleic acid by commercial trypsin preps. J., 1935, 29, 2433—2441).—The results differ from produces depolymerisation but not fission of the those of Dickens and Simer (A., 1930, 1468), no nucleotides (I) or nucleosides (II). significant differences being found between the R.Q. VIII. Data are given for the content and naturę 1530 BRITISH CHEMICAL ABSTRACTS.— A. of purines, free and as (I), (II), or nucleoprotein- H. W arembourg, and J. D riessens (Compt. rend. nucleic acid, in fresh and autolysed spleen, liver, and Soc. Biol., 1935,120, 181— 182).—Spleen extract does pancreas. not affect blood-sugar or the residual chromic index IX. Autolysis of liver, kidney, and spleen is accom- in normal subjects, but in cancerous and diabetic panied by formation of NH3, two important sources subjects the residual chromic index is depressed, of which are adenosine-mono- and -tri-phosphorie indicating that the breakdown of the intermediary acids. Added thymus-nucleic or guanylic acid is produets of carbohydrate metabolism is accelerated. deaminated to the same extent with each of the R. N. C. three tissues; yeast-nucleic acid differs to an extent Relation of adrenal cortex to carbohydrate dependent on the tissue. F. O. H. metabólism. T. K onosh (J. Biochem. Japan, Metabolism of the phospholipins. VIII. 1935, 22, 149—161).—Ligature of the panereatie duet Passage of elaidic acid into tissue-phospho- in rabbits produces a slight hyperglyesemia and an lipins. Evidence of the intermediary role of inerease in the size of the adrenal cortex and in its liver-phospholipin in fat metabolism. R. G. content of co-enzyme (I) for anaerobic decomp. of Sinclair (J. Biol. Chem., 1935, 111, 515—526; cf. hexose phosphate by striated muscle (A., 1934, 1400). this vol., 1397).—Rats are fed with elaidic acid (I) Similar effects follow injection of lactic acid. The and the % of (I) in the tissue-phospholipins is deter rate of blood-glycolysis is inereased by (I), whilst the mined by pptn. as its Pb salt. The phospholipins of ability to decoinpose hexose diphospliate lost by blood young rats on a diet rich in (I) contain up to 33% of on hsemolysis is restored. F. O. H. (I) and of adult rats up to 30%; in the liver the Effect of fatigue on the oxidation of phenol entrance of (I) into the phospholipins is much > in in various diets. A. V. P alladin and L. I. the muscles. It is suggested that there are two P alladina (Ukrain. Biochem. J., 1935, 7, No. 2, classes of phospholipins, one functioning as the con- 19—27).—On a basie diet (mainly oats) fatigue caused stituent of membranes containing a high % of un- rabbits to excrete nearly all the injected PhOH in saturated fatty acids and another functioning as the urine. With an acid chet (beet and liay) only intermediaries in fat metabolism and containing 30—40% of the PhOH was oxidised in fatigue, whilst chiefly saturated fatty acids. H. D. the normal animal oxidised 59—65%. Fatigue also Creatine formation in the organism. I. T aka- decreases the synthesis of conjugated PhOH com hashi and T. K tjmon (J. Biochem. Japan, 1935, 22, pounds, less being formed on a basie than on an acid 9—14).—Arginine, carnitine, or y-amino-3-hydroxy- diet. J. N. A. butyric acid in presence of autolysing liver-tissue (dog) Influence of hunger on administered phenol. at 37° produces creatine; similar results are obtained A. P alladin, S. Maliar, and A. R ozenberg (Ber. by perfusion experiments on the isolated liver. A Ukrain. Biochem. Inst., 1928, 3, 15—21).—During mechanism is advanced based on methylation or hunger, as on an acid diet, a smaller proportion of demethylation of these compounds and subsequent PhOH injected into rabbits is excreted in the urine addition of guanidine. F. O. H. as uncombined PhOH than on a normal diet. Creatine : creatinine ratio in hibernating and F. A. A. spaw ning frogs. F. Yamasaki (J. Biochem. Japan, Synthesis of conjugated glycuronic acids 1935, 22, 15—34).—Creatine (I) formation in małe during fasting. L. M. Makareyitsch-Galpkrin frogs (whole body) is somewhat > that in females. (Ber. Ukrain. Biochem. Inst., 1930, 4, 53—63).— In both sexes, the (I) content during April is only During fasting the excretion of conjugated glycuronic 50—80% of that during other months, whilst the acids in the urine of rabbits is decreased, as is also creatinine (II) level during winter hibernation is < the excretion of mentholglycuronic acid (I) after the tho summcr level. In tho female, (II) is also min. subcutaneous injection of menthol in oil. After pro- during April, and is therefore related to the spawning longed fasting the excretion of (I) rises somewhat, period. p. o. H. but is still < normal. W. O. K. Influence of acid diet on creatine excretion. Synthesis of thymolglycuronic acid on an acid L. P alladina (Ber. Ukrain. Biochem. Inst., 1928, 3, and alkaline diet. M. G. K usnetzova (Ber. 23—28).—In opposition to the findings of Underhill Ukrain. Biochem. Inst., 1930, 4, 17—29).—Rabbits, (A., 1916, i, 865), feeding rabbits on acid diet does subcutaneously injected with thymol in EtOH, ex- not produce creatinuria unless the food intake is creted more thymolglycuronic acid on an alkaline lessened. p . A. A. than on an acid diet. W. O. K. Synthesis of aspartic acid from fumaric acid Influence of the character of the diet on the in the liver. K. P. J acobsohn, J. T a pa d in h a s, synthesis of mentholglycuronic acid. A. P al and F. B. P ereira (Compt. rend. Soc. Biol., 1935, ladin and E. P ersova (Ber. Ukrain. Biochem. Inst., 120, 33—36).—Aspartic acid (I) appears in dog’s 1928, 3, 7— 14).—After the injection of menthol into blood that has been mixed with NH4 fumarate (II) rabbits, more mentholglycuronic acid is excreted on and pcrfused through the isolated liver. •£ 10% of an acid than on a basie diet. F. A. A. the (II) used is transformed into (I). Considerable Influence of the character of the diet on the quantities of (II) are converted by fumarase into malic acid. ~ r q oxidation of benzaldehyde in the rabbit. D. A. Z uverkalov (Ber. Ukrain. Biochem. Inst., 1930, Effect of injections of extract of spleen on 4, 174— 185).—The excretion of BzOH by rabbits metabolism of carbohydrates. M. P olonovski, ceases when they are on an acid but inereases on an BIOOHEMISTRY. 1531 alkaline diet. The oxidation of PliCHO to BzOH Adjustment of the minerał nutrition of test and the excretion of hippuric acid (I) are independent animals during investigation of the biological of the acid or basie character of the diet, except that value of proteins. S. E. B orshkovski and L. S. acid diets somewhat decrease the synthesis of (I). T schericasova (Ukrain. Biochem. J., 1935, 7, W. O. K. Nos. 3—4,199—216).—Feeding of Ca3(P 04)2 to rabbits Ketogenesis-antiketogenesis. II. Keto- on a diet of sedge hay inereased assimilation of Ca, genesis from amino-acids. N. L. E dson (Bio P, and N. The necessity for control of the minerał chem. J., 1935, 29, 2498—2505).—W ith rat-liver balance of the test animals during a determination slices the most strongly ketogenic NH2-acids are of the biological val. of proteins is emphasised. leucine (I), tyrosine (II), and phonylalanine (III), H. D. whilst hydroxyproline (IV) has a considerable action. Bile acids and calcium metabolism. XI. The other NH,-acids are either non-ketogenic, or Calcium excretion in thyroparathyroidectom- show a slight ketone formation. With the fed rat ised dogs. S. T uzioka (J. Biochem. Japan, 1935, only (I), (II), (III), and (IV) show ketogenesis, 22, 123— 137).—Excretion of Ca in dog’s bile is > whilst with the starved animal onty dl-(l) is keto that in the urine; thyroparathyroidectomy primarily genic, many of the others being antiketogenic. (after 1 day) decreases the former and does not Muconic acid is not ketogenic and arginine and affect the latter, but 6—7 days later markedly ornithine are antiketogenic, possibly because they diminishes both excretions. The diminished level of lower the effective concn. of NH3 by promoting urea bile-Ca, but not that of urine-Ca, is inereased (but synthesis. It is suggested that the catabolism of not to normal levels) by administration of thyro- (III) involves (a) conversion into (II) and breakdown parathyroid extracts and, to a greater extent, by through jj-0H ,C6H4,CH2*C0,C02H and homogentisic th at of cholic acid. F. O. H. acid, and (b) deamination and formation of Radioactive indicators in the study of phos- CH2Ph-C0-C02H. J. N. A. phorus metabolism in rats. O. Chiew itz and Influence of various carbohydrates on form G. H evesy (Naturę, 1935,136, 754—755).—The dis- ation of lactic acid and lactacidogen in aqueous tribution of P in the excreta and organs of rats fed brain extract. H. Gorodissici and S. E pelba u ji daily with smali amounts of Na phosphate containing (Ber. Ukrain. Biochem. Inst., 1930, 4, 115— 121).— 15P22 as a radioactive indicator is recorded. The Lactic acid and lactacidogen are formed from mannose, average time which a P atom spends in the organism glucose, galactose, maltose, dextrin, and starch in of a normally fed rat is approx. 2 months. Bone aq. extracts of cat’s brain. W. O. K. formation appears to be a dynamie process involving Lactic acid and lactacidogen during short continuous loss and replacement of P atoms. autolysis of aqueous extracts of cat’s brain. L. S .T . H. Gorodisski and S. E pelbatjm (Ber. Ukrain. Resorption and excretion of calcium, mag- Biochem. Inst., 1930, 4, 123—133).—During autolysis nesium, and phosphorus. Distribution of in- of aq. brain extracts, lactic acid (I) disappears and organic phosphate in the different sections of lactacidogen (II) is synthesised, (I) being utilised the digestive tract. J. Ma r ek , O. W ellm ann, and for the synthesis of (II). During the autolysis of L. U rbanyi (Math. nat. Anz. ung. Akad. Wiss., 1934, the whole brain, (I) may either increase or decrease, 51, 329—331; Chem. Zentr., 1935, i, 2039).—Analyt- but (II) always decreases. W. O. K. ical vals. are given for the contents of the yarious sections of the digestive tracts in young pigs after a Formation of acetaldehyde from lactic acid. long period of feeding with a basal diet supplemented A. U tevski (Ber. Ukrain. Biochem. Inst., 1930, by vitamin-D or different minerał substances. The 4, 89—97).—Addition of 005AT-Na lactate to the solubility of the latter in dii. HC1 and their elimin minced pectoralis of the pigeon did not result in ation as P04'" are established. R. N. C. an inereased formation of MeCHO, except in the presence of C204" or F'. W. 0. K. Comparative pharmacodynamic properties of some cardiotonic glucosides. A. B ea u n e (Buli. Velocity of resorption of alcohol in the “ smali Sci. pharmacol., 1934, 41, 590—594; Chem. Zentr., stornach ” (Pavlov). R. O. F aitelberg and B. M. 1935, i, 1413—1414).—The pharmacological actions ]\Iedvedev (Ukrain. Biochem. J., 1935, 8, No. 1, on the heart of a no. of drugs of the digitalis, stro- 169— 190).— ! c.c. of 40% EtO H (I) per kg. body-wt. phanthus, and intermediary groups are compared. is introduced into the smali stornach of a dog. After R. N. C. 20—30 min. (I) appears in the blood and in the breath, Determination of cardio-active glucosides by whilst the resorption of 02 and the elimination of the step-photometer. F. H ausckiłd (Arch. exp. C02 increase, and the R.Q. decreases. (I) is completely Path. Pharm., 1935,179, 255—259).—The aq. glucos- eliminated after 5 hr. Catarrh of the mucous mem- ide (0-004—0-00025% of digitoxin, g- or Ł-strophan- brane retards resorption of (I). E. P. thin) is treated with alkali and picric acid (A., 1922, Coefficient of ethyl alcohol oxidation and basal ii, 882) and the resulting colour is compared with metabolism in some homceothermic species. suitable standards by means of the step-photometer. E. LE Breton , M. Nicloitx, and G. Schaeffer (Compt. Tho average error is 1-3%. F. O. H. rend., 1935, 200, 1133—1135).—The veloeity of Ergot alkaloids.—See this vol., 1512. EtOH oxidation in the mouse, rat, guinea-pig, rabbit, and-pigeon oc the intensity of basal exchange. Pharmacology of ergometrine. G. L. Brown The fowl gives anomalous results. R. N. C. and H. H. D ale (Proc. Roy. Soc., 1935, B, 118, 1532 BRITISH CHEMICAL ABSTBAOTS.----A. 446—477).—Ergometrine produced central excitation differentiated from those of the 1 : 1 mol. mixtur with generał sympathetic stimulation, but with only of veronal and pyramidone by physico-ehemicE a tracę of the sp. paralysing action on motor sym- tests or by their pharmacological action in rabbit pathetic effeets. It causes eyanosis of the cock’s (cf. A., 1933, 74). F. O. H. comb, but, unlike ergotoxine (I), does not lead to Toxicity of pyramidone-veronal mixture. B gangreno. It is less toxic than (I) and causes a rise Salzer and R. F ischer (Arch. cxp. Path. Pharm in body-temp. in toxic doses. A pressor action is 1935, 179, 334—340).—The central action of pyi exhibited in the spinał cat, which is < that of the amidone (I) following administration of (I)-veron; alkaloids of the (I) group. H. G. R. (II) mixtures to rabbits rapidly and proportionatel Comparative toxicity of aqueous extracts of disappears, so that finally a pure (II) action is showr Ustilago maidis and ergot preparations. B. (I) also retards the excretion of (II) and hence prc D eagiśió and B. V arióak (Arch. exp. Path. Pharm., longs the narcosis. F. O. H. 1935, 179, 319—326).—Aq. extracts of U. maidis Asymmetrical arylalkylcarbamides.—See thi (corn-ergot) produce similar but more markcd syrnp- vol., 1488. toms of toxicity in mice than does ergotamine (I) or ergotine, indicating a high content of (I)-like sub Toad poisons. VII.—See this vol., 1502. stances. F. 0. H. Mode of action of commercial preparations c Toxicity of ripe poppy capsules. R. B unge histidine. A. Schwartz, L. I srael, and A. J aco (Arch. exp. Path. Pharm ., 1935, 179, 465—474).— (Compt. rend. Soc. Biol., 1935, 120, 124—126).— The pharmacological properties (mice, frogs) of the The production of urticaria on the skin by commercis crude contents and alkaloid fractions of ripe and preps. of histidine is due to traces of histaminę. unripe poppy capsules indicate that, in addition to R. N. C. morphine (I), other alkaloids present include codeine Hyperpolypeptidsemia induced by intraperi (II) and thebaine (III), but not narcotine or papaver- toneal injections of peptone in the rabbit. C ine. The toxicity of the crude alkaloid prep. is the L ambret and J . D riessens (Compt. rend. Soi same for ripe and unripe capsules, and is > that Biol., 1935, 120. 184— 186).—Injeetion of pepton corresponding with the (I) content owing to the induces const. liyperpolypeptidaemia, the intensit presence of (II) and (III). F. 0. H. of which varies with the rabbit. Non-protein-I Increase in local anassthesia by morphine. rises, whilst NH2-acids vary. The increased poh peptide content disappears in 24 lir. At the sam W. K eil and G. H e p p (Arch. exp. Path. Pharm., 1935, 179, 420—424).—Min. effective concns. for time corpuscular and plasma-Cl fali and blood-suga complcte ansesthesia of rabbits’ cornca for 15—20 rises. R- N. C. min. are novocaine (I) 2%, tutocaine (II) and cocaine Liberation of histamine-like substances in th (III) 0-5%, pantocaine (IV) 0-02%, percaine (V) infaretion of the intestine. G. U ngar, X. J 0-002%. At the conclusion of ansesthesia, intraven- Contiades, and R. G. P almer (Compt. rend. Soc ous injeetion of 5 mg. of morphine produces a seeond Biol., 1935, 120, 326—328).—Embolisms provoke anaesthesia of duration 20—25 min. for (I), (II), and by lyćopodiura in the intestinal arteries of the do (IV), 40 min. for (III), and 70 min. for (V). The cause an increase of gastric secretion both in th application of this phenomenon to the determination embolised animal and in another animal with whic of analgesic actirity is discussed. F. O. H. it is cross-circulated, suggesting that histamine-lik Increase and diminution of the convnlsive substances are liberated; infaretion appears in th action of local ansesthetics. W. Keil and I. intestine in 3—4 hr. The same effeets occur wit R u h lin g (Arch. exp. Path. Pharm ., 1935, 179, 415— non-embolising irritants. R. N C. 419).—The toxicity of intravenously injected novo- Effect of glycerophosphate and lecithin-fatt caine or percaine in rats is increased nearły 4 times acids on sensitivity of cats to adrenaline. A by administration of adrenaline or “ corbasil ” (o-dihy- von Jeney and J. von Mehes (Arch. exp. Patl droxyphenylpropanolamine hydrochloride). Similarly Pharm., 1935, 179, 403—414).—Aq. glyćeropho; ephedrine (d, l, or dl) increases the convulsive action phate (I) (0-001— 1-0%) has a slight choline-lik of cocaine by 200—250%. Slight novocaine con- peripheral action, inhibited by atropinę (II). Sus vulsions are reduced by NaN02 (2 mg. per kg.) or pensions of fatty acids (III) from egg-lecithin hav glyceryl nitrate (5 mg. per kg.); adonine has a similar a shght depressor action, decreasing on continuoc action. F. O. H. administration and inhibited by (II). The ester (IV Ansesthetic properties of trichloroethylene. from (I) and (III) has a choline-like depressor actio J. C. K rantz, jun., C. J. Carr, and R. Musser (J. and is inhibited by (II). (IV) enhances the presse Amer. Pharm. Assoc., 1935, 24, 754—756).—Anais- action of adrenaline, especially in decapitated, (II thesia by inhalation in the rat and rabbit is accom- treated cats even after adrenalectomy. (IV) prol panied by stimulation of the skeletal muscles and a ably combines with adrenahne-antagonistic cholin mild hyperglycsemia. No anassthesia is obtained on in the blood. F. O. II. rectal administration. H. G. R. Effect of tetrahydro-p-naphthylamine on th Pharmacological differentiation of veramon creatinephosphoric acid, creatine, and lac1 and a mixture of its components. R. F ischer acidogen of white and red muscle. A. P alladi and H. Salzer (Arch. exp. Path. Pharm., 1935, and E. Sayron (Ber. Ukrain. Biochem. Inst., 192! 179, 327—333).—Solutions of veramon cannot be 3, 65—70).—Tetrahydro-P-naphthylamine (I) leac BIOCHEMISTRY. 1533 to a diminutiou in tlie lactacidogen content of the or CHC13 (<0-55 mg.) is detected {e.g., in cadavers) biceps muscle of rabbits, and to a smaller dimin- by vaporisation in a current of H2, which on ignition ution in the semitendinosus. (I) increases the in contact with Cu produces a green flame (due to creatine (II) content of red and white muscle, formation of HC1). Aspiration of the products of and the increase in the red is > in the white. Rabbits combustion and absorption in aq. NH3, the Cl' poisoned with (I) show a greater % of (II) as content of which is subseąuently determined, affords creatinephosphoric acid than normal rabbits. a quant. method. CC14 and CHC13 are differentiated F. A. A. . by suitable colour reactions. F. O. H. Experimental intoxication by apiole : toxicity ; Relative toxicological effeets of synthetic lesions of the liver and kidney. A. Patoir,' G. ethanol and grain fermentation ethanol in Patoir, Bedrines, and Payen (Compt. rend. Soc. blended whiskies. C. W. Muehlbkrger (Amer. Biol., 1935, 120, 192—194).—The lesions are de J. Publ. Health, 1935, 25, 1132—1134).—The effeets scribed. The same alterations are produced by eryst. oh man are identieal. H. G. R. apiole, free from (o-C6H4Me)3P04, as by green apiole. Aluminium as a factor contributing to the R. N. 0. Physiological inversion of the hypertensive rise and progress of different pathological effeets of 3 :4-dihydroxyphenylaminomethyl- processes in the organism. A. L. T ch ijev sk i carbinol. Raym ond-H am et (Compt. rend. Soc. Biol., and T. S. T ch ijev sk a ja (Acta Med. Scand., 1934, 83, 501—504).—Food cooked in Al vessels increases i9 3 5 ,120, 421— 424).—-The pressor effect in the dog is the no. of cases of inflammation of the gastro-intestinal inverted by raising the arterial pressure by pincliing tract, colitis, and nephritic and hepatic diseases. Al the second carotid artery. R. N. C. salts and colloids react with biological membranes Effeets of dinitrocresol on oxidation and and may alter the charges they carry from negative fermentation. M. E. K r a h ł and G. H. A. Clgwes to pośitive. Feeding white mice from Al vessels in (J. Biol. Chem., 1935, 111, 355—369; cf. this vol., creases the no. of cases of spontaneous cancer. 1027).—The principal effect of 4 : 6-dinitro-o-cresol G. H. F. (I) on oxidation precedes and is not directly concerned Therapeutic action of organie arsenie com with 0 activation and transfer. (I) does not increase pounds. H. S c h lo ssb e rg e r (Ber., 1935, 68, [A], the rate of 0 2 eonsumption in dehydrogenase systems 149—163).—A review. or in a tissue which has been frozen and thawed, and Synthesis of mentholglycuronic acid in its effect on oxidations depends largely on the active arsenie poisoning. E. M. Persova (Ber. Ukrain. functioning of a naturally occurring O transfer system. Biochem. Inst., 1930, 4, 43—51).—After injection of (I) markedly stimulates the anaerobic fermentation a solution of menthol in oil into normal rabbits, up of yeast, the effect varying with the type of yeast. to 22% was excreted in the urine eombined with J. N. A. glycuronic acid, whilst in the case of rabbits poisoned Action of p-phenylenediamine on the chem with As only 1—10% was so excreted. W. O. K. ical processes in striped muscle. A. Parsciiin (Compt. rend. Acad. Sci. U.R.S.S., 1935, 3, 113—- Antagonistic effect of potassium iodide in 116).—Injection of £>-CąH4(NH2)2 hydrochloride or baldness due to thallium acetate. O. V. Hykes sulphate into the dorsal sac of the frog produces and F. A. D iakoy (Naturę, 1935, 136, 685).—K I rigidity of the muscles and an increased formation reduces the toxicity of TlOAc to rats and prevents of lactic acid. The amount of creatinephosphoric the loss of hair produced by Tl poisoning. L. S. T. acid is unchanged. J. N. A. Histo-spectrographic study of the fixation of Sodium salicylate poisoning ; favourable in manganese in experimental chronic intoxication fluence of glucose. H. Madisson (Deut. Arch. by manganese dioxide. A. Policard (Compt. rend. klin. Med., .1934, 176,. 612—625; Chem. Zentr., Soc. Biol., 1935, 120, 364—366).—R ats on a diet 1934, ii, 3277).—F atty degeneration is attended by containing Mn03 excrete most of it in their fćeces, disappearance of glycogen, and is lessened by treat- but exhibit renal sensitivity after some weeks. Mn ment with glucose. R. N: C. can be detected histo-spectrographically in the renal cortex and the liver, but in later stages tends to pass Effect of bromobenzene on the utilisation of the cerebral cortex and base; if the MnOa is then cystine and methionine by the growing rat. A. discontinued Mn may also be carried to the lung and White and R. W. J ackson (J. Biol. Chem., 1935, testicle. ' R. N. C. 111, 507—513).—The normal growth of rats fed on Influence of phosphorus poisoning on the a diet containing caseinogen (I), starch, sugar, and lard is inhibited by feeding PhBr; the effect synthesis of mentholglycuronic acid. B. N a z a r - is counteracted by feeding cystine or methionine j a n z (Ber. Ukrain. Biochem. Inst., 1928, 3, 159— 165).—A diminution in the spontaneous excretion of although taurine, Na2S04, or a digest of (I) is ineffect- ive. Bromophenylmercapturic acid is-isolated from glycuronic acid during P poisoning depends on the diminution in the food intake. P poisoning, if aecom- the urine of rats fed with PhBr. H. D. panied by pathological changes in the liver, is accom- Acute toxicity of ethyl chaulmoograte. G. A. panied by a diminution in the synthesis of menthol Emerson and H. H. Anderson (Proc. Soc. Exp. glycuronic acid. F. A. A. Biol. Med., 1934, 32, 289—291). R. N. C. Influence of phosphorus poisoning on the Toxicity of carbon tetrachloride. E. Cia r a- creatinephosphoric acid, lactacidogen, and vino (Boli. Chim. farm., 1935, 74, 741—748).—CCL creatine content of red and white muscle. A. 5 i 1534 BBITISH CHEMICAL ABSTRACTS.— A. Palladin and A. Kudejavzeva (Ber. Ukrain. Bio ing such treatment, intravenous injection of org. Ca chem. Inst., 1928, 3, 57—63; cf. A., 1924, i, 915).— before the onset of oedema alleviates or inhibits the Poisoning with large doses of P loads to an inerease toxicity. F. O. H. of creatinephosphoric acid (I) and creatine (II), and a Effect of sodium hydrogen carbonate on decrease in lactaeidogen in red and white muscle. glycaemia from pilocarpine and from ligature The inerease in (I) is much greater in red than in of the portal vein. V.Pa p ilia n and V. P re d a white muscle. Tho % of (II) combined with H3P04 (Compt. rend. Soc. Biol., 1935, 120, 58— 60).— is inereased, and the inerease is greater in red than in NaHCOg inhibits the hyperglycajmia produced by white muscle. Poisoning with smali doses of P leads ligature of the portal vein, by mobilising glycogen in to inerease of (I) and of bound (II) in red muscle, the liver. It has no effect on hyperglycsemia pro but the (I) content of white muscle remains normal. duced by pilocarpine. R. N. C. F. A. A. Treatment of poisoning due to inhalation of Effect of radium rays on living cells. C. S. hydrocyanic acid. W. Wibth (Arch. exp. Path. G ager (Science, 1935, 82, 327).—A discussion. Pharm., 1935, 179, 558—602).—S compounds (e.g., L. S. T. Na2S203, Na2S40 G), some heavy metals (Ni and Co Action of radium on glycolytic activity of and a few Fe salts), methsemoglobin-producing sub- neoplasic tissues. C. Grandclaude, M. Polo- stances (e.g., NaN02), aldo- and keto-derivatives (e.g., novski, H. Waeemboueg, and J. Dbiessens (Compt. glucose and dihydroxyacetone), and alkali carbonates rend. Soc. Biol., 1935,120,183—184).—Ra irradiation are efficacious, the prophylactic actm ty being > the disturbs carbohydrate metabolism in tumours; glyco curative power. Characteristic changes in blood-[H‘] lytic activity in the neoplasic tissues is depressed. occur in rabbits after inhalation of HCN. R. N. C. F. O. H. EfEects of rare earths on the polarisation Effeets of inhalation of hydrogen fluoride. II. capacity of frog’s skin and their significance in Response following exposure to Iow concen- relation to colloidal chemistry and permeability. tration. W. Machle and K. Kitzmillee. III. K. Yom ogita (Z. Biol., 1935, 96, 487—501).—The Fluorine storage following exposure to sub- salts of certain tervalent rare earths in Iow concns. lethal concentrations. W. Machle and E. W. (0 001—0-0005J/) irreversibly decrease the polaris S c o tt (J. Ind. Hyg., 1935,17, 223—229, 230—240).— ation capacity of surviving frog-skin, but in higher II. A concn. of 0 0152 mg. per litre, although slightly concns. (0-0025—0-0015J/) they produce only a irritating, was tolerated by guinea-pigs, but growth - reversible reduction, whilst in still higher concns. the rate was somewhat slower than usual. The erythro- effect is again irreversible. The results are con- eyte count was decreased and lesions, similar to but sidered in relation to the action of positively charged less severe than those observed with higher concns., multivalent cations on the negatively charged celi developed. colloids. W. O. K. III. Normal rabbits contain 10 mg. of F per kg., but this may be inereased as much as 10-fold by Influence of functional changes in the auditory exposure to sublethal concns. of H F. The bulk of centres on proteolysis. S. Fomin (Ber. Ukrain. the F is stored in the bones, but it is found in all Biochem. Inst., 1928, 3, 143—-146).—A lessening of other tissues except the blood, fat, and liver. auditory stimulation is accompanied by a retardation H. G. R. of proteolysis in the auditory centres, and the ratio Action of nitrites on the intestine. F. Been- of residual N to total N is less in the experimental heim (Arcli. int. Pharmacodyn. Therap., 1934, 48, animals (young dogs) than in Controls. F. A. A. 91—96; Chem. Zentr., 1934, ii, 3275).—M eN02 and Liberation of histamine-like substances by EtN02 relax guinea-pigs’ intestines, MeN02 being excitation of the peripheral end of the splanchnic 5—10 times more active. R. N. C. nerve : haemorrhagic lesions of the intestine by intra-arterial injections of histaminę. G. U ngab, Nitric oxide and toxicity of nitrous gases. X. J. Contiades, and A. Gbossiobd (Compt. rend. G. P f le s s e r (Arch. exp. Path. Pharm., 1935, 179, Soc. Biol., 1935, 120, 328—330).—Splanchnic excit- 545—557).—Exposure of mice to N O -fair in an ation in one dog causes inerease of gastric secretion in apparatus such that oxidation is retarded indicates another animal cross-circulated with it, haemorrhagic that NO is more toxic than equiv. concns. of other N lesions occurring in the intestine of the former animal. oxides. Thus max. concns. tolerated are 0-03% for Injection of histaminę in the afferent artery of an NO and 0-12% for N02, whilst the respective toxic intestinal loop produces similar lesions. R. N. C. symptoms are markedly different. The results are con'elated with the toxicity of mixed nitrous gases. Delayed effeets of denervation of the adrenal F. O. H. gland on adrenaline secretion. J. A. Sgbosso Toxicity of concentrated salt solutions. F. (Compt. rend. Soc. Biol., 1935, 120, 270—272).— L asch and D. R o lle r (Arch. exp. Path. Pharm., 1935, Electric excitation of the recently denervated adrenal 179, 459— 464).—Intravenous injection of hypertonic of the dog provokes a discharge of adrenaline (I), (20—30%) aq. Na or Li sulphate, tartrate, H phos- which does not occur 2—3 months after denervation. phate, citrate, or chloride has a lethal action, pro- (I) discharge is also provoked from the recently ducing tetanic convulsions, respiratory and circulatory denervated gland by nicotine, coniine, or candicine failure, and finally pulmonary cedema, due to dis- iodide (II), but the response decreases with the turbances of ionic equilibrium of the blood. Follow passage of time. The response to (II) is inereased BIOCHEMISTRY. 1535 by previous electric cxoitation, but is unafFected by łase content of rabbit muscle, whilst fatigue caused yohimbine. R. N. C. no essential change, but on the earlier trained muscle Displacement of ions in electrolytes during the it inereased the catalase activity. Experiments with very short discharges employed in electro- glutathione showed that after training the conditions physiology. P. Fabre (Compt. rend. Soc. Biol., for oxidation-reduction processes in muscle were 1935, 120, 23—26).—The inertia factor involved in improved. J . N. A. the displacement of ions by ordinary shocks of 10-4 Ascorbic acid and blood-catalase. II. sec. duration does not appear in shocks of 10 B sec. Demonstration of vitamin-C deficiency. G. duration. R- N. C. T ó ro k and L. N e u fe ld (Klin. Woch., 1934, 13, Determination of [the concentration of] en- 1816— 1818).—Injection of ascorbic acid inereases zym es. B. Rubin and L. Naumoya (Compt. rend. the catalase action of blood in cases of known Acad. Sci. U.R.S.S., 1935, 3, 83—86).—An investig- vitamin-C deficiency; it has no similar effect on ation of difficulties that arise in extracting completely normal cases. By this method, latent -C deficiency, and in determining the concns. of enzymes. with no clinical symptoms, can be recognised. J. L. D. G. H. F. Spectroscopy of an enzyme reaction.—See this Dilatometric studies in the enzymie hydro vol„ 1189. lysis of polysaccharides. III. Hydrolysis of starch, amylose, and amylopectin by taka- Embryo-chemistry of amphibia. VII. En- diastase. H. B. Sreerangachar (Proc. Indian zymes in eggs of giant salamander. I. T aka- Acad. Sci., 1935, 2, B, 333—341; cf. this vol., 250).— HASHI (J. Biochem. Japan, 1935, 22, 45—47).—After When sol. starch is hydrolysed by takadiastase, 2—3 weeks’ development, the embryos contain amyl- the dilatometric depression per milhmol. of maltose ase, nuclease, and glycerophosphatase, but not ester- liberated is 40, whilst the depression per 1° fali ase, trypsin, arginase, or urease. F. 0. H. in a is 10-7. For potato starch and two amylo Action of hydrogen cyanide on the oxidase of pectin (I) preps., the respeetive vals. are 4-0, 3-6, Altlicra rósea. V. Z a n o tti (Boli. Chim. farm., and 3-7 per millimol. of maltose and 10-7 [for one 1935, 74, 669—670).—Exposure to gaseous HCN of the (I) preps.] per 1° fali in a. F. O. H. temporarily inhibits the oxidase activity of A . rosea Taka-amylase. IV. Effect of alcohol and leaves. F. O. H. salts on amylase and maltase action. V. Influence of reduced glutathione and ascorbic Changes in amylase and maltase activities of a acid on the destruction of adrenaline by the taka-diastase solution on keeping. VI. Pro- oxidising enzymes of the potato. J. T. Rico and portion of amylase and maltase in taka-diastase A. M. B a p tista (Compt. rend. Soc. Biol., 1935, on purification. T. Kitano (J. Soc. Chem. Ind. 120, 45—48).—Asparagine, alaninę, glycine, and Japan, 1935, 38, 447b, 447—449b, 449—450b).— leucine inhibit the spontaneous oxidation of adrenal IV. Maltase (I) activity of a taka-diastase (II) ine (I) in decreasing order of activity, but have no solution is largely inhibited by 40% EtOH, but effect on the oxidation of (I) by potato juice. This amylase (III) inhibition is slight. No sueh prefer- oxidation is inhibited by ascorbic acid and by re ential inhibition is obtained with 25% NaCl. duced, but not by oxidised, glutathione. R. N. C. V. The (I) of a (II) solution is more thermolabile Spectroscopy of purified enzymes. I. than the (III). Acid destroys both enzymes to about Xanthine oxidase and catalase. R. Itoh (J. the same extent, but alkali destroys (III) more Biochem. Japan, 1935, 22, 139—148).—Purified rapidly than (I). xanthine oxidase (from milk) has an absorption max. VI. In the fractional pptn. of (II) with EtOH, a t 279 m[j. a t p n 7; with inereased alkalinity the val. the first fractions are rieher in (III), and the later shifts to a longer >.. Liver- and blood-catalase have rieher in (I). Dialysis, especially after keeping, mas. at 406 and 266 mfx and hacmin one at 406 mpt. causes a greater decrease in (I) than in (III). The activity of these catalases is not related to fiavins, E.A.H.R. traces of which occur even in highly purified preps. Salt activation. II. Influence of salts on F. O.H. the stability of amylase. K. V. Giri (J. Indian Catalase in embryonic development. III. Chem. Soc., 1935,12, 567—574; cf. this vol., 1162).— Catalase activity during growth period of The alteration of the rate of hydrolysis of starch by Salino irideUs and Esox lucius em bryos. U. the amylase of sweet potato is due to stabilisation or Sam m artino (Arch. Farm. sperim., 1935, 60, 372— sensitisation of the enzyme by the added salt. At 385).—Fertilised eggs of S. irideus exhibit a contin Pn < 6 (the optimum) 0-05AT-NaCl inereases the stabil uous inerease in catalase activity after approx. 12 ity ; at p a 6 it is without effect. Higher salt concns. days’ ineubation; this inerease is associated with the decrease the stability. The following orders of initiation of blood circulation and generał growth efficiency are found : NaF>NaCl>Na2S04>NaN03; of the embryo. Similar phenomena occur in E. CaCl2>NaCl>K C1 > LiCl. “ R. S. C.' lucius, in which catalase activity begins to inerease Action of different amylases on starch. E. on the 5th day. F. O.H. Ohlsson and O. Rosen (Svensk farm. Tidskr., Influence of training [by electrical stimulation] 1934, 38, 497—652; Chem. Zentr., 1935, i, 1402).— and fatigue on the catalase of muscle. A. V. The activities of taka-diastase, amylase from un- Palladin and E. J. Rasciiba (Ukrain. Biochem. J., germinated barley, and amylase from green malt 1935, 7, No. 2, 5— 18).—Training inereased the cata- are compared. Differences in the actmty curves 5 1 2 1530 BRITISH CIIEMIOAL ABSTRACTS.----A. for the two malt amylases were apparent under all AcCHO (II) is regarded as the true substrate of gly- experimental conditions (A., 1932, 303). Ungermin- oxalase action. From the rato at which lactic acid ated barley and saccharogen-amylase, as prepared is produced and the changes in free -SH which occur by the authors, contain smali proportions of dextrin- in the reaction between (I) and (II), it is concluded ogen-amylase. A. G. P. that (I) first combincs by means of its -SH with the Direct and quantitative study of amyloclastic substrate, (II), and then, as the enzyme-catalysed activity of amylases. M. L. Caldwell and F. C. reaction develops, enters into further transformations H ild eb ra n d (J. Biol. Chem., 1935,111, 411—420).— in which its "SH is again invólved. L. S. T. An accurate method for the measurement of amylase Inactivation of fumarase. K. P. Jacobsohn actmty depends on the determination of residual and J. T apadinhas (Compt. rend. Soc. Biol., 1935, starch or amylose (I) at any stage of its hydrolysis 120, 36—38).—The inactivation of fumarase (I) by by yarious amylases through its quant. pptn. by Ag' depends on the time of ineubation; (I) is com- EtOH. Under specified conditions the ppts. are not pletely inactivated in 6 hr. but a reactivation occurs appreciably contaminated by dextrins or maltose, in 24 hr. (I) in fresh liver extract is more resistant and the difference between the wts. of original (I) to Ag‘ than in old extracts. R. N. C. and pptd. (I) gives a measure of the amyloclastic Influence of different diets on the enzymes of activity of the amylase. J. N. A. the organism. IV. Fasting and the enzymes Blood-amylase response to acetylcholine and of the tissues. B. Goldstein and K. I. Katkova. its modification by eserine and atropinę. W. V. Protein-free food and the enzymes of blood Antopol, A. Schifrin, and L. Tuchman (Proc. and tissues. B. Goldstein, R. R. Sigalova, and Soc. Exp. Biol. Med., 1934, 32, 383—385).—Blood- V. D. M elnischenko (Ukrain. Biochem. J., 1935, amylase is increased by intramuscular administration 7, No. 2, 91— 101, 103— 129).—IV. In starving of acetylcholine. The response is increased by pre- rabbits there is no alteration in the lipase (I) of hver, vious administration of eserine and inliibited by kidney, and lung. The wt. of the liver decreases atropinę. 11. N. C. rapidly, due to a decrease in the total quantity of Emulsin. XXIII. Influence of substitution tissue, and this simultaneously produces a decrease in the benzene nucleus on the enzymie fission in the blood-(I). The amylase of the liver is not of phenol-p-d-glucosides. II. B. H e lf e ric h and affected. C. P. B u r t (Annalen, 1935, 520, 156— 163; cf. this V. Rabbits fed on a protein-free diet live 1-5—2 vol. 964).—Guaiacol with tetra-acetylglucosidyl brom- months. There is no alteration in the amylase of the ide and NaOH-aq. COMe2 affords the Ac4 derivative, blood and liver, or in the (I) of the lung. There is a m.p. 155— 157°, [aft0 -30-2° in CHC13, of guaiacol-p- very smali inerease of (I) in the liver, and a marked d -glucosidc (I), m.p. 155-5—157-5°, [aft- -66-8° inerease in the kidney. Sometimes there is an in in H20, obtained by deacetylation with NaOMe- erease of (I) in the blood. J . N. A. MeOH. By similar methods are obtained iso- Thyroid gland, lipase, and catalase. E. eugenol-$-d-ghicoside (II), m.p. 187-5— 189-5°, [aft0'5 K e e se r (Arch. exp. Path. Pharm., 1935, 179, 310— -60-0° in EtOH (Aci derivative, m.p. 140— 143°, 31S).—Liver-lipase is inliibited in vitro by thyroxinc [aft1 -24-8° in CHC13), and the 3-CH2Ph ether, (I), thyroid extraets, thyronine (II), di-iodotyrosine m.p. 165—168°, [aft -60-20° in EtOH, of proto- (III), and extracts of blood, brain, liver, spleen, catecJmaldehyde-i-fi-d-glucoside (III). The Ac4 de- and anterior and posterior pituitary lobes. The rivative of (III) with tetra-acetylgalactosidyl bromide- inhibition by (I) is suppressed by the anti-thyroid Na01I-aq. COMe2, and deacetylation of the Ac8 factor from thyroidectomised animal’s serum. Blood- derivative gives protocatechualdehyde-4:-{i-d-glucoside-3- and organ-catalase in vitro are activated by thyroid ęi-d-galactoside~\-H20 , [aft0 —100-5° in II20, hydrolysed and anterior pituitary preps. and inhibited by "(III), by emulsin, at p K 5-0, more slowly than the corre KI, and anti-thyroid factor, whilst (I), (II), iodo- sponding [3-rf-diglucoside (loc. cit.j. (I) (p-position dihydroxypropane (IV), and glutathione (V) are with- free) and (II) (C!C in p-position) are both attacked out action. The catalytic actmty of thyroid gland more slowly bv emulsin than is vanillin-p-ci!-glucoside sections is enhanced by (IV) and (V) and inhibited (p-CHO). ‘ J. W. B. by (III), NH4SCN, and quinol. The mechanism of Inactivation and regeneration of the glyco- these and allied phenomena is discussed. F. O. H. lytic enzyme system of muscle extract. L. Choline-esterase in invertebrates. Z. M. Bacq Michaelis and J. Rtjnnstróm (Proc. Soc. Exp. (Compt. rend. Soc. Biol., 1935, 120, 247—248).— Biol. Med., 1934, 32, 343—349).—The glycolytic Choline-esterase is present in the blood and tissues enzyme (I) of muscle extract, after inactivation by of molluscs, the blood of Sipunculus, and the muscles exposure to 0 2, can be reactiyated to a degree > the of Spirographis, Holothuria, and Ascidia. I t is original actmty by thioglycollic acid, thus corro- absent from crustacean blood and tissues, ascidian borating the oxidation-reduction reversible inactiv- and insect blood, and beetle and sponge tissues. ation hypothesis. There is evidence that (I) contains Crustacean muscles are insensible to acetylcholine, •SH. R. N. C. which disappears rapidly on injection without being Mechanism of glyoxalase activation by gluta- fixed by the tissues. R. N. C. thione. J. GirSaytćius and P. A. Heyfetz Cholesterol esterase in blood. W. M. S p erry (Naturę, 1935, 136, 645—646; cf. this vol., 476).— (J. Biol. Chem., 1935, 111, 467—478).—When serum The compound formed between glutathione (I) and or heparinised human plasma is ineubated at 37—40°, BIOCHEJIISTRY. 1537 the ratio of eombined to total cholesterol (I) increases ation const. (s) of pepsin (I) brought to p n < 7 falls several fold. Heating to 55—60° destroys this by about 1/3, although the (I) remains homogeneous. effect, attributed to an enzyme having an optimum Reduction of the p a of such a prep. to < 4-8 is accom- at p a 8. The free (I) of red blood-cells is not esterified panied by a large rise in s, and loss of homogeneity, under these conditions, and the esterification is less three distinct components being present having s in luemolysed whole blood. F. A. A. 10, 20, and 25 times that of normal (I). Thus alkali- Tyrosine-tyrosinase reaction in presence of inactivated (I) is unlike denatured proteina in being Z-ascorbic acid. F. Schaaf (Helv. Chim. Acta, homogeneous, but has undergone some change which 1935, 18, 1017— 1021).—In spite of the presence of makes it more readily denatured by acid. F. A. A. Z-ascorbic acid (I) the typical tyrosinase (II) reaction Cathepsin of tissues. B. Goldstein (Ukrain. (introduction of a second OH in the mol.) can proceed Biochem. J., 1935, 8, No. 1, 87— 104).—H 2S, used unchecked under the influence of (II); the solution as activator for cathepsin (I), sometimes restricts remains colourless, although frcąuently saturated with its activity. A weak activation or inhibition but 0 2, but the presence of appreciable amounts of 3:4- not a strong inhibition is converted into a strong dihydroxyphenylalanine (III) is soon detected by activation by dilution. E. P. FeCl3. Restriction of oxidation by (I) takes place Cathepsin in the embryo and in maternal only when the change does not require further aid tissues. I. B. Goldstein and E. J. Milgram from (II) and there is no evidence of direct influence (Ukrain. Biochem. J., 1935, 8, No. 1, 139— 168).— of (I) on the actual (II) action. (III) is also produced The difference between the amounts of activated (I) from tyrosine in presence of (I), but in much smaller and non-activated (II) cathepsin increases in the amount than when (II) is present. H. W. maternal organs during (and possibly parallel with) Antityrosinase function of glutathione in the growth of the embryo. In the placenta the val. vitro . F. C h o d at (Arch. Sci. phys. nat., 1935, [v], of (II) is very Iow; the difference between the amount 17, Suppl., 73—74).-—0-5% of glutathione completely of (I) and (II) is very great in rat’s, less in rabbifs inhibits tyrosinase reactions in vitro. H. G. R. and guinea-pig’s, and very Iow in human placenta. The concn. of (I) and (II) in the embryo is Iow and Occurrence of arginase in the giant sala increases with the growth. After birth the concn. m ander. T. K um on (J. Biochem. Japan, 1935, increases, being > in the corresponding maternal 22, 41—43).—In-vitro experiments in P04"' buffer organs. After reaching a max. it falls to the normal a t p n 6-6 indicate a high arginase content in the val. The difference between the amounts of (I) liver, smaller amounts in the kidney, blood, and spleen, and (II) increases rapidly. Thus the protein meta and its absence from the pancreas, heart, and skeletal bolism of the embryo i a controlled by the maternal muscle. F. O. H. organs and by the placenta. The difference between AfFmity relations of animal and vegetable the amounts of (I) and (II) increases parallel with the dipeptidases. W. Grassmann, L. Klenk, and synthetic action. E. P. T. P e te rs-M a y r (Biochem. Z., 1935, 280, 307— Proteinases and proteolytic processes of 324).—Animal (kidney) and vegetable (yeast) di muscle tissues. I. Activity of muscle proteinases peptidases do not differ as regards their affinities for on qualitatively different protein diets. S. dipcptides. The affinity for leucylglycine is 10 Fomin and M. M ischkis (Ukrain. Biochem. J., 1935, timcs that for alanylglycine (I) and the affinity for 7, Nos. 3—4, 135— 145).—The activity of the muscle (I) is 4—9 times that for glycylglycine (II), whilst proteinases of rats is increased by incomplete the affinity for glycyl-leuoine is > that for glycyl- diets of beans or gelatin. H. D. alanine (III) and that for (III) is > that for (II), Proteinases and proteolytic processes in although, in the second series, the differences are less pronounced. Regularities are also obsęrved muscle. II. Activity of muscle proteinases of in the variation of the degree of restriction of the the dog’s leg after training. S. V. Fomin and V. I. dipeptidases by NH2-acids, which then form tho Demin (Ukrain. Biochem. J., 1935, 8, No. 1, 73— 85).—The activity of the muscle proteinases in the series leucine > valine (IV) > alaninę (V) > glycine. weighted hind leg of a dog was increased > in the other Glutamic acid has no restrictive power, but phenyl- alanine and tryptophan are powerful inhibitors, and leg, due to increased oxidation. E. P. proline, asparagine, and arginine have effects inter- Tissue proteinases in organs of animals in mediate between those of (IV) and (V). Glycyl- different stages of phylogenetic evolution. B. aminobenzoic acids (VI) are slightly attacked by Goldstein and E. J. Milgram (Ukrain. Biochem. J., dipeptidases practically free from aminopolypeptidase 1935, 8, No. 1, 105— 138).—As regards concn. of (from yeast) and much more attacked by non-puri- cathepsin (I), the organs form the series : kidney> fied liver extracts of about the same dipeptidase liver > spleen > muscle; and the animals the series: content. The enzymie hydrolysis of (VI) is affected rat, frog, pigeon>dog, cat, hen, rabbit, guinea- by H2S much < is that of ordinary dipeptides. pig>cow. The concn. of (I) is possibly related to As regards enzymie hydrolysis (VI) do not differ the intensity of the metabolism, which decreases as qualitatively (cf. Balls et dl., A., 1931, 392). body-wt. increases. With mammals kidney-(I) is W. McC. strongly activated, but liver-(I) is slightly inhibited Behaviour of pepsin in the ultracentrifuge or slightly activated by H2S. With amphibia, after alkaline inactivation. J. St. L. P h ilp o t H2S has no action or restricts slightly the activity of (Biochem. J., 1935, 29, 2458—2464).—The sediment- liver-(I), but activates kidney-(I) slightly. With 1538 BRITISH CHEMICAL ABSTRACTS.— A. birds H2S strongly restricts the activity of kidney-(I) transformed into the Harden-Young fructose di- and slightly that of liver-(I). The different actions phosphoric ester. CH2I-C02H does not affect this of H2S on kidney cxtracts are possibly due to the reaction. Both reactions proceed independently if different end-products of protein metabolism with (I), (II), and P04"' are all added to the extract. mammals and birds. With mammals H2S activates R. N. C. spleen-(I); with frogs it greatly restricts its activity. Action of ultra-violet light on yeast-invertase. E. P. VI. The activating zone. G. G orbach and H. Intracellular proteinases. XVI. Activation R uess (Biochem. Z., 1935, 280, 213—216; cf. A., and inhibition of papain. E. Maschmann and 1934, 1033).—I t is light of >. 365— 366 nap which E. Helmert. XVII. Effect of arsenie com directly activates the invertase (I) of yeast autolysates pounds on the activity of liver-cathepsin. E. and dialysates on short irradiation. There is no Maschmann (Biochem. Z., 1935, 280, 184—203, eonnexion between the activation and the light blue 204— 212; cf. this vol., 1279).—XVI. Papain, if fluorescenco of tho (I) solutions. W. McC. activatcd as much as possible by a -SH compound Preservation and the rate of respiration of [cysteine (I), reduced glutathionc (II)], is further activ- yeasts. F. Chodat and A. Mirimanoff (Arch. ated by certain substances [e.g., citric acid, malic Sci. phys. nat., 1935, [v], 17, Suppl., 74—76).— acid (III), AcC02H, K4Fe(CN)6] which sometimes The ageing of yeast is much slower at 6° than at 25°. have sp. effeets. 02 and a heavy metal are also In 48 hr. at 25° the respiratory actm ty is reduced by involved. Very smali amounts of (I) [but not of 50%. H. G. R. reduced (II)] inhibit and even irreversibly inactivate papain with disappearance of (I). For activation Assimilation by yeast of high and Iow mol. (I), (II), or 0 2 and heavy metal can be replaced or wt. nitrogen compounds. N. Nielsen (Compt. (when these are present in insufficient quantity) rend. Lab. Carlsberg, 1935, 21, No. 6, 139— 150; cf. strengthened by Fe11 in complex combination [but A., 1934, 1034).—The N compounds of wort can be not by K4Fe(CN)6] if certain substances [e.g., ascorbic separated by dialysis into fractions of Iow and high acid (IV), (III), tartaric acid, but not lactic or glycollic mol. wt., tlie former of which is much the more acid or AcC02H] which bind Fe are present. Fe11 readily assimilated by yeast. E. A. H. R. in complex combination can be partly replaced by Action of glutathione on cytochrome-C in (IV). No part is played by any (I)-Fe compound. vitro . E. J. Bigwood and J. Thomas (Compt. Results differ according to the type of buffer (acetate, rend. Soc. Biol., 1935, 120, 69—72).—Glutathione (I) citrate) used. rapidly reduces cytochrome-C' (II) in vitro in neutral XVII. The degradation of gelatin (V) (at p a 4) solution. Reduced (I) is responsible for keeping and clupein (VI) (pB 5) by liver-cathepsin (pig) is (II) in its reduced form in boiled yeast, in plasmolysis usually inhibited by As compounds (15 tested), of which it is released in large quantities. R. N. Ć. although occasionally slight activation or no action Reaction chain of alcoholic fermentation. O. results. Tho degradation of (VI) is sometimes M ey e rh o f (Hclv. Chim. Acta, 1935, 18, 1030— unaffected by compounds which check that of (V). 1052).—A lecture. H. W. W. McC. Activation of the proteolytic enzymogen Chemical actions taking place in the ferment system of the ventricle. R. Ege and J. Obel ation (organie) celi. M. C. Potter (Zentr. Bakt. (Biochem. Z., 1935, 280, 265—275; cf. A., 1934, Par., 1935, II, 93, Reprint. 11 pp.).—During yeast 450).—-Neutral or slightly acid extraets of tho mucous fermentation of 1 mol. of sucrose, approx. 8 coulombs membrane of the stornach (man, dog, pig, ox, cod) of energy are liberated. The e.m.f. of a fermenting contain smali amounts of preformed enzymes capable celi depends on the chemical reactions involved, and of coagulating milk. Activation of the enzymes is developed in open or closed circuit. The electricity sets in at p H < 5 and the rat-e inereases as [H ‘] in liberated is independent of the p a of the medium if ereases, the degree of acceleration varying from species this does not restrict the activity of the organism. to species of animal. There is no relation between A. G. P. dependence of the rate on [H‘] and the ratio Kinetics of alcoholic fermentation of sugars pepsin: rennin. At alkaline reaction the stability by brewer’s yeast. III. Temperature co- of the enzymogen is in all cases > th at of the activated efficients of the rates of fermentation of glucose enzymes. W. McC. and fructose. R. H. Hopkins and R. H. Roberts (Biochem. J., 1935, 29, 24S6—2490).—The method of Initial phosphorylations of glycogen. J. K. Hopkins (this vol., 661) was used. The temp. coeff. P arnas and T. Baranowski (Compt. rend. Soc. of fermentation of glucose by yeast is independent Biol., 1935, 120, 307—310).—In the hydrolysis of of concn. between 0-25 and 5-0%, varying between adenosinetriphosphoric acid (I) by muscle pulp in 2-0 and 1-24 between 15° and 35°. W ith fructose presence of glycogen (II), the liberated P04"' pre- (I) the temp. coeff. decreases at concns. < 1 % . Below ferably esterifies (II), but a certain ąuantity forms 0-25% concn. the temp. coeff. agrees with that for free H3P04. The amounts of hydrolysis and ester- the mutarotation of (3-(2 : 6)-fructose, and it is con- ification increase with dilution and (II) concn. The cluded that the enzyme attacks only one form of (I), enzymes of muscle extract transform (I) into inosic and the rate of coiwersion into this form determines acid, and rapidly hydrolyse (II) in presence of P04"', the rate of fermentation at Iow concns. II. D. forming the Robison-Embden liexose monophos- Mechanism of oxidation processes. XLII. phoric ester. (I) and (II) in absence of free P04"' are Decomposition of citric acid by yeast. H. W ie- BIOCHEMISTRY. 1539 la n d and R. S o n d e rh o ff (Annalen, 1935, 520, 150— diminish the inhibiting action of their acids. All 156).—Contrary to the earlier statem ent (A., 1933, inhibitions are reversible on addition of glucose. 865) gaseous H2 (3 mols.) is evolved in the anaerobic F. A. A. fermentation of citric acid (I) by “ impoverislied ” Effeets of certain organie acids and protein yeast (II). Since no H2 is obtained with (II) alone, derivatives on the growth of Colpidium . A. M. whereas HC02Na and (II) give H2, it is assumed that E l l i o t t (Arch. Protistenk., 1935, 84, 472— 494).— the H2 is produced from the HC02H first split off Single NH2-acids were unsatisfactory N sources for from (I). A little MeCHO (but no COMe2) was de C. striatum and G. campylum, but proteins and their tected as its 2 :4-dinitrophenylhydrazone; 70% products of partial hydrolysis were suitable. Among decomp. in accordance with the eąuation given peptones examined those containing high proportions (loc. cit.) is thus observed. Since (II) is unable to of NH2-acids and NH2-N (Van Slyke) were the more decompose C0(CH2,C02H)2 (III) into C02 and effective. Relationsliips exist between p a, growth, 2AcOH, it is suggested that, in the anaerobic decomp. and the naturę of the N source utihsed. The Na of (I), fission of HC02Ii affords the keto-form of salts of the 5 lower fatty acids and Na citrate were (III) which decomposesAc0H+CH2(C02H)2, toxic at pa 5-8, whereas glycollate, pyruvate, and followed by CH2(C02H)2-> Ac0H+C02. In agree- tartrate were only moderatcly toxic. Growth of ment, it is shown that CH2(C02H)2 is decarbox}'l- C. striatum was accelerated by NaOAc at p a 6-5— 7-5 ated by (II) at p n 7-0. The aerobio decomp. of (I) and th at of O. campylum at p a 7-0. PrC 02Na acceler with (II) begins more rapidly than tho anaerobic ated growth of both species at p a >7-0. A. G. P. reaction, and the initial stage is probably the de Effect of certain carbohydrates and organie hydrogenation (C02H-CH2)2C(0H)-C0„H-2H+0 -> acids on growth of Chloroyonium and Cliilo- C0(CH2-C02H)2+C02+H 20. The velocity of de m onas. J. B. L o e fe r (Arch. Protistenk., 1935, hydrogenation of (I) by methylene-blue in presence 84, 456— 471).—Greatest acceleration of growth of of (II) is reduced as (I) is replaced by HC02H. Chlorogonium euchlorum was produced by fructose (I), galactose (II), maltose (III), and lactose (IV), less Action of organie substances on alcoholic by glucose (V), arabinose (VI), xylose (VII), and fermentation. V. Folii culin. A. M ossini rhamnose (VIII); negative effeets were obtained with (LTnd. Chimica, 1935, 17, 524—526; cf. A., 1934, sucrose (IX), starch (X), and dextrin (XI). G. 1261).—The evolution of C02 during alcoholic elongatum was similarly affeeted except that (IV) fermentation is inereasingly accelerated in presence provcd a poor source of C. The order of efficiency of amounts of folliculin rising from 0-00005 to 0-05 with Ćhilomonas was (XI)>(I), (IV), (II), (III)>(VI), mg. %. When the fermentation slackens owing to (V), (IX), (VII), whereas (VIII) and (X) were inactive. dccrease in the amount of sugar present, addition The growth of Ćhilomonas was accelerated by fatty of fresh sugar is followed by increased gas evolution. acid salts in the descending order AcOH, PraC02H, Degenerated yeast also responds to the stimulating BuC02H, EtC02H, Pr^C02H. Negative results were effect of folliculin. T. H. P. obtained with hexoate. The two species of Chloro gonium were affeeted similarly, except that EtC02H Pseudo growth-factors of grapę must. A. produced no effect. A. G. P. M irim anoff (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., 172— 178).—A feebly acidic substanee which Colloidal changes indicated by experiments inhibits yeast growth is formed by sterilisation of must on Param ecia as the basis of sympathetic a t 110°. H. G. R. nervous processes. T. Wense (Arch. exp. Path. Pharm., 1935, 179 , 475— 482).—In their influence Effeets of 2 :4-dinitrophenol on respiration on vacuole pulsations, chemotaxis, protoplasmic of commercial cake yeast. J. Field, jun., A. W. viscosity, and rate of movement of Paramecia, M artin , and S. M. F ie ld (Proc. Soc. Exp. Biol. Med., cholinę (I) and pilocarpine show a marked antagonism 1935, 32, 1043—1046; cf. A., 1934, 1262).—The total to adrenaline (II). The action of (I) is inhibited concn. of 2 :4-C6H3(N02)2’0H (I) causing optimal by atropinę and curare. K and Ca resemble (I) stimulation of yeast respiration cc p n, but the concn. and (II), respectively. These phenomena indicate a of undissociated (I) is const. for a wide p a rangę. colloid-chemical basis for the transmission of sympa Any fixed (I) concn. may stimulate respiration at thetic nerve stimuli. F. O. H. one p a and inhibit it at another. Reduction of p K Biological action of rays from radioactive to a sufficient extent in a suspension of yeast cells substances. I. Effect of smali dose radi- in hquid containing (I) suspends respiration im- ation on the reproductive activity of a unicellular mediately. The results suggest that the active agent organism . Y. K im ura (Sci. Papers Inst. Phys. in stimulating respiration is undissociated (I). Chem. Res. Tokyo, 1935, 28, 27—47).—Irradiation R. N. C. of Paramecium caudalum with p- and y-radiation Inhibitory action of the lower aliphatic acids from pitchblende, monazite, and a U-X prep. caused and aldehydes on cytochrome reduction in yeast. an increased rate of reproduetion, the y-rays being L. V. B eck (Biochem. J., 1935, 29, 2424—2432).— mainly responsible. No concomitant pathological Marked inhibition is shown by fatty acids (concn. effeets on the organism were produced. A. L. 0-0131), less by the corresponding aldehydes, and none by the alcohols or urethanes. H C02H and CH20 Mode of action of chemotherapeutically-used act differently from the other męmbers of the series. dyes. V. Fischl and E. Singer (Z. Hyg. Infektions- Strong acids have a smali action. The Na salts krankh., 1934, 116, 348—355; Chem. Zentr., 1934, 1540 BRITISH CHEMICAL ABSTRACTS.— A. ii, 3276).—T. nagana absorbs both trypafłavin (I) (New Phytol., 1935, 34, 211—231).—Removal of and atebrin (II), but only (I) is trypanocidal. The ekternal sugar supplies from A . niger causes a decline fluoresćence intensity produced by (II) is esceedingly in the respiration rate to a Iow level (starvation rate). smali. Immobilisation by light is not obtained with Prolonged starvation does not permanently injure fluorescent dyes other than (I). The therapeutic the fungus, which recovers when sugar is again effect of (I) is not related to its photodynamic pro- supplied. Addition of citric, malic, glycollic, or perty. (II) has an affinity for malaria plasmodia, oxalic acid to starving cidtures does not increase the whilst (I) is absorbed by certain development forms C02 output, although the acid disappears rapidly, of the parasite. R. N. C. probably through reduction to OH-aldehyde. Superiority of silver nitrate over mercuric A. G. P. chloride for surface sterilisation in the isol- Flavour of shoyu. I. K. Shoji (Buli. Inst. ation of Ophiobolus graminis, Sacc. F. R. Phys. Chem. Res. Japan, 1935, 14, 872—877).— The aromatic substances in shoyu, a seasoning D a y i e s (Canad. J. Res., 1935, 13, C, 168— 173).— The organism was isolated more readily from plant materiał prepared by fermenting koji with Aspergillus t.issue treated with AgN03 than from th at sterilised oryzcc, consist of AcOH, BuCO,H, and hexoic acid, with HgCl,. A. G. P. amyl, hexyl, and higher alcohols, aldohydes, ketones, and phenolic compounds, the last-named being the Reversible heat-activation inducing germin- most important. A. L. ation and increased respiration in the ascospores Reaction of the medium and the activity of of Neurospora tełrasparma. D. R. Gon d a r d (J. Gen. Physiol., 1935, 19, 45—60).—Heat-activated ordinary and preformed felts of an Aspergillus. N. tetraśperma ascospores may be rendered dormant V. B o lcato (Annali Chim. Appl., 1935, 25, 423— again by preventing respiration; these dormant 432).—When an Aspergillus capable of forming citric spores may be caused to germinate by reheating. (I) and gluconic (II) acids is grown in sucrose solution Respiration inereases after activation and again at containing minerał nutrients, (I) is formed when the time of germination; these changes also occur the pii is <, and (II) when it is > , 3-4. Preformed in the reversible activation-. The heat-activation felts, especially if they have had prolonged contact takes place within the temp. limits 49—52°; heat- with the culture liąuid, form (I) at p a vals. much > killing begins at about 62°. CH,,PCO*NH2 inhibits 3-4. Formation of (II), however, reąuires limited germination without greatly affecting respiration; conditions, outside of which (I) is formed. T. H. P. respiration is diminished by CN'. F. A. A. Interconversion of aromatic and hydroarom- Role of vitamin-/{, in nitrogenous meta atic compounds by micro-organisms. II. bolism of Phycomyces. W. H. Schobfer (Arch. Quinic acid and inositol. K. Bernhauer and B. Sci. phys. nat., 1935, [v], 17, SuppL, 113— 115).— G o rlich (Biochem. Z., 1935, 280, 394— 395).— The beneficial effect of vitamin-JQ1 is limited by the B. gluconicum, B. xylinoides, and P. griseofulmim amount of asparagine present in the medium. convert ąuinic into protocatechuic acid. With these H. G. R. organisms and inositol the formation of aromatic Mould sterols. I. Formation of ster ols by substances could not be detected, the mol. being Aspergillus niger. K. Bernhauer and G. Pat- degraded to AcOH and lactic acid. P. W. C. z e lt (Biochem. Z., 1935, 280, 388—393).—The form Effect of glucose and minerał elements on the ation of sterols on solutions of varying su gar content grow tb of B. pyocyaneus. J. Regnier, R. David, proceeds in generał parallel with the formation of and J. M orchoisne (Compt. rend. Soc. Biol;, 1935, mycelium, and on the Ca salts of gluconic and quinic 120, 418—420).—Growth in peptone-H20 is acceler- acids is only half that on glucose. The mechanism ated by glucose (I) or a mixture of NaCl, KC1, MgS04, of sterol formation is discussed. P. W. C. and Na nucleate, or by both together. (I) inereases Optimal conditions for accumulation of citric NH3 production. R. N. C. acid and the mechanism of citric acid formation Effect of the constitution of peptones on the [by moulds]. T. Chrząszcz and E. P ey ro s (Bio- grow th of Ii. pyocyaneus. J. Rśgnier, R. Dayid, chom. Z., 1935, 280, 325—336).—For optimal yields and J. Morchoisne (Compt. rend. Soc. Biol., 1935, of citric acid (I), the choico of strain of .organism is 120, 415—418).—The nutrient vals. of different very important, the initial concn. of sugar should be peptones are of the same order, and are unaffected 20%, the salts should include 0-3% NH4N03, 0-1% by dialysis except for mucus peptono, where rate of K H 2PO.j, and 0-l%MgS04 and a tracę of FeCl3, the growth is reduced considerably. Growth is also temp. should be 28—30°, and the duration of ferment- slow with gelatin peptone. The type of enzyme ation 7—11 days. Zn salts inhibit formation of (I). used for preparing tho peptones appears to have no It is advantageous partly to neutralise the (I) formed influence on the nutrient val. R. N. C. with CaC03, but the reaction fluid must be always Effect of bongkrekic acid on carbohydrate acidic. The view of Emde (this vol., 407) th at (I) metabolism. A. G. van Veen and W. K. M ertens is formed from sugar by way of ąuinic acid cannot (Rec. trav. chim., 1935, 54, 373—380, and Geneesk. he correct sińce yields of (I) much > theoretically Tijds. Ned.-Indie, 1935, 75, 1059— 1071, 1116— possible by this mechanism have freąuently been obtained. P. W. C. 1127).—Bongkrekic acid, C11_ł3H 16_20O3, containing OH and three double linkings,is obtained together with Utilisation of organie acids by Aspergillus toxoflavin (I) (cf. A., 1934, 454, 537) by the action of niger. T. A. Bennet-Clark and C. J. La Touche bongkrek bacteria on coconut. It is optically BIOCHEMISTRY. 1541 active and stable in a fatty medium, but in a pure in 24 hr. by some strains of B. coli and by B. para- state is prono to oxidation and polymerisation. iypJiosus B, possibly having some influence. Alkaline solutions are moro stable. It is extremely R. N. C. toxie to men and apes (lethal dose < 0-5 mg.), being Oxidations by means of acetic acid bacteria. much more virulent than (I), whilst the polymeride III. Formation of a reducing saccharic acid is non-toxic and optically inaetivo. It causes the (aldehydogluconic acid) and 5-ketogluconic acid. glycogen content* of tlie liver to disappear rapidly; K. Bernhauer and K. Irrcang. IV. Formation the blood-sugar at first inereases rapidly, but firialty of 2-ketogluconic acid by Bact. gluconicum. V. falls to the lethal limit. Administration of glucose Comparative experiments on the preparation alone or in conjunction with insulin, or of orgotamine, of I-sorbose by different bacteria. K. B e rn has no beneficial effect. The lactic acid, ŃH2-acid, hauer and B. Gorlich (Biochem. Z., 1935, 280, inorg. P, and “ guanidine ” contents of the blood 3G0—366, 367—374, 375—378).—III. In tlie action aro inereased, but the NaCl content is unchanged. of B. gluconicum on Ca gluconate (I) smali amounts Bongkrek poisoning is very similar to that caused by of Ca 5-ketogluconato are formed together with a “ synthahn ” (decamethylenediguanidine), but is largo amount (50% of the gluconate) of a reducing much moro sovero. . S. C. very sol. Ca salt which gives an intonse naphtho- resorcinol-HCl test and the samo osazone as 5-keto Dehydrogenase of B. aertrycke S. and R. E. gluconic acid (II) and is probably an aldehydogluconic Soru (Compt. rend. Soc. Biol., 1935,120,232—235).— acid (III) (Z-guluronic acid). The same substance The velocity of decolorisation of methylene-bluo is obtained in smali amounts when B. xylinum by B. aertrycke S and R varies with tho H donator, ferments a solution of glucose in presence of CaC03 or and decreases in the order glucose, Na lactate, containing (I). asparagine, Na succinate, glycorol; glycino does not IV. B. gluconicum produces, in addition to (II) and causo decolorisation. In all cases decolorisation by (III), also 2-ketogluconic acid, isolated as tho K salt the S bacillus is more rapid than by the R bacillus. and identified by comparison of its Me ester and R. N C. quinoxaline dorivative with authentic specimens. Respiration of acetone bacteria and bacterial V. The yields of 1-sorbose isolatod from glucoso autolysates. O. E iirism ann (Z. IIyg., 1934, 116, with B. xylinum, B. xylinoides, and B. gluconicum 490— 494; Chem. Zentr., 1935, i, 1887).—The effect were 48, 53, and 64%, respectively, the materiał with of redox indicators on respiratory activity in lactate- the latter organism being almost pure. P. W. C. oxidising cultures of COMe2 bacteria is a function of its redox potential. The solubility of the dye, its Butyl- and acetone-fermentations. I. Inter- composition (no. of S03H groups), and the electro- mediate products of the butyl alcohol-acetone lyte content of the medium aro important factors. fermentation. K. Bernhauer and K. Kurschner The enzyme system indicated by Barron and Hastings (Biochem. Z., 1935, 280, 379—387).—Using fresh (A., 1933, 533) for Gonococcus can be demonstrated in active cultures of Clostridium butyricum, AcOH is other species. A. G. P. coiwerted almost exclusively into COMe2 (yield 97%). Tho organism during fermentation loses its physio- Respiratory system of bacteria. W. F rei logical character and then converts AcOH chiefly into (Zentr. Bakt. Par., 1935, I, 134, 26— 35).—Bacteria EtOH (yields COMe2 30%, EtOH 70%). The organ aro classified according to the presence of cytochrome, ism after transfers in a cereal mash with and without indophenol oxidase, peroxidases, catalases, and sp. CaC03 recovered its power to give large yields of respiratory pigments. The chemical mechanism of COMe2. In fermentation of starch, PrC02H is the respiration in the yarious elasses of organisms is precursor of BuOH. Added acetaldol and (3-hydroxy- discussed. A. G. P. butyric acid are not converted into PrCOaH, but added Formation and structure of cellulose mem- crotonic acid is converted partły into BuOH and partly branes. W. K. Farr (Paper Trade J., 1935, 101; into AcOH and COMe2. P. W. C. T.A.P.P.I. Sect., 183—186).—The cellulose (I) mem Formation of hydrogen from glucose and brano present in cultures of Acetobacter xylinus is a formie acid by so-called “ resting " B . coli. II. part of the organism itself, and has not been syn- A. Tasman (Biochem. J., 1935, 29, 2446—2457; thosised from the culture medium by enzymes of cf. this vol., 1028).—The fermentation of glucose bacterial origin. Each bacterium also possesses a by both growing and resting B. coli takes place mainly coating of non-(I) materiał which serves as its contact by way of HC02H, but partly by way of AcC02H : surface with the nutrient solution. The presence of in only a few cases (different bacterial strains) is the this materiał, largely pectic in naturę, may be detected latter the chief reaction. F. A. A. by solubility tests, and located by staining with Determination of volatile acids in bacterial Ru-red. It constitutes only about 2% of the mem cultures. L. A. Allen and J. Harrison (Bio brano. In the filamentous alga Spirogyra, the (I) chem. J., 1935, 29, 2471—2476).—Volatile acids are units are definitely oriented with respect to the surface determined in bacterial cultures in the presence of of tho protoplasm. H. A. H. lactic acid and C02 by acidification and steam-distill- Fate of vitamin-C in the digestive tract. I. ation at const. vol. and each 100-ml. fraction is titrated Action of intestinal bacteria on vitamin-C. W. with aq. Ba(OH)2 until a const. titre is obtained. Stepp and H. S ch ro d e r (Klin. Woch., 1935, 14, The neutralised acids are acidified and tho process 147—148).—The effect of common B. coli and intest is repeated, the total titre in the latter case represent- inal bacteria on ascorbic acid varies. It is destroyed ing yolatile acids. H. D. 1542 BRITISH CHEMICAL ABSTRACTS.----A. Soluble dry filter for bacterial count in air. Accelerating effect of manganous ions on P. O e ste rle (Arcli. Hyg. Bakt., 1934, 113, 137— phage action. A. P. K ru e g e r and N. S. W est 142; Chem. Zentr., 1935, i, 2052).—A 2:1:1 mixture (J. Gen. Physiol., 1935, 19, 75—86).—Phage action of NaCl, cryst. MgS04, and Na2S04,10H20 is dried on Staphylococcus aureus is accelerated by the pre at 100—150° and sterilised a t 1S0°. J. S. A. sence of Mn". Phage formation is not inereased or Antigenic fixatives of tubercle bacilli. II. bacterial growth affected, but the Mn" lowers the Purification of the lipin fraction with hapten lytic threshold; lysis occurs when the phage/bacterium activity extracted from heat-killed bacilli. M. A. ratio is about 12 instead of 54. The phage distribution Machebceuf and A. Bónnefoi. III. Separation is altered in growing phage-bacterium mixtures, of the hapten-active phosphatides from the the extra-cellular phage concn. being 4 times that in nitrogenous impurities. M. A. M achebceuf, G. the absence of Mn". F. A. A. Lźvy, and M. F a u re (Buli. Soc. Chim. biol., 1935, Action of mercury-lamp radiations on various 17, 1201—1209, 1210—1234; cf. this vol., 256).— bacteriophages. C. Levaditi and J. Voet (Compt. II. Fractional pptn. with COMe2 of a CHC13 solution rond. Soc. Biol., 1935,120, 385—387).—The bacterio of the COMe2-insol. fraction of the lipins of the tubercle phages for B. coli, Staph. K, and the Ć16 bactoriophage bacillus does not lead to any concn. of the hapten are eąually sensitiye to Hg-lamp radiations, all being actmty. Fractional pptn. with MeOH, although destroyed by exposure for 1 hr. , R. N. C. somewhat more effective, shows that the difference Cultivation of human influenza virus in an in solubility between active and inactive substances is artificial medium. T. Francis, jun., and T. P. very smali and yields in tho least sol. fraction a M a g iłl (Science, 1935, 82, 353—354).—Tho culture product of inereased activity. virus has been readily transmitted to mice and ferrets. III. Repeated fractional pptn. of the C0Me2- Its capacity to infect experimental animals is inhibited insol. lipins with MeOH yields a product (I) of high by sp. anti-influenza immune serum. After repeated hapten activity sparingly sol. in MeOH and con- cultivation in vitro, certain alterations in tho immuno- taining P 3-36%, N 0-13%, 3-3% of reducing sugars logical characteristics of the yirus occur. L. S. T. after hydrolysis, and no unsaponifiable mattor. (I), although very active in the fixation of complement, Sensitivity of the influenza bacillus against has no pptn. activity. It is very sol. in H20, to which vitamin-C and quinol. O. Grootten and N. it passes from E t20 solutions, the ratę being dependent B ezssonoff (Compt. rend. Soc. Biol., 1935, 120, on the p B of the aq. layer. A. L. 121—123).—The development of the Bordet-Gengou Relationship between electrophoretic migra- bacillus (B. pertwssis) is arrested and the bacillus tion velocities, virulence, and types of diphtheria itself killed by reductone, ascorbic acid (I), and hydr- and diphtheria-like bacilli. K. P. Dozois and oxybenzenes. Generally, the bactericidal power oc K. F. R auss (Amer. J . Publ. Health, 1935, 2 5 ,1099— the reducing power, except in the case of ąuinol (II), 1102).—The diphtheroid strains show the max., which is a more effective bactericide than pyrogallol. avirulent strains the min., and virulent strains an Eh of the cultures falls approx. 170 mv. on addition intormediate velocity. The demarcation between the of (I), but only 5 mv. on addition of (II). R. N. C. zones is not sharp and determinations sliow an error Action of medicaments in vitro . E. Singer of 14% compared with virulence tests on guinea-pigs. and V. F isc h l (Z. Hyg. Infektionskrankh., 1934, H. G. R. 116, 356—360; Chem. Zentr., 1934, ii, 3276).— Variation in the buffering power of the culture Atoxyl (I) associated with liver-pulp is adsorbed more fluid during bacteriolysis. F. C h o d at and M. readily by Spiróchcetus recurrens, B. pro tez, red Raad (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., corpuscles, collodion, and animal C than when un- 109— 112).—During the true period of lysis there is treated with liver. Addition of glutathione (II) a diminution in buffering power. H. G. R. and lentils inerease As absorption in mtro by trypan- Action of respiratory and cellular ferment- osomes and spirochsetes. Liver or lentil pulp also ation inhibitors on transmissible bacterial lysis. inereases Au absorption by spirochsetes. Glycogen, F. W y s s -Ch o d a t (Arch. Sci. phys. nat., 1935, [v], cystine, SH,CH2,C02H, and Na thioglueose are 17, Suppl., 156— 160).—Lysis is inhibited by concns. inactive. Ascorbic acid destroys trypanosomes in of CH2I-CO.,H which do not affect bacterial growth. vitro, the effect being inereased by (I), but it attacks K C N , CO, or phenylurethane has no effect on lysis. spirochsetes onlyin combination with the Au-CS(NH2)2 H. G. compound. (I) solution becomes trypanocidal on Peroxidase and transmissible bacterial lysis. addition of (II). " R. N. C. F. W yss-C hodat (Arch. Sci. phys. nat., 1935, [v], Chemotherapy of bacterial infections. G. 17, 164—166).—Thermolabile peroxidase of the Domagk (Angew. Chem., 1935, 48, 657—667).— culture is not removed by ultra-filtration (cf. following The application of chemotherapeutic substances in abstract), but is rendered thermostable. H. G. R. infections due to various types of pathogenic bacteria Size of phage particles. Preparation of a is discussed. F. O. H. purified lytic principle. F. Wyss-Chodat (Arch. Effect of adrenaline on the utilisation of Sci. phys. nat., 1935, [v], 17, 161— 164).—Using a fructose introduced at constant velocity into the Seitz filter No. 6, the lytic activity can be filtered out circulation at the three levels of assimilation. and eluted with physiological salinę. It is not affected M. Wierzuchowski and H. Fiszel (Compt. rend. by washing with C6H6 or Et,O on the filter. Soc. Biol., 1935,120, 377—380; cf. this vol., 1017).— H. G. R. The blood-fructose (I) level reached on continuous BIOCHEMISTRY. 1543 injection of (I) into normal dogs 011 a protein diet is > Biochem. Inst., 1930, 4, 107—114).—Administration the carbohydrate diet level, but < the fasting level; of 5—20 clinical units of insulin (I) to rabbits results adrenaline (II) raises the three levels. Urinary (I) after 15 min. in a rise in the hexosemonophosphoric at the threo levels increases in the same order as acid (H) and a fali in the creatinephosphoric acid above, and is also further increased by (II); 1 mg. (III) and H4P207 (IV) in muscle. In pigeons, of (II) lowers (I) assimilation by 6-03 mg. at the muscle-(II) is unalterod but -(III) and -(IV) are carbohydrate, 10-5 mg. at the protein, and 23-18 mg. decreased after administration of (I). W. O. K. at the fasting level. Hence (II) determines tlie glyco- Influence of insulin on the production of genolysis of glycogen (III) formed from injected sugars optically active substances in muscle-glucose- sucli as (I), as wcTl as that of the body-(III). salt mixtures. P. Normark and E. Sayron (Ber. R. N. C. Ukrain. Biochem. Inst., 1930, 4, 31—42).—Mixtures Inactivation of adrenaline by extracts of of minced muscle, glucose, and NaCl in phosphate organs. J. T. Rico and A. M. Baptista (Compt. buffer (pn 7-3) with and without insulin (I) were rend. Soc. Biol., 1935, 120, 42—45).—Adrenaline is ineubated and then dialysed through a collodion inactivated in vivo by extracts of animal organs to membrane against isotonic aq. NaCl. The a and yarying extents according to the organ concerned and reducing power of the dialysate wero tho same whother the species. The max. efFects are obtained with (I) was present or absent. W. O. K. extracts of guinea-pig liver and kidney and dog spleen, whilst extracts of muscular tissue are always inactive. Inactivation of insulin. Effects of certain R. N. C. metal derivatives and of thiol compounds. E. D. Effect of cortin on adrenaline secretion. E. Schock, H. Jensen, and L. Hellerman (J. Biol. Zunz and J. la Barre (Compt. rend. Soc. Biol., Chem., 1935, 111, 553—559).—Insulin (I) is inactiy- 1935, 120, 248—250).—Injection of cortin in the dog ated by benzoąuinono (II) in 0-067J/-Na2HP04 (but induces hyporglycacmia by augmenting adrenaline not in 0-01AT-HC1) and by tliiolsalicylate. Cu20, secretion, the increased secretion appearing 20—40 phenylmercuric oxide, thiolglyoxaline, thiolhistidine, min. after injection and persisting for 60—90 min. ergothionine, and ascorbic acid do not inactivate (I). R. N. C. (I), inactivated by (II), suffers a decrease in NH2- Chemical basis of the panoptic reaction groups. H. D. applied to the detection of adrenaline in the Parathyroid hormone and vitamin-/l. F. H o ff tissu es. T. Pawlikowski and T. Slebodzinski and B. zu J e d d e lo h (Z. ges. exp. Med., 1934, 95, (Compt. rend. Soc. Biol., 1935, 120, 465—466).— 67—75; Chem. Zentr., 1935, i, 2036).—Parathyroid Adrenaline (I) reduces K2Cr20 7 in vitro, forming hormone injected into rats in large doses produces Ca Cr02, which oxidises methylene-blue to a green deposition in the heart muscles and subcutaneous compound. These reactions are responsiblo for the connective tissue as occurs in human ostitis fibrosa metachromatic green coloration of the cells of the generahsata. Excess of vitamhwl (I) (“ Vogan ”) in medulla in the panoptic reaction. R. N. C. growing rats induces skeletal decalcification and Absorption and fate of insulin following per- spontaneous fracture, but no Ca metastasis or hyper- cutaneous application. I. S. H erm an n and H. calcaemia. Symptoms follow resembling those in Kassowitz. II. S. Hermann (Arch. exp. Path. (I) deficiency. Tho obseryed fat deposition in the Pharm ., 1935, 179, 524—528, 529—536).—I. Applic organs is considered to be due to tho fat present in ation of pastę containing insulin (I) (5 units) to the the “ Vogan ” preps. ratlier than to (I). R. N. C. washed (light petroleum) skin of rabbits reduces the Relation of the thyrotropic hormone to the blood-sugar from approx. 90 to 14—30 mg. per sugar and ketone content of the blood. F. 100 c.c., producing conyulśions in 30% of the animals. Silberstein and F. Gottdenker (Klin. Woch., The effect is partly or wholly inhibited by addition of 1934, 13, 1434; Chem. Zentr., 1934, ii, 3269).— cholesterol to the pastę and is dependent on the site Injection of large ąuantities of thyrotropic hormone of application, being greatest above compact red (I) in normal cats causes a considerable increase in muscle. The hypoglycamiic actm ty of extracts from blood-ketones and -sugar (II). In thyroidectomised dog’s skin treated with (I) paste indicates that (I) animals (II) only is raised. Repeated injections of permeates both horizontally and vertically. (I) in both normal and thyroidectomised animals II. Presence of lipin-sol. acids (e.g., AcOH) inhibits cause a weaker (II) reaction. R. N. C. the action of (I) paste. For max. absorption of (I), Basic amino-acids yielded by thyroglobulin. the skin m ust be freed as far as possible from lipins and A. White and W. G. Gordon (Proc. Soc. Exp. an alkalisation of the skin induced (e.g., by m eat Biol. Med., 1934, 32, 354—357).— Thyroglobulin diets). The results are discussed with reference to contains 0-62% of histidine, 8-22% of arginine, lymph transport and celi permeability. F. O. H. and 1-93% of lysine. R. N. C. Action óf insulin in fasting pigeons. D. Significance of thyroid gland in antithyro- G igante (Atti R. Accad. Lincei, 1935, [vi]| 21, 763— tropic-protective action of the blood. H. E ite l 768).—Tho resistance of the pigeon to insulin (a and A. Loeser (Arch. exp. Path. Pharm., 1935, single dose) shows not so much gradual diminution 1 7 9 ,440— 447).—Stimulation of the thyroid gland by as fasting is prolonged, as a sudden fali when the crit. thyrotropic hormone from anterior pituitary gland stage of inanition is reached. T. H. P. increases the protectiye action of the blood for Influence of insulin on the phosphorus ex- antithyrotropie aetivity (this vol., 1171). Hence the change in muscle. S. F. E p ste in (Ber. Ukrain. thyroid is related to the formation of the protectiye 1544 BRITISH CHEMICAL ABSTRACTS.— A. prinoiple, a relation confirmed by diminution in obtained suggest that the effect of the yarious hor- proteetivo action on thyroidectomy and return to mones may depend on the presence of certain NH2- normal levels on subseąuent administration of thyroid acids, which form part of one or more polypeptide hormone. Thus the inerease in protective action is or protein mols. L. S. T. not a sp. result of anterior pituitary secretion, but Thyrotropic activity of pituitary gland in man. follows increased thyroid activity. F. O. H. R. M uller, H. Eitel, and A. Loeser (Arch. exp. Thyroid and ovary. Experimental basis for Path. Pharm., 1935, 179, 427—439).—The thyro the di-iodotyrosine treatment of climacteric tropic hormone content (A., 1934, 1410) of pituitary disturbance. A. L o ese r (Klin. Woch., 1935, 14, gland in men (74 post-mortem cases) approximates 4—6).—Remoyal of the ovaries in female guinea-pigs to that of animals. The leyel, which is independent causes a hyperactivity of the thyroid, due to increased of age and sex, yaries considerably, but the high secretion of the thyrotropic hormone of the anterior content in sufferers from tuberculosis and other pituitary. The enhanced secretion is suppressed infectious diseases is noteworthy. F. O. H. by oral administration of di-iodotyrosine. R. N. C. Testis-stimulating potency of frozen turkey Strengthening of the anti-thyroid protective pituitaries injected subcutaneously into young power of blood by the thyrotropic hormone of małe chicks. T. C. Byerly, W. H. Burrows, and the pituitary. H. Eitel and A. Loeser (Klin. H. W. T itu s (Poultry Sci., 1935, 14, 189— 190).— W och., 1934, 13, 1677— 1678).—If guinea-pigs are Cockerel pituitaries had higher gonad-stimulating injected with sheep serum and thyrotropic substance potency than did those of turkeys. A. G. P. (I) simultaneously, the two counterbalance each other; Gonad-stimulating potency of individual this is a method of assay of the anti-thyrotropic pituitaries. R. H. Jaap (Poultry Sci., 1935, 14, substanco (II) of serum. If serum donors are pre- 237—246).—The stimulatory effect of pituitary was yiously treated with (I), the anti-thyroid potency of increased by injection of blood-sera in ducks but not their blood is increased; it is not increased by pre- in chickens. A. G. P. vious treatment with thyroxino, and it is not high Hormone content of the pituitary of the blue in serum from cases of Graves’ disease. (II) is present w hale (Bnlaenoptera sibbaldi). J. Valso (Klin. in serum, and to a smaller extent in corpuscles. Woch., 1934, 13, 1819—1S20).—Neither prolan nor G. H. F. intermedin is found in the posterior lobe. R. N. C. Action of anterior pituitary fractions on the blood-sugar. K. J. Anselmino and F. Hoffmann Corpeus luteum hormone.—See this vol., 1195. (Arch. exp. Path. Pharm., 1935, 179, 273—285).— Dependence of the function of the corpus Single injections of total extracts of anterior pituitary luteum on the ovarian follicles and the place of lobe induce an inerease in blood-sugar in dogs. origin of the hormone in the ovary. A. W est- Repeated administration, howeyer, produces a re- mann (Arch. Gynakol., 1934, 158, 476—504; Chem. fractory period during which the level may even Zentr., 1935, i, 1726).—The lutein celi formed in the diminish. Anti-insulin preps. of Lucke (A., 1933, rabbifs oyary from the granulosa of a ripe follicle 643) have an indefinite hyperglycEemic action which by cauterisation of the ovum and of the follicle is is probably due to traces of posterior lobe hormone. abnormal in that it secretes no corpus luteum hormone Extracts of tho anterior lobe contain a hypoglycamiic (I). Destruction of the follicle also hinders the growth (pancreatropic) factor which markedly stimulates of an already existing corpus luteum, but growth is the islets of Langerhans. Ultra filtrates of the total normal if some follicles are left or follicular hormone extract at 5-4 have a hypoglycaemic action; heating (II) is administered. Hence (II) is necessary for tho at 100° for 15 min. to destroy the pancreatropic function of the corpus luteum to be fulfilled, and is hormone reveals, howeyer, the presence of the hyper- possibly used by the granulosa celi for the formation glycsemic factor. F. O. H. of (I). R. N. C. Antuitrin-S and blood-elements. S. H. G eist Extraction of folliculin and an associated and F. Spielman (Proc. Soc. Exp. Biol. Med., 1934, pharmacological problem. K. Gad-Andersen 32, 353—354).—Injections of arifcuitrin-iS do not and E. Jarlov (Acta med. Scand., 1934,84, 233—240; affect the formed blood-elements. R. N. C. Chem. Zentr., 1935, i, 1889).—The actiyities of com- mercial folliculin preps. when giyen subcutaneously Experimental dissociation of the effects and orally are compared. Preps. obtained without of anterior pituitary glands of various species the use of Et20 show good activity orally. R. N. C. on thyroid and ovary. L. Loeb, W. C. Ander son, J. Saxton, S. J. Hayward, and A. A. Doses of folliculin necessary to produce inter- Kippen (Science, 1935, 82, 331—333).—The changes sexuals and the limiting stage of interyention. induced in the ovarv and the thyroid gland of the E. W olff and A. Ginglinger (Compt. rend. Soc. immature guinea-pig by substances present in the Biol., 1935, 120, 114— 116).—The limiting stage of anterior pituitary glands of yarious species are de- ineubation of the hen’s egg, beyond which it is no scribed. Experimental changes in the preponderance longer possible to transform małe embryos into inter- of these yarious effects have been produced and the sexuals by injections of folliculin, is approx. tlie action of the gland of one species has been made like 8th day. The threshold dose for feminisation is that of another in its effect on the guinea-pig. This has approx. 25 units. R. N. C. been accomplished by tho use of H20, aq. NaCl, Gonadotropic substances in mare's serum. EtOH, Et20, glycerol, and dii. aq. CH20. The data H. H. Cole and G. H. H art (Proc. Soc. Exp. Biol. BIOCHEMISTRY. 1545 Med., 1934, 32, 370—373).—Pregnant and non- (II) eaused a partial recovery of the atrophied uterus pregnant mare’s serum eontains a prolan-like sub and vagina, the effect being less with (I). (III) eaused stance th at stimulates the gonads when. combined with a return towards the normal wt. of these organs and tho pituitary synorgist. Pregnancy serum eontains (III) together with (I) or (II) showed a co-operative a second substance that is active per se. R. N. C. recovery effect. It is suggested that tho małe hor Disappearance of prolan from the blood of mones, being natura! stimulants, may be used for the nephrectom ised fem ale rabbit. A. Lip- treating suitable human diseases. J. N. A. sciiutz, A. Fuente-A lba, and T. Vxvaldi (Compt. Vitamin-yl content of eggs as related to rate rend. Soc. Biol., 1935,1 20,323—326).—Prolan injected of production. M. C. K oenig, M. M. K ram er, and intravenously is removed from the blood less L. F. P ay n e (Poultry Sci., 1935, 14, 178— 182).— rapidly in tho nephrectomised than in the normal Eggs from low-producing pullets had higher vitainin-M rabbit, suggesting that under normal conditions it is contents than those from high-producing pullets not all excreted in the urine, but partly destroyed when nearing the end of the first year of production. in the organs. R. N. C. After only 4 months’ production no difference was Assay of the gonadotropic hormone of preg apparent, tho -A val. being intermediate between nancy urine on małe rats. V. K orenchevsky, those of the two groups after 1 year. A. G. P. M. D ennison, and S. L. Simpson (Biochem. J., 1935, Growth-promoting effect of flavin on the chick 29, 2522—2533).—The method is described. There S. Lepkovsky and T. H. Ju k e s (Science, 1935, is a regular relation between the dose of gonadotropic 82, 326).—Liver extraet eontains two H20-sol. hormone (I) and the effect on tho prostatę (II), factors which promote growth in chicks. The first seminal vesicles (III), and penis. It is suggested that promotes growth when added to a heated diet of ono małe rat unit (Ml. R.U.) be the min. total dose, yellow maize ineal, wheat middlings, and commercial injected in 6 eąual portions on 3 days, which on the casein, supplemented with salts and cod-liver oil, 5th day produces an increase of 40% in the actual and is the factor of Elvehjem and Koehn (this vol., wt. of (II) and about 70% in the wt. of (III). 1 669). The second factor is flavin, which has no effect Ml.R.U. was eąual to about 5 F.R.U. The qual. when added to this diet, but promotes growth when effect of (I) on the sexual organs is very similar to added to the unheated diet. Both factors are distinct that of androsteronediol, but different from that of from Yitamin-jBj. L. S. T. androsterone. J. N. A. Effect of heavy administration of viosterol Testicular hormone.—See this vol., 1500. on the metabolism of the rat. C. I. Reed (Proc. Synthetic preparation of testosterone.—See Soc. Exp. Biol. Med., 1934, 32, 274—277).—Smali this vol., 1371. quantities of viosterol increase the metabolic rate; larger (toxic) doses produce a transient elevation of Influencing of the secondary sex character- the metabolic rate followed by a decline below the istics of the carp (Rhodeus am arus) by hormones original level. R. N. C. and other means. W. W under (Med. Klin., 1934, 30, 874—876; Chem. Zentr., 1934, ii, 3267).—Sub- Carotene and vitamin-/l metabolism. H. cutaneous injection of testicle extract in normal W en d t (Klin. Woch., 1935, 14, 9—14; Chem. małe carp produces mating colours, which persist for Zentr., 1935, i, 1730).—Prolonged feeding of carotene a period dependent on tho amount of hormone and and vitamin-^4 inereased the proportion of these in the time of the year. Adrenalino and yohimbino (I) the serum to a max. of 58 Lovibond yellow units and also exhibit this actmty, and prolan at spawning 4-5 blue units, respectively. Large dosages of -A time, whilst folliculin (II), 0-9% NaCl, trichlorobutyl eaused hyperliptemia and hyperli pinami a in rabbits alcohol, and acetylcholine are inactive. The action but not in dogs. Diseases affecting fat resorption of (II) on the oviduct of the female carp is sp., 0-9% eaused Iow vals. for carotene and -A. Neither NaCl, tliyroid, and anterior pituitary hormones was present in cases of goitre, but administration being inactive. R. N. C. of I effected a return toward normal levels. Highest vals. occurred in diabetes. A. G. P. Prolonged treatment of małe and female rats with androsterone and its derivatives, alone or Carotenoids and vitamin-/l in cow's blood- together with oestrone. V. K o re n ch ey sk y , M. serum . A. E. G illam and M. S. E. R id i (Biochem. D ennison, and S. L. Simpson (Biochem. J., 1935, J., 1935, 29, 2465—2468).—The average contents 29, 2534— 2552).—Prolonged treatment of castrated of carotene, determined spectrophotometrically, in rats with androsterone (I), androsteronediol (II), eow’s and bull’s blood sera were, respectively, 0-40 and and their H20-sol. esters not only restored the sexual 0-08 mg. per 100 ml. in summer and 1-11 and 0-42 in organs to or towards the normal condition, but also Winter. The presence of yitamin-^l, lutein, and inereased the wts. of adrenals, thymus, liver, kidneys, occasionally cryptoxanthine in the serum was estab- and heart. (II) had all the properties of a true małe lished. H. D. hormone, but very large doses of (I) and H.,0-sol. Physiologically active erystalline esters of (II) had a depressing effect on the gain in body-wt., v ita m in -/l. S. Ham ano (Sci. Paper3 Inst. Phys. deposition of fat, and stimulation of the liver. (I) Chem. Res. Tokyo, 1935, 28, 69—73).—Vi tarnin-,4 and oestrone (III) had a co-operative effect on the concentrate (Biosterin) with (3-C10H7*COCl in C5H3N prostatę and seminal vesicles, but an antagonistic gave the physiologically active cryst. $-naphthoate, action on the adrenals. (I) and (II) have no rejuven- C31H3f)0 2, m.p. 76°, which readily promoted the growth ating effect. With ovariectomised rats large doses of of albino rats. and cured xerophthalmia. On hydro- 1546 BBITISH CHEMICAL ABSTBACTS.----A. lysis, vi tarnin-/!, O20H30O, was obtained. Similarly Vitamin-C in the medlar and alkekengi. E. an acfcivo ester, C35H360 2, m.p. 124°, was obtained Caseeio (Ind. ital. conserve ahment., 1934, 9, 190— from anthraquinone-2-carboxylic acid. J. N. A. 192; Chem Zentr., 1934, ii, 3272).—The juice of the Preparation of a potent vitamin-/l concentrate. ripe alkekengi contains twice as much vitamin-<7 H. N. Holmes, H. Cassidy, R. S. Manly, and as lemon-juice. The ripe medlar contains relatively E. R. H a e tz le b (J. Amer. Chem. Soc., 1935, 57, no vitamin. R. N. C. 1990— 1993).—Saponified halibut-liver oil (freed from Relation between the vitamin-C contents of unsaponifiable matter and most of the cholesterol) in various vegetable tissues and the presence or C5H12, when cooled in EtOH-solid C02 and filterod absence of chlorophyll. L. Randoin, A. Giboud, through solid C02 on sintored glass, gives a concentrate and C. P. Le blo n d (Compt. rend. Soc. Biol., 1935, with a blue val. 45,000—60,000. Filtration through 120, 297—300).—Tho chemical and biological vita- C and MgO gives a concentrate with a blue val. min-C vals. of tho green and white parts of the leaf 90,000—140,000. The blue val. is decreased by tissue show a elear relation to their chlorophyll about 10% if the liumidity of tho air around the contents. R. N. C. tintometer rises from 35 to 60%. R. S. C. Normal content of ascorbic acid in the organ Crystalline yitarnin-I^.—See this vol., 1510. ism . A. Gieoud, C. P. Leblond, R. Ratsima- manga, and M. Rabinowicz (Compt. rend. Soc. Biol., Relative vitamin-JJ2 contents of dried whey 1935, 120, 414—415).—The mean normal ascorbic and dried skim-milk" V. Heim an (Poultry Sci., acid contents of tho adrenals, liver, and museles of 1935, 14, 137— 146).—A rolationship between the animals are given. In animals in which scurvy cannot vitamin-J52 content of the diet and the growth rate be produced, the vals. on a yitamin-C-deficient diet of chicken is established. The -B2 ratio of dried are slightly less. R. N. C. skim-milk : dried whey is 1 : 1-5. Egg production is not appreeiably affected by the amount of -B2 supplied. Fixation and elimination of ascorbic acid. A. The hatchability of eggs from pullets receiving Gieoud, R. Chuć, R. Ratsimamanga, and C. P. suboptimal amounts of dried whey or skim-milk is L eblond (Compt. rend. Soc. Biol., 1935, 120, 330— slightly higher in the case of tlie former feed. The 333).—Ascorbic acid (I) injected intravenously in -B2 content of eggs and the greenish-yellow pigment of guinea-pigs is rapidly oxidised to dehydroascorbic the whites are directly related to tho -B2c ontent of acid and is stored in the adrenals, lirer, and kidney the diet. Dried egg whites are richer in -B2 than aro (greatest aceumulation). In all organs (I) reaches a dried yolks. The lactochrome content of dried max. and then falls. Kidney-(I) is excreted in the whey is > that of dried skim-milk and the ąuantity urine, excretion beginning immediately (I) rises. present is correlated with growth response and Some (I) is fixed by the liver. R. N. C. hatchability. A. G. P. Ascorbic acid (vitamin-C) and the blood- Suggested relation between cystine and aqueous humour barrier. H. Goldmann and W. vitamin-B2. F. T. G. P e u n ty and M. H. Roscoe B uschke (Klin. Woch., 1935, 14, 239).—Inerease (Biochem. J., 1935, 29, 2491—2497).—There is no of the permeability of the blood-aq. humour barrier relation between cystine (I) and the vitamin-i?2 by subconjunctival injection of NaCl lowers the ascor complex in the nutrition of the rat, and a deficiency bic acid (I) content of the aq. humour; it becomes of vitamin--B2 together with a deficiency of (I) such normal again with the permeability. Adrenaline, that growth was affected had no effect on the incidence which prevents the inerease of permeability, also of dormatitis. The (I) intake of rats had no effect brings the (I) of the aq. humour to normal if injected on tho glutathione content of the tissues. Some of the after NaCl; it has no effect when injected alone. purified caseinogen used in basal diets for vitamin work Injection of (I) into the blood-stream to one eye in is deficient in (I). J. N. A. ereases (I) in the anterior chamber of that eye only. Vitamin-jB and -C in preserved spinach and (I) probably diffuses from the blood into tho aq. acid preserved foods. S. V. Fomin and P. T. humour in the reversibly-oxidised form, and is then reduced by the cryst. lens. R. C. N. M a k a e o v a (Ukrain. Biochem. J., 1935, 8, No. 1, 191—202).—Vitamin-i? is destroyed; -O is almost Comparison of the antirachitic potency of cod- intact. E. P. liver oil and irradiated ergosterol on a curative Determination of ascorbic acid.—See this vol., and preventive basis. W. C. Russell, M. W. 1483. Tayloe, and D. E. Wilcox (J. Nutrition, 1935, 9 ,569—574).—The two sources of vitamin-Z) produced Electrometric determination of vitamin-C similar curative responses when fed to white rats on (ascorbic acid). J. di G lebia (Mezog.-Kutat., 1934, an equiv. preventive basis. With chickens, cod-liver 7, 226—235; Chem. Zentr., 1935, i, 1409).—Pure oil was superior. A. G. P. ascorbic acid (I) gives identical results when deter- mined by I or 2 : 6-dichlorophenol-indophenol (II). Antirachitic effect of ultra-violet radiation (I) is decomposed in feebly acid or neutral solution, transmitted by a smoky atmosphere. H. M. evon during the short time lag, but the decomp. is B a e b e tt (J. Ind. Hyg., 1935, 17, 199—216).— negligible atj>H >4. E h of (I) is strictly dependent on Development of rickets in rats on a rachitic diet is Pu, the change for 1 p n unit being 58 m v.; .Engci at not prevented by irradiation through smoke similar p n 0 is -fO-3295 volt. The I titration vals. in fruits to that of an average urban atm. H. G. R. and vegetables are > the (II) titration vals., the Crystalline derivatives of vitamin-JS. R. deviations occasionally being > 100%. R. N. C. K t m m (Sci. Papers Inst. Phys. Chem. Res. Tokyo, BIOCHEMISTRY. 1547 1935, 28, 74—76).—Vitamin-.E concontrate from rice Physiological gradients in citrus fruits. embryo oil when treated with (3-C10H/COCl in A. R. C. Haas and L. J. Klotz (Hilgardia, 1935, C5H5N gave a eryst. fi-naphthoate, C40H 54O2, m.p. 9, No. 3, 181—217).—Variations in the end-to-end 156°, from which the free vitamin-® is cale. to be distribution of N, sugar, oil, minerał matter, and C20H48O. On regeneration it liad a high activity. carotenoid substances of lomon, orange, and grape Three other eryst. substances, C43H 60O2, m.p. 158°, fruit are recorded. K manuring increased the K C40H 54O2, m.p. 134°, and an uninvestigated fraction, content of Valencia oranges. Deficiency of K is m.p. 168°, were obtained. An amorphous ester of associated with brcakdown of tlie peel. Fumigation anthraquinone-2-carboxylic acid was prepared. with HCN increased the permeability of the peel, J. N. A. notably at the calyx end. A. G. P. Vitamin-J5 content of eggs as related to the Inhibition of photosynthesis in Chlorella diet of the hen and to hatchability. G. L. ptjrenoidosa by the iodoacetyl radical. H. L. B arnum (J. Nutrition, 1935, 9, 621—635).—Yitamin- Koiin (J. Gen. Physiol., 1935, 19, 23—34).— E may be a limiting factor in the hatchability of eggs CH2I-CO-NH2 (I) inhibits photosynthesis in C. from hens on certain diets. Deficiency of -E is associ- pyrenoidosa, interfering with the dark (Blackman) ated with first-weok embryonic mortality, and may reaction. This action, which is slow owing to the be reduced by supplying -E in poultry diet. slow penetration of the radical, is also shown bv CH2I-C02H, but not by N H 2Ac. Concns. of (I) Pituitary. IV. Effect óf vitamin-JE deficiency which inhibit photosynthesis (about 10-4M) increase on the female albino rat. S. I. Stein (J. Nutrition, respiration; smaller concns. (> 10"5Jf) may increase 1935, 9, 611—619).—No difference in tlie wt.'of the the rate of photosynthesis by reaeting with the photo- pituitary, differential counts of cells in the anterior chemical complex, and higher concns. (< 10~3il/) lobe, or histology was observed between storile inhibit respiration. F. A. A. (vitamin-i?-deficicnt) and pregnant rats cured of the deficiency. A. G. P. Effect of blue-violet rays on photosynthesis [in plants]. R. H. D astur and R. J. Mehta (Ann. Salt-tolerance of Ruppia maritima in lakes Bot., 1935, 49, 809—821).—Rates of photosynthesis of high magnesium sulphate content. E. M cKay increase with the intensity of blue-violet rays from (Plant Physiol., 1935, 10, 425— 446).—Periodic ex- yarious sources. Photosynthetic activity is greatest aminations are recorded of the p H, d, and osmotic in white light, intermediate in red, and feeble in the pressure of the lalce-H20, and the sap composition blue-violet region. In white light, assimilation is of the plants growing tliereon. Ruppia tolerates related not only to the total intensity, but also to the high [Mg"] and [S04"], its distribution being limited distribution of radiations of different A. G. P. by the Na2S04 concn. of the H20. The time of flowering and seed development is influenced by the Wound healing in Tradescantia flumińetisis, salt concn. of the lake. The p n of the lake-H20 is V ell. R. B lo ch (Ann. Bot., 1935, 49, 651— 670).— not a factor governing plant distribution. A. G. P. Healing processes in wounded stems involve celi division and elongation, thickening of walls, formation Physiological role of asparagine and related of suberin lamellse, and the impregnation of walls with substances in nitrogen metabolism of plants. lignin and fatty matter. Disturbed metabolism A. E. Murneek (Plant Physiol., 1935, 10, 447— leads to increased protein and decreased carbohydrate 464).—A discussion of current views. A. G. P. contents of adjacent areas of stems, and the deposition of tetragonal CaC204,3H20 (distinct from the normal Stock-scion chemistry and the fruiting re- raphides) in pith parenchyma. A. G. P. lationships in apple trees. H. L. Colby (Plant Physiol., 1935, 10, 483—498).—The translocation of Non-dependence of carbon dioxide assimil nutrients and the distribution of reserves between ation of green plants on the presence of smali stock and scion are examined in relation to root and amounts of oxygen. Reversible inhibition of shoot development. A. G. P. assimilation by carbon monoxide. H. Gaffron (Biochem. Z., 1935, 280, 337—359).—Mol. 0 2 is Factors rendering the plasmolytic method not necessary either in the free or bound condition inapplicable in determining the osmotic values for C02 assimilation in green plants (Chlorella etc.) of plant cells. E. C. M. Ernest (Plant Physiol., and the hypothesis that the mechanism involves a 1935, 10, 553—558).—When the osmotic pressure reaction between irradiated chlorophyll and 02 is of the external liąuid surrounding the celi is only discounted (A., 1935, 1288). A reversible inhibition slightly different from that of the celi fluid, plasmolysis of assimilation occurs when the plants are exposed becomes so slow that secondary changes may occur to the action of CO in the dark, and suggests that the within the celi, M’hich invalidate the customary enzyme responsible for the Blackman reaction is interpretation of the data. A. G. P. closely related to catalase. P. W. C. Growth and composition of Deglet Noor dates Seasonal changes ,in the acidity of the rhubarb in relation to water injury. A. R. C. Haas and (Rheum hybridum). T. A. Bennet-Clark and D. E. B liss (Hilgardia, 1935, 9, No. 6, 295—344).— W. M. W o o d ru ff (New Phytol., 1935, 34, 77—91).— Changes in the minerał and org. constituents and in Sprouting of rhizomes is associated with an increase the H20 content of dates with advancing growth in NH4 compounds or in “ malate ” (I) [acids of the are recorded. The naturę of “ H20 injury ” and malic group and including citric acid]. Translocation factors affecting it are examined. A. G. P. of (I) from rhizome to young leaves takes place, 1548 BRITISH CHEMICAL ABSTRACTS.----A. but deamination of NH2-acids to form NH4 malate is that of middle and lower buds. Lanolinę preps. of probably not an intormediate stage. Formation of C2H4 and C3Hr> caused similar effects. The epinastic I-malic acid occurs principally at the height of was more suitable than the rooting response of tobacco summer and not during sprouting. The acid is for comparatiye tests. A. G. P. associated with carbohydrate rather than protein Presence of ozone in air and its effect on the metabolism. The mol. ratio of NH4’ : malic acid in growth of plants. E. Briner, F. Chodat, and H. the plant is at all times smali (0-1). A. G. P. P a illa r d (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., Testing plant tissue for emanations causing 128— 132).—Samples of the plants Zea mais and leaf epinasty. F. E. D e n n y (Contr. Boyce Thomp Avena sativa exposed for 8—25 days to air containing son Inst., 1935, 7, 341—347).—Apparatus and 0-01—10 p.p.m. of 0 3 showed a higher ratę of growth techniąue are described. Epinasty was produced by than samples exposed to de-ozonised air. 0 3 favoured yolatilc products from a no. of plants. Positiye production of pigments of the xanthophyll group responses were given by petals, anthers, pistils, S. J. G. immature fruits, leaves, and tubers. Potato tubers, Similarities in the effects of ethylene and the germinating maize, wheat, and oats, mycelium of plant auxins. W. Cbocker, A. E. Hitchcock, Rhizopus nigricans, and maturę sporophores of two and P. W. Zimmermann (Contr. Boyce Thompson Inst., species of mushrooms failed to produce epinasty. 1935, 7, 231—248).—Tho action of C2H4, C3H 6, C2H2, A. G. P. and CO on plants is principally-that of anoesthetics Effects of zinc and iron salts on the celi struc and stimulants, and resembles in many respects that ture of mottled orange leaves. H. S. R eed and of a no. of growth-promoting substances. A. G. P. J. D u fren o y (Hilgardia, 1935, 9, No. 2, 113—141).— Effect of auxins on Pliytophthora cactormn. Mottle-leaf of citrus is associated with a change in L. H. Leonian (J. Agric. Res., 1935, 51, 277—286).— tho oxidation-reduction eąuilibrium of the leaf cells. The presence of substances promoting growth and Nitrites occur in the sap of mottled but not of normal roproduction of P. cactormn, in canned peas and in leaves. Cytological changes in mottled trccs during sprouting maize roots, is demonstrated. The last recovery following application of Zn are described. named are active after crushing or autoclaving. In tho new shoots thus formed noither Ca deficiency Norit adsorbs growth-promoting but not sexuality- nor phloem nocrosis is apparent, whilst chloroplastids promoting substances. A. G. P. develop and form starch. Beneficial effects of Fe on liypoplastic cells of mottled leaves are negligible. Pantothenic acid as a nutrilite for green plants. Zn is intimately concerned with the oxidation- R. J. Williams and E. Rohrman (Plant Physiol., reduction potontial of tho celi. A. G. P. 1935, 10, 559—563).—The growth of Ricciocarpus natans is stimulated by panthothenic acid (A., 1933, Several chemical growth-substances which 982). ' A. G. P. cause initiation of roots and other responses in plants. P. W. Zimmermann and F. Wilcoxon Do sexual hormones influence the germination and growth of plants? K. Gad-Andersen and E. (Contr. Boyce Thompson Inst., 1935, 7, 209—229; J a r lo v (Acta med. scand., 1934, 84, 241—252; cf. A., 1933, 437; B., 1933, 1027).—Plant responses Chem. Zentr., 1935, i, 1889).—The favourable action to a no. of growth-stimulating substances are ox- of follicular hormone (I) preps. 011 the growth of amined. a-Naphthylacetic and indolylbutyric acids hyacinths is not due to (I), but to an associated plant- were the most active root-forming substances. Both growth hormono. R. N. C. caused less opinastic response than indolylacetic acid. Local application of C2H4 or C3Hr> in lanolinę pastę Effects of animal hormones on plants. L. stimulated root initiation. Evidence is obtained of H avas and J . C a ld w e ll (Ann. Bot., 1935, 49, 729— the utilisation of a-C10H7-CH2-CN by plants for the 747).—A prep. of the cestrogenic hormone was production of growth substance. Emanations from toxic to tomato plants when administered by the root plants (probably C2II4) causing epinasty were in or through cut petioles. Extracts of testis, ovary, ereased by treatment with growth-substance. Positive pituitary, adrenal, thyroid, and thymus produced 110 growth-responses were also obtained with [3-naphthyl- marked stimulatory or toxic effects. A. G. P. acetic, acenaphthyl-5-acetic, phenylacetic, fluorene- Changes in the chemical composition of acetic, and anthraceneacetic acids (see also Hitchcock, developing apples. H. O. Askew (J. Pomology, this vol., 795). A. G. P. 1935, 13, 232—246).—Starch formation begins in Tobacco as a test plant for comparing the apple tissue near the periphery and extends towards effectiveness of preparations containing growth- the core area. During maturation hydrolysis of substances. A. E. Hitchcock (Contr. Boyce starch proceeds from the core outwards. The decline Thompson Inst., 1935, 7, 349—364).—The relatiye in % of N and ash with advancing growth follows the efficiency of growth-substances in causing epinasty in relationship log10 C=aĄ-bt (C,=concn. of constituent tobacco leaves was, naphthylacetic (I) and indolyl concerned, i= time from first sample, and a and b are acetic (II) > indolylbutyric (III) and indolylpropionic consts.). The rate of inerease of dry matter dechned (IV) > phenylacetic (V) > phenylpropionic (VI) > slightly and that of N and ash intake considerably, phenylacrylic (VII) acids. The rooting response approx. 95 days from fuli bloom. After a further of tobacco was in the order (III)>(II)>(VII)> 25 days the intake of N and ash ceased. A. G. P. (\)>(I)>(VI)>(IV). Application of lanolinę preps. Accumulation of boron by reciprocally grafted of the substances to decapitated tobacco stems plants. F. M. Eaton and G. Y. Blair (Plant retarded the growth of upper buds but stimulated Physiol., 1935, 10, 411—424).—The distribution of BIOCHEMISTRY. 1549 B in plant organs is effected by tho transpiration 168).—The solubility of the proteins of tobacco stream and is irregular. B combines with org. seed is increased by phosphates but not by acids. mattor in the tissues, the compounds having Iow E. P. mobility. Accuraulation of B in leaves of grafted Alkaloids of hanfangehi.—See this vol., 1257. seions is partly controlled by that of the stock. The Tubocurarine.—See this roi., 1514. intake of B is controlled by the characteristics of the root cells, by the naturę of the B compounds in the Composition of purple-flowered i-mao-tsao plant, and by the form of the equilibrium between [Leontirus sibiricus, L.]. T. H. Tang and C. W. mobile and immobile B compounds. A. G. P. Hsu (Nat. Shangtung Univ. Chem. Lab. Repts., 1934, Solubility of potassium in maize tissues. Nos. 3—4, 93—104).—No evidence of the presence V. H. M orris and J. D. Sayre (Plant Physiol., 1935, of alkaloids was found. Ch. Abs. (p) 10, 565—568).—In maize tissue K exists entirely in Alkaloids of Cytisus caucasicus. A. O rekhov solution in the celi sap. There is no evidence of and S. N o rk in a (Arch. Pharm ., 1935, 273, 369— fixed or non-ionisable K in any tissue except, possibly, 372).—Tho loaves of this plant contain ri-a-lupanine, in cob tissue. A. G. P. pachycarpine, and a little of a base, m.p. 120— 122°, Changes in nitrogen compounds in the wheat insol. in Et20, but sol. in CHC13. R. S. C. grain at different stages of development. G, L. Characteristics of N icotiana species. M. I. T e l l e r (Plant Physiol., 1935, 10, 499—509).— Chmura (Sborn. R abot Chim. Tabak, 1935, Buli. Changes in the N distribution of developing grain 125, 107—116).— Nicotiana species contain alkaloids are examined. The early stages, marked by high pro- volatile and non-volatile with steam. The m.p. of portions of non-protein N, are associated with in their picrates are different from those of N . tabacum. creasing gliadin and decreasing glutenin contents, Some species contain much citric and maleic acids and a slight decline in albumins and globulins. These and ash. In N . glauca after topping, the amount of changes are partly due to the filling of the grain with alkaloids, N, proteins, and citric acid is increased, endosperm, which contains more gliadin and less that of carbohydrates is decreased. E. P. glutenin than the bran. The total N of the grain is influenced by seasonal conditions. A. G. P. Electrolysis in the isolation of plant products. A. A. Schmuk (Sborn. R abot Chim. Tabak, 1935, Distribution of nitrogen in the seed of Zea Buli. 125, 47—54).—Acids and bases (e.g., citric m ais at different stages of maturity. L. acid and nicotino) may be separated by electro- Z e le n y (Cereal Chem., 1935, 12, 536—542).— dialysis, which reduces the nicotine content of tobacco, Globulin and glutelin are synthesised at a relatively but has no influence 011 its ąuality. E. P. uniform rate throughout the growth period of the maize grain, whilst zein is present only in very smali Crystalline bitter principle from Andrograpliis ąuantities in the early stages and is rapidly synthesised paniculata. S. S. G. S irc a r and A. M o k ta d a r as the grain approaches maturity. This rapid in (Sci. and Cult., 1935, 1, 300).—A bitter principle of crease in the ratio of zein-N to total N is closely this plant (cf. A., 1914, i, 1118, 1204) is isolated as a paralleled by the decrease in H20-sol. non-protoin-N, substance (I), C20H30O5, m.p. 220° (decomp.), [a]D indicating that the H20-sol. N compounds are largely -123-5° in AcOfl, which contains OH (not acetylated utilised in the synthesis of the zein. The asparagine, under ordinary conditions) and CH202 groups, and glutaminę, or other content of the non-protein-N one double linidng (which is hydrogenated, and com fraction remains relatively const. throughout the bines quantitatively with HC1 and IC1). The pre growth period of the kernel. The simpler NH2- sence of a lactone group is shown by hydrolysis to compounds undergo rapid condensation (probably two isomeric Oli-acids, m.p. 156°and 180°,respectively, chiefly the condensation of NH2-acids into polypep- both reconverted into (I). (I) is readily dehydrated tides) as the grain approaches maturity. The basie above its m.p., and combines with POCI-, and with N of the H20-sol. non-protein-N inereases as the PhNCO. E. W. W. grain approaches maturity, simultaneously with a Concentration of heavy isotopes in cellulose.— considerable decrease in the basie NH2-N, which See this vol., 1469. indicates that tho H20-sol. basie N compounds in Cress-seed mucilage. K. B ailey (Biochem. J., maturę maize mainly consist of org. N bases which do 1935, 29, 2477—2485).—The dispersible cellulose not yield primary alkylamines on hydrolysis. Proteoso component of cress-seed mucilage gave Z-arabinose, or peptone is present in maize. E. A. F. d-galactose, Z-rhamnose, ri-glucose, and cZ-galacturonic Biochemical phases of oleoresin production. acid on acid hydrolysis. The mucilages of cress seed, E. G e rry and J. A. H a ll (Plant Physiol., 1935, mustard seed, and linseed are systems of polyuronides 10, 537—543).—The naturę and formation of oleo- and may be fractionated by their solubilities in dii. resins and their precursors are discussed. A. G. P. aq. Ba(OH)2, 1% NaOH, and in aq. EtOH. H. D. Insulin-like materials from plant tissues. Phosphorus of starches. T. Posternak (Arch. C. E. B ra u n and F. M. R ees (J. Chem. Edue., 1935, Sci. phys. nat., 1935, [v], 17, Suppl., 182— 183).— 12, 453—458).—A review and discussion. The Starches can be divided into two groups : (1) those presence of an insulin-like substance in plant tissues of rhizomes, where P is combined as an ester-salt is still a matter of doubt. L. S. T. with a glucose residue; (2) those of cereals where P Proteins of tobacco seed. II. G. S. I l j i n is in the form of lecithins and not directly linked to the (Sborn. R abot Chim. Tabak, 1935, Buli. 125, 163— polysaccharide. H. G. R. 1550 BRITISH CHEMICAL ABSTRACTS.— A. Isolation and determination of starch in plant 78-5°), belienate, m.p. 93—94°, and erucate, m.p. 60— tissu e. C. Niemann, R. H. Roberts, and K. P. 60-5°. These and similar esters give only slight de- Link (Plant Physiol., 1935, 10, 579—580).—Plant pressions of the m.p. when mixed and cannot be materiał is extracted with CrHs-EtOH (2:1) and separated by crystalhsation. R. S. C. the residue boiled with 1% HN03 in 85% EtOH R esin of Nicotianą rustica. V. N. Schirokaia (refiux). The filtered residue is washcd free from acid (Sborn. Rabot Chim. Tabak 1935, Buli. 125, with 95% EtOH, and after partial drying is extracted 151—162).—The acids obtained from the resin were with 20% EtOH. The extract is evaporated to esterified with MeOH. Palmitic and linolenic acids smali vol. and the starch polysaccharides are pptd. were identified. E. P. by pouring into COMe2-E tO H (1 : 1), separated by ceiitrifuge, dried, and weighed. For determining Point fern (Engelsiiss) and some of its relatives starch in the 20% EtOH extract, the latter is evapor- as medicinal plants. F. W. F re ise (Sci. pharm- atod to smali bulk, boiled with HC1, and examined by aceutica, 1934, 5, 129— 131; Chem. Zentr., 1935, i, customary methods for glucose. A. G. P. 1585— 1586).—The rhizomes, roots, and fronds of Polyj)odium mlgare, L., P. lepidopteri.s, Kunze, P. Constituents of lesser centaury (Erytlircra incanum, Schw., P. sgualidum, Yel., and P . x>crcussum, centaurimn). T. Kariyone and K. Kashiwagi Cav., yield a volatile oil (rhizomes and roots), d f (J. Pharm. Soc. Japan, 1934, 54, 1077— 1090).— 0-8385—0-8412, < 1-4855, [ (Science, 1935, 82, 179—180).—A modified Haldane C6H4(N02)2 formed is determined by the Smyth metabolism train is described. L. S. T. modification of the Elliott and Dalton method. Analysis of smali volumes of gas.—See this W. O. K. vol., 1476. Spectrophotometric methods for determining porphyrins. E. V ig il ia n i (Diagnostica tce. lab. Micro-method of gas analysis. J . A. Ca m p b e l l [Napoli], Riv. mensile, 1934, 5, 625—654).—Copro- and H. J. T a y l o r (J. Pliysiol., 1935, 84, 219—222).— porphyrin and protoporphyrin are yery unśtable Modifications introduced into. Krogh’s method render in HCI. A spectrophotometric method for urinary it easier, more rapid, and of wider application. porphyrins is described and is compared with the R. N. C. fluorometric method. Ch. Abs. (p) Determination of intracellular p n by the method of vital stains. L. Lison (Compt. rend. Isolation and determination of volatile sub Soc. Biol., 1935, 120, 102—104).—The presence of stances from biological fluids and other mix- chromotropes in cells introduces errors into the deter- tures. F. Ł a u e r s e n (Biochem. Z., 1935, 280, mination of intracellular p n by vital stains, sińce all 38—40).—An apparatus is described and its use illus- the basie p a indicators are metachromatic. The meta- trated by determinations of COMe2 and (3-hydroxy- chromatic error may reach 6 p n units. R. N. C. butyric acid in deproteinised blood filtrates. P. W. C. Electrodes for parallel determination of the Titration of fluorine in biological materials. oxido-reduction potential and p n in biological E. W. S c o tt and A. L. H e n n e (Ind. Eng. Chem. m edia. R. T so h a g o y e t z and Z. S. G e r s c h e n o - [AnaL], 1935, 7, 299—300).—A suitable technique for y ttsch (Ukrain. Biochem. J., 1935, 8, No. 1, 203— ashing, volatilisation of F as SiF4 by distillation with 209).—The apparatus is described. E. P. HC104, and titration with Ce(N03)3 or Th(N03)4 is Unpolarisable electrodes to carry action described (cf. A., 1933, 242). F. O. H. currents. E. S c h u t z (Z. Biol., 1935, 96, 510— Micro-determination of total sulphur in bio 512).—The connexion is made through Ringer’s logical substances. H. T o y o d a and S. K i s h i solution to a Pt electrode covered with Pt-black to (Gann, 1934, 28, 458—461).—Org. m atter is destroyed prevent polarisation. W. O. K. by fusion with KC103-Na202. The residue is disr Apparatus for physiological experiments. solyed in hot H20, treated with 50% HCI and Br, F. F. A n d e r s o n (Chinese J. Physiol., 1935, 9, 209— and S is pptd. as BaS04. Ch. Abs. (p) 212).—The following are described : EtaO bottle for Micro-determination of calcium in smali mammaliąn experiments, pressure bottle for anti- quantities of biological liquids. M. S a v ia n o coagulant, contact breaker for use with a sensitive (Diagnostica tec. lab. [Napoli], Riv. mens., 1934, 5, thermo-regulator, and apparatus for isolated smooth 460—463).—Norbo’s method (A., 1932, 531) is mod muscle prep. E. P. ified by substitution of an iodometric for the acidi- Cokrar reaction of fructose.—See this vol., 1484. metric titration. Ch. Abs. (p) Colour standard for cholesterol determin- Spectrographic determination of lead in bio C h o l a k ations. A. S h a p ir o , H. L e r n e r , and E. P o s e n logical materiał. J. (Ind. Eng. Chem. (Proc. Soc. Exp. Biol. Med., 1935, 32, 1300—1301).— [Anal.], 1935, 7, 287:—290).—The materiał (blood, A colour standard for use in Schoenheimer and liver, spleen, muscle, foods) is digested with II2S04- Sperry’s micro-method :for determination of serum- HN03, ashed at 500°, and the solution of the ash in cholesterol is prepared by diluting 1 ć.c. of Carter’s dii. HCI is examined spectrographically, using a Midnight Black Ink to 1 litre with 10% AcOH. microphotometer and comparing with known stand- The method is simplified by using a mixture of ards of Pb and Bi in suitable media (cf. thiś vol., H2S04 and Ac20. R. N. C. 399). The accuraey is ±0-01 mg. for 0-01—0*20 mg. Pb per 100 c.c. F. O. K.' Determination of urea. N. N. D a s t u r , R. Determination and recognition of lead in bio K a r n a d , B. N. S a s t r i, and A. V enkatasubban (Proc. Indian Acad. Sci., 1935, 1, B, 817—822).— logical tissues and fluids. C. N . M y e b s , F. G u s - (NH4)2C03 produced by enzymie decomp. of urea t a f s o n , and B. T h o r n e (J. Lab. Clin. Med., 1935, may be titrated directly with HCI in EtOH after 20, 648—657).—FairhalTs method gives satisfactory adding C0Me2 to the solution, using naphthyl-red. results in the micro-determination of Pb (0-02— The method is applicable to urine analysis. > 0-50 mg.) in biological specimens if a micro- A. G. P. burette is used in the finał titration. Certain elements Removal and determination of smali amounts (e.g., Cu, Bi) interfere. N u t r . A b s . (m) of benzene in biological materiał. W. P. Y a n t , Histochemical demonstration of gold. F. H. H. S c h r e n k , and P. H. M a u tz (U .S . Bur. Mines, G tjer cio and U . Ciu l l a (Diagnostica tec. lab. [Napoli], Rept. Invest., 1935, No. 3282, 7 pp.).—The m ateriał in Riv. mens., 1934, 5, 456—459).—Tissue is treated a macerated, finely-ground, or fluid condition is with 2% H2C204 for 24—48 hr., washed, fixed in mixed with H20 and acidified. The CGH6 is removed CH20, and paraffined in the usual way. The prep. is from the refluxing mixture by bubbling through a dipped in H202 for 24 hr. A red coloration due to current of N2, and absorbed in nitrating acid. The an oxide of Au develops. Ch. Abs. (p) W 5 ,\o