BRITISH CHEMICAL ABSTRACTS
A.-PURE CHEMISTRY
APRIL, 1936.
General, Physical, and Inorganic Chemistry.
Intensity variation in the fine structure of the Zeeman splitting of the No lines 5852 and 6074 A. Balmer lines H n and H^. B. Svensson (Pliysica, indicate that the jr-sum rule is valid to < 0 -1 %; 1936, 3, 91— 104).— Data are recorded for the in assuming the validity of this rule, elm is l-7580± tensity ratio (It/Ii) of short- and long-wave com 0-0014X 107 e.m.u. per g. L. S. T. ponents, for pressures of 0-005— 0-8 mm. at different Series lines of magnesium in the solar spec c.d. With varying pressure, the transition from trum. H. N. R u s s e ll, H. D. Babcock, and C. E. non-stnated to striated discharge corresponds with M oore (Physical Rev., 1934, [ii], 46 , 826— 827).— a discontinuity in the / * / / ; vals. L.,J. J. Members of the series 31D-7i1F° and 33D-7i3F° Comparison of theoretical and empirical observed in the arc spectrum of Mg (A., 1932, 315), values for Stark effect displacement of the together with additional members, have been found components of H -1 8 . K . B a s e (Z. Physik, 1936, in the infra-red solar spectrum. L. S. T. 98, 576—579). A. B. D. C. Spectra of phosphorus. I. Spectra of Source of doubly ionised helium. O. L u h r neutral and singly-ionised phosphorus. H. A. (Physical Rev., 1936, [ii], 49,317— 319).— A magnetron Robinson (Physical Rev., 1936, [ii], 4 9 , 297— 305).— type of low-voltage arc, giving about 2 % He++ by Using the discharge emitted by a Geissler tube multiple electron impact, is described. N. M. B. containing P vapour, 22 new terms classifying 36 Zeeman effect in helium. L. E. K i n s le r and lines of P I were located; these lines also’ appear W. V, Houston (Physical Rev., 1934, [ii], 46, 533— in a 25-amp. C arc containing Ca3P2. The revised 534).—The anomalous effect previously reported ionisation potential is approx. 10-9 volts. 52 new (A., 1935, 1437) is due to an experimental error. terms classifying 194 lines in the Schumann and visible The val. of e/m obtained from Zeeman splitting of regions were located in P ir. The singlet and triplet singlet lines of Zn, Cd, He, and Ne is 1-7570 J-0-0007 x sequences are located from more than 20 inter-system 107e.m.u.perg. L. S. T. combinations. Full data for classified lines of P i Analysis of 3 d —4 / for C XI, N III, and N II. and P ii are tabulated. The revised P rr ionisation Intercombinations in C n and N ill. B. E d l£ n potential is 19-56 volts. N. M. B. (Z- Physik, 1936, 98, 561— 568). A. B. D. C. Band spectrum of sulphur and the statistics New members of the Lyman-Birge-Hopfield of the sulphur nucleus. R. M. B a d g e r (Physical system [of N ,]. J. K a p la n and L. D. L evanas Rev., 1934, [ii], 46, 1025— 1026).— The analysis (Physical Rev" 1934, [ii], 46, 331).— A max. val. made by Naude and Christy (A., 1931, 540) is criti of 7-7 volts for D(N2) is obtained. L. S. T. cised. Consts. of the S mol. are revised. L. S. T. New bands of the ionised nitrogen molecule. Nuclear mechanical and magnetic moments • H . C W o r d and P. M. T sai (Physical Rev., of K39. D. A. Jackson and H. K u h n (Nature, ■ 34, [ii], 46, 935).— 400 new lines have been assigned 1936, 13 7 , 108; cf. A., 1935, 555).— Photometric in the bands Qf Na+ _ L . S. T . measurements of the intensities of the hyperfine structure doublets of the resonance lines of K show Zeeman efiect in the atmospheric oxygen that the shorter-X component is the stronger, thus *nds i production of a strong magnetic field establishing that the magnetic moment of the nucleus over a length of 80 c m . R . Sch m id (Physical of K 39 is negative. The val. calc, is —0-39 nuclear o'-, 1936, [ii], 49, 271).— A means of obtaining magneton. L. S. T. olds over the lengths necessary for the Zeeman effect is described. A qual. discussion of the observed Hyperfine structure of some vanadium enect is given. N. M. B. multiplets. H. Koffermann and E. Rasm ussen (Z. Physik, 1936, 98, 624— 637).— The mechanical Oxygen afterglow. E. M. S to d d a r t (Proe. moment of the V nucleus is 7/2. A. B. D. C. «°y. Soc., 1935, A , 153. 152— 157).— A reply to Rayleigh’s criticisms (A., 1935, 907). Experiments Photographic photometry of iron multiplets ‘ |e' ^oribcd showing the effects on the 0 2 afterglow in electric furnace spectra. R. B. K in o (Physical tl20 vapour in the gas phase and adsorbed on Rev., 1934, [ii], 46, 327). L. S. T. ie surfaces of the vessels, which are in agreement with Band spectra of rubidium and of its combin e results of other investigators. L. L. B. ations with other alkali metals. P. K u sch Zeeman efiect in neon. L. E. K i n s le r (Physical (Physical Rev., 1936, [ii], 4 9 , 218— 222).—The mag < n 4934, [ii], 46, 533).— Measurements of the netic rotation spectrum and absorption spectrum e e 397 398 BRITISH CHEMICAL ABSTRACTS.— A.
of Rb2 in the region 6500— 7100 A . have been measured line 2537 A. II. The a components. A. and correlated and a vibrational analysis is given. Zvtron as (Helv. phys. Acta, 1934, 7, 684— 708; The vibrational frequency in the ^ ground stato Cliem. Zentr., 1935, i, 35L6; cf. A., 1935, 3). is 57-31 cm.-1, and that in the excited 1n state is H. J. E. 48-05 cm.-1 The corresponding vais, in the magnetic Influence of pressure on the discharge-radi- rotation spectrum of NaRb are 106-6 arid 61-5 cm.-1 ation in mercury vapour. V. Fabrikant, F. A band system due to RbCs has been identified. B u ta ev a, and J. C irg (Compt. rend. Acad. Sci. N. M. B. U.R.S.S., 1935, 4, 183— 184; cf. A., 1934, 1280).— Characteristics of the long and short spectral Absorption in Hg discharge at low pressures has been lines. II. Silver, zinc, and iron. S. D a tt a and studied. R. S. K . M. Chatterjee (Indian J. Physics, 1936, 10, Fraunhofer’s spectrum in the neighbourhood 65— 73 ; cf. A ., 1935, 908).— The long and short lines of 96,000 A . A. A d e l, V. M. S lip h e r, and 0. of Ag, Zn, and Fe have been classified. The funda F o u ts (Physical Rev., 1936, [ii], 49, 288— 290; cf. mental generalisation previously given, with regard A ., 1935, 806).— The absorption of solar radiation to the relative changes in orientation of the L and S by the atm. of the sun and earth, examined in the vectors in the initial and final states for the long range 70,000— 110,000 A., is discussed in the vicinity and short lines, appears to be verified. M. S. B. of 96,000 A. Fine-structuro data for the 0 3 band Regularities in the spectrum of trebly ionised with centre at 1043-7 cm.-1 are given, and the structure iodine. S. G. Krishnamurti (Proc. Physical Soc., of the mol. is discussed. N. M. B. 1936, 4 8 , 277— 281).— The spectrum of a condensed Resistance to electric discharge in gas mix discharge through I has been photographed in the tu res. G. M. K o v a le n k o (Compt. rend. Acad. Sci. range 6000— 1900 À. under varying conditions of U.R.S.S., 1936,1, 15— 17).— The breakdown potential excitation. Data for 6 S lines ascribed to I IV and (F) for spherical electrodes at various distances classifications of 34 lines are tabulated. Term vais, apart in mixtures of N H 3 and N , at approx. 1 atm. and assignments are given on analogy with the decreases with increasing % of N H 3 to a mill, at isoelectronic spectra Te m , Sb II, and Sri i. approx. 30% N H 3. With mixtures of E t20 and N, N ; M. B. a min. occurs at 3 0 % E t20 . Since V for pure EGO Extinction coefficients of iodine and other and N H 3 is > V for N 2, the decrease in V on adding halogens. E. Rabinowitch and W . C. W o o d NH 3 and Et20 to N 2 is attributed to chemical action. (Trans. Faraday Soc., 1936, 32, 540— 546; cf. A., With N H 3 V decreases at each discharge with suc 1935, 586).— Extinction coeffs. of I vapour, measured cessive discharges (ultimately becoming const.) owing at 20° in the range X 4300— 6200 Â., are 2— 6 times to the formation of H 2, the presence of which in N8 > the accepted vais. Small humps on the extinction at a total pressure of 100 mm. is shown to decrease V. curves, appearing both in vapour and solutions, are R. S. B. due to absorption by vibrating mois. The “ limit Electric discharge in gases and the Debye- ing ” extinction curve, obtained by diluting the Hiickel theory. V. T. Chiplonkar (Current Sci., vapour to a very low partial pressure with an inert 1936, 4, 481).— The Debye-Hiickel electrolytic theory gas, has a max. at 5200 Â., and resembles in shape is applied to the phenomena in discharge tubes. the curve of a CS2 solution. The influence of the In approx. agreement with experiment the length solvent on the extinction curves of solutions of Cl2, of the cathode fall is shown to vary as the log of the Br, and I is investigated. F. L. U. p.d. across it. R. S. B. Band system of cæsium. P. K u s c h arid F. W . Ionisation steps and excitation energies of Loomis (Physical Rev., 1936, [ii], 49 , 217— 218; spectral lines according to the emission dis ef. A ., 1934, 1148).— A provisional analysis of the tribution in the arc light. H. S teph an (Z. wiss. complex system at 6250 À. is reported. N . M. B. Phot., 1936, 35, 33— 69).— The intensity of spark Magnetic moment of cæsium determined lines immediately in front of the cathode is dependent from the hyperfine structure of the 6p 2Pt state. on cathode temp. The increase of intensity of arc L. P. G ran a th and R. K. StranathAn (Physical lines just in front of the poles is due to higher v.d. Rev., 1934, [ii], 46, 317).— A g val. of 0-70 is obtained The best conditions for observation of ionisation for Cs. L. S. T. steps are obtained by the use of the smallest possible current through the arc. The arc and spark spectra Spark spectrum of mercury, H g i i and H g III. of Mg, Ca, Cu, and Zn were separated by examining T. S. Sdb b araya (J. Mysore Univ., 1934, 7, 100— the emission distribution of arcs. The cause of the 134; cf. A ., 1934, 1280; 1935, 3).— Additional pole effect with arc lines (displacement of XX in the lines are classified. The ionisation potentials of neighbourhood of the poles) is probably due to Hg I and Hg n are 18-67 and 26-1 volts, respectively. increased v.d. A. J• 51. Ch . A b s . (e) Second spark spectrum of mercury. R. Arcs in rare gases. R. C. M ason (Physical R ica rd (Compt. rend., 1935, 201, 1342— 1344).— Rev., 1934, [ii], 46, 630). L- S. T- 30 new terms belonging to the Hg m spectrum have Determination of the temperature in the been identified in the visible and ultra-violet spectrum column of a discharge from the intensity excited with an electrodeless discharge. T. G. P. measurement of rotational band spectra. 1- Anomalous Zeeman effect of single hyperfine Ham ada (Proc. K . Akad. Wetensch. Amsterdam, structure components of the mercury resonance 1936, 39, 50— 57; cf. A ., 1928, 930).— The radial I {a-c) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 399 temp, distribution in a special N 2 discharge tube of Ruled-grating wave-length of the copper J8S, known volt-amp. characteristics has been studied line. P. E. G o ttlin g and J. A. B e a r d e n (Physical by determination of the intensity of spectral lines. Rev., 1934, [ii], 46, 4 3 5 -4 3 6 ). L. S. T. The axial (max.) temp, varies linearly with the K spectrum of copper. Y. C'auohois (Compt. product of pressure and current. R. S. rend., 1935, 201, 1359— 1361).— Data for the Kfi Effect of evaporated films on energy dis regions are recorded and discussed. T. G. P. tribution in grating spectra. J. S tr o n g (Physical II radiation of elements from chromium to Rev., 1936, pi], 49, 291— 296).— Wood anomalies copper. M. P r iv a u lt (Aim. Physique, 1936, [xi], of intensity distribution can frequently be developed 5, 280— 324).— Three new lines in the Kfi spectra are by coating the grating, especially if of fine ruling, recorded. The effect of magnetisation of the anti with an evaporated film of Mg, Ag, or Al. The cathode on the Kfi spectrum of Fe lias been examined. phenomenon is shown typically by a double band Magnetisation to 75% saturation has no observable consisting of a dark band on the red side of a bright effect on the Kfa and K $2 lines. Temp, changes in band; the dark band is characterised by a sharp the neighbourhood of the Curio and y points are boundary on the blue side, agreeing with the Rayleigh similarly without effect (for 7Tp1 and Jip2). The formula. N . M. B. effect of combination on the K spectra has been examined by a fluorescence method. K 2Cr20 7, Ultra-rapid spectrograph at the Pic du Midi. M n02, and Fe20 3 show a more general splitting of H. Gakrigue (Compt. rend., 1936, 202, 44— 45).— An the lines than recorded by Yoshida (A., 1933, instrument operating at / 0-55 is described. 656). ‘ L. J. J. H . J. E. II Photographic method for determining the spectra of molybdenum and rhodium. H. H ulubei (Compt. rend., 1935, 201, 1356— 1359; distribution of light intensity in interference cf. A., 1935, 811).— Data for the K[I spectra are rings. J. R oig (Compt. rend., 1935, 201, 1346— recorded and discussed. T. G. P. 1348). T. G. P. Effects of chemical combination on the L Fixing scale of Röntgen wave-lengths in absorption limits of tantalum, tungsten, gold, absolute m easure. M. Söderm an (Nova Acta Soc. and lead. S. K a w a ta (Proc. Phys.-Math. Soc. Sei. Upsaliensis, 1935, [iv], 9, No. 8 ; Chem. Zentr., Japan, 1935,17, 89— 99).— The shifts of the Lm limits 1935, i, 2942— 2943).— The XX of the Al K lines in are (in volts): HTa03 + 2 -0 ; H2W 0 4 +3-0, Au20 the 9th and 10th orders are compared directly by a - 4 - 6 , Au20 3 -3-4; PbO -¡-3-4, Pb02 + 6 -8 . The combination of the plane and concave grating methods assumption of a selection rule for X-ray absorption "ith the Al spark lines at 50— 90 A., giving 1000 X spectra is supported. The Au L m absorption edge is (exP;)=l'00212— 1-00225 A. The calcite lattice double in Au20 3. Ch . A b s . (e) spacing is recalc., and e calc, as 4-806¿0-003 c.s.u. Probability of IIL ionisation and X-ray satel J. S .A . lites. R. D. R ich tm y er (Physical Rev., 1936, [ii], Accuracy of determination of emission and 49, 1— 8 ).— A theory of multiple ionisation produced absorption of monochromatic X-rays. H. by a fast-cathode electron in the target of an X-ray Küstxer and E. A rends (Ann. Physik, 1936, [v], tube is developed. The effective cross-section for 25, 385—412).— An examination of the accuracy of ls2s ionisation of K, the distribution of energy and methods previously employed (A., 1935, 556, 676). angular momentum, and the probability of 1 .s2p A. J. M. ionisation are examined. N . M. B. Theory of X-ray absorption by molecular fcneS-‘ H . P e te r s e n (Z. Physik, 1936, 98, Ionisation potentials of the N 2 molecule. J. < of- A., 1933, 332).— Calculations involved Savard (Rev. Fac. Sci. Univ. Istanbul, 1936, 1, m hronig’s theory are simplified; applied to GeCl4 1— 7).— Using the method of electronic impact, ey agree with experiment. A. B. D. C. 11 potentials in good agreement with calc. vals. are reported and the corresponding transformations are • .Polarisation of X-rays from thin targets. given. N. M. B. ' S- P/Ston (Physical Rev., 1936, [ii], 49, 275— Calculation of work of exit in the Richardson -/J)--—The polarisation of the portion of the con- effect by a method of O. Scherzer. A. Sommer- muous X-ray spectrum bctw-cen the K limits of f e ld [with E. Bartelink] (Helv. phvs. Acta, 1934, a and W, measured for targets of Al foil (0-7 ¡x) and 7, Suppl. II, 31— 32; Chem. Zentr., 1935, i, 2953).— -g foil (0-17 (x)j at voltages from the quantum limit Theoretical. An expression is derived connecting the p to 120 kv., is complete at the quantum limit, and work of exit with the at. vol., which agrees with ccreases, more rapidly for Ag than for Al, as the tube experimental data for the alkali metals. J. S. A. age is raised above the quantum voltage for the sPectrum band. N. M. B. Calculation of Townsend's a for neon. M. J. Druyvesteyn (Physica, 1936, 3, 65— 74).— Theoreti Wave-length measurements in the R-series cal. The velocity distribution of electrons diffusing tha r m^ um ' sulpfiirr, and chlorine, and in through an inert gas is calc., assuming elastic, exciting, in-«* f s-lries 2X110■ J- S h e a r e r (Phil. Mag., and ionising collisions. Calc, and observed vals. of a ; v 11]’ 21, 501— 505).— Vais, are tabulated for 9 the ionisation coeff. a agree for potential gradients t , s.ansiI1g from impurities in Ni during investigations of 5— 30 volts per cm. per mm. gas pressure. Deviously reported (cf. A ., 1935, 1293). N . M. B. E. J. J. 400 BRITISH CHEMICAL ABSTRACTS. A.
Electrons and positrons. C. H . D ix (Physical crepancies indicate a departure from the inverse Rev., 1934, [ii], 46, 329— 330).— Theoretical. square law for such energies. For a classical dis L. S. T. tance, therefore, of closest approach of about 6 X 10~13 Production of positrons by (3-rays. D. Sko- cm. the two protons cannot be treated as point b e ltz y n and E. Stepanova (Nature, 1936, 137, 272; charges, but on classical grounds this is not so down cf. A., 1935, 425).— Further evidence of the production to 10-16 cm. N. M. B. of electron-positron pairs by the passage of fast Formation of negative atomic ions of mercury. (3-rays through Pb and A1 is presented. With Al, F. L. A r n o t and J. 0. M illig a n (Nature, 193G, the predominating effect is the emission of a single 137, 150).— By means of the mass spectrograph positron accompanying the absorption of the primary negatively charged atoms but not negatively charged (3-particle. Production of positrons along the track mols. of Hg have been detected. Their energies of the (3-particle in the gas (N,) was also confirmed. are > can be accounted for by the total potential The effective cross-section in N 2 is of the order 5 X 1 O' 24 across the tube or by the dissociation of excited mols. sq. cm. L. S. T. L. S. T. Positron em ission accompanying' (3-ray Production of high-velocity particles in a cyclo activity. C. M o lle r (Nature, 1936, 137, 314).— tron by the use of multiphase oscillators. R. J. Theoretical. L. S. T. M oon and W . D. H a rk in s (Physical Rev., 1936, [ii], Emission of positrons by a source of Th-/J 49,273). ' N.M. B. ± C . S. de Benedetti (Compt. rend., 1936, 202, At. wt. of element 93. H. J. W a lk e (Phil. 50— 52).— Counts of the positron emission arc re Mag., 1936, [vii], 21, 262— 265).— By analogy with corded, using Cellophane and Al screens of varying the relations between the isotopes of Ru, Rli, and Pd thickness. H . J. E. arid between those of Th, Pa, and U, it is suggested Production of electron pairs. J. C. J a e o e r that the a-radioactive isotope of element 93 (eka-Re) and H. R. H u lm e (Proc. Roy. Soc., 1936, A , 153, has a mass no. 237. The mass nos. of the a-radio 443— 447).— Mathematical. A method, which avoids active isotopes of U and eka-Os arc probably U, the use of the Born approximation, for finding the 232, 233, 234, 235, 236, and 238; eka-Os, 238, 239, no. of electron pairs created by a y-ray traversing 240, 241, 242, and 244. The lighter isotopes of matter is described. The results are somewhat eka-Os arc probably short-lived, but eka-0 siU is > those of Betlie and Heitler (A., 1934, 1150), probably of long life and may exist terrestrially. but it is found that even for heavy elements the Born R. S. B. approximation may be expected to give good results Masses of some light atoms measured by for y-rays of high energy. L. L. B. means of a new mass spectrograph. F. IV. A sto n (Nature, 1936, 137, 357— 358).— Observations Thomson's theory of condensation on ions. on the doublets linking H , D, He, C, and 0 give the E. HiiCKEL (Physikal. Z., 1936, 37, 137— 138).— following as the most probable vals. of the isotopic The assumption made by Thomson, that the charge wts. on the physical scale : H 1-00812 ±0-00001, of the drop is uniformly distributed over the surface D 2-01471 ±0-00007, He 4-00391 ±0-00016, and C of a sphere, does not hold in the case of single ions 12-0035±0-0003. L. S. T. or electrons, where the charge is rather conc. at the centre of the sphere. An equation is derived on this Abundance ratio of isotopes of potassium in assumption. A. J. M. mineral and plant sources. A. K. B rew er (J- Amer. Chem. Soc., 1936, 58, 365— 370).—-Mass- Emission of positive ions by platinum when spectrographic data for a large no. of K-containing heated in oxygen. T. B. R ym er (Proc. Roy. Soc., minerals show only small differences in the isotope 1936, A , 153, 422— 442).— The variation witli temp, content. The ratio K 39/K 41 is about 14-25. Greater of the positive ion emission from Pt heated in 0 2 variation is found in plant ashes, the K 41 content has been examined, and the results are discussed differing by as much as 15% . Kelp show-s a pro in the light of the Saha equation. Satisfactory nounced deviation from the average. The ratio agreement with the theory is obtained, but a different varies with the variety, age, and section of the plant, val. from that determined experimentally must and the type of soil. E. S. H. be assumed for the electronic work function, on account Mass-spectrographic determination of the of the discontinuous nature of the emitting surface. constancy of the at. wt. of potassium in ocean L. L. B. Absorption of high-energy protons by matter. water. A. K. B r e w e r (J. Amer. Chem. Soc., 1936, 58, 370— 372).— The abundance ratio K 39/K 41 f°r J. Solomon (Compt. rend., 1936, 202, 204— 206).— Pacific Ocean H 20 is 14-20 for samples obtained from The energy lost by protons and electrons by radiation and ionisation is considered theoretically. different localities and at depths down to 2500 )»■ T. C. P. Variations in at. wt. are < ±0-00026. The dcrivei Scattering of high-energy protons in hydrogen. at. wt. of K is 39-094. E. S. H- M. G. W h ite (Physical Rev., 1936, [ii], 49, 309— Isotopic abundance ratios of carbon, nitrogen, 316).— Comparison of scattering frequency from argon, neon, and helium. A. L. V au gh an , J- h- 7340 photographs of high-energy proton tracks in W illia m s, and J. T. T a te (Physical Rev., 1934, H , with Mott’s wave-mechanical treatment showed [ii], 46, 327).;—Relative intensities of the peaks o strong anomalies for incident proton energies > 600 mass-spectrograph curves give the following abuni - kv. Since Mott assumes coulomb forces, the dis ance ratios with the average deviations indicated • I (d, e) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 401
C12; ci3 91-6 (2-2), N 14 : N 15 265 (8), A 40 : A 30 304 (12), difference in the shape of the ß-spectra of elements Ne20: He21 337 (20), Ne2« : Ne22 9-25 (0-08), and of low and high at. no. L. S. T. He4: He3 < 35,000. L. S. T. Absence of low-energy radiations from Isotopic constitution of rubidium, zinc, and potassium and rubidium. W. F. Libby (Physical argon. A. 0 . N ie r (Physical Rev., 1936, [ii], 49, Rev., 1934, [ii],46,745— 746).— Geiger-Müller counter 272).—The abundance ratio Rb85/R b 87 is 2-68;p0-02. experiments indicate that no a-particle of range The upper limits of abundance relative to Rb85 much > 0-05 cm. or ß-particle with energy much computed for undetected hypothetical isotopes > 500 e.v. is emitted by K . The emission of any are, Rb8«’ 82’89' so, 1 x 10-5 ; Rb83, 1/60,000; preliminary' radiation is improbable. With Rb it Rb84, 1/12,000; Rb8«, 1/13,000; Rb88, 1/22,000. is even less likely that a low-energy a- or ß-particle gn6i. 60. os, 67. to were found. The upper abundance is initially emitted. L. S. T. limits relative to Zn70 of Zn«5-63’ 69 are 1/200, 1/400, Evidence of an excited state in the a-particle. and 1/300, respectively. A 38 was confirmed. C. C. L a u ritsen and H. R . Crane (Physical Rev., A«/A36=325, and A 3«/A38= 5 - l . The upper 1934, [ii], 46, 537— 538).— The 12 m.e.v. y-ray abundance limits of hypothetical isotopes relative component observed when Li is bombarded with to A49 are A 41’ 39 1 x 10-4, and A 42' 37 0-5 x 10-A protons (this vol., 402) is ascribed to the process N. M. B. 3Li7-f-1H 1^-22He4, in which the product of the Mass ratios of isotopes from band spectra. reaction is presumably' the only possible source of W.W. W atson (Physical Rev., 1934, [ii], 46, 319).— the y-radiation. Analogous cases in which a y-ray' The effect of the perturbing interactions between the appears to be associated with an excitation level in various energy states of a mol. on the B consts. one of the final products of the reaction arc discussed. should always be investigated in obtaining accurate L. S. T. mass ratios from band spectra. The corrections Does the a-particle possess excited states ? to be applied in the case of CaH and CaD arc discussed. E. F een b erg (Physical Rev., 1936, [ii], 49, 328— L. S. T. 331).— Evidence from recent experiments (cf. Crane, Chemical elem ents and natural atom ic types A., 1935, 1186) is supported by computations on from the viewpoint of the investigation of three different nuclear models which indicate definitely isotopes. 0 . H a h n (Ber., 1936, 69, [A], 5— 20).— a singlet 2p level in the discrete eigenvalue spectrum A review of work published between the end of 1934 of the a-particle if the range of the intra-nuclear and of 1935. H . W . forces exceeds 2-0 XlO-13 cm. N. M. B. , Properties of ions. I. Electronic homologues a-Particles from lithium ions striking hydro m the periodic system. II. Periodic system gen com pounds. J. Z e le n y , C. J. Brasefield, wd the properties of ions. B. V. Nekrassov C. D. Bock, and E. C. P o lla r d (Physical Rev., (bull. Soc. chim., 1936, [v], 3, 151— 155, 155— 159).— 1934, [ii], 46, 318).— Bombardment of NH,C1 and A new presentation of the periodic system, based Al(OH)3 with 2 4 x l0 4 volt Li ions yields a small on the electronic structures of the elements in their no. of a-particles (approx. 12 and 9 per min. per different states of valency, is given. microamp., respectively) resulting from the dis H. The properties of ions are discussed in the light integration of Li, probably Li7. L. S. T. of the above classification. E. S. H. Ranges of a-particles in photographic emul System of masses of light atoms deduced sions. H. J. T a y lo r and V. D. D a b h o lk a r (Proc. rom nuclear reactions alone. I I . L. Isak ov Physical Soc., 1936, 48, 285— 298; cf. A., 1935, uampt'r rend- Acad- ScL U.R.S.S., 1935, 4, 141— 91 ()).— From measurements on Ilford R plates of > cf. (his vol., 7).— Using the data of nuclear the tracks of a homogeneous group of a-particles Si h10ns’ ibe at- ""’Is. of the light elements up to of range r, a distribution curve is drawn, from “ ni, a'-e been determined and are compared with which L, the extrapolated length of the tracks, is .. CDU«al ” and “ physical ” at. wts. When devi- calc. The ratio L/r is const. ¿ 1 % for a-particles ' l°ns 04 die at. mass vals. from the nearest integer of various ranges, and if L is measured r can be calc. the 316 P^°.tted against at. nos. between H and A1 This method, applied to the tracks produced by the wavCUrve. ‘s wave-shaped, the amplitudes of the disintegration of B and Li under slow-neutron bne is g^^^dim inishipg until ultimately a straight bombardment, gives ranges 1-14^0-02 and G-GI^ 0-06 cm., respectively', in air. Sm emits a-particles Iop°me ProPerties of radioactive series. E. of range 1-13^0-02 cm. in air, and other particles The n T * (ComPt- rend., 1935, 201, 1361— 1363).— of longer range. N. M. B. are ,. erent phases of radioactive disintegration Scattering of fast ß-particles by nitrogen scussed from the point of view of Perrin’s nuclei. F. C. Champion (Proc. Roy. Soc., 1936, model (A., 1932, 556). T. G. P. A , 153, 353— 358).— The scattering of fast ß-particles Continuous spectra of Ra-E and Ra-P3«. by' N nuclei has been examined between 20° and 180°. ICH^N0V’ A - I- Alichanian, and B. S. Over the whole range, the most satisfactory agree enerev T e ^ ature> *936, 137, 314— 315).— The ment is with Mott’s formula (A., 1929, 861). For reveal, i Stnblit4on curve of [3-particles from Ra-E the large-angle scattering the results support those low en * omission of a large no. of electrons with of Neher (A., 1931, 1347), and for smaller angles radio-P^^af- u ^'omPRrison with the (3-spectrum of those of Chadwick and Mercier (Phil. Mag., 1925, > vhich has a max., shows a considerable [vi], 50, 208). L. L- B. 402 BRITISH CHEMICAL ABSTRACTS.— A.
Anomalous absorption of [3-rays. D. Sko- 137, 185— 186).— The effect of screens or scattcrers of b e lz y n and (Miss) B. Stepanova (Nature, 1936, various elements on the radioactivity induced in Ag 137, 234). L. S. T. by neutrons has been investigated. The component Energy of y-rays excited by slow neutrons. of 140 sec. half-period is increased in amount by Si, S. K jk u ch i, H . A ok i, and K . Hiisimi (Nature, 1936, Fe, Cu, Zn, Ag, Cd, Sn, Hg, and Pb, but not by C or Al. 137, 186; cf. this vol., 266).— The energy of y-rays The 22 sec. product is enhanced by C, Al, Cu, Cd, ami accompanying the recombination of a proton with Sn, and weakened by Hg or Ag. L. S. T. a slow neutron to form a deuteron is 2 -2 x 10« e.v. Absorption of slow neutrons in carbon. Curves showing the energies of y-rays excited in G. A. F in k , J. R. D unning, and G. B. Pegray Cd, Cl2, Cu, and Fe by slow neutrons are given. (Physical Rev., 1936, [ii], 49, 340).— In view of The y-rays from Cd have at least two components, uncertainty as to whether C is responsible for some of whilst those from Cl2 appear to be homogeneous. the absorption of slow neutrons in paraffin (cf. A., L. s . t . 1935, 1186) data are given for neutrons detected per Absorption measurements of hard y-rays min. by a Li-lined ion chamber from a Rn-Be source from fluorine bombarded by protons. E. surrounded by a paraffin sphere and a C cylinder. M c M illa n (Physical Rev., 1934, [ii], 46, 325).— Results indicate that if C absorbs any slow neutrons y-Rays from various targets bombarded by T lx lO 6 this is > compensated for by neutrons slowed down in volt-protons and 2 -2 x lO 6 volt-deuterons have been the C. N. M. B. investigated. W ith proton bombardmerit B, Be, Li, and F give strong y-rays in increasing order of Capture of slow neutrons. O. R. F risch and intensity. The F radiation is homogeneous and no G. P la c ze k (Nature, 1936,137,357).— Cd is an efficient neutrons are indicated. With deuteron bombard absorber for neutrons of thermal energies, but becomes ment F, C, B, Li, and Be give strong ionisation, part almost transparent for neutrons of energy > 1 volt. of which is due to neutrons. L. S. T. The capture probability in Cd has a max. between Absorption of y-rays excited in cadmium 1 and 0-03 volt. L. S. T. by slow neutrons. H. Herszfinkiel and L. Neutrons of thermal energies. P. B. Moo.v Wertenstein (Nature, 1936, 137, 106— 107).— The and J. R . T illm a n (Proc. Roy. Soc., 1936, A, 153, amount of y-rays excited in Cd by neutron bombard 476— 492).— Experiment show's that a large proportion ment is practically independent of the thickness of of the “ slow' ” neutrons formed when fast neutrons Cd traversed between 0-1 and 1 mm. and decreases pass through H 20 or paraffin wax have thermal when thicker sheets are used. Further results velocities. The cross-sections for the absorption ol obtained with screens of Pb, Fe, and A1 indicate thermal neutrons by the nuclei Cu, V, Dy, Ag, Rk that the energy of these y-rays must be of the order I, and B increase when the temp, of the neutrons is of 107 e.v. ' L. S. T. reduced from room temp, to 90° abs., the increase y-Rays from boron bombarded with deuterons. depending on the geometrical conditions of the experi H. R. C rane, L. A. D e lsa sso , W . A . F o w le r , and ment. The apparent absorption of neutrons by 1 C. C. L a u ritse n (Physical Rev., 1934, [ii], 46, 1109— and by Ag is greatest wdien measured with the same 1110).-—The spectrum of recoil electrons produced by element as detector. L. L. B. the y-rays from B bombarded with deuterons consists Selective absorption of neutrons by gold. of components of < five different energies. O. R. F risch , G. H e v e sy , and H . A. C. McKai L. S. T. (Nature, 1936, 137, 149— 150).— Experiments on the High-energy y-rays from lithium and fluorine activation of Au by neutrons slowed down by paraffin bombarded with protons. H. R. C ran e, L. A. wax with a Cd filter indicate that there is a group of D elsa sso . W . A. Fowler, and C. C. Lauritsen neutrons of narrow velocity range which are strongly (Phvsical Rev., 1934, [ii], 46, 531— 533; cf. A., 1935, absorbed by Au, but transmitted through Cd. The 1186). L. S. T. no. of strongly absorbed neutrons is apparently only Nuclear photo-electric effect in deuterium. a small fraction of the total no. transmitted by Cd. G. Isin g and M. H e ld e (Nature, 1936, 137, 273).— L. S. T. The val. obtained for the mass of the neutron is 1-0080 Selective scattering of slow neutrons. J- R- (cf. A ., 1935, 1293). L. S. T. T illm a n (Nature, 1936, 137, 107).— The ¡W Existence of resonance levels for the capture activity induced in I, Ag, and Cu by neutrons slowed of neutrons. H. von Halban, jun., and P. P reis- down by paraffin wax is increased by different w e rk (Compt. rend., 1936, 202, 133— 135).— Reson amounts when the metals are backed with a further ance levels seem to exist. T. G. P. layer of paraffin wax. L. S. T. Energy distribution of neutrons slowed by Agreement between the balance of nuclear elastic impacts. E. U. C on d on and G. B r e it energy and the experimental masses of light (Physical Rev., 1936, [ii], 49, 229— 231).— Mathe elements. L. C a rta n (Compt. rend., 1935, 201- matical. The energy distribution of particles of mass 1363— 1366).— The mass of the H atom (0=16) h«8 m, initially of the same energy, which have made n been corr. to 1-00810^0-00010 from a study of the impacts with particles of mass 31, all initially at reactions Bu -f H 1= 3 H e 4, B e 9 + H 1= L i6+ H e 4, B10+ rest, is calc. N. M. B. D 2— SHe4, and B10-(-D2= B n -f H1, and vals. for P- Effect of scattering neutrons on induced radio He4, Li«, Li7,. Be9, 3 10, B11, and C12 calc, which agree activity. J. R o t b la t and M. Zvw (Nature, 1936, with those of Oliphant et al. (A., 1935, 910), excepting GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 403
those of Be9 and C12, which are 9 0152 and 12-0037 ± Recovery time of Geiger-Muller counters. 0-0010, respectively. T. G. P. W . E. D ani'O rth (Physical Rev., 1934, ii], 46, 1026— 1027). v L. S. T. Disintegration with the emission of protons induced by neutrons. F. N. D. K u r ie (Physical Artificial radioactivity and the conversion of Rev., 1934, [ii], 46, 330).— Disintegration by neutrons kinetic into y-ray energy associated with nuclear from Be bombarded with 3 x lO G volt-deuterons in disintegration by neutrons. W. D. H a r k in s which a proton or other particle of charge approx. and D. M. Gans (Physical Rev., 1934, [ii], 46, 827— 1 is emitted instead of the usual a-particle is described. 828).— A discussion. The at. nucleus is an efficient Possible reactions are -N 14+ 0w1= rC11-i-1H 1 or o0 16+ converter of large amounts of kinetic into y-rav 0„ i = 7yiG+ i H i. ' L. S. T. energy. L. S. T. ‘ Transformation of energy. (Lord) Ruther Disintegration, of nitrogen by neutrons. T. W. fo r d (Nature, 1936, 137, 135-—137).— A lecture. Bonner and W . M , B ru b a k e r (Physical Rev., 1930, L. S. T. [ii], 49, 223— 229).— Disintegrations observed in a Neutron capture and nuclear constitution. cloud-chamber filled with N 2 at reduced pressure are N. B o h r (Nature, 1936, 137, 344— 348).— A lecture attributed to one of the reactions: 7N 11-t-0w1-> 5B11+ in which new views are presented. L. S. T. 2He4;_ 7Nu + 0# ^ ?Cu i Hi; 7N i4+ oWi-> 2He4+ 2He4 -f3Li'. The first is valid for slow and fast neutrons, Nuclear stabibty and isotope shift. G. B r e it the energy of disintegration for the reaction being (Physical Rev., 1934, [ii], 46, 319).— Gamow’s 2-33T;0-26 m.e.v. The second and third reactions diagram (A., 1934, 939) is discussed in relation to the are less frequent. Full data for 91 disintegration observed isotope shifts of Hg and Pb, L. S. T. forks are tabulated. N. M. B. Neutrino theory of radiation and the emission of (3-rays. R. de L. K r o n ig (Nature, 1936, 137, Production of radioactive oxygen. M. S. 149).— A discussion. L. S. T. Liv in g sto n and E . M c M i l l a n (Physical Rev., 1934, Does conservation of energy hold in atomic t>i], 46, 437— 438).— Bombardment of Pt and Cu processes ? P. A. M. D ira c (Nature, 1936, 137, targets by 2 X 10° volt deuterons in a modified 298— 299). L. S. T. apparatus (A., 1935, 1441) produces a positron activity of 1264;5 sec. half-life in N 2 but not in 0 2, Negative protons in the nucleus ? J. H. jh or A. This activity is due to activation of N 2 B a r t le t t , jun. (Physical Rev., 1934, [ii], 46, 435; (1 atom, per 10° incident deuterons), probably ac- cf. A., 1933, 1226).— Attention is directed to a c®^g to the reactions 7N 14 -}-tH2-> gO15+ qR1 and certain regularity in the isotope pattern which may «0 54 ;N15-(-1e+. The max. energy of the positrons show how negative protons become incorporated in hom the second, radioactive process is approx. the nucleus. The case of Zn is discussed. Several 1'7X106 volts. L. S. T. elements, including In, Sh, and I, may bo found to have 3 odd isotopes. L. S. T. P-Ray spectra of some induced radioactive Heights of nuclear potential barriers. E. D. elements resulting from neutron bombardment. Eastm an (Physical Rev., 1934, [ii], 46, 744).— . ■ ■^ArDu and R. E. Sin a y (Proc. Physical Soc., Barrier heights calc, from Heisenberg’s theory are J36, 48, 332— 336).— Preliminary determinations compared with other indications of their magnitude. Gre given of the energies of the end-points, found L. S. T. rom block diagrams, of the 3-ray spectra of some Nuclear m om ents. S. F risch (Compt. rend. unstable elements produced by neutron bombard Acad. Sci. U.R.S.S., 1935, 4, 21— 22).— The nuclear ment of p, Si pvp Ag E u and Dy, a cloud chamber moments, I, of elements of odd at. no. are given being used. N. M. B. by I= L ^ z S , where L is the resultant moment of the Action of slow neutrons on rare-earth proton orbit and the nuclear residue, and S is the proton spin. Vais, are tabulated. H. J. E. S - n t s . G. H e v e s y and H . L e v i (Nature, 1936, of ii dccay periods and relative intensities Spin and magnetic moment of the potassium as arimcially radioactive rare-earth elements, K 39 nucleus. S. M illm an , M. Fox, and I. I. R abi *• etermined by various investigators, are sum- (Physical Rev., 1934, [ii], 46, 320).— Deflexion of a -nsed, together with new data for the absorption beam of neutral K atoms in a weak magnetic field „ s ow. eeutrons by the rare-earth elements. Dis- gives 3/2 for the spin of K 39. The liyperfine structure tn JfnCles *n Published data appear to be due mainly separation calc, for the 2St normal state is 0-0147 e Prcsence of small amounts of impurities. cm."1, giving 0-38 unit of the nuclear magneton L S T lzo/1838 for the nuclear magnetic moment. Dnur°Sm*C~ray particles of bigb penetrating L. S. T. 358)—v Leprince-Ringuet (Nature, 1936, 137, Molecular orientation and the probability of that tl W measurements agree with the assumption excitation and dissociation of the hydrogen nfNi*-.'e oro penetrating cosmic rays consist of molecule by electron impact. N. S asaki and ■iv e and negative electrons and of protons. T. N akao (Proc. Imp. Acad. Tokyo, 1935, 11, 413— q L. S. T. 415; cf. A., 1935, 1185).— From quantum-mechanical R a 4®ral interpretation of cosmic-ray effects, calculations it is deduced that the probability of cf' 7 (Physical Rev., 1934, [ii], 46, 329; excitation of the H 2 mol. to the l 32-state is a max. A-> taoo, o60). L. s . T. when the mol. axis is parallel to the electron beam, 404 BRITISH CHEMICAL ABSTRACTS.— A. I (h), II (o) in accord with experimental data 011 the dissociation Annihilation of positrons. J. C. J a eg er and of H , mols. J. W . S. H . R. H ulm e (Proc. Camb. Phil. Soc., 1936, 32, Calculation of eigenfunction of metallic elec 158— 160).— Theoretical. A. J. M. trons. H. B e th e (Helv. phys. Acta, 1934, 7, Space quantisation. I. I. R a b i (Physical Rev., Suppl. II, 18— 23; Chem. Zentr., 1935, i, 2954).— 1936, [ii], 49, 324— 328).— A discussion of the effect The method of calculation of Wigner and Seitz of a rapidly varying weak magnetic field on an oriented (A., 1934, 1283) is applied to the calculation of the atom having nuclear spin shows that on the basis eigenfunctions of electrons in metals and in free of the Phipps-Frisch modification of the Stern- atoms, and to calculations arising therefrom of Gerlach experiment nuclear spin can be measured cohesion, excited electronic terms, and free electrons even when the hyperfine structure separation is in alkali metals. J. S. A. very small. N. M. B. Limits of elementary theory of metallic Interrelationships of e, h /e, and e/m . R. T. electrons. L. N ordheevi (Helv. pliys. Acta, 1934, B irg e (Nature, 1936, 137, 187).— A crit. survey. 7, Suppl. II, 3— 17; Chem. Zentr., 1935, i, 2954).— The existence of a major discrepancy between the The classical theory of Sommerfeld is restated in grating val. of e, (4-8029¿0-0005) X 10-10 e.s.u., and terms of quantum mechanics, and extended to cover that obtained by various methods involving e/m effects at high temp. J. S. A. and 7i/e, (4-7824^0-0015) X 10~10 e.s.u., indicates Statistical basis of electron theory of metals. that either the Bohr formula for the Rydberg const, R. P eierls (Helv. phys. Acta, 1934, 7, Suppl. II, or the method of calculating e on the assumption 24— 3 0 ; Chem. Zentr., 1935, i, 2953— 2954).— of a geometrically perfect calcito crystal is incorrect. Theoretical. J. S. A. L. S. T. Sommerfeld’s theory of metals. K. F. N ie ssen Intensity distribution in band spectra of (Ned. Tijdschr. Nat., 1935, 2, 71— S9; Chem. Zentr., diatomic molecules. W . W e h r l i (Helv. phys. 1935, i, 3765).— An explanatory resume of the chief Acta, 1934, 7, 676— 683; Chem. Zentr., 1935, i, features of the Sommerfeld theory. J. S. A. 3515).— A discussion of anomalous data for Gal and I11I (cf. A., 1934, 1286). H. J. E. Errors of approximation in Jeffreys’ phases. F . L. A r n o t (Proc. Camb. Phil. Soc., 1936, 32, Reversal of a branch in a non-electronic hand. 161— 178).— The errors involved in the use of an A. A d e l (Physical Rev., 1936, [ii], 49, 340).— Atten approximation method due to Jeffreys of solving tion is directed to the first recorded instances of this the radial wave equation for the motion of an electron phenomenon. N. M. B. in the field of a spherically symmetrical atom are Chemical reactivity and light absorption. examined with reference to neutral Cl. A. J. M. N. R. D h a r and P. N. B h a rg av a (Indian J. Physics, Statistical theory of neutral atoms. P. L a l 1936, 10, 43— 47 ; cf. A., 1935, 144).— The increase and K . L a l (Indian J. Physics, 1936, 10, 1— 6 ).— in light absorption of a mixture of undried H2 and A simplified method is given for calculating the Br, above that of the separate constituents, is not binding energy of an atom by making use of the observed when the gases are completely dry and there Thomas-Fermi statistical model and neglecting the fore non-reactive. This is in accordance with the interaction between electrons. For the lighter atoms view that increased absorption is a measure of the the results are in good agreement with those derived reactivity of the system. M. S. B. by other methods. An expression for the radius Sodium resonance radiation and the polymer of a neutral atom has also been obtained. M. S. B. isation of ethylene. J. C. J u n g e r s and H. S. Dispersion of light in the region of magnetic T a y lo r (J. Chem. Physics, 1936, 4, 94— 96).— C2B4 dipole lines. B. Milianczuk (Bull. Acad. Polonaise, quenches the resonance radiation of Na vapour 1935, A , 438— 444).— Theoretical. The Kramers- between 130° and 250°, but no measurable poly Heisenberg formula for dispersion holds for magnetic merisation of C2H 4 takes place, contrary to the be dipole lines if the corresponding transition probabilities haviour with the resonance radiation of excited Hg are substituted. A. J. M. and Cd. Above 250°, however, the polymerisation of C2H 4 is catalysed by Na surfaces with an activation Magnetic dipole radiation. B. M ilia n c zu k energy of 20 kg.-cal. Reasons for the a p p aren t^ (Bull. Acad. Polonaise, 1935, A , 430— 437).— Theor greater efficiency of thermal activation, as com pared etical. The Zeeman separation and intensity ratios of spectral lines due to magnetic dipole radiation are with photo-activation, are discussed. M. S. B. calc, on Dirac’s theory. A. J. M. Spectrum emitted by a potassium bromide Limit to the quantum theory and the avoid crystal under X-rays. P. W. B u rb id g e and T. G- ance of negative energy transitions. H. T. M o o r c r a ft (Nature, 1936, 137, 278).— Bands with F l i r t (Nature, 1936, 137, 313— 314).— The prin- centres at 5310, 4520, and 3810 A. have been photo ciple of min. proper time, according to which inter graphed. L. S. T. vals of proper time < h[m0c2 have no physical signi Ultra-violet spectrum of ammonia. II- Rot- ficance, eliminates the conception of an electron ational structure of some bands in the Schum ann moving with a high velocity in a strong field of region. A. B. F. D u n c a n and G. R. H a r b i s o s force and sets a boundary to the region to which such (Physical Rev., 1936, [ii], 49, 211— 214; cf. A., I93aj a conception may be applied and to the domain where 912).— The seven (0, 2)— (0, 8 ) bands of the secow the quantum theory is valid. L. S. T. electronic state above the normal, in the range II («) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 405
1620— 1450 A., have been photographed, and their 1930, 1496).— The absorption eoeffs. of N 20 4 and N 0 2 structure is discussed. N . M. B. in the region 3200— 4105 A. have been measured. Ammonia bands in the near infra-red. S. K. T. G. P. Chakravorti (Indian Phys. Math. J., 1934, 5, 25— Absorption spectra of monoxides of alkaline- 33).—The fundamental frequencies of N H 3 are ealc. earth m etals. P. K . Se n -G otta (Bull. Acad. Sci. from wave mechanics, the mol. being regarded as a Agra and Oudh, 1934, 3, 203— 20S; Chem. Zentr., symmetrical pyramidal top, with N at the apex 1935, i, 2947).— The spectra of CaO, BaO, and SrO and H at each corner of the equilateral base. The show a limit of continuous absorption, corresponding calc, electric moment is 3-2 times the observed val. with dissociation into neutral atoms. J. S. A. Ch . A b s. (e) Absorption spectrum of sulphur trioxide. E. Band spectra of LiH, LiD, and NaD. P. H. F ajans and C. F. Goodeve (Trans. Faraday Soc., Crawford and T. J o r g en sen, jun. (Physical Rev., 1936, 32, 511— 514).— The absorption spectrum of 1934, [ii], 46, 939 ; cf. A ., 1935, 561). ' L. S. T. S0 3 vapour between 3000 and 2200 A. consists of weak diffuse bands superimposed on a continuous Absorption spectrum of magnesium hydride background. The bands are of an unusual typo and in the ultra-violet. B. Gr h n d st r o m (Nature, consist of flat max., -with sharp min. separated by an 1936, 137, 108— 109).— The absorption spectrum approx. const, frequency distance=430 cm.-1 The of MgH from Mg heated in H 2 at 1400° shows, in bands cannot be measured with certainty above addition to the band at 2430 Â. (A., 1929, 376), 2500 A. and are not due to S 0 2. O. J. W . a band in the ultra-violet corresponding with a transition from the ground-level 2S to a hitherto Absorption spectra of the tellurium oxides unknown activated state in MgH. L. S. T. T eO a and T eO . C. S. P ia w (Compt. rend., 1936, 202, 127— 128; cf. this vol., 134).— The absorption Intensities in the 3 4 0 0 band of phosphorus spectra of T e02, and of TeO which appears when hydride. P. N o lan and F. A . J e n k in s (Physical T e02 vapour is heated above 1000° at low pressures, Rev., 1934, [ii], 46, 327).— Line intensities in the have been studied. T. G. P. rotational structure of the 3H, 3S band of PH have Band spectra of the lead halides, PbF and PbCl. been measured. L. S. T. G. D. R ochester (Proc. Roy. Soc., 1936, A , 153, Absorption spectrum of nitrous oxide in 407— 421).— The emission band spectra of PbF and Schumann region. P. K . Se n -G o tta (Bull. Acad. PbCl arc described. Their similarity to the corre Sd. Agra and Oudh, 1934, 3,1 9 7 — 202 ; Chem. Zentr., sponding spectra of the Bi halides is shown to be a 1935, i, 2945).— Continuous absorption commences consequence of the identity of the vibrational consts. at 1850 A., with a region of transmission between Popov and Neujmin’s analysis of PbCl (Physikal. Z., bOO and 1580 Â. The absorption is attributed to Sovietunion, 1932, 2, 394) is incorrect. No definite the formation of excited N atoms according to evidence of Pb isotope effects is obtained, but large JjQ+*v (1 8 5 0 )= N O + N C~D) ; N 20 + A v (1580) = Cl isotope effects are observed. The relations of the a 0 +N (2P), the calc, excitation potentials agreeing vibrational consts. of the Pb halides to those of other with experiment. J. S. A. heavy mols. are considered. L. L. B. Doublet separation in the normal state of nitric Absorption spectra the halides of fifth group oxide and its thermodynamic quantities. E. E. elements. H. T r iv e d i (Bull. Acad. Sci. Agra and Wither (Physical Rev., 1934, [ii], 4 6 , 629). Oudh, 1934, 3, 229— 238; Chem. Zentr., 1935, i, L. S. T. 2946).— From the absorption spectra of SbCl5, pressure broadening in the y-bands of nitric AsBr3, SbBr3, PI3, and Asl3 the heats of formation oxide. 0. R. W u lf (Physical Rev., 1934, [ii], 46, per atom of halogen have been calc. Vais, so found ° 6).—An explanation of this effect is discussed. differ from accepted thermochemical data. Asl3 and „ L. S. T. SbBr3 show a second region of transmission. J. S. A. spectrum of the first discharge through Absorption spectra of formaldehyde and trogen peroxide. L. Gr illet and M. D uffteux hydrogen cyanide in the far ultra-violet. W. C. (toinpt. rend., 1935, 2 0 1 , 1338— 1340).— The emission Price (Physical Rev., 1934, [ii], 46 , 529; cf. A., spectrum of feebly excited N 20 4 streaming rapidly 1935, 805).— HCN shows bands extending from 1450 ’rough a discharge tube consists of (a) the phos to below 1000 A. The bands at lower XX probably phorescent spectrum of N 0 2, (b) O i bands, (c) N i form an electronic series corresponding with an « nets, [d) the second positive group of N 2, (e) the ionisation potential of HCN at 14-8 volts. ^ Two °f hvO ’ three unknown spectra consisting types of absorption are indicated. L. S. T. (/) a vibration-rotation band at 5996 cm.-1, (g) Fluorescence and absorption bands of some ands^ between 5936 and 5227 cm.-1, (h) bands derivatives of coumarin. W. Czapsk a -N a r k ie - vi i"?0? ancl 6547 cm.-1 degraded towards the whcz (Bull. Acad. Polonaise, 1935, A , ‘445— 447).— e ’ between 6405 and 6576 cm.4 degraded towards The fluorescence and absorption spectra of 7-hydroxy - red, and a band with a max. at 6350 cm.4 , and coumarin-3-carboxylic acid (I), Et 7-hydroxy- (II) numerous unknown lines in the extreme red and and 7 : 8-dihydroxy-coumarin-3-acetoacetate (III) >nfra-red. T G P have been investigated. The fluorescence max. are Quantitative data on the absorption spectrum at 4596, 4727, and 4679 A., and the absorption max. peroxide. M. L ajibr ey and J. Cor- at 3300, 4314, and 4517 A., for (I), (II), and (III), ***- (Compt. rend., 1935, 2 0 1 , 1334— 1335; cf. A., respectively. A. J. M. 406 BRITISH CHEMICAL ABSTRACTS.— A.
Absorption of ultra-violet light by some have been measured from 1 -5 to 2-5 g. The hydroxides organic substances. XL. L. Marchlewski and have bands at 2-30 and 2-45 g, the acids at 2-30 and B. Skarżyński (Bull. Acad. Polonaise, 1935, A , 474— 2-55 g, and the salts at 2-30, 2-45, and 2-55 g. The 478).— The ultra-violet absorption spectrum of PhMe band at 2-30 g is produced by hydration and at in EtOH solution was investigated. The mol. 2-45 g by OH'. M. S. B. extinction curve lias two max. at 2684 and 2720 A., Residual rays of magnesium oxide. M. respectively. A similar curve was obtained for P aro d i (Compt. rend., 1936, 202, 302— 304).— PhEt (max. at 2683 and 2620 A., respectively). Born’s method of calculation for cubic crystals of the A. J. M. NaCl type is applied to MgO. The calc. XX were Ergot alkaloids. Ultra-violet absorption 15-85 and 14-47 g, corresponding with observed vais, spectra of lysergic acid and related substances. of 15-3 and 14-8 g, respectively. H . J. E. W . A . Jacobs, L. C. C raig, and A. R o th e n (Science, 1936, 83, 166— 167).— Curves obtained for this acid Infra-red absorption spectra of liquefied gases. and some of its derivatives are reproduced and dis M ethane. C. C orin and J. H e r r y (Compt. rend., cussed. L. S. T. 1936, 202, 41— 44).— Data are recorded for the ab sorption bands of liquid CH4 and of its solutions in Emission spectra of cholesterol irradiated by liquid N , ( < 1 to 50% ). Eleven bands were observed sun- and ultra-violet light. A. H. R o f f o and at XX 0-8— 2-7 g, in positions agreeing with vais, for A. E. R o ff o , jun. (Compt. rend., 1935, 201, 1434— the gas. The data are compared with those for 1435).— Emission bands at 353-3 and 357-2 mg occur. c 6h 14. H. J. E. F. O. H . Carotene. X. Comparison of absorption Effects of isom erism on infra-red absorption spectra measurements on a- and (i-carotene and spectra. W. G o rd y and D. Williams (J. Chem. lycopene.— See this vol., 460. Physics, 1936, 4, 85— 87 ; cf. this vol., 9).—The spectra of MeCN, EtCN, BuCN, PhCN, MeCNS, Infra-red absorption band of heavy-water EtCNS, and their isomcrides, and also of PhCNS, vapour. W. V. N o rr is, H. J. U n o e r, and R. E. have been determined between 1-0 and 6-5 g. The H olm q h ist (Physical Rev., 1936, [ii], 49, 272).— characteristic CN band near 4-6 g is shifted to longer Data for a band at 1-5291 g are discussed. XX by about 0-2 g for NC, and its intensity is approx. N . M. B. doubled. This shift agrees with chemical data Vibration-rotation bands of hydrogen fluoride. indicating C11 and hence weaker binding forces in E. O. S a la n t and D. E. Kirkpatrick (Physical the NC compounds. The corresponding shift for Rev., 1934, [ii], 46,318).— 15 and 11 lines, respectively, the SCN isomerides is smaller, but the intensity of the (3-
+ H N O 3, (2) N a O H + H 2SO.„ (3) pyrogallol+02, quantitatively by the increased pressure of the 0 5 (4) glucose-f-KMn04, (5) Na2S20 4- f 0 2, (6 ) 0 ,-f- in the magnetic field. E. E. A. K 2SO,, (7) 0 2+ N a 2S 0 3) (8 ) M g -H g + H 20 , (9) N a - Polarity of nitrogen tetroxide and nitrogen H g + H 20 , (10) A l-H g + H 20 , (11) E t 0 H + H 2Cr04, dioxide molecules. J. W. W illia m s, C. H. (12) 2 B r + K 2C20 4, (13) 2B r+ N a 2C204, (14)“ 21+ Schwingel, and C. H. W in n in g (J. Amer. Cheni. Na2C20 4. Reactions (1)— (3), (5), (8 )— (10) are Soc., 1936, 58, 197— 203).— The electric moments shown by counters with cathodes of A1 or Cul, of N 0 2 and N 20 4 mols. have been calc, from measure (11)— (14) only by the former, and (4), (6 ), and (7) ments of dielectric const, of their gaseous equilibrium only by the latter. T. G. P. mixtures at 29S— 398° abs. and 150— 760 mm. Heterogeneity in crystals and phosphor The polarity of N 0 2 decreases with rising temp., escence. M. C u rie (Conipt, rend., 1935, 201,1352— probably due to the passage of the mols. into more 1353; cf. A ., 1932, 560).— The rôle of impurities is symmetrical higher vibrational states. The dipole discussed. T. G. P. moment of N.,0 . does not differ greatly from zero. Fluorescent power and experimental study of E. S. H. fluorescent power as a function of concentration. Permanent electric moment and structure J. B ou ch ard (J. Chim. phys., 1936, 33, 51— 71).— At of phosphorus pentachloride. P. T r u n e l (Compt. const. p n the fluorescent power of uranine solutions rend., 1936, 202, 37— 39).— Simons and Jessop's follows Perrin’s law
emission. For a gas, the paramagnetic part of the Cox, E. S h a r r a tt, W . W a r d la w , and K . C. W ebster susceptibility depends on the frequency in the same (J.C.S., 1936, 129— 133).— Cu(C5H 5N)2C12 (I) has been way as the electric part, but is determined by the prepared under various experimental conditions with magnetic absorption lines; the diamagnetic part is the object of identifying cis- and traws-isomerides. almost independent of the frequency up to X-ray Only the Irans-iorm was obtained, even by the action frequencies. N. M. B. of C5H 5N on Cu alkylglyoxime dichlorides, which must Werner complexes. Optical activity and con form cis-(I) initially. The cell dimensions of cryst. figuration of ions of the type M A 3. J. P. Mathieu (I), determined by X-ray methods (c-axis 3-84 A.), (J. Chim. phys., 1936, 33, 78— 96).— The optical show that it can only have trams-planar configuration, absorption and rotation of [Co en3]Br3,2H20 , in agreement with previous work (A., 1935, 920). [Rh en3]I3,H 20 , [Ir en3]Br3,2H20 , and [Cr cn3]I3,H20 Cu and N i bismethylethylglyoximes are isomorplious, are compared with those of K 3[Cr(C20 4)3],H»0, and occur in one form only. L. J. J. K 3[Rh(C20 4)3],2H20 , K 3[Ir(C20 4)3],2H20 , and Significance of non-localised linkings (“[p]- K 3[Co(C20 4)3]. The oxalates have the higher electron cloud ") of aromatic hydrocarbons in optical activities, but compounds containing the same formation of their molecular compounds with metal show close analogies. A parallelism exists dipolar molecules. G. B r ie g le b (Z. physikal. between the factor of dissymmetry in the active Chem., 1935, B , 31, 58— 78).— The secondary valency bands and the chemical stability of the compounds. in the above mol. compounds depends chiefly on a J. W . S. dipole induction of the polar groups of the dipolar mol. Optical activity dependent on co-ordinated on the polarisable charge of the unsaturated hydro bivalent ruthenium .— See this vol., 485. carbon. In mol. compounds of polar mols. with Theory of optical activity. III. Regular CgHr or condensed ring systems the polar groups of tetrahedron twisted through a small angle the dipoles induce moments in the localised o-linkings about a binary axis. B. Y. O k e (Proc. Roy. Soc., of the hydrocarbon (a-polarisation) and also perturb 1936, A , 153, 339— 352; cf. A ., 1935, 917).— A the charge distribution of the non-localised [/)]• system of 4 identical vibrators, mutually interacting, electrons ([p]-elcctron polarisation) (cf. A., 1932,901). at the corners of a tetrahedron gives 5 characteristic The induction effect changes the absorption spectrum frequencies. If one pair of vibrators is rotated of the hydrocarbon considerably, which is responsible through a small angle about the line of centres, the for the characteristic colour of the mol. compound. distorted system becomes optically active. The Both polarisations can be estimated from spectro rotatory power is calc, by a method of approximation; scopic data. Calc, heats of formation of eompoundsof it is oc the third power of the small angle of twist. unsaturated ring systems with N 0 2-compounds agree L. L. B. satisfactorily with the observed vals. If a dipolar Absolute configuration of lactic acid. mol. forms a 1 : 1 compound with an unsaturatcd Assumptions made in calculation of optical aromatic hydrocarbon with two Ph nuclei linked rotation.— See this vol., 454. by saturated or unsaturated hydrocarbon chains, it adds itself to a Ph nucleus and an induction perturb Magnetic rotatory power and dispersion of ation initially localised at that nucleus may be trans alkali mercuritetra-iodides. R. L u cas and F. mitted by the non-localised [p]-electrons to the other G a lla is (Compt. rend., 1936, 2 0 2 , 129— 131).— nucleus. Such spreading of the perturbation is The exceptional rotatory properties of K 2HgI4, which stopped, however, by a CH2 group. R- 0- have been measured, are due to a broad absorption band. T. G. P. Concepts of ‘ ‘ resonance ' ’ and * ‘ intermediate Electrical birefringence of compressed stages ” for organic substances with multiple nitrogen. H. B izette (Compt. rend., 1936, 202, linkings, and electronic formulae. F. A rn d t and 304— 305).— Measurements were made at 150 kg. B. E is t e r t (Z. physikal. Chem., 1935, B , 31, 125 per sq. cm. and with a field of 160,000 volts per cm. 131).— The modem concept of “ resonance between The val. of the Kerr const, found was approx. half that two mol. states” is equiv. to the authors’ “ inter given by Bruce and Brcazeale (cf. A ., 1933, 1232; mediate stage ” theory (A., 1925, i, 57; A., 1935,324). 1935, 1192). H . J. E. Modifications in the representation of electronic Electro-optic effect in zinc blende. C. Schramm formulae are suggested. R- C- (Ann. Physik, 1936, [v], 25, 309— 336).— The double Formation of mercury molecules. F. \- refraction and inliomogeneity of the crystals are due A e n o t and J. C. M illig a n (Proc. Roy. Soc., 1936, to cutting or polishing. Kerr consts. for Tl, X a, and A , 153, 359— 378).— Mainly a detailed account oi K light are given and compared with the piezo work already noted (A., 1935, 1917). The ionisation electric consts. ZnS has “ light ” voltage of 1240 or potential of the mol. is 9-65 volts. A max. is ob about one third the val. of PhN 02. W . R. A. served in the mol. ionisation at 11-5 volts, due to Constitution of thioether compounds of triplet excitation, and a second max. at 40 volts, platinum. II. K. A. J e n s e n (Z. anorg. Chem., due mainly to singlet excitation of the atom whin 1936, 226, 16S— 172).— An explanation of the results goes to form the mol. ion. L- IJ- of Lifschitz et al. (A., 1935, 1335), different from that Motions exhibited by anisotropic liquids of the authors, is given. M. S. B. under the influence of an electric field. ■ Planar configuration of quadricovalent com F r e d e r ic k s and V . T z v e tk o v (Compt. rend. Acad- pounds of bivalent copper and nickel. E. G. Sci., U.R.S.S., 1935, 4, 131— 133).— The motions GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 411 of p-azoxyanisole in an electric field depend on the The mode of application of these general formulas field strength and the thickness of the layer of liquid. to, special types of potential energy functions is The mol. axes of the turbulently streaming particles indicated. ” M. S. B. lie parallel to the force lines of the applied field. Potential functions of molecular groups and W . R. A. the vibrations of the halogen derivatives of “ Gas mists.” V. N je g o v a n (Z. Pliysik, 1935, methane. H. H. V oge and (Miss) J. E. R o sen th al 98, 415— 416).— Correction of earlier work (this (J. Chem. Physics, 1936, 4, 137— 143).— Assuming vol., 14). A. B. D. C. that, in a series of mols. Y Z 4, X Y Z 3, Z Y X 3, and Association of liquids at the b.p. K. B tt.t.tg Y X 4, the potential energy of the Y Z 3 is the same (Ber., 1936, 69, [£], 434-^136; cf. A., 1935, 815).— whether it is attached to an X or to another Z and Mathematical relationsliips are developed between the force between Y and X is not changed by the the association factor and surface tension at the nature of the other atoms in the mol., formulae b.p., sp. cohesion, and elevation of the b.p. by connecting the potential energy consts. of these dissolved substances. H . W . mols. are given. Application to the series CH4, Pressure effect on predissociation. W. MeCl, CHC13, and CC14 gives satisfactory results. Lochte-H oltgreven (Nature, 1936, 13 7 , 187— Frequencies calc, for CHC13 and CDC13 from those 188).—The dependence of predissociation on pressure of CH4, MeCl, and CC14 are in good agreement with is discussed for S. L. S. T. observed data. Vals. for the frequencies of CD3C1 are predicted. The CH4 consts. are discussed and Kinetics of dense fluids in two or three dimen it is shown that, although individual consts. may sions, E. F a h ir (Rev. Fac. Sci. Univ. Istanbul, vary with the method of determination, certain 1936, 1, 8— 13).— Mathematical. Tho electrostatic linear combinations of them, to which a definite potential and field on a mol. partly immersed in physical meaning can be attached, are practically an ideal fluid are examined. N. M. B. invariant. Tho C2H 6 consts. calc, from the CH4 Dissociation of SnCl and S nC l2. H. L e ssh e b i consts. are entirely different from those given by and R. Sam uel (Indian J. Physics, 1936, 10, 7— Sutherland el al. (A., 1935, 569), but account equally 12).—The covalent character of the SnCl and SnCl, well for the observed frequencies. M. S. B. linkings is reaffirmed (cf. A ., 1933, 996; 1934, 477; Dipole attraction and hydrogen bond form cf.Trivedi, A., 1935, 913). M. S. B. ation in their relation to solubility. J. H. Calculation of linking energies. W . L asareff H ildebrand (Science, 1936, 8 3 , 21— 24).— An (Physica, 1936, 3, 61— 64).— From the dissociation address. L. S. T. energy of CO, vals. of 108 or 124 kg.-cal. are calc, Rotation of dipoles in elastic and viscous for the_ transition Cdiamond -> C (3-P)gIL, at 0 ° abs., m edia. N . L. Y a t e s-Fis h (Phil. Mag., 1936, [vii], giving 51 or 59 kg.-cal., respectively, for tho C'C 21, 226— 233).— The couple acting on a rigid sphere linking in aliphatic hydrocarbons. A correction when this is rotated through a small angle in a term to account for the discrepancy with the observed medium possessing relaxing elasticity has been calc. val. (> 70 kg.-cal.) is suggested. Gershinowitz’ The result is applicable to the rotation of a dipole criticism (A., 1935, 1448) is rejected. L. J. J. in a solid (cf. this vol., 21). R. S. B. (a) Calculation of energy of H 3 molecule. (B) Applications of astrophysics to physics and J. H irsch- Calculation of energy of H 3+ ion. chemistry. W. N ern st (Oesterr. Chem.-Ztg., 1936, ino?ER’ and N. R osen (J. Chem. Physics, 39, 34— 36).— A lecture. 1J3°, 4> 121— 130, 130— 133).— Mathematical. Evaporation of small drops and the relation „ M. S. B. Aero point energy in determination of struc- ship between surface tension and curvature. J. L. Shereshefsky and (Miss) S. S t e c k le r (J. ure of solids. A. R. U rbelohde (Trans. Faraday Chem. Physics, 1936, 4, 108— 115).— Rates of evapor k°f , 3 3 , 525— 529).— Substitution of one ation of o-C6H4(C02Bu“ )2 droplets of radius 3— 0-5 \j. I0/! * ‘or another in a solid compound will lead to have been determined for different v.p. in a Hoag ! .e^ences in vibrational and rotational frequencies iich, in certain cases, should be large enough to type of Millikan’s oil-drop apparatus. Two inter pretations are given. According to one the surface mformation on the structure of the solid. tension of a droplet decreases -with increasing curvature. p . x F- L - U - nstants of the methane molecule. T. The other assumes a vapour film surrounding the droplet and leads to Kelvin’s equation. M. S. B. -urGEBAUER (Z. Physik, 1936, 98 , 638— 656).— - -sunnng the nucleus C“ 1 and externally the Ne Parachor, surface tension, and density of ^ on> If10 polarisation energy in the substituted phenols and phenolic ethers. A. field of the four protons, the. C-H B u r a w o y and I. M arkow itsch-B u r a w o y (J.C.S., I rations, and vibration frequencies are calc. 1936, 36— 39).— Data are recorded for the hydroxy- N A. B. D. C. and methoxy-azobenzencs and -benzaldehydes, and yy7 mal vibration frequencies of the molecule compared with vals. for the nitro-phenols and -anisoles. f;V (Miss) J. E. R o se n t h a l and H. H. V oge For the o-OH-compounds, but not the o-ethers, the exnmc"1' Ph-Vsics> 3 936, 4, 134— 136).— A general parachor is < both calc. val. and vals. for the m- tcfroi,S1i°ni1S Reived for the potential energy of the and p-compounds. Surface tensions and d for each fremip6 ra mo^ XYZ 3 and the normal vibration set of isomeric ethers agree among themselves, but ncies are given as functions of the consts. the vals. for o-OH-compounds are < for m- 412 BBITISH CHEMICAL ABSTRACTS.— A. II (gr), III (a, b)
and p-isomerides. m- and p-Nitrophenol and p- i, 3887).— Up to 25 a t.-% of Fe, the ZnS lattice shows OH-CgHpCHO are associated (as calc, from Ramsay— no expansion. From the observed X-ray intensities Shields const.), but the o-compounds and the Me the presence of empty spaces in the lattice is inferred. ethers are normal. The anomalies of the o-com J. S. A. pounds are probably due to interaction between the Properties of graphite derived from the trans two o-substituents, which reduces their polarity, and formation of diamond. P. Corriez (Compt. rend., those of o-hydroxyazobenzenes are not necessarily 1936, 202, 59— 61).— Measurements of the X-ray due to quinonoid structure. L. J. J. spectrum, electrical resistance, and magnetic suscepti Parachor and ring structure. II. Spatial bility arc recorded for graphite prepared by heating j configuration of bridged-ring compounds. S. K. diamond for 10 min. in vac. at 1900°. The X-ray R a y (J. Indian Chem. Soc., 1935, 12, 764— 767: cf. spectrum differs from that of sugar C heated to 2000°. A., 1934, 1058).— Data are given for cyc/ohexane, The differences are discussed. The resistance is < cycfohexanone, 3 - me t hy leycZohexanone, cyctohexanol, that of sugar C, but > that of natural graphite. The cyriohexyl acetate, menthol, menthyl acetate, di- susceptibility was approx. the same. H. J. E. pentene, camphoroxime, bromocamplior, camphene, bornyl acetate, fenchone, camphor benzoate, and X-Ray interference in diamond as a wave- a-pinene. The structures are discussed. E. S. II. m echanical problem . P. P. E w a ld and H. Ho.nl (Ann. Physik, 1936, [v], 25, 281— 308).— Mathe Parachor and chemical constitution. IV. matical. The appearance of the forbidden diamond Structure of aliphatic diazo-compounds. S. K. reflexions (2 2 2 ) is caused by a “ zwischenladung" R a y (J. Indian Chem. Soc., 1935, 12, 780— 7 8 2 ; between the atoms which is inactive for higher inter cf. A., 1935, 1306).— Data are given for the Me, Et, ferences because of their considerable spread. Pra, and w-amyl diazoacetates between about 0 ° W . R. A. and 100°. The variation of parachor with temp, (A) Changes of structure of crystals in an shows that these compounds are equilibrium mixtures electric field. (B) Compensation apparatus and of two forms. Low temp, favours the ring form, quantum fluctuation. A. NIcmet (Helv. phys. high temp, the open-chain structure. E. S. H. Acta, 1935, 8 , 97— 116, 117— 151; Chem. Zentr., Constitution of formic acid and formates. 1935, i, 3517).— ( a ) X -R ay intensity measurements in TT.pi— n R. M. H alasyam (J. Indian Chem. Soc., electric fields are recorded for NaCl, calcite, quartz, a 1935, 12) 813— 814).— Published work is mica, K Na and Na Rb tartrate, ice, (HCQs)^ X tj discussed. Parachor determinations M gS04, and tartar. The polarisability in various support the annexed formula as the most crystal directions is discussed. probable for the constitution of H C 02H. E. S. H . (b) The experimental method is described. Interpolation equation for photo-densitometer H. J. E. charts of X-ray diffraction patterns. W . S o lle r Electrolysis, dendritic growth, and discharge (Physical Rev., 1934, pi]., 46 , 331). L. S. T. in alkali halide crystals. A. v o n H ippel (2 Physik, 1936, 98, 580—596).—The movement of Influence of the slit on the distribution of electrons and Cu ions through alkali halide crystals has intensities in the lines of a powder diagram. been studied at 570°, and mobilities of the ions deter A. Rogoziński (Compt. rend., 1935, 201, 1354— mined. Dendritic growths appear on reversal of the 1356).— Theoretical. T. G. P. applied potential, and in NaCl the type of growth may Equation for X-ray crystal curves. R. C. change from the (100) to the (110) direction. Spen cer (Physical Rev., 1934, pi], 4 6 , 1108— 1109). A. B. D. C. L. S. T. Dendritic growth of crystals. A. P a p a p e t k o ! X-Ray diffraction with calcite in several (Z. Krist., 1935, 92, 89— 130).— Partly mathematical, orders of reflexion. L. G. P a r r a t t and F. M i ll e r partly a descriptive illustrated account under the (Physical Rev., 1936, [ii], 4 9 , 280— 288; cf. A ., 1932, following heads : part played by diffusion: effect of 1184).— Theoretical and experimental vals. of the four surface potential; observations on particular sub properties of reflexion, i.e., width of the (n, —n) stances (especially7 inorg. halides); p r o c e s s e s at the tip rocking curve, % reflexion, coeff. of reflexion, and a of the crystal; development near the tip and formation factor determined by the shape of the (n, —n) curve, of branches; crystallisation from the melt. are compared for calcite crystals in the XX ranges B. W. R- 0-71 < X < 5-83 A. in first order, 0-71 < X < 2-75 A. in Growing and testing large single c r y s t a ls of second order, and at 0-71 and 1-54 A . in third order, ice. W . L ew is (Physical Rev., 1934, [ii], 46, 328). and 0-71 A. in fourth and fifth orders. N . M. B. L. S. I- Crystal structure of ice a t low tem peratures. X-Ray examination of atomic vibrations in E. E. Burton and W. F. Oliver (Proc. Roy. Soc- zinc and cadmium. G. W. Brindley (Nature, 1935, A , 153, 166— 172; cf. A., 1935, 686).—Details 1936, 137, 315— 316).— The observed anomalous are given of the apparatus and method used. If.tne X-ray scattering of Zn and Cd is due to a greater lattice ice is formed above — 80°, the mols. have sufficient vibration along the c axis of the crystals than normal energy to arrange themselves into the highly7 organise! to it. " L. S. T. state of a cryst. solid; a t — 9 0 °, t h e energy of the moh Vacant positions in crystal lattice of ferriferous is just enough to build up crystals along ce^ uc' zinc blende. H. B r a e k k e n (K. Norske Vid. planes, whilst just below the crit. temp., ""I . Selsk. Forh., 1935, 7, 119— 120; Chem. Zentr., 1935, there are sufficient mols. arranged in parallel plane-' Ill (b) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 413
to give rise to two diffuse diffraction max., the size of more anions occupy large gaps than smaller gaps, the particles probably being of the order of 10~7 cm. but with a-Ag2S the anions are distributed uniformly L. L. B. over all the gaps. Cubic a-Cu,S is obtained only if Magnetic powder experiments on rolled nickel there is a deficiency of Cu, corresponding with iron. J. L. S n o e k (Physica, 193G, 3, 118— 124).— ~ Cuj.gS. The lattice of a-Ciij.8S is apparently Powder patterns (cf. Bitter, A., 1932,1077) on isotropic similar in structure to that of a-Cu2Se. In a-Ag2Te and anisotropic samples are described. L. J. J. and a-Cu2Se 4 cations per unit cell form with the Crystal structure of cristobalite, Si02. W. anions a Zn blende structure, whilst the remaining Nieuwenkaaip (Z. Krist., 1935, 92, 82— 88).— The 4 are statistically distributed in gaps. In the above cell is pseudo-cubic, a0 7-02 b0 6-92 A., with 8 mols. compounds the lattice changes from body-centred Si02, d (X-ray) 2-33, space-group P 4224. Parameters to face-centred when the ratio of the radius of the are determined. B. W . R. cation to that of the anion changes from 0-637 to 0-57. R. C. Anomalous structures of fine crystalline silica. Crystal structure of potassium, rubidium, N. A. Schischakov (Coinpt. rend. Acad. Sci. U.R.S.S., cæsium, and thallium silicofluorides and of 1936,1,19— 22).— Structures of S i02 have been studied LiMn04,3H20. J. A. A. K e t e la a r (Z. Krist., by the electron-diffraction method. Pused vitreous 1935, 92, 155— 156).— The silicofluorides are iso- Si02 is not amorphous, but consists of deformed morphous with (NH4)2SiF6 ; their lattice consts. and crystals of cristobalite, a 6-87 A ., cja TOG. Pine- parameter vais, are tabulated. Lattice consts. are grained sand (a-quartz) also shows a deformation in also given for LiMn04,3H20. B. W. R. its crystallites, a 4-735, c 5-210 (quartz a 4-903, c 5-393). Pumice gives a 6-82, c 7-23 A. It. S. B. Crystal structure of thallium fluoride. J. A. A, X-Ray investigation of the glassy state. N. K e t e la a r (Z. Krist., 1935, 92, 30— 38).— The cell Valenkof and E. Porai-Koschitz (Nature, 193G, is rhombic, spaco-group Vfh, a0 5-18, b0 5-495, c0 137, 273— 274).— Photographs showing gradual 6-080 A., 4 mols. in cell, d (X-ray) 8-48. This is a changes in the X-ray pattern on transition from new type of AB structure and may be regarded as vitreous Si02 to a mixture of cristobalite and tridymitc a deformed NaCl lattice. The high polarisability of arc reproduced. Similar transition patterns are T1+ is discussed. B. W . R. obtained when Na20 -S i0 2 glasses are subjected to a Anhydrous sulphates of the magnesium series. rising temp, and increased time of heating, leading F. Hammel (Compt. rend., 1936, 202, 57— 59).— to the gradual appearance of the cryst. pattern. The Comparative X-ray data are recorded for the anhyd. lack of a sharp boundary between the glassy and cryst. sulphates of Mg, Mn, Pe, Co, Ni, Cu, and Zn. states and the gradual growth of crystallites are thus H. J. E. demonstrated., L. S. T. Symmetry of tetragonal nickel sulphate. A. Crystal structure of boron carbide. P. L aves Schoev (Natuurwctensch. Tijds., 1936, 17, 233— (Nadir. Ges. Wiss. Gottingen, 1934, [ii], 1, 57— 58; 242).— Corrosion figures obtained by etching the them. Zentr., 1935, i, 2944).— The lattice is trigonal, (111) and (001) faces of N iS04,6H20 crystals indicate u jj'62,' c 12-12 A., giving 2-19 mols. of B GC per unit that they are holohedral, but those on the (112) and odl. It is considered that the compound must be (101) faces correspond with a hemihedral structure. Bic- J. S. A. NiS04,GH20 belongs to the enantiomorphic class of the tetragonal system, and single crystals are either Structure of aluminium boride, A 1B 2. W. dextro- or lævo-rotatory, with a 1-55° per mm. for ?, noEMAxx and W . Jan ic iie (Z. physikal. Chem., 1936, 5893 A. (cf. A., 1932, 986). D. R. D. B, 31 2U—222).— A detailed account of work already noted (this vol., 143). B .C . Crystal structure of tetramminocadmium Crystal structure of the high-temperature perrhenate, Cd(N H a)4(R e 0 4)2. K . S. P itz e r (Z. lorm of silver iodide, a -A g l. L. W . Strook (Z. Krist., 1935, 92, 131— 135).— The cell is face-centred Physikal. Chem., 1935, B , 3 1 , 132— 136).— In a-Agl cubic, a0 10-53 A., 4 mols. in cell, space-group (TjJ. e Ag ions are “ molten,” i.e., are distributed at Approximations to the parameters are made. random over the gaps between the I' ions, which form B. W . R. a body-centred cubic lattice. In a-Ag2HgI4 three Configuration of bisdimethylglyoximoammine occupy a four-fold point position (A., 1934, cobaltic chloride.— See this vol., 460. °b). The intensities of the X-ray diagram of a-Agl Crystal structure of tetrahydrated nickelous have been recalc. R. C acetate. R. B. H u l l (Physical Rev., 1934, [ii], Cubic high-temperature modifications of 46, 329).— a : b : c=0-7216 :1 : 0-4143 have been con uprous and silver sulphides, selenides, and firmed goniometrically, and (5 93° 25' by Laue photo «Uurides. P. R ahles (Z. physikal. Chem., 193G, graphs. Rotation photographs give a0 8-49±0-03, hni. — 1 ^ )-— a-Ag2S and a-Ag2Se have a i>o 11-77±0-05, Cq 4-87±0-03 A. The unit cell con ii ^ 'Ccatred cubic lattice with 2 mols. in the unit tains 2 mols. of Ni(0Ac)o,4H„0 ; d20 is 1-717±0-001. ! w"ilst a-Ag2Te, a-Cuj.8S, and a-CuSe are face- • L. S. T. fotr cubic, with 4 mols. in the unit cell. The Cell dimensions and space-group of calcium thn *a° .siructures °I a-AgoS and Crystallised p-toluidine. J. W y a r t (Bull. Soc. crystal lattice than the atoms are held within the mol. franij. Min., 1935, 58, 281— 293).— The crystals, The connexion between mol. structure and super- d 1-120¿0-003, are orthorhombic with nx 1-68 Ferrites. III. R. S. H ilp e r t and R . S chw ein- flint glass of the type S 231 the Si02 may be replaced iiagen (Z. physikal. Chem., 1935, B , 31, 1— 11; by an equal wt. of Ge02, giving a glass corresponding cf. A., 1933, 1234).— The graph of magnetisability, approx. with Pb2Ge04 and having d 6-92, nn 2-100, o, against composition, x, for C u0-F e20 3 mixtures and np—wc=0-073. The optical consts. of various exhibits a max. corresponding with 2CuO : 3Fe20 3. P b 0-G e02 glasses have been measured (cf. B., 1927, The d-x curve of slowly cooled mixtures has min. 42). R . c. at 2Cu0,3Fe20 3 and Cu0,3Fe20 3, and a max. at Cu0,2Fe20 3, but if the mixture has been cpienched Rock-salt structure of Li2T i0 3 and its form the first min. is absent. Zn ferrites have a max. ation of mixed crystals with MgO and Li2Fe,.Or o and min. d at 2Zn0,3Fe20 3, but the min. d is absent E. K o rd e s (Z. Krist., 1935, 92, 139— 153).— Lattice in quenched mixtures. The d suggests the existence consts., d, and n of Li2T i03 are determined; the of three series of Zn ferrites having, however, the intensities indicate a statistical distribution of Li+ same .X-ray diagram. The d-x curves of Sr ferrites and Ti+4. A continuous series of mixed crystals is and Fe20 3-P b 0,F e20 3 mixtures have no max. or formed with MgO, the lattice consts. and n of which min. For all these ferrites the property-composition alter continuously with the composition. A more curves show no indication of metaferrites. R. C. complicated mixed crystal of MgO, Li2Fe20 4, and Li2T i03 is prepared and examined; its consts. can Mathematical expression of the [magnetic] be deduced by an additive law. Possible applications hysteresis curve. J. N e u f e ld (Compt. rend., to ceramics and refractories are discussed. 1936, 2 0 2 , 125— 126).— Theoretical. T. G. P. B. W . R. Analysis of dynam ic curves for the m agnetic Refractive indices of metallic films showing permeability and losses in iron. V. A r k a d ie v Newton's rings. K. P rosad and B. N. G h osh (Compt. rend., 1936, 202, 39—41). H. J. E. (Indian J. Physics, 1936, 10, 49— 53).— Previous work (ibid., 1933— 1934, 3, 425) on the coloured con Non-orthogonality and ferromagnetism. J. H. centric rings, similar to Newton’s rings, obtained on Van Vleck (Physical Rev., 1936, [ii], 49, 232— 240).— the Al cathode of a Hadding’s X-ray tube with a Mathematical. N . M. B. Cu anti-cathode, has been extended to the examination Curie point of nickel. E. C. S to n e r (Proc. of the rings obtained using a Pt anti-cathode. Leeds Phil. Soc., 1935— 1936, 3, 127— 131).— A M. S. B. discussion of the derivation of theCurie point from Rotation of the plane of polarisation by oblique experimental data. H . J. E. crystalline refraction. G. B r u h a t and L. W e i l (Bull. Soc. fran5. Min., 1935, 58, 294— 313).— Discontinuities of m agneto-resistance. C. W . Measurements on quartz and calcspar verify, for Heaps (Physical Rev., 1934, [ii], 46, 1108; cf. A., small angles of incidence, Potier’s theory and Mac- 1931,480).— A reply to criticism (A., 1935, 287). Cullagli’s formula. L. S. T. L. S. T. Method of investigating the Hall effect. H. S. Plastic deformation of cadmium single Hatfield (Proc. Physical Soc., 1936, 48, 267— crystals. R. R oscoe (Phil. Mag., 1936, [vii], 21, -/6).—An improved method, avoiding thermo-electric 399— 406).— Measurements were made on the bending and other disturbing effects, is described and checked of single-crystal wires of very pure Cd, and of Cd aPprox. for Al, Cu, Pb, Ni, Ag, Zn, and Sn. containing 0-11% Pb and 0-03% Zn. Results N. M. B. indicate that, when the stress over the glide-planes Method for determining the optical constants is not uniform, slip begins when the max. val. of °£ crystals and its application to certain organic the resolved shear stress reaches the crit. val. for compounds. R . G. W o o d and S. H. A y l i f f e (Phil. deformation under uniform stresses. Surface oxid Mag, 1936, [vii], 21, 321— 336; cf. A., 1935, 434).— ation produces, in resistance to plastic deformation, slng Hie immersion method with a polarising an increase that cannot be due to the cohesion of microscope and a special microscope stage-goniometer, the oxide film, but probably arises from the healing measurements were made of the principal refractive of submicroscopic cracks in the film. N. M. B. indices and orientation of the indicatrix of red and I f ? picryl-p-toluidine, picrylaniline, P h ,0, and Plasticity of deformed metals. D. V. K o n - ^ 2b0 2- N. M. B. * v is a r o v (Compt. rend. Acad. Sci. U.R.S.S., 1935, 4, 139— 140).— For Al, Cu, and Fe the plasticity Superficial optical properties of spar. R . de diminishes as the torsional angles increase. 9iviLL^1UKN a H. S u h n er (Compt. rend., 1935, W . R. A. , ’ 1344— 1346).— The results of an examination Determinative elastic and deformation con 0 , . optical properties of a beam of rectilinearly stants of crystals, with applications to isotropic poarised monochromatic light after reflexion at a substances. P. B e c h te re v (Z. Krist., 1935, 92, eavage surface of spar indicate the existence of 1— 29).— Theoretical. A classification of elastic an isotropic surface layer 70 Ä. thick. T. G. P. consts. on a suggested scale of “ gradation.” The Crystallochemical relations between german- terms hygro-, ortho-, plagio-, and sclero-morphic * 5 silicon. W . S ch ü tz (Z. physikal. Chem., are given to extreme concepts of elastic behaviour; 7 A 31> 292— 308).— The pairs Zn2Si04 and e.g., a fully hygromorphic substance has liquid Be2Si04 and Be2Ge04, and Cs2SiFG and fluidity, and a fully scleromorphic one resists changes m * 6 i.are Pr°Lably isomorphous. The lattice of form without limit, but does not oppose vol. m> s. have been determined. In the heaviest alteration. Published elasticity figures for many 416 BRITISH CHEMICAL ABSTRACTS.— A. I ll (e,/), IV (6) substances (some isotropic) are summarised and He. Reduced resistivities computed by means of classified on this “ gradation ” scale. B. W . R. the Mathiessen-Nernst formula were in agreement Akulov’s theory of coercivity. V. S. Messkix with these calc, from the Grüneisen formula (A., and B. E. Somin (Z. Physik, 1936, 98, 610— 623).— 1933, 452) for liquid N 2 temp., but not for liquid Experiment disproves Akulov’s theory (A., 1931, Ho temp. L. L. B. 898). A . B. D. C. Tension coefficients of resistance of the hexa gonal crystals zinc and cadmium. (Miss) 51. Abrasion hardness of dolomite. H. T ertsch (Z. Krist., 1935, 92, 39— 48).— The amount of wear A l l e n (Physical Rev., 1936, [ii], 4 9 , 248—253; of a dolomite crystal by an abrasive plate is recorded cf. A., 1933, 559).— The cocffs. have been measured, for various directions and planes. The cleavage and are independent of secondary orientation. The plane gives an asymmetric hardness figure ; the basis curves correspond with those representing the points plane gives threefold symmetry'. B. W . R. as functions of the primary' orientation. Results are discussed in relation to the Bridgman-Cookson Polymorphic transformation of simple ionic theory (cf. ibid., 1935, [ii], 47, 194). N. M. B. lattices. I. Transformation of cæsium chlor Mean free electronic path in silver from ide into sodium chloride lattice by heating. electrical conductivity of very thin silver threads. G. W ag n er and L. L lppert (Z. physikal. Chem., A. E u ck en and F. Förster (Nachr. Ges. Wiss. 1936, B, 31, 263— 274).— At 4 4 5 ± 5 ° the lattice of Göttingen, 1934, [ii], 1, 129— 137; Chem. Zentr., ordinary CsCl changes into a lattice of the NaCl typo, with lattice const. 7-02 x lO ' 8 cm., the heat 1935, i, 2954).— A rdsume of and additions to published work (A., 1935, 153). J. S. A. of transition being 1-8 kg.-cal. Between 20° and 5S0° CsBr, Csl, T1C1, TlBr, andTlI exhibit no transition Variations in current in a conductor. L. points. R. C. B r illo u in (Helv. phys. Acta, 1934, 7, Suppl. II, 47— 67; Chem. Zentr., 1935, i, 2954).— Current Transition in aluminium at 7 9 °. W . B a n d variations are calc, from the distribution of electrons (Physical Rev., 1934, [ii], 4 6 , 934— 935).— The variety of lyystereses observed on heating an A1 by' a probability method. Magnetic interaction wire show that there is a transition of some kind at between the electrons is assumed. J. S. A. 7 9 ± 0 -5 °. L. S. T. Tem perature variation of the susceptibility of Distortion of ¡3-brass and iron crystals. (Miss) oxygen. H. L d e s (Z. Physik, 1936, 9 8 , 537— 54T)-— The susceptibility of 0 2 shows increasing deviation C. E. E la m (Pfoc. Roy. Soc., 1936, A , 153, 273— 301).— A comparison of the results obtained from from y_7’=const, with rise of temp, from 2S6° to experiments on the distortion in tension of the body'- 600° abs. A . B. D. C. centred cubic metals, Ee and [3-brass, indicates that Susceptibility measurements for oxygon and there is no essential difference between them. Stress- inert gases. K. E. M a n n (Z. Physik, 1930, 98. strain curves of the crystals are given, and the 54S— 560).— The susceptibility of 0 2 is independent o fracture of [3-brass crystals in tension and in rolling density and field strength from 90 to 750 mm. fig, and is described. The direction of slip is not a 1 wa_vs from i800 to 15,000 oersted. Vais, obtained for the a crystal direction, and it is suggested that the de inert gases are compared with theoretical vals. formation is brought about by' movements of a com A. B.D.C. plex nature, and not by slip on any definite crystal Magnetic studies on graphite and graphitio plane. L. L. B. oxides. N. Gangitli (Phil. Mag., 1936, [vii], 21- Mott’s theory of liquid metals, and the trans 355— 369).— The principal susceptibilities of eryst. ition points of metals and other solids. R. H. graphite along the vertical axis and along direction? F o w le r (Helv. phys. Acta, 1934, 7, Suppl. II, 72— in the basal plane are — 22 X 10-*' and —0-5 X JO-6 p® SO; Chem. Zentr., 1935, i, 3386).— Mott’s theory g., respectively. By' treating with conc. II2S04 anu (A., 1934, 1300) is discussed in relation to the changes H N 0 3 to form “ blue graphite ” the abnormal in state of metals, alloys, N H 4 halides, and other diamagnetism along the vertical axis is nearly de substances. H. J. E. stroyed, and that along the basal plane is almost unchanged; the anisotropy' is of the same order o Hume-Rothery conception of the metallic« magnitude as in aromatic mols. containing severe state. C. D. N iv e n (Phil. Mag., 1936, [vii], 21, condensed C6H 6 nuclei: 1 - 3 X 10~° per g. content of t- 291— 299).— The Hume-Rothery relation is restated A diminution in the particle size of graphite has near!} for the periodic groups IIIB — VIIB in the form “ in the same effect as oxidation as above. These effects crystallising each atom has 6 —N near neighbours, are attributed to a breaking up of the metallic linkings where N is the no. of electrons in the p system.” in graphite responsible for abnormal diamagnetism- The bearing of the relation on conduction and super conductivity'is discussed. R . S. B. Explosive antimony. III. Magnetic sus Electrical resistance of aluminium at low ceptibility. C. C. C o ffin (Canad. J. R«s., 1 » * temperatures. H. A. B oorse and H. N ie w o d 1 3 , A . 120— 125 ; cf. A., 1934, 1297).— Explosive btn n ic za ń sk i (Proc. Roy. Soc., 1936, A , 153, 463— less diamagnetic than the ordinary polycryst. met1»- 475; cf. A., 1935, 814).— The electrical resistances magnetic susceptibilities being —0-38X10"6 aIU of 6 polycryst. A1 wires were measured at 0° and — 0-88 X IO-8, respectively'. Explosive or amorpnom liquid N2 and liquid Ha temp., and those of 4 wires Sb should be regarded as a true glass of supercoo e drawn from 99-995% pure A1 at the temp, of liquid liquid. E. E. A. 17(65/) GENERAL,. PHYSICAL, AND INORGANIC CHEMISTRY. 417 Temperature variation of [magnetic] suscepti 0-22. cv increases more rapidly with T than would bility of solid nitric oxide. E. L ips (Helv. phys. follow from Debye’s relation. Qrj is > the val. given Acta, 1935, 8 , 247— 263; Chem. Zentr., 1935, ii, by Kaischew and Simon (A., 1934, 589), and changes 189).—-/ for solid NO between 63° and 90° abs. is from 37 at 1-2° and d 0-218 to 25 at 2-18° and d 0-201, const., and much < the theoretical val. The differ the Q-T relation being linear. The heats of fusion at ence is attributed either to the formation of double 2-5°, 3-0°, and 3-5° abs. are 0-835, 1-089, and 1-365 g.- mols., or to alterations in the electronic levels due to cal. per g., respectively. Data for co-existing solid electric fields in the crystal lattice. ,J. S. A. and liquid densities are also recorded. L. J. J. Magnetic susceptibility of vapours of some Effect of dissolved air on the specific heat of organic substances. J. S h u r and S. Sid o r o v water over the range 15— 20°. E. O. H erg us (Proc. (Nature, 1936, 137, 317).— A redctermination of the Physical Soc., 1936, 48, 282— 284; cf. ibid., 1935, 47, magnetic susceptibility of G'S2 showed no change in the 1003).— The effect is calc, thermodynamically from vals. for the vapour and liquid states (cf. A., 1935, 14). the solubility data for the case when no air is liberated. L. S. T. The sp. heat of H20 saturated with air at 20° and atm. Magnetic behaviour of alu m s of the iron group. pressure is > that of air-free H20 by 6xl0-6 g.-cal. A. Stogert (Physica, 1926, 3, 85— 90).— Theoretical. per g. ” N. M. B. ForCr+++, Mn+++, and Fe+++, the Bose-Stoner rela Atomic heat of nickel at low temperatures. tion can be explained on the basis of the known lattice K . C lusius and J. Goldm ann (Z. physikal. Chem., structure. For Ti+++ and V+++, deviations from cubic 1936, B, 31, 256— 262; cf. A., 1935, 574).— Measure symmetry must be taken into account. L. J. J. ments at 10— 30° abs. show an anomalous fall of Paramagnetic relaxation. C. J. G orter sp. heat with temp., which is reconcilable with (Nature, 1936,137, 190).— The relaxation time of the neither Bloch’s T 3/2 law for ferromagnetism nor magnetic vector is approx. 10_I° sec. for Fc*" alum. Sommerfeld’s T law for free electrons (cf. this vol., L. S. T. 148). R. C. Symmetry of the therm o-electric effects in Specific heat of Seignette salt. I. Anomaly single crystals. H. P. St a bler (Physical Rev., at upper Curie point. A. A. Rusteriiolz (Helv. 1934, [ii], 46, 938). L. S. T. phys. Acta, 1935, 8 , 39— 54; Chem. Zentr., 1935, i, 2957).— Work reported previously (A., 1935, 1454) Variation with temperature of the absorption is described in detail. Anomalies in the Curie point, °i ultrasonic waves by liquids. E. B a u m g a r b t calc, from Cp and from the dielectric const., and in ll(0mpt. rend., 1936, 202, 203— 204).— The absorption the inner field are discussed. J. S. A. of ultrasonic waves v = 7-9578x 10« by H 20 at 18— 40° ms been measured. The coeff. of absorption oc Heat capacity, entropy, and free energy of '■ ?o(o3> where tj is the coeff. of viscosity, p0 the rubber hydrocarbon. N. B e k k e d a h l and H. 'tensity, and F0 the velocity of sound. T. G. P. M atheson (J. Res. Nat. Bur. Stand., 1935, 15, 503— 515).— Vals. of heat capacity at 14— 320° abs. Existence of diffusion of ultrasonic waves in are given for the cryst. and amorphous forms of m T R BiQuard (Compt. rend., 1936, 202, rubber, prepared by digesting latex with steam at 1 119).—The existence of diffusion in ultrasonic 190° and extracting resins and hydrolysis products waves (Lucas, this vol., 148) v = 7 -9 6 x l0 6 sec.-1 in with EtOH and H ,0 . There was a transition temp, *- le has been confirmed experimentally. T. G. P. at approx. 199° abs. The cryst. form fuses at 284° Ultrasonic experiments. H . Sa c k (Helv. phys. abs. The entropy and standard free energy of 37f~lJr*’ 7’ 7— Chcm. Zentr., 1935, i, formation were calc. H . J. E. 3/68).—Relative velocities of propagation of Thermal properties of an incompletely de r e c S 'C n VGS in C«Ho> and * * ZnS0* are generate Fermi gas. N. F. M o tt (Proc. Camb. a 1100°, and are compared with vals. calc, on Andrade’s M e y e r (Z. physikal. Chem., 1936, 175, 275— 283).— theory of variation with temp. A t 1100° the decrease The determination of the b.p. of a liquid mixture and of 7] is 2% per 100°. N . M. B. the condensation point of a mixture of vapours by p -v -T relations of gaseous mixtures. E. R. heating and cooling curves, respectively, is desoribed. Gilliland (Ind. Eng. Chem., 1936, 28, 212— 215).— The apparatus is suitable for determining the propor The isometric (p -T curve, v const.) for a pure gas tion of condensable constituents in a gas mixture. approximates closely to a straight line at T > crit. R. C. temp. The slope of the isometric for a mixture can Ferromagnetism and liquid mixtures. C. be obtained from the molal average of the slopes of the Z en er (Physical Rev., 1934, [ii], 4 6 , 824— 825).— isometrics for the constituents, all measured at the Analogies between the development of magnetisation same mol. concn. This fact, in addition to a simple below the Curie point and the separation of two phases method for obtaining the internal pressure from the from a homogeneous liquid mixture of twro types of isometrics, enables the p -v -T relationships for a atoms are discussed. L. S. T. mixture to be calc, more accurately than by the use of Crystal structure of beryllium alloys. L. Dalton’s or Amagat’s laws. The theory is applied to M isch (Metallwirts., 1936, 15, 163— 166).— Alloys of A-CoH,, H2-CO, and CH4-N 2 mixtures. A. J. M. Be with several metals of the transition series have Viscosities of deuterium -hydrogen m ixtures. been examined, the majority being of the type A. B. Van Cle a v e and 0 . M aass (Canad. J. Res., AB., (B =B e). The results are discussed in relation 1935,13, B, 384— 389; cf. A., 1935, 432, 691,1455).— to the Hume-Rothery rule (cf. A., 1935, 926). Further measurements at 22° have shown that the C. E. H. diameters of D 2, HD, and H 2 mols. are identical. Solidification diagram of copper-tin alloys. Variation of with the temp, has been derived from W . B r o n ie w sk i, J. T. J ablo n ski, and S. M aj (Compt. measurements at — 78-5° and — 183-4°. Jeans’ rend., 1936, 202, 305— 307).—A complete fusion temp.-viseosityrelation holds approx. for the mixtures. diagram is given. Formation of the compounds A comparison has been made of various equations CujSn, Cu3Sn, and Cu3Sn2 is indicated. II. J. E. which are said to express the dependence of r, on the Zinc-indium alloy system. C. L. W ilson and composition of mixtures. E. E. A. E. A. Peretti (Ind. Eng. Chem., 1936, 28, 204— 205). Description of binary solutions. F. 0 . K oenig — Thirty alloys have been examined, and the equili (J. Amer. Chem. Soc., 1936, 58, 317— 318).— Theo brium diagram has been obtained. The eutectic retical. The changes associated with different inodes contains 96% In and 4 % Zn, and the eutectic temp, is oi description (i.e., the formula assigned to each com 143-5°. The alloys become softer as the proportion of ponent) are discussed. E. S. H. In is increased. A. J. M. Densities and refractive indices of bromo- Phase diagram of the system silver-gallium. form-benzenb . m ixtu res. J. L. W h itm a n and F. W e ib k e , K . M eise l, and (Fr l .) L. W iegels (Z. h. Clardy (J7 Amer. Chem. Soc., 1936, 58, 237— 239). anorg. Chem., 1936, 226, 201— 208).— Thermal, -Data at are recorded. The ¿-composition microscopic, and X-ray observations have been made. relation conforms closely to that for an ideal system. The data for the Ag-rich alloys agree with those of . ' E. S. H. Hume-Rothery et al. (A., 1934, 725). Five series of viscosity fo rm u la fo r b in a ry m ix tu r e s , the mixed crystals are indicated. The system is compared association degrees of constituents being taken with other systems containing Ag and Ga. The at. “ t° consideration. XII. T. I s h ik a w a and T. vol. of Ga in Ag, like that of Al, is > in Cu. «ABA (Bull. Chem. Soc. Japan, 1936, 11, 8— 18).— M. S. B. Ishikawa viscosity formula has been applied to Velocity of transformation in cadmium- >e experimental data for binary mixtures such as magnesium alloys in the region of composition ebe with alcohols or AcOH, in which one com M gC d. N. L. St epan o v and S. A. B u lach ponent shows marked association. The calc, and (Compt. rend. Acad. Sci. U.R.S.S., 1935, 4 , 147— o served vals. of vj are in close agreement. A com 151).— The electrical conductivity of alloys tempered parison is made with the Thiesen formula for gaseous from above the transition points and also of annealed mixtures (cf. A., 1929, 500). Where there is a max., alloys has been measured at 25°, 50°, 75°, and 100°. t calc, from the latter is not quite coincident with the The annealed alloys, stable at low- temp., have the o served r(, but no such divergency occurs with the highest conductivity. Transition velocities have been isnikawa formula (cf. A ., 1929, 387). M. S. B. determined at 100°. W . R. A. Viscosities of liquid m ixtu res. K . E. Spells (A) Platinum-antimony alloys. (B ) Platinum- Urans. Faraday Soc., 1936, 32, 530— 540).— Viseosi- rhodium alloys. V. A. N em ilov and N. M. r S * fixtures of PrOH, BurOH, CH2BUe-OH, and V oronov (Z. anorg. Chem., 1936, 2 2 6 , 177— 184, Th - , witb C6H6 have been measured at 22°. 185— 191 ; cf. A., 1935, 440).— (a ) The presence of a ^ e results, together with other data, are used to test solid solution on the Pt side seems to be indicated. ,%V] , V °I a siugle-const. expression connecting (b ) The thermoelectric power of systems of al > \ V hcucomP°slt10»- The curves for the tw-o amyl chemically pure Pt with different Pt-Rh alloys „> 0 , show no anomalies corresponding with those increases with the concn. of Rh, but more rapidly own by the dielectric const. F. L. U. at low than at high concn. Pt-Rh alloys are not Instigation 0f equilibrium between a boiling readily attacked by acids. By heating at 750° a " an 1 0 % Rli. A t 1150° the oxide is dissociated Laws of valency electron concentration in leaving a bright metallic surface. M. S. B. binary intermetallic alloys. H. P erlitz (Acta Comm. Univ. Tartu., 1933, A, 24, No. 2, 16 pp.; Transformation in the copper-gold alloy cf. A., 1934, 22).— The Westgren and Hume-Rothery C u 3A u . C. S y k e s and H. E v a n s (J. Inst. Metals, rulo applies to (3-, y-, and e-alloys, the vals. of the 1936, 58, Advance copy, 443— 472).—Erom X-ray ratio of the no. of valency electrons to the no. of examination and from measurements of the electrical atoms being 3:2, 21 : 13, and 7 :4, respectively. resistance and sp. heat of the Cu-Au alloy with A necessary condition for the existence of these 25 a t.-% Au it is shown that the general character structures is that one of the metals should con of the transformation is similar to that predicted tribute < 2, and the other > 1, valency electrons by Bragg and Williams (A., 1934, 954); it takes to the lattice structure. Various examples arc place continuously from the crit. temp, to a very discussed. Cn. A bs. (e) low temp, and the equilibrium is a dynamic one. The at. rearrangement proceeds first by the formation Formation of spherical eutectic inclusions in of nuclei having a relatively high degree of order alloys. W. Ge ller (Metallwirts., 1936, 15, 141— and then, at const, temp., by the growth of these 142).— Spherical eutectic inclusions have been observed nuclei to a size approximating to that of the individual in several Fe and Al alloys. The conditions for their crystals, or, at gradually falling temp., by growth formation are a narrow freezing range and rapid of the nuclei accompanied by an increase in their cooling just above the solidus. C. E. H. degree of order due to the fall in temp. Since nuclei The system M g-Cu-Al, particularly across formation is not taken into account in the statical the section MgCu2-M gAl2. F. L aves and H. theory of super-lattices it follows that the actual W i t t e -(Metallwirts., 1936, 15, 15— 22).—-Cumaybe rate of relaxation into the equilibrium state differs replaced by Al in MgCu2 without change of cryst. considerably from that predicted by the theory. structure up to approx. 35% MgAl2. With higher Very appreciable differences in the properties of the MgAl2 contents, hexagonal phases appear, but there alloy can be effected by variations in the heat-treat- are no definite limits of stability for the various ment, but all are strictly reproducible, which confirms structures. For the Al corner of the system previous the conclusion that the transformation is an intra- results are not fully confirmed. Two compounds, eryst. phenomenon almost independent of grain- Mg2Cu2Al5 and Mg3Cu7AlJ0, are reported. boundary effects. A. R. P. System iron-aluminium-carbon. R. Yogb I. Paramagnetism of nickel alloys. C. and H . M a d e r (Arch. Eisenhiittenw., 1935—1936, M a n d e r s . II. Magnetic properties of the 9, 333— 340).— The system contains six primary metallic state and energy of interaction between crystal phases : a-Fe containing A l'a ’ id Fe, ternaiy magnetic atoms. L. N £ el (Ann. Physique, 1936, y-Fe, graphite, ternary e (FeAl)„, ternary S (FeAh), [xi], 5, 167— 231, 232— 279).— I. Vais, for the sp. and A14C3. There are four 4-phase fhuilibria during susceptibilities of dil. solid solutions of Ag, Au, Al, solidification, viz., (1) liquid (Fe 83T ,'A 1 14-5%)+ Ti, Zr, Si, Sn, Pb, V, As, Sb, Cr, Mo, W , Mn, Ru, a (Fe 85-1. Al 1 4 -8 % )+ y (Fe 91-7, Al 7 - V % ) ^ f (Fe Pd, and Pt are recorded for various temp, above the 85-2, Al 13% ) at 1335°: (2) liquid (Fe 83-35, Al Curie point. Tho Curie point (0) and Curie const, 1 3 -5 % )+ y (Fe 90-3, Al 7;2%)(Fe 83-5, Al 13%)+ (c) are calc, for each alloy. Deviations from the graphite at 1132°; (3) liquid (Fe 56-7, Al 43%)+ Curie-Weiss law are observed, due to a superimposed S (Fe 54-8, Al 45% ) (Fe 55-8, Al 4 4 % )+ A l4C3 at paramagnetism (a), which is independent of temp. 1135°; (4) liquid (Fe 69-92, Al 2 9 % ) (Fe 70-65, II. Theoretical. The variation of c with concn. Al 29%)+graphite+Al4C3 at 1120°. In the solid of added metal, considered in relation to the results state three points of 4-phase equilibria exist, thus of Sadron (A., 1932, 679) for saturation magnetisation (5) Adsorption isotherm of heavy water on ation. J. H am pel (Z. anorg. Chem., 1936, 226, charcoal. A . K in g and C. G. L a w s o n (Trans. 132— 140).— The oxide mixtures were prepared by the Faraday Soc., 1936, 32, 478— 181).— The isotherms method previously described (A., 1934, 490; 1935, of D20 and of H 20 on outgassed charcoal at 110° 440), heated at various temp, up to 1000°, and the are shown to be very similar. No special theoretical sorptive power (s) measured for Congo-red, acid significance can be attached to the slightly greater fuchsin, and eosin (cf. A., 1935, 930). The 5-temp, adsorption of D ,0 . O. J. W . curves fall with rise in the temp, at which the pre Sorption of bromine and iodine by activated liminary heating takes place, but there are many charcoal. L. H. R e y e r so n and A. E. Ca m er o n irregularities resulting in max. and min. and points (J. Physical Chem., 1936, 40, 233— 237; cf. A., 1935, of inflexion. The curves are compared with those 696).— Equilibrium data for the sorption of Br bv for the variation of other physical properties with temp. activated C at 58°, 98-1°, 137-6°, and 178-4° and of M. S. B. 1 at 178-4° and 218-8°, and also rates of adsorption Sorption of gases and vapours by aerosol and desorption of Br and I at 137-6°, are given. particles. A. K rassilchikov (Kolloid-Z., 1936, M. S. B. 74, 138— 147).-— The concn. of a sorbablo gas or Dissociation equilibrium of hydrogen and its vapour is determined in the presence or absence of adsorption on tungsten. J. K. R oberts (Proc. aerosol particles by measuring its diffusion into a long Camb. Phil. Soc., 1936, 32, 152— 157).— The applic narrow tube, the vol. of which is small compared with ation of a formula derived from a kinetic treatment that of the experimental vessel with which it is of the process of desorption in which a const, evapor connected. By this means the sorption of Br vapour ation coeff. for desorbing particles is assumed (this by paraffin oil, resin, and N H 4C1 particles has been vol., 155) leads to vals, for the rate of evaporation determined. The sorption isotherms for the oil of 11 from W which do not agree with the dissociation indicate dissolution rather than adsorption. With equilibrium, if the results of Langmuir et al. (A., 1931, resin, bromination occurs. N H 4C1 shows purely 782) are used. The nature of the surface reactions surface effects, and the adsorption can be expressed occurring is discussed. It would appear that measure by Langmuir’s equation. With increasing [Br] the ments of the rate of removal of the adsorbed film of adsorption per sq. cm. reaches a max. and thereafter 0 2 on W do not afl'ord a measure of the rate of evapor decreases, apparently owing to rapid coagulation ation of 0 atoms, or that it is not possible to obtain and desorption at high [Br]. F. L. 13. a general first approximation formula for the rate Adsorption and diffusion in zeolite crystals. of evaporation of adsorbed;atoms in terms of the heat A. T iseliu s (J. Physical Chem., 1936, 40,223— 232).— of adsorption. ' A. J. M. The adsorption of N H 3 by analcite follows the Sorption of hydrogen and deuterium by Langmuir law and the heat of adsorption is const, copper and palladium. I. Behaviour of copper over a wide range, indicating a lack of interaction and copper oxides. II. Sorption by palladium between adsorbed mols. When N H 3 is adsorbed by and diffusion through copper. H . W . M elville a Cu chabasite, prepared by cationic exchange in and E. K . R id e a l (Proc. Roy. Soc., 1935, A , 153, aq. CuS04, the crystal has the absorption spectrum 77— 88, 89-— 103).— I. CuO is reduced by at. H and of a solution containing CuNH4 ions, showing that D at 20° with the same velocity. It is more rapidly co-ordination valencies play a part in adsorption. reduced by mol. H 2 than D 2 at 156— 269°, the differ The diffusion const, of H aO in a dehydrated heuland- ence in energy of activation being 0-4 kg.-cal. H 2 ite crystal has been determined by following, with and D2 are sorbed by, and desorbed from, Cu -with the the polarising microscope, the changes in double same velocity at 71—-200°; at higher temp., however, refraction during adsorption of H ,0 . The diffusion II2 is sorbed slightly more rapidly. The results is anisotropic. It follows the ordinary diffusion laws indicate that the process of activated diffusion of of solutions for small concn. differences, but for H 2 into Cu is composite, including a true activated larger is largely dependent on concn. Since concn. diffusion. There is also another process independent at the surface remains const, and equal to the satur of the nature of tho two gases which determines the ation val., during adsorption, diffusion in the crystal rate at low temp. must be the rate-determining factor. M. S. B. 11. H 2 diffuses more rapidly than does D 2 through Adsorption of electrolytes on crystal surfaces. Pd and through thin films of Cu and Ni supported on (Miss) L. d e B rouckL re (Chem. Weekblad, 1936, Pd, at temp, from 150° to 350° and pressures 1— 200 33, 104— 109).— A reply to criticism by Kolthoff mm. In Cu it has been shown by using composite (A.. 1934, 727: cf. A., 1933, 4 5 7 ; 1934, 359). films, Cu-Pd-Cu and Pd-Cu-Pd, that the rate- D. R. 11- determining step is not due to any process connected Adsorption at crystal-solution interfaces. IX. with tho gas-metal interface. H a is more sol. than Concentration of foreign substances in solution D2 in Pd, the difference in diffusion velocities being relative to the quantity adsorbed by the host due partly to this, and partly to the greater mobility crystal. W . G. F r a n c e and (Miss) P. P. Dams of f l2 in Pd. Potential barriers have been constructed (J. Physical Chem., 1936, 40, 177— 185).— There is from diffusion and solubility data. L. L. B. no relation between the no. of colloidal particles of Active oxides. XCVIII. Changes in sorptive dye in solution and the amount of dye adsorbed by a power of mixtures of calcium oxide with ferric given host crystal. Crystals containing adsorbed oxide, and of calcium oxide and beryllium oxide impurities have the same lattice consts. as the pure with chromic oxide, during chemical combin crystals. The dichroism frequently' observed in V(e) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 423 crystals containing adsorbed dye appears to be due to (I) when acid (I) is adsorbed at the interface. The orientation of the dye mols. with respect to the ad causes of the failure of Gibbs’ adsorption equation sorbing surface. The colour effects observed, when are discussed. M. S. B. crystals of NH4 alum containing Pontamine Sky Blue Direct measurement of absolute amount of OB are examined under a polarising microscope, adsorption in liquid surfaces. T. F. F ord and indicate that the long axes of the adsorbed dye mols. J. W . M cB ain (J. Amer. Chem. Soc., 1936, 58, 378).— are probably perpendicular to the cube faces of the An interferometer method is described. E. S. H. crystals. The data for the adsorption of dye by' alum and nitrate crystals are not in accordance with either Kinetics of sorption. A. Y . L y k o v (Kolloid-Z.; the Langmuir or adsorption isotherm equations, but 1936, 74, 179— 183).— The distribution of temp, in a are reproduced over nearly the whole range by sphere of cellulose during sorption of H 20 vapour a=kcVn—k'c-v "', where a is the mol. ratio of impurity has been determined. Curves showing change of to host crystal and c the ratio in the solution. The H„0 content -with time for different temp, are given. cause of the failure of the adsorption curves to pass F. L. U. through the origin is discussed. M. S. B. Adsorption and pyknometry. P. G. N u ttin g (J. Washington Acad. Sci., 1936, 2 6 , 1— 6).— A review Adsorption of anions by precipitated calcium of technique and errors in pyknometric determinations oxalate. T. P. Cilao, D. K. Wu, W. P. Chlang, of d for highly adsorptive clay's and similar materials. and T. F. Chao (J. Chinese Chem. Soc., 1936, 4, H. Perchlorates as solvents for cellulose and its The action of univalent cations is antagonistic to derivatives. (M m e .) A. D o b r y (Bull. Soc. chim., that of bi- and ter-valent ions; when uni- and 1936, [v], 3, 312— 318).— Cellulose acetate dissolves quadri-valent ions are present together antagonism in saturated aq. solutions of Ca, Mg, Cu, and Zn is observed only with LiCl. An interpretation of perchlorates in the cold, and in Li and Ag per the above phenomena, based chiefly on considerations chlorates and basic Pb perchlorate when hot. Mg(C104)2 of exchange adsorption, is advanced. R. T. is the most active. The dissolution is not accom Zonal effect in the electrolytic coagulation panied by chemical degradation. Cellulose nitrates of m anganese dioxide. S. S. J o s h i an d S. J. R ao and butyrate and benzylcellulose are insol. in these (Current Sci., 1936, 4, 481— 482).— In > 80 cases salt solutions. Cellulose dissolves practically un n during slow coagulation varies discontinuously changed in basic Be perchlorate solutions. E. S. H. with the time, in disagreement with Smoluchowski’s Viscosity of suspensions and solutions. I. theory. R. S. B. Viscosity of suspensions. E. G u t h . II. Coagulation of solvated sols by organic Theory of electro-viscosity. W. K r a s n y -E r g e n substances and salts. VI. Temperature-stable (Kolloid-Z., 1936, 74, 147— 172, 172— 178).— !. albumin sols which coagulate on cooling. B. Introductory and mathematical. J ir g e n so n s (Kolloid-Z., 1936, 74, 205— 208; ef. II. Mathematical. Von Smoluchowski’s formula A., 1933, 461).— Sols of ovalbumin containing 45— is shown to be an approximation formula suitable 55 vol.-% of Pr°OH or Pr3OH and 0-05— 0-54/ with for relatively good conductors. It is not valid for respect to NaBr, KC1, CaCl2, or Ca(N03)2, are stable non-conducting liquids. E. L. U. at room temp, or at 40°, and coagulate at — S° to Viscosity and lyotropic numbers. J. H. C. — 10°. The coagulum can be re-dispersed at 65°. Mk r c k e l (Rec. trav. chim., 1936, 55, 82— 84).— A An explanation is put forward. E. L. U. reply to Bruins (this vol., 285). D. C. J. Ionic structure, solubility, and coagulation Viscosity of organic colloids. W. Philippoff of proteins. E. H a u r o w it z (Kolloid-Z., 1936, 74, and K . H ess (Z. physikal. Chein., 1936, B , 31, 237— 208— 218; cf. A., 1935, 822).— Solubilities at different 255; cf. A., 1935, 31, 822).— The determination and Pa have been determined for products formed by variation of the consts. of the flow curve (cf. ibid., coupling albumin or globulin with. diazotised m- 692) are described. Eor various solutions at concns., N H 2-C6H4-S03H, p-N H 2-C6H4-AsO(OH)2, or o- c, of 0-01— 30% the variation of ■% with c is given N H 2*C6H,j'C02H. Data are recorded for the pptn. oi by 'Oiti— (l+ c /c 0)8, where c0 is a const, for a given various proteins by clupein (which ppts. only the solvent and solute. Eor solutions of cellulose nitrate protein anion), and” by ovalbumin into which -SC^E (I) in BuOAc v)w is oc c. Chemical and mechanical have been introduced as above until the isoelectric treatment of the solute, change of temp., and variation point is at p a < 1 , whereby only the protein cations of the solvent and particle size distribution shift are nptd. The results are discussed theoretically. the v)0-c curve along the c axis without altering its F. L. U. form, i.e., the above equation remains valid, with Mitogenetic radiations and Liesegang rings. variation in c0. With rise in temp. vjr that function of tho space demand of the solute only in of normal tissue. Ch . A bs. (p) tho sense that tho flow of tho solvent is impeded by Thixotropy and rheopexy of V20 3 sols. F. the vol. of tho solute. R. C. J uliusburger and A. P ir q u e t (Trans. Faraday Soc., Lyophilic colloids. II. Interaction of agar 1936, 32,445— 452).— The relation between thixotropv fractions. A. A. M o r o z o v (J. Gen. Chcin. Russ., and rheopexy (cf. A., 1935, 933) has been investigated 1935, 5, 1359— 1372; cf. A., 1935, 932, 1320).— The in more detail for V 20 5 sols. Freshly prepared fractions (I) of agar of smaller mol. wt. are extractable V 20 5 sols with amicronic particles are only thixotropiCj with cold H.,0, and are shown to exert a stabilising but as soon as large needle-shaped particles are formed action on sols of the fractions (II) of higher mol. wt., the sols become rheopectic. Rheopectic sols can be and to augment imbibition of H 20 by gels of the latter, made with Li salts or with acids, but not with K °r to an extent commensurate with difference in osmotic NH,j salts, although the latter can produce thixo- pressure between intra- and extra-micellar (I). *The tropic V20 5 sols. Li salts and acids are weak coagu ti of sols of (11) is < that of tho original product, lants for V 20 5 sols. Rheopexy appears to be an owing to their smaller structural vj, and to the smaller intermediate state between a stable sol and one vol. of the dispersed phase. R. T. coagulated by stirring, just as thixotropy is in niain Stability of colloids. II. Negative silver cases an intermediate state between a stable solanc one coagulated by electrolytes. 0 . J. " ■ iodide colloid. A. Basinski (Rocz. Chem., 1935, 15, 430- -449; cf. A ., 1935, 297).— Tho coagulating Mechanism and kinetics of thixotropic sohdi' action of cations on dialysed negatively charged fication. W. H e l l e r (Gompt. rend., 1936, ¿9 - A gl sol diminishes in the series L i > N a > K > N l l ,> 61;— 64).— Data are recorded for the rate^ o£ ge 11 > A g ; Cd > Mg > Mnll> C o> Z n > Ni > Ca > Sr > formation of Ee(OH)3 sols containing NaC-1, at e 0u>Ba>Pbu ; EoIlI>Lalli>CoItl> A l; Zrlv>Th1L centrifuging. This is determined by the rate a V (e), VI (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 427 which nuclei form, by the rate of growth of these 91— 93).— The percentage (P ) of cassava starch nuclei, and by the rate of their association. granules remaining undissolved in H 20 at any temp, H. J. E. has been determined microscopically"’ with Congo-red Structure and properties of thixotropic gels. as stain. P reaches an equilibrium val. in < 30 mill, B. S. K a n d e l a k y (Kolloid-Z., 1936, 74, 200— 205).— which increases with temp., following an S-curve Sols of Fe203 made by hydrolysis of Fe(OEt)3 can reaching 50% at 61-07° (by definition, the swelling set to thixotropic gels when containing as little as solution temp.) and 95% at about 65°. The results 6-3 g. of Fe20 3 per litre. With increasing val. of are similar to those of Arzichovski (Bull. Acad. Sci. Et0H /H,0 in the sol the particle size increases and U.R.S.S., 1918, 12, 349) for potato starch. Samec’s the stability decreases. The time needed for the method (A., 1912, ii, 144) gives vals. of 55-6— 59° for first setting is > for subsequent settings, owing to cassava starch and 59-1— 60-3° for potato starch, but the incomplete breaking up of the aggregates on these depend on the concn. D. R. D. shaking. No thixotropic gels can be obtained from Vapour pressure-water content relations for sols made from recryst. Fe(OEt)3 and containing no certain typical soil colloids. L. T. A l e x a n d e r excess electrolyte, whence it is inferred that at least and M. M. H a r in g (J. Physical Chern., 1936, 40, some stabilising charge is necessary. Ultramiero- 195— 205).— The colloids have been extracted from scopic observations establish the existence of a net four different types of soil representing a wide range work of aggregates in which the liquid is enmeshed. of progressive weathering, and the variations of v.p. That the intracellular liquid does not “ set ” is shown with different H20 content of the colloids have been by the appearance in it of small particles in Brownian determined. The curves are characteristically dif movement when the system as a whole is gelatinised. ferent for the different types of soil. The variation F. L. U. of free energy with H ,0 content has been calc, and Sol-gel transformations. II. Dilatometric the free energy of wetting determined approx. The investigations on iron hydroxide, gelatin, relation of v.p. to colloid composition is discussed. methylcellulose, silicic acid, and viscose. E. A theory of the nature of hygroscopic H20 in soil Heymann (Trans. Faraday Soc., 1936, 32 , 462— colloids is given. M. S. B. 113; cf. A., 1935, 822).—^Changes associated with sol-gel transformations have been studied with a Equilibrium constants of the exchange sensitive Hg dilatometer. With methylcellulose the reactions HCl-f-HD =DCl-pH2 and HBr-f-HD = vol. increases, with gelatin it decreases, whilst no DBr-f-H2. K. W ir t z (Z. physikal. Chern., 1936, vol. change occurs during the thixotropic sol-gel B, 31, 309— 318).— Assuming that the rotation transformation of Fe(OH)3 sol. It is suggested that of the mols. concerned is fully excited and the a vol. increase corresponds with a decrease in hydra vibration unexcited the equilibrium consts. are calc, tion, since the bound H 20 has a smaller sp. vol. than to be ([HD][HC1]) /([H2][DC1])=2-362e-186’7 T and that of the free H20 . In the formation of silicic acid ([HD][HBr])/([H2][DBr])=2-414e-128 lir. These agree gels from Na silicate and HCI, the vol. increase is with the observed equilibrium consts., using Pt to about 10—20 times as large. There is, moreover, a catalyse the exchange. In each case the partition further increase in vol. which continues for many ratio of D approximates to 1 and is practically months. Chemical dehydration due to polymerisation independent of the temp. From these data and the may he the cause of these large vol. changes. The equilibrium const, of H2-j-D2= 2 H D (cf. A., 1934, 30) maturing of viscose solutions is also discussed. the equilibrium consts. of all the other exchange reactions possible in the systems H-D-halogcn may O. J. W . Structures of precipitates. I. Influence of be calc. R. C. yarogen, lithium, sodium, and potassium ions Equilibrium of exchange reactions with °npeptisability of secondary particles of barium deuterium. K. W ir t z (Physikal. Z., 1936, 37, sulphate precipitates. B. T e z a k (Z. physikal. 165).— The exchange of D and H in HCI, HBr, and -hem. 1936,175, 2S4— 293).— The peptisability with NH3 has been studied by determining the equilibrium >0 of a BaS04 ppt. varies with the cation of the isotopic ratio for mixtures of D2 and the above gases Pptg. sulphate according to the lyotropic series in presence of a Pt catalyst by the thermal con ib l^ It is inferred that the revers- ductivity method. The results are in good agreement mty of the aggregation of the primary particles is with those calc, from spectroscopic data (cf. A., 1935, |e ermmed by the hydration of the adsorbed foreign 1460). A - J- M. ons. There may be differences in magnitude and Equilibria of the reactions between acetylene mgu of charge between different fractions of a peptised and heavy water at 25°. L. H. R e y e r s o n and B. ystem. For a BaS04 dispersion the dispersity G il l e sp ie (J. Amer. Chern. Soc., 1936, 58, 282— quotient falls linearly with increasing particle size. 984).— Equilibrium consts. for the reactions involving , . R - C- H20, HDO, D.,0, C2H2, CVHD, and C2D2 have been tomically divided silver. A . T oporec (Compt. determined. E. S. H. 1?ni!- 4 cad- Sci. U.R.S.S., 1935, 4. 27— 30).— The ^sorption spectra of Ag dispersed in KC1, KBr, and Concentration maximum of endothermic ,are ,recorded. The colloidal nature of the colour compounds at high temperatures. Application centres is discussed. H. J. E. to ozone and nitric oxide. E. B r in e r , B. S u sz, and E. R od (Arch. Sci. phys. nat., 1935, [v], 1 7 , Swelling solution temperature of cassava Suppl., 198— 200).— Previous results (A., 1931, 910) cn- A- J- Ophop (Chern. Weekblad, 1936, 33, have been recalc. using recent experimental data. 428 BRITISH CHEMICAL ABSTRACTS.— A. VI (a, b) The niax. concn. of 0 3 in 0 2 at 1 atm. is 2 -2 x l0 ‘ 5% Colorimetric researches on naphthazarin and at 3500° abs. and that of NO in air at 1 atm. is 4-7— dibromonaphthazarin. L. B r u l l and P. G ir o t t i 7-5% at 3500° abs. It. S. (Anhali Chim. Appl., 1936, 26, 19— 24).— The dissociation consts. of naphthazarin determined Relative values of the four butane-butene- colorimetrically with K H 2P0 4-N a 0 H and H3B03- hydrogen equilibrium constants. L. S. K assel KCl-NaOH buffers, and with NaOH, are IT. =6-3 X (J. Chem. Physics, 1936, 4, 144).— The method of Eidinoff et al. (A., 1935, 1064) has been developed 10-9, -K2= 2 -5 x 1 0 _ u ; those of dibromonaphthazarin, m.p. 163° (Ac., derivative, m.p. 212— 213°), are and applied to calculate the vals. of the sum of the A 4= 3 -2 X 10“7, A ',= 2 -5 x 10~10. The possibility of translational and the rotational entropies of the follow using naphthazarin as indicator in the colorimetric ing compounds at 25° : «-butane 75-366, isobutane determination of pa from 7 to 12 is considered; 71-249, A“-butene 72-98, cis-A^-butene 68-225, trans- the quantities of naphthazarin in 0-1JV-HC1 and Ah-butene 67-800, ¡sobutenc 68-215. The possibility O-liV-NaOH required to match the colour of a given of determining vibrational entropy is discussed. solution at each pn are tabulated. E. W . W. M. S. B. Activity of water in solutions of barium Application of the phase rule to systems con chloride. R. F. N e w t o n and E. A. T ippetts (J. taining distant phases. F . J. T r o m p (J. Chem. Amor. Chem. Soc., 1936, 58, 280— 282).— V.p. of Met. Soc. S. Africa, 1935, 36, 143— 145; cf. A., 1931, Bado solutions at 25° have been measured and the 1307).— When the phase rule is applied to systems activity of H 20 has been calc. E. S. H. such as H 20 vapour in contact with separate solutions Vapour pressures and activity coefficients of of different salts, the no. of components must be taken aqueous solutions of calcium and aluminium as > the no. of constituents in the system and so nitrate at 25°. J. N. P earce (J. Amer. Chem. the ordinary statement of the phase rule is inapplic Soc., 1936, 58, 376— 377).— Corr. data are given (cf. able. The author’s treatment can be extended to A., 1935, 302). E. S. H. such systems without introduction of special assump tions. J. W. S. Calculation of activity coefficients and molal volumes. 0. R e d l io h , P. R o s e n f e l d , and W . Crystalline varieties of the hydrated nitrites Stricks (J. Amer. Chem. Soc., 1936, 58, 375— 376).— of barium and strontium : the hydrate A criticism (cf. Pearce and Blackman, A., 1935, S r (N 0 2)2,4H 20 . J. B u r e a u (Compt. rend., 1936, 302). E. S. II. 202. 307— 309).— Ba(N02)2,H20 exists in hexagonal and rhombic forms. The equilibrium diagram tor Equilibrium and free energy relationships in Ba(N 02)2-H 20 is described. Sr(N 02)2 forms the the system acetone-diacetone alcohol. G. L. hydrate Sr(N02)2,4H20 (cubic), which undergoes a D avis and G. II. B urrows (J. Amer. Chem. Soc., peritectic transformation into the hexagonal mono- 1936, 58, 311— 312).— Tlio partial pressures of COMe2 hydrate at 15°. H. J- E. at 25° show that the mixture forms a perfect solution. Tho v.p. of diacetono alcohol (1) has been determined Decom position pressures of the ammoniates at 25°, 35°, and 45°. The free energy change and heat of sodium and ammonium chlorides. S. Abe, of reaction of transformation of COMe, into (I) have lv. W a ta n a b e , S. Sigetom i, and R. H av a (J. Soc. been calc. E. S. H. Chem. Ind. Japan, 1936, 39, 18— 20b).— The com pounds NaCl,5NH3 and N H 4C1,3NH3 have been Condition of iodic acid and iodates in aqueous prepared. Apparatus and methods for studying solution. N . R. D h ar and R . N . M ittra (J. Indian the decomp, are described. Results are given for Chem. Soc., 1935, 12, 771— 773).— The coagulating power of aq. H I0 , and KIO a on sols of Be(OH)2; the change NaCl ,5NII3 NaCl -f 5N H3 over the Cr(OH)3, and Th(OH),, and the variation of mol. temp, range — 10° to — 30° and for N H v C ljS N ^ ^ conductivity of aq. K IO s on dilution, indicate partial NII4C l-f 3NH3 over the range 5° to - 5 3 1 Heats ot polymerisation. Evidence from Raman spectra is formation are computed. T. W- P- inconclusive. E. S. H. Volatilisation of lead oxide from lead oxide- M am iitoldim olybdic acid.— See this vol., 453. silica mixtures. E. Presto n and W . E. S. Tur>'eb (J. Soc. Glass Tech., 1935, 19, 296— 31 It).— Measure Strength of isomeric bases of the type ments at 900— 1200° for mixtures containing 53-96 (Pt(NH3)2(OH).,]. A. A. G r u n b e r g and D. I. 99-8% of PbO show that the rate of volatilisation R jabtsciiikov (Compt. rend. Acad. Sci. U.R.S.S., exhibits discontinuities which are attributed to the 1935, 4, 259— 262).— Titration of the cis-compound presence of PbO:S i02, 2P b0,Si02, and 4 PbO,SiO.- with 0-1A -HOI at room temp, gives a colour change The heats of decomp, and evaporation of these com with Me-red when 8 0 % of the theoretical amount of pounds are — 56,000, — 49,000, and — 30,000 g.-caj- acid has been added owing to the formation of the weak per mol., respectively. The v.p. of pure PbO at 110'- acid [Pt(NH3).,(H,0).,]'\ The change is 70 mm. of Hg. The general results confirm tho=e [Pt(NH3)2(H20)2]C l[P t(N H 3)2Cl.,]+2H20 occurs previously obtained for the Na20 -S i0 2 and k ;" on warming and tho theoretical end-point may be SiO, systems. J- attained. The irans-compound gives an end-point at room temp, corresponding with 50 % of the theo Fusion curve of the system o - and retical amount of acid and this is attributed to the S. T su r u ta (J. Chem. Soc. Japan, 1935, 56, 4- formation of [Pt(NH3),(H20)(0H )]Cl. The final titra 432).— Dawson and Mountford’s results are confirm®1 tion val. is obtained on warming. R. S. (cf. J.C.S., 1918, 113, 923). C h . Abs. (e) VI (c), VII (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 429 The system : ;>-nitrotoluene-2-chloro-4- peculiar in that one of the compounds passes at the nitrotoIuene-2 : 6-dichloro-4-nitrotoluene. .0 . J. transition point into a ternary eutectic. R. T. Magidson and V. A. Schevelev (J. Appl. Chem. Specific heats of aqueous solutions of potass Russ., 1935, 8, 1431— 1434).— The m.-p. diagrams ium chloride. C. J. B. C lew s (Proc. Physical afford no evidence of compound formation. R. T. Soc., 1936, 48, 95— 99).— Data for 15— 45° and 0-1 — Equilibria in saturated solutions of salts 2-5N are tabulated. The temp, coeff. decreases with occurring in sea-w ater. I. T ernary system s concn. N. M. B. MgCl2-KCl-H20 , MgCl„-CaCl2-H 20 , CaCl2- Heat content of sodium chloride in extremely KC1-H20 , and CaCl2-N a C l-H 20 “at 0°. I. I g e ls - dilute aqueous solutions. T. F. Y o u n g and W . L. RtJD [with T. G. Thompson] (J. Amer. Chem. Soc., G roe n ier (J. Amer. Chem. Soc., 1936, 58, 187— 191). 1936, 58, 318— 322).— Equilibria have been deter — Theoretical. The chord-area method has been mined at 0°. The KC1 content of solutions saturated applied to published data for heats of dilution. with MgCl2,6H20 is very small. There is no evidence E. S. H. for double salt formation in the system CaCl2-K C l- Sodium hydroxide solutions. Heat of dilu H20. ' E. S. H. tion at 20°. J. W . B e r t e t ti and W . L. McCabe Thermodynamic study of systems of the (Ind. Eng. Chem., 1936, 28, 247— 248).— The heat of type PbCl2-RCl-H20 at 25°. V. E. H u n te r dilution has been determined at 20° for the concn. and A. J. A llm an d (Trans. Faraday Soc., 1936, 32, ranges 13-59— 26-14 and 17-16— 48-14% NaOIl. 302—511; cf. A., 1933, 906).— The v.p. at 25° of Results arc slightly lower than those of Fricke (A., solutions containing KC1 and PbCl2 in equilibrium 1929,1386) but agree with those of Tucker (A., 1915, ii, with various solid phases and also of certain unsat 674) after correcting for sp. heat. R. S. B. urated solutions have been determined. The results Heat of hydrogenation of di/sobutylene. B. L. do not agree with vals. calc, from electrometric data, C raw eord, jun., and G. S. P arks (J. Amer. Chem. which are probably not sufficiently accurate. Over Soc., 1936, 58, 373).— Direct calorimetric measure a narrow concn. region abnormally high v.p., approach ments give A/I]88= — 28,580^800 g.-cal. for the ing that of pure H 20, are obtained. In the region of reaction C8H16(i)+ H 2(j)=C gH 18(i). E. S. H. normal v.p. there is evidence of the presence of com Electrolytic conductivity of calcium hydrogen plexes in the solution. O. J. W . sulphite solutions at 20°. (System CaO-SO,- Ternary system NaCl-NaI-H20 . J. E. R icci H aO.) G. K. B ergman (Finnish Paper Timber J., and N. S. Y an ick (J. Amer. Chem. Soc., 1936, 58, 1935, Spec. Issue, 290— 293).— Vais, for the con 313—315).— Solubility data at 10°, 25°, 50°, 75°, and ductivity of C a 0-S 02 solutions are given. The [CaO] 100' are recorded. Within this range neither double can be deduced from the conductivity' and [SO,]. salts nor solid solutions are formed. E. S. II. Ch. Abs. (e) System mercuric iodide, ccesium iodide, water. Properties of electrolytic solutions. XVII. Conductance of salts in benzene and dioxan. (Mlle.) M. P e rn o t (Compt. rend., 1936, 202, 576— 578).—The existence of 3HgI2,2CsI, HgI2,2CsI, and W . F. L u d er and P. B. K ra u s [with C. A. K r a u s and HgI.2,3CsI has been confirmed. T. G. P. R. M. Fuoss] (J. Amer. Chem. Soc., 1936, 58, 255— 258; cf. A., 1935, 705).— Data are given for tetraiso- System Ca0-S02-H 20 . III. Precipitation amylammonium iodide in CGHG at 60°, for AgC104 in temperatures. P. E. Gishler and 0 . M aass CgH 6 at 25°, and for NBu4-C104 and NBuyOAc in CGHG (Cañad. J, Res., 1935,13, B , 370— 379).— A technique and dioxan at 25°. The equiv. conductances show is described for measuring pptn. temp., and the results min. at low concns., below which they rise in accord over a concn. range are tabulated. Colloidal matter ance with the mass action law. A marked sp. effect causes supersaturation. [H*] and [H S03'] at the of structure on conductance in solvents of very low' PPtn. temp, have been calc. [H‘] probably plays an dielectric const, is noted. E. S. H. important part in pptn., and the increased pptn. with High- and low-frequency conductivities of uonb *emP- above the pptn. temp, is explained. solutions of electrolytes in glycerol and glycerol- hSty concns. for a range of CaO and S 0 2 concns. from water m ixtures. J. H iegem ann (Ann. Physik, • > to 90° are given. The system acts as a buffer in so 1936, [v], 25, 337— 358).— Published conductivity- ar as ESOj' ions are concerned. E. E. A. data for gly'cerol solutions agree with the square root Fusion surface of the ternary system of law, but the slope is steeper than that required by the organic compounds. I. T. A sa h in a and K . Debye-Onsager theory-. Solutions of KC1 and MgS04 in iokoyama (J. Chem. Soc. Japan, 1935, 56, 415— glycerol and gly'cerol-H20 have been measured by the { The astern picric acid (I)-p-C10H7-OH (II)- abs. method of Malsch, using a miniature thermostat kone (Hi) has eutectic points at 70° [(I) 5-5, (II) (described). The results obtained are in close agree ment with the requirements of the Debyre theory for i n ® o1; 5,0/? 1’ 840 [(I)25>5’ (H )16’ (m ) and m [(I) 85, (II) 7-5, (III) 7-5% ]. Ch. Abs. (e) the solvents used. The ionic effects for both solutes are much > any previously' reported. W . R. A. Transformation of an incongruently fusing inary compound into a ternary eutectic. X. New method of determining hydration of S 0 4" arbamide-veronal-resorcinol. F. Adam anis from the electrolytic transport of water. J. ocz. Chem., 1935,15, 546— 553).— Thermal analysis Baborovsky (Chem. Listy, 1936, 30, 5— 6).— Tho icates the existence of three 1 : 1 compounds, three hydration of S 0 4" cannot be determined directly, ernary eutectics, and a peritectic. The system is owing to the solubility of the depolarisers which GO 430 BRITISH CHEMICAL ABSTRACTS.— A. VII (a, C, (I) have to be used; an indirect method is proposed, is attributed either to anodic formation of CC14 or based on measurement of the electrolytic transport of to liberation of K carbide at the cathode. H20 in a cell consisting of Ag-AgCl electrodes in J. W. 0. iV-KCl, separated by parchment-paper diaphragms Oxidation potential of the system potassium from a central chamber containing an equiv. eoncn. molybdocyanide-potassium molybdicyanide, of K 2S0 4. R. T. and the effect of neutral salts on the potential, Electrochemical study of lithium, rubidium, I. M. K olthoff and W . J. T om sicek (J. Physical and silver bromides in a solution of aluminium Chem., 1936, 40, 247— 255; cf. A., 1935, 1462).— The bromide in ethyl bromide. V. A. Pl o t n ik o v and normal potential of the system, extrapolated to zero E. J. G o r en bein (J. Gen. Chem. Russ., 1935, 5, ionic strength, is 0-7260 volt at 25°. Neutral salts 1434— 1440).— The val. of the max. sp. conductivity increase the oxidation-reduction potential to. a large of the system MBr-AlBr3-E tB r falls in the series extent. For univalent cations the effect decreases Ag>Li>CuI>K>Rb. Except with AgBr, A1 is in the order K '= N H 4'> N a ”> L i ’> H \ Bivalent deposited at the cathode in all the systems, the decomp, cations at the same ionic strength have a much potentials being : LiBr 2, RbBr 1-66, AgBr 1-3 volts. greater effect decreasing in the order B a "> S r ‘'>Ca". R. T. The vals. of log / 3//4, calc, from experimental data, Electrochemical study of solutions of acet- arc respectively < and > those calc, from the Debye- amide in bromine. V. A. P l o t n ik o v and S. I. Hiickel expression. M. S. B. J ak u bso n (J. Gen. Chem. Russ., 1935, 5, 1337— Polarographic studies with the dropping 1341).— The conductivity max. corresponds with mercury electrode. III. Cause of maxima on N H 2Ac,6Br; Br is liberated at the anode, and current-voltage curves. D. I l k o v iC (Coll. Czech. N H 2Ac at the cathode. R. T. Chem. Comm., 1936,8,13— 34).— Certain assumptions Metal-metal potential in the e.m.f. of electro lead to the view that the intensity of the electric chemical cells. E. L a n g e and K . N ag e l (Z. field is large close up to the dropping Hg electrode Elektrochem., 1936, 42, 50— 65).— Theoretical. The and falls rapidly towards the interior of the solution. source of the e.m.f. is discussed. E. S. H. This field attracts charged particles and dipoles Electrode potential of iron in relation to much more strongly than the electrokinetic potential, hydrogen-ion concentration. J. W. S htpley and and during the action of the “ charging (non-faradic) J. H. Sh itl e y (Canad. J. Res., 1936, 14, B , 31— current,” the electrically adsorbable particles oftke 40).— The final electrode potentials observed when depolariser are drawn into and stored in this non- Ee has been immersed for several days in phosphate, homogeneous field. If the applied e.m.f. is so larg? borate, and citrate buffers show sharp falls of 0-74, that the rate of exhaustion of the depolariser is > 0-75, and 0-77 volts which occur at pa 3-1— 4-0, its rate of adsorption, polarisation starts at the 4-3— 4-6, and 10-1— 10-9, respectively, for the three electrode surface, destroying the non-homogeneou; series of buffer solutions. Bubbling H 2 or 0 2 through field in solution and leaving a very steep fall of the solutions has little effect, but the presence of potential very close to the interface. From this Cl' causes the breaks to be less marked and displaces theory, conditions are derived mathematically, and them to higher vals. of pa. Corrosion takes place confirmed by experiments with 0-002— 0 -01ATKC1 when the p a vals. are below those at which the containing air, under which a large “ adsorption breaks occur. It is suggested that the electrode current ” and a small “ diffusion current ” with potential is determined by the presence or absence transition of the former into the latter appear on of a non-conducting film on the Fe. L. A. O’N. current-time curves during the charging in the Diffusion potentials and mobilities of ionised formation of a single Hg drop at const, applied e.m.f- gelatin. II. Neutral and alkaline solutions. The current-voltage curve derived .from these curves E. B. R. P r id e a u x (Trans. Faraday Soc., 1936, is confirmed experimentally. The theory’’ explains 32, 576— 582; cf. A ., 1935, 300).— Diffusion potentials the origin of the max. arising in current-voltage of K gclatinate have been determined in dil. solutions curves under various conditions with the dropping at pK 6— 10. The calc, mobility of the gelatin Hg cathode and predicts conditions under which anion, nearly 40, agrees fairly with that found (A., similar max. may be realised with large stable Hg 1932,470) in much more conc. solutions. F. L. U. electrodes. J. G. A. G. Decomposition and equilibrium reaction Simultaneous discharge of cadmium and potentials of fused potassium chloride. R. C. hydrogen ions from solutions of simple salts K ir k and W . E. B rad t (Trans. Electrochem. Soc., of cadm ium . O. E s s in , T. B eklemischeva, and 1936, 69, Preprint, 75— 88).— The decomp, voltage A. M a t a n tze v (J. Gen. Chem. Russ., 1935, 5, 13S3-- of fused KC1 at 800° is 2-8 volts. By substituting 1386).— An equation connecting the amount of C<| a Cl2 anode and using a supplementary cathode the deposited per unit of current with the concn. of acid equilibrium potential of the cell K[KC1|C12 has been present (A., 1935, 310) has been verified for solu determined. The p.d. between anode and cathode tions of 0-25— l-0iV-CdSO4 in 0-1— 10N-H2S04, f°r increases almost linearly with increasing anodic c.d., currents of 0-005— 0-1 amp. per sq. cm., at 2A- ^ and reaches a max. val. of 3-37 volts when the anodic c.d. is 1-0 amp. per sq. cm., which is in close Overvoltage and electrolytic separation of agreement with the calc. val. of 3-32 volts for a hydrogen isotopes. J. H o r iu t i and G. OkamoW cell with Cl2 at atm. pressure. With graphite (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 193b- electrodes depolarisation may reach 0-47 volt, and 28, 231— 242; cf. A., 1934, 153, 2 5 8 ).— Overvoltage v n (d, e), VIII (a) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 431 and current, and the velocity of exchange between Valency-linking shifting in cyclanes. J. H and D at an anodically polarised N i-H electrode B oeseken (Proc. K. Akad. Wctensch. Amsterdam, in 0'001iV-II2SO.,, and in contact with H2 containing 1936, 39, 28— 30; cf. A., 1932, 269).— The influence 3% of D2, have been determined. Parallel measure of l-hydroxycycib-heptane-, -liexane-, -pentane-, ments of the electrolytic separation factor have been -butane-, and -propane-1-carboxylic acids on the made. A theory of the electrode processes is put conductivity of 0-5J/-H3BO3 has been determined forward, and an explanation of Tafel’s empirical and compared with corresponding data for disub equation is given. F. L. U. stituted glycollic acids. Saturated ring compounds Polarisation discharges in multiple electrode with > 5 members increase the conductivity to the systems. H. H u n t , J. F. C h i t t u m , and H. M. same extent as the open-chain compounds, but in Grubb (J. Physical Cliem., 1936, 40, 239— 245).—■’ the case of 3- and 4-C rings the effect is much less. It The conditions governing the production of currents is inferred that tho valency linkings in rings containing between polarised exploring electrodes immersed < 5 C are shifted by the ring-closure. R. S. in an electrolytic cell have been investigated. The Explosive reactions and analytical geometry. phenomena observed originate in the polarisation at W . P. J orissen (Chem. Weekblad, 1936, 33, 83— 90). the ends of the electrodes and in the differential — Tho factors governing the form of the curves polarisation of each of the current electrodes at representing the explosion limits of ternary gaseous different points on the surface. The significance of mixtures are discussed. D. R. D. these phenomena in electrolytic investigations is indicated. “ M. S. B. Pressure dependence of unimolecular re actions. E. A. Ste w a r d so n (Phil. Mag., 1936, [vii], Anode process in electrolysis of aqueous 21, 233— 248).— Theoretical. The chanco that an alkali chloride solutions with impregnated and activated mol. in a quasi-unimol. reaction will non-impregnated graphite electrodes. I. II. dissociate, and the ratio (r) of the velocity coeffs. Liberation of chlorine and oxygen at the anode. (k) of the unimol. and bimol. reactions are calc. HI. Influence of im pregnation of the graphite In agreement with experiment it is inferred that electrode on the anode process. V. S. J o f e e . increases in temp, and pressure produce changes in r IV. Electro-capillary phenomena. V. S. J o f e e in opposite directions, and that tho addition of a light and M. M. S t r o g a n o v (Z. Elektrochem., 1936, 42, gas will maintain the unimol. rate. Good agreement 71-76, 76— 79, 79— 82, 82— 85).— I. The distribu is obtained with the dissociation of N 20, except at tion of current between the outer surface of the low pressures, giving an average life of an activated porous electrode and the inner pore surface depends complex (x) of 10~n sec. With other reactions agree on the resistivity of the electrode and on the nature ment is poor, but t may be approx. estimated to be °t the p.d.-c.d. relation. Discharge of ions occurs IOt6— 1(H. sec. tZ(log lc)/dT is greater for the bimol. throughout the whole cross-section of the electrode, than for the unimol. reaction by iT . R . S. B. out is cone, mainly in the outer layer. When the pores are filled by impregnation with linseed oil, Limits of inflammability of hydrogen and electrolysis occurs only at the outer surface. deuterium in oxygen and in air. W. P a y m a n and II. The ratio 0 2 : Cl2 is greater in the anode gas H. T itm an (Nature, 1936,137, 190).— The upper and "berated in the pores than in that liberated at the lower limits of inflammability of D2 in 0 2 and in air outer surface of the electrode, and passes through at 1 atm. differ slightly from those of corresponding a ■ at medium c.d. mixtures with H 2. L. S. T. III. Tho polarisation of the graphite anode in Prevention of gas explosions by controlling aq. AaClhas been studied. Under certain conditions oxygen concentration.— See B., 1936, 177. o impregnation with oil, oxidation of C occurs and Explosion limits. I. Influence of argon, 'tv71??0 Sll9'crs disruption, nitrogen, helium, and carbon dioxide on explo a- ] ™ ng anodic polarisation the electrolyte sion limits of hydrogen, carbon monoxide, f '«places air from the non-impregnated and oil from methane, and butane in air. II. Occurrence le 1,nPregnated graphite electrode. E. S. H. of explosion limits, their dependence on the Electrometallurgy of aluminium. P. D r o s s - pressure, and the influence of dilution with an wra (Z. Elektrochem., 1936, 42, 65— 70).— The inert gas. J. v a n H e in in g e n (Rec. trav. chim., equilibrium Na3AlF6-L i3AlFB-A l20 3 has been in 1936, 55, 65— 75, 85— 100).— I. The extinguishing fo igated at 750— 1000°. Current efficiency and action of the four gases is in all cases in the order poansation potential in the electrolysis of such C02> H e > N 2> A (cf. Coward and Hartwell, A., 1926, mures have been determined. E. S. H. 805). Addition of inert gas mainly affects the upper Passivity of iron and steel in nitric acid solu- explosion limits, the lower limit depending little on tho nature and amount of inert gas. The curves n n- i p 1, Y a m a m o t o (Bull. Inst. Phys. delimiting the explosion region of one particular I4fin' ml3, Japan’ 1936> 15> 15— 215 cf- A -> 1934> • , Ihe ability of H N 0 3 to render Fe passive combustible gas, obtained on the addition of the four ncreased and the concn. at which the effect appears inert gases, form a family having a common axis and G I’y bhe addition of nitrates, with tho ex- intersecting only at the two explosion limits for 0 % Cu(N0 3)2. H N 0 2 and higher nitrates of of inert gas. s are formed. A g N 03 is especially effective II. A simple mathematical treatment of explosion HNoCaUSes P r iv ity in relatively dil. solutions of limits is given without recourse to the theories of 3' R. S. B. chain mechanisms. Assuming that the velocity of 432 BBITISH CHEMICAL ABSTBACTS.— A. VIII (a) reaction of two gases A and B is bimol. obeying the according to the Riee-Herzfeld theory (A., 1934, relation s= k O A. Cb, where s is the velocity, the usual 369), that all the C2HB decomposes by chain reactions curve of the equation s= f(x ), where x is the no. of initiated by the formation of Me. Hence only a small g.-mol. of A and 1—a; is the no. of g.-mol. of B present part of the C2HG decomposes primarily into radicals. in v litres, is deduced. For certain vals. of s when II. The effect of pressure on the reaction velocity reactions become explosive, two explosive limits at 856— 910° abs. leads to the equation log £=14-1— occur at different concns. The effect of the change 69,800/2-3A7T for the velocity at infinite pressure. of thermal conductivity with concns. shows that the It appears that deactivation occurs in only 1 in ~ 102'5 explosive limits are not given by the intersections of collisions between an active and a normal mol. The the parabola s= f(x ) with a straight line parallel to the life of an active mol. is lO 6 sec. The theory of X axis. The conclusion is reached, with certain “ kinetically-effective degrees of freedom ” (cf. A., assumptions, that two explosive limits occur at high 1927, 26) is criticised. R. C. pressures and approach one another as the pressure Mechanism of, and constitutional factors con is decreased. Dilution with an inert gas is considered trolling, the hydrolysis of carboxylic esters. and an equation deduced which covers certain of the VIII. Energies associated with induced polar experimental results. The sp. action of an inert gas effects in the hydrolysis of substituted benzoic can be explained if it is assumed to influence the esters. C. K . I n g o l d and W . S. N a t h a n (J.C.S., reaction const, and an equation is derived for this 1936, 222— 225).— The rate of alkaline hydrolysis of effect, but if the changes in thermal conductivity p-CeH4X ’C 02Et, in which it is assumed that in are taken into account, A, N2, He, or C 02 appear to duced polar effects are isolated from local disturbances, have no appreciable influence on the reaction const. has been determined in aq. 85 w t.-% EtOH at 25° D. C. J. and 50°. The velocity coeff., k, varies with the sub Limits and speeds of detonation of some stituent, X , thus, N H 2< O M o < M e < H < C l< I < B r < gaseous mixtures. J. B b e t o n and P. L a f f i t t e N 0 2 over a 5000-fold range. The activation energy, (Compt. rend., 1930, 2 0 2 , 316— 318; cf. A., 1934, E, decreases from 20,000 to 15,000 g.-cal. thus, 969).— Vals. arc given for the upper and lower limits NH2>OMe>Me>H>halogens>N02. The linear and velocity of detonation for the following mixtures : relation between E and log k corresponds with a C3H 8-0 2, C4H 10-O 2, C2H2-0 2, C2H2-air, N H 3-0 2, const, val. of B in k — Be~EIRr, and the similar Et20 - 0 2, Et20-air, for the effect of pressure (1— 8-7 relation, considered on the same scale, between atm.) on the limits for H 2-0 2 and H 2-air explosions, existing data for the acid-catalysed bromination of and for the effect of small additions of H„ on the substituted COPhMe (A., 1935, 1209) is not incon lower limit for C 0 - 0 2 mixtures. PbEt4 has no sistent with a const, val. of B. J. G. A. G- appreciable influence on the detonation limits. H . J. E. Kinetic salt effect in saponification of ester Thermal study of the oxidation of hydro ions. R. F . N ie l s e n (J. Amer. Chem. Soc., 1936, 58, carbons. (Mi l e .) S. EsTBAnknE (Compt. rend., 206— 215).— A conductivity method has been 1936, 2 0 2 , 217— 219).— A relationship is determined used to study the hydrolysis of E t4 esters of maloric, between inflammation temp, of hydrocarbons and succinic, and adipic acids, and a photometric com the no. of C atoms; it is considered to run parallel parison method for EtHC„04 and the betaine ester with their octane nos. T. G. P. (NEt3-CH2-C02Et)C104 (I). No effect of the distance of the reacting group from the charge was observed Temperature and latent energy in flame gases. for the four homologous ions. The kinetic salt W . T. D avid (Phil. Mag., 1936, [vii], 2 1 , 280— 281; effect for hydrolysis of (I) at ionic strengths down to cf. A., 1935, 138, 598).— The temp, measured by a thin 0-0001 is that given by the Brônsted-Debye equation Pt-Rh wire in the flame gases on combustion at const, for vals. of y V < 0 -1 . E. S. H. pressure of various gas mixtures for which the ideal Influence of heavy water on the rate of estéri calc. temp, is 1900° has been recorded. The measured fication of benzoic acid in ethyl-alcoholic hydro temp, ranges from 1390° to 1745° and corresponds gen chloride. A. K a il a n and H. H o e n y (Ber., with latent energies of 28— 8 % of the heat of com 1936, 69, [B], 437— 440).— Under like mol. conditions bustion. Similar data are given for mixtures which the rate of estérification of BzOH by EtOH containing have the same measured temp., viz., 1550°. The HC1 is diminished less bv D 20 than by H ,0 . long-lived latent energy depends on the nature of 2 H. W. the combustible gas and of the diluents, and on the aa-Dimethylacetoacetic acid. Hydrolysis of pressure. R. S. B. the ethyl ester. Ketonic decomposition. Be" Thermal decomposition of ethane. I. Prob action with iodine and bromine. Dissociation ability of decomposition into two methyl radicals con stan t. K . J. P e d e e s e n (J. Amer. Chem. Soc., and into ethylene and hydrogen. II. Collision 1936, 5 8 . 240— 246).— The rates of (a) hydrolysis efficiency in activation and mean life in activated of the E t ester at 0° and 25°, (b) ketonic decomp- state. H. S a o h s se (Z. physikal. Chem., 1935, B , of the acid in mixtures of HC1 and N a d at 25 am 31, 79— 86, 87— 104).— I. In the decomp, at 560— 35°, (c) ketonic decomp, of the ion at 25° and 3o j 590° [H] is ~ twice as great as corresponds with the (d) reaction of the acid with I and Br at 25° have been equilibrium H 2; ^ 2 H in pure H 2, shoving that part studied. It is unlikely that the acid reacts direc J of the C2H6 decomposes primarily into Me radicals, with halogen ; an intermediate enol form is proba • which form H atoms by chain reactions. [H] is, It appears that the C 02 cleavage of fi-ketocarboxv however, only about 0-001 of the val. calc, assuming, acids leads directly to the enol form of the reach VIII (a) GENERAL, RHYSICAL, AND INORGANIC CHEMISTRY. 433 product. This reacts instantaneously with free p-Me, p-Et, p-Bu7, p -N 0 2, or CGH4X is 2:4- halogen; in absence of halogen it is transformed into CGH3(N 02)2, have been investigated in COMe2 at the corresponding ketone. The dissociation const, 20° and 40°. The energy of activation (18-4— 18-9 of the acid in solutions containing NaCl has been kg.-cal.) is independent of X and is identical for the determined at 25° and 35°. E. S. H. forward and reverse reactions. In all cases tho equili Course of reaction in the alkaline hydrolysis brium is largely displaced towards the left, probably of solutions of sodium chloroacetate. H. M. owing to an orientation effect when N 0 3' attacks the D a w s o n and E. R. P y c o c k (Proc. Leeds Phil. Soc., 0 atom. The velocity coeff. varies with X thus: 1935— 193G, 3, 135— 140; cf. A., 1934, 847).— The H As and Se oxides is independent of As oxides and deposited on the surface of aq. CuS04 by' H 2S induced cc [Se02]. Pd is a very strong catalyst, of which the a change which ultimately' extended some distance action is enhanced by H gS04 and raised to a max. around the metal. The reaction ceased when the by 10— 30% of Ag2S0 4, but is markedly depressed film was so thin that the mols. were judged to be by Se. Sp. proportions of H gS04 and Ag2S0 4, 0-6— 1-0 A. apart. The rate of the reaction oc y'temp. separately, raise the catalytic activity of Se02 to (approx.). T. G. P. max. vals. Mixtures of H gS04 and Ag2S0 4 are better Catalytic reduction of carbon dioxide to catalysts than the single salts, whilst an approx. methane and higher hydrocarbons.— See B., 1936, 1 :4 CuS04-IIg S 04 mixture has a max. catalytic 180. activity. The effect on the reaction velocity of varying the composition of ternary catalysts is represented [Catalytic] synthesis of «-heptane.—See B., quantitatively by triangular diagrams. Catalysis by 1936, 181. the systems Pd+Se+Ag, H g-f Se+Ag, P d+llg+A g, Properties of the methyl alcohol catalyst Cu+Hg-J-So was < the max. vals. obtained with the copper-zinc oxide-chromic oxide.—See B., 1936, binary systems. J. G. A. G. 191. Catalytic interaction of ammonia with deuter [Catalytic] synthesis of esters by dehydrogen ium. A. P ark as (Trans. Paraday Soc., 1936, 32, ation of alcohols.— See B., 1936, 181. 416—427).— The exchange of II atoms between D 2 (¿-Halogens. XXXI. Detection of iodine- and NHg has been investigated on an Pe catalyst at mixed halogens by measurements of the rate of 160—-230°/30— 400 mm. The rate of the exchange reaction between cyc/ohexene and iodine in the reaction is independent of N H 3 pressure and increases presence of salts of the heavy metals. L. B i r c - with pressure of D 2. The apparent heat of activation k e n b a c h , J. G o u b e a t t , and H. G. K ra ll (Ber., 1936, is 15 kg.-cal. The o-p conversion of II2 and of D2 69, [jB], 476— 484).— The reaction between I and and the reaction H 2-f-D2= 2 H D are much faster than cyclohexene in PhJVIe, CC14, or Et20 occurs very much the exchange reaction. For the o-p conversions the more rapidly in the presence of A g N 02, AgNCO, activation energy is 8— 9 kg.-cal. The conversion AgC104, or PbCl2 than in their absence. The depend is inhibited by NH3. The exchange reaction proceeds ence of the rate on the nature of the metallic salt is hy the following reactions in the adsorption layer : explicable on the basis of catalysis, which, however, does not account for the effect of the quantity of salt. \i3nNH?+H ’ D2->2I)> P+HA-HD, D+NH2-> aHjD. The last of these is the slowest and rate- The change is therefore attributed to the intermediate determining step. 0 . J. W . formation of mixed halogens : I2-pRHal(^-hah) -> IHal->(+>C:C<)>CI-CHaK. “ H. W. Thermal d ecom p ositio n of lig h t and heavy anunonia and phosphine on tungsten. R. M. Existence of a sharp temperature threshold for &SEER (Trans. Paraday Soc., 1936, 32, 490— 501).— catalytic decomposition of molecules on a hot elocity measurements have been made for the platinum surface, and the nature of this decom lernial catalytic decomp, on W filaments (a) of NH3 position. O. B e e c k (Physical Rev., 1934, [ii], 46, between 6x 10-2 and 6 x 10-4 cm. and 950— 1150° abs., 331— 332).— Decomp, of mol. beams of hydrocarbons projected on to a Pt strip filament have been investig sen n~ between 10-1 and 2 x 10~4 cm. and 970° abs. On various W catalysts and in the ated. Decomp, of C2I16 commences at approx. 800° early stages of the reaction (a) was of zero order, but and increases up to 1200° when all impinging mols. °wards the end of decomp, or at the lowest p the are dehydrogenated to C2H4 and II2. C2H4 shows no veocity diminished as the NH3 pressure decreased. decomp, below 830°, but at 850° every' impinging mol. eaction (6) was of first order at p = lC H to 5-0 XlO -3 yields C2H2 and H 2. L. S. T. e'l' a™ became of approx. zero order at about 10'1 Dehydrogenation and dehydration catalysed • ’ . e rate-determining step in both reactions by nickel-ahnmnium oxide catalysts. A. A. f fr° ves a rearrangement of a H linking, since B a l a n d in and A. M. R u b in s t e in (Z. physikal. Chem., omercilc% were found in zero-point energy of S00— 1936, B , 31, 195— 213; cf. A., 1935, 1348).— The parallel dehydrogenation and dehydration of fsoamyl and Pn u r NH-3 and N:D3> and 5»0 g.-cal. for PH3 . , :.3- Ro and N2 have no influence on the rate of alcohol and the secondary decomp, of the aldehyde nnri pcomp. of N H 3, but 0 2 produces a tem- formed have been studied. Catalysts prepared by 3 ,.‘ frT.P01S011ing of the catalyst. The energies of pptg. mixtures of Ni and A1 salts with NaOH are mnfl i°n’ raeasured by a compensating filament more active than those pptd. with Na2C03. Catalysts ’ ^r_c 42,400 g.-cal. for the zero order NH3 prepared from chlorides and sulphates may be as „ —5.000 g.-cal. for the first order and 32,200 active as the most active catalysts prepared from s-rai. lor the zero order PH3 decomp. O. J. W . nitrates. The ratio of the energy of activation of dehydrogenation to that of dehy'dration averages 0-51, sv^8r^e as basic material for the catalytic the corresponding vals. for dehydrogenation: alde ynthesrs of am m onia.— See B., 1936, 190. hyde decomp, and dehydration : aldehyde decomp, c o S ^ ^ 1 transformation of a thin layer of being 0-69 and 1-26, respectively. All three ratios C0Dnor s . Pbide under the influence of metallic vary little from one catalyst to another, but the senior*! mterruption of this transformation by a heats of activation themselves vary considerably. n f i D e v a u x (Compt. rend., The relation between the energy of activation and the 41 or ^ a— 1307).— A piece of Cu, Fe, Zn, Ni, coeff. a of Arrhenius’ equation previously noted (A., ’ 611 Placed I» contact with the thin layer of CuS 1933, 234) is valid for both dehydration and dehydro- 436 BRITISH CHEMICAL ABSTRACTS.— A. VIII (b , C) genation. It appears that the activity of a mixed Simultaneous discharge of Cd" and H ’ ions in catalyst is located at the lines of contact between its solutions of simple salts of cadmium. 0. E s s in , components. R. C. F. B eklemischeva , and A. M ata n ze v (J. Chim. A sym m etric m ain valency catalysts.— See this phys., 1936, 33, 72— 77).— The yield of Cd obtained vol., 476. by electrolysis of aq. CdS04 has been studied at 25° for [H2S0 4] 0 -1 W -1 0 A r and [CdS04] 0-125N— IN and Hydrogenation of ketones.— See this vol., 457. with c.d. 0-25— 1 amp. per sq. dm. The results are Catalytic reduction of aromatic carboxylic in accord with the equation of simultaneous discharge acid esters under high pressure and temper calc, from Volmer’s theory of overpotential. ature. K . M it s u i (Mem. Coll. Sci. Kyoto, 1935, J. W. S. A , 18, 329— 336).— The reductions were effected by Electrolytic separation of bivalent europium, H 2 at 100 atm. in the presence of reduced Ni. EtOBz A. B r u k l (Angew. Chem., 1936, 4 9 , 159— 161).— reacts rapidly at 150— 190° and the product contains Eu can be readily separated by electrolytic reduction 90 m ol.-% of E t hexahydrobenzoate ; CH,Ph-OH at a Hg cathode. For mixtures of rare earths con and BzOH were not produced. The product from taining < 2 % Eu20 3 it is necessary to co-ppt. the Eu CH2Ph-C02Et at > 1 4 0 ° contains 90 m ol.-% of (as E u S 0 4) with SrS04 (cf. Selwood, A., 1935, 950), Et cycZoliexylacetate. The product from Et salicylate the SrS04 being then removed by dissolution in hot at > 2 0 0 ° contains 75 m ol.-% of cycZoliexanol, cyclo- 50 % HC1, and further purification effected through hexane, and EtOH. m -0H -C6H4-C02Et at 170— 190° pptn. with H 2C20 4. Sa mother-liquors containing absorbs 3 mois, of H 2 forming products containing 1— 1-2% Eu20 3 were electrolysed using c.d. of 0-1 75 m ol.-% of Et m-hydroxyhexahydrobenzoate, and amp. per sq. cm. (0-12 amp. per sq. cm. gave Sr-Hg), p-OH• CgH.pCO2Et at 180— 200° absorbs 2 mois, of and after 8 electrolyses and subsequent separation of H , forming products containing 40 m ol.-% of Et SrS04, the Eu content increased to 30%. Tliree p-hydroxyhoxahydrobenzoate. J. G. A. G. further electrolyses without SrS04 gave a product Electrolytic separation of deuterium. A. J. containing 99-40% Eu20 3, the impurities being Sa 0-5, Gd 0-03, and Y b 0-02% . The yield was 12 g. from E d w a r d s , H . E. W alto n , R. P. B e ll, and J. H. 1-5 kg. of mother-liquor containing 1— 1-2% Eu203. W o lfen d en (J.C.S., 1936, 286— 287).— Vais, of the separation coeff., a, obtained by protracted electro D.C.J. lysis of aq. NaOH containing 0-5— 1% D 20 under Mechanism of electrolytic processes. 1- Anodic oxidation of some metals of the platinum apparently identical conditions fluctuate widely. Vais, of a for different cathode materials are recorded. group. J. A. V. B u tle r and G. D rever. H Electrolytic oxidation of sodium sulphite. J. A. V J. G. A. G. Electrolytic formation of persulphate. I. R. B u tler and W . M. L eslie (Trans. Faraday Soc., 1936, 32, 427— 435, 435— 444).— I. When electrodes M atsu d a (Bull. Chem. Soc. Japan, 1936, 11, 1— 7).— of Pd, Rh, and Ir are anodically polarised in acid and Aq. [N H 4]2S0 4 and H 2S0 4, in which the ratio of the alkaline solutions, an adsorbed layer of 0 is formed normalities varied from 0 : 10 to S : 2, have been electrolysed at different c.d. and the variation of prior to the establishment of the O overvoltage, as hi current efficiency for the formation of S20 8" examined. the case of Pt (cf. A., 1932, 1092; 1934, 154). With Current efficiency increases with c.d., the effect being Pd and Rh the slow formation of peroxidic oxides greatest in the more acid solutions ; it also increases has been observed as the second stage in the oxid as [H2S0 4] diminishes and the effect at low c.d. is > at ation. These oxides are reduced cathodically at a high. Increase in total concn. for a const. 5 : 1 ratio more positive potential than the adsorbed 0 , and the raises the efficiency, especially at higher c.d. The conditions of their formation have been studied. A results indicate that increase in [OH'] favours anodic mechanism of the anodic oxidation of insol. metals is oxidation. The effect of replacement of N H 4‘ by suggested. other cations Has been investigated. Current II. The electrolytic oxidation of Na2S03 at Pt j efficiency for K ’ , Na\ and N H 4\ which form acid electrodes in buffer solutions of various ptt has been sulphates, is > for the other cations, viz., M g", Li’, investigated. With pH 7 the oxidation takes place at A T ", Cd” , Ee"*, Cu", and Zn” ; it is greatest for K ’, a more negative potential than that at which adsorb«! but the catalytic decomp, of S2Os" by cations is in O is formed. Since no other primary process is the order Na’> K ’> N H 4\ ‘ ' M. S. B. observed in this region with the buffer solution alone, oxidation probably takes place in solutions of this }h Electrical synthesis of nitric oxide. J. W il l e y by direct transfer of electrons from the S03" ions to (Nature, 1936, 137, 274— 275).— With a 1 : 1 mixture the electrode. With pK 9 oxidation occurs in the of N2 and 0 2 the yield of NO at 5— 10 mm. pressure same region as that in which adsorbed 0 is formed, with rapid gas circulation is practically independent of so that oxidation by adsorbed O is possible. The the electrical power supplied. A liquid air trap placed effect of adding various salts has been studied. With near the discharge condenses 7 to 10 times more N 0 2 M n " salts, which are the most effective, suppression than one placed at a distance from it, although the of the initial stage of electrolysis is due to the formation equiv. time interval is only 0-05 sec. This effect of a film of MnO,. The results do not agree with disappears when a plug of oxidised Cu is placed Glasstone and Hickling’s theory (cf. A., 1933, 913) between the discharge and the trap, or when a large and an alternative mechanism is suggested. excess of 0 2 is used. It is apparently due to the 0 . J- w. simultaneous formation of active N which decomposes Effect of anode composition on zinc electro much of the NO formed. L. S. T. lysis.— See B., 1936, 201. v in (c, d) GENERAI/, PHYSICAL, AND INORGANIC CHEMISTRY. 437 Electrolytic lead-plating.— See B., 1936, 201. cf. A., 1933, 553).— The quantum yield in the photo Electroplating bismuth on metals.—See B., chemical production of 1 by C6H6 solutions of Mel, 1936, 201. CH2I2, BuvI, GH2Bu^I, and C ^H ^I has been deter mined at room temp, and in absence of 0 2. For Mel Photochemical union of hydrogen and chlorine. and BiPT the yield is approx. 1, and for the others IV. Reaction at low hydrogen pressures. 0-55— T75. Mel in EtOH gives a val. > 1. The Effects of wave-length, of temperature, and of results are discussed. F. L. U. traces of oxygen. H. C. Craggs and A. J. Allm and (J.C.S., 1936, 241— 252).— By irradiating 0 2-frce Photochemical decomposition of gaseous mixtures of 0-1— 0-6 mm. of H 2 and 1-7— 166 mm. methyl iodide alone and in presence of hydrogen of Cl2 with monochromatic light of X 546 mg, HG1 is and nitrous oxide. R. Sp e n c e and W . W il d formed, and the temp, coeff. leads to the activation (Proc. Leeds Phil. Soc., 1935— 1936, 3, 141— 144; energy 9-78 kg.-cal. (cf. 4-74— 5-5 at X 436 mg). cf. A., 1931, 1138).— Irradiation of Mel yielded CH4, No HC1 was obtained at X 579 mg. The quantum C2H6, and I. Increased yields of CH4 were not efficiency, y, relative to unity at 436 mg is approx. obtained in presence of H2. The approx. quantum 0-3 at 546 mg. These results may be correlated with yield of CH4 formation in terms of Mel disappearing the continuous background of the banded spectrum was 0-06. There was no detectable reaction between region of Cl2. Thus, Cl2 mols. in high vibration levels Me and N20. II. J. E. absorbing at X 546 nig acquire sufficient additional Photochemical formation of organic diradicals. energy to dissociate into atoms which initiate reaction III. Anthracene, the fulgides, thiophosgene, chains. At approx. 2 mm. total pressure, ultra and their derivatives. A. Sc iio n b e r g (Trans. violet light affords vals. of y < with visible light, Faraday Soc., 1936,3 2 ,514— 521; cf. A., 1935, 986).— hut at higher pressures this difference was not ob In order to explain the different chemical properties served. Cl3 formed by light of short X would accpunt of irradiated solutions of certain anthracenes, ful for these results. 0-1 mm. of 0 2 retards the reaction gides, and CSC12 in comparison with those of non between Cl2 and < 0-01 mm. H 2, but has no effect irradiated solutions, a photoequilibrium between when there is 0-5— 0-01 mm. H 2, although 0 2 is con the normal and diradical forms of the mol. is assumed, sumed. These effects are discussed. J. G. A. G. as was done in the case of rubrene (cf. A., 1934, 643). Properties of illuminated iodine solutions. The phenomena of plioto-oxidation, photoisomeris- I Photochemical dissociation of iodine mole ation, and photopolymerisation can be accounted for cules in solution. E . R abino w it c h and W . C. by this means. Objections to the theory arc dis | od (Trans. Faraday Soc., 1936, 32, 547— 556).— cussed. O. J. W. Improvement of the apparatus previously described Behaviour of di-serine, di-phenylalanine, di- (A, 1935, 586) has permitted the detection and alanine, di-lactic acid, and propionic acid to measurement of a reversible change in the extinction wards X-rays and ultra-violet light. J. P. coelf. (e) of I solutions under the influence of strong B e c k e r (Strahlenther., 1935, 52, 537— 544; Chem. illumination. In CC14 and C6H 14 e decreases under Zentr., 1935, ii, 203).— The decomp, of di-serine (I) 1 'niuation owing to dissociation of I2 mols. into and didactic acid (II) follows a different course from . om.s. The velocity of recombination of the latter that of di-alanine (III) and EtC02H ; this is ascribed S solution is about 1000 times > that of Br atoms in to the presence of an a-OH in (I) and (II). dl- ,.e .atin. pressure, agreeing with the assumption Phenylalanine also differs from (III) in its mode of 1 I ftiple collisions are necessary in gas and that in decomp. The physiological action of X-rays and solution every collision is effective. The quantum ultra-violet light is, in part, attributed to such action. U® . dissociation of I2 in solution is the same in II. N. R. p 0 continuous spectral region as in the band region. Comparison of the photochemical decom •vplanations of the results are offered. F. L. (J. position of l-aspartic acid, l-asparagine, and ■ i Election of a latent image in thallous brom- glycylglycine by X-rays and ultra-violet light. p J- G. F a r r e r (Nature, 1936, 137, 276).— J. P. B e c k e r (Strahlenther., 1935, 5 2 , 531— 536; -■ nufsions of TIBr in gelatin can receive a latent image, Chem. Zentr., 1935, ii, 203).— Both I-aspartic acid direct reduction of the exposed broinido to T1 and Z-asparagine yield MeCHO on irradiation with j; not possible. By treatment with aq. A gN 03 the X-rays or ultra-violet light; the decomp, products (j 111 ;le emulsion is replaced by Ag without destruc- of glycylglycine are different. H. N. R. °n 0 tiie latent image, and after removal of the Photolysis of aliphatic aldehydes. III. Hydro in °h S S0^‘ ^ 2 tlie plate can be developed and fixed gen from acetaldehyde. F. E. B l a c e t and J. G. 0 usual way. Replacement of the T1 by Ag R oof (J. Arner. Chem. Soc., 1936, 58, 278— 280; ’ uis apparently without alteration in crystal shape cf. A., 1933, 930; 1934, 1188).— The fraction of mols. wit! n!cturp- TIBr emulsions can be colour-sensitised yielding H 2 increases linearly from 10% at X 3130 to 7.es in the same way as Ag emulsions, but the 31% at X 2537. The mechanism of the primary c o a c h e d ^ C^e®ree sensitivity has not yet been process appears to be : RHCO-f-/iv->-R-f-HCO. L. S. T. E. S. II. Free «-propyl radical.— See this vol., 451. Photochemical reactions of cellulose. IV. a^ hot°dec°mposition of iodoform and of alkyl Relation between wave-length and strength of w L aUiylene iod id es. K . E. G ib s o n and T. light from a qmartz mercury vapour lamp. _S. Re d a l e (Trans. Faraday Soc., 1936, 32, 571— 576; O g u r i (J. Soc. Chem. Ind. Japan, 1936, 39, 3o 438 BKITISH CHEMICAL ABSTRACTS.— A. VIII (d), IX 36b).— A table shows the deflexions of a thermopile Silver solutions containing iodine. (Mlle.) galvanometer at XX of 2000—7000 Â. A. G. M. L. J o s ie n (Ann. Chim., 1936, [xi], 5, 147— 265).— Concentrations of sodium vapour in the The action of aq. I on aq. A g N 0 3 comprises a rapid reaction between the H I produced by hydrolysis of electric arc. T. P e c z a l s k i and N . S z u l c (Compt. the I and Ag‘ , yielding insol. A gl, followed by dccomp. rend., 1935, 2 0 1 , 1335— 1337 ; cf. A ., 1935, 1046).— of the H O I to give H I and H I0 3. The latter reaction The concns. of Na within and around a C arc burning is slow, being accelerated by increasing salt concn., in the presence of NaCl have been determined spectro by rise of temp., and by addition of acid. The re scopically. T. G. P. action is most rapid when the Ag salt of a strong acid Significance of potassium carbonate for the is used in the reaction. The reduction of I0 3' by corrosive action of potassium cyanide. H. HC1 and As20 3 is attributed to a cyclic reaction, E l b e l (Z. ges. gerichtl. Med., 1934, 24, 25— 29; probably with intermediate production of I and oxid Chem. Zentr., 1935, i, 3951— 3952).— The corrosive ation of the A s20 3, rather than to catalytic action. action of KCN depends on its alkaline properties, Sparingly sol. Ag salts react with I similarly to AgN03, and is weakened rather than strengthened by K„C 03. but the first step is not instantaneous. The reaction R . N. C. between AgCl and I is not a direct substitution, but Rubidium and cæsium fulminates. L. H acic- 3I2+5AgCl+3H20=5A gI+H I03+5HCl. It is con spill and W . Sch umacher (Compt. rend., 1936, cluded that there is no evidence of production of an 202, 69— 71).— The fulminates were prepared by intermediate product between OI' and I 0 3' in the treating the alkali-metal amalgam, prepared in vac., reaction between I and Ag salts or between I and with a suspension of Hg fulminate in anhyd. MeOH, alkali. J. W. S. and pptg. the salt with anhyd. E t20 . Dissolution Solid reactions at 1000— 1200° between mag in MeOH and repptn. with Et20 is necessary to remove nesium oxide or beryHium oxide and nickel, traces of the double fulminate of Hg and Rb or Cs. iron] chromium, manganese, and their oxides. The latter renders the product liable to detonate at L. N a v ia s (J. Amer. Ceram. Soe., 1936, 1 9 , 1—7).— < 50°. H. J. E. The reactions were carried out with the mixtures Cæsium mercury iodide. F. G a l l a i s (Compt. as loose and pressed powders and with loose powder rend., 1936, 2 0 2 , 54— 56 ; cf. A., 1935,592).— Measure on a high-fired pressed slab of MgO or BeO. The ments of electrical conductivity and of magnetic degree of reaction was noted by the extent ot dis rotatory power are recorded for mixed solutions of coloration at the interface. In an oxidising atm, Csl and HgCl2 in H 20 or EtOH. The formation of at 1200° the reaction with MgO and BeO increased Cs2HgI4 is indicated in 0-01— 0-517 solutions. in the order NiO (with BeO, none), Fe20 3, Cr20j, H . J. E. M n02, in all cases reaction with MgO being the Basic copper sulphates. 0. B i n d e r (Ann. Chim., greater. The same sequence was found for the 1936, [xi], 5, 337— 409).— A more detailed account metallic elements in an oxidising atm., but the of work previously described (this vol., 38, 172). degree of reaction was > with the corresponding 4C u0,S0,,4H 20 at 150° gives 4Cu0,S03,3H20, the oxides. In a H 2 atm. at 1200° only Mn02 showed A-ray photograph of which resembles that of any reaction, and of the metals, Cr and Mn oxidised 4C u0,S03,4H20. The four basic sulphates are formul with very slight reaction. Mixtures of oxides and of ated [Cu{(0H)2Cu}3]S04,H 20 ; [Cu{(0H)2Cu}3]S04 ; metals showed less reaction than the individuals. [Cu{(0H )2Cu}2]H04, and [Cu-OCu]S04. The first W et air gave most reaction between MgO and Mn, three are identified with langite, brochantite, and M n02, or Cr powders. J. A. S. antlerite (stelznerite), respectively. F. R . G. Double salt, KJYIg(C03)2,4H20 . F. H alla (Z. Yellow cuprous oxide. G. R . L e v i (Z. anorg. anorg. Chem., 1936, 2 2 6 , 139— 140).— On gradual Chem., 1936, 2 2 6 , 173— 174).— A claim for priority addition of aq. K 2C03 to aq. MgCl2, of suitable concn., over Straumanis et al. (A., 1935, 1332) with reference reaction takes place in two stages, a flocculent ppt- to the proof of the direct formation of Cu20 by re of MgC03,3H20 being first formed. This redissolves duction in aq. solution. M. S. B. and, as the addition of aq. K 2C03 continues, a cryst. Organic cupri-tetrachlorides and -tetrabrom- ppt. of K 2Mg(C03)2,4H20 is obtained. Solubility' ides formed by secondary and tertiary amines determinations have been made at 17° in aq. KC1 of and alkaloids. J. A m ie l (Compt. rend., 1935, varying concn. to reduce hydrolysis. The temp, cocff. 2 0 1 , 1383— 1385; cf. this vol., 212).— The following of solubility has also been determined. M. S. B. compounds have been prepared and in some cases Production of calcium sulphate hemihydrate their d and solubilities determined : CuCl,(NH„Et2)„ in the wet way, and the polymorphism of the CuCl4(NHEt3)2, CuBr4(NH2Et2), CuCl4(NH,PhMe).„ anhydrous sulphate. P. G a u b e r t (Bull. Soc. fran?. CuCl4(NH 2PhEt)2, CuC14(NHP1iMc2), " Min., 1934, 57, 252— 267; Chem. Zentr., 1935, i, CuCl4(NHPhEt2)2, CuBr4(NH2PhMe).„ 3523).— CaSO4,0-5H,O was obtained as hexagonal CuBr4(NH2PhEt)2, CuBr4(NHPhMe2), prisms by evaporation of a hot H N 0 3 solution ot CuBr4(NHPhEt2)2 ; -with nicotine, quinine, and CaS04. When dehydrated in air at 130°, or in a strychnine CuC14(C10H 14N,H ,),H ,O , neutral liquid at 170°, they maintain their form and CuC14(C10H14N2Ho), CuC14(C,0H ,4N2O2H„), optical orientation, but n decreases, whilst the double CuC14(C21H22N20 2H)2, C u B r4"( C j q H ^ H, H o ), refraction increases (y-form). This is transformed CuBr4(C20H24N2O2H2), and CuBr4(C.,1H»,N20 2H)2 ; at 180° into the (3-form (n < that of natural anhydrite)- and with brucine CuCl^C^HoglS^O.jH)2. T. G. P. At 520° the (3-form gives the a-form. H. J. E- IX GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 439 Zinc, even impure but perfectly smooth and Acid fluorides of univalent cations. C. F in b a k without external contamination, does not efferv and O. H a s s e l (Z. anorg. Chem., 1936, 226, 175— esce with dilute acids. P. R onceray (Bull. Soc. 176).— Determination of the lattice consts. of the T1 cliim., 1936, [v], 3, 206— 213).— The technique compound, obtained by the concn. of the solution of described for Fe (A., 1935, 834; this vol., 174) has T120 or T12C03 in excess of HF, indicates that it is a been applied to Zn with similar results. E. S. H. silicofluoride and not an acid fluoride as supposed by Barium arsenates. Characterisation of other investigators. Similar conclusions have been 2As205,3Ba0. H. G u e r in (Compt. rend., 1936, reached previously with regard to other so-called 202, 225— 227; cf. this vol., 173).— The thermal “ acid fluorides,” and doubt is thrown on the pos decomp, of Ba meta-, ortho-, and pyroarsenates has sibility of the existence of acid fluorides in general. been investigated. B a0,A s20 5 when heated in a vac. M. S. B. at 700° yields the sesquiarsonato 3BaO,2As2Q5. Reactivity of red and yellow lead oxide with silica. J. A. H e d v a l l and A. E l d h (Z. anorg. T. G. P. Chem., 1936,2 2 6 ,192— 196).—-The amount of reaction Purification of m ercury. B. P e sc e (Annali Glum. Appl., 1935, 25, 654— 657).— A pyknometer occurring between red PbO and Si02, when an intimate for determining the d of Hg is described. The mixture of the two is heated for 1 hr. at 450— 650°, presence of very small amounts of impurities in Hg has been determined and compared with the rate of can be detected most readily by d determinations. transition from red to yellow PbO at the same temp. Although the transition temp, is 488-5° both the rate Hg cannot be purified completely by distillation only, but two preliminary distillations followed by the of reaction with Si02 and the rate of transition begin to be appreciable at approx. 600° only. Above this treatment suggested by Boutell (A., 1910, ii, 105) give a pure product. A. M. P. temp, both increase rapidly. The temp .-reactivity curve for red PbO with Si02 is practically identical Reactions of mercuric oxide. E. M o n t ig n ie with that for yellow PbO, since the slight pressure (Bull. Soc. chim., 1936, [v], 3, 459— 460).— The re used in mixing results in partial transformation into actions of HgO with KCN, KCNS, K.,Fe(CN)G, the stable red form. M. S. B. K,Fe(CN)0, N aB02, Te, P, As, and Sb are described. E. S. H. Induced oxidation of nitrogen. M. Poljakov Action of mercuric oxide on solutions of (Compt. rend. Acad. Sci. U.R.S.S., 1935,4,35— 36).— sulphates and nitrates. E. M o n t ig n ie (Bull. A discussion of the formation of N oxides in gaseous Soc. chim.; 1936, [v], 3, 193— 196).— The products of explosions. H. J. E. reaction with Al, Tpv, Cera, FeTI, Mhn, Zn, and Cu11 Structure of nitrogen peroxide deduced from sulphates, and Bi, Zr, Cu11, andNi11 nitrates have been its action on potassium iodide. M. DodA (Compt. ‘ entified. HgO does not react with aq. AgNO, or rend., 1935, 201, 1378— 1380).— The reactions be l 08(NO3)2. E. S. H . tween N20 4 and K I or aq. K I havo been investigated; Mercuric chromates. E. M o n t ig n ie (Bull. Soc. they indicate that N20 4 exists in at least two forms in ™m., 1936, [v], 3, 460— 462).— The conditions of equilibrium. T- G. P. formation of HgCrO. and H gS04 in the systems ¡S-HaSOrX&O, (2) Hg0-H 2S 0 4-K 2Cr04, (3) Non-existence of the nitrosyl of Angeli.— See Hg'H,S04-Cr03, (4) H g 0 -H 2S 0 4-C r0 3 at 10— 15° this vol., 460. lave been determined. E. S. H. Nitrogen iodide. E. Roederer (Z. anorg. Chem., Action of mercuric oxide on potassium di- 1936, 226, 145— 167).— Attempts to employ N 2H 3l 3 chromate. E. M o n t ig n ie (Bull. Soc. chim., 1936, for the development of a now photographic process, I'b 3, 419—420).— With small amounts of HgO, the depending on photochemical reactions with the product is HgCrO,; further addition of HgO produces highest possible quantum output, were unsuccessful. basic chromates. E S. H. NJI3I3 show-s a max. stability in aq. solution at p n approx. 10. The requisite p a is a little higher in the Aluminium, even impure but perfectly smooth presence of aq. NH3 than in its absence. The equili 1 without external contamination, does not brium const, for the formation of N 2H3I3 from aq. NH3 ervesce with dilute acids. P. R o n ceray' (Bull, and I in aq. solution is AI=[N H 4-]2[OHT[I]3/ [ r ] 3 nbf'- , 1936< [v], 3, 213— 218).— The results and is approx. lte29 23. No N 2H 313 is formed by „ ^ d "ith Zn (see above) have also been observed the interaction of NH3 and I in CCl4. An additive 'nthA1- E.S.H. product is mainly obtained, as in the reaction between Recomposition of sodium aluminates. V. D. gaseous N H 3 and solid I, but there is also a small i o ^ ov anc* O- S. K o sh u ch o va (Kolloid-Z., amount of oxidation of NH3, probably to N2 and H 2, v ’ 106— 200).— The stability of solutions of and simultaneous reduction of I to I' with formation .alummate increases rapidly with increase of the of N H 4I. Similar behaviour is observed in CgHs pt]1?.-, 2O/AI20 3 above 1-4— 1-5. The solutions solution. A reaction scheme is suggested. The 4, ‘ blt lm,n- stability at a concn. of 120— 180 g. distribution coeff. of NH3 between CC14 and the gas the 31 -r e' -Addition of Na2Si03 first stabilises phase is 7-24fi;0-04. Ah S. B. t b r . ,ons> But at higher concns. causes coagulation, a ij.RP • yAjjOa being contaminated with Si02. Decomposition of nitrogen iodide. W . E. 10n agar-agar increases the stability, whilst G a r n e r and W . E. L a tch e m (Trans. Faraday Soc., and +m’ n}etBylene-bIue, and Me-violet have no effect, 1936, 32, 567— 569).— See A., 1935, 828. a tanmc acid very little. F. L. U. r . L. U. 440 BKITISH CHEMICAL ABSTEACTS.— A. IX Constitution and mechanism of formation of Oxidation of inorganic reagents by ozone. I. the solid, yellow hydride of phosphorus. P. Potassium iodide. G. G u A r o n , M. P r e t t r e , and R o ye n and K . H i l l (Naturwiss., 1936,2 4 ,1 0 8 ).— The J. G u £ r o n (Bull. Soc. chim., 1936, [v], 3 ,295— 312).— hydride of P, generally regarded as P12H B, is not a Experiments in buffered, neutral solutions show that definite compound, but arises from adsorption of PH3 the normal reaction 2 I'-f-0 3+ H 20 = I 2+ 0 2-)-20H' is on an amorphous, yellow P. X -R a y diagrams of accompanied by an independent, heterogeneous P12H g and P9H 2 show no interference. More diffi reaction, I'-)-3 0 3= I 0 3'-f-3 0 2. The latter reaction cultly volatile mois., e.g., NH3, piperidine, and PEt3, preponderates in presence of a large glass surface. can cause partial or complete removal of the hydride The influence of concn. has been studied. Preliminary as PH3. The formation of red alkali-metal salts in observations have been made on the simultaneous aq.-EtOH solutions is probably due to peptisation, oxidation of A s03" '. E. S. H. rather than to the existence of an acidic H in Pi2H 0. Constitution of sulphato-compounds. A. vox The formula of the hydride is dependent on surface K iss (Z. anorg. Chem., 1936, 226, 141— 144).—The conditions, and varies from P12H 5.8 to P 12H 7.2. It is dialysis method is not a conclusive test for the suggested that the reaction is 3P2H4= 4 P H 3+ 2 P , existence of true complex compounds, since a simple analogous to the reaction between PH3 and PEt2Cl, in association of ions without change of the constitution which an unstable intermediate compound, PH2-PEt., of the co-ordination zone will produce tho effect of is formed, and decomposes to give amorphous yellow increased ionic wt. The method must be combined P and PH2Et, PH Et2, and PEt3, some of these being •with spectroscopic determinations. These do not adsorbed on the P. A. J. M. confirm the formation of true complex sulphates Phosphorus pernitride P,,NC. H. M o u r e u and reported by Brintzinger et al. (A., 1935, 181). G. W e t e o f f (Compt. rend., 1935,2 0 1 ,1381— 1383).— M. S. B. Tho products of the reaction of PC13 on liquid N H 3, Transformation from vitreous to metallic heated in a vac. at 550°, yield P4N G, a white, insol., selenium. K . T a n a k a and H . Y . T ie n (Mem. Coll. non-volatile substance spontaneously inflammable in Sci. Kyoto, 1935, A, 18, 309— 310; cf. A., 1935, air, and hydrolysed at 215° thus : P ,N fi+ 1 5 H o0 = 920).—Between 65° and 80°, tho wt.-% of metallic 2(NH.,)2H P 0 4+ N H 4H 2P 0 4+ N H 4H 2P 6 3. Under Se, j), in the specimen annealed for t hr. is p= similar conditions P3N B-f l2 H 20 = 2 (N H 4)2H P 0 4-f- P(l— e~c(‘ ~,')), where P is approx. 78-5% , I' decreases NH 4H 2P 0 4. P4N 6 heated above 750° in a vac. gives from 4 to 0-65 and c increases from 0-062 to 1-11 as the PN, which condenses out in a pure state. PN is temp, is raised. J. G. A. G. completely hydrolysed only after 3 days at 215°. Purification and preparation of very intense The primary reaction is PN-|-3H20 = K H 4H oP0 3. polonium sources. M. Haissinsky (J. Chim. phys., T. G. P. 1936, 33, 97— 98).— Po can be separated from Te, Action of arsenic trichloride on the elements. Au, Hg, and Pt by reducing the latter with N2^i- E. M o n t ig n ie (Bull. Soc. chim., 1936, [v], 3, 190— Pptn. is preferably carried out in solution sufficiently 191).— At room temp. S, Bi, and A1 are unattacked; acid to prevent adsorption of Po by the pptd. metal with Se, Te, Pb, and Au, respectively, As is liberated (20% HC1 or AcOH). The Po can then be deposited and Se2Cl2, TeCl4, PbCl2, and AuC13 formed; Ag by introduction of a polished Ag disc. J. W. S. forms AsCtjAgg. “ E. S. II. Preparation of polonium sources from radon Formulae of basic salts of bismuth. M . P ic o n (Bull. Soc. chim., 1936, [v], 3, 186— 190).— The bulbs. L. R. H a f s t a d (J. Franklin Inst., 1936,221, 191— 213).— Details of the prep, of strong Po sources system advocated shows the ratio of acid radicals to metal atoms: e.g., Bi2n0o1,(N 02)1s,0Ho0 instead of by an elaboration of the Curie method (A., 1926,5) are 10Bi2O3,9N2O5,6H2O. “ “ E. S. H. given. R- S- Preparation of chemically pure hydrochloric Bivalent bismuth iodide. E. M o n t ig n ie (Bull. Soc. chim., 1936, [v], 3, 191— 193).— Unsuccessful acid.— See B., 1936, 190. attempts to prepare B il2 are recorded. E. S. H. Existence of chlorous anhydride [C120 3]- M- Preparation of bismuth iodosulphide by the K a n t z e r (Compt. rend., 1936, 202, 209—210).— wet method. F. François and M. L. Delwaulle The action of cone. H 2S 0 4 on KC103 at —15° ui (Bull. Soc. chim., 1936, [v], 3, 504—508).— BiSI is presence of undecenoic acid yields C102 and Cbth- formed by the action of H 2S or Bi,S3 on solutions of The absorption spectrum of C102 consists of three Bilg in H I, or by the action of H l"on Bi2S3. Deter groups of bands between 3895 and 4180 A. CI2O3 minations of Bi as Bi2S3 in solutions containing I are absorbs continuously between 3500 and 4260 A., aIlfl rendered invalid by pptn. of BiSI. E. S. H. has 10 broad bands between 4260 and 4649 A. T. G. P- Basic organic salts of bismuth.— See this vol., Mechanism of permanganate reduction and the 460. induced oxidation of chlorion. H. B a s s e t t and 1- Occlusion of protoactinium by sulphides in S a n d e r s o n (J.C.S., 1936, 207— 211).— M n" is the soluble in hydrochloric acid. Cheng Da-Chang first identifiable product when M n04' is reduced by and L. IIouang (Bull. Soc. chim., 1936, [v], 3 , 326— F e ". Induced oxidation of Cl' in permanganate 328).— The co-pptn. of Pa with CuS, Sb2S3, HgS, and reactions is attributed to Mn” ” and especially Mn .■ Bi2S3 has been studied under different conditions of because the process Mn” ‘-> M n " is probably simpler concn. and acidity. Pa sulphido is sol. in the aq. HC1, than M n04'->M n“ \ The end-point of the titration but is adsorbed incompletely by the ppt. E. S. H. FeCl2-K M n 0 4 is most nearly stoicheiometric when GENERAL, PHYSICAL, AND INOKGANIC CHEMISTRY. 441 Jin" or substances forming stable complexes with The salts Sr3Fe2F12,2H20 , d 3-71, and BaFeF5,H20 , Mn‘", e.g., S04" , P 0 4" ', F ', and Cl', are added. d 3-94, have been prepared and their chemical and Solutions 2— 3N with respect to H 2S 0 4 are best (cf. crystallographic properties determined. M. S. B. this vol., 44) but the end-point is always unstable, Complex chemical behaviour of o-amino- possibly owing to the change 2M n'"— M n "-j-M n "". phenol.— See this vol., 465. P04"' is almost completely pptd. as the M n " salts of complex Jin17 phosphoric acids by digesting with Complex salts of a-phenylethylamine. conc. HN03 and Mn or M n ". J. G. A. G. Equivalence of the four co-valencies of bivalent platinum and palladium.— See this vol., 462. Induced oxidation of potassium iodide by ozone. (Mme.) G. G u e r o n , J. G uAr o n , and M. Duration of analyses. R au ch (Document, sci., Pkettre (Compt. rend., 1935, 201, 1376— 1378; 1935, 4, 4 —10; Chem. Zentr., 1935, i, 3818).— The cf. A., 1935, 945).— The heterogeneous oxidation of time taken for completion of various routine analyses KI by 0 3 in aq. solution is not an induced oxidation. has been determined. J. S. A. With greatly diluted 0 3 an induced oxidation accom Quantitative spectrum analysis. I, II. W. panies, to a slight extent, the normal reaction 0 3+ van T ongeren (Chem. Weekblad, 1936, 33, 130— 2r+H20 = 0 2+ I 2+ 2 0 H '. T. G. P. 141, 151— 159).— A historical review, with full Iron of high purity. P. A dcock and C. A. experimental details of published methods. D. R. D. Bristow (Proc. Roy. Soc., 1935, A , 153, 172— 200).— Chromatographic analysis and its applic Fe has been prepared (1) by the electrolysis of a ations. H. W illstaedt (Svensk Kem. Tidskr., solution of PeCl2 and NaCl, using an “ Armco ” 1936, 48, 32— 48).— A lecture. Fe anode, and (2) by the decomp, of PeCl2 by steam, Adsorption analysis of aqueous solutions. in each case followed by treatment of the molten W . K oschara (Z. physiol. Chem., 1936, 239, 89— 96). metal with a stream of pure H 2 and subsequent — The differences involved in the application of melting in vac. The work was controlled by chemical adsorption analyses in aq. and org. media are dis and X-ray analysis. Measurable differences existed cussed. The use of natural or acid-treated fuller’s in the physical properties of different batches. The earth, Brockmann’s A120 3, and A120 3,H20 and the «-7 transformation in some of the samples, indicated dependence of efficiency on the p n of the solution by dilatometric observations, does not take place are considered. H . W . at a const, temp, but over a definite temp, range. L. L. B. Influence of temperature on p„ measurements Polished iron, even impure, does not oxidise in alkaline media. P. Szigeti (Nature, 1936, 137, in saturated moist air. P. R on cekay (Bull, 276).— Alkaline pu vals. are valueless unless temp, is hoc. chim., 1936, [v], 3, 320— 321).— A reply to also recorded. L. S. T. criticism (cf. this vol., 174). E. S. H. Analysis with fluorescent indicators. M. Dekt- Active oxides. XC III. Intermediate active BERf: (Ann. Chim. Analyt., 1936, [iii], 18, 37— 39).— states in the decomposition of needle iron ore Acid-alkali titrations are performed in ultra-violet mto i-iron oxide and water vapour. G. E. H uttio light, using the change of fluorescence colour at some ®n without the need of separating the water for each Fe(CN)G"" in the aq., layer. These findings are applied determination. 0 . J. W . to the detection of the individual anions when present together. R. T. Colour reactions of the chlorate ion. A. SA (An. Farm. Bioquim., 1934, 5 , 111— 114; Chem. Gravimetric determination of selenates. P. Zentr., 1935, i, 3573).— The same colours are given S p a c e (Bull. Soc. chim., 1936, [v], 3, 159).—The by C103', N 0 2', and N 0 3' with NHPh-C10H 7-a and slightly acid Se04'' solution is treated with aq. with NH (ClnH7-a)2. Different colours (described) are Pb(0Ac)2 and the mixture boiled. The ppt. is given with NHPh"C10H7-p, NH(C10H 7-j3)2, and phenyl- collected, dried in vac., and weighed as PbSeO,. dihydrodibenzacridine. H . N . R. E. S. H. Colorimetric determination of nitrates in Determination of iodine in iodised salt.— See B., water : influence of chlorides.— See B., 1936, 254. 1936, 232. Differentiation of constituents of nitrous Determination of oxygen dissolved in 1 c.c. of vapours by formation of nitrogen compounds. water.— See B., 1936, 254. A. S a n f o t t r c h e and J. B u r e a u (Compt. rend., 1936, Polarographic studies with the dropping 2 0 2 , 66— 69).— Tests are described in which various mercury cathode. LVII. Determination of mixtures of NO and N 0 2 were analysed (a) by oxygen in gases and solutions. V. V îte k (Coll. absorption in H 2S0 4 (d 1-833), and (b) by absorption Czech. Chem. Comm., 1935, 7 , 537— 547).— The in a solution of N H 2Ph,HCl. The latter method gave electroreduction of 0 2 causes two “ waves ” in the more trustworthy analytical results. H. J. B. current-voltage curve corresponding with reduction Determination of nitrate- and nitrite-nitrogen first to H 20 2 and then to H 20 , and the magnitude of with copper-zinc powder. T. A r n d and H. Sege- the saturation current of the total reduction of b e r g (Angew. Chem., 1936, 49, 166— 167).—The 0 2 oc [0 2] and permits [0 2] as low as 0-04 mg. per vals. formerly obtained (B., 1932, 201; 1933, 118) litre to be determined in a fraction of 1 c.c. 0-05—• were due mainly to the method of prep, of the Cu-Zn 100% of 0 2 in gaseous mixtures is determined within powder. Directions are given for this prep, and the ± 2 % of the total [0 2] by bubbling through MeOH method is recommended for fertilisers etc. and determining the solubility of the 0 2 polaro- D. C. J- graphically. J. G. A. G. Potentiometric titration of phosphates. E. Determination of sulphur in silicates. A. F. M ic h a l s k i (Rocz. Chem., 1935, 1 5 , 468— 480).— F io l e t o v a (J. Appl. Chem. Russ., 1935, 8 , 1461— Excess of standard A g N 03 is added to the alkaline 1464).— Total S is best determined as S 0 4" after solution, 0-liY-NaOH is added to neutrality (orang fusion with Na2C03-K N 0 3. S 0 4" is determined by coloration with phenol-red), a drop of N-AcOH is extraction for 1 hr. with boiling 10% HC1 in an inert added, and Ag is determined in the filtrate; the atm. ; atm. 0 2 leads to high vais., owing to oxidation results are 0-2% > the theoretical, owing to adsorp of sulphide 8 to S 0 4''. No satisfactory direct tion of Ag' by the ppt. of A g ,P 04. Ca, Sr, Ba, and method of determination of sulphide S was found. Mg do not interfere, but Cl, Br, I, N II4, Al, and Fe R, T. should be absent. R- T. Indirect colorimetric semi-micro-determin Sensitive reaction for phosphate. A. Steig- ation of the sulphate anion. F. A. G o in (An. m a n n (Chem.-Ztg., 1936, 6 0 , 129).— The sensitivity Farm. Bioquim., 1934, 5, 61— 68; Chem. Zentr., of the phosphomolybdate reaction is enhanced by 1935, i, 3573).— The colour reaction betweon benz adding a glycerol-gelatin solution, which is boiled idine and A c 0 H -N a N 0 2 in EtOII is applied to the until the protein no longer gives turbidity with determination of S 0 4" in urine. H . N . R. (NH4)2M o0 4. j . S. A. Determination of sulphate. Conditions neces Fluorine and ammonia as sources of error in sary for the precipitation of benzidine sulphate, determination of phosphate by the [hydroxy-j with special reference to the determination of apatite method. A. T. J e n s e n (K. Vcterin. Landsb. sulphates in urine. E. C. Owen (Biochem. J., 1936, Aarskr., 1935, 41— 50; Chem. Zentr., 1935, ii, 255).— 3 0 , 352— 360).— The pptn. of S 0 4" by benzidine (I) Modifications of Damsgaard and Sorensen’s method is optimal atpjj 2— 3 ; H P 0 4" is pptd. by (I) at p u > 2 aro described, eliminating errors due to the presence and may be removed before the S 0 4" determination of F'orNH3 (cf. A „ 1935, 718). J. S. A. by the method of Fiske (A., 1921, ii, 556). The [Cl'] Separate determination of arsine and phos- in the urine is not sufficient to produce appreciable phine in air. V. G. G urevltsch and B. A. R asch - errors. H . D. k o v a n (J. Gen. Chem. Russ., 1935, 5 , 1317— 1323).— Application of the systems water-ethyl alcohol- 1 c.c. of 12% KBr is added to the solution, containing potassium carbonate and -ammonium sulphate 0-2 mg. of H 3P0 4 and H3As04, the mixture is evapor to the rapid detection of certain anions. A. G. ated to dryness, 5 e.e. of 1— 7AT-HC1 are added, ant K o b e ja n s k i (J. Appl. Chem. Russ., 1935, 8 , 1494— the solution is again evaporated to dryness (twice), 1497).— In the two-phase liquid system E tO H - the residue is dissolved in H 20 , and H 3P04 is deter saturated aq. K 2C03, the anions S 0 4" , Cl', Fe(CN)6" " , mined colorimetrically. H 3As04 is determined in and Fe(CN)0" ' aro present chiefly in the aq., and I', presence of H 3P0 4 by reducing with nascent H t0 CNS', and S " in the EtOH, layer, whilst in E tO H - AsH3 (0-001— 0-05 mg.), absorbing the gaseous pro saturated aq. (NH4)2S04 I', Br', Cl', CNS', Fe(CN)6" ' ducts in conc. H N 0 3, evaporating the H N 0 3 to dry and Fe(CN)5NO ” are found chiefly in the EtOH, and ness, and determining H3As04 in the residue by the X g e n e r a l , p h y s i c a l , a n d i n o r g a n i c c h e m i s t r y . 443 ordinary colorimetric procedure. AsH3 and PH3 in Dithizone method for determination of lead. air are determined by absorption in cone. H N 0 3, P. A. C l i f f o r d and H. J. W i c h m a n n (.J. Assoc. evaporation, and analysis of the residue by the above Off. Agric. Chem., 1936, 19, 130— 156).— The trans methods. R. T. mission spectra of solutions of dithizone (I) in CHC13 Risk of error in determining traces of arsenic and CC14 show strong absorption at 600 nipt, and a in organic and inorganic materials. W . A . Davis weak band at 450 in a. The quant, relation between and J. G. Maltby (Analyst, 1936, 61, 96— 100).— Pb and (I) at p a vals. between 5 and 12, and the prin Before applying the Marsh or Gutzeit test AsO,,'" ciples and inherent errors of the different methods must be reduced to A s 0 3"', preferably by warming of extraction and colorimetric determination, are with aq. H2S03 or N aH S03, excess of which must be discussed. Procedures, based on the “ mixed-colour ” removed. During the actual test the Gutzeit flask method (cf. B., 1934, 379) with the use of a photo should be heated at 40— 60°. E. C. S. meter, are outlined for the determination of Pb in urine and bone etc. E. C. S. Colorimetric determination of sm all quantities of silica in solutions, minerals, and technical Volumetric determination of lead and of molyb- products. I. P. A limarin and V. S. Zverev (Trans. dates with adsorption indicators. C. C a n d e a Inst. Econ. Min. U.S.S.R., 1934, No. 63, 15 pp.).— and I. G. M urgulescu (Ann. Chim. Analyt., 1936, A crit. survey. Dienert and Wandenbulcke’s method, [iii], 18, 33— 36).— Pb, present as Pb(OAc)2 or based on the formation of H 8[Si(Mo20 7)6], is best for Pb(N03)2, is titrated against M o04" using eosin A 0005—5% Si02. In presence of large amounts of as adsorption indicator. J. S. A. mineral acids and their hydrolysable salts, NaOAc Gravimetric determination of lead as lead should be added. The effects of P and Fe are counter chromate. L. G u z e l j (Z. anal. Chem., 1936, 104, acted by adding excess of H 3P 0 4. The phospho- 107— 119).— The accuracy of the method is not molybdate colour can also be removed with tartaric affected by the presence of AcOH, NILOAc, KC1, or citric acid. The effect of F' is avoided by adding KBr, (NH4)2S0 4, or N H ,N 0 3, but [H N 03] should be AlClj, which forms H 3ALF6 from H 2SiFG. > 0-liV. Addition of N H , after pptn. may lead to Ch . A bs. (e) the formation of basic Pb chromate, which is hindered Rapid gravimetric determination of silicic by N H 4OAc or (NH4)2Cr04. [Pb] should be as low acid.-See B., 1936,190.- as is practicable. J. S. A. Quantitative spectrography of alkali metals. Determination of lead and antimony in pure P. Urbain and M. W ada (Bull. Soc. cliim., 1936, metals and their alloys. H. Vdoviszevski (Z. I'-], 3, 163— 169).— An electric arc between Cu elec anal. Chem., 1936, 104, 94— 107).— The determin trodes is used. To reduce the rate of vaporisation ation of Pb as PbS04 by Treadwell’s method, and of °f the alkali-metal compound, it is mixed with a Sb as Sb2S3 by Vortmann and Metzl’s method, is refractory substance. Determination is by com critically reviewed, and modifications of procedure parison of line intensities. E. S. H. are advocated. The determination of Pb as PbCrO., Determination of sodium chloride in salt.— See is rapid, but leads to slightly high results. J. S. A. 1936, 232. Gravimetric determination of certain metals Reaction for calcium. S. A. Celsi (An. [with thiolbenzthiazole]. III. Determination , ™n- Bioquim., 1934, 5, 85— 89; Chem. Zentr., of lead, thallium, bismuth, and gold. G. S p a c u n/MTT** B573).— A mixture of K 4Fe(CN)G and and M. K uraś (Z. anal. Chem., 1936,104, 88— 93).— bu(NH3)4S04,H20 g*ves with Ca” a sky-blue ppt. Pb is pptd. quantitatively by thiolbenzthiazole H . N. R. (I) from hot ammoniaeal solutions as the basic salt, . "PPRcation of copper ferrocyanide ammoniate C7H4NS2PbOH (II), which is dried at 110° and weighed “ testing for calcium. J. V. DubskX and A. as such. ” Any normal salt, (C-H4NS2)2Pb, is converted UifOEB (Coll. Czech. Chem. Comm., 1936, 8, 47— into (II) on' boiling in presence of NII3. Tl, Bi, p '■ By the action of K 4Fe(CN)6 on solutions of and Au are similarly pptd. by (I). C7H4NS2T1 is r r v . in i xpresence ------of N H 3, \ (-CH2-NH2)2 z / z v(on), / 1 unctidried au at jl.lv110°; , (C7H4NS2)3Bi and (C7H4NS2)3Au are the fnllnurirxrr following oavvicompounds m/a-j/'Vl /7 o haveli ft VO been jgnited to Bi20 3 and Au, respectively. J. S. A. 'f e îr a - x m Cu2Ca(NH4)2[Fe(CN)G]2,8NH3,6H20 ; Drop method for detection of cerium. L. m i ( .iv1?[Fc(CN)cl2JGII2° ; CuCa[Fe(CN)G],2, 5, K u l b e r g (J. Appl. Chem. Russ., 1935, 8, 1452— S I r ! ^>2H20 ; CuCa[Fe(CN)G],6NH3,3H20 ; 1456).— Ag and Tl1 are removed from 0-2 ml. of solu Î Î r ^ 4 “ ?’6H20 i CuCa[Fe(CN)6],en2,2H20 ; tu2Fe(CN)fi])4c 5H6N!GH20 ; tion by pptn. as chlorides, 2— 3 drops of saturated C3Ca[Fe(CN)G]2,8C5H5N,30H2O. Speculative co- aq. K 4Fe(CN)G, 0-5 ml. of 10% KCN, and 3— 4 ination formulæ are advanced. J. S. A. drops of lY-NaOH arc added (to ppt. or neutralise the interfering effects of Mnn, Co11, or Thm ), and an Potentiometric determination of calcium con AcOH solution of leuco-malachite-green is added, centrations in solutions. H. J. C. T b n d e l o o (J. when a green coloration is obtained in presence of «01. Chem., 1936, 113, 333— 339).— A method, -C 3x10-® g. of Ce™. R- T. JX a CaF2 electrode, is described. Absorption 1 y proteins decreases with increasing acidity. Potentiometric determination of cerous salts n . . H . G. R. with ferrocyanide. P. S p a c u (Z. anal. Chem., 1936, ■nn«tifirmiIlat'^on radium in carnotite and 104, 119— 122).— Ce111 is titrated potentiometrically pitchblende.— See B., 1936, 232. against K 4Fe(CN)G in 30% aq. EtOH solution. 444 BKITISH CHEMICAL ABSTRACTS. A. X The Ce must be added to the K 4Fe(CN)6 to avoid volumetrically with KCN in aq. N H 3 solution. The adsorption errors. J. S. A. precision is 0-05— 0-2 mg. of Ni. E. S. H. Colorimetric determination of aluminium in Oxidimetric determination of the oximes of waters.— See B., 1936, 222. nickel and copper. J. M i r o n o e e (Bull. Soc. chirn. Colorimetric determination of iron. L. U r - Belg., 1936, 4 5 , 1— S).— The volumetric method b a n y i (Mezog. kutat., 1935, 8, 279— 287).— The described by Tougarinoff (A., 1935, 187) gives quant, thiocyanic and sulphosalicylic acid reactions give results when small amounts of Cu and Ni are pptd. inaccurate results. Comparison of the colours in the ■with phenylglyoximc (I), diacetylmonoximo (II), case of the Prussian-blue reaction is much easier. diphenylglyoxime (III), or benzoinoximo (IV). The Best results were obtained when the acidity of the same procedure as with dimethylglyoxime can be medium corresponded to 0TAr-HCl and the solution used for (I) and (II), but with (III) hydrolysis must contained about 0-1— TO mg. of Fe per 10 ml. be performed carefully on account of frothing. N u t r . A b s . (m i) With (IV) the benzoin formed must be removed, or Determination of ferric oxide. A. F. F i o l e - high results are obtained. J. W. S. t o v a and S. C h a ik in a (J. Appl. Chem. Russ., 1935, Oxidation-reduction indicators. I. New in 8, 1467— 1469).— Someya’s Zn amalgam method is dicators for the bromate titration of tin and simpler and not less accurate than are the TiCl3 antimony. Z. Raichinschtein (J. Appl. Chem. reduction, the iodometric, and the colorimetric Russ., 1935, 8, 1470— 1475).— SnCl2 is titrated in methods. R. T. T15V-HC1 at 30— 50° with 0-lW -N aBr03, in presence Determination of iron and manganese in of 0-1% benzopurpurin B. SbCl3 is titrated in 31— water.— See B., 1936, 254. 3-5V-HC1 using benzopurpurin 4B as indicator. It. T. Determination of cobalt by electrolysis at Precipitation of thorium by sebacic acid. controlled potentials and using hydrazine hydrate L. E. K a u f m a n (J. Appl. Chem. Russ., 1935, 8,1520— and chloride as depolarisers. A. Jilek and J. 1524).— 3— 10 ml. of 3 % sebacic acid (I) in EtOHarc VuESfAL (Coll. Czech. Chem. Comm., 1935, 7 , 512— added to 100 ml. of the boiling neutral solution, 520).— The conditions for the quant, electrodcposition containing Th and Ce, the ppt. is collected, washed, of Co have been investigated. < 100 mg. of Co are dried at 100°, and warmed at 100° with fuming HN03 determined to within ¿ 0 -2 mg. as a coherent, com to disappearance of N 0 2, when the solution is evapor pletely acid-sol. deposit by electrolysing at 4 volts and ated to dryness, and dissolved in 100 ml. of H20. about 0-5 amp. with a rotating anode a solution of Th is then repptd. with (I), and the washed ppt. ii CoS04 containing 0-5 g. of N 2H4,HC1, 2 c.c. of conc. calcined and weighed as ThO.>. R. T. N2H4,H20 (I), and 45 c.c. of conc. aq. N H 3, diluted to 100 c.c. After 1 hr., 1 c.c. of (I) is added and tho Determination of oxides of vanadium in ores.— electrolysis continued for 2 hr. Small quantities See B., 1936, 191. of Cl' havo no effect, but tho results are somewhat Chemical differentiation of polished metallic low with 1 g. of K 2S0 4, and with 1 g. of N H 4N 0 3. minerals by the contact method. Ill, IV. R. Ni and Co-Ni mixtures can be determined under G a l o p i n (Arch. Sci. phys. nat., 1935, [v], 17, Suppl., identical conditions. J. G. A. G. 252— 257, 257— 261; cf. A., 1935, 463).— Details arc Volumetric determination of cobalticyanide given for the detection of the minerals Sb2S3, Bi2S3, ion. R. U z e l and B. J e z e k (Coll. Czech. Chem. FeS,Sb»S3, 3PbS,Sb2S3, 2PbS,Cu2S,Sb2S3, NiS, NiSb, Comm., 1935, 7, 497— 511).— Electrometric titration NiAs, CuFeS3, Fe»Sa+1, and (NiFe)S. R. S. of K 3Co(CN)f., with A g N 03 always gives results < Drop method of detection of bismuth. N. A. stoicheiometric owing to adsorption of Co(CN)6'" T a n a n a e v and A. V. T a n a n a e v a (J. Appl. Chem. on colloidal Ag3Co(CN)6. Analogous results are Russ., 1935, 8, 1457— 1460).— SnCl, is added to the obtained when Ag‘ is replaced by Hg\ H g ", and Cu". solution, when a brown coloration is given by < 2X With Cu", the end-point becomes more vague as the 10~® g. of Bi (Hg interferes). Alternatively, Ag and at. wt. of the added univalent ion increases, but Pb are pptd. by saturated aq. NaCl-Na2S04 and hi- and tor-valont ions do not interfere. K 2Cr04 SnCl2 and K I are added to the solution, when a yellow indicates the stoicheiometric end-point of the titration to orange ppt. is obtained in presence of < 10'5 g- of Co(CN),;" ' with A gN 03 even in the presence of of Bi. A third method consists in conversion into Z n " and M n " after boiling off excess of HCN in acid the chloride, followed by dilution, when BiOCl is solution and neutralising. Ni, Fe, and other metals pptd. (-£ 5 x l ( H g. of Bi). The limitations of the are eliminated earlier. Co(CN)6'" is formed from methods and their applications to special cases are Co" by way of the intermediate brownish-red anion discussed. R. T. [CoUI(CN)56 H ] '". J. G. A. G. Spectroscopic determination of adsorbed ions. Volumetric determination of nickel in presence (Miss) M. A n n e t t s and L. N e w m a n (J. Physical of cobalt. G. C h a k l o t (Bull. Soc. ehim., 1936, [v], Chem., 1936, 4 0 , 187— 193).— The spectroscopic 3, 324— 326).— The Ni and Co compounds are con method for the determination of very small concns. verted into K 4Ni(CN)6 and K 3Co(CN)6, respectively, of metal ions has been applied to the study of the by tho usual methods. By adding alkali, which ppts. action of NaOH and NaMn04 as stabilising agents, hfi20 3, and then aq. HC1 and H2C,0 4, the Ni complex and of AlClj as a coagulating agent, for Au sols, and is destroyed and Ni012 obtained in solution, the Co also of MgCr04 as a coagulating agent for Au and Cu complex being unchanged. Ni is then determined sols. The limits of sensitivity are M /l 00,000 for GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 445 Au and Mn, M/50,000 for Mg, Cr, and Na, and Abnormalities in characteristic of vacuum J//1000 for Al. M. S. B. photo-cells. H. G e f f c k e n (Z. tech. Physik, 1934, Volumetric determination of palladium by 15, 595— 598; Chem. Zentr., 1935, i, 2950— 2951).— means of oximes. M. G a iiid e (Bull. Soc. chim. Vac. photo-cells in which the work of exit from the Bclg., 1936, 45, 9— 14; cf. this vol., 444).— Oximes photosensitive layer is artificially lowered by suitable of Pd cannot be hydrolysed and titrated directly like chemical treatment of that layer show irregular those of Cu and Ni. By pptn. with excess of standard behaviour, the saturation current jumping reversibly salic3rlaldoxime in acid solution, filtering, and titrating from a lower to a higher val. The effect is not due to the excess of oxime, 5— 40 mg. Pd can be determined wall charges, but is attributed to changes in the in presence of other metals. J. W . S. cathodic space charge. Better compensation of space charges, and high sensitivity, may be attained Use of overhead heating in analysis. F. by admission of traces of gas. J. S. A. Heinrich and F. P e tz o ld (Chem.-Ztg., 1936, 60, 145—147).— Heating from above by electrical heating Electrophotometer of barrier-layer [photo-] elements is recommended for rapid, quiet evaporation cells intended for practical opacimetry. P. of liquids, drying of ppts., etc. R. S. C. M e g n ie r (Compt. rend., 1935, 201, 1371— 1373). Apparatus for measurement of thermal con T. G. P. Photometric determination of m.p. P. W o o g , ductivity of metal foil. A. E u c k e n and H . W ar- J. G iv a u d o n , R. S ig w a lt , and J. L ie n h a r t (Bull. KEXTiiur (Z. tech. Physik, 1935, 16, 99— 105; Chem. Soc. chim., 1936, [v], 3, 439— 442).— The fusion of the Zentr., 1935, ii, 191).— A centrally heated disc is used. substance produces a “ grease spot ” on a paper Measurements on Cu and A1 agree with previous data. screen, which is observed under unequal illumination J. S. A. from opposite sides, as in the Bunsen photometer. Thermoregulator. R. D . S t i e h l e r (Science, E. S. H. 1936, 83, 40).— Increased precision is obtained by Shielded-filament X-ray tube for pure X-ray placing metal foil in the bulb of an ordinary PhMe spectra. E. D e rs h k m (Rev. Sci. Instr., 1936, [ii], regulator. L. S. T. 7, 86— 89).— The target is shielded from visible light Quantitative spectral analysis under variable and from spattered W from the filament. Fogging of discharge conditions. V. N a e d l e r (Compt. rend. plates by visible light is practically eliminated, the Acad. Sei. U.R.S.S., 1935, 4, 23— 26).— A discussion intensity of characteristic radiation remains const., the of errors in the use of a spark for excitation. tubo current is nearly const., and the life of the H. J. E. filament is increased. C. W . G. Mercury-vapour lamp with very intense reson ance radiation. G. K o r n f e l d and F. M ü l l e r - Apparatus for X-ray patterns of the high- Skjold (Z. physikal. Chem., 1936, B, 31, 223— 226).— pressure modifications of ice. R. L. M c E a r la n A lamp is described which has an incandescent (Rev. Sci. Instr., 1936, [ii], 7, 82— 85).— Very rapid cathode of Konel metal and gives for 2537 Ä. twelve insertion and centring of the crystal, its rotation, and tunes the intensity of the ordinary Hg-vapour lamp. the evacuation of the diffraction chamber are possible. R. C. C. W . G. Counter measurements and Röntgen unit. Influence of dispersion on the reading of the Haber-Lowe gas interferometer. E. K a r w a t (Z. ff Wilhelm (Z. tech. Physik, 1935, 16, 2— 8 ; Chem. ¿cntr., 1935, i, 3012— 3013).— No general relationship Instrument., 1933, 5 3 ,12— 21, 70— 78; Chem. Zentr., between counter results and X-ray dose can be derived, 1935, i, 3957). H . J. E. hut between limits of X, and for homogeneous radia Simple comparator for absorption spectro tion, a fairly const, factor may be found. Tho use grams. E. R o s e b u r y (Science, 1936, 83, 86). of counters for measurement of very weak X-ray L. S. T. doses is described. J. S. A. p a measurements, dark-coloured substances, ri ^oto-electric analysis with fluctuating light. and indicator methods. F. A n s e lm (Chem. Fabr., !• " t a ® . and W . D ü r ic h e n (Chem. Fabr., 1935, 1935, 8, 269— 271).— The application of very thin -tu—269).— The insertion of a rotating perforated colorimeter cells (up to 0-65 mm. thick) is described. disc between the light source and the photo-electric J. S. A. Production of high-velocity lithium ions. h !?VeS r’Se a fluctuating photo-electric current Wuch may be amplified by means of thermionic R. L. T h o r n to n and B. B. K in s e y (Physical Rev., 'a!ve circuits. The light intensity may be then re- 1934, [ii], 46, 324)— The arrangement described need to give the max. sensitivity. Two barrier- yields a current of 1-5 micro-amp. at 5 x 105 volts. ayer cells may be used to provide a highly sensitive L. S. T. differential arrangement. J. S. A. Superconducting galvanometer. H. G. S m ith and F. G. A. T a r r (Trans. Roy. Soc. Canada, 1935, Significance of ions in gas-filled photo-cells. [iii], 29, H I, 23— 35).— A moving-coil galvanometer, R ic h t e r (Z. tech. Physik, 1934, 15, 598— 601; the coil of which is immersed in a liquid He cryostat, is „ lem' , , ntr-> 1935, i, 2951).— The relative import- described. H . J. E. nfCfl ionisation by collision, and of the formation bn eiectrons Ay bombardment of tho cathode, Weston normal cell as standard for the inter of S*b investigated. By delaying the inception national volt. A. K . K o l o s o v (Vses. Nauch.- p )i e siable glow discharge, the performance of the Issled. Inst. Metrol., 1932, No. 100, 131— 137; ef.. cell may be improved. J. S. A. A ., 1934, 625).— To avoid mixing of the components h h 446 BRITISH CHEMICAL ABSTRACTS.— A. XI during transport, the cathode limb has a constriction Determ ination of P oisson’s elastic constants to hold the Hg in place. The saturated CdS04 con by means of ultrasonic waves. R. B a r and A. tains approx. 0-004.Ar-H ,S 0 4. In washing the Hg2S0 4 W a l t i (Helv. phys. Acta, 1934, 7, 658— 661; Chem. with saturated aq. CdS04 washing must cease when Zentr., 1935, i, 3759).— The method is applied to the the concn. of acid in the washings is 0-004IV. High determination of the elastic moduli of glass. acid concns. lead to gas formation in the anode limb. J. S. A. Ch . A b s . (e) Air-damped balances. W. N . B o n d (Analyst, Resolving power in recording of coincidence by 1936, 61, 85— 90).— The theoretical and practical two counters arranged behind one another. J. N. advantages of critically air-damped over oscillating H um m el (Z. tech. Physik, 1934, 1 5 , 573— 575; balances are discussed. E. C. S. Physikal. Z., 1934, 3 5 , 997— 999; Chem. Zentr., 1935, Constant-level siphon. R. L a u t ié (Bull. Soc. i, 2942).— Data concerning resolving power are given. chim., 1936, [v], 3, 503— 504). E. S. II. J. S. A. Sensitive counter tube arrangement. E. B. Level control in funnels. W. R. T hompson A n d er sen (Z. Physik, 1936, 98 597— 604).— A (Science, 1936, 83, 168). L. S. T. counter for weak radioactive measurements is sur Apparatus for catalytic hydrogenation at rounded by other tubes, and the amplifier registers high pressure. L. P a l f r a y (Bull. Soc. chim., 1936, those impulses present only in this tube. [v], 3, 508— 511).— The apparatus consists of an A. B. D. C. autoclave and H 2 compressor, with automatic re Determination of the end-point of conducto- cording of temp, and pressure. It is suitable for metric titrations by calculation. J. H. Boulad the range 0— 300 kg. and 0— 300°. E. S. H. (Bull. Soc. chim., 1936, [v], 3, 408—412).— Mathe matical procedure, replacing the graphical method, is Determination of density of grains. W. F. described. E. S. H . d e J o n g (Zentr. Min., 1935, A , 140— 142; Chem. Easily constructed electrical relay. G. F. Zentr., 1935, ii, 252).— A flotation method, applicable K o e p f and J. F. M ezen (Science, 1936, 83, 109— to particles weighing about 1 mg., is described. 110). L. S. T. J. S. A. Improvised micro-manipulator. P. H. Sim ons Iron-free coil for production of maintained (J. S. African Chem. Inst., 1936, 19, 24— 25).—The intense magnetic fields. G. Gerloee and E. L ow e adjustments of a microscope sub-stage condenser (Z. Physik, 1936, 9 8 , 559— 560).— The apparatus may be used to manipulate needles, capillaries, gives homogeneous fields up to 5000 oersted. etc. in the field of the microscope. J. S. A. A. B. D. C. Pipette for measurement of aqueous solutions. Determination of contact angles from meas Y . P. Liu (J. Chinese Chem. Soc., 1936, 4, 20— 21).—, urements of the dimensions of small bubbles The pipette is provided with a two-way stopcock above and drops. I. Spheroidal segment method for the bulb. R. S. B. acute angles. G. L. M a c k . II. Sessile drop method for obtuse angles. G. L. M a c k and (Miss) Micro-burette. W . Spatz (Chem. Fabr., 1936, 9, 70).— A capillary connecting tube avoids the form D. A. L ee (J. Physical Chem., 1936, 4 0 , 159-167, ation of air bubbles between the burette and the 169— 176).— I. Acute angles of contact may bo de reservoir. J. S. A. termined as a function of the radius and vol. of a small spherical drop of liquid by a method which is practic Apparatus for determination of gases. M. L. ally independent of the solid surface concerned. Jean (Bull. Soc. chim., 1936, [v], 3 , 267— 269).— An expression for the effect of gravity on the form of The apparatus formerly described (A., 1935, 466) is the drop is given. modified. E. S. H. II. Average obtuse contact angles may be deter Accessories for gas analysis. W . A l l n e r mined from measurements o f ' the vertical height, (Chem. Fabr., 1936, 9, 70— 72).— A device for collect the horizontal radius, and the radius of curvature ing gases at const, variable pressure, and a modified at the apex of sessile drops or bubbles under a plate- Jaeger CuO tube for the fractional combustion of H 2 The third dimension required may be calc, fro m the and hydrocarbons, are described. J. S. A. capillary const, of the liquid by a simplified equation. Constant-volume gas analysis apparatus. B. N. Sin g h and P. B. Mat h u r (Biochem. J., 1936, Apparatus for maintaining circulation of gases 3 0 , 321— 322).— The apparatus is used for determin in laboratory apparatus. V. I. K u z n e t z o v (J- ation of O, and C 02 with an accuracy of ± 0 -1 % . Appl. Chem. Russ., 1935, 8, 1516— 1517).— A simple W . McC. laboratory pump is described. R- T- Multiple-unit distilling apparatus for deter Safety tube for preventing bumping of liquids mination of fluorine by Willard and Winter’s supersaturated with gas. V. I. K u z n e t z o v (J- method. D. S. R e y n o ld s , I. B. K ershaw 7, and Appl. Chem. Russ., 1935, 8, 1514— 1515).— A U-tube, K . D. Jacob (J. Assoc. Off. Agric. Chem., 1936, 19, containing 1— 2 drops of Hg, with one broad and one 156— 162; cf. A., 1933, 242, 654). E. C. S. narrow-7 limb, is fused to the lower part of the condenser Preparation of glass helices for use in fraction tube of a Kjeldahl set. The tube, by allowing gas^ ating columns. W . G. Y o u n g and Z. Jasaitis (J. to enter, but not to leave, the apparatus, perm it» Amer. Chem. Soc., 1936, 58, 377).— Technique is instant equalisation of pressure, thereby eliminating recommended. E. S. H. bumping. R- XI, XIII GEOCHEMISTRY. 447 Research applications of colloidal graphite. Determination of viscosity by the oscillation B. H. Porter (Rev. Sci. Instr., 1936, [ii], 7, 101— of a vessel enclosing a fluid. I. E. N. d a C. 106).—Applications to vac. technique, electronic A n d r a U e and Y . S. C h io n g . II. E. N. d a C. devices, electrical contacts, and other purposes are A n d r a d e and L. R o t h e r h a m (Proc. Physical Soc., described. C. W . G. 1936, 48, 247— 260, 261— 266).— I. An improved Determination of vapour pressure. V. A. technique and method of calculation are described. Accurate results are obtained for H 20 over the temp, Kireev and A. A. P o p o v (J. Gen. Chem. Russ., range 2-5— 65-2°. 1935, 5, 1399-—1401).— Apparatus is described, II. Instead of the energy of oscillation being whereby the v.p. of AcCl, CH2C1-C02H, and propylene oxide have been measured at different temp., arid dissipated by the viscous forces, energy is supplied empirical equations connecting temp, with v.p. have at every oscillation, by the discharge of a condenser, hence been derived. R. T. to maintain a fixed amplitude; i) is calc, from the amplitude and the energy supplied. The method is Glass apparatus for handling low-b.p. liquids. checked by measurements of -p for hexane in terms of S. F. B irch and P. D o c k s e y (Chem. and Ind., that of H 20. N. M. B. 1936, 169— 170).— The construction of a simple Arrangement for measuring the viscosity of apparatus which can he used also for the solvent gases. A. F o r t i e r (Compt. rend., 1935, 201, extraction of liquids is described. S. M. 1330— 1332).— A method which depends on deliver Mixing arrangement for large quantities in the ing a rigorously const, vol. of gas independent of laboratory. B. Flaschentrager and P. F a b er the pressure and of the capillary is outlined. (Chem. Fabr., 1935,8,272).— A rotary shaking machine T. G. P. is described. J. S. A. Measurement of absolute viscosity by the falling-sphere method. L. R. B a c o n (J. Franklin Determination of surface tension by the drop- Inst., 1936, 221, 251— 273).— The vais, given by weight method. K . C. B a ile y (Nature, 1936, 137, Stokes’ formula are shown to depend on the ratio 323). L. S. T. diameter of sphere /diameter of tube. Various cor rection formulae have been tested, but only that due Ripple method of measuring surface tension. to Faxen yields vais, in agreement with capillary- lb C. Brown (Proc. Physical Soc., 1936, 48, 312— tube determinations over the range 10— 10,000 poises. 322).—-An apparatus for the production, stroboscopic R. S. observation, and measurement of ripples for surface- Apparatus for automatically maintaining re tension determinations is described. Results for duced pressure. C. F. W inchester (Science, 1936, the fall of surface tension of a slowly adsorbed aq. 83, 64). L. S. T. solution of. cetylpyridinium bromide are similar to those obtained by a static method, showing that the Instruments for registration of vapour pres nPples do not retard attainment of surface equilibrium. sure [of water] and specific humidity. F. W e n k (Z. Instrument., 1935, 54, 15— 19; Chem. Zentr., N. M. B. Measurement of surface tension by means of 1935, i, 3957).— Apparatus is described. J. S. A. stationary waves on a vertical jet. J. Satter ly Vacuum in laboratory and technique. H. ®U(1_ J- C. Strachan (Trans. Roy. Soc. Canada, B a e rm a n n (Chem. Fabr., 1935, 8, 395— 404).— A 1935, [hi], 29, III, 105— 112).— Measurements with comprehensive review covering modern types of KB and Hg are described, using a modification of vac. pumps, measuring instruments, vac. sealing latterly and McPherson’s method (ibid., 1934, 28, media, automatic regulators, and vac. evaporating C"). Sources of error are discussed. H . J. E. and distilling technique. A. R. P Geochemistry. Spectra of meteors. P. M. Mtt.t.m an (Ann. Ast. depths. The absence of dissolved 0 2 at 1 m. and Harvard Coll., 1932, 82, 113— 146).— 9 spectra below is due to reduction by F e " and Sin", which are a,re (pcussed • Fe, Ca, Mg, Mn, Al, Cr, and Si were present in high concn. The high conductivity is ldent‘fied. C h. A b s . (e) due to CaS04. J. W . S. Evolution of helium from the earth. E. K. Radioactive waters at Starobelsk. E. S. B u r k - wiling (Compt. rend. Acad. Sci. U.R.S.S., 1935, s e r (Compt. rend. Acad. Sci. U.R.S.S., 1935, 4, 45— ’ 4 43).— Analyses are recorded for the H e + N e 48).— Complete analytical data are given for samples content of air in contact with the earth in various from depths of 400— 750 m. The Ra content was nets. In none of the localities examined was the 0-80— 6 1 X 10~u % . Th and mesothorium were val,:high. H . J. E. absent. H . J. E. Akanuma, a siderotrophic lake at the j v°lcano Bandai, Hukusima Prefecture, Mineral and medicinal springs of Switzerland. ioik I X oshimura (Proc. Imp. Acad. Tokyo, A n o n . (Mitt. Lebensm. Hyg., 1935, 26, 250— 328).— Analyses of 62 springs are given and a system of Pel rrii’ 42G~ 428)— Thc temP - Pn, [OJ; [Mn], sam’ i a SP" ’conductivity are recorded for classification is evolved based on mineral constituents, 'P es of H20 from the surface and from various physical properties, and clinical effects. J. G. 44S BRITISH CHEMICAL ABSTRACTS.— A. XIII Characteristics of Pearl River water. W . W . alteration and replacement of the severely-fractured H uang (J. Chem. Eng. China, 1935, 2, 139— 147).— wall rocks by S i02 which accompanied the formation Seasonal variations in chemical composition of this of the veins is described in detail. Analyses showing H 20 are recorded in detail. C. I. the chemical changes during alteration and a diagram Corpus Christi structural basin postulated showing gains and losses of oxides are given. The genetic relations of tho veins are also discussed. from salinity data. W . A. P r i c e (Bull. Amcr. Assoc. Petrol. Geol., 1935, 19, 317— 355).— Consider L. S. T. Geologic problems of the Canadian Pre- ation of lines of isoalkalinity indicates that original Cambrian gold fields. E. Y . D o u g h e r t y (Econ. oceanic H 20 diluted with surface H 20 entered at the Geol., 1935, 30, 879— 889).— Problems relevant to the outcrop and penetrated slowly down the dip. science of ore deposits and to the practice of mining Ch . A b s . (p) Difference in the isotopic composition of the geology are discussed. L. S. T. oxygen in air and water. N . M o r it a and T . T it a n i Natural glasses of the insoluble residues of the (Bull. Chem. Soc. Japan, 1936, 11, 36— 38).— By Pennsylvanian limestones of Texas. L. T. Patton preparing H 20 from light II2 and from 0 2 obtained (Science, 1936, 83, 83— 84). L. S. T. (1) from the air, (2) by the partial electrolysis (5% ) of Origin of cyanite. S. T a b e r (Econ. Geol., 1935, ordinary H 20 , and (3) by the complete hydrolysis of 30, 923-924 ; cf. A., 1935, 954). L. S. T. H20 , and by comparing d for the three samples, it has been shown that air is richer in O18 than ordinary Synthetic emerald. E p p l e r (Deut. Gold- H 20 . The distribution coeflf. of 0 18 between air and schmiede-Ztg., 1935, 38, 144— 146;. Chem. Zentr., H 20 is approx. 1-04. M. S. B. 1935, i, 3969).— Optical data are given for distinguish ing natural from synthetic emeralds. J. S. A. Analyses of phosphorite from the culm form ation of the Swietykrzyz mountains. S. Bis- Relations of amphibolites and peridotites at k u bsk i (Bull. Acad. Polonaise, 1935, A, 85— 91).— Sarrazac (Dordogne). M. R o q u e s (Compt. rend., Analytical data are recorded and discussed. Tho 1936, 202, 332— 334).— Tho rocks are described and Ca3(P04)2 content increases and that of CaC03 their relationships are discussed. Analyses are given. decreases with the age. Tho CaF2 was almost const, H.J.E. in all tho phosphorites. H . J. E. Assimilation processes, formation of mig- matites, and their signification in the origin ol Origin of guano minerals in the Domican m agm as. F. K . Drescher-Kaden (Chem. Erde, Grotto, Slovakia. J. V. IyaS par (Vestn. Stat. Geol. 1936, 10, 271— 310).— Cases of rock variation arouaf 1 Bst. Ceskoslov. Repub., 1934, 10, 104— 111; Chem. granite and gabbro masses at various well-knom Zontr., 1935, i, 3527).— Analytical data are given. localities, which have hitherto been ascribed to H . J. E. differentiation of the magma, are now asserted to be Symmetrical extinction angles of albite- due to assimilation of the surrounding rocks into twinned plagioclases. S. T su bo i (Proc. Imp. which the magma was intruded, with the production Acad. Tokyo, 1935, 11, 423— 425).— Tho curve given of migmatites or mixed rocks. The bearing of this by Wright (Amer. J. Sci., 1913, 36, Plate X ) for the on the origin of magmas and on petrological theory max. symmetrical extinction angles of albitc-twinncd is discussed (cf. Reynolds, A., 1935, 1477). L. J. S. plagioclases is shown to bo incorrect and a revised curve is given. J. W . S. Copper-bearing spathic iron veins in the Bober-Katzbach Mtns., Silesia. A. N e u i u e s Relations of later gabbro to sulphides at the (Chem. Erde, 1936, 10, 247— 270; Fortschr. Min- Horne Mine, Noranda, Quebec. G. G. S uffer Krist. Petr., 1936, 20, 50— 55).— These v e i n s were (Econ. Geol., 1935, 30, 905— 915).— Sulphide ores at discovered in 1922 and have been worked for Fe and this mine are definitely later than all other formations Cu ores. The principal mineral is clialybite (con oxcept, possibly, the later gabbro dykes. All the taining 3 % Mn), and the Cu ore is mainly chalcopyrite chalcopyrite, and probably tho pyrrhotite and pyrite, with associated rarer Ni and Co minerals. A detailed arc now shown to be post-dyke. L. S. T. description is given and the origin of the veins dis Differentiation in traps and ore deposition. cussed. L. J- S. L a n e A. C. (Econ. Geol., 1935, 30, 924— 927; of. A ., Geochemistry of barium. W . vox Engelhabdt i 1935, 955).— A discussion. L. S. T. (Chem. Erde, 1936,10,187— 246).— Numerous igneous Mylonitic sphalerite from Friedensville, and sedimentary rocks, minerals, meteorites, and org. Pennsylvania. R. D. B u t l e r (Econ. Geol., 1935, plant remains were examined spectroscopically for 30, S90— 904). L. S. T. Ba. In igneous rocks Ba goes with K , ranging from Large quartz veins of Great Bear Lake, 0-2% BaO in syenite to 0-0003% in peridotite, with an average of 0-048% . In sedimentary rocks it Is Canada. G. M. F u r n i v a l (Econ. Geol., 1935, 30, 843— 859).— These have been formed by the deposition adsorbed by clay, clay-slates containing BaO 0'05%- and limestone 0-01% . The average for the whole of quartz (I) from hydrothermal solutions at moderate lithosphere is 0-045% . The deposition of baryte temp. Minerals other than (I) are sparse and represent last-stago depositions. They are specular Haematite, under various conditions is discussed. L. J- S- bornite, chalcopyrite, covellite, chalcocite, pyrite, Rocks from Cape Verde Islands. H. Ermebt famatinite, and siderite. Pitchblende has also been (Chem. Erde, 1936, 10, 155— 186).— A collection of found in a large vein on Hottah Lake. The extensive rocks from the islands of Sao Vincente and Sal is XIII GEOCHEMISTRY. 449 described, with chemical analyses of foyaite, dioritic two main spectral ranges, one in the red, and the essexite, trachyandesite, gabbroid essoxite-dolcrite, other in the blue and violet. The phosphorescence and augitite. These when tabulated and plotted with exhibited by some specimens of calcite was also earlier analyses show a similarity to the rocks of the investigated. A . J. M. Canary Islands, and the two form a rock province Origin of tektites. I. Tektites as fulgurites characterised by the predominance of NasO. Mineral [formed in the atmosphere]. T. V o g t (Kong. analyses are given of sands from the same islands. Norske Viden. Selsk. Forh., 1935, 8, 9— 12; Chem. L. J. S. Zentr., 1935, i, 3527). H. J. E. Synthesis of m ontm orillonite. W . N o ll (Cliem. Erde, 1936, 10, 129— 154; cf. A., 1935, 601).—In Preservation of pyrite and marcasite. F. A. presence of little alkali both montmorillonite (I) and B a n n i s t e r (Museums J. London, 1933, 33, 72— 75).— kaolin are formed; with still less or none (or in a The decomp, of specimens of natural FeS2 can be slightly acid solution) only kaolin. With an excess arrested by cleaning with aq. NH3, washing, drying of NaOH analcime is formed. Similar results are at 70°, and coating with a 7 % solution of vinyl obtained in presence of Ca(OH)2 and Mg(OH)2. With acetate in 1 :1 PhMe-COMe2. C h . A b s . (e) excess of Mg(OH)2 this enters into the composition Lovchorrite of the Chiba swamps. I. K. of the (I) up to 15-3% MgO, which then corresponds C hazanovitsch (Razved. Nedr, 1935, 4, No. 1, 28).— with a fuller’s earth. In the natural formation of Lovchorrite contains approx. 16% of Ce and Ce clay minerals by the hydrothermal alteration of rocks, earths, 1% of Th, and some U. It resembles glue if alkalis accumulate, owing to feeble circulation, plates. Chibinite is similar. C h . A b s . (e) then (I) is formed, whilst if they are removed by an excess of H 20 kaolin is formed. L. J. S. Lake Bosumtwi [volcanic glass]. N. R. J unner (Rep. Geol. Surv. Gold Coast, 1932— 1933, 4— 7).— Rock-forming minerals from Belgian Congo. The volcanic glass contained 64-01% of Si02. A. Vandendriessche (Natuurwetensch. Tijds., 1936, C h . A b s . (e) 17, 243—247).— The crystallography, physical pro Preliminary staining studies of the Lehigh perties, and chemical analyses of olivine and augite Valley dolomitic limestone. J. F u l l e r (Proc. from near the Mikeno volcano, Kivu, are given. Penna. Acad. Sci., 1934, 8, S3— 87; Rev. geol., These minerals occur in soil derived from basaltic 14, 522).— Staining tests distinguish dolomitic kvas. D . R. D. from MgO-free limestones. Malachite-green and Colour of corundum . I. I. I s l a m o v and J. M. K 4Fc(CN)g with HC1 are satisfactory. Lemberg’s Tolmatschev (Compt. rend. Acad. Sci. U.R.S.S., solution gives the best results. C h . A b s . (e) 1®, 1, 11— 13).— Corundums have been analysed Iron deposits of southern Anhui. C. Y. H sieii spectroscopically, the red form containing Cr 0-18, (Bull. Geol. Soc. China, 1931, 10, 317— 347).— The “ 0-01, V 0-04, and Ga 0-005% , the blue, Cr 0-002, Fe ores are genetically related to diorito intrusions, h 0-2, V trace, and Ga 0-005% , and the light grey, and are of the contact metamorphic and hydrothermal ( r trace, Ti 0-03, V trace, and Ga 0-002% . Fe is types. In the former, magnetite occm-s with garnet present in approx. the same amount in each. A qual. and babingtonite. Ch. A b s . (e) analysis has been made for other elements in corun dum, and on disthene. The cause of colour is dis Genesis of the Mivirasando tin ores. W. C. cussed. R. S. B. S i m m o n s (Ann. Rep. Geol. Survey Uganda, 1932, 50— 52; Rev. geol., 14, 290).— It is suggested that Optical diagram for magnesium-iron mica Sn came up as K stannate, which, on meeting A120 3 (phlogopite). D. P. G r ig o r ie v (Zentr. Min., 1935, and Si02, deposited cassiterite and muscovite. The , .112—loo; Chem. Zentr., 1935, ii, 198).— The alkali manganates, tungstates, titanates, etc. may variation of the optic axial angle and refractivity of transport the respective metals. C h . A b s . (e) p ogopife with the FeO content deviates widely rom “*0 theoretical curve. The cause is discussed. Occurrence and distribution of staurolite in J. S. A. Gangpur State, Bihar and Orissa. M. S. classification of the granites of the southern Rrishnan (Quart. J. Geol. Soc. India, 1933, 5, 67— atanga according to the planimetric study of 73).— Staurolite occurs in mica-schists with quartz, in-r srec^ orLS• M. Gysin (Arch. Sci. phys. nat., biotite, muscovite, penninite, and garnet. i v. W , 17, Suppl., 243— 246).— The granites can C h . A b s . (e) or ^ ’nto 8 classes, belonging to the granitic Correlation between specific gravity, chemical ' lontic groups of the calco-alkaline series. constitution, and condition of formation of minerals and rocks. I). C. N a g (Quart. J. Geol. t ^ttinescence of calcite (with special reference Soc. India, 1932, 4, 29— 67).— The d has been calc, p . e.Polish deposits). S. K r e u t z (Bull. Acad. from analyses, assuming the mol. vol. of a compound .... onaise. 1935, A , 486— 500).— Specimens of calcite eoual to the sum of the mol. vols. of its constituents. C h . A b s . (e) heat iCd t0 300°’ 330°’ 360°’ 530°’ 680°’ and rcd ami ’«a on C00Hng> their luminescence was ex- Geology of the Orkneys. G. V. W i l s o n , W. Lin Luminescence is lost on heating, this fact E d w a r d s , J. K n o x , R. C. B. J o n e s , J. V. S t e p h e n s , escon cc®?ccte(l with loss of C 02. The blue lumin- and J. S. F l e t t (Mem. Geol. Survey Scotland, 1935, w, ncc °1 some samples changes to a bright yellow 205 pp.).— Deposits of galena associated with strom- of sn66-1 and ®80°. Although the luminescence nite, and the petrography of numerous basic dikes, pecimens from different localities differs, there are are described. Analyses are given. C h . A b s . (e) 450 BRITISH CHEMICAL ABSTRACTS. A. Minerals in diamondiferous concentrates. Space-group and cell dimensions of enargite. N. R. J u n n e r (Rep. Geol. Survey Gold Coast, 1932— S. K6zh and K . T a k a n (c (Proc. Imp. Acad. Tokyo, 1933, 14— 15).— Diamonds are often enclosed in 1935, 11, 421— 422; cf. preceding abstract).— Re pisolites of limonite with 0-15— 1-19% of Cr20 3. examination of the X-ray reflexions of enargite This suggests their origin from ultra-basic igneous crystals indicates the cell dimensions a0 6-39, 60 rocks. Analyses of garnets, ilmenite, and chryso- 7-35, c0 6-15 A. with two Cu3AhS4 mols. per unit beryl are given. Ch. A b s . (e) cell. It is concluded that the space-group is Cla. Arrangement of micro-crystals of silica in the J. W. S. onyx. M. Ic h i n o s e (Mem. Coll. Sci. Kyoto., 1935, Chemical formula of malachite. M. G uillot A , 18, 315— 316).— X -R ay diffraction patterns show and G. G e n e s l a y (Compt. rend., 1936, 202, 130— that micro-crystals of Si02 in onyx have a fibrous 137).— Artificial malachite (8Cu0,4C02,5H20) ident arrangement, of which the common axis is [1120] and ical with the natural product may be prepared by perpendicular to the surfaces of the banded layers (a) the action of saturated aq. Na2C03 or NaHC03 in the mineral. J. G. A. G. on saturated aq. CuSO., or (6) the hydrolysis of alkali cupricarbonates or Cu11 “ carboxydiammine.” Iron formations and associated rocks of the T. G. P. Eastern Bababudans, Kadur District, Mysore. Heavy mineral assemblage of white clay and C. S. P i c i i a m u t h u (J. Mysore Univ., 1 9 3 5 ,8 ,1 — 48).— ochres associated with the laterite of Sohawal Analyses are given, and the origin of the banded State, central India. N. L. S iia rm a and S. P ubka- ferruginous quartzites is discussed. C. W . G. y a s t h a (Quart. J. Geol. Soc. India, 1934, 6, 49—54). Viscosity of fused rocks. M. V olarovitsch Ch . A bs. (e) (Compt. rend., 1936,2 0 2 ,78— 80; cf. A., 1934,751).— Petrography of clay. C. W . C o r r e n s (Natur- Analytical and q data (1110— 1400°) are recorded for wiss., 1936, 24, 117— 124).— The distribution of a series of rocks, q increases, in general, with the nuclear size of clay particles in different specimens of acidity of the rock. H . J. E. clay, and the examination of the constituents of clay Violet fluorspars. H . A r s a n d a u x (Bull. Soc. by microscopical and X-ray methods, are discussed. fran§. Min., 1935, 58, 268— 277).— When slowly The effect of HC1, NaOH, and H 20 2 of various concns. heated, strongly-coloured fluorspars emit a relatively is reviewed. H ,0 „ is without appreciable action. prolonged thermoluminescence, which approx. oc the A.J.M. intensity of pigmentation. They differ from most Transformation of absorbed anions in A4- coloured fluorspars in emitting little or no fluorescence sharien red earth. B. B . P o ltn o v (Compt. rend, under the action of ultra-violet light until they have Acad. Sci. U.R.S.S., 1935, 4, 49— 50).— Analytical been decolorised by heat. The violet fluorspar from data are given showing the displacement of adsorbed the Isle quarry, near Limoges, is described in detail. Cl' and S 0 4" on treating samples of the soil with Mn may be responsible for the fluorescence in this 0-liY-NaH2P04. H. J. E. case. L. S. T. Podolian loess. I. Petrographical analysis Hydroxides of aluminium of the bauxitic of a loess profile from Grzybowice near Lwow. clays of Ayrshire. J. d e L a p p a r e n t (Bull. Soc. J. T q k a r s k i (Bull. Acad. Polonaise, 1935, A , 374— franij. Min., 1935,58, 246— 267).— These clays contain 398).— Microscopical and chemical investigations in a large amount of bcehmite (I) and a small quantity of 10 horizons indicate that the deposit belongs to the cliaspore (II). The origin of (I) and (II), which is latest diluvial epoch. The loess exhibits only slight formed after (I), is discussed. L. S. T. genetic relationship to the Tertiarv sand of Lwow. Elasticity and plasticity of rocks and artificial T. G.P. stone. R. H. E v a n s (Proc. Leeds Phil. Soc., 1935— Marine oil shale, source of oil in Playa del Rey 1936, 3, 145— 158).— Tests on numerous specimens field, California. H. W. H oots, A. L. B lo u n t , and in tension and compression are described and dis P. H . J o n e s (Bull. Amer. Assoc. Petrol. Geol., 1935. cussed. H. J. E. 19, 172— 205).— The migration of oil in the field 13 discussed. Ch . A bs. (e) Andesites of the Trojaga District in the Mar- moros Carpathians. M. K a m ie n s k i (Bull. Acad. Native hydrocarbons associated with oil shales Polonaise, 1935, A , 399— 407).— Microscopical and of the Lothians. H. R. J. C o n a c h e r (Trans. Edin chemical investigations of the volcanic rocks of the burgh Geol. Soc., 1934, 13, 89— 97).— Chrisniatite Trojaga indicate that they belong to the calc-alkali (m.p. 51°) occurs in cavities in igneous rocks. Zietn- series of the amphibole-andesites and amphibole- sikite (m.p. 84°) occurs in j oints in sandstone. Wurtz- biotite-andesites which show the character of ilite (m.p. 130°) is found in oil shales and ironstone dacitoids. The}’ were probably erupted in the second nodules, and resembles ixolite. Ch . A bs. (e) Mediterranean or the Samet epoch. T. G. P. Oil deposits in the Lena river basin and its Morphological studies of enargite. S. Kozu tributaries (Siberia). Organic substance of the and S. W a t a n a b e (Proc. Imp. Acad. Tokyo, 1935, m inerals from the river T olba. S. P. UseensW 11, 418— 420; cf. A., 1934, 244, 1060).— Examination (Neft. Choz., 1935, 27, N o. 2, 29— 32).— Analyses ate of many crystals of enargite (Cu3AsS4) leads to the recorded and discussed. Ch . A bs. (e) conclusion that this crystal is hemimorphic. Its Migration of Hungarian hydrocarbons. E. R- crystal habit and modes of twinning are discussed. S c h m i d t (Fold. Kozlony, 1 9 3 4 ,6 4 ,27S; Chem. Zentr., J. W . S. 1935, i, 3527).— A discussion. H. J- E- XIV (a) ORGANIC CHEMISTRY. 451 Organic Chemistry. Appearance of radicals in thermal decomposi Allylic rearrangements. II. Magnesium tion of organic m olecules.— See this vol., 433. crotyl and methylvinylcarbinyl bromides. W. G. Thermal decomposition of ethane. I, II. Y o u n g , S. Winstein, and A. N. P r a t e r (J. Amer. See this vol., 432. Chem. Soc., 1936, 58, 289— 291 ; of. A., 1932, 250).— The same mixture (method of analysis : Dillon et al., Free radicals and atoms in primary photo A., 1930, 888) of 5 6 -4 ± 2 % of A“- and 2 6 -5 ± l-4 % chemical processes. Free »»-propyl radical. cis- and 1 7 -2 ¿ 3 % ¿oms-A^-butene is obtained by- T. 6. Pearson and It. H. P urcell (J.C.S., 1936, hydrolysis (dil. HC1) of the Grignard reagents (A) 253—256).— Formation of Pr° by irradiation of from various mixtures of CHMelCH-CH2Br and COPr»., with ultra-violet light (A., 1935, 1221) is CH2lCH-CHMeBr. Rearrangement occurs during the proved by removal of As, Sb, and Te mirrors and formation of [A). H. B. reaction with Hg (forms a liquid, which with HgBr2 Thermal rearrangements of pentenes. C. D. gives HgPr“B r); excitation of the Hg is avoided by H u r d , G. H. G o o d y e a r , and A. R. G o l d s b y (J. filtration of the irradiating light through Hg vapour. Amer. Chem. Soc., 1936, 58, 235— 237).— A“-Pentene The half-life period of Pr* is 2-3xlO*3 sec. in S i02 at (I) undergoes 56— 58% decomp, at 580— 600° (contact room temp. R. S. C. time 13— 18 sec. ; method essentially that of A., 1934, Preparation of isom eric hexanes. P. L. 1089) to give liquid (probably mainly cycloalkenes Cramer and M . J. M u l l i g a n (J. Amer. Chem. Soc., and aromatic hydrocarbons) and gaseous products 1930, 58, 373— 374).— ?i*Hexane, b.p. 68-74— 68-78° (CH.,, 0 2H6, C2H4, C3H 8, and A“-butene in the mol. (CHEtPr-OH; A120 3 at 350°), (3-methylpentane, b.p. ratio 6 : 2 : 1 : 2 : 2 ; small amounts of H2, C3H8, 60-22—60-26° (CMe,Pr-OH; I at 122°), y-methyl- A^-butene, and butadiene). A little of (I) rearranges pentane, b.p. 63-16— 63-21° (CMeEt2-OH; I at 120°), to A^-pentene (II). The extent of decomp, of (II) at 33-dimethylbutane, b.p. 49-8—49-82° (CHMeBuv-OAc 580° and 600° is 23 and 54% , respectively. Essenti heated at 400°), and [iy-dimethylbutane, b.p. 57-82— ally the same products are formed and a little of the 38-020 (0H-CMe2-CMe2-O H ; H Br at 130— 150°), are (II) rearranges to (I). (I) prepared from MgEtBr prepared by reduction (H2, P t0 2) of the olefines and allyl bromide in BuaO contains a little CHXCHPr^ formed by dehydration (methods quoted) of the (removable by distillation) [the statement (B., 1934, alcohols quoted after the hydrocarbons. PI. B. 228) that this is produced during pyrolysis of (I) is erroneous], (II) (free from isomerides) is obtained Thermal study of oxidation of hydrocarbons. by dehydration (H2S0 4) of CHEt2-OH. H. B. ->Sec this vol., 432. Dimérisation of divinyl. J. M. S l o b o d i n (J. Polarisability of the ethylenic linking. G. Gen. Chem. Russ., 1935, 5, 1415— 1420).— The con 'Viitig (Ber., 1936, 69, [7J], 471— 475).— The additive densate obtained as a by-product of the catalytic •■■opacity of the CIO linking in CR2IGR2 depends on prep, of divinyl from EtOH by Lebedev’s method fne nature of the addendum and on that of R. The consists of p-xylene 66, and 4-vinyl-A1-cycfohexene-f- ^placability of the valency electrons on deformation PhMe-f-PhEt 3 3 % ; the probable intermediates are °f the state of union of the QIC group is much more CH,:CH-CHMe-CH:C'H-CH:CH2, pronounced than that of the C-C linking, and this CHM e<^:^>CHM e, and nm *-?11 Examples cited are the ability of AIMe.CH-CHO to undergo the aldol condensation, the fission of CPh2:CH-CH2jCH2-CH:G'Ph2 by alkali CHMe^fJjCH^ciCB^. R. T. metal, thepinacolin transformation of [OH-CPhR-C:]2, the action of NnOH on 2:6: 3-(N 02)2Cr,H2Me-CH0, Rôle of intermediate compounds in the pro cess of catalytic polymerisation of acetylene. I. J the dissimilarity in the behaviour of 2- and Reaction of acetylene with solutions of cuprous Tyrones. The conditions for the realisation of and ammonium chlorides, and a study of the encytautomerism are discussed. H . W . complexes formed. L. G. T z i u r i c h and A. A. Raman spectrum of rubber and related G i n z b u r g (J. Gen. Chem. Russ., 1935, 5, 1468— hydrocarbons. See this vol., 407. 1478).— The cryst. product obtained by saturating a solution containing CuCl 18 and N H 4C1 20% with eli^'Tai-ati0n of unsaturated hydrocarbons by C2H2 has the composition 6CuCl,3NH4Cl,C2H2 ; it mnjnation of halogen acids from corresponding readily dissociates into its components, with which o 5s - At B ell and R. H. Cl a r k (Trans. Rov. it is in equilibrium in the solution. R. T. ;«• Unada, 1935, [hi], 29. IH . 61— 68).— Quant. Person of the prep, of unsaturated hydrocarbons Hydrogenation of vinylacetylene. S. V. L e b e ,f° halides by the use of EtOH-KOH (I), dev, A. I. G ul j a e v a , and A. A. Vassiliev (J. Gen. quinolme (H), NH2Ph, NPhMe,, NPhEt,, C5H5N, Chem. Russ., 1935, 5, 1421— 1433).— The -CIC- and with e ^ ^ ca tes that (I) gives poor yields -C-C- groups of CH2:CH-C:CH (I) are hydrogenated toffetn 1CieS owh1" t ° formation of ethers, but, simultaneously and with equal velocity in presence ten 6PT1 *-he org. bases, is suitable for higher sec.-, of Pt catalyst, whilst with Pd (on Ni or Na prot- for » an i Gtcfc-halides, whilst (II) is recommended albinate) addition takes place chiefly at the triple are» I ower aec.-halides. Bromides and iodides linking; CHMelCHMe is not found amongst the O ™ better yields than chlorides. F. O. H. products of incomplete hydrogenation. (I) may be 452 BRITISH CHEMICAL ABSTRACTS.— A. XIV [a, b) quantitatively reduced to divinyl by nascent H (from 35 min., when 10 ml. of 0-05Xr-Na2C20 4 are added, Zn-Cu and H20 , or at a Pt-black cathode). It. T. the solution is warmed to 80— 90°, and excess of oxalate is titrated with 0-05AT-KMnO4. Esters to Action of anhydrous alkaline earths on mono- an amount of > 2 5 % of that of the alcohols present halogenated paraffins. J. B. Se n d e r e n s and J. do not interfere, but EtOH should be absent. A b o h l e n c (Compt. rend., 1936, 202, 104— 106).— R. T. When dropped on heated CaO or BaO (reaction temp, Mechanism of conversion of Ar-butenol into in parentheses) C„H2,l+1Cl decomposes cleanly to A^-butenyl bromide. L. W. J. N e w m a n and 0„Ho„+ HC1 (retained by catalyst). Thus Bu“Cl H . N . R y d o n (J.C.S., 1936, 261— 264).— Ah- (I) and (275— 285°) or BuQBr (300— 310°) gives C4H 8; Pr^Cl Av-Butenol (II) are stable to boiling alone, hot 30% (250°) or l ’ritBr (265°) gives CHMe!CH2, and Buy01 KO H , Ac20 , and AcO H ; Ah- (III) and Av-butenyl (210°) gives CMe„;CH2. No C is deposited. bromides are similarly stable and hydrolysis of the J. W . B. acetates does not cause isomerisation. Change of From iodoform to fluoroform. O. R u f e [with (II) into (III) by hot H ,S 0 4-H B r occurs by dehydr O. Bretschneider, W . Luchsihoer, and G. M ilt- ation to butadiene and addition of HBr thereto, s c u it z k y ] (Ber., 1936, 69, [/?], 299— 30S).— CI1F3 both the last reactions having been separately obtained by heating CHI3-A g F -S i0 2 is contaminated realised under the experimental conditions used. with CO and considerable amounts of SiF4. CaP2 CHdCMe-CHyOH reacts with HBr as does (I) and its is a more suitable diluent, the best results being bromide is hydrolysed at the same rate as is (HI). secured with A g F : CaF0= l : 4 and H g F : CaF2= l : 1-2. Mixtures of the Ah- and Ay-isomerides are analysed The prop, of CHF3, CtIIF2, and CHI2F from HgF, by the much more rapid psterification by HBr or CIII3, and CaFo (33-4 : 20 : 40) is described in detail. hydrolysis of the Ah-isomcride at room temp. At > 100° PbF.“, ZnFo, CuF2, CoF3, and SbF3 do not R. S. C. yield appreciable quantities of CHF3. Slow passage Action of micro-organisms on the diastereo- of CHC13 vapour over AgF-CaF2 gives about 57% meric forms of hexane-yS-diol. II. v a n Bisseo- of CHCl2F at 100° and about 4 8 % of CHC1F2 at 250°; hem (Bull. Soc. chim. Belg., 1936, 45, 21—35).— at 340° about 10% of CHF3 is obtained, but the Griner’s mixed [CH2:CH-CH(OH)-]2 with H2-Pd-black mixture sintors and becomes ineffective at this temp. in Et20 gives meso- (I), m.p. 90-1— 90-2°, b.p. At about 500° PbF2 gives a little CHC1.JB' among 115-l°/24 mm., and dl-hexane-y8-diol (II), f.p. 20-9°, other products. CHF3 has b.p. — S4-4°/760 mm., b.p. 108-65— 108-75°/24 mm. (I) with B. xylinwn or m.p. — 160°. It does not lose H F when heated 31. aceti gives d-hexan-y-one-Z-ol (III), b.p. 70"— alone or in presence of K F at 1150°. It is unchanged 71°/22 mm., [a® 61 +88-16°, and a little (EtC0]t by H N 0 3 alone or with cone. H 2S0 4, N 20 3, or A g N 03 (II) with B. xylinum slowly or M . aceti rapidly gives at 140°; at > 175° it is completely decomposed by the Z-form of (HI), whilst some Z-(n) remains un N20 3. NOF leaves it partly unchanged after 3 hr. attacked ; rZ-(II) thus reacts preferentially. It is at 100° and Mn20 7 is without action at 25°. Oxidising concluded that bacteria attack the d-G. Hydro agents transform it into COF, and HF. It is un genation of (Z-(ni) gives Z-(II), b.p. 105-7— 106-27 affected by CaO at 365°. Ioalodijhioromethane, b.p. 20 mm., [a]=»8l -12-24°. R. S. C. 21-6°/760 mm., is very sensitive to light and ah, but in their absence it is stable indefinitely. It is Lycoxanthine and lycophyll, two natural deriv only partly decomposed by Pt-asbestos at 700°. It atives of lycopene. L. Zechmeister and L. vo>' reacts readilv with A g N 0 3. Di-iodofiuoromethane, C h o l n o k y (Ber., 1936, 69, [B], 422— 429).—Re b.p. 100-3±6-5°/760 mm., m.p. -34-5°±0-5°, is fruits of Solanum dulcamara are ground with sand, sensitive to light and air. It slowly separates I washed with EtOH, and then extracted with Et.,0. when warmed; at > 250° it is almost completely After removal of the solvent the residue is dissolved in decomposed with production of HF. It reacts with C6H6and analysed chromatographicallyusingCa(OH!j- Mg only when irradiated. W ith liquid N H 3 it gives Alternatively, the dry residue is dissolved in benzine NH4F and NH4I. With Na2S03 in 50% EtOH at and the solution shakon with 90% M eOH ; the final 80° complete separation of F from C is observed. t reatment is with Ca(OH)2 in C6H 6-benzine. Thus are H . W . obtained lycoxanthine (I), m.p. 168° (corr.) (acetate, H ydrolysis of isopropyl brom ide.— See this m.p. 137°), lycophyll (II), C40H 56O2, m.p. 179° (corr.) vol., 433. [dipalmitate, m.p. 76° (corr.)], and lycopene (111)- Alcohol determination. R. M. M a y e r (Deut. Z. The absorption spectra of (I), (II), and (HI) are so gcs. gerichtl. Med., 18, 638— 646; Chem. Zentr., remarkably similar that the presence of 11 conjugated 1935, i, 3961).— A modified Nicloux method is and two isolated double linkings in each is regarded described. H . N. R. as established. On the assumption that the OH occupy the same positions as in other xanthophyl», Alcoholic fermentation in heavy water.— See this vol., 522. the constitution CMe„:CH-CH(0H)-CH,-[CxMe:CH-CH:CH]3- Determination of small concentrations. II. ' [CH:CMe*CH:CH]2-CH:CMe*CH2'CHR'CH:CMej Butyl and amyl alcohols. M. V. A l e x e e v a (J. is assigned with R = H in (I) and it= O H in (+)• Gen, Chem. Russ., 1935, 5, 1324— 1330).— 7 ml. of The quant, separation of (II) from (I) and (HI) 1S 0'05AT-KMnO4 and 10 ml. of 5A’-H 2S0 4 are added to described, also the determination of (I) and (H) in*ie 10 ml. of solution, containing 0-1— 1-5 mg. of BuOH crude materials. (I) and (II) do not appear to be or CsH n -OH, the mixture is kept in the dark for present in preserved tomatoes, but are detected in the XIV (b) ORGANIC CHEMISTRY. 453 fresh fruit. The berries of Tamils communis contain Interpretation of differences in properties of (III) a little (I), but not (II). The carotenoids are alkyl chlorosulphites and chloroformâtes from unesterified. (I) and (II) are absent from Rosa the electronic viewpoint. P. C a r r é (Compt. rend., canina, but present in traces in Actinophlcus Macar- 1936, 202,298— 300 ; cf. A ., 1935,606).— A discussion. thurii. (Ill) and its derivatives are not contained Reaction of complex sulphuric acid esters. in Coloneaster Iwrizontalis. II. W . L. Lison (Bull. Soc. Chim. biol., 1936,18, 225— 230). aS-[yC-]Anliydromannitol. F . V a l e n t in (Coll. — The colour change produced by org. esters of H 2S0 4 Czech. Chem. Comm., 1936, 8, 35— 42).— a-Methyl- of high mol. wt. on metachromatic dyes such as mannopyranoside 6-bromide (freed from N H 2Ac by toluidine-blue and cresyl-bluo is sp. for such EtOAc) with Ba(OH)2 gives a-methyl-y£-anhydro- substances and might be used in their qual. investig mannopyranoside, stable to H 2S, hydrolysed by 3 % ation. A. L. HC1 to y^-anhydromannofuranose (I), which with Polysaccharide hydrogen sulphates with 2-5% Na-Hg in slightly alkaline solution gives «8- heparin-like action. S. B e r g s t r o m (Z. physiol. anhydromannitol (50% yield), m.p. 148° (lit. 138°), Chem., 1936, 238, 163— 168; cf. A., 1935, 1519).— [*]D —23-75° in H 20 (dibenzylidene derivative, m.p. Details are given of the prep, and activities of the 125—126°, [a]D —48-8° in CHCln), which with Br esters [including that from pectic acid (I)]. Synthetic reverts to (I). CHPh! is determined by distillation chondroitintrisulphuric acid, c-hitindisulphuric acid, with 60% H2S0 4 in C 02 and detennination of the and (I) polysulphate have activities < that of the PhCHO in the distillate as phenylhydrazone. product (II) from cellulose. The activities of the It. S. C. other preps, are only 8— 50% of that of (II). Chloroalkoxylation of olefines by the action of W . McC. chlorine in presence of alcoholic alkali. M. V. Mannitoldimolybdic acid. Variation of the Lichosciiebstov and A. A. P e t r o v (J. Gen. Chem. p a of molybdic acid caused by addition of sugar. Russ., 1935, 5, 1348— 1354).— Compounds of the type (Mme.) Z. Soubarev-Chatelain (Compt. rend., 1935, OR-ClLMe-CHMeCl (I) (R =alkyl) aro obtained in 2 0 1 ,1390— 1392).— The effect of sugars, e.g., mannitol, 60—70% yield by adding a 3 0 % excess of NaOH to on the pa of molybdic acid and its salts (A., 1933, 909) the ROH, passing Cl2 continuously (25% excess), is explained by formation of mannitoldimolybdic acid and introducing CHMelCHMe intermittently. When (I), [C6H]4Or„HMo20 7]H, thus ; increase of the mixture is diluted with H 20 , a 3 : 1 mixture of ~ ’ pa, 2Na2Mo04+C 6H140 6+2H20-^(I)+3N a 0iI; de- (I) and (•CHMeCl)2 separates. It. T. crease of pa, 2[XIo03Cl2]H2-}-C6H140 G-j-H20-Tr-v (I) + Preparation of dim ethylacetal by condensing 4HC1. R. S. C. methyl alcohol with acetylene. S. Tamaru and Aminoethyl phosphate from tumours.— See >■ Tanaka (J. Chem. Soc. Japan, 1935, 56, 486— this vol., 364. ’74).—HgGlo or H 2S0 4 may be used as catalysts, •he optimum temp, being 40°; the former is prevented Specific reaction of dichlordiethyl sulphide in from losing its activity by addition of Fe2(S04)3. presence of other chemical warfare gases. M. Ch . A b s. (r) Obermiller (Angew. Chem., 1936, 49, 162— 164).— Mixed glycerides of salicylic acid and fatty S(CH2-CII2C1)2 (I) in small concn. gives with aq. m A Lukasiak (Rocz. Farm., 1934, 12, 1— solutions of AuC13 and PdCl2 a strong yellow colloidal '6; Chem. Zentr., 1935, i, 3005— 3006).— Resorption turbidity. On filter-paper reddish-brown and yellow ot salicylic acid (I) compounds is followed by deter stains are given with AuCl3 and PdClj, respectively. mination of (I) in the urine. Results with Et and Negative results were obtained w-ith the other V w ae ^p y^h es, the triglyceride of (I), salicylo- common war gases. A positive result was observed ^Morehydri11, and aa-distearo-P-salicylin are de with 1-5 mg. of (I) in 20 c.c. of liquid. By means of a scribed. The following are described: $-palmito-, special apparatus (I) could be removed from a large r. $-butyro-, b.p. 102— 103°/12 mm., and vol. of air and (I) in concn. of 10 mg. per cu. m. T r i 0'' b-P- fft4— 106°/S mm., --xy-dichlorohydrin; detected in 4 min. D. C. J. ™ ij'x\'Jro-y-monocliloroliydrin, b.p. 133— 136°/8 Mechanism of the sulphonation process. A. “*lsovalero-u.-iodoJiydrin, b.p. 153—155°/4 mm.; M i c h a e l and N. W e i n e r (J. Amer. Chem. Soc., 1936, V ®ovalerin, b.p. 146— 150°/5 m m .; aa-diiso- 58, 294— 299).— Contrary to Wieland (cf. A ., 1920, i, r^-salicylin, b.p. 210—21274 mm.; *-salicylo- 280), the reaction between C2H4 and oleum (I) does b-p‘ 398— 201°/3 m m .; p-palmito- not involve addition of H2S04 (as O H + S 0 3H). The rfi-buiyro-t m.p. 51°, and S-isoraZero-ay- results now obtained [and the data of Plant and ^hcyhn, m.p. 65°. H . N. R. Sidgwick (A., 1921, i, 153)] show that H 2S20 7 is the Spectrophotometric determination of ethylene reactive entity and leads to ethionic acid (II) [Ba salt ¡oCfi,o ?itrate- J- H- F oulger (J. Ind. Hyg., (4-0-5H20 )]; each mol. of H„S20 7 gives 1 mol. of Sflt > 3^7— 129).— The absorption of the coloured (II): CH^CHa+OH-SOyO-SOyOH-^ on o u ’^f”r-med by the action of OH-C6H3(S03H)2 S 0 3H-CH2-CH2-0-S 03H. When (I) contains more and (3), at 4900 A . has been determined, S 0 3 than is necessary to form H2S20 7, carbyl sulphate detorm- j tained by which the concn. of (I) can be (III), S 0 2< ^ 2> 0 , is als0 formed by the direct j.o q 7 eci from (o) the sp. extinction vaL (for concn. of nh f m^’ per 3^0 c.c.) and (6) a table of differences addition of S20 6 to C2H4- (IH) is also produced from loo ° ?meter rea(hngs (for concn. 0-5— 4-2 mg. per C2H4 (excess) and S 0 3 in the gaseous phase (C 02 used •°T J. N. A. as diluent). Isethionic acid, OH-CH2-CH2-S03H, is 454 BRITISH CHEMICAL ABSTRACTS. A. XIV (6, c) converted into (II) by (a) 100% H2S04 (1 mol.), undecoate, b.p. 174°/10 m m .; hydrolysis then leads (b) 100% HoS04 (1 mol.) followed by SO., (1 mol.), and to v-lcetotetracosanoic acid, m.p. 95°, reduced (Clem- (c) S 0 3 (1 m ol.); 2 mols. of S 0 3 give (111). mensen) to tetracosanoic acid (I), m.p. (a) 83-5— 84-5° Wieland’s mechanism (loc. cit.) of aromatic substit (capillary), (b) 83-8° (thermometer in melt), f.p. 83-5°. ution is held to be untenable. Sulphonation is con Br yields a-bromotetracosanoic acid, m.p. 71-5—72"' sidered to be an aldolisation (pseudo-substitution) (lit. 69-5— 70°), and thence is obtained a-hydroxy- reaction (cf. A., 1935, 1103). The formation of tetracosanoic acid, m.p. 99-5— 100° (lit. 94— 95°). Ph2S0 2 from C6II0 and (I) is explained : 2C0IIc+ Undecoyl chloride leads similarly to tricosanoic acid (II), m.p. (a) 79— 80-5°, (6) 78-86°,_ f.p. 78-75°. (I) S20 6 -> S02<^ > S P h 2(0H)2 -> Ph2S02+ H 2S04. and (II) give continuous solid solutions with a max. C61IG could not bo sulphonated by Me2S0 4+ A lC l3 ; depression of the m.p. of 0-45°. The product of methydation occurs owing to the production of MeCl. oxidation of cerebronic acid may be impure (I). H . B. R .S. C. [Addition of bromine to] unsaturated acids. Preparation of unsaturated acids from stearic C. E. S un (J. Chinese Chein. Soc., 1936, 4, 1— 5).— acid. E. M. P r i k (Plast. Massui, 1934, No. 6, 26— The activation energy for the addition of Br to 27).— Chlorination of stearic acid, followed by Py-unsaturated acids is probably the same as for elimination of I1C1 (Zn dust, or heating in vac.), yields defines (22-4 kg.-cal.), whilst that for aS-unsaturated an unsaturated product, b.p. 190— 214°/5 mm. acids is calc, to be 31-5 kg.-cal., in agreement with Ch. A b s. (r) the more facile reaction in the former ease. Reactions in monolayers of drying oils. I, II. R . S. C. — Sec this vol., 434. Exchange between organic compounds and Qualitative test for linolenic acid, its value and heavy water. F. K. M u n z b e b g [with W . O b e r s t ] lim itations. G. J. M a r t in (J. Amer. Chem. Soc., (Z. physikal. Chem., 1935, B , 31, 18— 22).— There is a 1936, 58, 364— 365).— Oils containing linolenic acid small exchange of H for I) in a solution of H C 02Na in (I) give a deep blue colour when 1 c.c. is heated with heavy H.,0 at 100°, but not below. With solutions of 5 c.c. of arsenophosphotungstic acid (Benedict, A., IIC 02H, C 02H-[CH2]2-C02H, and CII2C1-C02H at 50° 1931, 973) at 100°/1 hr. Approx. determinations of only the II of COaH is exchangeable, whilst with the amount of (I) present can be made; Me linoJcnafe CH2(C02H)2 all the H may be exchanged. R. C. is used as standard. Other fatty acids containing 3 Thermal decomposition of esters in presence double linkings give the reaction. H. B. of aluminium chloride. H. G a u l t and E. B e l o it Fatty acids of phrenosin and kerasin. A. C. (Compt. rend., 1936, 202, 71— 73).— Bu“OAc heated Ch ib n a l l , S. H . P ip e r , and E. F. W il l ia m s pBiochem. with AlCJg to 300— 330° gives Bu“Cl (50— 55% ), J., 1936, 30, 100— 114).— Brain contains at least.3 define (liquid at — 70°), and a mixture of CO, C 02, H 2, phrenosins and 3 kerasins, the components of which and CH4 with traces of C2HB, C3H 8, and define. The differ only in the chain-lengtli of the fatty acids. A amount of BuOAc decomposed oc the wt. of A1C13 sample of phrenosinic (cerebronic) acid (I), m-P- used. Rise of temp, gives more gaseous products, 102-3— 102-6°, [«]£ + 3 -3 3 ° in C5H5N (Ac derivative, but does not otherwise alter the course of the decomp. m.p. 66— 66-5°), obtained by hydrolysis of a highly H. B. purified specimen of phrenosin is shown to consist of Electrolytic reduction of organic compounds. a mixture of even-no. a-OH-acids of mean mol. wt I. Analogies between cathodic reduction and corresponding closely with C24, which on oxidation the action of dissolving metals. Reduction of with Cr03 in AcOH give a mixture of odd-no. vi-fatty sorbic acid. E. I saa c s and C. L. W il s o n (J.C.S., acids, identified as 8 5 % C23 and 15% C25. (I) consist 1936, 202— 207).— Evidence is reviewed showing that therefore of 85% of a-hydroxy-w-tetracosanoic aid the course of electrolytic reduction depends on the 15% of a-liydroxy-rc-hexacosanoic acids. (I) of 1°'' solvent used. H 2 overvoltage is important for reduc m.p. contains also a-hydroxy-w-docosanoic acid- tion of ketones and aldehydes, but not for sorbic acid Thudichum’s neurostearic acid probably consists ol (I). Reduction of (I) gives the following % of 25— 30% of (I), the rest b e i n g “ lignoceric acid Av-hexenoic acid in the product at Hg, Cd, and Cu (II). The acidic constituents of the kerasins are cathodes: in AT-NaOH, 40, 39, and 40; in 0-5iV- M-docosanoic, «-tetracosanoic, and w-hexacosanoic NaIIC03, 4i|— , — ; in 70% AcOH+0-5i¥-NaOAc, acids; (II) is thus also a mixture and the name 54, 50, and 50; in 2AT-H2S04, 52, — , — , respectively; should be abandoned. Several binary mixtures 0 these are very similar to the results obtained with «-fatty acids of chain-length from C21 to C25 have been N a-H g and A l-H g (A., 1929,1270). Hg as cathode or prepared and their m.p. and crystal s p a b i n g s recorder. amalgam leads to much “ pinacol,” b.p. 180— 1 8 3 °/< 1 mm. Anthracene gives the 9 : 10-H2-derivative with Absolute configuration of lactic acid. As N a-H g, A l-H g, or M g-H g in EtOH or, better, dioxan, sumptions made in calculation of optical rota or at a Hg cathode in alcoholic NaOII, (N H ,)9S 0 .+ tion. W . K u h n (Z. physikal. Chem., 1935, B, b N H 3, or NMeyOH. R. S. C. 23— 57).— The sign of the rotation of CHMebt’U Tricosanoic and tetracosanoic acids and their has been calc, by means of a simplified model in " Inc derivatives. R. A s h t o n , R. R o b in s o n , and J. C. the Me, Et, and active C are each replaced by a S m it h (J.C.S., 1936, 2S3— 285).— Lauryl chloride, isotropic resonator with the charge of the Et group . b.p. 134°/9— 10 mm., is condensed with CH2Ac-C02Et that at the centre of the Me or active C ; the resonant and Na, and the product treated with Et X-bromo- interaction between the three, taken as having XIV (c) ORGANIC CHEMISTRY. 455 same natural frequency, is calc, by an exact method. C1?H130 4C1Cu ; the Cu11 enolate of COMe-CHyCOPh If the optical vibration of the OH absorption band affords an impure enolate, C10H9O2C1Cu, whilst of longest X is assumed to be non-isotropic the the Cun enolate of COMe-CHyCOMe and (IV) yield model will be optically active, whilst if the OH group the pure enolates, CICu-OCMoICH-COMe and is isotropic there will be no activity. From the light CICirO'CMelCAc’COgEt, respectively, which with cold scattering and Kerr effects of OH-compounds it is HoO and aq. HC1 give the original enolates and probable that for the COH group the above absorption ketones, respectively. The results are interpreted band vibrates in the plane defined by the C, 0 , and by the theory (cf. loc. cit.) of the formation of po]y- C 02H mols. and their subsequent decomp. Related H atom. This leads to H— }— OH 'where the Me and reactions, e.g., the production of CH2ICO from Me CH2Br*COBr and Zn, are discussed briefly. C02H lie behind the plane of the paper, for the con (VII) and its (liquid) isomerido (IX), b.p. 139°/ figuration of d(— )-lactic acid. Calculation shows 1/5 mm. (from CH2Ac-C02Et and BzCl in C5H-N), that for CHRR'-OH the direction of rotation is absorb H„ and Br at about the same rate; (VII) independent of the sp. nature of R and R '. On both reacts somewhat faster with ONa’CMe!CH-C02Et to theoretical and experimental grounds vibrations corre give the Na enolate of CHBzAc-C02Et. (VII) and sponding with optical absorption bands of a mol. must (IX) could not be interconverted by heat or irradi be regarded as non-isotropic. The direction of the ation [whereby (IX) is destroyed and (VII) is un optical vibrations of the absorption band of longest X changed]. It appears doubtful if (VII) and (IX) can of a given mol. generally is that in which the polaris- be classed as ordinary stereoisomerides. H. B. ability, as measured by the Kerr effect and light aa-Dimethylacetoacetic acid.— See this vol., 432. scattering, is a max. In the most important cases optical activity appears to be an effect not of the Monohydroxypalmitic acid in butter fat.— See third, but of the first, or at most second, order. this vol., 361. R. C. Chlorohydroxystearic acids from oleic and Mechanism of reactions of metal enolates of elaidic acids. K. H a s h i (J. S oc. Chcm. Ind. Japan, acetoacetic ester and related compounds. III. 1936, 39, 18b).— Addition of HOC1 to oleic acid, or of Copper enolates. A. M ic h a e l and G. H. Ca r l s o n HC1 to its oxide, yields only a chlorohydrin a, m.p. (J. Amer. Chcm. Soc., 193C, 58, 353— 364; cf. A., 38-0— 38-3°; that of HC1 to elaidic acid oxide gives 1935, 474).— The Cu11 enolato (I) (1 mol.) of chlorohydrins p and y, m.p. 49-5— 51-0°, and 68-0— CH2Ac,C02Et and Cl (1-5 mols.) in CCL at 0° or the 69-5°, with scarcely any a, -whereas that of HOC1 to “•p. give Cu2Cl2 (1 mol.) and CHClAe-C02Et (II) elaidic acid yields a mixture, half of which is a sub "J?°ls-)\ flic formation of CuCl2 (Schonbrodt, A., stance of m.p. 51-0— 55-0°. E. W . W . 1890, 27) is ascribed to the use of an excess of Cl. Action of alkali metals on dialkylmalonic (11) and Cu2Cl2 are also formed from (I) and CuCl2 esters. F. K rollpeeieeer and A. R o s e n b e r g (Ber., ln boiling CgH"g. (I) and AcCl (1-5 mols.) in C0H, 1936, 6 9 , [B], 465— 470).— Na powder reacts vigor or Et,0 at room temp, afford Cu2Cb, (II), and ously with CMc2(C02Et)2 is anhyd. Et20 giving CO OAc'C.MeiCH-CO.jEt; CHAc2-C02Et (III) is not (95-3% of amount calc, for elimination of 1 C 02Et) lonned. The Cuu enolate (IV) of (III) with AcCl and Pr^C02Et (yield 35-8% ); the deficit of the latter similarly gives the 0 -Ac derivative of (III) and the is attribute”d partly to volatility, partly to formation (impure) enolate, CICu-O-CMeiCAc-CO.Et, which is of further products; acidic substances are also converted by colcl H 20 into (IV) and by AcCl in produced, which are less in evidence when a more , 1 C«H6 into (III), CuCL, and CukCL. The Cu11 difficultly hydrolysable malonate is used. K and enolate (V) 0f CH2Bz-C02Et (VI) and AcCl (2 cquivs.) CEt2(C02Etf2 react violently giving CO (1 0 4 % ), Or 0.1 ° aff°rd the 0 -Ac derivative of (VI), CHEtyCOoEt (29-8%), and C02H-CEt2-C02Et , 2> and some Cu2Cl2; reaction is slow at room (31-5% ); "the more turgid action with Na affords m jD<*an intermediate enolate cannot be isolated. CO (854% ), CHEtyCOoEt (46-5%), and dicarbonyl i l ? “ ClC02Et (2 equivs.) in boiling CGHG give compounds which could not be identified. K arid «• Aef A., 1892, 140) Cu„Cl2, some CHAc(C02Et),„ CPrL(C02Et), yield CO (11-6%), CIIPr“2-C02Et Tr,J ate> ClCu-0,CMeiC(C02Et)2, and unidentified (37-2%), and Et H di-v-propylmalonate, m.p. 43— L ,uctf 1 (V) and ClC02Et (1-5 mols.) similarly 44°; with Na the products are CO (83-2%), ’ , Cu2C12, CHBz(CO,Et)2, and a little of the CHPra-CO„Et (61%), and minor amounts of acidic £ '% ,a C t .-0 TJ!d,:C(C02Et)o. (I) and BzCl in products. ” a-n-Propylvaleranilide has m.p. 102— (V mg ■£«?« afford {cf- Ncf> A ., 1893, i, 628) Cu2Cl„ 103°. C(CH2Ph)2(C02Et)o and K react slowly at rtfi cii -r )’ CHBzAc-CO,Et, CBz2Ac-C02Et, and 15— 20°, more vigorously at the b.p. of Et20 , giving (®z-?Me.CH:C02Et (VII), b.p. 139°/l-5 mm., m.p. CO (4-6%) and CH(CH2Ph)2;C 0 2Et (32-5%) with of R ro varying proportions (according to amount considerable amounts of acidic products; with Ra and 'W UT ])'- (I) and dr-v HC1 (i equiv.) in Et20 the products are CO (58%), CH(CH2Ph)2-C02Et Oirs, o m r .'8^ the unstable, impure enolate, (3S 4% ), and very little acidic material. The m»ri;a+ ^ " 0 O 2Et [which is probably an inter- mechanism of the change is not elucidated. H . W . verfo i 111 0 reaction between (I) and AcCl], con st ml I cold H 2° into (I) and CuCL and by BzCl Optically active anhydrides. I. Anhydride into Cu2CL, (II), (V II); and the Cu11 of d-a-methylglutaric acid. E. B e r n e r and It. -of CHB2zAc-C02Et. (VIII) and HC1 L e o n a r e s e n (Kong. Norske Vidensk, Selsk. I or- 4 iv.) similarly give an impure CICu enolate, handl., 1935, 7, 125— 128; Chem. Zentr., 1935, i, 456 BRITISH CHEMICAL ABSTRACTS.— A. XIV (c, d) 3781— 3782).— Fractional crystallisation of the show that the decarboxylated, demethylated product strychnine salt of dZ-a-methylglutaric acid (I) yields arising from (I) is Py-diketo-8-methylenepentane (VI). d-u-methylglutaric acid, m.p. 81°, [ Quadrivalent com pounds of bivalent copper p-tolyl- and p-bromophenyl-hydrazine gas is rapidly and nickel. See this vol., 410. evolved at about 100°, 100°, 115°, and 1205, Hydrogenation of ketones in presence of nickel respectively. H. W . and platinised nickel. Influence of alkali. M. Change in optical rotation of glucose in dilute Del1!PINe and A. H oreau (Compt. rend., 1935, 201, solutions of boric acid. P. S. T a n o and P. N. 1301—1305).— The rate of hydrogenation of COMe2, S u n g (Nature, 1936,13 7 , 275).— Contrary to previous COMeEt, COMg-C9H 19, COMePh, a-phenyl-p8-di- observations (A., 1932, 120), changes occur in a of inethylhexan- (3-one, cyclohexanone, CH2Ac-CO,Et, glucose in H3B0 3 and Na2B40 7 at certain concns. CHEtAe-C02Et, lsevulic acid, CHMelCH-CHO, For 10% solutions of glucose [a]D falls to a sharp PhCIIO, o- and y)-OH,C0H1-CHO, galactose, fructose, min. with O-lSAf-HjBOs. L. S. T. and a-diethylaminopentan-8-ono to alcohols at room Simultaneous formation of two isomeric iso- temp, and atm. pressure in presence of Raney Ni is propylidene derivatives of 2-methyl-y-methyl- greatly increased by addition of a little NaOH. glucoside. D. J. B e l l (J.C.S., 1936, 186— 187).— Fixation of the second mol. of H 2 by mesityl oxide, The oily product from 2-mcthyl-y-mcthylglucosidc, methylheptenone, and CHPhlCH-COMe is similarly anhyd. CuS04, and 1% H 2S04-C 0M e2 is a mixture accelerated. The effect is not due to enolisation, as of 3:5- and 5 : 6-fsopropylidene derivatives. By it occurs also with COPh2 and Bz2. A similar, but methylation (Purdie), hydrolysis (0-5% HC1 at 100°), smaller, acceleration is caused by platinising the Ni conversion into the p-glucoside, and then into the with a little dil. alkaline PtCl4. Pd, Rh, and Ru have dinitrate, it yields 2 : 3-dimethyl-[3-methylglucosido slight similar effects. The effects of platinisation and 4 : 6-dinitrate, m.p. 99— 100° (lit. 98— 99°). The alkali are additive. R. S. C. material from the mother-liquor with Zn and Fo in Action of magnesium ferf.-butyl chloride on AcOH gives impure 2 : 6-dimethyl-P-glucoside, methyl propyl ketone and ethyl laurate. A. D. characterised as 3 : 4-di-p-toluenesulphonate, m.p. Petrov, K. I. K a r a s e v , and M. A. T so h e lzo v a 157— 158°. R. S. C. (Compt. rend. Acad. Sci. U.R.S.S., 1936, 4, 31— 33, Condensation products of acetoacetic ester. and Bull. Soc. chim., 1936, [v], 3, 169— 176).— With TV. Two highly reactive compounds of glucose COMePr“, MgBuyCl (I) affords some (3-tert.-butyl- and acetoacetic ester. C. U. M o o r e , R. J. pentan-fi-ol, b.p. 68-8— 69-8°/16 mm. (chloride, b.p. E r l a n g e r , and E. S. W e s t (J. Biol. Chem., 1936, W'2—65-o°/12-5— 13 mm.), together with large 113, 43— 47).— Et glucosecycfoacetoacetate (I) (A., amounts of products formed by self-condensation of 1927, 1173) is oxidised by H gS04 at room temp, to a ue ketone, but no Art.-alcohol is obtained with non-cryst. hygroscopic substance (II), C12H180 8, m.p. dmndecyl ketone (II) (reduced to carbinol, converted 65— 72°, [a]“ —70-9° in H 20 (no mutarotation). mto the olofino through the xanthate) (Kipping, (II) rapidly reduces cold Fehling’s solution, and im « 8 ., 1890, 57, 983). Et laurate and (I) in Et20 - mediately becomes reddish-brown when treated with ™cne at 110— 120° give only (II) : 2R-C02Et-> alkali. It gives unstable products with NHPlrNH., ¥'04-CO(CO2Et)2->CO2+Et2O (R=CnH23), but and NH2OH, and immediately affords CHI3 with with MgBu°Ci it affords c-n-bulylhexadecan-z-ol (III), KOI. It contains 3 OH and 1 Ac. Treatment of it P*. ^80—182°/15 mm. (unstable bromide), with with BzCl in CHC13-C 5H5N affords a Bz2 derivative, partial dehydration to c-n-butyl- At-hexadecenc, b.p. C26H2gOj0, m.p. 45— 49°, [?.]q — 52-5° in abs. EtOH ” ¡"~167-5°/15 mm., best obtained by dehydration of (no mutarotation). Oxidation of (I) with B z02H li 'ith H2C20 4 at 140— 180°. Similar results are in H 20-E t0 A c containing BaC03 at 7° gives an obtained with Et palimtate. (I) is not decomposed isomeric product, C12I1180 8, m.p. 57— 60°, [a]?,0 by heating to 1 1 0 ° . J. W . B. —33-4° in H 20, which closely resembles (II), but Diacetyl. J. Pien, J. B a i s s e , and R. M a r t i n contains only 2 OH groups which are reactive towards Ih n ’ 1 6 ’ 119— 138).— The formation of a A c20 . H. W . InW — azono *s recommcndcd as a qual. test Oxidation of a-methyl-d-mannopyranoside. P lotomicrographs of the crystals are given). A E. L. Jackson and C. S. H udson (J. Amer. Chem. Soc., onnictric determination (for dilutions down to 1936, 58, 378— 379).— Oxidation [aq. Ba(OBr)2] of ,m. 100,000) is described. The reagent used is a-methyl-d-mannopyranoside (I) removes C3 and gives '• oylenediamine, which reacts to give a yellow the acid (II), C 02H-CH(0Me)-0-CH(C02H)-CH2-0H 0,our- E. B. H. (Sr salt, [a]j>° —53° in H 20), which does not reduce Yrv!0Inenc*al'ure °1 methylated sugars. E. Fehling’s solution. Hydrolysis (hot H zO) of (II) and 15)T * . Czech. Chem. Comm., 1936, 8, 43— subsequent oxidation (Br-H 20) affords H2C20 4 and „ , la proposed to designate sugar Me ethers as d-glyceric acid, (n) is also obtained by successive . ymglucose etc. and C-Me derivatives as methvl- oxidation of (I) or a-methyl-d-glucoside with H I0 4 g'ucose etc. r . S. C. and B r-H 20 ; (II) should be similarly produced from all the a-methyl-d-aldohexopyranosides. H. B. Formation of osazones. J. K e n n e r and E. C. Glucoside derivatives. E . J o l l e s [in part with forai!r (Ber‘’ 1936> 6 9 ’ 341— 343).— The „ 10a °f osazones is ascribed to the oxidising M. B o t r i n i ] (Gazzetta, 1935, 6 5 , 1217— 1221).— beWQ?LSalts of NH Ph-NlI2. The lattor is stable JEsculin tclra-, m.p. 270° (decomp.), [a]J,8 + 4 6 -9 ° (all „ ’ ^>ul; mixtures of it and its hydrochloride rotations in C5H5N), amygdalin hexa-, m.p. 267° Ijp ence 1° evolve gas at 120° and the reaction (decomp.), [a]{? —25-4°, arbutin tetra-, m.p. 224— 225° mes Ver}’ vigorous at 165°. From o-, m-, and (decomp.), [a][f +23-3°, and salicin penta-Q^-phenyl- 458 BRITISH CHEMICAL ABSTRACTS. A. X Iv (/, 9) carbamate), m.p. 204° (decomp.), [a])? —42-8°, are variation from this % is accompanied by oxidation, obtained by action of PhNCO on the respective frequently with marked increase in the % of C0.,H. glucosides in C5H5N. E. W . W . Native cellulose (I) therefore consists of a chain of 96 C6 units. The presence of 0-28% of C02H can be Saponins from seeds of Barnngtonia asiatica, used as a criterion of the unaltered condition of (I), Kurz. Constituents of the sugar part of A x- but natural conditions appear to exist which induce barrinin.— See this vol., 396. alteration in the crude material. (I) is changed by Saponin-like substance of radix clematidis. NaOH, N H 3, CaC03, and many other substances at See this vol., 396. room tem p.; possibly the fermentative degradation of (I) in the soil is preceded by the action of CaC03. Glycosides of the flowers of Linaria vulgaris, The action of Cl2 in H 20 on (I) causes increase in the Ii. Constitution of linarin and pectolinarin. % of C 02II, and even in very dil. solution the reagent K . W . Merz and Y . H. W u (Arch. Pharm., 1936, 274, is unsuitable for the scientific investigation of poly 126— 148; cf. Schmid and Rumpel, A ., 1931, 738; meric carbohydrates. The technical processes of 1932, 621).— Extraction of the dried flowers with Et20 purifying cotton wool and linters cause chemical removes fatty material from which hentriacontane is alteration in (I). H. W. isolated. Further extraction with EtOH gives mannitol, the phenolic linarin (I), C28H320 14,H20 (cf. X-Ray studies of reactions of cellulose in non- Klobb, A ., 1908, i, 903), m.p. 256° (decomp.) (rapid aqueous systems. I. Interaction of cellulose heating), [a]},8 — 100-1° in AcOH, and amorphous and liquid ammonia. A. J. B a r r y , F. 0. P eter pectolinarin (II), C2nHM0 15, m.p. 240— 250° (decomp.). s o n , and A. J. K in g (J. Amer. Chem. Soc., 1936, 58, (I) gives a A c 7 derivative (III) (+ 2 H 20), m.p. 123— 333— 337).— Cellulose (ramie) (I) swells in liquid NH3 125°, and is hydrolysed (conc. HC1) to glucose, and gives N H 3-cellulose (II) (approx. 1 mol. of NH3 rhamnose, and linareginin (IV), Ci6H i205> m.p. 262° per CgH10O6), the X-ray diagram of which resembles (decomp.) [Ac.z, m.p. 200°, Bz2, m.p. 200°, and Br2-, that of N 2H4-cellulose (Trogus and Hess, A., 1932, m.p. 257° (decomp.), derivatives; M e ether (CH2N2), 149). (II) loses all its N H 3 at 105° and passes into m.p. 170°; M e ether acetate (V), m.p. 196°]. The Ac1 cellulose II [the X-ray diagram of which resembles derivative obtained from (III) and AcO H -H Br in that of hydrate cellulose (III)], which regenerates (II) CHClj is methylated (CH2N2) to (V). (IV) is degraded when treated with liquid N H 3. (II) could not be by conc. KOH in H 2 to HCO„H, anisic acid [also obtained from (I) and dry N H 3 or dil. or conc. aq. formed by oxidation (30% H ,,0o in 15% KOH) of N H 3. (I) is recovered from (ii) by treatment with (IV)], s-C6H3(OH)3, and p-OMe-C6H4-COMe. (IV) H 20 , dil. AcOH, or dil. or conc. aq. NH3. (in) and is, therefore, 5 : 7-dihydroxy-4'-methoxyflavone; the liquid N H 3 give a product resembling (II). H. B. disaccharide residue in (I) is at C7. (IV) is identical Perchlorates as solvents for cellulose and its with acacetin (Hattori, A., 1925, i, 1443), but (I) derivatives.— See this vol., 426. differs from acaciin (loc. tit.). (II) is hydrolysed (conc. HC1) to glucose, rhamnose, and pectolinarigenin (VI), Carbonisation of ramie cellulose studied by C15H80 4(0Me)2, m.p. 215— 216° [Ac2 derivative, m.p. means of X-rays and the ‘ ‘ net density m ethod. 151°; M e ether (CH2N2), m.p. 188°; M e ether acetate C. P a r k (Mem. Coll. Sci. Kyoto, 1935, A , 18, 311" (VII), m.p. 168°; il/e2 ether (Me2S0 4), m.p. 313).— As the temp, of carbonisation, t, is raised from 162°, identical with 5:6:7 : 4'-tetramethoxyflavone 260° to 290°, the X-ray pattern of the C changes from (Robinson and Schwarzenbach, A ., 1930, 785)]. The that of ramie cellulose to that of amorphous C, and Acj derivative obtained from the A c7 derivative, m.p. cl is a min. when t is approx. 290°. J. G. A. G. 134— 138°, of (II) and AcO H -H Br in CHC13 is Organic cupritetra-chlorides and -bromides. methylated to (VII). Degradation (KOH) of (VI) — See this vol., 438. gives HC0.,H, anisic acid, 2:4: 6-(OH)3CGH2-OMe and p-OMe-C6H4-COMe. (VI) is 5 : 7-dihydroxy- McCrae’s test [for salicylic acid]: special test 6 : 4'-dimethoxyflavone. (II) is the 6-OMe-deriv- for hexamethylenetetramine. F. W. Cheng (J- ative of (I). H . B. Chem. Eng. China, 1935,2,137— 138).— McCrae’s test depends on the production of a pink colour with Cellulose of native composition from cotton CH20 and H 2S0 4 disappearing on dilution with HR- wool. II. E. S c h m id t , W . J a n d e b e u r , M. It is more sensitive than the FeCl3 test and is aPFIC‘ H e c k e r , R. Sc h n e g g , and M. A t t e r e r [with W . able to derivatives without previous hydrolysis. lhe H a h n and J. W . P e d l o w ] (Ber., 1936, 69, [B], 366— addition of H 2S0 4 to (CH2)6N4 (I) liberates CH,0 so 374; cf. A ., 1935, 610).— Cellulose from cotton wool the test can be used for detection of (I). C-I- and linters which has not been subjected to chemical [Compounds of] copper ferrocyanide am- treatment but has been purified by the C102 method contains 0-28% of C 02H. This val. is unchanged m oniate.— See this vol., 443. by dissolution of the material in CuO-NH3 and Synthesis of a-amino-p -hydroxypropaRh- rcpptn. by AcOH or (NH4)2S0 4, and is also observed P. A. L e v e n e [with M. K tjna] (J. Biol. Chem., 19% in similarly treated specimens not purified with C102. 113, 153— 156).— CHMoBr-C02H is added gradually Since the latter specimens are free from all known to a solution of Li in CH2Ph-C)H and the mixture j impurity, it follows that cellulose is the sole carrier of heated to 150°, whereby v-a-benzyloxypropionic % ■ 0-28% CO,H and is a carboxylic acid. If 0-28% of (I), b.p. 123— 12870-2 mm., is obtained. It is slow) C 0 2H is present the material is unaffected by the resolved by cinchonidine in COMe2, the most action of CuO-NH 3 and AcOH or (NH4)2S0 4, but a sol. salt giving l-x-benzyloxypropionic acid, b.p- M*" XIV (g-j) ORGANIC CHEMISTRY. 4 5 9 12870-5 mm., [a]“ — 62-5° in CGHG. r-a-Benzyloxy- is treated with NH3 in CHC13, y-benzamidobutyramide, propionyl chloride, b.p. 79— 81°/0-5 mm., is converted m.p. 122— 123°, is isolated in about 10% yield. by NH3 in MeOH at — 10° into v-u-benzyloxypropion- H. W . amide, transformed by boiling SOCl2 into r-a-benzyl- Reactions of maleimide. E. J olles (Gazzetta, oxijpropionitrile (II), b.p. 91— 9 3 °/l mm. Reduction 1935, 65, 1221— 1225).— Maleimide in C5H5N and (Raney) of (II) affords u-amino-^-benzyloxypropane NHPh-OH yield a substance, C10H10O3N2, m.p. 178°, (hydrochloride-, platinichloride, m.p. 207°), whilst regarded as phcnylhydroxyaminosuccihirnidé, which treatment with H 2 in AcOH containing colloidal Pd is oxidised by FeCl3 to PhNO, and on prolonged heat gives r ■v.-mnino-Q-hydroxypropane (platinichlor ide). ing in C5H5N loses H20 to form anilinomaleimide, H. W . new m.p. 209°. NHPh-OH with o-C6H4(CO)20 forms Triethyl - ¡3 -hydr oxyethylam m onium hy dr - o-CGH4(CO)2NPh ; does not react with o-CGH4(CO)2NH ; oxide.—See this vol., 510. and with succinimide or pyrrole gives resinous products. E. W . W . Synthesis of taurine. F. Co r t e se (J. Amer. Chem. Soc., 1930, 58, 191— 192).— Taurine, decomp. Colorimetric determination of carbamide ; 300—305° (corr.) [Ar-phenylcarbamyl derivative, de its determination in blood, cerebrospinal fluid, comp. 195— 200° (corr.)], is prepared in 80% yield and tissues. J. A. Sa n c h e z (J. Pharm. Chim., from CH,Br-CH2-NH2,HBr, m.p. 174—175° (corr.) 1936, [viii], 23, 188— 199).— 0-5— 4 c.c. of 0-01% (modified prep. ; cf. Gabriel, A., 1917, i, 541), and aq. CO(NH2)2 solution and 1 c.c. of 0-02% N aN 02 solution Xa,S03. H. B. are mixed and made up to 10 c.c. with H 20 ; 2 c.c. of pure liquid paraffin and then 30 drops of conc. PI2S0 4 Alkaline hydrolysis of polypeptides [derived are added. The mixturo is kept at 60° for 25 min. from] /-alanine. P. S. Y a n g (J. Chinese Chem. 1 c.c. of a solution of 0-5 g. of p-NR,-CGH4-S03H and Soc., 1930, 4, 37— 41).— The rate of hydrolysis of 0-75 g. of PhOII in 100 c.c. of 2-5% H 2S0 4 is added f-alanyl-, di-, tri-, and tetra-Z-alanyl-Z-alanine by and the colour (due to azo-dye formed by the excess 0-2rV- and Ar-NaOH at 25° is independent of the of H N 0 2) is measured after 5 min. CO(NII2)2 is nature of the peptide, but is much greater with the determined in defibrinated (Folin’s reagent) whole more conc. alkali. Racémisation occurs only at the blood, plasma, or serum by matching against standard beginning of the reaction ; at least 3 N H 2-acicI units solutions. R. S. C. must be present for it to occur. " R. S. C. Cupric and cuprous compounds of thio- Behaviour of di-serine, di-phenylalanine, di- semicarbazide and of its derivatives. V. alanine, di-lactic acid, and propionic acid to H ar la y (Compt. rend., 1936, 202, 324— 325).— wards A'-rays and ultra-violet light.— See this NH2-NH-CS-NII2 with CuS04, Cu(N03)2, and CuCl2 Tolj 137. gives the sulphate, nitrate, and chloride of Cu tliiosemil Photo-decomposition of i-aspartic acid, /-a s carbazide in which the metal is linked to two org. paragine, and glycylglycine.— See this vol., 437. residues- through S. Acetoncthiosemicarbazone in C0Me2-H 20 with Cu(N03)2 and N H 3 gives the Cu Action of alkaline potassium hypobromite derivative [hydrochloride and sulphate (each + 1 COMe2) solutions on the amides of acylated amino- when cryst. from COMe2], which when boiled with aq. on'ds' - J; K a n e v s k a j a (Ber., 1936, 69, [/J], COMe2 gives the Cu1 derivative (sulphate and hydro -w—273).— The formation of cyclic compounds chloride are unstable to H ,0 ). NHyNH-CS-NH2,H01 ‘ wing the Hofmann reaction is characteristic only with CuoO gives the Cu1 derivative, ot amides of acylated 3-NH2-acids ; it is very probable [CuS-C(NH„):N-NH,]HCh easily oxidised in air. o v Hthe c'lan8e cau be used for the determination of J. L. D. ■/-AHj-acids even when they are present in complex Theory of biuret reaction. P. S. Y a n g (J. natural mixtures. Succinimide is converted by trcat- Chinese Chem. Soc., 1936, 4, 27— 36).— Z-Asparagine p n ^ -^OBr followed by KO H and BzCl into and the amides of cZZ-leucine, cZ-alanine, and glycine P enzamidopropionic acid, m.p. 120° (yield 51% ), form amorphous biuret compounds, CuX2, m.p. 302— and \r{fecl successive treatment with SOCl2 304° (decomp.), 248— 250°, 229— 231°, and 205— 207°, m( 3 -GHCI3 into fi-benzamidoprojiionamidc (I), respectively, in absence of alkali, the first two with *‘0—171°. (I) is converted by K O B r-H 20 at CuS04 or Cu(OAc)2, the last two only with Cu(OH)2. 131° T and tetrahydroglyoxal-2-one, m.p. To form a biuret compound a substance must have a vert " 1 . cr «imilar conditions, hippuramide is con- N carrying a replaceable H and a N which can co M * to benzarnidomethylamine (hydrochloride, ordinate with Cu, separated by > 3 atoms ; in some •P- 189—190°) ; occasionally, the reaction is cases the two N are provided by different mois., in Vl^lmTr1^ ky oxidation with production of N H 2Bz. which case 4 mois, of the compound combine with 1- c 1 br2]3-C02H,HCl is transformed by KO H and a 1 Cu. R. S. C. 1 ” i,_oCes? GzCl into y-benzamidobutyric acid (II), Rubidium and cæsium fulminates.—Sec this 90% ), the M e ester, m.p. 59— 60°, of vol., 438. 1 .).jC yiekls y-benzamidobiityraniide (III), m.p. 122— lmu ’ ^ th ,NHa-EtOH. (Ill) and KOBr afford Preparation of hydroxamic acids. G. O ddo ],-;(|Za!'\7L0^ mcthy]eneamme (hydrochloride, m.p. and E. D el e O (Ber., 1936, 69, [B], 287— 294).— Ac n • ? ^ ’s converted by SOCl2 or boiling Hydroxamic acids are immediately formed when an chan - ° ^ '^nzoylpyr roll done, m.p. 91— 92°; if the aldehyde sol. in H20 is treated with 1 mol. of N H 2OH ge is effected at a very low temp, and the product in E tO H -H 20 ancï then with 2 equivs. of 30% H 20 2. 460 BRITISH CHEMICAL ABSTRACTS.— A. X IV (j, I, *»), XV (a) As tho solubility of the aldehyde in H ,0 diminishes curichloride, m.p. 193— 194°, and phenylbenzyldi- reaction takes place less readily and to a limited extent methylarsonium picrate, m.p. 125— 126°, aro described. and does not occur when the solubility is slight. R. S. C. MeOH or EtOH cannot be substituted for H 20 , since Basic organic salts of bismuth, soluble in they are immediately oxidised to the corresponding organic solvents. M. P ic o n (Bull. Soc. ckim., aldehyde. No change takes place in COMe2. If a 1936, [v], 3, 176— 185).— The prep, of bimvlhyl suspension of tho aldehyde in H 20 is used, a sudden cyclo hcxanolacetate, a-carbethoxy-Aa-nonenoate, a- reaction leads to resinous products. Since the carbethoxy-fi-phenyl-n-butyrate, a-carbethoxycydo- reaction is confined to aldehydes sol. in H 20 , the hexylacetate, camphorcarboxylate, and carboxymellujl- possibility is excluded that it depends on a primary nonoate, by double decomp, between the Na salt and ■production of the oxime which is then oxidised by B i(N 03)3 in glycerol is described. These derivatives H 20 2 or that N H 2OH is oxidised by H 20 2 to NOH are sol. in org. solvents, especially CHC13, CBH6, CCh, which is added to the aldehyde. The scheme, and CS2. E. S. H. RCHO+NH,OH=OH-CHR-NH-OH (I), and (I)+ Preparation of tin alkyl and aryl trihalides. H 20 2= 2 H 20 + 0 iT C R IN *0 H is suggested. In sup A. T c h a k ir ia n , M. L e sb r e , and M. L evinsohx port of this view it is shown that CClyCH(OH)2 gives (Compt. rend., 1936 2 0 2 , 138— 140).— KSnCl3,H20 small amounts of tho product CCIyCIROHJ'NlTOH (Rimbach et al., A ., 1916, ii, 332) reacts with the and CHC12-C H (0H )2 yields the unstable adduct appropriate R I at 90— 110° to give (% yields in CHC12,C H (0H )-N H '0H , which immediately decom parentheses) SnMeI3 (43-7), Sn Et tri-iodide, b.p. poses into chloroacelhydroxamic acid (Cu salt) and 181— 184-5°/19 mm. (37), Sn Pra tri-iodide, b.p. OII-CHIN-OH. Under defined conditions MeCHO 200°/16 mm. (<25), Sn Ph tri-iodide, decomp. > 220° and N H 2OH give the substance OITCHMe-NH’OH, (reaction temp. 210°), all formed thus : KSnCI3r immediately transformed bv H 20 2 into OITCMelN-OH. RI->KI+RSnCl3+3IvI->3KCl+RSnI3 : and Sn l¥ The prep, of OH-CHIN-OH, OH-CMciN-OH, trichloride, b.p. 75°/16 mm. (> 40). J. W. B. OH-CEtlN-OII (Cu salt), and OH-CPr-IN-OH (Cu salt) is described in detail. H . W . Configuration of bisdimethylglyoximoammine cobaltic chloride. R. T s u c h id a , M. K obayashi, Additive products of aldehydes with the di and A. N a k a m u r a (Bull. Chem. Soc. Japan, 193G, sodium salt of nitrohydroxylamine and with 11, 38— 40).— By a method for showing the optical benzenesulphonhydroxamic acid; non-exist- activity of racemic substances by asymmetric adsorp ance of the nitrosyl of A. Angeli. G. O d d o and tion on quartz when other methods are not available E. D eleo (Ber., 1936, 69, [B], 294— 298).—No evid (J. Chem. Soc. Japan, 1935, 56 , 1339), it has been ence is obtained of the intermediate formation of found that the above compound is a dZ-mixture, an! nitrosyl NOH, OHN, or HN(OH)2 by tho action of is therefore a cis-compound, or has tho dimethyl- the reagents on N H 2OH and its subsequent union glyoxime groups in the 1 :2 instead of the 1:6 with the aldehyde to the hydroxamic acid and Angeli’s positions. M. S. B. hypothesis should be discarded. CCl3-CH(OH)2 and Substituted ci/ciohexyl nitrites. L. Huxtb SOoPh-NH-OH at room temp, slowly yield the and J. A. M arriott (J.C.S., 1936, 285—286).— adduct, CCl3-CH(0H)-N(0H)-S02Ph, which does not cycloHexyl nitrite, b.p. 31°/10 mm.,rapidly decomposes give the reactions of hydroxamic acids and yielding adipic acid. 2-Iodocyclohexyl nitrite, b.p. is decomposed by warm alkali into PhS02K, 110— 117°/20— 25 mm. (decomp.), is also unstable; CC]3-C(0H):N-0K,H 20 , and a colourless, cryst. com l-phenylcycZohexyl nitrite decomposes when distilled pound probably of cyclic nature. Similarly, p- at 10 mm. 1-, b.p. 46°/12 mm., 2-, b.p. 42°/10 nun., OMe-CgHpCHO and SO„Ph-NH-OH afford tho com 3-, b.p. 45°/12 mm., and A-methyl-, b.p. 45°/14 nun.. pound 0Me-C6H 4-CH(0H)-N(0H)-S02Ph,tI20 , m.p. 1-ethyl-, b.p. 63°/15 mm., 2-bromo-, b.p. 87°/10 nun., 153— 154°, also obtained in presence of KO H if heating and 2-chloro-cyclohexyl nitrite, b.p. 71°/12 mm., are, is avoided. MeCHO and 0N a*N !N 02Na give the however, stable for > 6 months. 2-Bromocydo- adduct, OH’CHMelNfONa) :N 0 2Na,0Na-N:N02Na, hexanol, b.p. 103— 104°/18 mm., is unstable. whilst under similar conditions EtCHO yields the R.S.C. substance 20H -C Et;N (0N a)!N 02Na,0Na,NlN0 2Na, Bixin solutions as colorimetric standards for each of which when dissolved in H 20 give the reactions determ ination of carotene.— See this vol., 396- of hydroxamic acids. H . W . Carotene. X. Comparison of absorption Formation of organo-metalloidal compounds spectra measurements on a- and (3-carotene and by micro-organisms. IV. Dimethyl- and lycopene. J. H . C. Sm it h (J. Amer. Chem. Soc.. methylallyl-n-propylarsine. P. C h alle n g e r and 1936, 58, 247-—255).— Curves are given for a- (I) and A . A . R a w lin g s (J.C.S., 1936, 264— 267).— P. (3- (II) -carotenes and lycopene (HI) using an improved brevicaule on bread crumbs with AsMePr“0 2H or photo-electric spectrophotometer (described in detail)- AsEtPr°02H gives AsMe2Pra and methylethyl-n-propyl- The absorption coeffs. of solutions in EtOH-Et>y arsine (also obtained, b.p. 129— 130°, from MgMel (20%) agree well with those found by Miller et ol- artd AsEtPr“I) [dimercurichloridc, m.p. 171— 172° (A., 1935, 1189); the curves for (I) and (II) are (decomp. 188— 189°); tnercurichloride, m.p. 137— essentially the same as those previously found (A- 13S°; benzylopicrate, m.p. 65— 66°; H N 0 3 leads to 1934, 458) for solutions in 9 5 % EtOH. The “ P'ire methylethyl-n-pro-pylhydroxyarsonium picrate, m.p. carotene” of McNicholas (A., 1931, 1110) is (J-*)- 108— 109°], respectively. Phenyldimethylarsine mer- The coeffs.for solutions of (I), (H), and (III) in CS2differ XV (a, b) ORGANIC CHEMISTRY. 461 considerably from those reported in the lit. (cf. derivative, m.p. 213— 214°, which with hot H N 0 3- Smakula, A., 1934, 1324). Variations in the positions AcOH affords 3 : 5 -dinilro-, m.p. 221°, and 3-niiro- of the absorption max. of (I) and (II), determined 4 - p - tolucncsulphonamido - 4' - methyldiphcnylsulphone, by spectrophotometric and spectroscopic methods m.p. 129— 130°, hydrolysed to 3 : 5-dinitro-, m.p. (supplemented by a Cu-N H 4 filter), are probably duo 216° after softening at 205°, and ‘¿-nitroA-amino-l'- to superposition of the absorption of the filter on that methyldiphcnylsulphone (VI), m.p. 184° [also obtained of the pigment ; the former should be the standard from (III) and N H 3], 4-Chloro-‘i-nitrobenzenesul- method. H. B. phonyl chloride (modified prep.), m.p. 61— 62° (lit. Significance of non-localised linkings of a rom 40° and 60°), with A ld s and CGHG gives 4-chloro-d- atic hydrocarbons in formation of their mole n i trod iph enylsulphonc, m.p. 127°, which is also cular compounds with dipolar molecules.— See obtained (diazo-reaction) from (V) and gives the same this vol., 410. piperidino-, OH-, and NH2-derivatives as does (II). \-Ghloro-'i-nitro-4'-methyl- [obtained from (VI)], m.p. Beryllium bromide as a catalyst in the bromin- 120°, and 2-chloro-5-nitro-diplienylsuIphone (obtained ation of benzene. M. F. T a b o u r y and R. P a j e a u from 2-chloro-5-nitrobenzenesulphonyl chloride), m.p. (Compt. rend., 1936, 202, 328— 330).— Ccll 6 (86 g.) 174°, undergo similar reactions; b-nitro-2-piperidino- is readily brominated in presence of BeBr2 ( > 3 g.). diphenylsulphone has m.p. 178°. Nitration of 4- Excess of Br converts CGHG or PhBr into p-CGH4Br, chlorodiphenylsulphone yields, according to the in good yield. J. L. D. conditions, the W-NOr , m.p. 139— 140° (also obtained Purification and determination of the degree from m -N 02-CGH4-S0.2Cl, A1C13, and PhCl), or 3 : 3'- of purity of toluene. W . Swientoseawski and E. (iV02)2-derivative, m.p. 146°, which latter leads to Rajiotowski (Rocz. Chem., 1935, 15, 422— 429).— 3 : W-dinilroA-piperidino-, m.p. 151— 152°, and -4- Pure PhMe, b.p. 110-612/4°, is readily obtained by amino-diphcnylsulphone, m.p. 238°. 4-Chloro-4'- fractionation with a series of condensers, or with a methyldiphenylsulphone gives similarly 4-chloro-W- special column ensuring slow distillation. Admixture nitro-, m.p. 103°, and -3 : 3 '-dinitro-, m.p. 152°, d 1:1 CGH„-xylene does not affect the b.p., but and 3 : 3'-dinitroA-piperidino-, m.p. 149— 150°, and increases the difference between the b.p. and the A-aminoA'-methyldiphcnylsulphone, m.p. 231°. The temp, of condensation of the vapour by 0 -001° per requisite chloronitro-compound and Na arylsulphinate 00024% of mixture present. R. T. in aq. EtOH or dioxan yield (II), (III), l-miro-5- phcnylsulphonylA-p-tolyl-, m.p. 180°, l-nitro-2-phenyl- Mechanism of aromatic side-chain reactions. sulphonyl-5-p-tolyl-, m.p. 212°, l-nitro-2-phenylsul- Wh—See this vol., 433. phonyl-5-m-nitrophcmyl-, m.p. 233°, and l-nitro-5-m- Action of sulphinates on 2 : 4-dinitrophenyl- nitrophenylsulphonyl-2-p-tolyl-sulphonylbenzene, m.p. sulphones. J. D. Loudon (J.C.S., 1936, 218— 232°. ' R. S. C. ArSjC)2Na reacts with o- and p -(N 02)2-com- pounds, replacing 1 NO.,. The combination, 1-N 02- Naphthalene series. V. 8-Chloro-l-nitro- 4ArS0,, activates A rS02 or Cl in the 6 position, naphthalene and 8-chloro-a-naphthol. N. N. '''inch can then be replaced by Cl, N H 2, OH, or ArS02, V oroschcov and V. V. K oslov (Ber., 1936, 69, efc. Examples are given, in which A r= P h , p-CeH,,Me, \E], 412— 415).— Treatment of 1 : S-NO2*C10H G-SO3Na an»-CGH4-N 02. The constitutions in the PhS02 with HC1 (d 1-19) and NaC103-H 20 in CGH4C12 at series are rigidly proved ; the others follow by ana- 96— 98° and distillation of the product with steam J°gy- 2 : 4-(NO2)2C0H 3*SO2Ph and PhSO,Na (I) in affords the two forms of 8 : 1-C10H gC1-NO2, m.p. jot aq. dioxan or (CH2*OH)2 yield l-nitro-2 : 5- 94— 95° (I) and 125°, respectively, and some 8 : 1- 'phwjlwlphmiylbeiizene (II), m.p. 157— 158°, which C10H cCl-OH, m.p. 67°, formed by hydrolysis. Chlorin » i FPeridine gives 3-nitroA-piperidinodiphenyl- ation of l-C10H 7’NO2 in presence of FeCl3 at 60— Wphone, m.p. 133°, and with N aOH -EtO H gives 70° affords (I), 5 : 1-C10H0C1-NO.,, C10U 7C1, and •nuro-i-ethoxy-, m.p. 147°, and -hydroxy-diphenyl- 1:4:5-C10H 3Cl3. ' H. W . , P"one, ni.p. 137°. l-Nitro-2 : 5-di-p-tolylsulphonyl- (similarly prepared), m.p. 220— 221°, Preparation of halogenomethyl derivatives of . jes similarly 3-nitroA-piperidino-, forms, m.p. 96— naphthalene hydrocarbons. Synthesis of 1 : 2- nj ‘1™ (stable) 107— 108°, respectively, -hydroxy-, and 1 : 4-dimethylnaphthalenes. G. D a r zen s m'P' ! 158°, and -ethoxy A'-methyldiphcnylsulphone, and A. LiiVY (Compt. rend., 1936, 202, 73— 75).— /Vn \ — HA". The appropriate chloronitro- or C10H 8 with a solution of trioxymethylene in A cO H - ^ ¡-comprands with (I) or p-C-H.Me-SOoNa in HC1 at 60° gives 95% (on C10H 8 used) of 1- Z ( ® 2-OH)2 yield o-, m.p. 147§, and p-nitro-, C10H 7-CH2C1, b.p. 148— 150°/13 m m , m.p. 32°; ¿ini 7 ’ anc^ m -P- 156°, and 4-nilroA'-methyl- the use oi HBr leads to l-C 10H 7-CH2Br, m.p. 56°. m-P- 170°- Reduction by SnCL,- 1-C10H-l\Ie similarly gives 1 : 4-C10H GMe-CH2Cl, b.jj. ii 77 affords 2-, m.p. 120— 121°, and 4-amino- 124— 125°/2 mm., m.p. 62° (picrate, m.p. 73— 74°), mn j j . Phenylsulphone (IV), m.p. 181°. p-Sulph- oxidised (alkaline KM n04) to 1 : 4-C10H G(CO2H )2 «««!dodiphmyhulpfume (prep, in CSH 5N), m.p. and reduced (Al, EtOH-HCl) to 1 : 4-C10H GMe2. afivn and hot H N 0 3-A cO H yield the 3-V 0 2-deriv- 2-C’i0H 7Me affords 2 : l-C 10H GMe-CH2Cl, b.p. 125— '¿-■nit’r ^hydrolysed by warm cone. H 2S 04 to 126°/2 mm., m.p. 65° (picrate, m.p. 99°), similarly *1ninodiphenylsvlphone (V), m.p. 169— 170°, reduced to 1 : 2-C10H GMe2, b.p. 265°/770 mm., m.p. at ? 0^tained from (II) and cone. aq. N H 3 — 3-5° (picrate, m.p. 130°). Small amounts of liquid Z:ii (Iv ) gives similarly its p-C^^Me-SO, products are also formed from the C10H 7Me. H . B. 462 BRITISH CHEMICAL ABSTRACTS.— A. XV (6, c) Photochemical formation of organic diradicals is considered to be an intermediate (causing a trans III.— See this vol., 437. ient bluish-violet colour), whilst the substances isolated (by fractional extraction of the brown Dissociable anthracene oxides : effect of nieso- reaction product with various solvents) are 2:5- tolyl groups. A. W ille m a rt (Compt. rend., 1936, dianilinobenzoquinone-l-imine-4-anil (III) (Ac deriv- 202, 140— 141).— Reduction of the appropriate ative, m.p. 212°), probably induline 3B (IV) (and a 9 : 10-dihydroxy-9 : 10-diaryldihydroanthracene with little induline 6B), ^-mauveino (V), and ungrcenabie K I-A cO H affords 9 : 10-di-o-, m.p. 350°, -di-m-, aniline-black (VI) [modified structure suggested (cf. m.p. 221— 222° (block) and -di-p-tolylanthracene Green and Wolff, A., 1913, i, 302)]. p-Benzoquinone (Ingold et al., A., 1927, 141), all giving dissociable and azobenzene are not isolated. The following oxides (evolve 0 2 at 180— 200°) when illuminated reactions are considered to occur : (a) XH 2Ph -> (sunlight) in solution in presence of air. The o-sub- NHPh-OH -> p-NH2-CGH4-NHPh -> NH:CGII4:XPh stituent is least effective in promoting reversible -> (II); (b) the conversion of (II) through emeraldine oxidation. J. W . B. (VII) and nigraniline into (V I); (c) conversion of Dissociable organic oxides. Naphthacene NHIC0H4!NPh into (III) and thence through the formula of the rubenes. Synthesis of 5:6:11:12- dianil and a phenazine into (IV ); (d) oxidative tetraphenylnaphthacene ; its identity with tetra- condensation of N H 2-CgH4-N!CgH4!NP1i and NH2Ph phenylrubene (old rubrene). C. Dueraisse and to give (V). Schemes (a) and (b) are supported by the L. V e llu z (Compt. rend., 1935, 201, 1394— 1396).— observed formation of (VII) from p-N H 2-CGH4-NHPh 6 : ll-Dihydroxynaphthacene-5 : 12-quinone and and (I) (as above); (II) is again an intermediate. MgPhBr give 5 : 12-diphenyl- (VII) is also formed directly from NHPh-OH and (I), naphthacene-6 : W-quinone, m.p. presumably by condensation of 8 mols. and subsequent 284°; with more MgPhBr this oxidation. Oxidation (Fenton’s reagent) of NHjPh yields 6 : ll-dihydroxy-5:6 :1 1 :1 2 - in dil. AcOH gives azobenzene and 2-amino-5-anilino- tetraphenylnaphthacene, converted (VIII) and 2 : 5-dianilino-benzoquinonc-\-anil, m.p. by loss of II20 into dehydro- 202° [also formed from (VIII) and NH„Ph in AcOH]. rubrene (I) and by reduction into H. B. 5 : 6 : 11 : 12-tetraphenylnaphtha- Orthanilic acid (aniline-o-sulphonic acid). cenc, identical with rubrene. Bis- E. W er th eim (Org. Syntheses, 1935, 15, 55—5S).— 2 : 2' - (1 -hydroxy-3-ketoindenyl) o-N 0 2-CgH 4-S02C1, prepared from (o-N02,C6li1'S')!, gives substances not belonging to IINOg, and Cl2, is hydrolysed and the sulphonic acid the rubene series (cf. A., 1935, 1492). The formation reduced with Fe in AcOH. Ch . Abs. (f| of dissociable rubene oxides is due to the 5-, 6-, 11-, 2 : 4-Din.itroaniline. F. B. W ells and C. P. H- and 12-C (cf. CPli3 and mesodiarylanthracenes). A lle n (Org. Syntheses, 1935,15, 22— 23).— 1:2:1 R. S. C. CgII3C1(N02)2 and A c0 2NH 4 yield m-Nitrobenzoylthiocarbimide as a reagent for 2 : 4-(N 02)2CgH3-NH2. The method cannot be the identification of amines. W. L. T u n g , applied to CGH4CkN02. Ch. Abs. (r) Ch eng H en g K a o , Ch u n g H si K a o , and P. P. T. Sa h (Sci. Rep. Tsing Hua Univ., 1935, 3 , [A ], 285— Complex salts of a-phenylethylamine. Equi 289).— m-Nitrobenzoylthiocarbimide, m.p. 94— 95°, is valence of the four co-valencies of bivalent plati obtained by heating NH,NCS in COMe2 with num and palladium. H. R e ih l e n and E. wi-N02-CGH4-C0Cl (I) in CGHG. For use as a reagent (Ber., 1936, 69, [5], 325— 330).— Werner’s hypo its isolation is unnecessary and the m-nitrobenzoyl- thesis of the equivalence of covalencies is applicable , thiocarbatmtes of the following amines are prepared without exception to hexaeovalent compounds, and by slow addition of their solution in warm COMe» to to quadricovalent substances with the exception w a hot mixture of N H 4NCS and (I) in COMe2 and certain Pt and Pd compounds of which so man) treatment of the product with cold H 20 : N H 2Ph, isomerides are known that their existence as stereo- m.p. 153— 154°; o-, m.p. 184— 185°, m-, m.p. 194— isomerides requires special ad hoc suppositions. Jor 195°, and p-, m.p. 178— 179°, -NOo-CGH4-NH2; a-, genson’s proof of the equivalence of the linkings ¡a j m.p. 180— 181°, and p., m.p. 194— 195°, -C10H 7-NH2; tetramminoplatinous dihalides is regarded as un o-, m.p. 1S4— 185°, m-, m.p. 126— 127°, and convincing. It is sought to obtain more suitab e p ., m.p. 158— 159°, -CGH4Me-NH2; NHPh,, m.p. conditions by the use of chemically similar but readi? 150° (decomp.); p-CGH4Cl\NH2, m.p. 1 6 0 ^ 16 1 °; differentiated amines [ ( + ) and (— )-CHPhMe-Eiy> y>-CGH4Br-NH2, m.p. 175— 176°; m-nitro-, m.p. 174— which, with Pd, afford sufficiently labile derivatives. 175 , and m-bromo-, m.p. 182— 183°, -p-toluidine; The replacement of amine linked to Pd by ammo o-, m.p. 205° (decomp.), and p-, m.p. 221—222°, solution, however, takes place so readily that t j -N H2-CGH4-C02H ; NHPhMe, m.p. 135— 136°. results throw no fight on the problem. K 2PtCl4 an H. W . (+)-CHPhM e-NH2 in H 20 at 15— 20° afford fcW- Peroxidase action. I. Oxidation of aniline. (-\-)-ct-phe,nylethylamminoplatinous dichloride, W3 R. J. G. M a n n and B. C. Sa u n d e r s (Proc. Roy. Soc., +62-5° in 50% EtOH. Tetra-(+)-^V^nVm 'Q 1935, B , 119, 47— 60).— NH2Ph (2% solution in dil. amminopalladium dichloride, [a]D +69-0 in 1 AcOH) is readily oxidised by the peroxidase (I) from EtOH, from PdCl, and amine in abs. EtOH a horse-radish or turnips in presence of H 20 2 (concn. 45°, and the corresponding 1 -compound, IV3 maintained at 10— 20 m g.-% ) at p n 4-5 and room - 7 2 ° in HoO, -6 9 -2 ° in abs. EtOH, are tram-- tem p.; benzoquinone-l-aniI-4-p-aminoanilinoanil (II) formed by HC1 at 60° into the frans-compou XV (c, e, /) ORGANIC CHEMISTRY. 463 [Pd(CHPhMe-NH2)oC]2], [«]D -6 5 -5 ° (I) and + 6 5 -8 ° adding an EtOH solution of benzidine ( > 30% (II) in abs. EtOH, respectively. (I) and r- EtOH) to aq. orthotelluric acid. The compound CHPhMe-NH2 (2 rnols.) in abs. EtOH at 35° H 2Tc04,(C8H4-NH2)2 was prepared similarly, using an afford tv&na-di(— )di(v)-phenylethylamminopalladium aq. or EtOH solution of polymetatelluric acid. Excess dichloride, [a]D — 33° in abs. EtOH. Similarly of base must bo used in each case. Solubility data are (I) with (+)-CHPhMc,N H 2 (2 mols.) or (II) with given. H . J. E. (—)-CHPhMe-NH, (2 mols.) yields the optically inactive telra-T-a-phenylethylamminopalladium di Preparation of methyl-substituted azo- and chloride. (II) and (— ) -CHPhMe*NH2 (6 mols.) azoxy-benzenes and rearrangement of the azoxy- afford tri(—)-mono(-|-)-v.-phenylethylamminopadladium benzenes. T. P a r s o n s , jun., and J. C. B a il a r , jun. (J. Amer. Chem. Soc., 1936, 58, 268— 271).— dichloride, [ Influence of degree of acidity on the velocity Nitration of thymol methyl ether. A. E. of the diazotisation reaction. H. A. J. S c h o u t is - T schitschibabin and M. A. B e s t u g e v (Bull. sen (J. Amer. Chem. Soc., 1936, 58, 259— 262; cf. Soc. chim., 1936, [v], 3, 423--124).— 1 : 4 :3 - A., 1921, ii, 34).— The velocity of diazotisation of CGH3McPH-OMe and 98% H N 0 3 in Ac20 at - 2 ° j)-C6H4Me-NH2, o-, m-, and p-CGH4CbNH2, and o- to 3° give poor yields of 2 : Q-ainitro-Z-methoxy-p- M12,C6H4,C02H in presence of varying amounts cymene (I), m.p. 56° (also prepared from the K salt of HC1 is not inversely oc the excess of HC1; reaction of dinitrothymol and KM eS04 in glycerol at 180— does not, therefore, occur between free N H 2Ar and 200°), and 4 : 6-dinilro-m-cresol Me ether (by replace HN02. The results with small concns. of HC1 show ment of Pr0). The odour of (I) is less pleasant than that reaction takes place between [NH3Ar]Cl and that of “ musc-ambrette.” II. B. HN02. The velocity coeffs. (which do not agree with calc, vals.) increase with rise in concn. of HC1 [Application of the Friedel-Crafts reaction to owing to decreased hydrolysis of the salt and a sp. methoxydiphenyl ether.] 0. v o n S c h io k h (Ber., 1936, 69, [B], 242— 244).— Gradual addition of action (being investigated further). H. B. AcCl and Ph20 to sublimed AIC13 gives 4 : ‘i'-dichloro- Chemistry of diazoamino-compounds. J. C. acetyldiphenyl ether (I), m.p. 102°, in 4 3 % yield; E a r l (Chem. and Ind., 1936, 192— 193).— A brief its constitution is established by its oxidation by review. KM n04 to 4 : 4'-dicarboxydiphenyl ether, m.p. > 2 8 5 °. Mesohydry. V. Acyltriazenes; particularly [Di-o-tolyl ether, b.p. 146— 147°/11 mm., is oxidised marked instance of mesohydric isomerism. G. to the corresponding dicarboxylic acid, m.p. 210— Oddo and A. A l g e r in o (Ber., 1936, 69, [£ ], 279— 217°. 3 : 3'-Dicarboxydiphenyl ether has m.p. 235— 282; cf. A., 1932, 44).— Gradual addition of diazotised 240°.] The new group does not invariably occupy XH2P1i to NH2Ac in H 20 at 0° gives colourless acetyl- the 4 position (if free). The directive influence of phenyltriazene (I), m.p. 101— 102°, the Ag salt of which OMe for example may override that of the O between is not affected by PhBr or Mel in MeOH. When the Ph groups. H. W . exposed to light (I) is rapidly transformed into a Polycyclic compounds related to the sterols. red isomeride (II), m.p. 96°, re-converted into (I) V. Methoxy- and hydroxy-derivatives of phen- by dissolution in NaOH and pptn. with HC1. The anthrene. G. A. R. K o n and F. C. J. R u z ic k a absence of colour in (I) camiot be explained by any (J.C.S., 1936, 187— 192).— Q-i-Methoxy-l-naphthyl- of the usual formulae, and the mesohydric constitu etliyl alcohol, m.p. 87°, obtained from 1 :4 - tions AcN-—N~NPh and 0 < ^ “ >N-N:NPli are C]0HGBr-OMe and (CH2)20, with PBr3 gives the bromide (I), b.p. 16I°/1*2 mm., which with Et cyclo- N b/ pcntanone-2-carboxylate yields Et 2-($A-methoxy-\- therefore assigned to (I) and (II), respectively. Similar naphthylethyl)cyclopentanone-2-carboxylate, b.p. -235— but very unstable compounds appear to be derived 248°/l-2 mm., hydrolysed to treated with SOCl2 followed successively by PhOH NHS solution, decolorised with C, and pptd. as the and AlClg yields on fractional distillation p- Ga salt with CaCl2. S. C. OH-C6H4-COPr“, reduced (Zn-HCl) to p-C0H4Bua,OH Halogenosulphobenzoic acids. M. P o l a c z e k (phenylurethane, m.p. 113°), which affords (Reimer- (Rocz. Chem., 1935, 15, 578— 582).— The position Tiemann) 5-butylsalicylaldeliyde, reduced (Adams) of the S 03H of 2-bromo- (Ph2 ester, m.p. 125— 126°) to p-btUylsaligenin, m.p. 81°. P. 0. H. and 2-chloro- (I) (Ph2 ester) -5-sulphobenzoic acid Liquid crystals of some cholesterol com has been established by conversion into 5-sulphosali- pounds. P. Ga u b e r t (Compt. rend., 2 0 2 , 141— cylic acid (II) by hydrolysis with 10% aq. K 2C03 143).—The following compounds melted with chole at 170°, and comparison of its Ph2 ester with that sterol may give liquid crystals: resorcinal, pyrocatechol, from synthetically prepared (II). (II) is obtained in phloroglucinol, pyrogallol, p-nitrophenol, saligenin, 93% yield from o-C0H4GTCO.,H and 20% oleum erythntol.phloridzin, saccharin, fsosaccharin,rhamnose, (100°; 3 hr.). “ R. T. nitrophthalic acid, and agaricic acid. The products are most easily obtained with equimol. proportions Preparation of 2-chloro-4-nitrobenzoic acid. of the two components. Especially if quickly cooled, A. A l b e r t and W . H. L i n n e l l (J.S.C.I., 1936, 55, 54t ).— they may pass to a solid form preserving their optical In converting 4-nitro-o-toluidine (I) into anisotropy but gradually increasing in hardness. o- chloro-p-nitrotoluene (II) by the Sandmeyer re The melting of such hardened products is described. action, max. yields are realised only under carefully controlled experimental conditions. The by-products B. W . R. are 3 : 3'-dinitro-6 : 6'-dimethylazobenzcne and 3 : 3'- Liebermann-Burchard reaction velocities of dinitro-6 : 6'-dimethyldiphenyl. The oxidation of sterols. I. Difference between free and ester (II) to 2-chloro-4-nitrobenzoic acid (III) by K 2Cr20 7 cholesterol applied to the determination of proceeds best -with 1-3 equivs. of the latter. Several cholesteryl esters. II. Test for coprostenol in unrecorded properties of (III) are given. The yields plasma. J. G. R e in h o l d (Amcr. J. Med. Sci., by this process are compared with those obtained 1935, 189, 302— 303, 303).— I. Cholesteryl esters by acetylating (I), oxidising with KM n04, and then (I) and coprostenol (adocholesterol) develop colour applying the Sandmeyer reaction. The identity of with Ac20 and H 2S0 4 more rapidly than does the 1 :2 : 4-nitroanthranilic acid obtained as an cholesterol (II). The difference is moro marked intermediate with the so-called “ 1:2:5 ’’-nitro- at low temp, and with dil. H 2S0 4, and disappears anthranilic acid of Ulknann is shown, and a no. of with high temp, and much acid. The Liebermann- unrecorded properties arc given. The reactions Burchard reaction at 0° in presence of 0-025 c.c. of (I) -> (III) gave lower yields in the case of the hyS04 determines (I), a small correction being neces- analogous Br-compounds. sar\'for free (II). At 38° the total (II) is recorded. If Coprostenol is determined as (I). None occurs Organic reactions with boron fluoride. XII. »plasma. Cn. Abs. (p) Preparation of esters of aromatic acids. F. J. Sexual hormones. XII. Amines of the S o w a and J. A. N ie u w l a n d (J. Amer. Chem. Soc., androsterone series. L. R u z ic k a and M. W . 1936, 58,271— 272).— C0H4R-CO2Alk are formed when C6H4R-C02H and AlkOH are heated with BF3 Ooldbeeg (Helv. Chim. Acta, 1936,1 9 , 107— 108).— (amount for max. yield varies with R) or BF3,Et20 ; ftrra tCr0ncox“ ne reduced by Na and boiling in general, estérification occurs less readily than with kH *° $ s'17-amirio-3-Kydroxyandrostane, m.p. 187— w (hydrochloride, m.p. about 365° after much de- AlkC02H (A., 1932, 728). The following are romp.). Similarly tmns-A5:6-dehydroandrosterone prepared : Me, Pte, Bu", Bd3, and sec.-Bu benzoates ; p -N 02-C6H4-C02Me ; o- and p-NH o-C0H4-CO2Me ; freS 1traTls'i'5 : -amino-S-hydroxyaiidrost&ne, m.p. o-C6H4CbC02Me ; o-OH-CUIyCOAIe ; Ph I • [hydmchloride, m.p. about 300° (decomp.)], ^biologically these compounds are much less active o-OH-CVH,-CO,Bus. BiVOBz is not prcparablc. a" tiie corresponding 17-OH-derivatives. H. B. y-Phenylbutyric acid. S. C. Overbaugh, C k- H - W ' omhined cestriol in human pregnancy urine. C F H. Allen, E. L. M a r tin , and L. F . F ie s e r (Org. Syntheses, 1935, 15, 64— 66).— CH,Bz-CH2-C02H is - S e e this v o l., 5 0 3 . reduced with Zn and HC1. C h. A b s . (r) Colourless compounds which accompany rarotenoids in plants.— See this vol., 533. Asymmetric carbon atom CHDR'R". I. Constitution of a deutero-(l-phenylpropionic acid Catalytic reduction of aromatic carboxylic from cinnamic acid and deuterium. H. E r l e n - sters. Sec this vol., 436. m e y e r and H. G a r t n e r (Helv. Chim. Acta, 1936,19, substituted benzoic esters.— See 145— 14S).— Treatment of CHPh ! GH • C O.Jl with m vol., 432. nascent D causes complete replacement of H by D. of Lm^ara^on cal°iuni or ammonium salts A12S3 and D 20 gives D2S, transformed by I in D20 ,1 D1oxybenzoic acid. F. R. Greenbaum (Amer. into D I which, in presence of red P, converts a L u T - 1 0 8 , 17— 22).— Very pure Ca CHPhICH,C02H into C6H2.18D2.g2,C2H1.G2D2-j8-C02H and Tr\ nzoate> free from the corresponding I - (I) which pas-ses when treated with Br and subse , ' comPounds and Cl, is obtained in excellent quently heated into CçH2.18D2.g2'C2HQ.74D1.28*G02il in dil H ^ idising o-CgH4I-C02H (prep, described) and is oxidised by K M n04 to CBH2.18D2.82-C 02H. c n X ' 2, 4 susPension with K B r03 at 85°. The Attempts to resolve (I) into its optical antipodes acid ls extracted with hot EtOH, dissolved in have been unsuccessful. H . W . 46S BEITISH CHEMICAL ABSTRACTS.— A. Condensation of esters of unsaturated acids (III) in EtO H -N aO Et gives the (B-diethylaminoetliyI with carbamide. II. Z. Jerzmanowska-Sien- ester (hydrochloride, m.p. 103°). H. B. kiewiczowa (Rocz. Chem., 1935, 1 5 , 510— 515).— Am inohydroxy-acids and their degradation CHPh:CH’CO.,Et and CO(NH2)2 (I) in EtOH in in the animal body. F. K n oop , F. D itt, W. presence of NaOEt yield cinnamojicarbamide (II) Hecksteden, J. M a ier, W . M erz, and R. HIrlk or cinnamamide (III), according to the conditions of (Z. physiol. Chem., 1936, 2 3 9 , 30— 46).— a-Amino- the experiment. (II) affords cinnamic acid and (III) (3-hydroxy-acids (I) are not degraded in the same when heated with EtOH -N aO Et or M eOH-KOII, manner as simple N H 2-acids, but are transformed cyanuric acid and (III) when heated alone at 210— by (1-oxidation into N-free acids containing fewer C. 220°, and 6-phenyldihydrouracil when fused with oc-Amino-(3-keto-acids, presumably intermediate pro (I) (180— 185°; 2-5 hr.). Fumaric acid and (I) ducts of the degradation of (I), have a very high (135— 140°; 2-5 hr.) yield biuret, triuret, and redox potential, much > that of ascorbic acid. hydantoin-5-acetic acid. R. T. CH2Ph-C0-CH2-C02Et is transformed by PhN2C1 and NaOAc in E t 0 H -H 20 into the corresponding o-Phenylpentadecoic and -/-phenylbehenic phenylhydrazone, C18H 180 3N2, m.p. 67°, which is acids. G. M. H ills and R. R o b in so n (J.C.S., 1936, converted by hydrogenation (Pd-C in 5% HC1- 281— 283).— Condensation of Et sodio-v-keto-|i-carb- EtOH followed by Pt-Fe in H 20) and subsequent ethoxymyristate and CH2Ph-CH2Cl and subsequent hydrolysis into a-amino- (i-hydroxy-y-phenylbutyric acid, hydrolysis by 5 % H2S04 and then by 3-5% aq. KO H decomp. 259° (Bz1 derivative, decomp. 181°); (?) leads to v-ketomyristic acid (4 6 % ; Et ester, b.p. 2 : 5-dibenzyl-3 : Q-dihydropyrazine, m.p. 75—76°, is 145— 160°/0-5 mm., m.p. 28—29°), and v-keto-o- formed as by-product. CH2Ph •CHyCH 0 and plienylpentadecoic acid (20%), m.p. 76—77° [semi- CH2(C 02H)2 arc condensed in C!5H5N at 90° and carbazone, m.p. 87—88°; Et ester (crude), m.p. the Na salt of the resulting acid, m.p. 103—104°, 33— 35°], reduced (Clemmensen) to o-phenylpenta- is transformed by Br into a-bromo- fi-hydronj-i- decoic acid, (I), m.p. 60— 61°. jc-Phenyldecoyl phenyl-n-valeric acid, m.p. 94— 95°. The correspond chloride, b.p. 204°/14 mm. (decomp.) (anilide, m.p. ing Et ester, b.p. 157— 163°/0-5 mm., is transformed 71— 72°; gives the Et ester, b.p. 199°/13 mm.), leads by NaN3 in E tO H -H 20 into the azido-cstev, decomp. similarly to v-keto-x-phenylbehenic acid, m.p. 81°, 100°/high vac., which is hydrolysed arid then reduced reduced to x-phenylbehenic acid (II), m.p. 81° (Et (Pt02 in anhyd. EtOAc) to a-amino-fi-hydroxy-i- ester, m.p. 53°). (I) and (II) cannot be injected and phenyl-n-valeric acid, decomp. 246° (Bzi derivative, arc unchanged when fed to rabbits. R. S. C. decomp. 196°). The Bz derivative, m.p. 175—17dt and the hydantoin, m.p. 191— 193°, of hydros)- Chemical constitution and local anaesthetic glutamic acid are described. a-NH2- and a-OH-acih action of alkamine esters of p-alkoxybenzoic react with Pb(OAc)4 in AcOH at 60— 70° with loss of acids. C. R o iq la n n and B. S chetjrle (Arch. C 02 and according to the principle of Criegee’s glvcol Pharm., 1936, 2 7 4 , 110— 126).— fission. Introduction of acyl into N H 2 or OH p-O R,CeH4,C 02,CH2*CH2Cl (I) (usually prepared from inhibits the reaction. Criegco’s assumption that the OR-Cgilj-COCl and CH2C1-CII2-0H ) and N H Et2 at method permits diagnosis of the groups •NH,CH,COiH 110° give p-OR’CgHyCOyCHyCJHyNEtg [isolated as is therefore too general. After acylation, therefore, the hydrochlorides (II)], which are local anaesthetics. serines and isoserines can be distinguished from one The influence of R on the activity is Me < Et < H < another by Criegee’s method. H. IV. Pr < Bu, isoamyl; Pra and Bu" impart more activity than Pr8 and Bu8. Introduction of NEt2 into R Iodination of nitrotyrosine. H. B au er and t. causes diminished activity. Increase in length of the Strauss (Ber., 1936, 69, [£], 245—246; of- A, alkamine group arid introduction of Aik in the 1935, 1122).— Slow passage of IC1 vapour into a 3 position cause increased activity. The following solution of (-tyrosine in dil. HC1 at 10° gives 3:-> are described : (I) R =11, m.p. 110°, M e, Et, m.p. 46°, di-iodotyrosine, decomp. 194°. Nitrotyrosine hydro Bua, m.p. 32°; (II) R = H , m.p. 183°, M e, m.p. 146°, chloride is converted similarly into 5 -iodo-3-nitro- Et, m.p. 174°, Pra, m.p. 137°, Pr8, m.p. 128°, Bua, tyrosine. H. VI. m.p. 147°, Pa8, m.p. 131°, isoamyl, m.p. 128°, allyl, Synthesis of certain alkeines derived m.p. 130° (lit. 193°) [from p-C3H ,0 -C BH4-C02H mandelic and tropic acids. E. P l a ze k and /■ (1 mol.), N E t2-CH2-CH2Cl (III) (1 mol.), and E tO H - R o d e w a ld (R ocz. Chem., 1935, 15, 481— 490).-- NaOEt (2 mols.)], and $-diethylaminocthyl, m.p. 180° The cyanohydrin obtained from COPhMe in E w [from p-0H -C 6Ii4-C02H and (III) in EtOH-NaOEt]. AcOH, and KCN at 0° yields when heated with y-Dicthylaminopropyl p-ethoxybenzoate hydrochloride, HC1 (130°; 3 hr.) CH2Cl-CHPh-C02H, the Me ester, m.p. 148°, is prepared from p-0E t-C BH4-C0Cl arid b.p. 93°/0-4 mm., of which affords M e fi-ethoxy-*- Cl[CH2]3-OH followed by N H Et2. z-Diethylamino- phenylpropionate (O-ethyltropale) (I), b.p- amyl anisate, p-ethoxybenzoate, and p-butoxybenzoatc 100°/0-3 mm., when treated with NaOEt in EtOlt hydrochlorides, m.p. 131°, 82— S3°, and 56°, respect The acid has b.p. 132— 134°/0T mm. (chloride, ively, are obtained from p -0R -C BH4-C02Na arid b.p. 88— 89°/0-6 m m .; dimethylaminoethyl ester, (CH2)5Br2 followed by N H Et2. Me p-allyloxybcnzo- b.p. 110— 112°/0-l mm.). $-Propoxyia-phenylproP' atc rearranges at 220— 250°' into Me 4-hydr6Xy-3- ionic acid, b.p. 135— 137°/0-15 mm. (chloride, b.p- allylbenzoate, converted by Pr°Br and KOH in 96— 97°/0-3 m m .; M e ester, b.p. 108°/0-l inm:; COMeEt followed by hydrolysis (10% NaOH) into dimethylaminoethyl ester, b.p. 113°/0T minA 4-propoxy-3-allylbenzoic acid, m.p. 13S°, which with obtained analogously. Tropyl, b.p. 169— 171/0' XV (k) ORGANIC CHEMISTRY. 469 mm. (picrate, m.p. 216—217°; picrolonate, m.p. AcOH gives a dehydro-acid, m.p. 222—223°, [a]i, 155—156°), and dimethylaminoethyl, b.p. 108— 110°/ +87-21° in 90% EtOH (Me ester, m.p. 136— 138°). 0-2 mm. (picrolonate of methiodide, m.p. 139°), #- W . McC. ethoxy-o.-phenylacetate (O-ethylmandelate) have been Fused rings. I. P. C. Mitter and D. K . prepared from the appropriate alcohols and ethoxy- B anerji (Ber., 1936, 69, [B], 456— 458).— Et phenylacetyl chloride, b.p. 84— 85°/0-4 mm.; tropyl, 2-methylcycZopentan-l-one-2-carboxylate, b.p. 170— 172°/0-4 mm. (picrate, m.p. 106°; picrolon C02Et-CHBr-CH2-C02Et, and Zn wool activated by ate, m.p. 164°), and dimethylaminoethyl, b.p. 110— 1 in anhyd. CGHG give a mixture of unsaturated and 112°/0-2 mm. (jncrate of methiodide, m.p. 162°), OH-ester transformed by P20 5 in boiling C6HG into 0 -propylmandelate were obtained similarly from the unsaturated ester, C17H2G0G, b.p. 176— 178°/3 propoxyphenylacetyl chloride, b.p. 85— 86°/0-8 mm. mm., which is hydrogenated (Pt02-E t0 H ) to Et., R. T. 2-carbethoxy-2-mcthylcyc\opentylsuccinate (I), b.p" Manufacture of arylamides of 2-hydroxydi- 173— 175°/4 mm. (I) with Na in boiling CGHG phenyl-3-carboxylic acid and of azo-dyes there affords Et2 7-methyldicyc\o-[0 : 3 : 3]-octo«-l-one- from.— See B., 1936, 229. 2 : 3-dicarboxylate, b.p. 150— 178°/3 mm. (slight de comp.) (semicarbazone, m.p. 195°), hydrolysed by Abnormal strength of 2 : 6-dihydroxybenzoic KO H -EtO H to the corresponding non-cryst. acid, acids. W . B a k e r (Nature, 1936, 137, 236).— The which slowly vields a semicarbazone, decomp. 198— increased acidity of salicylic acid and its derivatives 200°. H. W . over that of BzOII and other liydroxybenzoic acids is probably due to chelation of the anion, which would Thermal decomposition of the silver salts of hinder return of the proton and hence increase dis carboxylic acids. II. Experimental evidence sociation. By analogy with 2-nitroresorcinol, it of the reaction mechanism. S. J. K a n e v s k a j a , is suggested that an ionised C 02H can chelate with M. M. Sch em jakin, and E. M. B am d ass-Sc h em jakina two o-OH groups. L. S. T. (Ber., 1936, 69, [B\, 257— 265; cf. A., 1934, 1219).— Isolation of intermediate products and their behaviour Decomposition of phenolic ethers. III. when heated with Ag20 shows that thermal decomp, Thermal decom position of piperonylic acid in of the Ag salts of aklehydocarboxylic acids follows the presence of sand, acid clay, or active carbon. course : 2CH0-Rn-C02Ag -> K. 0 no and M. Imoto (J. Chem. Soc. Japan, 1935, CH0-RII-C0-0-C0-Ru-CH0+ Ag20+2A g+ 56, 347— 352).— When heated with the above cata lysts at 260— 280°/130— 135 mm., piperonylic acid C02H-Rn-C0-0-C0-Rn‘CH0 -> R ir< c O > ° + yields o-C6H4(OH)2 and a little pyrocatechol Me ether. Ri-C H 0 + C 0 2. Cautious heating of Ag opianate Ch. A bs. (r ) affords opianic anhydride (I) and products among Veratronitrile (3 : 4-dimethoxybenzonitrile). which heinipinic anhydride (II) is identified. Treat J. S. B uck and W . S. I de (Org. Syntheses, 1935,15, ment of (I) at a higher temp, with excess of Ag20 85—86).— 3 : 4-(OMe)2C6H3-CtIO is converted into yields about 30% of (II) and 20% of veratraldehyde. the oximo, which is then dehydrated with Ac20. About 21% of (I) remains unchanged and 5 % of Ch . A b s. (r) opianic acid is isolated. Similarly, Ag bromo- Homoveratric acid. H. R. S n y d e r, J. S. B uck , opianate yields about 16% of bromo-opianic anhydride, «nd; W. S. Id e (Org. Syntheses, 1935, 15, 31— 34).— about 25% of bromoveratraldehyde, 0-2% of bromo- dhe prep, is described in detail. Ch. A bs. (r) hemipinic anhydride, and 20% of bromohcmipinic Stability of aqueous solutions of potassium acid (probably a secondary product formed from traces hydrogen phthalate. I. H offm an (J. Res. Nat. of H 20 in the Ag salt and the anhydride); broino- ™r. Stand., 1935, 15, 583—584).— 1% aq. K H veratric acid does not appear to bo formed. Bromo- phthalate solution is permanently stable under labor hemipinimide has m.p. 236—237°. H. W. atory conditions. J. S. A. Choleic acid [complexes]. K. Y a m a s a k i (J. Biochem. Japan, 1935, 22, 243— 249).— The mixed Rabbits bile. I. a- and ¡3-Lagodeoxycholic m.p. method (A., 1929, 925) indicates the formation acid and lithocholic acid. S. K ism (Z. physiol, of a 4 : 1 deoxycholic acid (I)-p-carotene complex, bhem., 1936, 238, 210— 220).— From the bile there m.p. 167°. Treatment of the unsaponifiable fraction rave been isolated a-lagodeoxycholic acid (I), C24H40O4,. of cod-liver oil with EtOH -(I) yields complexes of (I) rap. 156— 157°, [a]“ + 80-21° in 90% EtOH [Ba with high alcohols (mainly selacliyl). The fraction, ono/ Me ester> m -P- 107— 108°, [a]?,2 +73-97° in m.p. 185°, converted into the xylene derivative and ■ J /o EtOH ; Et ester, m.p. 135°; fonnyl derivative hydrogenated, affords batyl alcohol (II). M.-p. curves 01), m.p. 202°; M e ester of (II), m.p. 103— 104°; indicate a (I)-(H ) (8 : 1) complex, m.p. 186-5°; such acetate (III), m.p. 188— 189°; M e ester of (III), a complex, m.p. 186— 187°, [a%° +47-37° in EtOH, mp. 144°], (i-layodeoxycholic acid (IV), m.p. 213°, crystallises from (I) + (II) in aq. EtOH. I . O. H. WS +37-43° in 95% EtOH (Me ester, m.p. 175°; « ester, m.p. 172°, [a])? +34-05° in 90% EtOH), Toad bile. III. Trihydroxyisosterocholenic and lithocholic acid. (I) gives dehydrodeoxycholic acid, C28H4g0 5, from winter bile. IV. Con acid when oxidised with Cr03 in AcOH and deoxy- stitution of trihydroxybufosterocholenic acid. 1. Shimizu and T. K azuno (Z. physiol. Chem., 1936, nonoV'u acid whcn oxidised With H N 0 3. Heated at -6 ,about 12 mm. and distilled in a high vac. (I) 239, 67— 73, 74— 75; cf. A., 1934, 1219).— III. Ex chdUtdie^ acid, m.p. 135— 137°, which with haustive extraction of the bile with Et20 , directly or 2 Ilia gives cholanic acid. (IV) with Cr03 in after saturation with C 02, and further acidification 470 BRITISH CHEMICAL ABSTRACTS.— A. XV (k, I) with AcOH or mineral acid gives triliydroxybufo- 154° transformed by boiling 9 5 % H C 02H into Me H sterocholenic acid (I), which is removed as the cryst. orcinoldicarboxylale M e2 ether, m.p. 124° (converted at Me ester; fractionation of the mother-liquors with 200° into Me p-orsellinate Me2 ether, m.p. 84°), and O-liY-NaOH affords trihydroxyisosterocholenic acid thamnol M e2 ether, m.p. 104° (semicarbazone, m.p. (II), C28H4g0 5, m.p. 227°, [a]“ +46-95° in MeOH, 216°), which dissolves in K O H to a yellow solution, which contains three sec.-OH and one double linking, does not give a colour with EeCl3, and is unaffected adds Br, and decolorises K M n04. (II) gives a Me by H 20 2 in alkaline solution. (II) is therefore ester, m.p. 220°, and is oxidised by Cr03 in AcOH to 6-4'-carboxy-3'-hydroxy-5'-methoxy- o -toluoyl-4-alde- trikeloisosterocholenic acid (III), C28H40Ô5 (Me ester, liydo-3 : 5-dihydroxy-o-toluic acid. m.p. 184— 186°, and its trioxime, decomp. 231°). L X V . Exhaustive extraction of the thalli of Reduction of (III) with Zn-H g in AcOH-HCl gives Ramalina farinacea, Acli., var. nervulosa, Mull. Arg., isosterocholenic acid, C28H40O3, m.p. 186-5— 187° (Me with Et20 affords sckikaic acid, the mother-liquors of ester, m.p. 117°), which adds Br, decolorises K M n04, which contain ramalinolic acid (IV), C23H280 8, m.p. does not give the Liebermann reaction, and is hydro 163— 164°, which gives an intense blood-red colour genated (P t02 in EtOH) to isosterocholanic acid, m.p. with alkali in EtOH, a violet-red colour with FeCL,, 149— 149-5° (Na and K salts; M e ester, m.p. 90— but no colour with CaOCl2. It is hydrolysed by 90-5°). Reduction (P t02 in AcOH) of (II) affords alkali to divaricatic acid and an acid, C12Hlfi0 5, m.p. trihydroxyisosterocholanic acid, m.p. 200° after marked 163°. Prolonged treatment of (IV) with CH2N, in softening at 133°, [a]D +38-96° in MeOH (Me ester, Et20 yields the corx-esponding M e ester Me3 ether, m.p. 162°), which is oxidised by Cr03 in AcOH to m.p. 75°, hydrolysed by K O H -E tO II to divaricatic triketoisoslerocholanic acid, m.p. 234° (Me ester, m.p. acid Mo ether, m.p. 63-5°, and M e amylpyrogallol- 223— 224°), also formed by hydrogenation (Pd-black carboxylate M e2 ether (V), m.p. 72—73°. Et 3:4:5- in EtOH) of (III). Bromination of (II) in AcOH trimetlioxybenzoylacetate is converted by Na and yields a Br-laclone, C28H4B0 5Br, m.p. 202°, insol. in Pr“i in EtOH into Et a-3 : 4 : 5-triniethoxybenzoijl-n- N H 3 ; (II) therefore appears to contain the double valerate, b.p. 214— 216° (trimethoxyphenylpropyl- linking in the side-chain and in the 8-position to C 02II. pyrazolone, m.p. 223— 224°), hydrolysed by 10% (II) does not givo the Hammarsten reaction so that KOH-EtOH to 3 : 4 : 5-trimethoxyvalerophcnone (VI), the three OH are not in the same position as in (I) or b.p. 190—-192°/6 mm. (semicarbazone, m.p. 145— cholic acid. (I) and (II) can be readily isolated from 146°). Treatment of (VI) with cone. H ,S 0 4 at 38° summer bile, which contains much < winter bile. leads to ■i-hydroxy-3 : 5-dimethoxyvalerophenone, m.p. IV- Ozonisation of Mo trihydroxyfsosteroeholenate 89— 90° (oxidised b}r K 2Cr20 7 and 10% II2S04 to in cold AcOH or oxidation of it with Cr03 in warm 2 : 6-diinethoxy-p-benzoquinone), which is reduced solution gives products which do not depress the m.p. (Clemmensen) to ‘i-hydroxy-3 : 5-dimethoxy-l-n-amyl- of a-bisnorcholanic acid and its Me ester. The double benzene (VII), b.p. 175°/7 mm. (Bz derivative, m.p. linking of (I) is therefore in the S-position to the C 02II 89°). (VII) is converted by HCN-HC1-A1C13 into of the side-chain. H . W." 3-hydroxy-2 : ‘i-dimethoxy-ti-w-amylbenzaldehyde, m.p. 52°, which is treated with ClC02Et in C5H3N at —15° Lichen substances. LXIII. Components of and then oxidised by K M n04 in COMe2 whereby B œ om yces varieties. Y. A s a h in a , Y . T a n a s e , 3-carbethoxy-2 : i-dimelhoxy-6-n-amylbenzoic acid, and I. Y o sio k a . LXIV. Constitution of tham- m.p. 110— 111°, is produced, transformed by CH2N2 nolic acid. IV. Y. A s a h in a and M. H ir a iw a . and subsequent hydrolysis into (V). (IV) is therefore LXV. Ramalinolic acid, a new depside. Y. 5-2'-hydroxy-4'-methoxy-6 '-propylbenzoyl-4 : 6-di- A s a h in a and T. Iv us a k a (Ber., 1936, 69, [B], 125— hydroxy-2-amylbenzoic acid. H. W. 127, 330— 333, 450—455).— LXIII. Extraction of B. Acids contained in the wood of Libocedrus placophyllus, Ach., with Et20 followed by COMe, form osna, Florin.— See this vol., 395. affords stictic acid, m.p. 272° (decomp.) after softening at 230°. Similar treatment of B. rosens, Pers., yields Interaction of hydrogen sulphite derivatives of bæomycesic acid, (I) decomp. 222° [anil, m.p. 211° aromatic aldehydes with potassium cyanide. S. (decomp.)] (cf. Roller, ct a l, A ., 1935, 1432). Me S ch uster (J. Pharm. Chim., 1936, [viii], 23, 142— bœomycesate, m.p. 207°, is reduced (Pd-C in AcOH) to 145).— The Na2S0 3 compound of PliCHO with KCh Me barbatate ; since it is also formed by the partial gives OH-CHPh-CN and a 12% yield of iV-benzyl- méthylation of atranorin, (I) is 4-3'-hydroxv- idenemandelamide [Ac derivative, m.p. 121° (block)], 4'-aldehydo-5'-methoxy-o-toluoyl-2-hydrox3'-3 : 6-di- converted byr HC1 in Et20 into a CZ-derivative. methylbenzoic acid. C15H120NC1, m.p. 164°, converted by alkalis into 2 : 4- L X IV (cf. A ., 1929, 818 ; 1932,275). Examination diphenyloxazole. Similarly the Na2S0 3 derivative of technical thamnolic acid (II), obtained by extraction of p-OMe• C6H4• CHO gives a substance, C25H210 5i»2’ of Cladonia polydactyla with COMe2, discloses the m.p. 154° (block), and resinous products. ^ ^ presence of dccarboxythamnolic acid (III), m.p. 215° (decomp.) (anil; p-nitrophenylhydrazonc, m.p. 219°), Action of acid chlorides on Schiff’s bases. also obtained when (II) is heated in C0Me2 at 120— Additive products of these bases. I. T a n a sesc c 130. (Ill) and CH2N2 in COMe2 at 0° give the M e and A . Selberg (Bull. Soc. cliim., 1936, [v], 3, 224— ester, m.p. 163°, whereas treatment of (III) with Mel 239).— Schiff’s bases, CHRINPh, and acid chlorides, and Ag2C03 in Et20 gives the M e ester M e2 ether, m.p. R'-COCl, in neutral solvents ppt. hydrochlorides, 183°. Exhaustive treatment of (III) with Ag„0 and CHR:NHPh}Cl (I) and N H 2Ph,HCl in varying pro Mel in boiling E t„0 yields the M e ester M ez ether, m.p. portions, whilst the solution contains R'CBU, XV (I, m) ORGANIC CHEMISTRY. 471 R'-C02H, and R'-CO-NHPh. lleaction does not occur a - Tetralone (a -ketotetrahydronaphthalene ). in complete absence of H 20 and depends 011 hydro E. L. M artin and L. F. F ieser (Org. Syntheses, lysis first of R'*COCl and then of (I) (demonstrated 1935, 15, 77— 79).— Ph-[CH2]3-COCl is treated with . on the isolated compound). Experiments are quoted AlClg in CS2. Ch . A b s. (r) in which R = P h , 0-, m-, and y)-N02'C6H4, R'=Me, Ternary catalyst Cu-Zn0-Cr20 3 as hydrogen Ph, m-NO2-C0H4. Addition to SchifF’s bases occurs ation catalyst.— Sec this vol., 298. on the N ; reaction -with Br proceeds th u s: CHR!NPhBr„ -> HBr+[CH RINPhBrjOH -> Molecular conversion of ketones into [dif OH-CHR-NPhBr -> R-CHO+H20+NHPhBr -> ferent] ketones by the action of zinc chloride at NH2-C6H4Br (II), followed possibly by bromination high temperatures. M. A. F avo r sk i [with (Ml l e .) of R-CHO or (II). Hydrochlorides of bcnzylidene-, T. E. Z alesskaja, D. I. R osanov, and G. V. m.p. 176°, m-, m.p. 181° after previous sintering, 0-, T sciielincev] (Bull. Soc. cliim., 1936, [v], 3, 239— m.p. 156°, and p-nitrobenzylidene-aniline, m.p. 190— 248).— Ketones, CRyCOPh (R is aliphatic), with 193°, are described. R. S. C. ZnCl2 at about 320° give CPhRyCOB, but ketones with no lert.-C decompose. Isomérisation may Hydrogen cyanide. V I. M echanism of G at- proceed by way of an oxide or by direct interchange termann's hydrogen cyanide aldehyde synthesis. of position between O and two radicals. COPhEt L. E. H estcel, E. E. A y l in g , and J. II. B e yn o n with ZnCl2 at 320— 330° gives CO, C 02, BzOH, (J.C.S., 193G, 184— 185).— Resorcinol (I), HCN, and EtC02H, H20, C2H4, Cr>Hr„ PhPr, and CHPlnCHMo; HC1 at room tempi, give resorcylaldehyde (72%), pyrolytic decomp., hydrolytic fission of the ketone, and at 0°, the solid, m.p. 1G6— 170° (decomp.), first reduction to the hydrocarbon and alcohol, and formed, corresponds with a mixture of aldiminc hydro dehydration of the alcohol must occur simultaneously. chloride and dichloromothylformamidine hydro cycloHexyl Ph ketone (semicarbazone, m.p. 167°), chloride. Iminoformylcarbylamine, HG1, and (I) obtained from cyc/ohexylphenylcarbinol, with ZnCl2 yield resorcylmcthyleneformamidine hydrochloride, m.p. at 350— 450° gives CO and phenylcyclohexane, b.p. 135° (decomp.), decomposed by H 20-HC1 to the 247— 249°. MgBuyBr and PhCIIO give phenyl-tert.- aldehyde, and also obtained from (I) and ehloro- butylcarbinol, m.p. 44— 45°, oxidised to Pli Buv methyleneformamidine. This confirms the primary ketone, b.p. 109°/22 mm. (semicarbazone, m.p. 159°), reaction as tendency to form iminoformyl chlorido which with Z11CI, at 320— 330° gives a-phenylisopropyl Wore derivatives of the dimeride. E. R. S. M e ketone, b.p. 97— 9 8 °/ll mm. (semicarbazone, m.p. Phenylglyoxal. H . L. R il e y and A. R. Gr a y 190— 191°; oxidised by NaOBr to CPhMeyC02H). (Org. Syntheses, 1935, 15, 67— 69).— COPhMe is CMe2Et\MgCl and PhCHO give phenyl-tert.-amyl- oxidised with Se02. Ch. Abs. (r) carbinol, b.p. 112— 114°/8-5 mm., m.p. 22°, oxidised Benzoin reaction. V . Effect of inhibitors on by Cr03 to Ph tort.-amyl ketone, b.p. 112°/10 mm. (semicarbazone, m.p. 127— 128°), which with ZnCl2 the reaction. B. F. F erreira and T. S. W h eeler (Proc. Indian Acad. Sci., 1935, 2, A , G04— 614).— at 320— 330° gives -phenyl-see.-bidyI M e ketone, The rate of reaction of PhCHO and solid KCN in b.p. 114— 116°/13 mm. (semicarbazone, m.p. 177— presence of S (cf. A., 1935, 1329) and the inhibition 178°; with NaOBr gives a.-phenyl-a-methylbutyric caused by benzoquinone, I, PhCNS, and CS2 are acid, m.p. 64°). R- S. C. studied. Inhibition is due to adsorption of inhibitors Reactions of benzoyl chloride [fluoride]. C. L. on the KCN. PhCHO (containing inhibitors) may be T seng and S. W . M a i (J. Chinese Chem. Soc., 1936, purified^ by keeping with a small quantity of KCN, 4, 22— 26).— BzF (prep, from BzCl and K H F 2 in a under N,, and filtoring, after which it gives improved Cu retort in 67— 80% yield) is unstable and attacks Reids of benzoin; 0-1 g. of KCN purifies 50 g. of glass if slightly impure ; with (NH4)2C03 it gives PhCHO. E. W . W . NHoBz and with C6H6 and freshly prepared A1C13 Kinetics of gaseous Diels-Alder reactions.—- in CS.> gives 64% of COPh2 more readily than does bee tins vol., 297. BzCl. ft- S. C. Kinetics of the benzoin reaction in presence 5 : 5-Dimethyl-l : 3-hexanedione (5 : 5-di- oi organic solvents.— See this vol., 297. methyldihydroresorcinol). R. L. S h r in e r and H. R. Tonn (Org. Syntheses, 1935, 15, 14— 16).— A Structure and absorption spectra of benzcycfo- modified prep, from CMe.,!CHAc and CH2(C02Et)2 aixanoneoxinies. (Mme.) P. R am art-L ucas and is described. Ch . A bs. (r) "• Koch (Conipt. rend., 1935, 2 0 1 , 1387— 1390).— ■ sorption spectra indicate that the oximes of Action of selenium dioxide on some cyclanones. 11 aild-one, 2 : 2-dimethylindan-l-one, and a-tetral- M. G odciiot and (Mlle .) G. Cau q u il (Compt. rend., 0110 have the CiN-OH structure, but that of 2 :2 - 1936, 202, 326— 328; cf. A ., 1932, 833).— cycfo-Hex-, ■methyl-l.tetralone has the isooxime structure, -hept-, and -oct-anonc with Se02 in EtOH at SO give 1 : 2-diones. The following are prepared^ simi C<^6 • Kenzcyc/oheptan-l-oneoxime exists mainly larly : 4,-methyleyclohexane-l : 2-dione, m.p. 37 38 in the .N-OH, but its 2 : 2-Me2 derivative mainly in [dioxime, m.p. 195— 196° (Bz2 derivative, m.p. 218 ); tli i!'s?oxlmeJ form. The structure of the oxime is diphenylhydrazjone, m.p. 148° ; affords p-methyladipic us dependent on the influence of valency angles on acid with 1I20 2 ; 4:-ethoxy-5-kelo-2-methyl-A6-cyc\o- « e elimination of H ,0 from OH-CRR'-NH-OH, which hexene, b.p. 118°/20 mm., is formed by a side reaction], ne primary product from a ketone and N H 2OH. and cycloheplane-l : 2-dione, b.p. 107— 109 /17 mm. R .S . C. (diphenylhydrazone, m.p. 135°; dioxime, m.p. 181 472 BRITISH CHEMICAL ABSTRACTS. A. X V (m) 182°; oxidised to pimelic acid). 2-MetliylcycZo- phenylodane-2-carboxylate (I), b.p. 210°/1 mm. (I) hexanone affords 2 : 3-diketo-l-methyl-As-cyc\ohexene, and NaOEt give a dihydroresorcinol derivative, which b.p. 92— 93°/lG mm. (diphenylhydrazone, m.p. 150°), with P20 5 affords \-kelo-l-mdhoxy-2-mdhyl- which probably results from the dehydration of. 1 : 2 : 3 : 4 : 9 : \0-hexahydrophenanthrcne (H), m.p. 3 - hydroxy- 3 - lnethylcycfohexane -1:2- dione. cyclo - 67— 68° (2 : i-dinitrophenylhydrazone, m.p. 221°), Octanone similarly affords S-cthoxycycloodane-l : 2- mixed with some 4-Me isomeride. (I) and H 2S04 dione, b.p. 133— 135°/15 mm. ' ' J. L. D. at — 15° give M e y-Q-methoxy-3 : i-dihydro-l-naphthyl- Methyl ß-m-nitrophenyl-ß-hydroxyethyl and a-methylbutyrale, b.p. 181— 183°/0-5 mm., the corre m-nitrostyryl ketones. W. Kraszewski and B. sponding chloride being cyclised by Darzens’ reaction. W eicöw n a (R o c z. Chem., 1935, 15, 506— 509).— The ketone obtained is identical with (II); this method »i-NO2*C0H4*CHO and COMe2 in presence of 1% proves the constitution but the first method is to be NaOH at room temp, yield a trimeride of m-nitrostyryl preferred for prep. F. R. S. Me ketone, m.p. 232° (phenylhydrazone, m.p. 183°), Sexual hormones and related substances. also obtained, together with $-m-nitrophenyl-$-hydr- VII. Carboxylic derivatives of the follicle hor oxyethyl M e ketone (I), m.p. 62° (benzoate, m.p. 107°; mone. VIII. Catalytic hydrogenation of the semicarbazone, m.p. 162°), which is the sole product follicle hormone and its acyl derivatives. W. at > 5°. (I) yields m-nitrostyryl M e ketone, m.p. 90° D ir s c h e r l (Z. physiol. Chem., 1936, 2 3 9 , 49— 52, (semicarbazone, m.p. 223°; Ur-derivative, m.p. 112°), 53— 66).— V II. Follicle hormone (I) is largely un with Ac20 (1 hr. at the b.p.). R. T. affected by treatment with an equiv. amount of Chrysene. I. K. F u n k e and E. M ü l le r . II. (C5H5N)2C0C12 in CgH6 but is quantitatively trans K. F u n k e , E. M ü lle r , and L. V ad a sz (J. pr. Chem., formed by an excess of the reagent at 70— 75° into the 1936, [ii], 144, 242— 250, 265— 272).— !. Chrysene chloroformate (II), m.p. 101— 102° (corr.). (II) is (I), BzCl, and A1C13 in CS2 give (probably) 2-benzoyl- converted by EtOH at 80° into the corresponding cliryscne (II), m.p. 191° [7 : 8-quinone, m.p. 249— Et carbonate, m.p. 115° (corr.), [a]“ + 1 1 4 ° in dioxan, 250°, formed on oxidation (Na2Cr20 -, AcOH)], which also obtained from (I) and ClC02Et in CGHG-C 5H5N is reduced (Clemmensen) to 2-benzylchrysene, m.p. at 70— 75°. (II) is transformed by MeOH into the 200°, and converted by A1C13 at 130° into (probably) M e carbonate, m.p. 127° (corr.), and by NHEt2 in a naplithobenzanthrone (not characterised). (I), CgHg into the dielhylcarbamale, m.p. 194— 195° AcCl, and A1C13 in CS2 afford 1-, m.p. 254°, and 2- (III), (corr.). (I) and C0C12 in alkaline solution afford the m.p. 144°, -acetylchrysene, reduced (Clemmensen) normal carbonate, m.p. 247° (corr.), and (II). (II) i f to 1-, m.p. 236°, and 2-ethylchrysene, m.p. 126° about 10 times as active physiologically as (I), (Ur-derivative, m.p. 122°), respectively. (Ill) is excelling all other hormone esters in this respect. oxidised (NaOCl) to chrysene-2-carboxylic acid, m.p. VIII. Hydrogenation of 17-keto-3-hydroxy-A1:3:5- 308° (lit, 303°) [chloride (IV), m.p. 167°; Et ester, cestratriene (III) (Pt02-E t 0 H ; room temp.) affords m.p. 124° (indef.)], also prepared by Liebermann and the dehydrohormone (IV), m.p. 174— 175°, [a]“ + 82° Zsuffa’s method (A., 1911, i, 202). (IV), C..Hr, and in dioxan, which is 5— 10 times as active as (III). A1C13 give (II). Similar results are obtained at 70°, in E t 0 H -H 20 at II. BzCl (excess), (I), and A1C13 afford two di- room or elevated temp, or when PtO, is reduced to benzoyl chrysenes, A , m.p. 208° [also obtained from Pt before hydrogenation, whereas hydrogenation (II), BzCl, and A1C13 in CS2], and B, m.p. 252°. does not occur with Pt-black under these conditions. Dibromochrysene, m.p. 270° [from (I) and Br in CC14], Under like circumstances (IV) is also derived from the and Cu2(CN)2 in quinoline give dicyanoclirysene, m.p. Bz, Ac, C1C02-, or EtC 02-derivative of (III). Hydro > 3 6 0 °, hydrolysed (powdered K O H in MeOH at genation (Pt02) of (I) in EtO H -H Cl gives a small 200°) to chrysenedicarboxylic acid, m.p. >360° amount of (IV) and unchanged (III) but essentially [chloride (V), m.p. > 3 6 0 °, best prepared using BzCl; affects the nucleus; the isolation of two odahydro- Et ester, m.p. 169°; amide; anilide, m.p. >360°], hormones, m.p. 210— 211° (corr.), [a]“ + 7 -2 ° in EtOH which could not be converted into an anhydride. (V), and m.p. 154— 155°, [a]},9 + 3 1 -4 ° in EtOH, Bromo-2-benzoylchryseiie, m.p. 176° [from (II) and respectively, and of two deoxohexahydrohormones, Br in AcOH], is similarly converted into the nitrile, m.p. 104— 105° after softening at 100°, [a]“ + 1 ‘8° m.p. 207°, of 2-benzoylchrysenecarboxylic acid, m.p. in EtOH, and m.p. 96— 100°, [a]“ +12-3° in EtOH, 286° (previous sintering), the chloride of which could respective^, is described. Hydrogenation of (HI) not bo prepared. (V), CGHG, and A1C13 give di- in AcOH affords (V) and lower-melting isomerides benzoylchrysene-Q, m.p. 232°, reduced (Clemmensen) to of it, deoxohexahydrohormones, and, apparently, a dibenzylchrysene-C, m.p. 254°. (V) and N2H4,H20 hexahydrohormone which yields a semicarbazone, m.p. afford a compound, C40H30O4NG, m.p. > 3 6 0 °. The 255°, [a]“ + 7 7 -2 ° in CHCl3-E tO H (3 : 1). In 60% colours of most of the above compounds in cone. or S0% AcOH hydrogenation proceeds similarly but H 2S0 4 are given. H . B. yields the products in different ratio. In 80% Synthesis of substances related to the sterols. AcOH at 40° the main product is a mixture of ketones VIII. A ketomethoxyxnethylhexahydrophen- from which a hexahydrohormone-2 : 4:-dinitrophenyl- hydrazone, m.p. 105— 110°, and a semicarbazone, anthrene. R . R o b in so n and J. W a l k e r (J.C.S., 1936, 192— 195).— The Ha compound of M e y-acetyl- m.p. 255°, [«|» + 4 6 ° in EtOH, are derived. H . W . a-methylbulyrate, b.p. 110— 112°/24 mm., and y-m- Sexual hormones. XI. Partial hydrolysis of methoxyphenylbutyryl chloride yield Me y-m- cis-tra»»s-androstane-3 : 17-diol and its partial methoxyphenvlbutyrate and M e o-keto-S-m-mcthoxy- esterification. Specificity of sexual hormone X V (in) ORGANIC CHEMISTRY. 473 action. L. R u zic k a and M. W . G oldberg (Helv. body-wt., rats require about 500 times as much hor Chim. Acta, 1936, 1 9 , 99— 106).— Partial hydrolyses mone as dogs. Distribution of cortin extracts of cîs-/ra»w-androstane-3 : 17-diol diacetate with KOH between pentane and 2 0 % MeOH permits the isola -EtOH gives cis-ira?is-androstan-17-ol 3-acetate, rn.p. tion of all the physiologically active material in suffi 183— 184°. Partial estérification of cis-inms-andros- cient purity to allow further concn. to be effected tane-3 : 17-diol with 90% AcOH or Ac20 in C5H 5N without marked loss. The total hormone can be gives good yields of cis-trans-androstan-3-ol 17- extracted from the concentrates by suitable ketonic acetate, ra.p. 191— 192° (corr.), oxidised by Cr03 reagents (NH2-CO-NH-NH2 or Girard’s reagent). in AcOH to androstan-3-one 17-acetalc, m.p. 158 The biologically active components from 1000 kg. (corr.), whence tr&ns-androstan-3-o?ie-17-ol (I), m.p. of cortex can thus be reduced simply to about 5-4 180— 1S1° (corr.), which is physiologically somewhat g. without appreciable loss of activity. The preps, less active than testosterone (II). Comparison of so obtained are essentially mixtures of OH-ketones the action of derivatives of (I) shows that 17-methyl- and diketones. They are free from N, S, P, and halo testosterone, not observed naturally, is physiologically gen and contain about 3 rat units per mg. The follow more active than (II) and that chemical structure ing cryst. substances, which appear to be very closely has little specificity in the male hormone action. inter-related and closely allied to the active com cis-Androstanediol 3-acetate is transformed by BzCl ponents, have been obtained partly from the active in C5H3N into cis-tra,ns-a?idrostanediol-‘3-acetate 17- concentrates and partly from the inactive by-products; benzoale, m.p. 198— 199° (decomp.), which when all are biologically inactive with the closes used. partly hydrolysed by KOH-M eOH affords cis- Substance A, C21H 380 5 ±2 H , m.p. 222— 224° (decomp.) androstanediol 17-benzoate, m.p. 203—204° (corr.) after becoming opaque at about 160°, [a]],3 + 1 6 ° (the use of a difficultly hydrolysable acid residue at (± 1 °) in a-bs. E tO H ; it contains 4 or 5 OH, gives a C-17 is particularly useful, but traces of the 3-acetate cryst. ppt. with digitonin in 50% MeOH, is not hydro are observed), oxidised to androstan-3-ol 17-benzoate, genated at 100— 140°/100 atm. in presence of N i- m.p. 200— 201° (corr.), hydrolysed to (I). H. W . Si02, yields a telra- or penta-acctate, m.p. 150— 151° 17-Ethylandrostenediol and 17-ethyltesto- (corr.), and a monoisopropylidene derivative, m.p. 209— 210° (corr.), and yields CH20 when oxidised sterone. A. B u t e n a n d t , H. Cobler, and J. Schmidt (Ber., 1936, 69, [B], 448— 450).— Dehydroandro- by Pb(OAc)4 in AcOH. Substance B, ClcH280 5 or, more probably, C12H 20O4, m.p. 253— 255° in sealed sterone is converted by M gEtl in Et20 into A5’8- capillary, is possibly a degradation product. Sub 17-ethylandrostene-3 : 17-diol, m.p. 198° (also stance C, C^H^Og, m.p. 253— 256° (corr.; decomp.), -rlH 20) (cf. Ruzicka et al., this vol., 76), which is M b + 6 9 -8 °± 2 '5 in abs. EtOH [monosemicarbazone, treated successively with Br and Cr03 in AcOH m.p. 265— 267° (corr.; decomp.)]. Substance D, and debrominated by Z 11 dust in MeOH thereby C2iH360 5 or C21Hm0 5, m.p. about 230— 238° (corr.; giving 17-ethyltestostcronc, m.p. 149° after softening decomp.) according to the rate of heating, [a]f,° + 66° at 144°, [a]n° — 35-3° in abs. EtOH [semicarbazone, ± 1 -5 ° in abs. EtOH [monosemicarbazone, m.p. 327— m.p. 210° (decomp.)]. H. W . 329° (corr.; decomp.)]. Substance F, probably Androsterone and related sterols. R. E. C18H 240 3, m.p. 220— 223° (corr.), [a]j,° + 2 6 2 ° in abs. -Ma r k e r , E. C. W hitm ore, O. Ivam m , T. S. Oa k w o o d , EtOH (disemicarbazone, gradual decomp. about and J. M. B latterm an (J. Amer. Chem. Soc., 1936, 270°). An acid, m.p. 223— 226°, [a]2? -f-166°±20° 58, 338— 340).— Oxidation (CrOs in dil. AcOH at (determined as Na salt in H aO), and substance E, 70°) of 3-cliloro-5 : 6-dibromocliolestane (from chole- m.p. (indef.) 126— 129° [semicarbazone, C22H370 5N3, steryl chloride and Br in Et20-A cO H ) and reduction m.p. (amorphous), 208— 210°, m.p. (cryst.), 280— (Zn dust, AcOH) of the product, formed gives 3- 285° (corr.; decomp.)]. Hydrolysis of the fat insol. chloro-A5-dohydrocho]anic acid and 3-chloro-A5-de- in pentane gives a substance, C4H 10O3S, m.p. 113— hydroandrosterone (I), m.p. 156— 157° (Butenandt 114-5° (corr.), probably an aliphatic trihydroxy- and Dannenbaum, A., 1935, 413). Reduction (H2, sulphido or dihvdroxysulphoxide, which is stable P t02, Et20) of (I) affords a-3-chloroandrosterone towards alkaline Ag solution but immediately (II), m.p. 165— 168°, converted by KOAc in valeric decolorises K M n04 at 0°, glyceryl palmitate, and acid, subsequent hydrolysis (aq. EtOH-NaOH), palmitic acid. H . W . and purification through the H succinate into andro sterone, m.p. 178°. (II) is also obtained from iso- 1:2: 3-Triketotetramethylcyc/opentane : a androsterone (III) (Ruzicka et al., A., 1934, 1221) blue triketone. C. W . S hoppee (J.C.S., 1936, and SOCl2. Hydrolysis of (I) gives A5-dehydro- 269— 274).— Francis and Willson (J.C.S., 1913, 103, /soandrosteronc which is reduced to (III). Reduction 2238) state that 1 : l-dibromo-2 : 2 : 3 : 3-tetramethyl- (H2, P t02, Et20-A cO II) of cholesteryl bromide eyefopentanedione (I) and NaOAc give a colourless affords cholestyl bromide, m.p. 115° [also prepared Br-free compound, m.p. 100°, regarded as a diacetate, from epfcholestanol (IV) and PBr.. in C0H 6], which is and converted by K O H into a substance, m.p. hydrolysed [as for (II)] to (IV). H . B. 68°. (I) with NaOAc-MeOH yields 1:2: 3-triketo- Cortin, the hormone of the adrenal cortex. tetramethylcyclopentane hydrate (II), m.p. 95°,^ which I. T. R e ic h stein (Helv. Chim. Acta, 1936, 1 9, forms a hydrate monosemicarbazone, m.p. 153° (de 29— 63).— There is 110 discrepancy between the comp.), 2 : 1-dinitrophe.nylhydrazone, m.p. 219—220°, Swingle-Pfiffner assay on dogs and the Everse-de 2 : 4:-dinitrophenylosazone (? 1 : Z-bis-2' : 4 '-dinilro- Fremery test on rats if it is assumed that the same phenylhydrazone), m.p. 268— 270° (decomp.), and a material is concerned in each method; per kg. quinoxaline, m.p. 108°, and a mol. compound of the 474 BRITISH CHEMICAL ABSTRACTS.— A. X V (m) ketone (1 mol.) and its hydrate (1 mol.), m.p. 119— b.p. 162°/14 mm., and diallyl ether, b.p. 146°/10 mm., 120°. (II) and KO H give the hydrate of the lactonic E t . 4 -0 -allyl-$-resorcylate, m.p. 42°, and the acid, acid of y-hydroxy-aapp-tetramethylglutaric acid, m.p. m.p. 155— 156°; 4-nitroresorcinol 1 -0 -allyl ether, 68°. (II) is dehydrated (80% ) in vac. to the anhyd. b.p. 157— 15S°/10 mm., rearranged (26%) to 4-nitro- triketone (III), m.p. 164°, bright blue prisms. (I) 6 (or 2)-allylresorcinol, m.p. 85-5°; nitroquinol diallyl and AgOAc-MeOH afford 1 : l-dimethoxy-2 : 2 : 3 : 3- ether, m.p. 22°, and 2-nitroquinol 4 -0 -allyl ether, m p. tetramethylcyclopentanedione (IV), m.p. 68°, rose-red 48°. F. R. S. cubes [2 : 4-dinitrophenylosazone, m.p. 266° (decomp.)], Reactions of o-hydroxybenzylidenediaceto- oxidised (H20 2) to the lactone of y-hydroxy-y-methoxy- phenones. VI. Diacetopbenones derived from a.a.fip-telramethylglutaric acid, m.p. 58°, and tctramethyl- 3-methoxysalicylaldehyde. G. H. B e a v e n and succinic acid. (IV) is hydrolysed (HC1) to (III) and D. W . H il l (J.C.S., 1936, 256— 258).— 3-Methoxy- 2 : 2-dimethoxytetramethylcyclopentane-l : 3-dione, m.p. salicylaldchyde, COPhMe, and NaOH give 3-methoxy- 62° (2 : 4-dinitrophenylhydrazone, m.p. 184°), also salicylidenediacetophenone (I), m.p. 145—146°, and obtained from (I) and KOH -M eOII. The absorption 3-methoxychalkone; with the appropriate ketone spectra of (III) show that the blue colour is duo to an the following are prepared: 3-methoxysalicylidenedi- absorption band with a max. at 685 mg and the red (p-methoxyacetophenone) (II), m.p. 163—164°, and colour of (IV) is due to an unsymmetrical band at 3 : 4'-dimethoxychalkone, m.p. 142°; 3-methoxysalicyl- 510 m g ; the blue colour must bo ascribed to the idenedi-(p-methylacetoplienone) (III), m.p. 112°, and contiguous association of the three CO groups. 3-methoxy-4'-methylchalkone, m.p. 131°. (I) in boiling F. It. S. AcOH for 1 hr. affords 8-rriethoxy-4-phenacylident- Chelation. III. Stabilisation of Kekule flavene, m.p. 192° (8-methoxy-4-phenacyljlavylium forms in o-hydroxy-carbonyl compounds. W. ferrichloride, m.p. 197— 198°), and for 10 min. yields B a k e r and (Miss) 0 . M. L othian (J.C.S., 1936, 8-methoxy-4-phenacylflavene, m.p. 136— 137°, and 274— 281).— 4 -0 -AXlylrespropioplienone (I), b.p. 174°/ with HCl-FeCl3 it forms 8-methoxyflavylium ferri 14 mm. (flu derivative, m.p. 158°), undergoes re chloride, m.p. 162° (lit., 157°). (II) and AcOH afford arrangement by heating to 3-allylrespropiophenone, 8 : 4'-dimethoxy-4-(p-meihoxyphenacylidene)flavene, m.p. 124° (Me2 ether, b.p. 180°/18 mm.), reduced to m.p. 195° (ferrichloride, m.p. 193°). (Ill) with AcOH 3-n-propylrespropioj)heno)ie, m.p. 109— 110°, also ob gives 8-methoxy-4-(p-methylphenacylidene)-4'-methyl- tained from 2-m-propylresorcinol, EtCN, and ZnCl2. Jiavene, m.p. 200° [ferrichloride, m.p. 192° (decomp.)], (I) is methylated (Me2S 0 4) to 2-0-methyl-4-0-allyl- with A c ,0 forms 2-acetoxy-3-methoxybemylidenedi- respropioplienone, m.p. 31°, rearranged on heating (p-methylacetophenone), m.p. 120°, ' and - with HC1- to 2-0-methyl-5-allylrespropiophenone, m.p. 132— FeCl3 affords 8-methoxy-4'-melhyljlavylium ferri 133° (Me., ether, m.p. 67°). 4-0 -Allyl-flresorcyl- chloride, m.p. 179° (decomp.). F. R. S. aldehyde, b.p. 149— 150°/3 mm., obtained from [3- resorcylaldehyde and allyl bromide, is rearranged 4'-Hydroxy-2-p-hydroxybenzoylbenzophenone. to 3-allyl-$-resorcylaldehyde (II), m.p. 129— 130°, F. F. B lick e and R. A. Pa te lsk i (J. Amer. Chem. which is methylated to 2 -0 -methyl-4-0-allyl-$-res- Soc., 1936, 58, 273— 276).— aa-Di-p-chlorophenyl- orcylaldehyde (III), m.p. 45°, and 2-mcthoxy-4-allyl- phthalide (I), m.p. 157— 158° [from o-CgH 4(COC1)2, oxystyryl M e ketone, m.p. 39— 40°. (Ill) is re PhCl, and A1C13], is reduced (Zn dust, aq. EtOH- arranged to 2-0-nielhyl-5-allyl-fi-resorcylaldchyde, m.p. NaOH) to 4' : 4"-dichlorotriphenylmethane-2-carb- 115— 146°, methylated to 2 : 4-dimethoxy-5-allyl- oxylic acid, which with conc. H 2S 0 4 gives 3-chloro- styryl M e ketone, m.p. 76— 77° : the isomeric 2 :4 - H 0]H 82— 83°/4 mm., 107— 108°/12 mm., also prepared Me\/ from campholenealdehyde (Arbuzov, A., 1935, 1246) and MgMel. The formation of (II) involves a ring- moit3 i O A-CO..H i Me < , ’l— CMeiCMe-COoH fission and subsequent ring enlargement. (II) is \ l / \]vie (YIX.) oxidised (Na2Cr20 7, dil. H 2S 0 4) to methylcamphol- enone, b.p. 73— 74°/4 mm. [semicarbazone, m.p. a little of a product (contains O), b.p. 101— 103°/14 175— 176° (corr.)]. Ethyl-, b.p. 88— 89°/4 mm., m m .; dehydrogenation (Se at 280— 300°) of this or n-propyl-, b.p. 100— 101°/4 mm., n-butyl-, b.p. 110— (I) affords indefinite products. Reduction (H2, 112°/4 mm., isobutyl-, b.p. 106— 107°/4 mm., and P t0 2 or Pd-CaCOj, EtOH) of (I) or (III) gives 1- phenyl-, b.p. 140— 142°/l-3 mm., -campholenols are hydroxy-2-kclo-3 : 4 : 9 : 10-tetrainethyl- 5 : 8 -endo- similarly formed from (I) and M gRX. Ethyl- methylene- 1 :2:3:4:5:8:9: 10-octahydronaplith- eampholenone has b.p. 80— 81°/2 mm. [semicarbazone, alene (IV), m.p. 82— 83° (acetate, m.p. 91°; oxime, m.p. 148— 149° (corr.)]. ' H . B. m.p. 169— 170°), oxidised (Cr03, aq. AcOH) to Norborneol and norbornylane. G. K o m p p a and the 1 : 2-dtfcefo-derivative (V), m.p. 141— 141-5° S. Beckm ann (Ann. Acad. Sci. fenn., 1934,- A , 39, [phenazine, m.p. 181— 182°, also formed from No. 7, 9 p p .; Chem. Zentr., 1935, i, 3940).— Mostly (IV)]. Reduction [H2 (1800 lb.), Raney Ni, 95% already reported (A., 1934, 658). 2-Carbamyl- EtOH, 185°] of (I), “(III), or (IV) affords 1 : 2- dicyclo-[l : 2 : 2]-heptane, m.p. 205— 206°, prepared dihydroxy-3 : 4 : 9 : 10-tetramethyl-5 : 8-cndomethylene- 3:4:5:6:7 :8:9: I0-odahydronaphthalene (VI), from the acid in the usual way affords norbornyl- m.p. 146— 147° (diacelate, m.p. 81— 82°), which could amino with KO H -K O Br. II. N. R. not be reduced further. (VI) does not give an oximo Borneol-isoborneol question. Y. A s a h in a , M. or a phenazine; on one occasion only it was oxidised I sh id a te , and T. Sano (Ber., 1936, 69, [E], 343— 348; (Cr03, aq. AcOH) to the 1 : 2-diketodecahydro- cf. A., 1935, 625; Lipp, ibid., 983).— d-trans-Tz-apo- derivative, m.p. 96— 97°, indicating that it can react Borneol-7-carboxylic acid, obtained by vigorous as the l-hydroxy-2-ketodecahydro-form. (I) isoxidised reduction of isokctopinic acid with Na and EtOH (15% H20 2, aq. McOII-NaOH) to p-(2-carboxy- (slow reduction causes some production of isoborneol 1 : 2 -dimethyl-8 : 6 -endomethylene- A4- cyclohexenyl) - derivatives), is quantitatively converted by AcCMn «-methyl-^-butenoic acid (VII), m.p. 239—240° C5H 5N into the corresponding acetate (I), m.p. 106— (decomp.) [? 4 : 5-dibromidc (VIII), m.p. 249—250° 107°, which with SOCl2 affords d-trans-r-apooceiyZ- (decomp.)], which is reduced (H2, Pd-CaC03, aq. bomeol-1 -carboxyl chloride, b.p. 124°/6 mm., trans Xa2C 03) to the -butyric acid, m.p. 229— 230°', also formed by I l2 in boiling xylene containing Pd-C into formed by oxidation (H20 2) of (V). Ozonolysis of d-tT&ns-Tz-il'poacelylborneol-i-aldehyde [reoxidised to 476 BRITISH CHEMICAL ABSTRACTS.— A. X V (0) (I)], the semicarbazone, m.p. 195°, of which is con New camphor derivative, “ ketobornylene.” verted by NaOEt-EtOH at 150— 155° into 7-bomeol Y . AsAniNA, M. I sh id a t e , and T . T ukam oto (Ber., (II). Similarly, Zra?is---apoisoacetylborneol-7-earb- 1936, 6 9 , [73], 355— 357).— 6-Acetoxycamphorquinone oxylic acid, from apocamphenecarboxylic acid (III) ■with N2H4,H20 in hot EtOH gives a- (I), m.p. 175°, by hydration according to Bertram-Walbaum, is and ¡3- (II), m.p. 99°, -G-acetoxycamphorquinone-3- converted successively into the corresponding chloride, monohydrazone. (I) with yellow HgO in boding C6HG b.p. 120°/6 mm., trxns---apoisoacelylbomeol-7-alde- affords 3-diazo-G-acetoxy camphor, m.p. 120°, also hydc (semicarbazone, m.p. 197°), and i'soborneol. obtained more slowly from (II); when distilled with 0-a?is-7t-apoCamphor-7-carbox3rlic acid is therefore a Cu-bronze it yields 6-acetoxy-$-pei'icyclocamphan-2- substituted camphor which, like the latter, on one (III), b.p. 145°/1S mm., hydrolysed to G-liydr- energetic reduction gives mainly a borneol derivative, oxy-^-pdvieyclocamphan-2-one- (IV), m.p. 234°. (Ill) whereas (III) is a substituted camphene passing, when or (IV) with H Br-AcO H at room temp, gives o-bromo- hydrated, mainly into an i’soborneol compound. G-hydroxy camphor, m.p. 123°, transformed Reduction of 7-ketodihydroteresantalic acid by Na by Zn dust and alkali into (IV) and by and EtOII yields the antipode of the Semmler- :o Zn dust and AcOH at 100° into keto Bartelt lactone, m.p. 196°, and d-cis-rr-opoborneol-7- (V.) bornylene [dehydrocamphor] (V), m.p. carboxylic acid (IV), m.p. 278°. Treatment of (IV) 14S°, [a%° -7 3 5 ° in abs. EtOH [semicarb with AcCl in C5H5N affords the corresponding acetate, azone, m.p. 234° (decomp.)], which immediately re b.p. 155— 158°/5 mm., the chloride, b.p. 124°/6 mm., of duces cold K M n04 and slowly decolorises Br in AcOH. which is converted d-cis-n-npoacetylbomeol-i-aldehyde, Catalytic hydrogenation (Pd-C in AcOH) of (V) the semicarbazone, m.p. 224°, of which affords (II). gives 7-camphor. H . W . r-isoBorneol is unchanged by N aO Et-EtO H at 155°, but passes at 170— 180° into borneol. H. W . Removal of water from camphenilol, 4-methyl- camphenilol, and 4-methylborneol. Santene Oxidation of bornyl acetate. Y. A s a h in a , M. displacement and Nametkin transformation. I s h id a t e , and T . T ukam oto (Ber., 1936, 69, [7 1 ], G. K omppa and G. A. N y m a n (Ber., 1936, 69, [B], 349— 354).— Oxidation of Z-bornyl acetate by Cr03 in 334— 340).— Ozonisation of camphenilene obtained by A c0II-A c20 at 80° affords unchanged material, and heating camphenilol (I) with K H S 0 4 leads to ap 'o- fractions, b.p. 115— 160°/15 mm. (I), and b.p. cyclene (II) unattacked by 0 3, and santene diketone. > 1 6 0 °/1 5 mm. (II), respectively. Treatment of (I) Dehydration of (I) takes place partly by pinacolin with 10% K 2C03 gives small amounts of 1 : 5 : 5-tri- transformation giving santene and partly by direct methylci/cZopentan-2-one-4-acetic acid (III) (semi loss of H 20 and subsequent ring-closure to (II). carbazone, m.p. 240°), and the unattacked portion is Similarly the “ 4-methyl camphenilene ” obtained oxidised by Na2Cr20 7 and dil. H 2S0 4 to 3 : 6-diketo- from 4-methylcamphenilol is shown to be a mixture camphane, m.p. 212°, [a]}? — 105-5“ in abs. EtOH of epicyclene, m.p. 116— 117°, and 1-methylsant- (idisemicarbazone, m.p. 295°), (III), and ketocampho- ene. The relative proportion of the hydrocarbons lenic acid (IV), m.p. 130° (semicarbazone, m.p. 218°). appears to depend on the mode of dehydration. (IV) is also obtained by the action of K O H -E tO H on Ozonisation of 4-methylcamphene (III) in AcOH 0-bromo-2 : 5-diketocamphane or 2-bromo-Z : 6-diketo- gives, as unattacked portion, 4- CB>CHMe-CH2 camphane, m.p. 145°, [a]j,° — 152-7° in abs. EtOH, from '2 methyltricyclene (IV), m.p. 109— 110° “ ÇMe2 I 3 : 6-diketocamphane (V) and Br in CHC1. Z-p-Keto- i (also obtained by oxidation of CH-| CH borneol (VI) is oxidised by Na2Cr20 7 and dil. H 2S04 4 - methylcamphorhydrazone with '^-C M e^' at 100° to (IV) and (V ); under like conditions, HgO) ; 4-methylcamphenilone, hydr Z-p-diketocamphane is largely unattacked. Catalytic (IV.) oxy - 3 - methylcamphenilonolactone, hydrogenation (Pd-C in AcOH) of (IV) gives optically and trimethylnorcampholide are also isolated. These inactive 1:5: 5-irimethylcycldpentan - 3 - one - 4 - acetic normal products are accompanied by considerable acid, m.p. 90° (semicarbazone, m.p. 229°). (II) when amounts of 7Z-fenchone (V) ; apparently (III) becomes oxidised with H 20 2 in alkaline solution and then partly hydrated, and the acetate thus produced suffers heated with alkali yields (VI) and d-2-hydroxycam- the Nametkin transformation and subsequent loss of phoric acid (VII), m.p. 165°, [a]“ + 7 -8 ° in abs. EtOH AcOH. 1-Methylcamphene is thus produced, which is (M e ester, b.p. 150— 151°/11 mm., m.p. 46°). ozonised to (V). Elimination of H 20 from 4-methyl Synthesis of (VII) is effected by treating 1-p-ketobomyl borneol occurs therefore in three directions. H . W . acetate, m.p. 78°, [a]^ — 87-9° in abs. EtOH, with Se02 in Ac20 at 130— 140°, thus yielding 6-acetoxy- Organic catalysts. XII. Asymmetric main camphor-2 : 3-quinone, m.p. 109°, [a%3 -1 9 1 -4 ° in abs. valency catalysis. I. W. L a n g e n b e c k and G. EtOH, which is oxidised by NaOH and H 20 2 to (VII). T r ie m (Ber., 1936, 69, [B\, 248— 250).— 7-Campho- 2-Acetoxycamphor-5: G-quinone, m.p. 109°, [a%3 glyoxylic acid (I) has [a]|° + 255-1° in V-NaOH- + 188-5° in abs. EtOH, is oxidised to l-2-hydroxy- <\\-Camphoglyoxylic acid (II), m.p. 84— 85° [oxime camphoric acid, m.p. 165°, [aj§j — 8-0° in abs. EtOH. ( + 1H20), m.p. 159°], is obtained from 7Z-camphor, Oxidation of (VII) affords d-1 : 5 : d-lrimethylcyc\o- Et2C20 4, and Na wire in ligroin. (I) and cZZ-alanine pentan-2-oncA-carboxylic acid, m.p. 122°, [a]“ (III) at 150° afford small amounts of 7-hydroxy - + 163-74° in abs. EtOH (semicarbazone, m.p. 215°; methjdenecamphor, [a]™ + 1 8 3 ° in EtOH. (II) and M e ester, m.p, 41°); the corresponding 1-acid has m.p. (III) yield TZ-hydroxymethylenecamphor, whereas 122°, [a]'" — 166-8° in abs. EtOH (semicarbazone, m.p. (II) and Z-alanine give a slightly laevorotatory product. 215°), and the r-acid has m.p. 117°. H . W . If Z-leucine is used, the product appears to be optically XV (o), X VI ORGANIC CHEMISTRY. 477 inactive. The stereochemical specificity of the carb new m.p. 165— 168°, [a]i,° — 91° in EtOH, is an iso- oxylase model is thus established. H . W . meride of abietic acid. It is dehydrogenated (Se) to retene, gives a compound, m.p. 226°, with maleic Chios turpentine. E . E m m a n u e l (Pliarrn. Acta anhydride, and is converted by AcOH at 100° into Helv., 1935, 1 0 , 12— 22; Chem. Zentr., 1935, i, Steele’s abietic acicl (A.,1922, i, 739). E. W . W . 3856).— The following are isolated from the resin of Pistacia terebinlhus, L. : terminthic acid, C14H 20O2, Plant cardiac poisons. VIII. Convallatoxin. m.p. 136— 137°; terminthinic acid, ^ 16^ 2404, m.p. R . T schesche and W . H aupt (Ber., 1936, 6 9 , [J3], 123-5— 124-1°, monobasic (EtOH-insol. Pb salt); 459— 464; cf. Karror, A., 1929, 684).— Convalla ~termintholic acid, m.p. 101-5— 102-1°, monobasic toxin (I), m.p. 238— 239°, or (hydrated) m.p. 225°, (EtOH-sol. Pb salt); termintholinic acid, C22H 34O3, is C29H 12O j0. It contains two double linkings, m.p. 127-5— 128°, monobasic; an ethereal oil, d15 one of which is saturated with great difficulty. 0-8695, w26'5 1-466S, [a] + 33 -5 °, separable into two (I) is hydrolysed with difficulty by acids to Z-rhamnose fractions, b.p. 157— 165° and 165°— 190°; a resin and monoanhydroconvallatoxigenin, isolated as the and a bitter principle. H. N. R. benzoate (II), m.p. 279—281°, [a® +22-2° in CHC13. In addition to the three double linkings of the CGH 6 Polyterpenes and polyterpenoids. C. Trans group, (II) contains three double linkings, one of which formations in rings A and E of oleanolic acid. is very resistant towards saturation. Its absorption Carbon skeleton of pentacyclic triterpenes. L. curve very closely resembles that of anliydrouzarigenin R uzicka and K . H ofmann (Helv. Chim. Acta, 1936, benzoate. (H) contains two, probably tert. OH 19, 114— 128).— Oxidation of acetvloleanolic acid (I) (Zerevitinov). Convallatoxigenin (III) therefore con by Cr03 in A c 0 H -H 2S 0 4 gives the substance (II), tains one sec. and two tert. OH. Like (II) it does not m.p. 230°, which could not be obtained homogeneous; ,,n react with ketonic re- its formula and the function of the O atoms are C—2-p rr>0 agents. The positive 0 Legal test establishes CH. C,=H (S / \ the presence of an ;=}C„h 34-c o 2h 25 40 0Ac-CH OAc •COoH unsaturated side-chain •c o ; h (I) (II.) which is opened by alkali, thus allowing the •°8 0 equiv. to be determined. ( ^ Acidification of the 25^10 •CO •C02Me 0Ac-CH ) OAc-CH2} C25Hm alkaline solution leads to of vanillin formation from spruce lignin- evidence in support of this view (cf. Freudenberg sulphonic acids in relation to lignin structure. et al., he. cit.) is given. II. B. G. H. T o m lin s o n II and H . H ib b e e t (J. Amer. Chem. Soc., 1936, 58, 340— 345, 345— 348, 348— Aesciilus saponins and their sugar-free deriv 353).— X X I I I . Spruce wood meal (extracted with atives. E. B u k eS and K . B a b o r , jun. (Casopis EtO H -C„H 6) (I) is heated with aq. Ca(HS03)2+ S 0 2 Coskoslov. L6k., 1935, 15, 3— 8, 25— 34; Chem. at 125° and the liquor treated with CaCl2, which Zentr., 1935, i, 3936).— Three saponins are isolated from chestnut seeds : saponin B, decomp. 80— 120°; salts out Ca a-ligninsulphonate (II) ; Ca [3-lignin- saponin C, m.p. 150° (decomp.), and saponin^.A, sulphonate (III) (37% of total salt) (Ca 5, S 10-4, which, when purified by repeated pptn. from EtOH OMe 10-45%) is isolated from the mother-liquors through the Pb salt. (II) is separated by further and by dialysis, has m.p. 190— 194° (decomp.) salting out (CaCl2) into fractions (lia) (19%) (Ca 3-5, and composition C24H390 9(0 H )7 (Ur-derivative, S 9-4, OMe 11-2%) and (116) (44%) (Ca 3-8, S 9-6, C24H450 j 6Br, decomp. 130°; hepta-aceiate, m.p. OMe 11-35%). All the salts are purified by dialysis 155— 160°). The latter is hydrolysed to the prosapo- and subsequent pptn. from aq. EtOII by E tO H - genin, aescin, decomp. 211— 225° [Ur-derivative, penta-acetate, E t20. The liquor from (I) and aq. K H S 03+ S 0 2 m.p. 217° (dccomp.); m.p. 169— 170°], which is further hydrolysed to aescigenin, m.p. 179— at 110° with quinoline hydrochloride gives (cf. Hagglund, B., 1933, 584; Freudenberg et al., A., 186°. H. N. 11. 1935, 861) a quinoline salt, subsequently converted Constituents of “ Senso." IV. Grignard into K lignmsulphonate (IV) (70%) (K 3-7, S 5-4%) ; cleavage of methyl deacetyltetrahydro-^-bufo- a K salt (V) (30%) (K 2-7% ) is isolated from the talinate. S. I k a w a (J. Pharm. Soc. Japan, 1935, mother-liquors (A) through the Pb salt. (V) is separ 55, 195— 217).— Grignard cleavage of Me deacetyl- able into K salts (Va) (16%) (K 5, S 6-6% ) and tetrahydro-0-bufotalinate yields deacetyltetrahydro- (V6) (14% ) (K 5-8, S 5-6%) by successive treatment dimethyl-ip-bufotalene-A, C28H44°4> m P- 125— 126° of (A) with (î-C10H7*NH2 and Pb(OAc)2 and sub (itriacetate, m.p. 98— 100°), which is oxidised to de- sequent conversion into the K salts. The efficiency acetyltetrahydro-tp-bvfotahne-A, C23H380 5, m.p. 158— of the following reagents as précipitants is NaCI < 159° (oxinie, m.p. 124— 125°; p-nitrophenylhydrazone, CaCl2 < quinoline, isoamylamine < p-C10H 7-NH2 < m.p. 15S— 159°; triacetate, m.p. 163— 164°). On Pb(OAc)2 (cf. Hagglund, loc. cit.). (IV) and (V) further Grignard cleavage this yields deacetyltclra-, (in aq. COMe2) are methylated [Me2S0 4 (1 mol.), kydromethyl->li-bufotalene-'B (I), C24II40O4, m.p. 120— 30% KOH (1-1 mois.), 20°] to fully methylated 121°, whilst oxidation affords a OH-aldehyde, products (VI) and (VII), respectively, containing deacetyltelrahydro-^-bufotal, C21tl340 5, m.p. 145— 30 and 31-6% OMe (calc, on K - and S 0 3H-free basis), 147°. (I), when heated in xylene, gives deacetyl- respectively, without loss of S. tetrahydromethyl-i/i- bnfotalindiene, C24H380 3, m.p. X X IV . In agreement with Iviirschner (cf. B., 1928, 118— 120°, oxidised to deaeetyltelrahydro-ip-bufotalenc- 292), vanillin (VIII) is obtained in yields of 3-44— B, C20H32O4, m.p. 127— 129° (p-nitrophenylhydrazone, 7-27% (based on lignin content) when waste sulphite m.p. 172— 175°; diacetate, m.p. 115— 117°); with liquor is boiled with NaOH, KOH, or (less satis A c0 2H this yields a subshnce, C20H32O5, m.p. 135— factorily) Ba(OH)2; the mixture is acidified (H2S0 4), 136° (p - nitrophenylhydrazone, decomp. 167— 169°), extracted with CHC1!CC12, and (VIII) is then isolated whilst Grignard cleavage affords deacetyltetrahydro- with N aH S03 and subsequently determined as the methyl-i/i-bufotalene-C, C21H340 3, m.p. 135— 136°. »i-nitrobenzoylhydrazone. The effect of the original This is oxidised to deacetyltetrahydro-t/i-bufotahne-C, cooking treatment on the yield of (VIII) is investig Ci8H 2804, m.p. 117— 119°, which, on Grignard cleav ated ; max. yields are obtained when sulphite liquors age, affords deacetyltetrahydromethyl-^-bufotalene-D, containing a relatively high proportion of “ free ” C19H30O3, m.p. 102— 103°, oxidised to deacelyltetra- S 0 2 arc used at 110— 125° (prolonged heating at hydromethyl-ip-bufotalene oxide, C19H30O4, m.p. 159— such temp, having little effect on the yield). 160°. This latter, with 0 3, yields deacetyltetrahydro- X X V . The yields of (VIII), calc, on metal- and methyl-ip- bufotalonal, Ci9H30O5, m.p. 110— 111° S 0 3H-free basis, obtained when the following salts (mono-, m.p. 105— 106°, and di-, m.p. 115— 117 , (see Part X X III) are boiled with 19-4% (wt.) NaOH -acehte\ oxime, decomp. 126— 127°), which, with in N2 for 12 hr. are: (lia) 6-1, (116) 6-6, (III) 8-4, A c02H, affords deaceiyltetrahxydromethyl-^-bnfotahnic (IV) 6-4, (Va) 8-6, (V6) 7-1. The other fission pro peroxide, C ^ H ^ O ^ decomp. 193— 195°, yielding, ducts contain less S but approx. the same OMe as with dil. NaOH, deacetyltetrahydromethyl-¡¡¡-bufotalonic the original compounds, indicating that a small non- acid, C19H30O6, m.p. 184— 185°. Ch. A b s. (r) methylated aliphatic fragment is also removed Identity of evodin, dictamnolactone, and. during the hydrolysis. Veratraldehyde (m-nitro- obakulactone. A. Fujita, T. Taku, and N. benzoylhydrazone, m.p. 221— 223°) is formed in K u t a n i (J. Pharm. Soc. Japan, 1935, 5 5 ,248— 251).— yields of 2-35 and 2-76% , respectively, from (VI) The identity is indicated by m.p. and [a]. and (VII) with boiling 3-8% NaOH. The presence Ch . A b s. (r) of the 4 : 3-(OH)(OMe)C6H3- group in sprnce-lignin Biliiuscin.— See this vol., 501. is thus proved. Unsulphonated lignin does not simi larly yield (VIII). It is suggested that a group such Preparation of tetrahydrofurfuryl bromide as 4 : 3-(0H )(0M e)C6H3-CH(S03H)-CH2- is hydrolysed and its reaction with magnesium. R. R o b in so n (S 03H replaced by OH), and that the resulting and L. H. Sm it h (J.C.S., 1936, 195— 196).— Contrary product gives (VIII) by a reversed aldol reaction; to Paul (A., 1933, 954) the product of the interaction XVII (a) ORGANIC CHEMISTRY. 479 of Mg with tetrahydrofurfuryl bromide (I) (improved in EtOH reduces (II) to a compound, b.p. 100— 101 °/4 prep.) in pure dry E t20, wet and commercial Et20, mm. ' E. W . W . and in Et20-E tO H (6 : 1) is always A5-penten-a-ol, Passage from the sugar to the pyran and only traces of tetrahydrosylvane and of recovered (I) pyrrole series. Methyl/sopyromucic acid. E. being obtained. J. W . B. V o to ce k and S. M a l a c iit a (Coll. Czech. Chem. Comm., 1936, 8, 66— 78).— Distillation of thamnono- (I), Hydroxyfurans. I. 3-Hydroxy-2 : 4 : 5-tri- d-fucono-, and (probably) d-glucono-lactone, and phenylfuran. E. P. K o h le r , F. H. W esth eim er , a(3x'p'-tetrahydroxy-a-methyladipdilactonc gives 3- and M. T ish ler (J. Amer. Chem. Soc., 1930,5 8 , 264— hydroxy-6 -methyl-1 : 2-pyrone (“ methylisopyromiicic 267).— Successive treatment of 3-acetoxy-2 : 4 ; 5- lactone ” ), m.p. 120— 121°, which gives a green colour triphenylfuran (I) (Thiele, A., 1898, i, 469) with with FeCl3, reduces Fehling’s solution and A g N 03, MgMel and cold dil. H 2S0 4 gives 3-hydroxy-2 : 4 : 5- and gives a Br-, m.p. 147°, and Bz derivative, m.p. triphenylfuran (II) (not isolable), which has no 121— 122°. Peligot’s sugar decomposes when dis phenolic properties, but resembles an active open- tilled. Ba fuconate gives an unidentified aldehyde. ehain enol. (II) (in Et20) and 0 2 afford the 2 : 3- (I) is resinified by HC1 at 150°. Distillation of (NH4)2 peroxidc (III), decomp, about 120°. Hydrolysis apa'p'-tetrahydroxy-x-methyladipate or N H 4 rham- (dil. H 2S0 4 in AcOH and N 2) of (I) gives 3-keto- nonate with (NH4)2C03, best in glycerol under NH3, 2:4: 5-triphenyl-2 : 3-dihydrofuran, m.p. 112° [the gives 2-methylpvrrole. R. S. C. ketonic form of (II)), which is only slowly oxidised Synthetical experiments in the chromone (02) to (III). The deep yellow colour of (II) precludes group. XVIII. Déméthylation with aluminium direct titration with B r ; indirect titration is vitiated chloride. K . C. G u l a t i and K. V enkataraman owing to the production of (III). Reduction (Ii2, P t0 2, (J.C.S., 1936, 267— 269).— Déméthylation of 2 : 4 : 6- EtOAc) of fill) gives 2-hydroxy-3-keto-2 : 4 : 5-tri- trimethoxyacetophenone (improved prep.) with A1C13 phenyl-2 : 3-dihydrofuran (IV), m.p. 191° [Me ether in PhCl gives the 2 : 4-dihydroxy-6-methoxy-com- (V), m.p. 138°, formed by the action of M e0H -H 2S0 4; pound (Sonn et al., A., 1925, i, 1267) (4-benzyl ether, Et ether, m.p. 111°; acetate (VI), m.p. 138— 139°), con m.p. 72°). 2-Benzoyloxy-i : Q-dimethoxyacetophenonc, verted by Br into 2-bromo-3-keto-2 : 4 : 5-triphenyl- m.p. 91° (from BzCI-C5H5N and the 2-OH-eom- 2 : 3-dihydrofuran (VII), m.p. 154° [decomp, yielding pound), with NaNH.> in Et20 and treatment of the (VIII) (below)], which is most conveniently prepared diketone with 2 0 % H 2S0 4-E t0 H , affords chrysin from (I) and Br in boiling CC14. (VII) is converted Me2 ether (I), m.p. 143° (lit., m.p. 115— 117°), also by MeOH into (V). Reduction of (III) by methods obtained from chrysin (II)-Me2SO4-COMe2-2 0 % other than the above affords (IV) and 3 : 3'-dikelo- NaOH, or by the action of 2 0 % H2S0 4-E t 0 H on 2 : 4 : 5 : 2' : 4' : 5'-hexaphenyl-2 : 3 : 2' : 3'-telrahydro - the product (containing 2-hydroxy-4 : 6-dimethoxy- 2 : 2'-difuryl (VIII), 272— 274° [also obtained from dibenzoylmethane) of the action of A1CI3 on 2 : 4 : 6- (VII) and Cu-bronze in C6HpJ. (IV) and S0C12 trimethoxybenzoylacetophenone (III) in P h X 0 2. give 2-chloro - 3 - keto - 2 : 4 : 5 -triphenyl-2 : 3 -dihydro (I) with AlCl3-P h N 0 2 at 100° affords tectochrysin furan, m.p. 149— 150°. (IV) and Na in Et20 give a (IV), but when heated with solid A1C13, (II) and (IV) Na derivative, which with C 02, AcCl, and Mel (or are obtained. (Ill) with H I (d T7)-Ac20 also gives Me2S0 4) affords (IV), (VI), and (V), respectively; (II) and (IV). The crude product of interaction of treatment with Br gives y-brotno-afiS-tnketo-zyS- phloroacetophenone and Bz20, with Me2S0 4-C 0M e2- triphenylbutane, m.p. 111°, which is reduced catalytic- 10% aq. NaOH gave, in one experiment, (1) and its aliy to (IV). H. B. 3-Bz derivative, m.p. 212°, and, in another, (II) and Occurrence of furan derivatives in volatile oils. 2 - hydroxy - 4 : 6 - dibenzoyloxy - o> - benzoylacetophcnone, II. a-Clausenan and di-a-clausenan. B. S. R a o m.p. 157°. (II) with either CH2PhCl-C0Me2-K 2C03 or CH2PhBr-aq. E tO H -K O H affords b-hydroxy-l- and K . S. Subramaniam (Proc. Indian Acad. Sci., 1935, 2, A , 574 579).— a-Clausenan (I) (A., 1935,134) benzyloxy-G-benzylflavone, m.p. 205°. J. W. B. combines with maleic anhydride to give the anhydride Hydroxy - carbonyl compounds. X. Cou- C14H 140 4, m.p. 85°, of the acid C14H 16C>5, m.p. marins and chromones from m-4-xylenol. D. G. (+ 9 H 20) 98°, (anhyd.) 248°. With HgCl2 (1) gives F l y n n and A. R o b e r tso n (J.C.S., 1936, 215— 217).— the substance C10H10O(HgCl)2. (I) is oxidised by Condensation of m-4-xylenol (I) with CHRAe,C 02Et FeS04 to a mixture of a-clansenyl alcohol, C10H 14O2, gives (a) coumarins by Pechmann’s method, and (b) b.p. 89— 90°/30 mm. (Ac derivative, b.p. 98— 102°/30 chromones by that of Simonis, when R = H , Me, Et : m m .; phthaloyl derivative), a primary alcohol, with when R = C H 2Ph or with CH2Bz*C02Et (b) fails to an isomeric tert.-alcohol, b.p. < 93°/30 mm., dehydr give condensation products. (I) and CH2Ac’C 02Et ated by Na to (I). With K M n04, (I) yields a ketone, with 86% H 2S0 4 give 4 : 6 : 8-trimethylcoumarin C9H10O2, b.p. 95— 96°/55 mm. (oxime), with traces of (II), converted (Canter et al., A., 1931, 1069) into an acid (anilide, m.p. 154°). H N 0 3 (d M 2 ) has little 2-methoxy-fi : 3 : 5-trimethylcinnamic acid, m.p. 139°, action on (I) at < 3 0 ° ; with fuming H N 03 in AcOH, oxidised to 2-metlioxy-3 : 5-dimelhylacelophenone, b.p. a nitroketone, C9H90 4N, charring at 130°, is formed. 134— 135°/21 mm. (semicarbazone, m.p. 193°), also HCOoH at 0° gives a resinous product, b.p. 240°/2 mm., obtained by méthylation of the 2-OH-compound and no di-a-clausenan (II) (loc. cit.). (II) does not (III). 3 : 4 : 6 : 8-Tetramethyl- (IV), 4:6:8 -fri- combine with maleic anhydride; with fuming H N 0 3 methyl-3-ethyl-, m.p. 112-5— 113°, 4-p>henyl-H> : S-di- it yields a substance, C18H180 8N2, charring at 140°, methyl-, m.p. 111°, and 3-benzyl-4 : 6 : 8-trimethyl-, and with HgCl2 the compound C2oH220,(HgCl)2. Na m.p. 112— 113°, -counuirin are similarly obtained, 480 BBITISH CHEMICAL ABSTBACTS.— A. X V II (a) whence 2-methoxy-u. : ¡3 : 3 : 5-tetramethyl-, m.p. 4 : 4 '-dicoumarinyl (VIII) (A, R = H ). m.p. 290— 139-5— 140°, and -( 3 :3 : 5-trimethyl- Preparation of 1 : 4-dithiens. R. H. B a k e r l-Methyl-2-pyridone. E. A. P r i l l and S. M. and C. B a r k e n b u s (J. Amer. Chem. Soc., 1936, 58, M c E lv a in (Org. Syntheses, 1935, 15, 41— 44).— 262— 264).— COAr-CH2-S20 3Na (from COAr-CH2Cl (C5H5NMe)MeS04 (from C5H5N and Me2S0 4) is and Na2S20 3) are hydrolysed (dry or conc. HC1 in oxidised with alkaline K 3Fe(CN)G. Ch. A b s. (r) EtOH) to COArCHySH, which are immediately con Phenylhydrazone of X-phenylaminochelid- verted into 2 : 5-dihvdroxy-2 : 5-diaryl-l : 4-dithians amic ester. E. K o e n ig s and H. G u h lt (Ber., and thence (by loss of 2H20) into 2 : o-diaryl-1 :4 - 1936, 69, [B], 358).— E t, acetonedioxalate and dithiens (59— 74% yield). Condensation occurs much NHPh-NH, in boiling Et'OH afford the phenyl- 4S2 BRITISH CHEMICAL ABSTRACTS.— A. XV II (d) hydrazone of Et2 l-cmilino-i-keto-l : ‘k-dihydropyridine- 2-Butoxyquinoline-k-carboxyldiethylamide * (from the 2 : 6-dicarboxylate, m.p. 194°, which is not reduced 2-Cl-derivative and NaOBu) has b.p. 270°/20 mm., to the corresponding NH„-compound by SnCl2 ■ and m.p. 62°. The above amides are converted by NaOBr HC1. “ H.W. into 2-chloro-k-amino-, m.p. 188° (hydrochloride, m.p. 250°), and k-amino-2-ethoxy-, m.p. 128°, and Indole compounds. J. G n e z d a (Rad., 244, 13— 15; Cliem. Zentr., 1935, i, 3574).— Several -2-butoxy-, m.p. 85°, -quinoline, respectively. (II) colour reactions are described. H . N. R. is dehydrated by SOCI2 to 2-chloroA-cyanoquinoUne, imp. 156°, which with NaOAlk gives k-cyanoA2- Halogenated ketones. Ilia. Pyrrole. IV«. etlioxy-, m.p. 86°, and -2-buioxy-, b.p. 198°/18 mm.) Skatole. G. S a n k a (Rend. Seinin. Fac. Sci. Univ. m.p. 31°, -quinoline, reduced (H2, P d-B aS04, AcOH) Cagliari, 1934, 4, 59— 61; Chem. Zentr., 1935, ii, to 2-ethoxy-* (III), b.p. 205°/20 mm., m.p. 53° [di- 219; cf. A ., 1933, 1169).— III«. Condensation of hydrochloride, m.p. 230° (decomp.)], and 2-butoxy-* CHMeBr-COCl with Mg-pyrrole affords 2-a-bromo- (IV), b.p. 225°/17 mm., m.p. 51° (dihydrochloride, jyropionylpyrrole, m.p. 106°, which gives a pvrrole- m.p. >230°), A-aminomethylquinoline, respectively. black with alkali. Catalytic reduction of the Schiff base from (III) and T V « [with F. A t h e n e ]. Condensation of Mg- the appropriate RCHO or CORR' affords 2-ethoxy-i- skatole with CHC12-C0C1 or CC13-C0C1 yields 1-di- propyl-*, m.p. 207°, -4-benzyl-, m.p. 131°, and -4-|3- or l-tri-chloroacetyl-Z-methylindole, which cannot phenyletliyl-, m.p. 250°, -aminomethylquinoline hydro readily be isolated as the}' break down into C 02, chlorides, and 2-elhoxy-4-isobutyl-*, imp. 115°, and CHClj, and skatole; 2-substituted compounds are -i-phcnylisopropyl-, m.p. 110°, -aminomethylqui?wline not obtained. H. N. R. dihydrochlorides. (IV) similarly gives 2-butoxy-i- Ring-closures of derivatives of 2-aminostyrene. propyl-*, m.p. 213°, A-benzyl-, m.p. 177°, -4-$-phenyl- T. W . J. T a y l o r and (Miss) P. M. H ob so n (J.C.S., ethyl-, m.p. 134°, and -i-phenylisopropyl-, m.p. 1936, 181— 184).— 2-Acetamidostyrene (I) with P0C13 156°, -aminomethylquinoline hydrochlorides, and 2- gives quinaldine, whilst adipodi-2-vihylanilide, m.p. butoxyA-isobutyl-*, m.p. 120°, and -4-phenyllsopropyl-, 202°, obtained from 2-aminostyrene and adipyl m.p. 115°, -aminomethylquinoline dihydrochlorides. chloride, similarly forms a8-di-(2-quinolyl)butane, m.p. 2-Ethoxy-4-y-methylamino- (trihydrochloride, m .p. 98°, and 2-n-hexamidostyrene, m.p. 61°, affords 121°), and -4-y-diethylamino- (trihydrochloride, m.p. 2-w-amylquinoline (picrate, m.p. 104— 105°; lit., 71°), -pp-dimethylpropylaminomethylquinolincs are I l l — 112°). (I) and Br yield (I) dibromide, m.p. similarly prepared from (III) and 125°, which with KO H gives indole. cis-2-Nitro- NHMe-CH2-CMe2-CHO and NEt2-CH,-CMe2-CH0, stilbene, obtained from 2-nitro-a-phenylcinnamic acid respectively. (Ill) and CH2ChCH,-NEt2,HCl at and Cu chromate, is reduced to the N H 2-compound, 150— 160° give 2-ethoxy-4-P-diethylaminoethylamino- of which the Ac derivative, m.p. 112— 113°, with methylquinoline (trihydrochloride, m.p. 128°). 4- P0C13, yields 3-benzylidene-2-methylindolenine, also Cyano-2-ethoxyquinoline (V) and MgMel ( 274, 153— 173).— a-Nitrostilbenes are hydrogenated (II) and (IV) with excess of CH2Br-GH2-OH give poor (Pd-black) in C6H5N at 40— 00° to deoxybenzoin- yields of 6 : l-znethyleznedibxy-3-phenyl-, m.p. 92— 93° oximes, which with 3 % N a-H g in EtOH -AcO H give (hydrochloride, m.p. 220— 222°), and -3-3' : i'-znethyl- the ap-diarylethylamines. These bases with liot aq. enedioxy - 2 - p - hydroxyethyl - 1 : 2 : 3 : 4 - tetrahydroiso - CH20 give Schiff’s bases, which are cyclised in excell quiziolizie, m.p. 49° (hydrochloride, m.p. 258°); attempts e n t " yield by hot 10% HC1 to 3-aryltetrahydroiso- to dehydrate these OH-bases by NaOEt, P20 5 in quinolines if, but only if, Ar has OR in the p-position. PhMe, and long boiling in tetralin were unsuccesful; A C-C chain could be attached to the sec.-N thus S0C1, in CHC13 led to mixtures. R. S. C. formed, but ring-closure with the 3-aryl nucleus could not be effected. The following are prepared by the Synthesis of succinic acid-i.soquinolinium- above methods, the direction of ring-closure being betaines. 0. L u t z and A. K r a u k l is (Ber., 1936, proved by the reactions described. $-Nitro-3-zneth- 69, [5], 419— 422).— isoQuinoline (I) and maleic oxy-afi-dipheziylelhylezie (from wi-OMe-Cr)H4-CHO, acid (II) in abs. E t,0 at room temp, afford iaoquiziol- CH2Ph-N02, and a little NHMe2 kept in EtOH at iziiuzn Id znaleate, m.p. 103°, which passes when heated room temp, for 4 days), m.p. 78°. Deoxybenzoin- into succiziic acid - isoquizioliniumbelaizie (III), oxime, m.p. 94°; 3 : 4-znethyleziedioxy-, m.p. 138°, 3-znethoxy-, m.p. 80°, 3:4-, m.p. 108°, and 2:4- C?7£ ^ f 2H’ m-p‘ (anhyd’) 151-152°’ m ‘P- diznethoxy-deoxybenzoizioxizne, m.p. 91°. a-Pheziyl-(i- (4 -lH 20) 149— 150°, better obtained by keeping 3 : 4-wleiliyleziedioxy-, m.p. 37— 38°, b.p. 222— 223°/ (I) and (II) in MeOH or H 20 for some time at room 17 mm. [acetate, m.p. 152— 153°; hydrochloride, temp, or by heating them in H 20 at 50— 60°. (HI) m.p. 258— 259° (decomp.); Bz derivative, m.p. 180°], is also obtained similarly from (I) and fumaric acid -4- (I), b.p. 202— 203°/12 mm. (acetate, m.p. 135°; and also appears to be produced from Abromosuccinic hydrochloride, m.p. 208—209°), and -3-znethoxy-, b.p. acid. H . W . 192°/11 mm. (hydrochloride, m.p. 205— 207°), -3 : 4-, m.p. 67°, b.p. 233°/16 mm. (H oxalate, m.p. 176°; Carbon double Unkings and nitrogen-carbon Bz derivative, m.p. 178°), and -2 : 4-diznethoxy-, linkings. XIII. Degradation of quaternary b.p. 230— 231°/1S mm. (hydrochloride, m.p. 214°; ammonium compounds by catalytic hydrogen Bz derivative, m.p. 183— 184°), and -4-hydroxy- ation. II. E m d e and H. K u l l (Arch. Pharm., 'plieziylethylamizie [from (I) and 38% HC1 at 150°], 1936, 274, 173— 184; cf. A., 1934, 515).— Many m.p. 159° (hydrochloride, m.p. 252° after sintering); quaternary N H 4 salts are hydrogenated to ter/.-bases “P-di-3.: 4-methylenedioxyphenylethylamine hydro but the reaction differs in ease and often in course chloride, m.p. 254° (lit. 245°). 6 : 7-Methylenedioxy- from the N a-H g reduction. CH2ICH-CH2-NMe3I (II), m.p. 82— 83° [hydrochloride, m.p. 245—240° with H2-P t (not Pd) in AcOH or H 20 gives NMe3 (decomp.); AO-derivative, m.p. 125°], 6 : 7-diznetlioxy- (63%), a little C3H0, more C3H 8, and much NMe3Pr“i m.p. 96° [hydrochloride, m.p. 258° (decomp.); ATI- (unaffected by hydrogenation). CHPli!CH*NMe3Cl derivative, m.p. 100°], and G-znethoxy-3-pheziyl- with H 2-P t or -P d gives PhPr° (70% ), NMe3, and 1:2:3: 4 - tetrahydr^oquinoline, (III), m.p. 72—73° Ph-[CH2]3,NMe3Cl (not degraded by hydrogenation, (hydrochloride, m.p. about 263°); 6 : 7-znethzjleziedi- but slowly giving the cycfohexyl derivative). oxy-3-3' : 4 '-zziethyleziedioxyphenyl-1 : 2 : 3 : 4 -tetra- CH2Ph,NPhMe2Cl with H 2-P d gives PhMe and hydroisoquiziolizie (IV), m.p. 124— 125° (hydrochloride, NPhMe2, with H2-P t methylcycfohexanc (I) and m.p. 250— 251°; AO-derivative, m.p. 149°). (II) cyc/ohexyklimethylamine (platizii-, m.p. 158°, and and hot aq. K M n04 afford 6 : 1 -znethyleziedioxy-3- auri-chloride, m.p. 105°). CH2:CH-CH2-NMeI-CH2Ph, izheziylisoqziizwlizie (23% yield), m.p. 128° [hydro CH2Ph'NMe3Cl, and CH2PlrNMc3I are unaffected by chloride, m.p. about 270°; znethiodide, m.p. 239° H 2-P d, but the two last salts with H 2-P t give NMe3 (decomp.) after sintering], BzOH, and a small amount (96%) and PhMe [or by longer hydrogenation (I)]. of a nitrogenous acid, m.p. 276°; (IV) and KMn04 (CH2Ph)2NMe2I with H2-Pd in 50% AcOH or give similarly a small amount of 6 : 7-znethylenedioxy- (CH2Ph)2NMe2Cl with H 2-P t in H 20 gives PhMe and 3-3' : i'-znethyleziedioxyphezizjlisoqiiizioline, m.p. 210— NMo2-CH2Ph very slowly. NPhMe3Cl in AcOH with 211°., (II) and Mel yield 6 :7 -znethylenedioxy- H 2-P t (not Pd) gives slowly NMe3 and C6H6 and then 3 -phenyl - 2 - znelhyl -1 : 2 : 3 : 4-tetrahzjdro\soquinoline eyefchexane. \-Methzjlpiperidizie znethiodide and znethiodide, m.p. 268°, which (a) With N a-H g in hot znethochloride, hygroscopic, cannot be hydrogenated. H 20 gives 4 : to-znethyleziedioxy-2-^-pheziylethzylbezizyl- 1-Methyltetrahydroquinoline methiodide (methoauri- dizziethylamine (V), an oil (oxalate, m.p. 173°), the chloride, m.p. 184°; methosulphate, m.p. 198°) with znethiodide, m.p. 211°, of which with N a-H g affords H 2-P t (not Pd) in H 20 (not AcOH) gives 4 : b-)nethylenedioxy-2-(i-pheziylethyltolziezic, m.p. 49°, Ph'[CH2]3-NMe2, and 2-znethyltetrahzjdroisoquizwlizie and (6) with hot conc. KO H gives 4 : 5-znethyleziedioxy- znethiodide, m.p. 189°, or methochloride (znethoauri- 2-diznethylazziizioznethzjlstilbezie, an oil (oxalate, m.p. chloride, m.p. 187°) yields similarly (i-o-tolylethyl- 221— 222°), hydrogenated (Pd-C) in warm H.,0 to dimethzjlamine, b.p. 223—224° [hydrochloride, m.p. (V-) and oxidised by hot aq. KM n04 to BzOH 221°; platinichloride, m.p. 168° (decomp.); picrate, and hydrastic acid. 6-M ethoxy-3-pheziyl-2-znethyl- m.p. 126— 127°; metho-aurichloride, m.p. 156°, 1:2:3: 4-tetrahzydroisoquiziolizieznethiodide [from (III) and -picrate, m.p. 152°]. Hydrogenation of o- and Mel], m.p. 255— 258°, with hot conc. KOH gives C H2:CH-CcH4-CH2-NMe2 affords o-ethzylbezizyldi- o-methoxy-2-diznethylazninomethylstilbezie (oxalate, m.p. zziethylazziizie (aziri-, m.p. 148°, and plalini-chloride, 181— 182°), oxidised by K M n04 to NHMe2, BzOH, m.p. 166— 167°; picrate, m.p. 133-5°; znethiodide, and 4-methoxyphthalic acid (azthydride, m.p. 92°). m.p. 226°; znethoaurichloride, m.p. 187°). R. S. C. 484 BEITXSH CHEMICAL ABSTRACTS. A. XVII (d) 2 : 8-DiaIkoxy-10-aJkylacridinium derivatives which vanishes if a second OMe is present. Pro with various kinds of amino-group in the tracted treatment of compounds of the above type 5-position. X. Synthesis of 2 :8-dialkoxy-5- with boiling H „0 causes elimination of the 5-N-chain p-aminoanilino-10-alkylacridinium derivatives and production of acridones. With conc. HC1 at and (2' : 8'-dialkoxy-10'-aIkyl-10'-suhstituted- 120— 125° the 5-aminoacridone is formed, déméthyl acridyl)-5 : 5 '-p-phenylenediamino-2 : 8-dialk- ation also occurring to some extent. The condens- ' oxy-10-alkylacridinium derivatives. XI. Syn ation of 5-chloroacridines with primary amines occurs thesis of 2 : 8-dialkoxy-5-piperazino-10-alkyl- only in presence of PhOH, since the 9-OPh-compounds acridinium and (2' : 8'-dialkoxy-10'-aIkyl-10'- readily react with amines under similar conditions, substituted-acridyl)-5 : 5' - pip erazino - 2 : 8-d i- they appear to be intermediates. alkoxy-10-alkylacridinium derivatives. K. cc-Diethylaminobutan-y-one is converted into the I sh ih aka (J. Chem. Soc. Japan, 1935, 5 6 , 289— 313, oxime, b.p. 141— 142°/15 mm., which is reduced by 457— 485; cf. this vol., 343).— X . The following Na powder in BuOH to y-amino-cn-diethylaminobidane, reactions are described for the 2 : 8-(OMe)2- and b.p. 72— 74°/12 mm. NH2-[CH2]2-NEt2, b.p. 145— -(OEt)2-compounds, with OH and Cl as 10-acridinium 149% atm. pressure, is obtained from o- anions : 5-chloro-2 : 8-dialkoxy-10-alkylacridinium Cr,H4(CO)2N'[CH2]2*Br and N H E t, in boiling xylene chloride (I) and p-C6H4(NH2)2 give the hydrochloride followed by hydrolysis -with 12W-HC1, and (II) of the 5-p-amitioanilino-derivntive (HI) and the X H 2-[CH2]3X-E t2, b.p. 55— 58° 12 mm., is derived (acridinium) dialkohalide of NN'-bts-(2 : 8-dialkoxy-o- from o-CsH4(Cti)oH‘[CHo]3'Cl and NHEt„ or from acridyl)-p-phenylenediamine, also obtained from (H) o-Ci,H4(CO)2NK “ and “XE t2-[CH2]3-Cl. z-Diethyl- and (III). aminoamylamine, b.p. 205— 208°, is obtained from X I . The (I) and piperazine (as above) give the NH Bz’[CH2]5'C1 and N H E t, at 100— 120°, followed by hydrohalide (I as well as Cl) (IV) of the corresponding hydrolysis with conc. HG1 at 125°. XHBz-[CH2]5,C1, b-piperazino-derivutive and the (acridinium) di PBr3, and Br give a - chloro - e - bromopentane, alkohalide (V) of NN'-6js-{2 : 8-dialkoxy-ti-acridyl)- b.p. 210— 212°, transformed by the successive piperazine. (IV), with K0H-CHC13, gives (V) and action of NaCN in MeOH and N H Et, into with H 20 gives the lQ-alkyl-o-acridone (VI), also c-dieihylaminohexonitrile, b.p. 92—97°/3-5 mm., formed by similarly treating either (V) or the (pvper- reduced by powdered Na in abs. EtOH to a-amino- azinium or acridinium) dioxalate or the (acridinium) B-diethylaminohexane, b.p. 216— 218° (aurichloride, iodide or (piperazinium) oxalate corresponding with m.p. 120— 122°). o-C0H4C1-CO.,H, Iv2C03, and j - (IV)- Ch . A b s . (r) OMe,C6H4‘N H 2 in boiling amyl alcohol containing a trace of Cu powder give JV-p-anisylanthranilic Sulphonation of acridone, and certain trans acid, m.p. 183— 184°, transformed by boiling P0C13 formations of acridone-3-sulphonic acid. M. into o-chloro-Z-meihoxyacridine, m.p. 152— 1535 P o la c z e k (Eocz. Chem., 1935, 1 5 , 565— 577).— Nitration of o-C6H4CTC02H and condensation of the Acridone and conc. H2S0 4 at 100° yield aeridone-3- product with p-OMe-C6H4*NH2 affords 5-«iiro-N-p- sulphonic acid (I) [Ba and Pb salts; chloride; amide; anisylanlhranilic acid, m.p. 216— 220°, transformed Et ester, m.p. 232— 233° (decomp.)], also synthesised into o-chloro-S-nitro-Z-methoxyacridinc, m.p. 220— by heating o-C6H4ChCO,K and K sulphauilate in H 20 221°. Aminoveratrole and 2 : 4-CRH3C]2-C02H afford in presence of Cu (115— 120°; 6 hr.), and condensing 4-cWoro-N-3' : 4'-dimethoxyphenylanthranilic acid, m.p. t he K 4'-sulphodiphenylamine-2-carboxylate obtained 190— 191°, whence 5 : 7-dichloro-( ?)2 : 3-dimethoxy- in presence of POCl3 at 115° (30 min.). When fused acridine, m.p. 202— 203°. Gradual addition of with KO H (I) yields 3-hydroxyacridone, m.p. 330— N H ,-[CH2]2‘N Et2 to a mixture of 5-cliloro-3-ethoxy- 370° (benzoate, m.p. 2S5— 287°), identical with the acridine and PhOH at 70— 80° affords 5-$-diethyl- product obtained from 4'-ethoxydipkenylamine-2- aminoethylamino-3-ethoxyacridine, m.p. 242—244 . carboxylic acid and H.,S04 (100°; 15 min.). (I) in The following -acridities are obtained by similar P0C13 and NPhMe, (120°; 1 hr.) yield 3-p-dimethyl- methods : 7 - nitro - 5 - 3 - diethylaminoethylamino - 3 - aminobenzenesulphonyl - 5-p-dimethylatninophenylacrid - ethoxy-, m.p. 246— 252°, 8-nitro-5-$-diethylaminoethyl- one, m.p. 264— 265°. (I) and 8 0 % oleum at 100° afford acridone-3 : 7-disulphonic acid (Ba and Pb salts), also 3-eihoxy-, m.p. 172— 175° [dihydrochloride, m.p. 243— 246° (decomp.)]; 7-nitro-5-y-diethylaminopropylamino- prepared from 2-chloro-3-sulphobenzoic acid and sulphanilic acid in presence of Cu and EL,C03 (115— 3-ethoxy- [dihydrochloride (+H ,0), m.p. 226—228°]; 7 - chloro - 5 - y - diethylaminopropylamitio - 3 - methoxy - 120°; 8 hr.), followed by condensation of the product with H2S04 at 100° R, T. [dihydrochloride (+3H 20), m.p. 249— 250°] : 8-nitro- o-y-diethiylamino - (J - hydroxypropylamino - 3 - methoxy -, Acridiae compounds and their antimalarial m.p. 124° (dihydrochloride, m.p. 213— 214°) ; 7-chloro- action. I. 0. J. M a g id so n and A. M. Gr igorovski 5 - (1 - hydroxy -y-d iethylaminop ropylam vno - 3 - methoxy -, (Ber., 1936, 6 9 , |B], 396— 412).— Compounds of the m.p. 105— 107° (dihydrochloride, m.p. 237— 239 ) ; type 8-chloro-5-diethyiamino-R-amino-3-methoxv- 7-chloro-5-8-diethylaminobiUylamino-3-methoxy-, m.p. acridine have a very powerful antimalarial action 76— 78° (dihydrochloride, m.p. 246— 248°) ; 7-chloro- which attains a max. when R = [C H 2]4. Introduction 5-8-diethylamino-a.-methylbutylamino-3-methoxy-,^ m.p. of OH into the side-chain diminishes the therapeutic S6— 88° (dihydrochloride, m.p. 246—248°); o-y-di- action if Cl is present, but increases it in the presence ethylaminopropylamino-3-methaxy- (dihydrochlondt’, of N 0 2. Compounds without a substituent at 7 or m.p. 240— 241°) ; 8-nitro-5-y-diethylaminopropyl- S are therapeutically inactive. Increase in the ammo-3-meihoxy-. m.p. 122— 123‘5° (dihydrochloride, size of 3-OAlk diminishes the therapeutic activity, m.p. 229—230°) ; 7-chloro-o-y-diethylaminopropyl- X V n (d, e) ORGANIC CHEMISTRY. 485 amino-( ?)2 : ‘3-dimethoxy- [dihydrochloridc (+ 2 H 20), Pyrimidines. CXLIX. Synthesis of aryl- m.p. 227— 228°]; l-cliloro-a-di-(y-diethylaminopropyl)- substituted dihydrouracils and their conversion cCmino-3-methoxy- (very unstable hydrochloride) ; 7- into uracils. T. B. J o h n s o n and J. E. L t v a k (J. chloro-5-8-diethylamino-a.-methylbutylamino-C,:)'2 : 3- Amer. Chem. Soc., 1936, 58, 299— 303).— Hydrobenz- dimethoxy- [dihydrochloride (+2H20), m.p. 217— amide and CH2(C02H)2 in cold EtOH give (3-amino-j3- 218°]; 7 - chloro - 5 - y - diethylaminop ropy la mirw - 3 - phenylethane-aa-dicarboxylic acid, m.p. 153°; in ethoxy- [dihydrochloride (+1H20), m.p. 246—247°]; the hot, p-amino-p-phenylpropionic acid (I) results l-cMoro-b-S-dicthylammobutylamino-3-ethoxy- [di (cf. Rodionov et al., A ., 1929, 557; 1933, 1307). (I) hydrochloride (+2H20), m.p. 254—255*5°]; 7-chloro- is also prepared from CH2(C02H)2, PhCHO, and ~)-y-diethylaminopropylamino-‘i-methyl- [dihydro - EtO H -N H 3 or -N H 4OAc. p-Amino-p-anisylprop- chloride (+2H20), m.p. 239—241°]; 7-chloro-5-z-di- ionic acid (II), m.p. 232° (decomp.), is similarly eihylaminoamylamino-Z-'inethoxy- [dihydrochloridc prepared using anishydramide. (I) and (II) with (+H 20), m.p. 266— 268°); 7-chloro-o-$-dielhylamino- ArNCO give the p-arylcarbamido-acids, which are ethylamino-3-methoxy- (dihydrochloride, m.p. 258— converted (usually by Ac20) -into 4-phenyl-l-aryl- 259°); l-chloro-o-y-dietiiylamino-rj.-diethylamino-'i- [A) and 4-anisyl-l-aryl- (B ) - 4 : 5-dihydrouracils, methylpropylamino - 3 - methoxy - [dihydrochloridc respectively; ArNCS leads to the 2-thion analogues. (H-lHjO), m.p. 253—254°]; 7-chloro-o-e-diethyl- Bromination of (A) in AcOH at 75— 105° gives the aminohexylamino-3-methoxy- (dihydrochloridc, m.p. 5-Br-derivative when aryl=Ph or o-tolyl; when aryl 232— 235°). H . W . = P-C10H7 or p -N 0 2*CBH4*, bromination is retarded or inhibited. With (B ), introduction of Br into the Manufacture of acridine derivatives.— See B., 3 position of the anisyl group first occurs; the result 1936, 299. ing compounds then behave as {A). The following are Water-soluble salt of 3 : 6-diarnino-10-methyl- described : ¡3-earbamido-, m.p. 192° [from (I) and acridinium.— See B., 1936, 220. HNCO], fi-phenylcarbamido-, m.p. 174°, P-o-tolyl- carbamido-, m.p. 172°, $-2-naphthylcarbamido-, m.p. Optical activity dependent on co-ordinated 201°, $-p-nitrophenylcarbamido-, m.p. 202—203°, bivalent ruthenium. F. H . B u r s t a l l (J.C.S., P-l-naphthylcarbamido-, m.p. 184— 186°, and 1936, 173— 175).— 2 : 2'-Dipyridyl with RuC13 at 250° p-phenylthiocarbamido-, m.p. 158°, -^-phenylpropionic gives tris-2 : 2'-dipyridylruthcnous chloride, from which acids\ $-carbamido-, m.p. 193°, $-phenylcarbamido-, the corresponding base, tris-2 : 2'-dipyridylruthcnous m.p. 167— 168°, p-o-tolylcarbamido-, m.p. 180— 181°, hydroxide octahydrate, [Ru dipy3](0H )2,SH20 , and the P -l- and -2-naphthylcarbamido-, m.p. 178° and 191°, bromide, iodide, perchlorate, nitrate, carbonate, and respectively, p-p-nitrophcnylcarbamido-, m.p. 171— r-tartrate have been prepared. All these salts form 172°, p-methylcarbamido-, m.p. 168— 169° [from (II) hexahydrates, the carbonate also forming a deca- and MeNCO], fj-phenylthiocarbamido-, m.p. 146°, and hydrate; they are more stable than the corresponding $-o-tolyllhiocarbamido-, m.p. 163°, -[i-anisylpropionic F e" and Ni” salts. Resolution of the d- and Z-tar- acids’, 4-phenyl-, m.p. 217° (5-Br-derivative, m.p. trates gave d-, [a]ffsl -|-860°, [AT] -{-7205°, and 1-Zris- 214°), ‘i-anisyl-, m.p. 228° [3’-Br-, m.p. 232°, and 2 : 2'-dipyridylruthcnous bromide hexahydrate, [a]“ 0i 5 : 3’-Br»- (III), m.p. 193— 194°, derivatives], 1 : 4- —815°, [M\ — 6828°, respectively. L. J. J. diphenyf-, m.p. 226° (5-Br-derivative, m.p. 220— Preparation of iVA'-disubstituted barbituric 223°), l-phenyl-4-anisyl- (IV), m.p. 210°, 4,-anisyl-l- and thiobarbituric acids. N. V . K o s c h k in (J. 0-tolyl- (V), m.p. 181°, i-phcnyl-l-Z-naphthyl-, m.p. Gen. Chem. Russ., 1935, 5, 1460— 1467).— Disub 240— 241°, 4:-anisyl-l-$-naphthyl- (VI), m.p. 256— stituted barbituric acids cannot be obtained from 257°, 4o-phenyl-l-p-nitrophcnyl-, m.p. 253— 254°, 1-p- sodiomalonic ester and substituted carbamides and nitrophenylA-anisyl- (VII), m.p. 268— 269°, d-phenyl- thiocarbamides, under various temp, conditions. \-a-naphthyl-, m.p. 192— 193°, A-anisyl-l-u-naphthyl-, mU'-DiphenyWarbituric acid, m.p. 238-5— 239°, was m.p. 218—219°, 4-phenyl-l-methyl-, m.p. 149— 151°, obtained by heating a mixture of CO(NHPh)2 (I) and and i-anisyl-l-methyl-, m.p. 138°, -4; 5-dihydro CH2(C02H)2 with AcCl in dry CHC13 at the b.p. for uracils’, 6-keto-2-thion-4-phenyl-, m.p. 238° (S-M e 4 hr.; NN'-di-o-tolylbarbituric acid, m.p. 176-5— derivative, m.p. 163-5°), -4-anisyl-, m.p. 228°, -1 : 4- 177°, and NS'-di-o-tolyl-, m.p. 216-5— 217°, NN'-cZi-a-, diphenyl-, m.p. 243°, -i-phcnyl-l-o-tolyl-, m.p. 188°, m.p. 250— 250-5° (decomp.), and WS'-di-fi-naphthyl- -1 -phenylA-anisyl- , m.p. 231— 232°, and -4-anisyl- thiobarbituric acid, m.p. 247-5— 248°, were obtained 1-o-tolyl-, m.p. 188°, -hexahydropyrimidines; 4-phenyl-, analogously. (I) and CH,(C02Et)2 in xylene at the m.p. 267°, and 1 : 4-diphenyl-, m.p. 292—294°, b.p. yield CH2(CO*NHPh).;. “ ‘ R. T. -uracils, obtained by elimination of HBr from the [Glyoxalinecarboxylic esters.] W . John (Ber., appropriate 5-Br-derivative with C6H5N (general 1936, 69, [B], 484; cf. this vol., 211).— The ability procedure); 4-3'-bromo-4'-melhoxyphenyluracil, m.p. of glyoxalinecarboxylic esters to lose C 02 when 304— 305° [from (III)]. Bromination of (IV) gives heated is also shown by certain indazole- and pyrazole- \-phcnyl-4-3'-bromo-4'-methoxyphcnyl-4 :5 - dihydro earboxvlic esters. jj yy uracil, m.p. 210°, and then the 5-Br-derivative, m.p. 242°, which yields l-phcnyl-4-3'-bromo-4'-methoxy- Synthesis of l-phenyl-4-p-hydroxyethylpiper- phcnyluracil, m.p. 326—328°. l-o-Tolyl-4-3'-bromo- azine. C. B. K r e m e r (J. Amer. Chem. Soc., 1936, 58 4'-methoxyphenyl-uracil, m.p. 312°, and -4 : 5-dihydro 379).— N(CH2*CH2*OH)3, N H 2Ph, and cone. H2SO’ uracil, m.p. 178° (5-JBr-derivative, m.p. 201°), are give 1-phenyl-4-fS-hydroxj-ethvlpiperazine, m.p 84° similarly obtained from (V). (VI) gives 4-3'-bromo- (corr.) (lit. 83° and 91°). jj_ j> 4' - methoxyphenyl -1 - [i-naphthyl -4:5- dihydrouracil, 486 BRITISH CHEMICAL ABSTRACTS. A. XVII (e) m.p. 238— 239°, which could not be brominated Derivatives of quinazoline. (Miss) T. M. further; similarly, (VII) afi’ords l-p-nitrophenyl-4-3'- R e y n o l d s and R. Robinson (J.C.S., 1936, 196— bromo-4'-methoxyphenyl-4 : 5-dihydrouracil, m.p. 194— 199).— In part a reply to Spath (A., 1935, 873), 196°. H . B. and a detailed account of work already summarised (A., 1934, 1014). The following data are new: Synthesis of 2-amino-4-ethylpyrimidine. W. T. 3-allylquinazolinium iodide-f-0-33EtOH, m.p. 101— C a l d w e l l and W . M. Z i e g l e r (J. Amer. Chem. Soc., 107° (picrate, m.p. 124°). When heated with MeN02 1936, 58, 287— 288).— 6-Chloro-2-ethylthiol-4-ethyl- in EtOH, 4-hydroxy-3-allyl-3 ; 4-dihydroquinazcdme pyrimidine, b.p. 110— 112°/4— 5 mm. (from the affords the 4-nitromethyl compound, isolated as its 6-OH-derivative and P0C13), is reduced (Zn dust, aq. picrate, m.p. 152— 153°, 4-nitromethyl-d-methyl-Z: 4- EtOH) to 2-ethylthiol-4-ethylpyrimidine, b.p. 105— dihydroquinazoline, m.p. 137°, being obtained simi 107°/4 mm., hydrolysed (conc. HC1) to 2-hydroxy-4- larly. Passage of dry HC1 into a mixture of cthylpyrimidine hydrochloride, m.p. 211— 213° (de HCO-NH2, 6-nitropiperonal, and C6H6 at 60° affords comp.) (sinters about 200°). This and P0CJ3 give (S-nitropiperonylidencdiformamide, m.p. 248— 250° (de 2-ch loro -4~ethylpyrimidine, b.p. 89—91°/7 mm., con comp.), converted by Zn dust-ice-AcOH into 6 :7 - verted by EtOH-NHg at 120— 130° into 2-amino-4- methylenedioxyquinazoline, and, under certain con ethylpyrimidine (I), b.p. 229°, m.p. 140— 141° (picrate, ditions, into a non-diazotisable base, C9H 0O3N2, m.p. m.p. 194-5— 195-5°; aurichloride, m.p. 98— 99°). 260— 261°. (I) when refiuxed with Mel in EtOAe 2-Amino-6-hydroxy-4-etJiylpyrimidme, m.p. 243— 245° gives 6 : l-methylenedioxy-Z-methylquinazolinhm (decomp.) (from guanidine carbonate and iodide, m.p. 239—240° (picrate, softens 183°, m.p. EtCO-CHvCOgEt in EtOH), and P0C13 give the 185— 186°), converted by AgCl into the chloride, 6-CZ-derivative, m.p. 129— 130°, reduced (Zn dust, hydrolysed by aq. K O H at 2— 10° to -i-hydroxy-G : 7- aq. EtOH) to (I). (I) differs from 6-aniino-4-ethvl- methylenedioxy - 3 - methyl - 3 : 4 - dUiydroquinazoline, pyrimidine (this vol., 344); the structure of the softens 154°, m.p. 158— 159°, converted by MeN0.> latter is thus established. H . B. into the 4-nilromethyl, m.p. 159— 160°, by COMe2- aq. Na2C03 into the 4-acetonyl compound (picrate, Piria reaction. III. Mechanism. W. Mi sinters 184°, m.p. 187°), and by boiling 2 % NaOH L a u e r , M. M. S p ru n g , and C. M. Langkammerer into 6-aminopiperonal. J. W. B. (J. Amer. Chem. Soc., 1936, 58, 225— 228).— The isolation of 1 : 5-dimethylbenziminazole [tartrate, Reaction between benzoyl chloride and arom m.p. 1S5-2— 185-8° (decomp.)] in 18-3% yield from atic amines, and their products, compounds the N aH S03-reduction products of 3-nitro-4-dimethyl- of the quinazoline series. K . Dziewonski and aminotoluene indicates the intermediate formation L. S t e r n b a c h (Bull. Acad. Polonaise, 1935. A, of the NO-derivative. If NO-compounds are formed 333— 348).— p-CgHjCl-NHo and BzCl with anhyd. in this way, then the Piria reaction (A., 1931, 720) ZnCl2 at 180— 200° afford G-chloro-4-hydroxy-2 : 4- should occur with either the N 0 2- or NO-derivative. diphenyl-3-p-chlorophenyl-3 : 4-dihydro- (I), m.p. 159° In agreement with this view, reduction (Na„S03, (hydrochhride, m.p. 353°; picrate, m.p. 178°; El NaHS03, or mixtures) of p-CGH,Mc-NO gives ether, m.p. 225— 226°), converted by heating at 250' p-C6H4Me-NH2 (44— 73% ) and p-toluidine-3-sul- into G-chloro-2-hydroxy-2 : 4-diphenyl-Z-p-chlorophenyl- phonic acid (I) (5-7— 14-8%), i.e., the same products 2 ; 3-dihydro-quinazoline (II), m.p. 199—201°. Hydro as are formed (loc. cit.) from p-C6H4Me-NO„ (II). lysis of (I) or (II) with EtO H -H Cl gives 5-chioro-2- Details are given for the isolation of Na., 3-sulpho-4- benzamidobenzophenone (III), reconverted by S0C12 methylphenylsulpliamate ( + H 20) (III),“ from the and p-CGH4ChNH2 into (II). Diazotisation of 5- N aH S03-reduction products of (II); (III) is hvdro- chloro-2-aminobenzophenone (IV) [by E tO H -H 2S04 Ivsed (dil. HC1) to (I) in quant, yield. (Ill) is also hydrolysis of (HI)] and coupling with fS-G10H7-OH prepared from (I) and 1 -pyridiniumsulplionic acid gives 4-chloro-2-benzoylbenzeneazo-(i-naphthol, m.p. (Baumgarten, A., 1926, 1130) in aq. Na2C03 at 10°; 184— 185°. With N H j-E tO H at 140° (I) ^ gives 6- (i2 and 'p-sulphophenyl-, •^-sulpho-2.-methylphetiyl- chloro-2 : 4-diphcnylquinazoline. m.p. 190-5°. With (+2H 20), and 4-sulpho-l-na,phthyl. (+ 2 H „0 ) -sulpli- XH yOH .H Cl in boiling EtOH (I) affords the oxime amates are similarly prepared. Reduction (alkaline anhydride, C6H3C 1 < ^ ^ > 0 (V), m.p. 186-187°, Na metabisulphite) of p -N 0 2-C6H4-0H gives p -N H 2• Cf,H4• OH and 4-aminophenol-2-sulphonic acid but (H) gives the oxime, m.p. 163°, of (III). With [since deamination (diazo-method) and subsequent H X 0 3 (d 1-52) p-C6H4Cl-NHBz gives its 2-NOr bromination affords s-CeH2Br3-OH], 5-Nitrosalicvlic derivative, m.p. 132— 133°, reduced by Zn-AcOH acid similarly yields 5-amino- and 5-amino-3-sulpho- to 6-chloro-2-phenylbenziminazole (Fischer et aU salicylic acid (deamination and bromination gives A.. 1906, i, 895), also obtained from (V) and EtOH- s-C6H2Br3-OH). In these cases, S 0 3H is introduced HC1 at 150°. Diazotisation of (IV) and t r e a t m e n t meta to N H 2, presumably owing to 1 ; 4-addition of with NTa2S0 3-N aO H at < 10° gives o-chloro-2-hydroxy- N aH S03 to the -X.'OCIC- of the intermediate nitroso- '4-phenylindazole, m.p. 113— 114°, reduced (SnCl^ phenol (as quinoneoxime). The Piria reaction on HC1) to 5-chhro-'4-phenylindazole, m.p. 125— 12/ • (II) thus involves the following reactions; (a) By similar methods from the appropriate amine and p-C6H4Me-N02 -> p-CGH4Me-NO BzCl are obtained 4-hydroxy-2 ; 4-diphe7iyl-'H-p-tolyl-G- p-C6H4Me*NH-SO.jNa -> p-CfiH4Me*NH„: (b) methyl- +COM e2, m.p. 141°, and solvent-free, m.p- p-CBH4Me-NO -> 2 : 4-S 03Na*C6H3Me-S03Na % 14S—-149° (hydrochhride, m.p. 320°; picrate, m.p- S 03H • CgHgMe -NH,. H. B. 143°; Et ether, m.p. 161°), and -6 : 8-dimethyl-3 '■ 4- XVII (e, f) ORGANIC CHEMISTRY. 487 dihydro- (VI), m.p. 163— 164° (¡derate, ra.p. 204°), isomerism of (II) and (III) is proved since both have converted into 2-hydroxy-2 : i-diphenyl-'.S-p-tolyl-Ci- the properties of an o-C6H4(NH2)2 and both give rnethyl-2 : 3-dihydro-, m.p. 194— 195°, 2 : 4-diphenyl-G- (X O )2-derivatives with H 2S0 4-N a N 0 2, (II) giving a methyl-, m.p. 176°, and -6 : 3-dimethyl-, m.p. 152°, (NO)2-derivative, m.p. 126°, and (III) an (xYO),- -quinazoline, and the -6-methyl-, m.p. 190°, and derivative, m.p. 109°, whereas (IV) gives no X O - -6 : 8-dimethyl-, m.p. 180°, -oximeanhydride [both as derivative. (I), (II), (III), and (IV) are all dehydro (V)]. From (VI) are obtained 'l-amino-3 : 5-dimethyl- genated, by Pd-C at 200°, to phenazine. (II) is benzophenone, m.p. 128-5°, and its Bz derivative, unchanged by treatment with N a-E tO H , H 2-P d - m.p. 162°, and G-henzoyl-2 : 4-dimethylbenzeneazo-fi- AcOH, or when passed over catalyst-15 at 180°, naphthol, m.p. 130-5°. J. W . B. but with catalyst-M it is converted into (IV). (Ill) is unchanged by treatment with N a-E tO H or H2— Quinazolines. XLII. Synthesis of 3 :4-di- Pd-AcOH, but passage of its vapour over catalyst-A hydroquinazoline derivatives from p-amino- at 180° converts it into (IV), and, over catalyst-R benzoic acid, formaldehyde, and hydrochloric at 180°. partial conversion into (II) occurs. acid. S. E. Ca ir n c r o ss and M. T. B o g e r t (Coll. J. W . B. Czech. Chem. Comm., 1936, 8. 57— 65; cf. A ., 1935, Hydroxy-compounds of the anthrapyrimidine 1134).— p-NH2-C0H4-C G p t, C H ,0, and (a) IICl se rie s.— See B., 1936, 182. at 25° or (b) HC1-H2S04 at 70° give Et2 methylenebis- p-aminobenzoate, m.p. 192— 193°, converted by HC1- Alkylated iminazoles of high mol. wt.— See B., EtOH into Et 3-p-car bet boxyphenyl-3 : 4-diliydro- 1936, 183. quinazoline-6-carboxylate (I), m.p. 186— 187°, also New cleavage product of guanine. G. H u n t e r obtained in small amount in (b) above or in fair yield (Nature, 1936, 1 3 7 , 405).— When guanine is auto- by condensation of p-NH2-C6H4-C02H, CH20, HC1, claved -with an acid, approx. 20% is converted into and H 2SO.j at 70° and subsequent esterification. C4H 7N5, probably 4- (or 5-)guanidinoglyoxaline. (I) leads to the amorphous acid (Na salt), Reactions are described. L . S. T. (CH.El-CH,,).,, m.p. 173— 174°, and Me., ester, Function of halogens in hsemin. K. L in d e n - m.p. 241— 243°, which last with XEt,2-CH2-CJH,-ONa i-'eld (Rocz. Chem., 1935, 1 5 , 516— 542).— The re in C6He affords the (NEt.sCHsCH*)^ ester, m.p. action between hsemin (HmCl) and M X (M = a cation. 114— 115°, with anaesthetic properties. (I) and X = B r , I, CNS, HCO.,) in C5H5N-AcO H is Hm Cl-f KMn04-MgSO4-COMe2 give Et 3-p-carbethoxyphenyl- X '= H m X -| -C r ; C5H3X (or quinine) merely acts ■i-quinazolone-G-carboxylate, m.p. 138-5— 139-5°, also as a solvent, since diethyllucmin in CHCI3-AcOH obtained from the 1-Et ester, m.p. 217— 219° (lit. undergoes the same changes in absence of the bases, 216-5— 218°), of 4 : 1 : 3-X H 2-CfiH3(C02H)2 and Et and HmCl may be recovered unchanged from C5H5X fonnamidobenzoutc (prep, by 4 0 % HCÖ2H at 80°), solutions. The prep, and properties of formylhcemin m.p. 147— 148°, at 140— 150°, a product, m.p. 1S2— are described; acetylhannin cannot be obtained by 183°, being also formed in the latter reaction. M.p. the above reaction. It is concluded that the Cl are corr. B- S. C. linking is heteropolar. R. T. Bromo-derivatives of 4-hydroxy-2-thion-3- Preparation of cryptoxanthine from paprika. phenyl-1 : 2 : 3 : 4-tetrahydroqninazoline. C. V. L . von Ch o ln o k y (Magyar chem. Fol., 1934, 40 , Gheorghitt and (M l l e .) L. M a n o l e s c u (Bull. Soc. 85— 89; Chem. Zentr., 1935, ii, 230; cf. A., 1934, ehim., 1936, [v], 3, 321— 323).— 5-Bromoisatin and 657).— A chromatographic separation is described. PliNCS in NaOH-aq. EtOH give G-bromo-4-hydroxy-2- H. X . R. thion-3-phenyl-1 : 2 : 3 : 4-tetrahydroquinazoline-4-carb- Abnormal reactions of hydroxylamine. P. oxylic acid, m.p. 156— 161° (decomp, from 142°), giving with EtOH G-bromo-2-thionA-ethoxy-3-phe.nyl- D reyetjss (Rend. Semin. Fac. Sei. Univ. Cagliari, 1934, 4, 55— 58; Chem. Zentr., 1935, ii, 46).— 1:2:3: i-tetrahydroquinazoline, m.p. 197— 204°, which in HClO.j yields &-bromo-4-liydroxy-2-thion-3- Formula; are proposed for the compound obtained phenyl-l : 2 : 3 : i-tetrahydroquinazoline perchlorate from N H ,O H and dibenzylideneci/cZohexanono (Poggi (formulated as 4-earbonium salt), cryst., red. and Saltini, A., 1934, 773) and that from phorone and R. S. C. N H 2OH (Vorländer and Gästner, A ., 1899, i, 259). Phenazine series. III. Isomeric octahydro- 4:5:4': 5'-Tetramethoxy-2 : 2'-dibenzoylbenzophen- one yields a compound with X H 2OH (formula phenazines. G. R. Clemo and H . M cI l w a in (J.C.S., 1936, 258— 261).— Reduction of 1 : 2 : 3 : 4- suggested). H . X . R. tctrahydrophenazine (I) with X a-E tO H affords the Chemistry of the antineuritic vitamin. K. ( ?) tram-1 :2:3:4:9:10:11 : 12-Hs-derivative (II), M arino and' I. I m ai (Z. physiol. Chem., 1936, 2 3 9 , m.p. 156° (A., 1935, 991, gives m.p. 150°), but with I— II).— The constitutions H2- p d-C at room tem p./100 lb. per sq. in., the (?) CMe:g-CH2-CHo-OH cis-1 : 2 : 3 :4 : 9 : 10 : 11 : 12-H8-derivative (HI), c h < £ X ^ ' ) > c -c h ’ 'n ' CH-S m.p. 147°, is obtained. Reduction of (I) with H„— for the antineuritic vitamin (I) and catalyst B [Xi from Xi(0H )„ at 370— 380° by Rupe"s C H < ^ J “ C'fJ > c ( N ° 2)-CH2-OEt for the nitrate method] at 180° gives mainly (II) and a little (III), but with catalyst-^4 [Xi from X i(X 0 3)2 at 300— 310° obtained therefrom (cf. Windaus et al., this vol., 253) by Gattermami’s method] at 1 8 0 °,'the product is are suggested as alternative structures. The oxid the If: 2 : 3 : 4 : 5 : 6 : 7 : S-Hs-derivative (IV), m.p. ation of (I) by K 3Fe(CN)? and XaOH to thiochrome 109 (Wallach et al., A., 1924, i, 862). The geometrical can then be explained by simple analogy. H. V . 488 BRITISH CHEMICAL ABSTRACTS.— A. XVII (/, g) Carbocyanine dyes.— See B., 1936, 184. C1GH28-CX(0H )-CH2C1 (chlorohydroxysolanidane). The formation of (HI) is established by the production Nornicotine. A . W e n u s c h (Pharni. Zentr., 1936, of tetra-acetylsolanidine, NAc2-ClfiH2n-CHX-GH(OAc),,, 77, 141— 143).— There is relatively little nornicotine m.p. 253° (acetate) by the action of AcOH-Ac,0- (I) in the smoke from tobacco rich therein; oxidation H 2S0 4 on (I). Attempts to remove Cl from (IV)"by of (I) either by K M n 04 or during smoking gives an Zn and AcOH, Na and EtOH or amyl alcohol, or alkaloid (picrate, in.p. 217— 218°) resembling myos- through the Mg compound were unsuccessful. (IV) mine. (I) is less toxic than nicotine. R. S. C. is smoothly oxidised by Cr03 in AcOH or by KMn04 in COMe2; with molten K O H it affords a mono- d-Nornicotine. E. S p a th , C. S. H ic k s , and carboxylic acid and a neutral substance, m.p. 145°. E. Z a jic (Ber., 1936, 6 9 , [B], 250— 251).— Partly Since solanidine-Z differs from (I) in the possession of racemised (Z-nornicotme (A., 1935, 1136) is purified by C7H7 and a tert. X , it is suggested that it may be conversion into the perchlorate, which is crystallised X-benzylsolanidine-s and that (I) is therefore the from M eOH -Et20 . The most active portion has parent of all the solanidines, which differ by the M d + 86 -3 °, whereas the optically pure substance presence of alkyl or aryl attached to X or to the has Mi? +88-8°. H. W. carbocyclic groups. IT W. Tobacco bases. IV. Syntheses of i-nor- Phenyl-^pelletierine. B. K . B l o u n t (J.C.S., nicotine. E. S p a th , L. M a r io n , and E. Z a jic . V. 1936, 287— 288).— Dropwise addition of XaOMe- Constitution of myosmine. E. S p a th , A. MeOH to a solution of CH2Ph-CHO and CH2:CH-CH0 W e n h s c h , and E. Z a ji c (Ber., 1936, 69, [B], 251— inMeOH at - 1 8 ° to 0° affords CHO-[CH2],-CHPh-CHO 255, 393— 396).— IV . Z-Xicotine (I) is cautiously oxid in solution, condensed with CO(CH2-CO2H)2-CaC03- ised with KMnQ4 and the more strongly basic por aq. M eO H -33% X H 2Me to give 6-phenylgranatan-3- tions are removed from the product by fractional one (phenyl-^-pelletierine), isolated as its 2 : 4-tfi- extraction -with HC1. They are then distilled with piperonylidene derivative, m.p. 210°. J. W. B. steam in vac., whereby (I) is volatilised. The residue is transformed into the dipicrate, from which, after re Synthetic experiments on eserine. V. Syn peated crystallisation, Z-nornieotine (II), [a]^° — 76-1°, thesis of I-eserethole. T. H o s h in o and T. K oba- raised to — 83-2° after further purification through y a s h i (Proc. Imp. Acad. Tokyo, 1935, 11, 416— 417; the perchlorate, is isolated. Treatment of (I) with cf. A ., 1935,1256, 1378).— cZZ-Eseretliole and d-tartaric Ag20 and of the product dissolved in Et20 with aq. acid in EtOH give the d-tartrate, m.p. 173— 171° NaCl containing HC1 gives a most strongly basic M i? + 1 1 5 ° in H ,0 , of the (Z-base and the mothei- fraction from which (II), [a]*,0 — 88-8°, is isolated. liquors with the Z-acid give the Z-tartrate, m.p. 173— V. Myosmine (III), after purification through the 174°, [a]]? - 1 1 5 ° in H ,0 , of the Z-base. The active picrate, m.p. 1S2— 183° (vac.), has m.p. 42— 43° picrates melt at 135— 136°, the tZZ-picrate at 151— (vac.), and is optically inactive in MeOH (c=20). It 152°. R. S. C. is dehydrogenated by Pd sponge at 200° Synthesis of bicuculline. I. P. W . G. G boexe- y i to 2-3'-pyridylpyrrole. Its composition, w o ttd and R. R o b in s o n (J.C.S., 1936, 199— 202).— I II—I J optical inactivity (assuming that it is not Bromonormeconin when heated with methylene sul k / y X- jr n a rnhbm racemate flfo onr? and lt«vnskA hence ^Ancidoes nAfnot nonl-nivi contain phate in aq. COMe2-X a O H (X 2 atm.) affords 6-bromo- (HI i an asymmet;ric G atom), and conversion \ 3 : 4.-melhylenedioxyphthalide, m.p. 196°, reduced (Al- by Bz20 in abs. E t ,0 with opening of Hg in boiling EtOH, Zn dust-aq. XaOH, or the ring into (Ï) 3-y-bcnzamidobiityrylpyridine, m.p. 118°, suggest formula (III). H. W . X 2H4,H20-Pd-SrC03-Et0H -K 0H ) to 3: 4-methyl- enedioxyphthalide, converted by H XO s (d 1-42) at 0 Constitution of solanidine from Solatium into its 6-Ar0 2-derivative (I), m.p. 222— 223°, which sodom aeum . G. O d b o and G. C a r o n n a (Ber., with cotarnine in EtOH gives anhydrocatarnine-G- 1936, 69, [B], 283— 2S7).— The action of UNO« on nitro-, m.p. 177— 178°, reduced (SnCl2-H C l at 0°) t° solanidine-s (I) gives azosolanidine (II), m.p. 260° atihydrocotarnine-Q - amino - 3 : 4 - melhytenedioxyphthal- (decomp.), which decolorises Br—H20 and does not ide, m.p. 204— 205° (decomp.). Lodal similarly con give the Liebermann reaction, and a quinhydvone denses with (I) to give nilro-x-adhimitie (anhydrolodal- ^ i8^ 29^ 2X .C lsH31ON, m.p. 120°, decomposed by HC1 G-nitro-3 : d-methylenedioxyphthalide), m.p. 180—181 into the hydrochloride of (I) and the quinone, (decomp.), reduced to the JVTZ^derivative, m.p. 218— CjeHogXlCO^. The reactions described by Oddo et 219°. Hydrastinine and (I) afford nitro-x-bicucullin(, al. (A., 1911, i, 671; 1914, i, 1174) are therefore sinters at 176°, blackens at 179°, reduced to the interpreted thus : XTZj-compound, m.p. 203— 204°. Diazotisation l- this and treatment with aq. K I affords iodo-x- >[ci6H2a<^X-CH (O H )2j bicuculline, m.p. 208— 209°, reduced (Al-H g in boiling EtOH-C6H6) to K-bicuculline (anhydrohydrastiniw- HNO, [>, pr ^CHX-CH(OH).-] ■ H-0 3 : ianethylenedioxyphthalide), m.p. 215°, resolution o L 16 26^N :N -O H J which gives the d-form, identical with the nature alkaloid (details later). J- W . B. Ergot alkaloids. Structure of lysergic acid. f llC! „ ' W . A. J acobs and L. C. Craig (Science, 1936,8 3 , 38— > A 20 + C 1GH27-CX!CHC1 [chlorosolanidene (IV)] 39).— The previous structure suggested for lysergic XVII (g) ORGANIC CHEMISTRY. 489 acid (A., 1935, 1512) is revised to (I). The base, X I . Mainly corrections of the work of Juneja et al. ntr n nr, tj C a H j.N , obtained by the alkali (A., 1935, 765, 995). o -N 02-CGH4-CH2-NH2 and 2 fusion of dihydrolysergic acid (II) (•CH2’C0)20 in Et20 and subsequently at 100° give Q}LNMe is 1 : 5-C,0H6Me\NH2. Thetribasic succin-o-nitrobenzylamic acid (II), m.p. 123— 124°, CH> safrole glycol is obtained, which is oxidised by i, 3955).— The greenish-yellow colour is said to be Pb(0Ac)4. When (III) is condensed with homopiper- due to the presence of a CHyOH in quinine. onylamine hydrochloride (Hahn et al., A ., 1935, 357) H. N. R. the products are: (I) homopiperonvlamine, which Niquidine. T. D o m a ń sk i and J. Suszko (Bull. cannot contain (I), since the compounds are readily Acad. Polonaise, 1935, A , 457— 464).— Quinidine with separated from one another by distillation in a high conc. HC1 or HBr (cf. A., 1935, 874, 1137) gives an vacuum, (2) 3' : 4'-methylenedioxybenzylidene-P- unsaturated alkaloid, niquidine (I), ClaH24N,0 ,, m.p. 3 : 4-phenylethylamine (IV), m.p. 115— 117°, the 161°, [a]“ -(-171° in EtOH {dioxalate, m.p. 206—^07° formation of which is attributed to the presence of a (decomp.), [a]],7 -(-189° in H » 0 ; diliydrobromide, m.p. trace of piperonal in (III), and (3) a non-cryst. 250° (decomp.); N-ArO-derivative, m.p. 80— 130°, material converted by CH20 into norhydrohydrastin- decomp. 160— 170°, [a]],7 — 73° in E tO H ; dibromide, ine unaccompanied by any trace of (II). It is there m.p. 170— 171° (decomp.), [a]g! + 1 4 2 ° in MeOH fore impossible that (I) is produced as reported by [diliydrobromide, m.p. 238° (decomp.), [a];,0 +152° Hahn et al. (loc. cit.) and their product is very probably in MeOH and H.,0; dinitrate, m.p. 186— 187° (de impure (IV). H. W . comp.)]; N-Ac, m.p. 206— 207°, [a]{? + 2 5 ° in EtOH; and N-Ac2, m.p. SO— 90°, [a]7? - 2 8 ° in EtOH, deriv Hydrates of quinine. G. Malq u o ri and M. atives}. (I) with 25% AcOH in a sealed tube C ovello (Annali Chim. Appl., 1935, 2 5 , G47— 654).— gives nichotoxin (nichicin) (II), m.p. 70°, [a]},7 —5° Neither the triliydrate nor the known higher hydrates (p-nitroplienylhydrazone, m.p. about 60°), and with can exist above 15°. Dehydration appears to be a H .,0, yields quininic acid. (I) may be as shown discontinuous process, but definite hydrates do not CHofCH-CH— ę i l— OH, result. Dehydration is complete at 50— 60° and is “ irreversible.” A . M. P. I [ W 2 ” CH,-N CH-CH(OH)-CaH5N-OMe. Origin of p-isocupreidine. R. L u d w ic z a k and and (II) C7H;0(CH,-NH,)(CH,-CO-C„H5N-OMe). J. Suszko (Bull. Acad. Polonaise, 1935, A , 104— 106). F. R, G. — A correction to previous work (A., 1935, 996) based Transformations of iso quinidines. T. Domań on the observation that, when heated with H 2S0 4, ski and J. Suszko (Bull. Acad. Polonaise, 1935, A, hydrocupreidine is unchanged but cupreidine is 465— 473).— Quinidine, a-, ¡3-, and y-isoquinidine, partly converted (equilibrium) into S-bsocupreidine. nichidine, and the corresponding toxins (cf. preceding J. W . B. abstract) are interconvertible in presence of acids. Hydrio do quinine and niquine. J. R e y m a n and F. R. G. J. Suszko (Bull. Acad. Polonaise, 1935, A, 360— Addition of organomagnesium halides to 373).— Hydriodoquinine-I (A )+ C 6H6, m.p. 93°, re ^-codeine types. I. Deoxycodeine-C. L. solidifies and decomp. 130— 140°, [a]j,° — 18° (Rosen- Sm all and K . C. Y u en (J. Amer. Chem. Soc., 1936, mund et al., A ., 1924, i, 982) (methiodide, m.p. 112— 5 8 , 192— 196).— Deoxycodeine-C (I) (salicylate, m.p- 114°, [a]},0 — 82-5°), is decomposed in boiling C8HG 195— 196°) (A., 1931,“ 1077) and MgMel give the to give p-nsoquinine (B) (not isolated) and an insol. phenolic methyldihydrodeoxycodeine (II), m.p. 145— basic hydriodide, (C20H25O2N2I),H I (C), m.p. 178— 146°, [a]jf + 6 9 -7 ° in EtOH or CHC13 (hydrobromide, 204° (decomp.), reconverted"into (A) by NH3 ; but (A) m.p. 245— 246°; hydriodide, m.p. 155— 158°; meth is unaltered by hot P -H I (d 1-7) and, contrary to iodide, m.p. 239°), presumably formed by 1:2- or Skraup (ref., loc. cit.) is converted into (B) by A g N 03. 1 : 4-addition involving the -O* linking. Zn dust Hydriodoquinine-II (D), decomp. 125— 150°, [ag? distillation of (II) gives a hydrocarbon, C15H12, — 217°, is similarly decomposed in boiling CBH6 to m.p. 103° (not sharp; sinters from 95°) [picrate, m.p. the insol. basic hydriodide ( E ) + CHC13, m.p. 76— 80°, 95— 9S° (sinters from about 85°)], and oily hydro- and solvent-free, m.p. 175— 192° (decomp.), [a]7,0 carbon(s) (picrates, m.p. 118— 119° and 138— 141 , 87 [reconverted into (D) bv cold N H 3] and (from not identical with 2- and 4 -metliylphenanthrene the mother-liquor) niquine (F) : 3C20H25O2N2I-> picrates). Hydrogenation of (II) affords methyl (C20H ,5O2N2I)2H I + C 20R24O2N,. (E) is also obtained tetrahydrodeoxycodeine, m.p. 128— 129°, [a]“ — 47-8° from (D) (3 mols.) and its dihiydriodide, m.p. 223° in EtOH [hydrochloride, m.p. 240-5°; hydrobromide, (decomp.) (1 mol.). Although it could not be pre m.p. 248— 249°; methiodide (+ E tO H ), m.p. 254 pared by admixture of (A) and (D), decomp, of the 255°]. (I) and M gEtl give a-e thy Id ihydrodeoxycodeine mixed hydriodides of (A) and (D) with NH3 in presence (III), m.p. 156— 164°, [a]“ -184-2° in CHC13 (hydr of CfiH6 affords a mol. compound, m.p. 93°, [a]}? —118° iodide, m.p. 205— 210°; perchlorate, m.p. 187— 200 ; [methiodide, m.p. 191— 195° (decomp.)]. Thus (A) methiodide, m.p. 210— 215°), and an oily product (Ah and (D ) are only stereoisomerides, but (B) and (F) are (III) and (A) are reduced (H „ PtO,, aq. MeOHi structural isomerides, both of composition C»0H ,lOi)N ). iV-HCl) to a-, m.p. 16S-5— 169°, [«]£ -5 4 -8 ° in CEUj With AcC1-C5H5N (F) gives a Ac2 derivative, m.p. (hydriodide, m.p. 234°), and p-, m.p. 148— 153°, [aJi> 142— 143° [a]» + 3 3 °, partly hydrolysed by 20% -3 7 -6 ° in CHCIg, -ethyltetrahydrodeoxy codeines, HC1 at room temp, to the known Ac4 derivative : respectively; (A) also gives an unidentified substance, hence (F) contains a OH. Oxidation of (F) with m.p. 215— 216°. The isomerism may be configm'- H „0 , at 100° gives quinic acid. All [a]D vals. are in ational or positional. (I) and MgPhBr afford < 83 /0 96“%"EtOH. J. W. B. of phenyldihydrodeoxycodeine (IV), m.p. 184-5 185-5°, [«]“ +129-3° in CHCL [picrate ( + H ,0 ) , m.p- Quinine-urethane solutions. L. N obili (G. (anhyd.) 129— 132°; benzoate, m.p. 203— 204°; meth Harm. Chim., 1935, 84, 15— 20 ; Chem. Zentr., 1935, iodide, m.p. 257-5— 258°], and a little of an oil (B)- x v n ( (IV) could not be reduced catalytically except with with one of the products of the dehydrogenation of P t02 in aq. M eOH-HCl; a hexahydrophenyltetra- matrine by Pd-asbestos (A., 1935,766). The chemical hydrodeoxycodeine (V), m.p. 132— 134°, [a]f,4 —48-4° in CHC13 (perchlorate, m.p. 255— 256°; methiodide, m.p. 250°), results. (B) is reduced to a phenyltetra- hydrodeoxycodeine, m.p. 218—220°, [a]“ +16-1° in CHClg. cycloHexyldihydrodeoxycodeine, m.p. 131-5— 132-5°, [a]„ — 51° in CHClg (perchlorate, m.p. 250— 251°), prepared from (I) and Mg cyefohexyl chloride in isoamyl ether (not obtained in Et20) at 100°, is reduced [as for (IV)] to cyclohexyltetrahydrodeoxy- codeine, m.p. 193— 193-5°, [a]“ — 14-2° in CHC13 (hydriodide, m.p. 235— 236°), which differs from (V). H. B. behaviour of (I) and its relationship to the known Alkaloids of Sinomeniuui and Cocculus. XL. leguminous alkaloids indicate for it the constitution Alkaloids of Stephania ccpharantha, Hayata. (I). Against this view, (II) is not converted into its III. H. K o n d o and I. K elmatsu (J. Pharm. NH2-derivativc by NaNH.,, and its Bu compound Soc. Japan, 1935, 55, 234— 241).— isoTetrandrine is not formed from (III) and LiBu in C6H 8 at 100°. (I), C38H420 6N2, m.p. 181— 182°, [a]" + 1 4 6 ° in (Conyrine and LiBu in C6H„ afford 2-propyl-G- CHClg, isolated from the above, yields a methiodide, butylpyridine, b.p. 228— 230°.) Successive treatment decomp. 242°, an a-, m.p. 171— 172° [methiodide of Me methylmatrate methiodide with Ag20 and (II), decomp. 255°], and a ¡3-, m.p. about 110°, K M n04 gives H 2C20 4, (-CH2-C02H)2, and glutaric -methine. (II) with M eOH-KOH affords de-N-iso- acid but no AcCO,H. A 3-methylpyrrolidone ring tetrandrine, m.p. 220°, not depressed on admixture cannot therefore be present in matrine, and the only with de-JV-tetrandrine or de-iV-berbamine methylate. remaining possibility is a pyrrolidone ring, thus leading KMn04 oxidises (II) to a substance, m.p. 305°, not to a choice of constitutions (A) or (B) for the alkaloid. depressed on admixture with Et2 6-methoxydi- H. W . plienyl-3 : 4'-dicarboxylate. The partial formula South American curare.— See this vol., 534. C3oHl1(I0)„(0Me)4(ls!Me), is proposed for (I). Alkaloids. R . R o b in so n (Ann. Rev. Biochem., Ch . A b s. (r) 1935, 4, 497— 518).— A review of the lit. for 1933— Alkaloids of Sinomeniiim and Cocculus. 1934. Ch . A b s. (r) XLV. Stereochemical and biogenetic relation ships of biscoclaurine alkaloids. H. K o n d o and Decomposition of aromatic arsines in the M. T omita (Arch. Pharm., 1936, 274, 65— 82).— Friedel and Crafts reaction. M. S. M a l in o v s k i The following alkaloids are considered to be derived (J. Gen. Chem. Russ., 1935, 5, 1355— 1358).— Aro from 2 mols. of eoclaurine [7-hydroxy-6-methoxy-l-p- matic arsines yield AsC13 and COPhMe or its deriv hydroxybenzyl -1 : 2 : 3 : 4 - tetrahydroi.soquinoline] : atives when treated with AcCl or CH2Cl*COCl in ( in PliNO, (f.-p. method) and indicate that the oxides in CHCI3, [«EX,, - 1 8 8 ° in 1 :1 CHCl3-COMe2. The solution of the (3-form in cold CHC13 sets to a jelly are probably mixtures of ArB<^Q^>BAr and which slowly crystallises at 40— 60° to the a-form. Interconversion of a- and [3-forms can be repeated in 0<^BAr-0^>BAr- H. B. definitely by such methods, using various solvents. Relative reactivities of organometallic com Assuming a tetrahedral arrangement of the 4 S in the pounds. VI. Boron. H . G il m a n and K . E. complex anion, resolution should be possible, but, M a r b l e . VII. Calcium. H . G il m a n , R. H. probably owing to very rapid autoracemisation, the K t r b y , M . L ichtenwalter , and R. V. Y ou n g Na2 salts were inactive and showed no mutarotation (Ree. trav. chim., 1936, 55, 76— 79, 79— 81).— VI. even at — 35°. One form is probably of type (III) B has the function of a metal in organoboron com and the other is assigned a 3 co-ordinated Hg structure. pounds, but these are less reactive than true organo By similar methods are obtained the a-, +a:CHCl3 metallic compounds. BPh3 with PhCHO and PliNCO (effloresces), and [3-, m.p. 157°, forms of diquinine ILl yields respectively C H PlvO H and NHBzPh. The bis-(l-chlorobenzene-3 : A-dithiol)cadmium and, from colour test (cf. A ., 1925, ii, 1011) is given more rapidly (I), the a-, m.p. 155°, and fl-, sinters 128°, m.p. 145°, by BPra3 than by BPh3, but less rapidly than by forms of diquinine H 2 bis(toluene-3: A-dithiol)zinc, organoaluminium compounds. similarly, interconvertible. An apparatus for rapid VII. Contrary to Gilman and Schulze (A., 1926, low-temp. polarimetry is described. J. W . B. 1130) CaPhI is more reactive than MgPhI, as it Organic thallium compounds. I I I . Syn converts PhCN into COPh2 5 times as rapidly, thesis of organic thallium compounds with converts diphenylene oxide into its -1-carboxylic acid simple substituents in the aromatic radical. (MgPhI does not), and converts NPhICPh2 into S. S. N a m e t k in , N . N . M e l n ik o v , and G. P. G rat- NHPh-CPhg (analogy with LiPh). F. R. G. s c h e v (J. Gen. Chem. Russ., 1935, 5, 1455— 1459).— Mercuration of nipasol, a propyl ester of The following substituted aryl T1 halides have been p-hydroxybenzoic acid. A . M. S a m s o n and A. C. prepared by the reactions : RB(OH)2 (I)+T1X3t Sa n t o s (Univ. Philippines Nat. Appl. Sci. Bull., H„0 -> RT1X2 (II)+H X+H 3B03; (I)+(II)+H 20 + 1935, 4, 149— 154).-^p-OH-C0H4-CO2Pr with R2T1X+HX+H3B03 : p-C6IIiBr-TlCl,, m.p. 202° Hg(OAc)2 in AcO H -EtO R affords a mixture (I) of (decomp.); p-C6H4BrTlBr2, decomp, at 190— 200°; Pr 3 : 5-bis(acetoxymercuri) - and 3- (acctozymercuri) - p-Cfllfil-TlCl,, m.p. >250°; p-Cc[IACl-TlBr2, m.p. 4-hydroxybenzoates. (I) with I -K I yields a product > 2 5 0 °; CH2P h T l B r m.p. 205° (decomp.); (p- of indefinite m.p., which affords 3 : 5-di-iodo-, m.p. C6H4Br)<,TlCl, m.p. >250°; (p-C6H4Br)2TlBr, m.p. 236— 237° (Me ester, m.p. 166— 167°; Et ester, m.p. > 2 5 0 ° ; (p-OMe-CGH4)2TlBr, m.p. >250°; (p- 123— 124°), and 3-iodo-, m.p. 190— 200° (Me ester, CGH4Cl)2TlCl, m.p. not given; (p-CGH4Cl)2TlBr, m.p. 156— 157°), -4-hydroxybenzoic acids on hydro decomp, at 240°. R. T. lysis with E tO II-K O H ; with Br (I) similarly affords Proteins in liquid ammonia. I I I . Reaction 3 : 5-dibromo-, m.p. 266— 267° (Me ester, m.p. 125— of sodium in liquid ammonia with proteins and 126°), and 3-bromo- (Me ester, m.p. 100— 107°), related substances. R. G. R o b e r t s and C. 0. -4-hydroxybenzoic acids. Ch . A b s . (r) M i l l e r (J. Amer. Chem. Soc., 1936, 58, 309— 310; Stereochemistry of some new complex thio- cf. A., 1934, 638).— Dry proteins react with Na in salts of mercury, cadmium, and zinc. W . H. liquid N H 3 as acids, H 2 being evolved; reaction is M il l s and R. E. D. Cl a r k (J.C.S., 1936,175— 181).— much slower than with N H 2-acids or dipeptides. 1 :3 : 4-CcH3Me(S02Cl)2 is reduced (Sn-HCl) to the Using a slight excess of Na, the vals. of the ratio mols. 3 : A-dithiol (I), b.p. "l74°/41 mm., m.p. 35°. p- H 2 evolved to g.-atoms N present for caseinogen, C6H4C1-NHAc heated with conc. H 2S0 4 affords p- edestin, gelatin, and zein are 0-215, 0-285, 0-35, and cliloroanilinesulphonic acid, converted through the 0-09, respectively; these vals. are generally > those diazonium xanthate and oxidation (H N 03, d 1-4) into calc, from the glutamic, aspartic, and hydroxy- the 3 : 4-disulphonic acid (Ba and Na salts), the glutamic acid content. H. B. sulphonyl chloride, m.p. 82— 83°, of which is reduced to l-chlorobenzene-3 : A-dithiol (II), b.p. 165°/32-5 mm., Physical chemistry of zein. C. C. W atson, m.p. 31°. When refluxed with yellow HgO, (I) in S. A r r h e n iu s , and J. W . W il l ia m s (Nature, 1936, KOEt—EtOH affords K 2 bis(toluene-3 : A-dithiol) - 137, 322— 323).— By the addition of 1I20 to the EtOH mercury, -fE tO H and solvent-free, of type solution, purified zein can be divided into 3 practically homogeneous fractions, which are now characterised [Ar caine, reddens 140°, m.p. 146— 147° (a, 0-4% solution), obscured by the colour of the solution. Cryptopine stovaine, m.p. 110— 112° (a, 0-02% ), antipyrine, (A., 1910, i, 502) does not interfere. J. L. D. m.p. 180— 182° {a, lCh2), and pyramidone, m.p. Use of Zimmermann's reagent for detection 168— 170° (a, 0-04% solution). Photomicrographs of glycine and for determining its position in are given in each case. J. W . B. polypeptides. E. A b d e r h a l d e n and A. N eum an n Recognition of papaverines by a colour re (Z. physiol. Chem., 1936, 238, 177— 182; cf. A., 1930, action with acetic anhydride and sulphuric acid. 897).— When free glycine (I) is present a ppt. is W . A w e (Pharm. Zentr., 1936, 77, 157— 160; cf. always produced. Of the other N II2-acids (not A ., 1923, i, 701).— Papaverine (5 mg.) in Ac20 (3 c.c.) mentioned by Zimmermann) of the protein mol. containing H 2S0 4 (5 drops) at 80° affords a solution only tryptophan (which gives a brown ppt. and green with a yellowish-green fluorescence in daylight. 0-05 solution) interferes. With polypeptides containing mg. can be recognised by observing the fluorescence the (I) residue the reaction is positive only when in ultra-violet light. When AcCl-ZnCl2 is used as this residue carries the N H 2 (negative with silk condensing agent, the fluorescence in daylight is fibroin, positive with silk peptone). W . McC. Biochemistry. Biochemistry and biophysics. P. L. d h N o u y membrane potential of 2— 5 mv., attains equilibrium (Bull. Soc. Chim. biol., 1936, 18, 138— 156).— A after 24 h r.; comparative measurements can be lecture. taken after 3— 24 hr. Relationships between the Response of the chemical receptors of the pressure and concn. of colloid and temp, are deter carotid sinuses to the tension of carbon dioxide mined. F. 0 . H. in the arterial blood in the cat. A. Sa m a a n and Electrodialysis of serum. A. V. M ariiovitsch G. S t e l l a (J. Physiol., 1935, 85, 309— 319). (J. Appl. Chem. Russ., 1935, 8, 1444— 1451).— Thepn It. N . C. of serum falls during electrodialysis (parchment Retention of carbonic acid in the dormouse cathode and bakelite-paper anode membranes) from (Myoxus glis) in course of carbon dioxide the original val. to 5-2. Max. pptn. of globulins narcosis and role of the tissues in the mainten takes place at pa 5-6— 5-7, at low concn. of electrolytes. ance of the alkaline reserve. L. D o n t c h e e e and R. T. C. K a y s e r (Compt. rend. Soc. Biol., 1936, 121, Effect of continued passage of current through 447— 449).— The amcsthetised animal retains con the external medium on the composition of siderable quantities of C 02, suggesting the presence blood in Scyllium canicula, the bronchial region of an “ alkaline reserve ” in the tissues equiv. to that being near the cathode. E. A. P o r a (Compt. rend. of the blood. R . N. C. Soc. Biol., 1936, 121, 411— 413).— The osmotic pressure and corpuscular vol. increase with the Nitrogen solubility in blood at increased air intensity of the current. Ca and proteins also pressures. J. A. H a w k in s and C. W . S h il l in g increase, whilst IC and alkaline reserve decrease (J. Biol. Chem., 1936,113, 273— 27S).— The solubility progressively. Vais, afterwards tend to return to coeff. of N 2 (at atm. pressure) in dog’s and ox blood normal. Serum-H20 falls, but inorg. salts and org. is 0-013S— 0-0148 and 0-0135— 0-0140, respectively. substances both increase at the expense of the muscles, With pressures of N2 of 1— 6 atm., the val. follows which take up H 20 . R. N. C. Henry’s law. H . G. R. Modifications of the blood of Perea fliiviatilis, Regulation of the oxygen output of erythro consecutive to deep-sea fishing. L. B au d in cytes. I. P. H im m e r ic h . II. Blood-glyco- (Compt. rend. Soc. Biol., 1936,121, 437— 439). lysis. F . H im m e r ic h and R. S. F e in b e r g (Bio- R. N. C. chem. Z., 1936, 284, 146— 151, 152— 162).— I. An Determination of the alkaline reserve in small apparatus for measuring the output is described. m am m als. L. D o n t c h e f f and C. K a y s e r (Compt. II. The glycolysis resulting from addition of glucose rend. Soc. Biol., 1936, 121, 4 4 6 -A 4 7 ).— 1The Van to human erythrocytes increases (up to 200%) their Slyke const.-vol. apparatus is used. Local ansesthetis- 0„ output. Similarly, in defibrinated human and ation during the draw in g of blood is necessary. rabbits’ blood the increased glycolysis due to an R. N. C. increase of 0-25— 0-3 in pa results in increases (up to Effect of physical training on blood-volume, > 300% ) in the 0 2 output. Apparently all factors haemoglobin, alkaline reserve, and o sm o tic which stimulate glycolysis increase *02 output. resistance of erythrocytes. J. E. D a v is and N- Probably the glycolysis occurs at the surface of the B r e w e r (Amer. J. Physiol., 1935, 113, 586— 591). erythrocytes and the accompanying production of Blood-vol. and haemoglobin per unit vol. (I) in the acid and liberation of heat may play important parts dog fall during the first week of training, and later in the process. W . McC. rise, but (I) is never > normal. The alkaline reserve Determination of colloid-osmotic pressure. is increased. Erythrocyte osmotic resistance rises in H. N a g a o k a (J. Biochem. Japan, 1935, 22, 351— swimming but falls in running animals. R. N. C. 366).— The colloid-osmotic pressure of horse serum, Analysis of the constituents of suspensions of measured by a collodion membrane with a standard erythrocytes by the method of neutralisation X IX (b) BIOCHEMISTRY. 495 curves. G. A ch ard (Compt. rend. Soc. Biol., 193C, Conductometric method for investigation of 121, 478— 481).— The buffering effect of erythrocyte colloidal suspensions. A. Sl a v in siu (Bull. Soc. suspensions, their excipients, and laked erythrocyte Chim. biol., 1936, 18, 195— 202).— The author’s solutions is due to factors other than the inorg. method (A., 1934, 860) for determining the vol. of salts present. R. N. C. colloidal particles is applied to blood-plasma. Human and horse plasma contain about 9 % of albumin associ Alteration, with time, of the buffering power ated with 4-5% of liquid, the tonicity of the plasma of suspensions of erythrocytes. G. A chard being that of 0-85% aq. NaCl. Measurements with (Compt. rend. Soc. Biol., 1936, 121, 481— 484).— hiemolysed blood indicate that the corpuscles contain After prolonged action of acids or alkalis on erythro “ lia2moglobules ” occupying 55% of the vol. of the cyte suspensions the neutralisation curves resemble corpuscles and containing 52% of haemoglobin and those obtained in suspensions laked with H 20. 4 8 % of liquid. A . L. R. N. C. Reduction of oxyhaemoglobin in the human Effect of haemorrhage of varying degree on skin. L. N icolai (Pflüger’s Archiv, 1932, 230, 238— blood and plasma volume, on blood-sugar, and 245; cf. A ., 1932, 1270).— Reduction of oxyliæmo- on arterial blood pressure. J. D. R obertson globin in the skin follows the equation c—cQe~kt. The (J. Physiol., 1935, 84, 393— 409). R. N. C. rate of reduction is unchanged in hyperæmia following Effect of splenic extracts on the blood picture. anoxæmia. R. N. C. T. I m ai (Tohoku J. Exp. Med., 1933, 22, 293— 313). Fate of haemoglobin in the organism. K. Cii. A b s. (p) Cyclic variations in the composition of fish B ingold (Klin. Woch., 1934, 13, 1451— 1452).— A pigment (I) with a band at 535 mg is formed by the blood. L. B a u d in (Compt. rend. Soc. Biol., 1936, action of alkaline Na2S20 4 on bilirubin-rich urine. 121, 501—502). R. N. C. It is found in old pleural exudates, but not in serum ; Ultrafiltration studies with normal horse its appearance in the urine is unaltered if the liver is serum . W . J. E le ord , P. Gr a b a r , and W . F isch er choked. (I) is considered to be free from Fe and not (Biochem. J., 1936, 30, 92— 99).— Analysis of the bound to proteins, the colour being due to formation state of aggregation of horse serum-proteins by ultra of a S derivative. Pigeons’ blood or liæmin decolorised filtration through graded collodion membranes show's with H 20 2 and boiled with K O H gives a band at that the simplest protein units correspond in particle 535 m g; Na2S20 4 is often necessary for production size with mol. serum-albumin (I) and pseudoglobulin of the spectrum “ Cultrues of Pneumococci on catalase- in dil. solutions, and that a second fraction is present free blood-agar break down the blood to (I). which is more readily retained by membranes and in R. N. C. particle size about twice that of (I). This fraction is Effect of diet on the haemoglobin concentration essentially a globulin (II) aggregate and may corre of the blood. L. N. E llis and 0 . A. B essey (Amcr. spond with the cuglobulin of serum. The antibody of J. Physiol., 1935, 113, 582— 585).— Haemoglobin in an aged sample of type I pneumococcus antiserum the rat at 1 month oc the Fe content of the diet, was retained by membranes simultaneously with the but is independent at 1 year, when it falls into one of more complex (II) fraction. P. W . C. two ranges of vais., according to the sp. diet given. Activity of the globulins of blood as alexins. R. N. C. M. D oladilhe (Compt. rend., 1935, 201, 689— 690).— Occurrence of several kinds of haemoglobin The globulins (I) pptd. from diluted serum with C 02 in human blood. R. B r in k m a n and J. H. P. are sol. in saline and are then separated by C 02 into J onxis (J. Physiol., 1935, 85, 117— 127).— Fœtal an insol. (0-2036% P) and a sol. (0-0782% P) frac hæmoglobin is replaced by a “ less resistant ” adult tion, w-hich may be components of a sol. complex. hæmoglobin after 7 months, and this in turn is replaced after 3 years by a hæmoglobin more resistant to alka The sol. fraction exhibits the central-group properties line dénaturation. The three haemoglobins differ in of alexin, of the same intensity as does the saline rate of alkaline dénaturation and in isoelectric point, solution of (I). J. L. D. and so far have been detected only in human blood. Total plasma-protein in normal and fasting R. N. C. rats. W . C. C u t t in g and R. D. C u t t e r (Amer. J. Relationship between specific gravity and Physiol., 1935,113,150— 158).— Total plasma-protein protein content in plasma, serum, and transud (I) is measured by determination of the blood vol. ate from dogs. A. A. W e ech , E . B. R eeve s, and (for which a method is described) and protein concn. E. G oettsch (J. Biol. Chem., 1936,113,167— 174).— Decrease of (I) during fasting oc time. Lymph- and The d of blood-plasma, -serum, or -transudate oc the plasma-proteins resemble each other in composition protein concn. H . D. and participation in body functions. R. N . C. Serum electrolytes. X. Water of serum and Tyramine as a pressor substance in pallid factors for calculation of molality of a solute in hypertension. H. A. H e in se n and H . J. W olf serum from measurement of specific gravity. (Klin. Woch., 1934, 13, 1688).— Blood fractions F. W . Sunderman (J. Biol. Chem., 1936,113, 111— obtained by extraction of the deproteinised blood 115).— The d of serum bears to the total solids a with C5H n -OH and give the col ur reaction linear relation (consts. given) from which concns. with 1 : 2-NO-C10H6-OH and H N 0 3, suggesting that of a solid related to [H20] may be obtained. tyramine is a cause of pallid hypertension. F. A. A. * R. N. C 496 BRITISH CHEMICAL ABSTRACTS.— A. X I X (b) Pharmacological determination of adenosine factory. A modified method replacing this by SiO., and histamine in blood. G. S. B arsoum and J. H. and using a photometer is described. Gaddum (J. Physiol., 1935, 85, 1— 14).— Tests de N u t r . A b s. (hi) scribed can detect 2 X 1(H g. of histamine (I) and Effect of glucose ingestion on the cholesterol 0-5 x lO -6 g. of adenosine (II). (I) is present in fractions of blood. F. F itz and M. B r u g e r (J. normal human, rabbit’s, guinea-pig’s, dog’s, and Biol. Chem., 1936, 113, 297— 302).-—The increase in probably cat’s blood. Corpuscular (I) and (II) are total cholesterol when glucose is fed to fasting sub > plasma-(I) and -(II), respectively. Clotting of jects is located in the cliolesteryl ester fraction. blood or shaking of citrated blood increases (II) H . G. R. without affecting (I). R. N. C. Physiology of blood-glycogen. I. G. Golan- d a s . II. H. Sta u b and G. Go lan da s ■ (Pfliiger’s Appearance of histamine in venous blood Archiv, 1935, 236, 230—238, 355—360).—I. The during muscular contraction. G. V. A n rep mean val. for fasting blood-glycogen (I) in the dog is and G. S. B arsoum (J. Physiol., 1935, 85, 409— 420). slightly > that in man or rabbits. Plasma- and — The histamine (I) contents of the arterial and serum-glycogen are the same for all three; the greater venous blood to and from resting. muscle are the part of (I) is contained in the corpuscles. (I) does same. Venous (I) is increased by diminution of the not vary in the same subject; it diminishes in sterile blood supply and by muscular contraction. blood stored at 37°, is scarcely altered at — 8°, and R. N. C. is increased in unsterilised blood at 37° by bacterial Presence of creatinine in blood. I. S. D a n ie l action. son (J. Biol. Chein., 1936, 113, 181— 195).— The major part of the chromogenic substance (in the II. (I) rises in dogs and rabbits after fasting for 144— 170 hr, ' Overcharging with carbohydrate gener Folin-Wu determination; A., 1919, ii, 308) in blood ally increases (I) in man (mainly in the corpuscles) H 2WO,j filtrates and plasma ultra-filtrates is adsorbed and rabbits. R. N . C. by kaolin. The colour developed in a kaolin-treated filtrate heated with aq. NaOH is approx. the same as Mechanism of the origin of alimentary hyper- that obtained with an ordinary filtrate, whereas pure glycsemia. Y. H u k u i (J. Biochem. Japan, 1935, solutions of creatinine (I), or the material eluted 22, 447— 496).— Direct application of glucose (I) to from the kaolin, on treatment with NaOH give no the duodenum of rabbits produces no significant colour with alkaline picrate. It is concluded that hyperglycemia. Direct administration of (I), galact the chromogenic material in blood filtrates is (I). ose, or fructose to the stomach or duodenum does H. D. not change the sugar content curves of blood from Variations of concentration of conjugated the portal, hepatic, or ear veins. Splanchnicotomy phenols in blood in passing different organs. and/or vagotomy lower the alimentary hyperglycemic A. D. Ma r en zi (An. Farm. Bioquim., 1933, 4, 36— 38; curve. Administration of ergotamine or atropine also Chem. Zentr., 1935, i, 3562).— The conjugated phenol lowers the curve. Oral administration of fructose content of portal blood is > that of the carotid and produces a hyperglycaemia due to blood-(I) and vena cava inferior. R. N. C. reduced by splanchnicotomy. The data support the absorption rather than the reflex-mechanism theory. Lipochromes of human blood-serum. E. vo n D an iel and T. B eres (Z. physiol. Chem., 1936, 238, F. 0 . H. 160— 162).— The material obtained from 3 litres of True blood-sugar level in insulin shock and the serum by chromatographic adsorption on Ca(OH)0 convulsions. L. B. D otti and M. C. H ru betz (J. (after pptg. with EtOH, etc.) consisted of 0-33 mg. Biol. Chem., 1936, 113, 141— 143; cf. A., 1934, of a yellowish-brown pigment (absorption max. at 565).— In rats, the true blood-sugar level falls during 502-5 and 472 mg), 0-15 mg. of lycopene, 0-08 mg. of the course of insulin shock, and at the onset of con a light yellow pigment (max. a't 455 and 425 mg), vulsions is zero. F. A. A. and 0-28 mg. of carotene. The unidentified pigments Variations of blood-sugar in rabbits following may be biologically active. The proportions in which subcutaneous injections of plienylhydrazine the pigments occur in the serum and the amounts of hydrochloride. P. D e r v il le e , L. Lansac-Fatte, the individual pigments vary greatly. W . McC. and R. Castagnou (Compt. rend. Soc. Biol., 1936, Determination of fat in 0-1 c.c. of blood or 121, 549— 552).— Hyperglycemia occurs in varying seru m . J. S u r a n y i and R. VSg h e l y i (Biochem. degree, but no hypoglycemia. R. N- C. Z., 1936, 283, 415— 421).—-Blood (0-05 c.c. in each Lactacidsemia in fowls with avitaminosis-R. case) was extracted with EtOH and COMe2 at 100° I. I. N itzescu and I. G ontzea (Compt. rend. Soc. and 75° and the filtered extracts were treated with Biol., 1936, 121, 562— 563). R- N . Of H C l-H 20-B u O H . The resulting turbidities were measured by the step-photometer. The total fat was Influence of prelim inary training on the lactic thus obtained in the EtOH extract whilst lecithin acid content of blood after intense work. A. v- P alladen and B. M. K old aev (Ukrain Biochem. was absent from the COMe2 extract. P. W . C. J., 1934, 7, No. 1, 30— 39).— Intense work causes Spectrophotometric determination of blood- accumulation of lactic acid in blood. Preliminary cholesterol by means of silica. H. F o y and A. training lowers the rate of accumulation. K o n d i (Brit. J. Exp. Path., 1935, 16, 349— 357).— Ch. A bs. (p ) Variations in the state of hydration of plaster of Mendel and Goldscheider’s method for deter Paris render the Myers and Warded method unsatis mining lactic acid in blood. R. M ilton (Analyst, X IX (6) BIOCHEMISTRY. 497 1936, 61, 91— 96; cf. A., 1926, 212).— The effect of a rise or fall in blood-Cl, but generally a fall in temp., time of heating, and concn. of H 2S0 4 and -Xa. F. 0. H. veratrole on the intensity of the colour produced is Blood-bromine. C. I. U r e ch ia and R e te ze a n u investigated and modifications are suggested. The (Presse mecl., 1935, 43, 701— 703).— Low blood-Br results obtained are slightly lower, but more consistent, was found only in manic-depressive psychoses. than those given by Friedemann and Kendall’s method Injection of drugs and therapeutic preps, did not (A., 1929, 677). E. C. S. reduce it. X u t r . A b s . (to) Determination of sodium formaldehyde- Blood-iodine. V. Blood-iodine after total sulphoxylate in blood-plasma. E. H ug (Compt. thyroidectom y in m an . G. M. C o rtis, L. E. rend. Soc. Biol., 1936, 121, 577— 579).— Plasma is B arro n, and F. J. P h illips (J. Lab. Clin. Med., deproteinised with U 0 2(0Ac)2, and N aH S02,CH20 1935, 20, 813— 816; cf. A., 1934, 1024).— Thyroid determined with I. R. X . C. ectomy is followed by a rapid transient increase and Partition of calcium and inorganic phosphorus a subsequent decline in blood-I to < normal. I then present in blood is probably absorbed from the ali in equine serum. P. B. P earson and H. 11. h b s Catchpole (Proc. Amer. Soc. Animal Prod., 1935, mentary tract. C . A . (p) Jan., 84— 86).— Average vals. for total Ca and P in Polysaccharide hydrogen sulphates with horses on a diet with adequate Ca and P were heparin-like action.— See this vol., 453. 13-13±l-03 and 3-37¿0-29 mg. per 100 ml., respect Effects of sodium citrate on the alkaline ively, and on a low-P diet vals. were 13-60¿0-70 and 2-61 ±0-21 mg. The vals. for diffusible Ca and P reserve and coagulability of the blood. D. de Souza and F. D. M. H ocking (J. Physiol., 1935, were 7-15±0-87 and 3-02±0-32 mg. for the former and 8-09±0-84 arid 2-47¿0-29 mg. for the latter. 85, 168— 172).— Alkaline reserve is increased; co agulability is increased with small, and reduced by X u t r . A b s . (to) Composition of the blood of dairy cattle. I. larger, doses. R. X . C. Effect of age and phosphorus intake on calcium Changes in the coagulability of the blood and inorganic phosphorus content of whole produced by citric acid and some of its decom blood of dairy heifers. A. H. v a n L a n d in g h a m , position products. D. d e So uza and F. D. M. H. 0 . H en derson, and G. A. B owling (J. Dairy H ocking (J. Physiol., 1935, 85, 173— 178).— Citric Sci., 1935, 18, 557— 572).— Feeding of P-deficient acid or X H , citrate (intramuscular) increases alkaline rations lowers the blood-inorg. P to extents approx. reserve and coagulability of cats’ blood. Acetonc- oc the deficiericy. The P requirement of growing dicarboxylic and aconitic acids may increase or animals is not oc the increase in body-wt. but de diminish coagulability without affecting alkaline pends on skeletal development as measured by the reserve, but their X a salts increase both; COMe, height of the withers. The requirement in proportion affects neither. R. X . C. to body-wt. decreases as the animal approaches Blood coagulation. H. D yc kerh ofe and H. F. maturity. Age and level of P intake were without K u rten (Biochem. Z., 1936, 284, 111— 132).— effect on blood-Ca. A. G. P. Thrombin (I) contains a very small amount of firmly Blood-calcium in newborn infants. X. P. bound Ca. The Ca-free material has no coagulating Costa, F. E scardo, and S. Schere (Rev. Soc. power, but very rapidly unites with Ca to produce Argentina biol., 1934, 10, 273— 279).— In newborn active (I). Circulating blood contains > sufficient infants blood-Ca was slightly < that of the mother. Ca to meet the requirements of (I). Under normal Ch . A bs. (p) conditions Ca” has no effect on coagulation. Pre Blood-magnesium in pregnant women.^ X. formed (I) probably occurs in circulating blood. Z aharesco-K a r a m a n , M. A l e x iu , and I. U rsu Thrombokinase (II) activates (I) by removing in (Compt. rend. Soc. Biol., 1936, 121, 559— 561).— hibitors, in the absence of which (I) causes coagulation Blood-Mg rises steadily to a max. in the 5th month, when Ca" and (II) are not present. W . McC. falls sharply in the 6th, rises again to the approx. Influence of novocaine anaesthesia on the val. of the first max. in the 7th, and then falls slightly fibrinogen content of the plasma and its coagul until the end of pregnancy. R. X . C. ation. W. L. D u l ie r e, A. H u s t in , and P. B ossaert Iodometric determination of iron in blood. (Bull. Soc. Chim. biol., 1936, 18, 234— 236).— L asausse and L. F rocrain (J. Pharm. Chim., Lumbar injection of novocaine causes a decrease in 1936, [via], 23, 82— 84).— Aq. X H 3 and milk of MgO haimatocrit, time of coagulation, and concn. of are added and, after evaporating to dryness, inciner fibrinogen, followed by gradual return to normal. ating at low temp., and igniting, the residue is freed A. L. from H X 0 3 by HC1, dissolved in HC1, and mixed with Technique for determination of fibrinogen in aq. K I. After 3 miri. 3 drops of amidone solution human blood : rate of coagulation of plasma. are added and liberated I is titrated with 0-005i\T- W . L. D u liere (Bull. Soc. Chim. biol., 1936, 18, X a2S20 3. W . McC. 231— 233) Effect of adrenalectomy on blood-chloride and T est for coprosterol in plasm a.— See this vol., -sodium . C. I. U r e c h ia, G. B en etato, and 467. R etezean h (Bull. Acad. .Med. Roumanie, 1936, Effect of spleen extract on the time of coagul I , 141— 14-1).— Adrenalectomy in cats produces ation, thrombocytes, and erythrocytes of the 498 BRITISH CHEMICAL ABSTRACTS.— A. X IX (b, C) blood. E. IIaen lkin and E. Sc h lieph ak e (Klin. Chemical specificity of heart muscle. B. Woch., 1935, 14, 79— 83). R. N. C. K isch (Klin. Woch., 1935, 14, 145— 146).— A review. Preparation of cobra-toxin for clinical pur R. N. C. poses, particularly for alleviation of cancer pain. Specific gravity and water content of the L. W . van E sveld (Biochera. Z., 1936, 283, 343— brains of vertebrate animals. I. Birds. L. P. 357).— A method is described for separating from K in g and M. C. H sung (Bull. Nat. Acad. Peiping, cobra-toxin the hæmolysin, haemorrhagin, and non 1935, 6, No. 1, 1— 47). Ch. Abs. (p) toxic albumin contents without any considerable Embryochemistry of Ilynobius. M. T a k a loss of the sp. neurotoxin. The purified prep., kept matsu (J. Biochem. Japan, 1935, 22, 203— 211).— p a in the dark at 5-2, remained completely active for Data are given for the ash constituents and N dis months while in clinical use. P. W . C. tribution of the components of the eggs of H. nebulosus Chemistry of immunity reactions. IV. Dis incubated for varying periods. The principal enzymes tribution of chemically distinguished antigens present aro esterase, nucleinase, glycogenasc, and in the organism of normal and sensitised glycerophospliatase. F. 0 . H. animals. F. H a u r o w it z and E. K ra u s (Z. physiol. Chem., 1936, 239, 76— 82 ; cf. A., 1932, 542 ; 1933, Chemistry of blow-fly larvæ. M. T omita and 411).— Injection of arsanilazoprotein (I) into normal T. K umon (Z. physiol. Chem., 1936, 238, 101— 104).— guinea-pigs is followed by accumulation of As in the The amounts of various inorg. ions (mostly Na and organs of the reticulo-endothelial system, particularly PO,) and the nature of the proteins and enzymes in in the liver. Similar results are obtained after the larvæ are recorded. R. S. C. injection of a suitable antiserum (loc. cit.). The Distribution of lead in human bones. S. L. gradual degradation of (I) in the organism has been T ompsett (Biochem. J., 1936, 30, 345— 346; cf. studied. After injection of iodoglobulin the main A., 1935, 1160).— In bones from persons having had portion of the antigen is found in the liver. H. W . no special exposure to Pb the amounts of Pb per kg. Recovery and stabilisation of the antibacterial of fresh material were : rib 4-0— 17-5, vertebræ 3-4— agglutinin and anti-sheep hæmolysin of serum. 16-5, femur 18-2— 108-3, and tibia 15-3— 96-5 mg. H. Goldie (Compt. rend. Soc. Biol., 1936, 121, 761— W . McC. 764).— Tho agglutinin of B. coli and anti-sheep Organic constituents of bone. T. I n o u y e hæmolysin are recovered from their respective com (Tolioku J. Exp. Med., 1935, 26, 4 3 3 -^ 4 0 ).— Total plexes by stabilisation with CH20 and pptn. with C of tho substantia compacta of the shaft of the 1 : 4 : 6 : 8-NH2’C10H4(SO;tNa)3 and citric acid. Both rabbit femur, excluding preformed C 02, ranged from show tho variation of pa and isoelectric point and 8910-5 to 11596-6 mg. (average 9744-6) and total N increase of thermostability on storage, exhibited by from 3119-6 to 3387-8 mg. (average 3269-4) per 100 antitoxin recovered by flocculation with the toxin, g. of dry substance. The ratio total C : total N and are not affected by heating to 85°, which denatures suggests that ossein forms the principal part of the tho associated globulins and reduces their anaphyl org. ground substance. Residual C was 333-1— actic activity. R. N. C. 568-3 mg. (average 443-2) and the residual N 94-9— Favourable effect of some lipins on the 171-1 mg. (average 132-1). There was no definite immunising action of antigens. G. R am on sex difference. Calc, on org. ground substance, (Compt. rend., 1935, 201, 687— 689).— Tetanus bones are richer in residual C and N than is blood. toxin in oil containing cholesterol (I) when injected The results indicate that carbohydrates and fats are subcutaneously into horses is at least 7500 times the most important substances metabolised in bone. as active in producing antibodies as when (I) is N u t r . A b s . (to) omitted. j . l. D. Copper content of some human and animal Specific antigen and antibody in the urine of tissues. P. E. H a h n and E. F a irm a n (J. Biol. Chem., 1936,113, 161— 165).— In the liver and spleen pregnant women. L. Grim ard (Compt. rend. Soc. Biol., 1936,121, 743— 746). R. N. C. of dogs suffering from experimental anæmia, Cu tends to riso to high levels as Fe falls towards zero. In Keten, a new reagent for detoxification of man, no marked change in Cu is found in various vaccine. J. T. T am ura and M. J. B oyd (Science, pathological conditions. Foetal and infant livers are 1936, 83, 61— 62).— Acétylation of B. dysenteriœ, comparatively rich in Cu, so are the livers of patients Shiga, with keten for 30 min. detoxifies the antigen with Mediterranean anæmia, although Fe (hæmo- L. S. T. siderin) is high. F. A. A .- Characters of antitoxins purified by floccul ation, stabilised by formaldehyde, and recovered Phosphorus compounds in the nymph and with sodium naphthylaminetrisulphonate. H. butterfly of Deilephilia euphorbiœ. J. H eller Goldie (Compt. rend. Soc. Biol., 1936, 121, 649— (Compt. rend. Soc. Biol., 1936, 121. 414— 416).— 652).— The recovered antitoxins become progressively Analytical vais, for the butterflies and for the whole acid during the first 2— 3 months of storage, the iso nymph and its organs are given. HCl-hydrolysable electric point is shifted, and the thermo-resistance P (adenosinetriphosphoric acid) is high in the butter increases. The antigenic power is not affected, but flies, especially in the male, but very low in the tho anaphylactic action is reduced by heating to nymph. Intestinal P in the nymph is entirely inorg. ; SO— 85° to denature the attacked globulins ; the anti total P in the adipose tissue is as high as in the toxin is unaffected by such heating. R. N. C. liæmolymph, muscles, and intestine. R- N. C. X IX (c) BIOCHEMISTRY. 499 Calcium and magnesium content of the flesh (I), (II), and (III); and the ovaries, (I), (II), and of various animals. M. T akam atsu (Z. physiol. (III). W. McC. Chera., 1936, 238, 99— 100).— Ca and Mg were deter Colorimetric determination of cholesterol in mined in the muscle of 20 animals. Unusually high liver oil. K. H otta and M. K a w a j i (Nagoya J. vals. are: adder, Ca 1-2524, Mg 2-5268; snail, Ca Med. Sci., 1935, 9, 23— 24).— Volatile acids are re 1-3202, Mg 2-7673; clam, Ca 0-7819; crab, Ca moved by heating the oil -with 0-9% aq. NaCl in a 0-8424% (as oxides) of the dried muscle. R. S. C. stream of air; after saponification with 25% aq. Sodium content of mammalian muscle. F. K O H at 150° for 30 min. cholesterol (0-34— 0-54%) P odolsky and G. M alor n y (Pfliiger’s Archiv, 1935, is determined by the Embden-Miyamori method. 236, 339— 347).— Na of the ash of mammalian muscle N u t r . Abs. (m) is slightly > that of the equiv. Cl, the excess repre Fate of carotene in the animal organism. O. senting Na of the fibres. The excess is of the same B a il l y (Bull. Acad, med., 1932, 108, 932— 935).— order of magnitude as in muscle of cold-blooded The adrenal glands are by far the richest organs of animals. Red and white muscles exhibit no import the body in carotene (I), which is localised in the ant differences in Na content, but in heart- Na is cortex in concns. of the same order as that in carrots. slightly > that in skeletal muscle, particularly in The (I) of bovine adrenals is fi-carotene, similar to pigs, rabbits, and man. R. N. C. that found in the ovary. R. N. C. am-Glucose in the animal organism. H. K. Carotenoid pigments in fishes. II. Effects B arrenscheen and II. F an ta (Biochem. Z., 1936, of coloured backgrounds and of ingested caroten- 283, 382— 389).— When 0 2 is bubbled through warm oids on the xanthophyll content of G ir e lla dil. glucose solutions, no oxidation occurs. On adding n ig r ic a n s . F. B. S u m n er and D. L. Fox (J. Exp. these solutions to blood, liver, or muscle the filtrates Zool., 1935, 71, 101— 123). Nutr. Abs. {m) obtained by pptn. with EtOH-COMe2 and treatment Anti-anaemic principle of liver. J. F. W il k in with colloidal Fe(OH)3 show a decrease in total son (Lancet, 1936, 230, 354— 356).— The claim (A., reducing power of 20— 50% , according to the duration 1935, 885) that Reinecke acid can be used further to of the experiment and the organ used. This decrease purify and increase the potency of the anti-anaemic is not due to oxidation, but concerns the fermentable principle has been confirmed. L. S. T. portion of the sugar, 60— 78% of which is now oxidis- able with animal C. This oxidisable portion may be Alleged occurrence of ‘ ‘ Krampfstoffe ' ’ in «»«-glucose. P. W . C. acetone extracts of the mammalian brain. E. Comparative determination of hepatic glyco H olmes (J. Physiol., 1935, 85, 400— 408).— COMe2 gen by the cupric and iodometric methods. H. extracts of the brain contain no substances affecting Bie rr y, B. G ouzon, and C. M agnan (Compt. rend. the central nervous system, but a cardiac depressor. Soc. Biol., 1936, 121, 616— 619).— The Cu method R. N. C. gives identical results whether or not the glycogen Nitrogenous constituents of the stomach wall has previously been pptd. with E tO H ; the results of dogs. K. I k ey a m a (J. Biochem. Japan, 1935, are also identical with those by the I method. The 22, 397— 407).— Total N and constituent N H 2-acids Cu-reducing power after Hg deproteinisation is due (most of which were isolated) were determined in the solely to an aldose. R. N . C. mucosa and muscle layers of the fundus, cardiac, and pyloric regions. F. O. H. Micro-determination of liver-glycogen. H. Bie r r y , B. G ouzon, and C. M agnan (Compt. rend. Significance of carnitine in muscle. E . Str ack , Soc. Biol., 1936, 121, 614— 616).— The liver is auto- P. W o rdeh off, and H . Sch w aneberg (Z. physiol. claved with 30% KOH, and again after acidification Chem., 1936, 238, 183— 196).— A simple process with HC1. After deproteinising with H g(N 03)2, and for isolating carnitine (I) (1-8% calc, as betaine) removing excess of Hg, the liberated glucose is from meat extract is described. (I) and acetyl- determined by the micro-modification of Bertrand’s carnitine (II) have little biological activity, but (I) method. ' R. N. C. is accompanied by very small amounts of a substance which persistently adheres to the Au salt of (I) and Mixed glycerides of salicylic acid, and fatty acids.— See this vol., 453. yields an active Ac derivative. Atropine counter acts the activity of this substance and phytostygmine Fatty acids of phrenosin and kerasin.— See this increases it. (II) vields a sparingly sol. compound vol., 454. with AuC13. W . McC. Halibut-liver oils. Vitamin- A content of Part played by carnosine in muscles. E. pilchard oil.— See B., 1936, 242. S a v ron (Ukrain. Biochem. J., 1934, 7, No. 1, 53— Polyethenoid acids of the n-octadecane (C18) 61).— The carnosine content of muscle varies in differ series in aquatic animal oils.— See B., 1936, 204. ent animals. Vals. for white aro > those for red Lipochromes of the frog (liana esculcnta). L. muscle. None occurs in pigeons, rats, guinea-pigs, or dogs. Ch. A bs. (p) o o iHi’,! - STER and P- Tuzsox (Z. physiol. Chem., 1936, 238, 197 -203; cf. this vol., 97).— The liver contains Micro-determination of creatine in muscle. carotene (I) (a- and B-) (25% of total pigment), A. V. P alladxn (Ukrain. Biochem. J., 1934, 7, No. I ! ttt zcaXim ’n (ill)» free and esterified xantho- l j 163__ 171).— Muscle is mixed with sand and boiled phyll (IV), and small amounts of other lipochromes; with aq. NaCl and AcOH. The filtered residue is the skin and fat glands, chiefly esterified (IV) with re-extracted 8— 10 times with H 20. The combined 500 BRITISH CHEMICAL ABSTRACTS.— A. X IX (C, d) extract is boiled with picric acid and the creatinine (NH4)2S0 4 contained 0-7 % P. After pptn. also with produced is determined colorimetrically. urea, the P content fell to 0-3% and the purine-N Ch . A b s. (p) to zero. The differences in total N, tyrosine, trypto Relation between functional requirements, phan, histidine, phenylalanine, cystine, arginine, acetylcholine reaction, and glutathione content lysine, etc. contents of the (I) and (II) fractions are of bird muscles. L. Cassel (Pfliiger’s Archiv, small and considerably < the differences with serum- 1935, 236, 30— 35).— The glutathione content of the proteins. P. W . C. wing muscles of flying birds is highest in birds that Thiol and disulphide groups of proteins. II, make long flights. Male birds contain > females. III. Reducing groups of proteins.— See this vol., Ascorbic acid in the breast muscles is the same in 352. good and bad flyers. It. N. C. Ultrafiltration of proteins through graded Muscle extractives of hibernating giant sala collodion membranes. II. Hsemocyanin m ander (Megalobatracus japonicus)'. T. Iw a - (Helix), edestin, and ovalbumin. W. J. E le o r d s a k i (J. Biochem. Japan, 1935, 22, 233— 242).— and J. D. F e r r y (Biochem. J., 1936, 30, 84— 91).— From aq. extracts of the muscles were isolated creatine, The influence of medium, of p n, and of concn. of creatinine, adenine, xanthine, hypoxanthine, histidine, neutral salts on the filterability of the above proteins methylguanidine, lysine, choline, and d-lactic acid. is investigated, the best results being obtained in F. 0 . H. Hartley’s broth at p H 7— 8. The filtration end Acetylcholine and choline in organ extracts. points for haemocyanin (Helix) of 55 mg and for F. P lattn kr and H. T sudzim ura (Pfliiger’s Archiv, edestin of 18 mg are established, indicating particle 1935, 236, 175— 180).— There is no evidence of a sizes of 18— 28 mg and 6— 9 mg, respectively. The correlation between acetylcholine, choline, and ester results confirm the val. of the factor employed for ase in the organs of the cat. Acetylcholine-like deducing particle size from porosity of the membrane substances are not affected by thyroidectomy or which just completely retains the disperse phase. adrenalectomy. It. N. C. P. W . C. Composition of the protamines of sturgeon. Action of radioactive substances on proteins.— M. A. JLissitzin and N. S. A lexakdrovskaja (Z. See this vol., 301. physiol. Chem., 1936, 238, 54— 58).— The protamines Electrical orientation of wool cells.— See this of the milt of Acipenser huso, guldenstddtii, and vol., 414. stellatus are probably identical, the sulphate being C35H 740 7N18,3H2S0 4 (amount of H 2S0 4 varies with Proteins of body-fluids. I. Quantitative aid method of prep.), [a] about — 55° in H 20 , and N H 2-, qualitative aspects. II. Application of phys arginine-, histidine-, and lysinc-N being about ical data. C. Ac h a r d (Bull. Acad. Med. Roumanie, 8, 72, 10-5, and 6 % of the total N, respectively. 1 9 3 6 ,1, 15— 25, 26— 30).— I. The nature and content R, S. C. of proteins in body-fluids in health and disease are Preparation of b-thymonucleic acid by nucleo- discussed. II. The Tyndall effect, a, adsorption on C, fluores gelase. F. F eu lgen (Z. physiol. Chem., 1936, 238, 105— 110).— 6-Thymonucleic acid (free from a-iso- cence, and effect of dilution and flocculation with meride) is prepared (a) from cell nuclei (e.g., heads Fe(OH)3 of normal and pathological body-fluids are of herring sperm) by digestion with slightly alkaline discussed. F. O. H. (Na2C03) 0-5% pancreatin solution, pptn. from alkaline Influence of high environmental temperature (NaOH) solution by EtOH, acidification with AcOH, on the secretion and composition of milk. S. dehydration with EtOH, and desiccation, or (b) B ar tlett (J. Dairy Res., 1935, 6, 283— 288).— High from natural organs (e.g., thymus glands) by lique temp, caused a lowering of the % of fat and solids-not- faction with about 5-5% NaOH (15 min. at 65°), fat in milk. The depression in total yield was small. addition of N H 4C1, pptn. with EtOH, and enzymic A. G. P. degradation of the ppt. as in (a) (cf. A., 1914, i, 888). Factors affecting milk and butter-fat secretion. - R, S. C. I. Variations in fat weight, fat percentage, and Form of proteins in blood-plasma and bone- the amount of fat in milk required to make a marrow in the normal organism. H. K eilh ack given weight of butter. II. Colour of the (Arch. exp. Path. Pharm., 1936, 180, 440— 457).— butter-fat. E. 0. W heth am and J. H am m ond (J. Data are given for the contents of the various proteins Dairy Res., 1935, 6, 320— 339, 340— 352).— I. The in rabbit’s plasma [7-0% total protein; approx. size of the fat globule is probably controlled by the 0-30% fibrinogen (I)] and bone-marrow [average rate of formation of fat in the cell and the rate of 3-2% total protein; 1-095% (I)]. The relation be milk secretion. The influence of age, stage of lact tween the high (I) content of bone-marrow and the ation, and breed are examined. The ratio of the blood constituents is discussed. F. 0 . H. wt. of fat in milk required to make 1 lb. of butter Chemical constitution of liver-proteins. F. F. is a measure of variations in the size of the fat U r b a n (Biochem. Z., 1936, 283, 435— 453).— The globules. protein of cat’s liver washed free from blood is in II. Effects of genetic and dietary factors are vestigated. About half of the protein is extractable examined. A. G. P- by salt solutions, the globulin (I) : albumin (II) ratio Daily variations in butter-fat content of milk. in the extract being 7 :3 . The (II) fraction is Z. Czu kas (Mezog. kutat., 1935, 8, 270— 278).— The P-free. The (I) fraction after repeated pptn. with daily average butter-fat % of cows’ milk varied greatly, X IX (d) BIOCHEMISTRY. 501 (2-4— 5-5). Morning milk contained 40 % < evening I. Cosjiulesco, and F. Serban (Bull. Acad. Med. milk and 30% < noon milk. These differences Roumanie, 1936, 1, 133— 140).— NaCl in presence of could not be eliminated by regulating the milking cerebrospinal fluid crystallises in various abnormal periods. N u t r . A b s. (m) forms dependent on the composition of the fluid; Component fatty acids of goat milk fat. R. W. the phenomenon is probably of diagnostic val. R iemenschneider and N. R. E llis (J. Biol. Cliem., 1936, 113, 219— 233).— The fat of the milk of,goats L ym ph-sugar. J. W . H e im , R. S. T hom son, fed on a regulated diet contained undecoic, penta- and F. C. B artter (Amer. J’. Physiol., 1935, 113, decoic, palmitoleic, oleic, hexoic, octoic, decoic, 548— 554).— Lymph- and plasma-sugar in the dog myristic, palmitic, stearic, and arachidonic acid, and are almost identical under certain conditions; the a mixture of saturated acids containing tetracosanoic glucose-tolerance curves are similar. Sugar adminis and cerotic acids. H . D. tered per os or intravenously enters the lymphatic system readily, and is removed at about the same Effect of type of feed on the solids-not-fat rate as from blood. R. N. C. content of milk. L. L. Roux, G. N. M u r r a y , and Salivary secretion. W. F eldberu and J. A. D. J. Schutte (Onderstepoort J. Vet. Sci., 1935, 4, 167— 197).— Rations containing identical amounts of Gu im arais (J. Physiol., 1935,85,15— 36). R. N. C. protein and total digestible nutrients were fed to 3 p,t of normal resting saliva. I. Variations groups of cows; group (1) received a high concen with age and sex. 11. E. B r a w l e y (J. Dent. Res., trate ration, group (2) high dry roughage, and group 1935, 15, 55— 77).— The average pK was 6-75, there (3) high succulent rations. In group (1) solids-not- being no significant difference between the two sexes. fat rose normally with advance of lactation, whilst N u t r . A b s . (to) groups (2) and (3) showed a fall. The milk produc Bile pigment metabolism. I. Breakdown tion of group (1) did not decrease as rapidly as that of blood pigments to protoporphyrin by the of groups (2) and (3). N u tr. A bs. (m) liver and other organs. Demonstration of a Yield and composition of ewe's milk. W. fermenting action. H. T. Sch reus and C. Ca r r ie (Klin. Woch., 1934, 13, 1670— 1673).— The liver is Godden and C. A. P u d d y (J. Dairy Res., 1935, 6, 307— 312).— Analytical data are recorded. No appre able to form protoporphyrin from hcemoglobin or ciable difference in milk composition resulted from hsematin; the process is not associated with life or survival of the cells, but probably with the action of wide variations of Ca in the ration. A. G. P. a haemase. Within certain limits the amounts of Milk of a typical herd of Shorthorn cows. fermented substances and of the products of reaction III. Nitrogen distribution, chloride, lactose, are proportional. Optimum conditions are 37— 60° copper, and iron contents over a period of two and pu 3— 5 ; the action of the enzyme is restrained years. W. L. D avies (J. Dairy Res., 1935, 6, by EtOH, Et20 , CHC13, COMe2, and glycerol, inhibited 362— 368).— Analyses are recorded and discussed. by cooling to"0°, and destroyed by boiling. A. G. P. R. N. C. Free lactic acid in fresh milk. B. Gross and Determination of bile salts in human bile. C. Ol iveira (Rev. Quim. Farm., 1935, 1, 117— R. G oiffon, F. N e p v e u x , and Ch a le il (Compt. 120).— Fresh milk, or its serum, had p H 6-65— 6-85, rend. Soc. Biol., 1936, 121, 425— 427).— Proteins are whereas the val. calc, on the assumption that its pptd. from bile with the Folin-Wu reagent, and acidity is due to lactic acid is about 2-8. Experiments pigments with FeCl3 and N H 3. The bile salts are described indicate that no free lactic acid or lactates dissolved in aq. EtOH, evaporated alone and with are present. L. A. O’N. AcOH, extracted with CGH6 to remove fats, dissolved So-called normal lead of human milk. M. in 0-lN -NaOH , and pptd. with 0-1V-HC1 saturated K asahara and S. I. Nosu (Jahrb. Kinderheilk., 1935, with (NH4)2S0 4, the homogeneous suspension being 145, 78— 80).— 52 out of 87 samples of milk from examined photometrically. R. N. 0. women living in an area having a service H 20 supply Determination of free and combined chole contained Pb (trace to 0-18 mg. per litre). Out of sterol in bile. C. R iegel and H. J. R ose (J. Biol. 15 samples from women in rural districts only 3 Chem., 1936, 113, 117— 124).— A modification of the contained Pb (0-04— 0-11 mg. per litre). Schoenhehner-Sperry (A., 1934, 1240) procedure for Nutr. Abs. (m) the determination of cholesterol hi bloocl is used. Excretion of drugs in milk. N. T. Kwit and F. A. A. R . A. H atcher (Amer. J. Dis. Children, 1935, 49, Rabbits bile. I.— Sec this vol., 469. 900— 904).— Morphine, codeine, and phenolphthalein are not secreted in human milk. Salicylic acid, I', Toad bile. I ll , IV .— See this vol., 469. and Br' appear in milk after administration. Bilifuscin. E. W e in be rg er (Z. physiol. Chem., _ Ch . A b s . (p) 1936, 238, 124— 128).— Bilifuscin is C12H180 3N. It Plasma-protein determinations in lactating is isolated impure from human biliary calculi (cf. A., w om en. S. C. Peacock and W . F. Hinman (Amer. 1901, i, 283). R. S. C. J. Physiol., 1935, 113, 235— 237).— The excretion of Effect of peptones and certain extracts of small cascinogen in the milk has no recognisable effect on intestine on the secretion of succus entericus. the blood-proteins. R. x . C. E. S. N asset and H. B. P ierce (Amer. J. Physiol., Crystallisation of [sodium] chloride in 1935, 113, 568— 577).— Witte’s peptone contains a presence of cerebrospinal fluid. P . T om esco, secretagogue which stimulates the jejunal glands when 502 BRITISH CHEMICAL ABSTRACTS. A. X I X (d, e) administered per os or intravenously. It is extracted, decreases (I) elimination without affecting (II) and free from depressor, by 70% EtOH, and is thermo urea; (II) elimination oc the glomerular filtration stable, but destroyed by erepsin or trypsin. It is rate. R. X . C. not present in other peptones. Another secretagogue, Excretion of inulin, creatinine, xylose, and which resists the digestive enzymes, but is destroyed urea in the normal rabbit. B. I. K apla n and by boiling in alkali, is extracted from the small H . W . Smith (Amer. J. Physiol., 1935, 113, 354— intestines of pigs or dogs by acidified 70% EtOH. 360).— Excretion of inulin (I), creatinine (H), xylose R. N . C. (III), and urea increases with urine flow. Simultane Acidity of gastric juice and the diluting ous excretions of (I) and (II) are equal, TCgardless secretion of the stomach. T. E ngestrom (Acta of urine flow or plasma-(II) level, and are > those of med. scand., 1935, Suppl. 66, 73 bp.).— Gastric secre (III) and urea. R. X . C. tion hi cats following administration of histamine (I) or EtOH is used to study regulation of gastric acidity. Excretion of kynurenic acid by the mam Intraglandular regulation by a diluting, HCl-free malian organism. Identification of small secretion is of primary importance. True hyper amounts of kynurenic acid. W. G. G o rdon, R. E. K aufm an, and R. W . J ackson (J. Biol. Chem., acidity, > about 170 millimol., exists. There was no parallel between blood-(I) and intensity of 1936,113, 125— 134).— 50— 100 mg. of kynurenic acid secretion. With continuous intravenous injection of (I) may be identified and determined as the Me ester. (I), intensity of secretion increased steadily and Tbe rat, guinea-pig, and Dalmatian dog excrete (I) after administration of tryptophan. The cat does not appeared to tend towards a max. N u t r . A b s . (m) excrete (I) under these conditions, but ingested (I) Histamine-like substance in the gastric juice. is excreted unchanged. F. A. A. C. L. B row n and R . G. Smith (Amer. J. Physiol., Properties of reducing material in certain 1935, 113, 455-463). R. N. C. fractions of normal urines. I. Nature of the Some physiological and physical aspects of free fermentable sugars and the fermentable the surface tension of urine. P. W. P er rym an sugars produced on hydrolysis in fasting urines. and C. F. Selous (J. Physiol., 1935, 85, 128— 144).— V. J. H a r d in g , T. F. Xicholson, and R. M. A r c h i A modification of the max. bubble pressure apparatus b a ld . II. Effect of diet on hydrolysahle sugar for determination of a is described; it can be used in urine. Nature of this sugar. V. J. H a rd in g , to follow changes of a with temp, and with time up T. F. Xicholson, and S. H. J a ck so n (Biochem. J, to 2 hr. The c-time curves for urine arc logarithmic, 1936, 30, 326— 334, 335— 341).— I. Cone, solutions of in both normal and pathological urines; the changes carbohydrate arc obtained from human urine by are not due to proteins or absorption of C 02, but successive treatment with basic Pb acetate (I), probably to slow' adsorption of capillary-active sub H gS04-B aC 03, and CuS04-C a(0H )2. Differential stances. The c-temp. curve is linear up to 54°, after fermentation of the solutions (e.g., with Saccharomyces which the decrease becomes more rapid. Variations Marxiamis) shows the presence, before and after dil. of a are not related to ingestion of food or liquid, but acid hydrolysis, of glucose (II) and galactose (III) and, in females a shows a cyclical variation corresponding in some cases, of very small amounts of fructose and with the menstrual cycle, a is not related to d, or the mannose. Probably most, if not all, of the fermentable presence of pathological constituents in the urine, sugar produced on hydrolysis is derived from the non- and is not correlated with any sp. disease or group of fermentable reducing fraction, not from a non- diseases. ' R,. N. q. reducing precursor. Almost all the sugar of urine is Chemical basis of the Elirlich diazo-reaction X-free. II (cf. A., 1931, 1443). Meals consisting chiefly with urine. I. „P. Sachs. II. P. Sachs and of fat, fruit, and starch, respectively (but not those H. K loss (Z. klin. Med., 119, 381— 402, 551— 563; consisting chiefly of protein), cause increase in the Chem. Zentr., 1935, i, 3019— 3020).— !. A cryst. amounts of substances giving rise to fermentable sugar dichloroazobenzene dye, C31H240 - X 6C14 (Bz, and Bz1 derivatives), is isolated. G on hydrolysis, excreted in the urine during 4 subse II. By-products of high mol. vt. arc formed in the quent hr., the increase being almost entirely due to reaction, the pathological significance of which is (II)-producing substances. A small amount of (II)- discussed. jj r producing material, pptd. by (I) and H gS04-B aC 03 but not by Lloyd’s reagent, occurs in fasting and Detection of histidine in urine as a reaction non-fasting urines, but not after fat and fruit meals. for pregnancy. X. C. L ouros (Klin. Woch., 1934 About 33% of the hydrolysahle material has reducing 1 3 ,11 5 6 ; Chem. Zentr., 1935, i, 3961).— The Kapeller- power, the reducing group being in the (II) mol. Adlcr reaction (A., 1933, 1094) is unsuitable, both for All (III) produced on hydrolysis exists combinco. detecting histidine arid as a reaction for pregnancy through its reducing group, possibly7 as lactose. H. X . R. W . McC. Elimination of xylose, creatinine, and urea Reducing power of urine. II. H. Iv. B arren - by the perfused mammalian kidney. A. H em ing screen and H. P rin z (Biochem. Z., 1936, 284, 99 w a y (J. Physiol., 1935, 84, 458— 46S).— The average 107; cf. A., 1930, 806).— The reducing material is creatinine (I)/xylose (II) and urea/(H) clearance separated (60%) by adsorption on A120 3 (optimal at ratios in the isolated perfused kidney are 1-72 and Pa 7-73) and kaolin (optimal at pa 1-17). The part 0-85, respectively, and are within the range of the of the material w'hich loses its reducing power on vals. obtained from normal animals. Plasma concn. treatment with CH20 is preferentially adsorbed (max. X IX (e j) BIO CHEMISTRY. 503 at pH 6-24 and 7-73) on kaolin, and is not removed methods for the determination of these substances in by successive elution with aq. N H 3 and dil. AcOH, urine are described. H . N . R. which removes the other part. This part appears to Spectrochemical study of aplysiopurpurin. consist of substances related to homogentisic acid. M. F ontaine and A. R a f f y (Compt. rend. Soc. Biol., W . McC. 1936, 121, 735— 736).— Aplysiopurpurin in acid Isolation and identification of combined Zn(OAc)2 solution (cf. A ., 1931, 1443) shows absorp cestriol in human pregnancy urine. S. L. tion bands at 501, 552, and 601 iujx and fluorescence Cohen and G. F. M arrian (Biocliem. J., 1936, 30, bands at 518, 568, 617, and 644 mu.. When obtained 57— 65).— A method is described for isolation from in the solid state by pptn. with (NH4)2S0 4, it does human pregnancy urine of a H 20-sol., Et20-insol., not fluoresce; it is therefore related to mesobiliviolin, non-cryst. substance, m.p. 193— 197° (decomp.), and is probably a breakdown product of chlorophyll containing approx. 50 w t.-% of cestriol. The com and phycochromoproteins absorbed by Aplysia^ position and the Ba content of the Ba salt agree with those required for an cestriolglycuronic acid, C24H320 9. Uroporphyrin in acute hsematoporphyrinuria. The substance gives strong naphthoresorcinol and E. M ertens (Z. physiol. Chem., 1936, 238, I— II).— Millon tests, but does not reduce Benedict’s solution The urine contained, in addition to a little copro until after hydrolysis. P. W . C. porphyrin, a uroporphyrin (I) [Me8 ester (II), m.p. Excretion of cestrin by the kidneys of the 258° (Cu compound, m.p. 304°)]. Decarboxylation pregnant m are. S. Ivober (Acta Brev. neerl. of (I) with HC1 under pressure gives coproporphyrin Physiol., 1935, 5, 34— 35; Chem. Zentr., 1935, ii, III and hence (I) is uroporphyrin III. The mother- 238).— The folliculin content of mare’s urine rises liquor from (II) contained a MeOH-sol. ester, m.p. suddenly during the 5th and 6tli months of pregnancy, 240°. W. McC. and falls again during the last two months. Urinary porphyrins in disease. K . D o br in e r G. H . F. (J. Biol. Chem., 1936, 113, 1— 10).— A method for Bence-Jones protein. H. T su tsu i (J. Biochem. separating and identifying porphyrins in urine is Japan, 1935, 22, 343— 350).— Reactions for urine described. An increased excretion of coproporpliyrin containing the protein (I) are given. The N distribu I is characteristic of most diseases, but pigment tion of isolated (I) {[a]D — 95-78° (1-305% solution cirrhosis and liver tumour lead to excretion of copro in O-lN-NaOH), isoelectric point pa 4-72} is tabulated. porphyrin III. In two cases uroporphyrin I was (I) is hydrolysed by gastric juice or trypsin. Its isolated, and an unknown porphyrin {Me ester, m.p. pathogenesis is discussed. F. O. H. 222°) was obtained. The formation of these por Colorimetric determination of urinary protein, phyrins is discussed. J. N . A. plasma-protein, urinary and plasma-albumin. Acriflavine as a urinary antiseptic. E. W . Salting out of these proteins. H. B e r c .l u n d and A ssin der (Lancet, 1936, 230, 304— 305).— Acriflavine W. d e M. S c r i v e r (Acta med. scand., 1935, 86, 82— S7).—Methods with an accuracy of 3— 5 % arc is strongly antiseptic towards the gonococcus. L. S. T. described. Na2S0 4, essentially in the concns. used by Howe, is used for fractionation. N is determined Phosphatase of the plasma and its variations by nesslerisation. The acid digestion of protein in disease. C. J im en ez D fiz, E. B a ssad o n e, and requires more heat than is required for determination S. Cl a r ia n a (Rev. espan. Enferm. Aparat. digest. Nutric., 1935, 1, 5— 20).— Average vals. found were of non-protcin-N of blood. N u t r . A b s . (m) 0-142 K ay unit in adults and 0-26 in children. Determination of sulphate in urine.— See this Increases in rickets, osteomalacia, bone diseases, vol., 442. degenerative rheumatism, and liver disease are noted. Determination in series of the oxalic acid N u t r . A b s . (m) content of urine. K . K o c h (Biochem. Z ., 1936, Scurvy in Addison's disease and the value of 283, 422— 432).— A method which requires 40 c.c. of the catalase index in adrenal insufficiency. L. urine and determines 0 04— 0-1 mg. of H 2C20 4 is N orpoth (Deut. Arch. klin. Med., 1935, 177, 499— described. 15— 30 double determinations can be 508; Chem. Zentr., 1935, ii, 245).— The blood-catalaso carried out per day. P. W . C. index has no diagnostic significance in Addison’s Spectrographic determination of phenol added disease. G. H . F. to urine. G. B arac (Compt. rend., 1935, 201, Adrenal disease in relation to hypoglycaemia 1433).— The urine is treated successively with basic and death. J. C. N orris (Amer. J. Clin. Patln, Pb acetate, Na2HP 04, and HC1, extracted with Et20, 1935, 5, 120— 130).— Hypogfycsemia under these con and the extract is examined (this vol., 126). ditions indicates a relationship between liver and F. O. H. adrenals in glucose metabolism. Ch . A b s . (p) Determination of p-bromophenylmercapturic acid in the urine of the dog. J. A . Stekol (J. Correlation of hypertrophy of the adrenal Biol. Chem., 1936, 113, 279— 288).— A gravimetric cortex with bodily work and the vitamin-/! (using the HgCl2 complex) and an iodometric titration content of the diet. A. vo n B e z n a k and J. P erjAs method are described. H. G. R. (Pfiuger’s Archiv, 1935, 236, 181— 189). R. N. C. Strychnine and barbituric acids. M. E. K e r - Amidopyrine and granulopsenia. Reappear gonou (Bull. Trav. Soc. Pharm. Bordeaux, 1935, 73, ance of granulocytosis in a case of recurring 53— 61; Chem. Zentr., 1935, i, 3822).— Extraction agranulocytosis after large doses of amido 504 BRITISH CHEMICAL ABSTRACTS.— A. X IX (/) pyrine. L. R. L im arzi and I. G. M u r piiy (J. cancer. W. Cram er and E. S. H o rn in g (Lancet, Lab. Clin. Med., 1935, 20, 616— 622). Ch. Abs. (p) 1936, 230, 247— 249). L. S. T. Goat's milk anaemia. G. 0. K o h le r, C. A. Cholesterol as a constituent of malignant cells. E lvehjem , and E. B. H art (Amor. J. Physiol., 1935, I. A. B ronstein and D. V. W olkensohn (Acta 113,279—284). R, N. C. Cancrologica, 1935,1, 205— 214).— The cholesterol (I) Comparison of the anaemia produced by feed content of the necrotic centre of the Jensen rat ing young rats on human, cow's, and goat's sarcoma is 2— 2-5 times that of the developing peri milk. H. H. B eard and T. S. B ocgess (Amer. J. phery. X-Irradiation in vivo does not alter the (I) Physiol., 1935, 113, 642— 646). R. N. C. of the periphery. The (I) of culture media is not changed by growth of sarcoma cells. Ch. A b s . (p) Blood regeneration in severe anaemia : frac tions of kidney, spleen, and heart compared Action of pituitary secretion on tumours. H. with standard fractions. F. S. R obscheit- D ru ck re y (Arch. exp. Path. Pharm., 1936, 180, R obbins, G. B. W a l d e n , and G. H . W h ipple (Amer. 367— 380).— Following castration in female rats, the J. Physiol., 1935, 113, 467— 475). R. N. C. gonadotropic hormone (I) content of the pituitary increases 15— 20-fold and, after approx. 7 months, Chlorophyll and regeneration of blood. Ad decreases; the thyrotropic hormone content is un ministration of chlorophyll derivatives in changed. During the period of increased level of (I), chronic hypochromic anaemia. A. J. P a t e k , jun. development and growth of tumour implants are (Arch. Int. Med., 1936, 57, 73— 84).— Chlorophyll inhibited, the initially increased respiration decreasing products when administered either parenterally or to zero vals.; such non-respiring tumours are not orally with comparable amounts of Fe produce blood re-implantable. Relations between hormonal influence regeneration. H. G. R. and tumour growth are discussed. F. 0 . H. Liver principle active in pernicious anaemia. Effect of cystine disulphoxide on spontaneous C. C. U n g l e y (Nature, 1936, 137, 210— 213).— A tumours of the mouse. F.S.H. for the Staff of review. L. S. T. the R esearch I n stitu te of th e L a n k e n a u H os Treatment of pernicious anaemia with Dakin p it a l, P hiladelphia (Science, 1936, 83, 108— 109).— and West's liver fraction (anahaemin). C. C. Tumour growth and cell proliferation are retarded. U n g le y , L. S. P. D avid so n, and E. J. W a y n e L. S.T. (Lancet, 1936, 230, 349— 354).— The prep, is highly Variations of polypeptidaemia in cancerous active for blood regeneration in pernicious anaemia. patients treated by intravenous injections oi L. S. T. com plex salts derived from vitam in-C (ferri- Pathological calcium deposits. D. R. M e e k e r scorbones). F. A rlo in g , A. M orel, A. J osserand, and H. D. K esten (J. Biol. Chem., 1936, 113, 289— M. Cham bon, and S. Celliere (Compt. rend. Soc. 296).— The average composition of calcified deposits Biol., 1936, 121, 683— 685).— Polypeptides arc in in arterial sclerosis is : CaO 49-5, P20 5 36-1, MgO creased. R. N. C. 0-90%. Calcification of implanted colloid material Effect of hematoxylin on respiration and is increased by toxic doses of vitamin-D preps, and glycolysis of cancerous tissue and spleen of the deposit has the average composition : CaO 46-8, cancerous rats. R. I w a tsu r u and M. K awaguchi P20 5 32-7%. H . G. R. (Biochem. Z., 1936, 284, 163— 168)— The R.Q. is Urinary sulphur in non-specific arthritis. increased, hi presence or absence of glucose, by B. D. Senturlv (J. Lab. Clin. Med., 1935, 20, 855— addition of hematoxylin whereas that of spleen and 861).— The total S excreted and the S partition in liver of healthy rats is unchanged or slightly urine of affected patients are approx. normal. The diminished; glycolysis in the diseased tissue and N /S ratio is lowered in only a few cases. spleen is practically unchanged. W . McC. Ch . A b s . (p) Blood-urea in botulism of cattle. P. Rossi Genetics, thiol, and cancer. F. S. H a m m e t t (Compt. rend. Soc. Biol., 1936, 121, 526— 527).— (Science, 1936, 83, 57).— A discussion. L. S. T. Botulism is accompanied by a rise of blood-urea and Cerebroside-containing cerebral cyst. C. a fall in renal excretion of urea, both returning to T ropp and B. E ckardt (Z. physiol. Chem., 1936,238, normal on recovery. r , q 31— 34).— The liquid from a cerebral cyst contained Blood-urea and Brucella infection in horses. no inorg. Fe, cholesterol, or P, very little fat and hsemo- P. Rossi (Compt. rend. Soc. Biol., 1936, 121, 611— globin products, but mainly cerebron and kerasin and 612).— Blood-urea is not appreciably affected. ’ some albumin. A small amount of solid deposit R. N. C. contained Fe and fat. R. S. C. Carcinogenic chemical compounds. H. A. Gastric secretion in cceliac disease. J- V\. W eidlich (Chcm.-Ztg., 1936, 60, 185— 187).— A Ogilvie (Arch. Dis. Childhood, 1935, 10, 93— 98).— review. The disease is accompanied by lowered [HC1] ni Carcinogenic action of thorium dioxide in the gastric juice without true achlorhydria. The increase white rat. G. R o u ssy , C. Ob e rl in g , and M. in total Cl' probably results from the higher [Cl'] in G u erin (Bull. Acad, mcd., 1934, 112, 809— 816). blood. ‘ Ch. Abs. (p) R . N. C. Sulphur metabolism in cystinuria. J. C. Experimental production by cestrin of pituitary A ndrew s and A. R an da ll (Amer. J. Med. Sci., tumours with hypopituitarism and of mammary 1935, 189, 301— 302).— In a case described, the out X IX (/) BIOCHEMISTRY. 505 put. of cystine (I) was unaffected by doses of NaHCO;, Paget’s disease, multiple myeloma, and neo and Na citrate sufficient to maintain urinary pa at plastic disease of the bones. A. B. G u t m a n , T. L. 7-0— 7-5 and to keep (I) in solution, by equimol. T y s o n , and E. B. G u t m a n (Arch. Int. Med., 1936, proportions of glycine and glutamic acid, or by a high- 5 7 , 379— 413).— Serum-phosphatase is augmented in egg diet. Orally administered (I) is completely oxidised the diseases studied. In hyperparathyroidism, to S 04". 60— 80% of di-methionine is oxidised to multiple myeloma, and neoplastic disease of the bones SO.,", the remainder being excreted as unoxidised S hypercalcaemia is observed, inorg. P being low in without change in urinary (I). Cysteine (II) is ex hyperparathyroidism, but normal in other cases. creted unoxidised. The (II) content of cystinuric In Paget’s disease both serum-Ca and -inorg. P are urine increases 25— 50% on keeping 24 hr. normal. H . G. R. C h . A b s . (p ) Blood-cholesterol in hypothyroidism. L e s n e , Sugar and glutathione contents of blood and B r i s k a s , and L a k d £ ) (Bull. Soc. Pediat. Paris, 1935, skin in dermatitis produced by croton oil and 33, 60— 62).— The finding of high blood-cholesterol by sunburn. C. M o n c o r p s , R. M. Bohnstedt, in hypothyroidism is confirmed. In infants, the val. and R. S c h j i i d (Arch. Dermatol. Syphilis, 1933, 1 6 9 , is 2— 4 and in children above 15 years 1-3— 1-6 g. per 67— 75).— The changes are functions of the intensity litre. ' N utr. Abs. (m) of skin inflammation and time. C h . A b s . (p) Blood-cholesterol in arterial hypertension. “ Soya water-bread ” and the use of soya meal A. H. E l l i o t and F. R. N u z u m (Arch. Int. Med., in the treatment of diabetes and corpulence. 1936, 5 7 , 63— 72).— Hypercholesterolsemia was not F. S c h e l l o n g (Klin. Woch., 1935, 14, 487— 490).— observed in uncomplicated hypertension or in hyper The composition of a comparatively carbohydrate- tension associated with vascular degeneration or free “ water-bread ” prep, from oil-free soya-meal is renal impairment or a low metabolic rate unaccom given, and its therapeutic use is indicated. R. N. C. panied by hypothyroidism. High vals. were generally associated with subnormal body-wt. II. G. R. Neuropathy in diabetes. Lipin constituents of the nerves correlated with the clinical data. Treatment of hyperinsulinism with insulin. W. R. J o r d a n and L. O. R a n d a l l (Arch. Int. Med., H. J. J o h n (Endocrinol., 1935,1 9 . 689— 694). 1936,57, 414— 421).— The phospholipins, cholesterol, R . N. C. and cerebroside of the nerves are reduced in diabetes, Hypoglycsemic headache. P. A. G r a y and H. I. the greatest effect occurring in those from the lower B u r t n e s s (Endocrinol., 1935, 1 9 , 549— 560).— part of the leg. H. G. R. Migraine and other headache conditions are often associated with low blood-sugar (I). The glucose Inorganic phosphorus in diphtheria. 1. tolerance curve is of the flat type. Reactivity to Natin and C. D a R i n (Semana med., 1935, I, 1148— insulin (II) is measured by the (II) tolerance test; 1149).— Blood-inorg. P is not appreciably abnormal. the fall of (I) below fasting level oc the height above C h . A b s . (p) the fasting level before injection of (II). Hyperglycasmia in diphtheria, carbohydrate R. N. C. metabolism, and treatment with glucose and Van der Bergh reaction (ring test technique) insulin. I. N a t i n and C . D a R i n (Semana med., and hsemoglobin-bilirubin interrelation in 1935, I, 1055— 1058).— In diphtheria, deviation of icterus neonatorum. N. W. E l t o n (J. Lab. Clin. glyciemia is small, but glucose tolerance is frequently Med., 1935, 2 0 , 817— 826).— No relationship was disturbed by factors of hepatic origin. apparent between the bilirubin content and changes C ii. A b s . (p) in haemoglobin content and no. of erythrocytes. Experimental epilepsy. III. Alteration in C h . A b s . (p) the protective quality of serum in epileptiform Variations of oxalaemia in liver diseases. A. convulsions produced by camphor. V . N e i i - R o d i g u e z -O l l e r o s (Rev. espaii. Enferm. Aparat. ltjdov (Kolloid-Z., 1936,74, 218— 221).— During and digest. Nutric., 1935, 1, 323— 332).— Blood-H2C20 4 between the convulsions produced in cats and dogs by in hepatic disease is > normal. No correlation was injection of camphorated oil, the quantity of blood- found between extent of bilirubinoemia and oxalaemia. serum needed to stabilise a sol of Congo-rubin is Ingestion of 1 g. of H2C20 4 produces in liver patients increased in severe attacks which end fatally, but is in 2 hr. a 10— 30% increase in oxalaemia, whereas diminished in less severe, non-fatal attacks. there is no increase in non-hepatic patients. Diets F. L. U. poor or rich in H 2C20 4 produce no const, variation Lipin diseases. IV. Lipin content of tissues in oxalaemia on the day following the diet. in status epilepticus, toxic encephalopathy, and N utr. Abs. (m) chronic leptomeningitis. D. M. C o w i e and M. C. Carbohydrate exchange after carbohydrate M a g e e (Amer. J . Dis. Children, 1935, 4 9 , 884— 893).— charging and its disturbance in liver diseases. The ratio of phospholipins to cholesterol in liver, spleen, and skeletal muscle in status epilepticus is I. Insulin-glucose-water charging. R. M e i e r > in other diseases examined (cf. A., 1934, 550). and E. S c h m i e d t (Z. ges. exp. Med., 1935, 9 5 , 277— 287; Chem. Zentr., 1935, i, 3950— 3951).— Injection C h . A b s . (p) of excess of insulin followed by ingestion of excess Role of uric acid in gout. H. L u c k e (Deut. of glucose and H20 by healthy man does not generally med. Woch., 1934, 6 0 , 1783— 1786). R. N. C. result in increased carbohydrate combustion, the Serum-calcium, -inorganic phosphorus, and R.Q. and 0 2 consumption showing little change. In -phosphatase activity in hyperparathyroidism, cirrhosis of the liver, combustion is retarded and 506 BRITISH CHEMICAL ABSTRACTS.— A. X IX (/, g) continues longer than normally. Lactic acid form Ca and -Mg vary irregularly. Tetany is not due to ation is increased in jaundice. In normal rabbits Mg deficiency but probably results from overfeeding glycogen is first synthesised, but is later oxidised; with protein. Ch . A b s . (p) it disappears from the liver 3 hr. after ingestion, and Concentrated diet in childhood tuberculosis is not deposited in the muscles. R. N . C. and malnutrition. G. E. Pratt (Arch. Pediatr., Glucose exchange in liver diseases. II. E. 1934, 51, 529— 533).— Supplementary milk feeding S c h m i e d t (Z. ges. exp. Med., 1935, 9 5 , 2 8 8 — 294; to increase the calorific val. of the diet and the intake Chem. Zentr., 1935, i, 3951).— Charging with glucose of fat, protein, carbohydrate, Ca, P, vitamin-A and is not suitable for the diagnosis of liver functional -B2 increased the gain in wt. and general condition of disturbance in man. 0 2 consumption shows no tuberculous children. Ch. A b s . (p) characteristic change, but R.Q.. exhibits a late rise Effect of irradiated ergosterol on the phospho- in cirrhotics. R. N. C. lipins of the blood in pulmonary tuberculosis. Biochemistry of blood of normal and malaria- J. II. R e ic h a r t (Diss., Amsterdam, 1935, 64 pp.).— infected monkeys. R. C. W ats and B. M. D as A photo-electric method of determining lipoid P was G utta (Indian J. Med. Res., 1934, 21, 475— 481).— found most accurate. The lipoid P content of the Blood-sugar, -non-protein-N, and -Ca were unchanged blood in 34 normal subjects varied as much as 12% by infection, whilst the plasma-eholesterol decreased. in 6— 7 days. The vals, in tuberculous patients, Treatment with atebrin, quinine, etc. caused an treated with irradiated ergosterol or untreated, were unexplained increase in inorg. P 0 4"'. not significantly different from one another or from Ch. A bs. (p ) normal vals. N u t r . A b s . (to) Bromide content of blood determined by the Blood-calcium in tuberculosis. P. M eersse- method of Leipert and Watzlawek, in mental m a n n and H. S é g u in (Rev. Tuberc. Paris, 1935, disease. M. N a g y and J. Strau b (Orvosi Hetilap., [v], 1, 514— 528).— Blood-C tends to be low. 1935, 79, 895— 897).— In 70% of cases of recurrent N u t r . A b s . (to) psychosis blood-Br' was subnormal (normal 0-9— Variations in living matter controlled by 1-4 mg. per 100 ml.). In the remaining cases and chem ical law s. O. R a h n (Biochem. Z., 1936, in other mental diseases it was normal or high. 284, 40— 62).— Vital processes (e.g., heat-inactivation N u t r . A b s . (to) of enzymes, fission processes in the cell, velocity of Mineral metabolism in osteogenesis im cell division, biological variation, death of cells) are perfecta. W. W. Sw an son and L. V. I ob (Amer. considered from certain mathematical aspects. J. Dis. Children, 1935, 4 9 , 958— 963).— In affected P. O. H. cases, retention of Na differs more from normal than Basal heat production of the rhesus monkey that of other minerals. Vais, for Ca and P are < (Macaca mulatto.). N . R a k ie t e n (J. Nutrition, normal, and those for S, K , Cl, and N are in the normal 1935, 10, 357— 362).— The average basal heat pro range. The Ca and P of bones increase. Viosterol duction, 608 kg.-cal. per sq. m . per 24 hr., is the same improves retention of Ca and P without affecting for both sexes and is not affected by administration that of other minerals. Ch . A b s . (p) of Na amytal. A. G. P. Diagnostic value of pigmentation in paludism. Basal metabolism and iodine excretion during Concentration [of pigment] in blood and urine. pregnancy. L. E n r ig h t , V. V. C o l e , and F. A. M. Canciulesco and R . H irsch (Bull. Acad. Med. H it c h c o c k (Amer. J. Physiol., 1935, 113, 221— Roumanie, 1936, 1, 31— 34). P. O. H. 228).— Growth of the fœtus and supplementary Poikiloderma atrophicans vasculare (Jacobi). tissues is largely responsible for the increased metabol A. Marchionini and P. B ohning (Arch. Dermatol. ism accompanying pregnancy, but in adolescent girls Syphilis, 1934, 170, 112— 122).— Changes in blood- there is another stimulatory factor absent in mature sugar, serum-protein, -alkali reserve, -lactic acid, women. The increase is smaller if iodised salt is -cholesterol, -K , and -Ca during a sweat bath with used during pregnancy. I excretion -increases 3 a normal patient and with one almost devoid of weeks before birth, suggesting a possible change in sweat glands are examined. Ch . A b s. (p) thyroid function. R. N. C. Rapid flocculation method for diagnosis of Basal metabolism and urinary nitrogen syphilis. P. R yt z (Amer. J. Clin. Path., 1935, excretion of Oriental women. A. H. T u r n e r 5 , 159— 161).— The reaction is made more rapid by and P. G. B e n e d ic t (Amer. J. Physiol., 1935, 113, coagulation of blood by heating for 2— 3 min. at 60°, 291— 295).— Basal metabolism is < the prediction sensitisation of serum by (NH,)2S0 4, and use of a stable standard and that of American women in the samo stock antigen. Ch . A b s. (p) environment. The urinary N excretion shows that Calcium therapy in “ staggers ” in the proteins in the diet are not abnormally low, and that bullock. (A) J. R. S h e e h y . (B) J. R. Greig (Vet. the fall of basal metabolism is not due to decreased Rec., 1936, 16, 147—148; 202). R. N. C. protein metabolism. R. X - l' Fistulous withers and poll-evil: calcium Interprétation of lowered basal metabolic therapy. W. W. Lang (Vet. Rec., 1936,16, 238). level. D. L. Se x t o n (Endocrinol., 1935, 19, 579 ■ R. N. C. 586). R. N. C. Tetany in calves. B. Sjollem a (Vet. J., 1935, Heat production in man. II. Output ^ of 91, 133— 137).— In tetany the mineral and, probably, carbon dioxide as a mea.sure of heat production the carbohydrate metabolism are disturbed. Blood- in basal metabolism. T. W . A d a m s and E. P- X IX (¡7) BIOCHEMISTRY. 507 P oulton (Guy’s Hosp. Rep., 1935, 85, 56— 75).— Behaviour of heavy water towards light water Calculations and deductions support the view that, in the organism. F. B re u sch and E. II o fer (Klin. under basal conditions, carbohydrate and fat aro Woch., 1934, 13, 1815— 1816; Chem. Zentr., 1935, burnt in a fixed ratio. C 02 production is a direct i, 3882— 3883).— From determinations of d to ¿ 5 X measure of the amount of combustion. Kb7 for H ,0 mechanically and chemically held in N u t r . A b s . (m) various organs, no fractionation of H 20 and D 20 Increase of the contents of reducing sub in the organism could be detected in normal cases, stances (glutathione and ascorbic acid) in the in sarcoma of the lung, in cirrhosis of the fiver, organs in training. K. W ac h h o ld e r and K . or in blood from tuberculous or cancerous cases. U hlenbroock (Pfluger’s Archiv, 1935, 236, 20— J. S. A. 29).— I-reducing substances (I) are increased in the Effect of ingestion of saline waters on the p a skeletal, heart, and stomach muscles, fiver, lungs, and of the intestinal tract, the nitrogen balance, and brain of the dog and the rabbit by regulated exercise, the coefficient of digestibility. V. G. H e l le r , the increases being due to glutathione in the first J. R. Ow e n , and L . P ortw ood (J. Nutrition, instance, but in many cases to ascorbic acid as well. 1935, 10, 645— 651).— Assimilation and digestibility (I) are decreased in many organs in over-exerted of foods, if affected at all, are improved by dissolved rabbits. In a well-trained dog (I) are decreased in salts provided serious disturbance of growth or re the thyroid and adrenals. R. N. C. production does not occur. The p a of the intestinal tract is not appreciably altered, but that of the stom Effect of muscular exercise on biological ach is somewhat affected. A. G. P. processes. E. T a k e d a (Japan. J. Exp. Med., 1935, 13, 471— 509, 511— 520, 521— 527, 529— 534, 535— Respective variations of weight, water, and the 541).— The following changes were observed in dogs constituents of the dry weight in the gudgeon as as the result of work for 1 hr. on the treadmill: functions of the external glucose concentration. increases in no. of leucocytes and lymphocytes, G. FoNTks, J. B r u n e r, and A. L in d e n b e r g (Compt. blood-fat, and -residual N, decreases in blood-sugar, rend. Soc. Biol., 1936, 121, 459— 462).— H 20 and no. of erythrocytes, haemoglobin content of the blood, “ H 20 impermeable to EtOH ” decrease, and non C02-combining capacity of the plasma, and total protein substances increase, as the glucose (I) concn. urinary N. In dogs fed from infancy on meat diets all increases. The dry wt. decreases, the curve being these changes were > in dogs fed on vegetable diets. linear. In a 1-25% (I) solution conditions tend to N u t r . A b s . (m) return to normal after 5 days. R . N . C. Changes of volume of muscle as an expression Immediate effects of reduced cooling powers of chemical processes. 0. M ey erh o f and W . on the water balance and related effects in the Mohle (Biochem. Z., 1936, 2 8 4 ,1 — 11).— The changes human subject. D. H. K. L ee and A. G. M u l d e r in vol. which occur in normal and poisoned [with (J. Physiol., 1935, 84, 410— 432). R. N . C. CH2I*C02H (I)] muscle on stimulation and in muscle with heat- or (I)-rigor aro accompanied by an un Permeability and ion concentration in muscle explained contraction, in Ringer’s solution some excitation. V. S. I l j i n (Pfluger’s Archiv, 1935, what > that in paraffin oil, and especially pro 236,148).— A reply to Ernst and Fricker (cf. A ., 1935, nounced during production of lactic acid (II). The 239). R. N. C. dilations are only 4 0 % (Ringer) and 50% (paraffin) Absorption of water from common salt and of those observed during enzymic (II) production, sugar solutions. E. J. M cD ougall and F. V er za r and the contraction of muscle poisoned with (I) is (Pfniger’s Archiv, 1935, 236, 321— 338).— H 20 and > the expected val. When valeric acid penetrates hypotonic NaCl solutions are rapidly absorbed in the muscle, slight contraction occurs. W . McC. rat and cat; isotonic NaCl is absorbed well in the Is the work of the kidney (due to excretion of rat, but in the cat an increase in vol. of the solution urea) a factor in specific dynamic action ? sometimes occurs, as in the case of isotonic xylose A. G. E aton , S. C. Cord ill, and J. L. Gou au x [with (I) solutions in both species. The increase in vol. V. Cl a y ] (J. Nutrition, 1935, 10, 429— 436).— The is not accompanied by a change of osmotic pressure, work done by kidneys in the concn. of urine during so that blood-crystailoids (II) diffuse into the in rapid excretion of urea is not a material factor in the testine. Glucose (III) is absorbed from isotonic sp. dynamic action of proteins. A. G. P. solution by the rat intestine after 15 m in.; the ab Coefficient K of Nicloux in the gudgeon (A) sorption depends on the amount of (II) diffusing in, living 24 hours in glucose solutions of increasing and is generally so intensive that the solution becomes concentrations, (B) living in glucose solutions hypotonic and H 20 isabsorbed. Absorption is as a function of time. G. F oN T is, J. B r u n e r , slower in the cat, no H 20 being resorbed from 5-4% and A. L inden berg (Compt. rend. Soc. Biol., 1936, (III). If (III) absorption in the rat is depressed by 121, 452— 455, 456— 458).— (a ) K diminishes as the CH2PC02H, H 20 behaves as in the case of (I), and concn. of glucose increases, the curve being linear. the solution becomes hypertonic through diffusion K becomes zero when the osmotic pressure becomes of (II) into the intestine. Increase of the hydro double the isotonic val. static pressure of the small intestine causes an increase (b ) K show's little variation in a 1-25% solution in rate of absorption of isotonic NaCl oc the increase of glucose, and becomes normal in 5 days. It falls in pressure. R. N . C. rapidly in 5 % solution, rises in 3 days, and then falls Relative significance of electrolyte con aSain- R. N. C. centration and tissue reaction in water meta- 508 BRITISH CHEMICAL ABSTRACTS.— A. X IX (g) holism. H. A. D avis and L. R. D ragstedt (Amer. sum of (I) oxidation by the liver and inhibition of J. Physiol., 1935, 113, 193— 199).— Dogs dehydrated normal fat oxidation; the increase in 0 2 consumption by simple H 20 deprivation retain 0-9% NaCl and due to the first process is > the decrease due to the 5 % glucose bettor than do normal dogs. Animals second, at all (I) concns. R. N. C. with gastric fistula; and consequent alkalosis retain Embryochemistry of amphibia. VIII. Oxid H20 slightly better than those with pancreatic ative processes in giant salamander’s eggs. F. fistulm; the latter are extensively depleted of base, Y a m a s a k i. IX. Urea and uric acid in incub chiefly Na, through loss of pancreatic juice, but still ated eggs of giant salamander. M. T a k a m a tsu cannot retain NaCl. R. N. C. and T. K a m a chi (J. Biochem. Japan, 1935, 22, 181—- Changes in the laid egg. P. U l r ik and D. 184, 185— 187).— V III. Development of the eggs D avidsen (Proc. 5th World’s Poultry Congr. Rome, produces an increase in •SH and in indophenol-oxidase. 1933, 2, 462— 474).— The pH of the egg increases from IX . The incubated eggs contain 0-0030— 0 0047 % of S-2 when new laid to 9-2 after 12 hr., and to 9-8 in urea, but only traces of uric acid. F. 0 . H. 9 days. Subsequent changes are insignificant. Titr ation with CH20 serves as an approx. index of egg Effect of frequency of contraction of the isol age. Ch . A b s. (p) ated mammalian heart on the consumption of oxygen. A. E. Cohn and J. M. Steele (Amer. J. Relation between metabolic processes and the Physiol., 1935, 1 1 3 , 65-F-658). R. N. C. ventricular electrogram. A. S. D ale (J. Physiol., 1935, 84, 433— 453). R. N. C. Influence of muscular work on oxidative Mechanism of intracellular respiration. D. processes in the animal organism. L. P al- K eilin (Bull. Soc. Chim. biol., 1936, 18, 96— 130).— la d in a (Ukrain. Biochem. J., 1934, 7, No. 1, 23— A lecture. 30).— The oxidation of PhOH, injected into rabbits, diminishes after muscular work. Ch . A b s . (p) Accuracy of the Barcroft differential mano meter in respiration studies. A. S. Corbet and Comparison of the rates of metabolic activity W . R. W ooldridge (Biochem. J., 1936, 30, 132— in the solitary and migratory phases of Locusta 140.— The standard error in the determination of 0 2 migratoria: C. G. B u tler and J. M. I nn es (Proc. by the Barcroft techniquo depends on the duration Roy. Soc., 1936, B , 119, 296— 304).— L. migratoria and replication of the experiments. A statistical may, according to the conditions, assume either a method for determining the significance of the migratory or a solitary phase. The rate of 0 2 uptake difference between means is recommended. H. D. per unit area of body surface is higher for locusts in Effect of viosterol on oxygen consumption of the migratory phase, in all instars after the first. The rate is higher for males than for females in all frog's m uscle. S. G elfa n (Amer. J. Physiol., instars and both phases. The rate diminishes from 1935, 113, 464— 466).— 0 2 consumption in isolated the first to the third instars, and increases again from frog muscle is increased by daily injections of viosterol. the fourth instar to the adult stage. F. A. A. R. N. C. Effect of thyroxine on tissue oxidation. G. N. Mechanical activity of gut muscle under M arkoff (Beitr. path. Anat., 1935, 94, 377— 388; anaerobic conditions. B. N. P r asad (J. Physiol., Chem. Zentr., 1935, i, 3561).— Thyroxine (I) aug 1935, 85, 249— 266).— The mechanical activity of gut ments tissue oxidation in the liver of the rat, but not muscle is arrested by asphyxia through exhaustion in the spleen or brain. The increase does not occur of its labile carbohydrates. Max. activity is main until the regular effects of (I) are established. The tained when both glucose and 0 2 are supplied to the increase in 0 2 consumption in the liver is noticeable muscle. CH2I-C 02H limits considerably the anaer 3 days after the last injection of (I), whilst the increase obic activity of the muscle, suggesting a low plios- of cellular oxidases is evident immediately after the phagen content. R. N. C. last injection. R. N. C. Relation of rate of growth to diet. III. Effect of liver feeding in relation to oxygen Comparison of stock rations. L. B. M e n d e l and want. H. B. P a rry (J. Physiol., 1935, 84, 454— R. B. H u bbell [with F . F rancis] (J. Nutrition, 1935, 457).— Exposure of rabbits to low 0 2 tensions 10, 557— 563). A. G. P. does not cause formation in the liver of any factor hemopoietic to rats. R. N. C. Effect of cereal diets on the composition of body-fat of rats. H. S. Olcott, W . E. A n d erso n , Choline and liver respiration. O. A. T roivell and L. B. M en del (J. Nutrition, 1935,10, 517— 523). (J. Physiol., 1935, 85, 356— 374).— Choline (I) in — The I val. of the body-fat varied with the cereal concns. > 0-12% increases 0 2 consumption by rat’s food given. A. G. P. liver- or kidney-tissue, decreases that of cardiac muscle and spleen, and does not affect that of brain. Alimentary value of (A) old, (B) new, maize. Added fatty acid or glucose does not affect the action G. N ic h ita, N. T uschak, and G. I ftimesco (Compt. of (I). Washed Uver-pulp oxidises (I) with uptake of rend. Soc. Biol., 1936, 121, 563— 566, 567— 570). 1 atom of O per mol. (I) does not affect O, consumption R. N. C. by aq. liver extract, but in concns. > 0 -01% it Effect of differently de-fatted soya-bean meals inhibits CH2Ac-C02H production to a degree oc the on the blood picture of domestic animals. I. concn., inhibition being complete at 1 % ; fatty acid E nver (Diss., Tierarztl. Hoclisch., Berlin, 1933; increases the inhibition. The effect of (I) on 0 2 Bied. Zentr., 1935, 6, A , 1).— Effects of extraction consumption by liver-tissue is probably the algebraic with C2HC13 and with CC14 are compared by means X IX (g) BIOCHEMISTRY. 509 of rabbits and guinea-pigs. The blood picture is not increase in N H 3 and a decline in urea. Catabolism appreciably altered by the use of these solvents. of body-tissue is high probably through excessive A. G. P. deamination with mild acidosis. C ystine deficiency Are potato- and maize-starch nutritionally has no effect. A. G. P. equivalent ? F. F isch ler (Munch, med. Woch., Utilisation of energy-producing nutriment and 1935, 82, 57— 58; Chem. Zentr., 1935, ii, 243).— protein as affected by individual nutrient Equivalence is established. G. H . F. deficiencies. III. Effects of the plane of Comparative rachitogenic property of oats protein intake. E. B. F orbes, R. W . Sw ie t, A. and maize. L. L. L achat and L. S. P alm er (J. B la ck, and 0 . J. K ahlenburg (J. Nutrition, 1935, Nutrition, 1935, 10, 565— 577).— HC1 extracts of 10, 461— 479). A. G. P. oats when purified and freed from excess of NaCl Effect of different percentages of protein in showed rachitogenic properties when fed to rats the diet on virgin rats. J. R. Slo n a k e r (Amer. receiving a mildly rachitogenic diet. With a severely J. Physiol., 1935,113, 159— 165). R. N . C. rachitogenic diet the extracts produced no additional effect. Rolled oats and yellow maize are rachitogenic Replacement of protein [in cattle rations] by to rats and especially to chickens. A. G. P. ammonium salts. S. V. F omin and Y. I. D em in (Ukrain. Biochcm. J., 1934, 7, No. 1, 133— 143).— , Influence of diet on the glucose tolerance of Replacement of proteins in the ration by urea and the dog. E. M. Gre ish e im e r and F. W . II oee- N H , salts lowered the rate of growth. batjer (J. Nutrition, 1935,10, 525— 534).— With low- Ch. A bs. {p) carbohydrate diets an increase in the proportion of Proteins of foodstuffs. V. Contents of fat or protein lowers the glucose tolerance. Effects cystine and tryptophan. T. T om iyam a (J. Bio- of other dietary variations are recorded. A. G. P. chem. Japan, 1935, 22, 341— 342).— The respective Effect of 1% of cod-liver oil on the rat with cystine, methionine (cf. A., 1934, 572), and trypto particular reference to the thyroid gland. C. B. phan contents of the proteins from silk-worm pupce Freudenberger and F. W . Clausen (J. Nutrition, (a), sardines (6), and soya beans (c) are : (a) 0 -86, 1935,10, 549— 555). A. G. P. 2-97, 1-50; (b) 0-76, 3-14, 1-40; (c) 1-05, 1-96, 1-35%. Effect of choline on the weight of young rats. F. O. H. E. W . M cH e n ry (J. Physiol., 1935, 85, 343— 349).— Formation of histidine from arginine in Choline (I) and vitamin-iix exhibit a complementary incubating hens’ eggs. T. K am ach i (J. Biochem. effect on the gain in wt. of young rats. Rats not Japan, 1935, 22, 199— 202).— Injection of arginine (I) receiving (I) exhibit symptoms resembling those of into incubating eggs is followed by an increase in vitamin-Rj deficiency. R. N. C. the free histidine (H), whilst injection of (II) does not Effect of deficient diets on the total ash, increase the level of (I). F. 0 . H . calcium, and phosphorus contents of bones. Origin of creatine from proteins and amino- R. Y eager and J. C. W inters (J. Nutrition, 1935, acids. H. H. B e a r d and T. S. B oggess (Amer. 10, 389— 397).— In animals stunted (to maintain J. Physiol., 1935, 113, 647— 653).— Creatine (I) the same body-wt.) by calorie, protein, and lysino de in the muscles of rats fed on diets containing only ficiency, the ash, Ca, and P of bones were > those 4 % of protein is increased by re-feeding on a diet of normal animals of the same wt. but < those of containing 25% of protein or 2 1 % of glycine or glut normal animals of the same age. Stunting by means amic acid. Total N, fat, and total solid in the muscles of a low-salt diet caused very much lower bone are scarcely changed. (I) is thus an exogenous vals. than in normal animals of the same wt. or age. catabolic product of proteins of NH„-acids. A. G. P. R. N . C. Rats' milk and stomach contents of suckling Methionine content of food proteins. A. E. rats. D. T. M a y e r (J. Nutrition, 1935, 10, 343— Sc h arpe n ack and G. P. J erjom in (Problems of 350).— Recorded data indicate that suckling rats Nutrition, Moscow, 1935, 4, No. 4, 11— 16).— Casein require a high-fat, low-carbohydrate diet. Although has a very high methionine (I) but low cystine (II) a large proportion of the calorific val. of rats’ milk content. Legume protein contains little (I), but some is derived from the fat, such a diet is not extremely (H). Egg-yolk protein contains relatively large ketogenic. A. G. P. quantities of (I) and (II). Proteins of equal S content Biological value of fresh milk and milk heated differ sharply in the character of their S compounds. l8r fJ:lort Periods> in experiments on rat-feeding. N u tr. A b s. (in) \ERTEIj, (z - Immunitats., 1935, 84, 321— 327).— Does bis-p-aminoethyl disulphide (cystamine). ulk heated for short periods is scarcely altered in its promote growth in the rat limited to an in nu, i 7°ir vaR and vitamin content, whilst pasteurised adequate intake of cystine and methionine ? mi v differs considerably in biochemical composition. R. W . J ackson and R. J. B lock (J. Biol. Chem., 10 short-period heated milk does not assure optimal 1936, 113, 135— 139; cf. A., 1933, 89; Mitchell, this or max. growth. q vol., 102).— Cystamine does not promote growth of Nutritive value of proteins for maintenance. white rats maintained on a diet low in cystine and methionine. F. A. A. I, _So-sooT-wdir- . ¿g-). vv ith maintenanceWRlGHT inylpropionic acid was ineffective, and (//-amino-JV- oxylic acids. B. F laschentrager and K . B e r n - methylhistidine was effective, in producing a growth h ar d (Z. physiol. Chem., 1936, 2 3 8 , 221— 232; cf. response in histidine-deficient rats. H . D. A., 1935, 1151).— Coconut oil and cooking fat (20% Influence of denervation on the carnosine butter), if given in sufficient amount, are degraded content of muscles. B. K o l d a e v and P. B u t k o v in the dog, yielding small amounts of sebacic (I) and (Ukrain. Biochem. J., 1934, 7 , No. 1, 63— 67).— suberic acid. The Me and Et esters of the C9—C12 Section of the ischiatic nerve in one pad of a rabbit monocarboxylic acids, given with fat, yield the corre does not affect the carnosine (I) content of the sponding dicarboxylic acids. Of the Na salts of the gastrocnemius muscle. After rigor (I) probably de CG—C12 and C14, Clc, and C18 monocarboxylic acids creases somewhat. Ch .. A b s. (p) only octoic, nonoic, and decoic acids yield dicarboxylic acids. The behaviour of the Me and Et esters of Influence of fatigue on the glutathione content these monocarboxylic acids is analogous. (I), even of muscle. A. V. Pa l l a d in , S. B o r sh k o v sk i, and when given in very small amounts, passes chiefly L. Pa l la d in a (Ukrain. Biochem. J., 1934, 7, No. 1, unchanged (partly p-oxidised) into the urine. The 7— 22).— Fatigued muscle shows an increase in oxid degradation of monocarboxylic acids probably pro ised glutathione (I). This is attributed to changed ceeds more rapidly than does that of the dicarboxylio conditions of oxidation which lower the capacity of acids and consequently p- rather than co-oxidation (I) to act as H acceptor. Ch . A b s . (p) predominates in the organism. W . McC. Aminohydroxy-acids and their degradation in the anim al body.— See this vol., 468. Fat metabolism in fowls : practical signific ance. E. T. H a l n a n and E. M. Cr u ic k s h a n k Formation of carbohydrate and fat from (Proe. 5th World’s Poultry Congr. Rome, 1933, 2, protein. F. H ölzl (Diss., München, 1933 : Bied. 612— 619).— Pullets at 15 -weeks of age commence to Zehtr., 1935, 6 , A , 2).— A discussion. A. G. P. store more fat than cockerels, the difference increasing Effect of ingestion of cottonseed oil before and with advancing maturity. The E t20-sol. matter in after hydrogenation on the composition of the the blood of laying hens is > that in the blood of body-fat of the rat. J. M. Spad o la and N. R. cockerels. The I val. of depot fat reflects that of E llis (J. Biol. Chem., 1936, 113, 205— 218).— The food fat. Ingestion of unsaturated acids, e.g., hemp normal acids of rat adipose tissue were myristic, palmi oil, causes an increase in unsaturated acids on egg- tic, stearic (I), palmitoleic (II), and oleic (III). Rats yolk fat. Ch . A b s . (p) fed with a low-fat basal dict-f-cottonseed oil deposited Deuterium as an indicator in fat metabolism. more (I) and (II) than those receiving partly hydro B. Ca va n a g h and H. S. R a per (Nature, 1936, 137, genated oil or the basal diet alone. The deposition 233— 234).— By the use of linseed oil containing D of linoleic acid oc the amount fed and replaced (II) for investigating the absorption of fatty acids in the and (III). Small amounts of arachidonic acid were rat, it is shown that lipins of the liver and kidney found in the fat after feeding with the oil. H. D. take up the D-containing fatty acids. L. S. T. Digestion of fats from crude plant tissues : Effect of liver feeding on the “ fat " content digestion of closed plant cells and their import of the liver. A. W. B eeston and H. W il k in so n . ance for physiology and pathology of digestion (Biochem. J., 1936, 3 0 , 121— 126).— Rats fed on a in m an. H. W eiss (Arch. Verdauungskr., 1935, diet containing chiefly dried liver developed fatty 5 7 , 42— 45; Chem. Zentr., 1935, i, 3565).— The fat livers (A., 1934, 104) ^ cholesteryl esters (I) rose to of the uninjured cells is digested by the intestinal 1-8% and glycerides (II) to 2 % . 214 mg. of extra lipases in the mouse. ' ‘ R. N . c. choline (III) added to the diet daily had no influence Carotenoids and oxidation of lipins. J. V e r n e on the % of (I) but lowered that of (II). Using (Compt. rend. Soe. Biol., 1936,121, 609— 610).— Only EtOH-extracted livers with added beef dripping gave those lipins of skin or adrenal sections that do not vals. for (I) and (II) of 0-45 and 1-67%, respectively; give a positive Feulgen-Verne reaction can be stained addition of the extracted cholesterol (IV) to the diet with carotenoids (I); autoxidation renders the reac raised the vals. to 3-62 and 3-19% so that the fatty tion positive, but prevents staining. (I) protect the fiver production is due to (IV) in the diet. H 20- lipins against autoxidation. R . N . C extracted fiver gave the same results as unextracted Can intact monoglycerides be resorbed ? G. fiver. Inclusion of extra (IV) in the diet produced R o senthal and H. T rau tw ein (Ber. Verh. sächs. increased fat deposition, whilst replacing the dried by Akad. Wiss., math.-phys. Kl., 1934, 8 6 , 325— 338).— raw liver or adding (III) had little effect. H . D. The depancreatised dog resorbs monoglycerides (I) Dietary prevention of fatty livers. Triethyl- better than triglycerides, probably because the (I) p-hydroxyethylammonium hydroxide. H. I • are absorbed without previous cleavage on account Ch an n o n and J. A. B. Sm ith (Biochem. J., 1936, 30, of their small solubility in H ,0 or of their capacity 115— 120).— Triethyl-$-hydroxyethylammonium tydr' to form emulsions; both these properties facilitate oxide (I) (aurichloride, in.p. 225°), prepared from NEt3 cleavage by intestinal lipases. Hydrolysis is further and CH2C1-CH2-0H , when fed to rats on a fatty liver- favoured by the surface activity of the (I), through producing diet caused an inhibition of fat accumul which they are more readily adsorbed on the lipases ation rather < that of choline. Large individua and more quickly saponified. R. N. C. variations in fat accumulation occurred which were Fat metabolism. XVI. Biological degrad not associated with food intake; the inhibitory action ation of fatty acids, esters, and fats to dicarb- of (I) on does was > on bucks. H- D ‘ X IX (¡7) BIOCHEMISTRY. 511 Carbohydrate and fat metabolism during reserves, these small amounts are not therefore development of H ynobius eggs. M. T akam atsu immediately burnt. The elimination of heat on (Z. physiol. Cliem., 1936, 238, 96— 98).— The glyco feeding carbohydrate does not synchronise with the gen, fat, and cholesterol contents of the embryos of 0 utilisation. P. W . C. H. nebulosus eggs decrease with development. The fat Acidosis, alkalosis, and carbohydrate meta is almost entirely sol. in both EtOH and Et20 . bolism. Influence of acid- and base-producing R. S. C. diets. C. M ori (J. Biochem. Japan, 1935, 22, 437— Utilisation of inulin for growth by the young 446.)— The assimilation of sugar by rabbits (as indi white rat. A. B e n d a n a and H . B. L eahs (J. cated by the change in blood-sugar after ingestion of Nutrition, 1935, 10, 507— 515, 578).— With rats glucose) on a diet producing acidosis is > that with a receiving a calorie-deficient diet utilisation of inulin diet producing alkalosis. F. O. H. was < that of sucrose or fructose. Inulin cannot serve as the sole source of carbohydrates for rats. Influence of calcium on intestinal absorption. A . G. P. E. J. M cD ougall (J. Physiol., 1935, 85, 109— 116).— Do the phosphorus and glycogen contents of Absorption of isotonic glucose, xylose, and sorbose frog muscle run parallel ? A. M oschin i (Bull. solutions injected into the small intestine in rats is Soc. Chim. biol., 1936,18, 160— 164).— The changes in not affected by a diet producing low serum-Ca. the P and glycogen content of frog muscle caused by R. N. C. injection of glucose into normal animals and those Mechanism of the suppression of ammonio- with muscles atrophied by fasting, by section of the genesis in muscle by pyruvic acid. J. K . P a r k a s , sciatic nerve, and by pancreatectomy do not run B. Sobczuk, and W . M ejbaum (Compt. rond. Soc. parallel. A lowering of the P content is always Biol., 1936, 121, 701— 704).— N H 3 production is associated with functional disturbance. A. L. suppressed by AcC02H (I) more rapidly in presence of hexose diphosphate, which accelerates N H 3 production Absorption and utilisation of carbohydrates per se. (I) probably reduces phosphoglyceraldehyde [by anim als]. H. B. P ierce (J. Nutrition, 1935, to phosphoglyceric acid, which is then transformed 10, 689— 716).— A review. A. G. P. into phosphopyruvic acid. The latter reacts with Fœtal carbohydrate metabolism following N H , and adenylic acid to form adenosinetripliosplioric adrenalectomy, insulin, and glucose experiments acid. R. N. C. on the mother. E. L. Co rey (Amer. J. Physiol., Transformation of adenosinetriphosphoric 1935, 113, 450— 454).— Adrenalectomy and adminis acid in muscle. II. Relation between dephos tration of insulin in the pregnant rat cause a fall of phorylation of the acid, production of ammonia, liver-glycogen in both mother and fœtus, whilst glu and degradation of creatinephosphoric acid cose (I) increases it. Cortical hormone is without during muscular activity. D. F e r d m a n n and effect. Placental and fœtal musele-glycogen are O. F einsciimidt (Biochem. Z., 1936, 284, 63— 71 ; relatively unaffected; the latter shows a slight rise cf. A., 1935, 778).— In the frog, muscular activity with (I). R. N. C. results in degradation of adenosinetriphosphoric Carbohydrate metabolism of gut muscle. (I) and creatinephosphoric acid (II) with production B. N. P rasad (J. Physiol., 1935, 85, 239— 248).— of Ii4P20 7 and H 3P 0 4, respectively. During recovery The isolated muscle contains only about 0-25% of of fatigued muscle, (1) and (II) are resynthesised with carbohydrate available for glycolysis; it oxidises disappearance of II4P20 7 and H 3P 0 4, the extent of about 1 mg. of carbohydrate per g. per hr. in presence resynthesis depending on the length of the period of of 0 2. In presence of glucose (I) it produces lactic recovery and being almost complete in 15 min. The acid under aerobic or anaerobic conditions ; even in adenylic acid produced by dephosphorylation of (I) oxygenated Ringer’s solution the deeper portions of is deaminated during activity and reanimated during the muscle probably receive an inadequate 0 2 supply. recovery. W . McC. Glycolysis under anaerobic conditions takes place at Effects of cod-liver oil and wheat germ on the about 2 mg. of (I) per g. per hr. ; it is inhibited by retention of iron, nitrogen, phosphorus, calcium, CH2PC02Na and increased by electric stimulation. and magnesium during human pregnancy. R. N. C. C. M. Coons and R. R. Coons (J. Nutrition, 1935, 10, Utilisation of sugars and polyhydric alcohols 289— 310).— Addition of wheat germ to a basal diet by the adult blowfly. G. F raen k el (Nature, 1936, improved the retention of Fe and N, the effect being 137, 237— 238).— The utilisation by Calliphora ery- due to the mineral rather than to the org. contents. throcephaUi of numerous carbohydrates and polyhydric Cod-liver oil enhanced the action of wheat germ. -alcohols is summarised. The results indicate the Increased retention of Ca, Mg, and P due to feeding presence of several enzymes (enumerated) in the gut cod-liver oil is small and irregular. A. G. P. of the fly. ' L g ,£ Spectrum analysis of hen-eggs and chick- Animal calorimetry. XI. Specific dynamic tissues. W. F. D r e a (J. Nutrition, 1935, 10, 351— action of carbohydrate. Z. A szôdi and J. Pélyi 355).— Al, Ba, Ca, Cu, Fe, Mg, P, K , Rb ( ?), Si, Na, (Biochem. Z„ 1936, 283, 3 9 3 -4 1 4 ).— The sp. dyn Sr, Ti, and V pass from food or H 20 into the egg and amic- action of carbohydrate on administration of thence into blood and tissues of the chick. Mn and large amounts of sugar is > that of fat but with Zn are absent from chicks’ blood. Al, Ba, Cu, Si, small amounts is not related quantitatively to the Sr, Ti, and Zn are uniformly distributed among the amount of sugar used. In presence of carbohydrate tissues. Ba, Fe, Sr, and V are more conc. in hens’ 512 BRITISH CHEMICAL ABSTRACTS.— A. X IX (g) blood and/or egg than in the food. B, F, and Ag and ultra-violet energy, poults receiving the higher are unnecessary or harmful to chicks. Cr, Pb, and levels of Ca (CaC03) were better able to adjust them Mo occur in hens’ blood in amounts corresponding selves to vitamin limitation. The Ca and P to those in the food but are not regularly present in requirements vary with the growth rate, which is eggs. When present in chicks, Mo accumulates in influenced by the quality and quantity of protein the liver, Pb in lungs, and Cr in brain and eye. and the supply of vitamins other than -D. Mn occurs in yolks but not in whites or shells, and in Ch . A b s . (p) chicks accumulates in the liver. A . G. P. Changes in lime content between various parts Chemistry of cephalopod embryos. T. of the hen’s egg during incubation. A. Ca z - K amachi (Z. physiol. Chem., 1936, 238, 91— 95).— z a n ig a (Proc. 5th World’s Poultry Congr. Rome, The Ca, Mg, S 04, N H 2, and enzyme contents of the 1933, 2, 444— 449).— The shell-Ca diminished rapidly embryo increase at the expense of the residue during from the 13th day of incubation. In the egg contents development of the eggs of Loligo bleekeri, Kefirstein, vals. increased subsequently. Ch . A b s . (p) but the P 0 4 and Cu contents remain unchanged; the Experimental sodium chloride deficiency in enzymes present resemble qualitatively those of man. R. A. M cCan ce (Proc. Roy. Soc., 1936, B, other eggs. R. S. C. 119, 245— 268).— In man, a severely limited intake Toxicity and rate of disappearance of intra- of NaCl (about 40 mg. of Na, 200 mg. of Cl, daily), cisternally injected calcium salts in the dog. accompanied by sweating, but without limitation M. F. Mason, and H . R esn ik (J. Pharm. Exp. Ther., of H 20 intake, causes a loss of at least 25— 30% of 1936, 56, 53— 59).— Aq. CaCl2, Ca gluconate and the extra-cellular Na and Cl. The N balance becomes lactate containing 0-25 mg. of Ca per kg. body-wt. negative, and the blood-urea rises. The body appears are injected into dogs without producing toxic to react partly by allowing the total vol. of body action. Larger doses cause respiratory depression, fluids to fall, partly by allowing their osmotic pressure 0 4 mg. of Ca per kg. being the lethal dose. Simul to fall. F. A. A. taneous injection of Mg does not increase the Ca Acidosis as a factor of fatigue in dogs. F. W. tolerance. A. L. Schlutz, M. M orse, and A. B. H astings (Amer. J. Influence of nutrition on metabolism during Physiol., 1935, 113, 595— 601).— Alkalosis from work. IV. Calcium. F. B ru m an and F. J e n n y NaHC03 reduces, whilst acidosis from N H 4C1 favours, (Deut. Arch. klin. Med., 1935, 177, 527— 543; Chem. the capacity of clogs for exercise; NaHC03 promotes Zentr., 1935, ii, 243).— The effects of Ca and K on lactic acid formation, whilst N H 4C1 depresses it. metabolism were antagonistic. G. H . F. Acidosis accompanying exercise is not a causal factor of fatigue. R. N. C. Calcium as a factor in the nutritional im provement of health. H. C. S h erm an (Proc. X at. Effect of sodium fluoride on the basal meta Acad. Sci., 1936, 22, 24— 26).— A discussion of recent bolism of the rat under several experimental work. A . G. P. conditions. P. H. P h illips, H. E. E n glish , and E. B. H art (Amer. J. Physiol., 1935, 113, 441— Effects of increasing the calcium content of a 449).— Normal basal metabolism in rats is not diet in which calcium is one of the limiting affected by feeding with NaF, but when previously factors. H. C. Sh erm an and H . L. Cam pbell (J. raised by thyroid it exhibits a sharp and rapid rise. Nutrition, 1935, 10, 363— 371).— Addition of Ca to EH alone causes a temporary reduction, which is the diet improved food utilisation and the general unaffected by simultaneous administration of NaF. development of rats. A. G. P. R. N . C. Calcium and phosphorus needs of pre-school Metabolism in the rat of the naturally-occur children. A . L . D an iels, M. K. Hutton, E. M. ring arsenic of the shrimp as compared with K n o tt, 0 . E. W right, and M. F orman (J. Nutrition, arsenic trioxide. E. J. Coulson and R. E. 1935, 10, 373— 38S).— The requirements are 45— R emington and K . M. L yn ch (J. Nutrition, 1935, 50 mg. of Ca (with adequate vitamin-D) and 60— 10, 255— 270).— In the shrimp As occurs in complex 70 mg. of P per kg. A. G. P. combination from which it cannot be liberated in the Calcium and phosphorus metabolism in chick animal organism. Following the digestive process embryos. T. ICam acht (J. Biochem. Japan, 1935, in rats slirimp-As appears in a sol. form and is elimin 22, 189— 197).— Injection of CaCl2, N a,H P 04, or ated through the kidneys; it is retained only to a very org. C a-P 04 preps. (I) into incubating eggs “diminishes small extent. No evidence of toxicity was obtained. the Ca content of tho embryo but not that of the A. G. P. , allantoic fluid; the effect is probably due to inhibition Physiological and clinical role of bromine of Ca mobilisation from the shell. (I), but not metaholism. L. A. Jacobsen (Presse med., Na.,IIPO.„ increases the P content of the embryo. 43, 452— 454; Chem. Zentr., 1935, i, 3565).-p * F. 0 . H. review. R. N- C. Calcium and phosphorus requirements of Human iodine balance. V. V. Cole and G. M- growing turkeys. F. E. M ussehl and C. W . Curtis (J. Nutrition, 1935, 10, 493— 506).— The A ckerson (Proc. 5th World’s Poultry Congr. Rome, combined urine- and stool-I may account for < 50 / 0 1933, 2, 664— 667).— A factor other than the Ca : P of the I intake in some cases. The output of I was ratio of the diet influences Ca and P assimilation. fairly uniform for an individual on a monotonous The acid : base ratio of the entire ration probably diet. Increased faecal I occurred in cases of hyper has an important effect. In the absence of vitamin-D thyroidism. A. G. P. X IX (fir) BIOCHEMISTRY. 513 Iron metabolism. E. N olte (Arch. Pharin., blood : effect on significance of their extraction 1936, 274, 107— 110).— The liver, lung, and kidney percentages. D. D. V a n Sl y k e , A. H il l e r , and of a goat kept during 5 months on a diet containing B. F. Miller (Amer. J. Physiol., 1935, 113, 611— a liver-Fe-protein adsórbate (ferripan) ( = 0-26 g. 628, 629— 641).— (a ) The plasma clearances and Ee per diem) contain considerably more Fe than the extraction % of Na4Fe(CN)0 (I), inulin (II), and same organs of a goat maintained on an Fe-free diet. creatinine (III) in the dog are approx. equal; they are The Fe content of the blood and milk is the same in independent of plasma concn. The clearance of both cases. II. B. urea is about 57% of those of the above substances, and is also independent of plasma concn. Iron metabolism of pre-scbool children. L. (b ) (I) and (II) injected intravenously in the dog Aschah (J. Nutrition, 1935, 10, 337— 342).— are not absorbed into the erythrocytes, but remain Retention of Fe by children of 4— 6 years averaged in the plasma. (Ill) enters the corpuscles very slowly, 0-07 mg. with an intake of 0-59 mg. A. G. P. so that it is not withdrawn from them as the blood Iron requirements of normal adults. G. E. passes through the kidneys, whilst urea diffuses very Farrar, jun., and S. M. Goldhajmer (J. Nutrition, readily into the cells, and is therefore withdrawn 1935,10, 241— 254).— The Fe requirement is normally from them in the kidneys. R. N. G. 3- 5 mg. daily. Normal urine contains 0-02 mg. of Excretion of phenol-red by the dog. J. A. Fe per 100 c.c. A. G. P. Shannon (Amer. J. Physiol., 1935, 113, 602— 610).— Nitrogen metabolism in soya bean-feeding Phenol-red (I) excretion is > insulin (II) excretion of horses. U. I. L istovnischa and M. F. G u l u u at low plasma-(I) levels, but the (I)/(II) excretion (Ukrain. Biochem. J., 1934, 7, No. 1, 153— 161).— ratio falls as the level increases. The depression Feeding of soya beans increases N metabolism. of (I) clearance as the level is raised is reversible. Urinary N (daily excretion) increases and the urea : The ratio is unaffected by phloridzin. R. N . C. total N ratio declines through increase in other N Metabolism of orally administered citric acid. constituents, especially N H 3. There is increased C. C. Sherm an , L. B. Me n d e l, and A. H . Smith excretion of creatinine owing to higher endogeneous [with M. C. T oothill] (J. Biol. Chem., 1936, 113, protein metabolism. Ch. A b s . (p) 265— 271).— Only 0-7% of orally administered citric Metabolism of women during the reproductive acid appeared in the urine of the dog, none appeared cycle. V I. Continuous nitrogen utilisation of a in the ficces, whilst the increased blood-content was multipara during pregnancy, parturition, puer- maintained for 3— 7 hr. The renal threshold was perium and lactation. H. A. H u n sc h e r, F. C. 2-2— 6-0 mg. per 100 c.c. H . D. Hummell, B. N . E rick so n , and I. G. Maoy (J. Citric acid formed in animal metabolism. Nutrition, 1935, 10, 579— 597).— N balances over C. C. Sh erm a n, L. B. M e n d e l, and A. H . Sm ith a period of 8 months are recorded and discussed (cf. [with M. C. T oothill] (J. Biol. Chem., 1936, 113, A., 1933, 304). A. G. P. 247— 263).— The quantity of citrate (I) excreted by Nitrogen and sulphur metabolism in supra- men oc urinary p B; addition of N aH C03 to a low- renalectomised rats. M. San d b e r g and D. citrate diet increases the excretion of (I); in dogs P erla (J. Biol. Chem., 1936, 113, 35—41).— There the increase is favoured by replacement of the dietary was no change in the excretion of uric acid, faecal caseinogen by sucrose. Ingestion of the diet pro N and S, and in Cu and Fe metabolism. There was duced an increased excretion of (I) which was not marked creatinuria and an increase in urea, urinary due solely to a raised blood-(I) or diuresis. II. D. N and S, and neutral S. The % of S 0 4" decreased Curves of sodium formaldehydesulphoxylate slightly. J. N . A. in the blood after intravenous or intragastric Effect of sulphur in the diet on the growth and administration. E. H ug (Compt. rend. Soc. Biol., wool production of sheep. Nutritive value of 1936, 121, 579— 581).— The compound disappears some vegetable oils in N. China.— See B., 1936, rapidly from the plasma of the dog after intravenous 218. injection, a large part being excreted by the kidneys. The relatively low plasma concn. after intragastric Food value of ethyl alcohol. H. H. Mitchell administration cc the quantity given. The curve (J. Nutrition, 1935, 10, 311— 335, 460).— The energy reaches its max. in 2— 8 hr. R. N. C. of ingested EtOH is largely available for physiological purposes. Added to a milk diet EtOH induces more Elimination of sodium formaldehydesulph rapid growth, a greater retention of N and fat, and oxylate by the digestive secretions. T. G. improved digestibility of the basal diet. Sucrose H in n h a a r (Compt. rend. Soc. Biol., 1936, 121, [ f ias a relatively greater growth-promoting action, 581— 582).— In the dog the compound is eliminated f *,e avai'akta energy, and no effect on the digestibility in very small quantities in the saliva, bile, and íe basal diet. (I) increases the faecal excretion pancreatic and intestinal juices. R. N . C. of metabolic products, but EtOH has no action. Degradation of mescaline and similar sub A. G. P. stances in the body. K . H. Slo tta and J. M u lle r (A) Clearance, extraction percentage, and.(Z. physiol. Chem., 1936, 238, 14— 22).— Mescaline es imated filtration of sodium ferrocyanide in (I), given orally, is excreted mainly as tde mammalian kidney: comparison with (0Me)3C6Ho,CH2,C 02H (II) in the urine of rabbits mtuin, creatinine, and urea. (B) Distribution and dogs. “ Instead of (II), human urine gives a o ferrocyanide, inulin, creatinine, and urea in OMe-rich oil, a mixture of probably two substances, 514 BRITISH CHEMICAL ABSTRACTS.— A. X IX (Ç, ll) which on hydrogenation (PtO.,) absorbs 3II2 and gives substances pass from the muscles to the blood. a substance, C9H140 2N,0Me, cryst. (no picrate, Blood-, serum-, and corpuscular-Cl, -Na, -proteins, auri- or platini-chloride). (II) is recovered in good the alkaline reserve, and k are all increased, whilst yield unchanged from the urine of dogs or rabbits -Ca falls. R. N. C. to which it is fed, and has no physiological effect on Effect of ultra-violet radiation on lens protein these animals or man. 3:4: 5-(OMe)3C6H2-CHO is in the presence of salts and the relation of radi recovered from urine as the acid, but [3-3 : 4 : 5- ation to industrial and senile cataract. J. H. tnmethoxyphenylethyl alcohol (III) yields a N-containing Cl a r k (Amer. J. Physiol., 1935, 113, 538— 547).— degradation product. (I) has very little effect on Ultra-violet irradiation of solutions of lens proteins schizophrenic patients, who are, however, profoundlv in aq. NaCl, KC1, and CaCl2 at p a 6-0— 7-2 and 4° affected by 2 : 3 : 4-(OMe)3CfiH2-[CH2]2-NH2, which denatures the proteins but produces no increase of is innocuous to healthy men. 3 :4 :5 - opacity except when CaCl2 is present. No increase (0Mc)3CgH3,C0C1 and CH2N2 give 3:4: 5-lrimethoxy- is found at pn 7-8, whilst the increase is general at is-diazoacetophenone, m.p. 103“ (and some Cl-ketone), pK 5-4. Opacity is not increased by heating to 40° which yields 3:4: 5-trimethoxyphenylacelamide, m.p. at jhi 7-2 without irradiation, but after irradiation 125°, hydrolysed by hot KOH-M eOH to (I), m.p. it is increased considerably in all solutions containing 121°. (I) and H N 0 2 afford (III), b.p. 95— 135°/0-01 Ca; Na, but not K , exerts a restraining action. mm. (p-nitrobenzoate, m.p. 100°). R. S. C. Light-coagulation probably consists of dénaturation Degradation of dimethylaniline and its oxide of the proteins followed by pptn. through Ca ; senile in the animal body. F. H orn (Z. physiol. Chem., cataract may be due to accumulation of denatured 1936, 238, 84— 90).— NPhMe2 is not converted by protein in the lens together with increased blood-Ca, dogs into NPhMe20. Both compounds are con whilst exposure to intense radiant heat is responsible verted, at least partly, into o-OH'CGH4'NH 2. The for cataract in metal and glass workers. R. N. C. toxic symptoms of NPhMe2 include methaunoglobin Factors concerned in the arrest of contraction formation. R. S. C. in an ischemic myocardial area. R. T en nant Tissue cultures exposed to the influence of a (Amer. J. Physiol., 1935, 113, 677— 682).— NaCN magnetic field. R. P a y n e -Scott and W . H. L ove and KC1, but not CH2I-C 02Na, arrest contraction, (Nature, 1936, 137, 277).— Exposure to magnetic which is also arrested' by perfusion of a ventricular fields of 5000 gauss produced no observable change zone in the normal heart with Na lactate in buffered in the growth of cells from the heart of chick embryos blood-Locke’s solution. R. N. C. cultivated in vitro. A slight tendency to protoplasmic Adrenaline glycsemia in the dog submitted disintegration in some of the resting cells was observed to slow continuous intravenous injections of in certain exposed cultures. L. S. T. alkaline mineral water. E. Chabrol and J. Changes in the blood-fluid of Scyllium canícula Sallet (Compt. rend. Soc. Biol., 1936, 121, 733— exposed to continuous current, when the bran 735).— Large quantities of 0-7% aq. N aH C03 reduce chial region is close to the anode. E. A. P ora considerably the blood-sugar and its response to (Compt. rend. Soc. Biol., 1936, 121, 503— 504).— subsequent injection of adrenaline. R. N. C. The increases of blood-osmotic pressure and -Ca oc I, Effect of buffered phosphate solutions on a thin but are < those obtained when the branchial region layer of living vascular tissue, in moist chambers adjoins the cathode, as are also the variations of introduced into the rabbit’s ear. R. G. A bell blood- and serum-Cl and -Na, whilst the increases (Anat. Rec., 1935, 64, 51— 73). R. N. C. of proteins and corpuscular Cl and the fall of the alkal ine reserve are higher. The fall of k is the same Reversible loss of the all-or-none response in cold-blooded hearts treated with excess potass in both cases. The increases of inorg. salts and org. substances are > the corresponding losses in the iu m . G. H . Z w ik ste r and T. E. B o yd (Amer. J. muscles. R. q. Physiol., 1935,113, 560— 567). R. N. C. Changes in the blood-fluid of the male Scyllium Deposition of strontium salts in hypertrophic canícula produced by continuous electric current. cartilage in vitro. R . R o bison , K . A. 0. E. A. P ora (Compt. rend. Soc. Biol., 1936, 121, L a w , and A. H. R osenheim (Biochem. J., 1936, 507— 508).— Passage of current for 12 hr. increases 30, 66— 68).— The deposition in vitro of Sr salts in muscle-H20 at the expense of the blood. Inorg. hypertrophic cartilage (dissected arvay from all salts in the muscles increase considerably, possibly calcified tissue) by immersion in solutions containing through penetration of salts from the external S r" (spectroscopically pure), P 0 4"', and C03'' ¡s medium, whilst org. substances fall in the muscles confirmed, the deposits being shown by spectrum and rise in the serum. The alkaline reserve increases, analysis to consist largely of a Sr phosphate or earbon- whilst blood-Cl falls. R. N. C. atophosphate. P- W . C. Changes in the blood-fluid of the male Scyllium Function of fluorine in the human organism. L. M ichaelis (Klin. Woch., 1935, 14, 94— 95). c a n í c u l a , produced by an opposing continuous electric current in the external medium. E. A. Theoretical. R- X - C. P ora (Compt. rend. Soc. Biol., 1936, 121, 660— Iodine injuries with particular reference to 662; cf. preceding abstract).— The blood loses H 20 “ complete salts” injuries. I. M ü h e (Deut. without a corresponding gain in the muscles. Inorg. Arch. klin. Med., 1935, 177, 345— 367; Chem. salts increase in both blood and muscles, but org. Zentr., 1935, i, 3949). R- N . C. X IX (A) BIOCHEMISTRY. 515 Action of iodine on basal exchange in intest Anthelmintic studies on hydroxyalkyl- inal closure. J. Glatzel (Wien. med. Woch., 1935, benzenes. VI. Alkyl polycyclic phenols. VII. 85, 397— 100; Chem. Zentr., 1935, i, 3565).— The Halogenated phenols. VIII. Phenolic ketones, high basal exchange in rectal cancer and artificial ethers, and esters, and organic acids. P. D. intestinal closure is reduced to normal in 7 days by L amson, R. W . Stoughton, and A. D. B ass (J. Lugol’s I solution. R. N. C. Pharm. Exp. Ther., 1936, 56, 50— 52, 60— 62, 63— 68).—VI. The in-vitro asearicidal properties of various Selenium in [animal] nutrition. H. A. polycyclic phenols are not significantly increased by Schneider (Science, 1936, 83, 32— 34).— Growth effects are described for rats receiving up to 70 introduction of alkyl groups. p.p.m. of Se as NaoSe0, with a normal diet. VII. High activity is shown by p-chlorocarvacrol, L. S. T. 4-chloro-2-hexyl-phenol and -2-heptyl-phenol. 2:4:6- Effect of sulphur on the weight and adrenaline Tribromo-phcnol and -resorcinol are, however, in content of the adrenal capsule and on the active. vasoconstrictor action of blood-serum. M. V III. Of > 100 phenolic ketones, ethers, esters, and acids, none shows marked in vitro asearicidal Mitani (Folia Endocrinol. Japon., 1933, 8, 104).— Intramuscular injection of large doses of S lowered activity. Some monoethers of dihydric phenols the wt. and adrenaline content of the adrenals. Con are active, but too toxic for use. A. L. tinuous small dosage of S produced a similar effect, Acid-base changes in the serum of the dog but the wt. of the capsules increased. associated with the hyperthermia of dinitro- Ch . A b s . (p) phenol administration. E. M u n t w y l e r , V. C. Sulphur-mercury compounds and their action M y e r s , W . H . D an ielson , and C. Z orn (Amer. J. on the blood. L . L ia c i (Arch. Farm, spcrim., 1933, Physiol., 1935, 113, 186— 192).— Oral administration 56, 372— 381; Chem. Zentr., 1935, i, 3952).— In of subletlial doses of 2 : 4-dinitrophenol (I) frequently jection of a S-H g compound in rabbits causes slight increases serum-Cl and decreases -H C 03\ Total modifications of blood-sugar, increases of erythropytes bases (II) are somewhat variable, depending on the and leucocytes, and decrease of resistance of erythro quantity' of (I) given; p„ remains within normal cytes to hypotonic NaCl solutions. Blood-Ca and limits, but tends to fall slightly' from the control level haemoglobin are unaffected. It. N. C. with large doses of (I). Subcutaneous injection of Chemotherapeutic activity of compounds of (I) lowers Cl and H C 03' ; (II) are decreased by' sub- arsenic with albumin breakdown products rich lethal and increased by lethal doses, the undeter mined acid concn. being increased in both cases : in sulphur. W . A. Collier and M. K r au se (Z. Hyg., 1935, 117, 190— 195). R. N. C. the pa remains fairly const. • R. N . 0. Physiological action of zinc in animals. G. Mechanism of the stimulating action on meta Bertrand (Bull. Soc. Chim. biol., 1936, 18, 213— bolism of dinitro-compounds. Acetaldehyde, 224).— A review. A. L. dihydroxyacetone, and glutathione as antidotes. H. H an d o vsk y , H. Casie r , and C. Sciiepens (Arch, Pharmacology of ethyl alcohol. I. Com int. Pharmacodyn., 1935, 50, 397— 446).— Dinitro- parison of grain and synthetic alcohols. II. cyc/opentylphenol (I) (“ pentyl” ) is the most stimu Correlation of the local irritant, anaesthetic, and lating and least toxic of all the nitro-derivatives. toxic effects of three potable whiskies with their An activator for dinitro-derivatives which varies in alcohol content. 0. W. B arlow [with A. J. its ease of extractability exists in muscle. The B eams and H. G oldblatt] (J. Pliarm. Exp. Ther., stimulation of metabolism in vitro is attributed to 1936, 56, 117— 146).— The toxic and physiological a respiratory' enzyme differing from the normal effects of synthetic and grain EtOH are indistinguish cellular respiratory enzymes in being cryolabile. able. The irritant and toxic effects of whisky are > (I) added to muscle diminishes its glutathione (II) those due to its EtOH content. Administration of content, and, in living pigeons, intravenous (II) synthetic or grain EtOH or whisky to rats in concus. equiv. to 7-5% of EtOH as the sole source of fluid prevents the hyperthermia which follows (I) injection. had no effect on growth, but at concns. of 15% growth A similar inhibition is shown by' dihydroxyacetone was retarded. Certain differences are observed in their and MeCHO. In vitro, the destruction of MeCHO actions on the stomach and intestine as between by muscular tissue is increased by addition of (I); synthetic or grain EtOH and whisky. W . 0 . K . hence MeCHO takes part in the oxido-reduction processes affected. N u t r . A b s . (m) [Action of] carbonyl chloride [on the blood].— See this vol.. 301. Comparative actions of cardiazole and cor- amine on the respiratory centre of man. I. effect of acetic and substituted Subcutaneous injection. II. St e in in g e r and E. Vvn u ef e u,n0i borneol. H. T su ji (Tohoku J. Gau batz (Klin. Woch., 1935, 14, 159— 160).— E x p . Med., 1934, 24, 3 7 4 -3 7 9 ). Ch . A b s . (p) Cardiazole is the more active compound. °,f I56??®116 in Pregnancy. G. B a rzilai R . N . C. ;C'i , ol. sperim., 1933, 8, 1388— 1392).— Action of large quantities of glucose in pro frr»° r'Yr 0m , m.lce ?re less resistant to narcosis longed intravenous infusion. E. B a u e r and H. A 8 in le inspired air. The effect is most K n u pper (Ber. Verh. sachs. Akad. Wiss. matli.- noticeable at aconcn. of 35-43 mg. of CGH6 per litre of phys. Kl., 1934, 86, 339— 350).— The max. intra air va i < l6 mg. per litre acute narcosis does not venous tolerance for glucose in the dog is normally occur R, N. C. about 1-4 g. per kg. per hr. Blood-lactic acid rises 516 BRITISH CHEMICAL ABSTRACTS.— A. X IX (h) some time before death, and the alkaline reserve 170% , as do acetylcholine, adenosine, and adenosine falls. The abnormal glycogen content of the liver triphosphate. The effect of yeast-(I) is < than that is not the cause of death. The relations between of muscle-(I). Inosic acid (except in large quantities), liver-glycogcn and X , and the liver and body wts. adenine, hypoxanthine, and camine are without are studied. R. N. C. effect. The N H 2-compounds and carbohydrate of Effect of camphor on the adrenaline reaction. muscle-(I) are responsible for the action. R. N. C. I. Blood pressure. J. Szeloczey. II. Dilat Influence of administration of tonsil extracts ation of pupil and increase of blood pressure. on sugar excretion in rabbits. C. T a t e ish i (J. J. Szeloczey. III. Permeability and adsorp Biochem. Japan, 1935, 22, 251— 261).— The sugar tion. J. Szeloczey and B. K olonits (Magyar excretion threshold is lowered by administration of orvosi Arch., 1935, 36, 37— 50, 51— 55, 56— 62; small, and increased by large, amounts of extracts of Chem. Zentr., 1935, ii, 241). G. H. F. pig’s tonsil; the diminished level returns to normal Spectrograpbic and biological study of on administration of cholic acid. F. 0 . H. phloridzin derivatives. I. Phloridzin hepta- Action of the oxidase of Cynara scolimus in acetate. A. L am bkechts (Bull. Soc. Chim. biol., decreasing the blood-sugar. A. Risi (Rass. ter. 1936, 18, 237— 238).— Phloridizin hepta-acetate (I) Pat. din., 1933, 5, 297—298: Bicd Zentr., 1935, 6, shows an absorption band with a max. at 275 mg and A , 7).— Injection of the artichoke oxidase modifies an extinction cocff. of 675. Injection of a solution of the carbohydrate metabolism and induces a marked 10 mg. of (I) in EtOH produces a glycosuria of 17% , hypoglycmmia in rabbits. A. G. P. but this may be due to the hydrolysis of (I) by the blood. A. L. Effect of yeast and yeast extracts on intestinal motion. H. W astl (Biochem. Z., 1936, 284, 24— Nutrition of the euglenia, Astasia cliattoni. 39). W . McC. A. L w off and H . Dusi (Compt. rend., 1936, 202, 248— 250).— Addition of fatty acid to the media Ether anaesthesia. Changes in serum-potass- considerably increases the reproduction. H . G. R. ium. during and following anaesthesia. B. H. R obbins and H. A. P ra tt (J. Pharm. Exp. Ther., Point of attack of acetylcholine in the heart. 1936, 56, 205— 208).— The normal serum-K is for Does nicotine inhibit the cardiac action of dogs 20 mg. and for guinea-pigs 34 mg. per 100 c.c. acetylcholine? F. P la tt n e r (Pfliiger’s Archiv, During Et20 anaesthesia, serum-K falls in both 1935, 236, 226— 229). R. N . C. animals, and returns to normal within 5 hr. Acetylcholine and the normal striped muscle W . 0 . K. of m a m m a ls. 'A . Sim onart and E. F. Sim onart Chem ical constitution and local anaesthetic (Arch. int. Pharmacodyn., 1935, 49, 302— 328; Chem. action of alkamine esters of p -alkoxybenzoic Zentr., 1935, i, 3003). G. 11. F. acids.— See this vol., 468. Influence of thyroparathyroidectomy and of Adrenaline secretion and blood-sugar content bile acids on bile secretion. S. T u ziok a (J. in dogs anaesthetised with avertin. H. Sato, Y. Biochem. Japan, 1935, 22, 367— 374).— The vol. of Sa t o w , and T. D egchi (Tohoku J. Exp. Med., 1934, bile and tho total bile acids of dogs (with biliary 24, 485— 494).— Anaesthesia did not affect adrenaline fistula;) are diminished and the bile-pu is increased. output but slightly decreased the blood-sugar. Administration of Na taurocholate produces a return Ch. Abs. (p) to normal vals. F. O. H. Muscle contractions without production of Influence of bile acids on calcium metabolism. lactic acid. E. Ma r t in i (Arch. ital. Biol., 1935, XII. Tetany and blood-calcium in thyropara- 88, 82— 90; Chem. Zentr., 1935, ii, 248). G. H . F. thyroidectomised dogs. T. HosraziMA (J. Bio Emetine sulphocamphorate. I. I maz and chem. Japan, 1935, 22, 375— 383). F. O. II. M. F. P astor (Rev. Assoc, med. Argentina, 1935, Influence of changes induced by cholesterol 49, 99— 104).— Effects of tho sulphocamphorate are on the calcification in vitro of rabbit aorta. similar to those of the hydrochloride, but its toxicity Iv. A. 0 . Law and R. Robison (Biochem. J., is lower. Ch. A bs. (p) .1936, 30, 69— 75).— Tho development of typical Effect of ergotamine on glycosuria and hyper- cholesterol (I) arteriosclerosis by feeding rabbits on a glycaemia produced by stimulation of the diet rich in (I) is not associated with any increased superior cervical sympathetic ganglion. D. A. proneness to calcification of the aorta in vitro, nor did Cle vela n d (Amor. J. Physiol., 1935, 113, 592— the deposits so obtained specially favour those portions 594).— Ergotamine inhibits the above effects. of the vessel in which the (I) lesions occurred. R. N. C. P. W . C. Heart activity and vegetative poisons. !• Cholesterol as a growth factor for flagellates. Effect of intravenous injections of atropine on R. Cajlleatt (Compt. rend. Soc. Biol., 1936, 121, the heart action. G. W. P a r a d e and J. G. J ag er. 424— 125). R. N. C. II. Effect of intravenous injections of adrenaline Action of muscle-adenylic acid and related and pilocarpine on the heart action. G. W. substances on the blood-supply of the skeletal P a rad e and H . R. F oerster (Klin. Woch., 1934, muscle. W. Sc h o ed el (Pfluger’s Archiv, 1935, 13,1684—1686,1709—1711). R. N. C. 236, 93— 101).— Adenylic acid (I) from muscle in Respiratory effects of morphine, codeine and creases tho blood-supply to skeletal muscle by 100— related substances. V. Effect of a-, ¡3-, and X IX (h) BIOCHEMISTRY. 517 y-isomorphines and their dihydro-derivatives Relative toxicity of acetone, methyl alcohol, on the respiration of the rabbit. C. I. W righ t and their mixtures. I. R. M. S k l ia n s k a y a , and F. A. B arbour (J. Pharm. Exp. Ther., 1936, F. E. U r ie v a , and L. M. Ma sh b it z. II. Action on 56, 39— 19).— Tlie min. subcutaneous doses of white m ice. L. M. M ash b it z, R. M. S k l ia n s k a y a , a-, p-, and y-fsomorphine and dihydro-a-, -(3-, and and F. E. U r ie v a (J. Ind. Hyg., 1936, 18, 106— -y-womorpliine required to depress the respiratory 116, 117— 122).— I. COMe2 depresses the activity mechanism of the rabbit are 0-55, 8-0, 8-0, 0-4, 0-55, of the isolated frog’s heart more powerfully than and 5-3 mg. per kg., respectively. A. L. MeOH, but recovery occurs more readily after Effect of morphine on the human ureter. COMe2. Mixtures of COMe2 and MeOH show the predominant effect of C0Me2. N. F. Ocker blad , H. E. Carlson, and J. F. Simon II. Measured by commencement of narcosis, the (J. Urol., 1935, 33, 356— 362). Ch. A b s. (p) toxicity of COMe2 is > that of MeOH, but according Effect of quinine on tissue respiration : to mortality, MeOH is more toxic than COMe2 or relation between quinine and various hormones their mixtures. With mixtures of 40, 50, and 60% in this respect. I. Insulin or adrenaline. II. of COMe,, the toxicity is < that of the separate com Genital glands. K. Miz u t a n i (Folia Endocrinol. pounds. J. N. A. Japon., 1933, 8, 97— 98, 98— 99).—-I. Injection of quinine (I) lowered the 0 2 consumption of liver, Toxicity and potential dangers of ethylene kidney, thyroid, spleen, and heart muscle to a small glycol. F. H. W il e y , W . C. H u e pe r , and W . F. extent, and that of skeletal muscle markedly. Ad von Oettingen (J. Ind. Hyg., 1936,18, 123— 126).— ministration of insulin increased this effect on liver A concn. of 300 mg. of (CH2*OH)2 per 1000 litres and thyroid and decreased it in all other organs. of air has no toxic effects on mice or rats, and prob Adrenaline in all cases retarded the action of (I). ably none on man, even with continued exposure of II. Feeding of dried testicle to male rats decreased 8 hr. per day for 34 months. J. N. A. these effects of (I) in all organs, especially thyroid. Simultaneous poisoning of frog's muscle with Interstitial tissue of the ovary had a similar, and corpus veratrine and iodoacetic acid. J. M arten sson luteum a reverse, action in the case of female rats. (Skand. Arch. Physiol.. 1935, 71, 229— 237; Chem. Ch . A b s . (p) Zentr., 1935, i, 3004). G. H. F. Site and m ode of action [of therapeutic sub Antiseptic properties of wine. E. Ceriotto stances) and interm ediary m etabolism . II. (Semana mdd., 1935, 42, 529— 532; Chem. Zentr., Freund (Arch. exp. Path. Pharm., 1936, 180, 416— 1935, ii, 290).— The antiseptic activity of wine in 436).— Intermediary metabolism is dependent on the vivo, not in vitro, is ascribed to the presence of condition of the organ. Tho site and mode of action colloidal metals. H . N. R. of a therapeutic substance are changed by changes in tissue metabolism. The relations between variation Toxicity of potassium perrhenate. L. C. H u r d , in metabolic processes and the action of drugs J. K . Colehour, and P. P. Cohen (Proc. Soc. Exp. etc. are exemplified. F. O. H . Biol. Med., 1933, 30, 926— 928).— In contradistinction Relation between the toxicities and the b.p. to K M n04, KReO.j had low toxicity when injected intraperitoneally into rats or mice. In rabbits Re of related substances. J. F ergu son (Nature, 1936, 137, 361— 362).— An exact linear relationship was conc. mainly in the urine with some distribution exists between the b.p./I atm. of a series of related in the organs, but not in the brain. Ch. A b s . (p) compounds and the log of the molar lethal doses to Relative toxicity of thiocyanate ions. P. B ru n insects for the most diverse cases. Data for the action (Compt. rend. Soc. Biol., 1936, 121, 543— 546).— of chlorinated ethylenes on Sitophilus granarius are CNS' is equally toxic to germinating seeds, infusoria, given. In a homologous series or a series of sub and fish, but the toxicity is very feeble compared with stituted derivatives the effect of the substituent is that of CN'. R. N. C. probably purely physical, increasing the availability Muscle metabolism in arsenic-treated rabbits. of the toxic grouping of the parent substance. W . N onnenbruch, Z. St a r y , A. B a r eu th er, and H. L. S. T. T helen (Arch. exp. Path. Pharm., 1936, 180, 437— Relation between toxicity, resistance, and 439).— The hcxosemono- and adenylpyro-phosphoric °* survival- IJ- R e in e r (J. Gen. Phvsiol., acid contents of the muscle are diminished, due to a t i 19’. 419~ 4 2 2 ; cf. A., 1934, 323, 551).— Theor etical. A more general form of the equations is decrease in phosphorylation processes (cf. A., 1934, given, consistent with a limiting toxicity with increas- 1250). * F. O. H. "-uig concn. of drug. D F. A. A. Halide distribution in body fluids in chronic °f mRitary gas poisoning. E. bromide intoxication. M. F. M ason (J. Biol. Chem. 1936, 113, 61— 74).— The distribution of Br' PL ( verap' d‘ Gegenwart, 1934, 75, 529— ’ Ghem- Zentr., 1935, i, 3814). H. N. R. and Cl' in simultaneously taken samples of blood, spinal fluid, urine, gastric juice, and saliva from dogs n £ hr°ni,C„ £ari30n monoxide poisoning. H. and patients with chronic bromism has been deter B uresch (Z. Hyg., 1935,117,153— 160). R, N . C. mined. The distribution ratio for Br' between cells r alcohol and some other poisons on and serum is slightly > for Cl', whilst that between /o,ar mhibition in the frog. C. G. San tesson serum and spinal fluid is much > for 01 . The (okand. Arch. Physiol., 1934, 69, 255— 292). replacement of Cl' by Br' in urine is < in serum. R. N. C. In gastric juice the replacement is sometimes > and 518 BRITISH CHEMICAL ABSTRACTS.— A. X IX (k, i) .sometimes < in serum. In dog’s parotid saliva the Role of the concentration (A) of the co-enzyme, replacement is approx. the same as in serum, whilst (B) of the substrate, in the rate of fermentation in human mixed saliva it is much greater. reactions. L. A m bard and S. T ra u t m a n n (Compt. J. N . A. rend. Soc. Biol., 1936, 121, 470— 472, 472-— 473).— Augmentation of the toxicity of fluorosis in (a ) The variations in the fixation of the co-enzyme the chick by feeding desiccated thyroid. P. H. with univalent anionic concn. at const. pa and in the Ph illies. H. E nglish, and E. B. H a r t (J. Nutrition, concn. of the co-enzyme 114411 [H ‘] at const, uni 1935, 10, 399— 407). A. G. P. valent anionic concn. are confirmed. Experimental salt poisoning in ducks. J. P. (b ) The rate of formation of the substrate- T o r r e y and R . Graham (Cornell Vegetarian, 1935, enzyme-eo-enzyme complex in the inversion of 25, 50— 53). Ch. A b s . (p) sucrose (I) by invertase is inversely cc the concn. of (I), but the rate of hydrolysis of the complex is Pharmacology of the nitrite effect of bismuth independent of (I) concn. R. N. C. subnitrate. E. J. Stieg litz and A. E. P alm er (J. Pharm. Exp. Ther., 1936, 56, 216— 222).— How can water intervene in the calculation of Bi(0H )2N 0 3 or N aN 03, added to cultures of B. coli, enzymic reactions ? L. T hivolle (Compt. rend. is partly reduced to nitrite (I). After oral adminis Soc. Biol., 1936. 121. 4 7 6 -4 7 7 ).— Theoretical. tration of B i(0H )2N 0 3 in therapeutic doses, the R, N . C. blood-(I) (normal, 0-5— 1-5 X 10-® g. per 100 c.c.) Effect of ultra-violet light on enzymic re usually rises significantly, whilst the arterial blood actions. II. Pepsin. S. B a n e r je e and H. K. pressure falls. W . 0 . K. S en (J. Indian Cliem. Soc., 1935, 12, 740— 746; cf. A., 1935, 1415).— Ultra-violet light does not affect Lead in drinking-water. E. W eyratjch and H. the action of pepsin on caseinogen at ;pH 1-8, when the M uller (Z. Hyg., 1935, 117, 196— 201).— Traces of Pb in the drinking-water of German towns are peptic val. is a max. The influence of various org. probably responsible for the Pb present in human and inorg. additions on the peptic val. is also in bones. R. N. C, vestigated and the mechanism of the action is dis cussed. R. S. Treatment of plumbism. I. Gr a y (J. Amer. Med. Assoc., 1935, 104, 200— 205).— A low-Ca, Similarity between the mechanism of the high-P (ratio 1 :3 —4) diet together with adminis rennin and pectase (pectin-methoxylase) re tration of NH4C1 and H3P0 4 increased the elimin actions. A. C. D ah lb erg and Z. I. K ertesz ation of Pb. Ch. A b s . (p) (Science, 1936, 83, 56). L. S. T. Biochemical behaviour of lead in the body. Lysozym e. K . M e y e r , R . T hompson, J. W. J. C. Aub (J. Amer. Med. Assoc., 1935,104, 87— 90).— P alm er, and D. K horazo (J. Biol. Chem., 1936, 113, A review. Ch. Abs. (p) 303— 309).— The method of prep, has been modified Acute poisoning from mercuric chloride. T. to include separation as the flavianate. Lysozyme is a Sollmann and N. E. Schreiber (Arch. Int. Med., basic polypeptide (15-3% N) active only in the re 1936, 57, 46— 62).— The average [Hg] in the organs of duced state. H. G. R. fatal cases of HgCl2 poisoning was : kidneys 3-8, Activation of villikinin. E. von K okas and liver 2-05, spleen 0-55, intestines 0-43, heart, skeletal G. von Luda n y (Pfliiger’s Archiv, 1935, 236, 166— muscle, and lungs 0-20— 0-30, brain 0-14, blood 0 015— 174).— Villikinin is activated only by the IIC1 of 0-12 mg. per 100 g. H. G. R, the gastric juice; it is also activated by other acids, Selenium in proteins from toxic foodstuffs. the activating powers of which vary, but not by IV. Effect of feeding toxic proteins or toxic NaOH, N a d , H 20 , EtOH, COMe2, urea, glycerol, protein hydrolysates with and without removal or sucrose. When activated, it is sol. in H20 , neutral of selenium. K. V . F r a n k e and E. P. P a in t e r salts, dil. alkali, and EtOH. It exists in the intestinal (J. Nutrition, 1935, 10, 599— 611).— Hydrolysates mucosa as an inactive heat-resistant precursor (H2S0 4) of toxic proteins retain the toxic factor, but (provillikinin). R. N. C. become innocuous after pptn. of Se compounds by Anhydrase activity in invertebrates. M. HgCl2. 'A. g. P. F lorkin (Arch. Int. Physiol., 1935, 40, 283— 290; Toxicant! occurring naturally in certain Chem. Zentr., 1935, i, 2997).— The occurrence of samples of plant foodstuffs. XI. Effect of carbonic anhydrase of Meldrum and Roughton (A., feeding toxic and control foodstuffs alternately 1933, 844) in many invertebrates is proved. K . W . Er an k e (J. Nutrition. 1935, 10, 233; cf. this G. H. F. vol., 105).— Further data relating to the effects of Influence of different diets on enzymes of the “ toxic ” maize are given. A. G. P. organism. I. The problem. II. Starvation Acridine com pounds.— See this vol., 484. and blood enzymes. III. Insufficient con sumption of proteins and the blood-enzymes. Succession of enzymic processes in muscular B. Goldstein (Ukrain. Biochem. J., 1934, 7, No. 1> tissue. J. K . P a r k a s (Bull. Soc. Chim. biol., 1936, 18, 53— S5).— A lecture. 79— 94, 95— 107, 109— 123).— I. A discussion. II. Starvation caused no typical changes in Mode of combination of an enzyme with an blood-catalase (I), a slight initial increase followed adsorbent and with a substrate. Iv. G. Stern by a decrease in -amylase (II), and a progressive and (Science, 1936, 83, 190— 191). L. S. T. marked decline in -lipase (III). The (IH) content X IX (i) BIOCHEMISTRY. 519 and the decomp, of albumin in the organism were is therefore similar in behaviour to that of suecino- unrelated. dehydrogenase from muscle. A. L. III. Insufficient consumption of protein (such as Action of neutral salts of the Hofmeister series to cause death in 30— 40 days) effected no change on diastatic enzymes. W. H a arm a n n and 0 . in (I) or (II) but an increase in (III) which is paralleled E olsche (Biochem. Z., 1936, 283, 312— 321).— In by the decrease in wt. of the animal. Elimination isotonic and unbuffered solutions, all neutral salts of NH2-acids (tryptophan, cystine, tyrosine) is of no inhibit the conversion of starch into sugar by diastase importance in the formation of (III), which may serve (I). Animal (I) is particularly strongly inhibited by as an index of protein sufficiency. Ch . A b s. (p) OAc', P 0 4'" , and I ' whilst S 0 4" , Cl', and tartrate Components of dehydrogenase systems. IX. are only feebly' inhibitory. Malt-(I) is strongly Cozymase and “ codehydrogenase II.” H. vo n inhibited by all the salts, least by I'. In alkaline E uler and E. A d l e r . X. Lactic acid dehydro solution the activity of animal (I) is increased by genase and malic acid dehydrogenase from neutral salts, particularly by Cl' and S 0 4" , and that heart muscle. E. A d le r and M. M iohaelts. XI. of malt-(I) is increased by S 0 4" , OAc', and tartrate Glucose dehydrogenase from liver. N. D as (Z. but not by Cl' and I'. The increase in alkaline physiol. Chem., 193G, 238, 233— 260, 261— 26S, solution does not occur at high conens. of the salts. 269— 274; cf. A., 1935, 1276).— IX . In addition to In acid solution practically no activation occurs. cozymase (I) yeast contains codehydrogenase II (II), P. W.C. (probably identical with the co-enzyme of red blood- Influence of the chlorides of alkalis and of cells), which is separated from (I) by chromatographic alkaline earths on the saccharification of starch adsorption on A120 3 and is a necessary component by diastatic enzymes. W. H aarm an n and K . of the dehydrogenase system of Robison’s ester; B artscher (Biochem. Z., 1936, 283, 301— 311).— In (I) is a necessary component of the alcohol dehydro neutral and acid solution Cl' in low concn. accelerates genase system of yeast, (II) being inactive in the by 2 0 % and in higher concns. inhibits the activity second system and (I) in the first. Both (I) and (II) of malt-cliastase (I); N a d and MgCl2 inhibit by 70% act as H carriers. and other chlorides (except Li Cl) by 50% . Animal X. The dehvdrogenation of lactic acid (III) by (I) under the same conditions is not or only slightly the enzyme of heart muscle is activated by flavin affected. In alkaline solution, the activity of animal enzyme (a necessary constituent), which is partly (I) was considerably increased whereas that of separated from (III) dehydrogenase by chromato plant (I) was inhibited. With increasing concn. the graphic adsorption on A120 3. In the (III) and malic action of Cl' varies in a characteristic way for each acid dehydrogenase systems (I) is the activating co- cation, the accelerating action with animal (I) being enzyme, (II) from yeast and red blood-cells having gradually decreased and the inhibition of plant (I) no effect. increased. P. W . C. XI. Both (I) and (II) activate the glucose dehydro Sisto- and eleuto-amylase. R. D e plan q u e (Z. genase system of liver and (II) occurs in liver. Spiritusind., 1936, 59, 60, 62).— A lecture. W . McC. Inhibiting action of hydrogen cyanide on bio Influence of heavy water on activity and logical oxidations. E. J. B ic.w o o d , J. T homas, stability of pancreatic amylase. M. L. Ca l d w e l l , and H; IIerbo (Bull. Soc. Chim. biol., 1936,18, 176— S. E. D oebbelin g , and S. H . Manx an (J. Amer. 181).— Determinations of the amount of uric acid Chem. Soc., 1936, 58, 84— 87).— The hydrolysis of formed in the aerobic and anaerobic oxidation of starch by pancreatic amylase (I) is not influenced hypoxanthine by xanthine-dehydrogenase from milk to any marked extent by D 20 (concn. up to 100%), indicate that the aerobic oxidation is inhibited by provided deterioration of (I) is avoided. Inactivation HCN. This suggests that indophenol-oxidase is of (I) occurs more rapidly and to a greater extent in involved. A. L. D20 than in 11 ,,0 at 25°. H . B. Histochemical investigation of oxidases by Taka-amylase. VII. Purification by adsorp the indophenol-blue reaction. Application to tion. VIII—X. Selectivity of different adsorp lipins. L . L i s o n (Bull. S o c . Chim. biol., 1 9 3 6 , tion materials. T. K it a n o (J. Soc. Chem. Ind. 18, 18 5— 1 8 9 ).— The indophenol-blue obtained on Japan, 1936, 39, 22— 24b , 24b , 25— 26 b , 26 b ; cf. treating certain fatty substances with the Nadi A., 1935, 1535).— Separation of taka-amylase (I) leagent is produced by the oxidation of the reagent from maltase (II) by adsorption is attempted. Adsorp r , . substances and not by the preferential tion is rapid, and greater at lower temp. Graphite -cussoiution of the autoxidised reagent or by the has no adsorptive action. The relative adsorptive presence of an oxidase. This view is supported by power, for (I) and (II), of various charcoals and ac. , Pure unsaturated lipins such as oleic earths, of kaolin, and of Cu(0H)2 and Fe(0H)3 is < , n len kept exposed to the air, bring about the examined. By none of these is (I) obtained free oxidation of benzidine by peroxidase. A. L. from (II). The optimum action on starch and on nvtiCt' ° n- carbon monoxide on the indophenol- maltose is at the same p a (4-6). (I) may be a form of ase m m ilk. E. J. B ig w o od , J. T homas, and Olilsson’s saccharogenamylase (p-amylase). E. W . W . l^ii r 121, 403— 464).— Amylolysis in paste is increased by firm the view that the enzyme-binding power of the K 2S2Og oc the concn., and by K B r03 and K 3B 0 3, ester group of the substrate is controlled by the elec which show max. effect in min. concn. R. N. C. trochemical nature of the adjacent groups. The predominating effect of the acid group in preventing Determination of amylolytic activity of pan- production of the enzyme additive compound can be creatin. A. d e Clercq (J. Pharm. Belg., 1935, 17, counteracted or restricted by increasing the distance 95— 98; Cliem. Zentr., 1935, i, 2997).— The methods between ester and C 02H group, by esterifying C02H of the Belgian, American, French, and Spanisli or converting it into C!0-NH2, and by reducing the pharmacopoeias are compared. The reaction on starch degree of dissociation of C 02H. W . McC. for < 1 hr. at 37° is recommended. G. H . F. Determination of activity of lipase and Hydrogen sulphide as a factor in the determin esterase. H. Pen Air and J. G u ilb ert (J. Pharm. ation of free and bound amylase in ungermin Chim., 1936, [viii], 2 3 , 57— 77).— The activity of the ated cereals. T. Chrzaszcz and J. J a x io iq (Bio- lipase (I) and esterase (II) of blood-serum is deter chem. J., 1936, 30, 342— 344; cf. this vol., 245).— mined by measuring the extent of hydrolysis (at 40° More bound amylase is liberated in aq. extracts of with shaking) in 2 hr. of tributyrin [for (I)] and barley, rye, and wheat by added H 2S than by added PraC02Et [for (II)]. After the digestion N aP 03 and papain. The amount liberated when shaking is 0’1jV-H2S04 are added (pa 3-5), the mixture is centri intermittent is > when it is continuous. fuged, and the liquor and washings are extracted 3 W , McG. times with Et20. After addition of EtOH and H20 Enzymic fission of glucosides in heavy water. the extract is titrated with OTIV-NaOH (bromo- F. Sa lzer and Iv. F. B onhoeffer (Z. physikal. thymol-blue). In the dog there is little variation in Chem., 1936,175,304— 321).— The results of investig the activities. Differences in the activities amongst ations of the fission of (3-glucosides by emulsin arc animal species may be due to the presence of activ examined in relation to the Michaelis-Menten theory ators and inhibitors. W . McC. of the velocity of enzymic reactions (A., 1913, i, 540). If the enzyme is almost saturated with substrate the Enzymic hydrolysis of tributyrin by pan rate of fission in D ,0 solution is < in H 20, showing creatic lipase. A. I. Virtanex and E. Lixdebero that the hydrolytic dccomp. of the enzyme-substrate (Suomen Kem., 1936, 9, B , 2).— The hydrolysis pro complex is slower. If only a small part of the enzyme ceeds in three stages : tributyrin -> a-dibutyrin-4- is combined with substrate fission is more rapid in monobutyrin -> glycerol. Each stage has a different D aO than in H 20, showing that the affinity of the reaction velocity. J- N. A. enzyme for the substrate in D20 is > in II20. Cathepsin and arginase in a melanosarcoma Similar considerations are applicable to hydrolyses of the horse. A. P u r r (Z. Krebsforsch., 1935, 41, catalysed by H\ The hydrolysis of salicin is more 483— 487; Chem. Zentr., 1935, i, 2998).— Melanomata rapid in D „0 than in H 20, indicating that the first of horse differ in their cathepsin (I) and arginase (II) step of the reaction is the formation of a complex of contents from other malignant tumours; compared H" and substrate at a speed which is high compared with rat sarcoma, the (I) content is much higher and with that of the subsequent decomp, into H ' and the (II) content very low. G. H. F. products of hydrolysis. If, however, the first step is Determination of amino-acids in crystalline the slower, the rate of reaction may be higher in H 20 pepsin. H. O. Calvery, R. M. Herriott and than in I)20. The Michaelis consts. of p-cresol- J. H. N orthrop (J. Biol. Chem., 1936,1 1 3 ,11— 14).— glucoside and w-butylglucoside are 0-14 and 0-22, Cryst. pepsin has been analysed for total N, NH2-N respectively, at 30°. R. C. (before and after acid hydrolysis), humin-N, amide-N, Action of emulsin. III. Sources of error in tyrosine, tryptophan, cystine, arginine, histidine, the polarunetric examination of enzymic hydro lysine, aspartic and glutamic acid. The low basic lysis of p-glucosides. S. V eibel and F. E r ik se n N val. and the very high N H 2-N val. after acid (Biochem. J., 1936, 30, 163— 167).— Before the polari- hydrolysis are noteworthy. Coagulation by heat at metric determination the enzymic reaction is stopped pa 4 appears to cause partial destruction of the pepsin by adding K 2C03, which raises the pK of the solution mol. and marked differences are shown by analyses of from 4-4 to 10-5— 10-6. The difference in rotation at the coagulated and non-eoagulable material. ^ ^ these two p a vals. is about 3— 1°/0. Glucose solutions are unstable at p„ 10-6; 0-lAf solutions decrease in Determination of peptic activity. H. Eschex- a by 0-0033° per hr. Salicin is used as a standard b re x x e r (Pharm. Ztg., 1936, 81 , 229— 231).—-A glucoside; a concn. of 3-972% should be used (cf. direct measure of peptic activity cannot be obtained Helferieh, A., 1931, 873). PhMe should not be used by a titration method or by the change in tj on d>ges" as a bactericide as it accelerates the rate of enzymic tion. Preliminary observations are reported dealing hydrolysis by 25— 35% . E. A. H. R. with the possibility of using the ratio of v¡ to titration Kinetics of ester hydrolysis by enzymes. VI. vals, as a measure of the activity. E. A. H. R- Relative specificity of esterases. E. B am an n Fission of arginine during proteolytic hydro and E. R en dlen (Z. physiol. Chem., 1936,238,133— lysis. S. K aahya (J. Biochem. Japan, 1935, 22, 144; cf. A., 1934, 218).— The varying affinity of pig’s 263— 277).— Liberation of arginine (I) during proteo liver esterase for Mex and Me, esters and Me ester lytic hydrolysis of edestin, caseinogen, and gelatin was amides of dicarboxylic acids (malonic to adipic) and followed by treating aliquots of the hydrolysate at the effects of altering [H'J and substrate concn. con- intervals with protease-free arginase preps, (from X IX (*) BIOCHEMISTRY. 521 pig’s liver) and then determining (I) by the urease rapid cleavage of H3P 0 4 from mononucleotides and method; increase in *C02H was followed by titration yeast-nucleic acid. The glycosidic linking in purine with (H jV-KOH . Pepsin (II) (7— 8 days) does not nucleotides is not attacked. H 3P0 4 is also liberated, liberate (I) whilst *C02H is increased by 8-5— 27% although less rapidly, from glycerophosphoric acid. of tho total •C02H hberation by (Il)-trypsin (III)— E. A. H. R. erepsin (IV). Subsequent digestion by (III) (7— 12 Rôle of water in the activation of renal phos days) liberates 26-9—-43-5% of the total (I) and phatase. L. T ihvolle (Compt. rend. Soc. Biol., increases -C02H by 43-3— 76-6% . Final digestion by 1936, 121, 474— 476).— The rate of fermentation by (IV) (22 days) liberates 63-4— 80-4% of (I). Liberation renal phosphatase (I) is increased by dilution, there of (I) by (II)-(IV) hydrolysis is > that by (II)—(III)— being an optimum dilution depending on the amount (IV) hydrolysis. F. 0 . H. of (I) present. R. N. C. Action of trypsin on substituted protein. A. Chemical difference between protein-linked Kies el and 0 . R oganova (Z. physiol. Chem., 1936, and free nucleic acid. G. Sch m id t (Science, 1936, 238, 149— 159).— Substitution products of edestin 83, 15).— Tho observed difference in the rates of (I) are less readily attacked by trypsin than is (I) dephosphorylation of thyinonucleic acid and thymo- itself, the eflect being moderate or slight in the case of nucleohistone by phosphatase is due to the linking of ethylated, sulphonated, and deaminated (I) and very the nucleic acid component with the protein. great with benzoyl- (II), benzoylmetliyl-, and benzoyl- L. S. T. deamino-cdestin (III). When the substituents arc Anaerobic decomposition of hexosephosphoric removed from (II) and (III) the product is nearly as acids by animal tissues. III. Hydrolysis by readily attacked as is (I) itself. Probably the N H 2 phosphatase. T. T a k a h a sh i (J. Biochem. Japan, and OH groups (but not C 02H) play an important 1935, 22, 303— 321).— Production of hexose mono part in the process. W . McC. phosphate and free sugar from hexose diphosphate Digestive enzymes in marine invertebrates. by autolysed tissue is not invariably accompanied I. Proteolytic enzymes in Polypus vulgaris by formation of AcCHO. F. O. H. (Lamarck). E. Sa w a x o (Sci. Rep. Tokyo Bunrika Phosphodiesterase and hydrolysis of lecithin. Daigaku, 1935, 2, B , 101— 126).— The acidity of the H. U d a g aw a (J. Biochem. Japan, 1935, 22, 323— digestive tract of P. vulgaris increases from the 340).— Diphosphatase preps, (from taka-phosphatase) pharynx \pa 6-8) to the intestino (pa 5-5). The free from monophosphatase hydrolyse lecithin distribution of proteinase, amino- and carboxy- (optimum pu 4— 5) to the corresponding glyceride polypeptidase, and dipeptidase in the digestive tract, and cholincpliosphoric acid, the latter being further anterior and posterior salivary glands, liver, and hydrolysed only by monophosphatase. F. 0 . H. pancreas is recorded. The pa optima of these four Animal lipins. X. Cerebrosidase. Its rel enzymes appear to be unaffected by the nature of the ation to the splitting of polydiaminophosphatide tissues in which they occur. A cathepsin-like pro by polydiaminophosphatase. S. J. T h a n n - teinase occurs in extracts of liver and pancreas. h au ser and M. R eichel (J. Biol. Chem., 1936, 113, E. A. H. R. 311— 317).— Cerebrosidase is inactive, its activators, Urinary phosphatase. II. Excretion by man. which depress polydiaminophosphatase activity, being H. W olbergs (Z. physiol. Chem., 1936, 238, 23— 30; H 2S, cysteine, reduced glutathione, and ¿-ascorbic cf. Kutscher, A., 1935, 1279).— Details are given of acid. H . G. R. work already reported (A., 1935, 1268). A difference (due to prostatic secretion) exists between the urines Hexokinase. 0. M ey erh o e (Naturwiss., 1935, of the two sexes. Injection of insulin has the reverse 23, 850— 851).— If glucose and adenyl pyrophosphate action to, and inhibits, that of glucose administration. are incubated with hexokinase (I), adenylic acid and F. O. H. hexose monophosphate are formed. If this mixture Urinary phosphatase. III. W. K utscher and is boiled and added to fresh muscle extract lactic A. W orker (Z. physiol. Chem., 1936, 238, 275— 279; acid is rapidly formed. (I) probably acts by causing u olbergs, this vol., 111).— When urine is dialyscd phosphorylation of sugars. E. A . H . R. through parchment the activity of the phosphatase is Fermentative enzymes. V. Phosphoryl increased. Subsequent electrodialysis, repeated with ation systems of alcoholic fermentation. A. the solution obtained by dissolving in H ,0 the active Schaffner and H . B e r l (Z. physiol. Chem., 1936, material which separates after 12— 24 hr. on the first 238, 111— 123; cf. A., 1935, 1026; this vol., 246).— Phosphorylation of hexose by macerated yeast is induced equally by hexose diphosphate (I) and adenosine triphosphate (II). Purification of the , ' v' Sciiu ch a r d t enzyme system results in induction by (I) [or by di- hydroxyacetonephosphoric acid (III)] but not by (ÏI) ; hence “ phosphatase ” is not identical with the wiien treated 5 S d f ? * % ? I“ d “ heterophosphatasc ” of Euler and Adler (A., 1935, Pu 3-3 and 5. q‘ Hs Was inactive between 1276) and thus at least two phosphorylating systems exist in yeast extracts. A third system, whereby 'ind^rS|i!lataSe a°A-°n emulsin. H. B r e d e r e c k the monoester is converted into the dicster, is probably a“? ;? : ri Eu.CHELT (Aaturwiss., 1936, 2 4 ,1 0 7 — 108).— also present, the mechanism being one of oxidation mu sin preps, from almonds bring about a to a phosphohcxonic acid and subsequent fission to 522 BRITISH CHEMICAL ABSTRACTS.— A. X IX (i,(j) AcCO,H (decarboxylated to MeCHO) and triose- factor (I). The remainder resemble Wildier’s yeast. phosphoric acid [2 mols. of which give 1 mol. of (I)]. (I) (bios V ; cf. preceding abstract) occurs in tomato Pyrophosphatase and Warburg’s intermediary en and lemon juice and is not identical with ascorbic acid. zyme are also concerned in phosphorylation processes. F. 0 . H. A consideration of the role of (III) and of phospho- Balance of alcoholic fermentation by yeasts. glyceric acid (IV) and of inhibition by CH ,I-C02H R. Guillem et (Compt. rend. Soc. Biol., 1936, 121, indicates that the reaction glucoseJ-phosphateV 465— 467).— Anaerobic fermentation of sucrose, hexose ester is coupled with the oxidation-reduction glucose, and fructose in aq. solution by yeasts reaches process (III)+MeCHO-?>-(IV)+EtOH. Intra- and equilibrium in a few hr., with production of equimol. extra-cellular phosphorylation processes are compared. quantities of EtOH and C 02. Maltose exhibits F. 0 . H. anomalies; some disappears without production of Transformation of the pyrophosphate fraction EtOH and C 02. being probably broken down to inter in yeast cells. M. M. L evito v (Biochem. Z., 1936, mediate products. Production of C0„ is independent 284, 86— 98).— Fresh yeast in aq. suspension loses of that of EtOH. R, N. C. very little of its pyrophosphate (I) content in 5 hr., Rate of fermentation of sugars by different but considerable loss of (I) and of orthophosphate kinds of yeast. R. G u illem et (Compt. rend. Soc. (II) occurs when glucose (III) is added. No appreci Biol., 1936, 121, 467— 469).— The rates of ferment able change in the (I) and (II) contents of fermenting ation of sucrose (I) and maltose (II) by “ grain ” (glucose) yeast occurs if fermentation is inhibited yeasts are the same; yeasts grown on molasses by CH2Br,C 02H and respiration by KCN but when ferment (I) more rapidly than do “ grain ” yeasts, fermentation is inhibited with NaF the (I) and (II) but attack (II) irregularly and less rapidly than (I). contents decrease. Addition of (III) checks the The rate of fermentation of (I) does not vary with the degradation of (I) which occurs on autolysis. Phos- age of the yeast, but that of (II) falls. Bakers’ phoglyceric acid acts more powerfully than does yeasts ferment (I) more rapidly than do brewers’ (III), thus causing the diminished (I) content to yeasts. R. N. C. increase. The (I) compound of yeast seems to act as a phosphate carrier in the same way as does Kinetics of alcoholic fermentation of sugars adenosinetriphosphoric acid in animal cells. by brewer's yeast. TV. Specificity. Rates of W . McC. fermentation of a - and (3-glucose. R . H . H o pk in s R . H . R o b e r ts Inverse Pasteur reaction. W. A. B e litzer (Bio and (Biochem. J., 1936,30, 76— 83).— chem. Z., 1936, 283, 339— 342).— Working with yeast, The initial rates of fermentation attained hv ar,(I), the inverse Pasteur reaction is observed only when ¡3- (II), and «(¡-glucose (III) are the same except vatk the respiration system is saturated with a suitable initial concns. of < 1 % , (I) with concns. of 0-5 and H donator. P. W . C. 0-25% attaining a max. rate > (II). K m vals. for (I) and (II) are respectively 0-0099 and 0-0118. It is Sporulation of yeast. II. H. St a n tia l (Trans. suggested that neither (I) nor (II) but an intermediate, Roy. Soc. Canada, 1935, [iii], 29, III, 175— 188).— probably opcn-chain, form of glucose is specifically Formation of ascospores by S. cerevisice is increased by fermented, (I) being converted more rapidly than grapefruit juice, the active constituent of which is a (II) into this form. Mutarotation of partly fermented carbohydrate [of 12 investigated, 8 (especially mann- (III) may be explained on this hypothesis. ose and maltose) were active], Aq. NaOAc or P. W . C. KOAc in presence of sugar is effective. Data for the Alcoholic fermentation in heavy water. 0. influence of temp, and pa on sporulation are given. R eitz (Z. physikal. Chem., 1936, 1 7 5 , 257— 274).— F. 0 . H . By the fermentation of sucrose (I) in pure Wildier’s bios. W . L. M i ll e r (Trans. Roy. Soc. D 20 CH2I>CD2-OD is formed. W ith decrease in the Canada, 1935, [iii], 29, III, 163— 165).-i-Amino- D content of the solvent, x, the proportion of it which hydroxybutyric acid (I) (from crotonic, isocrotonic, is incorporated into the Me group of the alcohol and phenoxyethylmalonic acid), aspartic (II)+am ino- formed, falls. Fermentation of (I) and d-glucose in ¿sobutyric acids, (II)+ J. N. Stannaiib (J. Gen. Physiol., 1936, 19, 461— 1935, 6, 345— 349).— Phycomyces grown on a synthetic 477).— The endogenous metabolism of Saccharomyces medium supplemented with vitamin-ii, does not cerevisice placed in a non-nutrient medium shows two absorb an appreciable amount of the vitamin. Rat phases; (a) a const, rate of 0 2 consumption and C 02 tests afford no evidence of the synthesis of -B 1 by the production as long as the stored material is ample, mould. Phycomyces produces a yeast-stimulating (b) a first-order decline in rate, which cc the concn. of substance and an auxogenic factor. The action of some substrate, probably glycogen. R .Q .= 1 in both -B 1 in stimulating the growth of Phycomyces is not a phases; their relative duration depends on the age direct one. Its presence is necessary to enable the of the cultures. F. A. A. organism to produce its sp. growth factors. Absorption spectrum of reduced cytochrome A. G. P. from baker's and brewer’s yeasts. E. E lion Growth factors and vitamins in plants. {Bull. Soc. Chim. biol., 1936, 18, 165— 172).— Effect of extracts of Aspergillus on the develop The method of Fink (A., 1932, 1167) for distinguishing m ent of Phycomyces. W . H. Sc h o it e r and A. between brewer’s and baker’s yeast is based on the J ung (Arch. Mikrobiol., 1935, 6, 334— 344).— Extracts finding that the absorption spectrum of the cyto of several species of Aspergillus activate culture media chrome of the former has two, that of the latter four, of Phycomyces. The active agent is probably bands. There are exceptions to this, some brewer’s vitamin-JSj, which is synthesised in very small yeasts having a four-banded, some baker’s yeasts quantities by the organism. A. G. P. a two-banded, cytochrome spectrum. A. L. Role of bios in the biology of fungi of the genus Effect of time and intensity of radium radi Fusarium. A. R. W er n e r (Compt. rejid. Acad. ation on the inverting capacity of yeast. G. Sci. U.R.S.S., 1935, 4, 61— 64).— The presence of bios in the growth medium is essential for sporulation. H arker (Nature, 1936,137,190— 191).— Exposure of yeast to Ra emanations permanently reduces its sugar- Low viability and the physiological need of activators inverting power. The effect reaches a saturation val. induce the fungus to invade living tissues. depending on the intensity of the radiation, and is A. G. P. due to some action on the living cells rather than on Availability of the nitrogen compounds the enzyme itself. L. S. T. eliminated by Aspergillus niger. A. R iprei, and G. B eh r (Arch. Mikrobiol., 1935, 6, 359— 361).— Polyose of yeast membrane. II. L. Z ech - N compounds appearing in the substrate of cultures meister and G. T 6 th (Biochem. Z., 1936, 284, 133— of A . niger have little nutrient val. for the fungus. 138; of; A., 1934, 810; Sevag etal., A., 1935, 1280).— The substances are possibly related to the colouring The polyose (I) occurs pre-formed in yeast and is matter and humin formed during autolvsis. obtained when it is degraded by enzymes. (I) is “A. G. P. not attacked by H^O at 100° but is hydrolysed by Absorption of oxalic acid by Aspergillus dil. acid and alkali. (I) in untreated yeast resists repens. D. B ach and J. F o u r n ier (Compt. rend., hydrolysis, being protected by impurities. 1.935, 201, 1416— 1417).— In media containing or W . McC. free from glucose, max. consumption of H 2C20 4 Isolation of adenosinetriphosphoric acid from occurs at pa approx. 3-5 and is nil at pa 7, indicating yeast. T. W a g n er-J au regg (Z. physiol. Chem., utilisation of HC20 4' and not of C20 4" . F. O. H. 1936, 238, 129— 130).— 100 g. of fresh yeast yield 60 mg. of adenosinetriphosphoric acid, [a]D —30-9° Chemical sterilisation of humus for fungus (as Na salt in H.,0), and some inosinepyrophosphoric cultures. D. L ih n e l l (Arch. Mikrobiol., 1935, 6, acid (?). " R. S. C. 326— 333).— Use of volatile antiseptics (Schweitzer 1932) gives only partial sterilisation. EtOH is the Mitogenetic radiations and Liesegang rings.— most effective of the substances examined, killing all See this vol., 426. fungus spores and reducing bacterial nos. to approx. Action of various growth-substances on the 2 % . ~ A . G. P. growth of certain fungi. L. R onsdore (Arch. Fungus fluorescence in vitro. A. S. v o n Mikrobiol., 1935, 6, 309— 325).— An apparent selec M allinckrodt-H au pt and C. Ca r r ie (Arch. Der tivity is shown in the response of various fungi to matol. Syphilis, 1934, 169, 519— 526).— Cultures of auxin, bios, and to Nielsen’s growth-substance-A pathogenic skin fungi in sucrose-urea-mineral salt and -B. Auxin disappears from nutrient solutions media showed fluorescence in vitro after 14 days. whether added before or after sterilisation. Inter Colour changes followed variations in the p a of the relationships between the various growth factors and medium. Fluorescence nearly disappeared at vitamin-R are discussed. A. G. P. neutrality. Ch . A b s . [p) Auxogenic action of normal and pathological Action of micro-organisms on the diastereo- tissues on the growth of Phycomyces. W . H. m eric form s of hexane-yS-diol.— See this vol., 452. (Compt, rend., 1936, 202 , 236— 238).— Formation of organo-metalloidal compounds Kabbit liver contained a thermostable, H 20 - and by m icro-organism s. IV .— See this vol., 460. ., . n growth-promoting substance, probably ^ nnun-Bv which was also present to a smaller Penicillic acid.— See this vol., 456. extent in a tumour and the EtOH extract. Correlation of qualitative microchemical tests H Gr R on the protozoan nucleus and the mode of S^S vitamin-iij by Phycomyces. nutrition. M. S. L ucas and C. A. E v a n s (J. Roy. • tl. oChopfer and A. Jung (Arch. Mikrobiol., Microscop. Soc., 1935, [iii], 55, 261— 264).— Certain 524 BRITISH CHEMICAL ABSTRACTS.— A. X IX (j) saprozoic protozoa contained no detectable thymo- accumulates Fe and S i02 which collect in a gelatinous nucleic acid or inorg. salts in their nuclei. H . D. condition between the calcareous concretions. A. G. P. Why have some investigators been unable to Bacterial proteases. III. Acidoproteolyte of grow Chilomonas paratnecium in inorganic or Gorini. G. G orbach and R. Ulm (Arch. Mikrobiol., simple organic solutions ? S. 0 . M ast and D. M. 1935, 6, 362— 368).— Milk, and the casein-containing P ace (Science, 1936, 8 3 , 18— 19).— Conflicting evi ppt. produced in skim-milk cultures of Mammococcus dence is discussed (A., 1935,1027). L. S. T. Gorini, contain a protease of the papain type exhibiting Fixation of quinine by Paramecin as deter max. activity in neutral media. Proteolysis of casein mined by its fluorescence. G. Y alette (Compt. increases and that of gelatin and peptone decreases rend., 1935, 2 0 1 , 681— 683).— The cytological effect with the age of the culture. A peptidase is also of the drug on P. caudatum is similar to that of neutral- present (optimum pB 4-8) which tends to become less red. J. L. D. active with the ageing of the prop. A. G. P. Glucose metabolism of trypanosomes (T. Reduction of methylene-blue by Ii. abort, equiperdum and T. Letcisi). L. R e is e r , C. V. infectiosi, Bang, and B. melitense. K . H. B au Sm y t h e , and J. T. P e d l o w (J. Biol. Chern., 1936,113, and K . W ang (Z. Hyg., 1935, 1 1 7 , 399— 402).— 75— 88; cf. A ., 1935, 125).— T. equiperdum decom The organisms reduce methylene-blue in presence poses 1 mol. of glucose anaerobically, forming 1 mol. of a no. of alcohols and carbohydrates, and also open- each of glycerol and AcC02H (I). Under aerobic chain N H 2-acids; the action of B. melitense is the conditions 2 mols. of (I) are formed, together with stronger. “ R. N. 0. small amounts of lactic acid and C 02. Presence of Influence of dicyanodiamide, guanidine, and serum or plasma does not alter the course of reaction, guanylurea on bacteria.— See B., 1936, 245. but increases the rate of the anaerobic process. T. Lewisi under anaerobic conditions forms succinic acid, Effect of metallic salts on lactic acid ferment AcOH, and EtOH, and in addition H C 02H and C 02 ation. A . Zlatar o v and D. K a ltsc h eva (Bio under aerobic conditions. There is no evidence that chem. Z., 1936, 2 8 4 , 12— 23).— Lactic acid fermenta phosphorylation is involved in the metabolism of tion of milk and whey by Streptococcus lactis is either species. J. N. A. restricted by Mn, Co, Ni, F e", and F e "' salts in concns. > approx. 0-011/ (M n < F e < N i< C o ), the extent of Trypanocidal action of azo-dyes. A. St . G. restriction depending on the conen. of salt. Lower H uggett and S. F. S uffolk (J. Pharm. Exp. Tlier., concns. have a slight stimulatory effect. W . McC. 1936, 5 6 , 188— 193).— Of the azo-dyes chlorazol- Biological activators of Azotobacter. A. 11. fast-pink B.K.S (I), chlorazol-sky-blue FFS and S.D. W er n er (Compt. rend. Acad. Sci. U.R.S.S., 1935, 2, all of which have an anticoagulant action, the 4, 57— 60).— Bios from yeast or from extracts of most highly trypanocidal, as tested by its action on soil-grown green algse stimulates the fixation of N T. equiperdum infection in mice, is (I), which is only by Azotobacter. A. G. P. slightly less active than germanin. Its high toxicity, however, reduces its chemotherapeutic index to Electrical method for killing bacteria in 3—7. W. 0. K. gaseous suspension. M. Pa u t h e n ie r and H. V olkringer (Compt.- rend., 1936, 2 0 2 , 250— 252).— Physiology of pigments of purple bacteria. B. prodigiosus in air or N2 is killed by passage through III. Carotenoids. E. S c h n e id e r (Rev. Fac. Sci. an electric field maintained by an e.m.f, of the order Univ. Istanbul, 1936, 1, No. 2, 74— 80; cf. A ., 1934, of 3000 volts per cm. H. G. R. 1265).— Two fractions were obtained. One is ad sorbed by A120 3, Ca(0H)2, or CaC03, and is probably Bactericidal action of ammonium persulphate. a lipochrome containing 0 . The second fraction H . L eu n ig (Z. Hyg., 1935, 1 1 7 , 257— 262).—The is adsorbed on A120 3 or Ca(OH)2, and is probably bactericidal action of dil. (NH4)2S2Og solutions is related to, but is more autoxidisable than, lycopene. augmented considerably by small quantities of org. Both fractions are mixtures of very similar com acids. R. N. C. pounds, probably isomerides. ' E. P. Chem istry o f virulence. L. H all a y (Wien, Carotenoids of purple bacteria.— See this vol., med. Woch., 1934, 84, 1254— 1256; Chem. Zentr., 340. 1935, i, 3800).— The virulence of pathogenic micro organisms is generally increased by acidification of Formation of putrescine from d-arginine by the inflamed regions, and reduced by restoration bacterial action. K . H irai (Biochem. Z., 1936, of the original [H‘] equiv., which can be effected by 2 8 3 , 390— 392).— A strain of B. coli was used and the active hyperajmia, sweat-production, antiketogenic base isolated as aurichloridc and platinichlorido in diet, and surface inflammation with buffer solutions. good yield (7-5 g. of putrescine hydrochloride from R. N. C. 10 g. of arginine hydrochloride). P. W . 0. Cultivation of B . diphtheria: on telluric media. Lime-precipitating bacillus and an iron- and J. Z opoth (Compt. rend. Soc. Biol., 1936,1 2 1 , 785 silica-accumulating coccus as stone formers. 788). R. N . C. A. B r ussoff (Arch. Mikrobiol., 1935, 6, 471—474).— (A) Fibrinolysis by streptococci of human and The rust-coloured layer found on the sides of animal origin. (B) Carbohydrate-fibrinolytic conduits for hot spring H 20 in Aachen is formed by linking in Streptococcus harmolyticus. (C) two types of bacteria. One ppts. 0aCO3 and the other Fibrinolytic streptococci from lower animals. X IX (j, k) BIOCHEMISTRY. 525 (D) Susceptibility of “ hybrid” fibrins to 1936, 22, 19— 24).— The amount of energy necessary Streptococcus fib rinoly sins. R. R. M adison to destroy 50% of the virus at 2250 A. is 20% of that (Proc. Soc. Exp. Biol. Med., 1934, 31, 1018— 1019; required at 2650 A. To inactivate E. coli the energy 32, 49— 50, 444— 445, 641— 644).— (a ) Human plasma requirement at 2250 A. is > that at 2650 A. clots were liquefied by 94% of cultures of S. hcemoly- A. G. P. ticus of internal human origin, by 17% of those from Effect of food and of exhaustion on the pituit superficial human tissue, and by 7 % of those of ary, thyroid, adrenals, and thymus glands of veterinary origin. Numerous strains of S. viridans the rat. D . H . A n d erso n (J. Physiol., 1935, 85, were non-fibrinolytic. 162— 167). R. N. C. (b ) The Tiilet-Garner sp. fibrinolytic titre of strains Epiphysis problem. W. A. d e n H. J ag er and of S. hcemolyticus was closely correlated with the J. F. H e il (Acta Brev. neerl. Physiol., 1935,5, 32— 34; Lamefield human-diagnostic “ carbohydrate ” titre. Chem. Zentr., 1935, ii, 242).— Removal of the epi (c) Strains of S. hcemolyticus from horse and hog physis or injection of epiphyseal extracts had no were sp. lytic for the fibrins of these animals. marked effects. G. H. F. (d ) Heterogeneous fibrinogen (I)-thrombin (II) com Enteral absorption of insulin. F. L asch and E. plexes vary in susceptibility according to the origin Sciionbrunner (Arch. exp. Path. Pharm., 1936, 180, of the (I). Both (I) and (II) from man are carriers of 469— 478).— Insulin (20 units) directly introduced susceptibility to antihuman streptococcus fibrinoly- into the small intestine of rats produces a significant sin. Similarly sp. phenomena occur in the horse and hypoglycaemia in approx. 25% of the rats used. hog. Ch. A b s. {p) The % response is increased by admixture of insulin Production of staphylococcal toxin and with glycerol, EtOH, serum, saponin, or Hg2Cl2. Acid anatoxin. G. R amon (Compt. rend. Soc. Biol., but not basic dyes completely protect insulin from 1936.121, 375—379). R. N. C. inactivation in vitro by peptic hydrolysis. F. 0 . H. Determination of staphylococcal toxin. G. Biological effects of pineal extract (Hanson). R amon and R. R ichou (Compt. rend. Soc. Biol., L. G. R o w n tre e, J. H . Cl a r k , A. Stein berg, and 1936.121, 379—382). R. N. C. A. M. H anson (Science, 1936, 83, 164— 165). p„ curve of certain smooth strains of tubercle L. S. T. bacilli. R. K . Go y a h (Compt. rend. Soc. Biol., Electrodialysis of oxytocin. N. D a s , B. N. 1936, 121, 390;—392).— The curves for seven strains Ghosh, and B. C. G uha (Z. physiol. Chem., 1936, over a period of 10 weeks are described; they are 238, 131— 132).— When electrodialysed, oxytocin affected by phenolsulphonephthalein to different moves to the cathode at p a 9-6, but not at pa 10, and extents. R. N . C. is, therefore, a base or adsorbed on a basic carrier. Chemistry of the tubercle bacillus : lipin R. S. C. Action of adrenaline on the respiratory compounds. M. Eran c ioli (R. 1st. lombardo Sci. Lettere, Rend., 1934, 67, No. 2, 737— 740; Chem. quotient. E. M. B r id g e and H. R. N oltie (J. Zentr., 1935, i, 3943).— Fractional extraction of the Physiol., 1935, 85, 334— 342).— Continuous intra living bacilli in the cold yields fat, phosphatides, wax, venous injection of adrenaline in unana;sthetised and C -H -0 compounds of high mol. wt. and m.p. rabbits reduces the R.Q. to the protein-fat level; R. N. C. the low vals. of liver- and muscle-glycogen suggest a Nuclear staining of myxobacteria and other purely glycogenolytic action. R. N. C. species. P. F. Milo v id o v (Arch. Mikrobiol., 1935, Comparative variations of blood-sugar and 6, 475— 509).— A no. of species show nuclear staining bile secretion due to slow and continuous intra after but not before hydrolysis with HC1. Applic venous injection of adrenaline. E. Chabrol and ation of the technique for ascertaining the distribution J. Sallet (Compt. rend. Soc. Biol., 1936, 121, 538— of nuclear material at various stages of development 540).— Increase of blood-sugar in dogs is accompanied is described. Thymonucleic acid occurred generally by a fall in rate of bile secretion. Injection of atophan in the organisms. A. G. P. prior to that of adrenaline has no effect. R. N. C. Staining and microscopical demonstration of Survival and increase of adrenaline in tissue filterable viruses. A . C. Coles (J. Roy. Microscop. cultures of adrenal glands from chick embryos. Soc., 1935, [hi], 55, 249— 255). H . D. M. R. L ew is and E. M. J. Geillng (Amer. J. Physiol., Isolation of crystalline tobacco mosaic virus 1935, 113, 529— 533). R. N. C. protem from diseased tomato plants. W. M. Differential depression of vaso-motor mechan Stanley and H. S. L oring (Science, 1936, 83, 85).— isms by adrenaline. L. C. W y m a n and C. t u m +ntyi q lYQ\ cp s!)*; Pr9;fei^ has been obtained from Suden (Amer. J. Physiol., 1935, 113, 271— 278). I r a ° P ^ L ^ f e c t e d with tobacco mosaic virus R. N. C. „ ' i • ’ , ) > ^ has the same cryst. form and Effect of adrenaline on the blood-sugar, -lactic properties as that isolated from tobacco plants. acid, and -inorganic phosphorus of completely L S T hypophysectomised dogs. I. L. Gh aik o f f, F. L. Irradiation of plant viruses and micro-organ- R eich ert, L. S. R e a d , and M. E. Mathes (Amer. J. Ylu m.onochr°matic light. I I I . R esist- Physiol., 1935, 113, 306— 311).— The increases pro , virus of typical tobacco mosaic and duced by adrenaline in completely hypophysectom J - coh t0 radiations of 3000—3250 A. A. H o l- ised dogs are < those in normal and control animals. la e n d e r and B. M. D u g g a r (Prac. Nat. Acad. Sci., R. N. C. K N 526 BRITISH CHEMICAL ABSTRACTS.— A. X IX (k) Comparison of the effects of sympathin and Effect of pitocin, pitressin, and antuitrin on adrenaline on the iris. W. B. Ca n n o n and A. fat tolerance tests. H. B lo tn er (Endocrinol., R osenbluetii (Amer. J. Physiol., 1935, 113, 251— 1935, 19, 587— 591).— Pitocin and pitressin (more 258). ' R. N. C. active), but not antuitrin or antuitrin- Substances stimulating the uterus in the blood per unit body-wt. for chicken and turkeys are > of pregnant and parturient women. F. Caroca those of mammals. A. G. P. and 0 . K oref (Endokrinol., 1935, 15, 244— 250; Influence of breed and ration on carotene and Chem. Zentr., 1935, ii, 238).— Whole blood or serum vitamin-A content of milk. W. M. B e eson (Proc. from men, or from women in the intermenstrual period, Amer. Soc. Animal Prod., 1935, Jan., 54— 56).— stimulates the contraction o f. the virgin guinea-pig The carotene (I) content was highest in Guernsey and uterus equally. Serum from pregnant, menstruating, lowest in Holstein and Ayrshire butters, and the and parturient women is one third as potent owing to vitamin-A (II) content was highest in Holstein and counteraction by corpus luteum hormone, but whole lowest in Guernsey butters, so that the total (II) blood from parturients is much more potent than its potency varied little with different breeds of cows. serum. The active substance is adsorbed on the Large amounts of (I) in the diet increased the (I) and fibrin during clotting. G. H . F. (II) contents of the butters. N u t r . A b s . (to) Action of hormones on the closed vagina. E. Application of the spectrophotometric method D ingem ansb and S. E. d e J ongh (Acta Brev. neerl. for the characterisation of photo-labile sub Physiol., 1935, 5, 27; Chem. Zentr., 1935, ii, stances by their rate of decomposition. A. 238).— Non-cryst. extracts of follicular fluids and of Ch e v a llie r and P. D ubotjloz (Bull. Soc. Chim. biol., urines are relatively more effective in causing opening 1936, 18, 190— 194).— The method is applied to of the vagina of infantile rats than are cryst. preps. (3-ionone and vitamin-A. A. L. Probably the former contain another biologically active substance. G. H. F. Determination of vitamin-A. A. P r zezd Action of sex hormones on the prostate and ziecka (Biol. Lekarska, 1935, No. 6).— A modific its accessories in the mouse. S. E. d e J o n g h ation of the SbCl3 method is proposed. If the (Acta Brev. neerl. Physiol., 1935, 5, 28; Chem. Zentr., mixture is heated with guaiacol for 2 min. at 60° a 1935, ii, 240).— Injection of folliculin (especially the rose or red colour is produced which is stable and benzoate) into young mice causes typical hypertrophy may be compared with a standard solution of Sudan 3. of the anterior lobe of the prostate. Injection of an N u tr . A b s. (to) equiv. amount of male hormone protects the mice Determination of vitamin-A. E. M. H ume against this stimulus; corpus luteum hormone gives (Nature, 1936, 137, 277).— A defence of the decisions no protection. G. H . F. taken by the International Conference on vitamin standardisation (cf. this vol., 390). L. S. T. Vitamin deficiency as a cause of disease and the vitamin requirements of man. H . J. J usatz IS-Avitaminosis and detoxication in rabbits. (Z. Volksernahr., 1935, 10, 97— 99; Chem. Zentr., T. K umon (J. Biochem. Japan, 1935, 22, 213— 224).— 1935, i, 3000).— A review. Daily requirements are Conjugation of administered BzOH, CH2Ph*C02H, given for -A , -B v and -B2 in adults, and -C and -D and CHoPluCHyCOoH with glycine is not affected by in infants and adults. G. H . F. R-avitaminosis ; excretion of BzOH following ad ministration of BzOH of hippuric acid (I) is, however, Vitamin-A, -B, and -C content of raw, boiled, diminished. The in-vitro hydrolysis of (I) by liver and pasteurised milk. L. De Carq and I. Sbeier and kidney tissue is not affected. Other detoxication (Quad. Nutrizione, 1935, 2, 171— 188).— A daily dose processes influenced include formation of ethereal of 3 ml. of raw milk (but not of the treated milks) or sulphates by PhOH and indole and of indican and 6 ml. of either, provided sufficient vitamin-A for rats. méthylation of C5H5N, but not conjugation with For the -B complex, 10 ml. of all three milks sufficed, glycuronic acid. F. 0 . H. but 8 ml. of raw milk was not enough. The ascorbic acid content of raw milk was 4-8— 14-5, of boiled milk Avian B-avitaminosis and enzyme action. S. 1 ‘2— 9-7, and of pasteurised milk 1 -6— 9-2 mg. per litre. T sunoo, M. T a k a m a t s u , T. K am ac h i, and M. Imai- N u t r . A bs. (to) zum i (J. Biochem. Japan, 1935, 22, 225— 231).— The Relation between vitamin-A and -D intake by enzymic activities of normal pigeon and fowl tissues the hen and the output in eggs. W . C. R ussell vary considerably in individual vais. No significant and M. W . T a ylo r (J. Nutrition, 1935, 10, 613— changes appear to be due to B-avitaminosis but the 623).— 11— 3 2 % of ingested vitamin-A reappeared data indicate a diminished activity of kidncy-phos- in eggs. The -A content of the liver varied inversely phatase and increased activity of pancreatic esterase with egg production. 10% of ingested -D was and hepatic amylase. F. 0 . H. transferred to eggs. Sunlight is more effective in Utilisation of sugars. Vitamin-B and aliment increasing the -D content of eggs than is the amount ary equilibrium . L. R a n d o in and F. Milhaud of cod-liver oil given. A. G. P. (Compt. rend., 1935, 201, 1426— 1428).— Death « Metabolism of vitamin-A. A. P rzezdziecka rats on a diet consisting only of glucose, fructose, (Wiad. farm., 1935, 62, 201— 203; Chem. Zentr., sucrose, lactose (I), or especially galactose (II) is more 1935, ii, 244).— A colorimetric method for determining rapid than that from actual starvation (H20 only). the vitamin in urine is described. G. H. F. Compared with vitamin-B-free diets containing these Minimum vitamin-A requirements with par sugars, life is prolonged to > 150 days by addition of ticular reference to cattle. H. R. G uilbert and -R except with (I) and (II). F. 0 . H. G. H. H art (J. Nutrition, 1935, 10, 409—427).— Effect of lack and excess of vitamin-B on the Vitamin-A requirement may be related to body-wt. calcium and magnesium content of the tissues rather than to energy requirement. Requirements of pigeons. S. M u rza-M urzicz and H. B o h d a n o - X IX (I) BIOCHEMISTRY. 529 wxcz6w a (Biochem. Z., 1936, 284, 139— 145).— The vival of rats on vitamin-B2-deficient diets is not due to Ca contents of muscle, heart, and brain, but not liver, a ccecal supply of -B2. are decreased by overdoses of vitamin-B, whilst IV. Vitamin-B2 is stored in the tissues, from which Mg remains unaffected or is slightly increased. Lack it is not readily lost during feeding of a deficient diet. of -B causes increase in Ca and Mg. W . McC. -B , may function, in part, as a tissue constituent. A. G. P. Differentiation of the antidermatitis factor. Vitamin-/i2 requirement of poultry. L. C. A. G. H ogan and L . R . R ichardson (Science, 1936, N o rr is, G. F. H e u se r, A. T. R in gro se, H . S. W ilg u s , 83, 17— 18).— When vitamin-B carriers are exposed to and V. Heim an (Proc. 5th World’s Poultry Congr. ultra-violet irradiation, at least one member of the -B Rome, 1933, 2, 510— 520).— The factor essential for complex is destroyed, and the preps, cause a severe growth, hatchability, prevention of a pellagra-like dermatitis and ultimate death of rats. This destruc syndrome and of leg and foot paralysis is probably tive action cannot be demonstrated when the diet vitamin-B2. The latter consists of at least two contains significant amounts of maize starch. EtOH factors, one preventing paralysis and another neces extracts of the starch heal the lesions, indicating that sary for growth. Ch. A b s. (p ) the preventive agent is not identical with -B2. L. S. T. Behaviour of vitamin-If7 towards various Vitamins and tissue-diastase in relation to solvents. E. M onteveco h i (Biochem. Terap. sperim., 1935,22, 143— 150; Chem. Zentr., 1935, ii, organ function. F. M a ig n o n (Ann. Physiol. Physiochim. biol., 1934, 10, 903— 904; Chem. Zentr., 244).— The vitamin is insol. in the usual fat solvents. 1935, i, 3000).— Diastase from various organs caused It is extracted completely by 95% and partly by 70% no improvement in pigeons suffering from B-avitamin- EtOH. G. H . F. osis or in scorbutic guinea-pigs. G. H . P. Influence of ascorbic acid on normal human carbohydrate m etabolism . S. StoIcesco and N. Vitam in-B complex in the root of the manioc. Gingold (Bull. Acad. Mdd. Roumanie, 1936, 1, 130— F. A. D e M oura Campos (Ann. Fac. Med. Univ. 132).— Intravenous or oral administration of ascorbic Sao Paulo, 1935, 11, 27— 31).— Manioc (cassava) acid (0-24— 0-50 g.) lowers the fasting blood-sugar and meal is a fairly good source of the -B complex. diminishes alimentary hyperglycannia. F. O. H. N u t r . A b s . (m) Accumulation of the antineuritic vitamin-B in Crystalline vitamin-C: its effects on the the animal organism. N. L. Ja r u sso va (Prob capillary fragility. I. S. W r ig h t and A. L il ie n - lems of Nutrition, Moscow, 1935, 4, No. 4, 98— 106).— eeld (Arch. Int. Med., 1936, 57, 241— 274).— A Tests on pigeons indicate a storage of -B v capillary-fragility test for diagnosing human vitamin- N u t r . A b s . (m) G deficiency is described. The val. of ascorbic acid Nitrogen metabolism of birds with vitamin- in various diseases is discussed. H . G. R. deficiency polyneuritis. B. A . L avr o v and N. L. Effect of ascorbic acid on the proliferation of Jarussova (Problems of Nutrition, Moscow, 1935, monocytes. L. E. B a k e r (Compt. rend. Soc. Biol., 4, No. 4. 88— 98).— Pigeons receiving a vitamin-Br 1936. 121, 427— 429). R. N. C. free diet lost more N than those receiving the same Cystine and vitamin-C deficiency. L. D e Caro amounts of diet which contained the -B 1. When and W . B e ltra m i (Quad. Nutrizione, 1-935, 2, 165— birds were completely starved addition of 1 g. daily of 170).— Death of guinea-pigs on a scorbutic diet is a -B1 concentrate did not result in increased N greatly accelerated by cystine (I) or HC1. Ascorbic retention.. N u t r . A b s. (to)’ acid counteracts the effects of (I). Nutr. Abs. ( m ) Is the occurrence of methylglyoxal in the urine Effect of diphtheria toxin on the vitamin-C specific for avitaminosis-B ? J. L e h m a n n content of guinea-pig tissues. C. M . L y m a n (Skand. Arch. Physiol., 1935, 71, 157— 165).— AcCHO and C. G. K in g (J. Pharm. Exp. Ther., 1936, 56, is present in the urine of rats deficient in vitamin-Bx 209— 215).— Subcutaneous administration of diph or -B2, and also in control animals in small quantities; theria toxin to guinea-pigs rapidly lowers the vitamin it is destroyed if the urine is kept for 12 hr. AcCHO in content of the tissues, especially adrenals, kidney, and the urine is therefore not sp. for avitaminosis-B^ pancreas. W . 0 . K . R. N. C. Antineuritic vitamin contents of some Fixation of ascorbic acid in the adrenal and oil-rich seeds. V. Zagam i (Quad. Nutrizione, 1934, the liver of the scorbutic guinea-pig. Determin 1, 284— 294; Chem. Zentr., 1935, i, 3949).— Vitamin- ation of the minimum curative dose of 1-ascorbic i occurs in varying quantities in walnuts, hazel acid. V. D emole and F. I pp e n (Compt. rend. Soc. nuts, peanuts, pistachios, and sesame, pine, and sun- Biol., 1936, 121, 687— 689).— The daily min. dose is llouer seeds; almonds and olive oil contain none, slightly < 0-5 mg. for an animal of 250 g. wt. The or only traces. R. N. C. ingested ascorbic acid is stored in the adrenals, but not in the liver. N . C. Antineuritic vitam in.— See this vol., 487. Ascorbic acid in course of cadaverisation. A. Growth studies. III. Avitaminosis-JBj and Gir o u d , R. R atsimamanga, M. R abin o w icz, and E. 2 111 cascectomised rats. IV. Vitaxnin-Iij and H artm ann (Compt. rend. Soc. Biol., 1936, 121, 739— -B2 contents of body tissues of normal and 740).— Ascorbic acid decreases slowly in the rat and experimented rats. W. H. Gritfit h (J. Nutrition, the guinea-pig during cadaverisation; the rate of fall in 1935, 10, 667— 674, 675— 682).— III. Prolonged sur the adrenals is > in the liver and kidney. R. N. C. 530 BRITISH CHEMICAL ABSTRACTS.— A. X IX (I) Secretion of ascorbic acid by the healthy and steadily from fœtus to 60— 80 years of age. The diseased organism. H. Sch roeder (KJin. Woch., same tendency was observed in the cerebrospinal 1935, 14, 4 8 4 -4 8 7 ; Chem. Zentr., 1935, i, 3001).— fluid, but the concn. was always < in brain. The Ascorbic acid administered to healthy individuals, concn. in serum did not appear to decline with age. but not in various pathological conditions, is excreted Daily treatment with 90 mg. of -C caused slow in increased amounts in the urine, although the vita progressive rise in the -C content of the fluid of min metabolism may he > normal. G . H . F. patients and a similar relationship between -C [Distribution of] ascorbic acid. A. Giroud and content of food and fluid was observed in rabbits. C. P. L eblond (Bull. Soc. Cliim. biol., 1936, 18, N u t r . A b s . (m) 173— 175).— By the use of acidified aq. A gN 03, Histochemistry. V. Vitamin-C concentra ascorbic acid is detected in the thymus, lymphatic tion of the corpus luteum with reference to the ganglia, intestines, liver, sympathetic ganglia, supra stage of the oestrus cycle and pregnancy. G. R. renal medulla and cortex, corpus luteum, ovaries, B isk in d and D. Glick (J. Biol. Chem., 1936, and pituitary. A. L. 113,27— 33 ; cf. A., 1935,1264).— The fully developed corpus luteum of the cow contained 1 4 mg. of Vitamin-C in fresh-water fish and crabs. G. vitamin-C per g. of tissue, which decreased to 0-3 mg. von L u d á n y (Biochem. Z., 1936, 284, 108— 110).— with regression. In gestation the content of -C Data for various tissues are tabulated. In some cases remained at 1-5-—2-2 mg. per g. for the first 7 months the amounts exceed those found in warm-blooded and decreased to 1-1 mg. in the Sth month. -C may animals. W . McC. be related to progesterone. J. N. A. Ascorbic acid in the lens of the eye. H. v o n Determination of vitamin-C and the influence E u le r and M. Malmberg (Arch. Augenheilk., 1935, of technological treatment on its preservation 109, 225— 234).— Indophenol titration of vitamin-0 in cabbage. S. G. V in o k u r o v , M. M. E id elm an , in the eye lens of animals revealed high vals, for sea and M. L. B utom (Kharkov State Med. Inst. Jubilee fish, and -O was detected hi the ox, rabbit, horse, and J., 1935, 142— 161).— Food extracts should always be guinea-pig. While the animal received a -O-deficient treated with H 2S before titration with indophenol in diet, the -O content of the eye lens fell in guinea-pigs vitamin-C determinations. 40— 70% of the -C con but not in rabbits. The -0 content of the lens in tent passed into H 20 when cabbage was cooked for 30 rabbits was uninfluenced by high doses of -O. The min. Cooking for longer periods involved heavy reducing capacity of the lens in the rat was largely losses of-C. N u t r . A b s . (in) due to glutathione, the -0 content being < in most cases investigated. No marked variation was de Provitamin-7) of heat-treated cholesterol. tected in the -0 content of the lens in rats fed on a M. L. H a t h a w a y and D. E. L obb (J. Biol. Chem., -_B2-deficient diet. The -O content of the human lens 1936, 113, 105— 110).— The provitamin of crude in cataract was < normal. Attempts to induce cholesterol (I) is destroyed by purification through the cataract in rabbits by C10H8 poisoning were unsuccess dibromide. When purified (I) is heated at 200° for ful and the poisoning did not affect the -C content of 2 hr. its proantirachitic activity is increased. It is the lens. Possibly part of the -C in the lens is syn concluded that irradiation of heat-treated (I) produces thesised there. Nutr. Abs. (m) a new form of vitamin-/) which more closely resembles natural -D from cod-liver oil than -D of irradiated Vitamin-C in the lens and aqueous humour in ergosterol. J. N. A. human cataract. B. N a k a m u r a and 0 . N a k a m u r a (Arch. Ophthalmol., 1935, 134, 197— 200).— A Evaluation of the antirachitic vitamin in diminution was observed. N u t r . A b s . (m) comparison with the international standard. Relative vitamin-C values of milk and curd. M. Podzimkovâ-Rieglovâ (Trav. Inst. Hyg. pub]. Tchécosl., 1935, 6, 20— 30).— The degrees of calci A. R . Ghosii and B. C. Guha (Indian Med. Gaz., 1935, 70, 382).— The vitamin-C content of curd was the fication of the head of the radius produced by 0 4 , same as that of the original milk, even though the 0-2,0-1, and 0-05 international units of vitamin-Ddaily, curdling process was carried out for 24 hr. at 35°. In and that observed in control rats receiving no -D are fresh milk stored at 0° for 24 hr., there was consider recorded. 0 4 unit was not always sufficient to pro able loss of -C. There appeared to be no synthesis duce normal calcification. After keeping for 13 of -C by the lactic acid bacillus employed. months at — 5° the activity of the international stan dard had not diminished. Nutr. Abs. (tit) Nutr. Abs. (m ) M ilk as a source of v ita m in -C . C. II. W h it n a h Size and structure of the thyroid gland of the and W . H . R id d e ll (Science, 1936, 83, 162).— The cat after the administration of irradiated ergo- milk of four major dairy breeds of cow gave an average sterol. A. M. L a n d s and 0 . 0 . St o l a n d (Endo val. of 25-9±4-3 mg. per litre. L. S. T. crinol., 1935,19, 701— 704). R. N. C. Vitamin-C in brain and cerebrospinal fluid. Calcium, inorganic phosphorus, and serum- Effect of diet on the vitamin-C content of the phosphatase in normal animals and in animals fluid : examination of the fluid in diagnosis of influenced by irradiated ergosterol. S. F ree latent scurvy. F. P l a u t and M. B ülow (Z. ges. m an and C. J. F arm er (Amer. J. Physiol., 1935,113, Neurol. Psychiat., 1935, 152, 84— 97, 324— 336).— 209— 220).— Toxic doses of irradiated ergosterol (1) The vitamin-C content of the brain in newly bom or increase serum-Ca and/or -P, and proportionately fœtal rabbits and mice was 2— 3 times > in the mother. decrease serum-phosphatase (II) in dogs and rabbits. In human cadavers the -C val. for the brain fell (II) is decreased by bleeding and a high-protein diet, X IX (I, m) BIOCHEMISTRY. 531 and increased by a high-carbohydrate diet; the in Chemical restoration in Nitella. II. Restor crease is enhanced by sub-toxic doses of (I). (II) ative action of blood. W. J. V. O s t e r h o u t (J. activity is probably inversely oc acid-sol. org. P of the Gen. Physiol., 1936,19, 423— 425; cf. A., 1935, 1038, whole blood. R. N. C. 1289).— The “ K effect ” in Nitella is restored by exposure to Ca-free blood-plasma (human, cat, calf, Isolation from wheat-germ oil of an alcohol, sheep). F. A. A. a-tocopherol, having the properties of vitamin-7?. H. M. E v a n s , 0 . H. E m erson, and G. A. E merson (J. Effect of potassium chloride on diurnal Biol. Chem., 1936, 1 1 3 , 319— 332).— The unsaponi- changes of carbohydrates of the potato leaf. fiable matter yielded (?) p-amyrin allophanate, m.p. D. J. W a t so n (Ann. Bot., 1936, 50, 59— 83).— 250°, the allophanate, m.p. 13S°, of an alcohol, Diurnal fluctuations in sucrose contents of leaflets C29H50O2, and the allophanate, m.p. 158— 160°, of were > those of reducing sugars. The rate of re a-tocopherol (I), C29H 50O2 (p-nitrophenylurethane, m.p. moval of dry matter (but rtot of carbohydrates) 129— 131°). (I) has a characteristic absorption band during darkness wras increased by applications of at 298 mg, and treatment with M e0H -A gN 03 yields KC1. KC1 probably increases the efficiency of photo a substance with bands at 271 and 262 nip. A single synthesis. The H ,0 content per unit of dry matter dose of 3 mg. of (I) enables vitamin-U-deficient rats was increased by KC1 and the increase did not vary to bear young. H. G. R. with time. A. G. P. Kinetics of penetration. XII. Hydrogen sul Action of radium emanation on the germin phide. A. G. Jacques (J. Gen. Physiol., 1936, 19, ation of grains. M. d e Caram a n and C. Cham py 397—418).— The rate of entry of total sulphide (H2S + (Compt. rend. Soc. Biol., 1936, 121, 750— 752).— S") into Valonia macrophysa is, during the first 5 min., The % germination is increased, and early growth is oc external concn. of mol. H 2S. H 2S thus differs from accelerated. R- N. C. NH4' and guanidine (cf. A., 1935, 671, 1179). The Energy balance of carbonic acid assimilation mode of entry appears to be diffusion of mol. H 2S [by plants]. K. W o h l (Z. physikal. Chem., 1935, through the cell wall; the rate deviates from a B , 31 , 152— 156).— Energy considerations show that unimol. law. F. A. A. it is impossible that CH20 + 2 H 20 2 should be the Amylogenic capacity and organic matter of intermediate product in the assimilation. The Franck-Willstatter-Stoll theory of the mechanism of plastids. A. M a ig e (Compt, rend., 1935, 201, 1411— 1414).— The relation of starch formation in C 02 assimilation (A., 1933, 326, 577; A., 1935, 794) potatoes, beans, etc. to the structure, constituents, is therefore untenable. R. C. and developments of starch plastids is discussed. Amino-acid content of plants at different F. 0 . H. stages of growth. A. I. V lrtanen and T. L a in e Transport in the cotton plant. III. Inde (Nature, 1936, 1 3 7 , 237).— The tryptophan and pendence of solute m ovem ent in the phloem . aspartic acid contents of peas and clover vary con T. G. Ma s o n , E. J. M a s k e l l , and E. P h ill is. TV. siderably during different stages of growth, indicating Simultaneous movement of solutes in opposite that the ratio of various proteins changes during directions through the phloem. E. P h illis and growth, or that in the growing plant the protein has T. G. Mason (Ann. Bot., 1936, 50, 23— 58, 161— 174; no fixed composition, new N H 2-acid groups being cf. A., 1934, 707).— III. Movements of carbohydrates continuously incorporated with the growing protein (I), N, P, K , and Ca in petioles and stems of cotton mol. L. S. T. plants, and the effects of ringing, are examined. Re Nitrogen metabolism of the apple fruit. II. sults are discussed in the fight of current conceptions Course followed by certain nitrogen fractions of the transport of solutes in plants. during the development of the fruit on the tree. IV. Examination of ringed and unringed plants A. C. H tjlme (Biochem. J., 1936, 30 , 258— 268; cf. grown in culture solutions shows that (I) and N may A., 1935, 422).— Non-protein-N was separated from movesimultaneously and in opposite directions through the peel and pulp of apples by extraction with aq. the phloem. A. G. P. EtOH and determined as total sol., free N H 3-, N H 2-, Influence of light on the permeability of plant and residual N. Titratable acid was also determined. tissues to sugar. L. B r a u n e r and M. B r a u n e r The changes in these fractions during the course of (Rev. Fac. Sci. Univ. Istanbul, 1936, 1, No. 2, 58— development of two series of fruits was determined. 73; cf. A., 1935, 671).— The action of fight probably The two series showed similar trends; an early stage causes a loss of electric charge in the electro-negative of rapid increase in sol. N compounds was followed by membrane cells, and a shrinking. H 20 or solutions a stage of relative equilibrium between protein and o salts having a dipole moment find less resistance non-protein compounds. When mature a state of on passing the membranes, whilst compounds having net synthesis of protein ensued. H. D. no dipole moment are hindered. E. P. Nitrogen-free aliphatic compounds as organic Effect of light intensity on manganese content nutrients of algje. H. M e y e r (Biochem. Z., 1936, of plants.^ M. M. M cCo o l (Contr. Boyce Thompson 28 3 , 364— 381).— The effect of 0-2% of 90 org. nst 1935, 7, 427— 137).— Visible injury to plants substances on the growth of Chlorella luteoviridis, as c ue to the addition of MnS04 to soil decreased with measured by increase in cellular vol. or dry wt. or the prevailing intensity of fight. The % of Mn in intensity of division, in a medium containing M gS04, eaves decreased, and, in some cases, that of stems CaCl2, FeCl3, (NH4)2HP 0 4, and phosphote buffer is increased, with declining fight intensity. A. G. P. investigated. With saturated acids, alcohols, and 532 BRITISH CHEMICAL ABSTRACTS.— A. X IX (m) aldehydes, the first member of the series (HC02H, H itchcock and P. W . Z immerman (Contr. Boyce MeOH, CH20) is toxic, the second member has the Thompson Inst., 1935, 7, 447— 476).— Application highest nutritive val. and the higher homologues of heteroauxin, indolyl- or phenyl-propionic acids, are utilised to a decreasing content, iso-Acids and un naphthyl- or phenyl-acetic or indolylbutyric acid to saturated acids are toxic. (3-Hydroxyhutyric acid soil induced responses in tomato and tobacco plants and CH2Ac*C02H are readily utilised. Polybasic and similar to those obtained by treatment of the aerial sugar acids are indifferent. Hexoses form the best parts of the plants. The rate of absorption of active source of C, pentoses are not utilised, polysaccharides substances was influenced by the amount present in are used according to the ease of hydrolysis, whilst the soil and by the transpiration rates of the plants. methylglucoside and glycerophosphoric acid are The action of growth-substances (I) applied to aerial indifferent. P. W . C. parts is not affected by transpiration rates. Within the plant translocation of (I) in living tissue was > Fat metabolism in plants with special refer in dead tissue and upward > downward movement. ence to sterols. P. L. M acL ac h lan (J. Biol. Chem., Strictly polar movement was not observed in either 1936, 113, 197— 204).— The sterol and fatty acid stems or leaves. Unilateral lighting favoured the constituents of soya beans during germination in the bending-response of stems to (I) but light was not light and dark were determined. A decrease in the essential. Addition of (I) to soil hastened flowering fat content occurred during germination accompanied without retarding vegetative growth. The optimum by a continuous synthesis and estérification of sterol. dosage for flowering was < that for root initiation. Small differences in the behaviour in the light and A. G. P. dark were observed. H. D. Response of roots to “ root-forming" sub Nitrogen fixation by the alder. A. I. V ir ta n e n stances. P. W. Z ehmerman and A. E. H itchcock and S. Saastamoinen (Biochem. Z., 1936, 284, 72— (Contr. Boyce Thompson Inst., 1935, 7, 439— 445).— 85).— Since peas inoculated with N-fixing bacteria Application of lanoline preps of a-naphthyl-, indolyl-, grow normally in an aerated N-free aq. medium it and phenyl-acetic acids, indolyl-butyric, -propionic, follows that there is no difference in this respect and -valeric acids to aerial roots of C'issus sicycoides, between leguminous plants and the alder. Inoculated L., var. Jacquini, caused the initiation of new root alder seedlings grow better in N-free media than do branches, inhibition of growth of the tip and/or non-inoculated in media containing NH4N 0 3 ; the swelling of the root. New rootlets ceased to grow growth of the former is optimal at pa 6. Inoculated when the main tip resumed elongation, but recom alder enables pine seedlings planted in the same N- menced on a second treatment of the tip. The free medium to grow normally and appears to give dominance of the tip disappeared when the treated up N compounds to the medium. W . McC. area was immersed in H 20. Results are discussed in relation to the movement of growth-substance in Interaction of factors in the growth of Lenina. roots. A. G. P. VII. Effect of potassium on growth and multi plication. H. L. W hite (Ann. Bot., 1936, 50, Selenium in native range plants occurring 175— 196).— Mathematical relationships between the on soils derived from Permian or Triassic (?) [K ‘] of the nutrient and the growth of Lemna minor sediments [of the Chugwater formation, Albany are established. Deficiency of K is associated with Co., Wyoming]. 0. A. B ea th (Science, 1936, 83, high starch and dry matter contents per unit area, 104). L. S. T. low rates of assimilation, and diminished amylolytic activity. A. G. P. Natural poisoning of hens by acid sorrel (llumex acetosella) : poisoning by oxalic acid Supply of iron to plants in water cultures. and potassium hydrogen oxalate. C. Orlan din i W . Schropp (Z. Pflanz. Diing, 1936, 42, A , 35— 42).— (Boll. Soc. Eustach., 1933, 31, 217— 229).— Poisoning In media containing PeCl3, the accumulation of Fe by the sorrel is attributable to H 2C20 4 and KHC204. by plants was inversely related to the reaction of the Ch . A b s. (p) nutrient. When Fe111 citrate was used, growth was Compounds of hydroxylamine in fresh leaves improved and the Fe intake was independent of pu. of higher plants. M. L em o ig n e, P. M onguillon, A. G. P. and 11. D esv eau x (Compt. rend., 1935, 201, 1437— Skatole as a growth-promoting substance. 1439).— Distillation of the juice of fresh leaves of J. Glo ve r (Nature, 1936, 137, 320— 321).— E x Poa pratensis yields N H 20 H (1— 2 mg. per litre); periments with young oat shoots indicate that skatole N H 2OH probably participates in the N metabolism (I) acts as a growth-promoting hormone. (I) and of higher plants. F. O. H. p-indolylacetic acid are both markedly light-sensitive. L. S. T. Excretion of amino-acids from root nodules Growth-promoting substance at the base of and their chemical nature. A. I. V l r t a n e x , 1- the oat coleoptile. H. Sôdin g (Ber. deut. Bot. L ain e , and S. von H ausen (Suomen Kem., 1936, 9, Ges., 1935, 53, S43— 846).— The growth hormone is B , 2).— The rate of excretion is greatest at an early present in the base of the coleoptile. No evidence stage of growth, before blooming. A cold-H2U was obtained of a “ bound ” or inactive form. extract of the sand on which peas had grown con A. G. P. tained exclusively N H 2-N. About 50% of the total Absorption and movement of synthetic N was due to aspartic acid, while the remainder was growth-substances from soil as indicated by probably lysine (I). Barley will grow with (I) as sole responses of aerial parts [of plants]. A. E. source of N . J. N. A. X I X (m, n) BIOCHEMISTRY. 533 Glutamine and asparagine in tobacco leaves. Sterols in the leaves and flowers of the lily. H. B. V ic k e r y and G. W . P ucker (J. Biol. Chem., M. Mir an d e (Compt. rend., 1936, 202, 238— 240).—- 1936, 113, 157— 160).— Glutamine (I) occurs, as well The distribution of sterols in species of lily is examined. as asparagine (II), in the leaves of the tobacco plant, H . G. R. and may be extracted. Of the total amide-N, (II) Determination of carotene and xanthophyll.— appears to account for about §, (I) for about but See this vol., 493. other amide substances may be present. F. A. A. Lycoxanthine and lycophyll.— See this vol., 452. Biologically active substances in the fruit of Occurrence of carotenoids in plants. P. the tomato (Solatium esculentum) with hist K a r r e r , F. R u b el, and F. M. Strong (Helv. Chim. amine-like action. Therapeutic action of fresh Acta, 1936, 19, 28— 29).— Treatment of the seeds of vegetable juice. F. Gle ich m an n (Z. klin. Med., Passiflora coerulea with EtOH followed by boiling 1934,127, 111— 131; Chem. Zentr:, 1934, ii, 3982).— CHC13, evaporation of the CHC13, and crystallisation The cryst. substance extracted from green or ripe of the residue from ligroin (b.p. 60— 80°) gives lyco- tomatoes or conserve is stable to heat, pepsin, and pene in considerable amount. ß-Carotene and zea- HC1, and resembles histamine in its pharmacological xantliiri are obtained cryst. from Iialyseris polypo- action. It. N. C. dioides but homogeneous fucoxanthin could not bo Chemical examination of Punar-Nava (Boar- isolated. H . W . lutuvia diffusa, Linn.). It. It. A garw al and S. Colouring matters of violet potatoes.— See this Dutt (Proc. Acad. Sci. U.P. India, 1935, 4, 73— 76).— vol., 480. Boiling EtOH extracts bosrhaavic acid, CioH180 3, m.p. 108— 109° (decomp.) (Pb salt; Br3-derivative, m.p. Colourless compounds which accompany 73°), tannins, phlobaphens, and glucose from the carotenoids in plants. L. Z echm eister and P. entire plant. J. L. D. T uzson (Z. physiol. Chem., 1936, 238, 204— 209; cf. Chemical examination of the roots of Citrullus Euler et a l, A., 1908, ii, 724; 1930, 1627 ; 1932, 785). — 100 kg. of carrots yield 1-06 g. of daucosterol (I), colocynthis, Schrader. It. It. A garw al and S. C35H G0OG, decomp, at 305°, [a%° —49-6° in C6H 5N, D utt (Proc. Acad. Sci. U.P. India, 1935, 4, 295— hydrolysed by acid to d-glucose and sitosterol. The 300; cf., J.C.S., 1910, 47, 99).— Boiling EtOH extracts a-elaterin (0-2% ); m.p. 229— 230° [Ac, sepals of the sunflower contain a dihydric sterol helisterol, derivative, m.p. 122— 123° (cf. A., 1907, i, 230)], C20H44O2, m.p. .242°, [a]*? + 4 5 -4 ° in CHC13 hentriacontane (?), saponins, and reducing sugars (diacetate, m.p. 166— 167° (corr.), [a]^ +58-7°), a monohydric sterol, m.p. 217°, [a]j,° -J-42*8° in CHC13, a from the powdered roots. J. L. D. sterolin, C^H^O«., m.p. 303°, [a]“ -50-5° in C5H5N, 2' : 6'-Dihydroxy -4 /-methoxy-|3-phenylpropio- which gives glucose and a sterol, C27II4G0, m.p. 159°, phenone from the essential oil of Populus bal- [a%° —49-9° in CHC13 on acid hydrolysis, an alcohol, sami/era, L. A. Goris and H. Ca n a l (Compt. rend., C21H50O, m.p. 73° (corr.), and hentriacontane. 1935, 201, 1435— 1437).— The oil from the buds W . McC. yields the above ketone, m.p. 16S°. F. 0 . H. Formation of anthocyanins in plants. R. Localisation of rotenone in derris root. P. A. R obinson (Nature, 1936, 137, 172— 173).—A v a n d e r L aan (Pharm. Weekblad, 1936, 73, 313— summary. L. S. T 318).— Cells containing rotenone (I) are coloured Glycosides of the flowers of Linaria v u l g a r i s . — green (transient) when treated with H N 0 3 and then See this vol., 458. with NH3, and the colour produced on samples of derris root may be used as a rough measure of the (I) Inulinogenesis in the Compositcv. H . Colin content. The (I) is localised in the parenchyma and (Compt. rend., 1935, 201, 1414— 1416).— Data for the pith cells present in both the wood and the bast. contents of reducing sugar, sucrose, and inulin (I) and S. C. for [a] before and after hydrolysis are given to illus Constituents of Ham am elis virginica. F. trate the discussed formation of (I) in the root, stem, Mercier and J. B alansard (Compt. rend. Soc. Biol., leaf, and wood of various Composites. F. 0 . H. 1936, 121, 671— 672).— The leaves contain choline, Determination of starch in plant tissue, par an acid saponin, and a sol. glucoside fraction. ticularly apple fruit. C. S. H an es (Bioehem. J., R. N. C. 1936, 30, 168— 175).— After a preliminary extraction Acid saponin of beetroot juice. K . Sm olen ski of the tissue with 70— 80% EtOH the residue is boiled ( locz. Chem., 1935, 15, 554— 564).— A review. with dil. HCl-EtOH which renders the starch (I) sol. R T in hot H 20 . The H 20 extract is then hydrolysed by Sterols of Achillea m illefolium . O. Gisvo ld ß-malt-amylasc (II), which produces maltose (III) as (J. Amer. Pharm. Assoc., 1935, 24,1071).— The sterols almost the only reducing product. The degradation consist of sitosterol and stigmasterol (cf. A., 1933, of (I) by (II) proceeds to a definite “ hydrolysis E. H. S. limit ” The amount of (III) formed is determined Phytosterol and resin of Fabiana denudata, either by an alkaline Fe(CN)6"' or a Cu method. im ers. L. F loriani (R ev. Centr. Estud. Farm. Apple-(I) is hydrolysed to the same extent by (II) throughout the season, with the production of 0-6 ? 3 imV 1?34, 25, G°— 6 2 ; Chem. Zentr., 1935, i, ° • )• A phijlosterol, C12H260 , a resin, m.p. 44°, an mg of (III) per mg. of (I), much the same val. as for a-resm-acid, m.p. 37°, and a ^-resin-acid, m.p. 39°, are potato-(I). The (I) content of apples on storage falls isolated. H . N. R. nearly to zero in 10 days. If taka-diastase (1 ^ ) is used BBITISH CHEMICAL ABSTRACTS. A. X I X (71, 0) instead of (II) the apparent (I) content is much higher Decomposition of nicotine by tbe fermentation and falls after 10 days to 1 -5 mg. per g. This is due to of tobacco. W. W eber (Mitt. Lebensm. Hyg., non-(I) fractions hydrolysed by (IV) but not by (II), some 1935, 26, 214— 249).— Aeration of moist tobacco or its of which are not metabolised, and so persist diming H 20 extract leads to loss of nicotine (I) by decomp, storage. Methods are given for the prep, of (II) and as distinct from atm. oxidation or volatilisation. control (I) from apples. E. A. H . R. This is inhibited by antiseptics and occurs in sterile Polysaccharides in sweet maize. M. W. P a r r k e media after inoculation with bacteria from tobacco (Plant Physiol., 1935,10, 713— 725).— Electrodialysis leaves. Bacterial decomp, of (I) takes place in of the sol. polysaccharide fraction yields an anodic artificial media, and there is evidence that oxidase, fraction and a further non-migratory fraction. With peroxidase, and catalase are produced. NH3 (but advancing maturity of the grain, the physical and no C5H5N) is produced, but unlike the N H 2Me found, chemical properties of the fractions approach' more it is not derived from (I) but from N H 2-compounds. closely to those of a- and p-amylose, and differ from A reagent suitable for determining (I) is best prepared those of dextrin. In maize the sol. polysaccharides by neutralising a mixture of 1 kg. of Na2W 0 4,2H20 may form the units from which starch grains are and 117-1 g. of 26-3% Na2Si03 with H 2S04, filtration, ultimately formed. A. G. P. extraction of the filtrate with Et20 in the presence of 50% H„S04, and slow evaporation of the Et20. Polysaccharides of Iridcca laminarioides. II. J. G. T. T ad o ko ro , K . Y oshim ura, and M. Y an ase (J. Nornicotine.— See this vol., 488. Chem. Soc. Japan, 1935, 56, 188— 191 ; cf. A., 1935, 268).— Hydrolysis of the product obtained by ex South American curare. F. W. F re ise (Pharm. traction with hot H 20 and pptn. with 70% EtOH Ztg., 1936, 81, 241— 243).— The characteristics and yielded galactose and smaller amounts of glucose, analyses of cork tissues of varying ages from 6 varieties fructose, and arabinose. The fraction not' pptd. by of Strychnos are given. The isolation of two alkaloids, EtOH contained an unidentified sugar having [a]j,° C23H280 4N2 (similar to or identical with vellosine), + 3 1 -4°, and yielding a phenylosazone, m. p. 125— 130°. and eucurarine, C20H23ON2, m.p. 135— 144°, decomp. Ch . A b s. (p) 182° (toxic dose for frogs, 0T3 mg. per kg.), is described. Hai-jen-tsao (IHgenia simplex, Ag). C. F. Hsu E. H. S. (Science [China], 1934,18, 1418— 1437).— This marine N ew alkaloid of ergot.— See this vol., 489. alga is used as a vermifuge. Alginic acid, extracted Alkaloids of Sinom enium and Cocculus.— See by 2 % Na2C03, contains uronic and either glycuronic this vol., 491. or mannuronic acids. The. boiling-H20 extract Barley proteins. I. S. J aitschnikov and A. D- yields galactan, d-pararabin, and small amounts of A vetisjan (J. Appl. Chem. Russ., 1935, 8, 1439— alkaloid and fucoidin. The I content is 0-20% . 1443).— The protoin-N of barley from different Ch . A b s . (p) localities of the U.S.S.R. varies from 2-16 to 3-07% ; Isolation of pectic substances from wood. E. the distribution of the N amongst the albumin, A nderson (J. Biol. Chem., 1936, 112, 531— 539).— globulin, glutenin, and prolamine fractions is recorded. The sap-wood and cambium of Robinia pseudacacia, Varying the order in which the various fractions are L., yield < 3 % and < 1 3 % , respectively, of pectic extracted (by HoO, aq. NaCl, and aq. NaOH) affects substances (yielding d-galacturonic acid but no the results. R. T. methylpentoses), probably present largely as Ca pectate, protected by later deposition of other Distribution of nucleic acids and proteins in materials. ” R. S. C. chromosomes. T. Caspersson (Naturwiss., 1936, 24, 108).— With the aid of a precipitant containing Vegetable chitin. J. M. D ie h l (Chem. Week- La, sp. for nucleic acids (I), ultra-violet photomicro blad, 1936, 33, 36— 3S).— Analytical data, including graphs of chromosomes (II) of extraordinarily fine determinations of Ac, show that animal and vegetable structure are obtained. Distribution of (I) is identical chitins from Crangon vulgaris, Amanita muscaria, and in both halves of chromosomes. The non-absorbing Phycomyces Blakesleennus are identical. Like other segments have the properties of proteins. Digestion chitins, that from Lycoperdon gemmatum gives Ac OH with proteolytic enzymes dissolves out one of the and not HCO,H on hydrolysis. S. C. components, the chromosomes disintegrating into Irritant principle in Mintosoidece. A . Soltys discs and granules of high (I) content. and K . U jir a th (Biochem. Z., 1936, 2 8 4 , 247— 255). E. A. H. R. — Fractionation of aq. extracts of Mimosa or Neptunia Highly polymerised compounds. CIII. Ap plena leaves (4 kg.) by Hg and Pb acetates, C5H5N, plication to biology of investigations on the EtOH, and Ba(OH), yields 10 mg. of a highly irritant constitution of highly polymerised c o m p o u n d s . (as indicated by plant movements) OH-acid of high H . Sta u d in g er (Zangger-Festschr., 1934, 939— 953; O content, equiv. wt. 250, and mol. wt. 500. The Chem. Zentr., 1935, i, 3528; cf. A., 1934, 1336).— activity is destroyed on acetylation but returns on The application of earlier work to biological problems, subsequent hydrolysis. F. 0 . H. especially protein and rubber chemistry, is discussed. Digitalis. I. New principles in evaluation. Terminal groups, present in relatively small amount, B. N ie l s e n (Acta med. scand., 1935, 8 4 , 315— 354; may be very important factors in determining the Chem. Zentr., 1935, i, 3162— 3163).— A biological chemical properties of fibres. H . N. R- method, employing the toxicity of digitalis preps, for Biochemical apparatus. E. M cD o n ald (J- mice, is described. H . N. R. Franklin Inst., 1936, 221, 103— 138). W . McC. X IX (0) BIOCHEMISTRY. 535 Spectrographic analysis of biological mater ating spores, etc. may be stained and mounted in ials. G. H . Scott and P. S. W illiam s (Anat. Rec., Amann’s lacto-phenol containing aniline-blue, cotton- 1935, 64, 107— 127).— A method is described. blue, or acid fuchsin either singly or in combination, Spectra of normal and pathological tissues are shown. with or without addition of 20— 25% AcOH. De R. N. C. tailed formulm are given. P. G. M. Nephelometric determinations using the Determination of carbamide.— See this vol., 459. photo-electric cell. J. R e n a u d in (Bull. Soc. Chim. Determination of alcohol in putrefied blood and biol., 1936, 18, 301— 304).— Nephelometric biological tissues. M. N ic lo u x (Compt. rend. Soc. Biol., 1935, determinations are liable to inherent faults in the 120, 1301— 1303).— The blood or tissue is treated apparatus and errors due to the difference in size of with A g N 03 and picric acid and distilled; the dis suspended particles, and to interfering constituents tillate is treated with KOC1, Na2C03, and A g N 03-N H 3, in the media. A . L. and again distilled, the distillate being acidified and Manometer for comparative study of physio again distilled. EtOH is determined in the third logical processes. B. N. Sin g h and P. B. Ma t h u r distillate by any standard method. This process (Biochem. J., 1936, 30, 323— 325).— Direct reading of practically eliminates reducing substances, and > 99% the scale suffices when the manometer is used for com of EtOH added to the blood can be recovered. parisons. When it is used for quant, determinations R . N . C. the degree of accuracy is ± 1 -2 5 % . W . McC. Micro-determination of alcohol in putrefied p u determination in biological liquids with blood and in corpses. M. N ic lo u x (Bull. Soc. the Thompson electrode. X. T h iesse, M. V e r a in , Chim. biol., 1936, 18, 318— 351).— The material is and A. Z iegler (Bull. Soc. Chim. biol., 1936,18, 203— first .distilled with picric acid and A gN 03, then with 207).— The glass electrode (A., 1933, 367) may be K0C1 in aq. Na2C03 to remove reducing substances used. A. L. which interfere, the determination being made accord Method for testing the sense of smell and for ing to the author’s method (A., 1931, 1327). EtOH the establishment of olfactory values of odorous administered to white mice previous to killing disap substances. C. A. E lsberg, I. L e v y , and E. D. pears from the bodies in a regular manner, the rate increasing wdth rise of temp. Considerable quantities Brewer (Science, 1936, 83, 211—212). L. S. T. (0-8 g. per kg.) of EtOH are formed during the Mosaic collodion membranes as analogues of putrefaction of corpses, this being accompanied in the plasma membrane. S. C. B rooks (J. Exp. some cases by 15% of BuOH. A. L. Biol., 1935, 12, 36— 38).— “ Anion-impermeable ” and “ cation-impermeable ” membranes arranged in Micro-determination of alcohol in biological pairs on glass cells did not accumulate or exchange material. R. N. [Ha r g e r (J. Lab. Clin. Med., 1935, ions except traces of Cl'. Ch . A b s . (?j) 20, 746— 751).— EtOH is removed from tissue, blood filtrates, urine, etc. by steam distillation. Histochemical detection of phosphate con The distillate is oxidised by H 2S0 4-K 2Cr20 7, excess of glomerates in tissue. C. H kide rm an n s and H. the latter being titrated with a solution containing Wurmbacii (Z. wiss. Mikrosk., 1935, 51, 375— 378 ; FeS04 and Me-orange. Ch. A b s. (p) Chem. Zentr., 1935, i, 3574).— The material is treated successively with uranyl sulphate, H N 0 3, and Determination of small amounts of citric acid K4Fe(CN)B, and observed microscopically. in biological material. G. W. P u c h er, C. C. H. N. R. Sh erm an, and H. B. V ic k e r y (J. Biol. Chem., 1936, Choice of counterstains. H. D. M u r r a y (J. 113, 235— 245).— Citric acid (I) (0-1— 1-0 mg.) was Roy. Microscop. Soc., 1935, [iii], 55, 233— 237).— determined in CC13-C02H extracts by oxidation with The absorption spectra of a no. of dyes are examined K M n04 and Br. The pentabromoacetone produced in relation to their suitability as stains. H. D. was extracted with light petroleum and treated wdth Histological applications of tannic acid and aq. Na2S ; the colour in the aq. phase was stabilised with C5H5N and its intensity determined spectro- ferric chloride. H. T. N o rth en (Stain Tech., 1936, 11, 23— 24).— The use of tannic acid or FeCl, with a photometrically. Non-volatile ketones and keto-acids interfere if present in large amounts. Small quantities cellulose-wall stain (light-green or crystal-violet) and a nuclear lignin stain (safranine) gives clear preps, of (I) occur in saliva and erythrocytes. H . D. of plant stems superior to those stained by the usual Isolation from human tissues of easily volatile safranine-crystal-violet and other combinations. organic liquids and their identification. A. O. n P. G. M.Gettler and H. Siegel (Arch. Path., 1933,19, 208— Comparative study of dehydration [of animal 212).— Eta, C2H4C12, C3H 6C12, CC14, CC12F2, CHC13, r UJP - T - Baird (Stain Tech., 1936, 11, CS2, C6H6, and Et20 were identified. Ch . A bs. (p) o — )• whatever method of fixation is used, Spectrographic determination of phenol in loxan is the best of known dehydrating agents, tissue. G. Barac and A. L ambrechts (Bull. Soc. «greatest distortion is produced by the E tO H - Chim. biol., 1936, 18, 239— 240).— The ultra-violet CHOlg method. P. G. M. spectrum of the Et20 extract of the material after Counterstains for Davenport reduced silver defecation with CC13‘C 02H is determined. Under preparations of peripheral nerves. J. O. F oley these conditions PhOH gives a max. at 280-7 mg with (Stain Tech., 1936,11, 3— 8). P. G. M. an extinction coeff. of 2400. A. L. ,o.LaCt^ ' pheno1 preparations. W . E. Ma n e v a l Diazo-coupling reaction for detection of o- and (‘ tain Tech., 1936, 11, 9— 11).— Fungi, algae, germin p-phenols in histological technique. M. Clara 536 BRITISH CHEMICAL ABSTRACTS.— A. X I X (o) (Z. wiss. Mikrosk., 1935, 51, 316— 337 ; Chem. Zentr., Colorimetric determination of copper in bio 1935, i, 3574).— Commercial, stabilised diazo-com- logical material. E. L asausse and L. F rocrain pounds are used. H . N . R. (J. Pharm. Chim., 1936, [viii], 23, 77— 82; cf. Fleury et al., A., 1929, 784; Delepine, A., 1908, i, Detection of intravenously injected substances 511).— Org. matter is destroyed by ignition at low (especially i-3 : 4-dihydroxyphenylalanine) in red heat after addition of M g(N03)2. The residue, side epithelial cells. Detection of reducing dissolved in HC1, is freed from Fe and Ca by addition sugar-like substances in the skin of men and animals, by means of silver nitrate. F.Schaae of aq. N H 3 and aq. (NH4)2C03, and Cu is deter mined colorimetrically by Na dithiocarbamate. and W . B urckhardt (Arch. Derm. Syph., 165, 157— W . McC. 173; Chem. Zentr., 1935, ii, 3018). H . N . R. Modifications of the 2 : 2'-dipyridyl method Chemico-toxicological detection of physo- for available iron. G. O. K o h l e r, C. A. E l veh je m , stigm ine. I. M alan dru cco (Biochim. Terap. and E. B. H art (J. Biol. Chem., 1936, 113, 49— 53; sperim., 18, 242— 247 ; Chem. Zentr., 1935, i, 3020).— cf. A ., 1935, 115).— Chlorophyll and all interfering A colour reaction is described. H. N. R. pigments are pptd. by Pb(OAc)2, and the method can Colorimetric determination of morphine and be applied to green vegetables and other pigmented its derivatives. G. R izzotti (Arch. Farm, sperim., products, as well as to animal tissues. Wherever pos 1935, 60 , 545— 563).— Blood or tissue extracts are sible, a fresh and not a dried sample should be used. deproteinised by Na2W 0 4-H 2S04, the resulting clear J. N . A. fluid is treated with K 3Fe(CN)6, Na2C03, and NaCN Non-interference of sodium chloride in the at 100°, cooled, and Fe2(SO,,)3 added, and the Prussian- determination of copper and iron in biological blue developed is compared with that from suitable material. L. F ro cr ain and E. L asausse (J. Pharm. glucose standards. The method is based on reduction Chim., 1936, [viii], 23, 84— 85).— If M g(N03)2 or of K 3Fe(CN)6 by the phenolic OH of morphine and MgO is present, no loss of Fe or Cu occurs when certain of its derivatives. F. O. H. material is ignited in presence of very large excess of Extraction and determination of small NaCl. W . McC. amounts of morphine in organs. B. Z an ella Quantitative spectrographic analysis of bio (Arch. Ital. Sci. farmacol., 1, 120— 140; Chem. logical material. I. Determination of lead in Zentr., 1935, i, 3020).— An improved isolation cerebrospinal fluid. J. S. F oster, G. 0 . Lang- process is described. H . N. R. stroth, and D. R. M cR ae (Proc. Roy. Soc., .1935, Embden’s cholesterol determination. S. M iy a - A , 153, 141— 152).— This micro-method is applicable m ori (Nagoya J. Med. Sci., 1935, 8, 135— 137).— The to concns. of lx K H —2xl0-5 g. per c.c. with a pre material (2 g.) is hydrolysed with* 2 5 % aq. K O H at cision of > 15% . It is based on the fact that when 100°, the E t20 extract of the product, dried and the atoms of a sample are excited by a d.-c. spark dissolved in CHC13, is treated with Ac20 and H 2S0 4, under suitable conditions, the intensity of a Pb line and the colour measured. The vals. obtained agree oc [Pb], if [Pb] is low. L. L. B. with those from the digitonin method. Determination of small amounts of lead in Nutr. Abs. (m) biological material. H. Cheftel and M. L. Colorimetric determination of small amounts P igeaud (Ann. Falsif., 1936, 29, 76— 92; cf. A., of cholesterol in blood and other liquids of the 1933, 621; B., 1933, 170).— The dithizone (I) method organism . M. N . d e l A g u ila (Bol. Soc. quim. is substituted for the PbS colorimetric method (loc. Peru, 1935, 1, No. 3, 73— 74).— Blood is extracted cit.), which is not sufficiently sensitive. Cu etc. arc with Et.,0 after addition of EtOH (with or without removed by treatment with KCN. Fe is then liable NaOH), and cholesterol is determined by Grigaut’s to interfere by producing a brown colour -with (I), Ac20 method. Ch. Abs. (p) but this is prevented by avoiding any excess of KCh • Determination of phytic acid. L. Y o u n g (Bio- Sn does not interfere if present as SnIv. E. C. S. chem. J., 1936, 30, 252— 257).— Phytic acid (I) is Determ ination of lead.— See this vol., 443. determined by addition of excess of FeCl3, pptn. of Fe phytate at 100° in AT/6-HCl, and determination of Micro-determination of f errocyanide in muscle the excess of Fe colorimetrically with CNS'. In and urine. J. G. E d w a r d s and W . D. L angley faeces extracts (I) is pptd. as before and the ppt. (J. Biol. Chem., 1936, 112, 469— 475).— Fe(CN)6', is separated and decomposed with NaOH, and after (1— 40 mg.) is determined in tissues by hydrolysis removal of Fe(OH)3 the liberated (I) is determined with H 2S0 4, absorption of the volatilised HCN m as above. H . D. aq. NaOH, and titration with A gN 03. H. P- Detection and determination of copper in Determination of nitrate in animal tissues. organic matter by benzoinoxime. Z. Gr u zew ska M. W h e la n (J. Lab. Clin. Med., 1935, 20, 7o-> and G. R oussel (Compt. rend. Soc. Biol., 1936, 121, 757).— The ground tissue is acidified (H2S04) anc 289— 291; cf. this vol., 260).— Cu is accurately extracted first with Et20 and then with hot 1 3 • determined in rabbit liver by incineration and pptn. E t,0 is removed from the combined extract, vine from the ash with benzoinoxime in slightly alkaline is then made alkaline, and diluted. An aliquot is solution after removal of Fe. The ppt. is sol. in treated with HgCl2 to remove interfering substances CHClo, forming a green solution which serves for the and NO,'is determined in the clear liquid. Ch . A b s . (p) detection of Cu. R- N . C.