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BRITISH CHEMICAL ABSTRACTS

A -P U R E CHEMISTRY & 01 APRIL, 1928.

General, Physical, and Inorganic Chemistry. Construction of wave-length scales for spectro­ “ Nebulium” spectrum in new stars. C. T. gram s. G. B arr (Trans. Opt. Soc., 1928, 29, 22— E lv e y (Nature, 1928, 121, 453).— The discrepancy 27).— A method is described by which an approximate between the conclusions of Pike (this vol., 210) and scale of wave-lengths may be projected geometrically those of the author are ascribed to the inapplicability on to a spectrogram from a uniformly divided scale of the theory of thermal ionisation. when a number of easily recognisable lines have been A. A. E ldridge. identified. C. W . Gib b y . Nebulium and hydrogen in new stars. B. P. Gerasbiovic (Nature, 1928, 1 2 1 , 422).—A modified Use of single thermo-junctions and of echlette method of calculation leads to a density of 6 X 10"1G gratings in the far infra-red. R. M. B ijdger as permitting the co-existence of hydrogen and (J. Opt. Soc. Amer., 1927, 15, 370—373).—Methods ionised oxygen lines in the spectra of new stars. of focussing radiation of the order of 100 g on to A. A. E l d rid g e. single thermo-junctions are described whereby Life of atomic states and the intensity of the diffuse images due to aberrations in reflexion are spectral lines. I. S. B o w e n (Proc. Nat. Acad. avoided. The construction of a simple echlette Sei., 1928, 14, 30— 32; cf. A., 1927, 997).— grating from plane parallel glass strips is also described. From the previously published explanation of the R. W . L u n t . strong nebular lines as due to electron jumps from E volution of the theory of spectra. T. N egresco metastable states in oxygen and and the (J. Chim. phys., 1928, 25, 142— 153).—Historical. known highly rarefied state of the gases in nebulae, it H. F. Gillb e. is concluded that motastable states are not absolutely Relativistic interpretation of the theory of metastable, but are states with mean lives of the fine structure of spectral lines of the hydrogen order of a second or so. W . E. D o w n e y . atom. S. M ohorovkSi6 (Arh. Heiniju, 1928, 2, 6— 14).—The use of the special relativity theory is Spark potentials in nitrogen. B. Fr e y (Ann. not permissible and the extended general theory is Physik, 1928, [iv], 85, 381— 424).— The influence of not capable of accurately defining the orbits of the water vapour on the potential of the spark discharge electron around the proton. The introduction of the in nitrogen has been studied. No change in the dis­ special theory into physics is regarded as wholly charge potential is produced by the passage of a unnecessary. R. A. M orton. secondary spark when the gas is dried by liquid air. As the amount of moisture present increases, however, Intensity distribution in Fraunhofer lines. the sparking potential diminishes to a minimum M. M in n a e st (Z. Physik, 1927, 45, 610—619).— The and then increases. Since the same phenomenon distribution of intensity in the Fraunhofer lines H„ is observed when hydrogen is introduced into the and CaK has been determined. The results are nitrogen, and since, also, the effect of moisture is discussed with reference to those of von Kliibcr (A., nullified by the presence of a heated tungsten wire in 1927, 909). R. W. L u n t . the tube, it is concluded that the behaviour of water vapour is duo to dissociation into its constituent Nebulium spectrum. J. C. M cL e n n a n and R. gases. The potential lowering caused by very small R u e d y (Nature, 1928, 1 2 1 , 319).—Following a dis­ quantities of hydrogen is probably due to the high cussion of observations on nebulae; it is stated that activity of the proton in ionisation by collision. With the energy to excite the nebulium lines would be increasing quantities of hydrogen larger ions are very small if the material (oxygen) were already formed, ionisation diminishes, and the sparking ionised, and that the lines are essentially emission potential increases. If sparking potental is plotted lines, having as yet no importance in absorption against the product of pressure and length of spark- spectra. It is concluded that the oxygen which is gap, for different mixtures of nitrogen and hydrogen, responsible for the nebular lines is present as a the minimum sparking potential is lower than the molecule or molecular ion. A. A. E ldridge. minimum for the pure constituents. This appears to Origin of the nebulium spectrum. M. Saha indicate that the hydrogen proton can ionise nitrogen ^Rature, 1928, 121, 418).— A discussion of the nature better than the positive nitrogen ion, and can also of the transitions, usually prohibited, from which the ionise nitrogen better than it can ionise hydrogen. ‘ nebulium ” lines of ionised oxygen and nitrogen The influence of the electrode materials has been arise (Bowen, A., 1927, 997). A. A. E ldridge. examined. In a state of moderate dryness the 337 338 BRITISH CHEMICAL ABSTRACTS.— A. sparking potential for magnesium electrodes is some The low terms result from two different outer electron volts lower than for silver, but the reverse is the case configurations, viz., cl's2 and d8sx. They are in agree­ in well-dried gas. This behaviour is explained by ment with the theory of Hund. J. S. Ca r t e r . the formation of a layer of magnesium nitride by the Spectra of krypton and xenon in the extreme discharge in the dried gas. In the presence of a little ultra-violet. J. H. A b b ix k and H. B. D orgelo moisture, however, this is destroyed. (Z. Physik, 1928, 47, 221— 232).— Vacuum grating M. S. B u r r . spectra of krypton and xenon under various conditions Regularities in the spectrum of ionised neon. of excitation have been tabulated for the region P. K. K ichlu (Proc. Physical Soc., 192S, 40. 41— 1500— 500 A. Certain lines ascribed by Taylor (A., 45).—Hund’s theory is applied in tracing doublet 1927, 178) to krypton appear to belong to xenon. terms and intercombinations between doublets and The following ionisation potentials are deduced : quadruplets. Almost all the lines between 2500 and krypton 13-9, xenon 12-0 volts. R. A. M orton. 3800 A. have been accounted for with few dis­ Spark spectrum of silver. K. Ma j u m d a r crepancies. C. J. Sm ith ells. (Indian J. Phys., 192S, 2, 257— 266).— The known Spark spectrum of neon. H. N. R u ssell, lines in the spark spectrum of silver have been analysed K . T. Compton, and J. C. B oyce (Nature, 1928,1 2 1 , and classified with a view to a comparison with the 357).—Fifteen new lines between 462-38 and 353-01 spark spectra of copper and gold. New lines deter­ have been observed; 203 lines have now been classified mined with the vacuum grating have also been in 59 multiplets. The ionisation potential of the given in the region from 3372-65 to 1932-76 A. neon ion is 40-9±0-05 volts. A. A. E ld r id g e . M. S. B urr. Spark spectru m of sodiu m . S. F r ish [with Intensity distribution in Wood's resonance (Fr l .) A. F erchmin] (Naturwiss., 1927, 15, 507; spectrum of iodine. O. Old e n b e r g (Z. Physik, Chem. Zentr., 1927, ii, 784).— Alkali halide is placed 1927 , 45, 451— 454).— By using plates sensitised with in the capillary of a silica Geissler tube, and the tube neocyanine the terms 27— 37 (7687— 8823 A.) of the filled with hydrogen or helium under low pressure. molecular spectrum of iodine, excited by the mercury The capillary is heated while a discharge is passed and green line, have been observed; the intensities of the tube placed in a magnetic field; the intensity of these newly-observed terms have been determined. the arc spectrum of the alkali metal is reduced, and R. W . L unt. new lines, belonging to the spark spectrum of the Recombination spectra of atomic ions and metal and the arc spectrum of the halogen, appear, electrons. F. L. M oh ler (Physical Rev., 1928, [ii], the intensity increasing with that of the magnetic 31, 187— 194).— With cæsium, continuous bands field. The effects are more marked with a Paschen extending to the violet from the limit 2P r of the concave cathode. A. A. E l d r id g e . subordinate series, from the limit of the F series, and faintly beyond the P series, were observed. Spectrum of ionised sodium. K. Majumdar Potassium shows a strong band beyond the sub­ (Nature, 1928, 121 , 423).—A preliminary statement ordinate series. Intensity measurements were made. of the result of an analysis of the spectrum of ionised Intensity distribution in the line spectrum indicates sodium. The lines 5L2(M y— >M 2) have been com­ a relatively high probability of recombination into pletely, and the lines 5L2(M S— Xil/3) partly, identified. levels of high quantum number, and relatively The ionisation potential is about 47 volts, and the improbable recombination into the normal level. radiation potential 32-8 volts. A. A. E ld r id g e . A. A. E ld rid g e. Polarisation of the sodium rumpf (core). H. Influence of vapour pressure on the intensity B artels (Naturwiss., 1927, 15, 4S7— 488; Chem. and broadening of mercury resonance lines. Zentr., 1927, ii, 784).— The polarisability of the IV. Orth m ann and P. Pringsheim (Z. Physik, 1927, sodium rumpf remains unchanged up to the eleventh 46, 160— 167).— The diminution of intensity and the member of the first sodium subordinate series. broadening of the resonance lines in mercury vapour Negative polarisability certainly does not occur up to have been determined in the mercury vapour pressure the 17d term. A. A E l d r id g e . range 0-01— 7-3 mm. The effect produced by the Intensity of the lines in the principal series addition of a neon-helium mixture of 250 mm. partial of potassium. F. R asetti (Atti R . Accad. Lincei, pressure is the same as that due to the increase in 1927, [vi], 6, 503—505).— By means of the anomalous mercury vapour pressure in the above range. The dispersion method described in a previous paper results are thought to afford evidence of abnormally (A., 1927, 1118) the number of electrons per atom large values of the effective radius of mercury atoms responsible for the dispersion (w) has been determined of the order of 10~7 cm. R. W. L u n t . in the potassium series 4-S—m~P for the lines corre­ Hyperfine structure and polarisation of sponding with ?a=4,5,6,7, and 8. The corresponding l 1^ —231>1 of mercury in resonance radiation. values of n are 1-0, 9-0 X 10~3, 7-8 X l0 '4, 2 x l0 ~ 4, and A. E llett and W . A. MacN air (Physical Rev., 1928. 1-3X10-4 within 5%. 0. J. W a l k e r . [ii], 31, 180— 186; cf. MacNair and Ellett, A., 1927, Structure of the cobalt i spectrum. II. 911).—The incomplete polarisation is due to either M. A. Ca t a la n (Anal. Fis. Quim., 1927, 25, 518— 548, or both of the outer hyperfine structure lines. and Z. Physik, 1928, 47, 89— 113; cf. A., 1925, ii, A. A. E l d r id g e . 611).—The discovery of new terms has led to the Density of a luminous gas and the emission classification of more than 700 lines, so that about of light by atoms in metastable states. B. 1200 lines in the arc spectrum have now been classified. V enkatesachar (Nature, 1928, 121, 356).—The fact GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 330

that the intensity of the forbidden line 2270 A. in the n ik o v , and T. Steoozky (Z. Physik, 1927, 45 , 548— arc spectrum of mercury increases as the density of the 556).—An examination of the Aa-lines of the metals vapour in a mercury arc is diminished is evidence in calcium, scandium, titanium, vanadium, chromium, support of Bowen’s view that the low density in manganese, iron, cobalt, nickel, and copper by an nebulæ is favourable to the emission of light by improved form of Siegbahn spectrograph has revealed atoms in metastable states (A., 1927, 997). the existenco of irregularities on one side of the A. A. E ld rid g e. maximum which are associated with the A(3-line. Sputtering of metals by disruptive discharge R. W . L u n t . in a magnetic field. H. N ag ao k a and T. F uta- Polarisation of the iron /fa-radiation. H. H aas g am i (Proc. Imp. Acad. Tokyo, 1927, 3, 643— 645).— (Ann. Physik, 1928, [iv], 8 5 , 470— 482).—Within the Previous experiments on sputtering produced by limits of experimental error, in an apparatus described passing a heavy current through metals in loose in detail, no polarisation of the iron Aa-lines has contact (cf. this vol., 97) were continued in a magnetic been found for a voltage interval of 7-4— 12-6 kilovolts field of 30 kilogauss. The paths followed by the (excitation limit 7-1 kilovolts). This is not in accord­ luminous particles ejected from different metals are ance with the observation of Bishop on the molyb­ described and photographed. Particles of titanium, denum Aa-linOs (A., 1926, 1187). M. S. B u r r . chromium, and manganese follow straight paths until Spectrographic researches in the intermediate near the end of luminosity, when they fork, owing to region. J. T iiib a u d and A. Soltan (J. Phys. separation into several parts. Aluminium particles Radium, 1927, [vi], 8,484— 494; cf. A., 1927,1000).— follow curved paths at the end, when the luminous The following new rays (in A.) have been detected by intensity becomes greatest. Tungsten and molyb­ the Thibaud vacuum spectrograph (A., 1927, 803), denum follow straight paths and show sudden in which a ray of fluorescent oil covering the plates increases in luminosity. These effects are ascribed has been found unnecessary : A-rays of nitrogen to the oxidation of the particles. The magnetic 31-8, and of boron 68-0; JY-rays of tantalum 58-3 and properties of the metals are not important, since the 61-4, of tungsten 56-0 and 59-1, of platinum 48-0 and temperature is above that at which ferromagnetism 51-0, and of gold 46-8 and 49-4; O-rays of thorium ceases. C. J. Smith ells. 64-5 and 68-1. The N -rays of the heavy elements Filtration of spark lines by disruptive dis­ constitute a regular doublet due to the transition O— N iv—v, the most intense components having the charge in magnetic field. H. N agaoka and T. longest wave-lengths. The quantum of the L ii— ill F utagam i (Proc. Imp. Acad. Tokyo, 1927, 3, 647— 649).— The spectra of the disruptive discharge level of the light elements has been calculated from (preceding abstract) in the absence of a magnetic the energies measured for the A-rays and from the field show both arc and spark lines of the metal. ionisation potentials, and a rise in Moseley’s curve When a magnetic field is applied the spark lines are for this level, relative to these elements, is shown to confined mainly to the neighbourhood of the poles, exist. The deviations from the results of Dauvillier and fade towards the middle, whilst the arc lines for the absolute wave-lengths of the A-rays of carbon show little difference in intensity across the gap. and boron increase rapidly with tho wave-length and Lines which show reversal in the absence of a magnetic are explained by the variation of the refractive index field appear strongly marked when the field is applied. at the high wave-lengths. This variation, which follows the Drude-Lorentz rule, must be allowed for C. J. Sm ithells. in the determination of high wave-lengths (above Discrepancies in Moseley’s law. V . D olejsek (Z. Physik, 1927, 46, 132— 141).— It is shown that 20 A.) from Bragg’s formula. J. Gr a n t . for the homologous elements of atomic number 36, Polarisation of spectral -Y-rays. E. W ag n er 54, and 86, the value of V v/Ii is given by the empirical and P. Ott (Ann. Physik, 1928, [iv], 8 5 , 425—469).— expression a+bN+cN2+dN^, where N is the atomic The polarisation in a wave-length range of AX=0-055 number and a, b, c, d are constants. The difference A., at about 2 A., has been examined by reflexion from between the experimental value of Vsi/R and that a sodium chloride crystal at a glancing angle of 45°. calculated from the above empirical expression is The degree of polarisation is defined as the ratio of shown to be a periodic function of the atomic number. the reflexion intensity perpendicular to the cathode rays, to the reflexion intensity parallel to the cathode R . W. L u n t. y-Ray spectrography by crystalline diffrac­ rays. The degree of polarisation increases with diminishing potential, the rate increasing as tho tion . F rilley (Compt. rend., 1928, 186, 425— 427). The wave-lengths and the corresponding minimum potential is approached. The degree of quantum energies of the rays measured have been polarisation is not influenced to any great extent determined by the author’s apparatus for y-rays by the material of the anticathode. Lead, silver, from various sources, the maximum error being 3%. copper, and iron, which were investigated, gave tho Hie y-radiation obeys the Einstein photo-electric same value, 1 -40• 2, for 10-88 kilovolts. A change in the degree of polarisation, due to tho simultaneous lav\, the uPPer energy limit investigated being 617 kilovolts (for the ray 20xl0-u cm.). The A-rays appearance of approximately equally^ hard rays of radium-0 and radium-O' result from the disintegr­ characteristic of the anticathode material, was not ation of radium-jB and radium-O, respectively. observed. M* S. B urk. J. Grant. Scattering of Y-rays from gases. C. S. B a r ­ Structure of the Jfa-lines of the metals between rett (Proc. Nat. Acad. Sci., 1928, 14, 20—23). calcium and copper. N. S elja ko v, A. K ras- Monochromatic radiation from an A-ray tube with a 340 BRITISH CHEMICAL ABSTRACTS. A. molybdenum target was obtained by means of filters view (A., 1927, 706) that the hyper fine structures of strontium oxide and zirconium oxide. When such are due to very narrow multiplet combinations brought radiation was passed through carbon dioxide, the about by a nuclear moment. The magnitude of the scattered rays showed interference; no interference, mechanical nuclear impulse moment is determined however, was shown by the rays scattered from from the Zeeman effect to be 4-5 A/2—. For the first hydrogen. W . E. D o w n e y . time, Landd’s theory of fine structure in the Paschen- Back effect receives experimental confirmation. Soft Ar-ray emission and absorption spectra R. A. M orton. with tangential grating. J. T h ibau d (Nature, Zeeman effect in band spectra. R. d e L. 1928,121, 321— 322).— By using an intense electronic K ronig (Physical Rev., 1928, [ii], 31, 195— 198).— current and elements of high at. wt. as anticathode, Anomalies observed by Kemble, Mulliken, and the author has demonstrated the emission of a Crawford (A., 1927, 1119) in the intensities of the continuous spectrum from solid bodies between 15 Zeeman components in the Angstrom carbon monoxide and 250 A. The continuous background is divided bands are explained. A. A. E l d r id g e . by a succession of fine bands with abrupt edges on the short wave-length sides. A sensitive method for Stark effect for the spectra of silver, copper, revealing minute quantities of gaseous matter is thus and gold. Y. F u jio k a and S. N a k a m u r a (Sci. available. The wave-lengths of the -edges of Papers Inst. Phys. Chem. Res. Tokyo, 1927, 7, 263— carbon, nitrogen, and oxygen, respectively, are 43-5, 276).— See this vol., 2. 31-1, and 23-5 A. A. A. E ld r id g e . Ionisation potential of helium according to Absorption of X-rays in various elements. Schrodinger’s theory. H. G. Grimm (Naturwiss;, E. Jonsson (Nature, 1928, 121, 283).— A question of 1927, 15, 561; Chem. Zentr., 1927, ii, 1123).— notation. A. A. E ld r id g e . Schrodinger’s theory gives term values 76-994, 77-316, 77-345, and 77-840, corresponding with values Polarisation factor in X-ray reflexion. It. W. of 22-904, 23'226, 23-255, and 23-750 for the difference, J ames (Nature, 1928, 121, 422— 423).—James and in volts, between the energy value of the normal Firth’s determinations of the atomic scattering factor state (IjS) and the ionisation potential of singly-ionised (this vol., 225) do not appear to be affected helium. The experimental term value is 78-564. by errors arising from the degree of polarisation of A. A. E ld r id g e . the incident beam. A. A. E ld rid g e . Constitution of the solar atmosphere. S. B. Fine-structure and Zeeman effect for the N icholson and N. G. P errakis (Compt. rend., 1928, m ercu ry resonance line. M. S ch ein (Ann. Physik, 186, 492— 495).— The solar atmosphere, so far as is 1928, [iv], 85, 257— 312).— The intensity of the known at present, contains neither the extremely secondary resonance radiation of mercury vapour stable nor the extremely unstable elements \filg., shows a sharp decrease in magnetic fields varying rare gases and radioactive elements, respectively). A from 0 to 1300 gauss (corresponding with 0— 5-8 X 10 comparison of the ionisation potentials of the elements A.). The curve- obtained by plotting intensity from hydrogen to xenon with their atomic numbers against magnetic fields over the range 0— 13,000 shows that the absence of the elements concerned is gauss (0—5-Sx lO - A.) shows 5 maxima, correspond­ reproduced periodically, and that they are grouped ing with five equally spaced components approx­ at the extremities of periods usually occupied by imately 0-01 A. apart. A similar curve of the absorp­ elements of high ionisation potentials. The exceptions tion of the resonance line shows minima in exactly (helium and boron) are apparent only, but the almost the same positions as the maxima in emission. The complete absence of heavy elements is difficult to resonance curve for absorption shows no further explain. J. Gr a n t . minima above 13,000 gauss, and it is concluded that [Constitution of the solar atmosphere.] H. the effective breadth of the resonance line under the D eslandres (Compt. rend., 1928, 186, 495; cf. given experimental conditions cannot exceed 0-076 A. preceding abstract).—The. high ionisation potential Each of the five components of the absorption line is and the exceptional nature of helium recorded by the resolved in a magnetic field into a triplet. authors are explainable by the ejection of radioactive If the resonance line consists of five equidistant, substances from solar volcanoes, accompanied by equally intense, lines, the maxima in the resonance doubly-ionised helium atoms in the form of a-particlcs. curve should be in the ratios 10 : 8 : 6 : 4 : 2, whereas These combine with electrons with great force, with the observed ratios are 10 : 6-5 : 5-4 : 3-6 : 2-3- the emission of an intense spectrum. J. Gr a n t . Qualitatively, Wood’s scheme of resolution is satis­ Photo-electric and thermionic work functions factorily confirmed, but the minima of energy emission of outgassed platinum. L. A. D u B r id g e (Physical in the magnetic field show uniformly higher intensities Rev., 1928, [ii], 31, 236—243).— With monochromatic than would be expected from W ood’s scheme, assuming the Doppler effect as the solo line-broadening agency. light the final value of the photo-electric threshold is 1962 A. (6-30 volts), and that of the thermionic work The maximal absorption coefficient for a layer of function 6-35 volts. A. A. E ld r id g e . vapour 1-1 cm. long at 0-0013 mm. pressuro is 3-77. It. A. M orton. Optical determination of the thickness of Nuclear moment and Zeeman effect for bis­ photo-electrically active rubidium films. H. E. m uth. E. B a c k and S. G ou d sm it (Z. Physik, 1928, Ives and A. L. Johnsrud (J. Opt. Soc. Amer., 1927, 47, 174— 183).— A study of the Zeeman effect on 15, 374—381).—The thickness of photo-electrically bismuth lines with a strong field confirms the authors’ active films -of sodium and of rubidium deposited GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 341 on glass and on platinum surfaces has been determined current passing through the gas depends on the sense from changes in the azimuth or phase of plane polarised of the applied field, and the tension required to pro­ light incident at 45° on the film. The results indicate duce saturation is six times as great when it is carried that complete photo-electric emission is obtained from by the positive as by the negative ions. A con­ an approximately unimolecular film of rubidium. centration of oxygen of 3X10-4, or more, produced a R. W. L u n t . deformation in the current-voltage curve in the Critical primary velocities in the secondary latter, but not in the former case, indicating that electron emission of tungsten. H. E. Krkfft oxygen molecules have a strong affinity for electrons, (Physical Rev., 1928, [ii], 31, 199—214).—The curve but not for the positive ions of argon. The latter showing the number (n) of secondary electrons pro­ may probably remove an electron from the neutral duced by one primary electron as a function of the molecules of oxygen they meet. A comparison of the primary velocity, obtained with tungsten at 1250— deformed curve With that obtained for positive 1450° Abs. and velocities of 10— 700 volts, shows a ions indicates that the mean mobility of the negative maximum at 15-3 volts, a minimum at 20 volts, 18 ion is a function of the applied field. At low tensions breaks between 25 and 600 volts, and a maximum at they are similar, but as the tension increases the 630 volts. The effect of adsorption of gas is investig­ deformed curve approaches saturation more rapidly. ated. A. A. E l d r id g e . The deformation decreases with the (atmospheric) Restored electron theory of metals and therm­ pressure. These results are in agreement with J. J. Thomson’s probability theory of ionisation. ionic formulae. R. H. E ow ler (Proc. Roy. Soc., 1928, A , 117, 549— 552).—The electron theory of J. Gr a n t . metallic conduction, as re-instated by Sommerfeld Existence of sub-electronic charges. F. E k r e n - (Naturwiss., 1927,15,825), is applied to the calculation h aft (Z. Physik, 1927, 45, 577— 560).— A review of of the density of evaporated electrons in equilibrium recent work which indicates the existence of sub- with the heated metal. A consideration of the electronic charges on small metallic particles and on equilibrium state of an assembly consisting of a oil droplets. R. W. L u n t . heated metal and an atmosphere of free electrons Errors in Ehrenhaft's technique for the detec­ shows that the vapour pressure has twice the value tion of sub-electronic charges. E. W asser (Z. commonly accepted, owing to the fact that each Physik, 1927, 45, 561— 587).— The probable errors electron has two orientations. This result is applied in Ehrenhaft’s technique are analysed at length. to the theory of thermionic emission, and gives values R. W . L u n t . in good agreement with the best determinations for Magnetic moments of the cupric ion. (Mlle .) the metals tungsten, molybdenum, tantalum, and P. Collet and F . B irch (Compt. rend., 1928, 186, platinum in a very pure state. L. L. B ircum shaw . 499—501).—The work of Cabrera (A., 1920, 7) has Extraction of electrons from cold conductors shown that a study of the thermal variation of the in intense electric fields. 0. W. R ichardson coefficient of magnetisation is necessary for the (Proc. Roy. Soc., 1928, A , 117, 719— 730).—The determination of the Curie constant. The magnetic experimental results of Gossling and of Millikan and moments of the cupric ion in solids and in their Eyring (cf. A., 1926, 448, 219) are discussed, and a solutions have thus been determined for temperature theory is developed to account for the phenomenon intervals for which the relation is linear. A dominant of an electron current which is independent of the moment of 10 magnetons was found, and also values temperature of the emitting substance, but is a of 9 and 9-6 magnetons, but the last may be due to a continuous function of the field intensity. The mixture of carriers of moments of 9 and 10, produced, sharpness of the photo-electric effect at a metallic e.g., by the formation of complex ions in solutions surface is explained, and, by treating the attraction of cuprous chloride at various temperatures. of an electron by its mirror image in a conductor as a J. Gr a n t . Schrödinger wave problem, a formula is derived for the Activation of hydrogen by electric discharge. field currents from cold conductors which agrees with R. W . L u nt (Nature, 1928, 121, 357).— A criticism the experimental data. The theory indicates that of Glockler’s hypothesis (this vol., 140) concerning in the neighbourhood of a nucleus, electrons are Elliott’s observations (A., 1927, 187). discontinuously coming into space, and are generated A. A. E ld rid g e. at a rate proportional to (¡I4)3'2. The experimental Active nitrogen. E. J. B. W il l e y (Nature, evidence does not support the view that the localis­ 1928, 121, 355).—In part, polemical against Lewis ation of the discharge in restricted areas is due to these (this vol., 258). Between 1 mm. and 10 mm. pressure areas being sharp protuberances. It is considered the process of decay of the after-glow is very complex, that the localisation must be attributed to the although bimoleeular with respect to the active possession by different parts of the surface of a nitrogen. Probably the luminosity and the chemical different constitution. L. L. B ircumshaw. activity are steps in an involved deactivation process, Affinity of oxygen for electrons. M. A. Da the first stage consisting of a ternary collision between Silva (Compt. rend., 1928, 186, 583—584).—The two atoms and a molecule. Objection is raised to author’s determinations of the ionisation of pure Lewis’ theory of the formation of ammonia from argon (A., 1927, 809) have been extended to the case atomic nitrogen and atomic hydrogen. of a thin layer of gas on the surface of a plate of the A. A. E ld rid g e. measuring condenser, the other plate, 5 cm. away, New effect in the electric discharge. I. R. being connected to a quadrant electrometer. The M erton (Proc. Roy. Soc., 1928, A , 117, 542—549).— 342 BRITISH CHEMICAL ABSTRACTS.— A.

A peculiar type of striated discharge has been observed what lower values are obtained in argon and in in vacuum tubes containing helium. The discharge hydrogen. R. W. Lhnt. tubes were provided with tubes of 2 cm. bore, 20— 40 Diffusion coefficients of flame gas ions in cm. long, in place of the usual capillary. Carbon relation to temperature. H. B uckert (Ann. electrodes were used, and the phenomena were best Physik, 1928, [iv], 85, 03— 80).— The diffusion observed at a pressure of 30—40 mm. A state is coefficient D has been measured for positive and reached at which the helium tube, when excited by negative ions from hydrogen, coal gas, and carbon the uncondensed discharge from a high-tension monoxide flames over the temperature range 20— transformer fed with alternating current at 50 oycles, 120°, and in electrical fields ranging from 0 to 16 volts, shows an almost uniform green glow. By introducing arid also for ions varying in age from 3 to 6-6 sec. a condenser and spark-gap into the circuit, it is For hydrogen D is almost constant at 0-00315 for possible to start a disturbance which gives rise to a the positive ion and 0-0037 for the negative ion from new type of disc discharge, which is described in detail. 20° to 50° ; the values thereafter show a steady increase The spectrum of the discs differs from that of the to 0-0068 arid 0-0079, respectively, at or about 120°. green glow in that the helium lines, which arc feeble Both carbon monoxide and coal gas exhibit similar in the green glow, and the comet bands are very curves, except that in the former the diffusion bright in the discs, whilst the Swan bands can be seen coefficients of positive and negative ions are almost only in the green glow, being absent from the discs. identical. The mean value of D for coal gas at 100° On examination of the discs by means of a beam of is more than twice that for hydrogen and thrice that sunlight it was found that the sunlight is strongly for carbon monoxide. Determinations of D in an scattered in the neighbourhood of the discs. The electric field show that the values at 16 volts for scattering is probably due to very small particles of both hydrogen and coal gas are about half those at carbon, and the discs seem to be surrounded by an zero voltage, the negative ions showing consistently envelope of these scattering particles. An examin­ higher values than the positive ions; in carbon ation of the discharge made by two stroboscopic monoxide the twro ions behave alike and the effect methods showed that, besides the stationary discs, of the field is less marked. there are rapidly moving striations throughout the The ageing of ions from 3 to 6 sec. brings about tube (cf. Aston, ibid., 1921, A , 98, 50). The disc reductions in D to 80, 60, and 40% of the original discharge is entirely unaffected by weak magnetic values for hydrogen, coal gas, and carbon monoxide, fields, unlike Langmuir’s streamer discharge (Science, respectively. The values of D indicate large ion 1924, 60, 392), which in some respects it resembles. complexes and the discontinuity at 50° shows that Investigations with unidirectional discharges are they are then split up into smaller aggregates. The described, and the mechanism of the disc discharge is complex ions in carbon monoxide resist disruption, discussed in the light of the results obtained. It is showing that since no water is formed in the com­ probably closely related to the migration of carbon bustion, carbon dioxide must be more strongly compounds. A similar type of discharge has also attached than water to ions. Lauster’s data (Z. been observed, although much less clearly, in a neon Physik, 1920, 3, 396) are in agreement with these tube provided with carbon electrodes, but experiments views. R. A. M orton. with a large number of mixtures of gases gave negative Scattering of canal rays in hydrogen. G. P. results. It is suggested that the phenomenon of T homson (Z. Physik, 1927, 46, 93— 105).— The “ ball lightning ” may be an example of a single disc scattering of hydrogen canal rays in hydrogen has descending from a charged cloud to earth. been determined by a thermopile method; the results L . .L. B ir c u m sh a w . agree with those obtained by the photographic High-frequency discharges in gases. S. P. method, which is thus established. R. W . Lhnt. McCallum (Nature, 1928, 121, 353). Magnetic analysis of a luminous canal-ray Electrical discharges in gases at low pres­ beam in hydrogen. C. J. B rasefield (Physical sures. I. L an g m u ir (Z. Physik, 1927, 46, 271— Rev., 1928, [ii], 31, 215— 219).— A luminous canal- 299).—An analysis is advanced of the motion of ions ray beam in hydrogen is separated by means of a and electrons in gases at pressures such that the transverse magnetic field into four component parts : mean free path is of the order of 1 cm. with particular neutral particles, and the charged ions H2+, H +, and reference to discharges between a straight wire emitting Hi., (ions which passed through the electric field electrons surrounded by a coaxial cylindrical anode. as H2+, but dissociated into H + before reaching the Methods of determining the velocity distribution of magnetic field). Measurements of the variation of the ions and electrons are described, and it has been the intensity of the H2+ and HLj beams with the shown that in mercury vapour the Maxwellian pressure lead to a value for the free path for dissoci­ distribution obtains. The “ electron temperature ” ation of a 1000-volt H2+ ion into H.t_, of 0-37 cm. at corresponding with the observed velocity distribution 0-01 mm., about 0-25 of the value, calculated from is not a function of the current, and it is therefore the kinetic theory, for the neutral molecule. ooneluded that the ions and electrons are not in A. A. E l d r id g e . thermal equilibrium with the gas molecules, the Theory of the Faraday effect in gases. R. d e L. temperature of which in such discharges is but little K ronig (Z. Physik, 1927, 45, 508— 511).—The higher than that of the walls of the containing vessel. author’s theory of the Kerr effect in gases has been “ Electron temperatures” up to 80,000° have been extended to an analysis of the Faraday effect. observed in discharges in mercury vapour; some­ R. W . Lhnt. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 343

Theory of the Kerr effect in gases. R. de L. «-particle, a theory is developed whereby values of K bonig (Z. Physik, 1927, 45, 458— 470).— Mathe­ the kinetic energy of the emitted a-particle may be matical. R. W . Lunt. calculated from the magnetic moments of the nucleus and of the a-particle and from the nuclear charge. Density, compressibility, and at. wt. of neon. Values calculated in this way are in fairly good G. P. B a x t e r and H. W . Starkweather (Proc. Nat. quantitative agreement with experiment for a large Acad. Sci., 1928, 14, 50— 57; cf. A., 1927, 194).— number of radioactive changes. R. W. L u n t . Crude neon was subjected to exhaustive chemical purification followed by fractional adsorption. The Protoactinium as a radioactive and chemical normal density of neon is found to be 0-89990 and elem ent. O. H a h n (Sitzungsber. Preuss. Akad. the at. wt. calculated therefrom 20-1S2. Wiss. Berlin, 1927, 275— 283).—New determinations W. E. D o w n e y . of the period of protoactinium have been carried out Density, compressibility, and at. wt. of argon. by Walling by measuring the rate of growth of the G. P. B a x t e r and H. W. Starkweather (Proc. Nat. element in uranium originally carefully freed from it Acad. Sci., 1928,14, 57—63; cf. preceding abstract). (cf. von Grosse, this vol., 259). A quantitative —The normal density of argon is found to bo 1-78364 examination of the amount formed has been made by and the at. wt. 39-943. The conventional method of using its isotope, uranium-Z, as a radioactive indicator. calculating the deviation from Boyle’s law makes the The period found is 20,000 years with a possible error assumption that the value of PV for one atmosphere of ±10%- The different views as to the origin and is correct. A more rational method is to find the at. wt. of protoactinium are discussed. Protoactinium best straight line to represent the observed values of in a suitable quantity in a pure state would form a some simple function of the density plotted against valuable source of actinium. It would also afford a the pressure and then to extrapolate to zero pressure. means of studying the special chemical properties This method of distributing the errors produces small of the elements of atomic number 91 in relation to differences between the calculated and observed those of the lower members of the same group, values of the densities at different pressures. The niobium and tantalum, and of the neighbouring effect on the calculated at. wt. is always less than elements, uranium and thorium. Protoactinium is 0-001 unit, although fortuitously the third decimal also interesting from the fact that elements of odd place is affected in the case of neon and argon. The atomic number, especially in the last horizontal values calculated by this method are: oxygen series of the periodic table, are comparatively rare. 16-000, nitrogen 14-008, neon 20-183, argon 39-944. M. S. B u r r . The value of the limiting density of oxygen is 1-42764, Charge of a-particles emitted per sec. by 1 g. which yields as the limiting value of molal volume of radium. H. J edrzejovski (Ann. Physique, 22-4146 litres (<7=980-616). W . E. D o w n e y . 1928, fx], 9, 128— 185).— A more detailed account of work already published (A., 1927, 710). At. wt. of titanium. III. Analysis of titan­ Recoil [3-particles from thorium-/?. K. D onat ium tetrabromide. G. P. B a x te r and A. Q. and K . P hilipp (Z. Physik, 1927, 45, 512— 521).— B utler (J. Amer. Chem. Soc., 1928, 50, 408— 415).— Using a modification of the technique of Barton, the The above analysis gives 47-90 (A g= 107-88) as the recoil ¡3-particles from thorium-1? have been investig­ at. wt. of titanium, in agreement with previous ated. The results are in agreement with those of results (cf. A., 1927, 86). S. K . T w e e d y . Barton on radium-I?. R. W. L u n t . At. w t. of copper. R. R u e r (Z. anorg. Chem., Retardation of ¡3-rays by matter. J. D’E spine 1928,169, 251— 256).—The amount of air taken up by (J. Phys. Radium, 1927, [vi], 8, 502— 507).— The copper under the conditions under which it was values of the retardation of [3-rays by aluminium, weighed in the determination of the at. wt. (A., copper, silver, or gold, as determined with an accuracy 1926, 1075) has been found by the method previously of 10% from the magnetic spectra of some of the described (A., 1927, 1134) to be 0-00102 g./100 g. principal groups of [3-rays from thorium-2? and Taking this into account, the at. wt. becomes radium-2?, have been compared with the results of 63-544±0-003. ' R. Cuthill. other workers. Bohr’s formula for the expression of this retardation gives a curve having the same Rare earths. XXVI. Purification and at. wt. shape as that derived from the experimental results, of erbium. A. E. Boss with B. S. H opkins (J. although the individual retardations are higher. Amer. Chem. Soc., 1928, 50, 298— 300).—The at. wt. of erbium as determined by the ratio of erbium Some previous results (A., 1926, 332) are revised. J. G ran t. chloride to silver (107-88) is 167-64 (cf. Hofmann, A., Study of atomic particles with the point- 1910, ii, 1073). Erbium material yielding a constant at. wt. for the element may be obtained from the counter. W. B othe and H. Fr a n z (Naturwiss., 1927, 15, 445; Chem. Zentr., 1927, ii, 780).— By erbium—yttrium material from gadolinite by fraction­ using a very pure polonium preparation as source of ation by the nitrate fusion method or by fractional a-rays, atomic particles can be detected not only with precipitation with sodium nitrite. S. K. T w e e d y . the Geiger point-counter, but also by the absorption The Bohr magneton and radioactivity. D. curve. Of the elements examined—boron, carbon, E nskog (Z. Physik, 1927, 45, 852— 868).— By nitrogen, oxygen, fluorine, sodium, magnesium, adopting the view that magnetic forces are responsible aluminium, silicon, phosphorus, calcium, and copper— for the attraction between an a-particle and the only boron, nitrogen, magnesium, and aluminium nucleus immediately previously to the emission of an clearly gave particles, the range in air being > 20, 16, 344 BRITISH CHEMICAL ABSTRACTS.— A.

13, and 16 cm. in air at 15°, respectively. Paraffin ii, 1121).— The mass 1-008 of the hydrogen atom is gave hydrogen particles of range 15 cm. regarded as that of the nucleus (1) plus that of 16 A. A. E l d r id g e . electrons (0-008), the latter mass being distributed in Validity of Geiger’s counter for (3-particles a spherical shell as radiation energy. and the (3-particle emission from radium-JS and A. A. E l d r id g e . radium-7). N. R ie h l (Z. Physik, 1928, 4 6 , 478— Scheme [for the prediction of the atomic 505).— The validity of Geiger’s counter for (3-particles masses] of isotopes. G. B e ck (Z. Physik, 1928, has been examined and it has been shown that for 47, 407— 416).— Theoretical. Aston’s results on particles of velocities 0-70— 0-94c a counter chamber isotopes are arranged in a tabular scheme and used pressure of 2-5 atm. should be used for quantitative to predict, by the regularities observed, other as yet work; the true number of particles is not obtained unobserved isotopes. It is further concluded that at pressures less than 1150 mm. The absorption there are arrest points in the building up of the in argon, as with a-particles, is less than that in air various atomic nuclei. W. E. D ow ney. at the same pressure. (3-Particles from radium:D, Quantum theory of the electron. P. A. M. 0-34— 0-4c, are completely absorbed in air at 7 mm. D ira c (Proc. Roy. Soc., 1928, A , 1 1 7 , 610— 624).— The ratio of the number of (3-particles emitted by The assignment to each electron of a spin and a radium-i? to the number of atoms disintegrated has magnetic moment, in order to make the quantum been shown to be not less than 1-2. Inconclusive results theory, when applied to the problem of the structure have been obtained with radium-/). R. W. Lunt. of the atom, agree with observation, is shown to be Thermo-dissociation of atom-nuclei. S. unnecessary. Agreement with experiment can be Suzu k i (Proc. Imp. Acad. Tokyo, 1927, 3 , 650— obtained without arbitrary assumptions by the 654).— On the assumption that radium exists in correct relativistic application of quantum mechanics thermal equilibrium with its disintegration products, to the point-charge electron. The Hamiltonian the heat of reaction calculated from the kinetic function on which the present theory is based is energy of an a-particle being —1-1 xlO 11 g.-cal., linear in energy and momentum, and leads to an log0^/(1 -.r 2) ,p=2-41 X 10w/T+2-51ogT-f-0-3S7. The explanation of all duplexity phenomena without temperature Tc at which the maximum degree of further assumption. The spinning electron model dissociation should occur is given by rf(2-4 X1010/ is, however, justifiable for many purposes, at least iP-f-2-5 log T )ld T = 0, whence Tc—1010 degrees. The as a first approximation. Its most important amount of radium should therefore decrease up to failure seems to be that the magnitude of the resultant 1010 degrees, but decompose into radon at higher orbital angular momentum of an electron moving in temperatures. Unless x2/(l—x2). p > 1027'8 atm. an orbit in a central field of force is not a constant, as no equilibrium can exist, and no observable change in the model leads one to expect. L. L. Bircumshaw. the degree of dissociation would be expected at the Quantum theory of homopolar valencies. F. b. p. of radium under a few thousand atmospheres London (Z. Physik, 1928, 46, 455— 477).— It is pressure. Since the heat of reaction is of the same shown that homopolar valencies calculated from the order for all the heavy elements, it is assumed that symmetry characteristics of Schrodinger’s character­ their disintegration into hydrogen, helium, and istic function are in agreement with the periodic protons would take place at about 1010 degrees. classification, and it is thought that they may be C. J. Sm ith ells. interpreted as quantum mechanical resonance effects. Internuclear reactions. B. Cabrera (Compt. R. W. L u n t . rend., 1928, 18 6 , 501— 503).— The theory (this vol., Explanation of some properties of spectra from 216) that the Aston packing fraction is a measure of the quantum mechanics of the spinning electron. the internal energy of the system and gives an indic­ J. von Neumann and E. W ig n e r (Z. Physik. 1928, ation of the evolution of atomic nuclei, is developed, 47, 203— 220).— The kinematic properties of any and extended to internuclear reactions. The theory system of spinning electrons (without further assump­ requires an emission of energyequivalentto 15-2 x 10-27 tions) have been deduced with the aid of the Dirac- g. during the disintegration of nitrogen by bombard­ Jordan transformation theory. R. A. M o rto n . ment with a-particles with the formation of a proton and an isotope of oxygen (O17). This probably takes Infra-red spectra of hydrogen halides accord­ the form of a radiation hitherto unnoticed. The ing to Schrodinger’s theory. M. Czerny (Z. theory is also applied to the evolution of elements in Physik, 1927, 4 5 , 476— 483).— An analysis of the the cosmos. J. Gr a n t . available data for the infra-red spectra of hydrogen halides by Schrodinger’s theory leads to values of the Relative masses of a proton and an electron. molecular constant somewhat different from those J. C. Ghosh (Naturwiss., 1927, 15, 445; Chem. derived from the quantum theory. R. W. L u n t. Zentr., 1927, ii, 779).— The observed relations are derived on the supposition that if two light quanta Refraction quotient of the De Broglie waves of frequency v impinge, a part E of the energy is of electrons. O. K le m p e re r (Z. Physik, 1928, 47 , converted into matter in the form of a proton and an 417— 421).— It is shown that there is a limiting angle electron, whilst the remainder is converted into for the total reflexion of cathode rays on the theory heat-motion. Each photon is transformed into a of wave mechanics. W. E. D ow ney. hohlraum. A. A. E ld rid g e . Theory of collision processes in hydrogen. Structure of the hydrogen atom. H. G hosh W. Elsasser (Z. Physik, 1927, 45 , 522— 538).— (Naturwiss., 1927,15, 506— 507; Chem. Zentr., 1927, Mathematical. R. W. L u n t. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 345

Theory of the collisions between atoms and Durham Phil. Soc., 1926— 1927, 7, 172— 181).— See slow electrons. (Frl.) L. M en sing (Z. Physik, A., 1927, 216. 1927, 45, 603— 609).— The collision process between Measurement of residual rays in the visible atoms or slow electrons has been analysed by wave region of the spectrum. G. Joos (Physikal. Z., mechanics; comparisons of the predictions of theory 1928, 29, 117— 118).— The absorption spectra of with experiment show that an atom cannot beregarded potassium chromium selenate crystals, and of other as a charged shell. R. W . Lunt. chromium double salts of the alum type, disclose Minimum proper time and its applications the existence of sequences of lines separated by about (1) to the number of the chemical elements, (2) 43 cm.'1 and containing as many as 11 terms. The to some uncertainty relations. H. T. F l in t and frequency difference corresponds with 232 g, a wave­ 0 . W. R ichardson (Proc. Roy. Soc., 1928, A, 117, length in the range of residual rays. R. A. Morton. 637— 649).— It has been shown that the proper time Absorption spectra of potassium ferro- and of a particle has a minimum value h/m0c2, where m is ferri-cyanides. F. H. Getm an (J. Physical Chem., the rest mass. This conclusion is now reached by a 1928, 32, 187— 191; A., 1921, ii, 287).—A further, method which is independent of the assumptions as more refined, spectroscopic examination of 0-0005J4- to the metrics of space and time, made previously. solutions of potassium ferro- and ferri-cyanides has An upper limit [?i/(?i-f 1)]*C is placed on the velocity been made. The absorption spectra differ markedly of an electron in an atom in an orbit of total quantum from each other. The molecular extinction co­ number n. This involves an upper limit 97 for the efficients of the compounds designated by Briggs atomic number of any chemical element, and also an (J.C.S., 1911, 99, 1019) as the a- and ¡3-ferrocyanides upper limit for the quantum number of an intra­ of potassium are identical, supporting the view of nuclear orbit. The limit is a function of the atomic Bennett (A., 1917, i, 449) that these salts are not number of the nucelus. L. L. B ircum sh aw . isomeric. The corresponding coefficients for the st­ [Use of Winther's gauze in] spectrophotometry. and 3-ferricyanides are different from each other, G. L andsberg (Z. Physik, 1927, 46, 106— 108).— however, confirming the previous finding of the The use of a blackened gauze as a constant extinction author (loc. cit.) and the view of Locke and Edwards filter (Winther, A., 1923, ii, 519) has been examined (A., 1899, i, 407). An apparatus for producing sparks in the visible region and up to 2026 A. The extinc­ under water between tungsten electrodes to detect tion of such gauzes is constant within 1 % in the range narrow or weak absorption bands is described. L. S. T h e o b a ld . examined. R. W. L u n t . Spectrochemical researches on some por­ Graphic representation of colours. S. R osoh phyrins and some compounds of haemato- (Physikal. Z., 1928, 29, 83— 91).— Every colour can porphyrin w ith iron. E. Bois (Can. Chem. Met., be defined by means of its “ relative brightness,” the 1927, 11, 261— 264).— The absorption spectra are relative width of its spectrum, and the mean wave­ considered to provide a new basis for the explanation length. An apparatus is described whereby any of molecular structure by spectra. The fluorescence colour may be compared by synthesis in terms of spectrum is the most sensitive reaction for the these three co-ordinates. W. E. D o w n e y . detection of porphyrin and blood-spots. Synthetic Characteristic of the hydrogen molecule in hsematm shows a stage in the transformation of foods Chemical A bstracts. the normal state. Y. S ug iu r a (Z. Physik, 1927, into blood. 45, 481 192).—Mathematical. R. W. L u n t . Spectrographic study of complex cyanogen Quantum levels and resulting constants of the compounds of iron. I, II. L. Cambi and L. Szego (Gazzetta, 1928, 58, 64— 71, 71— 76).— See hydrogen molecule. R. T. B irge (Proc. Nat. Acad, Sci., 1928, 14, 12— 19).— Theoretical. It is A., 1927, 809, 916. contended that the discrepancy between the observed Optically excited iodine bands with alternate value of the ionisation potential of hydrogen and the missing lines. R. W. W ood and F. W. L oomis theoretical value as calculated from Richardson’s (Nature, 1928,121, 283).—A study of the fluorescence analysis of the band spectrum (A., 1927, 916) is only bands which develop around the “ fundamental ” apparent. W. E. D o w n e y . doublets when iodine is excited, in presence of helium, by the green mercury line, shows that only those Hydrogen molecule. 0. W. R ichardson alternate lines occur in thespectrum of the fluorescence (Nature, 1928, 121, 320).—A discussion (cf. Birge, for which in' is even. Thus the rotational quantum this vol., 216). It now appears that the suspected number of the excited iodine molecules can change coincidence of the author’s 23P level with Dieke and only by even numbers during these collisions of the Hopfield’s C level is accidental; the case for the second kind. The result, although incomprehensible coincidence of the author’s 2bS level with their B on the classical Bohr-Lenz theory, affords direct level is much more convincing. An examination of evidence in support of the theories of Hund and Werner’s plates shows that the 21S states are formed, Dennison. A. A. E ldridge. and that they pass with difficulty into the lbS state; apparently the excitation energy is discharged by Band fluorescence of mercury vapour. P. dissociation of the hydrogen molecules on collision. Pringsheim and A. T erenin (Z. Physik, 1928, 47, A. A. E ldridge. 330—343).— Mercury vapour fluoresces under the Residual effect in the actinic absorption of influence of an uncooled mercury lamp or of an chlorine. W. T a ylo r and A . E lliott (Proc. aluminium spark. The intensity of the fluorescence 346 BRITISH CHEMICAL ABSTRACTS.— A. excited by a mercury lamp is not a quadratic function means of an optical rotating-wheel device. For of the intensity of the incident light. It increases, simple fluorescence the exponential decrease in lumin­ at first, very strongly with increasing thickness of escence after instantaneousillumination was confirmed. mercury vapour and then slowly. At small thick­ The mean lives (in 101 sec.) of crystalline uranyl nesses the effect of indifferent gases is very marked. sulphate and nitrate were 2-5 and 6-1, respective^. Hydrogen and oxygen weaken the effect. From the Solutions of the former in pure sulphuric acid gave effect of hydrogen it is concluded that the duration times and fluorescing powers of the same order as the of light emission has an upper limit of 10~3 sec. solid salt but slightly lower, and decreasing when the Parallel with the visible fluorescence there occurs an concentration or temperature was raised, or when emission of the line at 2537 A. W . E. D o w n ey. water was added. J. Grant. Absorption of ultra-violet light by dextrose, Fluorescence of mercury-inert gas bands. O. lsevulose, and lactose. L. K w ie c in s k i and L. O lden berg (Z. Physik, 1928, 47, 184— 202).— The M a h c h lew ski (Bull. Acad. Polonaise, 1927, A , question whether atoms can be excited by the joint 379—394).—Contrary to the statements of Purvis action of collisions and irradiation, can be tested (J.C.S., 1923, 123, 2515) and Niederhoff (A., 1927, indirectly by considering the reverse process, viz., 396), pure preparations of dextrose and lactose show the distribution of energy of excitation between no selective absorption in the ultra-violet. Even kinetic energy and emission. Investigation of the after several crystallisations d-lajvulose shows a band fluorescence spectrum of mercury vapour in the at about 2800 A. It is not certain, however, that all presence of helium or neon at atmospheric pressure traces of impurity are removed by crystallisation and discloses a range of continuous emission on both sides this particular result is not at present regarded as of the resonance line, extending from 2519 to 2570 A. conclusive.

indicating the formula (N02)3C-0-N0. The element­ —Tho crystal structure of p-nitrotoluene has been ary cell of tetramethylmethane has an edge of 12-48 A., oxamined by the Hull powder method and also by and contains 8 molecules; this molecule also has the Laue method. The unit cell appears to be made trigonal symmetry. The molecular constitution up of 8 asymmetric molecules and the edges of the cell cannot bo determined crystallographically. For have the following dimensions: a=10T, 6=11-18, trigonal triphcnylcarbinol the axes area 17-9,c 12-5 A.; and c=12-3 A. The crystal structure is the simple edge of unit cell containing 3 mols., 11-1 A. Corre­ orthorhombic lattice r o in the holohedral class and sponding values for triphenylbromomethane are belongs to the space-group Q}, (2Di— 1). Solid 14-05, 22-0, 10-S A., respectively. The probable p-nitrotoluene has d 1-305. M. S. B u r r . space-groups arc discussed. A. A. E ld r id g e . Preparation of large single crystals. H. C. Structure and dimensions of the ethane mole­ R am sperger and E. H. M elvin (J. Opt. Soc. Amer., cule. J. K. M orse (Proc. Nat. Acad. Sci., 1928, 1927,15, 359— 363).— The preparation of largo single 1 4 , 37—41).—Theoretical. A model of tho ethane crystals of substances of m. p. up to 1500° is described. molecule is described. W. E. D o w n e y . The essential conditions are : (1) a containing vessel Lattice structure of ethane. J. K. M orse sufficiently thin to yield under the strains produced (Proc. Nat. Acad. Sci., 1928, 14, 40—45; cf. preced­ by tho cooling crystal (pure platinum foil 0-025 mm. ing abstract).—The X-ray diffraction effects as calcu­ thick is satisfactory); (2) the formation of an initial lated from tho model of tho ethane molecule are in crystal at tho base of tho dish; (3) the temperature good agreement with those determined experimentally. isotherms should be nearly horizontal to prevent W . E. D o w n e y . convection currents; (4) the cooling must be suffi­ Crystal structure of iodoform. J. F. W ood ciently slow to remove all strains in the crystals. (Proc. Durham Phil. Soc., 1927, 7, 168— 171).— Lauc A furnace suitable for such operations is described and rotation photographs show the iodoform molecule together with a method of controlling the temperature. to be a tetrahedron in shape. The carbon atom is Single crystals of about 1 cm. edge of lithium fluoride, inside and tho hydrogen and iodine atoms are at the sodium chloride, sodium nitrate, and mercuric bromide corners. The line joining the hydrogen and carbon have been produced in this way. Tho optical proper­ atoms is the trigonal axis of the molecule. The unit ties of these crystals are under examination. cell contains 2 molecules. W. E. D o w n e y . R . W . L u n t . Structure of pentaerythritol. H. M a r k and K . Magnetic properties of single crystals of zinc W eissenberg (Z. Krist., 1927, 65, 499— 500; Ohein. and cadmium. J. C. M cL e n n a n , R . R u e d y , and Zentr., 1927, ii, 1537).—The enantiomorphism demon­ (Miss) E. Cohen (Nature, 1928, 1 2 1 , 351).— Crystals strated by Westenbrink and van Mello (ibid., 6 4 ,548) of zinc and cadmium wero obtained by Bridgman’s is not at variance with the pyramidal configuration of method, and tho magnetic susceptibility was deter­ the crystal molecule demonstrated by the authors. mined for every 15° on rotation, correction being A. A. E ld r id g e . applied for tho iron oontent. For zinc, the specific Pyro- and piezo-electricity in pentaerythritol. susceptibility in a direction parallel or perpendicular H. M a r k and K. W eissenberg (Z. Physik, 1928, 47, to the principal axis of the crystal is —0-183 X 10~® or 301).— The fact that pyro-electricity has been detected —0-147x10'°, respectively,; for cadmium, the corre­ in pentaerythritol is of importance in determining sponding values are —0-276x10'° and —0-169x10'°. the crystal structure (cf. preceding abstract). A. A. E l d r id g e . It. A. M orton. Relation of specific heat to ferromagnetism. A shw orth Polarity and piezo-electric excitation. A. H e t- J. R. (Nature, 1928, 121, 323).— The temperature coefficient of resistance and the thermo­ tich and A. S ch eed e (Z. Physik, 1927,4 6 , 147— 148). —Arguments are advanced claiming to invalidate the electric power of ferromagnetic substances are abnormal suggestion of Mark and Weissenberg (Z. Krist., 1927, below the critical temperature; the true specific heat 65, 435) that the piezo-electric excitation of penta­ rises to a high value (Ge) at the critical temperature, and immediately above this temperature there is an erythritol affords evidence of polarity in the direc­ abrupt change (AC) to a lower value. If m and n tion of the principal axis. R . W. L u n t. arc the numbers of atoms of at. wt. A in the molecule Symmetry of crystals of pentaerythritol. H. below and above the critical temperature, respectively, S eifert (Sitzungsber. Preuss. Akad. Wiss. Berlin, 1927, niaCe=5naAC. Further, ?iACJp=278R'/02, where 289—293).—As a result of crystallographic inves­ I 0 is the maximum intensity of magnetisation, It' the tigation pentaerythritol has been shown to belong to reciprocal of Curie’s constant, J Joulo’s equivalent, the symmetry class Si . Only the old tetrahedral and p the density of the material. Heusler’s alloy, model of the pentaerythritol molecule can be recon­ like iron, cobalt, nickel, and magnetite, satisfies ciled with this class, and not Weissenberg’s pyramidal these and other energy relations. model (A., 1926, 934). On the basis of the results of A. A. E l d r id g e. X-ray analysis the origin of the optical anomalies Grating theory of electrolytic conduction in of pentaerythritol is discussed. This compound is crystals. A. S m e k a l (Z. Physik, 1927, 45, 869— apparently the first chemically pure substance with 877).—Braunbek’s theory of the mechanism of such anomalies which has been crystallographically electrolytic conduction in crystals (A., 1927, 1016) is described. M.S. B urr. held to be unsound and the agreement with experi­ Crystal structure of p-nitrotoluene. B. N. ment in the case of potassium chloride consequently Breenivasaiah (Indian J. Phys., 1928, 2, 151— 166). spurious. R . W . L u n t . ¡152 lilllTXSn OHJMIOAL ABSTRACTS.—A.

Temperature valuation of the electrical con­ Internal strain in Y-ray photographs. K. ductivity of crystals. N, U ssataja and B. Hoon- Becker (Z. Physik, 1928,47, 454— 456).— Polemical RHlui (Z. I'hysik, 1927, 46, 88— 92).— The electrical against von Goler and Sachs (A., 1927, 1130). conductivities of fluorspar, sodium nitrate, sodium W . E. D o w n e y . chloride, and mica havo been determined in the Change in structure and electrical resistance following temperature ranges, respectively : 200— during cold working of metals. G. T am m a n n 500°, 20—-300 , 200— 7-10°, 100— 500°. The con­ and M. Straum anis . (Z. anorg. Chem., 1928, 1 6 9 , ductivity, a, is related to the absolute temperature, T, 365— 3S0).— The fall in resistance of hard-drawn aooording to the equation log a for the first copper wiro may bo considerable even when very two substances, and for sodium chloride below 000°; little rocrystallisation has occurred, whereas the in accordance with other work on hotoropolar crystals changes in tensile strength and extensibility run -4 is approximately constant (M Od)xlOl. Tho approximately parallel with the change in structure, data obtained are dismissed with refereneo to the floating the wire at above 600° causes the resistance phenomena of dieleotvie absorption. It. W. Le n t. to increase again, apparently owing to a change in Constitution of solid electrolytes. II. Cuprous the structure of the matrix in which the crystallites bromide. ,). N. Brers [with F, Lkotoi.o] (Bor., are embedded. At 800°, the crystallites are so soft 192S, 61, [£ ], 377— 892; of. A., .1927, 521).— Cuprous that their corners become rounded, with consequent formation of lacuna), which cause a further increase bromide, tested as described for cuprous chloride in t ho resistance. In copper, there is a definite direc­ (loc. c¿f-K Is found to be a true, mixed conductor in tion of slip, but this is not so marked in aluminium, which ionic and electronic conduction are due solely to the copper ion. A complete, continuous transition which probably accounts for the fact that the resist­ ance of pure aluminium is not affected by cold from exclusively electronic to exclusively ionio con­ drawing. R. Ccthill. duction is caused by rise of temperature within the range, about 200—330°. Increase in the electro­ Atom deformation in cold wrought tungsten. lytic component of tho conductivity is caused by sur­ \Y. G eiss and J. A. M. van L iejipt (Z. Physik, 1927, face action, prolongation of the duration of electrolysis, 4 5 , 631— 634).—From measurements of the electrical and, to a remarkable extent, bv the discharge of silver conductivity of tungsten it has been shown that atom or lead ions at tho cuprous Womide. The observ­ deformation exists in cold wrought specimens. ations are readily explained by the supposition of a R . W . L g n t . functional differentiation of the ions in the lattice. Effect of compression and tension on brass H. W ren. crystals. G. Sach s and H. S hoji (Z. Physik, 1927, Contact potential between the solid and 4 5 , 776— 796).— The mechanical deformation of single liquid phases of bismuth. P. H. Dowung crystals of brass in the form of rods has been examined (Physical R ev., 1928, [ii], 31, 24-D-250).— Solid for compressions and for tensions up to 200 kg.;mm.- bismuth has a contact potential with respect to the For forces of the order of 4 kg./mm.'- such crystals melted metal of —002 volt. The effect of surface exhibit mechanical hysteresis. R . W. L g n t . charges on melting conditions is discussed, A. A. E loridgk. Shrinkage in metals and alloys. F. Sa g e r - Reflexion, dispersion, and absorption of cal- w a l d , E. N o w a k , and H. Jgketzek (Z. Physik. 1927, cite in the neighbourhood of 7 u. F. Matossi 4 5 . 650—662).—Measurements have been made of and (Frl.) F. .Dane (Z. Physik, 1927,45, 501— 507). the shrinkage on solidification of copper, lead, tin. —The reflexion, dispersion, and absorption of caleite aluminium, zinc, brass, eopper-tin (30%), copper- have been investigated for various orientations of the tiu (20%), and cast iron. From observations in an crystal to the incident radiation in the range 6-40— inert atmosphere of hydrogen or nitrogen reproducible 7-10 g. R. W.L v n t . values were obtained which were independent of the nature of the containing vessel. The values were in Deformations and changes in optical pro­ agreement with the accepted values for thermal perties of quartz under the influence of the expansivities. Except in the cases of cast iron and electric field. V X. Zk (J. Phvs. Radium, 1928. bronze no expansion was recorded at the commence­ [vi], 9, 13—37)—The piezo-electric deformations in a ment of solidification. R. W. Lcnt. direction normal to the optical and electrical axes of a rectangular parallelepiped of quartz, placed in an Electrification produced by friction between electric field in the direction of its binary axis, follow gases and solid surfaces. I. M. A. Schermann Curie’s rule up to 3900 volts and then tend towards (Z. Physik, 1927, 46 . 209— 236).—Two _ types of a limit at about 160,000 volts. They are equal and electrification by friction have been identified during opposite to those found in the direction of the optical the operation of mercury vapour diffusion pumps : axis. The dielectric deformations are made up of a the first, which takes place at low rates of vapour contraction and an extension in the directions of, and flow, is due to friction between mercury droplets and normal to. the lines of force, respectively, and are glass surfaces; the second" takes place at flow rates proportional to the electrical energy per unit volume of the order of 10* cm. sec. and is due to friction of the condenser. The variations m birefringence are between the vapour and glass surfaces. Confirmatory linear. They change in sign with the sense of the experiments have been carried out by releasing com­ electrical field and are therefore an electro-optical pressed nitrogen from a highly insulated metal bomb phenomenon, distinct from the Kerr effect. in which the bomb attains a potential of several J. GKAKT; hundred volts. B. W, Lgnt. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 353

Relation between conductivity and thermo­ 17-5 at 600°, and 1-76 at 500“. No break point was electric power in magnetic fields. V. Giam balvo found in tho conductance-temperature ourvo at the (Nuovo Cim., 1927, 4, 176— 189; Chem. Zentr., 1927, temperaturo that corresponds with tho m. p. Borax ii, 1444).—Tlie thermo-electric power of antimony- at lower temperatures was in a vitreous state. In tho copper alloys in a magnetic field decreases with diagram of log k against 1/7' a straight line of tho increase of strength of the field; tho changes were typo log« —AjW 4*7? was found connecting tho points measured for weak fields. The results accord with found between 600° and 480° from tho molted to tho theoretical predictions. A. A. E ld r id g e . vitreous state; tho points for tho lower temperatures Schtschukarev's magneto-chemical effect. >S. were on another similar straight lino. The two G orbatsciiev (Trans. Sci. Chem. -Ph arm. Inst. intersected at about 480“, but tho significance of this [Moscow], 1925, 12, 31— 38; Chem. Zentr., 1927, point is not known. N. K a m EYAm a . in, 1797). Conductivity of, and electric absorption in, Electrical conductivity of palladium in a insulators (amber, sulphur, and paraffin wax], vacuum and in different gases. A. P uodziukynah and the effect on them of X- and y-rays. H, (Z. Physik, 1927, 46, 253—270).—The conductivity of Neumann {/. Physik, 1927, 45, 717— 748).— Tho untreated palladium wire increases by about 15% following values of tho resistivities of ambor, sulphur, when the gas contained in the metal is removed by and paraffin ivax have boon assigned from elaborate ionic bombardment in a vacuum; the increase in measurements in a vacuum: 10®—101S ohms, 2% conductivity was proportional to the amount of gas J0,8-~2 X 1011' ohms, and 3 X 1018 ohms, respectively. removed, and the total amount of gas evolved was The dielectric absorption and subsequent slow release approximately 300 times tho volume of the wire. of charge have also been examined in these substances, After treatment for 50 min. at bright red heat in pure R. W. Lil.vr. hydrogen the conductivity fell by 50% and 1486 Relation of diamagnetic susceptibility in the volumes of gas were absorbed. When the wire was licprid and vapour states. V. I. Vaidyanathan maintained in hydrogen at 1 atm. its conductivity (Indian J. Phys., 1928, 2, 135— 150).— Measure­ rose slowly, and more rapidly if the wire was in a ments have been attempted of the magnetic suscept­ vacuum until about 900 volumes of gas had been ibilities of the vapours of the following liquids : carbon evolved; this indicates that after glowing in hydrogen disulphide, benzene, n-pentane, «-hexane, carbon the metal is supersaturated with hydrogen. When tetrachloride, methyl acetate, ethyl and methyl the gas is removed by heating in a vacuum the wire formate, ether, chloroform, , and heptane. absorbs hydrogen slowly and nitrogen not at all; Tho method employed is based on the fact that a if, however, the ga3 is removed in the cold the wire dia- or para-magnetic rod tends to orient itself across becomes activated and absorbs approximately the or along the field when suspended in a suitable same amount of nitrogen or hydrogen. heterogeneous field, and this orienting force is different R . W . L e n t . when the rod is surrounded by different media (cf. Variation of the resistivity of thin layers of Glaser, A., 1925, ii, 82; Ilammar, A,, 1926, 1197). platinum as a function of their thickness, and The results are compared with those obtained by the the influence of oxygenated substances. A. author by a method described elsewhere. Fot carbon F e ry (J. Phys. Radium, 1928, [vi], 9, 38— 48).— Tho disulphide, benzene, pentane, and hexane vapours optical density, D, measured by the Fabry micro- both methods yield a value 20—35% higher than for photometer, is proportional to the thickness [a, in the corresponding liquids. This is larger than can mu) of a layer of platinum deposited on a sheet of be accounted for by the experimental errors, in the mica by cathodic disintegration, and the relation a -- other cases the differences arc smaller. The question 63-47) may be used for the determination of the of the influence of the proximity of neighbouring latter. By the elimination of water vapour, deposits atoms or molecules on the diamagnetic properties of 4-4—243 mu thick, and having resistivities (a in the atom is discussed, M. S. B urr. ohms-cm.) stable for more than a year, were obtained, Allotropic transition point of aluminium. W. for which the relation log 105p=5-7—0-0156« was Gtjertler and L, Anastastadis (Z. physikal. Chem., established. The adsorption of vapour of water or 1928, 132, 149— 156).— Aluminium undergoes no of its electrical analogues (sulphur dioxide, methyl transition at 560°; the observed thermal and electrical ) increased the resistance considerably, to phenomena are due to the presence of silicon, extents which increased with the specific inductive H , F. Gillke, capacities of the vapours at the temperature con­ Method of measuring the radiant heat emitted cerned. These deposits probably have an internal during gaseous explosions. C. If, John son (Phil. structure which differs from that of the compact Mag,, 1928, [vii], 5,301— 322).— A method is described but, as the nature of the results indicates, is enabling, discrimination to be marie between the homogeneous. J. Gr a n t . emission of radiant energy from the wave-front and Electrical conductivity of borax. $. Ok a (J. that from the hot products of combustion from a See. Chem. Ind. Japan, 1927, 30, 625—632).— The gaseous explosion. The experiments were, made in change.-of electrical conductivity o f borax from the a long, narrow explosion vessel in which the rapid molten state to the vitreous state was investigated. cooling of the burnt gases behind the explosion wave -The specific conductivity, of the molten borax was reduced to practically negligible proportions the found to be much less than that of most of the other amount of radiation from that source, A method of molten salts, e.g., *x 10a is 155 at 800“, 71 at 700°, calibrating a linear thermopile, placed at some distance A A 354 BRITISH CHEMICAL ABSTRACTS.— A. from the bomb, is described which has allowed of a /(0/T) the Debye atomic heat function. For pure quantitative extension of the previous work of annealed aluminium, copper, and gold the experi­ Garner and Johnson (A., 1027, 184). Water vapour mental values of w at 21-2°, 83-2°, 273°, and 373° Abs. and other catalysts have been shown to have a marked are in close agreement with those calculated by the effect on the infra-red emission from the wave-front above expression. In impure samples of metals the in explosions of carbon monoxide-oxygen mixtures. thermal conductivity does not become zero at 0° Abs., In a dry gas mixture 7% more of the total heat of but passes through a minimum in the neighbour­ combustion was radiated from the wave-front than hood of 30° Abs.; for such substances the thermal in a mixture containing 1-9% of water vapour. The conductivity is given by iv'=w+ajZT, where w refers importance of this radiation factor in connexion to the pure metal and a is a parameter depending on with the effects of water vapour and other catalysts the purity of the metal and its mechanical treatment. on the spreading of flame in explosions is stressed. R. W . L unt. A. E . M itch ell. Change of properties of substances on drying. Thermal data of tin. J. N . B rônsted (Z. physi- H. B. B aker (J. pr. Chem., 1928, [ii], 118, 96).— A kal. Chem., 1928, 131, 366—370).— Polemical. reply to Balarev (A., 1927, 613). The presence of H. F. Gil l b e . phosphorus in Balarev’s dried liquids is probably Molecular aggregation. Theory of lique­ due to phosphorus trioxide in the pentoxide used. faction. Y. R ocard (J. PhyW. Radium, 1927, [vi], C. H ollins. 8, 495—501).—The hypothesis of molecular aggreg­ Determination of vapour pressures of sodium ation independent of all molecular force, postulated and potassium chlorides. S. H oriba and H. by Duclaux and opposed by the author (A., 1925, B a b a (Bull. Chem. Soc. Japan, 1928, 3, 11— 17).— ii, 1045), is shown mathematically to be incompatible Measurements were made by a static method, using with the variations with temperature of the viscosity a quartz spring manometer sensitive down to a of a gas. The assumption of intermolecular forces, pressure of a few mm., on sodium and potassium with a dipole for each molecule, means that each chlorides over the ranges 800— 1240° and 900—-1250°, double molecule has a double dipole. Such double respectively. The heats of vaporisation, Q, calculated molecules will thus tend to aggregate more readily by the Clausius-Clapeyron equation were found to be than single molecules. A possible explanation of the 39-6 and 36-6 kg.-cal., respectively. Combining these mechanism of liquefaction is thus afforded, from which data with those of other workers for the latent heat the vapour-pressure curve of a gas at low temperatures of fusion, M, and the heat of dissociation of the solid may be derived. J. Gr a n t . into gaseous ions, U, by means of the relationship U—M + Q + D , the heats of dissociation, D, of the Conception of polarity derived from physical gaseous chlorides into gaseous ions were found to be measurements and its relations to the electronic 18 and 42 kg.-cal., respectively. The dissociation configuration of aromatic organic compounds. constant of gaseous sodium chloride was calculated J. F. T. B erliner (J. Physical Chem., 1928, 32, to be of the order of 10-39. S. J. Gregg. 293— 306; cf. A., 1927, 506).— Theoretical. The entropies of vaporisation of the nitroanilines and Efflorescence of sodium sulphite. D. N. toluidines are greater than 13-8 g.-cal. /degree, the T arassenkov (Z. anorg. Chem., 1928, 169, 407— value considered by Hildebrand (A., 1918, ii, 61) 412).— The vapour pressure of the system to be the normal for the conditions specified, and this Na2S03,7H20 ^ = N a 2S03+ 7 H 20 between 0° and 70° is considered to indicate association of these liquids. has been measured. At 15° the pressure is 9-3 mm. The mononitrotoluenes similarly considered are practic­ R. Cu thill. ally non-associated. Using Crocker's conception of Evaporation of tungsten under various pres­ the electronic structure of benzene (A., 1922, i, 924), sures of argon. G. R. F o n d a (Physical Rev., a relationship between electronic configuration and 1928, [ii], 31, 260— 266).— The rate of evaporation association derived from vapour-pressure measure­ of tungsten filaments at 2870° Abs. in a mixture of ments is shown to exist and is applied to interpret argon (86%) and nitrogen (14%) varies from 2 X10-9 the variations in the entropies of vaporisation of the to 230 XlO-9 g./cm .2 sec. as the pressure is reduced compounds in question. L. S. T h eo b ald . from 1650 to 0 mm. The author’s view that the evaporating atoms diffuse through a surrounding film Metal crystals. VI. Temperature variation of stationary gas is supported by the fact that woe of the thermal resistivity of normal metals. E. P log 6/a, where m is the rate of evaporation, P the Gr ln e ise n (Z. Physik, 1927, 46, 151— 159).— The pressure, and a and 6 are the diameters of the filament author’s earlier theory of the additivity of the and gas film (calculated from Langmuir’s equation “ metallic ” and “ non-metallic ” portions of thermal for heat loss), respectively, is constant for gas pressures conductivity of crystalline metals (A., 1927, 1017) above 100 mm. A. A. E l d r id g e . has been extended by showing that the temperature variation of each of these portions can be expressed Vitreous state and dilatation of glasses. M. in terms of the Debye atomic heat function for the ^S am soen (Ann. Physique, 1928, [x], 9, 35— 127).— metal concerned. The specific thermal conductivity, The linear and cubic dilatations of a number of soda, w, of a pure metal can on this basis be expressed in silica, silicoborate, and industrial glasses have been the form w=(l+kO/T)f(QlT)IZ, where k is the ratio determined by the Chevenard and ordinary industrial of the “ non-metallic ” term w, to the “ metallic ” methods, respectively, at temperatures between —200°« term wm (w =W i+w m), T is the temperature Abs., Z a and 1500°. Boron and phosphorus enamels, resins, universal constant, 2-2 X 10~8 watts degrees-2, and pitch, sucrose, “ orca ” (polymerised acraldehyde), GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 355 glycerol, and. sodium thiosulphate were also examined. III. Hydrogen chloride and methyl alcohol. The anomalous linear dilatation (A., 1926, 567, 568, J. Sh id e i (Bull. Chem. Soc. Japan, 1928, 3, 25— 42; 570; B., 1926, 709) previously considered to be a see this vol., 229).— The apparatus was arranged so property of silica dissolved in complex glasses is shown that the gases came in contact only with mercury and to be common to all the substances examined, when in glass, special care being taken to remove all traces of the amorphous state. In the case of cubic dilatation, adventitious air. The gaseous pressure of methyl the anomaly takes the form of a change in the dilat­ alcohol at several different concentrations was ation coefficient. Experiments on the influence of measured at a number of temperatures between 70° temperature on the rate of crystallisation of glycerol and 130°, and the relationship between the pressure led to the conclusion that the molecules of a solid in and the density of the gas was found to be rectilinear. the amorphous state are stationary with respect to The pressures of gaseous hydrogen chloride over the one another, and that all crystallisation is impossible range 50—130° show good agreement with van der in the true amorphous state below the transformation Waals’ equation if the temperature variation of the temperature. This is in accord with the perfect constants a and b be corrected for by van Laars isotropy of fluids and with the mechanical properties equations. Measurements on the mixture show a of solids. The transformation temperature, which diminution in pressure on mixing the gases, which is exists for all amorphous substances, depends only discussed in the light of the reactions MeOH + on the viscosity. With thiosulphate and sodium HC1 — MeOH,HCl; MeOH,HQ — MeCl+H20. silicates rich in sodium, glasses were obtained by The observed diminutions are too small, however, to rapid cooling of the substance below the trans­ permit the accurate determination of the extent of the formation temperature. With boric anhydride and reactions. S. J. Gregg. glycerol, the transformation temperatures were also Dielectric constants of binary mixtures. determined from the change in specific heat accom­ Electric moments of certain nitro-derivatives panying them, but a value 25° lower than that given of benzene and toluene. J. W. W illiam s and by the dilatation method was always obtained. This C. H. Sch w in g el (J. Amer. Chem. Soc., 1928, 50, is unexplained. The curves expressing the variations 362— 368).—Dielectric constant and density data for of the transformation temperature as a function of 25° are recorded for benzeno solutions of nitrobenzene, chemical composition showed maxima at compositions o-, m-, and p-dinitrobenzene, 5-trinitrobenzene, corresponding with what are usually considered to and o-, 7H-, and p-nitrotoluene. The changes pro­ be definite compounds, in particular with the com­ duced in the electric moments of the solute molecules pounds 2Si02,Na20, 2B203,Pb0, and 2B20 3,Na20. by substituent nitro-groups are closely parallel to Grenet’s law "of additivity is not acceptable in its the effects produced by hydroxy- and chloro-groups entirety, except perhaps in cases where the crystall­ (Smyth and Morgan, A., 1927, 611). The results, ine system does not correspond with a definite com­ which are critically discussed, are in agreement with pound or a eutectic. The m. p. of glycerol was found previously published work. S. K . T w e e d y . to be 18'07°. ” J. Gr a n t . Internal friction of solutions and mixtures. Chemical affinity, cohesion, compressibility, W . H erz and G. Scheliga (Z. anorg. Chem., 1928, and atomic volume. Effects of internal pres­ 169, 161— 172).— The viscosity at 20°, 40°, and 60° sures. T. W. R ic h ar d s (J. Chim. phys., 1928, 25, of solutions of iodine, phenanthrene, and naphthalene S3— 119).—A summary of numerous previous papers. in benzene, toluene, carbon tetrachloride, carbon H . F . G il l b e . disulphide, and ac.etone increases with increasing Reciprocal attraction and repulsion of gas concentration, the effect becoming less pronounced, molecules and their bearing on the theory of however, with rise in temperature, and being usually internal friction. L. Scham es (Physikal. /., 1928, greatest with phenanthrene, and least with iodine. 29, 91— 94).— Mathematical. It is shown that the With solutions containing both naphthalene and potential energy, , between two molecules when phenanthrene, the viscosity usually differs only represented by the expression —A jrm-\-Bjrn for the slightly from the value calculated additively from attractive and repulsive forces, respectively, leads to the viscosities of the corresponding solutions with the values m = 8, « = 8 for helium. W. E. D o w n e y . only one solute. The viscosity of mixtures of carbon Surface tensions and parachors of fused disulphide with benzene or toluene exhibits negative organic substances. S. S. B h a tn a g a r and B. deviations from the mixture rule. Equal amounts Singh (J. Chim. phys., 1928, 25, 21— 27).— The of maleic and succinic acids increase the viscosity of surface tensions of fused naphthalene, a-nitronaphtli- alcohol by nearly the same amount, but fumaric acid alcne, phenanthrene, , o- and p-nitrophenol, has a greater effect. The viscosities of aqueous and p-nitrotoluene have been determined by the use solutions of d-tartaric acid and racemic acid of the °f a modified form of Bircumshaw’s apparatus (A., same concentration are usually unequal, but the ^26, 895). The parachors of the nuclei of naphth­ difference varies both in sense and magnitude with alene and phenanthrene and of the hydroxyl group change in the temperature and concentration. With have been calculated and used in the determination Z-malic acid and dZ-malic acid, however, the difference of the theoretical parachors of the above substances, is always negligible. The viscosity at 20° of aqueous which agree well with those observed. solutions of sodium chloride can be represented fairly L . F. Gil b e r t. satisfactorily by an equation of the type 1 jx==hjn, Deviation of gaseous mixtures from Dalton's where y is the viscosity, x is the concentration in law of partial pressures due to chemical causes. g.-mol. of water/g.-mol. of salt, and k and n are 356 BRITISH CHEMICAL ABSTRACTS.— A. constants. With solutions of magnesium chloride, crystal starts to grow in a solution containing a however, no such equation can be employed, and the foreign salt, such as permanganate, the thickness of viscosities are considerably greater than those of the layer of permanganate solution adsorbed on the sodium chloride solutions of equivalent concentrations. surface increases as the crystal grows, and thus the R. Cu th ill. layer becomes less and less readily penetrated by Volume changes attendant on mixing pairs the barium sulphate molecules. When, however, the of liquids. J. B. P e e l , W. M. M a d g in , and H. V. A. crystal has reached a certain size, any further mcrease B riscoe (J. Physical Chem., 1928, 32, 2S5— 292; occurs in the form of deformed growths on its surface, cf. A., 1927, 521 ; this vol., 21).—Por 28 pairs of some of the adsorbed layer and a little mother-liquor non-aqucous liquids the volume changes have been thereby being mechanically included. With increase calculated from the densities at 25¿0-l° of the in the concentration of foreign salt, the maximum pure liquids and of various mixtures. The absence possible size of regular sulphate crystal diminishes. of any relation between the volume and temperature R . ClT Til ILL. changes accords with the values obtained for the heat Diffusion of thorium through tungsten. P. of mixing and the external work associated with the Clau sin g (Physica, 1927, 7, 193— 19S).— Experi­ change in volume, the latter being only an insig­ ments with thoriated tungsten wires, coated with a nificant fraction of the energy change involved. The layer of tungsten, show that at 2150—2800° Abs. thermal effect must be attributed to changes in the thorium moves outwards along the tungsten crystal internal work, and in many cases is due to chemical interfaces, whilst diffusion through the intact tungsten change. L. S. T h e o b a ld . lattice takes place to a negligible extent. Chem ical A bstracts. New kinds of mixed crystals. II. Formation Heterogeneity of iron-manganese alloys. of mixed crystals by barium sulphate and potass­ C. R. W ohrm an (Amer. Inst. Min. Met. Eng. Tech. ium permanganate. H. G. G rimm and G. W a g n e r Pub., 1927, No. 14, 32 pp.).— Photomicrographic (Z. phvsikal. Chem., 1928, 132, 131— 148; cf. A., study of iron-manganese alloys containing 30, 8, and 1927, 721).— Barium sulphate and potassium per­ 3% Mn leads to the view that the Widmanstattian manganate form a series of mixed crystals which at and martensitic patterns structures result from the 50° can be studied up to a molar percentage of 60% of breaking up of a solid phase into two. The latter potassium permanganate. The content of potassium structure is finer, less well defined, and less regular permanganate in the crystals is approximately pro­ than the former. On thorough annealing there is portional to the concentration in the solution with formed an aggregato consisting of a ferritic con­ which the crystals are in contact. Mixed crystals stituent, probably a solid solution of a little man­ containing more than 40% of potassium permanganate ganese in a-iron, and a cementitic constituent, an are metastable, and are rapidly decomposed by intermetallic compound rich in manganese. A acetone. Crystals stable to acetone are partly broken eutectoid of the two (6% Mn) is also believed to up by water ; the residue, which contains about 8% exist, at first martensitic and then pearlitic. The of potassium permanganate, is very stablo towards valuable properties of steels are considered to be reducing agents. Barium selenato and chromate, vested in the solid solutions which iron tends to form, strontium selenate and sulphate, and potassium the influence of carbon having been over-emphasised. fluoborate also form mixed crystals with potassium Chem ical A bstracts. permanganate. H. F. Gil l b e. Incomplete miscibility phenomena in aqueous New kinds of mixed crystals. VIII. D. solutions of ammonia and an inorganic salt. B alarev (Z. anorg. Chem., 1928, 169, 257— 263; E. Jan ec k e (Z. Elektrochcm., 1927, 33, 518— 526).— cf. this vol., 223).—If barium sulphate is precipitated When concentrated aqueous solutions of potassium by the free diffusion of barium chloride and potassium carbonate and ammonia are mixed, two liquid layers sulphate into a potassium chloride solution, the are formed, the upper being richer in ammonia and amounts of water and potassium sulphate included in the lower in potassium carbonate (cf. Newth, J.C.S., the precipitate pass through a minimum with increase 1900, 77, 775). Raising the temperature leads to in the potassium chloride concentration, but are the disappearance of one of the layers and for a never zero. When the anisotropic crystals of system of given composition there is a definite BaS04(K2S04,H20) are rendered isotropic by warming, “ clearing temperature.” For a fixed temperature they arc much more rapid!y penetrated by a potassium there is a critical ratio of ammonia to potassium permanganate solution, probably owing to the carbonate such that on dilution with water the com­ capillaries of the small regular crystals constituting positions of the two layers eventually become identical: the larger crystals becoming connected up in a with a higher ratio, dilution leads to homogeneity more regular manner. Similarly, a pure solution of through disappearance of the lower layer; with a barium chloride diffuses very slowly through a semi­ lower ratio, through disappearance of the upper permeable membrane of barium sulphate, but in layer. Similar phenomena are exhibited by using presence of sugar or potassium permanganate the rate tripotassium phosphate, rubidium carbonate, or is much increased, because these substances make potassium vanadate instead of potassium carbonate. the barium sulphate crystals isotropic, and so increase Equilibria in the systems Iy2C03-NH3-H 20 and their capillaries. The amount of a foreign salt K3P04-NH3-H 20 have been investigated in detail included in precipitated barium sulphate does not and the results exhibited by curves. The conditions appear to depend in any fundamental manner on for the separation of the solid phases K^CO^ILjO and structural considerations. When a barium sulphate K 3P0 4,8H20 are also indicated. A four-dimensional GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 357 equilibrium diagram of the system K 20 -C 0 2-N H 3-H 20 are adsorbed in the undissociated form. Zero or is given in perspective, together with a projection of negative adsorption in the case of strong inorganic this on the triangular base representing the co­ bases is confirmed, but a small positive adsorption ordinates of K 20, C 02, and NH3 (cf. A., 1927, 731). was obtained with ammonia. Aliphatic primary H. J. T. E llin g h am . amines are relatively well adsorbed and the secondary Miscibility-gap in molten iron-copper alloys. amines much more so : aromatic primary amines are A. M ü ller (Z. anorg. Chem., 1928, 169, 272).— strongly adsorbed. Notable adsorption is found with Polemical against Euer (A., 1927,928). E.. Cu t h il l . the strong aromatic and heterocyclic bases, but, whereas alkaloids of low mol. wt. are slightly adsorbed, Determination of vapour pressure of saturated zero or perhaps negative adsorption is exhibited by aqueous solutions. F. P ohle (Mitt. Kali- alkaloids of high mol. wt., although these substances Forschungs-Anst., 1927, 33— 43; Chem. Zcntr., 1927, have a very marked lowering effect on the surface ii, 2047).—Determinations were made of the satur­ tension of water. Salts of inorganic acids and bases ation pressure of saturated solutions of magnesium, sodium, and potassium chlorides and sulphates, and are only adsorbed “ hydrolytically ” by pure charcoal, the acid being adsorbed and the base remaining in of various mixtures of the salts. The b. p. were also solution. For salts of a given base, the sequence determined. A. A. E ld r id g e . for the extent of this hydrolytic adsorption is the Relation between water and salts in crystall­ same as that for the adsorption of the corresponding ine hydrates and in solutions. J. N. E a k s h it (Z. acids. The salts of surface-active organic acids with Elektrochem., 1927, 33, 578— 581; cf. A., 1926, 788). inorganic bases or of surface-active organic bases with —The molecular contraction observed wlifen a salt inorganic acids are adsorbed partly hydrolytically but forms a crystalline hydrate or a solution with water mainly molecularly. Salts of surface-active organic has been determined for various salts. The values acids and bases are almost entirely adsorbed molecu­ obtained for solutions are generally greater than those larly. The results obtained for salts of various types for the crystalline hydrates and increase notably are discussed. The polar character of surface-active with dilution, but for concentrated (including super­ organic acids and bases is regarded as the essential saturated) solutions of sodium acetate the molecular factor in giving rise to molecular adsorption. contraction is less than for the trihydrate, and for H. J. T. E llin g h am . manganous sulphate solutions it is almost negligible Comparative adsorption by active charcoal. compared with the values for the crystalline hydrates. II. Isoelectric point of charcoal. O. Spengler For solutions of sodium sulphate and of sodium and E. L an d t (Z. ver. deut. Zucker-Ind., 1928, carbonate at various concentrations, the molecular 81— 98).— The charcoal is added to a series of buffer contraction has been measured at various tem­ solutions at various p a values, and the isoelectric peratures between 15° and 90°, but no indication of point of the charcoal is taken to be the p u value of transition points corresponding with dissociation of the buffer solution which is not changed by the definite hydrates is obtained. It is inferred that the addition of the charcoal. The isoelectric points so relation between the salt and water in solutions is obtained fell between p a 5-7 and 8-7. different from that in the crystalline hydrate. W . O. K erm aok. H. J. T. E llin g h am . Adsorption of ferric chloride by crystalline Solubility equilibria. F. F lö ttm an n (Z. anal. barium sulphate. (Ml l e .) L. d e B rotjckere Chem., 1928, 73, 1— 39).— The solubility in water (Bull. Acad. roy. Belg., 1927, [v], 13, 827— 836).—The and the values of d and nD for saturated and for 1 % adsorption of ferric chloride by crystalline barium solutions of 22 common salts have been determined sulphate at 25°, and the influence of varying con­ at 15°, 20°, and 25°, and the results are compared centration of hydrochloric acid (0-1— O-OOIN) on the with those obtained by previous investigators. adsorption, have been investigated. In acid-free A. E. P o w e l l . solutions a larger value for the quantity of iroh Adsorption of strong electrolytes by pure adsorbed is found when the washed barium sulphate carbon free from ash. I. M . K olthoee (Z. Elek­ is fused with crystalline sodium carbonate than when trochem., 1927, 33, 497— 501).— Purified sucrose was it is digested with pure water; it thus appears that a carbonised and the finely-powdered product activated portion of the electrolyte is irreversibly adsorbed, the by heating for 24 hrs. at 900— 960°. The amounts digestion method removing only the active portion of of various inorganic acids adsorbed from 0TA7-solu- the micelle. Moreover, the amount of adsorbed iron, tions by this charcoal decrease in the sequence as determined by the former method, is much more thiocyanic, hydriodic, nitric, iodic, hydrochloric, than equivalent to the adsorbed chlorine (¿Fe: Cl hydrobromic, sulphuric, phosphoric ; the value for varies from 4 to 10) and hence adsorption of the sulphuric acid is very low and that for phosphoric micelle, which has the composition [Fe2(OH)6],„,Fe2Cl6, acid is zero. This sequence corresponds with that is also postulated. This is also the case with low' for the activity of the acids in lowering the surface concentrations of added hydrochloric acid, but the tension of water. Not only do neutral salts of a ratio ¿-Fe: Cl decreases towards a minimum value of strong acid increase the adsorption of that acid by 0-6 (corresponding with H4Fe2Cl10) as the concentra­ charcoal, but addition of a second inorganic acid has tion of the acid is increased. It is assumed that the a similar effect. Whereas phenol ,or addition of acid breaks down the micelle, adsorption practically prevents the adsorption of the strong acids, of which is the main factor. Other conditions being the the strong acids will partly displace acetic acid from a same, the adsorption of iron is 20— 100 times as great charcoal surface. It is inferred that the strong acids as that of uni- and bi-valent cations. J. W. B a r e r . 358 BRITISH CHEMICAL ABSTRACTS. A.

Adsorption at crystal faces. I. Growth and Molecular orientation at surfaces of solids. dissolution of single copper sulphate crystals I. Measurement of contact angle and the work in presence of gelatin and dyes. T. S. E ckert of adhesion of organic substances for water. and W. G. F rance (J. Amer. Ceram. Soc., 1927, 10, A. H. N ietz (J. Physical Chem., 1928, 32, 255—269). 579—591).—Kinematographic observations, at a mag­ — The contact angle for water, the effect on the surface nification of 1000, on the growth of crystals from tension of water, the spreading, and the work of saturated copper sulphate solutions are recorded. adhesion of 70 organic solids have been investigated Gelatin is very effective in retarding the rate of with results which are in accord with the work of crystal growth. It is probable that the gelatin is Harkins (A., 1921, ii, 242) and of Langmuir (A., 1917, adsorbed to different degrees at different crystal ii, 525). The Ablott cylinder method and the plate faces, thus changing the crystal habit. The ash of method for measuring the contact angle have been gelatin, per se, is without effect in modifying the compared in favour of the latter, the former giving crystal habit. Quinoline-yellow, Bismarck-brown, inconsistent results which arc as yet unexplained. and mothvlene-blue greatly change the crystal habit Substances which spread considerably do not always and decrease the rate of growth of copper sulphate greatly affect surface tension. The effect of humidity crystals, but naphthol-yellow, ponceau-2R, and during crystallisation or solidification of the solid is methyl-violet do not show such effects. The theory marked, increased humidity causing a large increase of adsorption in relation to the influence of gelatin in the work of adhesion. L. S. T h e o b a ld . and dyes is discussed. It is shown that specific Comparison of thickness of oxide films deter­ adsorption is largely responsible for changes in mined by interference colours and by weighing. crystal form. Viscosity and convection currents G. T am m ann and K. B ochov (Z. anorg. Chem., 1928, affect the rate of dissolution. A. T. G r e e n . 169 , 42—50).—Calculation of the thickness of an M olecule ion absorption. S. G orbatschev oxide film on the surface of nickel from its colour (Trans. Sci. Chcm.-Farm. Inst. [Moscow], 1925, 12, gives a value about 98 ¡ru. less than that determined 7— 30; Chem. Zentr., 1927, ii, 1801).— “ Sorption” by direct weighing. This must be ascribed to the of ions by neutral molecules is postulated; such presence on the surface both of the bright and the sorption accompanies dissociation in electrolytes. If oxidised metal of a film, which, from its loss in weight the solution contains foreign neutral molecules, one on reduction, appears to consist of hydrated nickel of the ions is “ sorbed,” and the degree of dissociation oxide and absorbed air and water vapour. On iron, and conductivity of the solution are increased. the film has a thickness of 85 uu, and on copper 91 (¿u A. A. E l d r id g e. (cf. Vernon, A., 1926, 110S). R. Chthill. Adsorption and chemical nature of some Surface tension of solutions. W. H erz and organic compounds. N . A. Schilov and B. V. E. K n a e b e l (Z. physikal. Chem., 1928, 131, 389— N ek rassov (J. R u s s . Phys. Chem. Soc., 1928, 60, 404).—The surface tension of an ammonium hydrogen 103— 112).— See A., 1927,‘ l 135. sulphite solution is identical with that of a mixture Retrograde adsorption of colloidal ferric hydr­ of equimolar solutions of sulphuric acid and ammon­ oxide. W. S t o ll e n w e r k and M. y o n W r an g ell ium sulphate of the same equivalent concentration. (Z. Elektrochem., 1927, 33. 501— 503).— Ferric The formation of an acid salt is indicated in general hydroxide “ gels ” prepared either (a) from ferric by an increase of the surface tension of the mixed chloride solution as a dark brown precipitate or (b) by solution over the arithmetic mean of the surface oxidation of ferrous hydroxide with hydrogen per­ tensions of the separate solutions. The influence of oxide, giving a yellow product, were shaken with the alkali and alkaline-earth chlorides and nitrates on solutions of mono-, di-, or tri-sodium phosphate of the surface tension of water is the same at 20° as at various concentrations, and the amounts of the 40°; for each group of cations the increase of surface phosphate radical adsorbed were measured at inter­ tension decreases with rise of atomic weight. The vals over a period of 4 days. In the more concen­ surface tension of aeetone-water mixtures is lowered trated solutions of the disodium phosphate, the by sodium, potassium, and barium salts to an extent preparation (a) adsorbs rapidly increasing amounts which is independent of the salt concentration; this of phosphate, but after about 12 hrs. a maximum is effect is probably due to the insolubility of the salts reached and part of the adsorbed phosphate is in acetone, since the solution will then have a lower gradually given up again, whereas the preparation (6) active water content, i.e., the acetone percentage will adsorbs smaller but continuously increasing amounts, increase and the surface tension of the water will so that eventually the amounts adsorbed by the two thereby be lowered. The chlorides and nitrates of preparations tend to approach one another. In more the other alkali and alkaline-earth metals produce dilute solutions the amounts of phosphate adsorbed in at first an increase of the surface tension, and then, the first 12 hrs. by the two gels are less divergent, at higher concentrations, a decrease. At low con­ and the subsequent retrograde adsorption by the gel centrations, complexes are formed between the salt (a) is less marked. The retrograde adsorption is and acetone, and the concentration of the latter strongly marked with the gel (a) in concentrated solu­ is lowered; as the salt concentration increases the tions of trisodium phosphate and is exhibited to a active water content diminishes, and the reverse effect slight extent by the preparation (6) in such solutions, is observed. A number of measurements have been but it is not shown by either preparation in solutions made of the surface tension of solutions of iodine, of monosodium phosphate. The interpretation of naphthalene, and phenanthrene in various organic these results is discussed. H. J. T. E llingham . solvents. In all cases iodine produces a decrease, GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 359 and the other substances an increase of the surface of particles resulting and the number of nuclei. This tension of the solvent. H. P. G il l b e . is due to the formation of colloidal particles by the sodium carbonate itself, these acting as false nuclei. Permeability of thin dry collodion membranes. If, however, the presence of sodium carbonate is J. H. N orthrop (J. Gen. Physiol., 1928, 11, 233— avoided by using hydrazine hydrate for the reduction, 237).—Dry thin collodion membranes, having a sols are obtained having particles the size of which is thickness of 2— 3 ¡x and having permeabilities similar uniform and determined by the number of nuclei. to those of the membrane of the sea-urchin egg, have Gold nuclei prepared with the aid of phosphorus also been prepared. The membrane is permeable to water, yield satisfactory results, and sols have also been ammonia, weak acids of low mol. wt., gaseous hydro­ prepared with saturated solutions of silver oxide. gen chloride, oxygen, carbon dioxide, and hydrogen It. Cu t h il l . sulphide, but impermeable to strong electrolytes and Colloid syntheses with the aid of titanium substances of high mol. wt. The rate of effusion of trichloride. VI. Colloidal palladium. A. gases through the membrane shows no connexion with G u tb ier and H. W eitiiase (Z. anorg. Chem., 1928, the density of the gas and thus the membrane camiot 169, 264— 266; cf. A., 1927, 933).— If a solution of be regarded as a sieve. The results as a whole titanium trichloride is nearly neutralised with sodium indicate that the rate of passage of a substance acetate, then boiled, and after cooling added to a 1% through the membrane is determined by the solubility solution of palladium dichloride, colloidal palladium of the substance in collodion and its diffusion coeffi­ is formed by the reaction Pd"+2Ti"'==2Ti""+Pd. cient in collodion, the former probably being the The product is relatively insensitive towards acids, more important factor. A. W orm all. owing to the presence of titanium dioxide as protective Function of carbon membranes in osmosis. colloid, and on dialysis passes into a gel, which can bo F. E. B a r te ll and H. J. Osterhop (Fourth Colloid peptised with water only after being treated with Symposium Monogr., 1926, 234— 245).— Experiments concentrated hydrochloric acid. Undialysed prepar­ with silica or carbon membranes show that the flow ations of palladium titanium purple are thixotropic. is from water to organic liquid with the former, and R . Cu th ill. eventually the reverse with the latter. Two liquids Preparation and stabilisation of colloidal were separated by a silica or carbon membrane, and mercury. A. Ch isto n i (Boll. soc. biol. sperim., the pressure resulting from the osmotic flow was 1926, 1, 408— 410; Chem. Zentr., 1927, ii, 905).— measured. The results indicate that in a strictly Mercuric chloride (0-5 g.), sodium hydroxide (2 g.), semi-permeable membrane one component is adsorbed and fresh egg-albumin (100 g.) form a gel which when to the practical exclusion of the other. When the warmed with water is converted into a black sol, membrane has greater permeability the initial osmotic stable towards boiling and towards heating at 110° in force and direction of flow are mainly determined by an autoclave. It is coagulated by an equal volume of the relative adsorption of the liquids; the membrane 10% barium chloride, but not by sodium chloride solu­ may or may not play an active part. tion. The electric charge is negative. The sol is not Chemical A bstracts. precipitated by hydrogen sulphide or ammonium Hydrolysis of sugars by membranes in pre­ sulphide; drying at the ordinary temperature and sence of electrolytes. J. L oiseleu r (Compt. rend. pulverising yields a substance which is again soluble. Soc. Biol., 1927, 96, 1273— 1275; Chem. Zentr., The disperse phase consists of a sulphide of mercury, 1927, ii, 678).— Fall in p R of an electrolyte solution in produced by hydrogen sulphide from the albumin. presence of a colloid is observed when sucrose or A. A. E l d r id g e . other hydrolysable sugar is hydrolysed. Presence of arsenious oxide in arsenic tri­ A. A. E l d r id g e . sulphide hydrosol. V. Gazzi (Zymologica, 1927, Chemical method of preparing carbon hydro­ 2, 1— 10; Chem. Zentr., 1927, ii, 26— 27).— The sol. E. Ch irn o ag a (J.C.S., 1928, 298— 301).— quantity of arsenious oxide, even in a highly purified By stirring small amounts of carbon in aqueous solu­ sol, is always much greater than that which can be tions of sodium hypochlorite a very stable sol is obtained by complete hydrolysis of soluble arsenic obtained which may be evaporated without suffering trisulphide. The solubility of precipitated arsenic irreversible coagulation. The size of the particles is trisulpliide is 2-10 X 10~G mol./litre, yielding 0-4135 mg. estimated at 60 ¡i[i. The negative charge carried by per litre of the trioxide, whereas 1-5—3-0 mg. are the sol is ascribed to the adsorption of chlorine or found. The value is not connected so much with the hydroxyl ions. A theory of the process is advanced solubility of the trioxide as with the loss of hydrogen and mention is made of the possible industrial applic­ sulphide. It is impossible to separate the ultra- ation of the sol as a resistant carbon ink. micellar liquid by ultra filtration without changing its H. I n g leso n . composition. A. A. E l d r id g e . Preparation of silver hydrosols free from Interpretation of the analysis of arsenic tri­ protective colloids and with particles of a uni­ sulphide hydrosol. V. Gazzi (Zymologica, 1927, form size. II. J. V oigt and J. H e u m a n n (Z. 2, 10— 12 ; Chem. Zentr., 1927, ii, 27).— The results anorg. Chem., 1928,169, 140— 150; cf. A., 1927, 932). obtained by Murphy and Mathews (A., 1923, ii, 156) If silver hydrosols with particles of a uniform size are considered to be due to the presence of a mixture are employed as nuclei in the reduction of a silver of arsenious oxide and sulphide. A. A. E l d r id g e . oxide solution with hydrazine sulphate and sodium carbonate, the silver submicrons grow in an irregular [Catalysts for hydrogenation in the cold.] manner, and there is no relation between the number M. B ourguel (Bull. Soc. chim., 1928, [iv], 43, 231; 360 BRITISH CHEMICAL ABSTRACTS.— A.

cf. this vol., 28).—A printer’s omission is corrected by a small proportion of very small particles. Values and the directions given in tho paper for the prepar­ obtained from tho rate of sedimentation agree closely ation of colloidal palladium are amplified. with those calculated from the absorption. Mie’s H. I n g leso n . theory requires the absorption coefficient to be A lu m in iu m hydroxide gels. D. G. R . B o n n e ll independent of the particle size, but this is shown (Z. anorg. Chem., 1028, 169, 345— 355; cf. A., 1927, experimentally not to be the case. The depolar­ 1025).— Aluminium hydroxides B and G form lakes isation coefficient 0O for small gold particles deviates with gold kydrosols, tho colour with the G gel depend­ from zero, since a certain fraction of the particles is ing on tho relative amounts of gold and alumina. non-spherical. The colour change which accompanies With hydrochloric acid, gels B and G are not peptised, coagulation is associated also with a decrease of 00, hut pass into crystalloidal solution. Gel A is attacked and is therefore not due to a greater deviation of the only slightly with hydrochloric acid if an excess of particles from the spherical form, but to an increase acid is used, but if heated with a small amount of of size. The sols contain chiefly metallic gold, with concentrated acid and then diluted it readily yields but little aurous hydroxide; the percentage of the hydrosols, with particles which are the smaller the latter in one case was 1-26. H. F. G il l b e . greater the quantity of acid used. These sols can be Stability of colloidal solutions towards elec­ concentrated considerably without the occurrence of trolytes. A. B outario (Bull. Soc. chim., 1928, [iv], gélatinisation, and when evaporated in a vacuum or 43,146— 155).— Measurements aredeseribed in which a subjected to ultrafiltration leave a residue again which spectrophotometer is employed to determine the time t passes into colloidal solution in water. R . C hth ill. required by a colloidal solution to reach its maximum Theory of the preparation of silica gel by opacity in the presence of an electrolyte of concentra­ means of water-soluble metal salts. P. N. tion c. By successively reducing the concentration Gbigorjev (J. pr. Chem., 1928, [ii], 118, 91— of electrolyte the equation t—f(c) can bo evaluated 95).— Silica gels are obtainable from water-glass and the highest value of c at which no coagulation (Na20,3Si02) by the action, not only of heavy metal occurs can be calculated, thus providing a measure salts (Holmes and Anderson, A., 1925, ii, 518), but of tho stability. When electrolytes with multivalent also of alkali and light metal salts. Salts of calcium, ions are employed, e.g., ferric chloride, the curve magnesium, strontium, and barium give silica gels of f=/(c) with certain sols reveals the existence of two low activity. The gel formation depends on the zones of flocculation. Gelatin, albumin, and gum, hydrolysis of the metal silicates formed by double when added to colloidal solutions of arsenic sulphide, decomposition. Ferric salts behave exceptionally (cf. ferric hydroxide, or gamboge in small amounts up to Jordis, A., 1907, ii, 876 ; 1908, ii, 291 ; 1910, ii, 416). a certain limit, reduce the resistance of tho colloid C. H o llin s. to coagulation by an electrolyte, but subsequent Size-distribution of colloidal particles. N. additions exert a protective action. When a sol is R a sh e v sk y (Physical Rev., 1928, (ii], 31, 115— 118). treated with an amount of electrolyte insufficient to —Theoretical. A. A. E ld r id g b . coagulate it, the sol is able to withstand the action State of polarisation of the Tyndall beam of of an amount of electrolyte which would have been sufficient to precipitate tho untreated sol. Contrary colloids. B. L ange (Z. physikal. Chem., 1928, 132, 1—26).—Gans’ formula for the depolarisation to many published statements, the nature of the visible coefficient 0o of individual colloidal particles has been light by which a sol is illuminated has no effect on the verified by measurements with arsenious sulphide, time required for coagulation, illumination by in­ ferric and aluminium hydroxide, cerium dioxide, and tense red and intense blue light giving tho same values vanadium pentoxide sols. For small spherical par­ as those found in the dark. H. I ng leso n . ticles 0() becomes zero, i.e., tho Tyndall beam is com­ Protection of colloidal solutions. A. B outaric pletely polarised; these conditions hold for caout­ (J. Chim. phys., 1928, 25, 120— 141).— An experi­ chouc, mastic, arsenious sulphide, and cerium dioxide mental investigation of the influences exerted on sols. Colloidal particles of ferric and aluminium colloidal solutions by small quantities of added hydroxides and of vanadium pentoxide deviate con­ substances. H. F. Gil l b e . siderably from the spherical form, and in the case of Kinetics of coagulation of colloids. K. the latter tho deviation increases on ageing. Thixo- Ja b lc zyn sk i and M. Soroczynski (Bull. Soc. chim., tropic gélatinisation of a cerium dioxide sol results in 1928, [iv], 43, 159— 163; see A., 1925, ii, 34, 35, 665, a reversible increase of 0o, indicative of aggregation of 666; 1926, 1203).— The equation previously estab­ the particles. H. F. Gil l b e . lished (using a spectrophotometer), (log tan a— Depolarisation and light absorption of solu­ log tan y.0)ji= K , is shown to be a particular case of tions of colloidal gold. B. L an g e (Z. physikal. the more general equation log [(log tan —logtan a0)/ Chem., 192S, 132, 27— 46).— A series of gold sols (log tan aM — log tan a )]= J f1i, where a0, a, and a«, are having particle sizes from 6 to 150 gg have been the angles of rotation of the Nicol at zero time, time t, prepared and the absorption coefficients measured. and infinite time respectively. The general equation The latter are in close agreement with Mie’s theoret­ expresses the fact that the rate of increase of opacity ical values when calculated on the assumption of at a given time is proportional to the difference of the spherical particles. The mean particle size calculated opacity in the final state and at the given time. thus from the absorption differs widely from the values Values of K x obtained experimentally with ferric obtained by ultramicroscopieal measurements ; this is hydroxide sols are in good agreement. attributed to the relatively large influence exerted H. I n g leso n . GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 361

Coagulation of colloids by electrolytes. II. was found to be 2-19 per 10°. The conclusion is Conductometric study of the coagulation of reached that tho rate of coagulation cannot be arsenic trisulphide sols. A. J. R abinovitsch and determined simply by the rate of diffusion of the W. A. D orfm ann (Z. physikal. Chem., 1928, 131, particles, since a rise in temperature of 10° increases 313—337).—Addition of a solution of an electrolyte the rate of diffusion by only 30% in this range of to an arsenious sulphide sol causes at first a rapid temperature. H. I n g le so n . increase of conductivity, which gradually slows down Kinetics of coagulation. B. N. D esai (Trans. and finally becomes linear. The initial rapid increase Faraday Soc., 1928, 24, 1S1— 195).—The coagulation is ascribed to the displacement of the rapidly moving of thorium oxide sols by electrolytes has been studied hydrogen ions by the cations of the electrolyte, a by an accurate optical method, which eliminates process which ceases as the conductivity curve those sources of error which probably have prevented becomes linear. The degree of acidity calculated other workers from observing tho period of slow from the form of the conductivity curve is not in coagulation. The rates of coagulation agree with agreement with the valuo obtained from potentio- Smoluchowski’s theory (A., 1917, ii, 129) only up to metric measurements with the quinhydrone electrode. a certain concentration of coagulator. Evidence for When salts of ter- and quadri-valent ions are em­ the autocatalytic nature of the coagulation process is ployed the degree of acidity cannot be calculated on adduced. A formula for the velocity coefficient of account of hydrolysis. The point at which the linear tho process has been derived. Freundlich’s theory portion of the conductivity curve sets in varies directly of coagulation is supported and extended. with the concentration of the sol and inversely as L. F. Gil b e r t . the concentration of the electrolyte, whilst the Action of ultra-violet light on some colloidal difference between the coagulative powers of cations dispersions of gold. J. J. B e a v e r and R . H. of different valencies diminishes with increasing sol M u ller (J. Amor. Chem. Soc., 1928, 50, 304— 321).— concentration. The Hardy-Schulze law is applicable Tho photochemical properties of gold sols depend on only to the coagulation and not to the completion of tho nature and conditions of preparation. Sols the displacement of the hydrogen ions by the adsorbed prepared with hydrazine, phosphorus, formaldehyde, cations; the two processes are essentially different. and acetyleno as reducing agents, and also Bredig’s In order to produce coagulation a cation must either gold sol, are quito stable towards ultra-violet light; partly or completely displace the hydrogen ions other sols turn blue after 2 days’ exposure and are which are attached to the colloidal particles; a certain finally peptised to stable red sols. The chango is excess of the cation is also necessary, which is the accompanied by an increase and a subsequent decrease greater the lower the valency of the ion. The adsorp­ in refractive index, and also in conductivity. The tion of cations of different valencies by the colloidal colour, rate of formation, and photochemical proper­ particles reaches a maximum at approximately the ties of chemical gold sols vary continuously with the same equivalent concentration, but the quantities hydrogen-ion concentration of tho reducing solution. adsorbed vary. The influence of the dilution of the The absorption spectra of some gold sols are recorded. sol on the coagulative power of various cations forms Tho photosensitive sols absorb radiation below an argument against the theory that coagulation is 2150 A.; tho radiant energy from this region clue to the solubility product of the added and decreases rapidly with ageing of the lamp. The stabilising ions being exceeded. H. F. Gil l b e . results are explained on the basis of Wilson’s theory of the structure of colloidal gold particles (A., 1916, Coagulation of colloids with electrolytes. A. ii, 604), it being assumed that radiation influences R abinovitsch and R . B urstein (Papers Pure Appl. the already unequal distribution of ions between the Chem. Karpov Inst., Bach Festschr., 1927, 35—53; particle surface and tho bulk of the solution. The Chem. Zcntr., 1927, ii, 1007).— An investigation of rate of precipitation of Bredig sols is not affected by mastic emulsions, prepared (a) by addition of water radiation. S. Iv. T w e e d y . to an alcoholic mastic solution and filtering, (b) by pouring alcoholic mastic solution into water and Coagulation of colloidal clay. R. B r ad field filtering; in this case the residue is greater. Con­ (J. Physical Chem., 1928, 32, 202— 208; cf. Oakley, ductometric titration of the latter sols is impossible this vol., 16).—The coagulation of a colloidal clay, for lack of a minimum; that of the former gives separated from a silt loam by centrifuging, by potass­ definite results. Both sols are feebly acidic. The ium and calcium hydroxides and chlorides has been particles of the (6) sols are greater than those of tho investigated by the method previously used (A., 1923, (a) sols. On coagulation of tho sols with neutral ii, 470). A portion of the clay was freed from ex­ salts, no development of acidity takes place, as with changeable bases and electrolytes by electrodialysis, arsenious sulphide sols; a corresponding amount of and its behaviour compared with the natural clay. the coagulating cation is retained in the precipitate. The coagulation values for calcium hydroxide in both A. A. E l d r id g e . cases were linear functions of the concentration of the Influence of temperature on rate of coagulation clay, but the much greater values obtained with the of colloids. K . Jablczynski and M. K n a s te r electrodialyscd material showed that base exchange (Bull. Soc. chim., 1928, [iv], 43, 156— 159).— From must play an important role in coagulation phenom­ spectrophotometric measurements of tho rate of ena. With potassium hydroxide as coagulant tho coagulation of a ferric hydroxide sol by potassium effect of electrodialysis is even more pronounced, and chloride solution at intervals of 10° between 0° and with the chlorides of potassium and calcium as 45° the average temperature coefficient of the rato coagulants tho concentration of clay is without effect 362 BRITISH CHEMICAL ABSTRACTS. A. on the coagulation value. Coagulation values are calcium chloride, calcium hydrogen carbonate, alumin­ very sensitive to kydrogen-ion concentration, and ium chloride, and the hydroxides of calcium, potass­ this is very pronounced with the electrodialysed ium, and ammonium. In these cases, Schulze’s clay. L . S. T h e o b a ld . valency law was found to be valid for the discharging effect of the electrolytes. Colloid researches on discharge phenomena Influence of dilute solutions of electrolytes on and adsorption with quartz suspensions. E. the movement of suspended quartz particles in R a m a n n and collaborators (Kolloidchem. Bcih., 1927, a filter of quartz sand. [With M. Storz.]—-A 25, 279—427).—Coagulation experiments and filtering apparatus was constructed by filling a lamp microscopical observations on quartz suspen­ glass, the bottom of which was closed by a mesh, sions. [With J. A. H a n l e y .]—Methods are given with quartz sand, and experiments were carried out for the preparation and preservation of quartz sus­ on the efficiency of such a filter towards increasing pensions containing particles of nearly uniform size, volumes of a fine suspension of quartz. It was graded according to the rate of fall under gravity. found that the weight of retained quartz particles In the sedimentation of suspensions containing the increases with increasing volume of the suspension, finer particles the production of layers was observed. at first linearly, and later tends to a constant value, The layers are very sensitive to light and heat, strong showing that the filter has a saturation capacity. In sunshine soon destroying them. The bounding sur­ presence of increasing amounts of electrolyte (hydro­ faces are usually concave, showing that the walls of chloric acid), however, the curve approaches more and the vessel hinder the fall of the particles. Experi­ more to a straight line, and with 0-0015AMiydro- ments were made both macroscopically and under the chloric acid in the suspension the quartz sand acts as microscope on the flocculation of quartz suspensions a nearly perfect filter. Experiments of a similar kind on addition of lime-water. Microscopical .observ­ were conducted on the amount of quartz suspension ation showed the coagulation to take place in a appearing in the filtrate in presence of various quan­ series of steps, and the first clustering of the particles tities of hydrochloric acid, in some cases finely - did not coincide with the threshold concentration of divided silica being distributed in the filter before the electrolyte necessary to produce macroscopic coagul­ experiment. Experiments in which the filter was ation, but the agreement was better the smaller were divided into vertical sections, each of which could be the particles. weighed separately so as to ascertain the amount of Preparation of chemically indifferent quartz quartz retained, showed that the weight of quartz of definite particle size and surface. [With G. retained diminishes with tho depth of the filter, the K r au ss.]— A detailed account is given of the puri­ gradient being greater in presence of increasing con­ fication of finely-ground quartz both from the pro­ centrations of hydrochloric acid. The capillary rise ducts with which it is naturally contaminated and of quartz suspensions into this type of filter was from those which aro picked up in the grinding also investigated. The amount of quartz passing up process. Directions are given for the preparation into the filter increases with the concentration of the and sterilisation of suspensions of the quartz powder. suspension, but decreases rapidly with increasing con­ The suspensions were separated into fractions of centration of added hydrochloric acid. The amount uniform particle size by means of élutriation. The of quartz thus transported in presence of A-hydro- size of the particles was determined by taking chloric acid is practically nil. A study of the sedi­ numerous photomicrographs of the suspensions. The mentation of quartz suspensions in presence of difficulty inherent in the pronounced irregularity of electrolytes has led to the construction of a filter of the particles was overcome by constructing on the glass balls by means of which the electrolyte in the photomicrograph a circle equal in area to the particle, region of its critical concentration produces rapidly a and taking the diameter of the circle as the mean visible effect on a suspension. diameter of the particle. A method is deduced from Effect of small concentrations of electrolytes theoretical considerations for estimating the surface on sedimentation of quartz suspensions. [With of the particles. H. Sal lin g e r .]-—Evidence is adduced to show that Slipping phenomena in sedimentation on in­ concentrations of electrolytes smaller than the critical clined surfaces. [With G. K r au ss and R. R ü g e r .] value required to produce complete flocculation have —When non-spherical particles of quartz of uniform some effect on suspensions. The effect of various size settle from a suspension in distilled water on to a concentrations of the following electrolytes on a glass surface inclined at an angle to the horizontal, quartz suspension was investigated : the chlorides of the particles readily slide down the plane and aluminium, calcium, potassium, and sodium, and accumulate at the bottom of the vessel. On the calcium hydroxide, sodium carbonate, and hydro­ other hand, when an electrolyte is present in the chloric acid. It is shown that the curve connecting suspension, either the slipping does not occur or the the velocity of sedimentation with the concentration angle which the surface makes with the horizontal of electrolyte consists of three parts. For low con­ has to be increased. It is shown that there is a quite centrations of electrolytes the sedimentation velocity definite “ sliding-angle,” which increases rapidly with is slightly accelerated, then at a certain critical con­ increasing concentration of the electrolyte, and that centration the velocity rises very greatly, and is this angle is a measure of the discharging effect. followed by a third region in which increase of con­ Particles of diameter 0-01— 0-02 mm. were most centration of electrolyte causes only a small increase favourable for the experiments, and the electrolytes in sedimentation velocity. It appears that the used were hydrochloric acid, potassium chloride, critical concentration of the electrolyte rises with GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 363 increasing concentration of the suspension in the case measurements of sodium carbonate and sodium of strongly adsorbahle ions such as aluminium and hydroxide on quartz. [With H. Sa l l in g e r .]— calcium, and the reverse is the case with weakly Since the adsorption of neutral salts by quartz is adsorbable ions. scarcely measurable, the adsorption of sodium car­ Adsorption measurements on quartz. [With bonate is due chiefly to the sodium hydroxide pro­ H. Sa l lin o e r .]—Suspensions of quartz were left in duced by hydrolysis. Therefore, in the adsorption contact with solutions of the hydroxides of calcium, equilibrium, an amount a; of adsorbed sodium hydr­ strontium, barium, lithium, sodium, potassium, and oxide must indicate a definite amount c' of dissolved ammonium, and the carbonates of lithium, sodium, sodium hydroxide. The hydrolysis constant K /, is and potassium, respectively. The amount of the given by the expressionI£/1=2c'(c-}-a;). 10"2/(c—x —2c'), electrolyte adsorbed by the quartz was measured where c is the total alkali titre of the solution after directly by titration with hydrochloric acid. Measure­ the adsorption. The values of c and x are obtained ments were also made of the total surface of the from adsorption measurements of sodium carbonate quartz, and tho results point to the formation of a on quartz, and o' can be determined, knowing x, from unimolecular adsorption layer. The quartz was the adsorption isotherm for sodium hydroxide on never left in the alkali solution for more than an hour, quartz. The value 3-4 X10'1 is given for the hydro­ for if left for a longer interval, chemical interaction lysis constant of sodium carbonate. takes place. Tho exponent n of the adsorption Calculation of the electrolytic dissociation isotherm for the hydroxides of calcium, strontium, constant of ammonia from adsorption data and barium is proportional to the reciprocal squares (quartz/ammonia and quartz/potassium hydr­ of tho radii of tho respective unhydrated cations. oxide). [With H . Sa l lin g e r .]— The formula Cause of formation of layers in suspensions. &=(c')2/i>(c—c') is derived, where lc is the dissociation [With G. K r a u s s .]—The production of layers in constant, v the volume of solution, c the total amount suspensions of quartz is considered to be duo to tho of ammonia after the adsorption, and o' tho effective operation of a uniform velocity of fall of tho particles. amount of ammonium hydroxide. Evaluating the This will operate when the diameter of the particles expression from adsorption data, the values 1c— is below a certain value (the velocity of fall increases 1-65 X 10~5 and 2-5 X 1 0 5 are obtained for two different with the third power of the diameter), and when the concentrations of ammonia. Comparison of c and o' mean distanco between the particles is such that a shows that in 0-00238ilf-ammonia only 8%, and in mutual attraction can be exerted. The presence of 0-00442ilf-ammonia only 7-2% of the total ammonia electrolytes, by partly discharging the particles, should is present in the form of ammonium hydroxide. also exert an effect. It is shown that these deduc­ E. S. H e d g e s. tions are in agreement with experiment. Actually, Ferric acetates. A. K r a u se (R ocz. Chern., layers were observed only when the diameter of the 1927, 7, 402— 435, Bull. Acad. Polonaise, 1927, A, particles was less than 1 g, and when the suspension 237— 272, and Z. anorg. Chem., 1928, 169, 273— fell between certain limiting concentrations. Layers 292).—The action of acetic acid on ferric hydroxide are not produced in presence of electrolytes. hydrogel is a typical Zsigmondy’s inhibited chemical Theoretical conclusions from measurement reaction. As the concentration of acetic acid in the of “ sliding-angle.” [With H. Sa l lin g e r .]— A sol rises, three types of sorption take place, i.e., mathematical treatment of the sliding of charged chemisorption, adsorption, and absorption, then particles of quartz down an inclined plane during peptisation, and finally chemical reaction. The sorp­ sedimentation (see p. 362). From the measurements, tion has a periodic character, the minimum value an expression is derived for the absolute value of lying at O-OfiflN-acetic acid (pH 3-05). Peptisation potential at the quartz-water interface, and, taken in coincides with absorption, being strongest in 0-035— conj miction with adsorption measurements, the 0-153AT-acetic acid (pn 3-2—2-8), and is complete in thickness of the electrical double layer. 0-79W-acid, above which value and up to l-58iV-acid Theory of adsorption in dilute solutions. there supervenes the ionising effect of the addition of [With H. Sa l lin g e r .]— The values obtained in experi­ acetic acid, as is shown by coagulation, change of ments on the adsorption of alkali and alkaline-earth colour, and augmentation of surface tension of the hydroxides on quartz (see above) are compared with sol. An examination of the dry residue from the some adsorption equations, and conclusions are above sols indicated a minimum acetic acid content reached concerning the hydration of the cations. from sols the acid concentration of which was 0-069AT; Dependence of the amount of adsorbed above this, the ratio [AcO]/[Fe] of the residues material on the amount of the adsorbent. [With increases with concentration of acid. Thus with H. Sallin g er .]—The expression x —Km . log djd0 is 1-58iV-acetic acid the monoacetate is formed, with deduced, where x is the amount of adsorbed material, ll-56AT-acid the diacetate, and with 14-45AT-acid the the amount of adsorbent, K a constant, and d0 triacetate. The monoaeetate is probably the only the thickness of the adsorption layer. The value chemical compound present in the system ferric of d is given by vjm . 0 lt where v is the volume of hydroxide hydrogel-acetic acid. The above ferric solution, and 0 1 the surface of 1 g. of adsorbent. acetates, obtained as dry residues, are unstable, Since d0 has been determined, it is possible to calculate losing acetic acid on exposure to the atmosphere, the specific surface 0 1 of the adsorbent from the with tho exception of that originating from the sol formula O ^v/m . d0 . 10*lXm. of 3-05, i.e., at the isoelectric point of ferric acetate, Calculation of the hydrolysis constant of the dissociation constant of which is estimated to be dissolved sodium carbonate from adsorption 10*13. R. T r u szk o w sk i. 364 BRITISH CHEMICAL ABSTRACTS. A.

Action of neutral salts on the artificial caking substances are oriented in polygons, and that sub­ of collagen. J. N ageotte (Compt. rend. Soc. Biol., stances which precipitate one another contain geo­ 1927, 96, 828— 830; Chem. Zentr., 1927, ii, 29).— metrically equal polygons oriented in an inverse The rccoagulation of collagen is affected by the pro­ sense. J. Gr a n t . cess, the acidity, and the quantity and nature of the Binding of acids and bases by proteins. J. electrolytes. ' " A. A. E l d r id g e . W eb e r (Z. physiol. Chem., 1928, 172, 1— 37).— Colloid-chemical model of the double-ring When fibrin is allowed to swell in 0-lV-hydrochloric phenomenon. R. D oerr and E. B erger (Klin. acid, tho binding of chlorine ions corresponds with Woch., 1927, 6, 1562— 1563; Chem. Zentr., 1927, ii, that of hydrogen ions and thus no electrolytic decom­ 1717).— A double ring of precipitate, such as is position of the protein hydrochloride occurs. The obtained when 0-1 c.c. of normal horse serum is binding of hydrogen ions by fibrin reaches a well- covered with 1 c.c. of 0-1% thorium sulphate solution, defined maximum and further addition of acid causes is also obtained when tho serum is replaced by 1 c.c. no increase. Tho acid-binding curve for fibrin is not of a 2% solution of sodium carbonate in 5 c.c. of an adsorption curve, and the titration curves of fibrin sodium chloride solution. A. A. E ld r id g e. with hydrochloric acid, sulphuric acid, oxalic acid, Cataphoretic protein mobility. H . A. A b r a m ­ and phosphoric acid and with sodium hydroxide are son (J. Amer. Chem. Soc., 1928, 50, 390— 393).— similar to those for soluble proteins. Washed fibrin, Quartz particles suspended in dilute protein solutions heated fibrin, and dried fibrin usually bind different under certain conditions move cataphoretically as if amounts of hydrogen ions, but in some cases washing the surfaces of the particles were pure protein. and drying of the fibrin has no influence on the binding Using the previously described apparatus based on capacity. Tho isoelectric point of fibrin is pK 4-7— this principle (Freundlich and Abramson, A., 1927, 4-8. During the digestion of fibrin (or other protein) 931), the migration data for egg-albumin at various by pepsin, the increase in acid-binding power shows hydrogen-ion concentrations recorded by Svedberg no connexion with the dissolution or digestion of the and Tiselius (A., 1926, 1104) are confirmed. fibrin, or with changes in optical activity, viscosity S. K . T w e e d y . (gelatin), surface tension (egg-albumin), or electrical Viscosity and cataphoretic potential of casein conductivity (egg-albumin, caseinogen, or fibrin). In sols. B. J. H o l w e r d a (Rec. trav. chim., 1928, 47, addition, no relationship exists between the increase 248— 263).— Viscosity measurements and kinetic in free amino-groups as digestion proceeds and tho potential determinations on alkaline casein sols were increase in bound acid, but the latter appears to run made to elucidate tho condition of hydration of parallel with the increase in free carboxyl groups. casein in various circumstances. The method of The results support the view that chemical union preparing the casein is detailed. The protein content occurs between acids and proteins and that acid- of casein being known, sols of a known casein content binding constituents other than the amino-groups are could bo prepared. Measurements of tho relative present. A . W orm all. viscosity of alkaline sodium caseinate and calcium caseinate sols at 25° showed agreement with Poiseuille’s Physico-chemical changes in egg-albumin law. The casein sols are liable to alteration of hydrosols caused by latex. I—III. S. V isco viscosity with time and temperature of storage, and (Arch. sci. biol., 1926, 9, 41— 73, 74— 77; Chem. with exposure to carbon dioxide. From observations Zentr., 1927, ii, 906).— On addition of papain from on tho influence of hydroxyl ions on the viscosity of Carica latex the viscosity and golatinising power of sodium and calcium caseinate sols it was- found that gelatin are reduced. In regard to gelatinising power, the viscosity (25°) reaches a maximum at pa 11-6 the optimal temperature is 70°, and the longer the and 11-4, respectively. In the case of calcium time of reaction the greater is tho effect; the action caseinate, the pa of the maximum is independent of is independent of pu. For viscosity, the optimal the concentration of casein in the sols. The influence temperature is 70°, and the effect is more noticeably of neutral salts in small concentrations on the maxi­ remote from the isoelectric point. The latex of Ficus mum viscosity of sodium and calcium caseinate sols carica is very effective; its action on the pa is more was measured, using equivalent concentrations of the marked than that of papain. The density of gelatin chlorides of sodium and calcium, and of hexammine- solutions is increased by tho latex. The results are cobaltic chloride. In all cases, viscosity and p B value considered theoretically. A. A. E l d r id g e . decrease with increasing concentration of the added Swelling of rubber. P. Stamberger (Rec. trav. neutral salt. chim., 1928, 47, 316— 320).— The swelling of raw A study of tho cataphoretic potential showed that rubber, of over-rolled rubber, and of over-rolled rubber the maximum of the viscosity does not correspond containing varying amounts of carbon black has been with the maximum of the electrokinetic potential. studied. Determinations were carried out in a liquid The results suggest a variation in the hydration of the medium and in its vapour, the lowering of vapour sol particles with a variation of pB. R. A. Pratt. pressiue being followed. At the point of maximum Geometrical molecular specificity. R. F er- swelling in benzene vapour, over-rolled rubber gave r ie r (Compt. rend., 1928, 186, 577— 578).— The a viscous liquid, whilst raw rubber under similar adsorption phenomena of certain colloidal substances conditions appeared to be stable. With increasing (e.g., proteins) which precipitate one another from quantities of carbon black, the hardness of these solution in a specific fashion may be explained by jellies was found to increase. Observations were also the assumption that the molecules of the different made with benzene containing 10% of triolein. The GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 365

variations in the amount of swelling of raw and of 263).—The practical difficulties of making direct over-rolled rubber, whether swollen in vapour or in measurements of the concentration are referred to liquid, were very marked, being 1880% by volume and an indirect method of calculation depending on a and 120% by volume, respectively. The results O. _ could not be brought into line with any known inter­ knowledge of the equilibria : I2+H 20= H + I+ H 10; pretation of swelling phenomena. R. A. Pr a t t . H20=H +O H ; l2+ l= l3, is described. The values New form of Raoult's laws. I. N. L o n g in eso u obtained are applicable only to the freshly prepared (J. Chim. phys., 1928, 95, 70— 82).— Raoult’s f.-p. solutions. Tho results indicate that for a fixed con­ and b.-p. formula; are given a form in which the centration of iodine, the hydrogen-ion concentrations “ constants ” are much less variable than is usually fall with increase in the amount of iodide, whilst for the case. A modified form of Raoult’s equation for solutions with a fixed ratio [KI]/[I2] they increase the lowering of vapour pressure, which is frequently •with the dilution. H. I ng leso n . met, viz., (P0—P)/P0=x/d, where d is the density of Equilibrium between methoxyl and hydroxyl the solvent, is incompatible with Clapeyron’s equation. ions in mixtures of methyl alcohol and water. L. F . G il b e r t . II. Electrometric hydrogen-ion measurements. E . D . E astm a n (J. Theory of the Soret effect. A. U n m a c k (Z. physikal. Chem., 1928, 131, 371— Amer. Chem. Soc., 1928, 50, 283— 291).— The equa­ 388).— The hydrogen-ion activity in alkaline mixtures tions (cf. A., 1926, 797) for the equilibrium states of water and methyl alcohol has been determined at resulting from reversible Soret effects are transformed 18° by electrometric measurements, and the partition into sA—dFAl d T = —SA, where sA is a Soret co­ coefficients of basic ions between water and watcr- efficient, PA the free energy change, and SA the methyl alcohol mixtures have been calculated. The entropy change, of the surroundings when one mole partition exponent at infinite dilution between water of constituent A is transferred. The coefficient Sj is and methyl alcohol is about 1-8. On tho assumption proportional to the ordinary coefficient, d\ogc NAldT, that the partition coefficient of the hydroxyl ion is when the solution is sufficiently dilute. The heats of equal to that of the hydrated hydrogen ion, tho transfer which determine reversible Soret effects in equilibrium constant of the reaction OH'+MeOH==±= electrolyte solutions are due to changes in the outer OMe'+H20, calculated on the basis of the Bjerrum- of three spheres surrounding the moving ions; the Larsson theory, is about 0-47. H. F. Gil l b e . two inner spheres (the “ ion-cavity ” and the strongly attracted and oriented molecules) move with the ion, Micelles and the activity coefficient in alkali whilst the outer changes with the environment of the silicate solutions. M. R a n d a l l and (Miss) J. Y. ion. Values of s are calculated for some electrolytes Ca n n (J. Amer. Chem. Soc., 1928, 50, 347— 358).— in water on the basis of this hypothesis; the results If the negative ion of a uni-univalent strong electro­ agree fairly well with the direct determinations, but lyte, AB, is replaced by an ionic micelle of the form are higher than those of Chipman (A., 1926, 1206). (B„)n-, then, neglecting hydrolysis, the mean molality Indirect determinations are probably capable of is m+ When n is infinite the whole of tho greater accuracy than the direct. The theory requires solute may be regarded as a single particle possessing that the Soret coefficients are additive, individual the entire negative charge of the solution, and sur­ values being assignable to all ions at infinite dilution rounded by univalent positive ions. As n increases (cf. A., 1927, 419). In infinitely dilute solution s is the micelle becomes progressively a weaker electro­ zero for the solvent but not for the solute; the theory lyte, and in the limit probably behaves as a non­ indicates a maximum value of s at higher electrolyte electrolyte. The activity coefficients of various concentrations, with the possibility of a minimum as sodium silicate solutions aro calculated from f.-p., well. Strong electrolytes in dilute aqueous solutions b.-p., dew-point, and vapour-pressure observations. have negative coefficients. In series of chemically Metasilicate solutions behave as typical uni-bivalent similar ions the Soret effects are of the same order. electrolytes; the value of v in the Lewis and Randall The Soret coefficient in non-electrolyte solutions, and f.-p. equation is taken as 3 instead of 4. The acid the irreversible Soret effect in all liquid solutions, aro silicates have very low activity coefficients, which are small. S. K . T w e e d y . explained by the formation of ionic micelles, and are not largely hydrolysed; the formula NaHSi03 is Theory of hydrates. E. N. G a pon (J. Chim. preferred and v=2. The fraction of silicate existing phys., 1928, 25, 154— 156).— The relationship T^Jmj as micelles, and the number and size of the micelles, d*/n—cv in which T is the m. p. in degrees Abs., m increase with the ratio of silica to sodium oxide. the number of ions composing tho molecule, d the The influence of the micelles on the activity coefficient density, n the number of atoms in the molecule, and of the sodium ion is discussed. S. K. T w e e d y . ci a constant, approximately 58, has been verified for a number of hydrated salts. If M X„ be a salt which Production of glycerol by fermentation. IV. forms a hydrate, MX„,mH20, of density d, the mole­ Dissociation of acetaldehyde-sodium hydrogen cular volume has the value given by 7m=M X„/d+ sulphite complex in alkaline solution. Y. wzHjOId; writing this as Vm=A-\-B, the quantity T om oda (J. Soc. Chem. Ind. Japan, 1927, 30, 747— AB/(A-\-B) has for a large number of salts an 759).— The dissociation equilibrium is represented by approximately constant value of about 0-45. al(l — a )= K + (K 1IK)[W ]-rKK2l['ii'], where a is the H. F. Gil l b e . degree of dissociation, K the dissociation constant of Hydrogen-ion concentration of aqueous iodine the complex=2-84xl0-fi, K x and K 2 the constants solutions. H. M. D aw son (J.C.S., 1928, 259— for the first and second stage dissociation of the acid. 366 BRITISH CHEMICAL ABSTRACTS.— A.

The above equation for a shows that at p n 6— 8 the respectively. The composition of the eutectic mix­ dissociation of the complex is not appreciable, but ture is 66% Sn. L. F. Gil b e r t . reaches 50% at p n 10-5. The variation of p a value Transformation of austenite into martensite during the titration of the complex by alkali was by liquid air. K. Sch roeter (Z. anorg. Chem., examined, and the p a of the solution, containing 1928, 169, 157— 160).— The conversion of austenite equimolecular alkali and the complex, found to be into martensite by liquid air is shown by the action 12— 13, which suggests that the sulphite-aldehyde of the steel on a magnet to occur during the cooling, complex is almost completely dissociated. In the and not during the subsequent restoration to the production of glycerol, the p a value of the fermenting ordinary temperature. Measurement of the magnetic medium scarcely exceeds 8-3, so that the dissociation saturation before and after cooling indicates a greater of the complex must be relatively small (less than relative transformation in a steel hardened in oil than 5%). The relation between the degree of dissociation in the same steel hardened in water, the strain due to of the complex and the value of the medium was the increase in volume accompanying the y — a change confirmed by measuring the distribution of the free being less in the former steel than in the latter owing aldehyde between water and benzene at various p a to its lower austenite content. R. Cu t h il l . values. When a solution of acetaldehyde containing an excess of sodium hydrogen sulphite was titrated Equilibrium pressure over co-existing salt with 0-lW-iodine solution at about p a 8, the total hydrates at temperatures below 0°. J. B. sulphite was titrated, whereas when the titration was A ustin (J. Amer. Chem. Soc., 1928, 50, 333— 386).— conducted at p n 1— 2, the free sulphite was titrated. The aqueous vapour pressure over a pair of co-existing The difference represents the amount of the combined salt hydrates is less than that over ice or water, and sulphite and therefore the acetaldehyde. When a it follows that the heat of hydration of salts per mol. solution of sodium hydrogen carbonate and the com­ of water is always less than the molar heat of fusion plex was distilled, the whole of the acetaldehyde was of ice, thus affording a criterion of the accuracy of evolved. S. Ok a . data on salt hydration. The data for the ten salts which apparently do not obey this rule are open to Graphical representation of the law of mass suspicion. S. K. T w e e d y . action. K. I. S karblom (Tekn. Tidskr., Iiemi, 1927, 57, 87— 90; Chcm. Zentr., 1927, ii, 2033).— A Dissociation of sodium sulphate decahydrate. triangular diagram is employed; a curve is obtained E. P. P erm an and W. D. U r r y (Trans. Faraday whereby the composition of a mixture can be read. Soc., advance proof, Feb., 1928).—The dissociation A. A. E ld r id g e . pressure of sodium sulphate decahydrate has been Combination and space. N. S. K u r n a k o v (Z. measured, using the method of Downes and Perman anorg. Chem., 1928, 169, 113— 139).— The relation of (A., 1927, 194). The results have been applied in the physico-chemical changes of matter to tho the calculation of (i) the free energy change associated geometrical transformations of space is considered, with the hydration of anhydrous sodium sulphate to and topology applied to the development of an decahydrate by ice, and (ii) tho heat of hydration of analogy between a property-composition surface and sodium sulphate by liquid water. The heat of a contour map. 11. Cu th ill . hydration of sodium sulphate has been measured at four temperatures between 20° and 30°, employing Graphical methods and empirical formulae the method of Harrison and Perman (A., 1927, 207). for the study of electrolytic dissociation. E. The results are in good agreement with the heats D enina (Notiz. chim.-ind., 1927, 2, 491— 497).— A calculated from the free energy changes by means of graphical method of representing tho ideal dissoci­ Nernst’s heat theorem. The chemical constant of ation formula is developed, and diagrams showing water is calculated, giving a mean value of 3-63. variations in the dissociation coefficient are discussed. W . A. R ich ardson. Chem ical A bstracts. Thermodynamic studies on zinc iodide and Influence of buffering capacity on the solu­ mercurous iodide. F. Is h ik a w a and E. S htbata bility of uric acid. A. J ung and F. L eu t h a r d t (Sci. Rep. Tohoku, 1928, 17, 99— 109).— See A., (Deutsch. Med. Woch., 1926, 52, 1985— 1988; 1926, 1103. Chem. Zentr., 1927, i, 3053).— For two different buffer mixtures the solubility of uric acid fell from Binary system manganous orthosilicate-cal- 0-67 to 0-14 on dilution from 1 : 15 to 1 : 1920, with cium orthosilicate. L. T o k o d y (Z. anorg. Chem., a corresponding increase of acidity. 1928, 169, 51— 56).— The results of Kallenberg’s investigation of the above system (A., 1915, ii, 348) A. A. E l d r id g e . Lead-tin system of alloys re-examined by an have been confirmed. R. Cu t h ill . electrical resistance method. F. H. J e ffer y M.-p. curves of the nitrobenzaldehydes in the (Trans. Faraday Soe., 1928, 24, 209— 211).— The presence of acetic anhydride. P. A. A. v a n der continuous method of recording change of electrical B e e k (Rec. trav. chim., 1928, 47, 309— 315).— The resistance as a function of temperature previously m.-p. curves were determined in presence of phos­ described (A., 1927, 1030) has been applied to the phorous or sulphuric acid as catalyst. Two modific­ lead-tin system. The equilibrium diagram has been ations of o-nitrobenzylidene diacetate were found, of determined down to 75° and is of the Roozeboom m. p. 56° and 75°, respectively, but they could not type 5, without any complication. The line of bo isolated in the pure state. The yield of diacetate eutectic points is at 183°, the phases forming the was greater when using sulphuric acid as catalyst eutectic mixture containing 16-5 and 97% of tin, and the product showed no discrepancy in m. p. The GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 367 m.-p. curve of the o-compound showed only the 1 : 1 System calcium oxide-alumina-ferric oxide. compound (m. p. 73°) to exist. This was confirmed W . C. H a n s e n , L. T. B r o w n m ille r , and R. H. by adding a drop of sulphuric acid to pure diacetate B ogue (J. Amer. Chem. Soc., 1928, 50, 396— 406).— and setting aside in a sealed tube. With sulphuric The above system exhibits one ternary compound, acid as catalyst, equilibrium is established from either viz., 4Ca0,Al203,Fe20 3, d 3-77, which melts con- side after 7 days. For m-nitrobenzylidene diacetate, gruently at 1415°, and forms with 2Ca0,Fc203 a phosphorous acid is a better catalyst. Here again complete series of solid solutions having a melting equilibrium between the substance and its components range of about 10°. The compounds Ca0,Al203 and is reached in 7 days. Only the 1 : 1 compound Ca0,Fe203 form limited solid solutions. A diagram (m. p. 57°) was found to exist, its existence being is given showing the fields in which CaO, confirmed by catalysing the pure diacetate with phos­ 4Ca0,Al203,Fe203, 3Ca0,Al20 3, 5Ca0,3Al203, and phorous acid. The m.-p. curve of p-nitrobenzalde- solid solutions of 4Ca0,Al20 3,Fe20 3 with 2Ca0,Fe20 3 hyde-acetic anhydride also shows only tho 1 : 1 separate as primary phases. Two quadruple and four compound (m. p. 126-8°) to exist, phosphorous acid quintuple points have been established, and extensive being used as catalyst. R. A. Pr a t t . optical data are recorded. S. K. T w e e d y . Systems uranyl nitrate, alkali nitrate, water, Conductometric and cryoscopic study of the at 25°. A. Co l a n i (Bull. Soc. chim., 1928, [iv], 43, dimethylpyrone compounds of acetic and the 194— 199).— See this vol., 131. chloroacetic acids in benzene. M. R abinovitsch (Z. physikal. Chem., 1928,132, 83— 100).—The occur­ Double salt formation. I. Formation of cop­ rence of salt formation by the action of dimethyl­ per sodium sulphate. II. Formation of man­ pyrone on acetic, mono-, di-, and tri-chloroacetic ganese potassium and ammonium sulphates. acids in benzene solution has been studied conducto- R. M. Ca v e n and W . J ohnston (J. Roy. Tech. Coll. metrically, and the cryoscopic relationships of the Glasgow, 1927, [4], 3 2 -A 1 ).— See A., 1927, 1142. dimethylpyrone acetate solutions have been investig­ Equilibria in systems containing water and ated. The maxima in the conductivity curves corre­ chlorides of iron, cobalt, and nickel. Y. Osa k a spond in each case with tho formation of tho diacid and T. Y a g in u m a (Bull. Chem. Soc. Japan, 1928, 3, salt. The conductivities of benzene solutions of the 4— 10).— The systems FcC13-CoC12-H 20 and FeCl3- four acids are less than those of the pure substances. NiCl2-H 20 form neither double salts nor solid solu­ The order of the conductivities of the three chloro­ tions. In the system CoCl2-NiCl2-H 20, the hcxa- acetic acids in benzene solution is tho same as that of hydrated chlorides form a complete series of solid their degrees of association; in presence of dimethyl­ solutions. The system FeCl3-CoCl2-NiCl2-H 20 has pyrone the order of both is roversed. As regards also been examined. S. J. Gr eg g . ionisation tho role of dimethylpyrone in benzeno is System potassium nitrate-calcium nitrate- similar to that of water in aqueous solution. sodium nitrate-water. F. Frow ein (Z. anorg. H. F. Gil l b e . Chem., 1928, 169, 336— 344; cf. A., 1927, 22).— Eutectic f.-p. depression in binary mixtures. Determination of the solubility isotherms for tho IV. Effect of pressure on eutectic equations. systems sodium nitrate-calcium nitrate-water and E. K ordes (Z. anorg. Chem., 1928, 169, 246— 250; potassium nitrate-calcium nitrate-water at 0° and cf. this vol., 117).— Taking Hasselblatt’s data for the 20° shows that in the latter system each salt increases effect of pressure on the m.-p. diagram of mixtures of tho solubility of the other, the effect being greater at the tetrahydrates of cadmium and calcium nitrates 0° than at 20°, whereas calcium nitrate depresses the (A., 1922, ii, 61), and assuming that the hydrates are solubility of sodium nitrate, and its own solubility is completely dissociated according to the equations not affected by sodium nitrate. The three-salt Cd(N03)2,4H20=Cd(N 03),,H20+ 3H 20, and points for the system potassium nitrate-calcium Ca(iSi03)2)4H20= C a (N 0 3)2,2H20 + 2 H 20, the relation nitrate-sodium nitrate-water at 0° and 20° have also (Tb—Te)jTi,: (Ta—Te)jTc—a : 6, where Te is the been determined. R . C u th ill. eutectic temperature, and a and b are the molecular Plane representation of multicomponent concentrations of the two components, with m. p. Ta systems. W. N. L o d o ô n ik o v (Z. anorg. Chem., and Th, respectively, in the eutectic, is true over the 1928,169, 177— 245).—The application of the method whole range of pressure. The equation {(Tb— of graphical representation previously described (A., Tc)l(Ta—Te)}k=zT(,ITa, where k is a constant (A., 1927, 1132) is also apparently independent of the 1926, 358) to systems of four or more components is C u th ill. pressure. R . Cu t h il l . explained in detail. R. Specific beat of electrolytes. K. B e n n e w it z Equilibria at higb temperatures in the system (Z. Elektrochem., 1927, 33, 540— 542).—Theoretical. iron-oxygen-carbon. R. E. Ga r r a n (Trans. H. J. T. E llin g h am . Faraday Soc., 1928, 24, 201— 207).— The equilibria Heats of dilution of strong electrolytes and m the systems iron-ferrous oxide-carbon dioxide, limits of Debye and Hückel's theory. E . L an g e carbon monoxide, and ferrous oxide-ferrosoferric and G. M essn er (Naturwiss., 1927, 15, 521— 522; oxide—carbon dioxide, carbon monoxide have been Chem. Zentr., 1927, ii, 790).— Tho heats of dilution of studied over the approximate range 600— 1300°. The O'OlAf-potassium, sodium, and lithium chlorides, results would seem to be concordant with those for , and potassium nitrate, O'OOO/- the temperature range covered by Bone, Reeve, and calcium nitrate, 0'0023-1-sodium and magnesium Saunders (cf. B, 1927, 4S4). L. F. Gil b e r t . sulphates, and 0'00236il/-calcium sulphate solutions 368 BRITISH CHEMICAL ABSTRACTS.— A. have been accurately measured by means of an and fatty acids, y/ZjL for the normal b. p. adiabatic differential calorimeter. The results are all has a value about 8-5 x 108. R . Cu t h il l. positive. For original concentrations below O-OliW Reversible mixing of substances in the con­ for the uni-univalent halides, or 0-002.3/ for the uni- densed state at the absolute zero of temperature. bivalent electrolytes the experimental values are R. D. K leem an (Science, 1927, 6 1 , 216—217).—The slightly below the theoretical. Potassium nitrate, internal heat of mixing a number of substances is however, in 0-01 J/-solution, exhibits a large negative zero at 0° Abs. if the substances and resultant mixture deviation from the theoretical value. With bi- are under the pressures of their vapours. Near bivalent electrolytes the heats of dilution for original 0° Abs. the internal heat of mixing is proportional to concentrations of 0-002J7 vary, and are greater than the cube of the absolute temperature. the theoretical values. A. A. E ldridge. A. A. E l d r id g e . Heat of dilution of moderately concentrated Errors in the determination of heat of com­ solutions. S. M. N au de (Z. Elektrochem., 1927, bustion. E. B e r n e r (Tidskr. Kemi Bergv., 1927, 33, 532—534;).—The theory put forward recently by 7, 31— 3 4 ; Chem. Zentr., 1927, i, 3211).— A discussion Nernst (this vol., 127) is further developed and heats of the precision of the temperature measurement and of dilution of solutions of sodium chloride, potassium of tho computation of the heat exchange with tho chloride, sodium nitrate, and potassium nitrate are surroundings. A. A. E l d r id g e . shown to bo represented by W = — 77(1 — ac, Determination of heat of combustion with where a is the true degree of dissociation of the Fery’s calorimeter. F. K aras (Chem. Obzor, electrolyte, U the heat of dissociation, and B is the 1926, 1, 121— 125; Chem. Zentr., 1927, ii, 1373).— Debye-Hiickel coefficient which is now shown to The maximum deviation of results obtained with increase linearly with temperature. Data are given Fery’s and the Berthelot-Mahler-Ivroeker calori­ for concentrations, c, ranging from 0-004 to 0-333 g.- meters is 1-21%; Fery’s method occupies half the mol. /litre. Wit h increasing concentration IF increases time of the latter method. Errors may arise from to a maximum and then decreases again, becoming the radiation from incandescence lamps; day- and negative at high concentrations. These variations night-values may differ by 2%. A. A. E l d r id g e . are represented very closely by the above formula, Heat of combustion of some secondary and H. J. T. E i.linGuam. tertiary amides. A. P arts (Z. physikal. Chem., Vapour pressure and heat of dilution. V. 1928, 1 3 1 , 405—408).—Tho following heats of com­ Activity. E. P. Perman (Trans. Faraday Soc,, bustion, in kg.-cali/mol., have been determined : advance proof, Jan., 1928).—At 80°, solutions of diacetamide 518-9, dipropionamide 809-2, acetyl- sucroso up to 500 g. per litre behave as perfect benzamide 1065-1, dibenzamkle 1634-8, tribenzamide solutions. The lower tho temperature, the lower is 2425-5. H. F. Gh l b e . the concentration up to which tho solution remains perfect. For dilute solutions of carbamide at 80° and Methods in use at the International Bureau 60° the activity is slightly higher than unity, and tliis of Physico-Chemical Standards. II. Calori- is attributed to the formation of traces of ammonia by metric precision measurements. L. Maricq and hydrolysis at these temperatures. Allowing for this M. B eckers (Bull. Soc. chim. Belg., 1928, 3 7 , 1— error carbamide solutions remain perfect at these 32).—A detailed description is given of a calorimetric temperatures up to a concentration n/N—0-8. method for the determination of heats of combustion. To calculate the activity of potassium chloride, it The experimental error does not exceed 1 part in was assumed that a2/Ar2= l at a dilution of AT1/A72= 4000 and might be further reduced by using a more 10,000. Tho activity of the solute reaches a high sensitive thermometer, e.g., a resistance thermo­ value in concentrated solution, and is greater at 60° meter instead of a mercury thermometer. The than at S0°. The activity coefficient y for a molal applicability of Regnault’s correction is discussed. solution is 0-52 at 80° and 0-60 at 60°. The activities The heat of combustion of pure benzoic acid prepared have been calculated in a similar maimer for calcium by Poulenc was found to be identical with that of the chloride solutions, and are shown to reach enormously benzoic acid standard supplied by the U.S. Bureau high values at high concentrations. of Standards (cf. Dickinson, Bull. Bur. Standards, 1915, 1 1 , 192— 203). M. S. B u rr. W . A. R ichardson. Heat of vaporisation and number of molecules Electrochemistry of the system benzamide- [in unitvolume], W. H erz (Z. anorg. Chem., 1928, bromine-nitrobenzene. W. F in k e l s t e in and 0 . 1 6 9 , 173— 176).— For non-associated liquids, and K u d r a (Z. physikal. Chem., 1928, 1 3 1 , 338— 346).— many associated liquids, the value of Zj-y/L, where Z The specific conductance of the additive compound is the number of molecules in unit volume at a bromobenzamide, NH2Bz,Br2, in nitrobenzene particular temperature (calculated from the molecular solution increases with increase of concentration up volume and Avogadro’s number), and L the latent to 52%. The curves at 25° and 35° are parallel, the heat of vaporisation at that temperature, is approxim­ temperature coefficient being negative. The mole­ ately constant over a wide range of temperature cular conductivity-dilution curves at 35° have a although a very flat minimum is usually present. The maximum at about 900 c.c. dilution. The relation­ value for liquefied gases falls slowly but continuously ship between the conductivity and the ratio benz- with rise in temperature, but data are available over ainide : bromine confirms the existence of the complex only a small range of temperature. For hydrocarbons as a true electrolyte;. on electrolysis bromine is and esters, but not for associated compounds such as liberated quantitatively at the anode. The decom­ GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 369 position potential cannot be measured on account of presence of alcohol; and of sulphates of heavy metals, the thermal decomposition products. including double ammonium sulphates, with barium H. F. Gil l b e . hydroxide solution. H. J. T. E llin g h am . Electrical conductivity of solid sulphide m ix­ Conductivities and p a values of mixtures of tures. P. F ischer (Z. Elektrochem., 1927, 33, acids in solution. J. A. Cr a n sto n and J. D u n c a n 571— 577).— Following work on mixtures of salts and (J. Roy. Tech. Coll. Glasgow, 1927, 4, 41— 47).— of oxides (A., 1926, 478; 1927, 23), the electrical The hydrogen-ion concentration (measured by a conductivity of compressed mixtures of powdered hydrogen electrode) and the conductivity of hydro­ sulphides has been determined for direct and for chloric acid solutions containing varying amounts alternating current at various temperatures. For of acetic, oxalic, citric, tartaric, and orthophosphoric mixtures of two sulphides the conductivity does not acids have been determined. Replacement of water vary in a simple manner with the percentage com­ in 0-5A-hydrochloric acid by solutions of acetic, position of the mixture. With silver sulphide and citric, or tartaric acid results in an increase of the lead sulphide the conductivity increases with hydrogen-ion concentration as determined by the increasing proportion of lead sulphide, but eventually E.M.F. method, whereas the conductivity falls. reaches a maximum at about 90% PbS. Although When phosphoric acid solution is substituted, the the conductivity of silver sulphide is essentially pa value increases, whilst the conductivity rises to a electrolytic and that of lead sulphide electronic, maximum and falls. It is suggested that some of the migration experiments on a 50% mixture indicate hydrogen ions supplied by the added acid arc suffi­ that only about 1% of the conductivity is electrolytic. ciently free to contribute to the potential of a con­ For mixtures of silver sulphide with ferrous sulphide, tiguous hydrogen electrode, but arc insufficiently which is practically a non-conductor, the con- free to contribute to the conductivity of the solution. ductivity-composition curve exhibits a minimum and When hydrochloric acid solutions of greater than a maximum. Mixtures of ferrous sulphide and lead Ar-concentration are used, substitution of water sulphide are practically non-conducting up to by solutions of varying oxalic acid concentration has 50% PbS, but with higher proportions the con­ no effect on the conductivity; when solutions of ductivity increases rapidly. Mixtures containing phosphoric acid are substituted, the conductivity of sulphides of copper, zinc, cadmium, and barium were the hydrochloric acid solution is diminished. It is also examined. It appears that the type of con­ suggested -that the hydrogen ions from the hydro­ ductivity exhibited by a solid substance may be chloric acid may not only prevent the dissociation of modified by certain conditions. The observed the phosphoric or oxalic acid into ions, but in the phenomena are attributed to distortion of the crystal case of the former acid, may also attach themselves lattices and electron orbits as a result of compression. transiently to undissociated phosphoric acid molecules, H. J. T. E llin g h am . since in phosphoric acid there is an oxygen atom Conductivity cells with, electrodes of 1 ‘ brom in- possessing a “ lone ” pair of electrons, which may be ated silver " instead of platinum. W . A. R oth shared by the hydrogen nucleus. L. M. Cl a r k . (Z. Elektrochem, 1927, 33, 508— 511).— Pure silver covered with a very thin film of silver bromide by Potential of the saturated calomel electrode exposure to bromine vapour or by dipping in a solution between 0° and 40°. E . V ellin g er (Arch. phys. of bromine in hydrobromie acid, is recommended as a biol., 1927, 5, 119— 122; Chem. Zentr, 1927, ii, cheap substitute for platinum in the construction of 674).— The relation I?=0-2622—0-00066Í holds. electrodes for conductivity cells. Such electrodes A. A. E ld r id g e . give, in conductivity measurements, a balance point Potentials and activities of the metals in zinc about as definite as is obtained with smooth platinum amalgam cells. J. N. P earce and J. F. E versole electrodes, whilst, if covered with a thin deposit of (J. Physical Chem, 1928, 32, 209— 220).— E.M.F. platinum-black, the minimum is as sharp as with measurements of zinc amalgam concentration cells platinised platinum electrodes. For dilute solutions have been made at 18°, 25°, and 30°, with amalgam of silver salts or of formic acid, brominated silver concentrations ranging from a mol. fraction of zinc electrodes give better results than platinised platinum. equal to 0-0003024 up to saturation. The changes in A number of demonstration experiments using a free energy, heat content, and entropy on dilution, conductivity apparatus fitted with an amplifier and and the activities of the zinc and the mercury in the a loud speaker are described. These illustrate the amalgams have been calculated. The deviation relative solubility of sparingly soluble salts, the between the observed and ideal potentials increases relative adsorption of sodium and potassium chlorides continuously with an increase in concentration of by soils, and of potassium chloride and nitrate by the zinc and approaches zero at infinite dilution. precipitated barium sulphate, and the principle of Hildebrand’s equation (A , 1913, ii, 470) expressing conductometric titration. For the last-mentioned the E.M.F. of a zinc amalgam concentration cell purpose a simple type of apparatus with vertical applies throughout a large portion of the range electrodes of brominated silver is described. Refer­ studied. The present results decide in favour of the ence is made to the conductometric determination of work of Richards and Forbes (A, 1907^ ii, 424) and chlorides, , or iodides of heavy metals by against that of Crenshaw (A , 1910, ii, 258). titration with thallium hydroxide solution in the L. S. T h e o b a ld . presence of alcohol; of metals with insoluble fluorides Palladium diffusion electrodes. C. D r u c k e r with silver fluoride solution; of potassium with lead (Z. Elektrochem, 1927, 33, 504— 507).—Two solu- fluosilicate or barium perchlorate solutions in the tions, A and B , are separated by a thin plate of B B 370 BRITISH CHEMICAL ABSTRACTS.— A. palladium which is charged with hydrogen by cathodic transport number of the silver ion, and k1 and k2 are polarisation, using as anode a platinum wire in the specific conductivities of the two electrode solution A. By means of standard electrodes solutions. Very good agreement was shown. The arranged with their tips close to the two sides of the results for such concentration cells support the plate respectively, the P.D. on both sides can be Nernst formula, and also show that the solution measured, and hence, if the hydrogen-ion con­ laws are obeyed in these solvents at least as nearly centration of A is known, that of B can be determined. as in water. R. A. Pratt. By using a rotating commutator the polarisation circuit is broken when the potentiometer circuits Modifications of the Sand auxiliary electrode. are made, and vice versa. With a polarisation current T. B. Smith (Trans. Faraday Soc., 1928, 24 , 216— of 0-07— 0-10 milliamp. at a plate with surface area 225; cf. J.C.S., 1911, 91, 373).— By the use of 20— 80 sq. mm. and thickness 0-004 mm., reproducible a porous diaphragm instead of the special “ con­ values were obtained, although the effective pressure ducting ” tap of the Sand electrode, and by other of hydrogen in the palladium was only about 0-01 atm. modifications, the working resistance of the auxiliary Preliminary experiments in which A and B were both electrode can be reduced to about one tenth of the O-liV-hydrochloric acid showed that under these former value. This enables the potentiometer volt­ conditions the effective hydrogen pressures on both meter to function also as a null-point detector without sides of the plate become equal after about 20 min. causing any appreciable error on account of concen­ and direct measurements are then possible. In tration polarisation of the half-cell. A second any case determinations can be made by making a modification is described in which the use of either measurement with solutions A and B, and then special taps or diaphragm in the electrical circuit is making a further measurement when a solution B' of avoided. It has about the same resistance as the known hydrogen-ion concentration has been sub­ first pattern, but permits the use of connecting stituted for B. The method has the great advantage liquids of high conductivity. The null-point detec­ of being applicable to the determination of the tion is thus brought within the range of a voltmeter hydrogen-ion concentration of solutions which change of relatively low sensitivity. This modification is to in composition if a stream of hydrogen gas is passed be preferred for most purposes, but the diaphragm through them, and of solutions which are mild pattern has the advantage that it may be used for a reducing agents. Measurements on solutions of considerable time without refilling with electrolyte. sodium hydrogen carbonate and of sodium hydrogen The second modification can be employed conveniently sulphite are recorded. The second dissociation con­ as a quinhydrone electrode. Use is made in the stant of sulphurous acid is thus estimated to be about electrical circuit of the better class of radio apparatus, 5xl0~7. Again, a blood-serum was found by the the compact design of which facilitates the enclosure diffusion electrode to have a hydrogen-ion concen­ of parts most easily attacked by acid fumes. tration of 1-4 x 107?, whereas the value obtained by L. F. Gil b e r t . means of the ordinary hydrogen electrode was E.M.F. of electrolytic thermocouples and 3-3xl0~8. H. J. T. Ellingham. thermocells and the entropy of transfer and absolute entropy of ions. E. D. E astm a n (J. Solution tension of silver in non-aqueous Amer. Chcm. Soc., 1928, 50 , 292—297).—Electrolytic solvents. F. K. V. K och (J.C.S., 1928, 2C9— 280). thermocouples of the type : electrode(T)/soln.I(7T)/ —The solution tension of silver has been measured in solii.II(T-i-dT)/so]n.l(jn)/clectrode(T) are discussed, solutions of silver nitrate in pyridine, aniline, methyl the solutions containing uni-univalent electrolytes and ethyl alcohols, acetone, and various nitriles with with a common anion, and the equations previously the view of correlating the results with the dielectric given for thermocells are modified by considering constants of the solvents and also to ascertain whether the entropy of transfer of tho ions. Utilising pre­ the solution tension in different solvents runs parallel viously published data and the principles of the with the solubility of the salt in these liquids. There preceding paper (this vol., 365), the entropy of transfer appears to be no kind of regularity in the series of of some ions in a 0-02V-solution at 25° is calculated, as corresponding values of dielectric constant, solution well as the partial molal entropy of the chloride ion. tension, and solubility, but the general result of the S. K. T w e e d y . investigation shows that in solvents of ammoniaeal Haber’s glass cell. W. S. H ugh es (J.C.S., 192S, or nitrile character the metal has a higher solution 491— 506; cf. A., 1909, ii, 785; 1925, i, 1201).— The tension than in those containing hydroxyl or lcetonic influence of the composition of the glass used for a groups. H. Ingleson. Haber cell on the reproducibility of results was Silver nitrate concentration cells in aceto- studied. The best results were obtained with a glass nitrile and benzonitrile. F. K. V. Koch (J.C.S., of small alumina content but of high sodium content. 1928, 524— 527; cf. A., 1927, 420, and preceding The manufacture of a modified Haber cell is described. abstract).—Previous work on the validity of the Such a cell showed no evidence of the “ mixed Nernst formula applied to concentration cells con­ electrode function ” in acid solution described by taining non-aqueous solutions is reviewed. Experi­ some workers. An explanation is put forward of mental results on the measurements at 0° and 25° of the means whereby the hydrogen-ion concentration E.M.F. of concentration cells of silver nitrate in in the glass phase is maintained relatively constant acetoiiitrile and in benzonitrile are recorded and when that of the solution changes. It is considered compared with the values calculated from the that the hydrogen-ion concentration in the glass formula E—2(1—7ic)RT/F log, kJ k^, where nc is the phase is held relatively constant by the buffer action GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 371 of the sodium silicate in the glass. If, however, in a Faraday Soc., 1928, 24, 225—233; cf. A., 1927, cell HgiHgd|KCl(satd.)|NaOH|glass|^-HCl|HgCl|Hg 317).—Polarisation data for silver cathodes in the concentration of the sodium hydroxide is in­ solutions of neutral and alkaline electrolytes have been creased to OTA7, the buffer action breaks down. At determined. A fixed value for the overvoltage is pn 9, the buffer action becomes less effective, and this attained for a particular current density after a p n value corresponds with the pR of a sodium acid certain time peculiar to each electrolyte. This time silicate buffer mixture half neutralised with respect decreases as the electrolytes approach the neutral to the first hydrogen ion of silicic acid (dissociation point. The phenomenon is independent of the constant 10'°). Beyond p R 13, the glass surface is current density except with regard to the final con­ rapidly attacked owing to neutralisation of the stant value attained. The overvoltages as measured second hydrogen ion of silicic acid (dissociation by both the “ commutator ” and the “ direct ” constant l(k13), and the E.M.F. falls rapidly. It method increase rapidly with the current density is shown that the glass is partly acting as a hydrogen when this is low. With the former method a con­ electrode in alkaline solution. The extent to which stant value is finally attained, but with the latter the glass cell E.M.F. departs from the value it would method the overvoltage increases at a lesser rate have if the glass had a perfect hydrogen electrode after a critical higher value. This value is close to function was also studied. the constant overvoltages obtained by the com­ Since the glass cell can be used to measure hydrogen - mutator method. The decay of polarisation was ion concentration under conditions which render the investigated by varying the interval of the commu­ hydrogen electrode useless, by measuring the pn tator. The decay curves of polarisation sink to of half-neutralised buffer mixtures, the following values which remain nearly constant over a con­ dissociation constants were determined : the second- siderable time, and usually approximate to the stage constants of arsenic and chromic acids (8-3 X 1 0 '8 constant overvoltages otherwise attained. The volt­ ancl 1-Ox.lQ-7 respectively), the first-stage constant age between a saturated calomel electrode and a of arsenious acid (6 x lO _I°), and the constants of hydrogen electrode placed in the solution varies azoimidc (2-56 X10-5) and hydrazine hydrate approximately linearly with the overvoltage. The (1 4 X 1 0 -6). deviations may be due to secondary influences. The hydrogen-ion activity of copper sulphate The conditions of the formation of a black deposit solutions was measured, 0-05i!I-solutions haying a on the silver and the effect of this on the overvoltages p n of 4-24. It was shown that hydrolysis of the have been investigated. In general, the results are sulphate is aslow reaction at the ordinary temperature. analogous to those already obtained for an antimony The basic copper sulphate formed by addition of cathode. L . F. Gilb er t. alkali has the composition 3Cu0,CuS0,4,a;Ii20. The pn of an iodide-iodate mixture was found to be “ Anode effect." H. v o n W ar ten ber g (Z. about 6-9 after two thirds of the iodate had been Elektrochem., 1927, 33, 526—527).— The author decomposed by the addition of hydrochloric acid. maintains his theory as to the origin of the “ anode It. A. P r a tt. effect ” in the electrolysis of fused salts (A., 1926, Reducing power of dextrose. S. A. Schott 912) against the views of Arndt (B., 1927, 659). and R. Wurmser (Compt. rend., 1928, 186, 367— H. J. T. E llingham . 369).—The production of the stable potential Maxima on current-voltage curves. Electro­ gradually set up when a platinum or gold electrode is lysis of nickel salt solutions with the mercury placed in a solution of dextrose protected from the dropping cathode. N. V. E m e lia n o v n a and J. air (A., 1927, 1218) may be followed by means of the H e y r o v s k y (Trans. Faraday Soc., advance proof, ultra-violet absorption spectrum of the solution, Feb., 1928).—The prominent maxima sometimes the constant maximum potential corresponding with shown on polarisation curves of electro-reductions a maximum absorption band at 2650 A. The nature obtained with the mercury dropping cathode have of the reducing substance responsible for this is been studied in electro-deposition from nickel salt discussed. It is not mcthylglyoxal, but may be the solutions. The effect of oxygen is to inhibit the result of an enolic transformation. J. G ran t. appearance of maxima, which become developed only after long bubbling of hydrogen through the solutions. [Influence of gelatin on the potential and dis­ This influence of oxygen appears to operate by the charge potential of zinc in zinc sulphate solu­ formation of mercurous ions, as tho addition of tion.] E. R a b a ld (Z. Elektrochem., 1927, 33, mercurous ions decreased the maximal currents by 532).—A reply to Isgarischev and Titov (A., 1927, amounts which were direct functions of their con­ 833). H. J. T. E llingilam. centrations. That the stability of maxima is greatest Decomposition potential of zinc sulphate and in tho presence of iodides, less in chlorides, and least ferrous sulphate. B. K am ieński (Przemyśl Chem., in sulphates, when the concentration of mercurous 1927, 11, 374— 381; Chem. Zentr., 1927, ii, 547).— ions can be tho greatest, is thus explained. The The decomposition potential of zinc sulphate for a suppressive effect of other substances was studied. sulphide anode is 1-8 volts and 2-62 volts with a lead Cations suppress maxima by degrees which run in the dioxide anode; when powdered zinc blende on a same order as the coagulating powers on negative carbon rod is employed as anode zinc is deposited at sols. The influence of anions was not specially 2 volts. ‘ A. A. E ld r id g e . examined, as it seemed to matter little. Fuchsin Overpotential at metallic cathodes. Silver in hydrochloride and dextrose solutions are also very neutral and alkaline solutions. J. Gr a n t (Trans. effective in suppressing maxima. The phenomena 372 BRITISH CHEMICAL ABSTRACTS.— A. of the formation of the maximum and its suppression an equation f(y ,x )—0. The form of this equation are considered to be due to adsorption of the reducible and the direction of the corresponding reaction curves matter at the mercury-solution interface and to the are discussed. B y choosing the initial concentrations replacement of the reducible ions by other adsorbable suitably, the reaction can give rise to the maximum matter, respectively. The sudden fall of current and minimum concentrations of all the reactants. after the maximum is explained by concentration By solving the equations, dyjdl=f(y,x) and dxjdl— polarisation, which starts when the velocity of f(y,x), the time taken to reach these maxima and deposition of ions becomes greater than the velocity minima can be found. R. A. P r a t t . of adsorption in the surface film at the mercury Homogeneous gas reactions. I. L. S. K assel dropping cathode. L. F. Gil b e r t . (J. Physical Chem., 1928, 32, 225— 242).— Lewis’ Maxima on current-voltage curves. II. definition of energy of activation as the minimum Maxima on the polarisation curves of uranyl internal energy which must be possessed by mole­ salt solutions. P. H e r a sy m e n k o (Trans. Faraday cules in order to react (A., 1925, ii, 799) is considered Soc., advance proof, Feb., 1928; cf. preceding to be preferable to the definition given by .Tollman abstract).—The current-voltage curves of the first (A., 1925, ii, 799). Further, it is shown that the reduction stage of uranyl ions in aqueous solution at activation by collision theory as treated by Hinshel- the mercury dropping cathode have been investigated wood (A., 1927, 26, 212), and further developed by with special reference to the maxima developed. The Rice and Ramspergor (A., 1927, 833), in which all maximal currents in pure uranyl salt solutions are activated molecules have the same specific reaction nearly proportional to the concentrations of uranyl rate regardless of their energy content, whilst agreeing ions. Added salts reduce the maximal current by with experimental data for propaldehyde, disagrees amounts depending only on the total number of with such data in the decompositions of diethyl electric charges in solution, so that equivalent ether, dimethyl ether, and azomethano. An expres­ quantities of ions of different valencies produce the sion is now developed showing the variation of the same effect. Some non-electrolytes also give an specific reaction rate of activated molecules with their appreciable effect. This difference as compared with energy content, and from this is derived an equation the behaviour of added ions on the maxima for nickel which gives this rate for a unimolecular reaction at salts may be ascribed to the presence of products of any pressure. This equation agrees with Rams- reduction of uranyl salts, i.e., of quinquevalent uranium perger's experimental results for the decomposition ions (see following abstract), which accumulate in of azomcthane (A., 1927, 737). The "differences the interfacial layer and are preferentially adsorbed. between the present theory and that of Rice and With increase of the polarisation voltage the current Ramsporger (loc. cil.) are considered (cf. also Fowler falls, after the maximum, to a constant value which is and Rideal, A., 1927, 114). L. S. T h e o b a ld . almost independent of the concentration of other electrolytes in solution, and is proportional to the Pressures developed in gaseous explosions. concentration of uranyl ions. From measurements W. T. D a v id and B. H. T horp (Nature, 1928, 1 2 1 , of the interfacial tension between cathodically 420).—The non-variation of the specific heat of steam polarised mercury and solutions of uranyl salts in over a wide range of maximum temperatures (Max­ presence of different concentrations of potassium well and Wheeler, this vol., 248) is doubted; the chloride it is deduced that the cathode potential apparent value, calculated from explosions of air varies only slightly with the polarising voltage, but with excess of hydrogen, is practically constant, but the decrease of current after a maximum is this result is ascribed to incomplete combustion. accompanied by a sharp increase in the polarisation Minimal values of the percentage of incomplete of the cathode. L. F. G il b e r t. combustion for various mixtures of hydrogen, nitrogen, and oxygen are tabulated. It is behoved Electro-reduction of uranyl salts by means of that combustion is far from complete even when the mercury dropping cathode. P. H e r a s y - excess of hydrogen is present. A. A. E l d r id g e . menko (Trans. Faraday Soc., advance proof, Feb., 1928; cf. preceding abstract).—The reduction of Effect of anti-knock materials on the con- uranyl salts at the dropping mercury cathode pro­ denser-discharge-spark energy required to ceeds in three stages, in which quinquevalent, quadri­ ignite a mixture of air with the vapour of ethyl valent, and tervalent ions are formed successively. ether. Y. N ag ai (Proc. Imp. Acad. Tokyo, 1927, At still greater potentials hydrogen ions deposit. 3, 670—671).—Values are given for the energy re­ The first reduction potential depends only on the quired to ignite a mixture of 4-25% of ethyl ether and concentration of uranyl ions, being uninfluenced by 95-75% of air by means of a spark, when various the concentration of hydrogen ions. Quinquevalent amounts up to 1-5 mol.-% of diethyl selenidc, tin but not quadrivalent uranium ions readily form com­ tetramethyl, and lead tetramethyl are present. The plexes with neutral salts. L. F. Gil b e r t . energy is increased by about 50% for 1 mol.-% in Simultaneous reactions of the type A ^ C. each case. “ C. J. Sm itiiells. F. E. C. S cheeeer and (Miss) A. E. K orvezee (Rec. Effect of anti-knock materials on the limits trav. chim., 192S, 47, 235— 247).—Theoretical. If of inflammability of ethyl ether and hydro­ the relative concentrations of the substances A, B, carbons. Y. N a g a i (Proc. Imp. Acad. Tokyo, 1927, and C taking part in a reaction of the type 3, 664—669).—The effect of lead tetramethyl and A B C arc designated by x, 1 —x —y, and y, tin tetramethyl on the limits of inflammability of the composition of the mixture can be expressed by mixtures of air and ethyl ether or hydrocarbons GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 373

was determined. A straight-line relation was found In a discussion of the subject it is shown that this between the molecular percentage of the tetramethyl objection may be invalid. H. J. T. E llin g h am . compounds and the upper and lower limits of com­ Explosion temperature and sensitivity to position of the mixtures. A similar explanation is shock of liqxiid and solid explosives. G. T am - given to that previously advanced (cf. A., 1926, mann and C. K r o g e r (Z. anorg. Chcm., 1928, 16 9 , 1106). The theoretical flame propagation temper­ 1—32).—Experiments with a variety of liquid and atures of the lead and tin compounds are both solid explosives have shown that the temperature at 1680°, that of diethyl selenide is 1750°, and that of which explosion occurs on heating usually increases ethyl ether and hydrocarbons 1450°. This value is in a linear manner with the rate of heating, and raised to that of the anti-knock material when a small decreases with increase in the amount of explosive. percentage is present. C. J. Sm ith ells. For substances exploding below their m. p., the lines representing the effect of rate of heating on the Chemically induced “ chain reactions” in explosion temperature for different quantities of mixtures of a halogen with hydrogen or methane. explosive are parallel, but with explosives which S. von Bogdandy and M. P6lanyi (Z. Elektrochem., melt and are appreciably volatile below their m. p. 1927, 33, 554— 559).—Previous work (Beutler and and explode above it the lines tend to converge at Polanyi, Naturwiss., 1925,13, 711) has indicated that high rates of heating. With explosives of the former the vapour of the alkali metals reacts with a halogen group, such as lead azide and mercury fulminate, the according to the equation Na+Cl2=NaCl4-Cl. explosion limit, i.e., the minimum amount which will Experiments have now been made to determine the explode with any particular rate of heating, is con­ reactivity of free halogen atoms liberated in this way. siderably depressed by heating in an inert atmo­ Hydrogen at 5— 10 mm. pressure was passed over sphere, oxidation thus being avoided, and increase in molten sodium at 150— 250°, whereby it took up the coarseness of grain has the same effect. The sodium vapour at 0-5—5 X HP'1 mm. pressure. On explosion limits of the more volatile explosives, on meeting a stream of chlorine at 0-2— 0-3 mm. pressure, the other hand, may be lowered by increasing the sodium chloride is deposited, but hydrochloric acid is pressure. By varying the factors determining the produced in enormously greater amounts. It is rate at which the heat of reaction is lost, e.g., by com ­ considered that this is due to a reaction chain of the pressing a powder into a tablet, the effect of rate of type postulated by Nernst for the photochemical heating and amount of explosive on the explosion formation of hydrochloric acid, viz., Cl-|-H2=HCl-j- temperature may bo partly annulled. With small H; H+C12=HC1+C1; etc. In the present case the amounts of load azide, the relation between explosion number of reactions in a chain is estimated to vary temperature and rate of heating is abnormal, appar­ from 700 to 10,000, according to conditions. Increase ently owing to the formation of an explosive basic of the pressure of the sodium vapour decreases the azide. The explosion temperature of silver azide length of the chain. But even under given con­ does not vary in any regular manner with the rate of ditions the length of the chain may vary greatly, heating and amount of explosive. From heating probably owing to impurities or the condition of the curves, 2 :4 :6-trinitrotoluene is found to begin wall of the reaction vessel. Thus, if the pressure of to decompose at 150°, and 2:4:6-trinitro-wi sodium vapour is increased and then decreased again cresol at 180°. If the former is heated at a steady to its initial value, the length of the reaction chain temperature for some time, there are formed decom­ may be much greater than it was originally : the position products, which raise the explosion tem­ sodium chloride deposited may prevent combination perature. A liquid explosive can be caused to of chlorine atoms on the wall of the vessel. With explode by the uniform propagation through it of a potassium instead of sodium the results, were similar shock. A shock applied to a solid explosive by actual but the reaction chains shorter. With methane contact with a solid is more effective than an equal instead of hydrogen, the essential product was methyl shock applied indirectly through hydrostatic pressure chloride, but the number of reactions in a chain was over all its surface. Under certain conditions, only 100— 300. With hydrogen, bromine, and crystalline explosives may explode when flowing sodium vapour very little action occurs and even through an orifice. R. Cuthill. when the sodium was heated to 385° only very short reaction chains were obtained. The influence of Velocity of ionic reactions. II. R. N. J. bromine vapour mixed with chlorine in inhibiting S a a l (Rec. trav. chim., 1928, 47, 264— 285; cf. this the reaction of the latter with hydrogen in the vol., 248).—The reaction constant of the reaction presence of sodium vapour was also investigated. C 02+ 0 H '— > H C O ?' was found to be 3-7 x lO 3 at Erom probability considerations it is concluded that 13-7° from conductivity measurements, the hydroxyl- if a is the ratio of the partial pressure of bromine ion concentration being so chosen that the amount to that of chlorine and W the ratio of the velocity of hydrogen carbonate in the solution was negligible. coefficients for the combination of hydrogen with The total concentration of the solution was found to bromine and chlorine, respectively, the number of have no influence on the reaction constant, thus reactions in a chain will be 2(alF-i-l)/alZ(a-j-l). The agreeing with Bronsted’s theory (cf. A., 1922, ii, experimental results are in reasonable agreement with 699; 1925, ii, 681). Determinations were made of this relation, if W is put equal to 0-13. The fact both the conductivity and the hydrogen potential that hydrochloric acid does not inhibit the reaction of the equilibrium I^COj^^H'+HCOq'and of the between chlorine and electrolytic gas has been quoted reaction H2C03— xC02+H20; but it was not as an objection to the Nernst reaction chain theory. possible to decide whether the carbon dioxide 374 BRITISH CHEMICAL ABSTRACTS— A.

originates from carbonic acid or whether it is the acid solutions containing 10—50 g. of dextrose in result of interaction of hydrogen and hydrogen 100 c.c. are given, and it is shown that the value of carbonate ions. The reaction constant of the re- k calculated from the equation for unimolecular aotion H‘+HC0:1'^ H 2C03— >■ C02+H 20 is S at reactions, divided by the relative hydrogen-ion I3'5°. The equilibrium constant of the reaction activity, is constant for all the solutions. The H2CO3===C02+ H 2O is 1-1 x 103 at 13-7°. It was van ’t Hoff method also indicates that the reaction possible to follow the behaviour of the p a during is of the first order. The critical increment of the acidimetric titrations with alkali containing carbon reaction is 33,500 g.-cal. The order of the reaction dioxide. is explained by assuming the condensation of dextrose The reaction dichromate > chromatc was also under these conditions to be a pseudo-unimolecular studied; the equilibrium Cr20 7"+ H 20^=±:2HCr04' change, in which the concentration of one of the exists with an equilibrium constant of 0-019fi;0-001. reactants (normal doxtrose) far exceeds that of the The decomposition of dichromate to cliromate may other (activo dextrose). The nature of this active take place in thrco ways : (i) In the alkaline region, form is discussed. W. A. R ic h ar d so n . Cr20 7" - f O H '— > CrO,,"+HCrO,'. (ii) In the acid and neutral region, Cr20 7"+ H 20 — > 2HCr04'. (iii) Kinetics of the hydrolysis of glucosides On largo dilution with acid and water, Cr20 7"+ (salicin, arbutin, and phloridzin). E. A. M oel- H-+H20 (^ H C r207'+H 20)—>2HCrO.,'+H\ w y n -H ughes (Trans. Faraday Soc., advance proof, R . A. Pr a t t . Feb., 1928).—The rates of hydrolysis at 60° and 70° of Primary salt effect in a zero type reaction. salicin, arbutin, and phloridzin by AT-hydrochloric M. K ilpatrick, jun. (J. Amer. Chcm. Soc., 1928, 50, acid have been determined polarimetrically. By 35S—362).—The reaction CH20+Cr[CO(NH2)2]r/" using dilute solutions (about 5%) the production of — > Cr(H20)8"‘+6C0(NH2)2 is investigated, the “ diglucose ” (ef. preceding abstract) is negligible rate of disappearance of the first-named ion being under these conditions. The critical increment of the measured by precipitation with potassium cobalti- hydrolysis of disaccharides and glucosides is a more cyanido. The reaction serves as a critical test of significant quantity than the velocity itself, as it theories of reaction rate; the results are in agreement lends itself more readily to comparative treatment. with Bronsted’s theory. S. K. T w e e d y . The mean critical increment for three fructosides (sucrose, raffinose, and melezitosc) is 25,700 g.-cal. Activation of chemical reactions b y neutral (±1%)> for thrco glucosides (maltose, salicin, and salts. II. Activation of the dissolution [in arbutin) it is 31,600 g.-cal. (±1% ), and for the acids] of marble b y neutral salts. N . I sgarische v galactoside lactose it is 27,100 g.-cal., whilst the and S. Schapiro (Z. physikal. Chem., 1928, 131, velocity coefficients show no simple relationships. 442— 445; cf. A., 1927, 945).— The velocity of dis­ The experimental value of the critical increment solution of marble in hydrogen chloride solutions in appears to depend on the nature (whether fructosidic presence of chlorides and in acetic acid solutions in or glucosidic) of the linking ruptured, and to bo presence of acetates has been determined by measure­ independent of the storeochomical (a or (3) character ment of the rate of evolution of carbon dioxide. In of the linking. The critical increment for phloridzin, the former case the velocity is in general increased, 23,100 g.-cal., is abnormally low. but there is no relationship between the velocity and W . A . R ic h ar d so n . the p a of the solution. In the acetate solutions the Mutarotation. TV. Consecutive reactions in velocity is proportional to the j)n. The results are in the mutarotation of dextrose and galactose. agreement with the Debye-Hiickel theory. F. P. W o r le y and J. C. A n d r e w s (J. Physical Chem., H. F. Gil l b e . 1928, 32, 307— 315; cf. A., 1927, 631, 736; this vol., Kinetics of the decomposition of nitrous acid. 25).— The mutarotation of a- and (3-glucose and of I and II. E. A bel and H. Sch m id (Z. physikal. a- and [3-galactose in aqueous solution has been Chem., 1928, 132, 55— 77).— The mode of decom­ studied polarimetrically at 0° in order to examine the position of nitrous acid has been studied, regarding initial stages of the action. In each case, an initial as the essential factor the reaction between nitrogen divergence from the subsequent unimolecular nature tetroxide and water. If supersaturation of the of the change has been observed. With a-galactose solution with is not prevented the rate an initial retardation is observed followed by an of disappearance of nitrous acid is not a measure of acceleration. In the case of (3-galactose muta­ the progress of the reaction 3HN02-—>H '+N 03 '+ rotation is arrested for 30 min. With a-glucose 2 N O + H aO. H. F. Gil l b e . there is an initial retardation, and with [3-glucose an Reactivity of dextrose in hydrochloric acid. acceleration. None of these changes can bo ascribed E. A. M o e l w y n -H ughes (Trans. Faraday Soc., wholly to a temperature effect. These divergences advance proof, Feb., 1928).—The chango of rotation are said to show that mutarotation is not a simple of solutions of dextrose (10— 50 g. per 100 c.c.) in unimolecular reaction, but involves two stages, e.g., A-hydrochloric acid at 60° and 70° has been investig­ a-sugar==i:X:^±: (3-sugar, with the formation of an ated. The observed increase in positive rotation, intermediate substance, X , the varying nature of the which is distinct from the ordinary mutarotation, is divergence being determined by the magnitude of complete in about 200 hrs. Following Harrison the rotation of X, and the relative values of the (A., 1914, i, 498), the change in rotation is ascribed velocity coefficients. For a rise of 10°, the velocity of to a condensation product “ diglucose.” The mutarotation is increased 2-8 and 2-9 times for dextrose relative hydrogen-ion activities in A-hydrochloric and galactose, respectively. L. S. T h e o b a ld . GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 375

Sulphite addition to unsaturated compounds. dilute solutions of electrolytes to one atom of iron, II. E . H a g g l u n d and A. RiNGBOM (Z. anorg. a consideration of the crystal structure leads to a Chem., 1928, 169, 9C— 98; cf. A., 1926, 363).— The value for the minimum amount of chromium necessary velocity coefficients at 80° of the reactions between to produce passivity which is considerably greater sulphite and methylpropiolic and phenylpropiolic than that actually found. It therefore appears that acids are considerably less than those of the reactions other factors, such as the presence of foreign sub­ between sulphite and the corresponding cthylenic stances, are also involved. Van Liempt appears to acids. With phenylpropiolic acid, the velocity have been under a misapprehension as to the true coefficient falls continuously dining the courso of the nature of resistance limits, and the values given by reaction, apparently owing to decomposition. him for mixed crystals of molybdenum and tungsten R. Cu tiu ll. (A., 1927, 196) are therefore to be rejected. Kinetics of chemical reactions between one R. Cu t h il l . solid and one gaseous component which result Effect of catalysts on the speed of flame, infra­ in the formation of complex compounds. A. red emission, and ionisation during the com­ Predvoditelev and A. W itt (Z. physikal. Chem., bustion of carbon monoxide and oxygen. W. E. 192S, 132, 47—54).—A micro-balance has been con­ Ga rner and C. H. J ohnson (J.C.S., 1928, 280—298; structed by the aid of which the kinetics of the cf. A., 1927, 184; Johnson, this vol., 353).— Measure­ reaction between anhydrous cupric sulphate and ments were made of the rate of emission of radiation, gaseous ammonia at the ordinary temperature and at the duration and magnitude of ionisation, and the various pressures have been studied. The reaction speed of flame for mixtures of carbon monoxide and follows the equation dc/d/=gp(j8 —C)(C0—O), where C oxygen to which various catalysts were added. It is the concentration of the cuprammonium sulphate, being already known that the loss of radiant energy the pressure, and q, B, and C0 are constants. increases with the introduction of water-vapour into H. F. Gil l b e . such mixtures, the effect of introducing other substances Decomposition of water and aqueous chloride containing hydrogen into the reaction mixture was solutions by powdered iron. S. M icew icz observed. A new experimental arrangement was (Przemyśl Chem., 1927,11, 501—511; Chem. Zentr., devised whereby the emission of radiation, the ionis­ 1927, ii, 1551).— The speed of reaction with powdered ation, and the speed of flame could be measured iron in aqueous solution increases in the series: sodium, simultaneously. The standard mixture was 2 vols. potassium, calcium, magnesium chloride. Nitro­ of carbon monoxide with 1 vol. of oxygen, dried for benzene is readily reduced to aniline by iron powder 2 hrs. over commercial phosphorus pontoxide. Its and magnesium chloride solution; the compound mean radiation on explosion was 6-00X 106 g.-cal., 2NH2Ph,MgCl2,6H20 appears to be formed inter­ and its mean speed of flame 100 cm. per sec. Addition mediately. " " A. A. E l d r id g e . of 1-95% of water vapour reduced the radiation to Action of acids on metals under pressure. 1-63 x l0 u g.-cal., but increased the flame speed more than tenfold. Similar results were observed with the G. T am m ann and K. B ochov (Z. anorg. Chem., 1928, addition of ethyl nitrate, ethyl iodide, ethyl bromide, 169, 33—41).—When dilute sulphuric or hydrochloric and chloroform. Carbon tetrachloride acted as a acid acts on metals such as iron and zinc in a closed negative catalyst, the radiation being increased and vessel, the reaction comes to an end some time before the flame speed decreased. Nitrogen peroxide was all the metal has been attacked. Measurements of an anomalous case, behaving as a feebly positive the resistance afford no indication of the existence of a catalyst in a dried mixture, but as a negative catalyst protective film of hydrogen, but E.M.F. determinations in an imperfectly dried mixture. show that the potential of the metal becomes more Analysis of the total radiation records showed that, electronegative, owing to the dissolution of hydrogen except for small residues, radiation ceases abruptly in the metal. The potential of the hydrogen also at times dependent on the nature of the catalyst becomes more electronegative, but to a smaller extent, so that under favourable conditions the reaction present. Evidenco is adduced pointing to a possible connexion between this residual radiation and the ceases. In the action of sulphuric acid on magnesium, persistence of ions in the gases after explosion. a coating of basic salts appears to be formed. The duration of steady radiation was correlated Pv. Citthill. with the duration of flame within the bomb. The Corrosion. J. Czo ch r alsk i arid E. Sc h m id .— bulk of the radiant energy has its origin in the wave- Bee B., 1928, 160. front where chemical change is proceeding, and not in Passivity and protective oxide films. U. R. the hot products of reaction. E vans (Nature, 1928, 121, 351— 352).— A discussion In the dry gases, two waves of ionisation accompany of the conditions influencing the thickness of protective the explosion wave. The first wave corresponds with oxide films. The X -ray method of examination, the explosion wave itself, but the second is associated employed by Kruger and Nahring; is unsuitable. with processes occurring some distance behind the Air-passivity appears to be a property of the pure wave-front. The persistence of the ionisation asso­ metal. ' A. A. E ld rid g e. ciated with the second maximum increases as the Passivity limit in mixed crystals. G. T a m ­ flame passes along the bomb. It is suggested that the mann (Z. anorg. Chem., 1928, 1 6 9 , 151— 156).— If it secondary emission of radiation in explosions of carbon is assumed that in mixed crystals of iron and chromium monoxide and oxygen discovered by Ellis and Wheeler each atom of the latter is able to impart its power of is caused by the recombination of ions produced becoming passive when brought into contact with behind the wave-front. These phenomena disappear 376 BRITISH CHEMICAL ABSTRACTS.— A. in tlie presence of hydrogen. Substances containing fall in pressure is explained by the adsorption of hydrogen increase the rate of attainment of thermal carbon monoxide on the reduced nickel. equilibrium both in, and behind, the explosion wave. S. J. Gregg. It. A. Pr a tt. Hydrocarbon synthesis from carbon mon­ Catalysis of hydrolytic reactions by acids and oxide and hydrogen. O. C. E lvins.— See B., 1928, bases. H. von E uler and A. Gr a n d e r (Z. Elek- 178. trochem., 1927, 33, 527— 532).— A detailed reply to Catalytic activity of metallised silica gels. Skrabal’s criticisms (A., 1927, 942) of the theoretical IV. Oxidation of methane. L. H. R e y e r so n principles put forward by Euler (cf. A., 1921, ii, and L. E. Sw e a r in g e n (J. Physical Chem., 1928, 32, 498; 1926,580). H. J. T. E llin g h a m . 192— 201; cf. Berl and Fischer, A., 1923, i, 641; Complex homogeneous catalysis of hydrogen Tropschand Roelen, A., 1924, i, 253 ; this vol., 252).— peroxide by sodium molybdate. E. S p ita lsk i Oxidation, of methane by oxygen in the presence of and A. F u n k (J. Russ. Phys. Chem. Soc., 1928, 60, metallised silica gels, prepared as previously described, 47— 74).— See A., 1927, 426. has been studied over the temperature range 200— 400°. The copper, platinum, and palladium gels, Catalytic decomposition of sodium hypo­ but not the silver gel, act catalytically, promoting chlorite solutions. I. M echanism . J. R . L e w is complete oxidation of methane to carbon dioxide (J. Physical Chem., 1928, 32, 243— 254; cf. Howell, and water. No partly oxidised products were found. A., 1923, ii, 634; Chirnoaga, A., 1926, 916).— The Both the silver and copper catalysts remove oxygen mechanism of the decomposition of sodium hypo­ from the gas stream in the initial stages of the reaction chlorite solutions using the oxides of cobalt, copper, ■without oxidation of the methane, and then the and iron as catalysts has been studied by two methods, copper or copper oxide acts as a catalyst initiating one at 35° and the other at 30°, the first being that the reaction at 200°. The platinised gel which is the used by Walton (A., 1904, ii, 319). The values most active catalyst for this reaction acts at 240°, the obtained by this method for k—x/t, where x is the palladised gel at 330°, and the efficiency of these two volume of oxygen evolved, remain constant at first catalysts depends on the oxygen content of the gas and then decrease after 20— 30% of the reaction has mixture. An optimum concentration ratio of methane been completed; those for the usual unimolecular to oxygen apparently exists. L. S. T h e o b a ld . coefficient increase as the reaction proceeds, whilst Behaviour of methyl alcohol over aluminium the greatest constancy is given when k is of the and zinc oxides. II. A d k in s and P. D. P er k in s form of the Freundlich equation given by Chirnoaga (J. Physical Chem., 1928, 3 2 , 221— 224).— The de­ (loc. cit.). The second method, in which a fresh supply hydration of methyl alcohol over the temperature of hypochlorite solution is passed over a fixed amount range 240— 440° has been investigated by the methods of catalyst, gives constant values for k=x/t over a and with the catalysts previously described (A., wide range of concentration (46-5— 34-2 g./litre), after 1925, i, 626). With the alumina catalyst, an almost which k diminishes with decreasing concentrations quantitative conversion of the methyl alcohol into of the hypochlorite. The rate of reaction is propor­ dimethyl ether results up to 350°. This is followed tional to the concentration of the catalyst, and the by a slight decomposition of the ether between 350° values of /c15/% 5 by the first method and k40/k30 by and 380°, after which decomposition is rapid. With the second are 2'02 and 2-0, respectively. The the zinc oxide catalyst, ether formation is negligible decomposition of the hypochlorite is considered to be and decomposition becomes marked above 325°. due to the formation of a catalyst-hypochlorite com­ The optimum concentration of water vapour for plex with subsequent decomposition, and the rate of maximum hydration of the dimethyl ether varies, decomposition remains constant so long as the catalyst at a constant rate of flow, with the amount of catalyst surface is completely covered by the reactant. present. L. S. T h e o b a ld . L. S. TnEOBALD. Experiments on the theory of heterogeneous Corrosion phenomena. XII. Apparent con­ reactions. G. A d h ik a r i and J. F e lm a n (Z. tradiction between the catalytic influence of physikal. Chem., 1928,131, 347— 362).— Iodine reacts silver on the dissolution of zinc in acids and its but slowly with the surface of pure mercury, although position in the overvoltage series. A. T hiel considerable adsorption takes place. The produc­ and J. E ckell (Z. physikal. Chem., 1928, 132, 78— tion of mercuric iodide is autocatalytic, combination 82).—The anomaly is ascribed to poisoning of the taking place with appreciable velocity only at the inter­ silver by zinc salts. H. F. G il l b e . face between the three phases. * H. F. Gillb e. Activation of the dissolution of marble by neutral salts. N. I sgarisch ev and F. S. Schapiro Decomposition of carbon monoxide in presence (J. Russ. Phys. Chem. Soc., 1928, 60 , 127— 137).— of reduced nickel. S. H oriba and T. Ri (Bull. See A., 1927, 945. Chem. Soc. Japan, 1928, 3, 18—25).— An improved apparatus is described whereby reaction velocities Acitivty of a nickel catalyst. E. J. L u s h .— as well as equilibrium quantities can be measured. See B., 1928, 182. The rapid pressure measurements necessary were made Electrolytic preparation of magnesium from possible by a special quartz spring manometer, and fused fluorides containing magnesium oxide. precautions were taken to avoid contamination by G. Gru be [with J. Ja isl e ] (Z. Elektrochem., 1927, grease from stopcocks. At 230° the reaction became 3 3 , 481—487).—The f. p. of mixtures of the fluorides unimolecular after 15 min., whilst the rapid initial of sodium, barium, and magnesium in various pro­ GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 377 portions have been determined and the results are and determination of indium in metallic gallium and expressed on a triangular diagram. The compound zinc, the metals were dissolved in hydrochloric acid, NaF,MgF2 has m. p. about 1030° arid the existence the free acid concentration being OTifI, when as of a compound, BaF2,MgF2, is also indicated. Three little as 10~5 mol. of indium chloride per litre could be ternary eutectics are recognised : MgF2-BaF2,MgF2- detected and determined. The deposition potential NaF,MgF2 (850°); BaF2,MgF2-BaF2-NaF,MgF2 of gallium could not be determined in acid solution. (800°); and BaF2-NaF-NaF,MgF2 (750°). Fused It. A. F r a t t . mixtures of various compositions containing excess Electrolytic oxidation of formic acid. E. of magnesium oxide were electrolysed using an iron M u lle r [with G. H in d em ith ] (Z. Elektrochom., 1927, cathode and a graphite anode. The mixture corre­ 33, 561— 568; cf. A., 1923, i, 743).— Further investig­ sponding with the 750° eutectic dissolves most ation has been made of the relations between anode magnesium oxide, but only sodium is obtained on potential and current density in the electrolysis of electrolysis. The 800° eutectic mixture gives sodium a M -formic acid-M -sulphuric acid solution, using as and magnesium, the current efficiency for the de­ anode material (a) rhodium, (6) platinised platinum, position of the latter being 22—25%. Electrolysis (c) platinum coated with finely-divided rhodium, or of the 850° eutectic mixture yields only magnesium (d) palladium coated with finely-divided palladium. at 900°; the current efficiency is about 50%, the At anodes (a) and (6) the current-potential curves loss being attributed to volatilisation and formation exhibit two distinct branches, one (A) lying at of “ anode fog.” Absence of sodium deposition in potentials about 1 volt less positive than the other (B). this case is regarded as due to thecompound NaF,MgF2 The transition from A to B occurs by a sudden jump. dissociating into Mg" and NaF3" ions in the presence With electrode (d) there is evidence of three branches of free magnesium fluoride. H. J. T. E llin g h am . of the current-potential curve, and with (c) and (d) the A branch is broken by pulsations between normal Preparation of a catalyst by the electrolytic values of the potential and values as much as 0-4 corrosion of nickel. S. I ki (J. Soc. Chem. Ind. volt less positive. In all cases, however, curves Japan, 1928, 31, 1— 9).— An active nickel catalyst obtained by decreasing the current follow the B is prepared by the electrolytic corrosion of nickel in branch until the current is practically zero. In order alkali hydroxide or carbonate solution (0-05— OTA7) to explain these complex relations, a theory is containing a small amount of alcohol. When only developed based on the supposed reactions of formic an alkali salt is used the current efficiency of corrosion acid and formate ions adsorbed in a polar manner is very low and the product is oxidised from the on the electrode surface. The transition from the A nickelous to the nickelic state. By addition of 3—5 to the B branch is regarded as due to superficial c.c. of alcohol to 1 litre of the solution the current oxidation of the anode material. Rise of temperature, efficiency increases remarkably and the product is or addition of sodium formate instead of sulphuric nickelous hydroxide. Acetaldehyde acts in the same acid, causes the A branches of the curves to extend way as alcohol. When the hydroxide is used the to higher current densities. In special experiments nickelous hydroxide produced tends to adhere to with lOili-formic acid-Af-sodium formate solution at the surface of the nickel anode, increasing the resist­ 0-015 amp./cm.2 at anode (c), the anode potential ance; this tendency is small when the carbonate is fluctuated periodically between —0-11 and +0-33 used. A current density of 0-01—0-05 amp./cm.2 volt (against the Ar-calomel electrode), -whereas with at 3—5 volts is used. The current efficiency of a 2iI/-formic acid-Ji-sodium formate solution at corrosion decreases with increase of current density. 0-21 amp./cm.2 the anode potential of +1-290 volts Alternating current alone has but slight effect on the remained steady when once established. In both anode. The nickelous hydroxide produced is easily cases, however, the products of electrolysis were separated from the alkali. The efficiency of corrosion hydrogen and carbon dioxide in amounts correspond­ is 78%. K. K a sh im a. ing exactly with the equation H-C02H + 2 faradays= Electrodeposition of indium with dropping- H2+ C 0 2.' H. J. T. E llin gh a m . mercui'y cathode. S. T a k a c i (J.C.S., 1928, 301— 306; cf. A.,r 1923, ii, 119; 1924, ii, 598; 1925, ii, Anodic oxidation of free propionic acid. F. 673, 678).—The behaviour of acidified indium tri­ M uller [with H. Sch w a b ] (Z. Elektrochem., 1927, chloride solutions when electrolysed with a dropping- 33, 568—571).—Contrary to statements in the mercury cathode was investigated, the results being literature, freij propionic acid can readily be oxidised applied to the determination of indium in the presence electrolytically. Using solutions of the acid in 2A7- of zinc and gallium. The electrodcposition from sulphuric acid in a diaphragm cell fitted with smooth solutions of indium trichloride in 0TA/-liydrochlorie platinum electrodes, the current efficiency of oxidation acid proceeded reversibly in conformity with the is found to increase with the current density and the Nernst. logarithmic equation. The normal deposition concentration of propionic acid, and reaches about potential of the indium ion in this concentration of 98% in a lOAi-solution at 0-09 amp./cm.2 The acid is —0-500 volt, with reference to the normal main products of oxidation are carbon dioxide and calomel electrode. This value depends on the con­ ethyl propionate, but small amounts of ethylene, centration of the hydrochloric acid, being more carbon monoxide, and pyruvic acid are also formed. negative the higher the concentration. The sulphate Two main processes appear to occur. In the more ion in presence of an insufficient concentration of important, complete oxidation to carbon dioxide hydrogen ions appears to remove indium ions, and water is believed to occur by way of lactic acid probably in the form of a basic salt. For the detection and pyruvic acid. In the other, ethyl propionate is 378 BRITISH CHEMICAL ABSTRACTS.— A.

produced either by direct oxidation or through the (J. Physical Chem., 1928, 3 2 , 270—284; cf. A., intermediate formation of ethyl alcohol. It is shown 1927, 428; this vol., 31).— Details are given of the that oxidation of lactic acid or pyruvic acid in 2AT- results previously announced on the photochemical sulphuric acid occurs at a lower oxidising potential dissociation of hydrogen iodide at pressures low at smooth platinum electrodes than is required for enough for the collision frequency to be comparable the oxidation of propionic acid, so that the former with the mean life of the excited state. Under these acids do not accumulate in the solution during the conditions the quantum efficiency is still about two, electrolysis of the latter. H. J. T. E llin g h am . which is the same as that found by Warburg for Photochemical yields with complex light. V. higher pressures. Hence, hydrogen iodide is con­ M. P a d o a and N. Vit a (Gazzctta, 192S, 58, 3— 6; sidered to dissociate in an elementary act as a result cf. A., 1926, 1014).— From a further survey of their of the absorption of radiation without the necessity own experiments and of those of Berthoud and of a collision (cf. Stern and Volmer, A., 1920, ii, 461). Beraneck (A., 1927, 52S) the authors consider their Further, the continuous spectrum shows dissociation view justified, that the sum of the photochemical to take place into a normal hydrogen atom and an effects p reduced by the component radiations is excited atom of iodine in the metastable 2P 1 state, different from and in general greater than that of the any excess energy being dissipated as kinetic energy. resulting complex light, not only owing to variations The time which elapses between absorption and in the intensity of the light, but also, and in some dissociation is less than 2 x l0 ~ 10 sec. The decom­ cases solely, on account of specific effects due to position of hydrogen iodide is discussed on the basis variations in the frequency of the light. The reactions of results already published. L. S. T h e o b a ld . discussed are the bromination of cinnamic acid, the Measurements of velocity, reaction per quan­ oxidation of hydriodic acid, and the decomposition tum, and effect of intensity of radiation in reac­ of feme oxalate. 0. J. W a l k e r . tions between chromic acid and organic acids. Photochemistry of the halogens. Action of A. K . B hattacharya and N. It. D h ar (Z. anorg. bromine on ethyl alcohol. A. B e r t h o u d and J. Chem., 1928, 1 6 9 , 381— 393).— The orders of the B eranecii (J. Chim. phys., 1928, 25 , 28— 39; cf. reactions between chromic acid and the following Bugarszki, Z. physikal. Chem., 1910, 71, 705).— The acids in sunlight and in the dark, respectively, are : rate of. reaction of ethyl alcohol and bromine in the citric acid, 2, 2-5 ; tartaric acid, 2, 3 ; lactic acid, presence of potassium bromide lias been studied in 3, 3. Manganous sulphate accelerates most of the the dark and under various intensities of blue and reactions, and, except with the reaction with tartaric violet light. Bugarszki’s results for the influence acid in light, reduces the order. With decrease in of the concentrations of alcohol and bromine are the order of the reaction, the temperature coefficient confirmed, but the retarding influence of potassium of the velocity coefficient usually rises. The tem­ bromide is less than stated by him. Potassium perature coefficient for the reaction in the light is bromide retards also in light. It is considered that always greater than unity, and less than that of the the effect of light is to dissociate bromine molecules, corresponding reaction in the dark. In all the and that, probably, an intermediate compound, EtO, reactions, numerous molecules react for each quantum is formed. The reaction is too complex to bo analysed of light absorbed, the number increasing with increase thoroughly from the data obtained. in concentration and also with rise in temperature. L. F. G ilber t. It is therefore concluded that Einstein’s law of photo­ Photochemistry of the halogens. Action of chemical equivalence is not valid for exothermic bromine on a-phenylcinnamonitrile. A. B e r ­ photochemical reactions. The rate of reaction in thoud and G. N icolet (J. Chim. phys., 1928, 25, either presence or absence of manganous sulphate is 40—64; cf. preceding abstract).—This reaction has directly proportional to the intensity of the incident been studied in the dark and in light; it is reversible. radiation, except in the reactions with citric acid In the dark, however, the inverse reactions are slower and tartaric acid in absence of manganous sulphate, than found by Bauer and Moser (A., 1907, i, 307), the rates of which are proportional to the square whose reaction vessels (of brown glass) did not root of the intensity of radiation. It. Cuth ill. exclude light completely. The photochemical results disagree entirely with those of Plotnikov (" Lehrbueh Luminescence of mercurous chloride of stan­ dcr Photochemie,” 1920, 250). Expressions are dard purity. J. K r e p e l k a (Nature, 1928, 1 2 1 , derived which describe the rate and Equilibrium of 457).—Pure, dry mercurous chloride exhibits a the reaction under different conditions. greenish-white luminescence when stirred with a glass rod ; the effect lasts for about 5 sec., and cannot L. F. Gilb er t, Photochemical union of hydrogen and chlorine. be again produced unless the rod is first cleaned. L. H arris (Proc. Nat. Acad. Sci., 1928, 14, 110— Luminescence is also produced if the soiled rod is 112).—Hydrogen and chlorine were carefully freed lightly rubbed with a dry cloth. from oxygen. Chlorine together with an excess of A. A. E ld r id g e . hydrogen was exposed to blue light and the quantum Tentative hypothesis of the latent image. II. efficiency of the union measured. A minimum yield A. P. H. T r iv e l li.— See B ., 1928, 212. of 6 X105 molecules of hydrogen chloride per quantum Action of sulphuric acid on copper. J. G. F. was obtained. W . E . D o w n e y . D ruce (Chem. News, 1928,1 3 6 , SI— 83).— The main Photochemical decomposition of hydrogen reaction which occurs when copper is heated at 130— iodide ; mode of optical dissociation. B. L ew is 170° with twice its weight of concentrated sulphuric GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 379 acid is represented by the equation 6Cu+6H2S04= of the interference lines (002) and (111). When 4CuS04 + Cu2S + S 0 2+ 6 H 20. With excess of acid at strongly compressed it becomes denser and more 270°, the reaction is C u+2H 2S0,1=C u S 0,,+2H 20 + suitable for Röntgen investigation without changing S02. " E . C d th ill. the position of the lines (cf. Lowry and Morgan, A., Reduction of magnesium pyrophosphate by 1925, ii, 1053; Ruff and others, A., 1927, 1138). When graphitic acid is heated at 200° under pressure, carbon. K. D. Jacob and D. S. R e y n o l d s (J. the “ carbon II ” thus produced is more distinctly Assoc. Off. Agric. Chem., 1928, 1 1 , 128—132).— crystalline and its Röntgen spectrum closely ap­ Mixtures of equal weights of pure finely-powdered magnesium pyrophosphate and carbon were heated proximates to that of lustre carbon prepared at 900° in a current of nitrogen at the desired temperatures except that the interference lines (002) and (111) are for definite periods. The residues, after burning off closer. When the graphitic acid is decomposed under sulphuric acid at 150°, a more highly crystalline the carbon below 800°, were analysed for magnesium oxide and phosphorus pentoxidc, and the percentage “ carbon III ” is obtained in which the arrangement of phosphorus lost by volatilisation was calculated is similar to that in retort graphite. All the types of carbon derived from graphitic acid differ from from the change of the ratio P205 : MgO of the lustre carbon and retort graphite in the remarkable residues, as compared with that found for the pyro­ phosphate used. The loss of phosphorus was negligible sharpness of their interferences. H. W r e n . below 975°. Heating for 1 hr. at 1000° resulted in a Gaseous silicon monoxide. K. F. B o n h o effer loss of 2-5%, at 1050° of 12-5%, and at 1100° of 32% (Z. physikal. Chem., 1928, 1 3 1 , 363—365).—Ultra­ öf the total phosphorus originallv present. violet absorption spectra indicate the formation of 3?. R. E n n o s. considerable quantities of gaseous silicon monoxide Composition of bleaching powder. C. T. during the reduction of the dioxide by carbon at K ingzett (J.C.S., 1928, 528).— Calcium hypochlorite 1500°. H. F. G il l b e . prepared from bleaching powder and rapidly dried Compounds of hydrated silica and ammonia. between sheets of filter-paper has the composition W . B iltz (Z. Elektrochem., 1927, 3 3 , 491—497).— Ca(C10)2,4H20, being mechanically associated with Preparations of hydrated silica prepared by methods some water." This formula does not represent its described by Schwarz (A., 1924, ii, 753; 1925, ii, constitution as a hydrate of calcium hypochlorite 222) were treated with liquid ammonia in a special (cf. O’Connor, B., 192S, 88). R . A. Pr a tt . extraction apparatus, until no more water could be Bleaching powder. VII. Decomposition of extracted. The composition and vapour pressure of calcium hypochlorite by heat in presence of tho products were examined at various temperatures. calcium chloride. S. U rano (J. Soc. Chem. Ind. From metasilicic acid the product had tho com­ Japan, 1928, 31, 46— 52).— The decomposition of position 6Si02,2H20,4NH3 at —78-5°, but with rise of calcium hypochlorite in presence of large amount of temperature it loses ammonia in stages of one mole­ calcium chloride, occurs chiefly according to the cule, and finally yields the compound 6Si02,2H20,NH 3 equation: Ca(OCl)2+CaCl2=2C aO -f 2C12 (i) and which is stable at the ordinary temperature. This partly according to the equations Ca(OCl)2=CaCL-f result supports the view that the minimum mole­ 0 2 (i'i) and 3Ca(0Cl)2=Ca(C103)2+2CaCl2 "(iii). The cular formula for metasilicic acid is 6Si0,,6H20. evolution of chlorine is caused by the mutual reaction Partly dehydrated metasilicic acid preparations gave between hypochlorite and chloride, but not by on treatment with ammonia the same compounds expulsion of chlorine monoxide ; reaction (i) is as the original substance yielded. Treatment of reversible. The phenomena attending the decom­ disilicic acid with ammonia yielded the additive position of bleaching powder result from these three product 2Si02,H20,NH3. Since this loses ammonia reactions. K . K a siiim a . in a continuous and not a step-wise manner when Production of carbon by the decomposition examined in the tensimeter, there is no evidence that of carbon monoxide, v o n W a n g e n h e im .— See the molecular formula of disilicic acid is more com­ B., 1928, 146. plex than 2Si02,H20. From similar experiments with the so-called “ granitic acid,” 3Si02,2H20, and Production of pure carbon at low temper­ with a preparation having the composition of “ tri- atures. E. F ischer and P. D il t h e y .— See B., silicic acid,” 3Si02,H20, it is concluded that these 1928, 146. are not definite compounds but mixtures of meta- Graphitic acid and the varieties of carbon and di-silicic acids and of disilicic acid and silica, obtained by its decomposition. U. H o fm an n respectively (cf. Schwarz, A., 1926, 1112). X -R ay (Ber., 1928, 61, [£], 435—441).—Graphitic acids, examination supports those conclusions. A few prepared by treatment of very finely-divided Ceylon experiments on the extraction of silica gels with graphite with a mixture of nitric and sulphuric acids ammonia did not lead to the isolation of any definite and potassium chlorate (cf. Kohlschütter, A., 1919, compounds. Hence only two definite silicic acids ii, 151), is crystalline and yields a characteristic, appear to exist. To prepare these substances the well-defined Röntgen spectrum somewhat similar to corresponding sodium salts must be used as the that of graphite. When heated cautiously to about starting material, since subsequent conversion of one 200° it decomposes explosively with formation of acid into the other has not been observed to occur. voluminous “ carbon I,” which is incipiently crystall­ The wider application of tho ammonia extraction ine but differs from graphite in the extreme smallness process to the study of the constitution of hydrates of its crystallites and the distinctly closer proximity is referred to. H. J. T. E llingh am . 380 BRITISH CHEMICAL ABSTRACTS.— A.

Preparation and properties of some german- portions vanadic anhydride with salts of the alkali ous salts. J. Ba r d e t and A. T c h a k ir ia n (Compt. metals, and especially of the evolution of oxygen rend., 1928, 1 8 6 , 637— 638).— Brown germanous u’hich accompanies the cooling of such molten systems oxide is produced with small quantities of germanous (cf. Prandtl, A., 1905, ii, 170). This evolution occurs hydride, by the reduction of gcrmanic salts with appreciably only when salts of the alkali metals or zinc and 25% sulphuric acid. It is stable when dry of thallium are used, and is independent of the anion and almost insoluble in hydrochloric or sulphuric with w’hich the metal is combined. The systems acid, and may be used for the detection of 0-1 mg. V20 5-Na20, V20 G-K 20, V20 5-Li20, and V20 5-T120 of germanium by means of titration with a solution have been investigated thermally and diagrams of of potassium permanganate. By reduction with state constructed. These show that vanadic anhydr­ hypophosphorous and hydrochloric acids at. 100° ide forms with the oxides of the alkali metals and of for 2 hrs., followed by neutralisation in the cold thallium three definite compounds corresponding with ammonia, the orange-yellow’ hydroxide is pro­ with the meta-, pyro-, and ortho-vanadates. The duced. It is very soluble in alkalis and in hydro­ evolution of oxygen is accompanied by the formation chloric or hydrobromic acid, but not in hydrofluoric of compounds of vanadic anhydride with its reduction acid, whilst sulphuric acid dehydrates it and forms product V204 of the type a;V20 5,yV204,zM20, w’here the soluble brown oxide. Hydriodic acid and M=Na or K (vanado-vanadates). By fusing vanadic oxidising agents convert it into a red, insoluble iodide, anhydride w’ith the alkali carbonates, the compounds and into the dioxide, respectively. The hydrochloric having the following values of x, y, and z, respectively, acid solution yields the chloride (GeCl2), which is have been obtained for sodium and potassium: hydrolysed by water to a white oxychloridc, and is a 5, 1, 1; 4, 1, 1; 4, 1, 2; 1, 1, 1, and in addition for strong reducing agent. The bromide behaves similarly, sodium the compound 5, 1, 3. 0 . J. W a l k e r . but the fluoride is stable towards water; Hydrogen sulphide precipitates the orange-red sulphide (GeS) Antimonic acid. A. Lottermoser (Z. Elektro- from solutions of the above salts. J. Gr a n t . chem., 1927, 3 3 , 514—518).—So-called “ soluble Oxidation of hydrazine. VIII. Mono-de- antimonic acid ” v'as prepared by gradual addition electronators and di-de-electronators. R. E. of antimony pentachloride to w’atcr at 0°, and solu­ tions of the filtered and washed product were made. K irk and A. W. B r o w n e (J. Amer. Chem. Soc., 1928, 50, 337— 347 ; cf. A., 1916, ii, 245).— Oxidation During dissolution to a clear liquid, the electrical is regarded as a process of dc-electronation, and the conductivity increases; afterwards, it decreases similarity in behaviour of various oxidising agents rapidly and then more slowly, approaching a limiting towards hydrazine is explained on the ground that value, whilst the solution gradually becomes opal­ mono-de-electronators— i.e., oxidising agents which escent. Rise of temperature raises the limiting accept one electron only per active unit—yield value somewhat and greatly increases the rate at which it is approached, but varying the initial con­ ammonia as the only by-product, whereas di-de- electronators yield both ammonia and azoimide. centration of the solution has practically no effect on the limiting value, unless the concentration is Many examples are considered in detail from this below about 0-1%. It is concluded that the more point of view. S. K . T w e e d y . concentrated solutions become saturated with a Sodium pyrophosphates. J. R. Pa r tin g to n mixture of complex hydrated acids, whereas more and H. E. W allsom (Chem. News, 1928, 1 3 6 , 97— dilute solutions remain unsaturated with respect to 100).— Repetition of the work of Salzer (A., 1895, this mixture. Determinations of the pa value of the ii, 14) and Giran (A., 1902, ii, 549) confirms the solutions by means of indicators gave similar results, existence of the salts Na3HP20 7, Na3HP20 ;,H20, and ultramicroscopical examination showed that, Na3HP20 7,4H20, and NaH3P20 7 and establishes the whereas in the more concentrated solution ageing led to existence of the salt Na3HP207,5H20. The salt a notable increase in the number of colloidal particles, formed on heating trisodium pyrophosphate has the no such increase was observed in the more dilute composition NaGP40 13 and is possibly a polymerised solutions. Conductometric titrations of concentrated metaphosphate. For analysis, pyrophosphates are fresh solutions with lithium, sodium, or potassium boiled with a large excess of dilute hydrochloric acid hydroxides (MOH) gave breaks in the titration curves for 2 hrs., and for a further 10 min. with magnesia when the ratio M : 8b was 1 : 3 and 1 : 2. With the mixture. J. S. Ca r ter . corresponding aged solutions, however, the breaks Sodium thiopyrophosphates. H. E. W a ll­ occurred at different points with different alkalis som (Chem. News, 1928, 136, 113— 115).— Sodium and these points did not in general correspond with thiopyrophosphates, Na2H2P2S7, Na3HP2S7, Na4P2S7, simple ratios of M : Sb. With very dilute solutions NaGP4S13, and Na2lIPS4, have been prepared by the the titration curves are unchanged by ageing and action of sodium sulphide or hydrosulphide on exhibit only one break, the position of which is phosphorus pentasulphide. They are easily decom­ independent of the nature of the alkali used, but posed by water with the production of hydrogen does not represent a simple ratio of M : Sb. Con­ sulphide and generally also of sulphur. ductometric titrations of potassium pyroantimonate C. W . Gib b y . solutions with hydrochloric acid are also recorded. Vanado-vanadates. G. Ca n n e r i (Gazzetta, H. J. T. E llin g h am . 1928, 58, 6— 25).— A study was made of the com­ Change in composition of compressed air after pounds containing quinquevalent and quadrivalent long storage in a steel cylinder. A. F. S ereque vanadium obtained by fusing in the required pro­ (J. Amer. Chem. Soc., 1928, 5 0 , 419).—The percent­ GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 381 ages of oxygen and of carbon dioxide in compressed mercury, aluminium, and tervalent iron, the last- air decreased by O-d and 0-01, respectively, after 17 named forming a white precipitate of ferrous chloride. years’ storage in a steel cylinder. S. K . T w e e d y . Mercuric chloride is thiohydrolysed to the black sulphide which later turns red ; the iodide crystallises Higher polythionic acids. I. Hexathionic out in the yellow form, wdiich becomes red. Insoluble acid. E. W eitz and F. A chterberg (Ber., 1928, mercurous chloride reacts to give mercurous hydrogen 61, [B\ 399— 408).— Potassium hexathionate is pre­ sulphide as a brown, gelatinous m ass; cuprous pared by the addition of a solution of potassium chloride and silver chloride are also thiohydrolysed. nitrite (1 mol.) and potassium thiosulphate (about Boron trichloride yields white crystals of BC13,12H2S. 3 mols.) to well-cooled hydrochloric acid. The Chlorides of non-metallic elements which are readily mixture is vigorously shaken until the colour passes hydrolysed by water are either soluble in liquid through brown and green to yellow, after which hydrogen sulphide in all proportions without change the nitrous fumes are removed in a current of air, (e.g., carbon tetrachloride; silicon tetrachloride, leaving a solution having an odour of sulphur dioxide ; which, however, produces a little silicon disulphide it is preserved in a freezing mixture until it becomes when kept for several weeks at the ordinary tem­ almost colourless. Precipitated potassium chloride perature ; and tin tetrachloride, which slowly pro­ is removed and the filtrate concentrated under duces stannic sulphide at the ordinary temperature) diminished pressure, whereby potassium hexathion- or else form thiohydrateS, additive products, or ate, mixed with potassium chloride, separates. The sulphides (e.g., titanium tetrachloride, which' forms chloride is removed by water and the residue the compound 2TiCl4,H2S ; cf. Biltz and Kcunecke, washed with alcohol and ether. The mother-liquors A., 1925, ii, 986), possibly together with a thio- from the hexathionate contain considerable quantities hydrate; phosphorus trichloride, which produces of potassium tetrathionate. The production of the trisulphide at the ordinary temperature; phosphorus latter compound is readily explained either by the and antimony pentachlorides, which form the respect­ intermediate formation of nitrosylthiosulphuric acid ive thiochlorides, PSC13 SbSCl, ; bismuth trichloride, or as a simple oxidation of the thiosulphate, but the wliich yields an orange-red solid, BiSCl,BiCl3). The mode of formation of the hexatliionate is obscure. conductivities of some saturated solutions of metal The smallest proportion of nitrite required to prevent chlorides in liquid hydrogen sulphide are recorded; precipitation of sulphur when the solution is acidified the specific conductivity of the pure solvent is 1 X 10-11 depends on the presence or absence of air and on the ohm-1 at about —80°. S. Iv. T w e e d y . concentration of nitrite and thiosulphate in the solution. Potassium hexathionate is stable when Molybdates of lanthanum and sodium. G. dry, but readily decomposes in aqueous solution With Carobbi (Gazzetta, 1928, 58, 53— 56; cf. Carobbi formation of sulphur or a higher polythionate. and Tancredi, following abstract).—At 25° the follow­ Addition of acid stabilises the solutions. It crystall­ ing two compounds are formed : ises with difficulty from aqueous or feebly acidic La.,(Mo0 ,)3,Na2MoO,,,2H.,0 and solutions, most readily from such as contain con­ La2(Mo04)3,2Na2M o04,3H,0. siderable amounts of mineral acid; from these solu­ O. J. W a l k e r . tions it can be salted out. Like the pentathionates, Tungstates of cerium and sodium. G. Carobbi it deposits sulphur when treated with alkali, gives and G. T an cr ed i (Gazzetta, 1928, 58, 45— 52; cf. yellow and yellowish-white precipitates with mercur- A., 1926, 810).— The system Ce2(W 04)3-N a2W 0 4- ous nitrate and mercuric chloride, no reaction with H.,0 has been studied at 25°. The three compounds copper sulphate, and a brown coloration passing into Ce2(W 04)3,Na2W 0 4,llH 20 ; a black precipitate with ammoniacal silver solution. Ce2(W 04)3,3Na,W 04,16H20, and It is more rapidly decomposed than pentathionates Ce2(W 04)3,5Na2W 0 4,23H20 are shown to exist. They by dilute ammonia, tetrathionate being the first are crystalline and stable in air. The dehydration isolable product; sodium carbonate solution behaves of these salts by means of calcium chloride or sulphuric similarly. Alkali sulphite rapidly converts hexa­ acid is not effected at a constant velocity; this fact thionate into trithionate. Potassium hexathionate points to the possible existence of other hydrates. gives crystalline -precipitates with hexammine-cobaltic O. J. W a l k e r . and -chromic chlorides and nitrates and with trans- Tungsten carbides and their applications. F. dichlorodiethylenediaminecobaltic chloride; this be­ S k a u p y (Z. Elektrochem., 1927, 33, 487— 491).— haviour is also shown by the lower polythionates The products obtained by heating tungsten powder towards the last-mentioned reagent. The anhydrous with lamp-black in hydrogen or in a vacuum at 1400° benzidine, salts of hexa-, penta-, tetra-, and tri-thionic or 2000° by means of a carbon-tube furnace or a acids are described. Preliminary examination of tungsten-virc furnace have been examined by chemical Wackenroder’s solution discloses the absence of analysis and by A-ray methods. The carbides W2C hexathionic acid and presence of acids containing a and WC are recognised. These compounds are also larger proportion of sulphur. H. W r e n . produced by heating a tungsten wire electrically in Reactions in liquid hydrogen sulphide. III. an indifferent gas (hydrogen or a mixture of hydrogen Thiohydrolysis of chlorides. A. W . R a ls to n and and nitrogen) containing a small proportion of meth­ J. A. W ilk in son (J. Amer. Chem. Soc., 1928, 50, ane. Wires carburised in this wray have their carbon 258—264; cf. Quam and Wilkinson, A., 1925, ii, content removed again if the methane concentration 542).— Metallic chlorides are mostly insoluble in falls below' a certain critical value dependent on the liquid hydrogen sulphide, except those of zinc, bivalent temperature and the composition of the indifferent 382 BRITISH CHEMICAL ABSTRACTS.— A. gas. The graph of the critical concentration of 1 :6-08. Some properties of iridium hexafluoride methane in hydrogen against temperature exhibits and pentafluoride are described. ' three branches, of which two correspond with WC H. J. T. E llingham . and W2C, respectively, whilst the third, which lies Magnitude of observation errors in chemical above 2400°, may correspond with the carbide W3C analysis. B. D. H artong (Chem. Weekblad, 1928, found by Ruff. The development of the alloy 25, 105—106; cf. Goudriaan, this vol., 262).—A “ Widiametall ” (tungsten, cobalt, carbon) now pro­ criticism of the calculations in the earlier paper. duced by Fried. Krupp A.-G. is referred to. The employment of approximated atomic weights H. J. T. E llingham . does not necessarily lead to errors as serious as Oxidations with fluorine. F. F ic h ter (Z. appears; the error introduced by using 107-9 for the Elektrochem., 1927, 33, 513— 514).— Mainly a review atomic weight of silver, for example, is only 0-02 of published work. W. Bladergroen has shown that and not 0-1. The method of calculating the cumul­ fluorine reacts with phosphoric acid or phosphate ative effect of errors is also criticised. solutions giving perphosphates. E. Brunner finds S. I. L e v y . that in the oxidation of chromic, thallous, or mangan- Drop reactions. F. F eigl (Mikrochem., 1928, ous salts with fluorine, the reaction proceeds smoothly 6, 50—62).—A claim for priority. Many of the drop only when the sulphates are used; this is regarded reactions recently described by Tananaev and his as due to the intermediate formation of sulphur co-workers (A., 1925, ii, 324; 1927, 223, 1159) had tetroxide. It is concluded that all oxidations with been described by Feigl and his co-workers several fiuorine are almost completely paralleled by electro­ years previously. A. R. P o w e l l . lytic oxidations at platinum anodes. Determination of dissolved gases in water. H. J. T. E llingh am . H. R ic h ter.— See B., 192S, 214. Black nickel oxide. G. L u n d e (Z. anorg. Chem., 1928, 1 6 9 , 405— 40G).— A reply to Le Blanc and Measurement of gases dissolved in water. Sachse (this vol., 142). R. Cu thill. L. D u n o y e r (J. Phys. Radium, 1928, [vi], 9 , 1— 12). —A more detailed account of work already published Oxidation states of ruthenium in its halide (A., 1927, 845). compounds. W. R. Crow ell and I). M. Y ost (J. Amer. Chem. Soc., 1928, 50, 374— 381).— Ruthen­ Determination of hydrogen-ion concentration ium compounds in hydrochloric acid solution are in very small volumes of liquid. S. Girgolov reduced by potassium iodide to the tervalent state, and J. Schukov (Z. ges. exp. Med., 1927, 5 6 , 710— in agreement with the conclusions of Ruff and Vidic 713; Chem. Zentr., 1927, ii, 1869).— An iridium (A., 1925, ii, 480). Ruthenium hydroxide prepared electrode, made by depositing an iridium mirror on by the method of Krauss and Kiikenthal (A., 1924, a fine glass capillar}’ , is employed in place of a ii, 196) contains both tervalent and quadrivalent platinised platinum wire. A. A. E l d e id g e . ruthenium. If the hydrochloric acid solution of the Applicability of the quinhydrone electrode in hydroxide is chlorinated, all the ruthenium is con­ electrometric titration. A. R abinovitsch and V. verted into the quadrivalent state, and electrometric K argin (Papers Pure Appl. Chem. Karpov Inst., titration of the solution with titanous sulphate, both Bach Festschr., 1927, 3— 33; Chem. Zentr., 1927, before and after chlorination, shows an end-point ii, 1054).— Strong acids can be titrated with the when all the ruthenium is reduced to the tervalent quinhydrone electrode in all concentrations; with and not the bivalent state (cf. Zintl and Zaimis, A., dilute weak acids the quinhydrone electrode shows 1927, 533). The dark blue compounds formed when at > 6 smaller p K values than does the hydrogen the titanous sulphate is in slight excess are com ­ electrode. The inflexion point of the titration curve pounds of bivalent ruthenium. If ruthenium chloride is reached with greater quantities of alkali than when is digested with bromine and liydrobromic acid, and the hydrogen electrode is employed. Presumably evaporated with potassium bromide, a black salt the hj-drogen-ion concentration of the solution is containing quadrivalent ruthenium is obtained, prob­ increased by dissociation of the quinol, atmospheric ably K2RuBr5OH. S. K . T w e e d y . oxidation of the quinol in alkaline solution tending Iridium fluorides. O. R uff and J. F ischer to reduce it. The deviation is maximal at p a 10, (Z. Elektrochem., 1927 , 33, 560— 561).— For the and is smaller in the presence of buffers. preparation of iridium hexafluoride and penta- A. A. E ld rid g e. fiuoride by the passage of pure gaseous fluorine over [Theory of end-point in electrometric titration.] heated finely-powdered iridium, the metal was con­ Correction. E. D. E astm a n (J. Amer. Chem. Soc., tained in a boat of calcined fluorspar supported in a 1928, 5 0 , 418).—An algebraical error in the previous tube of the same material and heated electrically. paper (A., 1925, ii, 594) is corrected. The result Vessels of fluorspar calcined at 1280° are resistant to obtained by Roller (this vol., 262) concerning the fluorine at high temperatures and are readily worked limiting strength of acid necessary for an inflexion mechanically by means of an emery wheel. For point to appear during titration with a strong base analysis of the hexafluoride, reaction with sodium is confirmed. " S. K . T w e e d y . carbonate in a platinum crucible was carried out at Simple continuous-reading method of electro­ the temperature of liquid air. Subsequent heating metric titration with bimetallic electrodes. to redness yielded insoluble iridium oxide, which was N. H. F urman and E. B. W ilson, jun. (J. Amer. reduced to the metal and weighed. The atomic ratio Chem. Soc., 1928, 59, 277— 283).— Platinum and of iridium to fluorine obtained in this way was tungsten wires are dipped into (e.g.) the reducing GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 383

solution, and connected in series through a variable an excess of titanous chloride and titrating back with high resistance and a galvanometer. The oxidising permanganate (Rothmund, A., 1909, ii, 434). Pro­ agent is added a drop at a time; the graph of the vided that the solution is not too concentrated, this galvanometer readings (ordinate) against volume of titration is not affected by the presence of chlorides, reagent added is exactly analogous to the graphs and the addition of manganous sulphate is actually obtained potentiometrically, there being a sudden disadvantageous. Small amounts of chromate do not permanent change in P.D. at tho end-point. This interfere with the determination. R . C u th ill. “ galvanometer method ” is as accurate as the Electro-analytical methods. III. Potentio­ potentiometric method. S. K . T w e e d y . metric titration. J. Gillis (Natuurwetens. Tijds., Simple bimetallic electrode systems for 1927, 9, 129— 148; cf. ibid., 8, 37, 115).— The potentiometric titrations. I. Application of changes of value in the silvcr-ion concentration and platinum-gold amalgam system to certain the potential of a silver electrode immersed in the oxidation-reduction titrations. II. Notes on solution arc calculated for the titration of chlorides, the use of the platinum-gold electrode system. iodides, and cyanides, by means of silver nitrate, N. H. Fcrm an (J. Amer. Chom. Soc., 1928, 50, and shown to agree with the values determined by 208—273, 273—277).— I. Amalgamated gold elec­ measurement during actual titrations. S. I. L e v y . trodes behave like calomel electrodes in solutions Analysis of bromine. Kubierschky.— See B., containing chloride and like mercurous sulphate elec­ 1928, 190. trodes in solutions containing sulphate. The con­ Determination of iodide in mixtures of halides. struction of small amalgamated gold electrodes is described; they are suitable for use as reference H . B a in e s .— See B ., 1928, 190. electrodes in oxidation-reduction titrations (ferrous Determination of hydrogen sulphide in sea­ iron with potassium permanganate and dichroinate, w ater. G. D r tjc k e r (Internat. Rev. Hydrobiol. and with vanadic acid) in solutions as dilute as Hydrogr., 1926, 16, 130— 133; Chem. Zentr., 1927, 0-051V; they also serve as indicator. electrodes for ii, 1189).— The sca-water is run directly into 15 c.c. of certain precipitation reactions, and for following the 0-0LY-iodinc solution acidified with 1—2 c.c. of con­ neutralisation of hydrochloric and sulphuric acids. centrated hydrochloric acid. A. A. E ld r id g e . II. A sharp change in E.M.F. occurs at the end­ Determination of sulphate in chromic acid. point of some oxidation-reduction reactions (e.g., W. H. D. (Chemist-Analyst, 1927, 16, No. 2, 8).— potassium permanganate and ferrous sulphate) in 01 The sample (10 g. in 200 c.c. of water) is treated with or 0'05i\7-solutions. The chief disadvantage of .the hydrochloric (10 c.c.) and acetic acids (15 c.c.) before amalgamated gold electrode system is the variable precipitation with barium chloride (10% solution, nature of the readings for the same type of titration. 5 c.c.), and the barium sulphate washed at least S. K. T w e e d y . 5 times with 1% hydrochloric acid. Determination of combined water in natural Chem ical A bstracts. sulphates. 0 . SEBELfK (Cliem. Obzor, 1927, 2, Iodometric determination of selenium. R. 46—49; Chem. Zentr., 1927, ii, 962).— Minerals con­ B erg and M. T eitelbaum (Chem.-Ztg., 1928, 52, taining alunite, a colloidal mixture of silica and 142).—Tho reduction of selcnious acid by hydriodic alumina, quartz crystals, and water lose water at acid to give the equivalent amount of iodine may be 350° upwards, complete elimination being effected carried out quantitatively when the reaction takes only at white heat. Sources of error arc discussed; place in the presence of carbon disulphide. The the methods of Kurizianov and of Dittrich give good iodine is then completely dissolved by the organic results. A. A. E l d r id g e . solvent and is not partly adsorbed on the precipitated Bromometric determination of chlorates. K. selenium as in the method of Muthmann and Schafer P eters and E. D eutsciilander (Apoth.-Ztg., 1926, (A., 1893, ii, 318). It is determined in the usual 41, 594— 595; Chem. Zentr., 1927, ii, 1055).—The way by titration with sodium thiosulphate solution. chlorate (0-05 g. C103) is dissolved in 0-LY-arsenious L. M. Cl a r k . oxide solution (25 c.c.) and dilute hydrochloric acid Detection of selenium in decolorised bottle (10 c.c.) and gently boiled for 10 min. after addition glasses. E. J. C. B o w m a k e r and J. D. Ca u w o o d . of potassium bromide (0-05— 0-1 g .); the solution is — See B., 1928, 192. then diluted to about 100 c.c. and titrated hot (using [Micro-jdetermination of nitrogen. R. E h r e n - methyl-orange) with OTA’ -potassium bromatc solution b erg (Z. ges. exp. Med., 1927, 56, 466—469).—The until colourless. A. A. E ld rid g e. Kjcldahl-ammonia is distilled in a silica vessel into a Direct j oxidimetric determination of per­ 10 c.c. flask containing 5 c.c. of 0-001A’ -lcad nitrate chlorate in presence of large amounts of chlorate solution; the mixture, diluted to 10 c.e., is centri­ and chloride. E. Spitalski and S. Jofa (Z. anorg. fuged, and 1 c.c. of the solution is treated with Chem., 1928, 169, 309— 318, and J. Russ. Phys. 0 5 c.c. of a radioactive (thorium-71) O-OOLV-lead Chem. Soc., 1928, 60, 75— 84).— By treatment of a nitrate solution and 0-5 c.c. of 0-001AT-potassium solution containing perchlorate and a large amount chromate solution. After removal of lead chromate of chlorate with sulphur dioxide, the chlorate is com­ by the centrifuge, 1 c.c. of the solution is evaporated, pletely reduced to chloride, and after removing the and its activity after 9 hrs. is determined with the excess of sulphur dioxide by passing a current of air electrometer. The activity of the solution is inversely or carbon dioxide through the solution near its b. p., proportional to the ammonia content. the perchlorate may be determined by boiling with A. A. E ld rid g e. 384 BRITISH CHEMICAL ABSTRACTS.— A.

Determination of small quantities of phos­ methods give average errors of -i-0-02%, —-0-02%, phorus by Deniges' method. V. V. C iu rea (Bui. respectively (ignition over a Mcker burner); in Soc. Chim. Romania, 1927, 9, 80— 89).— Small quan­ presence of molybdate ions the average error ranges tities of phosphorus may be accurately determined from 0T to 0-3%, although if the ignition is carried by a volumetric method involving the oxidation of out in an electric muffle at 1000° the error is —0-05%. the blue compound obtained in the usual Deniges In the absence of molybdate ions the acetate method colorimetric method with chlorine water, the quantity more easily produces a crystalline precipitate. of the latter required for decolonisation being directly S. K. T w e e d y . proportional to the phosphorus present. The phos­ Reinsch’s test. II. L e f fm a n n and M. T r um per phorus solution (5 c.c.) is shaken with 4 drops of the (Bull. Wagner Free Inst. Sci., 1927, 2, 89— 92).— sulphomolybdic reagent, 4 drops of a freshly-prepared The closed tube containing the copper strip should stannous chloride solution are added, and the solution be heated for a short time only with a spirit-lamp. is left for 10 mill, for the colour to reach a maximum. Chemical A bstracts. The solution is then diluted with 10— 15 e.c. of water Gutzeit method for the determination of and chlorine water added from a microburette until arsenic. H. H e id e n h a in (J. Assoc. Off. Agric. the colour is just destroyed. The operations are Chem., 1928,11,107— 112).— In the A.O.A.C. method repeated on a solution of known phosphorus content as modified by the U.S. Bureau of Chemistry, the and the volume of chlorine water used in each case is length of the arsenic stain is shown to be affected by directly proportional to the phosphorus present. In changes of temperature both of the generating and no case did the error exceed 4-1%, a value much of the absorption apparatus. Lower temperatures smaller than the errors in the colorimetric or nephelo­ of the former produce shorter and more intense stains metric methods. J. W. B ak er. than higher temperatures, the opposite effect being Influence of sulphates on the volumetric observed on varying the temperature of the latter. method for the determination of phosphorus. By immersing the whole apparatus in a water-bath C. M. B ible (J. A ssoc. Off; Agric. Chern., 1928, 11, at constant temperature, e.g., 30°, the stains obtained 12G— 128).—The A.O.A.C. volumetric method for the with definite quantities of arsenic are uniform both determination of phosphorus is unsatisfactory in in length and intensity, thus rendering the use of presence of sulphates, which may be derived either permanent standards possible. A modified Gutzeit from the original material or from the extraction method including in addition several minor changes solvent. Accurate results may be obtained without in the preparation of the solution is suggested. removal of the sulphate by careful control of the F. R . E n n o s. temperature when precipitating the ammonium Separation of arsenic from antimony. L. W. McCa y (J. Amer. Chem. Soc., 1928, 50, 368— 373).— phosphomolybdate. F. R. E n n o s. If excess of silver nitrate solution is added to a Iodometric determination of phosphorous acid hydrofluoric acid solution of arsenic and antimonio and the use of sodium hydrogen carbonate in acids which lias been made slightly alkaline with iodometry. P. Carre (Compt. rend., 1928, 186, ammonia, the arsenic is quantitatively precipitated 436— 438).— The production of iodate is shown to be as silver arsenate, free from antimony. The arsenic the cause of errors obtained in the determination of is determined by dissolving the precipitate in nitric phosphorous acid by oxidation wit h 0-1 A-iodine solu­ acid arid determining the silver by Volhard’s method. tion in the presence of sodium hydrogen carbonate If the filtrate from the. silver arsenate is treated with (5— 15 mols. per mol. of acid), the excess of iodine the minimum amount of hydrochloric acid for pre­ being titrated after 1-5 hrs. with sodium thiosulphate. cipitation of silver, mixed with concentrated sulphuric If, however, the solution is acidified with hydro­ acid, evaporated to fuming point, and then boiled chloric acid before the final titration, the iodate is with a piece of sulphur, the antimony may be deter­ reduced and the iodine regenerated; otherwise the mined by titrating the resulting solution with potass­ thiosulphate is oxidised to sulphate, A large excess ium permanganate or brómate (cf. Petriccioli and of hydrogen carbonate should be avoided in such Reuter, A., 1902, ii, 177; Gyory, A., 1893, ii, 554). cases, and loss of iodine in the carbon dioxide spray S. K . T w e e d y . is prevented by the use of a closed vessel. Phos­ Volumetric determination of antimony in phorous acid may be determined in the presence presence of lead, tin, and copper. A. V assiljev of phosphorous esters, P(OH)2-OR, by this method. and W . K argin (Papers Pure Appl. Chem. Karpov J. Gr a n t . Inst., Bach Festschr., 1927,143— 156; Chem. Zentr., Comparison of two methods used in deter­ 1927, ii, 1055— 1056).— The reaction (Gyory) : mination of phosphorus pentoxide as mag­ KBrOg+ 3SbCl3+ 6HC1=3SbCl5 + KB r+ 3H20,‘ using nesium ammonium phosphate. W . M. McN abb as indicator methyl-orange, which is decolorised by (J. Amer. Chem. Soc., 1928, 50, 300—304).— The excess of brómate, is employed. When the liquid ammonium acetato method (Schmitz, A., 1925, ii, 67) contains lead sulphate, low' (1— 3% ) values are is compared with the method in which this substance obtained; the solution is therefore siphoned off, the is not used (Treadwell and Hall, “ Analytical Chemis­ lead sulphate dissolved in concentrated hydrochloric try,” 1924, 2, p. 380). In each case a"final washing acid, and the diluted solution titrated with brómate. of the precipitate with a saturated ammoniacal solu­ The presence of tin does not affect the results. Low tion of ammonium nitrate previously to ignition is (0-3— 1-7%) values are obtained in presence of copper. recommended in order completely to oxidise any In presence of lead and copper 96—97% of the anti­ organic material which may be present. The two mony is found; treatment of the precipitate (as GENERAI,, PHYSICAL, AND INORGANIC CHEMISTRY. 385

above) indicates a further 2% of antimony. With or 0-20 c.c. The method should be applicable to the the pure metals, but not with technical alloys, tartaric determination of alkali halide in 0-0002ilf-solution. acid is not oxidised by the bromate. A. A. E l d r id g e . A. A. E l d r id g e . Influence of impurities arising from glass Determination of sodium borate. M. F rançois vessels on the titre of alkali hydroxides. K. and (Ml l e .) L. Se g u in .—See B ., 1928, 156. Seiler (Schweiz. Apoth.-Ztg., 1927, 65, 229— 233; Chem. Zentr., 1927, ii, 852).— A study of “ fixanal ” Volumetric determination of sodium. A. N au sodium hydroxide ampoules; silica, boric acid, and (Bull. Soc. Pharm. Bordeaux, 1927, 65, 67— 76; calcium wer'e detected, but not antimony, arsenic, or Chem. Zentr., 1927, ii, 467).— Blanchetière’s method iron. A. A. E ld rid g e. is modified in that the uranyl compound is reduced with zinc and sulphuric acid, and then titrated with Alkaline-earth metals in “ saccharate ” solu­ permanganate. A. A. E ld r id g e . tions and their use in alkalimetry. A. C. Sh e a d Determination of small quantities of sodium. (J. Amer. Chem. Soc., 1928, 50, 415— ‘116).—Metallic W eiland (Mitt. Kali-Forsch.-Anst., 1927, 21— 28 ; calcium of known purity may be weighed out directly Chem. Zentr., 1927, ii, 1871).—Manipulative details in air and dissolved in sucrose solution in order to are given for the method preferred, viz., the pre­ prepare a carbonate-free standard alkali solution with cipitation of sodium ions by a concentrated uranyl a single weighing. Warm calcium does not tarnish magnesium acetate solution, with the production of readily, and in any case the film formed is too thin the compound to affect the accuracy of the method. The chief 3(U02)(C2H30 2)2,Mg(C2H30 2)2,NaC2H30 2,9H20, which impurity is magnesium, which, together with its oxide, is practically insoluble in alcohol. is almost insoluble in 30% sucrose solution. A. A. E ld r id g e . S. K . T w e e d y . Uranyl acetate as a reagent in microscopic Qualitative separation of calcium, barium, qualitative analysis. E. M. Cham ot and H. A. and strontium. 0. M ac c h ia (Notiz. chim.-ind., B edient (Mikrochem., 1928, 6 ,1 3 —21).— In applying 1927, 2, 311— 312; Chem. Zentr., 1927, ii, 853).— the uranyl acetate test for sodium the best procedure The mixed carbonates are dissolved in a little dilute consists in evaporating the solution to be tested on hydrochloric acid, and the solution is evaporated to a microscope slide until a dry film is formed, placing 5—8 c.c. One portion is neutralised with ammonia, a drop of the reagent close to the edge of the film, and 4— 5 vols. of saturated potassium ferrocyanide and drawing a platinum wire through the drop, thence solution are added; the precipitate of the compound across the film. The formation of isotropic tetra- K 2Ca[Fe(CN)6],3H20 is collected, the barium in the liedra indicates the presence of sodium ; fine clusters diluted filtrate being precipitated as chromate, and of hair-like crystals the presence of the alkaline earths (after filtration) the strontium as carbonate. The or of lead; tetragonal prisms potassium, rubidium, other portion is slightly warmed and stirred with cæsium, silver, thallium, or ammonium ; square plates malonic acid (0-5 g.) and a slight excess of concen­ barium, and orthorhombic plates or prisms manganese, trated aqueous ammonia solution; the filtrate after magnesium, zinc, cadmium, iron (ferrous), nickel, removal of precipitated barium malonate is warmed cobalt, or copper. The presence of sodium together with 4—5 vols. of methyl alcohol to precipitate with a member of the last-named group results in the strontium and some calcium, calcium being pre­ separation of monoclinic triple acetates in the form cipitated from the filtrate as carbimide. of polysynthetic twins of somewhat indefinite chemical A. A. E l d r id g e . composition. In the absence of metals other than Rapid determination of calcium and mag­ alkalis the formation of sodium zinc uranyl acetate nesium. C. J. Schollenberger (Chemist-Analyst, is probably the most sensitive test for the presence 1927, 16, No. 2, 6— 7).— Calcium and magnesium of sodium ; so sensitive is this reaction that silica are precipitated together as oxalate and ammonium object slides should be used to avoid possible con­ arsenate, respectively; the precipitate is dissolved tamination from sodium of the ordinary glass slide. in dilute sulphuric acid, the oxalate determined volu- A. R . P o w e ll . metrically with permanganate, and the arsenate Potash charge removal from platinum cruci­ determined iodometrically. bles [in alkali determinations]. T. C. Gr e e n Ch em ical A bstracts. (Cliemist-Analyst, 1927, 16, No. 2, 16).— In the Detection and determination of small quantities Lawrence Smith method of determining alkali in of beryllium by means of l:2:5:8-tetrahydroxy- silicates the crucible is charged through a cork-borer, anthraquinone. H. F ischer (Z. anal. Chem., 1928, the space between this and the walls of the crucible 73, 54— 64; cf. A., 1927, 36).— Further details of the being filled with calcium carbonate. method previously described are given and the method . Chem ical A bstracts. is extended to the rapid determination of beryllium in Capillary analysis. R. D u b r isa y (Mon. Prod, alloys and minerals. Copper and nickel alloys (0-1 g.) chim., 1927, 9, No. 90, 4— 7 ; Chem. Zentr., 1927, are dissolved in hydrochloric acid and “ perhydrol,” ii, 1180).—The volume of 40 drops of 1 /GOOA-sodium the solution is evaporated to dryness on the water- hydroxide solution (free from carbonate), dropped bath, and the residue dissolved in a little warm from a constricted tube into “ vaseline ” oil containing water. The solution is treated with sufficient potass­ 1% of oleic acid, was 1-20 c.c., whilst if to the solution ium cyanide to convert the copper and nickel into an equal volume of 1/800 or l/80A-sodium chloride soluble double cyanides, then with sodium hydr­ solution was added, the volume of 40 drops was 0-98 oxide until the alkalinity is at least 0-25A. An c c 386 BRITISH CHEMICAL ABSTRACTS.— A. aliquot part of the clear solution is used for tho a further sharp change of potential occurs when the volumetric determination with a 0-05% solution of metal is entirely precipitated as hydroxide, but the quinalizarin in 0-25AT-sodium hydroxide. For the results obtained are accurate only to 1—-2% owing determination of beryllium in beryl, 0-2 g. of mineral to adsorption. The use of methyl-orange as indicator is fused with sodium carbonate and the silica removed for the determination of the acidity of solutions by evaporation with hydrochloric acid and filtration. containing the above-named sulphates gives results The filtrate is treated with sodium hydroxide to which agree with those obtained potentiometrically. 0-25A" and the determination finished as usual. The A. R. Powell. use of tartaric acid to retain aluminiun'i and other Sensitive microchemical reactions of cad­ metals in solution in the alkali leads to high results, mium salts. A. M a r t in i (Mikrochem., 1928, 6, as under these conditions aluminium reacts similarly 1— ?1).—Solutions of cadmium salts yield character­ to beryllium. A. It. P o w e l l . istic white, microcrystallino precipitates with sodium Detection of traces, and colorimetric deter­ bromide and brucine acetate and with sodium bromide m ination, of berylliu m . I. M. K olthoff (J. Amer. and a concentrated acetic acid solution of quinine Chem. Soc., 1928, 50 , 393— 395).— One drop of a sulphate. These reactions serve for the microchemieal 0-01% solution of curcumin in alcohol, 0-5 c.c. of detection of cadmium, a distinct precipitate being AA-ammonium chloride, and 6 drops of 4AT-ammonia obtained with 1 drop of a solution containing 0-3 solution are added to the solution. A red or an mg./c.c. A. R. Po w e l l . orange-red flocculent precipitate is obtained, the Precipitation of copper with sodium thio- sensitivity of this reaction extending to 0-05 mg. of sulphate. M. G. R o ed er (Tidskr. Kemi Berg., beryllium per litre. By comparison with a standard 1927, 7, 94— 95; Chem. Zentr., 1927, ii, 1740).— which has been kept for the same length of time after Precipitation of copper with sodium thiosulphate is precipitation a good quantitative determination may complete in the presence of nitric, hydrochloric, or be made. Magnesium decreases the sensitivity some­ sulphuric acid. The cuprous sulphide is washed with what ; aluminium and ferric iron must be first pre­ cold sulphurous acid solution. A. A. E ld r id g e . cipitated by addition of sodium fluoride. It is sug­ Gravimetric separation of copper and mer­ gested that curcumin may be useful for detecting cury. G. Spacu (Bui. Soc. Stiinte Cluj, 1927 , 3, amounts of magnesium between 1 and 10 mg. per 171— 174 ; Chem. Zentr., 1927, ii, 2087).— The neutral litre in strongly alkaline solution. Tho indicator or slightly acid solution containing copper and 1:2:5: 8-tetrahydroxyanthraquinonc was'unsuitable mercury is heated to boiling, excess of pyridine is for the colorimetric determination of beryllium. added with production of an intense blue colour, and S. K . T w e e d y . then, with vigorous shaking, solid ammonium thio- Pyrophosphate method for the determination cyanate. After 1 hr. the precipitate is collected, of magnesium and [of] phosphoric anhydride. washed with a cold solution containing ammonium (Miss) A. W . E pperson (J. Amer. Chem. Soc., 1928, thiocyanate (0-5%) and pyridine (5 c.c. per litre), 50, 321—333).—A critical examination of the pub­ dried at 140— 150°, heated slowly, and finally ignited lished directions for carrying out the above analyses to cupric oxide. After acidification of the filtrate leads to the formulation of standard procedures, which with hydrochloric acid, the mercury is precipitated are detailed in the original. A second precipitation as sulphide. Solutions containing much nitric acid under specified conditions is essential. In the first are first evaporated to dryness, the residue is dissolved case, when excess of potassium chloride is present a in hot water, and the solution mixed with much third precipitation is necessary. S. K. T w e e d y , pyridine. If too little pyridine is employed, the [Detection of zinc and calcium. ] R. W. H u f - copper is precipitated, and must be redissolved by FF.RD (Proc. Indiana Acad. Sci., 1926,36,183—184).— addition of a few drops of nitric acid. (a) Zinc is precipitated as sulphide with sulphur after A. A. E l d r id g e . addition of potassium dichromate, and tho hot hydro­ Micro-determination of mercury in organic chloric acid extract of the precipitate is tested with compounds and the determination of carbon potassium ferrocyanide or hydrogen sulphide. and hydrogen in such compounds. A. V er d in o (b) After removal of barium as chromate, the(Mikrochem., 1928, 6, 5— 12).— The destruction of filtrate is evaporated to 15 c.c., and diluted with the organic matter by heating with concentrated 45 c.c. of hot water; to half, one drop of saturated sulphuric and nitric acids leads to a small loss of calcium sulphate solution is added. Ammonium mercury, but good results are obtained by heating oxalate solution (5 drops) is added to each, and a for 2 hrs. at 250— 270° with fuming nitric acid in a precipitate smaller in quantity than that produced in sealed tube. The mercury may be recovered from the control is ignored. Chemical A bstracts. the solution by electrolysis with 2-5—3-2 volts, using Determination of the free acidity of solutions a gold-plated platinum gauze cathode. A. R . P o w e l l . of heavy metal salts. E. Mu ller and F. Mu ller (Z. anal. Chem., 1928, 73, 47— 51).—Potentiometric Potentiometric determination of cerium. K. titration with sodium hydroxide of the free acidity So m e ya (Sci. Rep. Tohoku, 1928, 17, 93— 97).— See of solutions containing the sulphates of zinc, copper, this vol., 146, manganese, cadmium, or nickel yields accurate results Quantitative microscopic analysis of com­ using a hydrogen or quinhydrone indicator electrode, mercial felspar. H. I n s l e y .— See B., 1928, 193. the end-point being marked by a very pronounced Action of hexamethylenetetramine on solu­ change or potential. If a hydrogen electrode is used tions of salts of metals of the third group, and GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 387

quantitative separation of iron from manganese, vanadium, and B is aniline or piperazine. The zinc, nickel, and cobalt. P. R ay' and A. K. respective colours of the precipitates are red, yellow, Chattofadhya (Z. anorg. Chem., 1928, 169, 99— and black; those containing aniline crystallise in 112).— Iron, aluminium, chromium, and titanium are triclinic prisms and plates, whilst those with piperazine precipitated as hydroxides from boiling solutions of separate out in tufted clusters of needles. their salts containing ammonium salts by liexa- A. R. P o w e l l . methylenetetramine. Under the same conditions, Separation of tungsten from silicon and tin. manganese, zinc, cobalt, and nickel are not precipit­ J. Ciochina (Z. anal. Chem., 1927, 72, 429— 434).— ated, because the hydrogen-ion concentration resulting Tungstic acid may be separated from a freshly- from the hydrolysis of their salts is not great enough precipitated mixture of tungstic and metastannic to furnish by hydrolysis of the precipitant a hydroxyl- acids or from a mixture of tungstic acid and silica ion concentration sufficient for precipitation. In dehydrated at 130° by treating the mass with a warm, order to separate iron from manganese, cobalt, nickel, concentrated solution of sodium tungstate, in which or zinc, ammonium chloride is added to the solution, it dissolves with the formation of metatungstate. which is then almost neutralised with ammonium Prolonged digestion of the mixture may cause dis­ carbonate, and the iron is precipitated at the b. p. solution of part of the silica to form silicotungstate, with a 10% solution of the reagent. It is not possible but a good separation is obtained by treating the to separate chromium from zinc, cobalt, and nickel mixed acids on the filter-paper with a warm 20—30% in this way. Kollo’s method of separating iron and solution of sodium tungstate and washing the residual manganese with hexamethylenetetramine (A., 1921, silica or metastannic acid with hot water, hydrochloric ii, 2l8) does not seem to give satisfactory results, acid, and hot water successively. For the determin­ and his explanation of the mechanism of the process ation of silica in ferrotungsten the finely-divided is apparently incorrect. R. Cuthill. metal is heated for 3— 4 hrs. with bromine at 50°, Determination of cobalt as Co30 4. R. Cer- the solution evaporated to dryness, the residue heated natesco and (Mm e .) V ascau tan u (Ann. Sci. Univ. at 130°, cooled, and extracted with 10% hydrochloric Jassy, 1928, 15, 69— 70).— The hydroxide is precipit­ acid, and the insoluble tungstic acid-silica mixture ated from boiling solution by potassium hypobromite, is collected, washed, and treated as described above. filtered, dried, and ignited with the filter-paper in a For the alkalimetric determination of tungstic acid Rose crucible in a current of oxygen. The temper­ it is recommended to wash the precipitated acid ature is raised as soon as the carbon is burnt, and with a saturated solution of sodium chloride until the conversion into Co30 4 is complete. Any remain­ the wash water ceases to react acid, transfer the ing alkali can be washed out, and the ignition repeated. filter and precipitate to a beaker containing an excess C. W . G i b b y . of 0JAT-sodium hydroxide, and titrate the excess of Microchemical reactions [with hexamethylene­ alkali with OTM-sulphuric acid using phenolphthalein tetramine sulphate and with piperazine]. A. as indicator. A. R. P o w e ll . Martini (Mikrochem., 1928, 6, 28— 33).— Addition Precipitation of earth-acids by sodium com­ of Jiexamefchylenetetramine sulphate and ammonium pounds and quantitative separation of tungsten thiocyanate solutions to a solution of cobalt chloride from tantalum and niobium. W. R. Schoeller yields glistening, blue, triclinic prisms of a complex, and K . Jaiin (Z. anorg. Chem., 1928, 169, 321— non-ionised compound. Under similar conditions 335).— See A., 1927, 32, 1047. copper chloride yields light yellow, trielinic tables, Titration of tin with “ chloraminę." E . R upp zinc chloride a mass of thin, white needles, ferrous (Z. anal. Chem., 1928, 73, 51— 53).— Chloraminę (the chloride light red crystals, vanadyl chloride light red sodium salt of p-toluenesulphonylchloroamide) may hexagons, indium chloride reddish-white, tetragonal be used instead of iodine in the titration of stannous prisms, and ammonium molybdate red, hexagonal chloride provided that the acidity of the solution crystals or yellow prisms. A mixture of antimonious does not exceed 3—5% ; a small crystal of potassium chloride and sodium iodide yields with an acetone iodide is added to the tin solution together with the solution of piperazine microscopic, monoclinic, yellow usual starch indicator. Solutions containing stannic tablets and prisms. Under similar conditions bismuth salts are reduced by means of zinc filings and the chloride gives intense red crystals isoraorphous with spongy tin is dissolved in warm concentrated hydro­ the antimony compound. Auric chloride, sodium chloric acid, the excess of which is neutralised by the bromide, and piperazine produce orange-yellow to addition of a solution of sodium hydroxide and red microscopic prisms. A. R. P o w e ll . carbonate just prior to titration. A. R. Po w e ll . Analysis of chrome iron ore. E. D ittler .— Use of liquid amalgams in volumetric analysis. See B., 1928, 195. X. Determination of vanadium, chromium, Metal complexes with pyrocatechol and their and nitro-compounds. K. S o m eya (Z. anorg. use in microchemical analysis. A . M a r t in i Chem., 192S, 169, 293— 300; cf. A., 1927, 746).— (ilikrochem., 1928, 6, 63— 66).— Addition of 1 drop Ammonium vanadate may be determined by reducing 0 a saturated solution of pyrocatechol acetate id- in concentrated hydrochloric acid solution with lead on ed by 1 drop of aniline or of a saturated solution amalgam, then titrating after removal of the amalgam 01 piperazine to solutions of sodium molybdate, with a 0-lJli-solution of cupric sulphate, the acid tungstate, or vanadate produces characteristic pre­ concentration being maintained at 10— 12 A7. Safran­ cipitates of the type [0M(0H)(0-GeHi0)2],Ac0B, ine or neutral-violet is used as indicator, 10 c.c. of a ere M is quinquevalent molybdenum, tungsten, or 0-1% solution being added to the vanadate when it 388 BRITISH CHEMICAL ABSTRACTS.— A. has been reduced to the vanadous state, and reduced and lead, even at high concentrations, and solid silver to the lcuco-compound by further, treatment with chloride do not affect the determination, but appre­ amalgam. The completion of the re-oxidation in the ciable amounts of palladium or platinum make the subsequent titration is then indicated by the reappear­ titration impossible, although the effect of palladium ance of the original colour of the indicator. If zinc may be partly overcome by addition of alcohol and amalgam is substituted for lead amalgam, iodine may potassium sulphate. When gold is titrated with be used instead of copper sulphate for the titration, titanous chloride after being oxidised with potassium and the method is then a convenient one for the bromate in hydrochloric acid solution, according to determination of vanadium in ferrovanadium, as Zintl and Rauch’s method (A., 1925, ii, 1005), any ferric salts do not interfere. Chromic salts may be excess of bromate may give rise to errors by causing determined by reduction to the chromous state with the solution to attack the platinum electrode. zinc amalgam (cf. ibid., 333) followed by titration R . Cu th ill. with iodine, iodate, or bromate, the indicator for the Osmium. II. Determination. E. F r itzm ah n first two of these being starch, and for the third (Z. anorg. Chem., 1928, 1 6 9 , 356— 364; cf. A., 1927, starch and potassium iodide. A solution of chromous 742),— Sufficient of the material for analysis to give chloride prepared in this way may also be employed about 0-1 g. of metallic osmium is heated with a to reduce p-nitroaniline or p-nitroplienol, which is mixture of 5 c.c. of concentrated sulphuric acid, then titrated with ferric alum, with ammonium thio- 10 c.c. of v'ater, and 5 c.c. of a 10% solution of cyanato as indicator. The results obtained in the chromium trioxido, a further 5 c.c. of this solution determination of picric acid by this method are, being added 10 min. after boiling commences, and however, about 1 % too low. R . Cu t h ill. again after 20 min., and after 30 min. 5 c.c. of vrater are added. Osmium tetroxide distils over, and is Determination of bismuth as oxyiodide. R. condensed into a solution of sodium hydroxide. Strebinger and W . Zins (Z. anal. Cliem., 1927, 72, Sodium sulphide is then added to the distillate, and 417-—429 ; cf. this vol., 39).— The microchemical the mixture acidified at 90° with hydrochloric acid, method previously described has been modified for ammonium chloride being added to cause the pre­ the determination of larger quantities of bismuth as cipitated sulphide to coagulate satisfactorily. The follows : The solution of the nitrate is evaporated to precipitate is ignited in a current of hydrogen, and dryness on the water-bath, the residue dissolved in weighed as the metal. This method cannot be used 1 c.c. of 1 : 1 nitric acid and 10—15 c.c. of water, for the determination of osmium in osmiridium, or and the solution treated with crystals of potassium in presence of ruthenium. R. Cuthill. iodide until the liquid above the black precipitate is pale golden in colour ; a further 50 c.c. of water arc Mercury spectrum tube. E. R umpf (Z. physi- added and the solution is heated on the water-bath kal. chem. Unterr., 1927, 4 0 , 205—206 ; Chem. until the black precipitate changes to copper-coloured Zentr., 1927, ii, 1869). scales of the oxyiodide. Hot -water is added until Ultra-violet refractometry. L. C. M a r tin the liquid becomes almost colourless, followed by a (Trans. Opt. Soc., 1927— 1928, 2 9 , 1— 21).—A critical- solution of sodium acetate (25 g./litre) until the colour angle method is described for determining the refrac­ entirely disappears. The precipitate is collected in tive indices of small quantities of liquid for ultra­ a glass filtering crucible, washed with hot water, violet light. Two quartz hemispheres, between which dried at 105°, and weighed as BiOI. Small amounts is a thin film of the liquid, are rotated in a beam of of lead do not interfere, but in the presence of much approximately parallel radiation, and the critical lead a preliminary separation of the bismuth must angles for various wave-lengths are measured by be made ; the boiling slightly acid solution of the means of a quartz spectrograph. A detailed pro­ metals is treated with a few drops of methyl-orange cedure is described and discussed. C. W. Gib b y . followed by 2iV-sodium formate solution until the liquid becomes yellow. The precipitate of basic Simple form of photo-electric photometer. bismuth formate, containing only traces of lead, is J. H. J. P oole (Nature, 1928, 1 2 1 , 2S1— 282).—The collected on a glass filtering crucible, washed with phenomenon of the intermittent discharge through a hot water, and dissolved in nitric acid for the iodide neon lamp is applied to the measurement of small illuminations with a vacuum photo-electric cell. The precipitation. A. R. Po w e l l . cell and the neon lamp are connected in series with a Potentiometric determination, of gold. E. high-tension battery, and the lamp is shunted with a M ü ller and E. W eisbrod (Z. anorg. Chem., 1928, condenser ; the frequency of the intermittent flashes 1 6 9 , 394—398).—In determining gold by the method increases with the illumination. A. A. E ld r id g e . previously described (A., 1926, 1117), the concen­ tration of free hydrochloric acid in the solution should Adiabatic microcalorimeter for radiological be small, as otherwise the auric ion combines to a researches. W. Swientoslawsk t and (Ml l e .) A. large extent to form chloroauric acid, and the change D o r ab ialsk a (Rocz. Chem., 1927, 7, 559—566).— in potential corresponding with the completion of See A., 1927, 1163. the reaction A u"'+ 3Fe" — -> Au+3Fe"‘ is therefore Micro-determination of mol. wt. H. Jorg indistinct. Nitric acid has an even more marked (Miltrochem., 1928, 6, 34— 49).— An apparatus is effect, but this may in a large measure be overcome described and illustrated diagrammatieally for the by adding to the solution potassium sulphate before micro-determination of the mol. wt. of organic sub­ the titration commences, and alcohol when the reduc­ stances by the depression of f.-p. method. It consists tion of the chlorine is complete. Copper, mercury, essentially of two thermostats containing tubes hold- GEOCHEMISTRY. 389 ing the liquid used as solvent and provided with on the top of a spherical container. The tubulure copper-constantan thermocouples either of which carries a side tube connected through a 3-way cock may he connected through a resistance to a sensitive either to the vacuum pump or to the atmosphere. galvanometer by means of a throw-over switch. One Another tube provided with a stopcock is connected of the vessels serves for standardising the galva­ to the lower end of the spherical container. nometer, which is adjusted to zero at the f. p. of the S. I. L e v y . solvent, and the other vessel is used for determining Laboratory cooling device using liquid sulphur the f. p. of the solution. When both solution and dioxide. A. P. Gill (Ind. Eng. Chem., 1928, 20, solvent are just melting the difference between the 212).— The “ cold test ” of castor oil for use in aircraft galvanometer readings corresponds with the depres­ engines requires the maintenance of a temperature sion of the f. p. Several examples are given of the of —10° for 10 days. This is conveniently obtained results obtained and the method of calculation is by placing the test-tube containing the oil in a small explained. A . R . P o w e ll . Dewar flask charged with slowly-boiling liquid sulphur Resistance wire for use in the laboratory. J. dioxide (b. p. —10°). The only attention required was addition of 100 c.o. of sulphur dioxide every Piccard (J. Amcr. Chem. Soc., 1928, 50,406— 408).—• second day. C. I r w in . “ White gold,” an alloy of nickel and gold, is a suit­ able non-corrosive material for the measuring wires Electrical solution-mixing device. K. H ic k ­ of Wheatstone bridges. The alloy is hard and ductile, m an and D. H y n d m a n (Ind. Eng. Chem., 1928, 20, and has a tensile strength greater than that of steel. 213—216).—The automatic control of the proportions The resistance, temperature coefficient of resistance, in which two solutions are being mixed is effected and thermoelectric force against copper are recorded by carrying forward in a current of air a gas which for two commercial specimens of “ white gold,” and is either a participant in the reaction or is added as for platinum and constantan. S. K. T w e e d y . an indicator, into a conductivity cell. Ammonia may be used either in the neutralisation of sulphuric acid Pipette for micro-analyses. A. T. S hoiil (J. ■with ammonia, or in the neutralisation of this acid Amcr. Chem. Soc., 1928, 50, 417).— Van Slyke and with sodium hydroxide, a trace of ammonia being Neill’s modified Ostwald pipette is fitted with a added in the last case. Other indicators are sulphur hypodermic needle (made of platinum if necessary). dioxide and chlorine. The resistance of the cell used Drops of the order 0‘00015 c.c. can be removed from with tap water was 2000 ohms. This is coupled to a such a tip. S. K . T w e e d y . 110-volt A.C. supply and the variable current pro­ Modified weighing pipette. G. E dg ar (Ind. duced actuates a solenoid which is capable of rotating Eng. Chem., 1928, 20, 158).— A Lunge weighing a hollow drum pivoted axially through a few degrees. pipette contains three bulbs of definite volume with In the sides of the drum are two outlets for the graduation marks between them. It enables triplicate liquor under regulation, one a feed and the other a weighings of nearly the same quantity of material to by-pass. In effect, a frictionless valve controls the be conveniently made. C. I r w in . feed actuated by the conductivity of the indicator I r w in . Apparatus for micro-filtration. A. T. S hoh l cell. C. (J. Amer. Chem. Soc., 1928, 50, 417— 418).—The Extraction apparatus for liquids. J. F r ie d ­ liquid is filtered by suction through a thin layer of richs (Chem Fabr., 1928, 91).—A new apparatus is asbestos packed over a glass bead in a filter funnel. described in which the usual glass spiral is replaced The precipitate can be washed five or ten times with by a porous filter plate. C. W. G ib b y . 1 c.c. of solution. S. K . T w e e d y . Metallographic etching. M. Sc h n e id e r (Z. Suction flask for quantitative analysis. G. W. physikal. chem. Unterr., 1927, 40, 175— 176; Chem. K ühl (Chem.-Ztg., 1928, 52, 131).— The suction Zentr., 1927, ii, 1001).— A lecture demonstration. funnel is carried in a stopper which fits into a tubulure A. A. E l d r id g e .

Geochemistry.

[Variation of] the layer of ozone in the upper nitrates hi the sea-water south-wrest of Plymouth are atmosphere during the night. D. C h a lo n g e used up by the phytoplankton during the summer (Compt. rend., 1928, 186, 446— 448).— The thickness but reappear during the autumn as their synthesis of the layer of ozone encircling the upper atmosphere during this period is moro rapid than their decom­ of the earth (Dobson and Harrison, A., 1926, 493) position. Nitrates from land drainage cannot be was determined for a few days and nights from the detected more than a few miles from the land. spectral intensities of the radiations (up to 3050 A.) W . 0 . K erm ack. from the sun and moon, respectively. It remained Seasonal variations in the phosphate and constant during a particular night (about 3 mm.) but silicate content of sea-water during 1926 and was less during the day (about 2-2 mm.). A longer 1927 in relation to the phytoplankton crop. series of measurements is required to confirm this. W . R. G. A tkins (J. Marine Biol. Assoc., 1928, [ii], J. Gr a n t . 15, 191— 205).— The silicate and phosphate contents Nitrate in the sea. II. H. W. H a r v e y (J. of sea-water undergo rapid reduction during the late Marine Biol. Assoc., 1928, [ii], 15, 183— 189).—The spring and early summer as a result of the rapid 390 BRITISH CHEMICAL ABSTRACTS.— A.

proliferation of diatoms. The silicates may show a Mineral phosphates in the province of Lecce. rise in late summer which is not exhibited by the G. T ar u lli and A. Marcucci (Annali Chirn. Appl., phosphate, and comparing various seasons a high 1928, 18, 40— 46).— The whole of the subsoil of the phosphate minimum may accompany a low silicate heel of Italy appears to contain higher or lower minimum and vice versa. The date of the fall of proportions of phosphates at varying depths, in some the phosphates in spring varies from season to season cases capable of economic utilisation. T. H. Pope . and is correlated chiefly with the amount of sunlight. Chemical and provincial relations of the W. 0 . Iv er m ack . younger eruptive rocks of Germany and northern Photosynthesis of diatom cultures in the sea. Bohemia. H. J u n g (Chem. Erde, 1927, 3, 137— S. M. Marsh all and A. P. Orr (J. Marine Biol. 340).—A large number of chemical analyses of Assoc., 1928, [ii], 15, 321— 360).—W ith increasing Tertiary igneous rocks from Germany and northern depth photosynthesis by diatoms, as determined by Bohemia, collected from the literature, are tabulated the oxygen production (Winkler’s method), reaches a and plotted on diagrams. Variation curves are maximum and then decreases. This maximum occurs given for each of the constituent oxides. The rocks very near the surface in winter or in the absence of of the “ Oligocene province ” are all alkali-rocks of direct sunlight, and occurs at a depth of 20—30 the “ Atlantic type,” whilst in the “ Miocene province ” metres in the summer, but under similar conditions there are also lime-alkali-rocks of the “ Pacific type.” is nearer the surface in the more turbid waters nearer L. J. Spen cer . the coast than in the open sea. W . O. K erm ack . Mineralogy of Western Australia. I. E. S. p a of the Black Sea compared with that of the Simpson (J. Roy. Soe. W. Australia, 1927, 12, 57— salt lake Tekir-Ghiol. N. L. Cosmovici (Ann. Sci. 66).—Lithiopli ilite (from near Wodgina) contained : Univ. Jassy, 192S, 15, 131—132).— values have P20 5 45-99, MnO 30-80, FeO 10-44, CaO 2-78, been determined colorimctrically in July in the Black MgO 0-94, Li20 7-87, Na20 0-34, K 20 — , H20 (<110°) Sea and in the adjacent salt lake T6kir-Ghiol. For 1-11, total 100-27%; d 3-39, hardness 5. Leucite the former, values between S-3 and 8-5 were found (from Fitzroy valley) contained : SiO, 52-45, A1,03 in all cases, independent of temperature, wind, and 8-64, Fe„03 5-48, FeO 0-94, MnO 0-13, MgO 6-42, the nature of the sea bed. The presence of algte CaO 2-01, Na20 0-38, K ,0 10-42, H20 (<110°) 1-99, increased the pa. The p n of the lake Tekir-Ghiol H 20 (>110°) 2-89, T i0 2 5-85, P20 5 1-58, BaO 1-19, was 8-6 under all observed conditions. total 100-37%; d 2-6. Ferrimolybditc (Mulgine) C. W. Gib b y . contained: Fe20 3 17-87, M o 0 3 62-90, H20 (over Comparison of the absorptive powers of calcium chloride) 10-20, H 20 (250°) 9-95, total, Russian and other clay. A. M o nosson (Papers 100-92%; d 2-99. The formula Pure Appl. Chem. Karpov Inst., Bach Festschr., (Fe20 3,4Mo03,5H20),5H 20 is proposed. Kyanite and 1927, 169— 173; Chem. Zentr., 1927, ii, 1009).— The staurolite are described. Chem ical A bstracts. absorptive power of clays for ozokerite in kerosene is increased by heating the material at 350—400°, but Crystals of cornetite, and their refractive not at 105° or 700°. Treatment with acid, and indices. A. Schoep (Natuurwetens. Tijds., 1927, pulverisation, also often increase the absorptive 9, 125— 128).— Very well formed crystals, distributed power. A. A. E l d r id g e . in a layer of chrysocolla covering a brown sandstone, probably from the Star of the Congo mine at Katanga, Kaolin content of clays. H. B oege (Chem. Erde, 1927,3,341— 369).— Chemical analyses are given are found to have the angles and axial ratios already of eight clays from German localities. By digesting measured by Cesaro and by Hutchinson and Macgregor the material in hydrochloric acid (d 1-1) for 2 hrs. (A., 1921, ii, 701); besides the forms m (100) and from 6-00 to 14-0S% Al203-rFe203 passed into v (221), a new form a (100) is recorded. Measurement solution, this representing the colloidal portion of of the refractive indices by the immersion method, the aluminium silicate. After ignition of the material using the powdered mineral, gives a= 1-765±0-003, at 700° hydrochloric acid extracted more (up to ¡3=1-79—1-80, y = l-8 3 —1-84. S. I. L e v y . 36-82%) alumina, the additional amount representing Structure of millerite. H. W . V . W illems the broken-down kaolin. From these results the (Physica, 1927, 7, 203—207).— Millerite, NiS, is amount of kaolin in the clay can be calculated. ditrigonal-bipyramidal, space-group C>, the co­ The amount of kaolin present in each of these clays ordinates behig Ni («, 0,0) (0, u, 0) (0,0, u), S (x, x, z) was also determined by the dehydration method of (z,x,x) (x,z,x), where u=0-265,a;=0-75, z=0-41; hence Calsow (A., 1927, 38). L. J. Spencer. one sulphur atom is surrounded by three nickel atoms Mineralogical constitution of clays. G. L in o k distant 2-24 A., two nickel atoms at 2-43 A., and one (Chem. Erde, 1927, 3, 370— 374).— Remarks on the nickel atom at 3-45 A. The elementary rliombohedron paper by Boege (preceding abstract). has a 116° 35', r 5-65 A., and contains 3 mols., d„k. L. J. Spencer. 5-25. Chem ical A bstracts. Kaliophylite. 0. MtiGGE (Z. Krist., 1927, 65, Association of water with serpentine. P. G. 380— 390; Chem. Zentr., 1927, ii, 1140).— Kaliophylite N utting (J. Washington Acad. Sci., 1928, 18, 81— from Mt. Somina contained Si02 39-04, A120 3 89).— An attempt is made to distinguish between 31-96, Fe20 3 0-98, CaO 0-33, MgO 0-15, K sO 22-84, dissolved, adsorbed, and chemically combined water. Na20 3-89, H20 ( > 105°) 0-60%, but no carbon dioxide, The material used for the experiments consisted of chlorine, or sulphur; <•> 1531G, z 15273, d 2-61. clear homogeneous yellowish-green grains of serpentine A. A. E ldridge. sieved to 0-15— 0-05 mm., and gave on analysis GEOCHEMISTRY. 391

Si02 35-56, A120 3 2-46, F e,0 3 4-62, MgO 39-88, and the iron are rapidly converted into limonite. The FeO 2-02, NiO 0-22, CaO 0-10, H?0 (at 110°) 0-88, formation of ferromagnetic trevorite, Ni0,Fe20 3, and H 20 (over 110°) 15-04, corresponding with the ratios of analogous cobalt and copper compounds, seems Si02 : Rln20 3 : R nO : H20 = l-7 3 : 0-16 : 3-00 : 2-59 established. Chlorides promote the formation of [differing appreciably from the formula amorphous hydrated ferric oxide. Terrestrial ferro­ 3Mg0,2Si02,2H20]. The weights of this material at magnetic iron oxide is not analogous to the oxidation temperatures of 26°, 36°, and 46° are plotted against product of meteorites. Chemical A bstracts. the humidities of the atmosphere; the curves show greater variations in the more arid and more Connexion between commercial oil deposits humid regions. The dehydration (weight-temper- and major structural features with special ature) curve shows no break, but the logarithmic reference to Asiatic fields. L. D. Stamp (J. Inst. curve shows breaks at 368° (corresponding with Petrol. Tech., 1928, 14, 28—63).-—A critical examin­ 2H20) and at 620° (corresponding with 1-25H20). ation of the occurrence of oilfields shows their frequent association with geosynclinal areas of L. J. Spen c er . deposition and occurrence round the margins where Bolivianite and Silesite. F. A h lfeld (Zentr. Min. Geol., 1927, A , 320— 321; Chem. Zentr., 1927, the deposits arc of a deep-water type, or in the centre ii, 1807— 1808).— Polemical against Pauly (Zentr. in the case of shallow-water deposits. No genetic connexion between oil and belts of folding or between Min. Geol., 1926, A , 43). A. A. E l d r id g e . oil and vulcanicity can be traced. H . S. Gar lic k . Blue rock-salt. K. Przibram (Kali, 1927, 21, 253—255; Chem. Zentr., 1927, ii, 1807).— Radio­ Telegdite, a fossilised resin. L. Z ech m eister activity develops a blue colour in rock-salt similar to and V. V r a b Isly (Z. Min. Geol. Palaont., 1927, A, that in the natural substance, especially under pressure 287— 290; Chem. Zentr., 1927, ii, 1461).— The resin, (400 kg./cm.2). Under a pressure of 100 kg./cm .2 a formerly regarded as succinite, and now named yellow colour develops. Potassium may be the telegdite, was found at Szaszcsdr; it has d 1-09, hardness 24, rif, 1-5416, and contains C 76-93, H 10-17, origin of radioactivity. A. A. E l d r id g e . S 1-71, O 11-17%; acid value 0, saponification and Mud from lake Tekir-Ghiol [Romania]. A. ester value 180. Decomposition with alkali yields a B tjrada (Ann. Sci. Univ. Jassy, 1928, 15 , 129— 130). crystalline acid. A. A. E l d r id g e . —A detailed analysis of wet mud from this salt lake shows 63-36% of solids, of which 4-43% consists of Proportion of barium in arable soil. G. soluble salts (mainly sodium chloride and sulphate). B ertrand and L. Silber stein (Compt. rend., 1928, 186, 477— 480; cf. this vol., 336).— Barium in soil L. J. Spen c er . (20 g.) is determined after destruction of organic Granite of C icurova [R om an ia]. D. M. Ca d e r e (Ann. Sci. Univ. Jassy, 1928, 15, 81— 88).— A matter by heat, by fusion for 30 ruin, with 60 g. of an petrographical description and a chemical analysis are equimolecular mixture of sodium and potassium given of this hornblende-granite, and the analytical carbonates. The ivashed, water-insoluble residue is results arc plotted on diagrams of various kinds. It is reheated and extracted with hydrochloric acid, the an alkali-granite bordering on syenite. remaining residue re-fused and again extracted, and the combined acid filtrates (125 c.c.) arc precipitated with L. J. Spen c er . Chemical constitution of natural hydrated 10 drops of 10% sulphuric acid. The barium sulphate is stirred frequently7, and filtered after 2 days. A iron oxide. N . S. K h r n a k o v and E. J. R o de (Z. anorg. Chem., 1928, 169, 57— 80).— See this vol., 41. number of soils from various parts of France were found to contain 0-082—0-829 g. (in an exceptional Meteoric irons from Bolivia, W. Arkansas, and case, that of Langlade, Gard, 1-717 g.) of barium per M ichigan. G. P. M errill (Proc. U.S. Nat. Mus., kg. If it is assumed that all the barium is present in 1927, 72, Art. 4, 1—4).—The Bolivian specimen the soil as sulphate, these values account for 10—38% (21-25 kg.) contained Fe 94-212, Ni 5-626, Co 0-320, (80-5% in the exceptional case) of the total sulphur Cu 0-0004, S 0-014, P 0-261, Pt trace, insol. 0-042, available for nutritive purposes. J. Gr a n t . total 100-475%. The Arkansas specimens (1-75 kg.) contained Fe 94-858, Ni 5-121, Co 0-353, Cu 0-013, “ Fossil" soils and tropical weathering. P. W . E. V a g eler (Z. Pflanz. Dung., 1928, 10A, P 0-020, S 0-009, insol. 0-013,Mntrace, total 100-387%. The Michigan specimen (11-5 kg.) contained Fe 193—205).—A formal statement of the author’s 87-77, Ni 11-41, Co 0-26, Cu 0-01, S 0-05, P 0-15, total views in -which a plea is entered against the too loose use of the term “ fossil ” soils. Laterite soils can 99-65%. Chem ical A bstracts. be formed only under certain well-defined climatic Oxidation of meteoric irons. N ew examples conditions. They can become “ fossilised ” by two of magnetic iron oxides from terrestrial sources. processes only ; (a) by becoming covered with a E. V. Shannon (Proc. U.S. Nat. Mus., 1927,_ 72, humus layer, and (b) by becoming covered by7 a hard Art. 21, 1— 15).—In the oxidation of meteoric iron, crust formed by the precipitation of material brought magnetite is formed in relatively small quantities to the surface by capillary7 action. Fossil loess soils as a transitory and unstable stage; the magnetite also undoubtedly7 exist. II. J. G. H in e s . 392 BRITISH CHEMICAL ABSTRACTS. A.

Organic Chemistry. Röntgen rays and organic chemistry. A. rigidity, but on the presence of hydrogen atoms with K a b S s e n (Chem. Weekblad, 1928, 25, 114— 127).— meso-valency and of atoms having affinity towards An account of the results achieved in the elucidation them. Isomerism arises only when the possibility of structure of organic compounds by X-ray analysis. of forming meso-valencies exists. Ethylenic iso­ S. I. Le v y . merism is never observed when the radicals at the Theory of the meso-structure of organic com ­ double linkings are aliphatic and saturated, hydrogen pounds. 1.1. K otjukov (Bull. Siberian Inst. Tech., atoms with meso-valencies being absent from such 1927, 48, 1— 35).— The basis of the arguments radicals. This isomerism is annulled by replacement developed in this theoretical paper is the great, of the hydrogen atoms with meso-valency by other often dominant, importance of hydrogen in structural radicals, even if these contain double linkings and organic chemistry. The more stable are the carbon- different radicals. The isomerism of fumaric and carbon linkings, the less stable is the carbon-hydrogen maleic acids, stilbene, nitrobenzylidenedeoxybenzoin, linking and hence the greater the residual affinity of the cinnamic acid, and hydroxylepidine is considered, carbon, this being termed meso-valency and being and meso-formula; are given. The isomerism of identical with Werner’s secondary valency. With p- and allylpropenyl is doubtful. halogens the reverse is the case, this explaining the The isomerism of the oximes is conditioned by the formation of linkings between halogens and hydrogen setting-up of meso-linkings between the oxygen of and also the specificity of the linking of halogen with the oximino-group and the hydrogen of the radical carbon. Linkings formed as a result of the reciprocal situate at the carbon atom. If this radical has an saturation of ineso-valencies are termed meso-linkings. unsaturated atom, the hydrogen and the oximino- Benzene has no central linkings, its carbon linkings groups take part in the isomerisation. The iso­ representing a peculiar whole, in consequence of which merism is completely annulled by replacement of the tlio hydrogen atoms oxhibit marked meso-valency. hydrogen atom with meso-valency or of the hydroxyl In the benzene hexachloridcs the chlorine is united, of the oximino-group by any inert radical. Here, too, not with carbon, but with hydrogen. Substitution the number of known isomerides is in accord with the reactions proceed so that the meso-linkings formed meso-theory and not with the requirements of the in the initial product of combination remain undis­ classical theory. Both isomerides of acctylacrylic turbed in the final product. Every substituent acid are regarded as anh’-compounds. The isomerism entering the benzene nucleus combines, not only with of the diazo-compounds is also explainable by the the carbon of the nucleus, but also with the neigh­ author’s theory. T. H. P ope. bouring oriAo-hydrogen atoms with formation of Slow combustion of hydrocarbons. S. Lauda meso-linkings, unless the entering radical possesses {Compt. rend., 1928, 1 8 6 , 589—591).—Slow combus­ unsaturated atoms. Introduction of a substituent is tion of paraffin, m. p. 51°, at 280— 300° yields the accompanied by redistribution of the affinity, which following identified products: methyl and ethyl in one case causes loosening of the ortho-para, and in alcohols, acetone, methyl ethyl ketone, acetaldehyde, another that of the »»eta-hydrogen atom; initiation propaldehyde, hexaldehyde, heptaldehyde, octalde- of meso-linkings enhances this phenomenon. Radicals hyde, nonaldehyde, and undecaldehyde. The identi­ possessing unsaturated atoms connected directly to fication of the alcohols amongst the products of the nucleus are or/Ao—para-dirigents, whilst meta- combustion is important in relation to the hydroxyl- dirigents are those with unsaturated atoms not ation theory of Bone (J.C.S., 1902, 8 1 , 535). combined with the nucleus; the cause of the directing G. A. C. G ough. influence lies in the unequal distribution of the [Preparation of] A^-pentene. J. F. N orris (Org. affinity. These views furnish explanations for a Syntheses, 1927, 7, 76— 77). number of problems, such as the velocity of reaction of substitution, the varying stability of radicals in Decomposition of methyl chloride at high the nucleus, etc. A meso-formula is suggested for temperatures. K. W iesler (Chem.-Ztg., 1928, 52, naphthalene. 182— 183).—Methyl chloride decomposes at high The phenomenon of steric hindrance is founded, temperatures, giving an equivalent quantity of not on tho magnitude of the radical, but on the hydrogen chloride. Decomposition is appreciable at appearance of meso-linkings between the radical and 500° and nearly complete at 900°. The presence of the neighbouring or/Ao-hydrogcn atoms and on uneven methane has no effect on the equilibrium, but the distribution of the affinity. Physical isomerism is decomposition is slightly increased by water vapour structural isomerism and is encountered only when and to a much greater extent by carbon dioxide. more than one meso-linking is possible; in the great C. J. Sm ith ells. majority of cases the number of isomerides known Catalytic oxidations in aqueous solutions. II. corresponds with the possible number. The isomerism Oxidation of primary alcohols. N. A. M ilas (J. of benzophenone, ß-dinaphthyl ketone, benzil, and Amer. Chem. Soc., 1928, 5 0 , 493— 499; cf. A., 1927, phenylmethylpicramide is discussed from this point of 973).—Addition of a solution of sodium chlorate view, meso-formulae being suggested for these com­ (73 g.) in aqueous 2-5% sulphuric acid (130 c.c.) to pounds. methyl alcohol (64 g.), water (50 c.c.), and vanadium The isomerism of ethylene compounds rests, not on pentoxide (0-3 g.), at 75— S0°, with stirring, with the presence of double linkings as such and on their subsequent heating for 10 hrs., addition of 6JV-sul- ORGANIC CHEMISTRY. 393

phuric acid (36 c.c.), and continued heating for acids. J. Cam pardou and M. S eon (Compt. rend., 36 hrs. affords methyl formate, formic acid, a trace of 1928,1 8 6 , 591— 593).— Acid anhydrides are converted chloroform, and an unidentified product. Similar into ketones by passage over heated thoria more easily oxidation of ethyl alcohol affords ethyl acetate in than the corresponding acids; thus at 300° acetic acid 60—61% yield, together with acetaldehyde and yields acetone, and a mixture of acetic and benzoic acetic acid. Acetal (100 g.) yields similarly ethyl anhydrides yields acetophenone. At 400° acetic acetate (45 g.), acetic acid (36 g.), and ethyl alcohol, anhydride yields some mesityl oxide. In the synthesis whilst an equimolecular mixture of paracctaldehyde from acids it is suggested that it is more probable that and ethyl alcohol (total 102-3 g.) yields ethyl acetate the ketones arise from the intermediate formation of (54 g.) and acetic acid (21-3 g.). Acetaldehyde alone the acid anhydrides than through the formation and yields paracctaldehyde, which then remains un­ decomposition of a thorium salt. This view is attacked. «-Propyl alcohol yields similarly propyl supported by the preparation of acetic anhydride propionate (48—51%), together with propionic acid from acetic acid by passage over titanic oxide at 300°. and small proportions of propaldehyde and a chlorin­ G. A. C. G ough . ated ester; «-butyl alcohol yields «-butyl butyrate Action of acetic anhydride on carboxylic acids. (47—49%); isobutyl alcohol yields isobutyl iso- A. W. V a n d e r H a a r (Rec. trav. chim., 1928, 47, butyrate (46—48%), together with carbon dioxide, 321—328).—The action of acetic anhydride on acetone, isobutaldehyde, and chlorinated products, simple monocarboxylic acids yields only the simple wliilst isoamyl alcohol affords isoamyl isovalerate (45— acid anhydride (which often crystallises with 1 mol. of 48%), isovalcraldehyde, chlorinated products, acetone, acetic anhydride of crystallisation) and not a mixed and carbon dioxide. It is concluded that aldehydes anhydrido as stated by Autenrieth (A., 1888, 230) and are the primary oxidation products, these then by Askenasy and Meyer (A., 1895, i, 506). Mol. wt. condensing with unchanged alcohols to form semi- determinations of the products were made, since the acetals, the secondary alcoholic groups of which are empirical formula of the simple anhydride containing then oxidised with formation of esters; any free acid 1 mol. of acetic anhydride of crystallisation is the present in the product is derived from the latter by same as that of the mixed anhydride. Thus when hydrolysis. P. G. W illso n . benzoic acid is heated with acetic anhydride for 0-75 hr. and the resulting solution concentrated over Catalytic dehydration of . potassium hydroxide in a vacuum, the crystalline W. J. A lla r d y c e (Trans. Roy. Soc. Canada, 1927, product has the composition Bz20,C4H603, m. p. [hi], 2 1 , III, 315— 321).— The catalytic dehydration 100— 105°. The crystals effloresce with loss of of isopropyl alcohol at 360° has been studied in acetic anhydride, and by warming with 5% sodium presenco of tertiary, secondary, and primary calcium carbonate solution the whole of the acetic anhydride phosphates, tertiary and secondary magnesium phos­ is removed, leaving benzoic anhydride, m. p. 40— 42°. phates, and aluminium phosphate and sulphate. In all cases the reaction was almost entirely represented By similar treatment p-dimethylaminobenzoic acid yields its anhydride with 1 mol. C ,lf60 3, m. p. 109°, to by the equation OHMeyOH — > CHMe;CH2+H 20. which the structure (NMe2-C(iH1-G0-)20;0Ac2 is The catalyst improved with use at first, but ultimately assigned, but by heating above’its m. p. acotic anhydr­ attained constant values which were much closer to ide is expelled, and the anhydride has m. p. 218°. one another than the initial values. Treatment of Thus with increasing mol. wt. of the acid the acetic the aluminium sulphate with ammonia gas, or with anhydride of crystallisation is more firmly held, hydrogen chloride, decreased its efficiency by about 2 %. confirming the composition previously assigned to the In the former ease the reactivity of the catalyst could compounds obtained similarly from the sugar be restored by treatment with carbon dioxide. Treat­ saponins (this vol., 68). When aldehydo- or keto- ment of fresh samples of aluminium sulphate or primary acids are heated with acetic anhydride the acid is calcium phosphate with carbon dioxide gave initial converted into the enol lactone form and the resulting yields 2— 3% higher than those given by the untreated samples, but had no effect on the yields after the hydroxyl group is acetylated, R < ^ (GA.c)> q constant value was reached. The yield of propylene Thus opianic acid yields acetyl-^-opianic acid, m. p. was varied over a range of 3% by changing the rate at 125°, which can be crystallised from water without which the alcohol was passed over aluminium sulphate. loss of its acetvl group (cf. Liebermami and Klerman, The catalyst darkens with time and the darkening is A., 1887, 47). J. W . B a k e r . not confined to the surface. Its extent varies with the catalyst. m| g, burr. Aromatic properties of some aliphatic Preparation of sodium formaldehydesulph- compounds. Local anresthetics derived from oxylate. N. Bach-Nikolajeva (Papers Pure Appl. aliphatic carboxylic acids. II . Gil m a n , L . G. Chem. Karpov Inst., Bach Eestschr., 1927, 92— 100; H eck er t, and R . M cCracken (J. Amer. Chem. Soc., Chem. Zentr., 1927, ii, 1014).— Thereduction according 1928, 5 0 , 437— 439).— The following compounds were f'° p.P . 276,984 is complete in 2— 3 hrs.; long prepared by treating diethylaminoethyl alcohol with boiling decomposes the product. A. A. E ld r id g e . the appropriate acid chlorides in benzene or ether : diethylaminoethyl acrylate hydrochloride, m. p. 93°; Electrolytic oxidation of formic acid. E. diethylaminoethyl $$-dimethylacrylaie hydrochloride, Muller.—See this vol., 377. m. p. 128-5— 130°; diethylaminoethyl trichloroacetale Decomposition of acid anhydrides. Prepar­ hydrochloride, m. p. 144— 145°, and diethylaminoethyl ation of anhydrides by direct dehydration of acetate hydrochloride, m. p. 116— 117°. Taking the 394 BRITISH CHEMICAL ABSTRACTS.— A. relative pharmacological activities of cocaine, apothe- diethyl, b. p. 135— 136°, d f 0-90085, n f 1-39185; sin (dicthylaminopropyl cimiamate), diethylamino- ethyl di-n-propyl, b. p. 190— 194°, d f 0-87129, n f ethyl thiophen-2-carboxylate, and diethylaminoethyl 1-40635; and ethyl di-n-butyl orthoacetate, b. p. 220— furan-2-carboxylate as 10, 8, 1, and <1, respectively, 225°, d f 0-86461, n f 1-41485. When the alkyl radi­ those of the above compounds, in that order, are cals of the imido-ether and the alcohol are not the 1, 1, <1, and 0, from which it is deduced that pharm­ same, the mixed orthoacetate is always accompanied acological activity ascribed to aromatic groupings can by the simple orthoacetate derived by replacement of be approached by suitable unsaturated aliphatic the lower alkyl radical by the higher (cf. Pinner, structures (cf. Gilman and Pickens, A., 1925, i, 333). A., 1883,1089). F. G. W illso n. $-Chloroethyl afi-dibromopropionate, b. p. 153°/20 mm., Configurational relationships of p-hydroxy- w301-9080, d f 1-5241, is described. F. G. W illso n . valeric and lactic acids, and of methylethyl- and Anodic oxidation of free propionic acid. F. ethyl-n-propyl-carbinols. P. A. L e v e n e and M u lle r .— See this vol., 377. H. L. H aller (J. Biol. Chem., 1928, 76, 415— 422; Allyl hexoate and octoate. V. D e u lo eeu cf. A., 1927, 643, 1053).— ■ 20CO2 + carbon-chain structure. The normal ozonide, 12Mn" +28H 20 (cf. Lange and Kline, A., 1923, ii, CalH460 5, gave ?i-nonoic acid and tridccane-ow-di- 180). ” Chemical A bstracts. carboxyiic acid, m. p. 113°. Selacholeic acid, Synthesis of apy-trimethylglutaric acid. F. E. CH3-[CH2]7-CH:CH-[CH2]13-C02H, is identical with R a y (J. Amer. Chem. Soc., 1928, 5 0 , 558— 563).— nervonic acid (cf. Klenk, A., 1927, 691). Treatment of ethyl ethylidenedimalonate with methyl K. K ashtma. iodide and alcoholic sodium ethoxide affords ethyl Esters of orthoacetic acid. P. P. T. Sah (J. y-methyl-n-pentane-$$88-tetracarboxylale, b. p. 190— Amer. Chem. Soc., 1928, 50, 516— 518).— Triethyl 195°/2—3 mm., from which the corresponding acid, orthoacetate, b. p. 144— 146°, d f 0-8847, n f 1-39485, m. p. 190°, is obtained on hydrolysis with boiling is obtained by keeping acetimidoethyl ether hydro­ aqueous hydrochloric acid. When heated at 190— chloride in absolute alcohol for 2 weeks, with occasional 200°, the latter loses approximately the expected shaking, and fractionating the filtrate from the precipit­ amount of carbon dioxide, but the residue is a mix­ ated ammonium chlorido under reduced pressure. ture. Condensation of ethyl tiglate with ethyl The following orthoacetates were prepared by con­ cyanoacetate affords ethyl a-cyano-ty-dimethyl- densation of alcohols as above with appropriate glutarate, b. p. 150— 170°/30 mm., from which ethyl acetimidoalkyl ether hydrochlorides : trimethyl, b. p. c/.-cyano-'ify-tri?nethylglularale, b. p. 140— 150°/1— 2 107— 109°, d f 0-94375, nf; 1*38585; dimethyl ethyl, mm., is obtained on methylation. The latter yields b. p. 123— 126°, d f 0-91915, n f 1-38885; methyl a-carboxy-zPy-trimethylglutaric acid, m. p. 144— 145° ORGANIC CHEMISTRY. 395

(decbmp.), on hydrolysis with boiling concentrated salt; magnesium salt (2H20 ); zinc salt (2H20); aqueous potassium hydroxide, and this, when heated lead salt, PbC4H40 6,2Pb0; cadmium salt (2H20 ); at 150— 160°, affords afty-trimethylglutaric acid, m. p. normal aluminium salt (from which the aluminium 134°. Condensation of ethyl malonate with ethyl is not precipitated by ammonia); normal manganese tiglate affords analogously ethyl y-methyl-n-pentane- salt (3H20). The copper, nickel, and iron salts $88-tricarbozylate, b. p. 121°/25 mm., from which could not be obtained in a state of purity. The the trimethylglutaric acid is obtained by hydrolysis solubilities of many of the salts are recorded. and decomposition of the resulting acid. The G. A. C. Gough. “ a (3 p - trim ethy lgl utar ic acid ” obtained by Noyes Inhibition of the precipitation of calcium and Skinner (A., 1918, i, 65) from Zsoaminocamphon- tartrate b y salts. M. E. Stas (Pharm. Weekblad, anic acid is shown to be identical with Perkin and 1928, 6 5 , 107— 108).—The commoner sodium, am­ Thorpe’s aap-trimethylglutaric acid (J.C.S., 1899, 75, monium, and magnesium salts inhibit the precipit­ 65). P. G. W il l so n . ation, especially in warm solutions; 0-1 g. of sodium a-i.soPropylglutaconic acid. K. V. Hariharan, chloride in 4 c.c. completely prevents precipitation K. N. Menon, and J. L. Simonsen (J.C.S., 1928, if not more than 10 mg. of tartaric acid is present. 431— 438).— Ethyl sodiodicarboxyglutaconate con­ For small quantities, therefore, the acid should be denses with isopropyl iodide at 140— 160°, yielding extracted by means of ether before applying the test. ethyl trimesate. Ethyl isopropylcyanoacetate con­ S. I. L e v y . denses with ethyl p-iodopropionate in presence of Composition of a series of bismuth sodium sodium ethoxide, yielding ethyl ot-cyano-ac-isopropyl- tartrates. W. F. v o n O e t tin g e n and Y. Ism k a w a glutarate, b. p. 195°/32 mm., which is hydrolysed (J. Amer. Pharm. Assoc., 1928, 17 , 124— 134).— by 50% sulphuric acid, giving a-isopropylglutaric The preparation of bismuth tartrate by the addition acid. Bromination of a-isopropylglutaryl chloride of sodium tartrate solution to an acetic acid solution yields, as main product, a-bromo-a-isopropylglutaryl of bismuth nitrate and of soluble sodium bismuth chloride (cf. A., 1925, i, 358), since esterification of tartrate has been examined. Both preparations pass the bromination product yields an acid ester, con­ through different compounds. The following com- verted by treatment with alkali into the lactone pounds were isolated: C4HjOcBi-OAc, C4H50 GBi, of y-hydroxy-P-methylpentanc-ye-dicarboxylic acid. C4H20 6NaBi, C4H ,0 8NaBi2, 0(C4H20 7NaBi)2, Treatment of ethyl potassioacetonedicarboxylate C4H20 7ClNaBi2, C4H20 7Bi2, C4H20 9NaBi3, C4H30 9Bi3. with isopropyl iodide in alcoholic solution gives ethyl E. II. S harples. a-isop>ropylacetonedicarboxylate, b. p. 142— 143°/9 mm., Optically active copper compounds. W. W ah l converted by prolonged reduction with a large excess (Soc. Sci. Fennica Comm. Pliys. Math., 1927, 4, of sodium amalgam into ethyl fi-hydrozy-a-isopropyl- (14), 1— 5).—Diethylcnediaminediaquocupric tartrate has been prepared from barium tartrate and the glutaralc, b. p. 145—146°/10 mm. The hydroxy- ester reacts with phosphorus pentachloride, giving complex sulphate which is obtained when aqueous ethyl fi-cJiloro-Qi-isopropylglittarale, which is converted solutions of cupric sulphate and ethylencdiaminc are mixed and evaporated to dryness. After filtration by treatment with dicthylanilinc at 180— 190° into from barium sulphate the copper complex salt is ethyl a-isopropylglutaconate, b. p. 148— 150°/15 mm. precipitated by the addition of alcohol to the solu­ Hydrolysis yields the acid, separated by treatment tion. The salt has [d/] +28-3°. After two extrac­ with acetyl chloride into c\s-a.-\s,opropylglulaconic tions with alcohol the residual compound has [AZ] acid, m. p. 101° (calcium, barium, and copper salts; —59-4°. When obtained by vacuum evaporation potassium salt of hydroxy-anhydride), and trans-a- of the aqueous solution, the salt has [M] —38-3°, isopropylglulaconic acid, m. p. 132° (barium salt). and of the residue after alcoholic extraction —134°. Neither acid is identical with the acid obtained from d-A3-carenc by oxidation with potassium perman­ The Z-diaquodiethylenediaminecupric ion must have [ill] at least 190°. A series of optically active ganate in acetone solution (J.C.S., 1923, 1 2 3 , 553). iodides has been prepared from the tartrates. Nickel Reduction of the monomethyl ester of caronic acid yields corresponding tartrates of varying activity, with sodium and alcohol yields the lactone of 8-hydr- the highest observed value being about +420°. oxy-fifi-dimethylvaleric acid, b. p. 137°/43 mm., 232— 235°/685 mm., converted by treatment with potassium H. F. G il l b e . Preparation and properties of i-mannono- cyanide at 275°, followed by hydrolysis of the resulting and d-glucono-lactones. F. W . U p so n, L. Sa n d s , nitrile, into pp-dimethyladipic acid. M. Cla r k . and C. H. W h itn ah (J. Amer. Chem. Soc., 1928, 50, Salts of mesotartaric acid. I. E. H eckele 519— 525).— Crystalline Z-gluconolactone, m. p. 134— (Osterr. Chem.-Ztg., 192S, 31, 28— 32).— The follow- 135°, [a]D —68-7°, to — 13-7° in 15 days, subsequent!}' mg salts of mesotartaric acid are described : disodium increasing (cf. Hedenburg, A., 1915, i, 76), has now salt; additive compound, C4H50 6Na,C4H60 6 (un­ been obtained from Z-arabinose by Fischer’s method altered by crystallisation from water); dipotassium (cf. A., 1890, 1389), through the brucine salt, m. p. salt (2H20 ) ; potassium hydrogen salt (this salt 181— 182°, [a]® —25-43°. \-Gluconophenylhydrazide, forms many soluble additive compounds with metallic m. p. 200°, [a]g — 11-7°, is described. l-Mannono-y- hydroxides); sodium potassium salt (H20 ); diam- lactone, m. p. 150-5— 151°, [a% —51-8°, obtained monium salt; ammonium hydrogen salt; potassium from Z-mannonolactone by Nef’s method (A., 1914, ammonium salt (H20 ); dilithium salt; lithium i, 490) was converted by methyl iodide and silver hydrogen salt (H.,0); potassium lithium salt (H20 ); oxide into methyl tetramethyl-l-mannonate, from which, calcium salt (3H20 ) ; barium salt (H20 ) ; strontium on hydrolysis, telramethyl-\-mannono-y-lactone, m. p. 396 BRITISH CHEMICAL ABSTRACTS.— A.

109°, [a]? — 65-51°, to —47-4° in 18 days, was given)], respectively, when regenerated from the obtained. The slow change in rotation, together dibromides. When the form of m. p. 12— 14° is with the slow titration with alkali at the ordinary treated with acetic acid and acetic anhydride at temperature, supports the 8-lactonic structure. Tetra- 150°, there is produced a diacetate, b. p. 160— 162°/ methyl-d-mannono-y-lactone, m. p. 151°, [a]j? +66-6°, 11 mm., d21 1-144, n21 1-4669, hydrolysed by cold was obtained analogously. Treatment of calcium alcoholic sodium hvdroxide to {iz-diethoxy-Av-hexinene- Z-mannonate with oxalic acid affords an l-mannono- aZ-diol, b. p. 125— 128°/3-5 mm., d18 1-026, it18 1-4503. lactone, m. p. 160— 162°, [a]?? -1 1 3-6°, to -3 0 -9 ° The form of m. p. 21° is unaffected by similar treat­ in 32-5 hrs., subsequently increasing, to which, as ment. The above dioxide is acted on by methyl well as to the corresponding d-mannonolactone of alcohol and a small amount of sulphuric acid, forming Hedenburg (loc. cit.), the 8-lactonic structure is a'Q-dimethoxy-Ar-he,xinene-$z-diol, b. p. 143— 143-5°/ ascribed, from theoretical evidence presented. Oxid­ 3-5 mm., d23 1-122, w23 1-477 (dibromide, m. p. 150— ation of tetramethyl-d-mannosc with bromine affords 151-5°), and by water, yielding Av-hexinene-a.$s£- a tetramethyl-d-mannonolactone, liquid, [a];? +132-3°, tetraol, m. p. 113— 114-5° (dibromide, m. p. 184— to +59-5° in 6 days, subsequently increasing, which •185°). H. B u r to n . also appears to be a 8-lactone. F. 6 . W illso n . Condensing action of mixed magnesium alkyl- Semiacetal formation and the refractive indices oxides. V. Gr ig n ar d and M. F lttchaire (Ann. and densities of mixtures of certain alcohols and Chim., 1928, [x], 9, 5— 54; cf. Grignard and Dubien, aldehydes. H. A d k in s and A. E. B r o d er ic k (J. A., 1923, i, 896).—Magnesium alkyloxyhalides, Amer. Chem. Soc., 1928, 50, 499— 503).— The refrac- RO-MgHal, for use as condensing agents (cf. Meer- t ive indices and densities of certain alcohol-aldehyde wein and Schmidt, A., 1925, i, 1239) arc prepared mixtures, taken over the range from pure alcohol by treating magnesium alkyloxides with etherated to pure aldehyde, indicate that condensation takes magnesium halides (Menschutkin, A., 1906, i, 131, place in all cases, presumably with formation of 552). The etherated halides themselves are inactive semiacetals. In the cases of acetaldchyde-ethyl as condensing agents, whilst the alkyloxides have alcohol, lieptaldehyde-ethyl alcohol, and acetalde- a smaller reactivity than the mixed derivatives. hyde-isopropyl alcohol, semiacetal formation appears During condensations of aldehydes two reactions to be almost quantitative. F. G. W illso n. usually proceed simultaneously, (a) aldol formation, Action of chloroacetaldehyde on the mixed (6) ester formation, 2R-CHO — + R-C02CH2R, whilst dimagnesium derivative of acetylene. Acetyl- with ketones only aldol condensation takes place. enic glycol and erythritol. R. Lespieatj (Bull. Acetaldchyde and magnesium butoxyiodide react Soc. chim., 1928, [iv], 43, 199—210).—When cliloro- in presence of ether to form ethyl acetate, aldol, and acetal is treated with oxalic and sulphuric acids there is butyl acetate, this being obtained from the inter­ produced, in addition to polymerised chloroacetalde­ action of ethyl acetate and the magnesium deriv­ hyde, some fi3-dichlorocrotonaldchyde, b. p. 80°/ ative. n-Butaldehyde and magnesium butoxy- 15 mm., d'20 1-361, w20 1-512, which with ethyl ortho- halides give «-butyl butyrate, y-hydroxy-fS-cthyl-n- formate, alcohol, and a trace of hydrochloric acid hexaldehyde, and ay-dihydroxy-^-ethyl-ri-hexyl butyr­ yields (3 5 - dicMorocrotonaldehyde diethyl acetal, b. p. ate, b. p. 255°, 148— 149°/15 m m , d\s 0-9473, rag 101— 102°/15 mm., d23 1-128, n23 1-4601, R 51-73. 1-4452, R 60-72. fi-Ethyl-n-hexane-ay-diol has b. p. This compound yields with sodium ethoxidc [3-chloro- 116°/5 mm., 133— 134°/i5 mm., d}5 0-9367, rag 1-4535. S-ethoxycrotonaldehyde diethyl acetal, b. p. 117°/13 mm., Benzaldehyde reacts slowly, forming benzyl benzoate d~l 1-033, n21 1-446. The action of chloroacetalde­ and benzyl oxide, whilst furfuraldehyde affords hyde on the product of reaction of acetylene and furfuryl alcohol, b. p. 75— 76°/15 mm., dj* 1-1359, magnesium ethyl bromide is to give a-chloro-$-hydr- n)| 1-4940, R 25-12, together with a-furfurylidene- oxy-Av-butinene, b. p. 157°/760 mm., 62—63°/14 mm., butaldehyde, b. p. 234—235°, 114r-115°/15 mm., d21 1-171, « 21 1-475, and a£-dichloro-Az-hexinene-Pe- d? 1-061, 1-5668. cliol (not isolated) [dibromide, m. p. 141— 142-5° Benzaldehyde and acetone condense in presence (crystallographic data given)]. The former com­ of magnesium butoxybromide to form benzylidene- pound when treated with dry potassium hydroxide and dibenzylidene-. in ether yields ethinylethylene oxide, b. p. 86—87°/ Condensation of methyl alkyl ketones proceeds 760 mm., d23 0-945, n23 1-427, hydrolysed to AY-butin- 2R-COMe — > R-CO-CH2-CMeR-OH. The alcohols ene-a^-diol, m. p. 39-5— 40-5° {diphenylcarbamale, formed are dehydrated by distillation either alone or in. p. 134—134-5°; dibromide, in. p. 47— 48°), whilst with traces of iodine and anhydrous oxalic acid to the latter furnishes the dioxide, the unsaturated ketones, R-CO-CHICMeR. Mag­ ?> C H -C :C -C H < ? , b. p. 87-5— S8-5°/10 mm., nesium butoxybromide causes the conversion of HoO C'Xii) acetone into diacetone alcohol (cf. Grignard and 98— 99°/20 mm., d23 1-1189, n23 1-4S71 (cis- and Dubien, loc. cit.), but prolonged treatment or the tTxns-dibrotnides, m. p. 57— 58° and 101— 102-5°). use of magnesium bromodiacetone alcoholate gives Ethyl ccp-dichloroethyl ether furnishes two stereo- phorone, isophoronc, and ^(-dimethyl-A’ -heplen-Pj-ol- isomeric a.£-dichloro-$z-diethoxy-Ar-hexinenes, having 8-one, b. p. 95—96°/5 mm., dg 0-9432, 7ig 1-4577. b. p. 136— 1370/11— 12 mm., m. p. 12— 14°, d21 Methyl ethyl ketone furnishes y-methyl-n-heptan-y-ol- 1-110, n21 1-4705 (dibromide, m. p. 107— 108°), and t-one, b. p. 85°/15 mm., djs 0-9315, «if 1-4367, de­ b. p. 138— 139°/13 mm., m. p. 21°, d21 1-112, m21 hydrated to y-methyl-Av-hepten-E-one, dg 0-8511, 1-471 [dibromide, m. p. 71—72° (crystallographic data «15 1-4469 (semicarbazone, m. p. 115°). Methyl propyl ORGANIC CHEMISTRY. 397

ketone gives 8-methylnonan-8-ol-£-one, b. p. 110°/ Verley, A., 1925, i, 783) (probably isolated from 15 mm., d\s 0-9076, n}J 1-4424, dehydrated to benzaldehvde and magnesium butoxybromide) thus : 8-methyl-A*-nonen-£-one, b. p. 90°/14 mm., 202°/ R-CHO+BuO-MgBr — ^ BuOCHR-OMgBr (I), with 755 mm., d'* 0-8494, n\] 1-4512 (oxime, b. p. 130°/14 subsequent condensation of 2 mols. into 2BuO-MgBr+ mm.). Methyl butyl ketone yields e-methylundecan- CHR-OCHR' — y R-C02CH2R. The production of e-ol-rj-one, b. p. l l l ° /4 mm., d'J1 0-8975, tiJ? 1-4445, I— "0-----^ dehydrated easily to z-methyl-A'-undecen-rj-one, b. p. the aldol (cf. Tischtschenko, A., 1907, i, 282, 284) is 120°/16 mm., d" 0-8472, 1-4541 (oxime, b. p. 149— formulated CHO-CHR-H+BuO-CH(0-MgBr)-CH2R 150°/12 mm.). From methyl isobutyl ketone there — >■ BuOH+CHO-CHR-CH(OMgBr)-CH2R, When are obtained $8t)-trimethylnonan-8-ol-£-one, b. p. 99°/ the aldehyde is reduced to the alcohol the following 3 mm., d" 0-8962, w}) 1-4427, and p80-trimethyl-As- change takes place: CH2Pr 0 • GHR- OMgB r — >- nonen-£-one, b. p. 108°/15 mm., d]® 0-8447, n}-, 1-4543 CH2R-OMgBr+Pr-CHO, and the formation of the (oxime, b. p. 145°/14 mm.). Methyl amyl ketone enol form of the ketone is postulated as gives £-methyl-A£-tridecen-0-one, b. p. 115°/4 mm., BuOCR'(CH2R)-OMgBr — > BuOH+ d f 0-8510, < 1-4592, R 67-48 (oxime, b. p. 165°/12 CHRiGR'-OMgBr. H. B urton . mm.), which when ozonised yields methyl amyl ketone and probably amylglyoxal. The molecular Reactions of nitrosyl chloride. H. R h e in - refractions of the above unsaturated ketones show boldt and M. D e w ald (Annalen, 1928, 4 6 0 , 305— exaltation, due to conjugation. 307).— It has been found (A., 1927, 229) that whilst Condensation of diethyl and dipropyl ketones pro­ some aldoximes and nitrosyl chloride gave crystalline ceeds with difficulty (cf. Ekelcy and Carpenter, A., chloronitrosohydrocarbons, higher aldoximes and iso- 1924, i, 369) under the influence of magnesium valor- and phenylacet-aldoxime gave oils. Some butoxybromide. There are formed 8-methyl-y-ethyl- higher aldoximes have now been converted into heplan-y-ol-e-one, b. p. 105°/14 mm., d f 0-9175, n’jJ crystalline products, although the two other oximes 1-4435, dehydrated to 8-methyl-y-ethyl-Av-hepten- named have not. With increase of mol. wt., the e-one, b. p. 92°/14 mm., d" 0-8515, n " 1-4509, and stability of the dimeric form of chloronitroso-com- z-etliyl-8-propyl-As-nonen-£-one, b. p. 224°/755 mm., pounds increases. (The higher members have only d" 0-8506, n\\ 1-4569, respectively. a feeble colour in benzene solution.) Again, the Magnesium butoxybromide converts cthylidene- higher members pass much less readily than the lower and propylidene-acetone into S-methyl-A^-nonatrien- into hydroxamic chlorides. ct-Chloro-a-nilroso-n- t-one, b. p. 102°/4 mm., d\2 0-9187, 1-4871, and octane, -n-nonane, -n-decane, and -n-dodecane melt, z-melhyl-A'/^-undecalrien-y-one, b. p. 120°/4 mm., respectively, at 42°, 60— 51°, 62°, and 63°. The 138°/18 mm., d\a 0-9103, «1? 1-4899, respectively. last-named compound was obtained from dodecald- When ethylideneacetone is treated with a deficit of oxime, m. p. 73°. E. E. T u r n er . magnesium ethyl bromide there is formed in addition [Preparation of] methyl n-amyl ketone. J. R. to the above condensation product some y-methyl-As- J ohnson and F. D. H ager (Org. Syntheses, 1927, 7, hepten-y-ol, b. p. 62°/15 mm., d" 0-8477, n\] 1-4421. 60—62). Improved methods of preparation of ethylidene-, propylidene-, and butylidene-acetones, methyl butyl Mechanism of carbohydrate oxidation. VII. and methyl isobutyl ketones are given. n-Hexan- Action of potassium hydroxide on dihydroxy- 8-ol-p-one has b. p. 83°/15 mm., d', 0-9639, nf, 1-4353, acetone. W. L. E v a n s and W. R. Co r n th w a ite R 31-42 (cf. Pastureau and Zamenhof, A., 1926, 272). (J. Amer. Chern. Soc., 1928, 50, 486—492; cf. A., $8-Dimet]iylhexane-$8-diol, prepared from magnesium 1926, 1226).— The action of aqueous potassium ethyl bromide and diacetonc alcohol, has b. p. 94— hydroxide on dihydroxyacetone under conditions 95°/5 mm., 0-9212, ?fln5 1-4437. precisely comparable with those previously applied When methyl isobutyl ketone is treated with mag­ to glyceraldehyde (loc. cit.) gives the same products, nesium butoxybromide and benzoyl chloride there is and the similarity between the variations of pro­ formed in addition to the abovo trimethylnonenone, portions of the different products with alkali con­ the benzoate, b. p. 123°/15 mm., d\4 0-9706, n\> 1-489S, centration and temperature in the two cases is of the enolic form of the initial ketone. The same brought out by graphical methods. These results benzoate is produced, together with methylethyhso- indicate that glyceraldehyde and dihydroxyacetone butylcarbinyl benzoate, from magnesium ethyl exist in alkaline solution in equilibrium with the bromide and benzoyl chloride. These results demon­ same enediol. In presence of phenylhydrazine, the strate the enolisating effect of the organo-metallic maximum production of pyruvaldehvde from glycer- compound. aldehydo and dihydroxyacetone occurs at the same It is shown that magnesium butoxyiodide has a alkali concentration, but the yields of pyruvaldehyde greater condensing action on butaldehyde than either (as osazone) arc not identical, from which it is con­ the chloride or the bromide, whilst in a series of cluded that the proportions of components present alkoxy-iodides the greatest effects are shown by Pr, at equilibrium vary with the triose used, as pre­ Bu, and isoamyl. The benzyloxy-compound is of viously noted by do Bruyn and van Eckenstein for the same order as the butoxy-derivative, and the dextrose, mannose, and kevulose. This is supported best results are obtained by using primary alcoholates. by the observation that the formation of pyruvalde­ The corresponding ketolates are much less reactive. hyde is a unimolocular reaction in each case, but The formation of esters from the aldehydes is that the rates of reaction are not identical. explained by the production of a semi-acetal (I) (cf. F. 6 . W illso n . 398 BRITISH CHEMICAL ABSTRACTS.— A.

Catalytic hydrogenation of oximes and their to 0-05 g. of dextrose), 20 c.c. of water, and 10 drops of transformation into (3-hydroxylamines. G. a 1% solution of picric acid are heated to boiling and V avon and K rajcinovio (Bull. Soc. chim., 1928, the sugar solution (approximately 5%) is added from [iv], 43, 231— 237).— Hydrogenation of dipropyl a burette until the yellow colour changes to red. ketoxime (1 mol.) in 70% aqueous-alcoholic solution When the sugar content is less than 2% an indirect in presence of platinum-black and hydrochloric acid method must be employed. The ferricyanide solu­ (1 mol.) yields 8-hydroxylaminoheplane, m. p. 52°. tion (4 c.c.), 6 c.c. of water, and a measured volume When the hydrogen oxalate, m. p. 115°, of this base (1—6 c.c.) of the sugar solution are boiled together is treated with benzaldehyde in presence of aqueous- for exactly 1 min., rapidly cooled, 100 c.c. of water alcoholic sodium hydrogen carbonate, there is formed and 5 c.c. of 20% sulphuric acid added, and the N - benzylideneheptane - 8 - nitrone, m. p. 53— 54°. ferrocyanide produced is titrated with a 1% solution P-Hydroxylamino-8-methylpentane, m. p. 63° (hydrogen of potassium permanganate, the titre being compared oxalate, m. p. 132— 133°), and $-hydroxylamino-$- with that of a 1% dextrose solution similarly treated. phenylethane (hydrogen oxalate, m. p. 150°), are ob­ The method is applied to the following cases : invert- tained from methyl fsobutyl ketoxime and aceto- sugar, obtained by hydrolysis of a 5% sucrose solu­ phcnoneoxime, respectively. tion with 1% hydrochloric acid and subsequent When aid oximes are hydrogenated by the same neutralisation before titration ; 10 c.c. of ferricyanide method, the main products are secondary hydroxyl - solution = 0-0467 g. of sucrose or 0-0491 g. of invert- amines, probably formed thus : R-CHiN-OH — y sugar; maltose, 10 c.c. = 0-637 g .; lactose, 10 c.c. = r - c h 2- n h - o h r - c h 2- n o : c h r — > 0-0676 g. (the technique for the determination of (CH2R)2N'OH. Thus heptaldoxime furnishes di- lactose in milk is described); sugar in urine, previously heplylhydroxylamine (90%), m. p. 74° (hydrogen defecated with lead aeetato and diluted until the oxalate, m. p. 137°); isovaleraldoxime yields di-y- sugar content is 0-5% ; blood-sugar previously methylbutylhydroxylamine (oxalate, m. p. 167— 168°); treated with 20% tricliloroacetic acid solution to beiizaldoxime affords dibenzylhydroxylamine, m. p. remove albuminous matter, and subsequently 123°, and piperonaloxime gives d ip ip eronylhydroxyl- neutralised. Reducing material in normal blood amine, m. p. 123— 124° (hydrochloride). varies from 0-80 to 1-2%. J. W . B a k e r . H . B ur to n . Pentabenzoates of dextrose. P. A. L e ven e First phases of the chemistry of the dissimil­ and G. M. Meyer (J. Biol. Chem., 1928, 76, 513— ation of the hexoses. A. J. R l u yv e r and A. P. 519).—Repetition of the work of Fischer and Freuden- Struyk (Proc. K. Akad. Wetensch. Amsterdam, berg (A., 1912, i, 887) and of Schlubach and Hunten- 1927 , 3 0 , 871— 884).— The effect of the addition of burg (A., 1927, 858) led to the preparation of a-penta- disodium hydrogen phosphate on the rate of ferment­ benzoylglucose, m. p. 187°, [a]jj +138-5° in chloro­ ation of dextrose by yeast juice varies with the form, $-pcntabenzoylglucose, m. p. 157°, [a]j? + 2 4° in sample of yeast employed; in one case (A) a rapid chloroform, «.-pentabenzoyl-y-glucose, m. p. 118°, [a]'{? rise to a maximum velocity is followed by a +79° in chloroform, fi-penlabenzoyl-y-glucose, m. p. fairly rapid and constant fall to the initial value, 146— 147°, [a]'j? —82° in chloi’oform. These new whilst in the other (B) the increase produced is values support the previous suggestion that the smaller in magnitude but extends over a longer difference between the molecular rotations of the period. Isolation of the phosphoric ester produced a- and (3-forms of a sugar differs with the ring struc­ by the method of Robison (A., 1923, i, 86) shows ture, and, further, that the sum of these rotations that in case B almost the whole of the phosphate is is less with a five-membered than with a six-membered present as a hexose monophosphorie ester, but in ring. C. R. H arin g ton . case A a larger proportion of the diphosphoric ester is present. Attempts to prove the presence of a S-Acetylchloroglucose. II. II. H. S ch lu b a c h , trioso phosphoric ester were unsuccessful, although P. Sta d le r , and I. W ole (Ber., 1928, 6 1 , [B], 2S7— the application of the triose reaction of Neuberg, 293; cf. A., 1926, 600).— Tho use of a particularly (A., 1918, i, 91) yielded mcthylglyoxal, isolated as its active form of silver chloride enables the time required p-nitrophenylosazone. These results are shown to for the conversion of acetylbromoglucose into (3-acetyl- confirm the authors’ theory of hexose dissimilation chloroglucose to be reduced from 3— 4 hrs. to 8— 10 (A., 1926, 97S). A critical summary of the literature min. with consequent increase in the yield of (3-product is also given. " J. W . B a k e r . on which silver chloride lias an isomerising action. Tho lowest value observed with the product is [a]j; Determination of reducing sugars by the — 17-4° in carbon tetrachloride (Hudson’s use of ferricyanide method. A. I onesco-Ma t iu (Bui. pharmaceutical chloroform in this connexion is Soc. Chim. Romania, 1927, 9, 68— 75).— Dextrose adversely criticised); this datum differs by about and other reducing sugars may be rapidly and accur­ 30° from that calculated by Hudson. A similar ately determined by titration with potassium ferri­ discrepancy is found with [3-nitroacetylglucose, for cyanide using picric acid as an indicator, the method which the values, m. p. 96°, [a]'jj —8-4° in carbon employed varying in the case of relatively large or tetrachloride, are now recorded. It is suggested small sugar contents. In the former case 10 c.c. of that the principle of optical superposition is not valid the ferricyanide solution (46 g. of potassium ferri­ in these cases and consequently that Hudson’s cyanide and 46 g. of potassium hydroxide per litre, methods of calculation cannot be applied. standardised by titration against a 5% solution of The dielectric constant of the solvent appears to pure dextrose and diluted so that 10 c.c. are equivalent be intimately concerned with the rate of isomerisation ORGANIC CHEMISTRY. 399

of P-acetylchloroglucdse into dextrorotatory acetyl- Cellulose formate. I. Formation [from chloroglucose in solution, but secondary reactions hydrocellulose and cellulose regenerated from not involving the production of equilibrium mixtures viscose]. Y. U e d a and K. H ata (J. Cellulose Inst. inhibit mathematical treatment of the data. Ether Tokyo, 1928, 4, 1— 2).— Hydrocellulose with anhydr­ is a potent stabiliser, whereas alcohols accelerate ous formic acid and sulphuric acid yields a product isomérisation; alkyl halides and acetonitrile occupy containing 22-90% of formic acid (theory for mono­ an intermediate position. Addition of small quan­ formate 24-21%), whilst the product from cellulose tities of water, acids, or bases to the ethereal solu­ regenerated from viscose contains 50-50% (cellulose tion does not cause marked acceleration of the change, triformate requires 56-09%). The ester is readily but silver chloride is a strong, positive catalyst. soluble in pyridine, but only sparingly soluble in The formation of P-acetylchloroglucose in small other organic solvents. Results showing the effect amount by Fischer and Armstrong’s method (A., of variations in the amount of sulphuric acid on the 1901, i, 257, 671) is confirmed, as is its isoméris­ degree of esterification are given. W. J. P o w e ll. ation when shaken in ethereal solution with sodium carbonate; the conversion of the crude material Lignin and cellulose. II. Methylcellulose. into tetramethyl-a-methylglucoside appears very im­ K. F r eu d en berg and E. B r a u n (Annalen, 1928, probable. Indications of the production of p-acetyl- 460, 288—304).—It was shown recently by Urban bromoglucose by Fischer and Armstrong’s method (cf. B., \ 1926, 531) that the mothylation of could not be observed. H. W r e n . cotton at 20° gives a trimcthylcellulose essentially different from previously obtained trimethylcelluloses. a-Methylmannoside. C. S. H u d so n (Org. Syn­ It dissolves to a clear and very viscous solution in theses, 1927, 7, 64— 66).— The preparation of chloroform, tetrachloroethane, and glacial acetic acid, a-methylmannoside from “ vegetable ivory ” waste whilst the specimens of Denham (J.C.S., 1921, 119, is doscribed. A. A. E ld rid g e. 81) and of Irvine and Hirst (J.C.S., 1923, 123, 529) Mannan acetate. I. Preparation of naannan did not. Further, it differs from the product obtained acetate and some of its properties. R. S iiin o d a by Hess (A., 1924, i, 142; 1927, 44) in being quite and C. A siiizaw a (J. Cellulose Inst. Tokyo, 1928, 4, insoluble in water and not crystallising from other 3).—Mannan triacetate is prepared by treating raw solvents. It is formed in 93% yield from unbleached Japanese konjaku powder (Amorphophallus Konjac) cotton, whilst previous preparations were obtained with an aqueous solution of chlorine peroxide, and only in about 75% yield. With methyl-alcoholic heating the product (in the form of threads) with hydrogen chloride it gives a 91% yield of 2 : 3 : 6-tri- glacial acetic acid at 100°. It is claimed that the methyl-methylglucoside and 9% of dimethyl-methyl- method is economical, the time of reaction is short, glucoside, corresponding with the original methoxyl and that no decomposition of mannan takes place. content (44-4%) of the sample used (the highest OMo Mannan triacetate may be used as a cellulose acetate content obtained was almost 45% instead of calc. substitute, since it yields a strong film ; a 1 % solu­ 45 ; i ------No trace of tetramethylglucose was found. tion in a mixed solvent containing tetrachloroethane This establishes the structural identity and stereo­ 40%, methyl acetate 40%, methyl alcohol 20% has a chemical similarity of all the glucose units (I) present suitable viscosity. W. J. P o w e ll . in the cellulose molecule. Epirhamnitol, reduction product of epirhamn- When trimcthylcellulose (for the preparation of ose. E. V otocek and J. M ik s ic (Bull. Soc. chim., which a few further details are given) is treated with 1928, [iv], 43, 220—224).—When epirhamnose {iso- hydrogen chloride in presence of ether (sealed tube, rhamnose) is reduced with sodium amalgam and 35°) l-chloro-2 : 3 : 6-trimethylglucose (II or III) is acidulated water there is obtained epirhamnitol, a formed. This gives a crystalline pyridinium salt, syrup, having [a% +9-18° in water when purified decomp. 180°, [a][J - f 26-6° in rvater. through the dibenzylidene derivative, ÇH ÇHC1----- ÇHC1— C fiH n oO ^ ^ C H P h ) , m. p. 196°, [a]g -3 6 -7 ° in H-y-OH H-y-OMe H-y-OMe chloroform. Epirhamnitol and ¿sorhodeitol (follow­ HO-Ç-H MeO-y-H MeO-y-H ing abstract) are optical antipodes. H. B ur to n . H-y-OH H-y-OH H-y-o— i «soRhodeitol, reduction product of isorhodeose. H-yo H-yo H-y-OH F. V otoôek and F. V alen tin (Bull. Soc. chim., CH2-0H CH2-OMe CH2-OMe 1928, [iv], 43, 216—220).—Reduction of an aqueous U-) (II.) (III.) solution of isorhodeose, [a ]D +30-3° (cf. A., 1910, b 274), with sodium amalgam gives isorhodeitol, a Powdered sodium converts the chloro-derivative syrup, [ct]D -8 -3 ° in water. When distilled in a in cold ethereal solution into 2 : 3 : 6-trimethylglucose nigh vacuum the alcohol has [a ]D —9-7°, and its anhydride (IV ?), a mobile oil, b. p. 83— 85°/0-l mm., rotation is lowered when mixed with sodium borate. [a]“ —10-1° (in water, - f 16-5°, in chloroform +14-6°), Ihe crude alcohol reacts with benzaldehyde in pre­ «P 1-1593, n\) 1-4656. The anhydride contains no sence of 50% sulphuric acid, yielding a monobenzyl- hydroxyl groups, is stable to Fehling’s solution, to permanganate, and to bromine water, and when idene derivative, C8H1203<° > C H P h , m. p. 158°, boiled with dilute hydrochloric acid gives 2 : 3 : 6-tri- ■whilst the redistilled alcohol gives a dibenzylidene methvlglucose, [*]g +90-7°, mutarotating to +70-2° derivative, m. p. 196— 197°, [«%8 +35-1° in chloro­ (cf. Irvine and Hirst, J.C.S., 1922,121, 1216). form- H. B u r to n. The complete dissimilarity of trimethylcellulose and 400 BRITISH CHEMICAL ABSTRACTS.— A. trimethylglucose anhydride (the latter gives a filtrable Hydrolysis of the latter with hydrochloric acid gives a mobile solution in chloroform and has a normal mol. trimethylhexose with [a]D + 9 5 -2 ° in water. Méthyl­ wt. in benzene ; a 2% chloroform solution of the former ation of this gives a methylhexoside with Mo +33°, is too viscous to be poured and the mol. wt. is im­ which when hydrolysed affords a tetramethylhexose, measurably large) shows that trimethylcellulose is not [a]D + 55°, not identical with tetramethylgalactose. a trimethylglucose anhydride and therefore that The hexose anhydride, however, is not a derivative of cellulose is not a unimolecular glucose anhydride as glucose. E. E. T u r n e r . suggested by Hess. Oxidation of amino-acids with sugars. S. The results of Micheel and Hess (A., 1927, 1056) for A k a b a r i (Proc. Imp. Acad. Tokyo, 1927, 3, 672— the preparation of two 2 : 3 : 6-trimethylglucoso 674).— When /-leucine is heated with d-glucoso at anhydrides could not be confirmed. The anhydride 120— 130° in glycerol there arc formed carbon dioxide, had a considerable b.-p. range and two fractions isovaleraldehydo (15% ), and a brown substance, obtained from it had [a]D +23° and +50° respectively, probably mcîanoidin (cf. Maillard, A., 1912, i, 169). the former giving rise to a trimethylglucose with /-Phenylalanine and (//-alanine afford phcnylacetaldc- [a]o only +63-5°. hyde (semicarbazone, m. p. 154— 155°) and aeetalde- l-Dimethylamino-2 : 3 : 6-irimethylglucose, from tri­ hyde, respectively. Ammonia is not evolved during methylglucose and dimethylamino in methyl alcohol, the reaction, probably because it is used in the has b. p. 109°/0T mm., [a]D +18-6° in water and formation of mclanoidin. The glycerol solution +7-2° in methyl alcohol. The corresponding quatern­ of the brown substance contains a small amount ary ammonium iodide and chloride had [a])1) —41-2° of hydroxymethylfurfuraldehyde. The oxidation and [a]“ —94° in water, respectively, whereas the is formulated NH2-CHR-CO2H +O=R-CH 0+CO2+ cldorido prepared by Micheel and Hess had [a]D NH3. “ H. B u r to n . Crystallisation of lysine. H. B. V ic k e r y and •9H - C. S. L e a ven w o r th (J. Biol. Chem., 1928, 76, 437— 443).— Lysine was recovered from the carefully H-Ç-OH purified picrate, m. p. 266° (decomp.), by shaking the OHO-Ç-H HO-QrH latter with dilute sulphuric acid and ether; the H-C-O- H-Ç-0—✓ sulphuric acid was for the most part removed by H-Ç-O— H-Ç-0— addition of barium hydroxide, and the solution CHyOH CH.,-OH concentrated; with precautions against access of carbon dioxide, the remaining sulphuric acid was ĆHo-OMo removed and the concentration continued; lysine (IV.) separated in needles, darkening at 210°, m. p. 224— 225o - — A survey of the main facts shows that there can bo (decomp.), [ajg +14-6°. C. R. H ar in g to n. no reversible intcrconversion of trimethylcellulose and Alkylation of a-cyano-G-alkylacrylic esters and trimethylglucose anhydride. Moreover, cellobiose of a-phenyl-p-alkylacryionitriles. J. A. M cR a e must be a product of degradation of cellulose, not a and R. H. F. M a n sk e (J.C.S., 1928, 484—491).— product of re-synthesis from glucose. In short, Ethyl a-ii-butyl-&1-cycloJiexenylcyanoacetate (I), b. p. ordinary co-valency linkings unite the glucose units 163— 164°/lo mm., ethyl a. - ethyl-1\1 - cyc,\oherenylcya?io- in cellulose, which is probably (V). H cellulose con­ acetate (II), b. p. 168°/22 mm., and ethyl a-cyano- tains the linkings ala-a s, bla~bit and cla~c6, degrad­

decomp, above 264°. Combination of tbe compound [Preparation of] guanidine nitrate. T. L. (IV) with hydrogen cyanide, followed by hydrolysis, D avis (Org. Syntheses, 1927, 7, 46— 48). gave a-nhenyl-a'-n-hexylsiiccinic acid and an acid, in. p. [Preparation of] nitroguanidine. T. L. D avis 170°. M. Cl a r k . (Org. Syntheses, 1927, 7, 68— 69). (Preparation of] chloroacetamide. W. A. [Preparation of] anhydrous hydrogen cyanide. Jacobs and M. H eidelberger (Org. Svntheses, 1927, K. Z iegler (Org. Syntheses, 1927, 7, 50—52). 7, 16— 17). Reaction of carbylamines and hydrocyanic Butenoic acid amides. P. B r u yl a n t s and A. acid with magnesium phenyl bromide. H. G il­ Castille (Bull. Acad. Roy. Belg., 1927, [5], 13, man and L. 0. Heckert (Bull. Soc. 'ehim., 1928, 767-—781).—The amides of crotonic and isocrotonic [iv], 43, 224— 230).— Magnesium phenyl bromide acids have been prepared by the action of 66% reacts with methylcarbylamine forming a small sulphuric acid on the corresponding nitriles for several amount of bcnzaldehyde (cf. Sachs and Loevy, A., days at the ordinary temperature. The nitrile of 1904, i, 307). Definite reaction products were not b. p. 121° thus treated yields exclusively crotonamide obtained from hydrocyanic acid or ethyl-, tert.-butyl-, {trans), m. p. 159— 160°, whilst that of b. p. 108° or p-tolyl-carbylamine. H. B ur to n. yields a mixture of this amide and isocrotonamidc, m. p. 100— 101°. The nitrile of lower b. p. is therefore Preparation of magnesium tert.-butyl chloride. related to isocrotonic acid [cis), the reverse conclusion H. Gilm an and E. A. Z o ellner (J. Amcr. Chem. Soc., to that obtained by a comparative study of the 1928, 5 0 , 425— 428; cf. A., 1924, i, 23).— Magnesium ultra-violet absorption spectra and heats of combus­ tert.-butyl chloride is obtained in 70% yield by adding tion of the nitriles and acids. Physical evidence of tert.-butyl chloride (0-5 mol.) in ether (7 mols.) to the latter type is therefore untrustworthy as a basis magnesium powder (200-mesh), with stirring, during for the determination of configuration (cf. Errera and 3 hrs., the ether being maintained in gentle ebullition. Henri, A., 1925, ii, 1137; Auwers, A., 1923, i, 295). F. G. W illso n . The same conclusion probably applies to the nitriles Lead tetraethyl. Y. T a n a k a and T. K u w a ta of a-methylcrotonic acids. In agreement with (Rep. Aeronautical Res. Inst., Tokyo, 1927, 2, 409— Stoermer (A., 1920, i, 614) and Auwers (loc. cit.), the 417).— Crude lead tetraethyl, prepared from lead b. p. of erotononitrile {trans) is 13° higher than that chloride and magnesium ethyl chloride, is best of Zsocrotononitrile {cis). Vinylacetamide is similarly purified by the passage of air through a solution in prepared from the corresponding nitrile if excess of dilute hydrochloric acid. This treatment converts alkali (which causes isomerisation to crotonamide) the contaminating lead triethyl into crystalline lead is avoided in working up the product, the absorption triethyl chloride, which in turn affords lead tetraethyl spectrum of the amide in OTV-sodium hydroxide with magnesium ethyl chloride (total yield 74%). solution after 15 days closely- resembling that of Magnesium and ethereal ethyl chloride react readily crotonamide in the same medium. The absorption if small amounts of iodine and ethyl iodide or bromide curves of cycZopropanecarboxylic acid and its amide are added. Pure lead tetraethyl, b. p. 85-4— 85-7°/ (obtained by alkaline hydrolysis of the nitrile) are 13 mm., dj8 (vac.) 1-6600, m1,? 1-5206, decomposes at plotted, and show a greater difference than is found in 400° giving metallic lead ; at the ordinary temperature the corresponding crotonic acid derivatives. The in sunlight it becomes turbid and alkaline, and when amide of methylacrylic acid, obtained by acid neutralised with hydrochloric acid yields some lead hydrolysis of the nitrile, readily polymerises to an triethyl chloride. G. A. C. G o ugh . amorphous mass. J. W. B a k e r . Auto-oxidation. I. ci/doHexene peroxide. Ureides of bromovaleric acids. II. In­ H. N, Stephens (J. Ainer. Chem. Soc., 1928, 5 0 , fluence of branched chains on physiological 568— 571).— When oxygen is circulated continuously properties. E. F o u r n e a u and G. F lorence (Bull. at atmospheric pressure and the ordinary temperature Soc. ehim., 1928, [iv], 43, 211—216).—The effect of through cycZohexene for 4 months, there is formed branching the chain in a series of a-bromovaleric about 0-75% of cyclo/iexe?te peroxide, b. p. 54—56°/ ureides is to cause an increase in the hypnotic action. 0-5 mm., together with a non-volatile syrup, which Bromopivalic ureide is a powerful hypnotic and as it appears to bo a dimeric form of the peroxide, con­ contains the bromine atom in the [1-position it is taining one peroxide group. F. G. W illso n . concluded that the group R-CH BrCO- is not specific Oxidation of unsaturated hydrocarbons by (J iffeneau). The following data are recorded (per­ free oxygen in presence of osm iu m . S. M e d v e d e v centage figures indicate solubility in water, and and E. A l e x e e v a (Papers Pure Appl. Chem. Karpov ordinary figures partition coefficients) : a-bromo-«- Inst., Bach Festschr., 1927, 110— 127; Chem. Zentr., valeric ureide, m. p. 162°, 0-833%, 0-42; x-bromoZ.so- 1927, ii, 1012).— The catalyst consisted of osmium valeric ureide, 1 -94%, 0-95; a-bromo-oc-methyl- dioxide deposited on alumina, ferric oxide, manganese butyric ureide, m. p. 132-5°, 5-3%, 1-98; bromo­ sesquioxide, or cupric oxide; benzene was preferable pivalic ureide, m. p. 93-5°, 5-4%, 2-02. «-Valeric acid to acetone as a solvent for the unsaturated hydro­ is obtained from magnesium butyl bromide and carbon carbon (cycZohexene or A2-methylcycZohexene), acetone dioxide in 78% yield. H. B urton. solutions exhibiting an induction period of several Additive compounds of allylthiocarbamide hours. A catalyst inactivated by air is reactivated and silver halides. S. E . S heppard and H. by benzene much more quickly than by acetone. The H u d son (Z. wiss. Phot,, 1928, 25. 113— 120).— See portion of the oxidation product of cycZohexene which A., 1927, 755. remained dissolved in the benzene contained peroxidic 402 BRITISH CHEMICAL ABSTRACTS.— A.

compounds, an aldehyde (semicarbazone, m. p. 240—■ Cla r k and N. M. Carter (Trans. R oy. Soc. Canada, 241°), and much A2-cydohexenol (naphthylurethane, 1927, [iii], 21 , III, 323—338).—Data for tho effect of m. p. 156°). The portion on the catalyst contained heat on 119 aromatic nitro-compounds containing from adipic acid, and a compound, C8H10O2, b. p. 108— one to five nitro-groups are recorded, and the results 110°/0-2 mm. A . A ."E l d k id g e . discussed from the point of view of the electronic Volume chemistry. II. Halogen derivatives conception of positive and negative valencies developed by Fry and others. In 96 of the compounds the of hydrocarbons. F. W ratschko (Pharm. Presse, 1927, 32, 130— 135, 172— 174, 205— 209; Chcm. results are in accordance with theory, in 9 the reaction Zentr., 1927, ii, 777).— Abnormal “ A-valucs ” for appears to be with the unstable electromeride, whilst cyclic hydrocarbons halogenated in a side-chain are the behaviour of the remaining 14 cannot be accounted avoided by supposing that the last hydrogen atom for on this hypothesis. M. S. B ur r . of the side-chain is attached to a nuclear carbon atom, Replacement of halogen atoms from the with ring closure. A. A. E ld r id g e . nucleus of various aromatic compounds. R. H. Nitration by means of nitrogen peroxide. M. Clark and R. H. H all (Trans. R oy. Soc. Canada, B attegay (Bull. Soc. chim., 192S, [iv], 43, 109— 1927, [iii], 21, III, 311— 314).— The maximum 134).—A lecture. replacement of halogen atoms, under the experimental Hydrogenation of cyclic compounds under conditions, has been determined for a number of pressure in presence of osmium and other aromatic halogen compounds, when heated under catalysts. V. S. Sa d ik o v and A. K. M ik h a ilo v pressure with sodium methoxide of different con­ (J.C.S., 1928, 438— 448).— The rate of hydrogenation centrations. The yields are compared with those of benzene, quinoline, and pyridine in a modified calculated on the basis of the electronic theory as Ipatiev apparatus has been investigated using as elaborated by Fry. The results are not as conclusive catalyst platinum, osmium, osmium-cerium oxide, or as corresponding measurements on the nitro-groups. palladium deposited on asbestos. In ever}’ case a M. S. B u rr. periodic absorption of hydrogen takes place, a period Nature of the alternating effect in carbon of activity being followed by a period of quiescence, chains. XXIII. Anomalous orientation by whilst the activity of the catalyst gradually diminishes halogens, and its bearing on the problem of the on account of the presence of impurities or of the orth o-pa ra ratio, in aromatic substitution. formation of products of hydration inimical to the C. K. I ngold and C. C. N. V ass (J.C.S., 1928, 417— catalyst. This periodicity is attributed to removal of 425).— The reaction mixture from ??i-fluoroacet- oxygen from the catalyst, followed by reactivation, anilide and bleaching powder yields, after treatment and is compared with the periodic evolution of hydro­ with hydrochloric acid, a mixture of 3-fluoro-4- gen when metals are dissolved in acids or alkalis (cf. cMoroacelanilide (I), m. p. 115°, 3-flmro-G(2 '{)-chloro- Hedges and Myers, A., 1925, ii, 309). The addition acetanilide, m. p. 143°, and S-fluoro-i : 6(2 : 6 ?)- of 1% of cerium oxide to a 20% osmium-asbestos dicMoroacetanilide, m. p. 124°. Hydrolysis of (I) gives catalyst for the reduction of quinoline causes con­ o-fluoro-4-chloroanilinc, m. p. 61— 62°, converted siderable initial acceleration of the reaction, which through the diazo-derivative into 3-fluoro 4-chloro- proceeds throughout at a higher rate than when nitrobenzene (II), m. p. 63— 64°, b. p. 114— 116°/ osmium alone: is used; in the case of pyridine, the 24 mm. Chlorination of p-fluoronitrobenzene in reverse effect results. In the reduction of benzene presence of anhydrous ferric clilorido gives 4-fluoro- and pyridine in the presence of osmium, there is an 3-chloronitrobenzene (III), m. p. 41-5°, converted by initial period during which the rate of reaction is elimination of the nitro-group into o-fluorochloro- considerably greater for pyridine than for benzene, benzene (IV), b. p. 138— 140°/75S mm. Nitration of whilst the rate diminishes more rapidly with pyridine. compound (IV) yields a mixture consisting essentially The total amount of reduction over a period of hours of compounds (II) and (III) present in the proportion is thus approximately the same for both (cf. this corresponding with the ratio direction by F : direc­ vol., 427). M . Cl a r k . tion byCl=78-7% : 21-3%. An explanation of this anomaly is based on the hypothesis that the op- Comparative reactivities of some chloro-, directive efficiencies of the halogens, which vary bromo-, and iodo-nitrobenzenes. Mechanism directly with the tendency of tho halogen atom to of activation of halogen atoms by a nitro-group share additional electrons (-fT) and inversely as its present in the same aromatic nucleus. A. attraction for electrons, shared and unshared (—T) B r e w in and E. E. T urner (J.C.S., 192S, 332— 334, (cf. this vol., 164), are also influenced by a third factor. 334—337).—The comparative reactivities of a number The inductive effect is regarded as originating in a of halogenonitrobenzenes have been measured, using contracted electron shell round the halogen atom, piperidine in benzene solution. It is concluded that and it is suggested that, as veil as electron displace­ reactions involving reactive halogen compounds are, ments relayed from linking to linking, modification as the majority of previous workers have assumed, of the existing electric fields might also occur by dependent on the initial formation of additive com­ direct action through space in such a way that the pounds. A mechanism of activation by nitro-groups potentially active electrons of the benzene ring is developed, and correlated with one for aromatic would be subjected to additional electrostaticrestraint. substitution. M. Cl a r k . This “ direct ” effect of halogens would therefore be a Replaceability of nitro-groups from the deactivating influence (— D) and the full expression nucleus of various aromatic compounds. R. H. for the directive action of halogens in halogeno- ORGANIC CHEMISTRY. 403 (+T—I—D). The variation of I) as CN-CPh(N0)-0-S03H, which breaks down into between different directing atoms would be the same benzoyl cyanide and eventually into benzoic acid. as that of the inductive effect, but, since it is prop­ The compound (II) undergoes analogous decom­ agated through space, its distribution in the ring would position, yielding wi-nitrophenylglyoxylic acid, m. p. be, not in the order op>m, but in the order o>m >p. 144-5— 145° (lit. 77— 78°). The compound (I) under­ The working of such an hypothesis in the case under goes partial rearrangement in ethereal solution, a discussion as well as in other cases cited is demon­ small percentage of bromine migrating to the m- strated. M. Cl a r k . position. The correlated behaviour of phenylcyano- /■sonitromethane (III), benzoyl cyanide (IV), and Nature of the alternating effect in carbon m-bromobonzoic acid (V) on nitration was also chains. XXIV. Directive action in aromatic investigated quantitatively. The compound (III) substitution of certain groups containing triple gives more than 99% of p-nitrophenylcyanoisonitro- linkings. J. W. B a k e r , K. E . Cooper, and C. K. methano in nitric acid \d 1-48); compound (IV) gives I nciold (J.C.S., 1928, 42G— 431).— The nitration of 87-6% of m-nitrobenzoyl cyanide and 12:4% of two acetylene derivatives and two nitriles has been o- and p-nitrobenzoyl cyanides, using nitric acid of investigated with special reference to the proportion d 1-52; compound ( V) gives 96% of o- and p-nitro- of m-isomeride formed, and tho results arc as follows : m-bromobenzoic acids and 4% of m'-nitro-m-bromo- Phenylpropiolic acid (8% meta), ethyl phenyl- benzoic acid, using nitric acid of d 1-48. Migration of propiolate (16%), benzonitrile (81%), phenylaceto- the nitro-group during oxidation of phenylcyanonitro- nitrile (14%). The results are discussed in relation methane is also shown to take place to the extent of to the other properties of the unsaturated groups 14 mol.-%. The mechanism of these various trans­ contained in the side-chains of those compounds and formations is discussed. Both phenylbromoeyano- an hypothesis is advanced to account for them. nitromethane, ON-CPh

172° (Meldola, J.C.S., 1906, 89, 1435, gives 169— 1 : 5-dichloro-10-phenyl-9-methylene-9 : 10-dihydro- 170° : acetyl derivative, in. p. 86—87°); -n-'propyl­ anthracene, m. p. 151°, thus placing beyond doubt amine, in. p. 129°; -n-butylamim, m. p. 89°; -n-amyl- the possibility of “ transannular tautomerism.” The amine, m. p. 74°; -n-heptylamine, m. p. 58°. By constitution of the methylene derivative is established similar methods are obtained 2 : 4-dinilronaphthyl-1 - by its almost quantitative oxidation to 1 : 5-di- semicarbazide, decomp. 185—187°; and -l-semi- chloro-9-phenylanthrone and conversion into 1 : o-di- oxamazide, decomp. 227—228°. By nitration of chloro-9 : 19-dibromo-\9-phenyl-9-methyl-9 : 10-dihydro- l-ehloro-2 : 4-dinitronaphthalene the chief product anihracene, m. p. 122°. H. W r e n . is l-chloro-2 : 4 : 5-trinitronaphthalene, m. p. 147— 9-Iodophenanthrene. J. S a l k in d and F. 148° (Hindi, J.C.S., 1913,103, 1911, gives 143— 144°), L ubinsicaja (Ber., 1928, 61, [B], 269—271).—9-Iodo- together with some 2:4: 8-trinitro-eompound. The phenanthrene, m. p. 87° (picrate, m. p. 137°), is pre­ 1-chloro- (or alkoxy-) group in the 2:4: 5-trinitro­ pared by the action of iodine on magnesium phen- naphthalene derivative is similarly replaced by amino- anthryl bromide in the presence of ether. It is oxid­ groups and thus are obtained oc-2 : 4 : 5-trinitro- ised to phenanthraquinone by chromic acid in glacial naphthyl-amine, m. p. 310° (acetyl derivative, m. p. acetic acid. II. W r e n . 275°); -methylamine, m. p. 206°; -ethylamine, m. p. 160° (Rindl, loc. c i t gives 157—159°); -n-propyl- Chlorination of anilides. II. Decomposition amine, m. p. 139°; -n-butylamine, m. p. 121°; -n-amyl- of iY-chloroacetanilide by heat. A. E. B r a d fie ld amine, in. p. 144— 145° ; -w-heptylamine, m. p. 99-5— (J.C.S., 1928, 351— 352).— In order to show that, 100-5° ; 2:4: 5-trinilronaphthyl-1 -semicarbazide, ex­ contrary to the statement of Porter and Wilbur (A., ploding 173°, and -l-semioxamazide, exploding 236°. 1927, 1041), the re-arrangement of fused W-chloro- The m. p. of the 1-n-alkylamino-derivatives of 2 : 4- acetanilide at 100° is a two-stage process involving dinitro- and 2:4: 5-trinitro-naphthylamine decrease the intermediate production of chlorine, the reaction gradually with an increasing number of carbon atoms has beon carried out with pure material in an open in the chain in a similar manner to that observed by vessel in an air-bath, and in a sealed tube in boiling Kam (A., 1926, i, 1240) in the case of the analogous water. From the products 7-0% and 4%, respect­ derivatives obtained from l-chloro-2 :4-dinitro­ ively, of 2 : 4-dichloroacetanilide were isolated, in addition to p-chloro-, 41-0%, 50-7%; o-chloro-, benzene. J. W . B a k e r . 18-2%, 16-5%, and acetanilide, 6-3%, 0-0%. Supposed stereoisomerism in the fluorene H. E. F. N otton. series. J. Cerezo (Anal. Fis. Quirn., 1927, 25, 567— [Preparation of] benzanilide. C. N. W ebb (Org. 587; cf. Wieland and Cerezo, A., 1927, 1183).— The Syntheses, 1927, 7, 6—7). alleged isomerism in the fluorene series is discussed and Interaction of sulphur and p-toluidine in evidence put forward which demonstrates that no such presence of litharge : thio-p-toluidine and re­ isomerism is shown by 9-acetoxyfluorcne, 9-amino- lated compounds. M. T. B ogert and L. Sm id th fluorene, or 9-methylfluorcnol. J. S. Ca r t e r . (J. Amer. Cliem. Soc., 1928, 50, 428-^—436; cf. A., meso-Alkylanthracenes and “ transannular 1924, i, 166).— Separation of the products of the tautomerism." IV. E. d e B. B ar n e t t and reaction between p-toluidine, sulphur, and litharge J. W. Cook (Ber., 1928, 61, [£], 314— 319; cf. A., at 140° is convenient^, effected by dissolution in 10% 1926,1030 ; 1927,140; this vol., 52).— 1 : 5-Dichloro- hydrochloric or sulphuric acid, followed by dilution anthrone is converted by methyl iodide and potassium to precipitate weakly basic resins, and fractional hydroxide at 100° into a mixture of approximately precipitation with ammonia solution. Purification equal amounts of 1 : 5-dichloro-9-methoxyanthracene, of the products is effected by repeating this m. p. 105°, and 1 : 5-dichloro-9-methylanthrone, m. p. process. In this way 535 g. of p-tohudine afforded 1S4°. The presence of the methyl group in the 70 g. of resins, 80 g. (17%) of dithio-p-toluidine, and meso-position in the latter compound appears to 121 g. (26%) of monothio-p-toluidine, 167 g. of p-tolu- hinder conversion into the enolic form, since 1 : 5-di- idine being recovered. Only small amounts of impure chloro-9-mcthylanthrone cannot be etherified by dithio-p-toluidine could be obtained by Hodgson’s treatment with potassium hydroxide and methyl process (B.P. 15,466 of 1911). When heated at 205— toluene-p-sulphonate and only slowly yields an 210°, thio-p-toluidine evolves ammonia, hydrogen acetate with boiling acetic anhydride and pyridine. sulphide, and p-toluidine, leaving a brown, amorphous By treatment with the requisite Grignard reagent, residue. Thio-p-toluidino yields only a small amount 1 : 5-dichloro-9-mcthylanthrone is converted into the of p-toluidine when heated with concentrated hydro­ following substances : 1:5- dicMoro-Q-victhyl -10 - chloric acid or 25% sulphuric acid for 6 hrs. at 200°, methylene-9 : 10-dihydroanthracene, m. p. 143° ; 1:5- and remains undecomposed when fused with sulphur. dichloro-9-methyl-10-ethylidene-9 : 10-dihydroanthrac- It is only slowly decomposed, with formation of basic ene, m. p. 153°; 1 : iy-dicJiloro-9-methyl-lQ-isopropyl- tars, when heated with sulphur and litharge at 140— idene-9 : 10-dihydroanthracene, m. p. 134°; 1 : 5-di- 150°. Tliio-p-toluidine could not be coupled with chloro - 9 - methyl -10 - benzylidene-9 : 10-dihydroanthrac- diazotised sulphanilic acid. Oxidation of the diacetyl ene, m. p. 165°. 1 : 5-Dichloro-l()-phcnyl-9-methyl- derivative to the corresponding sulphone is con­ 9 : IQ-dihydroanthran-lQ-ol, m. p. 144°, is converted veniently effected by treatment with concentrated by treatment with acetic acid containing hydro­ nitric and sulphuric acids (75 :30) at the ordinary chloric acid at 100° into I : 5-dichloro-l0-phenyl-9- temperature. Treatment of thio-p-toluidine with methylanthracene, m. p. 104°. Further treatment of acetic anhydride, glacial acetic acid, and hydrogen the latter compound with the same reagent produces peroxide affords bis-2-acetamido-o-melhylphenylsulph- ORGANIC CHEMISTRY. 407 oxide, m. p. 212°.. Bis-2-chloro-5-methylplmiyhitIph- Transformation of diazoaminobenzene into one, brown, amorphous, decomp, above 95°, is ob­ aminoazobenzene. E. R o se n h a u e r and H. tained by beating diazotised thio-p-toluidine with U nger (Ber., 1928, 61, [J3], 392— 398).— Evidence in hydrochloric! acid and copper powder, with subse­ favour of the view that the conversion of diazoamino­ quent oxidation with nitric and sulphuric acids; benzene into aminoazobenzene is due to primary replacement of the copper powder in this process by fission into diazonium salt and aniline followed by potassium iodide affords analogously bis-2-iodo-5- nuclear coupling and not to isomerisation is found methylphenylsulphone, pale brown, amorphous, de­ in the following observations. Dimcthylaminoazo- comp. about 82°. When diazotised thio-p-toluidine benzene is obtained from diazoaminobenzene, di- is kept over-night in excess of concentrated hydro­ methylanilinc, and dimethylaniline hydrochloride. chloric acid, and the solution then boiled, 2- The conversion of diazoaminobenzene into aminoazo­ chloro-5 : 5'-dimethyldiphenylsulphide-2 : ‘¿'-oxide, b. p. benzene is effected by glacial acetic acid, dilute 205°/80 mm., is obtained. 2-Bromo-b : o'-dimethyl- aqueous acetic acid, or formic acid in satisfactory diphenylsulphone, brown, amorphous, decomp. 09— yield. Quinoline and its hydrochloride may replace 72°, is obtained by diazotising thio-p-toluidine in aniline and aniline hydrochloride under the conditions aqueous sulphuric acid, with subsequent treatment usually employed, but reaction then occurs much with potassium bromide and copper powder, and more slowly. The weak point in the explanation oxidation as above. Thio-p-toluidine is not obtained appears to bo in the assumption of nuclear coupling. when dithio-p-toluidine is heated with p-toluidine This reaction is, however, general. Thus benzene- and litharge, or with sulphur and litharge, at 140— diazonium chloride and aniline hydrochloride at 0° 165° (cf. Hodgson, A., 1924, i, 1188). Diazotised and afford aminoazobenzene hydrochloride without inter­ coupled with H-acid, dithio-p-toluidine yields a dye mediate formation of diazoaminobenzene. Further, producing purplish shades on wool. JJithio-p-tolu- crude diazoaminobenzene, obtained from diazotised idine picrate, yellow, was prepared. Deduction of aniline and aniline in aqueous solution containing dithio-p-toluidinc affords 2-amino-5-methylphenyl acetic acid, sodium carbonate, or sodium hydroxide, mercaplan (zinc salt). F. G. W illso n. invariably contains about 2% of aminoazobenzene, Condensation ol ethyl cyanoacetate with some the proportion of which increases with rise of tem­ aryl- and alkyl-amines. Preparation of some perature. Coupling of diazotised aniline with aniline aryl- and alkyl-substituted cyanoacetamides. in neutral, feebly basic, or weakly acidic solution consists of two independent changes leading respect­ K. G. N a ik and Y . N. B iiat (J. Indian Chem. Soc., 1927, 4, 547— 551).—The following new compounds ively to diazoaminobenzene and aminoazobenzene. are described: cyanoaceto-o-toluidide, m. p. 125°; Increasing acidity favours the production of the latter cyanoaceto-m-toluidide, m. p. 132°; cyanoaceto-a- compound, which becomes exclusive at a certain napldliylamide, m. p. 175°; cyanoaceto-$-naplithyl- degree of acidity. Beyond this point coupling does amide, m. p. 174°; cyanoaceto-vic-m-xylidide, m. p. not occur. The yields of aminoazobenzene are better 107°; cyanoacetomethylamide, m. p. 101°; cyano- when aniline hydrochloride and aniline arc used than when aqueous or alcoholic solutions arc employed (icetoethylamide, m. p. 74°. C. D. L angford. owing to the stabilising action on the diazonium salt Properties of 2:5- and 2 :8-naphthylamine- of the aniline and its large excess. About 70% of sulphonic acids. H. I. W a ter m an and J. Groot aminoazobenzene can be obtained in acetic acid (Chem. Weekblad, 192S, 2 5 , 40—42).—The four solution if 3— 4 mols. of aniline are added. possible sulphonated (5-naphthylamines having one The volatility of diazoaminobenzene with steam sulphonic acid radical in the nucleus not containing is incidentally recorded. H. W r e n . the amino-group have been prepared in the pure condition. The solubilities in water at 20° are: Sulphonation of phenolic ethers by means of 2 : 8- and 2 : 5-acids, as anhydrous, 1 part in 1680 and aminosulphonic acid. A. Q tjilico (Atti R. Accad. 3025 parts, respectively; 2:7- and 2 : 6-acids, as Lincei, 1927, [yi], 6, 512— 517).— Like anisole (cf. monohydrates, 1 in 5040 and 7790, respectively. The Hofmann and Biesalski, A., 1912, i, 444), both solubility products of the 2 : 5- and 2 : 8-acids are phenetole and phenyl ether are converted by the calculated from these data and from the dissociation action of aminosulphonic acid into the ammonium constants recorded by Ebersbacli (cf. A., 1893, ii, salts of the corresponding p-sulphonic acids. Prob­ 450) as 1-08 x 10~" and 2-63 x 10~7, respectively. ably the first product of the reaction is an additive These values are in accordance with the fact that compound with the hydroxyl group of the amino­ the 2 : 5-acid separates first when an equimolecular sulphonic acid in the 1-position and the NHg-SOy mixture of the sodium salts of the two acids in solu­ in the 2-position, this then giving the ammonium tion is acidified; the solubility products calculated salt of the o-sulphonic acid, which undergoes isomeris­ from the solubilities given by Forsling (A., 1887, ation into the salt of the p-acid. Ammonium phenoxy- 962) and the work of Levi (cf. B., 1921, 503a) indicate benzene-p-sulphonale, 0Ph-C6H4-S03-NH1, the barium erroneously that the 2 : 8-acid separates first. ( + H 20), sodium, and potassium salts, the free acid, S. I. L e v y . m. p. 80°, the sulphotiyl chloride, and the sulphonatnide, Manufacture of anthracene derivatives [alkyl- m. p. 125° (? 88°), are described. T. H. P ope. aminoanthracenes] and of benzanthrene. I. G. Fries' transformation. K . vo n A u w er s [with F a r b e n in d . A.-G.— See B., 1928, 151. W . M a u ss] (Ber., 1928, 61, [B], 416—421; cf. A., Manufacture of aromatic oxamic acid halides. 1926, 608).— The observation that p-chloroacetyl- I. G. F a r b e n in d . A.-G.— See B., 1928, 151. phenol is not produced by the action of aluminium 408 BRITISH CHEMICAL ABSTRACTS. A.

chloride at 130— 140° on a mixture of phenyl acetate 210° (decomp.), and Ta(O-C10H7)5, m. p. 180°, if the and p-tolyl chloroacetate, whereas it is relatively action is very prolonged. From anthranol, the freely produced from phenyl chloroacetate under products N b(0-Cu Hfl)2Cl3 and Ta(0-C14H9)2C13 are precisely similar conditions, is strong evidence against derived. Careful regulation of the reaction between Skraup’s conception of the course of the Fries trans­ anthranol and tantalum pentachlori.de permits the formation (cf. A., 1925, i, 143 ; 1927, 659). Attempts isolation of the unstable, primary adduct, to prepare the o-p¡3-dimethylacrylylphenol, m. p. 88°, CI0H14O,TaCl3, and the intermediate product, of Skraup and Bong (A., 1927,560) were unsuccessful. Ta(0*C14H9)Ci4. The assumption that the metal Phenyl fsovaleratc is converted by aluminium in these compounds is united to oxygen is supported chloride at 130— 140° into a mixture of o-isovaleryl- by their properties, analogies with known compounds phenol, b. p. 138— 140°/20 mm. (p-nitrophenylhydr- such as those of zinc, and the established strong azone, m. p. 121— 122°; methyl ether, b. p. 142— 144°/ affinity of the metals for oxygen. H. W r e n . 12 rum. ; acetate, b. p. 164— 166°/20 mm.), andp-iso- valerylphenol, m. p. 95-5— 96-5°. Phenyl (ip-di- Formation of indigoid compounds from halo- methvlacrylate and aluminium chloride at 130— 140° genated naphthols. R. W illstatter and L. afford 7-hydroxy-3 : Z-dimethylhyirindonkb. p. 138— Sch uler (Ber., 1928, 61, [B], 362— 372).— Halogen- 142°/16 mm., d f 1-098, ?i“ e 1-5519 {semicarbazone, ated a-naphthols readily pass into indigotin-like m. p. 261—263°). o-Dimethylacroyl-p-cresol is con­ compounds owing to loss of hydrogen halide; for verted by protracted boiling with acetic anhydride 2 : 4-dibromo-a-naphthol the scheme is suggested : into the corresponding acetate, m. p. 63— 64°; the OH ketone is transformed by zinc chloride at 140° into 2 :2 :6-trimethylchromanone, identified as the n-nitrophenvlhydrazone, m. p. 199—200°. * 'CYVb.- H . W r e n . Nitrosation of . V. An o-nitroso- phenol. H. H. H odgson and J. S. W ig n a ll (J.C.S., O O 0 1928, 329— 332).— 5 - Chloro - 3 - hydroxyanisole is readily nitrosated to dark green 5-chloroA-nitroso-Z- hydroxyanisole, m. p. 132°, and nitrated to 5-chloro- 4[-nitro-3-hydroxyanisole (I), m. p. 105°, which is also formed by oxidising the nitroso-derivative with w alkaline ferribyanide. 3 : 5-Dicliloro-2-nitroanisole 2 : 4-Dibromo-a-naphthol dissolves readily in solu­ and 3 : 5-dichloro-4-nitroanisole yield with sodium tions of alkali hydroxides or carbonates and an mcthoxide ¡S-chloro-Z-nitroresorcinol dimethyl ether, indigo-blue precipitate rapidly separates. Atmo­ m. p. 171°, and 5-chloroA-nitroresorcinol dimethyl spheric oxygen takes no part in the change, but the ether, m. p. 123°, respectively. The constitution of product absorbs oxygen; it is decomposed by an (I) follows from its conversion by methyl sulphate excess of alkali, so that its formation is not observed and potassium carbonate into the latter ether. Oily in concentrated solution. It is also produced when 5-chloro-Z-methozydimethylaniline, prepared by heat­ solutions of 2 :4-dibromo-a-naphthol in acetone, ing 5-chloro-3-methoxyaniline with methyl sulphate ether, or benzene are poured on to aqueous solutions and methyl alcohol at 165°, is nitrosated to green of sodium carbonate or hydroxide, by contact of 5-chloro-±-nitroso-Z-methoxydimethylaniline, decomp. alcoholic solutions of the naphthol with metallic 155° (hydrochloride), which forms methylamine and copper, and, most satisfactorily, by preserving the products of profound decomposition when boiled naphthol in cold pyridine. The dye does not appear with 10% potassium hydroxide. to be quite homogeneous, but analyses indicate the H. E. F. N otton. composition C^H-^OoBr, (cf. I). Determinations Colour reactions of phenacetin. L. E k k e r t of mol. wt. are untrustworthy, since the compound (Pharm. Zentr., 1928, 69, 98— 100).— A scries of is unstable in solution. When suspended in ether colour changes, obtained when phenacetin is warmed and reduced with zinc dust and a little glacial acetic with resorcinol and sulphuric acid, and the mixture acid it gives dibromo-u-dinaphthol (constitution cooled, diluted, and treated with alkalis, with subse­ not decided), m. p. 219° (decomp.) (corresponding quent extraction, is described. S. I. L e v y . diacetate, C24H1804Br2, m. p. 239°; dimethyl ether, C22H160 2Br2, m. p. 225— 226°). a-Dinaphthol, ob­ [Preparation of] 3 :5-dinitroanisole. F. R e ver- tained from a-naphthol and ferric chloride, is con­ d in (Org. Syntheses, 1927, 7, 28— 29). verted by bromine in glacial acetic acid solution into Action of niobium and tantalum pentachlorides a fri&m??io-compound, transformed by boiling acetic on organic compounds. H. F u n k and K. N ie d e r - acid into the dibromo-a-dinaphthol, m. p. 219—220° l a n d e r (Ber., 1928, 61, [5], 249— 253; cf. Lindner (decomp.). 2 : 4-Dichloro-a-naphthol is converted by and Feit, A., 1924, ii, 320).— Phenol is converted by alkali carbonate or hydroxide but not by pyridine niobium pcntachloride in carbon disulphide solution into an analogous dye, C20H10O2Cl2- and in absence of atmospheric moisture into the 1 : 5-Dihydroxynaphthalene, in cold glacial acetic compound Nb(OPh).,Cl, m. p. 233— 235°; the analog­ acid, is converted by chlorine into 4 : 8-dichloro-\ : 5- ous substance Ta(OPh)4Cl, m. p. 240°, is described. diacetoxynaphthalene, m. p. 154° (corr., decomp.), P-Naphthol affords the compounds N b(O C 10H7)3Cl2, hydrolysed to 4 : 8-dichloro-l : o-dihydroxynaphtha- m. p. 215° (apparent decomp.), Ta(OC]0H 7)3Cl2, m. p. lene, m. p. 189— 190° (corr.). The main product of ORGANIC CHEMISTRY. 409 the action of a small excess of bromine on 1 : 5-di- appears to yield the same quinonè. Production of hydroxynaphthalene under similar conditions is tho oo'-dinaphthaqiiinones appears to be preceded by monoacetate of 4 : 8-dibromo-l : 5-dihydroxynaphtha- dehydrogenation of the naphthol to the radical (II) lene, m. p. 165-5° (corr.), from which the diacetate, followed by rapid polymerisation to the bimolecular m. p. 131°, is obtained by pyridine and acetic product (III). The very ready elimination of the anhydride. 4 : 8-Dibromo-l : 5-dihydroxynaphtlialene bromine atom in position 2 can be explained only has m. p. 147-5° (decomp.). 4-Bromo-l : 5-dihydroxy- on the assumption that it is not aromatically com­ naplithalene, m. p. 116°, and its diacetate, m. p. 138°, bined during the change. It cannot be removed by are described. The colour reactions of certain powerful reducing agents from 2 :4-dibromo-a- halogenated naphthols are described in detail. naphthol itself. H. W r e n . '2-CJdoro-4-bromo-a-naphthol, m. p. 112°, prepared by bromination of 2-chloro-a-naplithol, yields a blue dye Action of bromine on naph.th.olsulph.onic acids. with alkali hydroxide or carbonate with loss of A remarkable colour reaction in solution. G. hydrogen chloride and bromide. 4-Chloro-2-bromo-a- H ellér [with W. E isenschmidt’, G. R eich a rot, naphthol, m. p. 96°, behaves similarly to 2 : 4-dibromo- and H. W ild], (Z. angew. Chern., 1928, 41, 171— a-naphthol, but loses a little hydrogen chloride and 177).— On treatment with 2 mois, of bromine in mainly hydrogen bromide. 2-Bromo-1 : 4-dihydroxy- cold acetic acid solution naphthasultone gives 4-bromo- naphtlialene, m. p. 113— 114°, is prepared by reduction naphtliasultone, m. p. 199°; sodium naphthasultone- of 2-bromo-a-naphthaquinone. H. W r e n . 4-sulphonate and sodium l-naphthol-4 : 8-disulphon- ate afford the same product when bromine in acetic oo'-Diquinones of the naphthalene series. S. acid is added to their aqueous solutions acidified Goldschmidt and H. W essbecher (Ber., 1928, 61, with sulphuric acid. When treated with alkali [/?], 372— 377).— 4-Methoxy-a-naplithol' dissolved in in saturated solution in presence of excess of boiling benzene is readily oxidised by lead dioxide solid, undissolved crystals of sodium 2 : 4-dibronio- to a blue compound, m. p. 258°, for which Russig l-naphthol-8-sulphonale (obtained by brominating has established the formula C22H,604. Reduction sodium l-naphthol-8-sulphonate in a freezing mix­ of the product with zinc dust and glacial acetic acid ture) develop a reddish-blue colour which diffuses in the presence of benzene affords the leuco-com- through the solution and after some minutes fades pound, C22H1804, m. p. 205° in an atmosphere of to olive-brown. Tho coloration is due to the form­ carbon dioxide (corresponding diacetate, m. p. 180°; ation of the quinhydrone of 2-bromo-l : 4-naphtha- mol. wt. 440 in boiling chloroform), readily recon­ quinone-8-suIphonic acid (sodium salt, reddish-brown verted by air into the dye, for which the quinonoid crystals with green reflex), the latter being also pro­ structure is thus established. Distillation of the duced by the addition of potassium ferricyanide to dye with zinc dust yields two hydrocarbons, m. p. the filtered solution of the dibromonaphtholsulphon- 257° and 175°, respectively (picrate of latter, m. p. 145°), which do not correspond with any of the ate, and when the solution of sodium I-naphthol-8- sulphonate is only cooled with ice for bromination. expected products. Oxidation of the dye with nitric 1-Naphthol-2 : 4 : 8-trisulphonic acid affords the same acid affords 2 : 2'-di-a-naphthaquinonyl, identical quinhydrone. With excess of bromine (4 mois.) n o with the product obtained by sodium l-naphthol-8-sulphonate, -2 : 4 : 8-trisulphon- Meldola and Hughes (J.C.S., ate, and -3 : 8-disulphonate all afford sodium 2 : 3-di- 1890, 57, 393, 631, 80S) from bromo-y.-naphthaquinone-8-sulphonate, yellow, which 2 : 4-dibromo-a-naphthol, thus is readily reduced to a colourless quinol, and with establishing the constitution p-toluidine in alcohol yields 3-bromo-2-p -lolu idino-a.- (I). It is probable that the ?iaphtkaquinone-4:-'p-methylanil-8-sulpIionic acid, car- very unstable, violet-blue solu­ mine-red, anthranilic acid giving an analogous deriv­ tions obtained by the oxidation of a-naphthol contain ative. With 1 mol. of bromine, sodium l-naphthol- oo'-dinaphthaquinone. Similarly, the substance 3 : 8-disulphonate gives sodium 4-bromo-1 -naphthol- obtained by the oxidation of 2 : 4-dibromo-a-naphthol 3 : 8-disulphonale, which couples with diazotised by air in alkaline solution or by lead dioxide in benzene is probably constituted analogously to (I) p-toluidine to give 4-bromo-2-p-tolueneazo-\-naphthol- 3 : 8-disulphonate, and on treatment with a further (Br instead of OMe), since the change occurs with loss of bromine and the compound is oxidised to the mol. of bromine affords sodium 2-bromo-u-naphtka- product obtained by Meldola and Hughes. Reduction quinone-3 : 8-disidphonate, red needles, and traces of of it gives a leuco-compound and not the original sodium 3 : 4-dibromo-l-naphthol-8-sulphonate, which material, and the amount of hydrazobenzene required forms no quinonc. Bromination of sodium 1 -naphthol- 3 : 6-disulphonate gives the readily soluble sodium 2-bromo-a.-naphthaquinone-3 : 6-disulphonate, yellow, which could not be obtained pure. Treatment of zinc l-naphthol-4-sulphonato w-ith I mol. of bromine affords 2-bromo-l-naphthol-4-sulphonic acid (potass­ OO^fOOBr Br ium salt), the constitution of which follows from (OMe) (OMe) its inactivity towards alcoholic p-toluidine and diazonium salts. With a further mol. of bromine (H-) (III.) this potassium salt gives potassium 2 : 3-dibromo-l- to decolorise the violet solution is approximately naphtholA-sulphonate. With 4 mois, of bromine zinc that required theoretically. 4-Bromo-a-naphthol also l-naphthol-4-sulphonate gives 2-bromo-l : 4-naphtha- 410 BRITISH CHEMICAL ABSTRACTS.— A. quinone, nr. p. 127-5— 128° (Zincko and Schmidt, A., 1927, 53; Windaus, A., 1927, 557). It is con­ A., 1895, i, 56), together with a little 2 : 3-dibromo- cluded that cholestenone and cholesterilene are the naphthaquinone, m. p. 216—217°. primary products, the hydrogen evolved in the 4-Broinonaphthasultone is converted by 10% formation of tho former reducing the latter to sodium hydroxide into sodium ‘i-bromo-l-napMhol-8- 0-cholestene. H. E. F. N o tto n . sulphonate, which with 3 inols. of bromine gives Allophanates of certain sterols. U. T a n g e sodium 2 : 3-dibromo-a-naphthaquinone-8-sulphonate, and E. V. M cCollum (J. Biol. Chem., 1928, 76, and with diazotised p-toluidine, sodium 4-6romo-2-p- 445— 456).— Allophanates of the following sterols (olueneazo-l-naphthol-8-sulphonate, analysis indicating were prepared by passing cyanic acid vapour into displacement of bromine and coupling in the 4-position the cold benzene solution of the sterol; , to a slight extent. Sodium l-naphthol-2-p-lohiene- m. p. 235— 236°, isocholesterol, dihydrocholesterol, azo-8-sidphonate is described. m. p. 255— 256°, sitosterol, m. p. 246— 247°, copro- Sodium 2-naphthol-6-sulphonato yields sodium sterol, m. p. 210— 211°; the esters, except that of 1 - bromo - 2 - naphtliol - 6 - sulphdnate and a dibromo- isocholesterol, are sparingly soluble in fat-solvents; 2-naphthol-6■ sulphonote. 2-Naphthol-3 : 6-disulphonic they are very stable towards mineral acids but are acid similarly affords mono- and di-bromo-derivatives, fairly readily hydrolysed by alcoholic potassium and 2-naphthol-6 : 8-disulphonic acid an easily solu­ hydroxide. C. R. H ar in g to n . ble sodium tribromo-2-naphtholsidphonate. Sodium 2-naphthol-3 :6 :7-trisulphonate with 1 mol. of bromine Action of Grignard reagent on amino-acids. gives sodium 1 -bromo-2-naphthol-3 : 6 : 7-trisulphonate XIV. Decomposition of amino-alcohols by (sparingly soluble p-loluidine salt; does not couple alkalis. F. B ettzieche (Z. physiol. Chem., 1928, with diazonium salts). In no case was quinonc 1 7 2 , 69—71).—The decomposition of amino-alcohols formation observed in the bromination of p-naphthol- into ketone and amine by heating with alkali (cf. A., sulphonie acids. The quinone formation observed 1926, 154) has been investigated more fully. The by Armstrong and Graham (J.C.S., 1881, 3 9 , 137) small amount of ammonia formed under the influence was probably due to the presence of a-naphthol in of alkali at high temperatures is duo to the sidc- their p-naphthol. R. Brightman. reaction, R-CH(NH2)-CRyOH — > R-CO-CHR'2+ NH3, which accompanies the main reaction, isoEugenol. Sch im m el & Co. (Bericht, 1927, R-CII(NH2)-CR'2-OH — > R-CH2-NH2+CO-R'.,. 138; Chcm. Zentr., 1927, ii, 1472).— isoEugenol was Thus two ketones, ammonia, and an amine arc obtained in large crystals, m. p. 32°, stable at tho formed. No significant amount of ammonia is pro­ ordinary temperature in absence of air. Structural duced when the decomposition is effected by water isomerism is presumed. A. A. E l d r id g e . at high temperatures and for this side-reaction alkali Molecular rearrangement in the cyctoheptane is necessary. The amounts of amineammonia, series. M . Godohot and (Ml l e .) Ca u q u il (Compt. ammonia, and the different ketones formed from rend., 1928, 1 8 6 . 375— 377).— Monochlorocarbamide various aminols with sodium hydroxide are given, reacts with cycMieptene (cf. Detoeuf, A., 1922, i, 236, and a general relationship is found between the 327) to form 2-chlorocycloheptanol, b. p. 98°/16 m m ., relative amounts of ammonia and amine formed and rfis 1-1351, ni? 1-4948, which when treated with the decomposition effected by heating with mineral magnesium methyl iodido (A., 1926, 164) yields acids. Amino-alcohols which are stable towards cycZohexylmethylcarbinol, b. p. 189-5° (corr.), together mineral acids give little or no ammonia, with the with a small amount of cthylidenecyc/ohexano exception of “ glycinephenylaminol ” which is readily (nitrosate, m. p. 140°; nitrosoeliloridc, m. p. 130°; decomposed by acid but gives very little ammonia nitrosopiperidide, m. p. 108— 109°). A mechanism by decomposition with alkali. A. W orm all. explaining the formation of a six- from a seven- p-Tolyl triphenylmethyl ether and its reaction mcmberecl ring is postulated. H . B urton. with zinc chloride. J. v a n A lp h e n (Ber., 1926, Colour reactions of cholesterol. L. E k k e r t 61 , [B\, 276—277).—Repetition of the author’s ex­ (Pharm. Zentr., 1928, 69, 97— 98).— The colorations periments (A., 1927, 660) has confirmed the pro­ obtained by treating alcoholic solutions of cholesterol duction of p-tolyl triphenylmethyl ether, m. p. 81°, with an alcoholic solution of an aldehyde and shaking by the action of p-cresol on triphenylmethyl chloride with sulphuric acid are described. Using 0-1 mg. of in pyridine (contrast Schorigin, this vol., 59). Prob­ cholesterol in 2 c.c. of alcohol, 2 drops of a 1 % solu­ ably tho ether is trimorphous, giving forms of m. p. tion of furfuraldehyde in alcohol, and 2 c.c. of 81°, 95°, and 114°, respectively. The formation of sulphuric acid, the alcohol layer becomes blue, and triphenylmethanc in addition to triphenylcarbinol by the acid layer rose. S. I. L e v y . the action of zinc chloride on the ether has been overlooked by Schorigin. H. W r e n . Sterol group. II. Formation of i/i-cholestene and cholestenone in the dry distillation of Catalytic hydrogenation under pressure of p-hydroxytriphenylcarbinol and p-hydroxydi- cholesterol. I. M. II eilbron and W . A. S e x to n (J.C.S., 1928, 347— 351).— Distillation of cholesterol phenylmethane. V. I patiev and B. D olgov (Bull. in a carbon dioxide atmosphero at the ordinary Soc. chim., 1928, [iv], 43. 242— 24S).— See this vol., pressure yields principally cholestenone and ^-cholest- 169. ene, with water, hydrogen, and a complex mixture Action of Grignard reagent on amino-acids. of low-boiling hydrocarbons (cf. Diels and Linn, A., XIII. Phenylserine derivatives. F. B ettzieche 190S, i, 164; Fischer, A., 1926,399; Fantl and Kabos, and R. M e y e r (Z. physiol. Chem., 1928, 1 7 2 , 64— ORGANIC CHEMISTRY. 411

68; cf. A., 1927, 137).— By the action of magnesium acetanilide to yield acetanilide, aniline, and sulphur. phenyl bromide on phenylserine ester hydrochloride, Sulphur monochloridc reacts with a-benznaphthalidc $-aimno-o.a.y-iriphenylpropane-o.y-diol, m. p. 154— to yield dibenznaphthalide sulphide and a-benznaphth- 155°, is obtained in 40% yield (N-benzoyl derivative, alide; with thiobenzanilide to yield benzanilide, m. p. 174-5°). Magnesium benzyl bromide and sulphur, and dibenzanilide sulphide. The properties phenylserine ester hydrochloride yield p-amino-y- of the last-named compound uphold tho formula ■phe.nyl-oivL-dibenzylpropane-a.y-diol, m. p. 120-5° (yield ascribed by Rivier and Schneider (A., 1920, i, 229); 13% ; hydrochloride, difficult to obtain pure, m. p. it is very stable towards alkalis, and easily hydro­ of crude product, 115°). These aminols are not lysed by acids to thiobenzanilide and benzanilide. decomposed to any appreciable extent by heating Treatment with mercuric oxide yields only benz­ with 12% hydrochloric acid or 20% sodium hydroxide. anilide, whilst it is easily reduced by sodium amalgam A. W ormall. and alcohol to phenylbcnzylamine. It is suggested Permanganate oxidation in alkaline media. that an ester of thiosulphuric acid is the unstable R. Cornubert and H. Le Biiian (Bull. Soc. chim., intermediate through which it is formed. Benzene- 1928, [iv], 43, 248— 255; cf. A., 1921, i, 422).— sulphonyl chloride reacts with thiobenzamide to Oxidation of 2-methyl-2-allylcyc/ohcxanono with afford 1 : 5-diphenyl-1 : 3 : 4-thiodiazole, sulphur, and potassium permanganate in presence of sodium or a red condensation compound; with thiobenzanilide potassium hydroxide, or sodium hydroxide and to form dibenzanilide sulphide; with sodium thio­ calcium oxide, yields in each case a glycol, m. p. 103° benzanilide to form benzenesulphonyl monosulpliide, (corr.), together with an oil, probably a mixture of m. p. 101— 102°, and benzenesulphonyl trisulphide, isomeric glycols (cf. A., 1927, 1075). The solid glycol m. p. 133°. Hydrogen sulphide was detected in the when heated for 1 hr. in a vacuum yields the corre­ last condensation only. sponding ethylene oxide, also formed in small quantity VII. Since the condensation of benzonitrile with during the oxidation, which exists in a monomeric p-thiotoluamide in the presence of hydrogen chloride form, b. p. 110°/32 mm., and also in various poly­ proceeds normally to afford benzimvno-p-i&othiotolu- meric forms. Dilute sodium hydroxide solution has amide (hydrochloride, m. p. 132°; picrate, m. p. 116°; practically no action on the monomeric oxide, and oxidised by iodine to pdienyl-p-lolyl-l : 3 : 4-thiodiazole, it is concluded that this compound is not an inter­ m. p. 56°), whereas a similar experiment with p-toluo- mediate in the production of the glycol. nitrile and thiobenzamide affords benzonitrile and H . B urton. the same benzimino-p-isothiotoluamide, it is sug­ Union of benzoylacetonitrile with organic gested that, in the latter condensation, an inter­ bases in presence of salicylaldehyde. II. P. change of the aryl radicals takes place through the K rishnamurti (J.C.S., 1928, 415— 417).— In presence intermediate formation of the unstable di-imino- of traces of salicylaldehyde and piperidine, benzoyl- sulphides, only part of which are converted into the acetonitrilo combines (yield 40%, 20%, and 50%, bonzimino-compound. The following condensations respectively, of the theoretical) with aniline, »«-4- confirm this view : p-toluonitrilc and p-tliiotoluamide xyUdine, and p-, but not o- or »i-toluidine. These yield p-toluimino-p-isothiololuamide, m. p. 108° [hydro­ compounds, unlike the corresponding piperidine chloride, m. p. 161°; picrate, m. p. 160°; action of derivative (A., 1927, 766), easily afford dibenzoyl ethyl iodide affords S-ethyl-p-tohiimino-'p-iiiOthiotolu- derivatives, and their oximino-derivatives are decom­ amide hydriodide, m. p. 154° (freo base decomposes posed by benzoylation, yielding the benzoyl derivative to give mercaptan and tri-p-tolylguanidine); 2 : 5-di- of the amine. The p-toluidine compound, C10H 10ON2, ■p-tolyl-1 : 3 : 4-thiodiazole, m. p. 129° (hydrochloride, m. p. 1S2° (hydrochloride, m. p. 194— 195°; dibenzoyl m. p. 161°)]; »«-toluonitrile and »«-thiotoluamide derivative, m. p. 166°), gives an orange oximino- yield m-tolidmino-m-moihiotoluamide (23%), m. p. derivative, m. p. 158° (silver salt). The aniline com­ 58° [hydrochloride, m. p. 114°; chloroplatinale (not pound, G15HmON2, has m. p. 163° (hydrochloride, obtained pure), m. p. about 121°; S-ethyl-m-toluimino- m. p. 94— 96°; dibenzoyl derivative, m. p. 168°; red m-isothiotoluamide hydriodide, m. p. 136° (corre­ oxmino-derivative, ill. p. 182°), and tho m-4-xylidine sponding picrate, m. p. 145°); corresponding thio- compound, C17H 1301Si2, m. p. 145— 146° (benzoyl diazole, m. p. 49-5°]. The V-cthyl compound can be derivative, m. p. 153“ ; o.rimino-derivative, m. p. reduced by alcoholic hydrogen chloride and zinc to 150— 151°). H. E. E. N otton. n\-methylbcnzyl-m-toluamidine hydrochloride, m. p. 199°. Condensation of nitriles with thioamides. VI. p-Toluonitrile and »«-thiotoluamide, (3-naplitho- Action of sulphur' acid chlorides on thioamides. nitrile and thiobenzamide, and a-naphthonitrilc and VII. Toluonitrile with thiotoluamide, naphtho- thioacctamide yield typical condensation compounds nitrile with thionaphthamide, and others. S. which were not further examined; benzonitrile and Ishikawa (Sci. Papers Inst. Phys. Cliem. Res. Tokyo, »«-thiotoluamide yield probably a , mixture of the 1927, 7, 237— 248, 277— 292; cf. A., 1925, 917, possible products, from which a hydrochloride, m. p. 1149).— VI. Thionyl chloride or sulphur mono­ 135° [corresponding picrate (B2A), m. p. 140°; hydro­ chloride reacts with thiobenzamide to give benzimino- bromide, m. p. 136°; corresponding thiodiazole wothiobenzamidc, 2 : 5-diphenyl-1 : 3 : 4-thiodiazole picrate, m. p. 88°)], is obtained; »«-toluonitrile and (dibenzenylsulphime), and sulphur; and with thio- thiobenzamide yield a similar mixture from which a acetamide to yield acetamide and sulphur. Thionyl hydrochloride, m. p. 135°, a hydrobromide, m. p. 136°, -chloride reacts with thiobenzanilide to yield dibenz- and a picrate. m. p. 140°, are isolated. anilide sulphide, 111. p. 111°, and aniline; with thio- G. A. C. Go u c h . 412 BRITISH CHEMICAL ABSTRACTS.— A.

Condensation of nitriles with thio-acids. I. S. sodium bromide, and bromine, under conditions de­ I sh ik aw a (Sci. Papers Inst. Phvs. Chem. Res. Tokyo, scribed in detail, produces sodium 2-bromo-3-nitro- 1928, 7, 293—-300).— These condensations, carried benzoate. A. A. E l d r id g e . out in ether saturated with hydrochloric acid, result Constitution of elemic acid. K. H. B a u e r in the production of the thid-amide from the nitrile (Ber., 1928, 61, [7i], 343— 344).— Determination of and of the normal acid chloride from the thio-acid, the iodine value of a-elemic acid, C27H420 3 (cf. together with the secondary condensation products Tschirch and Cremer, A., 1902, i, 812; Buri, A., 1878, of these substances. It is suggested that the reaction ii, 439; Lieb and Schwarzl, A., 1924, i, 1312), proceeds through the intermediate formation of a indicates the presence of a double linking which is compound of the type R'CilNHJ-S’CCbR. In this confirmed by its catalytic hydrogenation in alcohol way benzonitrile and thioacetie acid yield thiobenz- in presence of palladised kieselguhr to dihi/droelemic amide, benziminoi'sothiobenzamidc, and acetic acid ; acid, C27H440 3, m. p. 238°. The methyl esters of p-nitrobenzonitrile and thioacetie acid yield p -nitro- elemic and dihydroelemic acid could not be caused thiobenzamide, m. p. 157° ; m-nitrobenzonitrile and to crystallise. H. W r e n . thioacetie acid yield m -nitrothiobenzamide, m. p. 130— 131°; benzonitrile and thiobenzoic acid yield benz- Addition of bromine to etbylenic compounds amide, benziminoisothiobenzamide, and benzoyl in non-hydroxylic solvents. D. M. W illiams and chloride. Nitriles react with hydrogen sulphide in T. C. James (J.C.S., 1928, 343— 347; cf. Sudborough ethereal hydrogen chloride to afford the arylimino- and Thomas, J.C.S., 1910, 97, 715, 2450).— Three a'sothioarylamides, through the intermediate form­ distinct types of reaction have been observed in ation of the diarylimino-sulphide. Thus benzonitrile dilute solutions in dry chloroform or carbon tetra­ gives benziminoisothiobenzamide, also produced chloride at 13° in the dark : (a) Addition to cis- and under similar conditions by the use of potassium, ¿rans-o-metlioxycinnamic acids, cinnamylideneacetic calcium, or zinc sulphide ; and S-naphthonitrilc gives acid and its methyl ester, a-phenylcinnamylidene- ¡3-thionaphthamide. G. A. C. Gough . acetic acid, (3-furfurylacrylic acid, oleic acid, and Action of metallic salts on tliioamides and elaidic acid proceeds rapidly and is accompanied by their derivatives. I. Mercuric chloride in substitution and formation of hydrogen bromide. ethereal solution. S. Ishikaava (Sci. Papers Inst. The bimolecular velocity coefficient decreases as the Phys. Chem. Res. Tokyo, 1928, 7, 301— 312).— reaction proceeds. (b) After an inhibition period Mercuric chloride additive compounds of the typo addition to cinnamic acid, its methyl ester, crotonic B2,HgCl2, arc quantitatively formed when ethereal acid, and methyl cinnamylidenemalonate proceeds solutions of the following thioamides arc titrated slowly with increasing velocity, (c) No measurable with ethereal mercuric chloride : thiobenzamide, addition to malcic anhydride, coumarin, and a-phenyl- m. p. 194—197° (decomp, with the liberation of cinnamonitrile is observed under these conditions. mercuric chloride and hydrogen sulphide) ; m-thio- Reactions of type (a) are probably catalysed by the toluamide, m. p. 183— 186° (decomp.); p-thiotolu- hydrogen bromide formed, since addition of this amide, m. p. 191— 194° (decomp.) ; m-nitrothio- substance greatly accelerates those of type (6). In benzamide, darkening at 206° ; p-nitrothiobenzamide, each case the inhibition period disappears and the m. p. 183° (decomp.); thioacetamide, m. p. 183°; reaction becomes bimolecular. Water and hydrogen phenylthioacetamide, m. p. 160° (decomp.) ; a-thio- chloride are less efficient catalysts. Reactions of naphthamide, m. p. 184° (decomp.); p-thionaphth- type (c) are not accelerated by these substances. amide, m. p. 221° (decomp.); thiobenzanilide, m. p. H. E. F. N otton . 100— 101° (re-solidifying at about 1S0° and unmelted Isomerism of phenylphthalimide [phthalanil] at the b. p. of sulphuric acid) ; a-thioacctonaphthalide, and a study of the nitro- and chloro-derivatives. decomp. 222° (previous darkening) ; (J-thioaceto- M. L. Sh er r ill, F. L. Sch aeffer, and E. P. Sho yer naphthalide, decomp. 225° (with previous darkening). (J. Amer. Chem. Soc., 1928, 50 , 474— 485).— By $-Thiobenznaphthalide mercuric chloride has m. p. extraction with chloroform, Gabriel and Thorpe's 184— 187°. The following form additive compounds “ phthalanilic acid,” m. p. 192° (cf. A., 1893, i, 466), of the type B,HgCl2 : benziminoi'sothiobenzamide, can be separated into phthalanil (soluble) and phthal­ m. p. 149° (decomp.) : p-toluimino-p-isothiotolu- anilic acid, ml p. 169°. It is also shown that whilst amido, m. p. 118° (decomp. 163°) ; m-toluimino-m-iso- van der Meulen’s. phthalphenylisoimide is the true thiotoluamide, m. p. 110° (changing to a yellow solid «.s-phenylphthalimide (A., 1897, i, 414), Kuhara’s at 159°) ; acetophenonethiosemicarbazone mercuric (Bx-phenylphthalimide is a mixture of phthalphenyl- chloride. The first-named is decomposed by potass­ isoimide and phthalanilic acid (cf. A., 1911, i, 205), ium hydroxide into potassium chloride, mercury, and his a-phenylplithalimide is a mixture of the water, and the thiodiazole. ■ G. A. C. Go u g h . normal and isophthalanils. The “ p-isonitrophenyl- phthalimide ” of Kuhara and Dobreff (A., 1895, i, ji-Iodohenzoic acid. F. C. W hitmore and (Miss) 360) is identical with p-nitro phthalanilic acid (am­ G. E . W o o d w ard (Org. Syntheses, 1927, 7, 58— 59). monium salt; disilver salt, brown); the “ m-iso- —p-Iodobenzoic acid is prepared in 72—81% yield nitrophenylphthalimide ” is a mixture of m-nitro- by the interaction of p-chloromercuribenzoic acid phenylphthalamide and m-nitrophenylphthalimide, and iodine in alcoholic solution. A. A. E ld rid g e. whilst the “ o-fsonitrophenylphthalimide ” is o-nitro- 2-Bromo-3-nitrobenzoic acid. P. J. Cu l h a n e phthalanilic acid, contaminated with o-nitrophthal- (Org. Syntheses, 1927, 7, 12— 14).— Interaction anil and o-nitroaniline hydrochloride. p-Chloro- of anhydro-2-hydroxymercuri-3 nitrobenzoic acid, phthalanilic acid is obtained by treatment of p-chloro- ORGANIC CHEMISTRY. 413

aniline with phtlialic anhydride in chloroform. 140-5°, which is expected to afford an example of m-Ohlorophthalanilic acid, m. p. 183—184° (decomp.), molecular asymmetry. H. W r e n . and o-chloropMhalanilic acid, m. p. 147—-148°, decomp. 155°, obtained analogously, are described. Fusion Auto-oxidation of benzaldehyde. P. A. A. v a n of phthalic anhydride with chloroanilines affords the d er B e ek (Rec. trav. chim., 1928, 47, 286— 300; respective o-, m. p. 132— 140°, ni-, m. p. 183— 184° cf. A., 1926, 519).—The oxidation of benzaldehyde to (decomp.), and p-chlorophenylphthalimide (cf. perbenzoic acid has been studied, using various Gabriel, A., 1870, 323). ' F. G. W illso n . metals and solvents. Iron powder considerably accelerates the oxidation, tin and aluminium powders [Preparation of] 3-nitrophthalic acid. P. J. having no particular accelerating action. On ex­ Cu lh a n e and (Miss) G. E. W o o d w a r d (Org. Syn­ posing benzaldehyde dissolved in acetone, carbon theses, 1927, 7, 70— 72). tetrachloride, benzene, or chloroform to diffuse light [Preparation of] 3-nitrophthalic anhydride. or to sunlight in the presence of oxygen, the form­ B. H. N icolkt and J. A. B e n d e r (Org. Syntheses. ation of varying quantities of perbenzoic acid was 1927, 7, 74— 75). observed, a conversion of 43% (determined by oxid­ [Preparation of] ethyl phthalimidomalonate. ation of iodide) being recorded with acetone solution. No perbenzoic acid was formed in pyridine solution. A. E. Osterberg (Org. Syntheses, 1927, 7, 78-—79). The oxidation of benzaldehyde in benzene solution [Preparation of] p-bromoethylphthalimide. produced a substance of sharp, penetrating odour P. L. Salzberg and J. V. S u p n ie w s k i (Org. Syn­ and having the properties of a peroxide. The auto­ theses, 1927, 7. 8— 10). oxidation being assumed as taking place in two stages: [Preparation of] a-cyano-p-phenylacrylic acid. (i) Ph-CHO — =>- Ph-COjjH, (ii) Pli-C03H +Ph-CH O A. L ap w orth and W. B a k e r (Org. Syntheses, 1927, — Ph-C02H, stabilisation of the intermediate pro­ 7, 20— 22). duct was necessary; acetone gave the best results (63-4% yield). A dilution of 10 vols. of benzalde­ [Preparation of] diphenic acid. E. H . H untress hyde in 80 vols. of acetone should not be exceeded; (Org. Syntheses, 1927, 7, 30— 33)-.:—Vorlander and the yield is then about 50%. Admission of water to Meyer’s method is applied to the preparation of large the reaction greatly decreases the yield. Pure per­ quantities. A. A. E l d r id g e . benzoic acid was obtained by oxidising a 10% acetone Hydroxyamhio-acids. II. F. B ettzieche and solution of benzaldehyde with oxygen until absorp­ R. Menger (Z. physiol. Chem,, 1928, 172, 56— 63; tion ceased. After removal of acetone by distillation, cf. A., 1926, 154).—BenzoylpHenylserine (a-benzamido- the peroxide was isolated either by distillation at [i-hydromfcp-phenylprop>ionic acid), m. p. 158°, when low pressure, or by removal of benzoic acid from subjected to steam distillation in 8% sodium hydroxide the acetone solution with dilute sulphuric acid, yields benzaldehyde, benzoic acid, and glycine, but followed by extraction with chloroform. no ammonia or hippuric acid. Ilippurylphenylserine By oxidising benzaldehyde in carbon tetrachloride (a-hippurylamino-$-hydroxy-$-phenylpropionic acid), solution, it is shown that perbenzoic acid is not m. p. 143°, in the same way yields benzoic acid, the first product of oxidation, since carbonyl benzaldehyde, glycine, and traces of hippuric acid, chloride, hydrogen chloride, and carbon dioxide are but no ammonia; thus no splitting of the acid into formed. R. A. Pr a tt. hippurylamide and phenylpyruvic acid occurs. Toluenesulphonylphenylserine when heated with 3% Auto-oxidation of benzaldehyde in presence of sodium hydroxide for 5 hrs. at 200° is partly decom­ acetic anhydride. P. A, A. v a n der B e e k (Rec. posed into benzaldehyde and toluenesulphonyl- trav. chim., 1928, 47, 301— 308).— Equal volumes of glyeine and partly into toluenesulphonamide and benzaldehyde and acetic anhydride were mixed with phenylpyruvic acid, the products of both changes the addition of one drop of phosphorus trichloride being isolated; the yields, however, are minimal on as catalyst, the mixture being kept over-night at a account of the high temperature. By the action of low temperature in the dark. Snow-white crystals benzoyl chloride on benzoylphenylserine in sodium of benzylidene diacetate, in. p. 40°, were formed in hydrogen carbonate solution, the azlactone of benz- large yield. M.-p. curves, obtained by a method amidocinnamic acid is formed and not the diacyl avoiding oxidation of benzaldehyde, were determined compound, which has not yet been obtained. The after the mixtures had been kept for 62 hrs. in an azlactone of benzamidocinnamic acid does not react atmosphere of carbon dioxide. Two maxima were with ethyl alcohol, but with methyl alcohol an found, one corresponding with the compound almost quantitative yield of the methyl ester of the 2P1i-CH0,Ac20 , m. p. about 17°, and the other with azlactone, m. p. 140°, is obtained. Benzamido­ Ph-CHO,Ac20, m. p. 40°. Despite attempts to cinnamic acid, in contrast with its azlactone, is isolate the new compound in the pure state, it was indifferent to both methyl and ethyl alcohols. impossible to preserve a solid substance with m. p. A. W o rm all. other than 45—46°. Apparently the new compound Triple spiran. P. P feiffer and P. B aokes decomposes during purification into benzylidene (Ber., 1928, 61, [J5], 434— 435).— Pentaerythritol is diacetate and benzaldehyde. The addition of a converted when heated with ethyl cycfohexanone-4- trace of phosphorus trichloride to the pure diacetate, carboxylate into the triple spiran the reaction mixture being kept for some months in a sealed glass tube, also produces a compound of C^C H 2-0>G - 1 : 2 : 4-oxadiazole and benzoylmetazonic acid are. HoX2l — > CXPh2$-NH-C B X |;OHXPh-NX-NH-C6 6 3 2 also formed. On heating the above a-compound with (X —Br or G), since the third halogen atom readily dilute acetic acid, ^-benzoylaminoglyoxime, m. p. 1S7° reacts with potassium cyanide to yield tho corre­ (dccomp.), is obtained; tho precipitates with nickel sponding cyano-dcrivative or with phcnylhydrazino and copper acetate are described, as is the dibenzoyl to yield intensely coloured azo-derivativcs which are derivative, m. p. 198°. not isolated. The product, m. p. 114°, obtained by The compound (I) is obtained by the first-mentioned bromination of benzaldehydephenylhydrazone in reaction only when the temperature rises, or by7 the glacial acetic acid has tho structure action of acetic anhydride in the cold on the a-com­ UBr^hIN‘ííH*CsH;lBr (I), and is not p -bromobenz- 3 pound, or by heating the a- or the ^-compound with aldehyde-2 : 4 -dioromophenylhydrazone as stated by ammonia solution; it is to be regarded as 3-amino-4- Ciusjv (A., 1910, i, 437). The latter, in. p. 125-5°, is benzoyl-1 : 2 : 5-oxadiazole (derived through the inter­ synthesised from p-bromobenzaldehyde and 2 : 4-di- mediate formation of benzoydoximinoacetonitrile bromophenylhydrazine. By treatment with potassium oxide). Its ld-oxide (“■ benzoylaminoglyoximo per­ cyanide in boiling alcohol (1) yields a-cyanobenzylidene- oxide ” ), m. p. 145° (decomp.), from which it can be 2 : •l-dibromopJienyJhydmzinc, m. p. 138°. By similar obtained by reduction, is prepared by oxidation of methods are prepared salicyhdene-p-bromophenyl- a-bcnzoylaminoglyoxime by, e.g., bromine water. hydrazinc, m. p. 175°; a.-bromobcnzylidene-2-bromo- Contrary to the statement of Boesekcn, the com­ i-nitrophenylhydrazine, in. p. 169°; a.-chIorobenzyl- pound (I) easily ydelds a benzoyl derivative, m. p. 1 dene-2 : 4-dichlorophenylhydrazine, m. p. S7°, from 139— 140°. which is obtained a.-cyanobcnzyUdenc-'2 :4 -dichloro- Similarly, di-p-toluoylglyoximc peroxide yields phcnyUiydrazine, in. p. 12S°; addoroanisylidcne- a- and ri-\')-toluoyl(iminoglyoximes, m. p. 114° and 188° : i-dtcblorophenylhydrazinc, m. p. °; tho corre­ 2 111 (each decomp.), respectively. 3--4mi wo-4 -p -loluoyl- sponding a-ci/aao-derivative, m. p. 150°. 1:2; 5-oxadiazole X-o.r/rfe (“ p-toluoylaminoglyoximc J. W . Ba k e r . peroxide ’’) has m. p. 145° (decomp.), and can be Nitration of benzaldoxime and some deriv­ reduced to the oxadiazole. The compounds regarded atives. O. L. BradV; and B. E. M. M iller (J.C.S,, by Boesekcn as 5-amino-3-p-toluoyl- and -3-y-anisoyl- 1928, 337— 342).— With nitric and sulphuric acids at 1:2: 4-oxadiazoles, m. p. 165° and 144° respectively, 0° and 5°, respectively, benzaldoxime and its are renamed 3-ammo-4-p-toluoyl- and -4-p-anisoyl- A-methyl derivative give exclusively m-nitro-dcriv- 1:2: 5-oxadiazoles. atives, the yields being diminished by hydrolysis and The above-mentioned product (II) may have the oxidation. a-O-Methylbenzaldoxime is attacked by nitrating agents only wit h difficulty, even on warming, structure CBz(X-0H)-C

hydroxypkorone, the latter must be capable of a the same methods from 3:3:4: 4-tetramethyleyelo- pentatwneoxime, m. p. 107° (hydrochloride, m. p. tautomerism, CO- (IV) — >- (II), which arc accom­ amine into the (y)-oxime (2-oximino-',i : 3 : 4 : 4-tetra- panied by a decrease in unsaturation and visible methyleyclopentanone), m. p. 115°, of (VIII), which-is colour, and by depression of the mol. rcfractivity also formed on regulated nitrosation of the ketone (IX ) and parachor (cf. Sugden, this vol., 410), runs in chloroform. In methyl-alcoholic solution (IX) parallel with the op-directing power in aromatic yields a S-oxime, m. p. 170— 172° (monohydrate, substitution of the group in position (a). The m. p. 83°; sodium salt, m. p. 200°), which is probably structure of the ketone (IX) (cf. Farmer and Kracov- stcreoisomeric with the y-oxime, since it affords with ski, A., 1927, 447) has been confirmed by its synthesis hydrochloric acid and formaldehyde aafip-tetra- by heating py-dibromo-Sy-dimethylbutanc and ethyl methylglutaric acid. The y-oxime is converted by acetonedicarboxjdate with sodium ethoxide and liydroxylamine into the above dioximc, m. p. 211°, hydrolysing the product with hydrochloric acid. It by sodium and alcohol into (?) o-hydroxy-2 : 2 : 3 : 3- gives a di-3 : 4-melhylenedioxybenzylidene derivative, telramethylcyclopenlylamine, isolated as the picrate, m. p. 125°, and a 2 : 5-dioximino-dcnvntivo, m. p. in. p. 220—221°, and by the Beckmami reaction into 223°, which is hydrolysed by hydrochloric acid in (?) 2 : 3-diketo-5 : 5 : 6 : 6-tetramethylpiperidine, m. p. presence of formaldehyde to oily tetramethylcyclo- 200°. If the oximino-group directly displaces the pentane-1 : 2 : 3-trione (trioxime, m. p. 168— 169°). benzoyl group in (X), the latter has thus been shown The ketone (IX) absorbs bromine (3 mols.) in to bo a derivative of (VI). Bromohydroxyphorone anhydrous solvents, forming probably 2 : 5-dibromo- is converted by sodium ethoxide and p-bromobenzyl and 2:2: 5-tribromo-3 : 3 : 4 : 4-tetramcthylcyc/o- bromide into an oily by-product (X I) and the p -bromo- pentanone. The latter is decomposed by water to benzyl ether, m. p. 65°, of (V), which is reduced by bromohydroxyphorone (V) or (VII) (d-bromocamphor- zinc dust and acetic acid to the p-bromobenzyl ether, sulphonyl derivative, m. p. 150°; p-nitrobenzyl ether, m. p. 86°, of (VI). This is fairly stable towards m. p. 111°). This is reduced by zinc dust and acetic bromine and alkaline permanganate and does not acid to the hydroxyphorone (VI) or (VIII) and yield a dihydro-derivative (cf. the methyl ether, below). the products of direct alkylation and acylation of the With boiling liydriodic acid it gives (IX) and with latter are also preparable by this method from the ozone, bromine, and an ozonidc which is hydrolysed corresponding derivatives of (V) or (VII). The ethers to p-bromobenzaldehyde and tetramethylsuccinie and esters described below fall into two groups, acid. The acetyl derivative, m. p. 84°, of its oxime, (i) derivatives of (V) or (VI), which are fairly stable m. p. 175° (hydrochloride, m. p. 133°), is reduced to towards reduction, oxidation, and bromination, and (?) 2-hydroxy-3 : 3 : 4 : 4-tetranietkylcyc\opentylamine (ii) derivatives of (VII) or (VIII), which yield dihydro­ [picrate, m. p. 215° (decomp.)], besides neutral derivatives and are easily oxidised and brominated. substances, m. p. 161— 162°, and oils. 1 -Cyano- (i) Bromohydroxyphorone does not form ketonic 2 :2 :3 : 3-tetramethyl-[0,l,2]-dicyclopenlan-4-ol-5-one derivatives, but hydroxyphorone (VI) gives a semi- (V or V II, R = C N ) hias m. p. 172— 173°. carbazone, m. p. 211— 213°, an anil, m. p. 104°, a (ii) The constitution of the acetate (1-bromo- p-dimethylaminoanil, m. p. 90°, and an a-oxime, m. p. 5 - acetoxy - 2 : 2 : 3 : 3 - tetrametliyl - A5 - cyc/opcnten- 96° [monohydrate, m. p. 76°; sodium salt, m. p. 200° 4-one) (Francis and Willson, loc. cit.) of bromohydroxy­ (decomp.); hydrochloride, m. p. 1S9— 190° (also phorone is established as follows : it is reduced by -rCCl4, m. p. 174— 175°); benzoyl derivative, m. p. zinc and acetic acid, first to b-aceloxy-2 : 2 : 3 : 3- 1^1— 135°], which is converted by cold ethereal telramethyl-Ab-cyclopantcn-4:-one,h.Y>. 120°/15— 16mm., hydrogen chloride into the hydrochloride, m. p. d f 1-0190, »55 1-4549, then to 5-acetoxy-2 : 2 : 3 : 3- 69—70°, of a fj-oxime, m. p. 114— 115°. The «- and tetramethylcyclopcntanone (X II), b. p. 127°/15— 16 mm. 3-forms are readily interconvertible, and since, the (hydrolysed to a hydroxylcetone, C9H le0 2, m. p. 140°), latter gives by the Beckmann reaction a substance and by sodium amalgam and acetic acid to 2 : 2 : 3 : 3- [( 1)2 : 3-diketo-i : 4 : 5 : 5-tetrameihylpiperidine], m . p. tetramcthylcyclopenlanone (XIII), b. p. 100°/16 mm., 113°, not identical with xx$[i-tetramethylghitarimide, m. p. 119° (semicarbazoTie, m. p. 222°), and a little of m. p. 200— 202°, they are probably stereoisomerides, the isomeride (IX). The oxime, m. p. 101— 102° -9 JjP and.9^ , respectively. The a-oxime (hydrochloride, m. p. 125°), of (XIII) is reduced by sodium and alcohol to 2 :2 :3 :3-tetramethylcyclo- is shown to be a derivative of (VI) by its reduction by pentylamine (XIV ) (picrate, m. p. 242— 243°; acetyl sodium amalgam and acetic acid or palladium and derivative, m. p. 115°), which is also obtained by hydrogen to 3:3:4: 4-tetramethylcyclopentylamijie, oximation and reduction from (XII). Similarly, the 111 • P -100— 102° [picrate, m. p. 255°; chloroaurale, ni. p. melhyl ether (\-bromo-5-metkoxy-2 : 2 : 3 : 3-tetramethyl- -30° (decomp.); hydrochloride, m. p. 30S° (decomp.); A5-cyc\openten-4-one), b.p. 120°/14 mm., 1-5131— acetyl derivative, m. p. 95°], which is obtained by 1-5147, d f 1-3159, of (VII) is reduced by zinc dust and 416 BKITISn CHEMICAL ABSTRACTS.— A.

acetic acid to 5-methoxy-2 : 2 : 3 : 3-tetramethyl-A5- constant for tliis system is therefore 20-7. The cydopentenA-one, m. p. (on one occasion) 37°, b. p. difference between this and the value (25-2) calculated 112— 115°/21 mm., 1-4687 [reducible through its for superimposed three- and five-membered rings is oxime, b. p. 140—150°/22 mm. to (XIV)], and to ascribed to the stabilising effect of the grem-dimethyl 5-methoxy-‘l : 2:3: 3-tetramethylcyclopentanone, b. p. groups. The anomaly of (d) is in accordance with the 88— 90°/10 mm., w]? 1-4580, which is reduced by structure, 5-acetoxy-2 : 2 : 3 : 3-tetramethyl-A5-cycfo- liydriodic acid to (IX) and through its oxime to (XIV). penten-4-one, and that of (c) with an equilibrium The by-product (XI) appears to contain the p-bromo- betwreen cyclic and open-chain forms, which must benzyl ether of (VII), since it is reduced by zinc and have nearly the same energy content, since the acetic acid to a substance, the oxime of which is parachor does not vary appreciably wdth temperature. reduced by sodium and alcohol to (XIV). Similarly, whilst distyryl ketone has a normal •The oxidation and halogenation of bromohydroxy- structure, its dibromo-derivative appears to exist phoronc are best explained in terms of formula (VII). partly in the dicyclic form. H, E. F. Notton. With sodium perchlorate and osmium tetroxide it Orientation phenomena with 2-methylciyefo- affords the lactonic acid (XV) of yy-dihydroxy- hexanone. R. C obn u bert (Compt. rend., 1928, aapp-tetramethylglutaric acid and the lactonic acid 186, 441— 442).— Alkylation of 2-methylcycfohexan- (dilactoiie anhydride, m. p. 177— 178°) of y-hydroxy- one bvmeans of sodamide yields mainly the 2 : 2-dialkyl aapp-tetramethylglutaric acid. The methyl ether of derivative, with a small proportion of the 2 : 6-dialkyl (VII) is ozonised to bromine and ozonides which yield compound (cf. Haller and Cornubert, A., 1927, 152; on hydrolysis a product containing the lactonic ester, Cornubert and Le Bihan, ibid., 1075). That this is 9Me2-CMe2-g(0H )-C 02Me b p 1.55— 1(35°/I3 mm., and not due to an inversion of the latter is shown by the b u U stability of both 2 : 2- and 2 : 6-dimetliylcyctohexan- its methyl ether, 111. p. 103°, previously regarded by ones towards sodium hydroxide and hydrochloric Rothstein and Shoppee (A., 1927, 447) as methyl acid; also, both ketones can be isolated without using y-keto-aapp-tetramethylglutarate. The acetate of sodium hydrogen sulphite. It is concluded that (VII) does not yield bromine when ozonised; it is sodium, unlike chlorine, substitutes in the 2- pre­ oxidised by permanganate to (XV). Hydroxyphorone ferentially to the 6-position. The “ tetrahydro- (VI) or (VTII) and the ketone (XIII) are both oxidised pyronc ” compound of 2 : 6-dimethylci/cZohcxanone to aapp-tetramethylglutaric acid. The constitution, has m. p. 175°, not 197— 198°, as previously stated. 1:1- dibromo - 2 : 2 : 3 : 3 - tetramethylcycfopentane- E. W . W ig n a ix . dione, proposed by Francis and Willson for the 2 :6-Dimethylcyciohexanones. R. Cornubert bromination product of (VII) is supported by the (Compt. rend., 1928, 186, 58&—586; cf. preceding observation that chlorination of (VII) and bromination abstract).— The mixture of dimethylcycZohexanones, of \-chloro-2 : 2 :3 : ‘¿-tdramethyl-[0,1,2]-dicyclopewto?i- obtained by the methylation of 2-mcthylci/cZohexanone 4-ol-5-o?ie (V or VII, R=C1), m. p. 116° (acetyl deriv­ by the method of Kotz and Blendermann (A., 1913, i, ative, m. p. 47°), yield the same l-chloro-l-bromo- 1069), is separated by crystallisation of the oximes 2:2 :3 :3-tetramethylcyc\opentanedione, hi. p. 178°, affording the oxime A , m. p. 119° (hydrolysed with which is reduced by carbamide to the chlorohydroxy- difficulty to yield the ketone A , b. p. 85°/41 mm., dcrivative. The close similarity between dibromo-, dls 0-914, ?i]) 1-4486), and the oxime B, m. p. 64— 65° chlorobromo-, and 1 : 1 -dichloro-, m. p. 187°, -tetra- (softening at 63°; easily hydrolysed to afford the methylcyclopentancdiones indicates that they are ketone B, b. p. 80-5°/41 mm., d18 0-911, 1-4482). analogously constituted. H. E. F. Notton. The ketone A gives pyrone-like compounds, m. p. 197-—198°, 175°, and 216°, of the common formula Parachor and chemical constitution. VIII. C22H2102, when treated with benzaldeliyde in the Ring-chain valency tautomerism in phorone presence of hydrogen chloride (A., 1925, i, 1070,1071), derivatives. S. S u g d e n (J.C.S., 192S, 410— 415). whilst tiie ketone B similarly affords the compound, — The constitutions assigned to these derivatives m. p. 175°, b. p. 271°/20 nun., and the compound, on chemical grounds by Ingold and Shoppee (this m. p. 216°. Oximation of the ketones in the presence vol., 414) are, in general, confirmed. The parachor of sodium acetate yields in each case mixtures of the and the calculated value for the formula, oximes A and B, whilst in the presence of alkali the CMc2!CR-CO-CR'!CMc2, with two non-polar double ketone A gives the oxime A alone and the ketone B linkings, are given for the following compounds : again gives a mixture. Both ketones give mixtures of (a) phorone, 367-9, 372-2; (b) dichloro-, 427-7, 446-6; semicarbazones (Zelinsky, A., 1897, i, 462). The (c) dibromo-, 463-2, 474-0; (d) acetoxy-, 459-4, results are attributed to the rapid interchange of the 476-0; (e) bromoacctoxy-, 506-4, 526-9; (/) bromo- cis-trans isomerides. G. A. C. Go ugh . methoxy-, 455-3, 4S2-1; (g) benzoyloxy-, 583-9, 609-9; (h) bromobenzoyloxy-, 642-4, 660-8; (i ) Relative ease of formation of rings. II. J. p-bromobenzyloxy-, 630-7, 655-0; (j) bromo-p- von Braun (Ber., 192S, 61, [B], 441— 443; cf. this bromobenzyloxy-, 684-0, 705-9, also for distyryl vol., 174).—It is shown in two instances that a ketone, 564-5, 562-0, and aa'-dibromodistyryl ketone, six-mcmbered carbon ring is more readily allied to a 650-7, 663-8. Thus, (a) agrees well with an open- benzene nucleus than a five-membered carbon ring chain structure, whereas the maximum deviations at (cf. Lcuchs and others, this vol., 287).— Benzyl- (/); (S'). and (i) probably indicate complete conversion fi-phenylethylacetyl chloride, b. p. 198—-202°/15 nnn., is converted by aluminium chloride in presence of into the dicyclic form ' . The mean structural carbon disulphide into l-keto-2-benzyl-l : 2 : 3 : 4- ORGANIC CHEMISTRY. 417 tetraliydronaphthalene, b. p. 220—225°/13 mm. meia-position to the acetoxyl group favours the (oxime, m. p. 119°), the constitution of which is formation of o-hydroxyacetophenones. Two meta- established by converting it by Clcmmensen’s method groups produco an even greater tendency in the same into 2-benzyl-l : 2 : 3 : 4-letrahydronaphtludene, b. p. direction. Thus, when 3 : 5-dimcthyl- and 3 : 5- 194—-195°/13 mm., transformed by heated lead oxide dietliyl-phenyl acetato undergo the Fries change, into naphthalene. Benzylsuccinic acid is converted no 4-hydroxyacetophenoncs aro formed. Similarly, by phosphorus pentachloride into be.nzylsucc.inyl 3 : 5-dimethylphenyl alkyl ethers give only 2-deriv­ chloride, b. p. 115— 117°/0'5 mm., which, with alumin­ atives in Fricdel-Crafts reactions. When one meta- ium chloride, affords l-lceto-l : 2 : 3 : 4-tetrahydro- alkyl group is present {e.g., m-tolyi acetate), the Fries naphthalene-3-carboxylic acid, m. p. 144°, b. p. 218— change gives a little p-compound. A second methyl 220°/16 mm. (also obtained from benzylsuccinic group in the ori/w-position (3-o-xylyl acetate) does anhydrido and aluminium chloride); the ethyl ester, not weaken the effect of the mei«-grouping in this b. p. 175—-177°/15 mm., and the semicarbazone, m. p. respect. 264°, are described. The acid is reduced by amalgam­ Phenyl acetates with a free ori/m-position give a ated zinc and hydrochloric acid to 1:2:3: 4-tctra- Fries change only if one alkyl group is in position 2 and hydronaplithalene-2-carboxylic acid, m. p. 97°. a second in position 5 (homologues of p-xylcnol or H. W r e n . i/rcumenol, 4 : 5-dimethyl-2-etkyl-, 2 : 4-dimethyl-5- Preparation of benzophenone. G. D o u g h erty ethyl-, and 5-methyl-2 : 4-diethyl-phenyl acetates). (J. Amer. Chem. Soc., 1928, 50, 571— 573).— o- The ethyl group is much more readily displaced than Benzoylbenzoic acid (300 g.) is stirred with its copper methyl (cf. 2 : 6-dimethyl-4-ethylphenyl acetate, salt (20 g.) at 200— 260° for about 4 hrs., or until where the Fries change is abnormal in giving rise to a evolution of carbon dioxide has ceased, in a distilling p-compound). When ethyl groups are present in both flask, and the benzophenone then distilled from the ortho- and pora-positions, the ortho-group is eliminated, mixture. The yield is 82—84%, calculated on the the displaced ethyl group wandering into the para- o-benzoylbenzoic acid, after crystallisation from position to that it originally occupied (2-mcthyl-4 : 6- alcohol, m. p. 47— 48°. F. G. W illso n . diethyl- and 2:4: 6-triothyl-phenyl acetates). Other new facts which show the greater valency requirement Preparation of benzophenone by organo-mag'- of ethyl over methyl aro the abnormal Gattermann nesium compounds. Mechanism of the reaction aldehyde and Friedel-Crafts ketone syntheses recorded between organo-magnesium compounds and with 2-methyl-4-cthyl- and 5-methyl-2: 4-diethyl- their carbonated derivatives. D. I van o fe (Compt. anisole. rend., 1928,186,442— 444).— When phenyl magnesium When 2 : 4-dimethyl-6-ethylphenyl acetate under­ bromide is treated at —20° with half an equivalent of goes the Fries change, both a methyl and an ethyl carbon dioxide for 8 lirs., a 60% yield of benzophenono group are displaced by the entering acetyl groups, but is obtained on hydrolysis, with 2—3% of triphenyl - in 2-methyl-4 : 6-diethylphenyl acetato only the ethyl carbinol; the reaction is unsuccessful with other is displaced. Again, whilst 2-methyl-6-ethylphcnyl ketones. From anhydrous magnesium benzoate and acetate gives mainly 4-hydroxy-3-methyl-5-ethyl- magnesium phenyl bromide a 35% yield of benzo­ acetophenone, some ethyl is displaced, giving 2-hydr- phenone is obtained. If the product of the first oxy-3-methyl-4-ethylacetophenone. Yet with 2 : 6- reaction is treated, before hydrolysis, with benzoyl or diethylplionyl acetate no ethyl displacement occurs. acetyl chloride, no trace of an ester is obtained; it is A further fact showing that methyl is more firmly therefore concluded that the complex CPh2(OMgBr)2, attached than ethyl is that acetyl groups are more is not formed, but rather the complex Ph2CO,MgBr2, readily removed from a hydroxymethyl- than from from which benzophenone can bo obtained by a hydroxyethyl-acetophenone, i.e., ethyl takes up more distillation, although not by extraction. of the nuclear affinity than does methyl. E . W . W ig n a ll. 2 : -I-Dimethyl-6-ethylphenyl acetate, b. p. 242°, [Preparation of] p-dimethylaminobenzophen- gives a mixture of ‘¿-hydroxy-3 : S-dimethyl-i-ethyl- one. C. D. H urd and C. N. W ebb (Org. Syntheses, acetophenone, m. p. 52— 53°, b. p. 153-—155°/11 mm. 1927, 7, 24—26). {oxime, m. p. 157-5— 158-5°; semicarbazone, m. p. Wandering of alkyl groups in the Fries trans­ 235— 236°; p-nilrophenylhydrazone, m. p. 212— 214°), formation. K. v o n A u w e r s and W . M au ss and 2 - hydroxy -4:5- dimethyl - 3 - ethylacetophenone (Annalen, 1928, 460, 240—-277).—A continuation of {semicarbazone, m. p. 219— 221°, p-?iitrophcnylhydr­ previous work (A., 1927, 608). The Fries trans­ ążone, m. p. 179— 183°). The former acetophenone is formation has been effected with a number of other converted into 2 : i-dimethyl-3 : G-diethylphenol, m. p. polyalkylphenyl acetates, using the methods of rapid 59-5— 60-5°, b. p. 250— 252°. 4 : 5-Dimethyl-2-ethyl- or of slow heating with aluminium chloride. In order anisole, b. p. 218— 220°, from the corresponding to determine whether wandering of alkyl has occurred phenol, alkali, and methyl) sulphate, is converted by or not during the transformation, the acetyl group is acetyl chloride and aluminium chloride into an oil removed from the resulting hydroxyacetophenone and from which only 2-hydroxy-5 : G-dimethyl-3-ethylacelo- the new phenol identified. Phosphoric acid used phenone, a yellow oil, b. p. 143— 145°/11 mm. .{oxime, formerly for this removal is often less effective than in. p. 153— 154° ; p-nitrophenylhydrazone, m. p. 251— boiling glacial acetic-hydrobromic acid. In general 253°), is obtained. It gives the original dimethyl- o-andp-hydroxyacctophenones are separable by steam ethylphenol when boiled with hydrobromic-acetic distillation. acid and when reduced (Clemmensen) affords 3 : 4- The new results show that an alkyl group in the dimethyl-2 : G-diethylphenol, m. p. 47— 48°, b. p. 246— E E 418 BRITISH CHEMICAL ABSTRACTS.— A.

248°. 3-o-Xylyl acetate, b. p. 220—228°, is converted 4-methyl-2 : 3 : G-triethylphenol, a yellow oil, b. p. only into 2-hydroxy-3 : 4-dimethylacetophenone, a steam - 242— 244°. volatile yellow oil, b. p. 122— 124°/12 mm. (p-nitro- o-Methyl-2-ethylanisole, b. p. 200°, gives a very little phenylhydrazone, m. p. 216—218°), undergoing re­ '2-hydroxy-6-methyl-3-ethylphenol, b. p. 137— 138°/ duction to 2 : 3-dimethyl-6-ethylphenol, m. p. 53— 54°. 12 mm., and mainly 4-methoxy-2-methyl-5-ethylaceto- The methyl ether, b. p. 216— 218°, of the latter gives phenone, m. p. 29— 30°, b. p. 139— 140°/12 mm., 4-methoxy-2 : 3-dimethyl - 5 - ethylacetophenone, steam- converted by hydrobromic-acetic acid into 5-methyl- volatile, b. p. 138— 140°/12 mm., which on reduction 2-ethylphenol and reduced to b-methyl-2 :4 -diethyl­ affords 2 : 3-dimethyl-4 : 6-diethylanisole, b. p. 234— anisole, b. p. 222— 224°. The latter is demethylated 236°, demethylated to 2 : 3-dimethyl-4 : Q-diethyl- normally to give 5-methyl-2 : 4-diethylphenol, b. p. phenol, b. p. 244— 246°. 4 : 5-Dimethyl-‘2-ethylphenyl 247— 249° (, m. p. 109— 110°), the acetofe, acetate, b. p. 247— 249°, is converted (Fries) into a b. p. 258— 260°, of which under Fries’ conditions steam-volatile mixture of hydroxyacetophenones, affords a mixture of 2-liydroxy-5-methyl-3 : 4-diethyl­ b. p. 145— 147°/12 mm., which when reduced gives acetophenone and (?) 2-hydroxy-3:5-dimethyl-6-ethyl- 3 : 4-dimethyl-2 : 6-diethylphenol, but is not separable. acetophenone. Acetyl chloride (A1C13) and 5-metliyl- Fractionation of the yi-nitrophcnylhydrazoncs shows 2 : 4-diethylanisolo give a mixture of 2-hydroxy- the presence of 2-hydroxy-5 : 6-dimethyl-3-ethyl- and 4-methyl-5-ethylacetophenone, m. p. 94— 95°, and 2-hydroxy-4 : 5-dimethyl-3-ethyl-acetophenone. 2-?nethoxy-G-methyl-3 : 5-diethylacetophenone, a pale 2 : 4-Dimethyl-Q-elhylanisolc, b. p. 210— 211°, slowly yellow oil, b. p. 146— 148°/li mm., the oily oxime of reacts with acetyl chloride (A1C13) to give some 2 :4- which when boiled with 20% hydrochloric acid gives dimethyl-6-ethylphcnol, and, as the mam product a base (cf. A., 1924, i, 743; 1925, i, 264, 265). R e­ (semi-solid, b. p. 17S—182°/15 mm.), 3-hydroxy- duction of the methoxyacetophenone gives 3-methyl- 2 : G-dimethyl-4-eihylacetopkenone (possibly containing 2:4: 6-triethylanisole, b. p. 252— 254°, converted by some 3-hydroxy-4 : 6-dimethyl-0-ethyl isomeride, and aluminium chloride into 3-methyl-2 : 4 : 6-triethyl- converted by phosphoric acid into 2 : 4-dimethyl-6- phenol, b. p. 256— 258° (sodium salt, sparingly ethylphenol), the constitution of which follows from soluble). its reduction to 2 : 4-dimethyl-3 : 6-diethylphenol. Reduction of 4-hydroxy-2-methylacetophenone Reduction of 3-liydroxy-4 : 6-dimethylacetophenone gives 3-methyl-4-ethylphenol, b. p. 228— 230°, the affords 2 : 4-dimethyl-5-ethylphcnol, m. p. 39— 40°, acetate, b. p. 239— 240°, of which undergoes Fries b. p. 242— 244°, the acetate, b. p. 254— 256°, of which transformation into 2-hydroxy-4-methyl-5-ethylaceto- is transformed (Fries) mainly into 2-hydroxy-3 : 5- phenone, reduced to 5-methyl-2 : 4-diethylphenol. dimethyl-4-etliylacetophenono (converted in poor 2-Methyi-4-ethylphcnol gives a benzoate, m. p. 47— yield by phosphoric acid into 2 : 4-dimcthyl-Z-ethyl- 49°, and an acetate, b. p. 238— 240°. The latter is phenol, m. p. 70— 71°) together with some 2-hydroxy - converted (Fries) into 2-hydroxy-3-methyl-5-ethylaceto- 3 : 5-dimethyl-6-ethylacetoplienonc, isolated only as plienone, a yellow oil, b. p. 129— 131°/11 mm. (p-niiro- the impure oxime, m. p. 120— 125°. phenylhydrazone, m. p. 196— 198°), which is reduced to In an attempt to synthesise 2 : 6-dimethyl-4- 2-methyl-4: G-diethylphenol, b. p. 234— 236°. The ethylphenol, 2-methyl-4-ethylanisole was treated with acetate, b. p. 250— 252°, of the latter undergoes Fries hydrogen cyanide and chloride in presence of alumin­ change to 2-hydroxy-3-methyl-4 : 5-diethylacetophenone, ium chloride and benzene. The main product was m. p. 50— 51° [oxime, m. p. 125— 126°, gives no base, 4-methoxy-3-methylbenzaldehyde, since it was reduced when boiled with hydrochloric acid; p-nitrophenyl- to 4-m-xylenol, the by-product being 2-hydroxy- hydrazone, m. p. 187— 190°), which on reduction 3-niethyl-5-ethylbenzaldehyde, a yellow oil, b. p. 120— affords '¿-methyl-3 : 4 : G-triethylphenol, m. p. 28— 29°, 122°/12 mm. [p-nitrophenylhydrazone, m. p. 167— b. p. 252°. 169°). The dimetliylethylphenol was successfully Whilst phenyl acetate under Fries’ conditions gives synthesised from 2-m-xylenol. The acetate, b. p. a 50% yield of p- in addition to o-hydroxyaceto- 214— 216°, of the latter was treated in the cold with phenone, the method of Wha (Diss., Kiel, 1928 : aluminium chloride and the mixture then slowly acetyl chloride and aluminium chloride on phenol in heated to 120° (see below). Some 2-m-xylenol and nitrobenzene solution) gives a 70% yield of p-com- (mainly) 4-hydroxy-2 : G-dimethylacctophenone, m. p. pound. Reduction of the latter gives p-ethylphenol, 150— 151° (sodium salt, sparingly soluble), were the acetate of which (Fries) gives 2-hydroxy-5-ethyl- formed. The latter was deacetylated normally to the acetophenone, a yellow oil, b. p. 119— 121°/12 mm. original xylenol and reduced to 2 : 6-dimethyl-4-ethyl- [oxime, m. p. 118— 119°), reduced to 2 : 4-diethyl­ phenol, m. p. 3G—37°, b. p. 228— 230°. The acetate, phenol, b. p. 228— 230° [phenylcarbamate, m. p. b. p. 245— 247°, of this substance is converted (Fries) 96— 99°). The acetate, b. p. 242— 244°, of this mainly into 4-hydroxy-3: 5-dimethyl- and some substance under Fries’ conditions passes into 2-hydroxy- 2-hydroxv-3 : 5-dunethyl-4-ethylacetophenone. Re­ 3 : o-dielhylacetophenone, a yellow oil, b. p. 138— 140°/ duction of 2-hydroxy-5-methyl-3-ethylacetophenone 12 mm. (p-nitrophemjlhydrazone, m. p. 136— 138°), gives 4-melhyl-2 : G-diethylphenol, m. p. 48— 48-5°, ivhich is reduced to 2:4: G-triethylphenol, b. p. b. p. 229—230° (benzoate, m. p. 103— 103-5°), the 244— 246°. 2:4: G-Triethylphenyl acetate, b. p. 261— acetate, b, p. 242—243°, of which affords (Fries) 262°, undergoes Fries transformation into 2-hydroxy- 2-hydroxy-5-melhyl-3 : 4-diethylacetophenone, a yellow 3:4: 5-triethylacetophenone, a yellow oil, b. p. 153— oil, b. p. 136— 137°/12 mm. [oxime, m. p. (?) 108— 109°; 155°/12 mm., together with (?) some 2-hydroxy- semicarbazme, m. p. 228—229° ; p-nitrophmylhydr- 3:5: 6-triethyIacetophenone, not isolated. azone, m. p. 254— 256°], undergoing reduction to 2-o-Xylyl acetate when heated rapidly with ORGANIC CHEMISTRY. 419 aluminium chloride at 130— 140° gives only 4-hydroxy- cold alcoholic solution gives 3 : a-diphenyl-A-methyl- 3 : 5-dimcthylacetophenone, whereas 2-methyl-Q-ethyl- oxazolone, m. p. 113— 114°. Similarly the N-cor6- phenyl acetate, b. p. 220— 222°, under Fries’ conditions el/wxy-derivative, m. p. 56—58°, of a-anilinobenzyl gives somo 2-hydroxy-&metJiyl-5-ethylacetophen6ne, methyl ketone, m. p. 90— 91°, yields 3 : ■l-diphenyl-5- steam-volatile, b. p. 130—132°/12 mm. (p-nitro- methyloxazolone, m. p. 162-5°, also formed by the phenylhydrazone, m. p. 191— 195°), but chiefly action of 50% sulphuric acid on a hot alcoholic solu­ ‘L-hydroxy-3-methyl-5-ethylacetophenone, m. p. 95-5— tion of the above phenylurethane. Hydrolysis of 96-5°. this oxazolone with alcoholic potassium hydroxide Fries’ conditions convert o-ethylphenyl acetate into regenerates a-anilinobenzyl methyl ketone. Benzoin- 2-hydroxy-2-elhijlacetophenone, b. p. 213° (p-w'tro- phenylurethane affords 3 :4 :5-triphenyloxazolone, phenylhydrazone, m. p. 213— 217°), reduced to m. p. 214— 214-5° (McCombie and Parkes, J.C.S., 2 : 6-diethylphenol, the acetate, b. p. 238— 240°, of 1912, 101, 1994, give m. p. 210°). which when rapidly heated under Fries’ conditions a-Bromoisobutyrophenone is decomposed by gives a little o-hydroxyketone (?), but mainly sodium hydroxide in dilute alcoholic solution into i-hydroxy-3 : 5-diethylacetop>henone, m. p. 92— 92-5°. benzoyldimethylcarbinol (semicarbazone, m. p. 188°; 3 : 5-Diethylphenyl acetate, b. p. 250— 251°, is acetate, b. p. 148—150°/14 mm., m. p. 61°). Acetyl- converted (Fries) into 2-hydroxy-4 : Q-dicthylaceto- phenylmethylcarbinol (semicarbazone, m. p. 183— phenone; b. p. 140°/12 mm. (sodium salt, sparingly 184°) is aeetylated by acetyl chloride, forming the soluble), which with boiling 84% phosphoric acid gives acetate, b. p. 152— 154°/14 mm. (semicarbazone, m. p. 3 : 5-diethylphenol. 183°). Benzoylcarbinolsemicarbazone acetate, has m. p. The colour reactions of the liydroxy-compounds 148— 149°. Numerous spectrochemical data for the with ferric chloride are noted. Some compounds above ketols and esters are tabulated. such as 4-hydroxy-3 : 5-diethylacetophenone give no H. B u r to n . colour with this reagent. E. E. T u r n e r . Tautomerism of a-diketones. Two forms of benzylmethylglyoxal and their reversible trans­ Benzoylmethylcarbinol and acetylphenyl- formation. H. M o u r eu (Compt. rend., 1928, 186, carbinol. II. K. v o n A u w e r s and H. M auss 380— 382; cf. A., 1927, 246, 1173).— Distillation of (Biochem. Z., 1928, 192, 200— 229; cf. A., 1924, i, the hydrolytic product of the intermediate piperidide 384).—Benzoylmethylcarbinol (a-ketol) and acetyl- (Dufraisse and Moureu, this vol., 180) gives benzyl­ phenylcarbinol (p-ketol) furnish the same semi- methylglyoxal (I), yellow’, b. p. 104°/10 mm., in. p. carbazono, m. p. 193°, tliiosemicarbazone, m. p. 197°, 17— 18°, which when kept in a sealed tube undergoes and phenylurethane, m. p. 143— 144°. To explain after several hours or days spontaneous transform­ these reactions it is assumed that each ketol reacts ation into a colourless form (II), b. p. 134°/10 mm., as a mixture of OH-CPh-O-CHMe and m. p. 69— 70° (Dufraisse and Moureu, loc. cit.). t I Treatment of (I) with traces of alkali in the cold Ph• Cli• O• CMo-OH. Oxidation of the semicarbazone causes transformation into (II), the rates of change I I being a few seconds for diethylamine and piperidine, prepared from a-ketol with lead peroxide and acetic 12 min. for potassium hydroxide, and 3 days for acid at 50° affords phenylmethylglyoxalsemicarb- benzylamine. When (II) is heated with the same azone, m. p. 211° (cf. Diels and van Dorp, A., 1903, catalysts and then distilled there is formed (I). i. 862). a-Ketol (benzoate, m. p.. 106— 107°, cf. H. B ur to n . Zincke and Zahn, A., 1910, i, 316) reacts with p-nitro- Tautomerism of a-diketones. Constitution benzoyl chloride in pyridine to yield p-nitrobenzoic of the two forms of benzylmethylglyoxal. H. anhydride and a-ketol p-nitrobenzoate, m. p. 120— M oureu (Compt. rend., 1928, 186, 503— 505).— 121°, also formed from potassium or silver p-nitro- Benzylmethylglyoxal exists in two tautomeric forms, benzoate and a-bromopropiophenone. Phenyl mag­ A and B. A has the constitution ClI2Ph-CO■ COMe. nesium bromide and a-ketol give aa-diphcnylpropane- The enolic form, B, CHPh;C(OH)-COMe, is far more «P-diol, m. p. 95—96° (monobenzoatc, m. p. 184-5— reactive than A with Grignard reagents, bromine, 185-5°), which when treated with boiling 10% and ferric chloride; it gives an antimony derivative, sulphuric acid gives benzhydryl methyl ketone. From m. p. 184— 185°, and benzoyl derivative, m. p. 82— P-ketol (regenerated from the semicarbazone) and 83°; with o-phenylenediamine it forms benzylmethyl- phenyl magnesium bromide there is obtained a3-di- quinoxaline, m. p. 57—58°. The “ a-phenylaceto- pl.cnylpropane-ap-diol (monobenzoate, m. p. 141— acetaldehyde ” of Weitz and Scheffer (A., 1921, i, 142°), which, contrary to the statement of Neuberg 869) was in reality the above B tautomeride. and Ohio (A., 1922, i, 480), yields with boiling 10% B. W . A n d erso n . sulphuric acid mainly aa-diphenylpropaldehyde, b. p. Influence of anti-auxochromic groups on the — 178°/12 mm, which when oximated and treated halochromy of ketones. P. P feiffer and B. with acetic anhydride affords aa-dipKenylpropionitrile, Segalu (Annalen, 192S, 460, 123— 137).— It is shown b. p. 178— 1S0°/12 mm. Favorsky’s conversion of that the nitro- and sulpho-groups, and to a lesser a- into S-kctol by treatment with alcoltol and sulphuric extent halogen atoms, exert a hypsochromic effect acid at 120— 130° (A., 1926, 500) has not been on the halochromy of unsaturated ketones. The confirmed. meta-directing nitro-group exerts its effect most a-Anilinopropiophenone reacts with ethyl chloro- markedly when it is in the meta-position with respect iormate yielding a.-TA-carbethoxyanilinopropiophenone, to the ethylenic linking, and least when it is in the m. p. 81°, which when treated with alkali in ice- pura-position. The ortho-para directive groups, OH, 420 BRITISH CHEMICAL ABSTRACTS.— A.

OMe, and NH2, best exert their effect, which is batho- phenyl is exceptional in giving the compound chromic, when in the jmm-position to the unsaturated 3CGH4Ph-OMe,2AlCL, the composition of which side-ehain. cannot be accounted for. The preparation of 3-nitro-4-methoxybenzaldehyde The aluminium bromide additive compounds of by the nitration of anisaldehyde is described. The methoxylated ketones have much less deep colours nitro-compound when condensed (this and other con­ than those of the methoxyl-free ketone3, a result due densations now described were carried out in aqueous- to the depression of the bathochromic effect of the alcoholic sodium hydroxide) with acetophenone, gave methoxyl group by its combination with aluminium phenyl 2-nitro-A-methoxystynjl lcetone, yellow, m. p. bromide, and analogous to the similar depression of 146°, whilst with p-methoxyaoetophenone, p -anisyl the bathochromic effect of an amino- or a derived 3-nitroA-methoxystyryl ketone, yellow, m. p. 160°, amino-grouping in perchlorate formation, with un­ resulted. The perchlorate, m. p. 177— 1S0° (decomp.), saturated amino-ketones (Pfeiffer, Kollbach, and of the latter is orange-red, whilst the perchlorate of Haack, following abstract). The group -OMCjAlBiVt, p-anisyl p-methoxystyryl ketone is red. Condens­ in fact, exerts a hypsochromic action. ation of o-nitrostyryi methyl ketone with o-nitro- The discovery that phenol others in general form benzaldehyde affords 2 : 2'-dinitrodistyryl ketone, yel­ additive compounds with aluminium bromide sug­ low, m. p. 170-5—-171°. The known 3 : 3'-isomeride gests that the probable mode of action of aluminium is greenish-yellow, and forms an orange-yellow per­ halides as demethylating agents is to bo repre­ chlorate, 'decomp. 143— 145° (softening at about 125°). sented as follows : It-OMe — > R-OMe,AlBr3 — >• 3-Nilro-4 : 4'-dimethoxydistyryl ketone, obtained either R ■ O-AlBr, -f MeBr — -> It-OH. In actual fact, the from 3-nitro-4-methoxystyryl methyl ketone or from additive compounds now described usually decom­ p-metlioxystyryl methyl ketone, is yellow and has pose smoothly when heated in benzene solution to m. p. 158-5°. 3 : 3'-Dinitro-4 : 4'-dimethoxydistyryl give the aluminium alkyloxybromides, which with ketone, yellow, has m. p. 220°, and forms an orange- water afford the corresponding phenols. It is pointed red perchlorate, m. p. 198° (decomp.). out that aluminium bromide is probably preferable 3-Chloro-4-methoxystyryl methyl ketone, bright yellow to the chloride, since it is readily soluble in benzene from aqueous alcohol or colourless from water, has etc., whilst the chloride is not. m. p. 111-5° and is formed together with some of the Precise directions are given for the purification of distyryl ketone (next below) when acetone is con­ the benzene and other solvents used for the prepar­ densed with 3-chloroanisaldehyde, m. p. 62-5— 63° ation of the aluminium bromide additive compounds* (prepared by the hydrogen cyanide method from a special apparatus being described. Most of the o-chloroanisole; Gattcrmann gave m. p. 53°). With additive compounds derived from methoxylated different proportions of reactants, 3 : 3'-dichloro-4: 4'- compounds lose methyl bromide merely on keeping, dimethoxydistyryl ketone, yellow, m. p. 177-5— 178-5° passing thereby into the aluminium alkyloxy- (perchlorate, chocolate-brown, subl. 153°, m. p. 205— bromides. The same decomposition occurs more 207° deconrp.), is formed. The similarly obtained rapidly in a vacuum at 100— 130°, but is accompanied phenyl 3-chforo-4-methoxystyryl ketone, bright yellowy by side reactions. Quantitative demetliylation is has m. p. 113—-114°. effected by heating the additive compound with 3-Bromo-4-methoxybenzaldehyde, prepared by an excess of benzene, avoiding ingress of moisture. The improved method, is converted by acetone into a above additive compound of aluminium bromide and mixture of 3-bromo-4-methoxystyryl methyl ketone, m. p. methoxydiphenyl is thus converted into a crystalline 101°, with some 3 : 3'-dibromo-4 : 4'-dimethoxydistyryl aluminium methoxydibromide, which with water ketone, yellowy m. p. 181° (perchlorate, deep brownish- affords 4-hydroxydiphcnyl. The additive compound red, but lighter in shade than the bromine-free com­ of p-naphthyl methyl ether with lAlBr3 behave3 pound, has m. p. 168— 169°, decomp.), obtainable similarly. better from bromoanisaldohydc and. bromostyryl Quinol dimethyl ether forms two additive com­ methyl ketone. Phenyl 3-bromo-4-methoxystyryl pounds, one with 1A1Bi-3, one with 2AlBr3. Decom­ ketone, bright yellowy has m. p. 112— 113i , and position of the latter in boiling benzene affords the \t-anisyl 3-bromo-4-methoxystyryl ketone, bright green­ yellow' crystalline compound, AlBr2-0-C6H4-OAlBr2, ish-yellowy has m. p. 120° (perchlorate, orange-red, from which quinol was readily obtained. m. p. 138— 139°). E. E. T u r x e r . p-Methoxyacetophenone gives a compound with 2AlBr3, readily converted into p-hydroxyacetophen- Behaviour of methoxy-compounds towards one. 4 :4'-Dimethoxybenzophenone gives a com­ aluminium bromide. P. P f e if f e r and E . H a a c k pound with 2AlBr3. If this ketone is heated in (Annalen, 1928, 460, 156— 179).—Previous work has benzene solution with aluminium bromide, the yellow' shown that when perchloric acid or stannic chloride R*OAlBr2 compound separates and may be converted forms additive compounds with unsaturated ketones into the corresponding phenol. 4-Methoxy-a- containing methoxyl groups, neither the latter nor naphthyl methyl ketone forms yellow' compounds (1 ) the ethylenio linking are concerned in the compound with lAlBr3, and (2) with 2AlBr3+ C 6H6. The latter formation, which is controlled by the carbonyl group decomposes to give an oily R-0-AlBr2 compound, solely. Aluminium bromide is now shown to form, convertible into the corresponding phenol. with unsaturated ketones, compounds in which each p-Methoxystyryl methyl ketone affords a red com- methoxyl and each carbonyl group can cause the pound with !AlBr3 and a deep yellow compound with union of a molecule of bromide, although here again 2AlBr3, through which demetliylation was effected. the ethvlenic linking plays no part. 4-Methoxydi- Phenyl p-methoxystyryl ketone gives a deep red ORGANIC CHEMISTRY. 421

compound with lAlBr3, decomposing in hot benzene nitrile, prepared by distilling lead terephthalate with without déméthylation, and a honey-yellow com­ lead thiocyanate. Benzaldehyde converts diacetyl- pound with 2AlBr3, decomposing particularly readily benzene in aqucous-aleoholic sodium hydroxide solu­ in hot benzene to give the yellow compound, tion (the condensing method used generally in this Br2A10-C6H4-CH:CHBz,AlBr3, from which thep-hydr- investigation) into 1 : 4-dicinnamoylbenzene (I, R = H ), oxy-ketone was obtained. m. p. 205-5—207-5° (no perchlorate obtainable). p-Anisyl p-methoxystyryl ketone forms a cinnabar- 1 : ‘i-Di-p-mcthoxycinnamoylbenzenc (I, R=p-OMe), red compound with lAlBr3, not undergoing déméthyl­ prepared from anisaldehyde, has m. p. 212° [per­ ation in hot benzene, and a honey-yellow confound chlorate, violet-black), and 1 : ‘i-di-o-chlorocinnamoyl- with 3AlBr3, demethylating with great readiness. benzene (I, R=o-Cl), from o-chlorobenzaldehyde, has 4 : 4'-Dimcthoxydistyryl ketone forms a bright red m. p. 251°, and was not obtained quite pure. compound with lAlBr3, and a honey-yellow compound Acetophenone-4-carboxylic acid has m. p. 210°, not with 3AlBr3, the latter undergoing déméthylation 205° as lit., and is converted normally into p -cinnam- with moderate facility. E. E. T u r n e r . oylbenzoic acid, pale yellow, m. p. 234°, 4-p-methoxy- cinnamoylbenzoic acid, yellow, m. p. 223° (perchlorate, Halochromie compounds of polyketones. P. chocolate-brown, exploding when heated), 4-o-cliloro- Pfeiffer, K . K ollbach, and E. H a a c k (Annalen, cinnamoylbenzoic acid, yellow, m. p. 214— 215°, and 1928, 460, 138— 156).— An investigation devised to i-p-dimethylaminocmnamoylbenzoic acid, reddish- test Pfeiffer’s theory that additive compounds of brown, m. p. 248°. These four substances dissolve ketones and inorganic chlorides etc. are not merely in concentrated sulphuric acid to give reddisli-orange, “ molecular ” compounds but that the oxygen of deep bluish-red, orange, and deep greenish-yellow the koto-group is definitely the prime factor causing solutions, respectively. combination. The theory is apparently proved, for 2 : 4-Diacetylmesitylene is readily converted into in the case of polyketones, additive compounds with 2:4-dicinnamoylmesiiylene (II, R = H ), m. p. 135°, aluminium bromide have been obtained which con­ 2 : i-di-p-methylcinnamoylmesitylene (II, R=p-Me), tain as many molecules of bromide as there are keto- m. p. (-j-lEtOH) 97°, 2 : A-di-p-mcthoxycinnamoyl- groups in the polyketonc. In the case of unsaturated mesitylene (II, R =p-O M c), m. p. ( + JEtOH) 105— ketones, no addition occurs at the ethylcnic linking. 106° or ( + iC 6Hc) 93°, 2 : 4,-di-o-chlorocinnamoyl- Perchlorates of the polyketones were also isolated, mesitylene (II, R =o-C l), m. p. 161°, 2 : i-di-p-chloro- but their composition did not uniformly correspond cinnamoylmesitylene (II, R =p-C l), m. p. 116° (per­ with the requirements of the above theory. chlorate, yellowish-grey, exploding when heated), Some further observations are made on the halo- and 2 : ‘i-bisdimethylaminocinnamoylmesitylene (II, chromy of “ double chalkones,” viz., compounds of R = p-N M c2), m. p. 234° (perchlorate, yellow, exploding when heated). The six last-named ketones give, in type I : R-CbH -CH:CH-C0<^^C0-CH:CH-CgH -R. 4 4 concentrated sulphuric acid solution, the following When R =H , R=p-OMc, ancTR==o-Cl, the diketone colours, respectively: deep greenish-yellow, deep is straw-yellow, bright yellow, and pale yellow, yellow, orange, greenish-yellow, greenish-yellow, and respectively; the solution in concentrated sulphuric yellowish-brown. acid is deep orange-red, deep reddish-violet, and p-Tolyl 4-diphenylyl ketone forms a lemon-yellow orange-red, respectively. Paler halochromy colours additive compound with lAlBr3, xanthone a yellow are shown by compounds of type II, additive compound with lAlBr3 + lC 6He, phenyl styryl R-C6H4-CH:CH-0C Me ketone an orange compound with lAlBr3, distyryl ketone a blood-red compound with lAlBr3, ch-ch-chc 6h4 340°; and p-hydroxybenzylidene-, m. p. 275°, -indan- n H " dionedi-indones (cf. Ill); p -acetoxybenzylidene-, m. p. 0 ,i ^ C 162°; p-toluylidene-, m. p. 151°; m-toluylidene-, m. p. co< >co co< >co 156°, and a-naplithylidene-, m. p. 172°, -indandiones 1 (I.) C6H4 (cf. I ); p -toluylidene-, m. p. 253°; m-toluylidene-, m. p. 236°; anisylidene-, m. p. 233°; piperonylidene-, C^H4< ^ > C H - C H - G H < ^ > C 6H4 m. p. 242°; and u-naphthylidene-, m. p. 230°, -bisdi- GGH5 C indones (cf. IV); the compounds C23H260 3 (VII, R=Pli), m. p. 202°; C24H2803 (VII, R=p-C7H7), c o < > c o m. p. 202°; C24H2S04 (VII, R=p-anisyl), m. p. 247°; (II.) c6h 4 compound (VII) (R=p-acetoxyphenyl), not analysed, in presence of piperidine. Benzylideneindandionedi- has m. p. 234°. Inadequate boiling in the prepar­ indone (II), m. p. 302°, is also obtained from ethyl ation of the compound C23H2G03 leads to the pro­ benzylideneindandionemalonate and dimethyldi- duction of (VI). hydrorcsorcinol. III. [with Y . N. G eoroesch], Methylenebisdi- CGH4CH -CH R-CH CGH4 indone, C37H20O6, yellow, m. p. 273°, gives with alkali 11 in boiling alcohol an indigo-blue, then reddish-violet C colour. Methyleneindandionedi-indonc, C28H160 5, c o < > c o has m. p. 305— 311° (decomp, and subl.), and gives a (III.) c gh 4 reddish-violet solution in alcoholic potash. A. A. E ld rid g e. c 6h 4< 5 $ > c h -c h r -c h < P P > c gh 4 Il II Factors disturbing valency fields. Action of c c substances with an active methylene group on co< >co co< >co the carbindogenides. I— II. M. Y . I onescu and C6H4 (IV.) C6H4 S. S ecareanu (Bui. Soc. Stiinte Cluj, 1926, 3, 112— 128, 250—284; Chcm. Zentr., 1927, i, 601— 602, ii, 71— 72).— I. It has already been shown (Bui. Soc. (V.) C6H4< ^ > C H - C H R - C H < ^ ; ^ “> C M e2 Stiinte Cluj, 1925,2,280) that the absorption spectrum of a chromogen is modified by the introduction of a m e2CH-CHR-CH<^°;^2>GMe2 co-ordinatively unsaturated group, in a measure 2 2 determined by the extent of the unsaturation. (VI.) According to the character of the absorption spectra, the carbindogenides (I) can be divided into (a) those CM c^ggj-^CHR-C^-gg^CM e, where R=phenyl, n-tolyl, w-tolyl, or p-aeetoxy- phenyl, the absorption curve lying below 4800 A., (VII.) A. A. E l d r id g e . (I.) C6H4< g > > C ’:CHR Dinitrobindone and its scission products. W. W islicentts and H. Schlichenmaier (Aimalen, 1928, 4 6 0 , 278— 288).—-Nitric acid (d 1-5) converts bindone (II.) C6H4CH*CHR-CH(C02Et)2 (indandionylideneliydrindone ; Wislicenus, Ber., 1887, 20, 598) in boiling glacial acetic acid solution into and (b) those where R=p-anisyl, 3 : 4-methylencdi- dinitrobindone (I), m. p. 183°. The latter in alcoholic oxyphenyl, p-hydroxyphenyl, or p-dimethylamino- potassium hydroxide affords the red dipotassium salt phenyl, the curve passing 4800 A. Only group (a) of the unstable acid (II, R = O II, R '= H ), m. p. 94°, gives products (II) by addition with ethyl malonate on whilst bromine and aqueous potassium hydroxide account of the presence of the co-ordinatively un- convert (I) into compound (III), pale yellow, explod­ saturated groups OMe, 0 2C’H2, OH, and NMe2. The ing at 117°. When dinitrobindone is treated with p-tolyl derivative, when heated at 175° or treated ice-cold potassium hydroxide and the red solution with cold, concentrated sulphuric acid, does not formed is at once acidified, phthalideneindandione yield a lactone, but is decomposed into its components. (IV,) m. p. 253°, is formed, dinitromethane being Ethyl a-mrbelhoiy-fi-indandion;/l-fi-pheny1propio7i- eliminated at the acidification stage. By prolonged ate, m. p. 10S°; ethyl (i-indaiidionyl-Q-jdienylpropion- heating of dinitrobindone with aqueous potassium ORGANIC CHEMISTRY. 423

hydroxide at 100°, tho potassium salt of dinitro- purpurin (0-243 volt) is in good agreement with that methane, exploding at 204°, is obtained. calculated from the corresponding constants of related compounds, whilst the value similarly cal­ <*•> c.a4c:cco culated for the tautomeride of naphtliapu rpurin (0-308 volt) is considerably higher, thus confirming oH4\ that the tautomeride of lower reduction potential (II.) c 6h 4- \CO-K predominates in the equilibrium mixture, according AJO C(n o ,):n o 2r ' to the above expression, and this is also supported by available data for two indophenols (cf. Clark, A., 1924, ii, 597). From determinations of normal #o:cc:?-^ reduction potentials of lapachol, its derivatives, and (III.) (IV.) a large number of similar compounds it is concluded Alcoholic potassium ethoxide converts (I) into the that both lapachol and wo-[3-lapachol are derivatives deep red potassium salt-ei/w/Z ester (II, R = O E t, of a-naphthaquinone (cf. Hooker, J.C.S., 1896, 69, R '=K ) (+2MeOH). Acidification of this affords the 1381). With regard to the influence of p a on the ethyl hydrogen ester (II, R = O E t, R '= H ), m. p. position of tautomeric equilibrium, it is shown initially 132°, rapidly changing to 124°. The potass- mathematically that the ratio of the equilibrium iumsslb-^methyl ester (II, R =O M e, R '—K) (+2M eOH) constant of the undissociated tautomeride to that and the methyl hydrogen ester (II, R=OMe, R'=H ) of the completely ionised substance is equal to the are formed similarly. The last-named potassium salt ratio of the dissociation constants of the two taut­ is converted by bromine water into the corresponding omerides. tribromodinitro-methyl ester, yellow, m. p. 139°. 4-n- Propoxy - ¡3 - naphtha quino n e, orange-yellow, m. p. Aqueous ammonia converts dinitrobindone into 116°, and 2-n-propoxy-a-naphthaquinone, pale yellow, the lactam corresponding with (IV), m. p. 265°, and m. p. 91°, are described. The following 3-methoxy- dinitromethane, whilst if ammonia gas is passed into 2-alkyl-a-naphthaquinones were prepared by treating a cold benzene solution of dinitrobindone, the red the corresponding hydroxy-derivatives with diazo- ammonium salt-amide (II, R=NH2, R'=NH4), de­ methane: 3-methoxy-2-y-methyl-Aa-butenyl-, m. p. comp. 183°, results. The latter undergoes decoloris- 53°; -2-y-phenyl-Aa-propenyl-, m. p. 90-5°; -2-benzyl-, ation when treated with anhydrous ether. Cold m. p. 83-5°, and -2-diphenylmethyl-a-naphthaquinone, aniline slowly converts dinitrobindone into the red m. p. 112-5°. Details are given of the preparation phenylammonium ao.\b-anilide (II, R=NHPh, R'= of a number of polyhydroxynaphthaquinones (cf. NHjPh), transformed by anhydrous ether into the Charrier and Tocco, A., 1923, i, 1028); the barium free anilide (II, R=NHPh, R'=H) and by warm salt of naphthapurpurin is described. isoNaphth- methyl-alcoholic hydrogen chloride into dinitro­ azarin dimethyl ether, yellow, m. p. 115°, is hydrolysed methane and the phenylimide, orange-yellow, m. p. by aqueous 1% sodium hydroxide solution to a mono- 234°, stable to acids and only slowly hydrolysed by methyl ether, yellow, m. p. 152°, which is very resistant alkalis. When the above lactam, m. p. 265°, is to further hydrolysis. 3-Hydroxy-2-[3-hydroxypro- warmed with aqueous sodium hydroxide, 2-o-carb- pyl-a-naphthaquinone yields 1-methyl-4: 5-benzo- oxybenzoylindandione, obtained anhydrous and coumaran-3 : 6-quinonc (I) when treated with hydro- + lMeOH, m. p. 155— 160°, results (copper salt; bromic acid in glacial acetic acid, and l-methyl-5 : 6- methyl ester, m. p. 123°). Bromination of (II) in benzocoumaran-3 : 4-quinone (II) when treated with chloroform gives the 2 Ammo-derivative, which concentrated sidphuric acid, reverse changes being rapidly passes over into dibromodiketohydrindene, effected in each caso by the action of aqueous sodium m. p. 176°, which is also formed by treating a solution hydroxide, whilst (II) yields (I) when treated with of the acid in sodium hydrogen carbonate with hydrobromic acid (cf. Fieser, A., 1927, 462). F. G-. W il l so n . bromine water. E. E. T u r n e r . 2-Hydroxy-l : 4-anthraqriinone. L. F. F ieser Tautomerism of hydroxyqninones. L. F. (J. Amer. Chem. Soc., 1928, 50, 465— 474).—-When Fieser (J. Amer. Chem. Soc., 1928, 50, 439— 465). treated with aqueous sodium hydrogen sulphite, —Tautomeric equilibrium between 2-hydroxy-a- 1 : 2-anthraquinono yields sodium 1 : 2-dihydroxy- naphthaquinone (a-form) and 4-hydroxy-jl-naphtha- anthracene-i-sulphonate, from which, by oxidation quinone ((3-form) has previously been evidenced (cf. with chromic acid, sodium 1 : 2-anthraquinone-4- Fieser, A., 1927, 59). Since both tautomerides yield sulphonate, red, is obtained. The corresponding the same trihydroxynaphthalene on reduction, the ammonium salt (I) is also obtained by treatment of value of the tautomeric equilibrium constant (K) nitroso-p-anthrol with aqueous sodium hydrogen can be deduced from their respective normal reduction sulphite, and oxidation, with 25% nitric acid, of the potentials, and it is shown that log K~(Ea—E*)j resulting l-amino-2-anthrol-&-sulphonicacid, (+ | H 20), 0-0296. The normal reduction potentials of certain yellow. Treatment of (I) with methyl alcohol and alkyl ethers of the a- and (3-isomerides were deter­ concentrated sulphuric acid affords 2-melhoxy-l : 4- mined, the values for the methyl ethers being 0-353 anthraquinone, yellow, m. p. 217°, which is hydro­ and 0-433 volt, respectively, and K was evaluated lysed by boiling aqueous sodium hydroxide to 2-hydr- assuming that the difference between these two oxy-1 : i-anthraquinone (II), yellow, m. p. 243° (de­ values approximates to that between those for comp.) (sodium salt, orange; silver salt, red; acetate, the two tautomeric hydroxynaphthaquinoncs. The yellow, m. p. 195°). When boiled with acetic an­ measured normal reduction potential of naphtha-- hydride, sodium acetate, and zinc dust, (II) yields 424 BRITISH CHEMICAL ABSTRACTS.— A.

1:2: ‘i-triacatoxyanthracene, m. p. 191°, which, on acid or on heating -with water under 3 atm., methy- oxidation with chromic acid in glacial acetic acid, sticol is obtained. With sodium in anisole i/r-methy­ affords triacetylpurpurin, m. p. 202— 203° (cf. Schunk sticin yields a sodium derivative giving, with acetyl and Roomer, A., 1877, ii, 624). Treatment of the chloride, methyl a-piperoylacetoacetatc. On reduc­ silver salt of (II) with methyl iodide in benzene tion -with hydrogen in acetone solution in presence affords d-methoxy-1 : 2-anthraquinone, yellow, m. p. of palladium-barium sulphate, 4 atoms of hydrogen 198°, together with about half its weight of the are absorbed, affording an oil which gives no copper above 2-methoxy-l : 4-anthraquinone, the former salt, and agitated with 2% sodium hydroxide in ether being completely isomcrised to the latter when gives an orange-brown solution from which carbon boiled with methyl alcohol and sulphuric acid. Allyl dioxide precipitates an oil. Under similar conditions bromide yields, similarly, the following three deriv­ methysticin absorbs 2 atoms of hydrogen, giving atives, in the proportions given : i-allyloxy-l : 2- a product 111. p. 113— 115°. On bromination with antliraquinone (70%), yellow, m. p. 173°, 2-allyloxy- the hydrobromide of pyridine dibromide in chloro­ 1 : 4-anthraquinone (11%), yellow, m. p. 139°, and form, methysticin affords a di&romo-derivative, m. p. 3 - hydroxy-2-allyl-l : i-anthraquinone (10%), yellow, 156° (dccomp.); ^-methysticin under similar con­ m. p. 215°. The o-quinonoid derivative is isomcrised ditions gives a monobromo-dcrivative, probably to the p-quinone when heated at 175°, whilst treat­ methyl a-bromopiperoylacetic acid, m. p. 98°, since ment with cold, concentrated sulphuric acid affords under similar conditions cinnamoylacetone gives 1 - methyl-5 : 6- (Sp -naphtha)coumaran - 3 : 4 - quinone, u-brcnno-a-cinnamoylacetone, m. p. 93—95°, identical orange-red, m. p. 186— 187°. When treated with with the product obtained by the action of bromine warm, dilute, aqueous alkali, the latter yields 3-hydr­ on the copper salt of cimiamoylacctonc in chloroform oxy-2 -^-hydroxy propyl-1 : i-anthraquinone, yellow, solution. These relations between methysticin and m. p. 211—212°. The reduction potentials of a- and (i-mcthysticin are parallel to those obtaining between 3-anthraquinones are from 81 to 101 millivolts lower the chalkones and flavones and support the 1 : 4- than those of the corresponding naphthaquinones, pjTone structure advanced for methysticin : whilst that of a-anthraquinone is 246 millivolts higher r,rr ^ o/N o h ic h -q h -c h ,—CO than that of 9 : 10-anthraquinono. It is concluded that there is complete analogy between a-anthraquinone CH°-

Acylation of thiophen in presence of tin tetra­ 2 :2'-dimethyl-Z-propyl-1 : 1 '-dipiperidyl, b. p. 295— chloride. G. St a d n ik o v and V. K a k o v s k i (Ber., 300°, is characterised by its hydroferrocyanide, 1928, 6 1 , [B], 268— 269).—Addition of tin tetra­ C i J l , nN.,, H,F eQ-6N B, methiodide, C, r'H.,nN„,2I\IeI, chloride to a solution of acetyl chloride and thiophen m p 269— 270°, and picrate, m. p. 191J (attempts to in light petroleum at 0° causes immediate separation recover the base from the picrate are accompanied by of a crystalline complex compound, decomposed by extensive resinification and the volatile product- gives water into thiophen and 2-acetothienone, b. p. 213— a hydrochloride, C15H26N2,2HC1, m. p. 157°); when 214°/760 mm. [semicarbazone, m. p. 188° (cf. A., evaporated with hydrochloric acid the base loses its 1917, i, 278); oxime, m. p. 81°; phenylhydrazone, methyl groups and affords the salt, C15H29N2,2HC1, m. p. 94-5°]. 2-Benzothienone, m. p. 55° (oxime, m. p. 258°. If asbestos impregnated with 20% of m. p. 93°), is prepared similarly. H . W r e n . osmium and 1% of cerium dioxide is used, the hydrogenation is extraordinarily accelerated and the Bromination of tertiary p-ketonic bases and product contains 34-6% of piperidine, 55-8% of synthesis of 3-hydroxy-l-methylpyrrolidine. 0. methylpropylpiperidine, and 91% of 2 : 2'-dimethyl- M annich and T. Gollasch (Ber., 1928, 6 1 , [13], 263— 3-propyl-l : l'-dipiperidyl. If reduction is effected 268).— a-Dimethylaminobutan-y-one does not react in an autoclave provided with a cooled side tube in simply with bromine, whereas its hydrobromide is which volatile products of the reaction can be converted by bromine and hydrogen bromide in condensed during the progress of the change, the less glacial acetic acid into S-bromo-a-dimethylaminobutan- volatile bases are obtained in high yield, thus indicat­ y-one hydrobromide, m. p. 103°, in 65% yield from ing that alkylation of the piperidine occurs in the early which potassium carbonate liberates the corresponding stages of hydrogenation. H. W r e n . unstable base, whereas barium hydroxide converts it into ‘¿-keto-1 : \-dimethylpyrrolidinium bromide, m. p. Local anaesthetics derived from p-piperidyl- 213—215° [oxime, m. p. 209°; ¿-keto-1 : 1-dimethyl- carbinol. L. T. Sa n d b o r n and C. S. M ar vel (J. pyrrolidinium chloride, m. p. 185°, and chloroaurate, Amer. Chem. Soc., 1928, 50, 563— 567).— 3-Piperidyl- m. p. 183° (decomp.)]. Reduction of the chloride by carbinol, b. p. 106—107°/3-5 mm., d f 1-0263, n f sodium amalgam in hydrochloric acid solution affords 1-4964, is obtained in 40—43% yield by reduction of a-dimethylaminobutan-y-ol, which is also produced by ethyl nicotinate with sodium and alcohol. The electrolytic reduction at a lead cathode together with following alkyl derivatives were prepared by the small quantities of '¿-hydroxy-1 : 1-dimethylpyrrol- action of the appropriate alkyl bromides or iodides in idinium chloride (chloroaurate, decomp. 260°), more boiling benzene : N-methyl-, b. p. 110— 112°/7 mm., readily prepared by catalytic hydrogenation in d f 1-0125, n f 1-4988; N-ethyl-, b. p. 110— l l l 0/6-5 aqueous solution under pressure in presence of mm., d f 0-9904, n f 1-4911; N-isopropyl-, b. p. 93— spongy platinum. ¿-Hydroxy-l-methylpyrrolidine, 94°/3-5 mm., d f 0-9881, n f 1-4916; N-n-butyl-, b. p. b. p. 77°/16 mm., obtained by thermal decomposition 100— 102o/4 mm., d f 0-9484, n f 1-4838; and N-allyl- of the above chloride in an atmosphere of nitrogen, ‘¿-piperidylcarbinol, b. p. 110— l ll ° /7 mm., d f 0-9873, gives a chloroaurate, m. p. 191° (decomp.), very n f 1-4982. These were converted into the p-nitro- hygroscopic hydrochloride, metliiodide, m. p. 260°, and benzoate hydrochlorides and p-aminobenzoate hydro­ benzoate hydrochloride, m. p. 146°. y-Piperidino- chlorides by the usual methods, the m. p. of the two methyl-A'-hexen-S-one liydrobromide is hydrogenated derivatives of each carbinol, taken in the above order, in aqueous solution in the presence of palladised char­ being as follows : 187— 190°, 174— 177°; 194— 195°, coal to y-piperidinomethylhexan-^-one hydrobromide, 188— 190°; 196— 200°, 235-5— 237-5°; 197— 198°, m. p. 151° (corresponding base, b. p. 126°/16 mm.). 205—207°; 186— 187-5°, — . The aminobenzoate The salt is transformed by bromine in chloroform hydrochlorides possess relatively low toxicity and solution into r,u- 221°. b. p. 88°/15 mm., is obtained in 40— 50% yield by the c o ~c h ( ^ c h !-c h ! ra- p action of sodamide and methyl sulphate on 2-amino- H. W r e n . pyridine in the presence of ether. Unchanged By-products of the hydrogenation of pyridine primary and secondary amine are removed from the under pressure. V . S. Sa d ik o v and A . K . crude mixture by means of acetic anhydride. The Mikhailov (Ber., 1928, 61, [B], 421— 427).— Hydro­ compound differs from dimethylaniline in its inability genation of pyridine under pressure in presence of to afford a nitroso-derivative or to couple wTitii osmium deposited on asbestos affords ammonia, diazonium compounds. Nitration yields %-nitro-2- piperidine (up to 70% ), and products of high b. p. dimethylaminopyridine, m. p. 154— 155°, and 3 : 5- from which the compounds C9H19N and C15H30O2 are dinitro-2-dimethylaminopyridine, m. p. 125— 126°. isolated. The former compound, regarded as The mononitro-compound is reduced by tin and l-rnethyl-^.propylpiperidine, b. p. 195— 200°, d 0-8415, hydrochloric acid to b-amino-2-dimethylaminopyridine, mol. wt. 151, yields a picrate, m. p. 106— 107°, and m. p. 55— 56° (dihydrochloride, m. p. 225—226°; methiodide, (C9H19N)2,MeI, m. p. 81°. With hydro- chlorostannite, m. p. 148— 150°), which gives the ferrocyanic and hydrochloric acids it appears to give customary diazo-reactions and yields o-iodo-2-di- the substances (C8H17N).,,H4FeC6N8 and C8H17N,HC1, methylaminopyridine, m. p. 55°, and 5-brotno-2-di- m. p. 200°. The latter compound, considered to be methylaminopyridine, m. p. 42— 43°. Bromination of 428 BRITISH CHEMICAL ABSTRACTS.— A.

2-diraethylaminopyridinc in dilute sulphuric acid 6-nitro- (I), m. p. 185— 186°, and 5-nitro-, m. p. 175— gives the 5-bromo-derivative (picrate, m. p. 208°) and 176°, -2-keto-3-acetyl-l-methyl-l : 2-dihydrobenzimin- 3 : 5-dibromo-2-dimcthylaminopyridine, isolated as azoles, which by boiling with alkali are converted the •picrate, m. p. 185— 186°. The 5-bromo-compound into 6-nitro- (II), m. p. 272°, and 5-nitro-, m. p. is also obtained by methylation of o-bromo-2-amino- 300°, -2-lceto-l-melhyl-l: 2-diliydrobenziminazoles. The pyridine with sodamide and methyl sulphate. 2-Di- latter are readily re-acetylated to the parent sub­ methylaminopyridine is converted by sodamide at stances and, by reduction with iron and hydrochloric 190° into dimethylamine and 2 : 6-diaminopyridine. acid, yield the hydrochlorides (+11,0) of the corre­ H . W r e n . sponding 6- and 5-amino-derivatives, whilst by treat­ Constitution of vasicine. I. Synthesis of ment with phosphorus pcntachloride in phosphoryl 4-hydroxy-2-propyl-(and isopropyl)quinazoline. chloride as a solvent they are converted into 2-chloro- A. K . D e and J. N. R a y (J. Indian Chem. Soc., 4, 6-nitro- and 2-chloro-5-nitro-l-methylbenziminazoles. 541—545).—Butyranilide and isobutyranilide con­ Synthesis of (II) is effected by the interaction of dense with ethyl carbamate in boiling xylene solution carbonyl chloride and 4-nitro-2-aminomethylaniline. in presence of phosphoric oxide to give 4-hydroxy-2- By a similar treatment for 72 hrs. 3:4: 6-trinitrodi- propylquinazoline, m. p. 197° (picrate, m. p. 184°), and methylaniline yields 5 : ()-dinitro-2-Jceto-l-methyl-l : 2- 4-hydroxy-2-isopropylquinazolinc, m. p. 227° (de­ dihydrobenziminazole, m. p. 294°, which yields a comp.) (picrate, m. p. 215—216°), respectively. The 3-acetiyl derivative, m. p. 191“, identical with that natural product has m. p. 196° (picrate, m. p. 199°) and obtained by nitration of (I). A similar reaction depresses the m. p. of the propyl derivatives above, applied to nitrodiethylanilines leads to the formation and thus Ghose’s suggested constitution (A., 1927, of derivatives of 3-keto-l : 2 : 3 : 4-tetrahydroquin- 785) is incorrect. Bischler and Lang (A., 1895, i, 250) oxaline. Thus 3 : 6 - dinitrodiethylaniline yields give the m. p. of the propyl and isopropyl derivatives 7-mfro-3-Areto-4-aceft/i-l-ei/M/Z-l : 2 : 3 : 4-tetrahydro- as 205° and 195— 196°, respectively, whilst Niemen- quinoxaline, m. p. 127°, from which, by hydrolysis, towski gives the m. p. of the latter as 224°. 7-nitro-3-keto-l-cthyl-l : 2 : 3 : i-lcirahydroquinoxaline, C. D. L an g fo rd . m. p. 206° (iiiZraso-derivative), is obtained. Similarly, Reactivity of ort/io-diketonic groups placed from 2 : 4-dinitrodiethvlaniline, G-nitro-3-lceto-l-ethyl- between two nitrogen atoms. P. K. De and 1:2:3: i-tetrahydroquinoxaline, m. p. 157°, is A. C. Sircar (J. Indian Chem. Soc., 4, 531— 534).— obtained. J. W. B a k e r . 2-Thio-l : 3-diphenylparabanic acid and o-phenylene- Derivatives of isoindigotin. A. W a h l and diamine (2 mols.) react in boiling pyridine to give F ericean (Compt. rend., 1928, 186, 378— 380; cf. o-phenyleneoxamido, aniline, and.( ?) thionyl-o-phenyl- A., 1927, 470).—Treatment of 5-cliloro- and 7-chloro- enedinminc. s-Diphenylthiocarbamide is probably isatin with hydrogen sulphide (A., 1925, i, 588) formed as an essential intermediate. s-Diphenylthio- affords 5 : 5'-dichloro- and 7 : T-dichloro-disulpho- carbamide and o-phenylenediamine under similar isatide, which are transformed in boiling pyridine into conditions afford aniline and thionyl-o-phenylenedi- 5 : 5'-dicliloro- and 7 :7 '-dichloro-isoindigotins, together amine. Dinitrothiophenylparabanic acid behaves with small amounts of 5-chloro- and 7-chloro-oxindoles like the parent acid. Diphenylparabanic acid affords (the corresponding benzylidene derivatives have m. p. o-phenyleneoxamide and s-diphenylcarbamide. 204° and 185°, respectively). The formation of the C. D. L angford. oxindoles is explained thus : 2C1Gir i0O2N2Cl2S2 — > Reaction of organic halogen compounds with C1GH802N2C12+2C8H60NC1+4S. Reduction of the copper and pyridine. P. K arrer, W. W e h r e i, dicliloro isoindigotins by zinc and acetic acid gives the E. Bie d e r m a n n , and M. dalla V ed o va (Helv. Chim. corresponding ^¿¿co-compounds. Condensation of the Acta, 1928,11,233—239).—When p-toluenesulphonyl chloroisatins with oxindole in presence of piperidine chloride is treated with copper bronze and dry affords the corresponding chloroisatans, which are pyridine there are formed di-p-tolyl disulphoxide, dehydrated by boiling acetic-hydrochloric acids (cf. di - p - tolyldisulphone, dipyridine copper chloride, A., 1924, i, 322) into o-cliloro- and 7-chloro-iso- f(G5H5N)2Cu]CIa, and a compound, probably indigotins. H. B u r to n . C6H4Me-&D3Cu(C5H5N)2. Similar treatment of liippuryl chloride yields AW-dibenzoyldiketopiper- Syntheses in the phenazine series. H. Mc- azine, m. p. 137°, hydrolysed by concentrated hydro­ Com bie, H. A. Scarborough, and W . A. W aters chloric acid to A'-benzoyldiketopiperazine, m. p. (J.C.S., 1928, 353— 359).— The method of Fischer and 205°. Phthalyl chloride furnishes a small amount of Heiler (A., 1893, 266) has been applied to the synthesis diphthaloyl, m. p. 335°. H. B ur to n. of various 1- and 2-substituted phenazine derivatives, the use of anhydrous sodium acetate (Kehrmann and Formation of derivatives of dihydrobenzimin- Havas, A., 1913, i, 298) not being suitable for the azole and tetrahydroquinoxaline by the action preparation of substituted phenazines. The yields in of acetic anhydride and zinc chloride on nitro- all cases are only of the order of 5% of the theoretical. derivatives of alkylanilines. P. v a n R omburgh By heating a mixture of o-chloronitrobenzene, and H. W . H u y se r (Proc. K. Akad. Wetensch. o-toluidine, and anhydrous sodium acetate for 20 hrs. Amsterdam, 1927, 30, 844— S49).— When dinitrodi- at 220—240° a 10% yield of 2-nitro-2'-methyldiphenyl- methylanilines are boiled with zinc chloride and acetic amine, m. p. 76°, is obtained. This, by reduction anhydride for 4— 5 hrs., acetyl derivatives of 2-keto- with alcoholic stannous chloride, yields the corre­ 1 : 2-dihydrobenziminazole are obtained. Thus 3 : 6- sponding 2-amtno-compound, m. p. 64°, which is and 2 : 4-dhiitrodimethylanilincs yield, respectively, converted by heating with litharge at 200— 240° ORGANIC CHEMISTRY. 429

under reduced pressure into l-methylphenazine, m. p. xantliine, this last exhibits acidic properties only. 108° (cliloroplatinate, decomp, above 200°). The same Attempts to prepare 8-iodo-9-phenyh'soxanthine and compound is obtained by the action of sodium 2: 6-di-iodo-7-methylpurine from the corresponding sulphate on 2 : 3-tolylenediamine and o-benzoquinone thiol derivatives by this method were unsuccessful, in anhydrous ether for 2 days. 2-Chlorophenazine, A large number of experiments on the production of m. p. 139°, is similarly obtained by the litharge xanthine from uric acid and 8-thiouric acid are method from 4-chloro-2-nitrodiphenylamine, whilst described. The optimum conditions, which must be 2-bromophenazine, m. p. 150°, is obtained from closely followed, for its preparation by Sundvik’s M-bro)no-2-aminodiphenylamine, m. p. 128°, obtained method (A., 1912, i, 321), a re: a mixture at 170° of by the reduction of 4'-bromo-2-nitrodiphenylamine, 500 c.c. of glycerol, 50 c.c. of 95% formic acid, and m. p. 167°, which is prepared by the interaction of 20 g. of crude uric acid is warmed during 30—40 min. o-chloronitrobenzene and p-bromoaniline. By similar to 230°, maintained at this temperature until 3— 10 methods, 2-nitroA'-mcthoxydiphenylamine, m. p. 89° min. after dissolution is complete, cooled rapidly, and (for which crystallographic data are given), is prepared poured into water. The xanthine (G g.) is extracted and reduced to the corresponding 2-ammo-compound, from the unchanged uric acid by 2Ar-hydrochloric acid m. p. 78°, from which 2-methoxypKenazine, m. p. 126° and completely freed from the latter by prolonged (chloroplatinate, decomp, above 250°), is synthesised, digestion with 23% nitric acid. Coloured impurities This compound is not identical with liemipyocyanine are removed by reerystallising the sodium salt. The (Wrede and Straclc, A., 1925, i, 844). A similar physical properties of xanthine, its lack of reactivity, attempt at ring closure with 2-amino-2'-mctlioxydi- and its insolubility in all chemically indifferent phenylamine, m. p. 58°, obtained by reduction of the solvents (except “ polyglycol,” from which it separates 2-nifro-compound, m. p. S3°, leads only to the pro- in microscopic crystals) indicate that, like cellulose, duction of phenazine, instead of the 1-mcthoxy-deriv- it is probably in a higldy associated molecular con­ ative. Reduction of 2-nitrodiphenylamine-2'-carb- dition. It affords a characteristic perchlorate (+ H 20), oxylic acid yields the 2-amino - derivative, m. p. 204° m. p. 262—264°, sintering from 250° (crystallographic (ammonium and double tin salts; hydrochloride, data), also a hydrobromide (+ H ,0 ), hydriodide decomp. 240°), but attempts to effect ring closure in (+H 20), decomp. 220°; fliioborate; hydrofluoride, order to synthesise a substance having the seven- C5H402N4,2HF; clilorostannite, membered ring lactam structure, assigned by Wrede (05H402N4)2,H2SnCl4,H20 , and zincichloride, and Strack (loc.cit.) to hemipyocyanine, were unsuccess- [Zn((%H40 2N4)2]Cl2, decomp. 310— 350°. Theo-, ful. The free amino-acid by heating or by treatment bromine perchlorate (-f HaO), decomp. 271—273°, with concentrated sulphuric acid yields a green sinters from 250°. Unsuccessful attempts to chlorin- substance, m. p. 255° (decomp.). J. W.- B a k e r . ate, brominate, and acetylate xanthine are described. The literature relating to the alkylation of xanthine I. 8-Iodoxanthines. II. Preparation and derivatives is comprehensively reviewed. Further properties of xanthine. III. Alkylation in the examples of the use of (a) diazomethane, (6) methyl xanthine series. TV [with R. L emberg] E thyl- sulphate and alkali, are given. Ethyl bromide may be ation of ^-uric acid. H. B iltz and A. B e c k (J. pr. used instead of the iodide with alkali in a sealed tube Chem., 1928, [ii], 118, 149— 224).—In continuation of at 100° (c), or under reflux (d). The thiol group in previous work (cf. A., 1922, i, 380— 384) it is shown 8-thiolxanthines may be alkylated in alkaline solution that 8-thiouric acids which have a hydrogen atom in at the ordinary temperature by means of methyl the 7- or 9-position (8-thiolxanthines) are converted iodide (e) or ethyl sulphate (/). The following com- by iodine and sodium hydrogen carbonate into pounds have been prepared by these methods : 8-iodoisoxantkines and 8-iodoxanthines, respectively, caffeine from xanthine (a)(6), or theophylline (b); Thus, 8-thio-l : 9-dimethyluric acid (A., 1921, i, 612) 8-bromocaffeine from 8-bromotheophylline (6); yields S-iodo-1 : Q-dimethyl-A! '8-i3oxanthine, dccomp. 7-ethyl theophylline from theophylline (c); 8-bromo- 280—320°, darkening from 230°, which is reduced by 7-ethyltheophylline from 8-bromotlieophylline (c); hydriodic acid to 1 : 9-dimethyli’soxanthine; 8-thio- 8-meihylthioltheobr online, m. p. 263°, from 8-thioltheo- 1:3: 9-trimetbyluric acid yields 8-iodo-l : 3 : 9-tri- bromine (e); S-methylthioltheophylline, m. p. 307— methyl-tf -Z-isoxanthine, m. p. 260—265°, losing iodine 310°, from 8-thioltheophylline (e); S-methylthiol- from 225° (periodide, C8Hg0 2N4I2), which is reduced caffeine from 8-thiolxanthine and its lower methyl- to tsocaffeine; 8-thio-?> : 7-dividhyluric acid, m. p. ation products (a)(6); 8-elhyUhiolxanthine, m. p. 302° 335—337° (decomp.), prepared from 8-chloro- or (decomp.), from 8-thiolxanthine (/); 8-ethylthiol- 8-bromo-theobromine and potassium hydrogen sul- theobromine, m. p. 217°, from 8-thioltheobromine pliide, yields 8-iodotheobromine, m. p. 330— 335°, (d)(f); 8-ethylthioltheophyUinc, m. p. 249°, from decomp, from 250°; 8-thio-l : 3-dimethyluric acid, 8-tliioltheophylline (d)(f); 8-ethylthiolcajfeine, m. p. decomp, 320° (cf. Boehringer & Söhne, A., 1903, i, 137°, from 8-thiolcaffeine (d)(f); S-ethylthiol-l-ethyi- 868), prepared from 8-bromotheophylline (A., 1914, i, theobromine, m. p. 136°, from S-thioltheobromine (c, 686), yields 8-iodotheophylline, decomp. 303—305°, at 80°). 8-Bromo-7-ethyltheophylline and potassium altering from 250°, which is reduced to theophylline; hydrogen sulphide afford 8-thiol-l-ethxjllheophylline, 8-thio-l : 3 : 7-trimcthyluric acid yields 8-iodocaffeine, m. p. 264°, from which 8-ethylthiol-1 -elhyltheophylline, m. p. 230°, and 8-thiouric acid (cf. Fischer and m. p. 115°, is obtained by methods (c) and (/) and the Tüllner, A., 1902, i, 664), prepared by an improved S-methylthiol derivative, m. p. 128°, by (6). When method, yields 8-iodoxanthine, decomp, from 200° 8-thioltheobromine is refluxed with allyl bromide and (potassium, sodium, and ammonium salts]. Unlike 10% potassium hydroxide it yields a mixture of 430 BBITISH CHEMICAL ABSTEACTS.— A.

8-attyltMoltheobromine, m. p. 212°, and 8-aUylthiol-l- Diphenylisooxazolone. Tautomerism of iso- alli/ltheobmniine, m. p. 118°, whilst 8-thiolcaffeine is oxazolones. E. P. K oh ler and A. H. B latt (J. similarly converted into 8-aJlylthiolcajfeine, m. p. Amer. Chem. Soc., 1928, 504— 516).-—When an 97— 100°. Diallyl ether is obtained in high yield by ethereal solution of diphenyh'sooxazolone is shaken heating allyl bromide with 50% potassium hydroxide with aqueous copper acetate, the mixed copper salt, in a sealed tube at 100°. O15H10O2KCuO-OAc, deep blue or purple, is precipit­ Attempts to ethylate i/>-uric acid or potassium ated. A magnesium bromide salt is obtained by7 .//-urate using ethyl sulphate or bromide, to mcthylate adding the i'sooxazolono to excess of ethereal magnes­ it with diazomethane or with methyl alcohol and ium ethyl bromide. Treatment of diphenyltsooxazol- hydrogen chloride, and to prepare carbethoxv- and one with bromine in carbon tetrachloride affords carbomethoxy-derivatives from it, were unsuccess­ 4-6romo-3 : 4-diphenylisooxazolone, m. p. 72°, whilst ful. H. E. F . N otton . phosphorus pentachloride in chloroform yields similarly i-chloro-S: k-diplienylisooxazolone, m. p. Transformation of hæmin and mesohæmin into 77— 18°. Diphcnydhsooxazolone is readily7 oxidised isomerides. R. K u h n and C. Seyffert (Ber., by ferric chloride, aqueous bromine, nitrous and 1928, 61 , [B], 307—314).—Attempts to acetylate nitric acids, potassium permanganate, and potassium œ-chlorohæmin by acetic anhydride in the presence of ferricyanide, with formation of the etlier chloroform and pyridine result in its isomérisation to CPh.'C— O— CPh-CO alio hæmin. The anhydride is the essential reagent ^>0 I >>0, m. p. 154— 156° (decomp.), and the same effect may be (less advantageously) GPhlN CPh=N produced by a large excess of boiling acetic anhydride. the constitution of which is established by its oïfoHæmin differs from hæmin I in crystalline habit, formation by condensation of the sodium salt of free solubility in chloroform, arid insolubility in cold diphenydfsooxazolono and the above 4-bromo-deriv- 2AT-sodium carbonate or boiling O02d/-disodium ative in ether. Bromine titration of alcoholic solutions hydrogen phosphate. The spectra of the two com­ of diphenydisooxazolone indicates the presence, in pounds are identical in dry or moist pyridine within solution, of the enolic tautomeride to the extent of the limits of experimental error. oKoHæmin loses the about 90% after equilibrium is established, whilst the FeCl group very slowly when acted on by formic acid lower results obtained with fresh solutions indicate and iron powder under the conditions laid down for that the solid substance is not the enolic modification. the preparation of protoporphyrin. With phosphonium Methylation of diphenylisooxazolone by a variety of iodide and hydriodic acid it gives mesoporphyrin much methods yields always 'N-rnethyl-3 : i-diphenyliso- more easily and in a purer form than does hæmin. oxazolone, m. p. 92°. The latter is unaffected by7 When boiled with methyl alcohol containing sulphuric boiling concentrated hydrochloric acid, but yields acid it affords tetramethylkæmatoporphyrin isolated deoxy7benzoin and benzoic acid when boiled with as complex iron salt agreeing in m. p. 178— 180° and methyl-alcoholic potassium hydroxide. The N-benzyl crystalline form with the product obtained by Fischer derivative has m. p. 123°, and behaves similarly7. and Lindner (A., 1927, S86) from hæmin. Catalytic Treatment of the methyl derivative with ozone hydrogenation in chloroform causes loss of iron. in carbon tetrachloride yields benzoydformic acid. With methyl-alcoholic hydrogen chloride it affords a Treatment of diphenydi'sooxazolone with benzoyl crystalline dimethyl ester similar to that obtained chloride yrields a benzoyl derivative, m. p. 138— 139°, from hæmin dimethyl ester and acetic anhydride whilst treatment of the sodium salt with ethereal in pyridine-chloroform ; it is uncertain whether the ethyl chloroformate affords a carbelhoxy-derivative, compounds are identical with one another and with m. p. 109— 110° after softening at 103°. Neither of Kiister’s hæmin dimethyl ester. If a solution of these derivatives forms an ozonide, but both are aifohæmin in chloroform is poured into hot, glacial readily hydrolysed with regeneration of the iso- acetic acid, kcemin II is precipitated. In solubility oxazolone, from which it is concluded that the acyl and spectroscopic behaviour, hæmin II is very derivatives have probably an O-acyl structure. similar to acetic acid hæmin (hæmin I), but differs Diphenylisooxazolone is very slowly attacked by 6% from it in crystalline habit and probably is a modi­ ozone, but does not yield an ozonide or any normal fication of the latter substance. In pyridine-acetic decomposition products of such a derivative, from anhydride, hæmins I and II yield the same allo- which it appears that the possible tautomeride, hæmin. aZZoHæmin, unless carefully freed from enclosed acetic anhydride, is gradually isomerised if C-Ph ^ ° es not ex^st’- F- G. W illso n . exposed to moist air, whereas the homogeneous com­ pound is stable. Preparation of thiolbenzthiazoles. L. B. Under similar conditions, mesohæmin is isomerised S ebrell and J. T epbema.— See B., 1928, 152. to allomeso/tœmm, C.MH,sOjN4ClFe, differentiated from the initial material byr insolubility in 2AT-sodium Heterocyclic dyes. K . F uchs and E. G r a n a n g carbonate and free solubility in chloroform. It is (Ber., 1928, 6 1 , [B], 57— 65).— Heterocyclic dyes are re-converted into mesohæmin by crystallisation from described analogous to pinacyanol but containing the glacial acetic acid. Manganesemesohæmin is iso­ group IGH-N.’N- in place of .'CH-GHICH-. They act merised by boiling acetic anhydride to allomungrnnese- as powerful desensitisers towards the photographic mesohccmin, C34H360,1N4C]Mn, readily soluble in plate whether in pre-treatment or as an addition chloroform but insoluble in cold 2Ar-sodium carbonate. to the developer. CM-Phenylethydthiocarbamidc is H. W h e n : transformed by7 bromine in chloroform solution into ORGANIC CHEMISTRY. 431

174°; . l-o-nitrophenyl-'i-allyltliiosemicarbazide, m. p. 1-imino-2-ethylbenzthiazoline, C6H4<^?^!]>C!NH, 160°; l-o-aminophenyl-i-allylthiosemicarbazide hydro­ m. p. 83— 84° (cf. Besthorn, A., 1910, i, 507), con­ chloride, m. p. 247—248° (decomp.); l-phenylthio- verted by nitrons acid into the corresponding carbamido-2-phenylthiosernicarbazidobenzene, m. p. wiZroso-derivative, decomp. 131— 131-5°, passing in above 290°; l-p-tolylthiocarbamido-2-phenylthiosemi- boiling xylene into 2-ethylbenzthiazolone, b. p. 170°/14 carbazidobenzene, not melting at 290°; 1-xylylthio- mm., and reduced by zinc dust and 50% acetic acid carbamido-2-phenylthiosemicarbazidobenzene, not melt­ to 2-ethylbenzthiazolonehydrazone, m. p. 77-5— 78-5°. ing at 290°; l-aUylthiocarbamido-2-phenylihiosemicarb- 2-Iodoquinoline methiodide, prepared from 2-chloro- azidobenzene, not melting at 290°; \-p-iolylthiocarb- quinoline and methyl iodide at a temperature not amido-2-p-tolylthiosemicarbazidobenzene, m. p. 281— exceeding 80°, is transformed by methyl hydrazine- 282°; the substance (I or II), m. p. 200°; 1 -carbamido- carboxylate in boiling alcohol into methyl l-methyl- 2-phenylthiosemicarbazidobenzene, not melting at 290°; 2-quinolonehydrazonecarboxylate, m. p. 167— 168° 1 - phenylcarbamido - 2 -plienylthiosemicarbazidobenzene, (decomp.), converted by boiling hydrochloric acid m. p. above 290°; the substance III, m. p. 145°; the into l-methyl-2-quinolonehydrdzohe, m. p. 126— 127° substance IV (R==Ph) as hydrochloride, m. p. 140°; (decomp.) [hydrochloride ; hydriodide]. Treatment the substance IV (R = C 7H7) as hydrochloride, not of 2-quinolylhydrazine with methyl iodide docs not melting at 290°; the substance V (R=Ph), m. p. afford a ready method for preparing the quinolone 83— 84°; the substance V (R =allyl), m. p. 81— 82° ; derivative. The action of a largo excess of hydrazine 1 - o-benzylideneaminophenyl - i-phenylthiosemicarbazide, hydrate on 2-iodoquinoline methiodide leads mainly m. p. 168— 169°; l-o-(o'-nitrobenzylideneaminophenyl- to the production of the corresponding ketazine, 4:-phenylthiosemicarbazide, m. p. 260°; the substance C20HiSN4, in. p. 257— 258° (perchlorate). 2-Iodo- VI as hydrochloride, m. p. 216— 217°. quinoline methiodide find 2-ethylbenzthiazolone­ hydrazone in boiling alcohol afford the 2-ethyl­ benzthiazolonehydrazone of \-methyl-2-quinolone, m. p. 137— 138° (perchlorate). The necessary aldehydic components for the preparation of the dyes are obtained by the action of p-nitrosodimethylaniline in the presence of piperidine on the quaternary. perchlorates or bromides of the (III.) (IV.) methylquinoline or methylbenzthiazole derivatives followed by fission of the condensation products by /\ n :c (Cch 4-n o 2)-s boiling dilute acid. The dyes from 2-ethylbenzthi- % ^ /N H ------N— =C-N H Ph azolonehydrazone are derived by treating a hot aqueous solution of its hydrochloride or perchlorate (V.) (VI.) with a solution of the corresponding Schiff’s base in C. D. L a n g f o r d . dilute perchloric acid. Those from methyl 1-methyl- Synthesis of nicotine, and Nagai’s work on 2-quinolonehydrazonecarboxylate are obtained by ephedrine. E. S rath and H. B retschneider hydrolysing the latter with boiling, fuming hydro­ (Ber., 1928, 61, [15], 327— 334).— Pyrrolid-2-one, pre­ chloric acid and adding a solution of the requisite pared by the reduction of succinimide at a lead aldehyde. The following compounds are described : cathode, is converted by methyl sulphate and sodium 2-ethylbenzthiazolenylhydrazone of pyridine-2-aldehyde in presence of benzene into l-methylpyrrolid-2-one, methobromide, decomp, (indef.) 234— 237°, quinoline-2- b. p. 82— S4°/10 mm., transformed by ethyl pyridine- aldeliyde methoperchlorale, decomp, (indef.) 230— 235°, 3-carboxylate in presence of sodium ethoxide and and benzthiazole-l-aldehyde methoperchlorale, decomp. benzene into 3' : 1 '-methylpyrrid-2-onyl 3-pyridyl ketone, 260—262°; l-methyl-2-quinolenylhydrazone of quinol- b. p. 152— 154°/0-02— 0-03 mm. (picrate, m. p. 154— ine-2-aldehyde methoperchlorale, decomp, (indef.) 155°). The ketone is converted by hydrochloric acid 210—212°; l-methyl-2-quinolenylhydrazone of benz­ at 130° into '3-pyridyl y-methylamino-n-propyl ketone thiazole-l-aldehyde methoperchlorale, decomp. 253— (chlor&platinate, partial decomp. 180— 185°), which is 255°. H. W r e n . reduced by zinc dust in alcoholic alkaline solution to 3-pyridyl-y-amino-n-propylcarbinol (chloroplatinate, o-Aminophenylhydrazine and heterocyclic decomp. 306—310° after darkening at 200° and compounds derived from it. III. Lengthened shrinking at 285°). With fuming hydriodic acid at o-di-derivatives of benzene and their ring- 100°, a-3-pyridyl-S-methylamino-n-butyl iodide is closure. P. C. G u h a and T. N . G hosh (J. Indian formed from the secondary alcohol and passes in Chem. Soc., 4, 561— 572).—The following compounds alkaline solution into ¿¿-nicotine, identical with the are described: l-o-nilrophenylA-p-tolylthiosemicarb- base obtained by racemising Z-nicotine sulphate in azide, m. p. 176°; 1 -o-aminophenylA-p-tolylthiosemi- aqueous solution at 200°; the picrate, m. p. 217— carbazide, m. p. 252—253° (decomp.); 4-p-tolyl-3- 218°, picrolonale, m. p. 238° (decomp.), and 2:4:6- thiol-l : i-dihydrobenz-l : 2 : ‘i-triazine, m. p. 182° trinitro-m-tolyloxide, m. p. 205— 206° (decomp.), are (corresponding disulpliide, m. p. 97— 98°, decom p.); described. The weak link in the chain is the reduc­ 1 - o - nilrophenyl - 4- (1' : 3' : 4') - xylylth iosemicarbazide, tion of the amino-ketone to the amino-alcohol, which m. p. 112°; l-o-aminophe.nyl-A-(\’ : 3' : ‘i ,)-xylylthio- is accompanied by extensive résinification. This can seniicarbazide hydrochloride, m. p. 255— 256° (de­ be obviated by using the catalytic method in aqueous comp.); 1-xylylthiaildihydrobenztriazine, m. p. 173— suspension in the presence of palladised charcoal. 432 BRITISH CHEMICAL ABSTRACTS.— A.

Nagai’s claim to the elucidation of the constitution more strongly acidic character of the isoacid in com­ and to the synthesis of ephedrine (Ber., 1927, 60, parison with yohimboaic acid is shown by the separ­ [A], 173) is adversely criticised. H. W r e n . ation of the former from solutions with p u 4-4, whereas the latter requires ps 4-8 for separation; Synthesis of evodiamine. Y. A s a h in a and T . this behaviour, combined with the different intervals Oh ta (Ber., 1928, 61, [B], 319— 321; of. A., 1924, of time required for crystallisation of the acids, forms i, 665).—Y-Methylanthranilic acid is converted by ethyl chlorofonnato into JX-methylisatic anhydride, a basis for their ready separation. Comparison of the strengths of the yohimba acids with those of ^ H ^ C O -T ’ m’ ^ ° ’ wkich *s transformed by- simple pyridinemonocarboxylic acids confirms the position 2 for the carboxy-group in y-ohimbenic acid aniline and 3-p-aminoethylindole, respectively, into and possibly in aZZoy-ohimboaic acid. In isoyohim- o-methylamimbenzanilide, m. p. 126°, and 3-(3-o- boaic and yohimboaic acids the carboxy-group appears methylaminobenzoylaminoethylindole, m. p. 113°. The to occupy positions 3 and 4 respectively. These views indole derivative and ethyl orthoformate at 175— receive support in the physiological action of the 1S0° afford r-evodiamine, m. p. 278°, converted by acids compared with that of the pyridinecarboxylic boiling alcoholic hydrogen chloride into isoevodiamine, acids. H. W r e n . m. p. 147°. H. W r e n .

Yohimba alkaloids. IV. G. H a h n and W - Alkaloids of Corydalis cava. XI. Constitution St e n n e r (Ber., 1928, 61, [B], 278— 286; cf. A., 1926, of bulbocapnine. E. Sp a t h , H . H olter, and R. 1263; 1927, 471).— Decarboxylation of yoliimbenic, P osega (Ber., 1928, 61, [2?], 322— 327).— Oxidative isoyolximboaic, and yohimboaic acids affords in each degradation of bulbocapnine under varied conditions case yohimbol, C,,,H21ON2, decomp. 306—307°, [a]'f? confirms the constitution (I) assigned to the alkaloid —100-0° in pyridine, so that the isomerism of the by Gadamer (A., 1911, i, tlireo acids and hence of the corresponding alkaloids 1012 and previous abstracts). depends on difference of position of the carboxv- iNMe Oxidation by nitric acid of group in the molecule. a/ZoYohimboaic acid, on the the methiodide of the metli- other hand, is dccarboxylated to an isomeric com­ ine base obtained by the pound, C19H 2lOX,,, decomp. 230°, [a])? +144-6° in OH,» Emde degradation of bulbo­ pyridine. The difference between the four alkaloids OMeM capnine yields benzeno- does not appear profound, and it is suggested that 1 : 2 : 3 : 4 - tetracarboxylic «//»yohimbine is a hydrogenated product of one of acid, m. p. 233—236° (decomp.), identical with the the three isomeridcs. Yohimbol (meihiodide) is also acid prepared similarly from thobencne and identified obtained by decarboxylation of quebrachoic acid (cf. as the methyl ester, m. p. 129°. Gentle oxidation Hahn, A., 1927, 888). of bulbocapnine by potassium permanganate in Yohimbenic acid methvlbetaine is converted by- alkaline solution affords hydroxy-hydrastinine, m. p. ethyl alcohol and hy-drogen chloride into ethyl 96— 97°. Bulbocapnine methyl ether, m.- p. 129— yohimbenate methochloride, C+H310 3N2C1,4H20 , which 130°, is converted by permanganate into hemipinio is readily reconverted into the betainc by short treat­ acid (identified as the anhydride and ethylimide) ment with potassium hydroxide; similarly, formation and 2 : 3 - methylenedioxy - 2' ; 3'-dimethoxydiphenyl - of the betaine takes place when the additive product 5:6: 6'-tricarboxylic add, m. p. 25S— 260° (decomp.) from methyl iodide and yohimbene or ethyl yohimben­ {anhydride, m. p. 266— 267°). Bulbocapnine ethyl ate is treated with alkali. Since a like result is ob­ ether, from the alkaloid and diazoethane in alcohol- tained with yohimboaic acid methylbetainc (Spiegel's ether, is oxidised to 4-mcthoxy-3-ethoxybcnzcne-l : 2- " methydyohimboaic acid ” ), the betaine structure dicarboxylic acid, thus establishing the relative of the two compounds is regarded as established. position of the hydroxy-- arid methoxy-groups in The attempted Hofmann degradation of ethyl bulbocapnine. The possibility that the groups are yohimbenate methylbctaine affords ill-defined pro­ in the 5 : 6-position in nucleus (I) (see formula) is ducts, but, under certain conditions, isomerisation not excluded, but is unlikely if the constitution of to the corresponding methyl ester takes placo; this analogous alkaloids is taken into account. ty-pe of change has been observed previously only H. W r e n . with d-betaines, so that the carboxy-group in yohim­ Opium alkaloids. IX. Constitution of proto­ benic acid appears to be in the a-position to the papaverine and synthesis of dl-codamine. E. nitrogen atom. It is highly probable that a quinoline Spath and H. E pstein (Ber., 1928, 61, [B], or at any- rate a py-ridine ring is present in the 334— 343; cf. A., 1927, 163).— Protopapaverine, yoliimbene skeleton and the assumption is made that C,9H ll(0,N , m. p. 279— 280°, is prepared by the methyl iodide or sulphate is added to this ring nitrogen thermal decomposition of papaverine hydrochloride atom, to which the carboxy--group stands in the at 235° and subsequently at 215— 216° (cf. Hesse, «-position. The acidities of the amino-acids increase A., 1903, i, 773; Pictet and Kramers, ibid., 358). in the order yohimbenic, aZZoyohimboaic, yohimboaic, It is not a partly demethylatcd papaverine, since and isoyohimboaic, in such a maimer that the differ­ the alkaloid is not re-formed by treatment with ences are very- marked between the pairs yohimbenic diazomethane. Contrary to previous assumption, it and oZZoyohimboaic acids, on the one hand, and contains only two methoxy-groups, the third methyl yohimboaic and isoyohimboaic acids, on the other, radical being attached to nitrogen. Reduction of wheroas the difference between the individual protopapaverine by tin and hydrochloric acid followed members of the same pair is slight but distinct. The bv treatment of the base with diazomethane affords ORGANIC CHEMISTRY. 433 f/Maudanosine, thus establishing the close similarity directed to the synthetic dimethoxydicarboxylic of the skeletons of papaverine and protopapaverino. acid for purposes of comparison with the acid pro­ Its solubility in alkali hydroxide establishes the duced from the tricarboxylic acid and hydriodic acid presence of at least one hydroxy-group. Oxidation (loc. cit.). Methyl 3-hydroxy-4 : 5-dimethoxybenzoate of protopapaverine by permanganate affords veratric is converted into its sodium derivative, which is acid, whilst treatment with diazomethane gives the heated with methyl p-bromobenzoate, copper powder, substance (I) (R=Me) (cf. Decker and others, A., and copper acetate at 180— 200°, whereby, after 1908, i, 204; 1913, i, 289; Spiith and Epstein, loc. hydrolysis, '¿-p-carboxyphenoxyA : o-dimethoxybenzoic cit.), reduced to 0-laudanine. The constitution (I) [2 : 3-dimethoxydiphenyl ether 5 : 4'-dicarboxylic] acid, (R=H ) is therefore ascribed to protopapaverine. m. p. 217— 218°, is produced, identical with the acid derived from ¿sochondodendrine; the non-crystalline methyl ester is described. Similarly, using o-bromo- OR11 benzoic ester, the isomeric 3-0-mrboxyphenoxy-4 : 5- NMe !NMe dimethoxybenzoic [2 : 3-dimethoxydiphenyl ether 5 : 2'- oiv y dicarboxylic] acid, m. p. 228-5— 229° (methyl ester,' CH ÇH2 m. p. 72—73°), is obtained; fusion with potassium hydroxide gives salicylic acid unaccompanied by (I.) / \ f \ (II.) 2i-hydroxybenzoic acid. Since migration of the OMe / ° M e carboxy-group is not observed, the “ degradation %/ L OMMe (» I e acid ” cannot contain the o'-carboxyphenoxy-group. The reactions of the other product of the alkaline Protopapaverine is converted by methyl iodide fission of the isomeric acids are identical with those into 7-hydroxy-Q-methoxy-3' : 4'-dim'ethoxybenzyliso- of the similar product from the “ degradation acid.” quinoline methiodide, which, when converted into the .. ... p., There is therefore no reason to corresponding methochloride and then reduced with 1 assume that the latter is not tin and hydrochloric acid, gives dZ-codamine (picrate, OMef y' \aH 2 derived from pyrogallol (cf. loc. m. p. 187— 188°). The identity of the base is con­ /N M e cit.). The constitution (I) can firmed by its méthylation to r-laudanosine and oxid­ therefore almost certainly be ation of its ethylated product to l-keto-6-methoxy- x Xtt assigned to methylisocliondo- 7-ethoxy-2-methyl-l : 2 : 3 : 4-tetrahydroisoquinoline. \ ' 2 dendrine. Confirmation of this In addition to protopapaverine (41%), the thermal G 4 C') conception is found in the observ­ decomposition of papaverine hydrochloride affords ation that the degradation product (II), obtained by 29% of the hydrochloride of the base (I) (R=Me), reduction of the hydromethine prepared from the about 10% of the isomeric compound (II) (R=Mo), alkaloid by Emde and Hofmann’s method (loc. cit.), and probably about 10% of the substance (II) is converted by mild oxidation into the carboxylic (R=H). The latter compounds havo not been acid (III) (barium salt; methyl ester, m. p. 252— isolated as such but as their reduction products, 253°), which does not yield p-hydroxybenzoic acid dZ-codamine and 6 : 7-dihydroxy-3' : 4'-dimethoxy- when fused with potassium hydroxide. The un­ benzyl-2-methyKsoquinoline. The latter base is usually high m. p. and the value obtained for the oxidised to veratric acid and converted by diazo­ mol. wt. of a-methyldihydroisochondodendrimethine methane into r-laudanosine, m. p. 114— 115°. Ethyl­ OMe OMe ation with diazoethanc followed by oxidation gives 4 : 5-diethoxybenzene-l : 2-dicarboxylic acid, identi­ om cÇ | C h :c h s OMe % 0 „H fied as the cthylimide, m. p. 199— 200°. For purposes (II.) (III.) of comparison, m-hcmipinic acid is demethylated by hydriodic acid (d 1-7) at 100° to 4 : 5-dihydroxy - 3H2 benzene-1 : 2-dicarboxylic acid and then converted o - c h - c h o - c h - c h by diazoethane into 4 : 5-dicthoxybenzene-l : 2-dicarb­ 6 4 2 6 4 2 oxylic acid, m. p. 165— 166° (decomp.), from which and a-methyh’sochondodendrimethine by Rast’s the corresponding anhydride, m. p. 157— 158°, and method suggest a complex constitution for the parent ethylimide, m. p. 199— 200°, are derived. alkaloid, but chemical evidence is adduced in favour H. W r e n . of the simple composition CjgHjoOgN; the pheno­ Constitution of /sochondodendrine. F. F a l t is mena of association appear to be characteristic of the and A. Troller (Ber., 1928, 6 1 , [B], 345— 355).— peculiar oxygen ring system. H. W r e n . Oxidation of the product, C18H10O3, obtained from 2>-Arsinophenoxyacetic acid. C. S. P alm er and wochondodendrine by a combination of the Emde E. B. K ester (Org. Syntheses, 1927, 7, 4— 5).— The and Hofmann methods of degradation has yielded product of interaction of sodium hydroxide, p-hydr- an acid, C12H50(0Me)2(C02H)3, derived from di­ oxyplienylarsinic acid, and chloroacetic acid is treated phenyl ether and converted by fusion with potassium with hydrochloric acid. A. A. E l d r id g e. hydroxide into p-hydroxybenzoic acid (cf. Faltis and Neumann, A., 1922, i, 569). Direct comparison shows Pure arsenobenzene and the molecular com­ the acid not to be identical with 3 : 4'-carboxy- plexity of arsenobenzene and arsenometbane. phenoxv - 5 : 6 - dimethoxybenzene -1 : 2 - dicarboxylic C. S. Palm er and A. B. Scott (J. Amer. Chem. Soc., acid. Since the isomeric acids theoretically possible 1928, 50, 536— 541).— Pure arsenobenzene, m. p. are not synthetically available, attention has been 195°, prepared by a modification of the method of F F 434 BRITISH CHEMICAL ABSTRACTS.— A.

Binz, Bauer, and Hallstein (A., 1920, i, 401), is compound (annexed formula), since by subsequent unimolecular in boiling carbon disulphide, but partly decomposition with ice, half the associated in boiling benzene (cf. Michaelis and phenoxthionine is recovered as Schafer, A., 1913, i, 783), and probably bimolecular oxide (donor) and half un­ in molten naphthalene. Both the yellow, liquid and changed (acceptor). Cautious red, solid modifications of arsenomethane appear to dilution of the corresponding exist as (MeAs)c in boiling carbon disulpliide. solution of plienoxselenine in F . G. W il l so n . concentrated sulphuric acid Manufacture of organic compounds of arsenic yields copper-red crystals of pure triplienoxselenylium [oxazinearsinic acids]. G. Newbery, and M a y dibisulphate sulphuric acid dihydrate (changing, in a and B a k e r.— Sec B ., 1928, 211. sealed tube, at 155° and m. p. 168°), of analogous structure to the corresponding tellurylium compound Arsenical derivatives of quinoline. S. B e r l in - (cf. following abstract), and, subsequently, a mixture gozzi (Annali Chim. Appl., 1928, 1 8 , 31— 30).— of this with dark purple crystals. Crystallisation of When coupled with diazotised arsanilic acid deriv­ this mixture from acetic acid containing a few drops atives, hydroxyquinolines yield the following red of sulphuric acid yields the pure copper-red com­ or brown hydroxyazo-compounds, which are being pound, which is decomposed quantitatively by cold examined as to pharmacological properties: 2-Methyl- water into sulphuric acid, plienoxselenine, and its ‘¿■azo-4-hydroxyquinoline-j>-phenylarsinic acid (not oxide. Decomposition with ice of the violet solution melted at 300°), S-azoS-hydroxyquinoline-p-plienyl- obtained by dissolving phenoxthionine oxide in sulph­ arsinic add, 2-phenyl-4-azo-Z-hydroxyquinoline-p- uric acid yields phenoxthionine, the tendency towards phmylarsinic acid, and 2-vietliylA-azo-‘,i-hydroxyquiii- the formation of thionylium salts being sufficiently oline-'p-phenylarsinic acid. All of these acids give red great to cause the sulphuric acid to act either as an colorations with concentrated sulphuric acid. oxidising or a reducing agent as required. Mechan­ T. H . P ope. isms of the various reactions are given. It is deduced [Preparation of] triphenylstibine. G. S. H iers that, in their compounds, sulphur may be associated (Org. Syntheses, 1927, 7, 80— 82). with 18 or 20 electrons, selenium with 36 or 3S, and Cyclic organo-metallic compounds. V. tellurium with 54 or 56, the tendency to become Plienoxselenine and phenoxthionine from associated with the higher number increasing in this phenoxtellurine. Selenylium and thionylium order. An attempt is made to interpret the quin- compounds. H. D . K . D r e w (J.C.S., 1928, 511— hydrones on a carbonylium structure, quinhydrone 524).—W ien phenoxtellurine or its derivatives (with the exception of nitro-compounds) are heated with itself being formulated as H 0 (^ 0 -^)— ^)0 H, sulphur or selenium, the tellurium is replaced by its generator, quinol, being regarded as able to these elements and the analogous phenoxthionine or plienoxselenine is obtained. These form mixed assume the carbonium structure H(~ 0 -~)OH. crystals and yield -ylium compounds analogous to the tellurylium salts. Thus when phenoxtellurine J 7 W . B a k e r . is boiled with sulphur it yields phenoxthionine, m. p. Cyclic organometallic compounds. IV. Tell­ 58° unchanged (Mauthner, A., 1906, i, 447, gives urylium compounds. H. D. K. D r e w (J.C.S., 60— 61°), contaminated with 6—7% of unaltered 1928,506—510).—The author’s method of ascertaining phenoxtellurine, from which it is separated by the relative proportions of donor and acceptor in addition of a few drops of bromine to its chloroform the molecule of a tellurylium compound (A., 1927, solution and subsequent treatment with acetone and 164) has been improved to give quantitative results, ether. It is converted by hydrogen peroxide in and its application to the compounds previously glacial acetic acid into 'phenoxthionine oxide, m. p. described (loc. cit.) proves the correctness of the 158— 159°, whilst prolonged action of the reagent formulae assigned except in the case of the compound yields the dioxide, m. p. 147— 148°. Plienoxselenine, previously described as diphenoxtellurylium hydroxy- m. p. 87— 88°, is obtained in a similar manner. The bisulphate monohydrate, obtained by crystallising original complex, composed of plienoxselenine (2 mols.) diphenoxtellurylium dibisulphate or its complex and phenoxtellurine (1 mol.), is separated by boiling with 2 mols. of sulphuric acid from glacial acetic the mixed dibromides with acetone and treating the acid. This is really triphenoxtellurylium dibisulphate, residue with ether, the phenoxtellurine dibromide fC GH 4C6H.1j (HS04)2. An expanded formula being insoluble. When treated with the appropriate halogen in chloroform solution it yields a dichloride, for this is suggested in which the three tellurium atoms m. p. 127° (decomp.), and dibromide, m. p. 147— are held together by four electrons. There exists, 148° (decomp.). Oxidation with hydrogen peroxide therefore, a series of compounds of the type converts it into plienoxselenine dihydroxide, which [R z](HSO.,)2 in which x may be 1, 2, or 3, some of readily loses 1 mol. of water, yielding the oxide, m. p. which have addenda of water or sulphuric acid 171— 172°, which is quantitatively converted into molecules. The compound of m. p. 59° described plienoxselenine by heating it above its m. p. The by Thomason and Drew (A., 1927, 267) as a com­ intensely coloured solutions of phenoxthionine in plex of phenoxtellurine and chloromethylphenox- sulplnuic (or phosphoric) acid are due to the presence, tellurine has been separated into these components not, as suggested by Hilditch and Smiles (J.C.S., by fractional precipitation of its chloroform solution 1911, 99, 408), of thionium salts, but of the thionylium with bromine. Phenoxtellurine dibromide separates ORGANIC CHEMISTRY. 435

first and then the dibromide, m. p. 315° (decomp.), above 175°, resembles boron triphenyl in that it is of chloromethylphenoxtellurinc, m. p. 46— 47° \di- sensitive towards air but forms stable additive com­ chloride, m. p. 300° (decomp.); diacetate, m. p. 230— pounds with nitrogenous bases which are indifferent 232° (decomp.); disulphate-, di-a-broinocamphor--- towards oxygen; the substances B(C-H7)3,NH3, m. p. sulphonate which could not be purified owing to its 225—226° in a sealed capillary; B(C7'H-)3,C5H 5N, tendency to hydrolyse], which is obtained from the m. p. 201— 202°, and B(C7H 7)3,C5H n lSi, m. p. 202° dibromide by reduction with potassium metabi­ after softening, are described. Like the phenyl deriv­ sulphite, and from which a tellurylium compound ative, boron tri-p-tolyl reacts with sodium and was obtained. J. W. B a k e r . potassium, but the products crystallise with difficulty. Boron tricyclohexyl, m. p. 98— 100°, is much more ci/eioTelluropentane. G. T. M organ and H. sensitive to air than the phenyl compound. Its B urgess (J.C.S., 1928, 321— 329).— The action of additive compounds with ammonia, B(CGH 11),NH3, aluminium telluride on as-pentamethylene dihalides m. p. 105— 106°, and pyridine, B(CGH 11)3,C5H 5N, are under varying conditions according to the halide readily affected by atmospheric oxygen, w’hereas the employed, yields cyclotelluropentane, b. p. 82— 83°/ compound B(CGHn )3,C5H n N, m. p. 135— 136°, is 12 mm., 44— 45°/l—2 mm., in accordance with the stable when solid, but rapidly oxidised when dissolved. equation Al2Te3+3C H 2X-[CK2]3-CH2X = 3 C 5H lp:T e+ Like boron tri-n-propyl, m. p. —56°, it does not 2A1X3 (X=C1, Br, or I), but this product is not react with the alkali metals. H. W r e n . isolated at this stage, since it interacts with more of the pentamethvlene dihalide to yield compounds Anhydro - 2 - hydroxymercuri - 3 - nitrobenzoic of the type C5H lo:TeX-CH2-(CH,]3-CH2X (I) and acid. F. C. W hitm ore, P. J. C u l h a n e , and H. T. C5H 10:TeX-CH2-[CH2]3-CH2-T5x:CriH 10 (II). A small N eher (Org. Syntheses, 1927, 7, 1— 3).— Experi­ amount of the cycZotclluripcntano dihalide, mental details for the preparation of anhydro-2- C5H 10!TeX2, is also obtained in the case of the hydroxymercuri-3-nitrobenzoic acid from sodium bromine and iodine compounds, but this is best 3-nitrophthalate and mercuric acetate are recorded. prepared by the addition of halogen to the com­ A. A. E l d r id g e . pounds (I) or (II) or their products of thermal decom­ Proteins. V. Glutamic acid. C. O k in a k a position (below). Thus are obtained: 1-e-chloroamyl- (Sexagint [Osaka celebration], Kyoto, 1927, 27— 59). cyc\otelluripentane-l-chloride, m. p. 149— 151°, -1- Glutamic acid probably plays an important part in bromide, m. p. 143— 145°, and -1-iodide, m. p. 135— the metabolism of proteins in plants. Ethyl glut­ 136°, resolidifying almost immediately and then amate passes readily into ethyl pyrrolidine-l-carb- having in. p. 197— 198°; pentamethylene-o.z-biscyc\o- oxylate and the free acid gives the corresponding telluripehtanc-1 : 1'-dichloride, decomp. 224— 225°, acid; this reaction is accelerated by heat or dilute -I : V-dibromide, exploding on rapid heating, and alkali but retarded by excess of strong acid or alkalis. -1 : l'-di-iodide, m. p. 216—217° (decomp.), cyclo- The reaction does not go to completion but attains an Telluripentane-1 : I -dichloride, m. p. 106— 107° (di- equilibrium. The optical properties of its solutions chromate), is prepared either by thermal dissociation, of various p a values indicate that the acid exists or by the action of a slight excess of chlorine, from normally to some extent in the form of an internal salt (I). The corresponding -1 : 1 -dibromide, m. p. 105— and this is probably the first step in the formation of 107°, is best prepared by heating either (I) or (II) the pyrrolidinecarboxylic acid. C. D. L an g fo rd . to 160—190°/25—30 mm. and the action of excess Combination, of gelatin with organic bases. of bromine on the cycZotelluropentane thus liberated, A. Petr UN k in and M. P e t r u n k in (Arch. Sci. biol., or by the direct action of bromine on (I) in carbon 1927, 27, 219— 234).— Sec this vol., 190. tetrachloride solution. By treatment with bromine Degradation of gelatin with acetic anhydride. in carbon tetrachloride it yields the corresponding A. F odor and C. E pstein (Z. physiol. Chem., 1927, -1 : l-bisperbromide, m. p. 102— 104°. The -1 : 1-di- 171, 222—241).—Various crystalline products, very iodide, m. p. 135— 136°, which is obtained in two hygroscopic and varying in solubility in alcohol, forms, one deep red with purplish-blue reflex (stable) have been obtained from the syrupy product of the and the other orange, transformation of the latter degradation of gelatin with boiling acetic anhydride. into the former occurring slowly at the ordinary Investigations were confined to the more soluble temperature, and at 105° on heating, is obtained by portions over the range [a]f) —76-92° to —101-4°. addition of iodine to cyc/otelluropentane in carbon These are identified by their chemical behaviour, tetrachloride. B y reduction with potassium meta­ mol. wt., and analysis as : hydroxyprolylalanine, bisulphite in aqueous solution, cyc/otelluripcntane- C8H 14N204, [«]g -76-92°; (C8H 14N20 4)4 (poly­ 1 : 1-dibromide is converted into ci/cZotelluropentanc merised hydroxyprolylalanine, ?), [a]]? —78-2°; (above), which must be distilled in an inert atmosphere, 4(C8H 14N20 4),3H20, [ajg -78-2°; 4(C8H 14N20 4),H20, since it is rapidly oxidised either by air or hydrogen [a]™ —88-8°; and (hydroxyprolylalanine + 3-hydroxy - peroxide to cyclotelluripentane-1 : 1 -dioxide, + H 20 , prolylglycine —3H20 ), [a]'g —101-4°. Depolymeris­ a white, amorphous powder which explodes on rapid ation of these by barium hydroxide or by sodium heating. J. W . B a k e r . hydroxide to dipeptide and amino-acid furnishes Valency problem of boron. III. Valency evidence on which suggested structural formulae for the phenomena of boron in boron tricj/cfohexyl and polymcrides are based. J- St e w a r t . boron tri-p-tolyl. E. K r au se and H. P olack Decomposition of soya-bean protein. V. De­ (Ber., 1928, 61, [13], 271— 276; cf. A., 1922, i, 694; composition of soya-bean protein by sulphuric 1924, i, 436; 1926, 628).— Boron tri-p-tolyl, m. p. acid. VI. Decomposition of soya-bean pro- 436 BRITISH CHEMICAL ABSTRACTS.— A. tem by organic acids. VII. Decomposition the ring (diketopiperazine) rather than the peptide b y Japanese acid clay. M . Ma sh in o and T. structure of the proteins. Although the 8 values for S h ish ido (J. Soc. Chem. Ind. Japan, 1927, 3 0 , 552— albumin increase much more quickly than for gliadin, 560, 561— 564, 565— 568; cf. A., 1927, 474).— V. the final values, after more prolonged digestion with Soya bean from which oil had previously been extracted alkali, are bigger for gliadin than for albumin. with light petroleum was treated for 6 hrs. with dilute P. W . Clu tte r b u c k . sulphuric acid (1—20%) at 4-7 atm. The action of Rapid determination of carbon, nitrogen, and the acid was much more rapid and the amounts of hydrogen in organic compounds. R. V a n d o n i ammonia and amino-nitrogen formed were much and M. A lgrain (Bull. Soc. chim., 1928, [iv], 43, larger than at atmospheric pressure. The amount 255— 260).— A modified Dumas apparatus is described of nitrogen appearing as ammonia increased with for the volumetric determination of carbon and increasing time of treatment, reaching 11-63— 20-05%. nitrogen at the same time. The combustion is carried of the total nitrogen at the end of 6 hrs. With 20% out using oxygen in slight excess of the calculated sulphuric acid the amount of amino-nitrogen formed amount, and the apparatus is arranged so that the increased rapidly at first, reached a maximum gaseous products can be passed over heated copper (about 80% of the total nitrogen), and then decreased oxide as many times as are necessary for complete gradually to about 60% at the end of 6 hrs. With burning. A similar apparatus is described for the more dilute acid no maximum was found. gravimetric determination of hydrogen. The methods VI. When soya-bean protein was treated with are quick and give trustworthy results. H. B urton . acetic, lactic, citric, tartaric, or oxalic acid for several Determination of halogens in organic com­ hours at 2-66— 5-8 atm., the ammonia-nitrogen pounds. M. P roner (Rocz. Farm., 1926, 4, 99— liberated was nearly the same in every case (10— 13% 106; Chem. Zentr., 1927, ii, 1596).— The method is of the total nitrogen). The amino-nitrogen liberated specially suitable for naphthalene derivatives, terpones, varied from 3-1 to 25-1% of the total nitrogen, and heterocyclic compounds. The substance (0-1— according to the acid used, and increased in the order : 0-2 g.) is slowly warmed with 95% alcohol, and small acetic, lactic, citric, tartaric, oxalic acid. pieces of sodium (1 g.) are added; the mixture is VII. When soya-bean protein was heated under warmed with 30% hydrogen peroxide solution (5 c.c.) pressure with acid clay and water, or with acid clay until evolution of oxygen ceases, acidified with nitric and sodium chloride solution, the ammonia-nitrogen acid, reduced with sodium sulphite, warmed, and the and amino-nitrogen liberated was about 8-5% and chloride precipitated with silver nitrate. about 5% of the total nitrogen, respectively. With A. A. E ld rid g e . acid clay and hydrochloric acid the amount of amino- Determination of selenium in organic com­ nitrogen liberated was somewhat less than with the pounds. W. E. B r a d t and R. E. L y o n s (Proe. acid alone. Y. N a g a i. Indiana Acad. Sci., 1926, 36, 195— 201).— The Nitrogen distribution of soya-bean protein. (halogen-free) substance is heated with nitric acid in M. M ashino and S. N ish im ura (J. Soc. Chem. Ind. a sealed tube, the solution being made alkaline with Japan, 1927, 30, 607— 610).—The nitrogen distrib­ potassium hydroxide (free from halide), slightly acid ution of several varieties of soya-bean protein has been with nitric acid, and then neutral with excess of zinc determined by the Van Slyke method. Y. N a g a i. oxide, and finally titrated with siver nitrate in presence of sodium chromate. Chem ical A bstracts. Purification of soya-bean protein. M. M a sh in o Thalleioquinine reaction. B. Olsze w sk i (R ocz. (J. Soc. Chem. Ind. Japan, 1927, 3 0 , 610— 617).— Farm., 1926, 4, 119— 130; Chem. Zentr., 1927, ii, Soya bean, from which oil had previously been 1598).— Optimally, 1 mol. of quinine is treated with extracted with light petroleum, was treated with 4— 8 atoms of bromine for 15 sec. In the micro­ various solvents to remove constituents other than the reaction, the precipitate is dissolved in 30% acetic acid, protein. Methyl alcohol proved best. The amount the acid removed by evaporation, and the residue, of extraction increased with temperature. Extraction after dissolution in water, treated with 1 drop of dilute by methyl or ethyl alcohol at 67— 68° or at 82— 83° bromine water. A. A. E ld rid g e. was almost complete in 1 hr. Soya-bean protein purified with methyl alcohol is no longer hygroscopic, is Determination of the isoelectric point of amino- acids, asparagine, or glycine. M. D. B ac h (Bull. odourless, and has only a light colour. Y. N a g a i. Soc. Chim. biol., 1928, 9, 1233— 1243).— The com­ Behaviour of proteins with alkali with some pound to be examined is added in equal amounts to conclusions in regard to their structure. J. each of a series of tubes containing suitable buffer T illm ans and P. H irsch (Biochem. Z ., 1928, 1 9 3 , solutions chosen so as to extend over a range of pa 216—236).—The changes of “ molecular binding including the isoelectric point required. An identical power, S” of egg-albumin and gliadin solutions on set of buffer tubes is also prepared to which none of the addition of acids and alkalis is investigated. These compound is added. Bv electrometric methods or proteins, especially gliadin, have very low 8 values, by the addition of a suitable indicator to each of the but the latter increases considerably on adding sodium two sets of tubes the particular p a is found which is hydroxide (especially in the case of albumin), due to such that the addition of the compound causes no the liberation of new acid and basic groups, the change in hydrogen-ion concentration. By this strengths of which correspond with those of peptides. method it has been found that the isoelectric points of Peptides, however, are only difficultly attacked by glycine and of asparagine are at p a 4-3 and 5-8, sodium hydroxide and the results favour, therefore, respectively. W . O. K e r m a c k . biochemistry . 437

Biochemistry, Glycerol and potassium hydroxide in the. saturated with picric acid, to a saturated picric acid microscopical detection of blood. K . M e ix n e r solution containing creatinine causes precipitation of (Deuts. Z. ges. gericlit. Med., 1927, 10, 253— 254; the latter; the precipitate can be decomposed with Chem. Zeh.tr., 1927, ii, 1742).— A mixture of con­ a mixture of alcohol and ether and the creatinine centrated aqueous potassium hydroxide and glycerol, re-precipitated by addition of picric acid to the or a glycerol solution of potassium hydroxide is filtrate. Picric acid is removed by shaking the pre­ preferred to aqueous potassium hydroxide; the cipitate with dilute sulphuric acid and ether, the formation of hsejmatin and htemochromogen takes creatinine is re-precipitated with basic lead acetate, place completely, but more slowly. The use of recovered with hydrogen sulphide in tho usual reducing agents for this purpose is objectionable. manner, and finally isolated as potassium creatinine A. A. E ld r id g e . picrate; in order to obtain the maximum yield of Value of benzidine reaction and the clinical the latter it is important to have the correct con­ significance of the hsematoporphyrin test in centration of potassium in tho solution. The above faeces. D. E. Sc ho u ten (Ned. miaandschr. geneesk., method has been applied to the isolation of creatinine 1926, 13, 651— 668; Chem. Zentr., 1927, ii, 963).— from blood which has been freed from protein by The pigment of the blood is partly or completely treatment with picric acid. Treatment of such converted in the intestinal canal into hiematopor- protein-free blood-filtrates with kaolin removes the phyrin; spectroscopic detection of the porphyrin is creatinine but leaves in solution other substances preferred. The test is not less sensitive than the which give the Jaffe reaction and also accumulate benzidine reaction. A. A. E l d r id g e . in those pathological conditions which lead to reten­ tion of creatinine. Creatinine may also be separated Effect of posture on the composition and from blood-filtrates by treatment with Lloyd’s volume of blood in man. W. 0. T h om pson, P. K. reagent, and decomposition of the precipitate by T hompson, and M. E. D a il e y (Proc. Nat. Acad. means of lead hydroxide. C. R. H ar in g to n . Sci., 1928,14, 94— 98).— In the standing-still position there occurs a net loss of approximately protein-free Determination of cholesterol in small amounts fluid from the blood. This seems to be due to an of b lood . S. M. L in g (J. Biol. Chem., 1928, 76, increase in capillary pressure. The loss amounts to 361— 365).— Blood is dried on iiltcr-paper and about 11% of the total plasma volume, and is pro­ extracted for 40 mm. with chloroform in a special bably greatest in the lower extremities. apparatus; cholesterol in the extract is determined W . E. D o w n e y . colorimetrically. C. R . H a r in g to n . Origin of the pigment of C hironom ns larvae. M. Comas (Compt. rend. Soc. Biol., 1927, 96, 866— Determination of dihydroxyacetone in blood 868; Chem. Zentr., 1927, ii, 100).— Hamioglobin in and urine. W. S. M cCl e lla n (J. Biol. Chem., Chironomus larvae does not arise from ingestion of 1928, 76, 481— 486).— The utility of the method of chlorophyll, but is hereditary. It is associated with Campbell (A., 1926, 443) for the determination of a green pigment similar in its properties to biliverdin. dihydroxyacetone in blood is confirmed; the method A. A. E ld rid g e. can be applied to urine, after preliminary removal of Coagulation of haemoglobin in presence of phosphates. C. R. H a r in g to n . organic substances. B. Jir g ensons (Biochem. Z., Methylglyoxal as intermediate product in 1928, 193, 109— 121).— The coagulation of haemo­ glycolysis in blood. H . K. B arrenscheen (Bio­ globin with potassium chloride and magnesium chem. Z., 1928, 193, 105— 10S).— The formation of chloride is sensitised by the presence of small amounts methylglyoxal during glycolysis in blood is detected of capillary-active substances having small dielectric by addition of semicarbazide with isolation and constants (ether, chloroform, amyl and i'sobutyl identification of methylglyoxal disemicarbazone. alcohols, acetone, methyluretliane), whilst in larger P. W . Clu tter b u c k. concentrations these substances may act either as Glycolysis of dextrose and lsevulose in the sensitisers if the salt concentration is small, or as stabilisers if it is large. Some capillary-inactive blood of normal and diabetic dogs. E . T urgatti (Rev. Soc. Argentina Biol., 1927, 3, 716— 720); substances (mannitol and dextrose) have a slight —Venous blood from dogs was incubated for stabilising action (cf. A., 1927, 512, 624). 6 lirs., alone, and with the addition of dextrose or P. W. Cl u tt e r b u c k . lsevulose. The greatest amount of glycolysis occurred Amino-acids in blood of insects. M. D u v a l, in blood of low blood-sugar level, and vice versa. P. P o r tie r , and A. C ou rtois (Compt. rend., 1928, Glycolysis was retarded considerably by the addition 186, 652— 653).—Amino-acids have been determined of dextrose and moderately by the addition of lsevul­ by the Sorensen titration method in the blood of ose. Glycolysis was slower in the blood of dogs from insects, in the chrysalid, larval, and fully-grown which the pancreas had been removed, and was states. The value is high in each case, and par­ retarded or even inhibited by addition of dextrose, ticularly in the chrysalis. W. K. S la te r . but the addition of lsevulose had, on the whole, little Blood-creatinine. O. H. G a e b le r and A. K. effect. . It is suggested that liyperglycscmia can be K e lt c h (J. Biol. Chem., 1928, 76, 337— 359).— considered not only as a symptom, but also as itself Addition of a 10% solution of phosphotungstic acid, a cause of disturbance. R- K- Ca l lo w . 438 BIRTISH CHEMICAL ABSTRACTS.— A.

“ Protein’’-blood-sugar. E. J. B igw ood and 1217; Chem. Zentr., 1927, ii, 1598).— The Hagedorn- A. W uillot (Compt. rend. Soc. Biol., 1927, 97, Jensen method is improved. A. A. E ld rid g e. 186— 187 ; Chem. Zentr., 1927, ii, 1162).— Hydrolysis Serum-calcium. I. Oral administration. of plasma-protein yields a small fraction of a reducible J. C. H o yle (J. Pharm. Exp. Ther., 1928, 3 2 , 309— and fermentable substance, having a reducing power 320).—No definite differences in the normal serum- about 6% of that of the sugar-free hydrolysatc; the calcium content of male and female rabbits have ratio of protein to the substance is about 1 : 0-0044. been detected, but a seasonal variation occurs. Loss A. A. E ld r id g e . of blood equivalent to about one fifth of the body- Reducing and fermentable substances in com­ weiglit causes a fall in the serum-calcium of approxim­ bination with proteins of the blood-plasma. ately 14-%. Administration by mouth of single or E. J. B igw ood and A. W uillot (Compt. rend. Soc. repeated doses of 1 g. of calcium carbonate per kg. Biol., 1927, 97, 187— 191; Chem. Zentr., 1927, ii, body-wcight causes an increase of serum-calcium up 1162— 1163; cf. preceding abstract).—Pure con­ to 16% which, when allowance is made for effect of stituents of the blood-serum were submitted to hannorrhage, is equal to an increase of 20— 25%. hydrolysis. Proteins give by acid hydrolysis 7-4% By administration of 2 g. of calcium carbonate per of reducing substance expressed as dextrose and day a permanent increase of serum-calcium of 5— 15% calculated on the original quantity of sheep blood- has been obtained. Single doses of calcium lactate proteins; the fermentable fraction is only 0-S— 1-2% , (3 g. per kg. body-wcight) cause an increase in serum- and is ascribed to traces of nucleoproteins. calcium of 15—22%, whilst repeated daily doses of A. A. E l d r id g e . 6 g. of the salt cause a maximum increase of only Presence of two reducing carbohydrates in 5%, or 12% if allowance be made for the effects of b lood . G. F onti-is and L. T h ivolle (Compt. rend. repeated bleeding. W. 0. K erm ack . Soc. Biol., 1927, 96, 994— 996; Chem. Zentr., 1927, Replacement of the serum-calcium and thyroid ii, 449).—The use of mercuric nitrate and of tungstic gland in rabbits after intravenous injections of acid (the former, but not the latter, precipitating oxalate. H. W. C. V in e s (Endocrinol., 1927, 1 1 , creatinine and uric acid) indicates the presence in 290—296).—The speed of replacement of calcium, blood, in addition to that of “ glucose,” of an ethereal which has been removed from the blood following the component the reducing power of which is unchanged intravenous injection of ammonium oxalate, was by hydrolysis. The amount is not increased by determined. Chemical A bstracts. muscular work or insulin. A. A. E ld rid g e. Blood-phosphorus in health and disease. I. Distribution of the carbohydrate reducing Distribution of phosphorus in human blood in substances between plasma and blood-cor- health. H . D . K a y and F . B. B y r o m (Brit. J. Exp. puscles. G. FoNTjfcs and L. T hivolle (Compt. Path., 1927, 8, 240—253).—The distribution of rend. Soc. Biol., 1927, 96, 997— 99S; Chem. Zentr., phosphorus in venous blood is fairly constant; the 1927, ii, 449).—Hirudin does not affect the natural ester phosphorus is greater, and the portion thereof distribution of reducing carbohydrates in the cor­ hydrolysable by phosphatase is less, in men than in puscles ; other anticoagulants affect the plasma and women. After a meal there is a slight diminution in corpuscles in the same sense. A. A. E ld r id g e . inorganic phosphorus, a diminution in phosphoric Determination of blood-sugar. II. S. R. ester hydrolysable by phosphatase, and a corre­ sponding increase in the ester fraction resistant to B enedict (J. Biol. Chem., 1928, 7 6 , 457— 470).— Evidence was obtained of the presence in protein- enzyme hydrolysis;' there is also possibly a slight rise in lipin-phosphorus. The phosphorus index (mg. of free blood filtrates of substances which affect the ester phosphorus in c.c. of red cells) is a more dissociation of the complex copper salt, in the solu­ 100 tions usually employed for the determination of stable constant than the p a of the blood. blood-sugar, rendering it more easily reduced by Chem ical A bstracts. Use of the quinhydrone electrode for the dextrose; this effect has been overcome by the addition of alanine to a new reagent of the Fehling determination of the ]>n of whole blood and serum . J. Ge w e c k e (Biochem. Z., 1928, 1 9 3 , type. The new reagent gives results for the blood- sugar about 22 mg.% lower than the reagent of Folin 181— 186).— The experiments of F. Schmidt (Z. Immun. exp. Ther., 1926,4 6 ,386) were repeated using and Svcdberg (A., 1926, 1282); further, dextrose added to protein-free filtrates of blood which have rabbit’s in place of guinea-pig’s blood, but the results been subjected to yeast fermentation can be quantit­ were not consistent and often very different from atively determined by the new reagent, which there­ those obtained by the hydrogen electrode. With fore appears not to be affected by the non-dextrose inactivated human serum the initial potential was reducing substances present in such filtrates. The highest and quickly fell, and the results again differed work of Somogyi (A., 1927, 1214) is criticised on from those obtained by the hydrogen electrode. the ground that insufficient time was allowed for P. W. Cl u tte r b u c k . fermentation; good results are obtained by diluting Determination of p a of blood. I. Accuracy blood with a suspension of washed yeast and keeping of quinhydrone electrode for determining p B of the mixture for 15 min. before precipitation with blood-plasma or serum. G. E. C u llen and I. P. tungstic acid, C. R. Harington. E a r le . II. Comparison of colorimetric method with hydrogen and quinhydrone electrodes. Micro-determination of blood-sugar. H . Cit ­ I. P. E arle and G. E. Cullen (J. Biol. Chem., 1928, ron (Deutsch. med. Woch., 1927, 53, 1216— 7 6 , 565— 581, 583— 590).— I. A modified technique BIOCHEMISTRY. 439 for the use of the quinhydrone electrode (cf. Cullen Ferrous sulphate and chloride, aluminium sulphate* and Biilmann, A., 1925, i, 1201) is described, by the and chrome alum hinder the coagulation of blood employment of which reproducible results for the p a owing to interaction with the blood constituents. of normal blood-plasma or -serum may be obtained, A. A. E l d r id g e . these results being always 0'06 p B more acid than the Chemistry of specific hæmagglutination. A. corresponding figures obtained with the hydrogen K on ik o v (¿urn. eksp. biol. med., 1926, 128— 145; electrode. Chem. Zentr., 1927, ii, 1046).— The erythrocytes can II. Figures obtained for the p B of normal diluted be regarded as an amphoteric protein of isoelectric human blood-serum by the colorimetric method of point pn 5. Probably only between p n 6 and 9 arc the Cullen (A., 1922, ii, 072) were 7-41— 7-50, and were stroma and agglutinin oppositely charged. The 0-14 p a more alkaline than those obtained with the presence of electrolyte is necessary in the first phase quinhydrone electrode. C. R. H a r in g to n . of hæmagglutination; the action of the salt is ex­ pressed by the scheme stroma—Na—Cl—agglutinin, Calculation of cell volume changes as a I______I function of p B. D. B. D ill (J. Biol. Chem., 1928, in which auxiliary valencies function. The subject is 76, 543— 545).— By mathematical extension of the discussed from this point of view. A. A. E ld rid g e. calculations of Van Slyke, Wu, and McLean (A., 1923, i, 1249) a relationship is developed between Rapid preparation of crystalline egg-albumin. the relative volume of the red blood-corpusclcs and W. L a R osa (Chemist-Analyst, 1927, 16, No. 2, 3).— thep B of the serum. C. R. H a rin g to n . The whites of fresh eggs are beaten well and mixed with an equal volume of saturated ammonium Effect of carbon dioxide equilibration on sulphate solution. After 15 hrs. the liquid is centri­ surface tension of blood-serum. J. M. J o h lin fuged and the clear supernatant liquid is siphoned (J. Biol. Chem., 1928, 76, 559— 564).— Neither the off. Acetic acid (10%) is then added, with stirring, absolute magnitude of the surface tension of blood- until a permanent turbidity appears, an additional serum nor the change in surface tension with time 1 e.c. for each 100 c.c. of liquid being finally added. is significantly affected by equilibration with varying Ch em ical A bstracts. tensions of carbon dioxide. C. R . H ar in g to n . Physiology of the foetus. T. S u g an o (Kinki Haemoclastic changes in vitro from agents Fuji. Gak. Zassi, 1926, 9, 97— 100; Chem. Zentr., causing anaphylactoid reactions. P. J. H a n z l ik , 1927, ii, 945).— Pepsin appears in the foetus at the F. D e E ds, L. W. E m p e y , and W. H . F arr fifth or sixth month. A. A. E ld rid g e. (J. Pharm. Exp. Then, 1928, 32, 273— 294).— Oxidising substances in animal cells. W. Various anaphylactoid reagents, copper sulphate, L oele (Arch. path. Anat. Physiol., 1926, 261, 484— arsphenamine, peptone, acacia, agar, and toxified 502; Chem. Zentr., 1927, ii, 943). serum added in vitro to oxalated blood-plasma or serum cause a decrease in surface tension and an Microchemistry of the cell. I. Chromatin increase in the albumin-globulin ratio. Albumin, content of normal and malignant cells. R. J. peptone, and agar increase the viscosity of blood- L udford (Proc. Roy. Soe., 1927, B , 102, 397— 406). serum, acacia and gelatin increase the rate of sedi­ —The chromatin content of various normal and mentation of blood-corpuscles suspended in plasma. abnormal animal cells has been investigated by means The fragility of the corpuscles is decreased by acacia of Feulgen’s “ nucleal ” reaction ” During oogenesis and gelatin and increased by arsphenamine and in the rat and in the mouse there is no increase in the copper sulphate. The results are considered to chromatin content of the nuclei, and when formation support the view that anaphylactoid changes are of of the chromosomes takes place no chromatin is the nature of a disturbance in the equilibrium of the extruded into the cytoplasm ; the heads of the body colloids. W. 0. K erjiack. spermatozoa of the rat and the mouse contain chrom­ atin. Experiments on the nuclei of gland cells Variations in the coagulability of the blood before and after secretory activity indicate no appre­ normally and after ingestion of food. C. A. ciable diminution in chromatin content. There is Mills and H . N e c h e le s. Relation of blood no correlation between the amount of chromatin in coagulability to body metabolism and to the the nuclei of tumour-cells and the rate of growth of specific dynamic action of food. H . N echeles the tumour ; the nuclear extrusions occurring in and C. A. M ills (Chinese J. Physiol., 1928, 2 , 19— 23, certain tumours do not consist of chromatin. 25—32).—The coagulation time of blood is decreased E. A. L u n t . after a meal containing protein, but not after one Oxidising and reducing powers of mito­ containing only carbohydrate or fat. It is decreased chondria. P. J o y e t -L averc. n e (Compt. rend., also after administration of glycine, which, like 1928,186, 471— 473).— Histological studies have been proteins, has a marked specific dynamic action. The made on the effect of certain comparatively non­ decrease in coagulation time appears to be related, not toxic substances which become coloured on oxidation, directly to the increase of metabolism which occurs e.g., quinol, “ metol,” pyrogallol, and of aqueous after a meal, but rather to the presence in the blood­ solutions of gold chloride and of silver nitrate on stream of substances which exert specific dynamic fresh liver cells, and are held to indicate the oxidising action. W. 0. K e r m ack . and reducing properties of the chondriosomc system. Action of soluble iron salts on coagulation E. A. L u n t . of blood. P. B ordet (Compt. rend. Soe. Biol., Spectropbotometric studies of the two com­ 1927, 96, 1061— 1063; Chem. Zentr., 1927, ii, 450).— ponents of trypan-blue. (Adsorption theory of 440 BRITISH CHEMICAL ABSTRACTS.— A.

vital staining.) N. O k u n e ff (Biochem. Z., 1928, Osmotic concentration of secretions. J. 193, 70—84).—Aqueous solutions of trypan-blue Straub and L. S oep (Arch. Neerland. Physiol., 1928. possess a definite absorption constant (max. 0-911) 12, 346— 367).— A series of analyses of secretions and and a definite absorption maximum (580— 590 ¡41). sera before and after dialysis, with an interpretation The absorption constant is independent of the con­ of the results in the light of modern theories. centration within certain limits (1/5000— 1/100,000), W . R obson. but differs with the different commercial samples of Bacterial growth as a factor in the deposition the dye. When strips of filter-paper arc dipped in of calcium from saliva. W. A. P e a b o d y , I. C. dilute solutions of the dye, the solution gradually H a l l , and R. C. L e w is (Dental Cosmos, 1927, 69, becomes red and the paper blue, the absorption 10S7).— Direct precipitation of calcium in centri­ constant then showing a progressive decrease and the fuged saliva determines at least 93% of the total absorption maximum a displacement to the left. calcium. Incubation of raw saliva with or without The blue component is adsorbed much more firmly excess of fermentable carbohydrate produces, re­ than the red. Addition of gelatin, protein, or plasma- spectively, an acid reaction with an increase of soluble colloids increases the adsorption constant and dis­ calcium, or an alkaline reaction with a decrease of places the absorption maximum to the right. The soluble calcium. Chem ical A bstracts. fate of the two components in the organism is there­ Composition of synovial fluid. F . A . Cajori fore conditioned, not only by tlicir different diffusi- and R. P em berton (J. Biol. Chem., 1928, 76, bilities, but also by their different adsorbabilities. 471— 4S0).—The concentrations of the non-protein P. W . Clu tte r b u c k . nitrogenous compounds of synovial fluid and of Microchemical detection of potassium and blood-plasma are similar; synovial fluid has . a calcium in histological sections. W. J acobi and variable content of globulin, and usually a higher W. K eusch er (Arch. Psych. Ncrv., 1927, 79, 323— albumin : globulin ratio than plasma. Glycolysis is 326; Chem. Zentr., 1927, ii, 1985— 1986).— The tests rapid in synovial fluid containing many leucocytes, and depend, respectively, on the formation of potassium probably accounts for the high acidity and low sugar chloroplatinate and calcium sulphate. content of such fluid; glycolysis does not occur in the A. A. E ld r id g e . absence of leucocytes. C. R. H ar in g to n . Chemical composition and histological struc­ Differences in the behaviour of raw, pas­ ture of normal and atrophied muscle. T. Ca h n teurised, boiled, evaporated, and dried milk at (Ann. physiol, physicochim. biol., 1926, 2, 646— 681; Chem. Zentr., 1927, ii, 846— 847).—A critical review. the hydrogen-ion concentration of the stomach. A. M. Co u r tn e y (J. Can. Med. Assoc., 1927, 17, Composition of human epidermis. Y. Jo no 919— 922).—The characters of the casein precipitated (J. Biophys., 1927, 2, xlviii).— Human epidermis by acid, but not the soluble calcium and protein contained water 20%, ash 1-5% (the silica content contents, differed. Chem ical A bstracts. being high; sulphur content of ash 0-78%), fat 2%. Detection of lactic acid in stomach contents. Hydrolysis of the protein yielded tyrosine, leucine, B. B isb in i (Rinasc. rued., 1926, 3, 514— 516; Chem. alanine, valine, isoleucine, proline, glutamic acid, Zentr., 1927, ii, 964).— The stomach liquor (20 c.c.) arginine, and lysine. Chem ical A bstracts. is evaporated at 70° to 2 c.c., thoroughly extracted Ferments of human skin. N . M elczer (Der­ with ether (40—50 c.c.), the residue after removal of matol. Z., 1926, 49, 252— 261; Chem. Zentr., 1927, the ether is dissolved in lukewarm distilled water ii, 945).— Diastase, phenolase, catalase, peroxidase, (30— 40 c.c.), made alkaline with calcium oxide, and glycolytic ferment are present in human skin; filtered, and the filtrate evaporated to dryness. The .lipase is produced by the epidermal cells. In fatal residue is treated with a little water, the solution pulmonary or peritoneal tuberculosis the skin lipase filtered, evaporated on the water-bath to 0-5 c.c., is practically or completely absent. and the solution placed on an object slide in a A. A. E l d r id g e . desiccator. The formation of calcium lactate crystals Organic content of human enamel. C. Sp r a w - is observed with a microscope; 0-05% of lactic acid son and F. W. B ury (Proc. Roy. Soc., 1927, B, 102, can be detected. A. A. E ld r id g e . 419—426).—The protein content of human enamel Detection of reducing sugars in urine by calculated from the nitrogen and the carbon contents Castellani's mycological method. P. Pietra of enamel is, respectively, 0-15% and 0-21%; it is (Giorn. batteriol. immunol., 1927, 2, 1— 10; Chem. suggested that the discrepancy in these results is due Zentr., 1927, ii, 963).— Characteristic organisms to the contamination of the enamel with carbon suitable for symbiotic fermentation with yeast of from the steel used in filing the enamel from the dextrose, kevuloso, maltose, galactose, lactose, tooth. The organic content of enamel is independent pentoses, sucrose, and inositol by Castellani’s method of the dentition or the age of the tooth. are described. Within limits, several sugars present E. A. L u n t . together in urine can be detected. A. A. E l d r id g e . Determination of glutathione. A. B l a n c h e - Determination of bismuth in urine. H . B a g - TifiRE and L. M elon (Compt. rend. Soc. Biol., 1927, 97, 242— 244; Chem. Zentr., 1927, ii, 1495).— g esg a a r d -R a sm u sse n , K . A. J a c k er o tt, and S. A. Tunnicliffe’s method is preferred to that of Thompson Sch o u (Biochem. Z., 1928, 193, 53— 61).— See A., and Voegtlin. The lower limits of sensitiveness are 1927, 788. for cysteine, 200 mg. per litre, and for reduced glut­ Pigment obtained from fseces. L. F. Hewitt athione 125 mg. per litre. A. A. E ld rid g e . (Brit, J. Exp. Path., 1927, 8, 333— 335).—The rose- BIO CHEMISTRY. 441 red pigment obtained when faeces are subjected to (Proc. Imp. Acad. Tokyo, 1927, 3, 699— 701).— In­ prolonged heating with alcoholic hydrogen chloride jection of Leptospira iderohcemorrhagice, ideroides, is believed to be a dye of the diphenylmethane type, and hebdoniadis, coli and typhus vaccines, and tetra- derived by oxidation of the product of condensation hydro-p-naphthylamine in aqueous emulsion, into the of a pyrrole derivative, e.g., skatolo, with aldehyde rabbit, guinea-pig, rat, and mouse, or overheating present in the alcohol. Ch em ic al A bstracts. the animal at 40—41°, and subsequent determination Chemical changes of the blood in asphyxia. I. of the p a values of the tissues of various organs, shows that there is a decrease in the normal value of 7-0— 7-3 R. R ittm an n (Z. ges. exp. Med., 1927, 5 6 , 262— 270; Chem. Zentr., 1927, ii, 951).— The blood-calcium rises, to 6-7— 6-9. H. B urton . and -potassium falls; the residual nitrogen is not Iodine metabolism. I. Urinary excretion of increased. Fibrinogen, globulin, and albumin are iodine by the inhabitants of a Norwegian scarcely affected. A. A. E l d r id g e . goiterous district. G. L u n d e (Biochem. Z., 1928, Carbon dioxide tension in tissues in relation 1 9 3 , 94—-104).—The urinary iodine excretions of a to cancerous cells. J. C. M ottram (Nature, 1928, large number of men are tabulated and the high 121, 420—421).—A mechanism whereby localised values correlated with the type of diet. increase of the carbon dioxide tension in the tissues P. W. Clu tter b u c k . may induce abnormal cell division is indicated. Excretion of hippuric acid in renal disease. A. A. E l d r id g e . I. Snapper and A. Gru n bau m (Presse med., 1926, Fractionation of the Rous chicken sarcoma. 3 4 , 1524— 1526; Chem. Zentr., 1927, ii, 1977).— Oral K. Sugiura and S. R. B en ed ic t (J. Cancer Res., 1927, administration of 5 g. of sodium benzoate to healthy 11, 164— 186).—The nitrogen content of the Rous men results in 12 hrs. in its quantitative excretion as chicken sarcoma (dried) was 11 -0— 12-2% and the hippuric acid. In renal disease with nitrogen reten­ ash 5-69—8-01%. The tumour-producing substance tion the excretion (but not the formation) is incom­ is carried down with the globulin fraction of the plete. A. A. E ld r id g e . tumour proteins on addition of ammonium sulphate. Metabolic changes in rickets. H. H en tsc h e l Chem ical A bstracts. and E. Z oller (Monatsschr. Kinderheilk., 1926, 34, Lipin metabolism in the transplanted tumour. 248— 253; Chem. Zentr., 1927, ii, 952).— In rachitic J. H omma and T. Issnu (Gann, 1927, 31, 38— 40).— rats the total phosphoric acid was unchanged; the The blood-lipin and -lipase of tumour chickens is ability to synthesise a lactacidogenic substance from subnormal; the blood-lipin and serum-lipase in the inorganic phosphoric acid and hexose was diminished. tumour wing are also less than that in the normal A. A. E ld r id g e . wing. Chem ical A bstracts. Role of calcium in the nutrition and biological Effect of radiation on blood-cholesterol in processes of the animal organism. A. W. malignant disease. W. L. M at tic k and K. B u c h - Popova (Arch. Sci. Biol., 1927, 27, 377— 392).—The w ald (J. Cancer Res., 1927,1 1 , 86— 100).— A solution variations in blood-calcium have been determined in of cholesterol in chloroform is affected by radiation of the guinea-pig as an index of the progress of the short wave-length, the amount of change depending diseases of scurvy and tuberculosis, and it is con­ on the condition of the solute. cluded in the latter case that these variations give Chem ical A bstracts. results which can be correlated with the corresponding Hyperallantoinuria in experimental polyuria variations in temperature and body-weight; the and diabetes insipidus in man. A. E . y Costa author regards hypercalcsemia as an index of serious (Cornpt. rend., 1928, 1 8 6 , 650— 652).— Allantoin is pathological catabolism. E. A. L unt. determined by a variation of Wiechowski’s method. Blood-sugar level in pulmonary tuberculosis. The precipitate with mercury is decomposed by G. Sa y a g o , T. d e V. L astr a, and C. M. V ocos (Rev. hydrogen sulphide and half the solution used for the Soc. Argentina Biol., 1927, 3, 585— 595).— It was determination of carbamide by xanthydrol. The found that the mean blood-sugar level was lower in other half is hydrolysed with hydrochloric acid in an acute cases of pulmonary tuberculosis than in mild autoclave and the ammonia determined. The differ­ cases, but the range of variation was much greater ence between total and carbamide ammonia represents in acute cases. Administration of dextrose per os 92% of the nitrogen of the allantoin. Polyuria caused a prolonged subnormal reaction in acute cases produced by the ingestion of water, injection of and a subnormal or normal reaction of normal duration “ novasurol,” and in diabetes insipidus is always in mild cases. Both rise and fall of blood-sugar level accompanied by a high allantoin excretion. were observed following pneumothorax of different W. K . Sl a t e r . origin, but no definite conclusion could be reached as Acetates in normal and diabetic blood. A. A. to the cause of variation. R. K. Ca l l o w . B runo (Rev. Soc. Argentina Biol., 1927, 3, 617— 620). The blood of normal dogs contained 1-0— 1-5 mg.-% Buffering power of serum and immunity. of acetic acid. Higher proportions were found in W . K opacze w sk i (Compt. rend., 1928, 1 8 6 , 635— diabetic dogs and lower proportions in dogs after the 637).— The physico-chemical properties of the medium injection of insulin. It is concluded that acetic acid in which pathogenic organisms arc grown begin to is not formed directly from carbohydrates. change only when the number of organisms has R. K. Ca l l o w . increased to such an extent that the regulating Reaction of tissues. I. Hydrogen-ion con­ mechanisms of the medium are exhausted. It is centration of tissues during fever. J. Ogaw a suggested that the periods of incubation in, and 442 BRITISH CHEMICAL ABSTRACTS.— A.

immunity from, certain diseases are to be attributed water only was administered, diminishing alternations to this effect. W. K . Sla te r . of the rise and fall of the two first-named variables were observed. G. A. C. Gough. Respiration of the frog’s heart. I. Oxygen consumption of the surviving frog’s heart per­ Metabolism with regard to calcium supply. fused with Ringer, Tyrode, and Locke solu­ W. Iyra ne (Pfliigers Archiv, 1927,2 1 7 ,24— 35; Chem. tions. T. H ir a o k a . II. Influence of acid and Zentr., 1927, ii, 1166).— The requirement for calcium alkali on the oxygen consumption of the surviv­ equilibrium is 1-2— 1-5 g. of calcium per day. The ing frog’s heart. W. A r n o l d i and T. H ir a o k a value is higher for a diet rich in meat. Calcium (Biochem. Z., 1928, 193, 197— 202, 203— 206).— I. administration has no influence on the nitrogen The oxygen consumption of the frog’s heart is much metabolism. Faecal nitrogen diminishes during more constant with Tyrode than with Ringer solution. administration of calcium. Deposition of calcium No difference in oxygen utilisation was obtained on in the body causes loss of chlorine and removal of perfusing with Tyrode solution (pn 7-7) with or sodium and potassium from the body. without dextrose, the oxygen usage being 0-1 c.c. A. A. E l d r id g e . per g. per hr. more than during perfusion with Effect of variations in calcium, magnesium, Ringer solution (pn 6-7). and phosphorus of the diet. J. R. H aag and Ili The oxygen consumption of the surviving L. S. Palm er (J. Biol. Chem., 1928, 76, 367— 389).— frog’s heart perfused with 121 c.c. of Tyrode solution Normal growth in rats could be obtained only so long (without dextrose), on addition of 0-001iV-hydro- as a balance was preserved between the above- chloric acid, at first rapidly decreases (with 0-5 c.c.), mentioned elements in the diet; in particular, it was then rises to the original value (0-5— 3 c.c.), then found that a high concentration of magnesium, in again decreases (3—8 c.c.), and finally increases combination with low concentrations of calcium and again (8— 11 c.c.). Similar addition of O-OOliV- phosphorus, retarded growth and calcification. sodium hydroxide causes with the first 0-5 c.c. a rapid 0 . R. IIa r m e TO N . fall, followed by a more gentle fall (0-5—7 c.c.) of Action of sugar in the organism. IV. oxygen utilisation. P. W. Cl u tt e r b u c k . Behaviour of blood-sugar after intravenous injections of methylglyoxal, dihydroxyacetone, Gas and sugar metabolism of the vivi-perfused and dextrose. F. F isc h ler and 0. H irsch (Arch, stom ach. T. G. N i and R. K. S. L im (Chinese J. exp. Path. Pharm., 1928, 1 2 7 , 287— 307).— The Physiol., 1928, 2, 45— 86).— In the vivi-perfused authors advance a scheme of the mechanism of sugar stomach there is an increase in oxygen consumption regulation in the body. Methylglyoxal is considered during secretion from 3- to 9-fold as compared with the to be an intermediate in the decomposition of sugar. quiescent oxygen consumption of 0-007 c.c. per g. It is produced whenever there is a large and rapid per min. (corresponding with a basal coefficient of breakdown of sugar, and then it acts as a central the gastric mucosa of 0-013 c.c. of oxygen). The nervous stimulant whereby the store of glycogen is respiratory quotient of the stomach may vary from mobilised and sugar produced. Dihydroxyacetone 0-6 during motility to 1-31 during secretion. After a is able to prevent the excessive action of methyl­ meal the metabolism of the stomach may account for glyoxal in this direction. W. R obson. an increase of 10— 12% of the basal metabolism. Relation between vegetable and animal carbo­ W. O. K erm ack. Relation between glutathione and the intra­ hydrate degradation. A. Gottschalk (Ergebn. Physiol., 1926, 2 5 , 643— 663; Chem. Zentr., 1927, cellular oxidation-reduction potential. P. J o y e t - ii, 953).—A discussion. Three types of carbohydrate L avergne (Compt. rend. Soc. Biol., 1927, 9 7 , 140— 142; Cheru. Zentr., 1927, ii, 1168).— Glutathione degradation are differentiated. A. A. E l d r id g e . is an important factor in the rn value, and therefore Is there a proportionality between the per­ influences intracellular respiration. In organs the formance of work and the lactic acid, phos­ regions rich in glutathione appear to be those of the phorus, and sugar contents of blood ? N. P. most intensive carbohydrate metabolism. R iabouschinsky (Biochem. Z., 1928,1 9 3 , 161— 175). A. A. E ld r id g e . —By increasing the performance of work, the per­ Urinary excretion of ketonic substances by centage content of lactic acid which reaches the blood the fasting dog. F. M a ig n o n and E. K n it h a k is from the muscles increases in direct proportion. The (Compt. rend., 1928, 1 8 6 , 463— 465).— The daily lactic acid is not distributed throughout the body average urinary excretion of (3-hydroxybutyric acid uniformly immediately after the work or in the resting falls from 0-077 to 0-023 g. during S— 16 days’ starv­ period. After lifting weights, the lactic acid content ation, during which water only was administered, of the blood of the active arm is increased, the increase whilst that of acetone rises from 0-001 to 0-005 g. being conditioned by congestion and insufficient oxygen E. W . W ig n a l l . supply. During this static work, the lactic acid Variations of the p a and the alkaline reserve content of the blood of the inactive arm remained of the blood of the fasting dog. [F.] M a ig n o n almost unchanged. Immediately after the work, a and E. K n it h a k is (Compt. rend., 1928, 1 8 6 , 600— considerable increase of inorganic phosphorus is 602).— In dogs given nothing but water the acidosis found which is proportional to the amount of work leads generally to a fall in the pn and to only slight done. In the resting period, the inorganic phosphorus variations in the alkaline reserve and the total carbon of the blood in the working arm decreases below the dioxide content of the blood; in a few eases rapid original level, the decrease being the greater the larger adjustment is observed. In prolonged fasting, when the amount of work done. Immediately after work, BIOCHEMISTRY. 443

a slight increase of blood-sugar is usually observed, A. R abbeno (Arch. sci. biol., 1926, 9, 161— 167, and in the resting phase, a decrease, but these changes 168— 177, 178— 183; Chem. Zentr., 1927, ii, 1163).— are not in proportion to the amount of work done. The effect of life at a high altitude, and that of main­ P. W. Clu tter b u c k. tenance at a constant temperature throughout the Metabolism after extirpation of [dog’s] liver. year, on the cholesterol and neutral fat content are V. M. V esselk in a (Z. ges. exp. Med., 1927, 55, investigated. A. A. E l d r id g e . 198— 213; Chem. Zentr., 1927, ii, 453).—After Biological activity of the porphyrins. K. extirpation of the livers of fasting dogs (after which R eitlin g er and P. K lee (Arch. exp. Path. Pharm., death occurred in 3— 16 hrs.), the urine was free from 1928, 1 2 7 , 277— 286).— Haemato-, copro-, and uro­ albumin and was strongly acid. The ammonia, porphyrin increase the tonus of the surviving small amino-nitrogcn, uric acid, and purine- and allantoin- intestine of the guinea-pig, cat, and rabbit. The nitrogen were increased. ‘A. A. E l d r id g e . action is strongest in the case of the dibasic baemato- Growth on diets practically devoid of arginine. porphyrin and the tetrabasic coproporphyrin, Relation of glutamic and aspartic acids to weakest in the case of the octabasic uroporphyrin. nutrition. W. E. B u n n e y and W. C. R ose (J. Atropine is unable to inhibit the action of porphyrin. Biol. Chem., 1928, 76, 521— 534).— Good growth was No relationship between the actions of porphyrin and obtained in rats on a diet in which the source of choline has been found. The porphyrins are unable nitrogen was hydrolysed caseinogen from which to sensitise the intestine to light rays. practically all the arginine had been removed by W. R obso n . precipitation with flavianic acid; in some experi­ Alcohol. III. Variations in the alcohol con­ ments, in which a large proportion of the dicarboxylic tent of human blood. H. K io n k a . IV. D eter­ amino-acids had also been removed, growth continued mination of ethyl alcohol in urine. P. H ir sc h . to be satisfactory. C. R . H a r in g to n . V. Excretion of alcohol by the kidneys. H. Nitrogen minimum. Effect of protein-free K io n k a and M. H au fe (Arch. exp. Path. Pharm., diet on urinary nitrogen and on heat production. 1928, 1 2 8 , 133— 145, 146— 149, 150— 164; cf. A., Effect of thyroxine following protein-free diet. 1924, i, 1366).— III. The concentration of alcohol H. J. D eu el, jun., I. Sa n d ifo r d , K . Sa n d ifo r d , and in the blood has been determined in individuals W. M. B oothuy (J. Biol. Chem., 1928, 76, 391—406, fasting and after the administration by mouth of 407—414).—After 30 days on a protein-free diet the various quantities of alcohol. The maximum con­ urinary nitrogen excretion of a normal man was centration found in the blood increases with the 2-1 g. per day; the basal metabolic rate fell about quantity of alcohol taken from a mean fasting value 20%; at this stage thyroxine was administered, and of 0-0031% to a mean value of 0-0452% after exerted its characteristic effect in increasing the basal administration of 114 e.c. of alcohol. The effect of metabolic rate and the excretion of carbamide. various factors on the blood-alcohol curve has been Continuance of the protein-free diet after treatment investigated, and in particular the previous con­ with thyroxine finally reduced the daily excretion sumption of a meal and also the induction of marked of nitrogen to 1-75 g. Practically all variations in diuresis causes the maximal values attained to be lower. nitrogen excretion were due to variations in carbamide. IV. The interferometer method previously devised The total excretion of nitrogen throughout the whole by Kionka and Hirsch (A., 1924, i, 1366) for the protein-free period was 291 g. and indicates that the determination of alcohol in blood has been developed reserve protein of the body is greater than has been so as to be applicable to the determination of alcohol previously supposed. C. R. H a r in g to n . in urine. V. The quantity of alcohol excreted in the urine, Limit of acid taste and hydrogen-ion con­ always a small percentage of that administered, centration. A. B er l a tzk y and T. G u ev a r a (Rev. increases relatively when the quantity administered Soc. Argentina Biol., 1927, 3, 721— 724).— The values is very small. The major part of the alcohol excreted of pn at the limiting concentrations for perception of in the urine is eliminated during the 3— 4 hrs. follow­ acid taste were : sulphuric acid, 2-9; nitric, 3-2; ing consumption. Relatively more appears in the citric, 3-9; tartaric, hydrochloric, and lactic, 4-3; urine when it is administered in a concentrated form. acetic, 4-5; phosphoric, 4-7. If acid taste is due to hydrogen ions, this series is explicable if the anion The maximum urine concentration never exceeds about 0-1%. With increased diuresis the quantity has an antagonistic cation, which is probably depend­ of alcohol excreted is increased. The concentration ent on the ionic mobility. Thus sulphate ions depress of alcohol in the urine depends on the concentration the sensitivity of the nerves more than chloride ions, in the blood, but no simple relationship appears to magnesium sulphate having a higher concentration limit of bitter taste (due to magnesium ions) than the exist. W. 0. K e r m ack . chloride. Similar results were obtained with sodium Higher toxicity of methyl alcohol in presence and potassium nitrates and chlorides. of ethyl alcohol. M. P a n t a l e o n i (Ann. Igiene, R. K. Ca l l o w . 1927, 37, 537— 540; Chem. Zentr., 1927, ii, 1980— o Effect of p-indolethylamine on blood-sugar. 1981).—A mixture of equal parts of methyl and ethyl S H aseg aw a (J. Biophys., 1927, 2, xlvi— xlvii).— alcohols is much more toxic to cats than either With small, but not large, injections, hypcrglycaemia alcohol alone. A. A. E l d r id g e . occurred. Chem ical A bstracts. Effect of on blood-sugar level. Influence of climatic factors on the cholesterol M. A. Mag en ta (Rev. Soc. Argentina Biol., 1927, 3, of the blood and suprarenal capsule. I—III. 681—686).—The blood-sugar level of dogs injected 444 BRITISH CHEMICAL ABSTRACTS.— A. with chloralose, after slight irregular variation, fell limited to those cases in which hydrogen sulphide is to a minimum after 5— 7 hrs. and then regained the of use. W. R obson . normal value. The variation from normal is small, Detoxication of hydrogen cyanide. A. W. and chloralose is therefore a good anaesthetic for use F orst (Arch. exp. Path. Pharm., 1928,1 2 8 , 1— 66).— in the study of hyperglycsemia. R. K. Ca l l o w . The toxic action of hydrogen cyanide is inhibited (except in the case of white rats) by previous adminis­ Elimination of morphine. F. de Cam elis (Arch. Farm, sperim., 1927, 44, 77— 92).— Only a very tration of sodium thiosulphate or, even more effect­ small proportion of a dose of morphine is eliminated ively, of colloidal sulphur. These compounds are in the faeces. The urine contains morphine 24 or 48 quite ineffective against poisoning by aromatic hrs., but not on the third day, after the administration. nitriles. Administration of dextrose protects against Repeated administration of morphine results in the four times the lethal dose of hydrogen cyanide. appearance of reducing substances, probably owing Insulin alone has very little action, whilst insulin to the presence of morphine-glycuronic acid. and dextrose are practically no more effective than is dextrose alone. Dihydroxyacetone effectively pro­ T. H. P ope. tects against nine times the lethal dose of the poison. Pharmacological assay of ergot. I. B. vo n If dihydroxyacetone is administered after the I sse k u t z and M. v o n L e in z in g e r . II. M. v o n symptoms have developed, the symptoms disappear L e in z in g e r and J. v o n K ele m e n (Arch. exp. Path. Pharm., 1928, 128, 165— 172, 173— 178).— I. The but death is not averted. When, however, dihydroxy­ antagonistic action of ergotamino and adrenaline on acetone and sulphur are administered together (after the isolated rabbit intestine may be used to determine poisoning by 9— 10 times the lethal dose of hydrogen the activity of the alkaloids of ergot. cyanide), recovery is effected even after the symptoms II. Determination of the alkaloid content of ergot of poisoning have developed. W. 0. K erm ack . by the Iveller-Fromme method (cf. Z. anal. Chem., Barium and sulphate as antidotes. L. Scre- 1894, 3 4 , 115; 1907. 46, 743) gives a very good indic­ m in (Arch. int. pharmacodyn. ther., 1926, 3 2 , 207— ation of its biological activity. W. 0. K er m ack . 215; Chem. Zentr., 1927, ii, 954).— When injected slowly; but not when injected rapidly, colloidal Comparative behaviour of animal charcoal barium carbonate is somewhat less toxic than barium and activated aluminium in toxicology. G. chloride. The toxicity is not reduced by simultaneous Sen si and C. D e R osa (Annali Chim. Appl., 1928,18, injection of equimolecular sodium sulphate; a solution 3—18).—Aqueous alcoholic extracts of alkaloids five times as concentrated is required. Barium obtained from animal organs in toxicological investig­ hydrogen carbonate is apparently formed in the blood. ations may be conveniently purified by means of On slow injection elimination of sulphate runs parallel activated aluminium, prepared by immersion of with injection, and in dilute solutions the conditions sheet metal or turnings in 10% mercuric chloride do not favour the formation of complex salts contain­ solution for 3 min., washing with much water, then ing anionic barium. A. A. E ld r id g e . with alcohol, and finally with ether, and storing the dried metal under light petroleum; the latter is Chemical changes in blood in mercuric removed and the metal weighed immediately before chloride poisoning. H. M. T r u sle r , W . S. use. Activated aluminium is easier to prepare, and F ish e r , and C. L. R ichardson (Arch. Int. Med., more convenient to use, than animal charcoal. 1928, 4 1 , 234— 243).—Mercuric chloride poisoning by From none of the alkaloid solutions tested is more intravenous injection causes a lowering of the blood- alkaloid removed by the aluminium than by animal chlorides in dogs, but not in rabbits. The dogs charcoal, and in some cases considerably less is suffer from violent vomiting, whilst the rabbits do removed. T. H. Po p e . not. Other symptoms are similar, hence it is con­ cluded that the chlorides are lost by vomiting. Iiypo- E ffect of sodium fluoride on blood-sugar chlorcemia was found to cause gastric tetany associated level. M. A. M ag e n ta (Rev. Soc. Argentina Biol., with acidosis. Intravenous injection of 2% sodium 1927, 3, 691— 693).—Injection of sodium fluoride into chloride solution prevents tetany but does not in­ dogs had little effect on the blood-sugar level, in­ fluence the other symptoms. The clinical aspect is creasing it only when the toxic dose (50 mg. per kg.) discussed. W . K. Sl a te r . was reached. R. K. Ca l l o w . Preventive action of metals against syphilis. Degree of dispersity and pharmacological C. L e v a d it i, V. S. B a y a r r i, R. Sch oen, and Y. Ma n in (Ann. Inst. Pasteur, 1928, 4 2 , 105— 169; cf. action of colloidal sulphur. M. M e ssin i (Arch, exp. Path. Pharm., 1928, 127, 366— 382).— The A., 1927, 587).— Administration of finely-divided toxicity of colloidal sulphur depends on the mode of tellurium and bismuth and of certain derivatives its preparation, its age, its concentration, and on the of these metals to rabbits renders them resistant rate of its injection. With these factors the degree to subsequent experimental infection with syphilis. of dispersity of the colloidal sulphur varies, and with The protection given by bismuth may exceed that the latter in turn its surface of contact with the body conferred by arsenobenzene and other arsenicals. fluids which reduce it to hydrogen sulphide. The The degree and duration of immunity depend both pharmacological and toxic actions of colloidal sulphur on the dose and on the nature of the metal derivative depend on its conversion into hydrogen sulphide, and administered. W . O. K e r m ack . hence its therapeutic action must be assigned chiefly Azo-dyes containing antimony in the treat­ to the hydrogen sulphide and in general its application ment of trypanosomiasis. F. D u n n in g and BIO CHEMISTRY. 445

D. I. M acht (J. Pharm. Exp. Ther., 1928, 3 2 , 205— stable than the extract. Whereas the latter becomes 213).— Azo-dyes of the general formulae inactive on keeping for a few hours, the purified Na203Sb-06H4-N:N-C6H3R-0H or enzyme solution loses only about half its activity in Na203Sb'C6HyN;N-CGH,-NR2 do not cure rats 24—48 hrs. Sodium fluoride acts on the purified infected with Trypanosoma equiperdum. Of the enzyme much less than on the extract, attacking dyes formed by coupling diazotised stibanilic acid probably the protein substances accompanying the with a-naphthol-4-sulphonic acid, |3-naphthol-3 : 6- enzyme. The action of arsenate is, however, the disulphonic acid, 1 : 8-dihydroxynaphthalene-2 ; 0- same for both. P. W. Clu tte r b u c k . disulphonic acid, S-amino-a-naphthol-3 : 6-disul- Lipase. I. Optimum action of gastric lipase. phonic acid, 6-amino-a-naphthol-3-sulphonic acid, and II. Lipase of organs and its resistance to acids p-naphthylamine-3 : 6-disulphonic acid, respectively, and alkalis. III. Action of quinine on lipase the sodium salts of the last three possess marked of organs. K. G y o t o k u (Biochem. Z., 1928, 183, curative action, the ratio of tho maximum tolerated 18— 26, 27— 3S, 39— 52).— I. The optimal p n for the dose to the minimum curative dose being 6— 7, 4— 5, action of rabbit’s and human gastric lipase is 6-0, and 4— 5, respectively. W . 0 . K erm ack. and after purification 7-6— 7-8. When pig’s gastric Effect of catalase injected into the circulating lipase, the optimal p u of which lies on the alkaline blood. Catalase and anticatalase content of side, is kept in the dry condition, its optimal p H is various tissues. L. B e l k in e , R. E a l k , and L. displaced to 6-0— 6-5, the change not being obtained K rem lev (Compt. rend. Soc. Biol., 1927, 97, 525— with the gastric lipase of rabbit, dog, and man. When 526; Chem. Zentr., 1927, ii, 1480).— Catalase, when the enzyme is kept in solution, the optimum is dis­ injected into the blood, disappears in 3 hrs. The placed to the alkaline side. Normal gastric lipase is catalase content of tissue is at first increased, probably combined with substances -which activate particularly in the kidneys and muscles, and then the lipolytic action in acid, and inhibit in alkaline gradually falls to the normal value. Anticatalase medium. changes show no such regularity. A. A. E ld r id g e . II. Gastric lipase is more resistant to acids than Action of light on the decolorisation process alkalis and pancreatic and liver lipases are more resist­ in a dehydrogenase-methylene-blue system. A. ant to alkalis, but gastric lipase is much more stable K restovotkov (Skand. Arch. Physiol., 1927, 52, than other organ lipases to such reagents. Purific­ 199—208; Chem. Zentr., 1927, ii, 1478).— The ation of gastric lipases of man, dog, and pig causes decolorisation of methylene-blue in the presence of decrease of resistance to acids, the enzyme becoming dehydrogenase and a hydrogen donator is accelerated no more stable than pancreatic lipase. Pancreatic by light; hence in Thunberg’s method the illumination and liver lipases also lose their resistance to alkalis must be weak and uniform. A. A. E ld r id g e . on purification. Unpurified gastric lipase retains its resistance to acids for a long time on keeping. Strong Preparation of succinodehydrogenase. N. acids and alkalis cause great injury to lipases, the Andersson (Skand. Arch. Physiol., 1927, 5 2 , 187— degree of injury being directly related to the concen­ 198; Chem. Zentr., 1927, ii, 1479).— Chopped muscle tration of hydrogen or hydroxyl ions; addition of (100 g.) is washed with 100 c.c. quantities of 0-25% proteins or peptones protects the enzyme to some sodium chloride solution until the mass is colourless; extent. it is then ground with M /15-disodium hydrogen III. Pancreatic, liver, and gastric lipases are often phosphate solution, shaken for 1 hr., and the ferment sensitive to quinine and may be either activated solution separated by centrifuging. or inhibited. Refractory lipases, on purification, A. A. E l d r id g e . become considerably inhibited by quinine. When Purification of the lactic acid-forming enzyme. dried lipases of organs are kept for several months, K . M e ye r (Biochem. Z., 1928, 193, 139— 160).— the extent of the quinine inhibition decreases. With Purification of the lactic acid-forming enzyme of pig’s liver lipase an 80— 90% activation is obtained. muscle from protein may be effected either by re­ The action of quinine on the lipase is the sum of two peated acetate precipitation at p a 5 with subsequent opposed effects, that on the enzyme itself and that on elution by dilute phosphate at p a 7-5— 8, or by the substances accompanying it which are lost on adsorption of the enzyme on alumina followed by purification. The organ lipases of man and dog are phosphate elution. The first method occasionally gives much more sensitive to quinine than those of rabbit, an enzyme of high degree of activity (50 times the pig, cat, sheep, and guinea-pig, and serum-lipases of original), but the result is difficult to reproduce. The man and dog are much more sensitive than pancreatic second method gives much more consistent results, lipase. P. W . Cl u tte r b u c k . the activity being increased 20 times. The amount of the increased activity depends on various factors, Influence of cations on the action of lipase. especially on the dilution of the alumina adsórbate S. U exo (J. Biophys., 1927, 2, xxxiv).—Potassium and on the distribution of enzyme between precipitate and (to a smaller extent) sodium retard, whilst and solution. To elute the enzyme, short, gentle manganese and cobalt accelerate, the action of shaking with phosphate is used, since vigorous pancreatic lipase on cream. Strontium, calcium, shaking inactivates it. In this case only the heat- barium, magnesium, nickel, uranyl, copper, and sensitive part of the enzyme is freed from protein. mercury depress the action in that order. The Addition of the heat-stable co-enzyme (boiled muscle depressing action of sodium is neutralised by stron extract) is always necessary for the formation of tium, barium, calcium, and magnesium. lactic acid. The purified enzyme is relatively more CHEancAL A bstracts. 446 BRITISH CHEMICAL ABSTRACTS.— A.

Melibiase. II. R. W e id e x h a g e n (Z. Ver. deut. trinitrate, alanyl- and leucyl-fi-amino-n-butyric acids, Zucker-Ind., 1928, 99— 110; cf. ibid., 1927, 699).— glycyl- and alanyl-a-amino-n-hexoic acids, leucyl-e- Purified yeast melibiase has a maximum activity at amino-«-hexoic acid, glycyl anhydride, glycylalanine p a 4-8, but it docs not vary much between pn 3-5 and anhydride, alanylphenylalanyl anhydride, glycyl­ 5-5. With varying concentrations of enzyme the serine anhydride, phenyldiketopiperazine, leucyltri- same percentage of melibiose is hydrolysed in times glycyl-leucine, leucylheptoglycine, leucylnonaglycine, inversely proportional to the concentration of the a-bromoisohexoylnonaglycine, a-bromoisohcxoyl- enzyme provided the other conditions are kept con­ triglycyl-leucylnonaglycine, leueyltriglycyl-leucyltri- stant. The activity of melibiase in certain pre­ glycyl-leucylnonaglycine, leucylglycyltyrosine, glycyl- parations is within limits approximately represented alanyltyrosine, glycyltyrosylglycine, glycylalanyl- by the formula for a unimolccular reaction. Suitable glycyltyrosinc, and p-naphthalenesulphonylglyeyl- units in which to measure the activity of melibiase tyrosine. The dipeptides occupy an exceptional and the concentration of it in any particular material position, since, independently of the nature of the are suggested, following the principles used by amino-acids from which they are derived, they act as Willstatter (A., 1920, 1, 795) in relation to maltase. specific substrates for erepsin; a possible exception is Methods are described for the preparation of meli­ diarginine trinitrate, which may not have the con­ biase solutions and for the determination of melibiase stitution ascribed to it by Eischcr and Suzuki (A., in yeast. W. 0. K erm ack. 1906, i, 73). Fission of higher peptides by pancreas trypsin, which is inactive towards all dipeptides, Decomposition of urea by urease. S. M o r i (J. Biopliys., 1927, 2, xxiii).— When the solution is depends on the presence of certain amino-acids, of sufficiently buffered against the ammonia formed, the which tyrosine is an example. An indication of the reaction is shown to be unimolecular. cause of the specific differences in the actions of Ch em ical A bstracts. trypsin and erepsin is found in the alteration of the Decomposition of caseinogen by trypsin. S. behaviour of glycyltyrosine consequent on the introduction of the p-naphthalenesulphonyl group; M ori (J. Biophys., 1927, 2, xxiii).— The velocity is proportional to the amount of enzyme. The glycyltyrosine is hydrolysed only by erepsin, fi-haph- optimal reaction takes place at 55° with p a 7-76— thalenesulphonylglycyltyrosine only by trypsin. Erepsin appears to require the presence of a free amino- 7-7S. Chem ical A bstracts. group, which is unnecessary for trypsin. Dénaturation of proteins. VI. Effect of dé­ H. W r e n . naturation on the digestibility of ovalbumin by Growth of the yeast Saccharomyces cerevisice. pepsin and trypsin. K . H. L i n , H. W it, and I. The growth curve and the effect of tem­ Ch en T. T. (Chinese J. Physiol., 1928, 2, 107— 130).— perature on the yeast growth. 0. W . R ic h ar d s Natural and denatured egg-albumins are digested by (Ann. Bot., 1928, 42, 271— 2S3).— The growth curve pepsin or trypsin at different rates. The optimal pH is an asymmetrical S-shaped curve in which, in the varies according to the method of dénaturation. The medium employed, maximum growth is attained results are considered to support the view that the within 100 hrs. following seeding. Cell-voluine fundamental change in dénaturation is similar in increase exceeds cell-number increase for the first nature to some of the early stages of .tryptic digestion. 15 hrs. and then decreases; both have the same value W. Ô. Ivermack. after 90 hrs. Analyses of the curve indicate that the Digestibility of racemised caseinogen and limiting master reaction is quinquemolccular. egg-albumin. K. H. L i n , H. Wit, and T. T. Ch e n E. A. L u n t . (Chinese J. Physiol., 1928, 2, 131— 137).— Racemised Acetylmethylcarbinol formation in the egg-albumin and racemised caseinogen are subject alcoholic fermentation of sugar. L. E lio n (Ned. to putrefaction, and are hydrolysed by enzymes tijdschr. hyg. microbiol., 1926, 1, 171— 179; Chem. provided the hydrogen-ion concentration of the Zentr., 1927, ii, 1042).— The appearance of acetyl­ medium is suitable, but the rates of hydrolysis are methylcarbinol as a product of the fermentation of less than those of the natural proteins. These results sugar fixes the acetaldehyde, which can no longer act do not agree with those of Dakin and Dudley (cf. as hydrogen-acceptor. Free hydrogen, however, is A., 1913, i, 1249), who claim that racemised protein not evolved, but a complex reduction process takes undergoes neither hydrolysis by enzymes nor putre­ place, the nature of which is under investigation. faction. The racemised egg-albumin is purified by A. A. E ld r id g e . utilising its low solubility at the isoelectric point, Comparison of the actions of arsenate and Pn 4-45. W. O. K erm ack. organic derivatives of arsenic acid on alcoholic Specificity of animal proteases. XII. Speci­ fermentation of sugar. P. M a y e r (Biochem. Z., ficity of pancreatic trypsin and intestinal erepsin. 192S, 193, 176— 180).— A number of aromatic E. W aldsch m idt-L e itz, A Sch affner, H. derivatives of arsenic acid can accelerate fermentation Sch latter, and W. K lein (Ber., 1928, 61, [B], of hexosediphosphate, especially phenvlarsinic and 299— 306; cf. A., 1927, 1112).— Investigation has arsanilic acids, but none of these substances has as been made of the hydrolytic action of intestinal great an effect as potassium arsenate. erepsin, trypsin kinase, and, in some cases, of trypsin P. W . Clu tte r b u c k . towards glycylglycine, leucylglycine, leucyl-leucine, Thermophilic and thermoduric micro-organ­ glycylserine, alanylserine, I eucy 1 m eth y lisoserine, isms, with special reference to species isolated glycylcystine, dileucvlcystine, leucylglutamic acid, from milk. I. Review of literature. III. phenylalanylglutamic acid, glycyltvrosine, diarginine Description of non-spore-forming, thermoduric BIOCHEMISTRY. 447

organisms isolated. A. H. R obertson (New of volutin by Bacillus alvei depends on the size of York Agric. Exp. Sta., Tech. Bulls. 130 and 131, the cell, and hence on the sodium chloride content. Aug. 1927, 56 and 62 pp.). A. A. E l d r id g e . Fat metabolism of llyphomycetce. I. A. von Thermopliilic fermentation processes. C. M allinck r o d t - H a l pt (Zentr. Bakt. Par., 1927,1,103, Coolhaas (Ned. tijdschr. hyg. microbiol., 1926, 1, 73— 87 ; Chem. Zentr., 1927, ii, 1041).— Trichophyton 338— 350; Chem. Zentr., 1927, ii, 1159).— A rapid gypseum grows on Uschinskv’s medium with butter thermophilic fermentation of formate, acetate, oxalate, or lard, but not cod-liver oil; growth was poor on gluconate, and lactate, and a slower fermentation of beef- or mutton-fat. Olive and castor oils were butyrate and propionate to carbon dioxide and suitable, as well as pure triacetin and triolein. The methane took place with spore-forming rod-bacteria optimum pa for tributyrin hydrolysis is 6-0, and for of very different lengths. In a fermentation of peptone 7-0. A. A. E ld r id g e . peptone to carbon dioxide and methane, most of the nitrogen was converted into ammonia. A motile, Oxidation of waxes by micro-organisms. spore-forming, aerobic bacterium caused the extra­ W . O. T ausson (Biochem. Z., 1928, 193, 85— 93).— ordinarily rapid conversion of starch into maltose and Aspergillus jlavus can utilise as a source of carbon the dextrin ; another bacterium fermented various carbo­ esters of higher fatty acids with glycerol and with hydrates to carbon dioxide, hydrogen, butyric acid, the higher alcohols. There is a close correspondence between the power of the mould to use these substances and active lactic acid. A. A. E l d r id g e . and to oxidise paraffin. The absolute amount of Action of digestive juices on lactic organisms. wax oxidised by the mould is proportional to the age C. A. Sagastum e and A. Solari (Rev. Soc. Argentina of the culture and is smaller than the amounts of Biol., 1927, 3, 573— 580).—When a mixture of 71. acidi paraffin oxidised under the same conditions. The lacti, a lactic streptococcus, and a torula from milk was results support the view that such esters are formed incubated in acid and alkaline media (pu 1-2— 1-9 and as an intermediate stage in the oxidation of paraffin. 10-4— 10-8), the first two alone were affected, being P. W . Cl u tte r b u c k . killed at p n <1-4. B. acidophilus and B. bulgaricus Formation of citric acid by Aspergillus niger. were tested in the same media and in hypochlorhydric, E. Challenger, L. K le in , V. Sttbramaniam, and normal, and hyperchlorhydric gastric juice, and in T. K. W a lk e r (Nature, 1928, 121, 244).— Potassium duodenal j uice. Whilst B. acidophilus was practically citrate has been isolated from cultures of A . niger on unaffected, B. bulgaricus was killed in the acid media potassium hydrogen adipatc and on potassium and in hyperchlorhydric gastric juice. muconate. A. A. E ld r id g e . Since the nutritive requirements of B. acidophilus Formation of an o-diphenol at the expense of and B. bulgaricus are similar, the difficulty of adapt­ sugars by certain m icrobes of the soil. L emoig n e ation of the latter to the human intestine which is (Compt. rend., 1928, 186 , 473— 475).— B. subtilis and generally recorded can be attributed to its lower other soil bacteria which give a butyleneglycol resistance to the digestive juices, combined with the fermentation are cultivated on an acid medium bacterial antagonism of the intestinal medium. containing sugar as the sole organic constituent; the R . K . Ca l l o w . product gives with ferric chloride, after precipitation Fermentation of dextrose by Bacillus coli. and re-dissolution of ferric phosphate, a green color­ R osnatovsky (Zentr. Bakt. Par., 1927, I, 102, ation attributed to the presence of an o-diphenol. The 145— 148; Chem. Zentr., 1927, ii, 1481).— When product on concentration shows all the reactions of B. coli is grown on acid or neutral bouillon in presence o-diphenols, but no chemical individual is isolated. of 0-5—2-0% of dextrose, the amount of gas produced E. W . WlGNALL. (hydrogen : carbon dioxide=6 : 1 to 10 : 1 in acid, Nitrate reduction by Azotobacter. S. K o s t y t - always 2 : 1 in neutral bouillon) is variable, and sch ev and O. S ch tezov a (Z. wiss. Biol., Abt. 3. independent of the sugar content. Intermediate Planta, Arch. wiss. Bot., 1926, 2, 527— 529; Chem. products therefore appear to bo concerned. Zentr., 1927, ii, 1159).— A discussion. A. A. E l d r id g e . A. A. E l d r id g e . Biochemical preparation of a disaccharide- Biological reduction of mineral phosphate. monophosphoric ester. C. N kuberg and J. K. I. R u d a k o v (Zentr. Bakt. Par., 1927, II, 70, 202— Leibowitz (Biochem. Z., 1928, 193, 237— 244).— 214; Chem. Zentr., 1927, ii, 947).— Reduction of phos- Dephosphorylation of sodium hexosediphosphate by phoric acid in soil to phosphorous andhypophosphorous the action of B. coli and B. lactis a'èrogenes gave poor acids and phosphine by micro-organisms in soil has results, the action being slow and incomplete. With been observed. The reduction process is diminished the lactic acid bacterium, B. Delbriicki, however, by addition of potassium nitrate and magnesium a disaccharidemonophosphoric ester was obtained, sulphate. A pure culture of the reducing organism determinations of carbon, hydrogen, barium (of was obtained. A. A. E l d r id g e. barium salt), and phosphorus agreeing with the formula for the barium salt of C12H210 14PBa, Decomposition of fats by the tubercle bacillus. « d +55-2°. p yy Clutterbuck. A. S edych and G. S elib er (Compt. rend. Soc. Biol., 1927, 97, 57— 58; Chem. Zentr., 1927, ii, 1158).— Influence of sodium chloride on the formation Fats are hvdrolysed by the tubercle bacillus. Oi volutin in the cells of spore-form ing bacteria. A. A. E l d r id g e . P. Sm irnov (Zentr. Bakt. Par., 1927, II, 70, 29— 36; Electrodialysis of tuberculin. VIII. F. B. Chem. Zentr., 1927, ii, 1480— 1481).— The formation Seibert and M. T. H a n k e (J. Biol. Chem., 1928, 448 BRITISH CHEMICAL ABSTRACTS.— A.

76, 535— 541).— Electrodialysis causes a more efficient Mode of action of insulin. C. L u n d sg a a r d removal of the last traces of electrolytes from tuber­ (Acta med. scand., Suppl. Bd., 1926, 1 6 , 473— 484; culin than does ordinary dialysis, although the initial Chem. Zentr., 1927, ii, 1974).-—The action of insulin stages of the process are no quicker; no loss of depends on an intramolecular rearrangement of the activity is brought about by the electric current, sugar, with formation of neoglucose; sufficient insulin but under its influence small amounts of the protein for the purpose is normally present. The effect of diffuse through parchment; in the absence of the insulin depends on the presence of some substance electric current such diffusion takes place only through present in fresh muscle; if this is provided, the collodion membranes prepared from a solution of action can be reproduced in vitro. collodion in a mixture of ether and 95% (not absolute) A. A. E l d r id g e . alcohol. C. R. H ar in g to n . Hormonal processes after administration of dextrose. IV. Detection of insulin in human Antigens. F. Pr zesm yc ki (Z. Immunitatsforsch., blood after peroral administration of dextrose. 1927, 5 1 , 408—420; Chem. Zentr., 1927, ii, 1717— H . H ausler and R. W e ebe r (Klin. W och., 1927, 6, 1718).— For the preparation of the residual antigens 1521— 1522; Chem. Zentr., 1927, ii, 1974).—Insulin of bacteria, an aqueous extract is boiled with 10% was detected. A. A. E l d r id g e . acetic acid for 5 min., and the precipitate is separ­ ated in a centrifuge; 10 vols. of 95% alcohol are Colorimetric determination of iodine in added, the precipitate is dissolved in water and homoeopathic and biochemical preparations. reprecipitated with alcohol. The process is repeated C. A. R ojahn (Apoth.-Ztg., 1927, 4 2 , 551; Chem. 6 times in alternately alkaline and acid medium. Zentr., 1927, ii, 149).— An aqueous extract (5 c.c.) is The aqueous dialysate is then precipitated with filtered, and the filtrate is treated with sulphuric acid, acetone. A. A. E l d r id g e . potassium iodate, and chloroform; after shaking, the colour of the chloroform layer is compared with Does adrenaline act through calcium ? L. that of a standard solution. A. A. E l d r id g e. Jendrassik and A. C z ik e (Klin. Woeh., 1927, 6, 1521; cf. Jendrassik and Antal, ibid., 1338; Chem. Determination of uric acid [in body fluids]. Zentr., 1927, ii, 1722— 1723).— Zondeck’s theory of C. Cdrrado (Pediatria, 1926, 2, 216; Chem. Zentr., parallelism between the action of adrenaline and 1927, ii, 306).— Benedict’s method is preferred. calcium ions is unsupported by experiment. A. A. E l d r id g e. A. A. E ld r id g e . Rapid volumetric determination of amino- Influence of amino-acids and their derivatives acids, organic acids, and bases. I. Determin­ on adrenaline hyperglycaemia. M. Ch ik a n o (J. ation of ammonia and volatile amines in bio­ Biophys., 1927, 3, xlv—xlvi).—Dihydroxyphenyl- logical fluids and determination of the different alanine and pyrocatechol cause considerable, and classes of acid radicals represented in the total tryptophan slight, hyperglyccemia. Tyrosine, hydr- alcohol titration value. II. Quantitative re­ oxyphenylpyruvic acid, and tryptophan augment moval and determination of the carbonic acid adrenaline hyperglycsemia; leucine and histidine radical especially in bacterial cultures. F. W. counteract it, and phenylalanine exerts no action. Forem an (Biochem. J., 1928, 22, 208— 221, 222— Glycine and glutamic acid have no influence on 229).—I. A detailed description of the methods which blood-sugar. Ch em ical A bstracts. are an extension of the author’s original method (cf. A., 1920, ii, 564). Influence of some protein derivatives on the II. The method is based on the observation that regulation of blood-sugar. I. Effect on the concentrated alcohol in which carbonic acid and small blood-sugar curve and the hyperglycaemic quantities of “ free ” volatile acids are dissolved very reaction after adrenaline. F. N ord (Acta med. readily parts with the whole of the carbon dioxide, scand., 1926, 65, 1— 115; Chem. Zentr., 1927, ii, but completely retains the volatile acids on aeration. 1717).— Glycine, glutamic acid, and W itte’s peptone Hydrogen carbonates of “ weak ” nitrogenous bases exercise a sugar-mobilising effect, but do not increase lose their carbon dioxide by this treatment. the action of adrenaline on the blood-sugar. Glycine S. S. Z il v a . and glutamic acid can completely suppress insulin Stain solubilities. III. W. C. H olmes (Stain hypoglycaemia; the action of Witte’s peptone is Tech., 1928, 3, 12— 13).—The solubilities in water irregular. A. A. E l d r id g e . and 95% alcohol of 45 dyes are tabulated. Inner secretion of the pancreas. VI. Sub­ H . W. D u d l e y . stance in human urine which diminishes the Fast-green, a substitute for light-green S. F. blood-sugar. K. K o zu k a (Tohoku J. Exp. Med., yellowish. R. H a yn e s (Stain Tech., 1928,3,40).— 1927, 9, 130— 147).— Human urine.contains a very Fast-green, a triphenylmethane dye (see Johnson variable quantity of a hypoglycpcmic substance. The and Staub, B., 1927, 404), is slightly greener, stains substance cannot be isolated in diabetes unless sugar more intensely in a shorter time, destains safranine is eliminated from the urine by treatment with the more slowly (making differentiation easier), and is pancreatic hormone, with which the substance is much more permanent than light-green. probably identical. Chemical A bstracts. H. W . D u d l e y .