BRITISH CHEMICAL ABSTRACTS
A.-PURE CHEMISTRY
NOVEMBER, 1927.
General, Physical, and Inorganic Chemistry. Revision of Rowland's preliminary tables of to the production of soft X-rays in the gas which are solar spectrum wave-lengths. C. E. St. J o h n capable of exciting the gas molecules. (Proc. Nat. Acad. Sci., 1927, 1 3, 678— 683).—An W. E . D o w n e y . account is given of the methods adopted in fixing Emission of light from hydrogen atoms. standard wave-lengths, and of the scheme in operation R. d ’E. A tk in so n (Proc. Roy. Soc., 1927, A , 116, at Mount Wilson Observatory, for the accurate 81— 103).—Experiments are described in which a determination of solar wave-lengths in the inter non-luminous beam of canal rays, some distance national system. It. A. M o rto n. after their entry into the vacuum, were made to emit the Balmer lines by excitation at approximately Intensity and width of spectral lines. B. one point only, so that any interval between excitation T r u m p y (Z. Pliysik, 1927, 44, 156).— By using in and emission could bo directly measured. Tho error the number of atoms instead of the number of method of point-excitation used was to pass the resonators in earlier work (this vol., 179) when cal canal rays across the mouth of one or more fine jets, culating the radius r0 of mcrcury atoms, values from which air, or some other gas, was streaming, slightly too low were obtained. R. W. Lunt. and to rely on rapid pumping to keep the general Intensities in the hydrogen fine structure. pressure low. It was found impossible to confine W. V. H ouston (Physical Rev., 1926, [ii], 28, 428).— the excitation region to less than about 1-5 mm. in Sommerfeld and Unsold’s treatment of the intensities length, but the distribution of excitation over the of the hydrogen fine structure components is criticised. region could be definitely determined, and the position The forbidden components opx—2pv 3_p2—2p2, and of its maximum fixed within one or two hundredths 3s—2s are to be expected in this order of decreasing of a mm. The distribution of intensity in the Balmer intensity, and the current in a discharge tube is lines was measured photographically and compared likely to produce them in hydrogen. These com near the maximum with that to be expected on tho ponents will increase with an increase in current, assumption that the intensity due to strict point- and will also show a resultant polarisation. excitation would begin at the point and would fall A. A. E l d r id g e . off exponentially from the start. The results obtained Doublet separation and fine structure of the support this assumption, and are in direct disagree Balmer lines of hydrogen. 1ST. A. K e n t , L. B. ment with the conclusions reached by McPetrie T a y l o r , and II. P earson (Physical Rev., 1927, [ii], (A., 1926, 652). Several considerations arising out 30, 266— 283).—The wave-length difference between of this result are discusscd. It is suggested that the the components X' and X" (X'>X") of Ha, H^, and process of excitation consists in an instantaneous Hy are determined as 0-1370, 0-0791, and 0-0666 placing of the hydrogen ion (or atom) into a definite, A., respectively. Another component in X' in H a, •and preferably fairly deep, quantised state. A Eg, and Hy is present, and there are indications of number of further experiments made possible by the other components in X". The magnitudes of the success of the method are outlined, including a components agree with those given theoretically by proposal for observing the “ negative radiation effect ” the new quantum mechanics with the spinning postulated by Einstein. L. L. B ir c u m sh a w . electron. A. A. E l d r id g e . Origin of the nebulium spectrum. I. S. B o w e n Spectral intensity distribution in a hydrogen (Nature, 1927, 120, 473).—The behaviour of tho nebulium lines accords with their identification as discharge. E. W. T schudx (J. Franklin Inst., regards wave-length, source, and series designation, 1927, 204, 219—225).— A cold cathode discharge tube has an auxiliary tube attached from which as follows: 7235-0, O n , 2£> -2P; 6583-6, I n , 3P2—1D ; 6548-1, N n , ZPX-^D \ 5006-84, 0 m , cathode rays are projected against the main cathode. 4958-91, O ra, z p ^ D ; 4363-21, O ra, The relative intensity distributions of Hy and H« were measured, by means of a photo-electric coll, 3728-91, O n , 4£ - 2Z>3; 3726-16, O n , from the main cathode through the cathode dark iS —2D2. A. A. E ld r id g e . space into the negative glow, with and without Origin of the nebulium spectrum. A . F o w l e r excitation of the auxiliary tube. The intensity of (Nature, 1927, 120, 5S2— 583).— The author’s observ spectral illumination in the negative glow is increased ations lend support to the view (preceding abstract) by about 20% when the main cathode is bombarded that the two green lines of the nebular spectra are by the electron stream. This increase is attributed due to 0 ra. On the whole, the numerical evidence 3 u 997 998 BRITISH CHEMICAL ABSTRACTS.— A. also supports the assignment of nebular lines to N n selection principle have been observed and classified. and 0 n. A. A. E l d r id g e . The broadening of some of the mercury and calcium Transition probabilities in the lithium atom. lines was found to be similar in nature to that produced B. T r u m p y (Z. Physik, 1927, 44, 575— 584).—The by the Stark effect. Since the effects observed in transition probabilities associated with the Is—4^ chlorine at a constant arc current are approximately to \s—12p lines of the principal series of the lithium reproducible in air with four times the arc current, spectrum have been calculated from experimental it is concluded that the marked broadening and the determinations of the intensities and widths of these appearance of enhanced and forbidden lines now lines as absorbed by lithium vapour. For Is—dp to recorded are due to the presence of chlorine ions in Is—\2p the values agree well with those calculated the arc. R. W. L e n t . by Pauli according to Schrodingcr’s theory, whilst Anomalous dispersion in the principal series those for Is—ip to Is—9# agree well with those of potassium. Ratio of the dispersion constants calculated by Sugiura in which Pauli’s treatment is of the red and violet doublets. W. P r o k o f ie v modified. R. W. Ltjnt. and G. Gam ov (Z. Physik, 1927, 44, 887— 892).— The Nitrogen series in the ultra-violet. J. J. ratio of the dispersion constants of the red and violet H opfield (Physical Rev., 1926, [ii], 27, 801).— doublets of potassium is 111-5+1-5 and is independent Two new series of triplets probably converging to of the vapour density over a wide range (1 : 65). The a common head and belonging to the quadruplet ratio of the probabilities of the transition 2p1—ls to system, and two series of doublets also having a the transition 3 ^ — Is is 30-7. R. W. L u n t . common limit and belonging to the doublet system, Extreme ultra-violet spectrum of titanium. have been observed in nitrogen. The short wave R. C. Gib bs (Physical Rev., 1926, [ii], 27, 799).— The length lines of one of the triplet series are given hot spark spectrum of titanium was photographed by: 117353-109677 (ra+0-845685-0-022749/m2- from 192 to 1718 A. Lines not due to titanium 0-026562/m4)-2, where m— 1, 3, and 4 (known) and were eliminated; Lang’s 25 titanium lines, and 90 2 (new), and 1
Ionisation potential of terbium. L. R oll a and collides with an activated molecule, the energy of G. P ic c a r d i (Atti R. Accad. Lincei, 1927, [vi], 5, activation of the molecule may be converted into 818— 819).— The ionisation potential of terbium deter kinetic energy of the electron by a collision of the mined by the flame method (cf. A., 1926, 769) is second kind. A. A. E l d r id g e . 6-74 volts. This again confirms the earlier observ Ionic mobility in gaseous mixtures. H. M a y e r ation that the ionisation potential of members of (Physikal. Z., 1927, 28, 637— 644).— The presence of the rare-earth group increases with increasing atomic a trace of impurity in a gas frequently brings about number (cf. A., 1926, 11S7). M. Ca r lt o n . a sudden large chango in the mobility of one ion. Determination cf critical potentials and the The values at 760 mm. for k+ and the mobilities ionisation potential of mercury vapour. E. 0. in pure, dry hydrogen, have been determined as L aw re n c e (Physical Rev., 1926, [ii], 27, 515).— 6-00 and 10-07 cm./sec. per volt/cm., respectively. A method of high precision gave a value of 10-4 The addition of chlorine in amounts 0-3, 0-9, 1-5, and (±0-5% ) volts for the ionisation potential of mercury 3-0% resulted in the values for k+ of 5-55, 5-35, 4-95, vapour. A. A. E l d r id g e . 4-25, respectively, whereas the corresponding values for Voltage-intensity relations of mercury lines k_ were 5-15, 4-60, 4-40, 4-12. A largo decrease is thus shown in with the addition of quite small below ionisation. D. R. W h it e and H. W . W e b b (Physical Rev., 1926, [ii], 27,243—244).—The voltage- amounts of chlorine, but larger amounts do not intensity relationship for each of 20 mercury lines maintain the rapid alteration. With small quantities between 2500 and 5800 A. is primarily a function of of chlorine in oxygen the mobility of the negative ion decreases fairly rapidly until the chlorine con the outer energy level involved. Abrupt changes of slope of the curves apparently correspond with certain centration reaches 2 % and after this point it falls much more slowly. Water vapour decreases the mobilities critical potentials. A. A. E ld r id g e . in oxygen. For 0, 1-6, 2-4, and 3-0% of water Ionisation by collision and a 11 photo-electric vapour the values of k+ were 1-38, 1-38, 1-35, and theory " of the sparking potentials. J. T a y l o r 1-25, respectively, and of k_ 2-11, 2-00,1-85, and 1-63. (Phil. Mag., 1927, [vii], 4, 505— 511).—A reply to Hydrogen-oxygen mixtures have been investigated. criticisms by Huxley (this vol., 709) of the author’s For 2-2% of oxygen k+ is 5-6, ¿ .9 -3 ; for 99-3% of theory of sparking potentials (Proc. Roy. Soc., 1927, oxygen £+ is 1-44, /¿_ 2-15. The results are discussed A, 114-, 73; Phil. Mag., 1927, [vii], 3, 753). in terms of the cluster theory. R. A. M o rto n . A . E . M it c h e l l . Ionisation in ñames of various organic sub Photoelectric emissivity and sparking poten stances. J. A. J. B e n n e t t (Trans. Faraday Soc., tials. J. T a y l o r (Nature, 1927, 120, 477—478).— 1927, 23, 307— 311).— To study the relation between Evidenco in favour of the author’s photoelectric ionisation and detonation the ionisation in flames of theory of sparking potentials (preceding abstract) is hexane, coal-gas, “ B .P . petrol,” benzene, pentane, adduced. A. A. E l d r id g e . acetone, etc., and the effect of adding carbonyls, Diffusion of slow electrons (2—30 volts) in amyl nitrite, aromatic bases, halogens and halogen hydrogen and argon. E. Z a c h m a n n (Ann. Physik, compounds, and other substances which alter the 1927, [iv], 84, 20—60).—Electrons of velocities. highest useful compression ratio of a fuel, have been between 30 and 11 volts in argon undergo an increase determined. Although in many cases knock-inducers in diffusion with decreasing velocity. Between 11 and increase and anti-knocks decrease the ionisation of 7 volts velocity the diffusion decreases rapidly and flames, this is not general. Thus, although ionisation at 6-5 volts it is not noticeable. Between 6-5 and accompanies detonation, there is no simple relation 2 volts velocity, no diffusion is detectable. In between them, and ionisation does not appear to be hydrogen the diffusion increases with decrease of either a cause or an effect of detonation, but mainly electron velocity between 30 and 2 volts. a temperature effect. This is not in agreement with W. E. D o w n e y . either Wendt and Grimms’ theory (B., 1924, 856) Heats of condensation of electrons and positive or that of Charch, Mack, and Boord (B., 1926, ions on molybdenum in gas discharges. C. C. 570). M. S. B u r r . Van V oorhis (Physical Rev., 1927, [ii], 30, 318— Ionisation processes in hydrogen, nitrogen, 338).—A new calorimetric method for measuring the and argon. K . E . D orsch and H. K a l l m a n n (Z. electronic work function of a metal in a gas discharge Physik, 1927, 44, 565— 574).— Previous experiments is described. Values of the heat of electron con (this vol., 604) have shown that the ratio of the densation for molybdenum in argon, hydrogen, and concentration of H+ ions to H2+ ions formed in nitrogen are: 4-76; 4-04, 4-35; 4-77, 5-01 volts, hydrogen is approximately constant when produced respectively, according to the treatment of the by electrons of energies corresponding with 16— surface. The heating effect on molybdenum due 50 volts. The variation of this ratio produced by to the surface neutralisation of an argon positive the addition of argon, and by increasing the ionisation ion is about 1 volt. The presence in a low-pressure space, has now been examined over a 1 : 10 pressure gas discharge of Langmuir’s high-speed “ secondary ” range. At any given pressure the ratio is unaffected electrons is indicated. A. A. E l d r id g e . by these factors, but the ratio H3+ : H2+ is increased Collisions of the second kind in activated by increasing the ionisation space at all the pressures ozone. H. D. Sm y t h (Physical Rev., 1926, [ii], 27, examined. These results show that the primary 108—109)-:—With ozone some experimental evidence ionisation process is the formation of H2+ ions (no 'was obtained in support of the view that if an electron other primary process takes place which is more than 1002 BRITISH CHEMICAL ABSTRACTS.— A.
0-5% of this process), that H3+ ions are formed in 762— 767).— An improved technique is described for considerable amount according to the reaction examining the fine structure of the hydrogen spectrum H2++H 2=H 3++H, and that the reaction H,+ = emitted by canal rays. The changes produced as the H+4-H takes place only in the neighbourhood of the beam moves from the region of an electric field to a electrodes. region where no field exists are recorded and discussed. From measurements of the ionisation in argon- R . W. L u n t . hydrogen, argon-nitrogen, and hydrogen-nitrogcn Polarisation of the light from canal rays. II. mixtures as function of the electron energies (14— 19 E. R u pp (Ann. Physik, 1927, [iv], 84, 94— 110; cf. volts) relative values of the ionisation potentials ibid., 1926, [iv], 81, 615). have been obtained. By assuming Meissner’s recent value for argon, 15-6 volts, computed from optical Structure of the radioactive atom and origin of evidence (this vol., 177), the values 1G—16-5 and the a-rays. (Si r ) E. R u t h e r f o r d (Phil. Mag., approximately 16-5 volts are assigned to nitrogen 1927, [vii], 4, 580— 605).— For the first time a theory and hydrogen, respectively. R. W. L u n t . of the structure of the nucleus of a radioactive atom Effect of the medium on gas ion mobility. is put forward and discussed in terms of the experi H. A. E r ikson (Physical Rev., 1927, [ii], 30, 339— mental data. In the radioactive atom one of the 348).—Addition of carbon dioxide or water vapour neutral a-satellites is regarded as circulating in a to the air through which air ions move diminishes quantised orbit round the central nucleus. When for the mobility, that of hydrogen increases the mobility, some reason this becomes unstable the satellite escapes that of ethylene or chlorine has no effect, whilst that from the nucleus, losing its two electrons, and the of ammonia results in the formation of a single positive electric field falls to a critical value. It escapes as a ion of the same mobility as that of the negative ion, doubly-charged helium nucleus with a velocity which which is not affected. Acetylene gives rise to an ion is a function of the quantum orbit and the nuclear which has a mobility only slightly less than that of charge. The two electrons liberated from the satellite the initial air ion. When acetylene remains in air a fall towards the nucleus and probably circulate close substance is formed which, when it becomes charged, to. the central nucleus and inside the region occupied has a lower mobility. A. A. E l d r id g e . by the neutral satellites with a speed of the order of that of light. On the occasion of one of these being Impact of slow cations on lithium chloride in hurled from the system a disintegration electron a high vacuum. E. B a d a r e u (Physikal. Z., 1927, results. The disturbance of the neutral satellite 28, 634— 637).—When canal rays impinge on a metal system by the liberation of an a-partiele or a swift collector the galvanometer readings increase rapidly electron may lead to a rearrangement involving the at first and then more slowly as the voltage increases transition of one or more satellites to a different between 0 and 900. If, however, a surface of lithium quantum orbit and the emission in the process of chloride is used, the galvanometer deflexion becomes y-rays of frequency determined by quantum relations. constant at about 500 volts if the experiments are It is pointed out that before further progress in the conducted in a high vacuum. On the other hand, solution of the problem of the origin of the y-rays experiments at pressures of about 0-1— 0-5 mm., can be obtained a knowledge of the precise frequencies instead of showing deflexions of the same order of of the main y-rays and their intensities is essential. magnitude for the metal and salt surfaces, disclose A. E . M it c h e ll. wide differences; e.g., a copper collector gave at Possible mechanism of atomic disintegration. 462 volts a deflexion twenty times as great as that G. P ic c a r d i (Nature, 1927, 120, 442—443).—The with a collector covered with lithium chloride. The “ excess weight ” (Harkins’ “ isotope weight ” ), differences between the experiments at relatively low P —2N, where P is the atomic weight and N the pressure and with high vacuum are ascribed to the fact atomic number, is regarded as constituted of P —2N that the emission of positively-charged particles from dipoles, externally to the atomic nucleus, formed by the salt increases with increasing current density in one positive and one negative electron sufficiently the exciting current (cf. Volker, A., 1919, ii, 43). close together to form an electrically neutral com R . A . M o rto n . plex. For the inactive gases, and for zinc, cadmium, Ionisation probability in collisions between and mercury, the maximum excess weight (that of electrons and atom s. F. M. P e n n in g (Physica, the higher isotope of each element) is doubled each 1926, 6, 290— 297).—A lecture. time a given atomic structure is repeated, values C h em ical A b strac ts. being : neon 2, argon 4, krypton 14, xenon 28, Divergence of magnetic electrons. W. B othe radon 50, zinc 10, cadmium 20, mercury 44. These (Z. Physik, 1927, 44, 543—546).— A mathematical elements are also in maximal positions on the curve analysis of the effect of the magnetic moment of of ionisation potentials; hence the excess weight is electrons on the divergence of a cathode beam. definitely related to the atomic structure. R. W . Lunt. A. A. E l d r id g e . Charged state of atoms before light emission. Actinium series and the order of stability of R upp E. (Aim. Physik, 1927, [iv], 84, 154— 160).— radioactive isotopes. A. S. R u ssell (Nature, It is shown that the majority of hydrogen atoms 1927, 120, 402— 403).—Protoactinium is identified as emitting light in canal rays are positively charged the most stable isotope of element 91 and actinium before the emission. W. E. D o w n e y . as the second stablest isotope of element S9, from Luminescence of canal rays. H. R a u sc h v o n relations between atomic mass and stability deducible T r au b en b e r g and R . G e b au er (Z. Physik, 1927, 44, from Aston’s results on non-radioactive elements. It GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1003
follows that actinium may not have the mass 227 minerals; other Z-haloes and X-haloes to proto which has been ascribed to it by all of those who actinium and lead separated either from uranium or consider that the masses of members of the actinium uranium-thorium minerals. There is no need to series are of odd number; it follows also that the mass regard hibernium, as did Rosseland (Nature, 1922, of protoactinium is 233 and therefore that of actinium 109, 711), as a radioactive element of atomic number 229. On the basis of these results the masses of all approximately 40. If the views put forward are the actinium products are known unless it can be correct the radioactive series are partly extended to shown either that one or more a-particles have been mercury ; hibernium is identified as thorium-Q. overlooked or that a massive particle other than an A. S. R u sse ll. a-particle is expelled by some member of the series. Mode of disintegration of radium-i), -E, and Two rules, also, are deducible. (1) For aradio S. K ik u c iii (Japan. J. Phys., 1927, 4 4 , 143— 158).— element of even atomic number the massesof The its tracks of rays from an equilibrium mixture of a-ray and of its (3-ray isotopes are in decreasing order radium-D, -E, and -F have been examined by the of stability when arranged in the orders x, x —2, Wilson cloud method. Each atom of radium-2? x —1, X-4-, £—3, etc., and x, x + 2 , *+1, £+4, £+3, emits one (3-particle only on disintegrating, and the etc., respectively, x being an even number and the heterogeneous nature of the (3-particles so produced atomic mass of the stablest isotope. (2) For an cannot be traced to encounters with planetary elec element of odd atomic number the masses aretrons. in The (3-particles from radium-2) are of second decreasing order of stability when arranged in the ary origin ; this substance emits, in addition to same order as the (3-ray isotopes of an element of radiation of 0-264 Â., radiation of mean wave-length even number. Applied to the isotopes of non-radio 0-4 Â. which is possibly homogeneous ; the L-radiation active elements these rules are partly successful only of this element was also detected. R. W. L u n t . they are inapplicable to the isotopes of tin, magnes ium, and silicon, but apply better to those of xenon, Ionisation produced by radon in spherical cadmium, mercury, sulphur, selenium, krypton, vessels. G. Glockler (J. Physical Chem., 1927, neodymium, and lead. On the theory put forward 31, 1322— 1331).— Theoretical. A comparison is the end-product of the actinium series has a mass made of the ionisation produced by radon and its of 209. A. S. R u sse ll. decomposition products as calculated by the average path law (cf. Lind, A., 1912, ii, 1027) and by the Radioactive haloes. Possible identification of method of Mund (A., 1925, ii, 732). For spherical “ hibernium .” A. S. R ussell (Nature, 1927, 120, vessels of a diameter up to 10 cm., the two methods 345— 546).— Observations of Joly (Proc. Roy. Soc., give similar results, which are also in agreement with 1922, A, 102, 682) and of Iimori and Yoshimura (A., the experimental value obtained by Lind (A., 1919, 1926, 990) on the rings of radioactive haloes are con ii, 210). A new derivation of Mund’s original equation sidered in the light of Marckwald and Russell’s work (A., is given, but the assumption that the whole of the 1911, ii, 360) on the alteration of radioactive minerals radium-4 and the radium-C' decomposes on the wall by agencies like percolating water and of Russell’s view of the vessel is modified. Using the experimental (preceding abstract) of the atomic masses of the value of Lind and Bardwell (A., 1924, ii, 11) for the products of the actinium disintegration series. Iimori average path (0-61 X radius of the reaction vessel), it and Yoshimura ascribed their 2-haloes, Joly’s X - is calculated that 30% of the radium-4 and 7% of haloes, and possibly Joly’s so-called radon haloes to the radium-C decompose in the gaseous phase. the products of the actinium series. They regard the Mund’s efficiency factor is recalculated on this basis actinium series as independent of the uranium- and the new values are tabulated. radium series; two inner rings sometimes found in L. S. T h e o b a l d . Z-haloes are ascribed by them to two uranium Scattering of a-particles by helium. (Si r ) E. isotopes at the head of the actinium series. The Rutherford and J. C h a d w ick (Phil. Mag., 1927, author criticises this. If uranium minerals have been [vii], 4, 605— 620).— Investigations of the collisions altered by chemical agencies in the past, different of a-particles with helium have shown that in general radioactive products may have been isolated from the collision relations for these particles are similar the rest depending on their solubility, etc. From to those representing the collisions between a-particles these products three different kinds of haloes should and hydrogen nuclei. For large collision distances result: the uranium halo resulting from uranium or the forces between the particles are given by Coulomb’s ionium or radium, the actinium halo resulting from law, but with closer approaches (less than 3-5 X 10~13 protoactinium, and a lead halo resulting from the cm. for central collisions and less than 14 x 10-13 cm. end-product of the actinium series if it should be for glancing collisions) powerful additional forces are feebly radioactive. Similarly from thorium minerals involved. It is suggested that these additional two haloes may be obtained : the thorium halo and forces originate in the magnetic fields of the nuclei. a lead halo due to a possible feebly radioactive end- A. E. M it c h e l l. product. It is concluded that the radius of the ring Probability law and the a-particle emission of made by the a-particles from the thorium end- polonium. W. K u t z n e r (Z. Physik, 1927, 44, product (mass 208) should be smaller than that from 655— 683; «cf. A., 1924, ii, 226).— The a-particle the actinium end-product (mass 209). The hibernium emission of polonium has been re-examined, and it is ring is ascribed to the first of these; an unnamed ring found that Bateman’s expression for the time prob discovered by Joly to the second. Some Z-haloes are ability of emission gives values of the emission ascribed to protoactinium isolated from uranium probability the agreement of which with experiment 1004 BRITISH CHEMICAL ABSTRACTS.— A. diminishes as the thickness of the polonium prepar two protons and one electron results in a recoil proton ation is increased. The discrepancies cannot be moving with a minimum velocity 0-6c and a quantum accounted for by recoil atoms, and are thought to be of wave-length 1-9 x 10~5 A. or less. due to impurities in the polonium preparation which A . A . E l d r id g e . impede the emission of the true total emission of Application of Schrodinger’s wave functions to polonium. R. W. Lunt. the calculation of transition probabilities for the Scattering and absorption of the y-rays of principal series of sodium. Y. S u g iu r a (Phil. radium . H . M. Ca v e and J . A. G r a y (Physical Mag., 1927, [vii], 4, 495— 504).—In accordance with Rev., 1926, [ii] 27, 103).— y-Rays filtered through the result of Kramers (Z. Physik, 1926, 39, 828) 2 cm. of lead have an effective wave-length in the that a rational first approximation to the quantum- neighbourhood of 0-012 A. A. A. E l d r id g e . mechanical calculation may be obtained by using an orbital model fixed by the usual quantum conditions, Internal conversion of y-rays. (Miss) B. if in these half-number values are introduced for the Sw ir l es (Proc. Roy. Soc., 1927, A, 116, 491— 500).— radial and azimuthal quantum numbers, the proper Theoretical. The results of Ellis and Wooster (this functions according to Schrodinger (Ann. Physik, vol., 393) are discussed on the lines of quantum 1926, [iv], 79, 361) have been found for the 31; 32, mechanics. An expression is obtained for the and 4, states of the sodium atom. These functions coefficient of absorption in the K -levels. have then been used for the calculation of the trans W. E. D o w n e y . ition probabilities and the number of dispersion Variation of radioactivity of hot springs. K. electrons for the principal series of sodium. The Sh ir a to r i (Sci. Rep. Tohoku Imp. Univ., 1927, 1 6, result so obtained for each D-line of sodium is in close 613—620).-—A comparison is made between the radio agreement with that deduced from the experimental activity of a number of hot springs in Japan before residts of Minkowski (A., 1926, 650). and after a period of eleven or twelve years during A . E . M it c h e ll. which earthquakes have taken place. Changes in Intensities in the secondary spectrum of temperature are also recorded. M. S. B u r r . hydrogen at various temperatures. J. C. Transmutation of elements. A. Smits (Nature, M cL e n n a n , H . Gr a y s o n -Sm ith , and W. T. Collins 1927,120,475— 476).—Renewed experiments indicate (Proc. Roy. Soc., 1927, A, 116, 277— 312).— The that the mercury found in the earlier experiments, in intensities of the lines of the secondary spectrum of which a discharge was maintained between lead hydrogen have been studied. A specially constructed electrodes under carbon disulpliide, originated partly, discharge tube was arranged in a liquid-air flask if not entirely, from the carbon disulphide. Thus with the capillary vertical. Special precautions were there is still no conclusive evidence of the reproducible taken to obtain pure hydrogen. Photographs were conversion of lead into mercury. A. A. E l d r id g e . taken at the ordinary temperature and at the tem Failure of the mercury-to-gold transmutation perature of liquid air, nothing else being varied. The experiment. H. H. Sheldon and R. S. E s t e y intensities were obtained by a Moll self-registering (Physical Rev., 1926, [ii], 27, 515).—A repetition of microphotometer and most of the lines measured by Miethe’s experiments failed to produce any trans Merton and Barratt were examined. Richardson’s muted gold. A. A. E ld r id g e . series system is thereby included and the variation of intensity with temperature is in good agreement with Radiation arising from the formation of theory. The alternation of intensity between the helium from hydrogen. G. E. M. J a u n c e y and odd and the even members of the series was observed. A. L. H ughes (Physical Rev., 1926, [ii], 27, 509).— Other regularities have been examined and are Four processes are considered: (1) The protons and discussed. W. E . D o w n e y . electrons initially at rest produce a helium nucleus recoiling in the opposite direction of the quantum. Intensity distribution among the lines of (2) The protons and electrons all initially having certain bands in the spectrum of the hydrogen velocity (3c produce a helium nucleus at rest. (3) One m olecule. O. W. R ic h a r d so n (Proc. Roy. Soc., proton with velocity [3c meeting 3 protons and 2 elec 1927, A , 116, 484— 491).— Theoretical. The results trons at rest produces a helium nucleus at rest. of McLennan, Grayson-Smith, and Collins (preceding (4) One electron with velocity ¡Be meeting 4 protons abstract) are discussed. W . E. D o w n e y . and one electron at rest produces a helium nucleus at Bands in the secondary spectrum of hydrogen. rest. In (1), (2), and (3), X=0-0004 A .; in (4), II. H . S. A l l e n and I. Sa n d e m a n (Proc. Roy. Soc., X=0-000S A. In (1) and (2), p=0-008; in (3), p = 1927, A, 116, 312— 327; cf. this vol., 394).— Theoret 0-03; in (4), (3=0-9995. The reverse of (4) is the ical. Further work on the system attributed to photo-electric effect. By analogy with X-rays, triatomie hydrogen is described. Further bands 0-004 A. and 0-0008 A. may be considered as critical have been added and it is concluded that these are absorption wave-lengths. A. A. E l d r id g e . only the strongest in an extensive system. The Radiation from the mutual annihilation of spacing in groups with a difference of 92 wave- protons and electrons. A. L. H u g h es and numbers is not attributed to the vibration quantum G. E. M. J a u n c ey (Physical Rev., 1926, [ii], 27, number but possibly is dependent on a new quantum 509—510).— The collision of two electrons and one number. W. E . D o w n e y . proton results in a recoil electron moving with a Interpretation of the continuous spectrum of minimum velocity 0-9999995c and a quantum of hydrogen. Y. T a k a h a s h i (Japan. J. Phys., 1927, wave-length 2-6 x lO '5 A., or less. The collision of 4, 103— 108).—It is claimed that the difficulties GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1005 which face the explanation of this spectrum by been remeasured and Rowland’s values for the a'-band Bohr’s theory are obviated by assuming that it have been corrected by subtracting 0-216 Â., so that arises from the recombination of two hydrogen atoms the wave-lengths given are all expressed on the neon of which one at least is excited. R. W. L u n t . scale. The empirical structure of the bands is worked Hydrogen band spectrum in the extreme out in the form ultra-violet. T. H o r i (Z. Physik, 1927, 44, 834— Pi(j)=FiU)-Fi"Ê-m 854).— The band spectrum of hydrogen excited by RiiS)=Fi'V)-F>"U-1 ) /’ the glow discharge has been examined with a vacuum spectrograph of dispersion 8-28 Â. per mm. in the which makes the bands analogous to other well- range 1027— 1249 Â. A large number of lines have known bands. The significance of the empirical been recorded, and arranged according to the term structure is not fully elucidated, but the relation scheme of Dieke and Hopfield. The moment of JB=7i/8i-2cJ leads to values for the moment of inertia inertia of the hydrogen molecule in the normal state J for the 0 2 molecule in the normal and in the excited is found to be 4-67 X10~41 g. cm.2, and the nuclear state of 19-27 and 19-93 XlO-40, respectively, corre spacing 0-75 xl0~8 cm.; for the excited state the sponding with l -205 and 1*225 xTO-8 cm. as distances corresponding values are 9-2 X 10-'11 g. cm.2 and 1-06 X between the nuclei in the two states. 10~8 cm. R. W. Lunt. R. A. M o rto n . Half-integral vibrational quantum numbers Structure of the hydrogen molecule. H. C. and rotational energy data for the MgH bands. U r e y (Physical Rev., 192G, [ii], 27, 800).— Dieke’s W . W . W atson (Physical Rev., 1926, [ii], 27, SOI).— and Takahashi’s arrangements of the Fulcher bands The magnitude of the isotope effect in the 5211 Â. of hydrogen are reconsidered. It is assumed that the band accords with the assumption that and molecule is symmetrical about the median plane, and n "= \ ) the zero points of this band system are that it has no angular momentum in the electron represented by the equation v—19217 + (1603-5«/— system. It appears necessary to assign the steady 34-75?i'2) —(1493-5w/'—31-25«."2), where n' and n " states involved to the vibration electron orbits of the assume half-integral values from \ to 31. For the median plane. This would give no first-order Zee final state in the 5211 Â. band, the rotational energy man effect as required, and a diamagnetic model for F—Bm2 + Dm4 + F?>iG, where m = j + |—e (e=0-47). the normal state. A. A. E l d r id g e . The presence of a Kramers and Pauli effect is indicated. Structure of the hydrogen molecule ion. H . C. The value of e for the initial state is approx. 0-43. U r e y (Physical Rev., 1926, [ii], 27, 800— 801).— 0A. A. E l d r id g e . The energy levels of the vibrational model of the Fine structure of the 4842 A. band of AlO. hydrogen molecule ion have been calculated, including W. C. P o m e r o y (Physical Rev., 1926, [ii], 27, 640).— the energy contributed by the vibration and rotation The doublet separation of band lines is represented as of the nuclei. The emitted bands should consist of a function of k (a half integer representing the single band systems, each band having a zero branch resultant molecular momentum) of the initial state only. A. A. E l d r id g e . for both P and R branches by tho equation Av= Combinations in the ultra-violet spectrum of 0-0116Æ-M2X 10~6Æ2—7 x lO'11^4. Attributing the the hydrogen molecule. G. H . D ie k e and J. J. doublets to a double energy level in the initial state, H opfield (Physical Rev., 1926, [ii], 28, 849).—• (F')+~ = (0-6019 ± 6 x 10-6)m2 - (1-1630 x 10-G± 3-5 x Between 1050 and 1650 Â. there are two systems of 10'n )m4-i-0-54x 10~12m6, where m —k— 0-0074;±; bands degraded towards the red, and all are of similar 0-00482 ; (i’")=0-6386»i2-l-1 0 9 4 x 10 6m4-0 -4 3 x structure ; they have the same final states, which are 10~12mG—-5-2x 10~18m8. A. A. E l d r id g e . the states of lowest energy of the hydrogen molecule. The first system includes a progression which, in a Colouring of glass [containing manganese] mixture of argon and hydrogen, appears without the in tdtra-violet light. C. L. Cross (Physical Rev., rest of the spectrum. In the initial electronic state 1926, [ii], 27, 108).— The effective light has a wave of this system the nuclei arc more tightly bound than length only slightly greater than 2900 Â., the absorp in the initial state of the other system, although their tion limit of the glass. The tinting takes place only distance apart is larger. A. A. E l d r id g e . near the surface, and is hastened by heating. De- colorisation is accelerated by heat or visible light. Zero-zero band of the second positive band A. A. E l d r id g e . spectrum of nitrogen. G. Nakamura (Japan. Band spectrum of silicon fluoride. R. C. J. Phys., 1927, 4, 109— 117).— The band has been J ohnson and H. G. J e n kin s (Proc. Roy. Soc., 1927, analysed by examining the spectrum of a low-tension A, 116, 327— 351).— Tho discharge through silicon arc in nitrogen between tungsten electrodes. It is fluoride has been examined. Purified and dry silicon found that the formulas of Zeit and Lewis (Z. wiss. fluoride was streamed through a discharge tube at Phot., 1922, 21, 1) are not applicable to the high 1 mm. pressure. The discharge is of a strong blue members of the band lines. R. W . Lunt. colour, due to a system of intense bands in the blue Structure of the atmospheric absorption bands region. Several groups of bands have been measured, of oxygen. G. H. D ie k e and H. D . B a b co ck (Proc. some being favoured by high current density, others Nat. Acad. Sci., 1927, 13, 670— 677).— The lines in by low. Special precautions were taken to eliminate the ¿-band (7624-493—7594-970) and the A '-band impurities and it is concluded that the bands are (7022-998—7603-212), the 5-band (6886-743— due to SiF4. The structures of the a-, [3-, and y- b869-626), and the a-band (6289-397— 6277-533) have systems of bands have been determined. The heat 1006 BRITISH CHEMICAL ABSTRACTS.----A. of dissociation as calculated from the vibrational states 4, 99— 109; cf. A., 1926, 830).—The results of a is found to bo 116,000 g.-cal. W. E. D o w n e y . study of the absorption spectra of a number of coloured substances are found to be in agreement Structure of Fraunhofer's lines and the with their unsaturation as measured by the ease of dynamics of the sun’s chromosphere. A. hydrogenation in the presence of hydrogen and U nsold (Z. Physik, 1927, 44, 793— 809).—From an colloidal palladium. In benzene derivatives, a analysis based on the theory of dispersion and on chromophore is regarded as a seat of strain which Schwarzschild’s theory of radiation equilibria, and by may be partly absorbed by dynamic equalisation in making the assumption that the partial pressure of the ring, unless the structure is made static by the calcium in the chromosphere is 5 x 10~8 atm., which is introduction of an auxochrome. The latter point is in satisfactory agreement in order of magnitude with illustrated by the comparison of the absorption St. John’s data (Astrophys. J., 1910, 32, 36), the spectrum of alizarin (dynamic structure) with that of structure of the H- and X-lines of the singly-ionised calcium atom in the chromosphere has been deduced. the potassium salt (static, quinonoid structure). The loading effect of substituents in dyes on their absorp R. W. L u n t . Photochemical absorption of iron salts. J. tion spectra is shown to be the greater, the nearer the substituent is to the point of strain. P lo tn ik o v and M. K arsch ulin (Z. Elektrocliem., G. A. C. Gough. 1927, 3 3 , 212— 217).—The absorption bands of Theory of colour on the basis of molecular potassium ferricyanide and of green and brown strain. III. Decomposition of dyes under the ferric ammonium citrate extend into the infra-red, but the region of photochemical sensitiveness does influence of solar radiation. K. K . B ar a t and not extend into the infra-red. Tlio use of gelatin 5. D utt (J. Indian Chem. Soc., 1927, 4, 265—270; coated on glass instead of sized paper as the medium cf. A., 1926, 830, and preceding abstract).—The absorption spectra of aqueous solutions of a number for the light-sensitive substances results in a shift of the sensitivity maximum towards the longer wave of typical dyes have been determined during various lengths and an alteration in the general sensitivity. stages of bleaching by solar radiation. The measure The results indicate the invalidity of the Einstein ments indicate that the dyes are decomposed to photochemical equivalent law. A simple method of colourless substances without the intermediate form demonstrating the photochemical absorption is given. ation of less coloured substances. In accordance The photochemically active region of “ Ozalid” with the authors’ theory, the dyes which absorb the paper extends from 4750 to 2470 A., with a maximum longer wave-lengths decompose most rapidly. G. A. C. Gough. at 4000 A. W . Cl a r k . Vibration frequencies of organic compounds. Absorption spectra of aragonite and strontian- W. H er z (Z. anorg. Chem., 1927, 16 6 , 110— 112).— ite in the near infra-red. F. I. G. R a w l in s and The vibration frequencies of the molecules of numerous E. K. R id e a l (Proc. Roy. Soc., 1927, A, 116, 140— organic compounds have been calculated by the 152; cf. this vol., 5).—The absorption spectra of method previously applied to inorganic compounds aragonite and strontianite have been examined in the (this vol., 817). The frequency decreases on ascending near infra-red by means of two types of apparatus: a homologous series and when hydrogen is replaced by (a) an infra-red spectrometer, thermopile, and moving- the halogens, and for analogous compounds with the magnot galvanometer of the Hill-Downing pattern, same number of carbon atoms is greatest for the ono and (b) an infra-red spectrometer (Littrow principle) containing a triple linking and smallest for that with and a modified Boys radiomicrometer. From the single linkings only. R. C uthxll. results it has been found possible to compare the two allotropie modifications of calcium carbonate, and the Series due to halogens in infra-red absorption bi-axial crystals of the alkaline-earth carbonates. In spectra of organic compounds. J. W. E llis the former case, definite displacements of the three (Physical Rev., 1926, [ii], 27, 639).—The absorption fundamental frequencies of the carbonate ion occur in spectra of methylene dichloride and chloroform con the two crystal forms. From the overtones of the tain, in addition to the C-H scries, bands which fit a fundamental at 7 [x it is shown that the frequencies linear series starting at 16-8 (¿, and bands accounted do not follow the order vv 2vv 3v1} but that a correc for by combinations. Similar bands are observed tion must be used analogous to the Kratzer correction with methylene dibromide and bromoform (17-2 ¡¿) for an harmonic coupling in gases (Z. Physik, 1920, and with methyl iodide and methylene di-iodide 3, 289). This correction is greatest for the less (17-5 ji), as well as with more complex molecules con symmetrical form of calcium carbonate. In the bi taining halogen and hydrogen atoms, but not with axial group, it appears that whereas at the absorp carbon tetrachloride or tetrachloroethylene. tion wave-lengths increase with the molecular volume, A. A. E l d r id g e . the reverse holds for the bands at v2 and v3, and the Spectrochemical studies of hydroxyazo-com- same is true for calcite and aragonite. The values of pounds. IV. T. U e m u r a and S. T a b e i (Bull. have been determined for the various bands Chem. Soc. Japan, 1927, 2, 229— 236; cf. this vol., with the help of Schaefer’s data for Xrff. (cf. this 396).—The absorption spectra of neutral and alkaline vol., 5). These are generally positive, in confirm solutions of the dyes obtained by coupling diazotised ation of Schaefer’s results, but are smaller than the toluidines with each of the three cresols have been values obtained by him. L . L . B ir cu m sh a w . examhied. The colour changes observed on addition Theory of colour on the basis of molecular of alkali are due to the change of the substance from strain. II. S. D utt (J. Indian Chem. Soc., 1927, the A- to the 7?-form. There is but one absorption g e n e r a l , p h y s i c a l , a n d i n o r g a n i c c h e m i s t r y . 1007 band when the hydroxyl group in the cresol ring creases with increasing quantum number, and that occupies the p-position with respect to the azo- therefore in the vapour state the molecules of these sub group, and two when it occupies the o-position. stances are compounds of atoms, as has been estab Comparison of the present absorption curves with lished previously for silver iodide. R. W. L u n t . those of the corresponding hydroxyazobenzenes and benzeneazocresols shows that the methyl group has Fluorescence yield of solutions [of sodium a hyperchromic influence only when introduced into fluorescein]. S. Szczeniovski (Bull. Int. Acad. a non-methylated compound. The effect of a methyl Polonaise, 1927, A, 127— 174).— The absorption group is apparently independent of its position. spectra of solutions of sodium fluorescein in glycerol and in water have been determined over the range J. S. Ca r t e r . Absorption of ultra-violet rays by the ten 4000— 6000 A. by a photo-electric method. The isomerides of dichloronaphthalene. H. De curves exhibit maxima at 4850—4900 A. and absorp tion coefficients near 600, whilst an inflexion near L aszlo (Compt. rend., 1927, 1 85, 599— 601).— The absorption curves and m. p. of the ten dichloro- 4600 A. shows itself most clearly in the glycerol naphthalenes fall into three groups according as the solutions; it is considered that the observed curve is chlorine atoms are in the am-, ßß-, or aß-positions. due to the summation of at least two simple bands. As with the ^-substituted benzene derivatives, the Over the concentration range 1 X 10‘4—8xl0~ 4 g./ m. p. are highest when the substituents are sym litre Beer’s law is not obeyed since the absorption metrically placed, and as far apart as possible. With increases more slowly with increasing concentration the exception of that of the 1 : 2-compound, the than the law requires, whilst the wave-length of maximum absorption is shorter for the more con spectra all show a large electronic interval in the region of about 1420 cm.-1, and this is most clearly centrated solutions. In glycerol solutions the marked with the ßß- and aß-derivatives. The maximum is some 100 A. nearer the red than is the corresponding aqueous solution. absorption bands of the vapours indicate two In order to study the fluorescence it was necessary different states of electronic activation. J. G r a n t . to prove that Wien’s law for the spectral distribution Infra-red absorption of fluids. E. N. G apon of intensity applies to the visible spectrum from a (Z. Physik, 1927, 44, 600— 602).— If vc denotes a carbon-filament lamp; the spectral sensitivity curve characteristic infra-red frequency of a liquid defined of the potassium photo-electric cell had also to be so that u —2Tcrut, where u is the velocity of a molecule determined. It was then possible to measure the of mass to in orbital rotation at a radius r about its fluorescence yield for monochromatic radiations centre of gravity, then topVc2=constant X T, where between 4400 and 5100 A. The yield was independent T is the temperature of the liquid. Since Stefan’s of concentration over the range of aqueous solutions, law gives P VT= constant X T, where P is the internal but it showed an increase with longer exciting wave pressure and V t the molecular volume of the fluid, lengths, which was most marked with the glycerol the above expression can be written ?;irVc2=constant x sohitions. The fluorescence spectrum exhibits a Fr/ßr, where ß is the coefficient of compressibility. maximum at approx. 5140 for the aqueous, and By substituting m = M/N and r = constant x i/Vr, 5220 A. for the glycerol solutions. The fluorescence where N is Avogadro’s number, the following ex yield at 5100 A. for the 4x10^ g./cm.3 solution is pression for vc is obtained: vc= k ( F^/iliß)!, where 0-71, but for the glycerol solution it is nearly 1-00. the constant ¿=0-34 xlO12. The values of vc have R. A. M o rto n. been thus calculated for the following substances : Photometric and spectrophotometric studies. benzene, toluene, o-, to-, and p-xylene, hexane, VI. Light ^intensity measurements in the silent mesitylene, chloroform, and chlorobenzene. The electric discharge. K. S ch a u m and R. T r a u t l u f t values so obtained agree fairly well with those (Z. wiss. Phot., 1927, 24, 416— 423).— Since chemical calculated from known spectroscopic data by Marton’s change in the silent electric discharge occurs at the equation (A., 1925, ii, 1025) for the frequency v,- of brush discharge, a correlation between the intensity the absorption bands: vi=vc-\/n, where n is an of electroluminescence, the electrical conditions, and integer and vc an infra-red frequency which is identi the chemical reactions seems desirable. Experi fied with that defined by the author. ments have been carried out on the minimum voltage R. W. L u n t. in a Siemens tube containing oxygen, carbon monoxide, Time interval between excitation and emission carbon dioxide, ammonia, (a) for the discharge merely for fluorescein. L. G. H o x t o n and J. W. B eams to pass and (b) for it to run continuously. Measure (Physical Rev., 1926, [ii], 27, 245).—The time ments of the brightness of the luminescence show that elapsing between the beginning of incidence and the this is greater for the streaming gases than for the beginning of fluorescence emission was 3-2+0-3 X 10~8 stationary gases. Alternative mechanisms for the sec. for an aqueous solution, and 3-7;t0-4x 10-8 sec. ozonisation process are discussed in connexion with for an alcoholic solution, of fluorescein containing the luminescence. R. A. M o rto n . 2-5 x l0 -s g. per c.c. A. A. E l d r id g e . Luminescence of solid nitrogen under cathode- Absorption and fluorescence of silver bromide ray bombardment. J. C. M cL e n n a n , H. J. C. and of silver chloride vapour. J. F r a n c k and H. I r e to n , and K . T hom son (Proc. Roy. Soc., 1927, A, K uhn (Z. Physik, 44, 607— 614).— From an analysis 1 1 6 , 1— 15).— Two types of apparatus are described °f the absorption and fluorescence spectra of the for the examination of the phosphorescence spectrum vapours of silver bromide and chloride it is shown of solid nitrogen and the spectrum of the light emitted that the size of the nuclear vibrational quanta de by solid nitrogen when irradiated by cathode rays. 1003 BRITISH CHEMICAL ABSTRACTS.— A.
In the phosphorescence spectrum the band N2 was for determining the nature of the collisions between found to have the components 5240, 5235, 5229, nitrogen molecules and electrons, for a range of 5224, 5220, 5214, 5210, and 5204 A., 5214 having the accelerating voltages from 2-0 to 15-0, is described. strongest intensity. The band N4 was shown to be The collisions become inelastic when the electrons composite and to have the components 5944-47, attain an energy of 6-30 volts, and are then inelastic 5938-8, and 5932-0 A., the strongest being 5944-47 A. up to 9-3 volts. The addition of hydrogen produces In addition to the bands N2 and N4, the luminescence practically no effect, hence the effect observed is spectrum contained three diffuse bands, N^ which probably due to nitrogen alone, and not to nitric oxide shaded into each other and had the mean wave present as an impurity. The wave-length correspond lengths 5554, 5617, and 5658 A. A number of faint ing with 6-3 volts is 1940, and with 9-3 volts 1318, diffuse bands wero also observed, each shaded off so that the inelastic collisions are probably associated towards the red in the blue and violet spectral region with the excitation of a system of bands in the ultra between 4573 and 2480 A. The N x bands were found violet, having for the final state the normal state of to decrease in intensity after the solid nitrogen had the nitrogen molecule. Down to 2-0 volts, no critical been irradiated for some time, but the groups N2 and potential was observed which might be associated N4 did not show this phenomenon. The view is held with the surplus energy of metastable molecules of that the solid nitrogen initially deposited in a form active nitrogen (cf. Willey and Rideal, A., 1926, 893). A is rapidly transformed into a form B under elec M. S. Burr. tronic irradiation, the phosphorescence investigated Variation of dielectric constants of certain being due to form B. No trace was observed of the organic substances with temperature. M. group of wave-lengths N3 obtained by Vegard (A., Velasco Durante/. (Anal. Fis. Quim., 1927, 25,252— 1924, ii, 436). From a study of the structures of the 305).— On the supposition that a molecule has no bands N2 and N4 the moment of inertia of the mole permanent electrical moment the relation of Mossotti cular system involved in the phosphorescence of and Clausius, (s— l)/(s + 2)?=constant, follows. If solid nitrogen is shown to be 3 X10-40 g. cm.2 approx. a permanent electrical moment be assumed, the It is not considered possible on the evidence obtained relation of Debye, (z—l)l(s+2)p=b+a/T, follows. to decide whether the band observed by Vegard in The dielectric constants of benzene, toluene, xylene, the auroral spectrum near 5230 is identical with tho cymene, chlorobenzene, and «/cZohexanol have been band N2 in the spectrum of solid phosphorescent determined at different temperatures. The dielectric nitrogen, or with the band 5228, the fourth member constant of all the compounds studied is a quadratic in the first negative band system of gaseous nitrogen. function of temperature, the coefficient being positive L . L. B ir cu m sh a w . except for benzene. Benzene, toluene, and xylene give Spectra of high-frequency discharges in super- results in agreement with the equation of Mossotti and vacuum tubes. R. W . W ood and A. L. L oomis Clausius. The remaining compounds, except cydo- (Nature, 1927, 120, 510).— If a discharge tube, while hexanol, satisfy Debye’s equation. As the constant being exhausted with a Holweck molecular pump, is a in Debye’s formula is negative for benzene, toluene, excited by an oscillating circuit giving a 3-metre wave, and xylene, it is inferred that the molecules of these a blue hydrogen discharge at first appears, being compounds have no permanent electrical moment. replaced by the olive-green discharge characteristic The effect of asymmetry produced by substitution of pure oxygen. The walls of the tube phosphoresce in the benzene nucleus on electrical moment is dis with a brilliant ruby-red light. The spectrum in cussed. It is concluded that the molecules of the cludes the line and band spectra of oxygen (possibly compounds studied which have asymmetric formulae from silica) and many carbon lines (doubtless from are electrically bipolar. G. W. R obin son. stop-cock grease). A. A. E l d r id g e . Electrical conductivity of vapours and liquid Heat of dissociation of N, and N2+. H. Sp o n e r drops during incipient combustion. J. A. J. (Physical Rev., 1926, [ii], 27, 641).— The o ”/?i curve for the final state of the first positive group gives B e n n e t t (Trans. Faraday Soc., 1927, 23, 295— 301). —To obtain some insight into the mechanism of the £,+£„=11-87 volts, approx.; for N2+, <2'=9-06, chemical action immediately preceding detonation in 9-7 volts, the second value being probably too great. an engine cylinder, the electrical conductivity with If 1—16-5 volts, /'=14-16 volts. A. A. E l d r id g e . rise of temperature of mixtures of air with various Heat of dissociation of 0 2 and 0 2+. R. T. vapours, viz., ether, »-hexane, phenol, aniline, B irge (Physical Rev., 1926, [ii], 27, 641).— The true iodine, toluidine, or mixtures of these, has been heat of dissociation, Q, of the molecule 0 2 is calculated determined. With rich mixtures of the less volatile from the njn curve for the excited state to be 7-05+ substances marked ionisation was obtained above 0-03 volts, and from the curve for the stable state to 400° when fogging occurred in the combustion tube. be 6-666+0-5 volts. Values of Q' are obtained from Gold electrodes were used in place of platinum, since the 02+ bands as 6-46 volts from the curve for the the latter caused surface combustion. Similar ex stable state and 6-49 volts from that for the excited periments were carried out in liquid drops-air systems state. Tho ionisation potential of the atom is containing mixtures of undecane with a large number 13-54 volts, and that of the molecule 14-1 volts. of other organic compounds, e.g., alcohols, nitrogen A. A. E l d r id g e . compounds, aromatic bases, and phenols, and also Critical potentials of nitrogen and the nature some miscellaneous anti-knockers. The behaviour of active nitrogen. A. S. L e v e s l e y (Trans. was similar to that observed in the former systems Faraday Soc., 1927, 23, 552— 560).—An apparatus after fogging had taken place. The conductivity GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1009 increases exponentially with temperature. The Cl3 molecule and is applied to a few simple reactions. action of ultra-violet light is to lower the temperature A trimeric formula for polymerised water is obtained, of initial combustion without affecting the conduc which has the hexagonal symmetry of ice crystals. tivity. It is suggested that the slow combustion of J. G r a n t . a disperse system of liquid drops of organic substances Variability of valency. (Si r ) P. C. R a y (J. in air is accompanied by profuse liberation of elec Indian Chem. Soc., 1927, 4, 89—95).—A discussion trons, whilst few electrons are present in mixtures of of modern conceptions of valency with special refer air and vapours. Recombination of electrons and ence to the compounds of auric chloride with mer- ions may be the source of the energy which causes captans. G. A. C. G ough . ignition at a lower temperature in mixtures of gaseous Intramolecular rearrangements in the com fuels containing liquid drops than in a completely plex cobalt compounds. A. U s p e n sk i and K . vaporised mixture. M. S. B u r r . T sch ibiso v (Z. anorg. Chem., 1927,164, 326— 334).— Optical dissociation of metallic halides. A. It is suggested as a general rule that if a reaction gives T e r e n in (Z. Physik, 1927, 44, 713— 736).—The rise to stereoisomerides which can be represented by limiting frequencies at which lines characteristic of the formula [Co(NH3)4R1R2]R3 or [Co en2R1R2]R3, the metal atoms are emitted when the vapour of the where R x, R 2, and R 3 are negative groups, then in the halide is irradiated with intense ultra-violet light have system in equilibrium in the solution a preponderance been determined for sodium and thallium iodides : of the trans-lorm exists. If, however, R 1 and R 2 are 2450 + 50 and 2080+20 A. for the sodium D-line and electropositive groups, the cis-form predominates. the thallium 3776 line, respectively. The optical The transformation of irarcs-dichlorodiethylencdi- dissociation corresponds thus with the formation of aminecobaltic chloride into the cis-form on evaporation an excited metal and a neutral halide atom. The of the aqueous solution, which appears to conflict vapours of mercuric chloride, bromide, and iodide and with the above generalisation, does not, however, of the iodides of cadmium, zinc, and lead emit a band occur quantitatively, and is complicated by the spectrum when irradiated with light of wave-length unequal solubilities of the two forms. Absorption shorter than a given limiting value characteristic of spectrum observations show that when a strongly the substance. For these substances it is shown that acid solution of the trans-form is warmed, there is no the optical dissociation corresponds with the form marked tendency for the formation of the cis-form, ation of an excited diatomic molecule and a neutral and on warming an aqueous solution of the aquocliloro- or an excited halogen atom according to the general sulphate an equilibrium with the diaquo-salt is set up. equation MX2==(MX)'+X. The band spectra of In general, the ratio between the amounts of two the mercuric halides observed are given , in tabular stereoisomerides produced in a reaction does not form with an accuracy of 1—2 A. R. W. L u n t. appear to be influenced by their relative solubility, Molecular scattering of light in a binary unless the solution becomes saturated in respect of one liquid, mixture. C. V. R am a n (Phil. Mag., 1927, form. R. Cu t h il l. [vii], 4, 447— 448).— A reply to a criticism by Kar Substitution reactions in the inner sphere of (this vol., 295) of the paper by Raman and Rama- complex compounds. A. U s p e n sk i and K. nathan (Phil. Mag., 1923, [vi], 45, 213) in which the T schibisov (Z anorg. Chem., 1927,164, 335— 340).— author’s improvement on Einstein’s equation for the The absorption spectra of oxalato-, carbonato-, and molecular scattering of light in a binarjr liquid diaquo-compounds of the cobalt-tetrammines have mixture is justified in that whilst Einstein finds been examined. For each of the first two groups, the merely the work necessary to change the concentration spectra of the various members are qualitatively by an infinitesimal amount from one value to another, similar, being only slightly dependent on the nature both differing from that of the bulk of the mixture, of the anion, and with increase in concentration the they evaluate directly the total work necessary to molecular absorption coefficient increases. If carbon change the concentration of a small volume of the dioxide is passed into a solution of diaquotetrammino- mixture from its mean value to one slightly different, cobaltic sulphate, the spectrum of the earbonato- the work being done in a strictly reversible manner. sulphate is ultimately obtained, but the mechanism It is shown that Kar’s assumptions involve a proccss of the change is not clear. The action of sulphuric which is not reversible. A. E. M it c h e ll. acid on the carbonato-compounds gives absorption Valency and additive compounds. J. P e r r in curves corresponding with those of the aquo-salts. (Compt. rend., 1927, 185, 557— 561).— The current R. Cu t h il l. theories of valency and of atomic structure are re Optical absorption and constitution of complex viewed and correlated with a developed form of salts. H. L e y (Z. anorg. Chem., 1927, 164, 377— Kekuld’s conception that chemical action between 406).— Solutions of the nickel, cobalt, and cupric salts two substances involves the formation of an inter of the amino-acids, which may be regarded as simple mediate additive compound, which then breaks down salts with internal complexes, have been investigated in a different sense. Such intermediate compounds by measurements of the conductivity and optical are held together by a single electron linking (semi- absorption. The dissociation of copper, nickel, and valency), which is weaker than a double electron link silver aminoacetates as derived from conductivity ing (valency), and is characteristic of a rigid system measurements increases in this order. E.M.F. built up from two octets, or from two closed electronic measurements with solutions of the copper salts systems, having in common one instead of two elec indicate very low concentrations of the metal ion, but trons. The theory explains the oxistence of the are not wholly conclusive. The behaviour of such 1010 BRITISH CHEMICAL ABSTRACTS.----A.
compounds in solution depends, not oidy on the transition classification, the abridged classification strength of the primary valency between the metal then including only elements most closely related to and the group with which it is associated, but also on the typical elements of the short periods, and con the character of the subsidiary valency between the sisting of a primitive period of two elements, 5 simple metal and the nitrogen, so that as a rule metals giving periods of 8 elements each, and a final incomplete highly-dissociated ammonia complexes manifest but period assumed to be also a simple period. The little tendency to form stable internal complexes with transition elements then form a separate table of 4 amino-acids. There is no general relation, however, periods, each period consisting of 8 valency groups but between the degree of dissociation of the internal beginning with Group III and ending with Group II. complex salt and the strength of the acid from which Each transition period consists of 10 elements, 3 it is formed. Conversion of the copper aquo-complex, being allotted to Group VIII, but to effect the [Cu4H20], into the corresponding ammino-complex, reduction to 10 elements in the third long period [Cu4NH3], displaces the maximum absorption towards containing 24 transition elements, 14 rare-earths proper shorter wave-lengths and increases the extinction. to Group III are relegated to a transition sub-series The wave-length of maximum absorption of the which is not capable of being arranged in a period of internal complex with aminoacetic acid is practically 8 groups. The abridged and the transition classific the same as that of the ammine, whilst the extinction ations are then recombined to form a complete periodic is intermediate between those of the ammino- and classification embodying all the features of the two. aquo-complexes. Measurements with ammoniacal The foregoing arrangements and the allocation of the solutions of copper sulphate indicate that these various elements to their proper classifications, solutions contain complexes such as [Cu6NH3] and periods, groups, and series aro discussed, and detailed [Cu2NH32H20] in addition to the tetrammino- experimental evidence is cited in support. It is complex. The absorption of nickel sulphate closely indicated that this classification of the elements is to resembles that of the acetate. Ammoniacal solutions be the basis of a complete scheme of the distribution of the sulphate, which appear from distribution of electrons in atomic structures. experiments to contain a liexammino-complex, vary F . S. H a w k in s . in colour with the ammonia concentration. The Rare earths. J. D. M a in Sm it h (Nature, 1927, internal complex with aminoacetic acid occupies an 120, 5S3— 584).— The rare earths have no real intermediate position between the aquo-complex and relation to any other series of elements, and the the ammino-complex. Both the cupric and nickel observed colour resemblances are fortuitous. The salts of aminoacetic acid obey Beer’s law over a sequence of colours of the (tervalent) salts of the considerable concentration range, indicating the first eight rare earths is identical with that of the last presence of very stable complexes. Addition of eight in the reverse order. Dysprosium salts are ammonia to solutions of the copper salt, however, yellow; terbium salts are faintly rose in thick layers; increases the extinction, new complexes being formed illinium salts should be yellow. The identity in the by the expulsion of aminoacetate ions by ammonia. colour sequences indicates that the same colour is Determination of the distribution coefficient of obtained in two different ions when one has as many ammonia between chloroform and an aqueous solution electrons (after deducting 54) more than zero as the of cupric aminoacetate points to the addition of two other has less than 14, and that the 14 electrons ammonia molecules to the salt. The constitution of concerned aro arranged in only two sub-groups. It such a salt is, however, uncertain. Nickel amino- is further inferred that gadolinium has electrons in acetatc shows a similar unsaturated character in both sub-groups, but also that the second sub-group respect of ammonia. It is suggested in explanation begins when the first is complete. The author’s law of the optical variability of these internal complex of uniform atomic plan is supported. salts that the groups bound by two principal and A. A. E l d r id g e . subsidiary valencies are arranged about the central Analogies of scandium with the rare-earth atom in a plane, in which there is sufficient space for elements and with the tervalent elements of the the introduction of, e.g., ammonia molecules. The iron fam ily. G. U r b a in and P. B. Sa r k a r (Compt. internal complexes of cobalt, on the other hand, are rend., 1927, 185, 593— 596).—The resemblance be remarkably inert both chemically and optically, tween scandium and the other tervalent elements of which may be ascribed to an octahedral configuration the periodic system is discussed. Apart from its protecting the metal atom. A complex compound of simple, anhydrous salts, scandium compounds always cupric aminoacetate and ethylenediamine, differ in composition from the corresponding salts of Cu(C2H40 2N)2,2 en,2H20, lias been prepared. the rare earths, and no case of isomorphism is known. R. Cttthill. Scandium acetonylacetato and salts of the types Electronic structure of atoms. I. The M3[ScFe] and K3[M(C204)3],5H20, however, strongly periodic classification. J. D. M a in Sm it h (J.C.S., resemble those of the tervalent elements of the iron 1927, 2029—2038).—It is shown that the feature of family, and the author furnishes evidence of this the classification of most importance to chemists is analogy in the following new compounds which are the octet arrangement of the elements into eight isomorphous with the corresponding compounds of the valency groups, and that modifications of the classi iron fam ily: (NH4)3[Sc(SCN)6],4H20, fication most serviceable in chemistry must give Kj[Sc(SCN)6],4H20, and Na3[Sc(SCN)6],12H,0. True greater prominence to this octet arrangement. It is scandium alums could not be obtained, but micro proposed to abridge the periodic classification by the crystalline double salts with the sulphates of potassium, relegation of the transition elements to a separate rubidium, csesium, and ammonium, which had the com- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1011 position of anhydrous alums, were prepared. The salt of the rare gases alone, but appears in all the gases T13[Sc(S04)3], also, is analogous to Étard’s salt, examined. The results are plotted as before and K 3[Cr(S04)3]. J. G r a n t . the curves can be divided into three groups. Argon, krypton, xenon, hydrogen chloride, and methane all Electron distribution in sodium chloride. have eight outer electrons and each yields an area A. H. Compton (Physical Rev., 1926, [ii], 2 7, 510— against electron velocity curve which slowly rises 511).—The electron density falls to zero for the to a maximum and then more slowly falls away sodium ion 1-1 Â. and for chlorine at 2-0 Â. from the again. Nitrogen and carbon monoxide with ten centre. Sodium has a group of eight electrons outer electrons yield curves which rise very sharply (probably K and L22) near the centre, with two to a maximum, followed by an equally sharp descent, electrons (probably L2±) at 0-9 Â. from the centre. which in turn is followed by a very flat maximum. Near the centre of the chlorine ion are 10 electrons Nitrous oxide and carbon dioxide with sixteen outer (K and L) outside which are 8 others, resolvable into electrons yield curves having a small, sharp maximum, 4 (? 3 3) at 0-74 Â., 2 ( ?3,) at 1-14 A., and 2 ( ?3,) at followed by a similar but very flat maximum. 1-60 Â. A. A. E l d r id g e . W . E. D o w n e y . Relationship of classical stereochemistry to the Effective cross-sectional area of the carbon new w ork of W eissenberg. M. v o n St a c k e l b e r g dioxide molecule against slow electrons. C. (Z. angew. Chcm., 1927, 40, 1023— 1027 ; cf. A., 1926, R am sau er (Ami. Physik, 1927, [iv], 83, 1129— 1135; 459, 934).— The fundamental postulates of classical cf. preceding abstract).— It is concluded that the stereochemistry are (1) the valencies of the carbon difference between total and absorbing cross-section atom are directed towards the corners of a tetra is in part due to definition and experimental difficulties. hedron, (2) a substituent group or atom can rotate The total cross-section would appear to be that given freely about a single linking ; whereas those of Weis by Lenard. W. E . D o w n e y . senberg are (1) the valencies have no fixed direction or length, but the substituents so arrange themselves Periodicity of molecular numbers. L. W. that their potential energy is a minimum, (2) every T ib y r iq a (Nature, 1927,120, 585).— Curves indicating symmetrical arrangement corresponds either with a the percentage of occurrence in each of four groups stable (energy minimum) or a labile (energy maximum) of molecular numbers, 4, 12, 20, 28; 6, 14, 22, 30; configuration, (3) of the large number of theoretically 0, 8, 16, 24; 2, 10, 18, 26, of a number of gases, acids, possible symmetrical arrangements, only those occur bases, and ions exhibit significant differences, which in practice in which identical atoms occupy similar are considered theoretically. A. A. E l d r id g e . positions, and different atoms dissimilar positions. Activated molecules. L. J. W a l d b a u e r and These postulates are difficult to apply, however, since 1. J. P atto n (J. Physical Chem., 1927, 3 1 , 1433— only in the case of the simplest substituents can the 1434).— The hypothesis is put forward that mole symmetry arrangements be definitely worked out, and cules are in an activated condition when the valency also it is not always possible to distinguish labile from electrons are at their greatest distance from the stable configurations. Further, there are often nucleus and at their lowest speed in their elliptical several configurations giving energy minima. orbits. Absorption of radiation quanta, on this Optical activity is due to the fact that a plane of view, merely moves the valency electron to an outer symmetry will be absent where the four substituent orbit further removed from the nucleus, and pro groups are dissimilar; racémisation is explained by duces a higher degree of activation. The temperature the existence of an “ energy mountain ” between two coefficient of a reaction can be explained by an equally stable configurations, so that a powerful increase in the number and in the force of molecular shattering effect {e.g., thermal agitation) will enable collisions arising from the increase in velocity of the the molecules to surmount the mountain and fall in molecules with a rise in temperature. equal numbers on both sides ; the Walden inversion L. S. T h e o b a l d . is similarly easily explained. Constitution of homogeneous acids. A. Since free rotation is no longer present, a great H antzsch (Ber., 1927, 60, [-B], 1933— 1950).—All number of isomerides are theoretically possible, but homogeneous acids, available for investigation, are are not experimentally observable, owing to the not 11 true ” acids in the sense of Werner’s complex smallness of the “ mountains ” and “ valleys ” of the formulas, [X 0 2]H, [X 0 3]H, and [XO]4H with ionically- “ energy surface ” ; the possibility of finding such combincd hydrogen atoms, which are therefore in isomerides at low temperatures is thus still open. themselves heteropolar substances and consequently The final test of the theory lies in X-ray measurements, electrolytes, but are rather homopolar hydroxy- but since the atomic numbers of the atoms composing compounds, OX’OH, 02X'0H, and 03X‘0H. Free, organic compounds lie so closely together, the ionically-combined hydrogen and free hydrogen ions spectrographs are difficult to interpret. do not exist. In the unimolecular state, the acids S. J. G r e g g . are homopolar non-electrolytes with structurally Effective cross-sectional area [of molecules] united hydrogen atoms, and hence are pseudo-acids and m olecular structure. E. B rü c h e (Ann. in accordance with a nomenclature which has become Physik, 1927, [iv], 83, 1065— 1128; cf. this vol., superfluous. This is strictly true only for hydrogen 492).—The previously described experiments have chloride, bromide, and iodide, which are uni been extended to include oxygen, methane, carbon molecular as liquids and therefore non-electrolytes; monoxide, carbon dioxide, nitrous oxide, and nitric for other acids, it holds only in the gaseous state at oxide. The Ramsauer effect is not characteristic a sufficiently high temperature. In the liquid con 1012 BRITISH CHEMICAL ABSTRACTS.— A.
dition the oxygen acids, •with certain exceptions, are Determination of crystal orientation in metallic more or less strongly associated; since the association single crystals. Y. S h im izu (Sci Rep. Tohoku has an optically bathochromic effect it is not brought Imp. Univ., 1927, 1 6 , 621— 625).— A simple method about by participation of the oxygen atoms of the of determining the crystal orientation of a metallic acid radical but, as in the case of water and the single crystal, without the use of X-rays, is described. alcohols, solely by means of the hydroxyl groups; The crystal is etched and the direction of brightest as dimerides they correspond with the formula reflexion observed. M. S. B u r r . OX— 0 < g > 0 —XO. Like bimolecular hydrogen Intensity measurements of X-ray reflexions fluoride, they arc partly converted into electrolytes from fine powders. J. B r e n t a n o (Phil. Mag., by association, since, in consequence of a restricted 1927, [vii], 4, 620— 629).— Measurements of the displacement of the hydrogen atoms according to the X-ray reflexion from finely-powdered rock salt have scheme (OX-OH)2— >[X(0H)2]+[02X]~, they yield been made and the results compared with those of acylium salts, which are dissociated in the unchanged Compton and others obtained from single crystals portion and thus convert such pseudo-homogeneous and from coarse powders. In general, the measure acids (regarded previously as equilibrium acids from ments are in good agreement except that for the true and pseudo-acids) into electrolytes. Free halo- most powerful reflexions the present measurements geno-acids do not exist, since, by reason of the non give slightly higher values. This indicates a small existence of ionogenic hydrogen, they decompose amount of primary extinction in the measurements spontaneously into halogen hydride and the halogen from larger crystals. In general, it is concluded compound of the corresponding element. Their that the reduction of a crystal to a coarse powder is “ hydrates ” or “ alcoholates,” like other strong sufficient to eliminate secondary but not primary acids, are oxonium salts. All acids behave towards extinction, and it is only with such substances as water as “ pseudoelectrolytes,” since they are more sodium chloride, the crystal units of which are initially or less completely transformed by addition of water sufficiently small, that grinding can reduce materially to the “ acid ” hydrogen atoms into hydroxonium primary extinction. A. E. M it c h e l l. salts and dissociated. The phenomena can be most Size of the ideal synthesised lattice-range in definitely expressed electrochemically by the phrase true crystals. A. Sm e k a l (Ann. Physik, 1927, “ only salts and not acids are electrolytes.” Acids [iv], 83, 1202— 1206).— Polemical against Kast (this are compounds of hydrogen with negative atoms or vol., 816). W. E. D o w n e y . atomic complexes; oxy-acids are at the same time derivatives of water in which a hydrogen atom is Orientation of aluminium crystals. K . T a n a k a replaced by more negative atoms or atomic com (Japan. J. Pliys., 1927, 4 , 137— 140).—The orientation plexes. Consequently, acids have the tendency to of long crystals in commercial aluminium wire in replace their hydrogen atoms by more positive atoms relation to the axis of the test piece has been examined. (metals) or atomic complexes and thereby to pass The (210) axis is more favoured than others for the into salts. Their degree of acidity (strength) is orientation of crystals, a result not in agreement measured by their tendency towards salt formation. with the results of Elam (A., 1925, ii, 945). The acidity of the acids X H or X'O H increases with R. W. L u n t. increase in the negative nature of the substituent X Crystallite orientation in aluminium. G. and is also determined by the differingly strong T am m an n and A. H e in ze l (Z. Metallk., 1927, 19, tendency of the acids towards salt formation or, 338— 341).—When commercial aluminium ingots are conversely, by the differing stability of their salts. rolled down to sheet the proportion of cube planes The strength of acids is most certainly determined in a section parallel to the direction of rolling gradually by comparison of their tendencies towards additive decreases to zero with a 66% reduction in thickness, salt formation with unsaturated substances, par whilst the proportion of octahedral and dodecahedral ticularly with water and related oxides in the produc planes remains practically constant or falls slightly tion of oxonium salts. up to a 90% reduction, and the proportion of eicosi- The absorption curves of tetrahydronaphthalene- tetrahedral planes rapidly increases. Rolled sheet with 2-sulphonic acid, its salts and ethyl ester, m. p. 35°, 60—90% reduction commences suddenly to develop are incidentally recorded. H. W ren. new crystals with varying orientations after annealing at 350°; the orientation of the new grains remains Electron lattice theory of metals. B. E. practically unchanged at higher temperatures and W a r r e n (Physical Rev., 1926, [ii], 27, 797— 79S).— consists of 40— 45% of (111), 35—40% of (110), and It is predicted that the metals of Groups I and III 18—21% of (100) planes on the surface of the rolled should utilise a complete lattice of the rock-salt typo, sheet. No twinned crystals are formed and pro the sub-lattice of the positive ions being face-centred longed annealing at a temperature just below the cubic; exceptionally, the sub-lattice of the alkali m. p. does not produce cube planes over the entire metals should be face-centred tetragonal. The sub- surface as is the case with copper. Progressive lattice of the metals of Groups II and IV should be planes cut parallel to the cooling surface of a sand- either face-centred cubic or hexagonal close-packed; cast aluminium ingot show little change in the that of and VI should bo body-centred cubic. The crystal orientation, the (111) planes predominating lattice of a Group VII metal should not be of a simple and few (100) planes occurring on the cut surfaces. type. The predictions are in agreement with the In ohill-cast ingots, however, the predominating experimental results. A. A. E ld r id g e . orientation is (100) followed by (111), except very GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1013 close to the cooling surface, where the converse is perature p-brass retains a body-centred lattice, but true. A. R. P o w e l l . the parameter has the value d100 3-007 A. against d100 2-956 at the ordinary temperature. The Rhombic sulphur isolated from volcanoes. F. A. values are for brass containing 51-1% of copper. R anfaldi (Mem. Accad. Lincei, 1927, [vi], 2, 266— W. E. D o w n e y . 318).— A comprehensive comparative survey of exist Hexagonal structure of thallium crystals. ing crystallographic data referring to the rhombo- G. R. L e v i (Z. Physik, 1927, 44, 603—606).—The hedral sulphur produced by volcanic eruption. contention of Becker (this vol., 503) that crystalline R. W. L u n t . thallium has a tetragonal structure is contradicted Lattice constant of metallic cobalt. S. S e k it o by photographs and crystallographic measurements (Sci. Rep. Tohoku Imp. Univ., 1927, 16, 545— of actual crystals, which show that the structure is 553).—X -R ay examination of annealed cobalt by hexagonal. R. W. L u n t. the powder-photographic method, at ordinary tem peratures, indicates that it has a hexagonal close- Crystal structure of magnesium telluride. W. packed arrangement of lattice constant 2-498 A. and Zachariasen (Z. physikal. Chcm., 1927, 128, 417— axial ratio 1-622. At about 700°, however, it has 420).—The crystals of magnesium telluride belong a face-centred cubic lattice with lattice constant to the wurtzite type, with a=4-52±0-02, c=7-33± 3-558 A. This confirms Masumoto’s conclusion (this 0-04 A .; u is approx. § ; dajo. is 3-86. The distance vol., 21) that there are two allotropic modifications between neighbouring magnesium and tellurium of cobalt which have a transition point lying between atoms is 2-76 A. H. F. G illb e . 400° and 500°. Electrolytic cobalt may also consist Crystal structure of potassium dihydrogen wholly of the hexagonal form, although Hull found phosphate. S. B. H e n d r ic k s (Amer. J. Sci., a mixture of the two forms in the powder obtained 1927, [v], 14, 269— 287).—The space-group of by rapid electrolysis'(A., 1922, ii, 624). The amount ammonium and potassium hydrogen phosphates is of discontinuous change at the transition point, JDJ5 (Hassel, A., 1925, ii, 1130). The unit cell of calculated from the lattice constant, is in satis the potassium salt contains 4 molecules. Using factory agreement with the result obtained by W yckoff’s notation, the phosphorus atoms are at (a), Masumoto from his elongation-temperature curve. the potassium atoms at (6), and the oxygen atoms M. S. B u r r . at (e), the locations of the latter being fixed by the Coherence of the reflected X-rays from parameter ranges: *==0-045—0-075; y ==0-120— crystals. G. E. M. J a u n c e y and A. H. C om pton 0-135; 2=0-145—0-165 A. The eight hydrogen (Nature, 1927, 120, 549).—For the /fa line of molyb atoms are at (c) and (d), the parameter u not being denum reflected from the (100) planes of rock-salt determined. This structure offers evidence against in the nth order, the ratio of the energy of recoil the assumption that the shape of a phosphate group (given to a sodium atom by the impulse imparted is independent of its ionic surroundings. In the by the reflected quantum) for each order to the rotating-crystal method of analysis the duration of energy of a quantum of Reststrahlen is 0-017, 0-067, exposure varies for different parts of the photo 0-15, 0-27, 0-42, 0-60, 0-82, respectively, for values graphic plate. The method of calculating the of n from 1 to 7. The fact that the ratio is always effective times of exposure is described. less than unity indicates that the energy of recoil S. K. T w e e d y . is always less than that of a quantum of thermal Crystal structures of ammonium, potassium, agitation; hence the impulse is imparted to the and rubidium cupric chloride dihydrates. S. B. crystal as a whole, and there is no reason to anticipate H e n d r ic k s and R. G. Dickinson (J. Amer. Chcm. an absence of coherence in the reflected rays. Soc., 1927,4 9 ,2149—2162).—X-Ray methods indicate A. A. E l d r id g e . that the unit cell contains 2 molecules of hydrate, the X-Ray analysis of hafnium. K . K im u ra (Z. space-group symmetry probably being D]f, with physikal. Chcm., 1927,128, 394— 398).—The hafnium w=0-213, r=0-217 for the potassium and rubidium content of a mixture of hafnium and zirconium salts and 0-217 and 0-221 for the ammonium salt. oxides or phosphates may be determined by mixing The 2Cu are probably at (a), 4K at (d), 4C1 at (/), the substance with sufficient lutecium oxide or 4C1 at (g), and 4H20 at (e) (Wyckoff’s notation). phosphate to cause the hafnium i p 1 line and the This structure, which is in agreement with the cassiopeium line to appear of equal intensity. behaviour of the substances in solution as double Such a mixture corresponds with a Lu203/H f02 ratio rather than complex salts, represents a new type. of 2-55 for an oxide mixture, and 2-75—2-85 for a S. K. T w e e d y . phosphate mixture. The application of the method Crystal structure of zirconium oxide. W. P. to the analysis of alvite is described, together with D a v e y (Physical Rev., 1926, [ii], 27, 798).— Of the the method of calculation when other metallic oxides several forms in which zirconium oxide may crystallise, are present. H. F. G illb e . one is a face-centred cubic lattice of Zr02, o=5-098 A.; X-Ray study of the p-transformation in copper- the second is a triangular close-packed lattice of zinc alloys. A. P h illip s and L. W. T h e l in (J. Zr02, a=3-598, (7=1-633. Both structures give Franklin Inst., 1927, 204, 359—368).— Diffraction d 6-13. A. A. E ld r id g e . data have been obtained for [3-brasses at the ordinary Oxides. Density and crystal structure of the temperature and at 520°. The lattice of |3-brass is oxides of antimony, and the nature of the oxygen body-centred and the lattice parameter increases linking. IV. A. Simon (Z. anorg. Chem., 1927, with zinc content. Above the transformation tem- 165, 31— 40).— The oxides Sb203, Sb204, Sb6013, 3 x 1014 BRITISH CHEMICAL ABSTRACTS.— A.
and Sb20 5 all have approximately the same typo of pounds have been determined ; 6 is the semidiagonal lattice. The elementary antimony tetroxide cell con of a face of tho rhombohedron and D is the diagonal tains eight double molecules; antimony tetroxide through the crystal in A. : magnesium fluosilicate, and the oxide Sb60 13 have a similar type of lattice 6=9-56, D=9-89 ; manganous fluosilicate, 6=9-66, to the trioxide, whilst the Debye diagram of the D—9-75; ferrous fluosilicate, 6=9-62, D = 9-6S; pentoxide indicates that this substance is partly cobaltous fluosilicate, 6=9-31, Z>=9-69; nickelous colloidal; the fifth atom of oxygen is held much fluosilicate, 6=9-62, £>=9-50 ; zinc fluosilicate, more loosely than the others, and its introduc 6=9-32, .0=9-04 ; magnesium titanium fluoride, tion into or removal from the molecule has but little 6=9-77, J>=9-S5; zinc titanium fluoride, 6=9-55, influence on the dimensions of the lattice. These -D=9-88 ; zirconium zinc fluoride, 6=9-77, Z )= 10-ll ; facts accord with the chemical properties of the magnesium fluostannate, 6=9-77, 25=10-02 ; zinc pentoxide and its derivatives, notably with tho fluostannate, 6=9-71, D=10-19. Measurements for influence of heat on the hydrated form, and with other co-ordination compounds are : the production of the tetroxide from antimony by Co(NH3)eCo(C]S06) 6=10-S9, D=10-81; the action of nitric acid. The density of antimony Co(NH3)6Cr(CN)G, 6=11-15, D=10-90; trioxide, determined pyknometrically, is 5-19, whilst Co(NH3)5H2OCo(CN)G, 6=10-74, D=10-S5; the X-ray method gives the value 5-49. That of Co(NH3)5H2OFe(CN)B, 6=10-74, D=10-84; the tetroxide increases with increase of time of Co(NH3)4(H20)2Co(CN)6, 6=10-62, D =ll-01. These heating, at 840° : after 1 hr., the density is 5-99, compounds are all of very similar structure, one ion and after 150 hrs., 7-50. The change is ascribed to being at the corner and the other at the centre of the production of the crystalline form from the a rhombohedron of about 96° inclination. The amorphous. Similar irregularities are foimd when arrangement of the six surrounding groups is prob the densities of SbG013 and antimony pentoxide are ably such that the true elementary cell is a rhombo determined; the values from the X-ray diagrams are hedron of four times the size of the simple one and 7-52 and 7-86, respectively. H. F. G il l b e . of inclination about 112°. Replacement of one or Crystal structure of palladium oxide (PdO). two of the ammonia molecules in the hexammine compounds by water produces very little alteration W. Z ac h ariasen (Z. physikal. Chem., 1927, 128, 412— 416).— Palladous oxide crystallises in the tetra in the X-ray diagram. H. F. Gil l b e . gonal system, with a=3-029+0-005, 0=5-314+ 0-005 A. The elementary cell contains two atoms Structure of xenotime and the relation between of palladous oxide, the palladium atoms forming a chemical constitution and crystal structure. L. body-centred lattice; the positions of the oxygen V eg ar d (Phil. Mag., 1927, [vii], 4, 511— 525).— The atoms have not been determined on account of tho structure of xenotime has been investigated by smallness of the scattering. Palladous oxide is means of the powder method and the previous result probably isomorphous with stannous oxide and red that xenotime and zircon have practically identical lead monoxide. H. F. G illb e . space lattices confirmed. Both belong to the space- group Z>JJ. In the xenotime lattice all four oxygen Crystal structure of tetramethylammonium atoms are of equal consequence, whilst the old chloroplatinate. M. L. H u g gin s (Physical Rev., chemical constitution formula would assign to one 1926, [ii], 27, 638).—The structure has cubic sym of them a singular position. On the octet theory of metry; a0= 12-65 A. Each platinum atom is sur molecular structure the atomic arrangement in the rounded by six chlorine atoms (24a) at the comers solid state is in agreement with the constitutional of a regular octahedron, and each nitrogen atom by formula. The close packing necessary for the four carbon atoms (32a) at the corners of a regular stability of a lattice of the zircon type indicates tetrahedron. The symmetry is that of the space- that such crystals may be stable under high pressures. group 01 or O3. The platinum-chlorine distance is Xenotime is gradually changing its crystal structure 2-35 A. if the nitrogen-carbon distance is assumed to with maintenance of its external form, and it is be 1-47 A. A. A. E ld r id g e . concluded that crystals of this type have probably Crystal structure of mercuric oxide. W. been formed under very high pressures. Zachariasen (Z. physikal. Chem., 1927, 128, 421— A. E . M it c h e ll. 429).— Powder measurements of the rhombic form of Quartz. A. M e iss n e r (Physikal. Z ., 1927, 28, mercuric oxide indicate the existence of two mole 621— 625).— If a quartz plate cut at right angles to cules in the elementary cell, of dimensions a=3-296, one of the electric axes is subjected to high-frequency 6=3-513, and c=5-504, with an error of +0-006 A.; oscillations of variable frequency, two characteristic rfmlc.= 11-22. The mercury atoms form a body- oriented oscillations manifest themselves at 1665 centred lattice, but it is not possible to differentiate and 1160 metres. By dusting the quartz surface between the numerous possible positions of the with lycopodium powder a clear pattern appears on oxygen atoms on account of the small scattering. excitation, and a photograph of the pattern discloses H. F. G il l b e . orientation in two directions from the optical axis, Crystal structure of heteropolar compounds of a = —48+2° (1160metres), fJ = + 7 1 ± 2 ° (1665metres). the composition MG6-LH?, MGjD-LRj, and The effect is connected with the inclination of planes MG4D2-LR which crystallise in the trigonal of like atoms against the optical axis and the values system. 0. H assel and J. R. Sa l v e se n (Z. a= —44+2° and ¡3=+63±2° are calculated from physikal. Chem., 1927, 128, 345—361).—-The crystal the not unequivocal X-ray data. Piezo-electric structures of the hcxahydrates of the following com observations considered in the light of the foregoing GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1015 lead to values for the modulus of elasticity of E— in liquids is not, however, claimed. Computed 7-8 xlO 11 and 15-6 x lO 11 cm.-1 sec.-2 for the con values of the densities of the alcohols are recorded. ditions corresponding with the angles p and a, A. A. E l d r id g e . respectively, the separations of the planes concerned X-Ray diffraction in liquids. C. V. R am a n and in the phenomena being 2-3 and 34 A., respectively. C. M. S ogani (Nature, 1927, 1 2 0 , 514).— A general R . A. M o r to n . account of experiments being described elsewhere. Equilibrium position of the atoms in p-quartz When the benzene ring is unsymmetrically loaded and its relation to double refraction and optical there is a broadening of the halo. Acetic acid and rotation. E. A. H y l l e r a a s (Z. Physik, 1927, 44, glycerol each give two haloes, corresponding respect 871—8S6).—The following values of the oxygen para ively with the mean distance between neighbouring meters a and u in p-quartz have been computed molecules which lie side by side, and that between from an electrostatic evaluation of the grating those lying end to end. A. A. E l d r id g e . energy and from data referring to double refraction and to optical rotation, respectively : 77-9°, 0-216; Electrolytic crystallisation processes. I. V. 77-4°, 0-215; 77-1°, 0-214. The values are in satis K ohlschutter . II. Aggregation forms of factory agreement with those of Bragg, but those incoherent metal deposits. V. K ohlschutter of Wyckoff are thought to bo in error. and A. G o o d . III. Formation and properties of R. W. L u n t . coherent metallic films. V. K ohlschutter and Structure of silicates. W. L. B ragg (Proc. Roy. F. Jakober (Z. Elektrockem., 1927, 3 3, 272— 277, Inst., 1927, 25, 302— 310). 277— 289, 290— 308).—I. In characterising cathodic metal deposits, the mode of arrangement of the Crystal structure of tetrahedrite. J. P a la c io s individual crystals to form the aggregate (aggregation (Anal. Fis. Quhn., 1927, 25, 246— 251).— Data are form) must be considered as well as the form, habit, given for the crystal structure of tetrahedrite by the and size of the individuals. As in other crystallis methods of Bragg and of Debye and Scherrer, respect ation processes, growth of existing crystals and ively. The unit cell contains four molecules in a formation of new nuclei are differently affected by cube, ec=10-39 A.; it is considered that the formula changing conditions, and wide variations in the should bo 3Cu2S,Sb2S3, and not 4Cu2S,Sb2S3, as character of such deposits are possible. In review supposed by Rose, Dana, and Moissan. ing theories as to the mechanism of the formation of G. W. R o bin so n . cathodic metal deposits, it is shown that numerous Crystal structures of anatase and rutile. M. L. factors may possibly operate in determining their H uggins (Physical Rev., 1926, [ii], 27, 638).— character, the growth of the deposit being affected, Vegard’s and Greenwood’s results for rutile, and not only by the forces of crystallisation (cf. Blum and Vegard’s for anatase, have been verified. Anatase Rawdon, A., 1923, ii, 732), but also probably by has a0 3-78, c0 9-50 A., 'with titanium atoms at forces in the solution. An attempt is to be made (0, 0, 0)(0, i, £)(£, 0, f)(i, £) and oxygon atoms at to determine the dependence of the character of (0,0, ttJip.i.w+iKiO, «'+1)^,1, «+i)(0,0,u)(0,i, 1 - electrodeposited metals on the nature of the metal u)(h 0) $—u)(b & h~u)> where m=0-20±0-01 ; space- and the conditions of deposition. group JD'Jr Rutile has a0=4-58, c0=2-95 A., with II. The electrodeposition of metals giving in titanium atoms at (0, 0, 0)(i, |) and oxygen atoms coherent, outgrowing deposits (cadmium, zinc, tin, at (u, u, o)(u, u, o )(l—u, u+%, £ )(« + i, i —u, i), where silver, and thallium) has been investigated with «=0-30+0-01; space-group D'Jt. reference to the character and rate of formation of A. A. E l d r id g e . the outgrowths. In previous work (A., 1924, ii, A'-Ray diffraction in liquids. Primary normal 528) Kohlschutter and Uebersax showed that under alcohols. G. W. S t e w a r t and R. M. M o r r o w suitable conditions lead is deposited from nitrate (Physical Rev., 1927, [ii], 30, 232—244).—Two solutions in the form of thread-like chains of minute significant distances are measured by the molyb octahedra attached to one another by their apexes. denum Ka. X-ray diffraction curves for the primary This form is favoured by high current density, low normal alcohols containing from 1 to 11 carbon electrolyte concentration, and low temperatures. atoms; the first is linearly dependent on the number Raising the temperature leads eventually to the form of carbon atoms, and the second is the distance of ation of leafy structures difficult to characterise. separation perpendicular to the chain. The first The chains of octahedra probably arise by the con distance increases about 1-3 A. for each carbon atom, vergence of current lines at the apex of the octa the second is 4-6 A. for lauryl alcohol, decreasing hedron, resulting in the formation of a new nucleus slowly to 4-4 A. for butyl alcohol, and then rapidly at that point. From a comparison of the forms to 3-8 A. for methyl alcohol. It is concluded that exhibited by various metals under various conditions the diffraction is produced by planes containing the it is concluded that the deposits obtained with a polar groups, which are not perpendicular to the given metal belong to a characteristic morphological direction of the parallel chain molecules. The effect type by which the metal can be recognised, in spite is not caused by crystal fragments, but is ascribed of modification due to variation of conditions. The to a non-crystalline molecular space array termed size of the individual crystals is determined by the cybotaxis.” The cybotactic state permits mobility, relation between rate of crystal growth and rate of but not random motion; the molecules have the nucleus formation, which in turn depends on current same orientation in groups too small to produce density, electrolyte concentration, and temperature. optical anisotropy. The universality of cybotaxis High chemical polarisation is known to be an accom 1016 BRITISH CHEMICAL ABSTRACTS.— A. paniment of low rate of crystal growth, but this temperature is higher the smaller is the amount of effect cannot be referred to complex formation, since deformation to which the metal has been subjected; the latter is found to favour crystal growth in some for silver, the minimum temperature lies between cases. High rate of crystal growth favours regular 250° and 300° and for platinum it is about 650°. orientation of the crystals in the chains. The Annealing at temperatures just above the limit attachment of one to another occurs in a favoured yields a fine grain which becomes rapidly coarser crystallographic direction and depends therefore 011 with rise of temperature. For silver the relation the habit of the individuals, which is itself largely between annealing temperature and grain size is determined for a given metal by the composition of almost linear above 350°, whereas for platinum the the electrolyte. The development of regular chains curve is hyperbolic and concave to the axis of tem seems to be favoured by a certain current density perature, i.e., a relatively small rise in temperature and is, 110 doubt, connected with the chemical polaris between S00° and 900° causes a large increase in the ation, the magnitude of which affects the distribution size of the crystals, but a similar rise of temper of current lines. With silver, chains of crystals ature between 1200° and 1500° has a very slight were not obtained, there being 110 favoured direction effect on the size of the crystals. By plotting the of growth of the crystals, and probably a suitable grain size against the logarithm of the deformation relation between rate of growth and rate of nucleus a straight line is obtained in both cases for all formation was not attained under the experimental temperatures. A. R. P o w e l l . conditions. It is concluded that even incoherent Tyndall's experiments on magne-crystallic cathodic metal deposits exhibit definite regularities action. (Sir ) W. B ragg (Proc. Roy. Inst., 1927, and that their formation can be referred to the 25, 162— 184). operation of forces at the crystal surface and in the electrolyte. The observations are discussed in detail Grating theory of the electrolytic conductivity and are compared with the results of Glocker and of rock salt. W. B r a u n b e k (Z. Physik, 1927, 44, Kaupp (A., 1924, ii, 518) on the X-ray examination 684— 699).— From a statistical analysis of the energy of coherent metallic deposits possessing a fibrous distribution of sodium ions in the rock-salt grating structure. an expression is derived for the probability that an III. Mechanical strains developed during the ion will move from the grating, i.e., for the number cathodic deposition of thin films of nickel have of ions crossing a given boundary per sec. A con already been investigated by the “ contractometer ’ sideration of this movement in a uniform electric method (A., 1922, ii, 648). This method has now field leads to an expression for the ionic conductivity, been improved and applied to the deposition of X, in the following form : log y_=log 2e2/3rac^0— other metals which give very fine-grained coherent 0/kT, where e is the electronic charge, t the time deposits. The magnitude of the “ contraction ” period of the ions in the grating, a the grating constant, developed during the deposition of films of nickel, c a grating distortion factor, k the gas constant per cobalt, iron, chromium, and palladium on platinum mol., T the temperature Abs., and <^0 the minimum cathodes has been determined under various shearing energy per unit cell. The value of c has conditions of current density, temperature, and been calculated from grating theory, that of - from composition of electrolyte. Deposits obtained on the frequency of residual rays, and that of platinum cathodes previously coated electrolytically
Viscosities, electrical conductivities, and ammonium sulphide increases steadily with the amount specific volumes of acetic acid-stannic chloride of arsenic present, sufficient copper being dissolved to solutions. J. D. St r a n a t h a n and J. Str on g cause an error in qualitative analysis. Colourless (J. Physical Chem., 1927, 31, 1420— 1428).— The ammonium sulphide does not dissolve cupric sulphide viscosities, electrical conductivities, and specific under the same conditions. With solutions of sodium volumes of solutions of stannic chloride in acetic acid polysulphide the influence of arsenic on the solubility have been measured at 25-2° for concentrations of of cupric sulphide is much less pronounced. the former up to a mol. fraction 0-4111 at which two F. S. H a w k in s . layers are formed. Mixing is accompanied by a large Effect of one salt on the solubility of another in evolution of heat, and by a large contraction in volume ethyl alcohol solution. I and II. F. E. K in g and which, at a mol. fraction 0-3608 of stannic chloride, is J. R. P ar tin gton (Trans. Faraday Soc., 1927, 23, 32-1% of the volume calculated on the additive law. 522— 535).— The influence of lithium iodide and The viscosity-concentration curve shows a pro sodium thiocyanate on the solubility of sodium nounced maximum which is 282 times the viscosity iodide in ethyl alcohol at 25° has been investigated, calculated additively. The maximum occurs at the and conductivities and viscosities of the sodium concentration corresponding with the compound iodide-sodium thiocyanate solutions have been deter SnCl4,3AcOH, to the formation of which the change mined. The solubility data for sodium thiocyanate in the properties of the system is attributed. and those for lithium iodide, at concentrations below L. S. T h e o b a l d . one equivalent per litre, may be represented by the Constitution of certain salts and acids in ordinary salting-out formula, log s/s0=£c, where s0 solution as determined by observations of and s are the solubilities in g./litre of saturated solu critical solution temperatures. S. R. Carter and tion of sodium iodide, alone and in presence of an N. J. L. M e g so n (J.C.S., 1927, 2023— 2028).— The added salt of concentration c equiv./litre, respectively. elevation of the critical solution temperature in the Methods of calculating the ionised and unionised systems phenol-water and i'sobutyric acid-water by fractions in the mixture of sodium iodide and thio the addition of other substances (Patterson, A., 1925, cyanate are described and compared, and certain ii, 389) is used to detect complex formation in hydro values adopted. As the concentration of sodium chloric acid solution. For mixtures of hydrochloric thiocyanate increases, both the concentration of un acid with sulphur dioxide, selenium dioxide, ferrous dissociated sodium iodide and the solubility product chloride, and cupric chloride, the rise of the critical of the ions decrease at approximately the same rate. solution temperature is normal and there is no M. S. B u r r . complex formation. Mixtures of hydrochloric acid Influence of electrolytes on the solubility of with ferric chloride, mercuric chloride, and cuprous other electrolytes in non-aqiieous solvents. C. A. chloride show, however, considerable complex form K ra u s and R. P. Sewtar d (Trans. Faraday Soc., ation, the compounds FeCl3,3HCl and HgCl2,HCl 1927, 23, 488— 491).— The solubility of sodium being indicated. F. S. H aw k in s. chloride in isopropyl alcohol in the presence of sodium nitrate and ammonium nitrate, respectively, Interdiffusion of immiscible solid salts. C. has been determined at 25°, and also the solubility T uban dt and W. J ost (Z. anorg. Chem., 1927, 166, of sodium bromide in acetone in presence of sodium 27— 30).— Immiscible solid salts may diffuse into each nitrate. The results show that addition of a second other when in contact if the ion carrying the current salt with a common ion depresses the solubility, has the same kind of charge in each, and if each salt whilst addition of a salt without a common ion is able to form mixed crystals by exchanging its own increases it. The magnitude of the effects is not in mobile ion for that of the other salt. These con accordance with that required by the Debye-Hiickel ditions are fulfilled by the forms of cuprous sulphide theory. It is possible that, in solvents of lower and silver iodide which are stable at higher tem dielectric constant, it will be necessary to abandon peratures, diffusion occurring in this case by exchange the assumption that the simple ions are the only of the metal atoms. Diffusion is slowest at the molecular species present. M. S. B u r r . surface of contact of the solids, indicating a not inconsiderable resistance to the transfer of ions from Physico-chemical analysis by ebullition of one lattice to another of a different type. saturated solutions. E. Co rn ec and P. K lug R. Cu t h il l. (Bull. Soc. chim., 1927, [iv], 41, 1009— 1017).—The Determination of solubilities by potentiometric b. p. of solutions which are saturated with regard to titration, and the “ insoluble" form of silver pairs of salts are said to afford information concerning chloride. F. L. H a h n and R. Sch u l ze (Z. anorg. the state of the salts in solution. Sodium and Chem., 1927,166, 213— 218).— Determinations of the potassium chlorides, or nitrates, do not combine in solubility of silver chloride by the potentiometric solution; sodium (or potassium) chloride and bromide method previously described (this vol., 743) have form a continuous series of mixed crystals; ammon failed to confirm the existence of the particularly ium and copper sulphates, and ammonium and zinc insoluble form reported by Lorenz and Bergheimer sulphates, form double salts, CuS04,(NH4)2S04,2H20 (A., 1924, ii, 757). R. Cu t h il l. and ZnS04,(NH4)2S04,6H20, respectively, exhibiting Solubility of cupric sulphide in alkali sulphides congruent solubility. S. K . T w e e d y . in presence of sulpharsenates. C. D a v ie s and Partition coefficients and the influence of salts. A. D. M unro (J.C.S., 1927, 2385— 2386).— The W. H erz and E. St a n n e r (Z. physikal. Chem., 1927, amount of cupric sulphide dissolved by yellow 128, 399— 411).— The partition coefficients of tri- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1021 methylamine between benzene and aqueous solutions tion, accompanied by an endothermic activation of lithium, sodium, potassium, strontium, and barium process, occurs on the most active spaces. Since, in chlorides, and sodium and potassium bromides, adsorption, that reaction which involves the smaller iodides, and sulphates have been determined at 25°. free energy decrease is favoured, the question arises The salting-out effect is greatest for chlorides and as to whether free energy change is a true measure of least for iodides, i.e., it decreases with rising atomic adsorption velocity. S. K . T w e e d y . volume, whereas the effect of the cations increases Hydrolytic adsorption by spongy platinum with increasing atomic volume. Neutral salts have and charcoal. A. F r u m k in and A. D o n d e (Ber., a corresponding influence on the solubility of dipropyl 1927, 60, [B], 1816— 1820; cf. this vol., 106).— amine in water. Measurements of the partition Spongy platinum, prepared by the action of mag coefficients of phenol and of bcnzoie acid between nesium on chloroplatinic acid and purified by succes benzene and aqueous salt solutions indicate that in sive w'ashings with hydrochloric acid and conduc the case of acidic substances the sodium ion has the tivity water in an atmosphere of hydrogen, adsorbs greatest influence and the potassium ion the least, alkali from a solution of sodium sulphate; the alkali the other cations giving intermediate values. The is not completely removed by washing with a con salting-out effect for a neutral substance such as siderable quantity of water, so that the amount of acetone is greatest for the sodium and potassium acid liberated is always hi excess of that of the alkali. ions. H. F. Gil l b e . It has not been found possible to prepare spongy Actinium. L. I m re (Z. anorg. Chem., 1927, 166, platinum in presence of oxygen wiiich adsorbs acid 1— 15).— Experiments on the distribution of the and liberates alkali. Charcoal treated with platinum nitrates of thorium and radioactinium between nitric and activated in ah’ adsorbs acid from potassium acid solutions and ethyl ether reveal a closc similarity chloride solution and liberates alkali, wiiereas the in the behaviour of the two salts. A method of opposite effect is observed in an atmosphere of removing cerium from actinium preparations has been hydrogen. Addition of thiocarbamide to the potass worked out (cf. this vol., 844). R. Cu t iiil l . ium chloride solution poisons the platinum and the charcoal then adsorbs only acid independently of Dynamics of salting out. E. A. H a f n e r the gaseous atmosphere. H. W r e n . (Biochem. Z., 1927,188, 259—269).— Phenol is salted out of aqueous solution by ammonium sulphate, more Adsorption of ions and of sols at interfaces and readily in presence of glycine, carbamide, and acetone, its application to certain problems of colloid less readily in presence of glycerol and alcohol, whilst chemistry. N. R. D h a r (J. Indian Chem. Soc., dextrose and sucrose have but little effect. The 1927, 4, 173— 181).— The adsorption of ions by sols salting out of euglobulin and total globulin by of mercuric and antimony sulphides, aluminium magnesium, ammonium, and sodium sulphates is and ferric hydroxides, and vanadium and manganese investigated and the results are discussed theoretically oxides shows that the greater the valency of the ion (cf. A., 1925, ii, 2S3). P. W. Clu t t e r b u c k . the less is the amount of adsorption. No experi mental support is found for the view that ions of Adsorption of gases on the surface of mercury. greater valency have greater coagulating power. M. L. Oliph an t and R. S. B urdo n (Nature, 1927, Although sols are capable of adsorbing ions carrying 120, 584— 585).—Measurement of the change of the the same charge as the sol, the adsorption is greatest concentration of carbon dioxide in admixture with when there is chemical affinity between the ion and hydrogen or helium when subjected to a shower of the sol. Sols of ferric hydroxide, silver and lead mercury droplets indicates that for 5, 10, and 15% chromates, but not sols of manganese oxide, antimony of carbon dioxide a complete unimolecular layer of and cadmium sulphides, are adsorbed readily by their the gas is formed in 0-2 sec. after formation of the respective solids. The theory of Liesegang rings surface. For 0-5% the adsorption is less, and for (A., 1925, ii, 959) based on the last observations is 50% more, than that which corresponds with a extended. G. A. C. G o ugh . unimolecular layer. It seems possible that the drop- Physical chemistry of colour lake formation. weight method for measuring surface tension gives I. General principles. [Adsorption of anions different values according to whether the liquid wets and hydrogen-ion concentration.] H. B. W eise r the tube or not. A. A. E l d r id g e . and E. E. P o rte r (J. Physical Chem., 1927, 31, Heats of adsorption on poisoned and heat- 1383— 1399).— As a preliminary to the study of treated catalysts. G. B. K istiakowsky , E. W. colour lake formation, the adsorption of sulphate and F lo sdo rf, and H. S. T a y l o r (J. Amer. Chem. Soc., oxalate ions, both separately and together, by the 1927, 49, 2200— 2206).— The curves representing the hydrated oxides of iron, aluminium, and chromium heat of adsorption of hydrogen by copper catalysts as at various hydrogen-ion concentrations has been a function of the amount adsorbed (cf. this vol., 426) investigated. Preparation of the oxides in sol form exhibit a maximum, which corresponds with a smaller by a special method gave products of much greater amount of adsorbed gas when the catalyst is partly purity than the precipitated gels usually employed in de-activated (by heat treatment) and disappears adsorption experiments with dyes. The pa values when the de-activation is complete. The curve for were measured by means of the hydrogen electrode. adsorption by a poisoned copper catalyst is typical An increase in concentration of the hydrogen ion of that for adsorption without activation. These increases the positive charge on the sol particles, results support the theory that a catalyst surface thus enhancing their adsorption capacity for anions. contains variable elementary spaces and that adsorp- The adsorption of the latter diminishes rapidly on the 1022 BRITISH CHEMICAL ABSTRACTS.— A.
alkaline side of the neutral point, becoming zero at condition never realised in practice. The fundamental pn 9-2. Further, the [-adsorption curves show no equation of Gibbs provides for more than two com evidence of the formation of a compound between ponents: [do)T= —r 1
Lability in ferric oxide hydrosols. C. H . Sorum in quartz tubes are less homogeneous than those (Science, 1927, 65, 498— 499).—A ferric oxide sol obtained by illumination in tubes of Jena glass. prepared by hydrolysis of ferric chloride at 100°, No sol-formation occurs on exposing pure silver and containing 3-5788 g. of iron per litre, was partly nitrate solution to ultra-violet light unless a pro coagulated by shaking, stirring, or addition of tective colloid is present. A series of experiments mechanically coagulated ferric oxide. After removal was made using a protein degradation product as the of the coagulum, the supernatant sol, which contained protective colloid, and the results arc compared with 3-2 g. of iron per litre, was completely stable towards those obtained with gum arabic. agitation and inoculation. Dilution decreased the L. L. B ir cu m sh a w . coagulation until a limiting concentration was reached Colloidal mixed solutions of calcium carbonate below which coagulation did not occur. and calcium phosphate. G. St e ll a (Kolloid-Z., A. A. E l d r id g e . 1927, 43, 21—26; cf. A., 1926, 1204).— Colloidal “ Photo-sols.” I. S. S. B h a t n a g a r , N. A. mixtures of calcium carbonate and calcium phosphate Y a j n ik , and V . D. Z adoo (J. Indian Chem. Soc., 1927, have been prepared by mixing sodium carbonate, 4, 209—219).-—The reactions of gold and silver sols sodium phosphate, and calcium chloride solutions with arsenic and antimony trisulphide sols are shown in aqueous gelatin solution at 95°. The ratio of the to be photo-sensitive and therefore similar to the two salts in the mixture can vary within wide limits, reaction between silver and sulphur sols (Frcundlich and the highest concentration which either salt can and Nathansohn, A., 1921, ii, 536). Excepting reach depends both on the gelatin concentration and cases when silver sol and arsenic or antimony tri on that of the second calcium salt. The calcium sulphide sols are mixed in certain proportions, no carbonate may not exceed a maximum concentration changes are observed when the mixtures are kept in of 0-005— 0-006.5/ above half the calcium phosphate the dark. Rapid colour change is produced by concentration. The phosphate may reach a con exposure to sunlight, and the product is found to centration two or three times as great as that which consist of metallic sulphides, free sulphur, and arseni- it could possess alone at the same gelatin concentration. ous or antimonious acids. G. A. C. G o ugh . The mixed precipitates of the two salts form a gel in water (provided that the carbonate does not exceed Stability of suspensions. II. Rate of sedi half the phosphate), which is readily peptised by mentation of kaolin suspensions containing gelatin at SO— 90°. The excess of calcium carbonate colloidal silicic acid. W . 0 . K e r m ac k and W . T. H. separates slowly from the colloidal solution in a W illiam son (Proc. Roy. Soc. Edin., 1927, 47, 202— crystalline state, without causing any change in the 221 ; cf. A., 1925, ii, 523; B., 1925, 464).— The rates appearance or stability of the solution. The results of sedimentation of kaolin suspensions have been support the hypothesis that a complex salt, or a examined in presence of salts of the alkali metals. In homochemical compound (in von Weimarn’s sense), acid suspensions, the inhibiting action is least in the is formed, in which two calcium atoms of the phosphate case of cæsium and greatest in the case of sodium. are bound with one of the carbonate. Peptisation The influence of small quantities of colloidal silicic experiments show that the mixed precipitate is more acid has also been examined at various hydrogen-ion readily peptised, and offers a greater resistance to the concentrations and in presence of univalent, bivalent, modifying action of temperature, than the phosphate and tervalent cations. Small quantities of silicic alone. L. L. B ir cu m sh a w . acid appear normally to have a protective action, but under certain conditions produce precipitation of Investigation of colloidal systems. N. N a film of insoluble material over the surface of the A n d r e e v (Kolloid-Z., 1927, 4 3 , 14— 17).— A modi particles. An abnormally rapid rate of sedimentation fication of the method used by Lottermoser (ibid., of the particles is then observed, as, for example, in 1914, 15, 145). The scattering of the light which presence of certain salts of the alkali metals or of passes through a colloidal solution is measured by calcium at ^ > 7 -5 . Li presence of calcium phosphate means of a potassium photo-element. From observ between p a 4-5 and 9-2 the effect of silicic acid is to ations with colloidal solutions of colophony, sus prevent formation of a precipitate, and in this case pensions of barium carbonate, and emulsions of the abnormal sedimentation occurring in the absence Staphylococais albus, it is found that the galvanometer of silicic acid tends to disappear. deflexions become relatively smaller with increasing W. 0 . K e r m ac k . concentration, due to the fact that the light scattered Rigidity and other anomalies in colloidal from the lower particles is intercepted by the upper solutions. E. H a t sc h e k (Proc. Roy. Inst., 1927, particles. The method has been used to investigate 25, 245— 259). the formation of colloidal sulphur solution and the Protected silver hydrosols. V. Reduction of coagulation of mastic with barium chloride solution. silver nitrate solution by irradiation with ultra It has the advantage over tyndallometric measure violet light in the presence of protective colloids. ments in that it gives absolute values. Some J. V o igt (Kolloid-Z., 1927, 43, 30— 35).— Gum applications of the method are discussed. arabic has no reducing action on pure silver nitrate L. L. B ir cu m sh a w . solution in absence of light or in diffused daylight, Theory of peptisation of metallic hydroxides but illumination by ultra-violet light leads to the in presence of non-electrolytes. K. C. Sen formation of a silver hydrosol. The greater the (Kolloid-Z., 1927, 43, 17— 21).—Experiments on the concentration of gum arabic the more finely divided peptisation of cerium, iron, and chromium hydroxides is the sol, and sols obtained by illuminating solutions in presence of non-electrolytes (sucrose and glycerol) GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1025
show that if an exactly equivalent quantity of alkali chloric acid, but is not peptised. The hydroxide A is added to the solution, precipitation occurs even readily forms true hydrosols and therefore contains in the presence of the protective non-electrolyte. A very small primary particles which, when combined minimum excess of hydrogen or hydroxyl ions is in large numbers to secondary particles, form the necessary for peptisation. It is inferred that the suspension of the preparation A. H. W r e n . protective action of the so-called protective colloids and non-electrolytes is dependent on the presence Phenomena caused by the low refractive of easily adsorbable ions in the solution. The pro indices of the alkali fluoborates. J. H. d e B o er tective action of the non-electrolyte appears to be (Proc. K. Akad. Wetenscli. Amsterdam, 1927, 30, subordinate to that of the ions. It probably acts 350— 354).—The apparent precipitation of potassium only on the surface of the colloid particles, diminishing fluoborate as a jelly when potassium chloride solution the surface energy, increasing the hydration, and is added to hydrofluoboric acid is due to the low preventing the growth of the particles. refractive index of the salt. Precipitation of the cæsium salt by the same method yields a perfectly L. L. B ir cu m sh a w . Peptisation of metallic hydroxides in the transparent solution, which exhibits brilliant colours owing to the difference of the dispersions of the solid presence of sugars. M . R. M e h r o tr a and K. C. and liquid phases. Cæsium fluoborate has nD between S en (J. Indian Chem. Soc., 1927, 4, 117— 129; cf. A., 1923, ii, 834).— The minimum amount of dextrose 1-3563 and 1-3502, in agreement with the theory of or of lsevulose necessary to prevent the precipitation the deformation of the electron layers in an ion, of metallic hydroxides when sodium hydroxide which requires the refractive index to be greater (3 mols.) is added to a solution of the metallic chloride than 1-33. The refractive indices of potassium and and the sugar, is found to increase in the order Cu, Fe, rubidium fluoborates should be still smaller and Hg, Ce in both cases. Sucrose and lactose give the experimental values for the latter are about 1-33. orders Cu, Ce, Fe, Hg, and Cu, Fe, Ce, Hg, respectively. The sodium and lithium salts have refractive indices At low concentrations there is a direct proportion below that of water : for 12% solutions ?if, for between the amount of metallic hydroxide peptised sodium fluoborate is 1-3321, and for lithium fluoborate and the sugar required, but at higher concentrations a 1-3303. For a 20% solution of the free acid ?iD is 1-3284. H. F. G il l b e . greater proportion of sugar is needed. This, together with the fact that peptisation is a specific effect, Volumetric chemical observations on forces of indicates that the formation of metallic sucrates is aggregation. I. T r a u b e (Ber., 1927, 60, [B], improbable. In tho case of mercuric chloride, the 1815— 1816).—The theory that complex substances, effect of a larger excess of alkali is to increase such as cellulose and the proteins, should bo regarded, the sugar required, whereas cupric chloride, under the not as compounds in the sense of the older structural same conditions, requires less sugar. Whilst the chemistry, but as built up by aggregation from peptisation of cupric and ferric hydroxides requires smaller units, is examined from the volumetric chemical considerable time, the keeping of peptised mcrcuric point of view. It appears that the forces of aggreg hydroxide causes precipitation. G. A. C. G ough. ation and valency are identical in their mode of Peptisation of iron and chromium hydroxides action and differ in that tho former aro not operative in presence of non-electrolytes and influence of from atom to atom, but act solely in causing a greater or less diminution of the co-volume. H. W r e n . acid and alkali on the peptisation. K . C. Sen (J. Indian Chem. Soc., 1927, 4, 131— 135).— Experi Hydration of univalent ions. E. Sc h r e in e r ments in presence of glycerol show that an excess of and E. B. Sc h r e in e r (Z. anorg. Chem., 1927, 166, alkali is necessary to prevent precipitation; this 219—224).— The calculations of hydration numbers excess can be reduced by the addition of larger previously made (A., 1924, ii, 524) have been revised, amounts of glycerol to a limit beyond which further using for the activity, a, Bjerrum’s formula, log a = addition is ineffectual. The specific protecting powers log.X — kC113, where X is the molar fraction, k the of non-electrolytes (preceding abstract) are appar activity constant, and G the concentration in g.-mol./ ent only when the minimum amount of alkali necessary 1000 g. of water. R. Cu t h il l. for peptisation is present. G. A. C. Gough. Electronic theory of valency. V. Molecular Sensitisation of cholesterol sols. R. St e r n structure of strong and weak electrolytes, (a) (Bioehem. Z ., 1927, 187, 315— 323).— Further experi Complete ionisation. T. M. L o w r y (Trans, ments (cf. A., 1926, 576) on the flocculation of Faraday Soc., 1927, 23, 508— 515).—Theoretical. In cholesterol sols by acetate, lactate, and tartrate general the ions of a strong electrolyte are prevented buffers in presence of electrodialysed ox serum confirm from neutralising their opposite electric charges by the author’s view that the coagulation point is the operation of factors which find expression in the dependent on the concentrations of cholesterol, “ octet ” rule. Badly-conducting solutions may, how protein, and hydrogen ions (cf. Rona and Deutsch, ever, be obtained by dissolving a salt in a medium A., 1926, 792). P. W. Cl u t t e r b u c k . with a low dielectric constant, when abnormal vari Aluminium hydroxide gels of Willstatter ations of conductivity with dilution are generally Kraut, and co-w orkers. R. Z s ig m o n d y and observed. The small “ degree of dissociation ” is D. G. R. B o n n ell (Ber., 1927, 60, [B], 1916— 1918).— probably due, not to the neutralisation of the ionic Aluminium hydroxide C, regarded as a colloid, is charges with tho formation of a chemical “ bond,” composed of very coarse particles; it is gradually but rather to the formation of neutral ionic doublets. temperatures other than that at which the acidity alkali halides exhibit no linear relation between the is measured. A. A. E l d r id g e . concentration and elevation of the critical temper Application of the hydrogen electrode to ature ; neither are tho elevations produced by organic bases : piperidine and its use as an different salts at the same equivalent concentrations alkaline buffer. E. B. R. P r id e a u x and P . L. equal. Experiments with coloured salts prove that Gil b e r t (J.C.S., 1927, 2164—2168).—The neutral at the critical temperature very little salt enters the isation of piperidine by hydrochloric acid can be vapour phase unless the contents of the vessel be accurately followed by the hydrogen electrode, and stirred, in which case the vapour becomes saturated the dissociation constant obtained by this method is with salt; the temperature at which the meniscus 1 X10-3 at 18°. The constant slowly decreases during disappears, however, remains unaltered. the neutralisation, but since the addition of sodium H. F. G il l b e . chloride has no appreciable influence on the potential, Ebullioscopic paradox. A. B erthottd, E. the decrease cannot be attributed to the formation B r in e r , and A. Sch idlof (Helv. Chim. Acta, 1927, of the salt. The alkalinities of partly neutralised 10, 585— 5S8).—The fact utilised in the Landsbcrger solutions calculated from the constant were checked process of mol. wt. determination that vapour of by colorimetric titration, and found to agree. It solvent at its b. p. is able to raise a solution to a follows that such solutions can be used as alkaline higher temperature is not at first sight in accordance with the second law of thermodynamics and the buffers. F. S. H a w k in s . suggestion that the necessary heat is supplied by the Buffer action. VI. Phase buffers. K. latent heat given out on condensation is incomplete. K l in k e (Helv. Chim. Acta, 1927, 10, 627— 642).— Assuming that tho external compensating work per The systems considered are distinguished by the mitting the heat transfer is the osmotic work caused presence of weak acids and by the limited solubility by the dilution of the solution by the condensed of at least one of the substances concerned. Equa solvent, the authors re-obtain the classical equation tions representing the change in the hydrogen-ion of van ’t Hoff for the elevation of the b. p. concentration on the addition of a completely dis On passing water vapour at 100° into a concen sociated acid to solutions of salts of sparingly soluble trated solution of ammonium nitrate contained in a buffer acids and suspensions of sparingly soluble salts Dewar flask the temperature of the solution is rapidly of soluble and sparingly soluble buffer acids are raised and a b. p. of the order of 120° attained. derived. Where possible illustrative titration curves J. S. Ca r t e r . are given. J. S. Ca r t e r . Occurrence of points of inflexion in the con- Mechanism of titrations with adsorbed indic centration-vapour pressure curves of aqueous ators. J. W- H o d a k o v (Z. physikal. Chem., 1927,129, solutions of certain electrolytes. A . J. A ll m a n d 128).— The work of Fajans and Wolff (A., 1924, ii, (Trans. Faraday Soc., 1927, 23, 477— 480).—The con 776) and of Hassel (A., 1924, ii, 738) renders the final centrations at which the curves connecting lowering conclusion of the author’s previous communication of vapour pressure with concentration, for solutions invalid (this vol., 743). H. F. G il l b e . of sodium, potassium, and lithium chlorides, show minima, and the vapour pressure-concentration Titration potential curves for precipitation curves show points of inflexion, have been calculated reactions. E. L a n g e and E. S c h w a r tz (Z. physi by Harned’s equation (A ., 1920, ii, 664). The values kal. Chem., 1927, 129, 111— 127).—The maximum are not in agreement with those found experimentally potential change during a titration in which a spar by various investigators. M. S. B u r r . ingly soluble uni-univalent precipitate is formed is given by AE=RT[riFxp/2v\/L, where -i/L is the Intermetallic compounds. VI. Reaction be solubility of the precipitate, v the volume of the tween solid magnesium and liquid tin. W. solution titrated, and p the volume of each successive H u m e -R o th er y (J. Inst. Metals, Sept., 1927, advanco small quantity of solution added. The greatest slope copy, 5 p p .; cf. A., 1926, 356).—The reaction between of the potential curve is at a distance P —\/2 X v\/L solid magnesium and liquid tin has been investigated from the end-point, P being the total volume of between 250° and 350° in order to see whether reac solution added; the accuracy of determination of tions of the type primary solid 2i+liquid—»-secondary the end-point can thus be calculated. The influence solid Y can proceed when the solid phases concerned of neutral salts on the sharpness of the end-point is do not form solid solutions. According to tho hi accord with the Debye-Hiickel theory. Flattening equilibrium diagram, when a rod of magnesium is of the potential curve due to the adsorption of ions suspended in a limited amount of molten tin, tho is discussed, together with the influence of temper magnesium should dissolve until the liquid has tho ature on the potential in the neighbourhood of the equilibrium composition, after which a slow reaction end-point. H. F. G il l b e . of the type solid magnesium-}-liquid — >- magnesium Critical state. I. Critical state of water and stannide (Mg2Sn or Mg4Sn2) should take place. of aqueous solutions. E. Sc h r o e r (Z. physikal. Actually when sufficient magnesium has dissolved to Chem., 1927, 129, 79— 110).—The most probable give the equilibrium composition, all further direct value of the critical temperature of water, determined action is stopped by a thin film of magnesium stannide from the temperature-density diagram, is 374-20°+ which shows no thickening even after 3 weeks at the 0-20°. The densities of the liquid and vapour phases above temperatures. A few large crystals of magnes do not become identical until the temperature is about ium stannide are, however, sometimes formed by a 0’5° above the critical temperature. Solutions of the slow reaction, which is probably analogous to crystal 1030 BRITISH CHEMICAL ABSTRACTS.— A. growth due to surface energy effects, since the thin annealing, and in the course of these experiments surface film has a high surface energy and so tends to the existence of a miscibility gap in the solid state form a more compact mass, but since dissolution at was revealed. The solidus and liquidus curves for any point exposes more magnesium to the liquid, the the system palladium-nickel pass through a minimum action proceeds slowly in spite of the absence of solid at a point corresponding with 60% of palladium, solutions. W. H u m e-R o t h e r y . and here also there is a miscibility gap in the solid Method of measuring variations of electrical state. Determination of the freezing surface for resistance for the determination of the thermal the system gold-palladium-nickel shows that the equilibrium diagram of an intermetallic system. minima exhibited by the binary systems gold-nickel and nickel-palladium become one in the ternary F. H. J e f f e r y (Trans. Faraday Soc., 1927, 23, 563— 570).—Two continuous methods are described system. R. Cu t h il l. for measuring the change of electrical resistance of Systems sodium chloride-lead chloride-water alloys with change in temperature, as determined by and lithium chloride-lead chloride-water. a chromel-alumel couple. The first is a null method, G. E. R. D eacon (J.C.S., 1927, 2063—2065).—The using Callendar records, and the second involves a equilibrium relations at 25° afford no evidence of “ back E.M.F.” method of measuring temperature double compounds. F. S. H a w k in s . and the measurement of variations of resistance by means of the current through an Ayrton-Mather Electrometric study of the system potassium galvanometer. The accuracy of the second method chloride-lead chloride-water at 25°. A . J. A l l - has been tested by application to copper-tin alloys m an d and L . J. B u r ra g e (Trans. Faraday Soc., containing from 40 to 98 atoms per cent, of tin. The 1927, 23, 470— 477).— In the above system a detailed results are in almost complete agreement with those study has been made of the activity of the lead of Heycock and Neville, but deviate from those of chloride by measurements on the cell Pb(amalgam- Isihara (J. Inst. Metals, 1924,1, 315) and of Haughton ated)[solution, AgCl(solid)|Ag. If N v N2, and N3 (ibid., 321). The higher transition point of tin, as are the molar fractions of lead chloride, potassium determined by this method, is 162°. This electrical chloride, and water, respectively, then continuous resistance method, with slow cooling, is very sensitivo addition of potassium chloride to a solution of con to the formation of a new phase, but for accurate stant N 1/N2 ratio causes first an increase in the work there is an upper limit to the rate of cooling. activity of lead chloride and then a decrease. By This, however, is not necessarily the same for every making certain assumptions, based on the published alloy. Preliminary experiments to fix the solidus, data for the vapour pressure of potassium chloride when solid solutions are formed, gave results in solutions, it is shown that the addition of lead chloride agreement with those of micrographic analysis. to a solution of constant N jN 3 ratio causes a decrease of the activity of potassium chloride if N2/N3 is small. M. S. B u r r . System aluminium-thorium. A. L e b e r (Z. This becomes less pronounced, and is finally con anorg. Chem., 1927, 166, 16— 26).—The equilibrium verted into an increase, as N2/N3 becomes larger, diagram for concentrations up to 56% of thorium has but the increase also becomes less marked as satur been obtained. In addition to the compound Al3Th ation with potassium chloride is approached. (Honigschmid, A., 1906, ii, 173) it would seem that a M. S. B u r r . compound richer in thorium is formed, or that mixed Systems boron tri oxide-sulphur trioxide- crystals separate from the more concentrated solutions. water and boron trioxide-phosphorus pent- oxide-w ater. M. L e v i and L . F. G il b e r t (J.C.S., R . Cu t h il l . 1927, 2117— 2124).— The equilibrium relations at 25° System phenol-water. E. R.. J on es (J. Physi cal Chem., 1927, 31, 1316— 1321).—The system and 45° show the formation of B203,S03,4H20 and phenol-water at temperatures below 13° has been 3B203,S03,3H20 ; this result is confirmed by direct studied, and the phase diagram established. Two analysis. Difficulty was experienced owing to the eutectic points, phenol hydrate, solution, ice, and supersaturation and high viscosity of the liquid phase. solid phenol, solution, and ice, respectively, have The data for the second system at 25° indicate that been observed at respective temperatures and con orthoboric acid and boron phosphate (BP04) occur centrations of —0-S43° and 4-607 g. phenol/100 g. as solid phases. Measurements of the viscosity of solution, and —1-174° and 6-839 g. phenol/100 g. solutions of orthoboric acid in sulphuric acid are solution. An unstable invariant point (ice and two recorded. F. S. H a w k in s . liquid phases) has also been observed at —1-252°. Equilibrium between two liquid phases. Solubility measurements are given, and the f. p. of IV. System o-toluidine-lactic acid-water. M. pure phenol is found to be 40-71°. L. S. T h e o b a l d . A ngelescu (Bui. Soc. Chim. Romania, 1927, 9, 19— 25).— The isotherms for 20° and 30° and the partition Gold-palladium-nickel alloys. W. F r a e n k e l coefficient at 30° have been determined. The and A. Ste rn (Z. anorg. Chem., 1927, 166, 161— 169; cf. A., 1926, 344).—The solidus curve for miscibility curves for given concentrations of lactic alloys of gold and nickel cannot be determined from acid indicate the existence of a lower critical solution cooling curves in the usual way, since with the temperature, but chemical action between the com normal rate of cooling the mixed crystals do not ponents occurs before the upper critical solution reach equilibrium with the liquid. It was therefore temperature can be realised. F. S. H a w k in s. necessary to trace the curve by observation of the Equilibria in the reduction, oxidation, and heating curves of alloys rendered homogeneous by carburation of iron. III. R. Sc h e n c k and T. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1031 Dingmann [with J. Bokmann, W . E bert, W . R est of an aqueous solution separated from the vapour ing, G. Lepetit, J. Muller, and W . Pratje] (Z. phase by a semipermeable membrane. anorg. Chem., 1927, 166, 113— 154; cf. this vol., H. F. G il l b e . 939).— The equilibria Fe30 4+ C 0 3 F e 0 + C 0 2 and Precipitation laws. P. P. v o n W e im a r n (Kol- FeO+CO F e + C 0 2 have been examined between loid-Z., 1927, 43, 26—30).—The author’s three pre 600° and 1100° by gradually removing the oxygen cipitation laws are summarised and discussed. The from ferric oxide by means of carbon monoxide at view is held that the laws are supported by the constant temperature, the composition of the gas recent investigations of Odén (cf. A., 1926, 678). phase being ascertained at each stage when equi L. L. B ircu m shaw . librium had been established. The experimental Equation of state of solid substances. IV. conditions were such that carbide formation was Heats and pressures of evaporation, sublim prevented. At a given temperature, with decrease ation, and melting in the neighbourhood of in the amount of oxygen in the solid phase the absolute zero, and Nernst's so-called heat composition of the gas phase first remains constant, theorem. J. J. v a n L a a r (Proc. K. Akad. Wetensch. then the carbon dioxide concentration falls rapidly Amsterdam, 1927, 30, 383— 400).— Polemical. The for a time, after which it ultimately becomes steady Nernst theory is invalid for all cases except that of again, and decreases further only when the solid the equilibria between two solid phases at very low phase contains less than about 0-5 atom of oxygen temperatures. H. F. G il l b e . per 3 atoms of iron. The first steady state corre Source of error in conductivity measurements. sponds with the coexistence in equilibrium of ferroso- F. A. Sm ith (J. Amer. Chem. Soc., 1927, 49, 2167— ferric oxide and a solid solution in this oxide of 2171).— Conductivity values determined by the use ferrous oxide. During the second period of constancy, of cells with differently-disposed electrodes agree only the solid phases are solutions of ferrous oxide in for that range of conductivity which corresponds with metallic iron (“ oxoferrite ” ) and of ferrosoferric that of the potassium chloride solution used to deter oxide hi ferrous oxide. The two solid solutions of mine the cell constants (cf. Washburn, A., 1917, ii, ferrosoferric and ferrous oxides are to be regarded 10). S. K. T w e e d y . as the extreme portions of a conthiuous series of mixed crystals of the two oxides, for which the name Conductivity of strong electrolytes in dilute “ wiistite ” is proposed. The data obtained permit solutions. P. D e b y e (Trans. Faraday Soc., 1927, of the construction of the diagram of state for the 23, 334— 340).— Theoretical. The interionic attrac system iron-oxygen, which shows that at 560° tion theory offers an adequate explanation of Kohl- wiistite, ferrosoferric oxide, and oxoferrite coexist rausch’s square-root law, provided two factors are in equilibrium, but below this temperature the first taken into account. The first is the variation in of these breaks up into the other two. At none of dissymmetry of the charge density in the ionic the experimental temperatures does ferrous oxide in atmosphere, as the ion moves under the influence the pure state appear as a solid phase. All substances of an electric field, in solutions of different con which are able to form compounds or solid or liquid centration. It may be shown that, as a result of the solutions with the oxides of iron influence the reduc finite time of relaxation responsible for this dis tion in the sense that a larger proportion of carbon symmetry, the ion is acted on by a force which tends monoxide must be present in the gaseous phase to to decrease its velocity, and that this apparent effect reduction than when the oxides of iron alone frictional force increases with increasing velocity. are present, i.e., more carbon must be used in the The second factor, which also tends to increase the furnace. The effect of magnesium oxide has been frictional force on the ion, is a cataphoretic effect, examined in some detail. With a mixture of the due to the movement of the ion in a solvent containing composition Fe20 3 + llM g 0 the ferric oxide is reduced ions. M. S. B u r r . directly to the ferrous state without passing through Ionisation of some typical strong electrolytes. ferrosoferric oxide and wiistite, and solid solutions D . A. M acI n n es and I. A. Cowperthwaite (Trans. of ferrous oxide and magnesium oxide exist in equi Faraday Soc., 1927, 23, 400— 404).— Transference librium with oxoferrite in the stage corresponding and conductance measurements have been made on with the second period of constancy of the com nitrates and chlorides in 0TI\r solutions, and the position of the gas phase when no foreign substance results indicate that, if the alkali chlorides and is present. This mixture of oxides must be regarded hydrochloric acid are completely dissociated, then as a mixture of a magnesium ferrite, Mg0,Fe20 3, nitric acid and ammonium nitrate are also of this with an excess of magnesium oxide. If, on the other class. Sodium, potassium, and silver nitrates, how hand, the ferric oxide is in excess, as in the mixture ever, must be partly associated. M. S. B u r r . 2Fe203+M g0, ferrosoferric oxide is present along with the magnesium ferrite in the first part of the Revision of the conductivity theory. L. reduction. R. Cuthill. Onsag er (Trans. Faraday Soc., 1927, 23, 341— 349).—The Debye-Hückel theory of the conductivity Equilibrium in systems the phases of which of strong electrolytes may be modified by taking are separated by a semipermeable membrane. into consideration the Brownian movement of the XX. F. A. H. S chreinemakers (Proc. K. Akad. ions. A knowledge of the ionic radius then becomes Wetensch. Amsterdam, 1927, 30, 401— 410).— A unnecessary and all arbitrary constants are elimin mathematical discussion of the influence of pressure ated from the limiting formula. When A is plotted on the osmotic relationships of a system consisting against Vn\x, where n is the sum of the valencies 1032 BRITISH CHEMICAL ABSTRACTS.— A. of the two ions and ¡j. the concentration, deviations at —33-5° (cf. this vol., 1023). Values of AOT are at higher concentrations from the limiting slope at calculated by Kraus and Bray’s method. Except zero concentration probably indicate association. in the case of succinimide, the salt is always a better M. S. B u r r . conductor than the corresponding acid, although the Mobilities of the elementary ions in methyl difference is small for the “ strong ” acids which alcohol. H . H a r t l e y and H . R . R a ik e s (Trans. probably form ammonium salts. Mercury succin Faraday Soc., 1927, 23, 393—396).— The mobilities imide has a very low conductivity. The conductivity of all the univalent and most of the bivalent ions in of ammono-carbonic acids and of their alkali salts methyl alcohol at infinite dilution are tabulated and increases with de-ammonation of the acid and compared with those in water at 25°. The general decreases with polymerisation. Sulphur nitride be relationships are the same in both solvents, although haves as a typical binary electrolyte; this compound the relative mobility of the ions in the two solvents is the mixed “ anammonide ” of ammonosulphurous is not constant. For the bivalent ions the value is and ammonothiosulphuric acids, and it probably approximately unity, as is the case for lithium. dissociates in ammonia solution into the two anarn- Applying Stokes’ law, the ionic radii in water and monous radicals which on ammonation would give methyl alcohol are compared with one another, and these acids. S. K. T w e e d y . also with the effective ionic radii in the crystal lattice Electrolytic transference of water, true trans as determined by other investigators. The radii of ference numbers, ionic mobilities, and water all ions in methyl alcohol are greater than in water. sheaths of the ions. H. R em y (Trans. Faraday The fact that the radii in water of several of the Soc., 1927, 23 , 381— 388).—True transference num alkali and halide ions appear to be smaller than their bers have been calculated from the available data effective radii in the lattice throws doubt on the for the electrolytic transference of water in normal absolute values of the ionic radii obtained by these aqueous solutions of inorganic electrolytes. A com means. M. S. B u r r . parison of solutions of homologous types shows that Ionic mobilities in non-aqueous solvents. H. the product of the true mobility of an ion and the U lich (Trans. Faraday Soc., 1927, 23, 388— 393).— viscosity of the solution varies much less from solu According to Walden the product of the mobility I tion to solution than the product of the apparent of a large ion, which may be regarded as not solvated mobility and the viscosity. This applies similarly because of its size, and the viscosity v) is a constant to the quotient of the mobility and the coefficient and independent of the solvent. This is shown to be of conductivity. On the assumption that large true for a number of solvents, including water, in organic ions do not carry water sheaths (cf. von the case of certain large organic ions such as the Hevesy, A., 1916, ii, 594; Lorenz, ibid., 312), values tetramethyl- and tetraethyl-ammonium ions and the have been deduced for the amount of water carried picrate ions. On the assumption that Stokes’ law by chlorine and bromine ions in normal solutions holds, and that solvation is indicated when the of aniline and p-toluidine hydrochloride and hydro product It] is not constant, the number of molecules bromide. Hence the absolute values for the number of solvent per ion has been calculated for the alkali of water molecules carried by hydrogen, alkali, and and halide ions in different solvents and the results alkaline-earth metals, iodine, and also some small are tabidated. M. S. B u r r . organic ions have been determined and the results Debye-Hiickel theory. H . H a r t l e y and R. P. tabulated. M. S. B u r r . B e ll (Trans. Faraday Soc., 1927, 23, 396— 400).— Electrolytic conduction of potassium through Examination of a large number of conductivity data glass. V. Z w o r y k in (Physical Rev., 1926, [ii], 27, in organic solvents shows that, in general, the Kohl- 813).— Burt’s experiments on the introduction of rausch square-root relation is confirmed in dilute sodium into a thermionic vacuum tube by electrolysis solution. This is in accordance with the Debye- have been extended to potassium. When a soda- Hiickel theory. A further test of the latter may be potash glass is immersed in potassium nitrate, the applied by calculating b, the harmonic mean of the metal introduced is primarily sodium; the glass is ionic radii, from the Debye-Hiickel equation, and enriched in potassium and becomes brittle. With comparing it with the value calculated on the assump potash glass, potassium passes into the tube without tion that, at infinite dilution, the motion of the ions corroding or embrittling the glass. A. A. E l d r id g e . obeys Stokes’ law. Divergences between the two Ionic mobilities in mixed crystals and their values for solvents with dielectric constants less relationship to those in the pure salts. C. than 20 are rather large, but the approximate agree T u b a n d t , H. R e in h o l d , and W. J ost (Z. physikal. ment among the remainder is regarded as evidence Chem., 1927, 129, 69—78).—A quantitative method of the essential correctness of the Debye-Hiickel of expressing the degree of interlocking between the theory. The results also show that conformity to various components in a mixed crystal has been the square-root law is no guarantee that the con- derived by comparing the ionic mobilities of the ductivity-concentration curve will be in accordance pure salts with those of tho mixed crystals, as calcul with Debye’s equation. This may arise from incom ated from measurements of conductivity and of plete ionisation. * M. S. B u r r . transport number. From the relationship between Conductivity of acids and salts in liquid the mobilities it is possible to determine the extent ammonia. F. A. Sm ith (J. Amer. Chem. Soc., to which the diffusion coefficients obtained from 1927, 49, 2162— 2167).— Solutions of amides, imides, diffusion measurements represent the true diffusion etc., and of their monoalkali derivatives were examined coefficients of the pure components. H. F. G il l b e . LtlSKJSKAJL., i'll YaJ-UAL,, AJNJU 1JN UUUAJNIU uujsjumxux . 1UOO Effect of temperature on diffusion potentials. of lead from the amalgam increases with increase of E. B. R. P r id e a u x (Trans. Faraday Soc., Sept., the concentration of the lead nitrate solution: change 1927, advance proof).—From the ionic mobilities of concentration from 0-01 to 0-1 ilf increases the of a series of univalent electrolytes, it is shown that velocity about one hundredfold, but at higher con the temperature coefficients of the diffusion potentials centrations the rate of increase diminishes. A method are small and possibly zero; this is attributed to the is described for measuring the velocity when the tendency towards equalisation of the mobilities of time of contact between the amalgam and the solution anion and cation as the temperature is raised. is a minimum. The mean velocity at 18°, calculated Measurements of the diffusion potentials at 18° and for a saturated amalgam, is 0-0051 g./cm.2/sec. 25° and over the concentration range from 0-1 to Qualitative observations with bismuth indicate that O-OIjV, using a flowing junction, are in agreement tho velocity is greater than l-5x 10~5. with this view. For univalent electrolytes of varying H. F. G il l b e . character the observed change in diffusion potential Electrochemical studies of titanium. E. D. is less than 0-5 millivolt. For acetic acid, the increase B otts and F. C. K r a u sk o pf (J. Physical Chem., 1927, in the diffusion potential with the temperature is 31, 1404—1419).—The preparation of titanium, its larger, amounting to 0-7 millivolt between 18° and single potential, and its power of replacing other 25°. G. A. E l l io t t. metals from salt solutions have been studied. The method of Nilson and Pettersson, as modified by Cells of the standard-cell type with low Hunter (A., 1910, ii, 302), yielded crystalline titanium E.M.F. W. C. V o sb u bg h (J. Amer. Chem. Soc., of 99-6— 99-9% purity in pieces varying in size up 1927, 49, 2222—2229).—The E.M.F. of the cells to 5 g. The optimum conditions are described, and (Cd+Pb)Hg|CdCl2,2-5H20 (sat. soln.)|CdCl2,2-5H20 + sodium is shown to be preferable to potassium, or to PbCl2 (sat. soln.)|Hg(Pb) and (Cd+Pb)Hg|CdI2 (sat. a mixture of both, as tho reducing agent. Single soln.)|CdI2+ P b I2 (sat. soln.)|Hg(Pb) were measured potential measurements of titanium in 0-25.3/ solutions at 5° intervals between 15° and 40° over a period of of the trichloride and of the corresponding sulphate several months. The former cell is the more repro gave average values of 0-23 and 0-18 volt, respectively. ducible, but exhibits a transition point at 26-2°. The The presence of hydrofluoric acid in the titanous E.M.F. of the corresponding cells containing pure solution increased the single potential by 0-22 volt, cadmium amalgam are given by 23=0-13759— but additions of hydrochloric and sulphuric acids 0-000193(i—25)—0-0000012(i—25)2 and ¿7=0-0996+ to the corresponding salt solution lowered it. Alkali 0-000235(i—25)—0-0000002(i—25)2, respectively. The salts having an ion in common with the titanium former equation gives values in slight disagreement salt caused a slight increase. Replacement experi with those of Obata (Proc. Phys. Math. Soc. Japan, ments do not agree with these measurements except 1921, [iii], 3, 64, 136) and of Taylor and Perrott in solutions of the fluorides, copper, silver, lead, and (A., 1921, ii, 303). The E.M.F. of the corresponding cadmium, but not cobalt, nickel, zinc, or iron, being cells with pure metal electrodes are given by E = replaced by titanium only from a solution of the 0-1824—0-000453(i—25)—0-0000012(i—25)2 and E = respective fluoride. L. S. T h e o b a l d . 0-1444—0-000025(i—25)+0-0000002(i-25)2, whence for the reaction Cd+PbCl2+2-5H 20 (in sat. soln.)= Helmholtz double layer related to ions and CdCl2,2-5H20+Pb, Ai’=-8417 g.-cal., A5= — charged particles. E. F. B u r to n (Fourth Colloid 20-9 g.-cal.^degree, and A27= —14,650 g.-cal. at 25°, Symposium Monograph, 1926, 132— 144).— There and for the reaction Cd+PbI2=CdI2+Pb, AF = appears to be mutual action of charged particles, and —6664 g.-cal., A S = —1-15 g.-cal./degree, and AH— interaction of colloid particles and ions in solution; —7008 g.-cal. These values agree with tho thermo this opposes the view that within molecular distance chemical data. None of these cells is suitable as a of the surface there exists an electrically equivalent standard cell; their temperature coefficients arc layer of opposite charge. Gouy’s equations indicate large and the iodide cells exhibit persistent hysteresis. that the thickness of the outer Helmholtz double S. K. T w e e d y . layer decreases as the concentration of the electrolyte Electrical action due to the atomisation of a increases, the decrease for electrolytes of the same solution of a univalent electrolyte. A. B u h l molar concentration being the greater the higher is (Ann. Physik, 1927, [iv], 83, 1207— 1224).— The the valency of the ions; if the ions have the same effects produced by the air spraying of solutions of valency their concentrations remain proportional, electrolytes and the charged particles resulting thereby but if they differ in valency their concentrations in have been investigated. The number of charged the neighbourhood of the surface differ. particles depends on the concentration of the solution Ch em ical A b st r a c t s. and the velocity of the air stream. The results are Thermodynamic P.I), at the boundary between discussed in terms of Lenard’s conception of the tw o liquid phases. V. S. V osnessenski and K. structure of the surface layers of liquids. A stachov (Z. physikal. Chem., 1927, 128, 362— W. E. D o w n e y . 368).— A method is described for measuring the P.D. Dissolution velocity and the electrolytic solu at the interface between two liquid phases in which tion pressure of lead and of bismuth. J. Gr6 k various electrolytes are dissolved. If the partition (Z. physikal. Chem., 1927, 128, 449— 458).— The rate coefficient of the electrolyte be constant, the P.D. is of exchange of lead between lead amalgams and constant at moderate concentrations. At concen aqueous solutions of lead nitrate has been measured trations above about Q-5N the P.D. remains constant, by an electroscopic method. The rate of dissolution even although the partition coefficient undergoes 1034 BRITISH CHEMICAL ABSTRACTS.— A. change. The partition of the cations sodium, silver) dipping into the same solution. The current potassium, and hydrogen is in the same order as that passing through the system, of which tho zinc forms of their degree of hydration, and a similar relation the anode, was measured under various conditions, probably obtains for the commoner anions. and changes in the rate of dissolution of the zinc H. F. Gil l b e . could be followed from measurements of the rate Experimental investigation of the theory of of hydrogen evolution from the complete cell. In local currents. M. Centnerszwer and M. St r a u - accordance with the “ local element ” theory of m a n is (Z. physikal. Chem., 1927, 1 2 8 , 369— 393).—• corrosion, it was found that with given external Simultaneous measurements have been made of the resistance lower currents were obtained when cathode electrode potential, current strength, and internal metals of higher hydrogen overvoltage were used. resistance of typical polarisable cells. Tho logarithm Also the single potentials of tho various cathode of the current strength at constant anode potential metals combined with the zmc are of the order of decreases in direct proportion to the time, a con magnitude to be expected from known overvoltage clusion which follows from Boguski’s law. With the data. If v0 is the rate of dissolution of the zinc cell short-circuited, rise of temperature produces before connexion with tho other metal and v the a logarithmic increase of the current strength. On velocity when so connected, then if ve is the rate of anodic dissolution of a metal in acid its potential “ enforced ” dissolution which corresponds with the increases; increase of external resistance causes the current passing under the latter conditions, it is anode to become more negative, whilst increase of found that i;0~f-f£=v + A , where A is a positive internal resistance has tho reverse influence. With quantity named the “ difference effect.” Provided increase of current strength the potential of the anode that v0 exceeds a certain critical value, A —kl, where increases up to a limiting value dependent on the I is the current and k is a constant independent of the electrolyte. The velocity of dissolution of an anode nature of the cathode metal. For low values of v0, in different acids or in the same acid at different however which can be obtained by using a polished concentrations increases as the equivalent conductivity zinc surface, k is no longer constant, but falls of the solution increases and is the greater the smaller towards zero as v0 is diminished. Experiments with the overvoltage at the cathode. The properties aluminium in Ar-sodium hydroxide solution yielded of tin, cadmium, and iron anodes are very similar similar results, but the value of k is notably greater to those of zinc. H. F. Gil l b e . in this case. A negative value of A for aluminium in dilute hydrochloric acid is being further investigated. Passivation of metals by anodic polarisation. The results described give strong support to the G. G rttbe (Z. Elektrochem., 1927, 33, 389—399).— local element theory of corrosion of metals, but it Theories of passivity are briefly reviewed and recent is pointed out that, when conditions are such that work, mainly by the author and his collaborators, hydrogen evolution from the surface of the dissolving on the anodic passivation of metals in alkaline metal is very rapid, the rate of diffusion of hydrogen solutions is discussed (cf. A., 1921, ii, 49; 1922, ii, ions towards that surface can become a determining 570; 1923, ii, 118; 1926, 362, 687; B., 1923, 233). factor, so that eventually the phenomenon passes At low current densities iron, cobalt, manganese, over into that described by Nernst and Brunner (1904) and lead dissolve anodically in bivalent form in for the dissolution of other solid substances in acids. solutions of sodium or potassium hydroxides, but The difference effect is attributed to the retardation with increasing current density the polarisation event of diffusion of hydrogen ions towards the metal ually increases sufficiently to permit oxidation of surface caused by accumulation of salts of the dis the bivalent ions to the tervalent or quadrivalent solving metal in that region. Provided that v0 is stages. Relatively insoluble intermediate oxides, high enough for diffusion to be the ruling factor, such as Fe304, Co304, and Mn30 4, can then be A may be expected to be proportional to I which deposited as a film on the anode. Passivity then determines vc and hence the extent of this accumulation ensues, the polarisation increasing rapidly and higher of metallic salt. Measurements of the single potential oxides being formed, which may decompose, giving of zinc when combined with a platinum cathode in oxygen evolution, or, at least in part, dissolve in the 0-5iV-hydrochloric acid show an increasing ennoble electrolyte as in the formation of ferrates and man- ment as the current increases, which corresponds with ganates. The behaviour of chromium is similar, an increasing concentration of zinc ions at the metal but passivation occurs at an exceptionally low current surface. Wide variations in the values of v0 observed density. Anodic passivity in acid solutions, however, with discs of zinc cut from the same rod are found does not seem to be of this mechanical type. An to be accompanied by corresponding variations in anomaly in the behaviour of chromium in acid the microscopic appearance of the metal after solutions is discussed. H. J. T. E ll in g h a m . corrosion. An exceptionally pure sample of zinc Corrosion of metals as an electrochemical showed no corrosion during 2 Ins. in 0-5A7-hydro- problem. A. T h ie l [with J. E c k e l l] (Z. Elektro chloric acid, but scratching with a diamond led to chem., 1927, 33, 370— 386).— One side of a disc of formation of hydrogen bubbles along the crevice, a specially purified zinc was exposed to 0-5A7-hydro- result which is attributed to decreased hydrogen chloric acid, which was vigorously stirred, and, when overvoltage at an irregular surface. Palmaer’s view the rate of dissolution of the metal had become (B., 1926, 589) that the increased rate of dissolution practically constant, the disc was connected through of iron containing graphite can be attributed to a an external variable resistance with a plate of a low overvoltage of the latter is disputed and con nobler metal (platinum, copper, lead, tantalum, or clusions of Centnerszwer and Zablocki (A., 1926, 1010)< GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1035 as to the mechanism of the dissolution of aluminium reactions. For a special case of consecutive reactions in acids are criticised. H. J. T. E l l in g h a m . accompanied by side reactions an expression for the velocity has been deduced, and is discussed in its Photo-voltaic cells. C. W. T u c k e r (J. Physical application to the reactions between hydrogen per Chem., 1927, 31, 1357— 13S0; cf. Case, B., 1917, oxide and the bromine ion and molecule. 1102; Garrison, A., 1923, ii, 728; 1924, ii, 339, 401).— H. F. G il l b e . The cuprous oxide and silver halide photo-voltaic Thermal decomposition of hydrogen peroxide systems have been studied in cells of the type— vapour. L . W. E l d e r , jun., and E . K . R id e a l illuminated metalj oxide or halide-solution-oxide or (Trans. Faraday Soc., 1927, 23, 545— 552; cf. Hinshel- halide|metal. Illuminated electrodes of cuprous wood and Prichard, J.C.S., 1923, 1 2 3 , 2726).— An oxide deposited in the meshes of platinum gauze gave apparatus for the measurement of the rate of decom small but definite photo-voltages. In reducing position of hydrogen peroxide vapour at constant solutions, photochemical reduction of cuprous oxide volume is described. By comparison of the vapour tends to occur, and oxidation in oxidising solutions. pressure of the original mixture, obtained from a Substitution of copper for platinum has a specific hydrogen peroxide preparation of approximately 60%, influence on the behaviour of the copper-cuprous with that of the resulting water vapour, it has been oxide electrode, and cells with copper in the form of shown that hydrogen peroxide vapour, under about gauze show the so-called “ Minchin effect,” i.e., the 85 mm. pressure at 85°, consists of simple unhydrated illuminated electrode is at first anodic, changing to molecules. The decomposition bulb was made of cathodic on continued illumination. The initial quartz, since glass gives no reproducible results. The anodic effect is more permanent with an oxidising thermal decomposition at 85° is a reaction of zero than with a reducing solution in the cell. Removal order, inhibited by molecular oxygen, which brings of the light results in an increase hi cathodic tendency the reaction to an end when only about 20% of the and the P.D. between the two cell electrodes slowly hydrogen peroxide is decomposed. The inhibiting returns to zero. When the gauze is replaced by reaction is stronger still at 95°. On a platinum sur sheet copper, the anodic effect is magnified as the face the reaction is apparently unimolecular, and is local cell formation is decreased, but the voltage probably determined by the rate of diffusion through maximum indicates that local cell action is still an adsorbed or dissolved layer of oxygen. The appreciable and that sign reversal of the electrodes reaction on a mercury surface consists of a pre would still occur with continued illumination. The liminary direct oxidation of mercury to mercurous anodic effect is now greatest in reducing solutions. oxide, followed by oxidation of the latter to mercuric The general form of time-voltage curve is independent oxide, with simultaneous liberation of an equivalent of the solution used. The behaviour of platinum | amount of atomic oxygen which oxidises a further silver halide electrodes closely resembles that of the quantity of hydrogen peroxide. The mercuric oxide copper]cuprous oxide electrodes, and the photo is not reduced by hydrogen peroxide vapour. A voltage with silver chloride is, in general, greater method is described for the preparation of pure than that with the bromide, which, in turn, is greater concentrated hydrogen peroxide from “ Hyperol.” than that with the iodide. Tho silver]silver halide M. S. B u r r . electrodes have also been examined. The above Thermal decomposition of hydrogen peroxide. results are explained in terms of local cell formation, F. O. R ice and O. M. R eiff (J. Physical Chem., 1927, which will be at a minimum on the illuminated 3 1 , 1352— 1356).— The decomposition of pure aqueous surface when the photosensitive substance on this solutions of hydrogen peroxide, prepared by the surface is present as a uniform layer; in these circum method of Kilpatrick, Reiff, and Rice (this vol., 120), stances the exposed electrode is the anode. On the arid of commercial solutions at 80-2° has been studied. other hand, when the layer is non-uniform, local The rate of decomposition of the former, freed from cells are set up in the illuminated electrode, which suspended matter and heated in vessels with smooth becomes the cathode on continued illumination. walls, is very slow. Pure, aqueous solutions, free When the local cells are completely reversible, the from inhibitors but not from dust, give a linear behaviour of the electrode is determined by the decomposition curve; addition of chlorides, alkalis, oxidising or reducing nature of the cell solution; and inhibitors gives curves which are often uni it is a cathode in the former and in a neutral solution, molecular in type. Merck’s perhydrol, and pure and an anode in a reducing solution. solutions to which were added inhibitors such as The work of previous investigators is summarised barbituric or uric acid, or benzamide, show an and discussed. L. S. T h e o b a l d . initial induction period on the decomposition curves. Velocity of coupled reactions. J. A. Ch r is The catalysis of hydrogen peroxide by the iodine- tiansen (Z. physikal. Chem., 1927,1 2 8 , 430— 438).— iodic acid couple (Bray, A., 1921, ii, 629) appears to The method of instantaneous velocities is shown to be be a heterogeneous reaction occurring on the surface applicable to the kinetics of reaction. For the velocity of dust particles. The ordinary decomposition of of a series of consecutive reactions, without side hydrogen peroxide also takes place on these surfaces reactions, an expression has been derived which is in and on the walls of the vessel, and an inhibitor evid agreement with thermodynamic considerations if ently acts by poisoning the surface. with Bronsted the assumption be made that the L . S. T h e o b a ld . probability of reaction is proportional to the product Thermal dissociation of carbonyl chloride. of the activity coefficients of the reactants and a H. I ngleson (J.C.S., 1927, 2244— 2254).— The divisor f x which is common to the two opposing thermal dissociation of carbonyl chloride has been 1036 BRITISH CHEMICAL ABSTRACTS.— A. investigated between 357° and 480° in quartz vessels. acetaldehyde is influenced less, and in a different way, Trustworthy residts coidd not be obtained in glass, by hydrogen. These results are consistent with the - as it is attacked by the chlorine produced. The heat assumption that tho activation of acetaldehyde of reaction at constant volume is 25,500 g.-cal. at a involves oidy a few degrees of freedom, whilst that of mean temperature of 416°. A linear relation is found propaldehyde is a more complex process, and that in between the reciprocal of the absolute temperature the propaldehyde process a time lag exists between and the logarithm of the reaction velocity constant. activation and transformation. Christiansen’s view that the decomposition is acceler L. L. BmctFMSHAW. ated by the products (A., 1923, ii, 62) is supported Esterification in mixed solvents. B. W . B ih d e qualitatively (cf. Atkinson, Heycock, and Pope, and H. E. W atson (J.C.S., 1927, 2101—2107).—The J.C.S., 1920, 117, 1410). C. W. G ibby. velocities of esterification of suberic and «-butyric Oxygen required for the propagation of hydro acids in mixtures of tsoamyl alcohol with benzene or gen, carbon monoxide, and methane flames. petroleum have been measured in the presence of G. W. J ones and G. St . J. P er ro tt (Ind. Eng. hydrochloric acid as catalyst. The velocity co Chem., 1927, 19, 985— 989).— The minimum propor efficients given by the formula of Goldschmidt and tion of oxygen necessary to propagate the flames of Udby (A., 1907, ii, 852), k t= (r—a) log a/(a—x)—x, methane, hydrogen, and carbon monoxide in admix are satisfactory and increase on dilution of the alcohol ture with varying proportions of nitrogen was deter in an approximately hyperbolic relation with tho mined. With less than 12% of oxygen no methane- composition of the solution. Conductivity and nitrogen mixture was combustible, but for sufficiently viscosity measurements show that ionisation of the high proportions of hydrogen and carbon monoxide catalyst has no influence on the velocity, and it is (4% and 14%, respectively) the minimum oxygen suggested that the latter depends on the molecular concentration is 5— 6%. The presence of carbon ratio of catalyst to alcohol. C. W . Gib b y . dioxide raises the oxygen concentration necessary. Coefficient of hydrolysis of ethyl acetate by Helium has a similar effect on the combustion of sodium hydroxide. (Miss) E. M. T e r r y and J. hydrogen. C. I rwist. S t ie g lit z (J. Amer. Chem. Soc., 1927, 49, 2216— Inflammation of mixtures of the paraffins and 2222).— The experiments were carried out in approx air in a closed spherical vessel. G. B. M a x w e l l imately 0-01Ar-sodium hydroxide solution, the appar and R. V. W h e e le r (J.C.S., 1927, 2069— 2080).— atus being an improvement of that described by The pressures in mixtures of air with the first five Reicher (A., 1885, 1034). The coefficient is 6-76 members of the paraffin series developed on ignition (±0-75% ) at 25° (concentrations in mol./litre) and centrally in a spherical bulb have been measured, and increases 0-045 per 0-1°. Improved experimental are compared with the calculated values. Dis technique is described in detail. S. K. Tweedy. crepancies are probably due to errors in specific heat Hydrolysis of ethyl acetate. W. T. Gooch (J. and equilibrium data. The mean temperature of the Amer. Chem. Soc., 1927, 49, 2257).—Intensity vari explosion is the main factor in determining the mean ations of diffused daylight do not influence the rate of rate of development of pressure. C. W. Gib b y . hydrolysis of ethyl acetate in aqueous sodium hydr Influence of hydrogen on two homogeneous oxide at 25°. S. K. T w e e d y . reactions. C. N. H in sh e l w o o d and P. J. A s k e y (Proc. Roy. Soc., 1927, A, 116, 163— 170; cf. this Kinetics of the hydrolysis of glyoxal tetra vol., 26, 212).— If a molecule in a gaseous reaction is acetate. A. S k r a b a l and E. Gitschthaler (Z. activated by collision, transformation may follow physikal. Chem., 1927, 128, 459— 471).— The hydro immediately, or it may be delayed until the molecule lysis constants of the hydrolysis of glyoxal tetra passes through a suitable internal phase. If the acetate in neutral, acid, and alkaline solution are for transformation is immediate, the reaction is kinetic- the first stage 0-000138, 0-01640, and 2740, and for ally bimolecular, but if there is a time lag, then, as the second stage 0-000069, 0-00820, and 1370, Lindemami has indicated (Trans. Faraday Soc., 1922, respectively. The relationship between the consti 17, 599), the reaction appears to be unimolecular. tution of a number of esters of acetic acid and their The time lag after activation is considered to be most rates of hydrolysis is discussed. H. F. G illb e . probable when the structure is complex and the Kinetics of oxime formation. A. O la n d e r (Z. energy distributed among a number of degrees of physikal. Chem., 1927, 129, 1— 32).— The quantity freedom, whilst its absence is to be expected when of iodine reduced in the iodometric determination of the mechanism of activation is very simple. The hydroxylamine is not directly proportional to the reactions involved in the decomposition of prop- amount of the latter. The relation between them aldehyde and dimethyl and diethyl ether are uni- has been ascertained for quantities of hydroxylamine molecular at higher pressures, but betray their up to 5-5 mg. The dissociation constant of hydroxyl dependence on molecular collisions by decreasing in amine at 20° is 1-07 x 10"8, and that of dibromo- rate when the pressure of the reacting gas is reduced cresolsulphonephthalein in presence of 0-1 if-phosphate below a certain limit. In the case of the two ethers, is 7-4 X 10~7. Free hydroxylamine reacts slowly with it has been found {Joe. cit.) that the rate of decompos acetone, but the hydroxylammonium ion reacts com ition maintains its unimolecular character at low paratively quickly and reversibly; ' for the reaction pressures if sufficient hydrogen is present, and it is between the ion and acetone the bimolecular velocity now shown that the decomposition of propaldehyde coefficient is 84. The additive reaction product is similar, but that the bimolecular decomposition of decomposes reversibly with the formation of acet- GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1037 oxinie and water; the unimolecular velocity constant Influence of diffusion of oxygen on the rate of the reverse reaction is 0-07. The optimum p n, at of combustion of solid carbon. J. T. W ar d and 20° and 0-003iY solution, is 4-5 for the formation of J. B. H am b le n (Ind. Eng. Chem., 1927, 1 9 , 1025— the oxime and 2-3 for its decomposition; the forward 1027).—A carbon block was burned in air and by reaction is complete only at pn> 7. The velocity very slow sampling the gas was drawn off from the and degree of completeness of the reaction have been carbon side of the gas film by a quartz capillary determined in 0-003Ji solution in presence of acid at sealed into the end of the block. The analyses showed various concentrations. H. F. G il l b e . an average ratio of 28-07 mols. of oxygen to 100 mols. Reactions in the solid state at high temper of nitrogen, carbon dioxide and carbon monoxide atures. II. Reaction velocity of exothermic being returned as oxygen, as against an air ratio of 26-58. This is in accordance with the theory that changes. W. J a n d e r (Z. anorg. Chem., 1927, 166, 31— 52).— Extension of the theory that reactions in the rate of the reaction C + 02=C 02 is limited by binary mixtures of solids are governed by the ordinary the rate of diffusion of oxygen through the gas film laws of diffusion (this vol., 736) to solids between surrounding each particle of carbon. C. I r w in . which an exothermic reaction occurs shows that the percentage reaction, x, is related to the time, t, by Corrosion of non-ferrous metals and alloys. the formula 1 — [(100—a;)/100]1/3=2-3{log i+log b'— T. S. F u l le r (Proc. Amer. Soc. Testing Materials, [advance copy], 1927, No. 19, 1— 18).—Modified pro 2 log [1—-^(lOO—a:)/100]}/c. Here b' measures the cedures are given for the total immersion and alternate diffusivity at the start of the reaction, and c is a immersion tests. The spray test and the electrolytic function of x and the temperature, T. This equation test do not'appear to be generally applicable. is in good agreement with the experimental results Chem ical A b str ac ts. for mixtures of barium carbonate and tungstic anhydr Corrosion fatigue of non-ferrous metals. ide and of silver sulphate and lead monoxide. Both D. J. M cA d a m , jun. (Proc. Amer. Soc. Testing b' and the velocity coefficient at the final stage of Materials, [advance copy], 1927, No. 36, 1— 26).—An the reaction are related to the temperature by an examination of 18 non-ferrous metals and alloys with exponential expression. R. C u t h il l. fresh and salt water. For nickel and Monel metal, Application of Tammann’s method of thermal the fully annealed and strain-hardened metal have analysis to reactions between solid phases. J. the same “ corrosion-fatigue limits,” but this is not G u illissen (Bull. Acad. roy. Belg., 1927, [v], 13, the case for copper-nickcl alloys. The corrosion- 233— 238).— The application of Tammann’s method fatigue limits of these alloys may depend chicfiy on (A., 1926, 921), i.e., comparison of temperature their electrode potentials. The stress-cycle curves time curves of the hiitial reaction mixture and of for aluminium and for aluminium-manganese alloys the reaction product, to the study of the formation give a corrosion-fatigue limit far below the endurance of certain ferrites not yielding a trustworthy indication limit in air. Each metal and alloy appears to have of the temperature of commencement of reaction, an an intrinsic corrosion-fatigue limit depending chiefly attempt has been made to increase the sensitivity of on the corrosion agent and the corrosion resistance of the method by using a Le Chatelier-Saladin differ the metal. Possibly this limit depends on the ease ential galvanometer and constructing a temperature- of removal of atoms from the space lattice under the temperature difference curve. combined influence of electrolytic solution pressure The reaction between barium carbonate and ferric and cyclic strain of the lattice. oxide commences at about 800°. An equimolar Chem ical A b strac ts. mixture, when heated for 3 hrs. at 830° in a slow Passivity of iron mirrors. H . F r e u n d l ic h , G. current of air, undergoes a change in weight corre P at sc h e k e, and H . Z ocher (Z. physikal. Chem., sponding with the formation of 87-5% of barium 1927, 1 2 8 , 321— 344).— The physical and chemical ferrite. The direct addition of barium oxide to ferric properties of iron mirrors on glass, produced by the oxide occurs at about 300°. Owing to secondary thermal decomposition of iron pentacarbonyl, have disturbances no definite indication of the temperature been studied in their relationship to the problem of of reaction between calcium carbonate and ferric passivity. The mirrors are rendered passive by treat oxide could be obtained. The reaction certainly ment with concentrated nitric acid, and are then in occurs at relatively low temperatures. the same condition as ordinary passive iron. Mirrors J. S. Ca r t e r . maintained out of contact with air are considerably Temperature of formation of zinc ferrite from more active than those to which air has access, being the solid constituents. J. G u il lisse n and readily dissolved by nitric acid; this activity is R ichard (Bull. Acad. roy. Belg., 1927, [v], 13, unaffected by carbon dioxide, nitrogen, or water. 238—240; cf. preceding abstract).—Interaction be The passivity produced by contact with the atmo tween zinc and ferric oxides commences at 620— sphere cannot be destroyed by placing the mirror in a 650°. On account of the stability of zinc ferrite vacuum, although in certain cases heating the mirror towards dilute acids the importance of considering its in a vacuum restores its activity. Similar conditions probable formation during the roasting of zinc blendes obtain for mirrors rendered passive by acids. Con preparatory to an electrolytic process is emphasised. siderations of “ vacuum activity ” and “ air pass After being heated at 890° a mixture containing 34% ivity,” together with observations of the brown film of zinc oxide yielded only 8% of zinc oxide to an of insoluble matter which remains when an iron ammoniacal solution of ammonium chloride. mirror is dissolved in acid, lead to a simple oxidation J. S. Ca r t e r . theory of the passive state. H. F. G il l b e . 1038 BRITISH CHEMICAL ABSTRACTS.— A. Catalysis in homogeneous gas reactions. when benzidine hydrochloride is used for the test, a- A. vo n Kiss (Chem. Weekblad, 1927, 24, 466— 471).— positive reaction may be obtained in absence of any The modern theories of the relations between kinetic ferrous salt, unless there is also present some acid, and internal energies of molecules and frequencies of such as tartaric acid, which forms a vei-y stable molecular collisions and reaction velocities are con complex with the ferric ion. Light exerts no appreci sidered in the discussion of the mechanism of catalysed able effect on the loss of activity of the water, except reactions. If an unalterable energy of activation be in so far as it influences the rate at which carbon postulated, it becomes impossible to understand the dioxide escapes. The present results thus confirm action of a “ physical ” catalyst, i.e., of one which those of Simon and Kotschau (this vol., 843). takes no part in the reaction; the effect of a chemical R . CUTHILL. catalyst, on the other hand, is readily explained by Activity of hydrogen. C. F. H olm boe (Z. komp. the theory. S. I. L e v y . fluss. Gase, 1927, 26, 17— 19).— Hydrogen prepared from steam and iron is less efficient in catalytic Acid and salt effects in catalysed reactions. hydrogenation than electrolytic hydrogen; possibly X. Hydrolysis of ethyl acetate with acetic acid the latter is “ activated.” Ch em ical A bstr a c ts. as catalyst. H. M. D a w s o n and W. L ow son Active nitrogen. III. Active nitrogen and (J.C.S., 1927, 2107— 2114).— If the effect of the the metals. E. J. B. W il l e y (J.C.S., 1927, 2188— reverse reaction is neglected in the calculation of the 2196).— The relative catalytic efficiencies of various true velocity coefficient for ester hydrolysis, correct metals for the destruction of active nitrogen have been values are obtamed only at low concentrations of the determined by measuring the rise in temperature ester. produced when the gas is passed over filaments of the The rate of hydrolysis of ethyl acetate in the metals. With platinum, iron, silver, zinc, tungsten, presence of acetic acid has been measured and and molybdenum a linear relation was found between the velocity at various stages compared with the the rise in temperature and the rate of flow, but in the theoretical values. The catalytic coefficient for the case of copper the rise in temperature was much hydrogen ion is calculated to be 1-14 x 10"4 at 25°. greater. The decay process is bimolecidar with respect C. W. G ib b y . to the active nitrogen, and the energy of active Significance of iso-catalytic data and the nitrogen is calculated to be 46,000 g.-cal. per g.-mol. so-called protion theory of chemical reactivity. It is considered that the mechanism of the process H. M. D aw son (J. Physical Chem., 1927, 3 1 , 1400— is the alternate formation and decomposition of the 1403).— A reply to Bergstein and Kilpatrick (this nitrides of the metals. C. W. Gi b b y . vol., 214) and a criticism of their conclusions on the catalytic minimum point. The interpretation of Catalytic activity of metallised silica gels. observations on the reaction between acetone and V. N. M orris and L. H. R e y e rso n (J. Physical iodine is also discussed (cf. Dawson, this vol., 320) Chem., 1927, 3 1, 1332— 1337).— The hydrogenation of and the factors determining minimum reaction acetylene using silica gels metallised with platinum, velocity are considered in relation to the catalytic palladium, and copper has been studied by the method catenary. Further, it is shown that Rice’s protion employed in the ease of ethylene (this vol., 839). theory is at variance with established facts. Ethylene and ethane are both produced, thepalladium- L . S. T h e o b a l d . silica gel becoming active at 50°, the platinum gel at Catalytic properties of mineral waters. II. 100°, and the copper gel at 200°. Palladium is the The benzidine reaction of the Wiesbaden hot better catalyst for the production of ethylene, spring. L . F r e s e n iu s and H. L e d e r e r (Z. anorg. regardless of the original mixtures used, whilst Chem., 1927, 166, 99— 109; cf. this vol., 320).— platinum favours the production of ethane. Further, Artificially prepared solutions containing no iron, but as the ratio of acetylene to hydrogen increases from otherwise similar in composition to the water of the 1 : 10 to 3:1, the production of ethylene passes Wiesbaden hot spring, do not give the benzidine through a maximum. It is probable that the com reaction unless ferrous hydrogen carbonate is added, bined adsorptions of gel and metal produce a more or unless manganese is present and the water is made satisfactory condition for the catalysis of ethylene alkaline, in which case part of the manganese passes formation than does the adsorption of either alone. into a higher state of oxidation. Since the natural The ready production of ethylene is noteworthy, water is acid in reaction, its activity must therefore especially in view of the work of Ross, Culbertson, depend on the presence of iron. It is found, further, and Parsons (A., 1921, i, 761). L. S. T h e o b a l d . that the gradual loss of the ability to give the benzidine Adsorption of hydrogen and ethylene on a reaction which occurs on keeping the natural water copper catalyst poisoned with carbon monoxide. runs parallel with an increase in the amount of ferric C. W. G r if f in (J. Amcr. Chem. Soc., 1927, 4 9, 2136— iron present, and a decrease to zero of that of the 2145).— The above adsorption was investigated at 0° ferrous iron, and that the rate at which the activity and 20° in the manner previously described (cf. A., is lost depends on the rate at which the dissolved 1923, ii, 842, 862). An increase of poison causes carbon dioxide escapes. The disappearance of the progressive decrease of adsorption at higher pressures, activity must consequently be attributed to the and an increase of adsorption at lower pressures, oxidation of ferrous hydrogen carbonate -with sub which, however, persists at higher pressures in the sequent precipitation of the product. If there is case of hydrogen than of ethylene. For either gas present an acid which is able to form some ferric ions the smallest amount of poison causes the greatest before settling out is complete, e.g., hydrochloric acid increase or decrease of adsorption. The results GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1039 possibly indicate that each poison molecule is adsorbed initial gases are in the ratio 0 2/NH3<0-8 is on a very active centre and thereafter takes up remarkable. H. W r e n . hydrogen or ethylene molecules to such an extent Decomposition of ammonia on iron catalysts. that the total adsorption at low pressures is greater than on the unpoisoned catalyst. The poison, how C. H. K unsm an (Sciencc, 1927, 65, 527— 528).—The ever, prevents dissolution of the hydrogen in the catalytic activity of iron catalysts (unpromoted iron catalyst, iron catalyst promoted with aluminium and copper, so that at higher pressures the adsorption potassium oxides, catalyst poisoned by tin) used in the appears to decrease when the catalyst is poisoned. synthesis of ammonia was investigated by the decom This explanation is not readily deduced in the case position of ammonia on specially prepared surfaces. of ethylene. The extra sorption at low pressures Values of E in Arrhenius’ expression Ae~E,RT for the does not leave the gases activated. rate of chemical change are 38,000— 42,000 g.-cal. per S. K . T w e e d y . Catalytic combustion of ammonia in presence g.-mol. for the various catalysts, although the ratio in catalytic activity was 18-1. It is concluded that of alkaline surfaces. L. A n d r u sso v (Z. anorg. the primary effect of promoters on the iron catalysts Chem., 1927,166, GO—62).— The fact that the presence is to increase the number of atoms on which decom of alkaline surfaces in the catalytic oxidation of position takes place; that the effect of heat-treatment ammonia causes a quantitative yield of nitrites and and poisoning is to decrease that number; and that nitrates, no nitrogen being produced, is readily explained by supposing that the nitroxyl formed as an poisoning, heat-treatment, or promoter action does not sufficiently alter the quality or nature of the atoms intermediate stage in the oxidation (cf. B., 1927, 217) on which the reaction takes place to cause an combines with the alkali, and is then oxidised to appreciable change in the heat of activation. nitrite and nitrate, instead of breaking down with A. A. E l d r id g e . liberation of nitrogen. R . Cu t h il l. Low-temperature oxidation at charcoal sur faces. IV. Active areas for different acids and Rapid catalytic processes in currents of gases relative rates of oxidation. W. M. W r ig h t and the oxidation of ammonia. V. L. A n d r u s (J.C.S., 1927, 2323—2330; cf. A., 1925, ii, 806; 1926, sov (Ber., 1927, 60, [B], 2005—2018; cf. B „ 1926, 582).— The rates of oxidation of formic, oxalic, 318).— The interaction of ammonia and oxygen when malonic, and aminoacetic acids on charcoal surfaces, passed through heated platinum capillary tubes of and the effect of poisoning by hexoic acid have been varying length at 1100°±100° has been investigated. determined. Identical amounts of poison are required Even with very rapid currents of gas only traces of ammonia are present at the end of a sufficiently long to inhibit the oxidation of all the acids, and the effective area is 4— 8% of the total area. All except capillary. If the capillary is sufficiently shortened, malonic acid are oxidised more rapidly on promoted the great bulk of the ammonia is burnt immediately charcoal prepared from sugar, carbamide, and ferric at the end of the capillary to nitrogen. A flame cone chloride. The depolarising capacities of the acids is then formed which, under certain conditions, can were measured, and follow the same order as the have a very unstable existence within the capillary. velocities of the reactions. C. W. Gi b b y . Under favourable conditions the cone is very stable and cannot be destroyed by great increase in the Chemical effect of electric discharge in ethane. velocity of the gas. If oxygen is deficient, it does not S. C. L in d and G. G l o ck le r (Amer. Electrochem. appear. Nitric oxide is comparatively stable in the Soc., Sept., 1927, advance copy, 9 pp.).— Ethane cone, but possible decomposition to the extent of was submitted to a silent discharge in a Siemens 10% must be assumed, so that the actual change at ozoniser through which it was circulated continuously the wall of the capillary is certainly 10—20% greater by means of an all-glass magnetic pump. Most of than is indicated by the yield of nitric oxide. The the ethane is decomposed in 3 hrs., yielding a gas con dependence of concentration distribution on the sisting mainly of hydrogen, methane, and propane velocity of the gas current is examined in detail. The with smaller amounts of higher homologues, but as quantity of undecomposed ammonia increases very much as 45— 55% of the ethane is converted into little with increasing velocity and considerable a very viscous, reddish-yellow oil, d 0-862, n20 1-490. quantities of ammonia escape combustion on the This oil has the composition C 85-48%, H 13-09%, explosion zone only with short capillaries. With and its apparent mol. wt. from f.-p. depression of excess of oxygen (more than 1-5— 1-7 mols. 0 2 to 1 mol. benzene is 467. It readily forms substitution pro NH3) the production of nitric oxide is little influenced ducts writh bromine. The production of 5 g. of oil by the initial concentration. At very great dilution requires about 10 kw.-hrs. The action of the silent (02/NH3>5 ) slight diminution of the yield is observed, discharge on ethane is compared with that caused by corresponding with a broadening of the reaction zone, a-particles from radon (cf. A., 1926, 1077). but, in such cases, the mean temperature of the H. J. T. E l l in g h a m . mixture is considerably lowered by the cooling effect Nature of the activating radiation in photo of the excess of gas. With mixtures poor in oxygen chemical action. W. T a y l o r and A. E lliot the production of free nitrogen is still considerable, (Trans. Faraday Soc., 1927, 23, 583— 592; cf. this and undecomposed ammonia is first observed with an vol.,. 216).—Actinic extinction curves have been initial gas ratio 02/NH3= l-3 . The thermal decom obtained by allowing light filtered through various position achieves increased importance and becomes concentrations of chlorine to activate a mixture of more comparable with the actual combustion. The hydrogen and chlorine. The results can be accounted co-existence of free hydrogen and oxygen if the for on the assumption that the efficiency is independent 1040 BRITISH CHEMICAL ABSTRACTS.----A. of the frequency throughout the range 3500— 5500, hydrogen peroxide were never produced. The zinc and that, for a given frequency, the activation is oxide to be effective must be in the solid state, and directly proportional to the light intensity. There is its previous exposure to sunlight enables the oxidation thus no evidence that there are two different types of aqueous ammonium salts to be accomplished in the of absorption, “ actinic ” and “ thermal,” nor that absence of light. Photochemical reduction of carbon activation is due to a few superposed bands, rather dioxide was not observed, and no complex nitrogen than to the whole general absorption band. This compounds could be produced from ammonia and latter may account for the failure to separate isotopes carbon compounds. The positive photosynthesis of chlorine by photochemical methods, since the claimed by Moore (“ Biochemistry,” 1921), by Dhar general absorption is continuous. The chlorine and Sanyal (A., 1925, ii, S84), and other workers is molecule absorbs the same actinic radiation when challenged. L. S. T h e o b a l d . in the gaseous state as when dissolved in carbon Photochemical oxidation of alcohols by the tetrachloride. M. S. B u r r . dichromate ion. E. J. B o w e n and C. W. B u n n Action of light on chlorine. G. B. K is t ia - (J.C.S., 1927, 2353— 2358).— The photochemical oxid k o w s k y (J. Amer. Chem. Soc., 1927, 49, 2194— 2200). ation of methyl, ethyl, w-propyl, and isopropyl alcohols — Intensive drying of chlorine has no appreciable by the dichromate ion has been investigated. The influence on the structure of its absorption spectrum quantum efficiency is independent of the light or on the total amount of light energy absorbed. Less intensity over a range of 1 : 80, of added acid above a than 5% of the latter is re-emitted as fluorescence. certain limit, of dichromate-ion concentration between It is difficult to reconcile these data with those theories 0-IjV and 0-01A7, and of temperature between 15° and requiring the presence of foreign molecules for the 50°. Tho reaction rate diminishes regularly with primary photochemical process in chlorine. It is decreasing acid concentration. In acid solution suggested that chlorine is dissociated into atoms on aldehyde is formed without the production of any absorption of light energy in the region of continuous precipitate. In neutral and alkaline solutions the absorption independently of its degree of purity; chromate ion is photochemically insensitive towards water is assumed to have a catalytic influence on the alcohols, and in neutral solution a precipitate of rate of recombination of the atoms and, therefore, uncertain composition is formed. The mechanism also on the rate of thermal dissociation of chlorine of the reaction is discussed. C. W. G ib b y . molecules. S. K. T w e e d y . Photosynthesis of naturally occurring com Function of water vapour in the photosyn pounds. I. Action of ultra-violet light on thesis of hydrogen chloride. B. L e w is (Nature, carbonic acid. E. C. C. B a l y , J. B. D a v ie s , M. R. 1927, 120, 473— 474).— The Ncrnst atomic chain J o hn son , and H. Sh a n a ssy (Proc. Roy. Soc., 1927, A, provides the most plausible mechanism for the photo 116, 197—211).—When carbonic acid in aqueous chemical union of hydrogen and chlorine. The chain solution is illuminated with ultra-violet light, a cannot be initiated in the absence of water vapour, photostationary state is established, involving as one but there is no evidence that water vapour functions of the components a complex aldehyde. In an in the chain itself. Two mechanisms for the inter attempt to effect the photosynthesis of carbohydrates action of moist hydrogen and chlorine in visible light, by the addition of a reducing agent to the carbonic and of dry hydrogen and chlorine in ultra-violet light acid solution, it was found that ferrous hydrogen are considered. The mechanism of the moist reaction carbonate in aqueous solution is converted by ultra is considered as involving a primary dissociation of violet light in absence of oxygen into ferric hydroxide, the chlorine molecules under the influence of water organic compounds with reducing properties being vapour, followed by an atom chain—that of Nernst formed simultaneously. This reaction appears to or of Thon. The dry reaction is regarded as involving take place chiefly on the surface of the quartz tubes activation of a chlorine molecule and its interaction containing the solution, and also on the iron rods with hydrogen molecules to form 2 mois, of hydrogen used. Complex organic compounds may be synthes chloride. If water has a rôle in the chain mcchanism, ised by the action of ultra-violet light on suspen no chains should be propagated when a dry mixture sions of various insoluble powders (aluminium powder, of hydrogen and chlorine is exposed to a-radiation. barium sulphate, freshly-precipitated aluminium A. A. E l d r id g e . hydroxide, and the basic carbonates of aluminium, Photosynthesis with ammonia. D. B u r k (J. magnesium, and zinc) hi water through which a Physical Chem., 1927, 31, 133&—1351).— Possible stream of carbon dioxide is maintained. Aluminium photochemical reactions between ammonia and hydroxide which has been in contact with water for various carbon compounds, including carbon dioxide, some hours loses its efficacy, due to the fact that it formic acid, formaldehyde, and dextrose, have been then has no affinity for carbonic acid. The organic investigated. Suidight condensed through 30 cm. compounds thus produced may be recovered by lenses in combination with coloured inorganic catalysts evaporation of the solution after removal of the was used, the exposures being made in very thin insoluble powder, and appear to be of the nature of glass vessels. Some 500 experiments were made, but complex carbohydrates. Photosynthesis of complex the results were generally negative, only one .type organic compounds containing nitrogen takes place of reaction being observed. This was the oxidation in presence of ammonium hydrogen carbonate or a of ammonia, in the presence of ferric chloride, to soluble nitrite. Rigid proof is given that the carbon nitrates, and in the presence of zinc or mercuric dioxide and other materials used were free from all oxide, to nitrites and nitrates. Hy d r oxy 1 a mine and organic impurity, and negative results wrere obtained GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1041 in control experiments in which powders incapable appears that in both, the rate of photosynthesis must of adsorbing carbon dioxide were employed. not exceed the rate of this slow reaction. It appears L. L. B ir c u m sh a w . that the yield of carbohydrates photosynthesised Photosynthesis of naturally occurring com in vitro per hr. per cm.2 of surface is not greatly at pounds. II. Photosynthesis of carbohydrates variance with that observed in nature. It is suggested from carbonic acid by means of visible light. that the constant ratio of chlorophyll-^ to chlorophyll- E. C. C. B a l y , W . E. Ste p h e n , and N. R. H ood B, observed by Willstatter and Stoll hi the living (Proc. Roy. Soc., 1927, A, 116, 212— 219).—Photo leaf, is maintained by the carothi, which becomes synthesis of organic compounds occurs when carbon oxidised to xanthophyll, and that, since the xantho- dioxide, rigidly free from organic impurities, adsorbed phyll: carotin ratio tends to increase during photo on the surface of a fine coloured powder (nickel or synthesis, the slow recovery process present hi the cobalt carbonate) suspended in water, is exposed leaf is that in which the xanthophyll is reduced again to visible light. The carbonates must be free from to carotin. L. L. B ir cu m sh a w . alkali, nitrate, chloride, and sulphate. One of the products of the photosynthesis is a carbohydrate Photochemical rearrangement of acetylchloro- which reduces Benedict’s solution, gives well-marked aminobenzene. C. W . P o rter and P. W il b u r (J. Molisch and Rubner reactions, and forms a solid Amer. Chem. Soc., 1927, 49, 2145— 2149).— The osazone. The reducing power of the photosynthesised ultra-violet absorption spectra of acetylchloroamino- compounds is materially increased by hydrolysis benzene and its isomeride, j)-chloroacetanilidc, are with hydrochloric acid. The total quantity of recorded. Conversion into the isomeride occurs in material photosynthesised by means of a coloured the solid state in the radiation of a mercury vapour surface in visible light, and also the percentage lamp, and also at 100°. The change is rapid above reducing power, is greater than with a white surface the m. p. Mechanisms involving intermediate pro hi ultra-violet light (cf. preceding abstract). In this ducts cannot apply to the reaction in the solid phase. case, the products are not so liable to undergo photo S. K. T w e e d y . chemical decomposition. When moist nickel and Optical sensitisation with dyes. K . B u r g h e r r cobalt carbonates are exposed to visible light in (Z. wiss. Phot., 1927,2 4 ,393— 408).—When a molecule presence of carbon dioxide, a surface film of nickel of sensitiser absorbs a quantum of light and enters and cobalt oxide, respectively, is formed, and it is the phototropic state, it acquires an electrical polaris found that the oxygen set free during the photo ation designated E{i and the positive and negative synthesis tends to poison the surface. Increased poles in the molecule act as cathode and anode in a yields of the carbohydrates are obtained with unit kind of molecular electrolysis. The idea is illustrated quantity of light when the intensity of illumination in the photolysis of a solution of ammonium oxalate is decreased, owing to the fact that the poisoned and mercuric chloride in the presence of eosin, surface slowly recovers under water. When the -> C 0 2 E {i surface has become completely poisoned the photo - +HgCl2— ^ HgCl+Cl'. synthetic process ceases, and then with intense Using silver nitrate and sucrose, glycine, or glycerol illumination the carbohydrates previously formed are as cathodic and anodic depolariscrs, respectively, photochemically decomposed. Complex nitrogen the sensitising action of the following dyes has been compounds may be photosyntliesised by exposing studied : rhodamine-2?, eosin, safranine-Cr, pheno- to visible light ammonium hydrogen carbonate safranine, fluorescein, methyl-violet, chromotrope-2i£. solution containing nickel or cobalt carbonate in The photolysis results in the separation of silver suspension. L. L. B ir cu m sh a w . (which can be determined by means of ammonium thiocyanate) and the concomitant formation of Photosynthesis of naturally occurring com oxidation products. Some silver was liberated in pounds. III. Photosynthesis in vivo and in the binary systems silver nitrate-dye, silver nitrate- vitro. E. C. C. B a l y and J. B. D av ie s (Proc. Roy. sucrose, but a larger amount was set free in the Soc., 1927, A, 116, 219— 226).— A marked similarity ternary systems composed of dye and depolarisers. is shown to exist between the laboratory photo The sensitised photolysis very soon reaches a synthesis of complex carbohydrates in a single oper stationary state, apparently owing to the formation ation from carbonic acid (cf. preceding abstracts) and of a new anodic depolariser which begins to compete the natural process of photosynthesis in the living with the existing depolariser. Experiments carried leaf. In neither case does ordinary formaldehyde out with air-containing and air-free solutions show tako part in the reaction. The photosynthesis in that the most likely agent for this effect is the finely- vitro has been achieved by the action of light on ^ Ag’ divided silver, i.e., E {i ' carbonic acid adsorbed on a surface, and there are '+ A g ‘ • Ag strong indications that a limiting surface exists in the The experiments with glycine and glycerol show that chloroplast and is necessary for the occurrence of these substances can be further oxidised, so that it is the normal photosynthesis. In each case a visibly not possible to ascribe the stationary state to their coloured surface and visible light are involved. The appearance as the first decomposition products of fatigue effect observed when the living leaf is exposed sucrose. The investigation lends support to the to too long and intense illumination may be compared inner polarisation mechanism for sensitisation. with the fatigue effect observed in the laboratory, R. A. M o r t o n . due to poisoning of the surface by oxygen. In both Light sensitivity of guaiacum resin and its processes there is a slow recovery reaction, and it possible application in photography. C. 1042 BRITISH CHEMICAL ABSTRACTS.----A. Schweckendiek (Diss., Giessen, 1927).— Guaiaconic A trihydrate, LiC103,3H20, separates from the corre acid, like guaiaretic acid, is sensitive to light, the sponding solution at —20°. R . Cu t h il l. sensitivity being increased by the addition of collodion, Phosphates. V. Hydration of sodium mono Zapon lacquer, or a solution of sulphur in carbon metaphosphate in alkaline solution at 75°. disulphide. The green image is fixed with a mixture S. J. K ie h l and H. P. Coats (J. Amer. Chem. Soc., of ammonium acetate and benzene. The insolubilising 1927, 49, 2180— 2193; cf. this vol., 312).—The action of light on guaiaretic acid is an oxidation hydration of sodium monometaphosphate (for which process. Ch em ical A b str a c ts. crystallographicdata are recorded) in sodium hydroxide Mechanism of formation of the latent photo solution was investigated at 75° in silver vessels. graphic image. F. C. T o y (Nature, 1927, 120, Both pyro- and ortho-phosphate in equimolecular 441).—Although the formation of the latent photo quantities are end-products of the hydration: graphic image does not appear to be due to a complete 3NaP03+2H20=N a2H2P?0 7+NaH2P04. The rate liberation of electrons from silver bromide crystals, of hydration increases with increase in the sodium it appears to be closely connected with the photo hydroxide concentration. Pyrophosphate is precipi conductivity effect. Experimental evidence is tated in presence of orthophosphate by adjusting adduced in support of the view that the formation of the hydrogen-ion concentration of the solution to the latent image involves the transfer of valency 5xl0~4 mol./litre (by addition of acetic acid) and electrons from bromide ions to silver ions, resulting adding zinc acetate solution of the same hydrogen- in the production of metallic silver and free bromine. ion concentration. Orthophosphate may be deter The observed decrease in photo-conductivity in the mined in the filtrate. S. K. T w e e d y . violet and its absence in the ultra-violet portion of Influence of the concentration of hydrogen ions the spectrum are due to the thickness of the film on the displacement of copper from its solutions employed. A. A. E l d r id g e . at high pressures and temperatures. V. I p a t ie v Chemical reactions in the gaseous phase in and V. I p a t ie v , jun. (Ber., 1927, 60, [5], 1982— electromagnetic fields of high frequency. R. 1986).— The action of hydrogen on. solutions of M oens and A. J u l ia r d (Bull. Acad. roy. Belg., copper formate and acetate between 90° and 1S0° 1927, [v], 13, 201— 2 0 5 ; cf. ibid., 72).—In an attempt at pressures between 0 and 150 atm. and at acidities to investigate the chemical behaviour of gases in between 0 and 12-oiV has been investigated. In electromagnetic fields of high frequency, the changes neutral solution at 100° hydrolysis occurs with conse produced in certain gases and gaseous mixtures by quent separation of copper oxide, which is only with the passage of an electrodeless discharge were followed difficulty reduced by hydrogen. In the presence of manometrically. The discharge usually appears at acid, this hydrolysis is repressed and the dissolved pressures of the order of 1 cm. and in the case of cupric salt is reduced to the corresponding cuprous simple gases, e.g., hydrogen, oxygen, nitrogen, is salt. If the hydrogen-ion concentration is insufficient, accompanied by an increase of pressure. On interrup the cuprous salt is hydrolysed and crystalline cuprous tion of the discharge the pressure falls instantly to a oxide separates from the solution. If, however, the value indicative of a contraction or an expansion hydrogen-ion concentration is sufficient to inhibit depending on the nature of the gas and the duration hydrolysis, an actual displacement of copper from and intensity of the discharge. A mixture of 2 vols. tho cuprous salt occurs. At a sufficiently high tem of hydrogen and 1 vol. of oxygen shows a contraction perature (130— 180°), the anions of formic and acetic corresponding with complete conversion into water acids become decomposed with production of hydrogen, vapour. Although a mixture of 3 vols. of hydrogen which, according to the degree of acidity of the and 1 vol. of nitrogen shows a slight expansion, in solution, causes separation of cuprous oxide or presence of sulphuric acid the pressure falls almost to metallic copper. H. W r e n . zero. A mixture of hydrogen and carbon di( ?)oxide Reduction of copper sulphate by sodium shows a slight expansion, but returns to the initial hypophosphite. S. R amachandran (Chem. News, pressure after the passage of the discharge even in 1927, 135, 214— 216).— Copper sulphate is reduced presence of concentrated sulphuric acid. Mixtures by sodium hypophosphite in aqueous solution only of nitrogen and oxygen undergo an appreciable when acidified to a definite extent. The temperature expansion, the pressure, however, returning to its required is the higher the greater is the proportion original value on interruption of the discharge. Acetylene and benzene yield solid deposits, the of hypophosphite present. C. W . G ib b y . pressure falling to almost zero. Ethyl ether and Composition and behaviour of precipitated ethyl and amyl alcohols are decomposed and the copper and iron sulphides. F. F e ig l [with E. volume is increased almost threefold. With carbon B a c k e r and L. Rosenberg] (Z. anal. Chem., 1927, disulphide and carbon tetrachloride the discharge 72, 32— 43).— Copper sulphide, freshly precipitated appears only at pressures of the order of 1 mm. by hydrogen sulphide, consists chiefly of cupric sulph J. S. Ca r t e r . ide with small quantities of cuprous sulphide and Hydrates of lithium chlorate. L. B erg (Z. sulphur, but on keeping, the cupric sulphide con ariorg. Chem., 1927, 166, 231— 236).— A monohydrate tinues to decompose into cuprous sulphide and of lithium chlorate, LiCl03,H20, may be prepared sulphur. The extent of the decomposition was by cooling a solution of composition corresponding determined by replacing the copper by mercury, with the formula to below —25° and adding a few boiling with sodium sidphite solution, and determin crystals of tho hydrate 3LiC103,H20 (A., 1926, 1014). ing with iodine the thiosulphate formed. The pre GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1043 cipitate obtained in an alkaline solution is a mixture ation experiments with the hydrates. X-Ray dia of the two sulphides, but, as before, the composition grams and dehydration experiments show that the of the fresh precipitate is dependent on the conditions removal of the last molecule of water from the of precipitation. The precipitate obtained by mixing hydrates of sodium monoborate is accompanied by a ferric salt and ammonium sulphide, of empirical a change in the structure of the crystal. With the formula Fe2S3, was treated with mercuric chloride diborate it is apparently the last three water mole solution. Ferrous chloride was formed and free cules which are of structural importance, but the sulphur was found in the precipitate. This indicates pentahydrate stable above 60° appears to occupy that the compound has the formula FeS,FeS2, as an exceptional position. The pentahydrate of potass the possible reactions with mercuric chloride are ium pentaborate reported by Hermans (A., 1925, Fe2S, + 3HgCl2=3HgS+2FeCl3, and FeS,FeS2 + i, 500) seems to have been the tetrahydrate. Attempts 2HgCl2=2HgS+S+2FeCl2. F. S. H a w k in s . to prepare an ammonium monoborate by treating the tetrahydrate of the diborate with ammonia, have Crystallisation of some hydroxides. R. F r ic k e been fruitless, although it is apparently possible in [w ith C. G o ttf rie d , W . Sk a l ik s, A. M u n c h m e y e r, this way to replace 1 mol. of the water of crystall and F . E n g elh a rd t] (Z. anorg. Chem., 1927, 166, isation with an ammonia molecule. The structure 244—256).—The conditions for the production of of the polyborates has been worked out with the various hydroxides in the crystalline state have been aid of Hermans’ theory of the constitution of boric investigated. Varieties of beryllium hydroxide which acid (A., 1925, ii, 697). R. Cu t h il l. give the same X-ray diagram but differ in crystalline form may be obtained by slow hydrolysis of sodium Reduction of refractory oxides by tungsten beryllate in aqueous solution, and by allowing a at high temperatures. H. v o n W a r t e n b e r g and 40% solution of sodium hydroxide saturated with H. M oehl (Z. physikal. Chem., 1927, 128, 439— amorphous beryllium hydroxide at the b. p. to cool 444).— Oxides such as those of aluminium, zirconium, slowly. Beryllium hydroxide aged with ammonia and thorium are reduced by metallic tungsten at (Haber and van Oordt, A., 1904, ii, 257) has a quite 2000° in an atmosphere of nitrogen, volatile tungsten different crystal structure. The solubility in sodium dioxide being produced. H. F. G il l b e . hydroxide solutions at 30° of the form obtained by Aluminium sulphate and its hydrates. Double hydrolysis of sodium beryllate in the cold is maximal sulphates and their components. II. F . K rau ss for solutions containing about 33% of sodium hydr and A. F r ick e (Z. anorg. Chem., 1927, 166, 170—■ oxide ; for lower concentrations the solid phase is 176).— Dehydration of the hydrate A12(S04)3,27H20 beryllium hydroxide, whereas for higher concen in the tensi-eudiometer points to the existence of trations it is sodium beryllate. One form of crystall hydrates with 27, 18, 16, 10, and 6 mols. of water. ine zinc hydroxide may be obtained by slow hydrolysis The anhydrous salt commences to lose sulphur of alkali zincate solutions at the ordinary temperature, trioxide at 605°. R. C u th ill. or by ageing the amorphous hydroxide under weak Displacement of metals or their oxides from acids such as phenol. A metastable variety differing solutions by hydrogen under pressure. Separ both in crystalline form and structure is produced by ation of crystalline hydroxides of aluminium diluting zincate solutions very considerably. Zinc and chromium from solutions of their salts at hydroxide precipitated with a slight excess of sodium high temperatures and under high pressures. hydroxide from a solution of a zinc salt represents V. I p a t ie v and B. M ourom tsev (Ber., 1927, 60, [2?], a third modification. Slow hydrolysis of alkali 1980— 1982).— For the separation of crystalline hydr aluminate solutions gives a form of aluminium oxides of aluminium and chromium the acidity of hydroxide which at first has the crystalline structure the solution is of primary importance. A solution of hydrargillite, but after keeping for some years of the requisite nitrate, acidified with nitric acid, is gives an X-ray diagram which belongs neither to placed in a golden tube (or silica tube if the tem hydrargillite nor to bauxite. Specimens of magnesium perature does not exceed 330°) and brought under hydroxide obtained by precipitating magnesium pressure of hydrogen or air in the high-pressure sulphate with sodium hydroxide in the cold, or by apparatus. The temperature is varied between 320° precipitating the chloride with ammonia in the cold, and 360°, pressure between 200 and 370 atm., and or by precipitating a mixed solution of magnesium duration between 12 and 24 hrs., although the change and ammonium chlorides with ammonia at 60° and is complete in 12 hrs. At lower pressures amorphous ageing the precipitate in contact with the supernatant products separate. Aluminium nitrate or acetate in liquor at 30° all have the same crystalline structure, the presence of nitric or acetic acid and hydrogen or and there seems to be no evidence for the existence air gives the monohydrated oxide with all the properties of two allotropic forms as suggested by Gjaldbaek of the mineral diaspore. Neutral aluminium nitrate (A., 1925, ii, 652). R. Cu t h il l. in presence of air gives a scarcely crystalline pre Boric acids and alkali borates. III. Solid cipitate. Chromium nitrate in nitric acid solution alkali mono- and poly-borates. H. M e n ze l [with under the influence of hydrogen gives monohydrated J. M eckwttz] (Z. anorg. Chem., 1927, 166, 63—98; chromium oxide closely resembling chrome ochre. cf. this vol., 937).— The literature relating to those I f air is used in place of hydrogen, smaller crystals borates of the alkali metals which can be crystallised are obtained and the separation is not quantitative, from aqueous solution is critically reviewed, and a portion of the oxide being converted into chromic supplemented in some cases with solubility deter acid. Small amounts of dark red crystals are also minations at 18° and 25° and with isothermal dehydr occasionally obtained. H. W r e n . 1044 BRITISH CHEMICAL ABSTRACTS.----A. Azidodithiocarbonic acid. IV. Ammonium on magnesium ethyl or phenyl bromide (this vol., and tétraméthylammonium azidodithiocarbon- 865) is hydrolysed with sulphuric acid at 0°, and ates ; tétraméthylammonium thiocyanate. L. F. the ethereal layer is separated, neutralised, and dried, Audrieth, G. B. L. Smith, and A. W. Browne after which the ether is evaporated. When magnes [with C. W. Mason] (J. Amer. Chem. Soc., 1927, ium ethyl bromide is used, crystals of chromium 49, 2129—2133).—Ammonium azidodithiocarbonate, carbonyl, Cr(CO)6, separate during the evaporation; NH4SCSN3, is obtained by neutralising azidodithio otherwise, the residue has to be sublimed under carbonic acid with aqueous ammonia or, preferably, reduced pressure. By grinding the product under in ethereal solution, with gaseous ammonia. It is benzene and resubliming at 160°, the pure carbonyl also formed by the prolonged action of carbon disulph is obtained as colourless, orthorhombic crystals, ide on aqueous ammonium azide solution (cf. Browne dis 1-77, slightly soluble in benzene and ether, but and Hoel, A., 1922, ii, 848). It forms white, non- more soluble (2%) in chloroform and carbon tetra deliquescent, ortliorliombic plates, soluble in water, chloride, the solutions being stable only in the dark. alcohol, and acetone, but insoluble in benzene; m. p. The crystals decompose rapidly at 210° into chromic 120° (decomp.) : NH4SCSN3=N H 4SCN+S+N2. The oxide; in a sealed tube they melt at 149— 150° and salt becomes orange when heated at 90° or on illumin irreversibly deposit a chromium mirror at 230°. The ation, the change in the latter case being partly carbonyl is unattacked by dilute acids, bromine, reversible. Tétraméthylammonium azidodithiocarbon and iodine; fuming nitric acid converts it into ate is best prepared by digesting an aqueous solution chromic nitrate and free carbon. S. K . T w e e d y . of tétraméthylammonium azide with a slight excess Co-ordination compounds of quinquevalent of carbon disulphide (NMe4N3 + CS2=N M e4SCSN3). molybdenum. R. G. J am es and W . W a r d l a w Its properties are similar to those of the ammonium (J.C.S., 1927, 2145—2156).— Physical and chemical compound; m. p. 95— 98° (decomp.). Tétraméthyl properties of salts of the type R 2[MoOC15] have been ammonium thiocyanate is conveniently prepared by investigated, and a scheme of their hydrolysis and boiling under reflux an alcoholic solution of tétra ionisation is outlined. The preparation of diquinolin- méthylammonium azide with carbon disulphide. It ium molybdenyl pentadiloride, (C9H8N)2Mo0C16,H20, does not undergo molecular rearrangement into monotrimetliylammonium molybdenyl tetrachloride, tetramethylthiocarbamide. Crystallographic data NHMe3MoOCl4,H20, and dimolybdenum tetraoxy- are recorded for each of the above compounds. hydroxychloride, Mo„04(0H)C1,35BU0 is described. S. K. T w e e d y . C. W . G ib b y . Formation of crystalline silicates in an aqueous Oxygen compound of fluorine. P. L ebeat; medium under pressures and at high temper and A. D am ie n s (Compt. rend., 1927, 185, 652— atures. V. I p a t ie v and B. M ou rom tsev (Compt. 654).— In the presence of water the method for the rend., 1927, 185, 647— 649; cf. A., 1926, 1219).— preparation of fluorine by electrolysis of molten acid Silicic acid or silicate gels obtained by a double potassium fluorides below 100° results also in the decomposition reaction may be converted into production of a gaseous oxygen compound of fluorine. crystalline forms by heating at a constant tem The compound is less active chemically than fluorine, perature for 2— 3 days in a silver tube containing and studies of its mixtures with oxygen point to the hydrogen or carbon dioxide under pressure. Any formula F20. Such mixtures have the odour of oxides formed are removed by means of hydrochloric fluorine, but are stable in the presence of water and acid. The product obtained depends on the con of glass even at high temperatures. The gas, which ditions, and on the presence or absence of small was not isolated in the pure state, liberates iodine amounts of impurities. Thus, crystalline Si02 and from potassium iodide, is soluble in alkali, but only 5Si02,2H20 are produced using hydrogen and carbon sparingly soluble in water. J. G r a n t. dioxide, respectively, and silicates of magnesium, calcium, manganese, aluminium, zinc, and iron of Chloro-acids. R. Sc h w a r z and G. M e y e r (Z. varying compositions have also been obtained. The anorg. Chem., 1927, 166, 190— 212).—Attempts have crystalline compound 6Si02,3H20 was obtained from been made to detect the combination of hydrogen a manganese silicate gel free from any soluble chloride with various chlorides by determining pressure manganese salt. J. G r a n t . isotherms with the aid of the tensi-eudiometer. In no instance does any combination occur in absence Action of stannous chloride on silver mirror of water, and in the case of the tetrachlorides of formation. 0. M a c c h ia (Chem. News, 1927, 135, silicon and titanium no chloro-acid is formed owing 197— 200).— The formation of a silver mirror and its to hydrolysis. With ferric chloride, it is probable adherence to a glass plate are greatly facilitated by that the compounds Fe2Cl6,3HCl,9H20, previous immersion (10 sec.) of the plate in a dilute Fe2Cl6,4HCl,llH20, Fe2Cl6,5HCl,12H20 and solution (preferably 1 in 2000) of stannous chloride. FeCl3,3HCl,7H20 are capable of existence. Hexa- The effect is attributed to the deposition of a very aquochromic chloride forms no compounds, but adherent film of gelatinous stannous hydroxide, dichlorotetra-aquochromic chloride dihydrate appar formed by the hydrolysis of the stannous chloride, ently gives rise to the compounds CrCl3,HC1.6-5H20, and was observed for plates of glass, cellulose, wood, CrCl3,2HCl,8-5H20, and CrCl3,3HCl,10-5H20. Alu and galatite. G. A. E l l io t t . minium chloride forms no compounds. Chromium carbonyl. A. J ob and A. Cassa l R . Cu t h il l. (Bull. Soc. chim., 1927, [iv], 41, 1041— 1046).— The Manganese molybdates. F. Z a m b o n in i and V. solution obtained by the action of carbon monoxide Ca g l io t i (Rend. Accad. Sci. fis. mat. Napoli, 1927, GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1045 [iii], 33, 181— 203).— Irrespective of variations in the Elementary method of qualitative analysis method of preparation, a single compound having the without the use of hydrogen sulphide, thioacetic formula 4(NH4)20,Mn203,13Mo03,9H20, is obtained. acid, or sulphides. O. M a c c h ia (Notiz. chim.-ind., This is identical with that described by Struve (J. pr. 1927, 2, 191— 196).—A detailed scheme is presented. Chem., 1854, 6 1, 449), Friedheim and Samelson Ch em ical A bstr a c ts. (A., 1900, ii, 547), and Friedheim and Alleman (Mitt, Continuous electro-conductivity titration. E. naturf. Ges. Bern, 1904, 23). As appears from the B u t te r w o r th (Mem. Manchester Phil. Soc., 1926— ratio Mn203 : M o03 the manganese is to be considered 1927,7'1, 53—62).— A new continuous-reading method present in tne bi- and quadri-valent states, the formula of electro-conductivity titration is described, giving being [Mn""(Mo20 7)fi](NH4)8,Mn"Mo04,9H20. This an accuracy of 0-2— 0-3%. The sensitivity is easily confirms Struve’s result that manganese in the form controlled within wide limits. C. W. G ib b y . of Mn203 may be considered to be MnO and Mn02, [Absolute] potentiometric titration. B. and also Pochard’s suggestion that the ratio Cavan ag h (J.C.S., 1927, 2207— 2216).—A new abso Mn02 : Mo03 is 1 : 12 in analogy to the silicomolybd- lute method of potentiometric titration is described ates. M. Ca r lt o n . for strong acids and halides, in which no potentio Sublimation of iron in a vacuum. E . B otolf- meter, standard cell, or normal electrode is required. sen (Compt. rend., 1927, 185, 649— 650).— Iron may It can be used for very dilute solutions and with very be sublimed in a high vacuum at temperatures below small quantities of liquids, and a high degree of its m. p. The effect is independent of the origin of accuracy is obtained. C. W. Gib b y . the iron and of the presence of certain substances likely to act as catalysts, and at 1300° its rate is of Effect of sodium hydrogen carbonate on the the order of 0-07% per hr. The sublimate takes the titration of iodine with thiosulphate. O. E. form of a thick deposit of metallic crystals, and is Schupp, jun. (Science, 1927, 65, 284).— Low values, due to the formation of hypoiodite and iodide, and almost pure. J. G r a n t . oxidation of the thiosulphate to sulphate, are obtahied Ferric thiocyanate. K. C. B a il e y (J.C.S., 1927, if the iodine solution is initially neutral and sodium 2065—2069).—The red compound produced by dis hydrogen carbonate is added. The results for an solving ferric hydroxide in thiocyanic acid is found, initially acid solution containing less than iV-sodium by a repetition of the work of Tarugi (A., 1905, i, hydrogen carbonate are as accurate as those for a 176; 1926, 259), to be ferric thiocyanate. No neutral solution of iodine. A. A. E ld r id g e . evidence is obtained in favour of his formula Determination of sulphuric acid in water FeHC3N3S303. C. W. G ib b y . analysis by means of benzidine. L. W. H a a s e . Preparation of low-conductivity water. G. D . —See B., 1927, 798. B en gough, J. M. St u a r t , and A. R. L ee (J.C.S., 1927, 2156—2161).— Improvements in Bourdillon’s Analysis of polythionate solutions. A. ICu r t e - still (J.C.S., 1913, 103, 791) are described. About n a c k e r and E . G o ld b a c h (Z. anorg. Chem., 1927, 4 litres of water per day can be produced, with a 1 6 6 , 177— 189).— Billeter and Wavre’s sulphide conductivity of 0-065 gemmho. C. W. G ib b y . method of determining trithionate (A., 191S, ii, 330), depending on the reaction S30 6"-j-S"=2S203", has Germanium. XX. Preparation of fused been extended to tetra- and penta-thionates, both germanium directly from germanium dioxide. together and separately, and to mixtures of these (Miss) K. M. T r e ssl e r and L. M. D en n is (J. Physical with trithionate, the reactions being S40 G"+ S " = Chem., 1927,31,1429— 1432).—Fused, metallic germ 2S203"+ S , and S50 6" - f S"= 2 S 203"+ 2 S . Sulphite anium has been prepared by reduction of the dioxide present along -with trithionate only does not interfere with carbon under a flux of sodium chloride in a with the determination if it is first caused to combine graphite crucible heated in an induction furnace. with formaldehyde, but if tetra- or penta-thionate is A 90% yield of the metal, containing approximately also present the sulphite combines with tho sulphur 1% of dioxide and other impurities in amount not produced in the above reactions to form thiosulphate. greater than 0-01 %, was obtained. Of the germanium This difficulty may be overcome by first titrating the lost, 70% can be recovered. Slight modifications in sulphite wrth iodine, or as follows. The solution for the method shoidd make this loss negligible. Prepar analysis is heated for 10 min. at a temperature near ation of germanium by electrolysis of the dioxide the b. p. with 20 c.c. of 0-42V-sodium sulphide and dissolved in molten cryolite, or molten potassium 20 c.c. of 0-4Ar-sodium sulphite, and the excess of fluogermanate, and by reduction of the dioxide with sulphide then precipitated with zinc acetate or car aluminium resulted in heavy losses of germanium as bonate. An aliquot portion of the filtrate is mixed germanous oxide. L. S. T h e o b a l d . with 5 c.c. of 40% formaldehyde, acidified with 10 c.c. Precautions [against explosion] in preparing of 20% acetic acid, and titrated with iodine. In this lead bromate. V ic to r (Z. angew. Chem., 1927, 40, case, the tetra- and penta-thionate radicals react 841).—Fatal explosions have occurred when lead according to the equations S40G"-f S"+S03"= bromate, prepared by interaction of lead acetate and 3S203" and S50 6"+ S " + 2 S 0 3"= 4 S 203". By means potassium bromate (cf. Gmelin-Kraut’s “ Hand- of "this method and those previously published (A., buch,” IV, 376) has been pulverised. The sensitivity 1924, ii, 497, 564; 1925, ii, 239, 434, 1189; this vol., to shock is due to the presence of diacetodiplumbous 534, 638) a mixture of tri-, tetra-, and penta-thionates, bromate (Giinzel and Marcus, A., 1925, ii, 1086). thiosulphate, hydrogen sulphite, and hydrogen sulph W. A. Sil v e s t e r . ide can be analysed. R. Cu t h il l . 3 z 1046 BRITISH CHEMICAL ABSTRACTS.— A. Volumetric determination of azoimide by interfere with tho reaction, and small quantities of oxidation with eerie sulphate in acid solution. sodium can be determined. F. S. H a w k in s . J. M a r t in (J. Amer. Chem. Soc., 1927, 49, 2133— Microchemical reactions of beryllium. V. 2136).—Tho nitrometer method of determining azo Ca g lio ti (Rend. Accad. Sci. fis. mat. Napoli, 1927, imide (Sommer and Pincas, A., 1916, ii, 97) : 2Ce'"'-f- [iii], 33,177— 180).— The usual microchemical methods 2HN?=3N2-)-2H'-l-2Co'", may bo applied iodo- of determining beryllium by means of the double metrically; tho reaction is carried out with the oxalate of potassium and beryllium and of the chloro- exclusion of air in a closed vessel, excess of potassium platinate and sulphate are not entirely satisfactory. iodide is added, and the liberated iodino titrated with The most satisfactory residts are obtained by Streng’s standard thiosulphate. Hydrazine must be absent reaction involving the formation of uranyl sodium (azoimide may bo separated from it by distillation), beryllium acetate, (U 02)3BeNa(0Ac)9.9H20, as pale but the ammonium ion may be present. The acid yellow, rhombohedral crystals. The presence of concentration must be kept lowr. S. K. T w e e d y . aluminium docs not affect the reaction, but -iron Colorimetric determination of carbon mon must be carefully removed. oxide with ammoniacal silver solution. H. For microchemical research the most satisfactory K ast and A. Sc h m id t .— See B., 1927, 748. method of determining beryllium is by formation of Conversion of alkali chlorides into carbonates beryllium acetylacetonate (cf. Jaeger, A., 1914, i, by means of oxalic acid. L. N. M u r a v l e v (Z. 797) as clear, colourless, monoclinic prisms which on anal. Chem., 1927, 72, 15— 19).— The reactions in examination under the microscope show very char volved are not quantitative. The conversion of acteristic interference figures. M. Ca r l t o n . chloride into oxalate is not complete, and the form Application of Kolthoff's reaction for mag ation of carbonate from oxalate is finished only at tem nesium in plant microchemistry. H . E ilers peratures high enough to cause loss by volatilisation. (Chem. Weekblad, 1927, 24, 448— 150; cf. Kolthoff, The smallest error was 0-48%. F. S. H a w k in s . this vol., 639).—The reaction with titan-yellow is not Volumetric determination of potassium. G. specific for magnesium in plant tissue, but may be Jandbr and 0. Peundt (Z. anal. Chem., 1927, 71, employed if the test is carried out after removal of 417— 434).— Potassium may be determined by con- oils, fats, and resins on tissue before and after treat ductometric titration with sodium perchlorate if the ment with dilute acid, and the colorations obtained solution used is at least 0-3N with respect to potassium in tho two cases are compared. S. I. L e v y . and the perchlorate solution is 5—6N. To reduce Diphenylamine [acetate] as a qualitative the solubility of the precipitated potassium perchlorate reagent for zinc. W. H. Con e and L . C. Ca d y to a minimum the titration is carried out in a vessel (J. Amer. Chem. Soc., 1927, 49, 221^-2215).— The cooled with ice; under these conditions the super group filtrate containing chromium and zinc is natant liquid above the precipitate at the end of the acidified with acetic acid and chromium is tested for titration is 0-01iY with respect to potassium. The on one portion. To the remainder 5 drops of a solu presence of magnesium sulphate, sodium chloride, and tion of 1 g. of diphenylamine (or diphenylbenzidine) calcium chloride is without effect on the results, so in 100 c.c. of glacial acetic acid and 5 c.c. of 0-5% that tho process is applicable to the control of liquors aqueous potassium ferricyanide solution are added. obtained in the potash industry. The ond-point is The presence of zinc is indicated by a turbidity, the sharp and the results are good when the solution is darkness of which increases with the amount of zinc standardised against a potassium solution containing present. Unless its concentration cxcecds 10 mg./c.c., the same quantity of the metal as the trial. potassium dichromate does not influence the test. A. R. P o w e l l . Contrary to the statement of Knop (A., 1924, ii, 351), Determination of potassium and sodium in diphenylamine sulphate immediately produces a blue the presence of each other. A. M e y e r (Chem.- coloration with potassium dichromate at concen Ztg., 1927, 51, 778).— The metals arc first weighed as trations greater than 0-05 mg./c.c. S. K. T w e e d y . ohloride (or sulphate), the mixed salts dissolved, and Rapid separation of lead and silver by either tho chlorine is determined titrimetrically, or the sulphuric acid gravimetrically. In the latter case, a potentiometric method. E. M u l l e r and H. to prevent the presence of traces of hydrogen sulphate, H en tsch el (Z. anal. Chem., 1927, 72, 1— 5).—The the salts should first bo evaporated with ammonium metals are determined by titrating the solution first with sodium chloride, and observing the potentials carbonate. The proportions determined algebraically in the usual way are subject to a smaller error than with a silver electrode, and then with potassium those obtained by weighing the cldorides and sulphates. ferrocyanide, using a platinum electrode. The poten tials measured against a normal calomel electrode at B. P. R id g e. which the titrations are finished are 0-23 volt and Determination of sodium. D. I. P e r ie t e a n u (Bui. Soc. chim. Romania, 1927, 9, 17— 18).— 0-36 volt, respectively; and the titration is carried Sodium is determined as the salt out by applying these voltages to the cell, and 3U0(C2H302)2,Mg(C2H30 2)2,Na(C2H30 2) by precipit titrating until no current flows. Accurate titration ation with an acetic acid solution of magnesium and of the silver with potassium iodide is prevented by uranium acetates. After i hr., the precipitate is adsorption phenomena and the separation of lead collected in a Gooch crucible, washed three times with iodide. F. S. Ha w k in s . the reacting liquid, three times with 95% alcohol, Determination of lead in bismuth by spectrum and dried for 30 min. at 105°. Only phosphates analysis. III. E. Sc h w e it ze r (Z. anorg. Chem., GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 1047 1927, 1 6 5 , 3G4— 370).—The spectrum of bismuth fluoride, excess being avoided, and if no considerable containing lead is coupled with that of tin containing amounts of alkali chlorides are present. lead by making the times of exposure of the photo R. Cu t h il l . graphic plate such that a selected line in the bismuth Analysis of iron and steel. Determination of spectrum appears of the same intensity as a selected silicon, phosphorus, sulphur, and manganese. lino in the tin spectrum. This pair of lines is chosen M. M a r q u e y r o l and L. T o q u e t.— See B ., 1927, 751. by photographing the spectra of tin and bismuth Rapid determination of nickel. G. Spa c u and each containing the same relative number of atoms J. D ick (Z. anal. Chem., 1927, 7 1, 442—446).—The of lead under such conditions that the lead lines in nickel solution is diluted to 100 c.c., treated with one spectrum have the same intensity as those in the 0-5 g. of ammonium thiocyanate for every 0-1 g. of other spectrum. If the two spectra are related in this nickel present, heated to boiling, and treated drop by way, corresponding lead lines are always equally drop with 1—2 c.c. of pyridine. After cooling com intense whenever the lead concentrations in the main pletely, the precipitate of glistening, sky-blue prisms metal are the same. The lead in a sample of bismuth is collected on a filtering crucible and washed success may therefore be determined by coupling its spectrum ively with water containing 4 g. of ammonium with that of pure tin, and searching for a lead line thiocyanate and 6 c.c. of pyridine per litre, 35% and a tin line of equal intensity, as previously alcohol containing 15 c.c. of pyridine and 1 g. of described (this vol., 845). R. Cu t h il l. ammonium thiocyanate per litre, absolute alcohol Use of titanous chloride in the volumetric de containing 5 c.c. of pyridine per 100 c.c., and ether, termination of copper and iron. W. G. E m mett to 20 c.c. of which are added 2 drops of pyridine. (J.C.S., 1927, 2059—2062).— In determining cupric or The crucible and contents are dried in a vacuum ferric salts by titration with titanous chloride in desiccator for 10 min. and weighed. The compound, presence of potassium thiocyanate as an indicator, error Ni(SCN)2,4C5H5N, contains 11-95% Ni. may be introduced by the decomposition of ferric and A. R. P o w e ll . cupric thiocyanates. By carrying out the titration Analytical chemistry of tantalum, niobium, in cold acid solution immediately after adding the and their mineral associates. VII. Precipit thiocyanate the error may bo reduced below 0-2%. ation of tungstic acid by tannin. VIII. Separ The preparation of a standard copper solution by ation of tungsten from tantalum and niobium. dissolving electrolytic copper in a solution of sodium W. R. Sch oeller and C. J ah n (Analyst, 1927, 5 2, peroxide in hydrochloric acid is recommended. 504— 514).—VII. To obtain total precipitation of C. W. G ib b y . tungstic acid in one operation 100—150 c.c. of the Sensitive reaction for aluminium and colori alkaline tungstate solution containing alkali chloride metric determination of this element. I. M. are neutralised with dilute hydrochloric acid to the K olthoff (Chem. Weekblad, 1927, 24, 447— 448).— hydrogen carbonate stage, treated with a freshly- 1:2:5: S-Tetrahydroxyanthraquinone gives an in made solution of 0-5 g. of tannin, part of which tense violet coloration with aluminium compounds in flocculates as a white precipitate if the chloride-ion faintly acid solution. The reagent is very suitable concentration is high, and dilute acid is added until for the determination of small quantities of aluminium, the solution is acid to litmus, when the brown especially within the limits 0-02— 0-5 mg. per litre. turbidity due to the tungsten complex appears. On Of the metals which interfere, copper is removed by boiling, the precipitate becomes dark brown and thiosulphate, and tin, antimony, and bismuth are flocculent, and a 5% solution of cinchonine hydro rendered inactive by addition of sodium tartrate; chloride (5 c.c. diluted with water) is added, boiling iron must be precipitated (cf. A., 1924, ii, 785). continued for 5 min., and after keeping in the cold S. I. L e v y . for 6 lirs. the clear liquid is decanted, the precipitate Determination of manganese and magnesium mixed with pulped filter fibre, washed on the filter in aluminium alloys. F. M u g r a u e r .— See B,, with 5% ammonium chloride solution containing a 1927, 783. little tannin, dried, ignited, and weighed as W 0 3. VIII. Tungsten may be separated from tantalum Potentiometric titration of iron and aluminium and niobium, since sodium tungstate is freely soluble, with bases. P. D rossbach (Z. anorg. Chem., 1927, whilst the tantalate and niobate are nearly insoluble 166, 225—230).— If pure solutions of ferric or alumin in solutions of high sodium-ion concentration. Small ium chloride lying within a certain concentration quantities of tungsten may be separated from large range are titrated with sodium hydroxide, the poten quantities of earth acids by the method previously tial of a hydrogen electrode dipping into the solution described (this vol., 32). To separate small quantities changes suddenly at the equivalence point. Tho ]in of earth acids from large quantities of tungstic acid at this point is 6-8—7-0, and the titration of ferric the solution should be free from potassium ions; chloride may actually be effected with bromothymol- fusion is effected with sodium hydroxide in a nickel blue as indicator. If the cliloride solutions contain crucible, and the fused mass extracted with half- free acid, the second sudden change in potential saturated sodium chloride solution. Sodium tantal corresponds with the complete reaction of the hydr ate and niobate remain undissolved and tungstic oxide with both chloride and free acid. The amount oxide is determined by difference. Satisfactory results of free acid in aluminium chloride solutions may be were obtained by both methods. D . G. H e w e r . determined by direct titration, using bromothymol- blue as indicator, if the aluminium is first converted Potentiometric method for separation of tin into the cryolite complex by addition of potassium and antimony. H. B r in t z in g e r and F. R odis 1048 BRITISH CHEMICAL ABSTRACTS.— A. (Z. anorg. Chem., 1927, 166, 53—59).—If a mixed dissolved in ferric chloride solution in an atmo solution of stannic and antimonio chlorides containing sphere of carbon dioxide, and titrated with perman in 100 c.c. 30 g. of crystallised calcium chloride and ganate. Bismuth can also be determined by reducing 20 c.c. of concentrated hydrochloric acid and free with alkaline formaldehyde solution and titrating from dissolved oxygen is titrated at 90— 100° with the excess with iodine. F. S. H a w k in s . chromous chloride solution, the first sudden change in Thermostat heater. I. A. Cowperthwaite (J. the potential of a platinum electrode immersed in the Amer. Chem. Soc., 1927, 49, 2255).—The usual lamp solution indicates the complete reduction of the is replaced by a resistance of graphite flakes packed in antimony salt to the tervalent state, and the second, a U-tube of pyrex glass. S. K. T w e e d y . which is relatively small, that of the tin salt to the stannous state. The addition of chromous chloride Micropyrometer. H. v o n W a r te n b e r g and H. should he spread over 30— 40 min., and, especially M oeh l (Z. physikal. Chem., 1927, 128 , 445— 448).— near the end-points, sufficient time should be allowed A micropyrometer is described which may be employed for the potential to become steady before a reading at any distance above 8 cm. from the heated body and is made. R. Cu t h il l. gives a sufficiently large image of such an object as the Separation of vanadium from tungsten. S. G. filament of an electric lamp. Its applications to the measurement of high m. p. and to the determination Cl a r k e .— See B., 1927, 752. of the relationship between the current through an Separation of vanadium from tungsten. S. G. electric lamp filament and the temperature are Cla rk e (Analyst, 1927, 52, 527).—Small amounts of described. H. F. G il l b e . vanadium may be separated from an impure tungstic oxide in steel analysis in the same way as larger Apparatus for the determination of melting amounts (B., 1927,752), except that 50 g. of ammonium tem perature. G. L y n n (J. Physical Chem., 1927, chloride should be dissolved in the solution before 31, 1381— 1382).— The apparatus described by adding the cupferron to assist separation of the Washburn (A., 1924, ii, 344) has been modified by precipitate, which is collected, washed, ignited, and the addition of an electric heating coil and of the residue fused with fusion mixture. The vanadium removable sampling tubes. The present form may is then determined colorimetrically in the aqueous be used from temperatures below 0° to 400°; 1 c.c. extract by the hydrogen peroxide method of Meyer of recoverable material is required, and the heating and Pawletta (A., 1926, 1020). H . G. H e w e r . and cooling curves obtained give for the m. p. a value which is more trustworthy than that obtained by the Sensitive test for bismuth. H . K u b in a and capillary tube method, which may be up to 3° too J. P lich ta (Z. anal. Chem., 1927, 72, 11— 14).—If high (Andrews, Lynn, and Johnston, A., 1926, 668). dimcthylglyoxime and sufficient ammonia are added L. S. T h e o b a l d . to a hot very dilute bismuth nitrate or chloride Simple automatic pipette. F. F r ie d r ic h s solution, an intense yellow colour is developed, and (Chem.-Ztg., 1927, 51, 688).— A rubber bulb supplies in more concentrated solutions a precipitate is formed. the suction and an overflow regulates the quantity The colour is developed with a bismuth concentration as in other automatic pipettes, but the expansion of of 1 in 7 X101. No colour is obtained with bismuth the bulb is regulated by a rod and pressure disc, sulphate solution until a chloride is added, and permitting accurate regulation. A side tube is arsenic, antimony, zinc, cobalt, manganese, and provided for the eventual removal of the overflowed ferric salts interfere with the reaction. Bismuth liquid. C. I r w in . cannot be determined by this method owing to the occlusion of salts. P . S. H a w k in s . Laboratory hydrogen and oxygen generator. C. G. F in k and C. L. M a n te ll (Amer. Electro- Volumetric determination of bismuth. W. chem. Soc., Sept., 1927, advance copy, 5 pp.).—An St r e c k e r and A. H errm an n (Z. anal. Chem., 1927, apparatus is described for furnishing a continuous 7 2 , 5—11).—The bismuth solution is added drop supply of hydrogen at constant pressure for long by drop, when boiling, to a standard solution of periods, the hydrogen being generated by electrolysis disodium hydrogen phosphate; the liquid is filtered of 30% sodium hydroxide solution using nickel when cold, neutralised with sodium hydroxide, and electrodes. H. J. T. E llin g h a m . mixed with an excess of sodium acetate and standard silver nitrate solution. After dilution the excess Rubber stopcock lubricants for high-vacuum of silver in an aliquot portion is titrated with ammon and other uses. M. S h e p h e r d and P. G. L e d ig ium thiocyanate. In a second method of determin (Ind. Eng. Chem., 1927,19, 1059— 1061).— Lubricants ation, the bismuth solution is neutralised with compounded of rubber, “ vaseline,” and paraffin wax ammonia until a slight turbidity appears, dilute were studied. Pale crepe and smoked sheet rubber hydrochloric acid is added, the boiling solution gave the best results. Good results were obtained cleared with hydrochloric acid or ammonium chloride, with paraffin wax of m. p. 30— 40°. For high-vacuiim and the oxychloride is precipitated with hot water. work a mixture of pale crepe rubber (31 p a r t s ) , white The oxychloride is dissolved hi nitric acid, and the “ vaseline ” (24 parts), and paraffin wax (5 parts) is chloride determined by Volhard’s method. A third recommended. It should be stirred for 190 hrs. at method of determination consists in reducing the 155°, and then quickly cooled. For lighter lubricants hot bismuth solution with magnesium, adding the proportion of rubber should be less. There is ammonium sulphate solutiop, and heating until the evidence of chemical reaction and the time and ammonia is removed. The reduced bismuth is then temperature conditions stated should be precisely MINERALOGICAL CHEMISTRY. 1049 followed. The lubricant retains a satisfactory con 1927, 10, 614— 619).—The absorptive powers of sistency for 12—24 months. C. I r w in . liquids are measured by comparing the effects recorded Equations for design of fractionating columns. by a thermopile when cells containing the liquids under L. H. S h ir k and R. E. M o n t o n n a .— See B., 1927, examination are placed between the thermopile and a 735. constant light source. The intensity of the light transmitted by an aqueous solution of a coloured Rapid [method of] extraction. A. G. K u h l - substance does not decrease with increasing concen m an n (Z. anal. Chem., 1927, 72, 20—27).— The tration according to the requirements of a formula of substance to be extracted is contained in a glass an exponential type. Examination of the variation weighing bottle with a perforated bottom, which can of the absorptive power of dilute “ solutions ” of be covered by a glass cap. The bottle rests in a con silver chloride with time shows that as aggregation of striction in the neck of a flask, which is fitted With a the particles proceeds the absorptive power of the condenser, and contains the extracting liquid. On “ solution ” increases. J. S. Ca r t e r . boiling, the vapour rises through and around the sides of the bottle, and the condensed liquid drops back Polishing and etching lead, tin, and some of into it. The extraction is rapid and quantitative, their alloys for microscopical examination. and the all-glass construction allows of the use of J. R. V il e ll a and D. B e r eg e k o f f (Ind. Eng. Chem., strong acids as extracting liquids. For a series of 1927, 19, 1049— 1052).—The sample is cut with a extractions at the temperature of the condensed sharp, oiled hacksaw and then ground with a series liquid, a large Soxhlet apparatus can be used to hold of emery papers of increasing fineness smeared with a a number of the glass bottles. Determinations of concentrated solution of paraffin wax in kerosene. the soluble matter in lmseed-oil cake and wheat flour Wet polishing is carried out on soaped broadcloth showed good agreement with the usual Soxhlet method. with the finest levigated alumina. For etching lead F. S. H a w k in s . and lead-antimony alloys a mixture of concentrated One-way safety valves for vacuum pumps nitric acid (1 vol.), glacial acetic acid (1 vol.), and and gas generating apparatus. F. H e in (Z. glycerol (4 vols.) is suitable. For lead-tin alloys twice angew. Chem., 1927, 40, 864— S65).— The valve, of as much glycerol is necessary. The structure is which various applications are described and figured, best developed by alternate polishing and etching, the consists of a pipette-like vessel containing a diaphragm etching being conducted for only a few seconds at a of sintered glass (a Jena glass filter-plate). The pores time. C. I r w in . in the diaphragm are small enough to retain mercury under the pressure likely to prevail in the apparatus. [Diagrammatic] representation of the ele The diaphragm is covered by a layer of mercury 3— 4 ments for instruction. A. P iu t t i (Rend. Accad. mm. deep. W. A. Sil v e s t e r . Sci. fis. mat. Napoli, 1925, [iii], 31, 142— 143).—A new spiral chart of the elements (cf. Oddo, A., 1925, Direct-reading hydrogen-ion meter. C. G. ii, 623) is reproduced and described. P ope and F. W. G o w l e tt (J. Sci. Instr., 1927, 4, 380—387).—An apparatus is described for obtaining E . W . W ig n a l l. Mosandrum. R. C. W ells (J. Washington Acad. direct readings of p a values. A four-electrode valve Sci., 1927, 17, 385— 388).—Mosandrum, claimed by and a potentiometer circuit are used. With a Smith (Coinpt. rend., 1878, 87,146) as a new element, hydrogen electrode the maximum error in p a is 0-09 was a mixture of at least two elements— samarium and with a quinhydrone electrode 0-10. and gadolinium. The history of the subject is C. W. G ib b y . sketched. C. W. G ib b y . Sodium voltameter. R. C. B u r t (Physical Rev., 1926, [ii], 27, 813).— The sodium voltameter, in which Early experiments on ultra-filtration. E. sodium passes through glass by electrolysis, yields H atsciie k (Nature, 1927, 120, 515).— Schmidt’s results correct to 1 in 2 X103, and probably correct to observation (Ann. Phys. Chem., 1856, 99, 337) that 1 in 6 x 103. A. A. E l d r id g e . an animal membrane is less permeable to colloids Measurements with an absorptiometer of than to sugar or salts antedates Graham’s papers on objective type. W. T s c h u d i (Helv. Chim. Acta, dialysis. A. A. E l d r id g e . Mineralogical Chemistry. Distribution and transportation of chlorides registered, and after a fall of snow 0-0346 g. per litre. in the atmosphere. F. B o rd as and A. D esfem m es There is no exact relationship between the number of (Compt. rend., 1927, 185, 603— 605).— The chlorine solid particles in the air and its salt content. contents of samples of rain-water may be considered J. Gr a n t . to be an indication of the salt content of air in the Chemical analysis of mud collected on the neighbourhood of the sea. At Cette (Midi) the upper terrace of the Musée Océanographique at highest normal value recorded (for the dust) was 3-4% Monaco, after the storm on October 31, 1926. of sodium chloride, and at 35 km. from the sea H. Ma r c e l e t (Compt. rend., 1927, 185, 662— 663).— 0-00267 g. per litre of Water. The results depend The dried mud was chestnut-brown in colour, and largely on the atmospheric conditions; thus, after a 97-3% passed a sieve having 4900 meshes/cm.2, and dust-storm 8-41 g. per m.2 of sodium chloride were the remainder a sieve of 2700 meshes. It contained : 1050 BRITISH CHEMICAL ABSTRACTS.— A. Si02 46-56, A1203 10-69, Fe,Os 6-01, CaO 18-09, MgO 37-35, A1203 26-27, Fe203 0-0037, CaO 12-65, BaO 2-09" S03 0-47, C02 (by difference) 16-09%. Assum 0-21, SrO 0-019, K 20 3-00, H20 20-32, total 100-022%, ing the existence of free silica, alumina, and ferric corresponding with the formula R2Al4Si5O18,9H20. oxide, the remaining elements may be grouped as Dehydration was effected over sulphuric acid and then CaC03 31-67, CaS04 0-71, and MgC03 4-36%. by heating in a current of air. On dehydration over J. Gr a n t . sulphuric acid, gismondite attained equilibrium after Temperature and salinity observations in the 900 hrs. and pseudophillipsite after 450 hrs. De Gulf of Aden. D. J. M at th ew s (Nature, 1927, hydration proceeds rapidly in the first few hours, 120, 512).—The phosphorus content of the water in then continues very slowly; there is no sudden break and off the Gulf of Aden is 0-03 mg. P20 5 per litre in in the curve, indicating the absence of a definite the upper 50 m., increasing from 200 m. downwards hydrate. On exposure to moist air at 18-3° the lost to 0-143 mg. at 1750 m. The arsenic content is 0-005 water was reabsorbed much more rapidly than it was mg. As203 per litre at 500— 1750 m., but less than emitted. 0-001 mg. in the upper 50 m. It is probable that On heating the minerals in dry air up to 700° the arsenic is removed by plankton organisms much as curves obtained for both minerals are continuous, phosphorus is. A. A. E l d r id g e . showing that the water is dissolved or absorbed. After exposure to moist air for 19 hrs. at different Chemical composition of the earth, of temperatures, the amount of water reabsorbed is meteorites, and of the atmosphere of the sun. not in complete agreement with that evolved. More H. S. W ash in g to n (Bull. Nat. Res. Council, 1926, 2, over there is a notable variation in the rate of absorp II, 30—32).—The earth is considered to possess a tion between 270° and 310°. Samples which have central core of iron or iron and nickel, surrounded by been completely dehydrated do not reabsorb water. a “ lithosporic ” shell, in which silicates are included M. Ca r lt o n . sporadically in the metal, then by a “ ferrosporic ” Chemical composition of herschellite from shell in which iron occurs sporadically in silicate rock, Acicastello. V. Ca g lio ti (Rend. Accad. Sci. fis. next by a shell of peridotite, and then by the crust. mat. Napoli, 1927, [iii], 33,156— 163).— The results of The composition of the earth is given as : Fe (metal) previous analyses of the mineral herschellite are not 31-82, Ni (metal) 3-16, Co (metal) 0-23, 0 27-71, concordant and it is doubtful whether the samples Si 14-53, Mg, 8-69, Fe (silicate) 7-94, Ca 2-52, A1 1-79, analysed were pure. The greatest discrepancies arise S 0-64, Na 0-39, Cr 0-20, K 0-14, P 0-11, Mn 0-07, in the values obtained for calcium and sodium and C 0-04, Ti 0-02%. Of the 11 most abundant elements potassium; these, however, may be due to the fact in the earth, 9 are among the 11 most abundant that the herschellite obtained from Acicastello is elements in the atmosphere of the sun. accompanied by phillipsite and analcime and the Chem ical A b str a c ts. separation of these latter from herschellite is difficult. Crystalline nature of the chief constituent of The mineral contains: SiO„ 44-73, A1203 21-18, ordinary coal. C. S. F ox (Nature, 1927,120, 547). Fe203 0-00126, CaO 1-65, K 20“ 4-53, Na20 8-04, H20 —When thin sections of coal are examined in ordinary 20-11, total 100-24%. Neither barium nor strontium transmitted light, practically all of the bright coal and could be detected spectroscopically. The formula much of the dull coal layers appear to consist of a deduced from these results is R 2Al4Si70 18,llH 20. madder-red, somewhat granular, translucent sub Loss of water from the mineral over sulphuric acid stance (“ coal substance ” ) ; in very thin sections or was 6-27%, equilibrium being attained after about with strong sunlight it is golden-yellow. Pleochroism 358 hrs.; the curve obtained is smooth as with other is absent, but the substance is isotropic. Sections zeolites. Reabsorption of the lost water was complete cut perpendicularly to the planes of lamination show after 6 lirs.’ exposure to air saturated with water that the substance has the crystalline character of a vapour, i.e., in about 1/60 of the time required for its uniaxial crystal. The presence of three types of emission. minor constituents of coal : resinous substances, A sample of the mineral heated at 182° lost 11-20% amorphous “ mineral charcoal,” and inorganic of water and reabsorbed it again from a moist atmo matter, is revealed. The nomenclature of the con sphere in about 20 hrs. at 22°, the amount reabsorbed stituents of coal is discussed. A. A. E l d r id g e . exceeding that emitted by 0-062%. Again the curve Zeolites from the leucites near Rome. Gis- is characteristic of other zeolites. M. Ca r lt o n . mondite from Capo di Bove and pseudophillipsite Sericite-lazulite pseudomorphs after ortho- from Acquacetosa. V. Ca g lio ti (Rend. Accad. clase from Bolivia. E. V. S h a n n o n (J. Washing Sci. fis. mat. Napoli, 1927, [iii], 33, 163— 177).—A ton Acad. Sci., 1927,17, 388— 390).—A description of carefully selected sample of pure gismondite, dis certain specimens in the U.S. National Museum. 2-277— 2-279, contained Si02 33-89, AL>03 28-14, C. W. GrBBV. Fe203 0-0044, CaO 13-96, BaO 0-27, SrO 0-025, Ferrimolybdite from Bivongi (Calabria). G- K 20 2-86, H20 20-76, total 99-91%, corresponding Ca r o b b i (Rend. Accad. Sci. fis. mat-. Napoli, 1927, with the formula (Ca,Ba,Sr,K2)Al2Si20 8,4H20 in [iii], 33, 53— 57).—-The yellow mineral accompanying agreement with Zambonini and others. It is also Bivongi molybdite is ferrimolybdite (cf. Pilipenko,. in accord with Clark’s view that gismondite is similar Festsch. Vernadsky, Moscow; Neues Jahrb. Min- to hydrated anorthite. Ref., 1915, 191), for which the formula Pseudophillipsite, dis 2-257—2-259, contained Si02 4Fe203,13Mo03,44H20 is found. E. W . W ig n a l l. . ORGANIC CHEMISTRY. 1051 Organic Chemistry. Mechanism of molecular rearrangements. phenylpropane, but the treatment of this substance (M m e .) R a m a r t-L ucas (Compt. rend., 1927, 185, with solid potassium hydroxide or sodium ethoxide 561— 563).— A theoretical explanation of common yielded no definite product. W. J. P o w e l l . examples of molecular rearrangements involving the H ydrogenation of squalene. M. T su jim oto movement of single electron linkings. (Chem. Umsehau, 1927, 3 4 , 256— 258; cf. A., 1916, H. B u rto n . i, 786; Heilbron, Hilditch, and Kamm, this vol., 130). Carbon monoxide and bivalent carbon. H. — Kurozamo oil (from the liver of the black shark, S cheduler (Z. angew. Chem., 1927, 40, 1072— 1081). mainly of the genus Zameus) on hydrogenation in the —A review of recent work. presence of a nickel catalyst yields a product, m. p. Synthesis of hydrocarbons of the allene series. 46— 47°, acid value 3-2, saponification value 82-8, M. B otjis (Bull. Soc. chirn., 1927, [iv], 41,1160— 1165). iodine value 1-2, unsaponifiable matter 51-43%. The —Alkyl derivatives of allyl alcohol of the type unsaponifiable portion contains dodecahydrosqualeno 0H-CHR-CH;CH2 when treated with phosphorus tri- (for which the name squalane is suggested), batyl bromide (in presence of pyridine to prevent addition alcohol, derived chiefly from selachyl alcohol (cf. A., of hydrogen bromide to the double linking) yield a- 1922, i, 297), and probably hydrogenated cholesterol. and not y-brominated derivatives, CHRICH-CH2Br, Dodecahydrosqualene as isolated from the crude in excellent yield. These substances are readily con hydrogenated product by distillation is a colourless verted by bromine into alkylated glycerol tribromo- liquid of very low volatility, b. p. 272°/15 mm., df hydrins, which with solid potassium hydroxide yield 0-8084; nf, 1-4515; flash point (Pensky-Martens epidibromohydrins, CHRBr-CBriCH,, and from these, apparatus) 190°. It is unchanged by treatment with on treatment with zinc powder in presence of alcohol, sulphuric acid at 70°. W. J. P o w e l l . allene derivatives may be prepared in 70—75% yield. Action of cyanogen bromide on dimagnesium The following substanccs were prepared : u-bromo- acetylene dibromide. A. S. N e k r a sso v (Ber., AP-pentene, b. p. 123— 124°/760 mm., d'10 1-2545, n f 1927, 60, [B], 1756— 1758).—Dibromoacctylidene, 1-4731; a-bromo-AP-hexene, b. p. 42— 44°/10 mm., CBr2!C, b. p. 76—76-5°, is prepared by the action of dla 1-2119, nf; 1-4778; a-bromo-A^-lieptene, b. p. 62— cyanogen bromide on dimagnesium acetylene di 64°/10 mm., d'~ 1-16S2, nf, 1-4760. The foregoing bromide (cf. Lawrie, A., 1907, i, 3). H. W r e n . substances were characterised by conversion into the corresponding acetates and alcohols, viz., AP-pentenyl Action of trichloroethylene, aap-trichloro- acetate, b. p. 149— 151°, dn 0-9019, nf, 1-4219; ethane, and aaap-tetrachloroethane on mag AP-hexenyl acetate, b. p. 171— 173°, d13 0-8976, rig nesium phenyl bromide. L. Bert (Bull. Soc. 1-4282; A^-heptenyl acetate, b. p. 192— 194° (corr.), chim., 1927, [iv], 4 1 , 1173— 1174).—The chloro- d13 0-8915, nf, 1-4314; At-penten-a-ol, b. p. 138— 139°, derivatives mentioned undergo 110 reaction when 1 d23 0-8444, nf; 1-4359; hfi-hexen-a-ol, b. p. 158— 160°, mol. of each is added to a solution of 1 mol. of dK 0-8490, < 6 1-4403; AP-hepten-u-ol, b. p. 177— 179° magnesium phenyl bromide in anhydrous ether, even (corr.), d20 0-8421, nf, 1-4410 : the tribromohydrins after prolonged boiling. If the ether is replaced by prepared were on treatment with hydrochloric acid, yield 0-keto- methylsuccinic acid could not be detected among the stearic, £-hydroxy-0-ketostearic, and 0-ketobehenic products. The sodium salts of a-hydroxy-a[3-di- acids (cf. Baruch, A., 1894, i, 170, 171; Goldsobel, A., methylsuccinic, a-hydroxy - a - methylsuccinic, and 1895, i, 81; Holt, A., 1892, 812). Mercuration of a-hydroxy-a-methyl-j3-ethylsuccinic acids have been methyl behenolate proceeds analogously, but definite subjected to the same treatment. In each case compounds could not be obtained similarly from methylsuccinic acid is produced in 25— 30% yield. y-butinene-aa-dicarboxjiic acid and y-butinene-a- In addition, fission of the molecule occurs with carboxylic acid. F. G. W ills ox. production of methane, carbonate, and a series of Existence and preparation of methyl ortho- monobasic acids. Formic and acetic acids are invariably produced, the yield being highest (45%) carbonate. H . v o n H a r te l (Ber., 1927, 60, [5], 1841).—Methyl orthocarbonate, in. p. —5-5°, b. p. with a-hydroxy-a-methylsuccinic acid and lowest 114°, d-H'-l T0232, ni? 1-3S64, is readily obtained by the (16%) with a-hydroxy-a-methyl-3-ethylsucciiiic acid. action of trichloronitromethane on sodium methoxide The yield of higher monobasic acid increases in the in pure methyl alcohol. It volatilises to a marked inverse order; with a - hydroxy - a-methyl - [3 - ethyl- succinic acid butyric acid is obtained in 30% yield, extent -with methyl alcohol or ether. H. W e e n . due to fission between the a- and (3-carbon atoms. In Preparation of ethoxalyl chloride. L. B ert all cases an intensely odorous oil, similar to that (Bull. Soc. chirn., 1927, [iv], 41, 1165— 1166; cf. derived from sodium lactate (loc. cit.), is produced in A., 1926,56; Barré, this vol., 228).— In the preparation quantity too small for extended examination. of ethoxalyl chloride by the action of phosphorus H. W r e n . pentachloride on ethyl oxalate, yields of 80% may be Reduction of polybasic a-hydroxy-acids under obtained provided that the starting materials are of a the influence of the combined action of catalysts. high degree of purity. The phosphorus pentachloride V. I pa t ie v and G. R a z u b a ie v (Ber., 1927, 60, [5], is best prepared beforehand from phosphorus tri 1973—-1976; cf. A., 1926, 1124, and preceding chloride and chlorine in the flask .used for the reaction abstract).— The action of hydrogen under pressure on with ethyl oxalate. W. J. P o w e l l . heated solutions of sodium malate, tartrate, and Lanthanum, cerous, praseodymium, neodym citrate in the presence of aluminium oxide and ium, and samarium maleates. L. Co n ig lio (Rend. nickel oxide is characterised by reduction of the Accad. Sci. fis. mat. Napoli, 1927, [iii], 33, 80— 82).— hydroxyl group by hydrogen with production of the Salts of the general formula [(iCH-CO^JjR^lOHaO, corresponding saturated polybasic acid and decom where R is C e '", Pr, Nd, La, or Sm, are prepared, of position of the molecule into monobasic acids. The which the respective solubilities of the anhydrous first change is observed only with malic and tartaric salts in water at 25° arc 8-05, 6-05, 5-64, 4-19, and acids, which give succinic acid in 50% yield and very 1-45 g. per 100 g. of solution. E. W. W ig n a l l . small amount respectively. Decomposition of the acids affords formic and acetic acids, carbon dioxide, C4-Saccharinic acids. IV. Preparation of and methane, Methylsuccinic acid is obtained from the two f/i-ap-dihydroxybutyric acids. J. W. E. citric acid in rather more than 30% yield. GlatteEld and S. W o od ru ff (J. Amer. Chem. Soc., H. W r e n . 1927, 49, 2309—2315; cf. A., 1925, i, 881).— Catalytic reduction of fi-gluconic acid to The a-chloro-[3-hydroxybutyric acid obtained from rf-glucose. J. W . E. Gl a t t f e l d and E. H. S haver crotonic acid by a modification of the method of (J. Amer. Chem. Soc., 1927, 49, 2305—230S).— Melikoff and Zelinsky (A., 1888, 1056) yields, when ¿-Gluconic acid was treated in faintly acid aqueous treated as the barium salt in aqueous solution with solution at the ordinary temperature with hydrogen silver oxide., an a[3-dihydroxybutyric acid, (I), m. p. under a pressure of 17 lb./sq. in., in presence of 81-5°. Oxidation of crotonic acid with permanganate platinum oxide. Glucosazone was isolated from yields an a (3 - dihydroxy butyric acid, ( + 1H20) (II), the reaction mixtures in amounts corresponding with m. p. 73-5—74-5° (cf. Fittig and Kochs, A., 1892, 956), 14— 28% yields of dextrose, the latter also being also obtained by the oxidation of crotonic acid with obtainable in crystalline condition. chlorate in presence of osmium tetroxide (cf. Milas F. G. W il lso n . and Terry, A., 1925, i, 780). The following deriv Behaviour of aldehydeacetals on hydrogen atives of (I) and (II) respectively were prepared : ation. Formation of ethers from acetals. F. phenylhydrazides, m. p. 103° and 129-5°; o-tolyl- Sigm und and G. M a r ch a r t (Monatsh., 1927, 48, liydrazides, m. p. 103° and 111-5°; and barium and 267—288).—Hydrogenation of benzaldehydediethyl- silver salts. F. G. W il lso n . acetal at 180° by the Sabatier and Senderens process Combined action of catalysts (nickel oxide and yields benzyl ethyl ether (45%), b. p. 185—187°. aluminium oxide) on solutions of substituted From phenylacetaldehydedimethylacetal there is hydroxysuccinic acids under high pressure of produced methyl (3-phenylethyl ether (50%), b. p. hydrogen and at high temperatures. G. R a z u - 189— 190°. Similarly, heptaldehydediethylacetal b a ie v (Ber., 1927, 60, [£], 1976— 1980).— The yields ethyl heptyl ether (61%), b. p. 165—167°; behaviour of sodium lactate under the conditions heptaldehydedi-n-propylacetal, b. p. 112-5°/9 mm., expressed in the title (cf. A., 1926, 1124) has been affords ?i-propyl heptyl ether (64%), b. p. 182-5— explained by the scheme : 20H-CHMe-C0.,H — >- 183°; heptaldehydediisobutylacetal, b. p. 126-6° (corr.)/10 C0,Na-CMe(0H)-CHMe-C02Na — -> mm., gives isobutyl heptyl ether (64%), b. p. 194— 196°; C 02Na- CMe ICH • C 0¡>Na— > phenylacetaldehydedi-n-propylacetal, b. p. 136-6° (corr.)/ C02Na-CHMe,CH2-C02Na, but a - hydroxy - a[3 - di - 12 mm., furnishes fj-phenylethyl n-propyl ether (80%), ORGANIC CHEMISTRY. 1055 b. p. 225— 227° (corr.); and cinnamaldehydediethyl- A3-hexen-5-one (12-5), and methylw-amyl ketone (4*6). acetal yields ethyl y-phenylpropyl ether, b. p. 220— An equimolecular mixture of calcium acetate and 222°. H. B u r to n . calcium butyrate yields on distillation acetone, mesityl oxide, methyl ethyl, methyl propyl, ethyl a-Bromo- and a-hydroxy-aldehydes. R . D w o r - propyl, and dipropyl ketones. If 4-5 mols. of calcium za k and P. P fiffe rlin g (Monatsh., 1927, 48, 251— 266).— Bromination of parapropaldehyde with 2 acetate are used to 1 mol. of calcium butyrate the atoms of bromine at —10 to —5°, followed by treat products are acetone, methyl ethyl and methyl propyl ment with alcohol, yields the acetal of a-bromoprop- ketones. ' H. B u rto n / aldehyde. With 4 atoms of bromine there are Trifluoroacetone. P. Sw a rts (Bull. Acad. roy. produced whilst the pyrrole derivative has ra. p. 175°. o-Amino- — 8-7° in chloroform, re-converted into 2:3: 6-tri- phenol did not appear to react. W. J. P o w e ll. methylglucose by 5% hydrochloric acid. It is con Spectrographic investigations on carbo verted by hydrogen chloride in the presence of acetyl chloride at —15° to —18° into amylene-oxidic 1 -chloro- hydrates in the ultra-violet. L. K w ie c iń s k i and 4:-acetyl-2 : 3 : 6-trimethyl-cc-glucose, b. p. 143— 146°/ L. M a r ch le w sk i (Z. physiol. Chem., 1927, 169, 300; cf. this vol., 291).—The conclusion of Niederhof (this 0-04 mm., [a]“ +146-9° in chloroform, which with vol., 396) that sugars containing an aldehyde or a alcoholic trimethylamine affords amylene-oxidic ketone grouping have an absorption band at 2800 A. is 4 -acetyl - 2 :3 : G-triniethylghicosidotrimethylammonium refuted. Very pure preparations of dextrose and chloride, [a]1,? —3-7° in chloroform, to which the galactose show a continuous absorption and this band (3-configuration is assigned. If this material is treated is evident only with less pure preparations. The with warm barium hydroxide solution ring closure results are not quite so definite with Isevulose, but occurs with production of 2:3: 6-trimethylglucose the absorption band becomes much weaker as the anhydride in 62% yield. The product is a mobile liquid, b. p. 107— 108°/0-05— 0-07 mm.', which shows preparation is purified. A. W o rm all. the expected mol. wt. in solution, does not reduce Percentage formula of pentosans. G. Schorsch Fehling’s solution, but reacts immediately with cold (Papier-Fabr., 1927, 25, 576— 577).—The formula permanganate. It contains about 75% and 25%, (C5H804)„ for the pentosans, due to Tollens, cannot be respectively, of the trimethylanhydroglucoses (I) and regarded as definitely established. A critical examin (II). When treated with 1% methyl-alcoholic hydro ation of results given in the literature shows that gen chloride at the atmospheric temperature it gives elementary analysis of amorphous and ash-containing 2:3: 6-trimethylmethylglucoside, only one anhydride preparations is not conclusive, whilst the C-value ring being opened, whilst the other is stable. Separ given by Tollens and Wheeler is the arithmetic mean ation of the glucoside and unchanged anhydride of the theoretical C-values of C5Hs0 4 and C10H18O9. has not been effected, but the presence of each is That a hexosan formula is improbable is show’ll by the established by the methoxyl content of the preparation results of other investigators on the hydrolysis of and the results of further methylation by methyl xylan, no dextrose or other hexose having been found, sulphate and subsequent hydrolysis of the product hence only C5H804, C10H,8O9, or similar anhydride with 5% aqueous hydrochloric acid to amylene- formula need be considered. The hydrolysis of xylan oxidic 2:3:4: 6-tetramethylglucose and amylene- to xylose does not illuminate the problem, since oxidic 2:3: 6-trimethylglucose. It appears certain 100% yields of xylose are never obtained. The usual that neither of the trimethylanhydroglucoses is determinations of xylan by its yield of furfuraldehyde identical with trimethylcellulose and that either the phloroglucide show that no 100% value is obtained, cryoscopic behaviour of the latter in glacial acetic calculated on the dry, ash-free substance, in spite of acid solution must be ignored or that the constitution the fact that no other sugars than pentoses can ever of trimethylcellulose cannot be based on the pro be found. The Tollens method for the determination duction of 2 : 3 : 6-trimethylglucose. H . W r e n . of pentoses in xylose and arabinose was worked out experimentally on crystallised pure products, and the rf-Glucose-£-chlorohydrin and its derivatives. above anomalies are removed only by the use of other B. H elferich and H . B r e d e r e c k (Ber., 1927, 60, calculation factors. With these, together with hydro [5], 1995— 2001).— The triphenylmethyl ether of lysis formula}, it is shown that all xylan values within acetyl-fZ-glucose or acetyl-a-methylglucoside is con the ordinary limits of experimental error give 100%, verted into triacetyl-a-methylglucoside-6-chloro- which points to (C10H18O9)„ as the composition of the hydrin in the manner described previously, except pentosans. B. P. R id g e . that the triphenylmethyl group is removed in the Oxygen bridges in sugars. III. Anhydrides form of its sparingly soluble bromide and is then of py£-trimethylglucose. Attempted synthesis transformed by aqueous hydrochloric acid into of trimethylcellulose. F. M ic h e e l and K. H ess d-glucose-Z-chlorohydrin, m. p. 135— 136° (corr.), [«]» (Ber., 1927, 60, [B ], 189S— 1906; cf. A., 1926, 1230; +78-3° to +35-0° in aqueous solution; the osazone is this vol., 43) —If trimethylcellulose is a 2 : 3 : 6-tri- described. Similarly, fi-tetra-acetyl-d-glucose-6-chloro- methylanhydroglucose it must possess the constitution hydrin, m. p. 114— 115° (corr.), [a]'„8 +17-6° in chloro (I) or (II); the former is almost free from strain, form, is prepared by the action of phosphorus penta- <3 chloride on p-tetra-acetyl-cf-glucose 6-triphenylmethyl -ÇH— — 9 H ether; the mother-liquors obtained in the preparation H-Ç-OMe I H-Ç-OMe of the latter compound yield small quantities of a O O OMe-C-H.Ta.O.TT 9 OMe-Ç-H 0 crystalline material, m. p. 120— 126°, consisting fructose is III. A. H a h n and W. L aves (Z. Biol., 1926, 85, justified by the reference of crystalline derivatives of 280—288).—The tetra-acelyl-d-ghicoside of 2-methyl- its degradative oxidation products to standard com anilino-Q-oxypyrimidine has been isolated 'as a pounds of known constitution. Cautious oxidation crystalline compound, m. p. 145°, [a]'“ —45-04° in of tetramethyl-y-fructose with nitric acid (d 1-42) toluene, by the action of the silver salt of 2-methyl- followed by esterification of the product yields anihno-6-oxypyrimidine on a xylene solution of tetra- essentially the lactol ethyl ester, C11H20O7, [a]“ acetobromoglucose at 155°. From this substance +25-8° in water, which after methylation yields the 2-methylanilino-6-oxypyrimidine-cZ-glucoside, m. p. amide, CJ0H)9OGN, m. p. 99— 100°, identical with 116— 118° (indef.), [a]1,? —66-39° in alcohol, has been that obtained from the corresponding methyl ester isolated after deacetylation with methyl-alcoholic (this vol., S59). Oxidation of the lactol ethyl ester ammonia. with alkaline permanganate followed by esterific The tetra-acetyl-d-glucoside of 2-methylanilino-G- ation of the product with methyl alcohol gives an oxy-o-methylpyrimidine, m. p. 143— 145° (indef.), [a]'jj ester, C7H14Os, [a]'“ +19° in water, from which — 63-9 in benzene, has been isolated in an analog hydroxydimetlioxybutyramide, m. p. 104— 105°, [a]1,’ ous manner from the silver salt of 2-methylanilino-6- +33° in water, is obtained. Application of Weer- oxy-5-methylpyrimidine. By deacetylation with man’s reaction to this amide indicates that it is not methyl-alcoholic ammonia, 2-methylanilino-G-oxy-5 - an a-liydroxy-compound (A., 1917, i, 546). Since methylpyrimidine-d-glucoside, m. p. 135— 136°, [ocjg the amide is not oxidised by nitric acid as it would be -57-54°, is formed. if it were a y-hydroxy-compound, it is probably the The picrate, m. p. 109— 110°, of the tetra-acetyl- P-hydroxy-compound. The lactol acid, prepared glucoside of 2-elhylthiol-G-oxypyrimidine has been pre by hydrolysis of the lactol ethyl ester described pared by the addition to a saturated aqueous solution above, is oxidised in dilute sulphuric acid solution of picric acid of a boiling alcoholic solution of the with barium permanganate to give d-trimethyl- condensation product of tetra-aeetobromoglucose arabonolactone, m. p. 32— 33°, [a]D +44-5 to +25-5° and 2-ethylthiol-6-oxypyrimidine. The free glucoside, in water in 18 days. The m. p. of this substance is m. p. 103°, [a]g —13-73°, is described. Deacetylation identical with and the rotatory power equal and of this substance with methyl-alcoholic ammonia pro opposite to that of the i-isomeride already obtained duces 2-ethyUhiol-G-oxypyrimidine-d-glucoside, m. p. (this vol., 750). Oxidation of the lactol methyl ester 144— 145°, [oc]b —68-47°; its hydrolysis by emulsin yields the same product. G. A. C. G ough. proves it to be a ¡3-glucoside. None of those synthetic Transformation of a ¡3-glucoside into an glucosides reduces Fehling’s solution until after a-glucoside. B. H e l f e r ic h and A. Schneidmüller fission with dilute hydrochloric acid except 2-methyl- (Ber., 1927, 60, [B], 2002— 2005).— á-P-Methyl- anilino-6-oxypyrmidine-d-glucoside, which, although glucoside is converted by successive treatments with stable in alkaline solution, is hydrolysed into its triphenylmethyl chloride in pyridine and acetic components by keeping in neutral aqueous solution. anhydride into lriacelyl-$-methyl- —40-2° in chloroform. It is converted by barium Aminohydroxy-compounds which show the hydroxide into o-glucosidosulphamidobenzoic acid, biuret reaction. III. Separation of y-amino- C6HiiO5-NH-SO2-C0H4-CO2H, [a] +2-8° in water [3-hydroxybutyric acid into optically active com (corresponding sodium salt, incipient decomp. 119°, ponents. M. T o m ita and Y. Se n d j u (Z. physiol. [a] —14-9° in water), which readily reduces Fehling’s Chem., 1927, 169, 263—277; cf. Tomita and Fuka- solution. Hydrolysis with methyl-alcoholic ammonia gawa, A., 1926, 1235).— iZ-y-Amino-p-hydroxybufcyric appears to convert tetra-acetylglucosidosaccharin acid has been resolved into the active components into glucosidosaccharin, which passes readily into by means of the brucine salts of the benzoyl deriv o-glucosidosulphamidobenzamide. H. W r e n . ative. The amino-acid is benzoylated and an alcoholic solution of brucine is added. After some Amphoteric nature of cellulose. E. O m a n days at 0°, brucine benzoyl-l-y-amiyio-^-hydroxy- (Papir-Joumalen, 1927, 15, 91— 96, 107— 110, 116— bulyratc, m. p. S7°, separates as colourless plates, 120).—The chemical activity of cellulose is demon whilst colourless needles of the brucine benzoyl-d-y- strated by its reduction, by chemical combination, amino-$-hydroxybutyrate, m. p. 41°, are obtained of the acidity or alkalinity of dilute aqueous solutions. from the mother-liquor. The former brucine salt The extent to which hydrogen ions are taken up by yields two isomeric \-y-benzamido-$-hydroxybutyric the cellulose is variable, and dependent on the acids, m. p. 172°, [a]-JJ —7-59° and m. p. 114° and hydrogen-ion concentration of the water. [a]]? -11-84° (-flH ,0 , m. p. 80— 81°); the other Chem ical A b strac ts. brucine salt gives two d-y-benzamido-$-hydroxy- Cellulose. XXX. Acetolysis of cellulose by butyric acids, m. p. 17S°, [a]'“ +4-08°, m. p. 116° and hydrogen bromide and acetyl bromide. De [a]“ +10-0° ( + 1H20, m. p. 78-—80°). Hydrolysis gradation to a trihexosan. K. H ess and F. of the benzoyl compounds with hydrobromic acid M ic h e el (Amialen, 1927, 456, 69— 86; cf. Hess, yields two l-y-amino-$-hydroxybutyric acids, m. p. Weltzien, and Kunau, A., 1924, i, 146).— By the 213°, [a]™ -3 -4 0 ° and m. p. 212°, [«]g -21-06°, action of hydrogen bromide and acetyl bromide respectively, and two &-y-amino-[i-hydroxybutyric cellulose acetate undergoes complete fission into acidj, m. p. 214°, [a]f? +3-21° and m. p. 214° (decomp.), brominated dextrose derivatives in 15 days at 0° fa]“ 4-lS-30°, respectively. The d- and \-y-amino-?j- or in 10— 12 days at 4— 6°. The progress of the hydroxybutyric acids all give positive biuret reactions. acetolysis is followed (i) polarimetrically, (ii) by On exhaustive methylation they yield two 1 -y-tri- bromine determinations, (iii) by mol. wt. determin melhyl-fi-hydroxybutyrobetaines, [a]'JJ —7-25° (gold salt, ations. The bromine content of the final product m. p. 151— 152°, [a]f; —20-98°, gold salt, m. p. (above 24%) is greater than required for dextrose 155°, platinic salt, m. p. 220°, and mercury salt, monobromide acetate (19-5% Br); more than half m. p. 204°, respectively, the second compound being this bromine reacts with silver acetate and is thus identical with carnitine, and two d-y-trimetliyl-$- attached to the C, atom of an aldehydic sugar. The hydroxybutyrobetaines, [a]'“ +8-42°, gold salts, m. p. mol. wt. of the final product, freed from cellobiose 150— 151°, [a]D +20-20°, and m. p. 155°, respect bromide acetate, is 630—3S0 (disaccharide 700, ively. A. W orm all. dextrose 410, as bromide acetate). Cellobiose bromide acetate under similar conditions is practically un- Acylation of derivatives of AW'-ethylenebis- attacked by 5% hydrogen bromide in acetyl bromide, (3-aminocrotonic acid and similarly constituted but by 7-5% at 15° it is converted after treatment substances. E. B e n a r y (Ber., 1927, 60, [B], with silver acetate into equal amounts of dextrose 1826— 1836; cf. A., 1923, i, 37, 201; this vol., 45). penta-acetate and a dextrose bromide acetate. — In general, O-derivatives camiot be obtained from The final product of complete acetolysis of cellulose compounds of ay-diketones with bases of the type acetate with 6% hydrogen bromide in acetyl bromide NHR'-CR!CHX by means of acid chlorides, whereas at 5° for 17 days, on acid hydrolysis under special they are prepared from substances in which X repre conditions, yields a water-soluble trihexosan, sents an ester, nitrile, or acid amide group. From (C6H j0O 5)3,H 2O, m. p. 184— 1S9° (decomp.), [a]'D7 the former compounds the preparation of p-hydroxy- 4-90-5° in water, [a]]? +96-8° in methyl alco pyrroles cannot therefore be effected. hol, which is without reducing action on Fehling’s Ethyl iYiY'-ethylenebis-p-aminocrotonate is con solution. The trihexosan forms crystalline additive verted by chloroacetyl chloride and pyridine in products with toluene and xylene and is thus separated presence of ether into ethyl -ethylenebis-fi-amino- from the reducing sugars which accompany it. It is a-chloroacetylcrotohate, purified by fractional crystallisation of the acetate, [-CH2-NH-CMe:C(C0;CH2Cl)-C02Et]2, m. p. 124°, ^36^ 43024, m. p. 123— 126°, [a];J +86-6° in chloro which is transformed by potassium hydrogen sulphide form, which is a nona-acetate of a trisaccharide into ethyl 4-hydroxy-2-methylthiophen-3-carboxylate, anhydride. Celloglucosan is not present in the m. p. 64-5—66° (cf. A., 1915, i, 576), and passes when products of acid hydrolysis. Methylation of tri heated into the compound “ 9 ---- CO^ hexosan with methyl sulphate and alkali gives >C:CMc-NH-CH„- m. p. 290° (decomp.). smoothly the nonamethyltrihexosan, m. p. 84— 91°, CH2-CO [a]}? 4-94-8 ° in chloroform, which on hydrolysis yields It is transformed by alcoholic ammonia into ethyl only ¡3y£-trimethyldextrose. Trihexosan must thus 1 : V-ethylenebis-Z-hydroxy-5-methylpyrrole-4-carboxyl- have one of the constitutions assigned by Irvine to ate, decomp. 180—200° after darkening at 160°. cellulose, from which, however, it differs completely. The aqueous solution of the latter ester is converted C. H o llin s/ by ferric chloride into the pyrroline derivative, ORGANIC CHEMISTRY. 1059 COoEt-C-COG------— C-COC-C02Et , onno glutaconamide pier ate, CgH120 6N2,CcH2(N02)3*0H, was " -J-riTT mr ir , decomp. 200 . CMe-N-CH2-CH2-N----- CMe 1 obtained. B. W . A n d er so n . Ethyl 1 : 1 ethylenebis -2-h ydroxylamino - 3 - kelo - 5 - New reference compounds in the sugar group. methylpyrrolineA-carboxylate, m. p. 168° (decomp.) Methylamides of d-, 1-, and i-dimethoxysuccinic after darkening at 160°, and ethyl 1 : 1'-ethylenebis-2- acids and of i-arabo- and i-xylo-trimethoxy- niirimino-3-keto-5-methylpyrrolirie-4:-carboxyiate (an glutaric acids. W. 1ST. H a w o r t h and D. I. J on es hydrous and dihydrate), decomp, about 198°, are (J.C.S., 1927, 2349 — 2353). — d-Dimethoxysuccino- described. methylamide has m. p. 205°, [a]1,] +132-6° in water. Diacetonitrile is readily transformed by ethylene- Methyl \-dimethoxysuccinate, b. p. 83°/0-07 mm., diamine in acetic acid solution into l^l^'-ethylenebis- n\] 1-4345, [a]o —78-8° in methyl alcohol, gives diacetonitrile, [CN-CH;CMe-NH>CH2-] 2, m. p. 194— \-dimethoxysuccinamide, m. p. 278° (decomp. 294°), 195°, which, with chloroacetyl chloride and pyridine, and 1 -dimcthoxysuccinomethyiamide, m. p. 205°, [a]J; affords NN' - ethylenebis - 2 - chloroacetyldiacetonitrile, — 131-8° in water, i-Dimethoxysuccinomethylamide m. p. 220°; it is transformed by successive treatment has m. p. 210°. Methyl i-trimethoxyglutarate, b. p. with ammonia and formaldehyde into the compound, 102— 104°/0-09 mm., nD 1-4402, obtained by the cautious oxidation of trimethyl S-xylonolactone with nitric acid (d 1-42) followed by esterification with Ethylenebis-z-acetyldiacetonitrile, m. p. 230°, is con methyl-alcoholic hydrogen cldoride, gives i-a•ylo-tri- verted by phenylhydrazine into l-phenyl-3 : 5-di- metliylglutaramide, m. p. 195— 19S° after darkening methylpyrazoleA-nitrile, m. p. 89— 90°, identified by at 195°, and i-xylo-trimethoxyglularomethylamide, m. p. hydrolysis to 1-phenyl-3 : 5-dimethylpyrazole-4-carb- 167— 168°. Trimethyl S-arabonolactone, m. p. 45°, oxylic acid. [a]]} +179° in water, prepared from trimethyl- Acetylacetono-ethylcncdiamine, chloroacetyl chlor [3-methylarabinoside, is similarly oxidised to give ide, and pyridine afford ’NN'-ethylenebis-N-chloro- finally methyl \-arabono-trimethoxyglutarate, b. p. 105°/ acetyl-aeelylacetonamine, 0-14 mm., [a]” +37-6° in water, +41-2 in methyl [CHAc:CMe-N(CO-CH2Cl)-CH2-] 2, m. p. 108°, which alcohol; 1-arabono-trimethoxyglutaramide, m. p. 230° is converted by alcoholic alkali hydroxide into N3ST- (decomp.), and 1 -arabono-trimethoxyglutaromethylamide, ethylenebis-N-hydroxyacetylacetylucetonamine, m. p. m. p. 172°, [a]if +59-9° in water, are described. 275° (decomp.) after darkening at 260°. -Ethyl- G. A. C. G ou gh . enebis-'N-benzoylacetylacetonamine, m. p. 192°, N-benz- Nitroalkylguanidines. T. L . D avis and S. B. oylbenzoylacetonamine, m. p. 114°, J$-acetylbenzoyl- L uce (J. Amer. Chem. Soc., 1927, 49, 2303—2305; acetonamine, m. p. 101°, and NN'-ethylenebisbenzoyl- cf. this vol., 863).— The following nitroalkylguanidines, acetonamine, m. p. 183°, are described. Chloroacetyl- obtained from nitroguanidine and the corresponding acetylacetonamine is converted by potassium hydro amines in aqueous solution, are described : nitro- gen sulphide into thiobis-'N-acetylacetylacctonamine, methyl-, m. p. 160-5— 161-0°; -dimethyl-, m. p. 193-6— S[CH2-CO-NH-CMeICHAc]2, m. p. 123°; it does not 194-5°; -n-propyl-, m. p. 98-0— 98-5°; -isopropyl-, appear to give a pyrrole derivative with alcoholic m. p. 154-8— 155-6°; -isobutyl-, m. p. 121-0— 121-5°; ammonia. -n-amyl-, m. p. 98-8— 99-3°; -isoamyl-, m. p. 145-5 Formylacetonanil and formylacetophenonanil give 146-2°, and -tevi.-amyl-quanidine, m. p. 154-8— 155-6°. 0 -chloroacetyl derivatives, m. p. 137-5° and 144°, F . G. W illso n . respectively. Formylacelophenonanilphenylhxydrazone, Methylation with diazomethane. M. N ie r e n - m. p. 225— 226°, is described. H. W r e n . stein (Ber., 1927, 60, [5], 1820— 1821).— Ethylene glycol does not react with diazomethane. Its mono So-called “ diethyl dicyanoglutaconate ” and acetate is readily converted by the reagent into some derivatives. Y. U r u s h ib a r a (Bull. Chem. fi-methoxyethyl acetate, b. p. 143— 144°. The latter Soc. Japan, 1927, 2, 236— 241; cf. this vol., 345).— substance is hydrolysed by alcoholic ammonia to In the condensation of ethyl cyanoacetate with chloro fS-methoxyethyl alcohol, which cannot be methylated form and sodium ethoxide, excess of the latter two ):y diazomethane. Triphenylmethyl chloride, p-meth- compounds gives an improved yield of ethyl sodio- oxyethyl alcohol, and pyridine afford triphenylmethyl ay-dicyanoglutaconate. From the silver derivative fi-methoxyethyl ether, m. p. 104°. II. W r e n . of this compound an ammonium derivative, CuH1204N2,NH3,2H20, losing 1 mol. of water at 130°, Reaction between lithium w-butyl and organic was obtained (cf. Ruhemann and Browning, J.C.S., halogen compounds. C. S. M a r v e l , F . D. H a g e r , 1898, 73, 283). An attempt to synthesise the true and D. D. Coffman (J. Amer. Chem. Soc., 1927, 49, ethyl dicyanoglutaconate by heating together ethyl 2323—2328; cf. A., 1926, 1232).—Treatment of cyanoacetate, ethyl orthoformate, and acetic an lithium w-butyl with n-heptyl bromide in light petrol hydride yielded ethyl sodiodicyanoglutaeonate, the eum affords w-undecane. Methylene iodide yields desired product possibly having been formed initially. similarly rc-nonane, whilst p-bromostyrene affords Methyl cyanoacetate and chloroform condensed with cL-p)henyl-\a-n-hcxene, b. p. 97— 100°/8 mm., d%‘ sodium methoxide in methyl alcohol, giving methyl 0-9455, nf; 1-5377, together with trans-trans-a.8-di- sodio-ay-cliciyanogluixiconatc, C9H704N2Na,H20, from phenyl-A“v-butadiene (cf. Rebuffat, A., 1891, 76). an acidified solution of which methyl ay-dicyano- The initial deep coloration of the reaction mixture glutaconate semihydrate, (+0-5H 20), m. p. 225°, was supports the view that the products of the last precipitated. This compound yielded an indefinite reaction are derived from intermediately formed bromine derivative from which ay-dicarbomelh oxy- free radicals. Lithium w-butyl and triphenylmethyl 1060 BRITISH CHEMICAL ABSTRACTS.----A. chloride yield mainly aotx-tripJi&nyl-n-pentarie, m. p. copper, nickel, or iron oxide yielding disubstituted 153— 154°, b. p. 170— 180°/0-01 mm. o- and m- benzenes containing very little benzene, naphthalene, Bromotoluenes yield similarly toluene, but p-bromo- methylnaphthalene, 2-ethylnaphthalene, dihydro- toluene affords ^-butyltoluene in 75% yield. Definite phenanthrene, and unchanged phenanthrene. Dis products could not be obtained from lithium «.-butyl sociation occurs therefore with intermediate produc and a-chloropyridine, trimethylene bromide, carbon tion of dihydrophenanthrene and fission of one ring tetrachloride, o-dichlorobenzene, hexabromobenzene, with the formation of naphthalene and alkyl naphth and tetrachloroethylene. F. G. W il lso n . alenes, the process representing the converse of the Magnesium diethyl and its reaction with synthesis of phenanthrene from naphthalene and ethylene. The second possible mode of dissociation, acetyl chloride. H. Gil m a n and F. Sch u l ze (J. into diphenyl and ethylene, does not appear to bo Amer. Chem. Soc., 1927, 49, 2328—2330).—The pro duction of magnesium diethyl from magnesium powder realised in these experiments, as indicated by the and mercury diethyl at 130° is greatly facilitated by almost complete absence of benzene and toluene the presence of a small proportion of mercuric chloride from the products. Probably the dissociation of (cf. Lohr, A., 1891, 682; Fleck, A., 1893, i, 622). phenanthrene into naphthalene is caused by its Magnesium diethyl reacts with ethereal acetyl cliloride tendency to isomerise to the symmetrical anthracene, with production of methyldiethylcarbinol (cf. Fleck, a process which would bo interrupted in its initial stages by the hydrogen and thus give riso to alkyl- loc. cit.). F. G. W il lso n . naphthalenes. It is probable that a dynamic isomer Pyrogenic dissociation of certain aromatic ism exists between 9 : 10-dihydrophenanthrene and compounds under pressure of hydrogen and the dihydro-product formed by addition of hydrogen by the combined action of catalysts. V. I p a t ie v to the neighbouring ring. II. W ren. and N. Or lo v (Ber., 1927, 60, [B], 1963— 1971).— The dissociation of a series of substances has been Nitration of xylene with dilute nitric acid in investigated in the presence of a catalyst (aluminium presence of mercury. E. I. Or l o v (Ukraine Chem. oxide, alone or with addition of oxide of copper or J., 1926, 2, 370— 375).— See A., 1926, 1130. iron) to depress the temperature of dissociation and Nitration of cumene. L. B e r t and P. C. D o rie r . in an atmosphere of hydrogen to combine with the (Bull. Soc. chim., 1927, [iv], 41, 1170— 1171; cf. dissociated fragments. The initial pressure of the A., 1926, 56, 285).— The observation of Vavon and hydrogen is about 70 atm. and a minimum temper CaUier (this vol., 455) that nitration of cumene by ature of 400° is necessary to ensure a reasonably the Pictet method yields almost exclusively the rapid action. Under these conditions, diphenyl 2>-nitro-derivative is confirmed. W. J. P o w e ll. ether is partly decomposed into phenol, traces of benzene, and a non-volatile resin. Phenol affords Arylsulphur chlorides and arylsulphuranilides. benzene in 20% yield. o-Cresol gives very little resin E. G e b a u e r -F ulnegg (J. Amer. Chem. Soc., 1927, and about 30% of a mixture of benzene and toluene. 49, 2-270—2275).—Treatment of 2 : 5-dichlorothio- Pyrocatechol yields benzene, much phenol, and a phenol with chlorine in cold carbon tetrachloride brittle resin. Aniline decomposes into benzene, affords 2 : 5-dicMorochlorothiolbenzene, b. p. 92°/3 mm., ammonia, and a little diphenylamine; the change which, on treatment with aniline in chloroform or appears reversible, since aniline is produced hi small carbon tetrachloride, yields 2 : 5-dichlorobenzene- amount from benzene and aqueous ammonia. Tri- sulplienanilide, m. p. 85°. ■p-Chlorochlorothiolbenzene, phenylmethane gives benzene and a little diphenyl- b. p. 94°/6 mm., was prepared analogously, and con methane; the latter substance is more stable, giving verted by treatment with aminoazobenzene into the only a small proportion of benzene. Naphthalene corresponding substituted ji-chlorobcnzenesutyhen- and a mixture of hydrocarbons are derived from amide, red, m. p. 1S8°. Treatment of 4-chloro-2- tetrahydronaphthalene; diphenyl readily yields benz nitrochlorothiolbenzene with methylaniline in absolute ene. Acenaphthene affords naphthalene and liquid ether affords i-chloro-S-nitrobenzenesulphenmethyl- hydrocarbons, together with saturated gaseous hydro anilide, non-crystalline, red, and an analogous sub carbons. Anthracene is converted almost completely stituted 4-chloro-2-nitrobenze,nesidphenamide, brown into coke. Mesitylene appears to suffer loss of methyl ish-red, was also obtained from 2 : 4-diaminoazo- groups to some extent. The uniform production of bcnzcne. A study of absorption spectra indicates substances with simply constructed molecules is note that 4-chloro-2-nitrochlorothiolbenzene, its anilide, worthy. Solvent naphtha is converted into benzene, and 4-chloro- and 2 : 5-dichloro-ehlorothiolbenzencs toluene (accompanied by xylenes or ethylbenzene), have similar structures, whilst 2 : 5-dichlorobenzene- naphthalene, and small amounts of resin; phenols sulphenanilide has a structure differing from these. appear to bo formed in very small quantity. Coal-tar Variations in colour amongst these derivatives are heavy oil affords “ light petroleum,” benzene, toluene, ascribed to “ approached quinonoid structures ” of xylene, naphthalene, and, probably, polymerised the molecules concerned (cf. Lecher and Holschneider, products. ' H. W r e n . A., 1924, i, 728). F. G. W illson . Pyrogenic dissociation of phenanthrene in the Oxidising action of “ chloram ine-T ” [sodium presence of hydrogen under pressure. N. A. 2>-toluenesulphonchloroamide]. G. Schiemann Orlov (Ber., 1927, 6 0, [2?], 1950— 1956).— Phen and P. N o v a k (Z. angew. Chem., 1927,40,1032—-1033). anthrene is decomposed when heated at about 500° — Contrary to Engelfeldt’s statement (A., 1923, i, 454), in the presence of hydrogen under initial pressure of “ chloramine-T” is stable on boiling a 10% aqueous about 75 atm. and ahnninium oxide mixed with solution for 3 hrs., and elimination of sodium hypo ORGANIC CHEMISTRY. 1061 chlorite does not occur. Oxidation by ‘‘ chloramine-T ’ ’ 1173).—A reply to Bourguel’s criticisms (this vol., in acid solution is represented by the equations 337) of tho authors’ work on this subject (A., 1925, 2Cr,H,Me-S02NaNCl+2H-==CfiH,1Mc-S02-NH2+ i, 803, 1373; 1926, 391). W . J. P o w e l l . C6H,1Me-S02-NCla+2 N a -; CGH4Me-S02-NCl2+ 2 H 20 = C6H4Me,S02,NH2-|-H0Cl, whilst in neutral solution System acetanilide-propionanilide. E. C. G il b e r t and L. Cla rk e (J. Amer. Chem. Soc., 1927, it follows the equation, C8H4Me-S02NaNCl+H20 = C6H4Me'S02-NH2+ N a C l+ 0 . In alkaline solution 49, 2296—2299).— Tho f.-p. curvo of mixtures of only does elimination of sodium hypochlorite occur. acctanilide and propionanilide shows that a com In agreement with Chattaway (J.C.S., 1905, 87, 145) pound, m. p. 79-2— 79-4°, almost completely dis and Engelfeldt (loc. cit.) tho constitution of “ chlor- sociated in tho liquid state, is formed between the two substances, but the shape of the curve does not amino-T ” is given as CGH4Me-S0(:NCl)-0Na,3H,0. permit the composition of this compound to be deter S. J. Gr e g g . Bivalency of carbon. I. Displacement of mined (cf. Hurd, A., 1924, i, 140). F. G. W il l so n . chlorine from diphenylchloromethane. s-Tetra- Tautomerism of the amidines. VII. Methyl- phenyldim ethyl ether. A. M. W a r d (J.C.S., 1927, ation of benzenyl-p-nitrodiphenylamidine [A7- 2285— 2295).—The chlorine group in diphenylchloro phenyl-iV'-jj-nitrophenylbenzamidine]. C. Chew methane is displaced by ethyl alcohol or aqueous and F. L. Pym an (J.C.S., 1927, 2318— 2323).— ethyl alcohol, both alone and in the presence of N-Phenyl-~N'--p-nitrophenylbenzamidine, m. p. 184° sodium hydroxide, to give mainly benzhydryl ethyl (corr.; hydrochloride, m. p. 261°), prepared by an ether together with benzhydrol. Tho velocity co application of tho method of Hill and Cox (this vol., efficients of the reactions at 25° and at 35° under 144), and methyl iodide give a 28-8% yield of Ar-phenyl- each of the above conditions and also in an experi jV'-^-nitrophenyl-JV-methylbenzamidine, and 24-9% ment whero alcoholic sodium ethoxide was used of the IV'-methyl isomeride. These results confirm tho are those of a unimolecular reaction. Thus the suggestion (Pyman, J.C.S., 1923, 123, 3359; A., sodium compounds, which merely accelerate the 1926, 1156) that the preferential alkylation of the reaction, play no direct part in the displacement. nitrogen atom attached to an aryl group of N-aryl-N'- It is suggested that the slowest reaction is the ionis alkylbenzamidines is due to the tendency of the aryl ation of the diphenylchloromethane, which is followed group to attract the double linking into the afS-position. by the rapid reactions of the diphenylmethyl ion If the difference in basicity of the two nitrogen atoms with hydroxyl and ethoxyl ions to give benzhydrol (which must be considerable in the present case) and benzhydryl ethyl ether (cf. Nef, A., 1898, i, 102). determined the proportion of the isomerides in tho Benzhydrol gives s-tetraphenyldimethyl ether on methylation product, a large preponderance of one boiling with dilute hydrochloric acid; on raising tho isomeride would be expected. N-P/tenyZ-N'-p-miro- concentration of the acid the yield of this product phenyl-l$-methylbenzamidine, m. p. 138° [corr.; picrate, falls and diphenylchloromethane finally becomes the m. p. 206° (corr.)], prepared by the interaction of principal product. Boiling 2IV-hydrochloric acid is p-nitrobenzanilide-iminochloride (free from traces without action on s-tetraphenyldimethyl ether, but of hydrogen chloride) and methylanilino in dry the concentrated acid, or better ethereal hydrogen ethereal solution, could not bo prepared by the method chloride, converts it into diphenylchloromethane. of Hill and Cox. N - Phenyl-W -p - nitrophenyl -3ST- G. A. C. G ou gh . methylbenzamidine [oil; hydrochloride -f-EtOH, m. p. Reduction of 2-nitrofluorene. F. E. Cislak, 226° (corr.; with effervescence); hydriodide, m. p. I. M. Eastman, and J. K. Senior (J. Amer. Chem. 225° (corr.); picrate, m. p. 194° (corr.)], was obtained Soc., 1927, 49, 2318— 2322).— Reduction of 2-nitro by the method of Hill and Cox, but could not be fluorene with zinc dust and calcium chloride in isolated from the products of the interaction of boiling aqueous alcohol affords 2 : 2 '-azoxyfluorene, benzanilide-iminochloride and ^-nitromethylaniline. orange-yellow, m. p. 279° (decomp.). Owing to its G. A. C. G ough . insolubility, the latter can be reduced to 2 -amino- Crystalline products formed by the action fluorene only by zinc dust and hydrochloric acid in of aromatic amines on thiosemicarbazide and phenol solution. If this reduction is carried out with its derivatives. H. M acurevitsch (Bull. Soc. glacial acetic acid instead of hydrochloric acid, at chim., 1927, [iv], 41, 1065— 1074).—The mol. wt. of below 40°, the product appears to be tho result of tho crystalline substances of high m. p. obtained by an o-semidine rearrangement of the corresponding the action of aniline, o-, m-, and p-toluidines on hydrazo-derivative. It is colourless, has m. p. 257—- hydrazodithiodicarbonamide, and of o-toluidine on 258° (decomp.) after becoming red at 240— 245°, and phenylhydrazodithiodicarboxylamide (this vol., 777), is considered to be either 2'-amino-2 : 3 '-difluorcnyl- have been determined in various solvents, and the amine or 2-amino-l : 2'-diftuorenylamine. When values obtained show that the formulas previously boiled with acetic anhydride, it yields an oxygen- assigned to them should be halved. On heating with free compound, m. p. 179°, to which the correspond bonzophenono ehloridc these compounds do not give ing alternative constitutions, Z-(2-fluorenyl)-2-methyl- blue colorations (see Tschugaev, A., 1902, i, 630), 2 : 3-fluoreniminazole and \-(2-fliiorenyl)-2-methyl-\ : 2 - and it is concluded that the groupings ’CS'NHg and fluoreniminazole, are ascribed. F. G. W il l so n . •CS'NII- are not present in their molecules. The suggestion that these compounds are substituted Preparation and constants of phenylpropinene tetrazines is abandoned, and they are formulated as and certain of its homologues. L. B e r t and thio-1 : 2 : 4-triazoles, formed by elimination of 1 P- C. D o rie r (Bull. Soc. chim., 1927, [iv], 41, 1171— mol. of hydrogen sulphide from the intermediate 4 A 1062 BRITISH CHEMICAL ABSTRACTS.— A. substance NH2-CS-NH-NH-CS-NIiR, which is ob Actually, when heated in the solution in which it is tained from 1 mol. of the amine and 1 mol. of liydrazo- formed, it undergoes further condensation with dithiodicarboxylamide, by elimination of ammonia. production of what is evidently a mixture (m. p. range H . B u r to n . about 30°). Determination of the amino-group in nitro- 4-Bromo-4'-nitrodiphenyl was nitrated to give arylamines. I. Determination of nitroanilinę 4-bromo-Z : é'-dinitrodiphenyl, m. p. 135°, which on and nitroacetanilide. N. Semiganovsky (Z. anal. further nitration yielded 4-bromo-2' : 3 : 4'-trinitro- Chem., 1927, 72, 27— 30).— The amine is refluxed diphenyl (Le Fèvre and Turner, A., 1926, 1029). with sodium hydroxide solution, which, throughout Small quantities of the latter compound were readily the analysis, is never more concentrated than 25%, converted into 2' : 3 : 4' - trinitro -.4 - aminodiphenyl and the ammonia evolved is collected and titrated (m. p. 192— 193°) on heating in a sealed tube with with standard acid. When the ammo is completely alcoholic ammonia, but the large-scale conversion decomposed, the water-jacket of the reflux condenser proved unsatisfactory. On dissolving 4-bromo- is disconnected, the ammonia being distilled over 2' : 3 : 4'-trinitrodiphenyl in boiling nitrobenzene and through a second condenser. The results obtained passing in dry ammonia, 4 : 4'-bis-op-dinitrophenyl- agree within 0-2%. F. S. H a w k in s . 2 : 2'-dinitrodiphenylamine (II), m. p. 256— 257°, was Determination of secondary nitrosoamine obtained. Under the same conditions, picryl chloride groups. K . L e h m st e d t (Ber., 1927, 60, [£ ], yielded trinitroaniline, l-chloro-2 : 4-dinitrobenzene 1910— 1912).— Reduction of nitrosoamines by mer gave 2 : 4-dinitroaniline, 2 : 5-dichloronitrobenzene cury and concentrated sulphuric acid does not was unaffected, and 4 : 4'-dibromo-2 : 3'-dinitro- generally proceed quantitatively, since the acid fre diphenyl was partly converted into the corresponding quently causes partial conversion into the (7-nitroso- bromo-amino-compound. compound. Reduction may, however, be effected From the nitration product of 2-nitrodiacetyl- with ferrous chloride and hydrochloric acid in boil benzidine, which is mainly 2 : 3'-dinitrodiacetyl- ing solution : NR'R"-NO+HCl+FeCl2=N H R'R"+ benzidine (Le Fèvre and Turner, loc. cit.), 2:5:3'- FeClj-fNO. The liberated nitric oxide is measured. trinitrobenzidine, dark red, m. p. 276° (diacetyl deriv The results are generally somewhat low, since ative, m. p. above 300°), was obtained in the form of reduction to ammonia occurs to some extent and a the sparingly soluble sulphate. The constitution of little nitric oxide usually remains in the evolution this base was proved by its conversion by the per- flask. C-Nitroso- and O-nitro-groups do not cause bromide method into 4 : 4 '-dibromo-2 : 5 : 3'-trinitro- complication. Analyses of diisobutyl-, phenyl- diphenyl, m. p. 251— 252°, which reacted readily with methyl-, diphenyl-, piperidyl-, and acetylphenyl- piperidine to give 2 : 5 : 3'-trinitro-4 : 4'-dipiperidino- nitrosoamines are recorded. H. W r e n . diphenyl, m. p. 160°. The occurrence of this trinitro- benzidine shows that some 2 : 5-dinitrodiacetyl- Orientation effects in the diphenyl series. IV. benzidino must be formed in the nitration of 2 -nitro- Reduction of Bandrowski’s and of Strakosch’s diacetylbenzidine, since the 2 : 3'-compound is dinitrobenzidines, and condensation of the pro unaffected by even more drastic nitrating conditions ducts with benzil. Nitration of 2-nitrodiacetyl- than those used. Nitration of 4 : 4'-dibromo-2 : 3'- benzidine and of 4:4'- dibrom odiphenyl. dinitrodiphenyl yielded 4 : 4'-dibromo-2 : 3' : o'-tri- R. J. W. Le Fevre, D. D. Moir, and E. E. Turner nitrodiphenyl, m. p. 176— 177°, which with piperidine (J.C.S., 1927, 2330— 2339).— The observation of afforded 4 - bromo - 2 : 3' : 5' - trinitro - 4' - piper idinodi- Brady and McHugh (ibid., 1923, 123, 2047) that phenyl, m. p. 194° (cf. Lellmann, A., 1883, 343). Bandrowski’s dinitrobenzidine, m. p. 233° (originally 3 : 4 '-JDinitroA-anilinodiphenyl has m. p. 155— 156°, supposed to be 3 : 3'-dinitrobenzidine, but recently 3 : 2' : ‘i'-trinitroA-anilinodiphenyl, m. p. 190— 191°, shown to be the 2 : 3'-derivative, m. p. 236—237°; Le and 3 : 2' : A'-trinitroA-methylanilinodiphenyl, m. p. Fdvre and Turner, A., 1926, 946), yields the same 212°. W . J. Powell. quinoxaline, m. p. 313° (corr.), as 3 : 3'-dmitro- benzidine (Strakosch’s dinitrobenzidine) when reduced Compounds of aromatic j>-diamines with and subsequently treated with benzil has been sulphur dioxide. I. G. Farbenind. A.-G.— See verified, but the yield from Bandrowski’s dinitro B., 1927, 742. benzidine is small. The latter is very difficult to The two 73-nitroazoxybenzenes. A. Angeli and purify, and it is shown by examining artificial D. Bigiavi (Atti R. Accad. Lincei, 1927, [vi], 5, 819— mixtures that any sample of m. p. 233° or lower 823).— When treated with excess of bromine in contains 2% or more of Strakosch’s dinitrobenzidine, presence of a very small quantity of iron filings, which is sufficient to account for the quinoxaline -p-nitroazoxybenzene (a), m. p. 148° (cf. Angeli and formed. Samples of Bandrowski’s dinitrobenzidine, Alessandri, A., 1911, i, 1045), yields (1) the tribromo- m. p. 237° (uncorr.), yield no quinoxaline. By derivative, C6H2Br3;N :N 0-C GH4-N 02, m. p. 206— analogy with the benzidine-benzil condensation 208°, which is obtained also on brominating mono- product, this quinoxaline should have the structure I, bromonitroazoxybenzene, m. p. 203°, in the cold, and should condense further with benzil at higher and (2) the isomeric ^-nitroazoxybenzene (6). Under temperatures. similar treatment, the latter yields a monobromo- compound, C12H 80 3N3Br, m. p. 135— 137°, which may be identical with the compound, m. p. 127°, described by Valori (Atti R. Accad. Lincei, 1912, [v], 21, i, 794). T. H. Pope. ORGANIC CHEMISTRY. 1063 Reduction of nitro-compounds by aromatic 226— 228°, and 167°, and from p-phenetoleazo-p- ketols. I. Some p-azoxy-compounds. H. B. naphtliylamine, 186°, 267°, and 212°. T. H. P o pe . N isb e t (J.C.S., 1927, 2081— 2086).— Hot alcoholic Action of hydrazines on semicarbazones. III. solutions of henzoin, anisoin, or furoin reduce W . B a ir d and F. J. W ilson (J.C.S., 1927,2114— 2117; aromatic nitro-compounds to the corresponding azoxy - cf. A., 1926, 1141).—That the thermal decomposition compounds in the presence of a trace of sodium of acetone-S-anilinosemicarbazone to give acetone- methoxide or ethoxide. The ketols are oxidised to CO-NTT-NTT the 1 :2-diketones. In this way tho following phenylhydrazonc and 4-aminourazole, T i azoxy-compounds are prepared : p-azoxybe.nzylide.ne- ’ N(NH2)-CO aniline, decomp. 226° (sintering at 185°); p -azoxy- (previously described in error as 1-aminourazole), benzylidene-'p-toluidine, m. p. 217° (decomp.; sintering proceeds through the intermediate formation of at 189—190°); p - azoxybenzylidene - p - aminoaceto- acetonecarbohydrazono and diphenylcarbohydrazide, phenone, m. p. 217° (decomp.; sintering at 187°); is confirmed by the formation of tho same final y-azoxybenzonitrile, m. p. 221°; p -azoxystilbene, m. p. products by the interaction of the hypothetical 271— 272° (dccomp.; sintering at 259°); y-azoxy-2- intermediates. Some dimethylketazine is formed in nitrostilbene, m. p. 208— 210°; -p-azoxy-2 : 3'-dinitro- both reactions probably by the decomposition of the stilbene, m. p. 212° ; y-azoxy-2 : 6-dinitrostilbene, m. p. carbohydrazone. In a similar way pinacolin-8- 270°; ^-azoxy-2-nitro-M-metlioxystilbene, m. p. 208°; anilinosemicarbazone affords pinacolinphenylhydr- -p-azoxy-2-nitro-Z' : 4'-methylenedioxystilbene, m. p. azone, pinacolinazine, and 4-aminourazole; benzyl- 230°; j)-azoxy-2 : Q-dinitroA'-methoxystilbene, m. p. idene-8-anilinosemicarbazone affords benzaldehyde- 297° (decomp.); -p-azoxy-2-nitro-4:'-dimethylamino- phenylhydrazone and 4-aminourazole; acetone-S- stilbene, unmelted at 305°. Methyl and ethyl p -azoxy - diphenylaminosemicarbazone affords acetonediphenyl- cinnamates may conveniently bo prepared by this hydrazone, dimethylketazine, and 4-aminourazole. method. The nitrostilbenes were prepared by a In the last decomposition some of the intermediate modification of Bishop and Brady’s method (J.C.S., compound, tetraphenylcarbohydrazide (Acree, A., 1922, 121, 2367; cf. A., 1916, i, 24) and of them the 1903, i, 861), was actually isolated. Pinacolinazine, following are new : 2:4: 4'-trinitrostilbene, m. p. b. p. 213—216°/17 mm., was identified by comparison 234—235°; 2 : i-dinitro-Z' : 4'-methylenedioxystilbene, with the synthetic product obtained by the inter m. p. 178— 180°; 2 : 4 : §-trinitro-M-metlioxystilhene, action of alcoholic solutions of hydrazine hydrate and m. p. 167— 168°; 2 : i-dinitro-i'-dimethylamino- pinacolin. Attempts to prepare 8-anilinothiosemi- stilbene, m. p. 181° (chloroplatinate, m. p. 211°). carbazones by the interaction of the thiosemi- carbazones of acetone, acetophenone, and dibenzyl G. A . C. G o u gh . Metallic derivatives of azo-compounds. G. B. ketone with phenylhydrazine resulted in the form ation of thiosemicarbazide and the ketonephenyl- Cr ippa (Gazzetta, 1927, 57, 497— 504).— The metallic complexes formed by the union of an atom of copper, hydrazones. Dibenzyl ketone thiosemicarbazide, m. p. nickel, or cobalt with 2 mols. of arylazo-p-naphthyl- 165— 166°, and methyl ethyl ketone 8-anilinosemicarbaz- amine or arylazo-p-naphthol and obtained either by ide, m. p. 137°, are also described. G. A. C. G ough . the action of the metal ammonium sulphate on the Azides. A. A ngeli (Atti R. Accad. Lincei, 1927, ammo- or hydroxy-azo-derivatives in alcoholic [vi], 5, 732— 736).— The molecular structure of the suspension or by boiling solutions of the aminoazo- azides is discussed. The fact that tho presence of a derivatives in aniline or nitrobenzene with powdered small proportion of acid effects the isomerisation of nickel or cobalt exhibit properties which suggest for the nitroso-derivative obtained from benzylmethyl- these complexes formula; of the hydrazine, CH2Ph*N(NO)’NHMe — >• N2Ar type annexed, where X = N H 2 or CH2Ph’NH-NMe-NO, renders it possible that the M OH. These complexes yield the formation of phenyl azide by the action of an acid on azo-derivativc when treated with nitrosophenylhydrazine is accompanied by a similar dilute mineral acid or acetic acid, change : NO-NPh-NH2 — =>- NHPh-NH-NO — > sometimes in the cold; but they remain unchanged NPhIN:N. An analogous transformation is possible when boiled in a strongly alkaline medium. Neither in the conversion of the sodium derivative of nitroso the complexes derived from the benzeneazonaphthols phenylhydrazine into isodiazo-oxides and nitrous oxide nor the aminocupric complexes are obtainable by the by the action of alcoholic nitrite solution : latter of the two methods mentioned, but are readily NHINPhiN'OH — > NO-KNPhiN-OH — -> formed by the former method. NPhlN'OH-f-NgO. It appears likely that the tauto [With U. M a r t e g a n i.]— Cupridi--p-anisylazo-$- meric form of nitrosophenylhydrazine belongs to a wphtliol, C34H280 4iSr,1Cu, forms burnt-sepia needles, group of compounds which contain a quinquevalent m- p. 271°; the corresponding nickel and cobalt nitrogen atom united to the aromatic nucleus, such as complexes have m. p. 279° and 265°, respectively. o:NPh:o, o:NH2Ph, o:npii:nh, o:npii:n-oh. Gupri-, nickelo-, and cobalto-di-o-anisoleazo-fi-naphthols T. H. P o p e . have m. p. 225°, 300° (decomp.), and 254° (decomp.), Diazo hydroxides. L. Ca m b i (Atti R. Accad. respectively. Gupri-, nickelo-, and cobalto-di-j>- Lincei, 1927, [vi], 5, 837— 840).— Our knowledge of phenetoleazo-fi.naphthols have m. p. 267°, 265°, and the structure of the alkali salts of the normal diazo- *24°, respectively. The corresponding complexes from hydroxides is in agreement with the structural formula o-phenetoleazo-fi-naphthol have m. p. 219°, 295°, and ascribed by Angeli to these hydroxides themselves (A., 5 from p-anisoleazo-p-naphthylamine, 157°, 257°,1926, 947). Hantzsch’s views on this question are and 236°; from o-anisoleazo-P-naphthylamine, 170°, refuted. T. H. P o p e . 1064 BRITISH CHEMICAL ABSTRACTS.— A. Organic compounds of quinquevalent bismuth. Nitrosation of phenols. IV. 3 :5-Dichloro- G. Ch a r r ie r (Atti R. Accad. Lincei, 1927, [vi], 5, phenol. H . H . H o d g so n and J. S. W ig n a l l (J.C.S., 889—892).— In hydrochloric acid solution, bismuth 1927, 2216—2221; cf. Hodgson and Moore, ibid., trichloride reacts with aryldiazonium chlorides giving 1923, 123, 2499).— During numerous unsuccessful stable crystalline compounds containing quinque attempts, both direct and indirect, to nitrosate valent bismuth : BiCl3+A rN 2Cl— >-ArN2BiCl4. The 3 : 5-diclilorophcnol, it was found that tho supposed chlorine atoms in these chlorobismuthates are readily 3 : 5-dichloro-4-nitrosophenol obtained by Blanksma replaceable by sulphuric or nitric residues. Benzene- (Rec. trav. chim., 1908, 27, 25) as a by-product in diazonium chlorobismuthate, N2PlvBiCl4, has m. p. the conversion of 3 : 5-dichloroaniline into the phenol, 85— 87° (decomp.); the toluene-o-diazonium com and by Willstatter and Schudel (A., 1918, i, 399) by pound, m. p. 115— 120° (decomp.); toluene-m-diazon- the action of nitrous acid on sodium 3 : 5-dichloro- ium, m. p. 120° (decomp.); toluene-'p-diazonium, m. p. phenoxide, is identical with 3 : 5-dichloroA-nitrophenol, 120° (decomp.); ^-metlioxybenzenediazonium, m. p. m. p. 150° (acetate, m. p. 99°), obtained together with 145— 147° (decomp.); 'p-clilorobenzenediazonium, m. p. 3 : 5-dichloro-2-nitrophe?iol, m. p. 51°, by direct 105— 107° (decomp.); -p-bromobenzenediazonium, m. p. nitration of 3 : 5-dichlorophenol. 3 : 5-Dichloro-2- 135—140° (decomp.). T. H. P o p e . nitrophenol does not form a hydrate (cf. 3-chloro- 2-nitrophenol, Hodgson and Moore, A., 1926, 281). Halogenated tertiary amines. C. S. M a r v e l , 3 : 5-Dichloro-2-aminophenol, m. p. 132°, and 3 : 5-di- W. H. Z a r tm a n , and O. D. B l u th ar d t (J. Amer. chloroA-aminophenol, m. p. 154°, are prepared by Chem. Soc., 1927, 49, 2299—2303).—Treatment of reduction of the nitrophenols with sodium hypo boiling diethylamine with y-phenoxypropyl bromide sulphite. 3 : 5-Dichloro-2-nitroanisole, m. p. 75°, and affords diethyl-y-phenoxypropylamine, (I), b. p. 147— 3 : 5-dichloroA-nitroanisole, m. p. 70°, were prepared 150°/20 mm., df 0-9425, ?ijj 1-4987 [hydrochloride, by methylation of the appropriate nitrophenol. The m. p. 98— 102° (decomp.)], together with diethyldi- latter by reduction with tin and hydrochloric acid y-phenoxypropylammonium bromide, m. p. 77-5— 79°. gives 3 : 5-dichloro-p-anisidine, m. p. 71°, from which When boiled with hydrobromic acid under such 3 : 5-dichloro-4:-?iitrosoanisole, m. p. 125°, was obtained conditions that water and phenol are continuously by oxidation with Caro’s acid. On hydrolysis with boiled off, (I) yields diethyl-y-bromopropylamine hydro concentrated sulphuric acid, it gives colourless bromide, hygroscopic, m. p. 91— 94°. Treatment of 3 : 5-dichloro-i-nitrosophenol, m. p. 165°, dissolving in the latter in ethereal solution with concentrated alkali with a green colour. It resembles the nearly aqueous sodium hydroxide affords the corresponding colourless 3-ehlorobenzoquinone-4-oxime (Hodgson base, (II), b. p. 60—64°/7mm., d f 1-1524, nf, 1-4580, and Moore, loc. cit.) and is possibly better formulated which isomerises rapidly when kept into a quaternary as 3 : 5-dichlorobenzoquinone-4-oxime. No evidence ammonium bromide, m. p. 180— 185°, presumably an of conversion or of geometrical isomerism was 8-membered ring compound (cf. Knorr and Roth, A., obtained. 1906, i, 457). Condensation of (II) with ethyl sodio- 3 : 5-Dichloro-p-anisidine may be prepared from malonate in absolute alcohol affords ethyl y-diethyl- 3-chloro-4-nitroanisole by simultaneous reduction aminopropxjlmalonate, b. p. 163— 170°/23 mm., df and chlorination with tin and concentrated hydro 0-9686, nf, 1-43S0. Treatment of S-phenoxy-n-butyl- chloric acid, whilst iron and acetic acid effect normal amine with ethyl bromide and aqueous sodium reduction to 3-chloro-^-anisidino (cf. Hodgson and hydroxide yields diethyl-B-phenoxybutylamine, b. p. Handley, A., 1926, 515). Tho latter on oxidation 152— 158°/21 mm., df 0-9424, ?i“ 1-4975, from which yields 3-chloroA-nitrosoanisole, deep green, m. p. 59°. diethyl-S-brotnobutylamine, b. p. 68—70°/6 mm., df Since 3 : 5-dichloro-4-nitrosoanisole is 1-0187, n'f 1-4415 (hydrobromide, hygroscopic, m. p. colourless, whilst 3-chloro-4-nitrosoanisole is deep green, the 62— 68°), was obtained as above. When kept, the suppression of colour may be ascribed to the chlorine latter isomerises, presumably into diethylpyrrolidinium atom in tho 5-position. 3 : 5-Dichlorodimetliyl- bromide, m. p. 170— 175°. Ethyl o-diethylaminobutyl- aniline is nitrated by nitrous acid in formic acid malonate has b. p. 170— 175°/24 mm., d f 0-9621, solution, yielding 3 : 5-dichloroA-nitrodimethylaniline, ng 1-4468. F. G. W il l so n . m. p. 142°. The direct nitrosation of 3-chloro-5-iodo- Nuclear carboxylation of aromatic amines. phenol was attempted without success. A. P. T e r e n t ie v and A. M. R u b in ste in (Ber., 1927, W. J. P o w e ll. 60, [B], 1S79— 1882).—Magnesium powder, activated Complex metallic ammines. IX. Introduc by iodine, reacts readily with o-anisidine in the absence tion of nitrophenol radicals into cobaltammine of air, giving the compound (OMe-C6H4*NH)2Mg, complexes. Distinctive behaviour of mononitro- which is transformed by carbon dioxide at 150° into phenoxides. J. C. D u f f and E. J. B ills (J.C.S., magnesium ~N-o-anisylcarbamate. If tho latter com 1927, 2365— 2375).—Unlike o- and m-nitrophenoxides, pound is heated with an excoss of o-anisidine at 250— sodium ^-nitrophenoxide reacts with aquopent- 270° it is converted into 3-amino-2-?nethoxybenz-o- amminocobaltic nitrate to give p -nitraphenoxopent- anisidide, m. p. 178° (NN'-di-o-anisylcarbamide has amminocobaltic p-nitrophenoxide [ I ; X = m. p. 182°); the formyl derivative, m. p. 133°, is more j3-C6H4(N02)‘0-]. This compound is hydrolysed in stable than the anisidide itself. Hydrolysis of tho (I.) [Co(NH3)5X]X 2 [Co(NH3)5,H20]X 3 (II-) anisidide gives o-anisidine and Z-amino-2-rncthoxy- benzoic acid, m. p. 153°, identified by de-amination (III.) [Co(NH3)5X](OH)X and subsequent oxidation to phthalic acid. presence of platinised electrodes to [H20 -Co(NH3)5]X3. H. W r e n . Sodium 2 : 4- and 2 : 6-dinitrophenoxides give simple ORGANIC CHEMISTRY. 1065 aquopentammino-salts, aquopentamminocobaltic 2 : 4- ethers of carvacrol and o-cresol, and anisole yield no dinitrophenoxide (+3H20), and aquopentammino nitroso-derivatives and the reaction thus forms the cobaitic 2 : Q-dinitrophenoxide [II; X = C flH3(N02)2-0-]. basis for the approximate determination of thymol in Sodium picrate gives picratopentamminocobaltic carvacrol; it is shown that carvacrol obtained from picrate (+ 3 H 20) [I; (cf. Morgan sodium cymenesulphonate contains no thymol, the and King, J.C.S., 1922, 121, 1723). This compound sulphonic acid group entering exclusively the position is alternatively prepared by reaction of picric acid ortho to the methyl group. J. W. B a k e r . with carbonatopentamminocobaltic nitrate. If the latter be present in excess, however, a basic salt, Direct introduction of substituents in aromatic picratopentamminocobaltic hydroxypicrate [III; X = mercaptans. T. v a n H ove (Bull. Acad. roy. C6H3(N02)3,0']-|-2H20, is produced. Belg., 1927, [v], 13, 206—224; cf. this vol., 555).— Sodium m-nitrophenoxide reacts with bisaquo- Attempts to brominate p-thiocresol in carbon tetra bisethylenediamminocobaltic bromide, giving bis-m- chloride solution were unsuccessful, the resulting nitrophenoxobisethylenediamminocobaltic m-nitrophen product being di-p-tolyl disulphide, m. p. 45-2°, oxide -fm -nitrophenol [IV; X=m-C6H4(N02)’0 ] + converted into p-nitrobenzoic acid by dilute nitric H20. acid. Under similar conditions p-methylthioltoluene yields 3 - bromo - 4 - methylthioltoluene, m. p. —16°, (IV.) [X 2-Co en2]X ,H X ¿ C o en2Jx 2 (V.) b. p. 275—275-5°, d\* 1-4696. Proof of the con stitution of this compound is afforded by the The o-isomeride gives o-nitrophenol-o-nitrophenoxo- preparation of the same substance from the corre bisethylenediamminocobaltic o-nitrophenoxide [V ; X = sponding mercaptan obtained from 3-bromo-p-tolu- o-C0H4(NO2),O>](+ H 2O). Sodium p-nitrophenoxide idine by Leuckart’s method (A., 1890, 603). Oxid yields, under varying conditions, four compounds : ation with acid permanganate gives 3-bromo-4:-methyl- (A) p-nitrophenol-p-nitrophenoxobisethylenediammino- sulphonyltoluene, m. p. 99— 100°, and 3-bromoA- cobaltic p-nitrophenoxide (V) (-f3H 20); (B) aquo-p- methylsulphonylbenzoic acid, m. p. 202— 203°. Bromin- iiiirophenoxobisethylenediamminocobattic p-nitrophen- ation of tliioahisole in carbon disulphide solution oxide (VI) (+ 2 H 20); (C) aquo-p-nitrophenoxobisethyl- results in the formation of the additive compound, enediamminocobaltic p-nitroplienoxide+p-nitrophenol CGH4Br-SMeBr2, m. p. 90—91°, which is readily (VII) (+ li20 ); and (D) bis-p-nitrophenoxobisethylene- hydrolysed to form p-bromophenylmethylsulphoxide, diamminocobaltic p - nitrophenoxide + p - nitrophenol m. p. 83°, previously described (loc. cit.). Bromin- (IV) (+2H20). The compounds (B) and (C) are ation of p-bromothioanisole in carbon tetrachloride changed in dilute solution in presence of platinised solution at the b. p. gives a dibromo-denva.iive, m. p. electrodes into (D). 48°, oxidised by acid potassium permanganate to the corresponding sulphone, C6H3Br2-S02Me, m. p. 121— (VI.) p ^ P c o e n J ] x 2 [jj^qC oen 2J x 2,H X (VII.) 122°. 4:-Mcihylthiolphenetole, m. p. 21-5°, b. p. 250— 251°, is prepared by treating the corresponding (VIII.) ( ^ ° C o e * ] ° = mercaptan, obtained from jj-phenetidine by Leuckart’s process, with methyl sulphate. Bromination in The colour reactions of the compound (A) and of the carbon tetrachloride solution yields, among other corresponding o-nitrophenol derivative are regarded as products as yet unidentified, 2-bromoA-methxjlthiol- indicating a quinonoid structure for the nitrophenol phenetole, m. p. 17-4°, b. p. 301—302°, d'J 1-4454. The molecule which is linked up with the cobalt in the constitution of this compound is established by its complex through residual valency. Sodium m-nitro preparation from the corresponding mercaptan phenoxide, on the other hand, is not quinonoid in obtained from 2-bromo-p-phenetidine. structure. Sodium 2 : 4- and 2 : 6-dinitrophenoxides J. S. Ca r t e r . react with bisaquobisethylenediamminocobaltic Relative directive powers of groups of the bromide to give aquo-2 : 4-dinitrophenoxobisethylene- forms RO and RR'N in aromatic substitution. diamminocobaltic 2 : 4:-dinitrophenoxide (VI) ( + 1H20) VI. Nitration of m - and p-chlorobenzyl ethers and aquo -2:6- dinitrophenoxobisethylenediammino - of guaiacol. A. E. O x f o r d and R . R o b in so n cobaltic hydroxy-2 : 6 dinitrophenoxide (VIII). Sodium (J.C.S., 1927, 2239—2244).—The directive powers of picrate gives aquopicratobisethylenediamminocobaltic substituted benzyloxy-groups are studied by putting picrate (VI) (+ 4 H 20). M. Cl a r k . them separately in competition with methoxyl, and it has been shown that the directive powers of the m- Detection and determination of thymol. F. W. and p-nitrobenzyloxy-groups are approximately equal K lengstedt and E. Su n dstrom (J. pr. Chem., 1927, (67; M e0=100 ; A., 1926, 397). By the nitration [ii], 116, 307—313).—Whilst thymol ethyl and methyl of m- and p-chlorobenzyl ethers of guaiacol, and ethers are unaffected either by alcoholic hydrogen analysis of the products, wrhich behave thermally as chloride or by dilute aqueous alcoholic sodium nitrite, binary mixtures, it is now found that the m-chloro- the two reagents together yield nitrosothymol. This benzyloxy-group has the directive power 69, and has m. p. 169— 170° (higher than that usually given), y-chlorobenzyloxy- 82. The close approach of the but is reduced to aminothymol of the accepted m. p. directive power of m-chlorobenzyloxy- to that of The best yields (93 and 90%, respectively) of the m-nitrobenzyloxy- shows that the electron affinity of nitroso-compounds are obtained by the action of chlorine is almost as strong as that of the nitro-group, aqueous sodium nitrite on a solution of thymol or its whilst the higher value for p-chlorobenzyloxy- is methyl ether in alcohol-water-acetic acid. The interpreted as being due to conjugation. The 1066 BRITISH CHEMICAL ABSTRACTS.----A. following were prepared : 2-m-chlorobenzyloxyanisole, cholesterol dibromide is not. The effect increases m. p. 46—47°, b. p. 207— 208°/15 m m .; 4-rairo-2-m- with rise in temperature, cholesterol at temperatures chlorobenzyloxyanisole, m. p. 129— 130-5°; 5-nitro- above its m. p. showing photo-activity without 2-m-chlorobenzyloxyanisole, m. p. 121°; 2-^-chloro- irradiation due to spontaneous oxidation. benzyloxyanisole, m. p. 70° (a crystallographic P. W . Clu tte r b u c k . description is given); 4-nitro-2-^-chlorobenz.yloxy- Phosphorus derivatives of sterols. H. v o n anisole, m. p. 115— 117°; o-nitro-2--p-chlorobenzyloxy- E u l e r and A. B ern ton (Ber., 1927, 60, [B], 1720— anisole, m. p. 120— 120-5° (crystals described). The 1725).— Cholesterol is converted by successive treat nitration product of 2-?>i-chlorobenzyloxyanisole con ments with phosphorus trichloride and water into tains 41% and that of 2-p-chlorobenzyloxyanisole cholesteryl phosphite, m. p. 158— 159° (aniline, salt, 45% of the 5-nitro-isomeride. The m. p. of mixtures C33H52NP03> m. p. 170°), transformed by bromine of the 4- and 5-nitro-isomerides in each case are given. into the d? 6 totoo - c o mp o u nd, m. p. 148°, also obtained W . J. P o w e l l. by brominating cholesterol and treating the product Chlorination of creosol. W. Qv ist [with G. with phosphorus trichloride. Acetic anhydride con W uk] (Ber., 1927, 60, [B], 1847— 1850).— Creosol, verts the ester into cholesteryl acetate, m. p. 114°. dissolved in glacial acetic acid, is converted by Cholesterol and phosphoryl chloride in benzene afford chlorine in the dark or in diffused daylight at 20— 25° dicholesteryl phosphate, m. p. 195— 199°, which is into 2:5: 6-trichlorocreosol, m. p. 130— 131°, which, also obtained when phosphoryl chloride is added to in alcoholic solution, can readily be titrated with alkali an equivalent quantity of cholesterol in pyridine. If, hydroxide in the presence of phenolphthalein. however, a solution of cholesterol in pyridine is slowly Further chlorination at 100° affords pentachloro-3 : 4- added to the chloride in the same solvent and the diketotetrahydrotoluene (anhydrous, monohydrate, and product is treated with water, monocholesteryl phos dihydrate, m. p. 86— 88°). H. W r e n . phate, m. p. 195— 196°, is produced. The latter ester is precipitated from alcoholic solution by cadmium Fission of the methylenedioxy-group. E. chloride; its sodium salt is described. H. W r e n . Spa th and H. Q u ie t e n sk y (Ber., 1927,60, [J3], 1882— 1890).—With the object of elucidating the most Action of phosphorus pentabromide on the promising conditions for the removal of the methylene- isomeric (3-methoxyphenylethyl alcohols. J. B. dioxy-group from methylene ethers with the sub Shoesmith and R. J. Connor (J.C.S., 1927, 2230— sequent isolation of the dihydroxybenzene thereby 2234).— With phosphorus pentabromide in benzene produced, the behaviour of piperonylic acid, pyro- solution the isomeric p-methoxyphenylethyl alcohols catechol methylene ether, and dihydrosafrole has been give nuclear-brominated derivatives of the expected investigated. The action of concentrated acids on (3-methoxyphenylethyl bromides, the orientation of these compounds gives complex condensation pro which has been proved by elimination of hydrogen ducts of the liberated formaldehyde and phenolic bromide and subsequent oxidation to the corre substance. It is therefore necessary to conduct sponding bromomethoxybenzoic acid, [i-o-Methoxy- operations in the presence of a compound which reacts phenylethyl alcohol, b. p. 130— 131°/11 mm., prepared more readily than the liberated o-dihydroxybenzene from o-bromoanisole (Grignard, A., 1905, i, 593; with formaldehyde. For this purpose phloroglucinol Shoesmith and Connor, this vol., 962) yields $-t>-bromo- may be replaced by the cheaper resorcinol or phenol. 2-methoxyphenylethyl bromide, m. p. 55°, b. p. 160— Methylene ethers of phenolic bases may be hydrolysed 165°/12 mm. : p-m-methoxyphenylethyl alcohol, b. p. by treatment with sulphuric acid (d 1-39) at 100° in 135— 137°/12 mm., affords \i-Q-bromo-'.i-methoxyphenyl tho presence of phloroglucinol or resorcinol. If the ethyl bromide, b. p. 163— 165°/13 mm.; p-p-methoxy- methylene ether and the fundamental phenol are only phenylethyl alcohol, b. p. 138— 140°/11 mm., m. p. slowly sulphonated at the ordinary temperature, the 24°, gives fi-Z-bromoA-methoxyphenylethyl bromide, change can frequently be effected by concentrated b. p. 187— 188°/19 mm., with excess of phosphorus sulphuric acid with addition of phloroglucinol, pentabromide, whilst with a limited quantity, resorcinol, or phenol. If these methods give poor yields it is advisable to try the effect of fuming hydro P p-methoxyphenylethyl bromide, b.p. 130— 131°/11 mm., is obtained. All these bromides are non-pungent and chloric acid at 100— 130° in a sealed tube in the non-lachrimatory. P-Phenylethylamine with nitrous presence of phenols which combine with formaldehyde. acid in hydrochloric acid solution gives considerable In the absence of other groups capable of reacting with quantities of p-phenylethyl chloride, whilst with magnesium methyl iodide, the methylenedioxy- nitrous acid in sulphuric acid solution poor yields eompound may be transformed by the Grignard of the alcohol are obtained. m-Methoxybenzaldehyde reagent into the monoethyl ether, which is subse with nitromethane and alkali yields m-7iiethoxy-u- quently hydrolysed by hydriodic acid. H. W r e n . nitrostyrene, light yellow, m. p. 93— 94°, which on Photoactivity of cholesterol. J. StM t e s k y treatment with zinc dust and acetic acid affords (Biochem. Z., 1927, 187, 388— 397).— Ultra-violet m-methoxyphenylacetaldoxime, m. p. 92-5— 93°. Re rays have a much stronger effect on cholesterol than duction of the latter by means of sodium amalgam X-rays and the latter are a little stronger than sun yields a small quantity of p-m-methoxyphenylethyl- light. The photo-activity is due to the production amine, but this substance is more readily prepared by from cholesterol in the presence of oxygen of a volatile the method of Haworth, Perkin, and Rankine (A., substance and is probably dependent on the presence 1924, i, 1098). A trustworthy method for the prepar of the double linking, since, whereas cholesterol ation of o-methoxybenzaldehyde from salicylaldehyde and its stearate and benzoate are photo-activated, is described. ” W . J. P o w e ll. ORGANIC CHEMISTRY. 1067 Reactions of sodium compounds of aromatic aminodiphenylethan-o.-ol, m. p. 228°; from pp'-te,tra- ketones. I. Synthesis of triarylcarbinols and methyldiaminobenzophenone and pp'-tetraethyldi- of triarylmethane dyes. E. H. R o d d and F. W. aminodiphenylmethane, aa-4 : 4'-tetramethyldiamino- L in ch (J.C.S., 1927, 2174— 2178).—pp'-Tetramethyl- diphejiyl - ftp, - 4 : - tetraethyldiaminodiphcnylethan-x-ol, diaminobenzophenone (Michler’s ketone) reacts with m. p. 229— 230° (corresponding ethylene, m. p. 212°); sodium in an inert solvent to form a sodio-compound, from acenaphthene and Michler’s ketone, 4 : 4’-tetra- which in turn reacts with aromatic chloro-compounds, methyldiaminodiphenylacenaphthenylcarbinol, m. p. 232° if these are concurrently added, to give the sodium (dehydrated by boiling aqueous hydrochloric acid salt of a triarylcarbinol. The reaction constitutes a to 4 : 4:'-tetramethyldiaminodiphenylmethyleneacenaphth- new synthesis of triarylcarbinols and of dyes from ene, m. p. 209°); from fluorene, 4 : 4’-tetramethyldi- them. Michler’s ketone in this way affords the aminodiphenylmethylenefluorene, m. p. 239—240°. following substances : from chlorobenzene, pp'-tetra- The last compound is formed by dehydration of the methyldiaminotriphenylearbinol; from o - chloro- carbinol at a stage in the preparation not determined. toluene, ’p’p'-tetramethyldiaminodiphenyl-o-tolylcarbinol, Toluene is unattacked when less than 1 atomic m. p. 132-5°, and hi presence of toluene, pp'-tetra- proportion of sodium is taken for the reaction with methyldiaminodiphenylbenzylcarbinol (see following Michler’s ketone in toluene solution, the principal abstract), m. p. 190° [basification of the oxalate of products being Michler’s hydrol, p-dimethylamino- the former substance with ammonia yields pp'-ieira- benzoic acid, and crystal-violet base. methyldiaminodiphenyl-o-lolyhnethylamine, m. p. 163°, G. A . C. G o u gh. and reduction with zinc and 2A7'-hydroehloric acid [Tetraphenylethane dyes.] F. K e h r m a n n (Ber., yields pp'-tetramethyldiaminodiphenyl-o-tolylmeth- 1927, 60, [2?], 1913— 1914).— The tetraphenylethane ane, m. p. 102° (cf. Noelting and Saas, A., 1913, i, dyes described by Wizinger (this vol., 764) can readily 522; Noelting and Gerlinger, A., 1906, i, 607)]; from be formulated as quinonoid di-imonium or dioxonium 4-chloro-m-xylene, Tpp'-tetrametkyldiaminodiphenyl- salts; there is no evidence in favour of the carbonium mA-zylylcarbinol, m. p. 145°; from p-chloroanisole, structure. H. W r e n . 'p'p’-telramethyldiaminodiphenyl--p-a7iisylcarbinol, m. p. 153°; from (3-chloronaphthalene, pp’-tetramethyldi- Colour and chemical constitution. XXI. aminodiphenyl-$-naphthylcarbinol, m. p. 181°; from Methyl derivatives of the phenolphthaleins. J. a-chloronaphthalene, -pip'-tetramethyldiaminodiphenyl- M o ir (Trans. Roy. Soc. S. Africa, 1927, 14, 233— a-naphthylcarbinol, m. p. 167° (basification of the 236).—^ince the complete series of bromine deriv oxalate with ammonia gives pp'-tetramethyldiamino- atives of phenolphthalein could not be obtained diphenyl-ct-naphthylmethylamine, m. p. 186°). The (cf. A., 1921, ii, 365), the author has prepared and aodto-compound of pp'-tetraethyldiaminobenzophen- examined ten of the possible methyl derivatives, and, one reacts with p-chloronaphthalene to afford pp'- in addition, plienoltetrahydro-a-naphtholphthalein tetraethyldiamino-$-naphthylcarbinol, m. p. 177°. The (X 584) phenolthymolphthalein (X 578), phenolcarv- carbinols form green salts with acids which dye tannin- acrolphthalein (X 580), thymolphthalein (x 597), mordanted cotton bright green shades. carvacrolphthalein (X 601), pp'-phenol-a-naphthol- G. A. C. G ough. phthalein (X 601), pp'-a-naphtholphthalein (X 650), Reactions of sodium compounds of aromatic phenol - 8 - hydroxyquinolinephthalein (X 598), and ketones. II. Their reaction with methyl and phenol-6-iodo-o-cresolphthalein (X 576). All the methylene groups and their products of decom values found for these sixteen compounds agree position. E. H. R o d d and F. W. L in c h (J.C.S., within experimental error with the values obtained 1927, 2179—2188).—A toluene solution of Michler’s by adding to the number 554 tho calculated additive ketone reacts with sodium to give pp'-tetrametliyl- value for each substituent (cf. A., 1921, ii, 6; 1923, diaminodiphenylbenzylcarbinol (preceding abstract) ii, 108). Comparison of tho value of X calculated for and Michler’s hydrol together with small amounts of 2 : 3-diethylphenolphthalein (577) with that observed p-dimethylaminobenzoic acid, hexamethyltriamino- for phenoltetrahydro-a-naphtholphthalein (584) indic triphenylcarbinol, and dimethylaniline. This new ates that the effect of ring closure of the two adjacent type of reaction may be expressed : ethyl groups into the eyefobutane ring is only + 7 , 2(NMe2-CGH,)2CO +2N a+P hM e= a result in agreement with previous observations (NMe2-C6H4)2CH-ONa + (NMc2-C6H4)2C(ONa)-CH2Ph. on tho absorptions of dihydroxyxanthhyclrol and Acids form blue salts with the benzylcarbinol and, on succinylfluorescein. Phenol-p-cresolphthalein shows heating, convert it into $$-pp'-tetrdmethyldiamino- a band at X 563, phenol-as-m-xylenolphthalein, 573, diphenylstyrene, m. p. 135°. Oxidation with lead phenol-as-o-xylenolphthalein, 578, phenol-p-bromo- peroxide of the benzylcarbinol yields phenylacetic acid, phenolphthalein, 559, phenolbromo-o-cresolphthalein, and of the styrene, first a blue dye, then benzaldehyde. 570, phonolbromo-p-cresolphthalein, 569, phenol-s.- By extension of this reaction to substances containing m-xylenolphthalein, 572, phenol-^-cumenolphthalein, a methylene group, the following are prepared : from 581, phenol-P-naphtholphthalein, 570, broad, phenol- pp'-tetramethyldiaminodiphenylmethane, octamethyl- 2-a-naphtholphthalein, 612, whence the additive teira-aminotetraphenylethanol, m. p. 255°, oxidised to effects appear to be, 3- and 5-methyl-, 11; 3- and a violet dye by lead peroxide and converted by warm 5-bromo-, 7; 4-methyl, 13; 6-methyl-, 7. sulphuric acid into the corresponding ethylene, m. p. R. B r ig h tm a n . 314—316°; from pp'-tetraethyldiaminobenzophenone Pinabietic acid. O. A s c h a n and P . L e v y [w ith and pp' . tetramethyldiaminodiphenylmethane, eta- H. B ru n o tte] (Ber., 1927, 6 0 , [B], 1923— 1927).— 4 : i'-tetraethyldiaminodiphenyl -fipA : 4 '-tetramelhyldi- Pinabietic acid yields tetrahydroxyabietic acid when 1068 BRITISH CHEMICAL ABSTRACTS.— A. oxidised by potassium permanganate and isophthalic concluded that (I) is the primary product of the above acid when treated with warm nitric acid. The pro bromination, (II) being subsequently produced from duction of the tetrahydroxy-acid establishes the (I) by the action of the hydrobromic acid liberated. presence of a common component in pinabietic acid Bromination of cycfopropane-1 : 1-dicarboxylic acid and abietic acid from American colophony, whereas in carbon tetrachloride in ultra-violet light affords the production of isophthalic and irans-hoxahydro- bromo- p-bromoethylmalonic acid. In chloroform, the phthalic acids from the two parent acids is evidence product is a viscous oil, which loses carbon dioxide against the presence of one and the same compoimd on distillation, with formation of 2-bromocyclopropane- in each. ' H. W r e n . 1 -carboxylic acid, b. p. 140°/20 mm. Bromination of ethyl 1 -cyanocycfopropane-1 -carboxylato affords ethyl Manasse’s ketonic acid, C10H16O3, from cam- 2-bromo-l-cyanocycloprojKine-l-carboxylale, and ethyl phorquinone. M. Bredt-Savelsberg, K . Zau n - a.y-dibro?no-0L-cyanobutyrate, b. p. 136— 140°/11 mm. brecher, and L. K nieke (Ber., 1927, 60, [JB], 1801— Bromine is without action, in ultra-violet light, on 1808; cf. A., 1903, i, 45).— The ketonic acid, C'ioH i 603, cyanocycZopropane and l-cyanocycZopropane-l-carb- obtained from camphorquinone by the method of oxylic acid. Hypochlorous and hypobromous acids Manasse and Samuel (loc. cit.) has m. p. 67— 68° and iodine monochloride do not react with cyclo- (+ H 20), b. p. 150°/3 mm. (anhydrous); the semi- propane-1 : 1-dicarboxylic acid or 1-cyanocyciopro- carbazone, decomp. 220° and methyl ester, m. p. pane-l-carboxylic acid. F. G. W il lso n . 81— 83° (cf. Gibson and Simonsen, A., 1925, i, 919), are described. The ethyl ester, b. p. 115— 117°/ Catalytic reduction of certain hydrophthalic 3 mm., d“ 3 1-0382, n“ 3 1-46858, [«]',? +38-52°, yields anhydrides. F. P. M a z za [with G. Di M a s e , two isomeric semicarbazones, needles and leaflets, A. CALd, and A. Crem on a] (Rend. Accad. Sci. fis. mat. decomp. 216-4°. The acid is proved to be 2 : 2 : 3- Napoli, 1926, [iii], 32, 137— 146).—See this vol., trixnethylcyclohexan-i-one-l-carboxylic acid (cf. Gibson 664, 665. and Simonsen, loc. cit.) by the ability of its methyl Nature of the alternating effect in carbon and ethyl esters to yield benzylidene derivatives, b. p. chains. XXI. Directive influence of the 180°/l-75 mm. and 150— 155°/0-3 mm., respectively, groups -CH2-CH(C02Me)2, -CKCfCOjMeJj, thus proving the presence of the •CO,CH2* group in -CtCOsMe^CH,,, and -CH:CH-CH:C(C02Me)2 in the ring. Bromination of the anhydrous acid in aromatic substitution. J. W . B a k e r and A. chloroform solution without cooling gives the di- E ccles (J.C.S., 1927, 2125—2133).—The following bromoketonic acid, C10H14O3Br, in. p. 158— 159° nitrations were effected by addition of the ester to (decomp.), whereas at 0° the monobromolactone, nitric acid (d 1-49; 10 times the weight of ester) at C10H13O3Br, m. p. 116— 117°, is obtained, converted — 15° and the proportion of isomerides in the product by cold sodium carbonate solution into the substance, determined by oxidation to the nitrobenzoic acids (this Ci0H12O3, m. p. 211— 212°. 2 : 2 : 3-Trimethylcf/cZo- vol., 454). Methyl benzylmalonate gave 8% of m- hexan-4-ol-l-carboxylic acid, m. p. (anhydrous) 132— and 68% of p-nitro-derivative; methyl benzylidene- 134°, prepared by reduction of the ketonic acid by malonate, b. p. 174— 177°/15 mm., m. p. 41°, prepared sodium amalgam in the presence of carbon dioxide, by the condensation of benzaldeliyde and methyl is converted by acetic anhydride at 140— 150° into malonate, gave 3% of m- and 67% of p-nitro-deriv- a mixture of the corresponding acetyl derivative, ative (65% of methyl jj-nitrobenzylidenemalonate C12H20O4,H2O, m. p. 85— 87°, and the anhydride, isolated); methyl atropate gave 5% m- and 55% p- [C9H16(0Ac)*C0]20, m. p. 115— 116°. H. W ren. miro-derivative (m. p. 110°); methyl cinnamylidene- Spectrophotometric comparison of natural malonate gave less than 1% of m- and 40% of p- and synthetic thyroxines. E. A b d e r h a l d e n and nitro-derivative. Partial decomposition of the nitra E. R ossner (Z. physiol. Chem., 1927, 169, 223— tion product takes place in the last case unless the 225).—The absorption curves of natural thyroxine nitration mixture is poured into alkaline ice-water, and a commercial synthetic preparation (Hoffman- the precipitate removed and rapidly dried in a vacuum. La Roche) prepared by the method of Harington and These results are in agreement with the previous Barger (this vol., 358) .appear to be identical. observations (loc. cit.) as to the propagation of the A . W o rm al l. m-orienting effect of the fractional dipoles of the Suggested mechanism of the splitting of the carboxyl groups through the side-chain. The follow cyclopropane ring by bromine. B. H. N ic o l et ing compounds were prepared for comparative and H. Sa t t l e r (J. Amer. Chem. Soc., 1927, 49, purposes : methyl -p-nitrobenzylidenemalonate, m. p. 2066— 2071).—The action of bromine on ethyl cyclo- 136— 137°, from p-nitrobenzaldehyde and methyl propane-1 : 1-dicarboxylate affords ethyl 2-bromocyc\o- malonate; methyl m-nitrobenzylidenemalonate, m. p. propane-1 :1 -dicarboxylate (I), b. p. 135— 140°/15 99— 100°; methyl o-nitrobenzylidenemalonate, m. p. mm., and ethyl bromo-g-bromoethylmalonate (II), 65— 66°; methyl o-nitrobenzylmalonate; m-nitrobenzyl- b. p. 146— 151°/10 mm., neither of which could be malonic acid, m. p. 164° (decomp.; amide, m. p. 203°; obtained free from the other by repeated fraction methyl ester, oil), prepared from m-nitrobenzyl ation. The former preponderates when the reaction chloride, methyl malonate, and sodium, methoxide in is carried out at a low temperature. Hydrolysis of methyl alcohol; methyl di-m-nilrobenzylmalonate, (II) with boiling aqueous hydrobromic acid, with m. p. 162— 162-5° (by-product in the previous pre subsequent treatment of the product with silver oxide, paration) ; methyl p-nitrobenzylmalonate, m. p. 82-5— affords ay-dihydroxybutyric acid, which is also 83-5°; methyl cinnamylidenemalonate, m. p. 67°, obtained in the same way from (I). It is therefore obtained by esterification of the acid; inethyl m-nitro- ORGANIC CHEMISTRY. 1069 cinnamylidenemalonate, m. p. 125— 126°, prepared by requisite amine; amide (+ 3 H 20), m. p. 136°, re condensation of m-nitrocinnamaldehyde and methyl solidifying at 180° and again melting at 220°; methyl- malonate; methyl o-nitrocinnamylidenemalonate, m. p.' amide (+ H sO), m. p. 186°; dimethylamide, m. p. 114°; methyl y-nitrocinnamylidenemalonate, m. p. 179°; ethylamide, m. p. 159°; propylamide, m. p. 146— 147°. G. A. C. G o u gh . 146°; allylamide, m. p. 144°; benzylamide, m. p. Diphenyl series. VII. Relative stability of 240°; piperidide, m. p. 246°. Deoxycholamide, m. p. optically active diphenic acids. F. B el l and 186° after softening at 162°, deoxycholmethylamide, P. H. R obinson (J.C.S., 1927, 2234— 2239).— The m. p. 168°, and deoxycholdimethylamide, m. p. 203°, “ obstacle ” theory advanced to account for the are described. H. W r e n . asymmetry of certain diphenyl derivatives (cf. this vol., 876) is supported by new experiments on optic Tautomerismin the phthalonic and phthalide- ally active diphenic acids. As may be predicted, carboxylic acid series. A. Co rn illo t (Ann. Chim., 6-nitrodiphenic acid, with only three groups in the 1927, [x], 7, 275—-313, and 8, 120—205; cf. this vol., central position, is optically less stable than 562).—The relations between phthalonic acid and its 4 : 4' : 6 : 6'-tetranitrodiphenic acid, which resists anhydride and their derivatives and compounds of racemisation by boiling acetic anhydride to a much the phthalidecarboxylic acid series afford little greater extent. d-6-Nitrodiphenic acid has [a]5401 evidence of tautomerism or of the existence of desmo- +65-2° (c=3-01 in ethyl alcohol), [a]M(J1 —434° (c= tropic mixtures of isomerides. Throughout this series 4-73 in 0-426AT-sodium hydroxide); Z-6-nitrodiphenic of compounds each grouping of substituents appears acid has [a]5461 —66-4° (c=4-91 in ethyl alcohol), to involve a characteristic redistribution of the affinity M.14G1 +433° (c=4-69 in 0-261iV-sodium hydroxide); capacities and in any reaction a new and independent Z+dZ-tetranitrodiphenic acid, m. p. 224— 226°, has distribution takes place. This behaviour is attributed Wwm —138-5° (c= T 7 in ethyl alcohol), whilst d-tetra- to the unstable nature of the linkings of the carbon nitrodiphenic acid, m. p. 226— 227°, has [a ]^ +142-3° atom occupying the a-position with respect to the (0-3696 g. in 20 c.c. of ethyl alcohol). By the action aromatic ring, this quaternary lactonic carbon being of thionyl chloride on Z-6-nitrodiphenic acid, the surrounded by saturated radicals, and also to the Z+eZZ-dichloride, m. p. 65— 68°, [a]M51 —209-5°, is strong residual affinity of the ketonic oxygen. In obtained. Attempts to resolve 5-nitrodiphenic acid consequence, compounds of this series cannot saturate (Schmidt and Lumpp, A., 1909, i, 34) and 2 : 2'-di- their affinity capacities in either the ketonic or the nitrodiphenyl-4 : 4'-dicarboxylic acid were unsuccess lactonic structure. The complex affinities of the ful. 5-Nitrodiphenic acid readily forms an anhydride, keto-lactonic system lead tho authors to propose m. p. 193— 195°, and with sulphuric acid easily partial valency formulae (cf. Skraup, A., 1919, i, 598), undergoes condensation forming 6(f)-nilrofluorenone- which are non-rigid and indicate the energy conditions 4-carboxylic acid, m. p. 282°, whilst 4:4': 6'-trinitro- of the linkings. diphenic acid is unaffected by sulphuric acid at 160°. Oxidation of tetralin in aqueous suspension at 64— 5-Nitrofluorenone-4-carboxylic acid (Moore and Hunt 68° by addition of potassium permanganate affords ress, this vol., 665) cannot be resolved by crystallis only 56% (cf. von Braun and Braunsdorf, A., 1924, ation of its morphine or quinidine salts, this result i, 48) of the theoretical yield of phthalonic acid, m. p. being interpreted as indicating that the 4 : 5-positions 148— 149° (hydrate, + 2 H aO, m. p. 37°). The acid of fluorene are further apart than are the 6:6'- is dibasic with thymol-blue, phenolphthalein, or positions in a diphenic acid. 2:5:7(l)-Trinitro- litmus as indicators, but only monobasic with methyl- jluorenone-i-carboxylic acid, obtained by the action orange (cf. Tcherniac, A., 1898, i, 263; 1917, i, 33). of nitric acid (d 1-5) at 100° on 5-nitrofluorenone-4- Anomalies observed in the dissociation of phthalonic carboxylic acid, has m. p. 254— 255°; the quinine acid in aqueous solution are attributed to anomalies salt of 4-nitrodiphenic acid has m. p. 180° (indef.), X'(0H)-C02- [a]5151 +106-4°, but the liberated 4-nitrodiphenic acid in the mobility of the ions CGH4<^ ^>0 and is inactive. W. J. P o w e l l. C H •"C'O' CO \6 4 / \ , tho structure of tho monobasic ion Constitution of acids formed by decomposition CO C02- of cholic acid. W. B orsohe (Z. physiol. Chem., affording an explanation of the weakness of the acid 1927, 1 69, 306— 307).—A reply to the criticism by (K = 9xl0~5) as compared with benzoic acid. It is Wieland (this vol., 767) of a previous paper (Borsche suggested that the increased conductivity observed and Frank, this vol., 459). A. W o rm all. by Boeseken (A., 1921, i, 844) on addition of boric Constitution of the bile acids. XII. Chol- acid is due to hydration and formation of boric acid amine, amides of cholic and deoxycholic acids. complexes with the neutral molecule only of phthalonic W. B orsche and A. Sc h w arz (Ber., 1927, 6 0 , [B ], acid, the proportion of neutral molecules decreasing 1843— 1846).—Repetition of the work of Curtius (A., as the dilution increases. In view of the readiness 1906, i, 400) and of Bondi and Müller (A., 1906, i, with which phthalonic acid undergoes hydration, no 633) has confirmed the transformation of ethyl cholate conclusions as to the structure of the anhydrous acid into cholylethylurethane, but the conversion of the can be reached from the reactions of phthalonic acid latter substance into cholamine could not be effected in aqueous solution. With hydroxylamine in neutral and the identity of the latter compound appears aqueous solution phthalonic acid appears to afford insufficiently established. The following derivatives first an oxime hydrate, °f cholic acid have been prepared by shaking freshly- COaH'CeHj-CiOHXNH-OHJ'CO^, which is unstable prepared cholazide in aqueous suspension with the and affords phthalic acid derivatives by loss of 1070 BRITISH CHEMICAL ABSTRACTS.----A. carbon dioxide. The corresponding oxime acetate, toluene at 30°; the inactive form is also obtained C02H-CcH1-C(0Ac)(NH-0H)-C02H, obtained in cold with zinc ethyl iodide. On hydrolysis with alcoholic acetic acid, decomposes at 100° into phthalimide, potassium hydroxide, both isomerides afford phthal water, acetic acid, and carbon dioxide, but no phthal onic acid and phthalide-a-carboxylic acid. imide was observed in the decomposition of Graebe The foregoing facts indicate a lactone structure for phthalonic acid, but the formation of a-chloro- and Triimpy’s anhydro-oxime, o o o phthalide-a-carboxylic acid (III) from phthalonic (A., 1898, i, 318). In alkaline solution the latter anhydride (I) involves the opening of the glutaric oxime afforded phthalamic acid, for which a theor ring : etical explanation is offered. With hydroxylamine cci-cocr c 0H, CO-COC1 hydrochloride and sodium acetate in acetic acid at -> CcH'O^^CO-CI „< 100°, phthalonic acid affords, in addition to the <£° anhydro-oxime, a little of a neutral substance sub (I.) (II.) (III.) liming at 250°, C22H140 7N4 or C22H4fi0 7N4. Dehydra possibly an unstable intermediate chloride (II) is first tion of the oxime hydrate with cold acetic anhydride formed (cf. Haller and Guyot, A., 1900, i, 170). The yields o-cyanobenzoic acid; dehydration at 20° also formation of a-chlorophthalide-a-carboxyl chloride affords the nitrile, and it is suggested that an unstable from phthalonic acid is, however, more easily inter oxime, C02H-CgH4,C(N,0H)-C02H, forms an inter preted on the basis of a ketonic structure for phthal mediate stage in all cases, the anii-form of which onic acid. The authors propose the term “ meso- readily cyclises to the known anhydro-oxime, the merism ” for the structural relationships of this type, syn-iorm of which affords the nitrile at 20°, or and structural formulas involving partial valencies phthalamic acid at 0°. Formation of phthalamic acid are proposed for the chlorophthalidecarboxylic deriv from the anhydro-oxime at 100° is attributed to atives (IV), phthalonic acid (V), and phthalonic simple oxidation of the phthalonic acid by hydroxyl anhydride (VI) : amine. Phthalonic anhydride, m. p. 190— 191° (decomp.), ÇOR 0O2H is best obtained by dehydration of the acid with /C—O !—O acetyl chloride. Using acetic anhydride, the reaction c gh / C0H,, y product may contain, according to the duration of \ * > C 1 CO-OH heating, up "to 50% of a-acetoxyphthalide-a-carboxylic (IV.) (V.) acid, decomp. 180°, also obtained by suspending- phthalonic anhydride in glacial acetic acid; it is Phthalonic dianilide, m. p. 217—218°, affords with phenylcarbimide a derivative, decomposed by water or alcohol into phthalonic acid and acetic acid or ethyl acetate. With aniline C O < ^ oi> C < ORGANIC CHEMISTRY. 1071 phthalonimide. With hydroxylamine in neutral able oil, which by the action of semicarbazide is shown alcoholic solution phthalonic acid affords only neutral to be a mixture of the neutral lactonic and ketonic products (the normal ketoxime, esters. In alcoholic solution in presence of sulphuric acid methyl a-chlorophthalide-cc-carboxylate affords CcHi< c o ^ H H^CO lN'HPh> being therefore absent), only the neutral lactonic ester, and there is no evidence an oxime, m. p. 168°, which dissolves in dilute potass that the lactonic and ketonic esters are to be regarded ium hydroxide, and on hydrolysis with hydrochloric as desmotropic forms. R. B r ig h t m a n . acid affords phthalic acid, aniline, and ammonia, together with a smaller amount of a substance, m. p. Action of aminoacetals on phenols. II. O. 168°, for which the structure (IX) is proposed. The II in sberg and R. M e y e r (Ber., 1927, 60, [jB], 1914— oxime, m. p. 168°, is evidently a-hydroxylamino- 1916).—The product of the action of aminoacetal phthalide-a-carboxyanilide. Both substances are also on gallic acid, regarded previously as r-p-amino-a- formed from hydroxylamine and phthalonanilic acid liydroxy-a-carboxytrihydroxyphenylethane (A., 1923, in aqueous solution, but not in alcoholic solution or i, 556), is shown to be the anhydride of 2-fi-amino- with excess of hj^droxylamine. With excess of a-hydroxyethylgallic acid, phthalonanilic acid no oxime is formed, but the (Om?C,R above methyl ether. 2-(5'-Bromo-2'-methoxyphenyl)- hydroxyl group; the supercooled liquid shows a slight phtnalide, m. p. 137-5— 138-5°, and 5 : 6-dimethoxy- absorption. E. W . W ig n a l l . 2-(4'-hydroxy-3'-methylphenyl)phthalide, m. p. 185— Hydroxyalkyl derivatives of vulpinic acid. 186°, are also described. A. P itttti and F. P . M a zza (Rend. Accad. Sci. fis. When phenols are condensed as above with excess mat. Napoli, 1925, [iii], 31, 148— 155).— The lichen of opianic acid, diphthalidyl derivatives are obtained, Lepraria chlorina contains 18% of its dry weight of of which the following are described: 4 : 6-di- vulpinic acid, with other substances containing a (5' : &-dimethoxyphthalidyl)-phenol, m. p. 204-5— 206°; higher proportion of oxygen, suspected to be hydroxy -anisole, m. p. 210—211°; -2-methylphenol, m. p. alkyl derivatives. Some substances of the latter type 205—207°; -3-methyl/phenol, m. p. 227-5—229-5°; are synthesised, but are not identical with any of the and -2-bromophenol, m. p. 215—216°; and 3 : 5-di- natural products. (4'-bromo-5' : 6'-dimethoxyphthalidyl)-o-cresol, m. p. The method of Volhard (A., 1895, i, 99) for synthesis 266—268° (decomp.). Reduction of the above of vulpinic acid by way of diphenylketipinodinitrile phthalides with zinc and sodium hydroxide affords is extended. o-Methoxyphcnylacetonitrile is con the corresponding benzylbenzoic acids, of which the densed w-ith ethyl oxalate and sodium ethoxido, and following are described : 5 : G-dimethoxy-2-{p-hydroxy- the product is acidified with acetic acid, giving di- benzyl)benzoic acid, m. p. 173— 174°; -(o-hydroxy- o-methoxyphenylketipinodinitrile, m. p. 250° (decomp.) m-methylbenzyl)-, m. p. 138-5— 139-5°; -(p-hydroxy- after turning brown at 190°. This is hydrolysed by m-melhylbenzyl)-, m. p. 140—142°; -(p-methoxy- benzyl)-; and -(o-methoxy-~p-metkylbenzyl)-benzoic acid, sulphuric acid to the dilactone, m. p. 124-5— 126-5°; and 2-(o-methoxybenzyl)benzoic 9°-o acid, m. p. 115— 116°. Some of the latter were also MeO-C6H4-C:C-C:C-CGH4-OMe, which on boiling with obtained by catalytic reduction. F. G. W il lso n . ° — C ° sodium carbonate solution yields di-o-methoxypulvinic Constitution and physical properties of vul- acid, m. p. 195°, of which the methyl ester, di-o-meth- pinic acid. F. P. M a z za (Rend. Accad. Sci. fis. oxyvulpinic acid, m. p. 121° (acetyl derivative, m. p. mat. Napoli, 1925, [iii], 31, 182— 193).— Spiegel (A., 111°; benzoyl derivative, m. p. 151°), is obtained by 1884, 841) ascribed to vulpinic acid (methyl pulvinate) dissolving in methyl-alcoholic potassium hydroxide the formula (I), ^ ( O H ^ X p C O ^ and V d . solution and acidifying. An aqueous solution of this VV (J substance when heated with piperidine gives a sub herd (A., 1S95, i, 99) the formula (II), stance, m. p. 98°. C02H-CPh:C—C:CPlrC02Me (J) theSimilarly acidic are prepared : 3:4:3': 4 '-tetramethoxy- diphenylketipinodinitrile, m. p. 204° (decomp.); properties to the enolic hydroxyl group; it should 3 : 4 : 3': 4'-tetrametlioxypulvinic acid, m. p. 160°; thus be possible to prepare derivatives of the ketonic methyl ester of the latter, tetramethoxyvulpinic acid, form (III), ?HPh-C0-9:CPh-C02Me wHch musfc alsQ m. p. 97° (acetyl derivative, m. p. 103°; benzoyl vU (J derivative, m. p. 134°; piperidine salt, m. p. 93°). be considered. The mol. wt. in benzene solution 3 : 4-Methylenedioxyphenylacetonitrile, b. p. 180— shows no polymerisation, indicating that a hydroxy- 190° in a eathode-ray vacuum, is prepared from compound is not present; the dissociation constant, homopiperonyl chloride; it yields di-3 : 4-methylene- it2,=4-94 X10'6, is that of an extremely feebly acidic dioxyphenylketipinodinitrile, m. p. 225° (decomp.), substance, and is of the order of that of a phenol. di-3 : 4-methylenedioxypulvinic acid, m. p. 167°, and The increase in molecular conductivity of a solution its methyl ester, di-3 : i-methylenedioxyvulpinic acid, of the sodium salt on dilution is abnormally great. m. p. 103° (acetyl derivative, m. p. 122°; benzoyl In an alkaline medium, a benzoyl derivative, m. p. derivative, m. p. 141°; piperidine salt, m. p. 101°). 171°, is obtained which is absolutely neutral; phenyl- E. W. W ig n a l l . carbimide does not react in the cold, but at 165° a Radical dissociation of derivatives of arylated neutral phenylurethane, m. p. 237°, is formed. These succinic acids. III. 2 : 2'-Dihydroxytetra-aryl- reactions exclude the structure (II), and suggest that succinodilactones. A. L o w e n b e in and H. the normal form is (III), converted in the presence Sch m idt (Ber., 1927, 60, [5], 1851— 1861; cf. A., of alkali or on heating into (I ); correspondingly, 1926, 168).— Bromo-2-hydroxydiphenylacetolactone in neutral media a semicarbazone, in. p. 175°, is is converted by boiling methyl alcohol into melhoxy- obtained. 2-hydroxydiphenylacetolactone, m. p. 116°, and by Values of [Ri\a, [-B/Jd, and [R£]p in various copper bronze in boiling benzene into 2 : 2'-dihydroxy- solvents are given; although exalted, they are all tetraphenylsuccinodilactone, 0 The red colour developed by Schiff’s reagent on is shown to be dependent on the positions of the nitro- heating disappears on cooling, provided that much groups in the aldehyde residue. The colours of the sulphur dioxide is not allowed to leave the solution. nitro- and jp-bromo-phenylhydrazones of these alde pp'-Diaminotriphenylcarbinol undergoes a similar hydes, both as solids and in aqueous and alcoholic reaction, the solution being violet when hot, colourless alkaline solution, are discussed in relation to positional when cold. W. J. P o w e l l . influences. M. Cl a r k . Preparation of nitrohydroxybenzaldehydes Preparation of 2 : 5-dihydroxybenzaldehyde and colour relationships of their substituted (gentisaldehyde). H. H. H o d g so n and H. G. phenylhydrazones. H . H . H od g so n and H . G. B ea rd (J.C.S., 1927, 2339—2340).—The method B ea r d (J.C.S., 1927, 2375— 2384).—Nitration of described gives an improved yield of a less crude 6-nitro-3-hydroxybenzaldehyde gives a mixture of product than that of Neubauer and Flatow (A., 2 : Q-dinitro-Z-hydroxybcnzaldehyde, m. p. 94° [sodium 1907, i, 771). m-Hydroxybenzaldehyde is treated at and ammonium salts; p-nitroplienylhydrazone, ex 30— 35° with potassium persulphate in alkaline solu ploding 240—242°; p-bromophenylhydrazone, m. p. tion, and, after keeping, the mixture is rendered 166— 167° (decomp.)], and 4 : Q-dinitro-Z-hydroxy- faintly acidic and the unchanged material extracted benzaldehyde, m. p. 106° [sodium and ammonium with ether. When the solution is strongly acidified, salts; p-nitrophenylhydrazone, decomp. 282— 283°; a dark brown, amorphous substance, which constitutes p-bromophenylhydrazone, m. p. 249—250° (decomp.)]. 40% of the yield, is precipitated. This substance Nitration of 2- and 4-nitro-3-hydroxybenzaldehydes chars above 330°, and contains an aldehyde group, gives as single products the 2 : 6- and 4 : 6-dinitro- since it yields a p-nitrophenylhydrazone, which gives derivatives respectively. Further nitration of either the characteristic magenta colour with alkalis. 2 : 5- compound yields 2:4: 6-trinitro-Z-hydroxybenzalde- Dihydroxybenzaldehyde, m. p. 89— 92°, is extracted hyde, m. p. 161— 162° (decomp.) [(sodium salt; from the filtrate with ether. The pure product has p-nitrophenylhydrazone, exploding 228— 230° ; p- m. p. 98—99° (cf. Tiemann and Müller, A., 1882, 52). bromophenylhydrazone, exploding 218— 220°; azine, The p-nitrophenylhydrazone, brick-red, has m. p. exploding 150— 160°)]. Nitration of 6-nitro-3-meth- 256—257° (dccomp.); the dibenzoate, m. p. 106— oxybenzaldehyde yields in like manner a mixture 107°, forms a p-nitrophenylhydrazone, orange, m. p. of 2 : 6-dinitro-3-methoxybenzaldehyde, m. p. 157° 272°; the dimethyl ether, m. p. 51° (cf. Tiemann and [p-nitrophenylhydrazone, exploding 260°; p-bromo Müller, loc. cit.), forms a p-nitrophenylhydrazone, red, phenylhydrazone, m. p. 196— 197° (decomp.)], and m. p. 216°; the monomethyl ether yields a p-nitro 4 : 6-dinitro-3-methoxybenzaldehyde, m. p. 131° [p- phenylhydrazone, orange, m. p. 206°. nitrophenylhydrazone, m. p. above 300°; p-bromo- W. J. P o w e l l . phenylhydrazone, m. p. 254— 256° (decomp.)]. Tie- Condensation of cyciohexanones with aromatic mann and Ludwig’s a-dinitro-m-methoxybenzalde- aldehydes. Alkylation of cyciohexanones. E.. hyde (cf. Ber., 1882, 15, 2043) is thus the 2 : 6-di- Co rn u b e rt and H. L e B ih a n (Bull. Soc. chim., nitro-compound, whereas their ¡3-isomeride is a mix 1927, [iv], 41, 1077— 1087; cf. A., 1921, i, 422, 730).— ture of the 2 : 6- and 4 : 6-dinitro-derivatives. Nitr Allylation of 2-methylcycZohexanone with sodamide ation of 3-nitro-4-hydroxybenzaldehyde with pure and allyl chloride, bromide, and iodide gives a mixture nitric acid gives 3 : 5-dinitroA-hydroxybenzaldehyda, of 2-allyl-2-methyl- and 2-allyl-6-methyl-cycZohexan- m. p. 102— 103° [(sodium salt; -p-nitrophenylhydr ones (80 : 20 from chloride, 88 :12 from bromide and azone, decomp. 283— 284°; p-bromophenylhydrazone, iodide). Hydrogenation of these allyl compounds decomp. 242— 244°; phenylhydrazone, m. p. 203°)], furnishes the corresponding w-propyl compounds, whereas if sulphuric acid is present only picric acid which condense with bcnzaldehyde in presence of is formed. Nitration of 2 : 5-dichlorobenzaldehyde hydrogen chloride, yielding benzylidene-2-methyl-G-n- gives a mixture of 2 : 5-dichloro-6-nitrobenzaldehyde propylcyclohexanone, m. p. 25°, and a “ tetrahydro- and, in lesser yield, 2 : 5-dichloro-Z-nitrobenzaldehyde pyrone,” C2tH2o02, m. p. 136— 137° (cf. A., 1926, [phenylhydrazone, m. p. 171°; p-nitrophenylhydrazone, 953), respectively. Allylation of 4-methylcycZohexan- m. p. 290— 292° (decomp.)]. 2 : b-Dichloro-2-nilro- one with allyl cliloride and bromide affords 2-allyl-4- benzoic acid has m. p. 220°; 2 : 3 : 5-trichlorobenzalde- methylcycfohexanono together with a mixture of hyde has m. p. 56°. The compounds described as 2 : 2-diallyl- and 2 : 6-diallyl-4-methylcycZohexanones 4-chloro-6-nitro-3-hydroxybenzaldehyde and 4-chloro- (75 : 25 from chloride, 88 :12 from bromide), all of 2-nitro-3-hydroxybenzaldehyde (A., 1926, 1040) are which on hydrogenation yield the corresponding now shown to be 4-chloro-2-nitro-3-hydroxybenzalde- n-propyl compounds. 4-Methyl-2 : 6-di-n-propyl- hyde and 2-chloro-4-nitro-3-hydroxybenzaldehyde, cyclohexanone thus obtained using allyl bromide had respectively, the last-named compound being derived b. p. 129— 129-5°/20 mm.,0-8925, n\J 1-4600, and from 2-chloro-isomeride present as impurity in the yielded an oxime, m. p. 70°, b. p. 164— 168°/26 mm., 4-chloro-3-hydroxybenzaldehyde used in the pre and a semicarbazone, m. p. 185-5— 190°. The ketone paration. The following are also described : p-nitro- on condensation with bcnzaldehyde in presence of yhenylhydrazone, m. p. 247— 249° (decomp.), and hydrogen chloride yields a benzylidene derivative, V-broinoplicnylhydrazone, m. p. 192— 193°, of 3-nitro- b. p. 215— 216°/16 mm., and the “ tetrahydropyrone,” 4-hydroxybenzaldehyde; 2 : Q-dinitro-'i-methoxybenz- C^H^O^ m. p. 145°. Similar condensation of oic acid, m. p. 199°. benzaldehyde with 4-methyl-2-?i-propylcycfohexanone The facility of decomposition of the j)-nitrophenyl- affords a benzylidene derivative, b. p. 194— 196°/16 hydrazones of the various nitrohydroxybenzaldehydes mm. (semicarbazone, m. p. 161°), whilst with sodium 1076 BRITISH CHEMICAL ABSTRACTS.— A. methoxide as the condensing agent there are obtained chloride and by magnesium sec.-butyl bromide, the the benzylidene derivative and a compound, C17H2G02, chief product being hydrobenzoin. W. J. P o w e l l . in. p. 150° (diacetyl derivative, m. p. 86°), which has Pyrogenic decomposition of ketones under probably the fommla high pressures. V. N. I p a t ie v and A. D. P etro v (Ber., 1927, 60, [jB], 1956— 1963).— Acetophenone, 2-Allyl-4-metliylq/cZohexanonc and benzaldehyde in when heated under pressure at 270— 300° in the presence of sodium methoxide yield an impure presence of aluminium hydroxide, affords unchanged benzylidene derivative, b. p. 202—203°/17 mm. (semi- material, triphenylbenzene, 3 : 4-diphenylfuran, and carbazone, m. p. 141°), together with a small amount a red resin; at 380— 420° the reaction is complete of a compound, C17H240 2, m. p. 135°, analogous to and gives a mixture of benzene, toluene, ethylbenzene, that obtained from the propyl derivative. Hydrogen and o-xylene (15% in all), the remainder being a ation of 6-benzylidene - 4 - methyl - 2 - n - propylcycZo- resin which does not appear to contain diphenyl or hexanone yields impure (i-benzyl-A-mcthyl-2-n-propyl- 2>-diplienylbenzene and in which benzoic acid is cyclohexanone, b. p. 189-5°/14 mm., which condenses present oidy in traces. The primary products of the with benzaldehyde in presence of hydrogen chloride change are therefore benzene and toluene, whereas to yield a small amount of a “ tetrahydropyronc,” ethylbenzene is formed by subsequent hydrogenation C31H3402, m. p. 172°. H. B u r t o n . of acetophenone. Benzophenono remains unchanged Semipinacolic and hydrobenzoinic transposi at 430°, but suffers complete decomposition at 500— tions in the alkylhydrobenzoin series. Alkyl- 550°, yielding mainly carbon and gases; benzene and hydrobenzoins with branched chains. II. The diphenylmethano, but not diphenyl or p-diphenyl- ci/cZohexane chain. A. Or e k h o v and M. T if f e - benzene, are identified among the liquid products n e a u (Bull. Soc. chim., 1927, [iv], 41, 1174— (12%). When heated with hydrogen in an iron tube 1185).— a-q/cZoHexylhydrobenzoin, m. p. 159— 160° at 400— 430° in the presence of aluminium oxide, (cf. Danilov, A., 1926, 519), undergoes a trans benzophenono affords diphenylmethano in very good position of the semipinacolic type on dehydration yield; only about 20% of the ketono dissociates into with concentrated sulphuric acid forming q/cZohexyl benzene and resin. Acetone, under pressure in the benzhydryl ketone, m. p. 57— 58°, its behaviour being presence of aluminium oxide at 350— 400° yields therefore analogous to that of the corresponding mesityl oxide, tsophorone, xylitone, and mesitylcnc, benzyl and tsopropyl derivatives of hydrobenzoin (cf. reversible and irreversible reactions thus taking place. A., 1923, i, 333). Dehydration with hot dilute acid, Increase of temperature to 500— 550° favours the however, leads to the formation of the three products irreversible changes accompanied by maximal elimin theoretically possible, viz., q/cZohexyldiphenylacet- ation of water whereby the unsaturated cyclic ketones aldehyde, m. p. 124°, by a semihydrobenzoinic (tsophorone and xylitone) are partly converted by change, cydohexyl benzhydryl ketone by a semi loss of water into a mixture of aromatic compounds, pinacolic transposition, and ct/cZohexyldeoxybenz- mainly mesitylene, and partly by loss of methane oin, m. p. 120— 121°, by dehydration followed into s.-m-xylenol. H. W r e n . by isomerisation without migration of the phenyl Electrolytic reduction of ketoximes and ald- group. The last may be sjoithesised by the action oximes of the aromatic series. S. K a p l a n s k y of cyclohexyl bromide on deoxybenzoin in presence (Ber., 1927, 60, [5], 1842— 1843; cf. Gulevitsch and of sodium ethoxide. The formation of a ketone others, A., 1924, i, 1285).— Aromatic ketoximes are rather than an aldehyde on dehydration is charac considerably more smoothly reduced by Tafel’s teristic of hydrobenzoin derivatives in which the method than in the presence of colloidal palladium; substituent is a radical of feeble affinity. Since the the yields of primary amine vary from 50% to 70%. benzyl derivative •with dilute acid undergoes ex Tafel’s process is applicable also to aldoximes. The clusively the semipinacolic change, whilst the iso- electrolytic reduction of the oximes of benzophonone, propyl like the q/c/ohexyl derivative gives a mixture, acetophenone, dibenzyl ketone, benzaldehyde, and the relative affinities arc in the order Bz anthranil and benzenylphenyleneamidine, m. p. 285°, anhydride in anhydrous benzene solution on a boiling are produced. The /»-oxime is almost quantitatively water-bath, ethyl fiS-diphenyl-a-methyl-lactate is con transformed by diazotisation into phenylindoxazene; verted solely into ethyl (3-phenyl-a-methylcinnamate, if, however, the mixture is kept for some time before this being partly transformed into 3-phenyl-2-methyl- being heated and the small amount of resin is not indone if the action is prolonged for about 8 hrs. immediately removed, 4 : 5-benzo-6-phenyl-l : 2 : 3- Thus, although phosphoric anhydride readily removes triazine -1 - oxide separates. The configurations the first molecule of water from the phenylmethyl- ^•CAgPh 8nd M W ,® f o t t h o „ . m d lactic ester, hydrolysis of this ester by phosphoric HO-N N-OH acid proceeds slowly. It is concluded that the form Ti-oximes are therefore considered to be confirmed. ation of indones from the lactic esters proceeds by The iV-acyl derivatives of o-aminobenzophenone- ring-closure of the ciimamic acid. 2 : 3-Diphenyl- oxime readily form soven-membered rings, the indone, previously obtained in about 30% yield by the tendency being particularly marked in derivatives action of phosphoric anhydride on ap-diplienyl-lactic of the /i-oxime. Evidence with regard to configur acid (A., 1915, i, 542), may be prepared in almost ation cannot be deduced therefrom, since the precise theoretical yield by the action of concentrated mode of action is uncertain. Reopening of the ring sulphuric acid on ap(3-triphcnyl-lactic acid; the occurs more uniformly and leads in all circumstances phenylhydrazone of this indone has m. p. 175— 176° (in alkaline and hydrochloric acid solution and with (cf. García Banus and Medrano, A., 1924, i, 180). superheated water) to the acyl-iV-oxime whereby T. H . P o pe . tra?is fission of the ring must be assumed. Indones. IX. Truxones. R. d e F a z i (Gaz Whereas aqueous sodium hydroxide causes trans zetta, 1927, 57, 551— 554).—With reference to Brass’ formation of benzophenone-n-oxime into the /¿-oxime, statement that the author assumes the bimolecular the homogeneous oximes are obtained by the action constitution of the aryl- and alkyl-truxones (A., 1926, of concentrated alcoholic sodium hydroxide on the 838, 839) the author points out that he showed by corresponding benzoyl derivatives. In dilute alcoholic mol. wt. determinations that the products of the solution the benzoyl-/i-oxime is unchanged by sodium action of concentrated sulphuric acid on ethyl pp-di- hydroxide, whereas the benzoyl-?i-oxime is quantit phenyl-lactate include two diphenyltruxones (A., 1915, atively transformed into the benzoyl-A-oxime. i, 1063; 1916, i, 151 ; 1920, i, 316). Not all truxones o-Aminoacetophenoneoxime is converted by diazo are obtainable by a single method. Thus the action tisation and subsequent boiling of the solution into of concentrated sulphuric acid on (3-phenylindone methylanthranil, 4:5- benzo - 6 - methyl -1:2:3- tri- yields two diphenyltruxones, whereas this acid does azine-1-oxide, decomp. 185— 188°, being formed inter not act under similar conditions on 3-phenyl-2- mediately. Attempts to rcduce the oxide to the methjdindone. The latter is converted into dimethyl- corresponding triazine resulted in the exclusive pro diphenyltruxones by the radiations from a quartz duction of 3-methylindazole as defined product. mercury vapour lamp, and these also transform into Conversion of the triazine oxide into methylanthranil two other isomerides the two diphenyltruxones formed proceeds readily in cold, dilute sulphuric acid or boil by the action of sulphuric acid on fS-phenylindone. ing water, whereby o-azidoacetophenone is produced, T. H . P o p e. identified as the dinitrophenylhydrazone, decomp. Ring-closure in additive compounds. III. 182— 183°; an additive compound of o-azidoaceto- Determination of configuration of stereoisomeric phenone and mercuric chloride is described. The hydrazones. W. H ie b e r and F . So n n e h a l b triazine oxide dissolves rapidly in aqueous or alcoholic (Annalen, 1927, 456, 86— 110; cf. A., 1925, i, 1325). alkali hydroxide and the dark red solution, if immedi — The configurations of stereoisomeric compounds ately acidified, affords o-acetophenylazohydroxylamine may be determined from a consideration of their (or o-acetanilinoazohydroxide), decomp. 116— 117° cyclic co-ordinated additive compounds with metallic after softening, which with phenylcarbimide affords salts. Benzil-a-osazone in chloroform combines with m-phenyl-W-o-acetophenylcarbamide, m. p. 170° (de- 0-5 mol. of stannic chloride to form a yellow com comp.) in a pre-heated bath. The carbamide deriv pound, decomp, above 145°, and with 1 - mol. of ative is also obtained from o-aminoacetophenone and stannic chloride to give a red compound, m. p. 120° phenylcarbimide. The conversion of o-aminobenz- (decomp.). The (3-osazone, on the other hand, forms aldoxime into 4 : o-benzo-l : 2 : 3-triazine-l-oxide only a single (equimolecular) additive compound, (Bamberger’s “ indiazoneoxime ” ) occurs with very m. p. 60°. No isomérisation takes place, for the poor yield, but the corresponding change is easier corresponding osazones are regenerated by treatment with 3 : 5-dimethyl- and 3 : 6-dichloro-2-aminobenz- with water. In similar manner stannic chloride aldoxime. The two latter oximes must certainly combines with 2 mois, of benzaldehydephenylhydr- have the same configuration as o-aminoacetophenone- azone, giving a yellowish-brown compound, m. p. oxime, the hydrogen and hydroxyl groups being in 70— 75° (decomp.) ; with 2 mois, of benzophenone- the cis-position to one another. It appears probable phenylhydrazone (red compound, m. p. 190°); with that the more readily preparable and more stable 2 mois, of benzylideneaniline [yellow compound, m. p. forms of aromatic aldoximes have the aromatic 200° (decomp.)]; with 1 mol. of benzophenoneanil nucleus and hydroxyl group in the omfi-position (cf. (yellow compound, m. p. 180°) ; with 1 mol. of benzil- Brady and Bishop, A., 1925, i, 930). H. W r e n . dianil [yellow compound, m. p. 225° (decomp.) ; also a red compound containing more stannic chloride]; _ ^dones. VIII. R. d e F a z i (Gazzetta, 1927, 57, with 1 mol. and 1-5 mois, of benzilmonoanil (orange —550).—When heated for 2 hrs. with phosphoric and red compounds, m. p. 175° and 90°, respectively) ; 4 B 1078 BRITISH CHEMICAL ABSTRACTS.— A. with 1 mol. of benzilmonophenylhydrazone (brownish- 77—79°; 2-hydroxy-4-ethoxyphenyl p-3 : 4-methylene- red compound, m. p. 165°). The evolution of heat dioxyphenylethyl ketone, m. p. 117° (this and all the during the reaction with benzylideneaniline and preceding ketones are prepared by reduction of the benzophenoneanil and the great stability of these corresponding chalkones) ; 3 : 4-dimethoxybenzoyl- products indicate that in all the compounds the tin aeetone, m. p. 71—72°; 4-methoxy-T-ethoxydibenzoyl- is attached to doubly-linked nitrogen atoms. This methane, m. p. 90— 91°; dianisoylmethane, m. p. is confirmed by the colours of the compounds, and 114°; a-anisoyl-y-phenylacetone, m. p. 75—76° (the last four compounds are prepared by Claisen con leads to the formula for the CPh.N(NHPh)' densations). P-osazone product; i.e., the p-osazone is the anti- The author’s conclusion, from absorption spectra, compound, the a-osazone the syn-compound. The that rutin is of the hydroxypyroneglucoside type (A., only known benzilmonophenylhydrazone has an anti- 1925, i, 1445) has since been confirmed chemically configuration. by Atree and Perkin (this vol., 231). Rutin com 2:3:5: 6-Tetraphenylpyrazine gives with 1 mol. pared with quercetin is appreciably hypso- and hypo of stannic chloride a yellow compound, decomp. 135°; chromic. C. H ollin s. with 2 mols. a red compound, m. p. 100°. 5 : 6-Di- Synthesis of 4-hydroxy-3-methoxystyryl phenyl-2 : 3-dihydropyrazine is more closely analogous n-butyl ketone. H. N o m u ra and S. T s u r u m i (Sci. with the osazones in constitution, and gives a yellow Rep. Tôhoku Imp. Univ., 1927, 16, 563—564; cf. compound, sintering at 75°, with 0-5 mol. of stannic A ., 1925, i, 1156).— Vanillin and methyl n-butyl chloride, and an orange equimolecular compound, ketone, when heated for 6 hrs. under a reflux con m. p. 115— 120° (decomp.); this confirms the syn- denser with alcohol and potassium hydroxide, con configuration for the a-osazone. Mol. wt. determin dense to form 4-hydroxy-3-methoxystyryl n-butyl ations in benzene and in ethylene dibromide give ketone, m. p. 39— 40° (1H20, m. p. 66— 100°). values (allowing for dissociation) in accord with these B. W. A n d er so n . views. C. H o llin s. Homologues of zingerone. II. H. N o m u ra and S. T suru m i (Sci. Rep. Tôhoku Imp. Univ., 1927, Absorption spectra of derivatives of aceto- 16, 565— 579).— Vanillin was condensed with methyl phenone. T. T a s a k i (Acta Phytochim., 1927, 3, w-nonyl ketone to form 4-hydroxy-3-methoxy sty ryl 259— 315; cf. A., 1925, i, 1444, 1445; ii, 838).— n-nonyl ketone, m. p. 55-5— 56-5° ( + 1H20, m. p. The absorption spectra of acetophenone, deoxy- 68— 100°), and this was reduced to 4-hydroxy-Z- benzoin, benzylacetophenone (hydrochalkone), benz- methoxyphenylethyl n-nonyl ketone, m. p. 42-5— 43-5° oylacetone, propionylacetophenone, dibenzoylmeth- (benzoyl derivative, m. p. 51— 52° ; methyl ether, m. p. ane, benzyl plienacyl ketone, and of 49 methyl, 33-5— 35°; oxime of the latter, m. p. 73-5— 74-5°). hydroxy-, alkoxy-, and acetoxy-derivatives of these The preparation of the n-hexyl, n-heptyl, and n-octyl were examined. Acetophenone and phenyl benzyl homologues of the above is also described (cf. A., ketone in M \1000 alcoholic solution give indications 1926, 1145). B. W. A n d er so n . of a band at 3600 A., the latter compound being markedly hypochromic compared with phenyl styryl Nuclear condensation of phenols and phenolic ketone. All the diketones show in M /10,000 alcoholic ethers with nitriles to ketimines and ketones of solution a single band, which lies at 3200 A. for phenols and phenolic ethers. II. Syntheses benzoylacetone, propionylacetophenone, and benzyl with anisóle, o-bromoanisole, phenetole, o-, m-, phenacyl ketone, but is displaced to 2900 A. in di- and p-tolyl ethers, veratrole, and resorcinol benzoylmethane; as in the monoketones, replace ethers. J. H o u b e n and W. F is c h e r (Ber., 1927, ment of methyl by benzyl has little effect. Intro 60, [jB], 1759— 1778; cf. this vol., 143).— The exten duction of hydroxyl or alkoxyl exerts both batho- sion of Gattermann’s synthesis to mononuclear chromic and hyperchromic effects, the increased phenolic ethers and various nitriles is reported. effect due to o- or ^-position of the hydroxyl group a-Naphthol yields nuclear substituted products with being less marked in diketones than in monoketones, acetonitrile, chloro- and trichloro-acetomtrile, benzo- owing probably to the overwhelming influence of the nitrile, and phenylacetonitrile even in the absence of two carbonyl groups. Acetylation of hydroxyl groups zinc chloride, whilst considerably enhanced yields are is without effect. Methyl groups have not the auxo- obtained in its presence. With benzene derivatives, chromic effect here which they show in the benzo- the presence of halogen in the ortho-position to the phenone series. alkoxyl group greatly diminishes the yield without The following new compounds are described: entirely inhibiting the change. A methyl group in 2 :4 :5 -trimethylphenyl fi-phenylethyl lcetone, m. p. the ortAo-position facilitates the reaction, whilst in 37— 38°; phenyl p-p-tolylethyl ketone, m. p. 48— 50°; the meto-position it diminishes the yield somewhat. o-, m-, and p-hydroxyphenyl fi-phenylethyl ketones, The methoxy-group facilitates the reaction if in the m. p. 36— 37°, 40— 42°, and 62— 64°, respectively; meto-position. If the para-position to the alkoxy- phenyl $-va.-hydroxyphenylethyl ketone, m. p. 73— 74°; group is replaced by methyl, condensation is still phenyl p-Z-mdlwxy-4-ethoxyphenylethyl ketone, m. p. possible to a limited extent, but not if the alkoxy- o4— 55°; p-anisyl p-o-hydroxyphenylethyl ketone, m. p. group is here present. o-Nitro- and o-acetamido- 59— 60°; p-phenelyl ^-Z-methoxy-4-ethoxyphenylethyl groups inhibit reaction completely. o-Carboxy- ketone, m. p. 70— 71°; 3 : 4-dimethoxyphenyl p-p- groups introduce complications, since they react with ani-sylethyl ketone, m. p. 65— 66°; 2-hydroxy-4-ethoxy- the nitrile. Ether is the most suitable solvent. phenyl $-'&-methoxy-4-eihoxyphenylethyl ketone, m. p. Methyl acetate may be used, but gives a less pure ORGANIC CHEMISTRY. 1079 product, whilst small amounts of ketones are obtained hydrogen chloride, giving a compound which is when ethyl bromide is employed. Acetyl chloride, oxidised by permanganate to ip-benzoquinonedisulphone acetic anhydride, glacial acetic acid, and dioxan are [1:1- diethanesidphonyl - A2'5 - eyclohexadiene - 4 - one], quite unsuitable. It is frequently possible to improve m. p. 84°, black-violet crystals, giving brownish-red the yield of ketone to a considerable extent by use solutions in organic solvents. The compound does of an excess of nitrile. The following substituted not yield an oxime, semicarbazone, or phenylhydr acetophenones are described; cocooy-trichloro-4-ethoxy-, azone ; it is readily reduced to a colourless compound m. p. 63-—64° (sulphonic acid; compound of corre which becomes oxidised when exposed to air. It is sponding ketimine hydrochloride and zinc chloride); converted by cold bromine into 2:3:5: Q-tetra- coco(0-trichloro-4-mdhoxy-, m. p. 33— 34-5°; cococo-tri- bromo-1 : 1 - diethanesulphonyl - A2'5 - cyclohexadiene - 4 - chloro-4-eihoxy-Z-methyl-, m. p. 67— 68°; cococo-trichloro- one, m. p. 286° (closed capillary), and by warm 4-methoxy-2-methyl-, b. p. 130°/0-8 mm.; cococo-tri- bromine into 2:2:3:3:5:5:6: 6-octabromo-l : 1- chloro-2-methoxy-5-methyl-, b. p. 150— 155°/12 mm. diethanesulphonylcyclohexan-4-one, m. p. 276° after (accompanied by p-tolyl trichloroacetate, m. p. 67— softening at 230°. a-Naphthaquinone affords simil 6S°); o>w-lrichloro-3 : 4-dimethoxy-, m. p. 101— 102°; arly 4 : 4-diethanesulphonyl-a.-7iaphthaquinone, m. p. cow-trichloro-2 : 4-dimethoxy-, b. p. 153°/0-5—0-6 mm. 86°, reduced by zinc dust to l-hydroxy-4 : 4-diethane- (quinol monoethyl ether affords p-etlioxyphenyl tri sulphonyl-1 : 4-dihydronaphthalene, m. p. 91°. 2-Ethyl- chloroacetate, m. p. 49—50°); (o(o(o-trichloro-3-bromo- thiol-1 : 4-nnphthaquinone, m. p. 142°, is obtained as 4-methoxy- (N-trichloroacet-o-methoxybenzamide, by-product during the preparation of the naphtha- OMe-CGH4-CO-NH-CO;CCl3, m. p. 184— 185°, from quinonedisulphone. H. W r e n . o-methoxybenzoic acid); (o(oco-trichloro-4-phenoxy-; (o-chloro-4-ethoxy-, m. p. 65— 66-5°; a-bromo-4-ethoxy-, Action of substances containing an active m. p. 59—60° [accompanied by dibromodiacetamide, methylene group on quinones. M. V. I on e scu m. p. 195° (decomp.) after darkening at 190°]. (Bull. Soc. chim., 1927, [iv], 41, 1094— 1096).— a-Naphthjd ethyl ether is converted by trichloro- Acetylacetone reacts with p-benzoquinone in pyridine acetonitrile, zinc chloride, and hydrogen chloride solution forming a dark green compound, m. p. above into 164— 165°. 4-Hydroxynaphthyl benzyl ketone, m. p. quinones from o-dichlorobenzene. M. P h illips 185— 187°, is derived from a-naphthol and phenyl- (J. Amer. Chem. Soc., 1927, 49, 2335; cf. preceding acetonitrile. p-Naphthol, trichloroacetonitrile, and abstract).—Acknowledgment of Fierz-David’s cor hydrogen chloride give trichloroacetimino-$-naphthyl rection. F. G. W illson . ether hydrochloride, C10H7-O-C(CCl3):NH,HCl, and P-naphlhyltricMoroacetate, m. p. 86— 87°. Phenyl Determination of the structure of a-hydroxy- 2-hydroxynaphthyl ketone, m. p. 141°, is derived anthranols. A. Gr e e n (J.C.S., 1927, 2341— 2345). from P-naphthol, benzonitrile, hydrogen chloride, and —The reduction of an a-hydroxyanthraquinone to the zinc chloride at 60°. anthranol may occur in two ways, viz., 1-hydroxy- Unsuccessful attempts to mduce isomerisation of anthraquinone may yield either 1:9- or 1 : 10-di- trichloroacetiminoplienyl ether hydrochloride by heat hydroxyanthracene or a mixture of the two. m the presence or absence of zinc chloride are Structures may be assigned to these compounds by recorded. H . W r e n . observing the differences in the resistance of the derived benzanthrones to methylation (Miller and Quinonedisulphones. A. R ecsei (Ber., 1927, Perkin, A., 1926, 174), but this method is tedious and 60; [B], 1836— 1840).— The term “ quinonedisul the yields are low (cf., however, Cross and Perkin, phones ” is applied to compounds, 0!ArI(S02R)2, this vol., 771). The reaction of the dihydroxy- which contain two sulphonyl groups in place of a anthracene with thionyl chloride at the ordinary quinonoid oxygen. jj-Benzoquinone dissolved in temperature may also be used for this purpose, since glacial acetic acid condenses with ethyl mercaptan only those phenols possessing two hydroxy-groups in 311 the presence of concentrated sulphuric acid and the o- or pen-position to each other yield thionyl loso BRITISH CHEMICAL ABSTRACTS.----A. derivatives (cf. this vol., 354, 457). 1 : 8-Dihydroxy- a white turbidity at 235— 245°, and at 275—277° naphthalene, when treated with thionyl chloride in gives a clear brown-coloured melt. carbon disulphide-pyridine solution, yields 1 : 8- tMonyldihydroxynapkthalene, in. p. 97°, in quantit co _____9^ h ative yield, whereas, in the case of the 1 : 5-dihydroxy - ć o \ h \r oxyanthraquinone yields a thionyl derivative, m. p. CH2\ / —> -CH CHJR > 9 — 9 112 115° (decomp.), and is therefore 1 : 9-dihydroxy- G—CH-c h 2 \ / C0c o 2H-CHh -Ch CO anthracene, whilst that of 4-chloro-l-hydroxyanthra- }H CO V- N/ quinone is 4-chloro-l : 9-dihydroxyanthracene, m. p. CO,H \ / 1 (II.) c h 2 170— 171° (diacetyl derivative, m. p. 157°), since with c h 2 [R = C 10H19-CO2H.] thionyl chloride it yields 4-chloro : 9-thionyldihydr- -1 The lactonic acid is formed through the intermediate oxyanthracene, m. p. 123— 124° (decomp.). Anthra- hydroxytetracarboxylic acid, which cannot be isolated, gallolanthranol yields with thionyl chloride oidy but its presence is proved definitely by titration complex chlorine-containing mixtures, indicating that values. H. B u r t o n . this anthranol is not 1 : 2 : 3 : 9-tetrahydroxy- anthracene, since this would be expected to yield a New derivatives of caoutchouc. G. B r u n i and thionyl derivative (cf. J.C.S., 1926, 2202) but E. Ge ig e r (Atti R. Accad. Lincei, 1927, [vi], 5, 823— 1:2:3: 10-tetrahydroxyanthracene (cf. Cross and 828).— In benzene solution, nitrosobenzene (3 mols.) Perkin, loc. cit.). Liebermann and Mamlock’s method and caoutchouc (1C5H8) readily react (cf. Angeli, (A., 1905, i, 521) for the preparation of anthranols Alessandri, and Pegna, A., 1910, i, 552; Alessandri, from anthraquinones yields products which are more A., 1915, i, 555), giving azoxybenzene, together with readily purified than that of Breare and Perkin a 94—98% yield of a yellow iso caoutchouc nitrone, (J.C.S., 1923,123, 2606), but the reduction of 4-chloro- •CH:CMe-C(:NPh:0)-CH2- or 1 -hydroxyanthraquinone must be carefully controlled •CH2-C(:CH2)-C(:NPh:0)-CH2-. The formation of this to avoid removal of the chlorine atom. 1 : 8-Di- compound, which is obtained also when the latex acetoxynaphthalene has m. p. 155° (lit., 147— 148°). of Hevea brasiliensis and nitrosobenzene react in W. J. P o w e l l . pyridine solution, serves well for the determination Structure of quinizarin. A. Gr e e n (J.C.S., of crude caoutchouc. It unites with bromine to 1927, 2384— 2385).— A solution of diacetylquinizarin, form the compound (IC5H GBr2*NOPh)x. m. p. 207— 208°, in thionyl chloride deposited the Treatment of caoutchouc (1C5H 8) with ethyl polymorphic form, m. p. 200°, after being boiled for o-nitrosobenzoate gives azoxybenzene and a colloidal 2 hrs. This lack of reactivity of a quinizarin deriv acid, (ICsHgiNO-CgH^CO^)*, decomp, about 100°. ative in which the hydroxyl hydrogens are replaced, Caoutchouc reacts also with the £>-nitroso-derivativcs renders improbable the second mechanism suggested. of dimethylaniline, methylaniline, diphenylamine, (J.C.S., 1926, 1430) for the conversion of quinizarin and o-toluidine. Gutta percha reacts with nitroso- into 10 - chloro - 1 - hydroxy -4:9- anthraquinone by compounds in the same way as caoutchouc. treatment with thionyl chloride. It is therefore These nitrones do not react with hydroxylamine, probable that quinizarin assumes an or/Ao-quinonoid but with phenylhydrazine the nitrone of isocaout- state (1 : 10-dihvdroxy-4 : 9-anthraquinone) in this chouc yields the phenylhydrazone of a ketone which reaction (cf. Perkin, J.C.S., 1899, 75, 433). contains the carbonyl in the caoutchouc chain and M. Cl a r k . is termed cauccione: •CH;CMe*C(!NPh!0),CH2,+ Derivatives of the anthraquinone series. I. G. NHvNHPh — ^ •CH:CMe-C(:NO-NHPh)-CH2-+ F a r b e n in d . A.-G.— See B., 1927, 743. NHPh-OH. T. H. P o p e . Formation and decomposition of ketonecyano- Bile acids. XVII. M. Sc h e n c k and H. K ir ch o f hydrins. Some compounds recently classified (Z. physiol. Chem., 1927, 169, 164— 176; cf. this as such. A. Lapworth, R. H. F. Manske, and vol., 665).—Oxidation of the ketolactam-carboxylic E. B. R o b in s o n (J.C.S., 1927, 2052— 2056).—The acid, C23II35O4N, m. p. 218—220° (this vol., 666), formation of the cyanohydrin of menthone, as with with potassium permanganate gives a lcetolactamdi- other ketones, is a reversible reaction, and equi Qjj carboxylic acid, C^HgjOgN (I), librium is attained in a few min. or sec. in strongly 2 m. p. 277° (decomp.), a reaction alkaline solution. The extraordinary stability of the C jj Qji'i similar to the preparation of the “ menthonecyanohydrin ” obtained from the nitro- CO2 OKI^ diketodicarboxylic acid from imine by Houben and Pfankuch (this vol., 364) is ' pyrodeoxybilianic acid (Wieland probably due to a Wagner transformation during and Kulenkampff, A., 1921, i, the preparation. True menthonecyanohydrin has NR 112)- been prepared and shown to have a higher dissociation Stt When bilisoidanic acid (Schenck, constant than cyctohexanone cyanohydrin. The A., 1924, i, 179, 131S), is heated stability of the two supposed “ camphorcyanohydrins ’ (I) OR sodium hydroxide solution (ibid.) is similarly explained. C. H o llin s . 2 it undergoes a benzilic acid re arrangement, and the product isolated is a lactonic Menthone series. V. rf-jieoisoMenthylamine. Odd, Cg^HggOg^HjO (II), which on heating shrinks J. R ea d and G. J. R obertson (J.C.S., 1927, 2168— at about 155°, becomes a frothy mass at 165°, assumes 2174).— Of the 12 mcnthylamines all but the 3-neo- ORGANIC CHEMISTRY. 1081 ¿somenthylamines have previously been described, Sander, A., 1915, i, 148) has m. p. 93— 95°, b. p. 152— d-neoisoMenthylamine is now isolated from the 154°/15 mm. Attempts to alkylate the tolyl ester mixture of formylated bases obtained by heating with sodamide in ether or in benzene were unsuccess 7-menthone with ammonium formate. The free base ful, and even in toluene and xylene oidy 25% and has [a]D + 9 ° and gives the following derivatives : 50%, respectively, of the theoretical amount of hydrochloride, not melted at 250°, [a]1,? +20-9°; ammonia was liberated, and no substitution product formyl derivative, [«]„' +3-9°; acetyl derivative, was obtained with butyl iodide. Similarly the methyl m. p. 99— 100°, [a]',5 —2-6°; benzoyl derivative, ester could not be benzylated. Possibly the ester m. p. 151°, [a]jj —10-4°; $-naphthalenesulphonyl group is attacked affording an amide, converted by derivative, m. p. 120°, [a]\] —10-7°; carbamide, the alkyl halide into a substituted amide (cf. Ramart m. p. 115— 116°, [oc]i> —3-1°; phenylcarbamide, and Haller, A., 1924, i, 732). ¡3-Camphornitrilic acid, m. p. 149— 150°, [a]55 —12-1°; plienylthiocarbamide, m. p. 108— 109°, obtained in 67% yield from cam- m. p. 99°, [a]1,“ —6-7°; benzylidene derivative, m. p. phorimidc (Rupe and Splittgerber, A., 1907, i, 1016), 68— 69°, [a]u —34-2°; salicylidene derivative, m. p. is converted by thionyl chloride into the chloride 98— 100°, [a]’,5 —17-9°. The hydrochloride is con (yield 80%), b. p. 148— 149°/17 mm., from which verted by nitrous acid mainly into partly racemised the o-tolyl ester, m. p. 68—69°, b. p. 219—221°/ d-A3-mcnthene, and a little cZ-i'somenthol. The 15 nun., [a]1,} —105° 39', is obtained in the usual way. salicylidene derivatives of neo- and d!-neoisomenthyl- o-Tolyl a-camphornitrilate and 5 mols. of mag amines are non-phototropic, whilst those of menthyl- nesium methyl iodide in ethereal solution afford amines and isomenthylamines are disthictly so. The 3-cyano-l-x-hydroxyisopropyl-1 : 2 : 2-trimethylcyclo- molecular configuration of neowomenthylamine is pentane (2:2: 3-trimethyl-3-oi-hydroxyisopropylcyclo- discussed and numerical powers of derivatives of the pentane-l-carboxylonitrile), m. p. 93— 94°, [a]g four stereoisomeric types of menthylamines arc +78° 15' (phenylurethane, m. p. 169— 170°), together pointed out. C. H o llin s. with a compouiid, Cu H 17ON, m. p. 164°, which gives Mononitriles of camphoric acid. F. S a lm o n - iodoform when treated with potassium hydroxide and L e g ag n eu r (Ann. Chim., 1927, [x], 7, 385— 407; 8, alcoholic iodine and forms no oximc or semicarbazone. 5— 70).— The action of Grignard reagents on the With bromine in chloroform it gives a monobromo- esters of camphoric semi-nitrile (i.e., of a-camphor- compound, m. p. 161— 162°, does not react with nitrilic acid) is in general more complex than in the phenylcarbimide, whilst with potassium permangan case of cyanocampholic esters, and may take either ate it yields only the above compound, Cu H 17ON. course (A) or, in addition, course (B), according to Substitution of ether by toluene is accompanied by the nature and proportion of Grignard reagent and the formation of 3-acetyl-1-¡x-hydroxyisopropyl-l : 2 : 2- solvent used. It is, however, only slightly affected trimethylcyclopetitane, m. p. 95—96° (semicarbazone, by variation of the ester group : m. p. 221— 222°), giving, when distilled at 144— 145°/ 15 mm., 3-acetyl-l-a.-methylethenyl-l : 2 : 2-trimethyl- •CMe (COoR,) • CMe2 • CH (CN) • cyclopentane (yield 47%), m. p. 164°, [ajjj +40° 44' •CMe(CR2OH)-CMe2-CH(CN)- (oxime, m. p. 103— 104°; semicarbazone, m. p. 229— •CMe(CR2OH)-CMe2-CH(CO-R)-. 230°), which yields indefinite products with bromine Thus with 5 mols. of magnesium methyl iodide in in chloroform, and is oxidised by potassium per ether course (A) is followed, the yield of product manganate to 1 : 3-diacetyl-l : 2 : 2-lrimethylcyclo- varying from 43% ■with the methyl to 32% with the pentane, b. p. 154— 156°/19 mm. \disemicarbazone, o-tolyl ester; in the latter case rather more of a m. p. 305— 307° (decomp.)]. compound, m. p. 164° (below), is produced. In When the product of interaction, in ether, of boiling benzene or toluene solution course (B) is also magnesium phenyl bromide (4 mols.) and the methyl followed. With magnesium phenyl bromide course ester of a-camphornitrilic acid is acidified with hydro- (B) is followed even in ethereal solution, the inter bromic acid there is formed the ketimine hydro mediately-formed ketimine being isolable, together bromide, COPh-C8H14-CPh:NH,HBr, m. p. 211—213°, with an amide. Course (A) is followed when mag fa]1,} —53° 16', converted by boiling alcoholic, hydro nesium ethyl bromide is used, but other products are chloric, or hydrobromie acid into 1 : 3 -dibenzoyl- also formed (below). 1:2: 2-trimethylcyclopentane, m. p. 118°, [a]“ —60° When either the syn- or the anti-iorm. of zsonitroso- 10' (ct-monoxime, m. p. 199—200°), together with the camphor is treated in benzene solution with thionyl amide, m. p. 172— 175°, [a]j5 +44° 51' (oxime, 194— chloride and the product formed is treated with an 196°), of 3-benzoyl-l : 2 : 2-trimethylcyclopentane-l- alcohol or a phenoxide, the corresponding a-camphor- carboxylic acid, m. p. 169— 170° (silver salt). The nitrilic ester is formed in the yield indicated : methyl, structure of the amide follows from its formation m. p. 40° (85% ); ethyl, m. p. 25— 28°, b. p. 162°/ by hydrolysing 3-benzoyl-l : 2 : 2-trimethylcyclopent- 18 mm., phenyl, m. p. 76— 77°, b. p. 215—225°/ ane-l-carboxylonitrile, m. p. 58— 59° (oxime, 152— 18 mm., [a]^ + 30° 27'; o-tolyl (70%), m. p. 99— 100°, 153°), formed from the chloride of (3-camphornitrilic b. p. 228—233°/18 mm., [a]]J +25° 7'; p-tolyl, m. p. acid, benzene, and aluminium chloride. The chloride 96—97°, b. p. 228—233°/18 nun., [a]f,‘ +28° 52'; of a-camphornitrilic acid, however, under similar benzyl (86%; a little camphorimide is also formed), conditions, affords in 75% yield a nitrile, C15H19N, b. p. 223—224°/17 mm., [«]* + 59° 24' (in alcohol), b. p. 153— 15573-5 mm., [a]1,} + 21° 12', slowly hydro [a]i> +56° 3' (in benzene). The chloride of a-cam- lysed at 125— 130° by acetic-hydrochloric acid to an phornitrilic acid obtained in 86% yield by the action acid, CjgHaoO^ m. p. 140°, identical with that obtained ■of thionyl chloride on the pure acid (Borsche and from benzene and camphoric anhydride by Biircker 1082 BRITISH CHEMICAL ABSTRACTS.— A. (A., 1896, i, 179) and Blanc (A., 1899, i, 925) (“ phenyldi- by a unimolecular reaction affording limonene. The hydroisolauronolic ” acid). Ethereal magnesium p- reaction velocities are smaller than those for nopinene. tolyl bromide similarly affords 1 :3-di-j)-toluoyl-l: 2 :2 - In the production of limonene from nopinene it appears trimet]iylo.yclopentane, m. p. 143— 144°. Ethereal improbable that pinene is the intermediate product, magnesium ethyl bromide and the methyl ester of and alternative mechanisms for the formation of a-camphornitrilic acid afford camphorimide, 3-cyano- limonene from pinene and nopinene, through the 1 - oc - hydroxyisopropyl -1 : 2 : 2 - trimethylcyclopentane, intermediate tsopinene, are formulated. m. p. 79— 80°, b. p. 185— 187°/18 mm., [a]',? + 63° 54' H . B u r to n . (o-nitrobenzoate, m. p. 112— 113°), together with an S-d-Bornylsemicarbazide and S-d-neobornyl- oil, [a]“ -® + 40° 48', which is probably a mixture of semicarbazide. J. A. G oo d so n (J.C.S., 1927, isomerides, CloHn0N, and oL-ethylidene campliolidene, 1997— 2000).—Acetonesemicarbazone, when heated ,C:CHMe with anhydrous (Z-bornylaminc at 175° gives acetone- C8H14/ > N H , m. p. 206°, b. p. 200°/18 mm., 8-d-bomylsemicarbazone, m. p. 141— 148°, [a]* +25-5°, which is hydrolysed with 10% hydrochloric acid to [a]1,? +11° 16' (yield 30%) [hydrochloride, C12H20ONC1, S-d-bornylsemicarbazide, m. p. 75°, [a]^ + 17° (hydro m. p. 230— 235°, hydrobromide, (C12H19ON)2,HBr(?), chloride, m. p. 190— 19S°, [a]yj +2-6°). 8-d-Bornyl- m. p. 245—248°], which is very stable both to acids semicarbazones of the following ketones are described : and alkali but which affords a dibromide, softening isopulegone, m. p. 224— 226°, [a]“ + 9-2°; 4-methyl- at 140— 145° (decomp.). Decomposed with cold water q/c/ohexanone, m. p. 154°, [aj$ +27-2°; 3-methyl- the latter affords a substance, C12H18ONBr, m. p. cycZohexanone, m. p. 172— 177°, [a]^ +27-4°; cZ-3- 126—127°, boiling water giving an isomeride, m. p. methylq/cZohexanone, m. p. 173— 179°, [a]jJ +7-4°. 67— 68°. These isomerides probably possess the Acetone-8-d-neobomylsemicarbazone, m. p. 175— /C.'CMcBr /C-CHMeBr 179°, [cc]f, —92-1°, similarly prepared, gives on hydro structures 0 8H14<^ '>N H or C8H14<^ , the lysis 8-d-neobornylsemicarbazide hydrochloride, m. p. 198—202°, [a]“ —50-8°. i-Methylcycloheocanone-S- d- CH2-C=9-CHMeBr neobomylsemicarbazone, m. p. 151— 155°, [a]“ —91-3°, structure I CMe2 is’ H being less probable. and the 3-methyl isomeride, m. p. 157— 161°, [a]jJ CILj’CMe—CO —91-2°, are described. All m. p. are corrected. Oxidation of a-ethylidenecampholidone with No resolution into optical cnantiomorphs could be chromic-sulphuric acid yields camphoric and acetic achieved by means of the active semicarbazides. acids, whilst sodamide and benzyl chloride in toluene C. H o llin s. convert it into a.-ethylidene-if-benzylcampholidone, Action of bromine on dimethylpyrone. J. N. m. p. 140— 141°, [a]\? +43° 46', oxidised by chromic- Collie and L. K le in (J.C.S., 1927, 2162— 2164).— sulphuric acid to camphoric acid, a little camphoric Bromination of dimethylpyrone in chloroform with anhydride, acetic acid, and benzylamine; this re 1 mol. of bromine yields dimethylpyrone hydro action establishes the structure of a-ethylidenecam bromide perbromide, C14H170 4Br3, m. p. 136° pholidone. a.-Ethylidene-'N-allylcampholido?ie, m. p. (Hantzsch and Denstorff, A., 1906, i, 745). Excess 125— 126°, [a]2,} +67° 34', is prepared similarly. of bromine gives Feist and Baum’s dibromodimethyl- Reduction of the benzyl or ^-tolyl ester of a-cam pyrone, m. p. 163° (A., 1905, i, 914), and in the phornitrilic acid with sodium and absolute alcohol absence of a solvent tetrabromodimethylpyrone, m. p. at 150— 160° affords a-campholidone, a-aminocam- 229°. When bromine is added to an aqueous sus pholic acid, and a-aminocampholic alcohol (yield 36%), pension of the barium salt of dimethylpyrone there b. p. 163— 165°/9 mm., [a]„ —14° 39' (hydrochloride, is formed a compound, C7H703Br, m. p. 106°, b. p. m. p. 190— 200°; chloroplatinate; phenylcarbamide- about 310° [decomp.; monobenzoyl derivative, m. p. urethane, NHPh-C0-CH,-C8H14-CH2-0-C0-NHPh). 112°; phenylhydrazine compound, m. p. 142° (de 14 R. B r ig h t m a n . comp.)], similar in all respects to the iodine compound [Camphorchloroanilic] acids and camphoro- obtained by Collie (J.C.S., 1921, 119, 1550). chlorophenylim ides. M. Sin g h and R. Sin g h C. H ollin s. (J.C.S., 1927, 1994—1997; cf. Wootton, ibid., 1910, Coumarin series. I. Action of the Grignard 97, 405).— Camphoric anhydride is condensed with reagent on substituted coumarins. I. M. H eil- the three chloroanilines to give mixtures of the b ron and D. W. H il l (J.C.S., 1927, 2005—2013).— chloroanilic acids and the chloroanils, separable by Magnesium phenyl bromide reacts with 4-hydroxy- means of sodium carbonate. The chloroanilic acids coumarin and its methyl ether to give 4-hydroxy- have increasing mol. rotatory power in the order 2 : 2-diphenyl-t^-chromen, m. p. 230— 231°, and the o-, m-, p-, and melt at 165° (o-), 216— 217° (to-), 4-meZ/ioa;?/-compound, m. p. 135°, respectively. The and 197° (p-). The chlorophenylimides have m. p. constitution of the latter follows from its conversion 128° (o-), 176° (to-), and 165° (p-). Rotatory powrers by boiling concentrated alkali, into benzophenone. of the six compounds in various solvents are given. 4-Methoxy-2 : 2-di-j>-anisyl-A3-chromen melts at 155°. C. H o llin s. 2 : 2-Diphenyl-4-methyl-A3-chromen, m. p. 89°, pre Hydration of nopinene. III. Comparison of pared from 4-methylcoumarin and magnesium phenyl the hydration of pinene and nopinene. G. Aus- bromide, gives on hydrolysis phenyl benzhydryl t e r w e il (Bull. Soc. chim., 1927, [iv], 41, 10SS— ether, CHPh2-OPh, m. p. 56°. 2 : 2-DiphenylA : 6- 1094; cf. this vol., 60, 156).—The reaction between dimethyl-A3-chromen, m. p. 126°, similarly prepared, pinene and organic acids forming bornyl esters is is hydrolysed to p-tolyl benzhydryl ether, m. p. 96°. bimolecular as for nopmene, and it is accompanied By the action of magnesium phenyl bromide on ORGANIC CHEMISTRY. 1083 4 : 7-dimethylcoumarin the ring is opened, with The above results, taken in conjunction with other formation of dipJienyl-o-hydroxy-fi-p-dimethylsti/ryl- data, suggest that purgative properties depend on the carbinol, m. p. 146° ; the main product is 2 : 2-di presence, or formation by hydrolysis, of free hydroxy- phenyl- 4 : 7 -dimethyl-&-chromen, m. p. 87° (also groups. That the two phenyl groups must also be obtainable by heating the carbinol in acetic acid), free in other respects is shown by the fact that which is hydrolysed to m-tolyl benzhydryl ether, m. p. fluorescein, thiofiuorescein, and similar compounds, 125°, and lactaldehyde, m. p. 103— 105°. have no purgative action. Phenolhomophthalein, On the other hand when 3-methylcoumarin is however, is a powerful purgative. This compound, treated writh magnesium phenyl bromide the product m. p. 227°, is obtained by heating together, at 125°, is 2 : 4-diphenyl-3-methylchroman-4-ol, m. p. 149°, which homophthalic anhydride, phenol, arid zinc chloride. is converted into 2 : 2-diphenyl-Z-methyl-A2-chromen, It dissolves readily in alkalis, but the solutions m. p. 91°, by boiling with acetic acid. 3-Phenyl- exhibit oidy a yellow colour, like that of 4-hydroxy- eoumarin behaves similarly (Lôwenbein, A., 1924, coumarin; this indicates that a quinonoid modification i, 1221 ; Lôwenbein and Rosenbaum, A., 1926, 955). is not formed, and if this is so, the hypothesis that These reactions are explained on the assumption purgative properties are associated with a quinonoid that the initial reaction with either 3- or 4-substituted arrangement is disproved. coumarins is ring scission with formation of p-un The (di ^-acetyl derivative, m. p. 161°, is weakly saturated ketones, the subsequent reactions of which purgative; the tribenzoyl derivative, m. p. 185°, is follow^ the Kohler rule (A., 1907, i, 535). C. H o llin s. inactive. Homophthalic acid does not yield its Constitution oî gentisin. J. S h in o d a (J.C.S., chloride when it is heated with phosphorus penta- 1927, 1983— 1985).— Since 1 : 3-dihydroxy-l-methoxy- chloride; the product is 4-chlorpisocoumarin, m. p. antlirone (“ isogentisin ” ), m. p. 241° (acetyl deriv 96—97°. Bis-(4-hydroxyphenyl)isatin (Baeyer and ative, m. p. 211— 212°), synthesised by condensing Lazarus, A., 1886, 154) is also an active purgative, 2-hydroxy-5-methoxybenzonitrile, m. p. 136°, with but its acetyl derivative is weak and its phthalyl phloroglucinol in ether in presence of zinc chloride derivative, m. p. about 280°, is inactive. Phenol- and hydrogen chloride and hydrolysis of the resulting naphthalein is more active than phenolphthalein; its ketimine hydrochloride, differs from gentisin, the latter diacetyl derivative, m. p. 198°, acts mildly, whilst its must have the structure of 1 : 7-dihydroxy-3-methoxy- phthalyl derivative, m. p. 175° (decomp.), which is not xanthone as indicated by Perkin (J.C.S., 189S, 73, readily hydrolysed, is inactive. These results demon 1028). The nitrile is prepared by dehydration of strate that the important grouping in respect to 2-hydroxy-G-methoxybenzaldoxime, m. p. 118°. iso- purgative properties is the 4 : 4'-dihydroxydiphenyl- Gentisin gives on déméthylation gentisein, m. p. 318°. methylene radical. In accordance with this conclusion C. H o llin s. it is found that 4 : 4'-dihydroxybenzophenone is an Synthetic medicináis. II. Theory of lax active purgative; its acetyl derivative is mildly active, atives. H . P. K attfmann [with H . H a as] (Z. angew. its phthalyl derivative, m. p. 125° (decomp.), is more Chem., 1927, 40, 831— 836, 858— S63).— Laxatives can stable and inactive; and 4 : 4'-dihydroxydiphenyl- be differentiated from, and stand between, drastic dimethylmethane and 4 : 4'-dihydroxytetraphenyl- purgatives and mild aperients, although the classi methane both also possess laxative properties. fication is not precise. The copious literature of this W. A. Sil v e st e r . subject is reviewed, and attention is drawn to the Synthesis of pyrylium salts of anthocyanidin anomalous position of phenolphthalein and its type. XII. D. D. P r a t t , A. R o b e r tso n , and analogues, which are usually classed with the anthra- R . R obinson (J.C.S., 1927, 1975— 1983; cf. this vol., quinone derivatives and other substances the action of 974).— Benzoylacetaldehyde condenses with phloro which is chiefly on the lower bowel. Succinylphenol- glucinol in formic acid to give trianhydrobisbenzoyl- phthalein, prepared by heating together phenol acetaldehydephloroglucinol, C^H^O,, which chars phthalein and succinyl chloride at 120° for 5 hrs., is without melting above 280°, and is converted by amorphous and has m. p. 170° ; it is readily hydrolysed boiling hydrochloric-acetic acid into chrysinidin by alkali and is also a mild aperient, acting slowly. chloride (5 : 7-dihydroxyflavylium chloride), obtained Phthalylphenolphtlialein, apparently also by condensing the components in ether or glacial XO-Ov /C,H,-Ox /O-COv acetic acid in presence of hydrogen chloride. \ C £ ------\ C 6H4, amor- O-Benzoylphloroglucinaldehydo and acetophenone in 'C 6H4-0 / ethyl acetate saturated with hydrogen chloride yield phous, m. p. 250° (decomp.), on the other hand, resists O-benzoylchrysinidin chloride, from which chrysinidin hydrolysis and is inactive as a purgative. It is chloride is obtained by treatment with methyl- prepared by heating phenolphthalein and phthalyl alcoholic ammonia and addition of hydrochloric acid. chloride at 120— 130° ; the preparation of the latter is Chrysinidin perchlorate melts at 244° (decomp.). described and its b. p. at various pressures are recorded, From 2?-methoxyacetophenone O-benzoylacacetinidin thus, 147°/13 mm., 150-5° ¡15 mm., 153— 154°/21 mm. chloride and acacetinidin chloride [dimorphic per In passing it is noted that Pawiewsky’s compound (A., chlorate, m. p. 278— 280° (decomp.); picrate, m. p. 1895, i, 219; 1896, i, 50) is a bisphthalidenehydro- 231— 233° (decomp.)]. Demethylation of acacetinidin quinone ether, chloride with hydriodic acid and phenol gives a purer co-o o -c 6h 4-o 0-CCK apigenidin iodide (chloride, mercurichloride, per c6h 4------*C6H4, as the chlorate, and periodide prepared) than previously o *c 6h 4 obtained. mol. wt. in molten phenol agrees with this formula. Hydroxymethyleneacetoveratrone (copper compound, 1084 BRITISH CHEMICAL ABSTRACTS.— A. decomp. 188°) condenses with phloroglucinol in ether Pyrylium salts of anthocyanidin type. XIV. in presence of hydrogen chloride to form 5 : 7-di A. R obertson and R . R obinson (J.C.S., 1927, 2196— hydroxy-Z' : é'-dimethoxyflavylium chloride, decomp. 2206).—Flavylium salts containing free hydroxyl 272°, which gives on déméthylation a luteolinidin groups in positions 3,5,3', and 4' have been prepared. chloride monomethyl ether (probably 5 : 7 : 4'-dihydr- Their colour reactions with alkalis are described and oxy-Z'-methoxyflavylium chloride), decomp. 282°, and compared with those of cyanin and mecocyanin. eventually luteolinidin chloride. 7-Hydroxy-3 : 2' : 4- 2 : G-Dimethoxy-4-methylbenzoyl chloride, m. p. 84— 85°, trimethoxyflavylium chloride, decomp. 185°, from obtained by the action of phosphorus pentachloride cj : 2 : 4-trimethoxyacetophenone and (B-resorcylalde- on ^-orsellinic acid dimethyl ether, yields a corre hyde, and its déméthylation product, resomorindin sponding p-toluidide, m. p. 168— 169°, iminochloride, chloride, decomp. 216°, are described. The copper amide, m. p. 199°, and nitrile, m. p. 138— 139°. compound of hydroxymethylene-2 : 4-dimethoxy- Reduction of the last-named compound by Stephen’s acetophenonc has m. p. 190°. Phloroacetophenone method (A., 1925, i, 1131) gives 2 : (y-dimethoxy-é- trimethyl ether condenses with ethyl oxalate to give methylbenzaldehyde, m. p. 90—91° (p-nitrophenyl- ethyl 2 : 4 : §-trimethoxybenzoylpyruvate, m. p. S4°. hydrazone), which could not be condensed with C. H o llin s. co-mcthoxyacetoveratrone. Application of the Gatter- Synthesis of pyrylium salts of anthocyanidin mann synthesis to m-xylorcin .yields m-xylorcyl- type. XIII. Some monohydroxyflavylium salts. aldehyde, a bright yellow substance, m. p. 155— 156°, F. M. I r v in e and R . R obinson (J.C.S., 1927, 2086— which condenses with cû-4-dimethoxyacetophenone in 2094).—Attempts to demethylate 8-methoxyflavylium formic acid solution under the influence of hydrogen chloride, m. p. 190° (decomp.), prepared from o-vanillin chloride giving 5-hydroxy-Z : 4'-dimethoxy-6 : 8-di and acetophenone, or iodide, m. p. 134°, were unsuc methylflavylium chloride (ferrichloride, m. p. 211— cessful. Condensation of 5-methoxysalicylaldehyde 212°). Déméthylation yields 3 : 5 : 4'-trihydroxy- with acetophenone in aqueous-alcoholic potassium 6 : 8-dimethylflavylium chloride (iodide). Similar con hydroxide gives 40% of 5-methoxysalicylidenediaceto- densation of m-xylorcylaldehyde with co-methoxy- phenone fay-dibenzoyl-p-2-hydroxy-5-methoxyphenyl- acetoveratrone yields 5-hydroxy-3 : 3' : 4'-trimethoxy- propane], m. p. 125°, and 50% of phenyl-2-hydroxy- 6 : 8-dimethylflavylium chloride (ferrichloride, m. p. 5-methoxystyryl ketone, m. p. 104°, which is converted 200— 203°). Déméthylation gives 3 : 5 : 3' : 4'-tetra- by hydrochloric-acetic acid into G-methoxyflavylium hydroxy-6 : 8-dimethylflavylium chloride (iodide). chloride, m. p. 97° [+ 2 H 20 ; ferrichloride, m. p. 203°; Rhamnetin was acetylated and reduced by zinc dust iodide, m. p. 143°; periodide, m. p. 86— 87°; per in boiling acetic anhydride solution. The product chlorate, m. p. about 200° (decomp.)]. Careful was hydrolysed with aqueous-alcoholic hydrogen déméthylation with phenol and hydriodie acid gives chloride, giving rhamnetidin chloride and insoluble ^-hydroxyflavylium chloride (ferrichloride, m. p. 198°; by-products. Salicylaldehyde condenses with [J3], 1717— 1720).—p-Cymene is converted by sulph- carboxylic acid, decomp, about 250°, and the corre urylazide at 180° into nitrogen, sulphur dioxide, and a sponding 2-( ^methoxyphenyl-, m. p. about 199° non-acetylable base, C9N13N, isolated as the picrate, (decomp.), 2-styryl-, m. p. about 210° (decomp.), m. p. 146°, and chloroplatinate, m. p. 163— 164° 2-me thy lenedioxyphenyl -, m. p. about 245° (decomp.), (decomp.). Since the base does not lose ammonia 2-( 1)dihydroxy-( ?)-tolyl, m. p. about 175°, and when repeatedly evaporated with hydrochloric acid, 2-methyl-, decomp, about 260°, derivatives. the presence in it of a seven-membered ring appears E. W . W ig n a l l . excluded. It and the isomeric base derived from Synthesis of “ p ” acid (2 : 6-dihydroxyquinol- ^-xylene and carbonyl azide (A., 1926, 509) are ine-4-carboxylic acid) obtained from crude therefore considered to be the two possible methyh'so- “ cryzanin ” by hydrolysis. Y. Sa h a s h i (Proc. propylpyridincs containing the alkyl groups in the Imp. Acad. Tokyo, 1927, 3, 437-—438).—2-Hydroxy- 2 : 5-position. In addition, a neutral substance, (?) 6-methoxyqiiinoline-4-carboxylic acid, synthesised by C10H10NC1, m. p. 79°, is obtained in small amount Halberkann’s method (A., 1922, i, 174) on hydrolysis owing to the presence of chloride in the azide solution, by Zeisel’s method affords 2 : 6-dihydroxyquinoline- whilst the mother-liquors from the picrate, m. p. 146°, 4-carboxylie acid, identical with the “ ¡3-acid ” obtained yield a second picrate, m. p. 149°. H. W r e n . from crude oryzanin (A., 1926, 846). Manufacture of quinoline derivatives [zinci- R. B r ig iit m a n . Manufacture of alkoxyamino- [8-amino-6-alk- chlorides]. B r it is h D y e st u ffs Co r p., L t d ., etc. oxy-]quinolines. I. G. F a r b e n in d . A.-G.— See B., —See B ., 1927, 809. 1927, 797. Condensation of acetaldehyde and paracet- aldehyde with aniline in the presence of alumin Quinoline derivatives and condensation pro ium oxide as contact substance. A. E. T s c h it - ducts from 6-amino-3-methoxybenzaldehyde. sciiib a b in and M. P. Op a r in a (Ber., 1927, 60, [5], J. T rog er and C. Cohaus (J. pr. Chem., [ii], 1927, 1873— 1876; cf. A., 1924, i, 709, 766).— Condensation 117, 97— 116).— The condensation of 6-amino-3- is effected between aldehydes and aniline in much the methoxybenzaldehyde (Troger and Fromm, A., 1926, same manner as between aldehydes and ammonia 68; acetyl derivative, m. p. 187°) with various (loc. cit.), but the use of considerably higher tem carbonyl and cyano-compounds is investigated. With peratures is advantageous for the production of ethyl acetoacetate and ethyl benzoylacetate in hot quinoline bases in general and of 4-methylquinoline in alcoholic solution in presence of a few drops of particular. The production of 2- and 4-methyl- sodium hydroxide it yields respectively ethyl G-meth- quinolines from acetaldehyde and aniline is precisely oxy-2-methylquinoline-Z-carboxylate, an oil (chloro- analogous to that of 2- and 4-methylpyridines from platinate), and ethyl 6-methoxy-2-phenylquinoline-3- acetaldehyde and ammonia. Probably crotonalde- carboxylate, m. p. 115° {acid, m. p. 232°; chloro hyde is intermediately formed. Skraup’s reaction platinate and silver salt of the aeid), whilst when heated appears therefore as a special case of the reactions of together in a sealed tube at 160° for 4 hrs. without Dobner and von Miller (production of 2-substituted solvent or catalyst the products are respectively quinoline homologues) and Tschitschibabin (pro 2-hydroxy-G-methoxy-Z-acetylquinoline, m. p. 297° duction of 4-substituted quinoline homologues). (phenylhydrazone, m. p. 252°), and 2-hydroxy-G- H . W r e n . methoxy-3-bcnzoylquinoline, m. p. 293° (phenylhydr Condensation of crotonaldehyde with am azone, m. p. 229°). Condensation with compounds of monia in the presence of aluminium oxide. the type R ,CH2*CN in alcoholic solution with sodium A. E. T schitschibabin and M. P. Op a r in a (Ber., hydroxide as a catalyst yields 2-aminoquinoline 1927 , 60, [5], 1877— 1879).—Substitution of croton derivatives : thus p - bromobenzenesulphonaceto- aldehyde for acetaldehyde in the synthesis of pyridine nitrile, phenylacetonitrile, and malononitrile yield, bases from aldehydes and ammonia in the presence of respectively, 2-amino-G-methoxy-Z-^-bromobenzenesul- aluminium oxide causes a very marked reduction in plionyl-, m. p. 89— 90°; -Z-phenyl-, m. p. 143° (hydro the amount of the picoline fraction (the formation of chloride ; yields 2-hydroxy-G-methoxy-Z-phenylquind- these is due to the partial depolymerisation of ine, m. p. 109°, on treatment with nitrous acid), and crotonaldehyde to acetaldehyde) and a great increase -Z-cyano-quinoline, m. p. 243— 244° [which, on in the proportion of collidines of which the main treatment with nitrous acid, yields 2-hydroxy-G- component is |3-collidine. The yield of the latter methoxy-3-cyanoquinoline, m. p. 263°, and, on hydro substance amounts to 20% of the crude bases. The lysis, 2-amino-G-methoxyquinoline-Z-carboxylic acid, isolation of a collidine picrate, m. p. 163— 164°, is m. p. above 300° (silver salt; chloroplatinate) whilst recorded. H. W r e n . subsequent treatment with nitrous acid yields Synthesis of quinoline-4-carboxylic acids. S. 2-hydroxy-G-metkoxyquinoline-3-carboxylic acid, m. P- B e rlin gozzi and A. T urco (Rend. Accad. Sci. fis. 283° (disilver salt)]. In all three cases the 2-amino- mat. Napoli, 1927, [iii], 33, 50—52).—Substituted group is eliminated as ammonia on reduction with derivatives of 2-phenylcinchoninic acid (“ atophan ” ), tin and hydrochloric acid. Condensation with ethyl shown by Nicolajer and Dorn (Det. Arch. klin. Med., cyanoacetate yields 2-hydroxy-6-methoxy-3-cyano- 1908, 93, 331) to increase excretion of uric acid in the quinoline (above) whilst the corresponding -3-carb- urine, are prepared by condensing pyruvic acid and oxylic acid is also obtained by condensation with acetylbenzidine with various aldehydes by the method malonic acid. Condensation with phenacyl cyanide of Knorr (A., 1884, 1198). The following are yields 6-methoxy-Z-cyano-2-phenylquinoline, m. p. 170 described: &-^-acetamidophenyl-2-phenylquinoline-ii- (chloroplatinate), irrespective of the method of con- ORGANIC c h e m i s t r y . 1087 densation employed. Condensation with barbituric 4-amino-l-phenyl-5-pyrazolone-3-carboxylic acid, and acid in the presence of alkali yields 2 :4 -diketo- finally to the two stereoisomeric diaminosuccinic 1:2:3: 4-tetrahydro-Q - methoxijquinoline-1 : 3 - diazine acids. CO When l-phenyl-4 : 5-diketopyrazoline-3-carboxylic acid 4-phenylhydrazone is brominated in glacial MeO/\/\ /\NH acetic acid the product is the 4-p-bromophenyl- CO hydrazone, m. p. 258° (decomp.), which is synthesised (I.)n 1 Nw NHAm from l-phenyl-5-pyrazolone-3-carboxylic acid and 2>-bromodiazobenzene. The following esters of l-phenyl-4 : 5-diketopyrazol- or M e O / y one-3-carboxylie acid 4-phenylhydrazone are prepared by action of alcohols and hydrogen chloride on \NTH anhydrodiketosuccinic acid phenylosazone : methyl, (I), m. p. 273° (sodium and silver salts). 6-Amino-3- m. p. 138°; ethyl, m. p. 153°; n-propyl, m. p. 116-5° ; methoxybenzaldehyde itself is unstable and readily n-butyl, m. p. 117°. C. H o llin s. condenses to a yellow solid substance, possibly (II) or Condensation of dimetbylbarbituric acid with (III). J. W . B a k e r . aldehydes. Colour reaction of furfuraldehydes. (3-Substituted derivatives of “ atophan ’' [2- S. A k a b o r i (Proc. Imp. Acad. Tokyo, 1927, 3, 342— phenylquinoline-4-carboxylic acid]. S. B e r l in - 344).— Dimetbylbarbituric acid condenses readily gozzi and A. T urco (Rend. Accad. Sci. fis. mat. in aqueous or alcoholic solution with benzalde- Napoli, 1925, [iii], 31, 191— 193).— On condensing a hyde, vanillin, furfuraldehyde, methylfurfuraldehyde, solution of isatin in potassium hydroxide solution with hydroxymethylfurfuraldehyde, '¡3 - indolealdehyde, co-phenoxyacetophenone in alcohol, there is obtained, cinnamaldehyde, and citral, forming crystalline pro on acidification, ‘i-phenoxy-2-phenylquinolineA-carb- ducts, m. p. 159— 159-5°, 222-5—223-5°, 194-5— 195°, oxylic acid, m. p. 232° (heavy metal salts insoluble, but 172— 172-5°, 181— 182°, 291— 292° (decomp.), 195-5— barium salt soluble in water), which when heated yields 196°, and 101— 101-5°, respectively. Barbituric and 3-phenoxy-2-phenylquinoline, m. p. 130— 131°. dimethylbarbituric acid derivatives of furfuraldehyde, E. W . W ig n a l l . methylfurfuraldehyde, and hydroxymethylfurfuralde- 3-Substituted quinolines. S. B e r lin g o zzi and hyde give intense colorations with aniline and aniline W. E. B urg (Rend. Accad. Sci. fis. mat. Napoli, 1927, acetate, recognisable up to dilutions of 1 in 10G. [iii], 33, 39— 40).— By condensing AT-£)-hydroxy- B. W. A n d e r so n . phenacylphthalimide (obtained from ^-chloroacetyl- Barbituric acid derivative. E. H. V o l w il e r .— anisole and potassium phthalimide) with o-amino- See B., 1927, 797. benzaldehyde, and hydrolysing, Z-amino-2-p-methoxy- Action of the Grignard reagent on alkyl- phenylquinoline, m. p. 138° (acetyl derivative, m. p. barbituric acids. A. W. D ox (J. Amer. Chem. 165°), is obtained, which on diazotisation yields Soc., 1927, 49, 2275—2279).—Treatment of 5 : 5'-di- 3-hydroxy-2-;p-methoxyphenylquinoline. alkylbarbituric acids with Grignard reagents results Using isatoic acid, Z-amino-2-p-methoxyphenyl- in reaction of two carbonyl groups, with subsequent quinoline-i-carboxylic acid, decomp, about 150° (acetyl elimination of 1 mol. of water. The products are derivative, m. p. 212°), is obtained, which on diazotis highly resistant to hydrolytic agents, and are therefore ation yields the corresponding 3-hydroxy-compound regarded as endo - ethers of 4:6- dihydroxy - 2 - keto - (Berlingozzi and Capuano, A., 1924, i, 1345). 4:5:5: 6-tetra-alkylhexa- E. W . W ig n a l l . CR3-NHs hydropyrimidines (I). [Nitro- and amino-acridines.] H . J e n se n ^>0 \CO Derivatives of this type (Ber., 1927, 60, [B], 2033).—The constitution of the Transpositions in discatole. B. O d d o and The base is yellow, gives red salts, and absorbs oxygen Q. M in g o ia (Gazzetta, 1927, 57, 480— 485).— Acetyl- from the air, forming a dioxy - derivative, C27H2202N2, discatole, C^H^ONj, m. p. 180°, and benzoyldiscatole, decomposing at 168° with incandescence. By the m. p. 207°, are resistant to hot aqueous alkali, and form action of aqueous potassium hydroxide on the silver compounds with the silver atom attached to the methosulphate a deep green substance, C28H24N2,2H20, imino-nitrogen atom. These derivatives are hence is obtained. This is probably the hydrate of the carbon-substituted compounds, and it must be anhydro-base (III), similar in nature to the quin- assumed that the mobility of the imino-hydrogen atom hydrones, pyranhydrones, and flavanhydrones. of the tetrolic nucleus remains unaltered in the discatole C. H o llin s. molecule and that transposition of the substituent Isomeric relationships in the pyrazole series. group to the only available carbon atom, that in the XI. Alkyl derivatives of 3(5)-phenylpyrazole. a-position of the tetrolic nucleus, takes place : K. v o n A u w e r s and C. M au solf (Ber., 1927, 60, [J3], 1730— 1736).— Ethyl 5(3)-phenylpyrazole-3(5)- 'CH—- carboxylate, m. p. 140°, prepared from ethyl benzoyl- C«H4 carboxylic acid corresponding with coproporphyrin, Derivatives of 2:3:5: 6-dibenzo-l : 8-naph the four additional carboxyl groups are most probably thyridine. R. D. H a w o r t h and H . S. P i n k (J.C.S., attached to the same carbon atoms as the remaining 1927,2345—2349).— Homophthalimide condenses with four; i.e., uroporphyrin contains four malonic acid o-nitrobenzaldehyde in pyridine solution in presence groupings. This view is confirmed by the synthesis of a trace of piperidine, giving o-nitrobenzylidenehomo- of isouroporphyrin. phthalimide, m. p. 236°, which is reduced with stannous Bromination of ethyl 2 : 4-dimethyl-3-|3(3-dicarb- chloride in alcoholic solution to l-keto-2 : 3 : 5 : 6-di- ethoxyethylpyrrole-1-carboxylate (Fischer and Ander- benzo-1 : 8-dihydro-l : 8-naphthyridine (I), m. p. 246— sag, unpublished work) in ether gives the 4-bromo- 247° (potassium salt; sodium salt). Further reduction methyl compound, m. p. 90° (i-anilinomethyl com with zinc dust in glacial acetic acid saturated with pound, m. p. 100°), which is converted by boiling with hydrogen chloride gives l-keto-2 : 3 : 5 : 6-dibenzo- water or methyl alcohol, with loss of formaldehyde and 1 : 4 : 7 : 8 : 9 : 10-hexahydro-l : 8-naphthyridine (II), hydrogen bromide, into bis(l-carbethoxy-2-metliyl- m. p. 250° (monohydrochloride, decomp. 270°; nitroso- ‘¿-{i[i-dicarbethoxyethyl-4:-pyrryl)mcthane, m. p. 126°; amine; picrate, m. p. 270°). The corresponding when methyl alcohol is used there is also formed, by derivatives from iV-|3-phenylethyl- and Ar-|3-piperonyl- exchange of alkyl groups, bis(l-carbethoxy-2-methyl- ethylhomophthalimidc were also prepared : o-nitro- 3-$$-dicarbomethoxyethyl-4-pyrryl)methane, m. p. 168°. benzylidene-^-^-phenylethylhomophthalimide, m. p. The hexasodium salt (free acid, m. p. 176°), obtained 146°; 7-keto-8-fi-phenylethyl-2 : 3 : 5 : 6-dibenzo-l : 8- by alkaline hydrolysis, is converted, when heated in dihydro-1 : 8-naphthyridine, m. p. 220°; l-keto-8-&- formic or acetic acid, into a mixture of copro- and phenylethyl-2 : 3 : 5 : 6-dibenzo-l : 4 : 7 : 8 : 9 : 10-liexa- isocopro-porphyrins, separable by means of their hydro-l : 8-naphthyridine, m. p. 217°; o-nitrobenzyl- tetramethyl esters. This loss of four “ malonic ” idene-1$-$-piperonylethyUiomophthalimide, m. p. 176°; carboxyl groups is prevented, however, by aerating a 1 -keto-8-$-piperonylethyl-2 : 3 : 5 : 6-dibenzo-l : 8-di solution of the hexasodium salt in 95% formic acid hydro-l : 8-naphthyridine, m. p. 217°; l-keto-8-$- maintained at 40°. Under these conditions isowro- piperonyleihyl-2 : 3 : 5 : 6-dibenzo-l : 4 : 7 : 8 : 9 : 10- porphyrin separates after 24— 48 hrs. The octa- hexahydro-1 : 8-naphthyridine, m. p. 211°. When (I) methyl ester, m. p. 263° (cf. uroporphyrin octamethyl is heated with phosphorus oxychloride and phosphorus ester, m. p. 292°), gives complex iron and copper salts. pentachloride at 180° and the resulting unstable MoUroporphyrin loses 4C02 at 150— 170°, forming chloro-compound is reduced with phosphorus and isocoproporphyrin, and is reduced by sodium hydriodic acid at 160— 170°, a base, 2:3:5: 6-di- amalgam to a fewco-compound, readily re-oxidised to benzo-4: : Q-dihydro-1 : 8-naphthyridine (?), m. p. 232° the porphyrin. Oxidation of isouroporphyrin with (monohydrocldoride; hydriodide), is obtained, in chromic acid gives a carboxyhaematic acid, a-methyl- addition to (II). M. Cl a r k . ¡}(PP-dicarboxyethyl)maleinimide, m. p. 178°, which Cyanine dyestuffs. I. Synthesis of pinacyanol. sublimes in a vacuum at 115— 120° and is identical II. Synthesis of pinacyanol using trioxymethyl- with the oxidation product from natural uroporphyrin ene. T. Ogata (Proc. Imp. Acad. Tokyo, 1927, 3, [crystallographic data by Ste in m etz], isoUropor- 334— 338).—2-Methylquinoline ethiodide reacts with phyrin strikingly resembles uroporphyrin in physio 2-$-hydroxyelhylenequinolinc ethiodide, decomp. 214— logical action, but is more poisonous. 218° (obtained from 2-P-hydroxyethylenequinoline), in Reduction of ethyl 2 : 4-dimethyl-3-p(3-dicarb- presence of sodium ethoxide to form pinacyanol ethoxyethylpyrrole-1-carboxylate with hydriodic acid iodide. 6-Ethoxy-2-methylquinoline when heated gives cryptopyrrolecarboxylic acid, m. p. 138° with formaldehyde and alcohol, yields G-ethoxy-2-fi- (picrate, m. p. 153°). Fischer and Nenitzescu’s bis- hydroxyethenylquinoline, m. p. 85—86° (platinum (2 : 4-dimethyl-3-!3[3 - dicarbomethoxyethyl - 5 - pyrryl)- derivative, in. p. 135— 140° [decomp.]), the ethiodide, methene (A., 1926, 178) forms a complex copper salt, decomp. 193— 195°, of which combines with 6-ethoxy- C50H62O1GN4Cu. C. H o llin s. 2-methylquinoline ethiodide, yielding 6 : 6'-diethoxy- Action of diacetyl on magnesylpyrrole. N. A. 1 : 1'-diethyl-2 : 2'-carbocyanine iodide (diethoxypina- cyanol iodide), m. p. 290—291°. Similarly 6-ethoxy- Narysch kin (Ber., 1927, 60, [5], 1928— 1930; cf. A., 1926, 183; this vol., 162).— Diacetyl is con 2-methylquinoline ethiodide combines with 2-¡3-hydr- verted by magnesium pyrryl iodide into a compound, oxyethenylquinoline ethiodide to form 6-ethoxy-l : 1'- C12H10O2N2> converted by hydrochloric acid into an diethyl-2 : 2'-carbocyanine iodide, m. p. 278—279° (decomp.). unstable, coloured hydrochloride. H. W r e n . 2-Methylquinoline ethiodide (2 mols.) reacts with 1 : 8-N aphthyridine. G. K o lle r (Ber., 1927, trioxymethylene (1/3 mol.) in presence of sodium 60, [5], 1918— 1920; cf. this vol., 367, S86).— 1 : 8- (2 mols.) to give a 75% yield of pinacyanol iodide. Naphthyridine, m. p. 98— 99° after softening at 95° B. W. A n d e r so n . (in an evacuated tube), is isolated from the products Condensation of 2-amino-3-methoxybenzalde- °f the catalytic reduction of 2 : 4-dichloro-l : 8- hyde, its acyl derivatives and quinazolines de naphthyridine by cautious fractional distillation in a rived from them. J. T ro g er and V. Sa b e w a (J. pr. vacuum. Its sensitiveness towards hydrogenation Chem., 1927, [ii], 117, 117— 141).— 2-Amino-3-meth- and oxidation is remarkable. The picrate, m. p. oxybenzaldehyde readily condenses with itself, the 207—208° after softening at 200°, and methiodide, best yield of crystalline anhydrobis-2-amino-Z-methoxy- C9H9N2I, m. p. 180— 181°, are described; the latter benzaldehyde, m. p. 265°, possibly substance regenerates 1 : 8-naphthyridine when CHO heated. H. W r e n . OMe'CcH3< N:CH.c eH3(OMe)-NH2 or 1090 BRITISH CHEMICAL ABSTRACTS.— A. GMe-O H^H-C H3(°Me), ^ by keep_ dimethyl-1 : 2 : 4-triazole, m. p. 93— 94° (pierate, CH(OH) NH m. p. 166— 167°) (cf. Hernler and Matthes, this vol., ing its solution in acetic acid for 12—15 hrs. The 468), is prepared in good yield from 3 mols. of same product is obtained in an amorphous form diacetamide and 1 mol. of ^p-bromophenylhydrazine. in the preparation of various of the acyl derivatives It is also obtained by the usual method from the described below. When the aldehyde is heated for corresponding amino-compound, which in turn is a long time in benzene solution with ethyl chloro- prepared from the bromo-derivative by the action of formate, anhydrotris-2-amino-'i-methoxybenzaldchyde, ammonia in presence of copper bronze. 1-p-Cyano- m. p. 259°, possibly phenyl-Z : 5-dimethyl-1 : 2 : 4-triazole, m. p. 68—70° CHO (pierate, m. p. 143-5— 144°), is hydrolysed by alcoholic OMe'C6H3<]sT;c II.C6li 3(OMe)N;cH -C(,H3(OMe)-NH2 potassium hydroxide to l-'phenyl-Z: 5-dimethyl-l: 2 :4- OMe-96H3-N:CH------96H3-0Me j b_ triazole-4'-carboxylic acid, m. p. 293—294°. This CH[NH-C6H3(OMe)(CHO)-NH acid is also obtained from the bromo-compound by tained as a dark yellow powder. Either product is the action of cuprous potassium cyanides (cf. Rosen- reconverted into the original aldehyde (isolated as its mund and Struck, A., 1920, i, 44), but not by the chloroplatinate) by hot concentrated hydrochloric acid, action of magnesium and carbon dioxide. but subsequent treatment with phenyl hydrazine yields H . B u r t o n . a phenylhydrazone, m. p. 190°, of the bis- or tris-com- 7 : 9-Dimetbyl-[A3:1-]isouric acid. H. B iltz and pound. A series of acyl derivatives of 2-amino-3- H. B u lo w (Annalen, 1927, 457, 103— 131).— 8-Thio- methoxybenzaldehyde has been prepared, the method 7 : 9-dimethyl-,/,-uric acid (Biltz and Bulow, A., 1922, varying somewhat from case to case. By the action i, 381) dissolves in sodium hydrogen carbonate of acetic anhydride in ether is obtained 2-acetamido-, solution with evolution of carbon dioxide; after m. p. 156° (‘phenylhydrazone, m. p. 214°); the action cooling with ice, iodine is added, whereupon carbon of butyric anhydride for 2 hrs. at 100° yields 2-butyr- dioxide is again evolved, and 7 : 9-dimethyl-A3:i-isouric amido-, m. p. 100° (phenylhydrazone, m. p. 165°); acid, decomp. 262— 263°, separates. This gives a 2-benzamido-, m. p. 115° (phenylhydrazone, m. p. 166°), strong murexide reaction. The dihydrate, mono is obtained by the action of benzoyl chloride on a hydrate, anhydride (all of the above decomp, tem suspension of the aldehyde in potassium hydrogen perature), hydrochloride (darkens from 270°, decomp. carbonate solution, whilst by the Schotten-Baumanh 350— 360°, easily hydrolysed by water), nitrate method using the appropriate acid chloride are (decomp. 130°), perchlorate (probably obtained 2-phenylacetamido-, m. p. 98° (phenyl C7H803N4,HC104,2H20), and hydrogen sulphate (sinters hydrazone, m. p. 194°) [which on treatment with at about 190°), potassium salt (C7H703N4K,H 20), alcoholic potassium hydroxide solution yields 2-hydr- sodium, ammonium, and lead salts are described. oxy-8-methoxy-3-phenylquinoline (Troger and Gero, Attempts to determine the position of the replace A., 1926, 1045)]; 2-toluoylamido-, m. p. 150° (phenyl able hydrogen atom by the action of methyl sulphate hydrazone, m. p. 180°); 2-o-chlorobenzamido-, m. p. or of methyl iodide on the salts give no crystallisable 140° (phenylhydrazone, m. p. 212°); 2-(2 : 4)-dichloro- product, whilst diazomethane has no action on the benzamido-, m. p. 161° (phenylhydrazone, m. p. 225°); free dimethyh'souric acid. Oxidation by chromic and 2-p-bromobenzamido-, m. p. 134° (phenylhydrazone, acid yields dimethylparabanic acid : the methylated m. p. 192°) -Z-methoxybenzaldehyde. It was not glyoxaline ring is more resistant than the unsaturated found possible to prepare the 2-^-nitrobenzamido- pyrimidine ring. 7 : 9-Dimethyluric acid yields the compound, the only product obtained by the action of same product. y-nitrobenzoyl chloride being the condensation pro DimethyHsouric acid is not reduced by ordinary duct of the aldehyde, m. p. 265°. These acyl deriv reducing agents even at high temperatures. Zinc atives, on treatment with alcoholic ammonia, yield and hydrochloric acid give oily products. Chlorine 8-methoxyquinazoline derivatives in accordance with and water cause oxidation to 7 : 9-dimethyluric acid the scheme OMe-C6H3(CHO)-NH-COR+NH3= glycol, or, in presence of alcohol, to the dimethyl ether of the glycol. OMe,C6H3< C ^ '^ ,+ 2 H 2Q, and thus from the appro A boiling solution of sodium 7 : 9-dimethyh.so- urate with hydrochloric acid yields 7 : 9-dimcthyl- priate acyl derivative are obtained 2-methyl-, m. p. uric acid; this transformation does not occur when 128° (chloroplatinate', chloromercurate, m. p. 140°; acetic acid is used, nor when the solution is well pierate, m. p. 118°); 2-n-propyl-, m. p. 60° (chloro- cooled during acidification. Treatment of the acid aurate, m. p. 116°; pierate + 2 H 20, m. p. 140°); with hydrochloric acid in a sealed tube has the same 2-phenyl-, m. p. 99° (chloroplatinate + 1-5H20 ; pierate, action; on boiling with water, however, only one m. p. 178°; perchlorate)’, 2-benzyl-, m. p. 88°; fifth of the theoretical yield of dimethyluric acid is 2-p-tolyl-, m. p. 70° (chloroplatinate + 4 H 20 ; pierate, obtained, the rest decomposing. m. p. 169°); 2-o-chlorophenyl-, m. p. 118° (chloro The action of organic acids on 7 : 9-dimethyh'souric platinate; chloromercurate)', 2-(2 : 4-)-dichlorophenyl-, acid causes a new condensation. The hydrocarbon m. p. 132° {pierate, m. p. 105°); 2-p-6rorrwphenyl-, radical of the acid becomes attached to the 4-carbon m. p. 127° (incrate, m. p. 129°; chloromercurate) atom, and hydrogen to the 3-nitrogen atom, carbon - S-methoxyquinazolines. J. W. Baker. dioxide being evolved. It is suggested that the first Triazoles. VII. Substituted l-phenyl-3 :5- product is a 4-hydroxy-3-acyl derivative, which then dimethyl-1 : 2 : 4-triazoles. F. H ernlbr (Mon- inverts thus : •N;C< — > •N(COR)-C(OH)< —-> atsh., 1927, 48, 391— 403).— l-p-Bromophenyl-3 : 5- -NH-CR<-f-C02. This is thought to be more p r o b a b le ORGANIC CHEMISTRY. 1091 than the intermediate formation of •NII(C02R)!0 4-Phenyl-7 : 9-dimethyl-4 : 5-dihydrouric acid yields (cf. the formation of 8-alkylxanthines by the action with sodium hydroxide 4-phenyl-l : ‘¿-dimethylglyozal- of acid anhydrides on uric acid; Biltz and Schmidt, one-5-carboxylic acid, decomp. 217— 218° (silver salt, A., 1923, i, 489). decomp. 195°, giving a methyl ester, m. p. 124°), When formic acid is used, the group R becomes which when heated with aqueous or alcoholic hydro hydrogen and the acid is reduced. Thus on boiling chloric acid gives 4-phenyl-l : Z-dimethylglyoxalone, the dihydrate with 80% formic acid, 7 : 9-dimethyl- m. p. 92° (hydrochloride, m. p. 93— 94°). This is 4 : 5-dihydrouric acid, sintering from 250°, decomp. oxidised by nitric acid in acetic acid to N-/omyZ-N'- 268°, is obtained. A sodium salt is prepared; benzoyl-NN'-dimelhylcarbamide, m. p. 115° (decomp.), although the substance is soluble in hydrochloric and is converted by chromic acid into 5-hydroxy-5- acid, no hydrochloride can be isolated, in agreement phenyl-l : 3-dimethylhydantoin, m. p. 115— 118°. The with the absence of an unsaturated tertiary nitrogen latter is reduced by hydriodic acid to 5-phenyl-l : 3- atom. Oxidation by chromic acid yields a substance dimethylhydantoin, m. p. 105— 106° (cf. Gabriel, A., which may be formylmelhylbiuret, 1907, i, 91). E. W. W ignall. CHO-NH-CO-NH-CO-NHMe, m. p. 250° (decomp.), and dimethylparabanic acid; by chlorine water, 3 : 9-Dimethyl-A5:7-isouric acid, its chlorin amorphous products are obtained. ation products and degradation. H. B il t z and DimethyKsouric acid dihydrate in hot acetic acid H. K r z ik a l l a [in part with K. Sl o tta] (Annalen, gives, with evolution of carbon dioxide, 4:7: 9-tri 1927, 457, 131— 139).—Experiments on the chlorin methyl-4 : 5-dihydroisouric acid, decomp. 250°, soluble ation of 3 : 9-dimethyluric acid (Biltz and Krzikalla, in alkali without change on acidification, soluble in A., 1921, i, 614) gave under very similar conditions hydrochloric acid. As the murexide reaction is not varied products. Continuing this work, a 3 : 9-di given, a methyl group is considered to be present in methyl-A517-isouric acid has been prepared by reduction the 4-position; chromic acid oxidation yields the of the chloro-derivatives, the structure of which has same products as 7 : 9-dimethyl-4 : 5-dihydroisouric been established. By degradation, hydantoins are acid. obtained, including one with a new fused ring system, DimethyKsouric acid when heated with benzoic a hydantoinohydantoin. acid at 150— 160° gives, with another substance, m. p. The preparation of 3 :9-dimethyluric acid by 241— 244°, 4 - phenyl - 7 : 9-dimethyl-4 : 5-dihydrouric methylation of dipotassium urate is improved at all acid, m. p. 244° (decomp.), which is only slightly stages. For the methylation, methyl toluene-p- soluble in sodium hydroxide solution, gives no sulphonate is now employed, at atmospheric pressure murexide reaction, and is not reduced by hydriodic in o-dichlorobenzene at 145—155°, and much of the acid. In accordance with the formulation, dimethyl decomposition causcd by methyl sulphate is thus parabanic acid canjiot be obtained by oxidation. avoided, improved yields being obtained. The above dimethyldihydrouric acids on heating There are three main products of chlorination, with sodium hydroxide solution evolve ammonia, according to the conditions. and by fission of the pyrimidine ring are converted (1) Chlorination in acetic acid, followed by removal into glyoxalonecarboxylic acids. Thus 7 : 9-dimethyl- of chlorine in a current of air and precipitation by 4 : 5-dihydrouric acid gives 1 : %-dimethylglyoxalone- ether, gives 4-chloro-3: 9-dimethyl-A5:7-isouric acid, (I), 5-carboxylic acid, sintering from 205°, decomp. 220° which (+0-5AcOH) sinters from 70° to 80°, and then (silver salt, from which the methyl ester, m. p. 127°, decomposes, and gives a strong murexide reaction. is obtained, although unobtainable from the acid by This on treatment with water yields 3 : 9-dimethyl the action of methyl alcohol and hydrogen chloride). uric acid glycol, and in methyl and ethyl alcohols the This is oxidised by chromic acid to dimethylparabanic corresponding dialkyl ethers (loc. cit.). By reduction acid, and on distillation gives 1 : 3-dimethylglyoxalone, with hydriodic acid, the original 3 : 9-dimethyluric m. p. about 100°, which becomes oily in contact with acid is obtained. Other reducing agents yield a water, and forms a hygroscopic hydrochloride. different product (see below). By the action of Heating the o-carboxylic acid with hydrochloric acid hydrogen chloride in acetic acid, 1 : 7-dimethyl#piYo- gives, however, other decomposition products. dihydantoin (loc. cit.) is formed. 1 : 3-Dimethylglyoxalone in water, alcohol, or acetic Similarly 1-acetyl-3 : 9-dimethyluric acid (loc. cit. : acid gives with bromine a dark violet coloration, the method of preparation has been improved) turning red and then yellow on further addition of chlorinates to the 4-c/iZoro-derivative, decomp. 205°. bromine. Chromic acid oxidation yields dimethyl This, which is remarkably stable to water and to parabanic acid. Attempted catalytic hydrogenation alcohol, liberates iodine from potassium iodide was unsuccessful, as was an attempt to isolate solution, and gives on reduction 3 : 9-dimethyluric ■s-diformyldimethylcarbamide from the products of acid. The formulation is confirmed by the production nitric acid oxidation. of methylamine on heating with sodium hydroxide 4:7: 9-Trimethyl-4 : 5-dihydrouric acid yields solution, and of 4-hydroxy-3 : 9-dimethyl-A5-7-isouric 1:3: 4-trimethylglyoxalone-5-carboxylic acid, decomp. acid, m. p. 265— 267°, by hydrolysis with 30% acetic 179° (silver salt, decomp. 182°, yielding a methyl ester, acid. The hydroxy-compound is converted by ttt. p. 88—89°, unobtainable from the acid). The acid diazomethane into tetramethykpirodihydantoin, with easily loses carbon dioxide in water at 100° to the probable intermediate formation of the 5 : 7 -glycol. give 1:3:4-trimethylglyoxalone, b. p. about 210°. That the acetyl group in acetyldimethyluric acid is in Attempted catalytic hydrogenation failed, as did the 1-position is confirmed by implication in the above oxidation by nitric acid, which gave syrupy products. reaction, for the shifting of the double Unking from 1092 BRITISH CHEMICAL ABSTRACTS.----A. the 4:5- to the 5 : 7-position is probably due to C7H80 3N4,HI3, decomp. 107°, and a ■perchlorate, in addition of chlorine at the 5- as well as at the 4-position (see also II, below), followed by loss of agreement with its possession of the ~C;N-C- grouping. hydrogen chloride by removal of the 7-hydrogen atom, 3 : 9-Dimethyl-A5:7-isouric acid is oxidised by which would not be possible if acetyl were present at hydrogen peroxide on the water-bath to ammonium the 7- instead of at the 1-position. A definite proof methyloxalurate (Slotta, A., 1925, i, 1189). At the is, however, given by metliylation : by the action of ordinary temperature, an intermediate substance, methyl sulphate and sodium hydroxide solution, regarded as 4 : 5-dihydroxy-4-oc-methylcarbamido-Z- followed by removal of the acetyl group by heating methyl-2-glyoxalidone, decomp. 175— 180°, is formed; in absence of methyl sulphate, 3:7: 9-trimethyluric this on heating with acetic anhydride yields an acid is obtained. isomeride (?), m. p. 226°. (2) Chlorination of 3 : 9-dimethyl-A5:7-isouric acid The inversion of the iso-acid to 3 : 9-dimethyluric in a similar manner, using carefully dried materials, acid, which occurs on melting, is produced on heating gives on slow crystallisation, instead of precipitation at 310— 320°, or on heating with acetic or formic acid. by ether, 4 : o-dichloro-3 : §-dimethyl-4 : 5-dihydrouric The inversion in presence of acetic acid explains the acid (II), decomp. (+0-5AcOH) from 210° to 230°, formation of dimethyluric acid when the above chloro- with some 1 : 7-dimethyls^iVodihydantoin. The di- derivatives are reduced by zinc and acetic acid. The chloro-compound does not react with cooled methyl action of chlorine upon the iso-acid in methyl alcohol alcohol, and gives no murexide reaction. It is reduced yields 4 : 5-dichloro-3 : 9-dimethyldihydrouric acid, by zinc and acetic acid to 3 : 9-dimethyluric acid; free from acetic acid, darkening from 200°, decomp, attempted removal of hydrogen chloride to give an about 310°. isouric acid gave no crystalline product. The sub Degradation of the above chloro-derivatives yields stance was at first thought to be 4 : 7-dichloro-3 : 9- a substance C5H704N3, possibly as the result of dimethyl-4 : 5-dihydrouric acid, which formulation inversion with rupture of the pyrimidine ring, to give would make the formation of a hydantoin derivative a carbamylhydantoin (cf. following abstract for (see later) more easily understood; this formula was, synthesis). Thus 4 : 5-dichloro-3 : 9-dimethyldi however, discarded. hydrouric acid dissolves slowly in boiling water, with (3) Chlorination in acetic anhydride, or in an equal the evolution of carbon dioxide and separation of mixture of the anhydride and the acid, gives 4-chloro- methylamine hydrochloride to form 5-hydroxy-l- 5-acetoxy-4: 0-dimethyl-4 : 5-dihydrouric acid (III) (sintering from 190° to 200°, followed by decom carbamyl-3-methylhydantoin, ¿ q NMe ¿ 0 ° ^ (V)’ position), also obtainable by the action of acetic decomp. 216— 217°, resolidifying at 230°, decomp. anhydride on I. The new substance reacts with 235°, b. p. about 200°/20 mm. (?), which crystallises alcohol, but no product has been isolated; it gives no out on cooling. The same substance is obtained from murexide reaction. Reduction by zinc and acetic 4-chloro-3 : 9-dimethylisouric acid, or from 3 : 9-di- acid yields 3 : 9-dimethyluric acid. methylisouric acid itself by passing chlorine into a Similarly l-acetyl-3 : 9-dimethyluric acid yields its suspension in water. This substance gives no 4-c/iZoro-5-aceio£y-derivative, decomp. 168— 170°, also murexide reaction; it is unaltered by boiling water, obtainable from the 4-chloro-derivative. by hydrochloric acid, by concentrated sulphuric acid, All chlorination products in the above three groups by boiling anUine or nitrobenzene, by gentle heating (the usual starting material being the dichloride) are re with hydriodic acid or hydrochlorostannic acid, by duced by potassium iodide and sodium thiosulphate to diazomethane or by nitrous acid; it is oxidised, 3: Q-dimethyl-A5:7-isouric acid, i ^ ^0 9'^ 9 (IV), however, by ammoniacal silver nitrate solution. J CO-NMe-CH-NMev 1 Attempts to prepare a derivative by action of benzoic decomp. 418— 420°, the same temperature as that of anhydride or benzoyl chloride were unsuccessful, as 3 : 9-dimethyluric acid, into which it inverts. The were those to induce reaction with phenyl- or methyl- new acid is distinguished from the latter by giving no carbimide. murexide reaction, whether treated with nitric acid The hydantoin (V) on heating in a flame gives the or with chlorine water. By hydrolysis with barium acrid odour of cyanic acid; it is oxidised by chromic hydroxide solution, or with dilute mineral acids (in acid to methylparabanic acid, and reduced by fuming which its solubility is a characteristic), methylamine is hydriodic acid in presence of phosphonium iodide at produced, and a substance described below. Diazo- 100° to l-carbamyl-3-methylhydantoin (see below), methane causes no metliylation, although nitrogen is and 3-methylhydantoin. evolved (cf. acetylcarbamide, which behaves similarly). 5-Aceioxy-l-carbamyl-3-methylhydanioin, m. p. 212— Unlike 3 : 9-dimethyluric acid, the iso-acid crystallises 215° (slight decomp.), is obtained by acetylation of without water; it reduces ammoniacal silver nitrate the hydroxy-compound in boiling acetic anhydride, solution. The solid has df‘ 1-591 (L. Klemm); the or by treating 4-ch]oro-5-acetoxy-3: 9-dimethyl- mol. vol. is thus 123-2 c.c., 1-6 c.c. greater than that 4 : 5-dihydrouric acid (in the reduction of which, of the stable 3 : 9-dimethyluric acid (Klemm and above, it is formed as a by-product) with boiling water, Klemm, this vol., 498). or, better, with 50% acetic acid. The acetoxy- Reduction of 4-chloro-5-acetoxy-3 : 9-dimethyl- compound is hydrolysed by concentrated sulphuric 4 :5-dihydrouric acid gives an acetoxycarbamvl- acid, is oxidised to methylparabanic acid, and reduced methylhydantoin (see below). to l-carbamyl-3-methylhydantoin. 3 : 9-Dimethyl-AS:7-isouric acid forms a loosely The compound (V) is nitrated by fuming nitric acid combined hydrochloride, a hydrotri-iodide, to o-hydroxy-l-nitrocarbamyl-Z-methylhydantoin, m. P- ORGANIC CHEMISTRY. 1093 180°, reduced to 3-methylhydantoin more easily than chloric acid on 3 : 9-dimethyli'souric acid, or by the the parent substance. action of fuming hydriodic acid to which a small Degradation of (V) by treatment with barium quantity of water and some phosphonium iodide are hydroxide solution gives a barium salt, which on added, or from 5-hydroxy-l-carbamyl-3-methyl- dissolving in hydrochloric acid and precipitating the hydantoin, in which case some 3-methylhydantoin is barium as sulphate, yields oxalic acid; whilst treat formed as a by-product. Chromic acid prepared from ment with sodium hydroxide solution, followed by potassium dichromate and sulphuric acid has no action, acidification and addition of phenylhydrazine, gives but when chromium trioxide dissolved in acetic acid is glyoxylic acid phenylhydrazonc. The filtrate from used, methylparabanic acid is obtained. Reduction by the above barium salt yields co-methylbiuret (cf. Biltz fuming hydriodic acid yields 3-methylhydantoin. and Jeltsch, A., 1923, i, 1074). The hydantoin ring The product of the nitration of l-carbamyl-3- has thus been broken between the 3- and the 4-, and methylhydantoin by fuming nitric acid is the 1-nitro- between the 5- and the 1-positions. carbamyl derivative, m. p. 170°, reduced more readily Degradation of 3 : 9-dimethyl-A5:7-i'souric acid by to 3-methylhydantoin by hydriodic acid than is the dilute acids yields, as mentioned above, methylamine parent substance. hydrochloride, and a compound CcH 504N3. This, to The action of barium hydroxide solution gives a (3) (8) (4) which is ascribed formula barium salt; that of 2Ar-sodium hydroxide solution NMe In the hope that a nitro-derivative would, as before, and oxidised by chromic acid to bromocitraconimide, be more easily reduced, nitration was attempted, but m. p. 174°. H. W r e n . without success. Methylation of the sodium salt by Manufacture of vat dyes of the 1-thionaphthen- methyl sulphate yields \-methylcarbamyl-3-methyl- 2'-indoleindigo series. I. G. F a r b e n in d . A.-G.— hydanloin, m. p. 128— 130°, also, and better, obtainable See B ., 1927, 743. by the action of an ethereal diazomethane solution; the product is oxidised by chromium trioxide in acetic Preparation of arecoline. F . C h e m n it iu s (J. acid to methylparabanic acid, showing that the pr. Chem., 1927, [ii], 117, 147— 150).— Details are 3-position is again substituted by methyl. Attempted given for the extraction of arecoline from betel nuts synthesis by heating 3-methylhydantoin with methyl- in 500 kg. quantities. The yield of pure hydrobromide earbimide was unsuccessful. When, however, is 0-35—0-4%. J. W. B a k e r . hydantoin itself is heated in a sealed tube with methyl- l-Methylephedrine, an alkaloid from Ephedra carbimide, 1-methylcarbamylhydantoin is obtained. species. S. Smith (J.C.S., 1927, 2056—2059).— 1 -Carbamyl-3-ethylhydantoin, m. p. 205—208°, is The Chinese drug Ma Huang contains, in addition obtained by the action of carbamyl chloride on to d-ijj- and Z-ephedrines, a third alkaloid, Z-methyl- 3-ethylhydantoin, prepared from 9-ethyluric acid ephedrine, m. p. 87— 88° (corr.), [a]D —29-2° [hydro glycol. The product gives with fuming nitric acid chloride, m. p. 188—1S9°, [a]D —29-8°; methiodide, l-nitrocarbamyl-3-ethylhydanloin, m. p. 99°. On m. p. 212—213° (corr.), [a]D —21-8°; jncrate, m. p. treatment with 2iY-sodium hydroxide solution, the 144° (corr.)], identical with the product of methylation sodium salt, m. p. 125°, of 1 - ethylcarbamyl- of Z-ephedrine. cZ-^-Methylephedrine, m. p. 30° (corr.), hydantoin, m. p. 185— 187°, is obtained; this is [a]D +48-1° [methiodide, m.p. 216—217° (corr.); picrate, oxidised to parabanic acid, is synthesised by the action m. p. 152—153° (corr.); hydrogen tartrate, m. p. 84° of ethylearbamyl chloride (prepared from s-diethjd- (corr., +2H 20), or 152° (corr., anhyd.)], is obtained by carbamide) on hydantoin, and is methylated by methylation of ¿-^-ephedrine. C. H o llin s. diazomethane to l-ethylcarbamyl-3-melhylhydanioin, isoQuinoline alkaloids. I. Constitution of m. p. 93—94°. The isomeric l-methylcarbamyl-3- nandinine. II. Constitution of domesticine ; ethylhydantoin, m. p. 91— 92°, is obtained by heating isodomesticine. III. Constitution of coptisine. 3-ethylhydantoin with methylcarbimide, and gives IV. Worenine. V. Synthesis of some new a sodium salt, decomp. from 40°; by the action of isoquinoline alkaloids. VI. Spectrographic re fuming nitric acid, a m'Zro-derivative, C7H,0O5N4 (?), searches. Z. K itasato (Acta Phytochim., 1927, 3, m. p. 91— 92°, is obtained. E. W . W ig n a l l . 175—258).— By an improved method of extraction, Synthesis of a substance resembling’ por nandinine, C19H1904N, (I), the amorphous alkaloid phyrin. W . K ü ste r and G. K o p p e n h ö f e r (Ber., isolated from Na7idani domestica, Thunb., by Eijk- 1927, 60, [B], 1778— 1781).—Ethyl 3 : 5-dimethyl- mann (A., 1885, 565), is obtained crystalline, m. p. pyrrole-2 : 4-dicarboxylate is converted by hydrogen 145— 146°, [a]D +63-2° in alcohol. It contains one peroxide and hydrochloric acid in presence of glacial phenolic hydroxyl and one methoxyl group, and gives acetic acid into a substance, Cl2H1304NCl4, m. p. with diazomethane a racemised methyl ether, m. p. 166° after softening at 150°, decomp. 170°; the 166°, identical with cZZ-tetrahydroberberine. Under analogous bnwio-derivative, C12H150 4NBr2, m. p. special conditions, rf-nandinine methyl ether, m. p. 131°, decomp. 180°, is similarly prepared. 4-Carb- 139°, [a]D +246-73°, identical with ¿-canadine, is ethoxy-3 : 5-dimethylpyrrole-2-carboxylic acid, hydro- obtained. The d-ethyl ether, m. p. 109°, obtained by bromic acid, and hydrogen peroxide yield the com- the action of diazoethane on nandinine, is converted, ■pound C30H34O8N4Br4, m. p. 137° (possibly 1 : 3 : 5 : 7- by oxidation with iodine followed by reduction, into tetracarbethoxy - 2 : 4 : 6 : 8 - tetrabromomethylpor - the dl-ethyl ether, m. p. 128°. Reduction of berber- phyrin, but differing in optical properties from known rubine (Frerichs, A., 1910, i, 500) with zinc and porphyrins). If the dye remains in the solution in sulphuric acid gives ¿Z-tetrahydroberberrubine, m. p. which it was prepared for several days, the colour 168°, which is resolved by means of its cZ-bromocam- gradually disappears and carbethoxybromcmethyl- phorsulphonate into cZ-tetrahydroberberrubine, m. p. maleinimide, m. p. 130° (decomp.), is produced. The 144°, [a]D +62-9°, identical with nandinine, and a production of a bromine-free substance, C36H380 8N4, little impure Z-isomeride; iZZ-tetrahydroberberrubine m. p. 208° after softening at 190°, is occasionally ethyl ether, m. p. 128°, is identical with cZZ-nandinine observed during the synthesis. H. W r e n . ethyl ether. The positions of the hydroxyl and methoxyl groups in nandinine must therefore be as Degradation of hasmatoporphyrin to bromo- in (I). From the residues after extraction of nandin- bromohydroxyethyltetramethylporphindipropi- me second crystalline alkaloid, domesticine, onic acid. H. F is c h e r and F . K otter (Ber., 1927, 60, [jB], 1861— 1S65).— Hsematoporphyrin o - c h 2 hydrochloride and bromine in glacial acetic acid O afford an unstable perbromide which with acetone yields bromoacetone and bromobromohydroxyethyl- tetramethyljjorphindipropionic acid (bromoporphyrin I), C32H3o0 5N4Br2 or ^32H320 5N4Br2; the iron, cobalt, copper, nickel, and zinc complex salts are described. HNMe It is converted by methyl-alcoholic hydrogen chloride m. p. JLio— 117 , [a]« +60-51° (hydro- into the dimethyl ester, C34H340 5N4Br2, m. p. 273°, chloroplatinate described), is isolated, ORGANIC CHEMISTRY. 1095 ■which also contains a phenolic hydroxyl, a methoxyl, gives ethylcarbomtohomovanillic acid, m. p. 138— and a methylenedioxy-group, but has the absorption 139°, also prepared by the action of ethyl chloro spectrum of a phenanthraquinoline alkaloid (see formate on homovanillic acid, m. p. 140—141°, below). The methyl ether, m. p. 139°, [a]D -|-101-7° obtained by oxidation of eugenyl acetate, m. p. 30°, in chloroform, differs from bulbocapnine methyl with permanganate in acetone. The acid at 200°, ether, dicentrine, and synthetic d-epidicentrine, and or the corresponding acid chloride in benzene, is con has probably the i’sodicentrine structure (II). For densed with homopiperonylamine, and the resulting the synthesis of dl-epidicentrine, m. p. 119° (hydro homopiperonylamide is cyclised by means of phos chloride, m. p. about 147°), homopiperonylhomovera- phoryl chloride in toluene to a dihydroisoquinoline trylamine, m. p. 130—131°, obtained from homo- derivative, which is reduced and hydrolysed to the piperonyl chloride and homoveratrylamine, is con oily 6:7- methylenedioxy -1 - p - hydroxy - m - methoxy - verted by phosphoryl chloride in toluene into 6 : 1-di- benzyl-1 : 2 : 3 : ‘i-tetrahydroisoquinoline (ethyl ether, methoxy-1-(3' : 4'-methylenedioxybenzyl)-Z : 4 - dihydro - m. p. 99°). Condensation of this compound with isoquinoline (methiodide, m. p. 135— Í38°), and thence, formaldehyde gives tetrahydro-^-berberrubine, which by reduction of the methoehloride, into 6 : 7-dimethoxy- on methylation with diazomethane yields tctrahydro- l-(3' : 4' - rnethylenedioxybenzyl) - 2 - methyl -1 :2 : 3 : 4- i/i-berberine, m. p. 177° (Haworth, Perkin, and telrahydroisoquÍ7ioline, m. p. 116° (sulphate, m. p. 110°). Rankine, A., 1924, i, 1098). This is nitrated, giving the 6'-?uiro-compound, m. p. Tetrahydroprotoberberine, m. p. 254—260°, is syn 151°, and a substance, m. p. 198°; the 6'-amino-com thesised by condensing formaldehyde with tetrahydro- pound, m. p. 110°, by diazotisation and treatment protopapaverine (sulphate, m. p. 174— 175°) obtained with copper, yields dZ-epidicentrine, which is resolved from dihydroprotopapaverine (Pictet and Gams, by means of d-tartaric acid to give the (¿-compound, A., 1909, i, 671; cf. Riigheimer, A., 1900, i, 522). m. p. about 110°. Oxidation of domesticine with For the synthesis of its 2 : 3-methylenedioxy-deriv- alkaline permanganate yields 4 : 5-methylenedioxy- ative, m. p. 169°, phenylacethomopiperonylamide, benzene-1 : 2 : 3-tricarboxylic acid, m. p. about 170°, m. p. 97—98°, is converted into the dihydroiso- thus confirming the structure (II). quinoline, reduced to 6 : 7-methylenedioxyletrahydro- The acid mother-liquor, after removal of nandinine protopapaverine, m. p. 57°, and condensed with and domesticine, contains a third alkaloid, iso-domes- formaldehyde. ticine, m. p. 85°, which gives the same methyl ether Hmnoveratroyl-$-phenylethylamine, m. p. 105— 106°, as domesticine, but a different ethyl ether, m. p. 82°. is described. The m. p. of the alkaloids indicate that domesticine is The absorption spectra of 42 alkaloids are examined. the 9-hydroxy-10-methoxy-compound, iso-domesticinc Alkaloids of the tetrahydroisoquinoline series con the lO-hydroxy-9-methoxy-compound (see II). taining methylenedioxy- or methoxyl groups show a Coptis japónica, Mak., contains, in addition to single band at about 3500 A. Those of the apo- berberine and the yellow alkaloid coptisine already morphine type in the phenanthraquinoline series show reported (A., 1926, 1160), a now, crystalline alkaloid two bands at 3200 and 3650 A., the former being due worenine, C20H17O5N (hydrochloride, m. p. 295°), to methylenedioxy- or two methoxyl groups in posi isolated as tetrahydro-derivative, m. p. 212—213°, tions 1 : 2, the latter in positions 10 : 11; absence of from which it is regenerated by the action of iodine. 1 : 2-substituents results in a flat curve at 3200 A., Coptisine iodide decomposes above 280°: the chloride whilst 9 : 10-substitution in place of 10 : 11 has a is not melted at 300°. Tetrahydrocoptisine, m. p. bathochromic effect on the second band. The 217—218° (previously given as 215°), is different from methylenedioxy-group is rather more bathochromic tctrahydro-i/i-coptisine (2 : 3 : 10 : 11-bismethylene- than two o-methoxyl groups. Change from tervalent dioxytetrahydroprotoberberine; Buck, Perkin, and to quinquevalent nitrogen, especially from carbinol Stevens, A., 1925, i, 958), m. p. 214°, which is syn form to ammonium form, exerts a hyper- and batho thesised independently by the method of these chromic effect. Absorption spectra curves are given authors. Tetrahydroworenine yields a N-methyl de for the following substances: Class I (structure rivative (hydrochloride, m. p. 281°; hydriodide, m. p. analogous with I ) : (a) Hydrohydrastinine, 6 : 7- 263°). Since 8-methyltetrahydrocoptisine, m. p. 215°, methylenedioxytetrahydro - protopapaverine and obtained by the action of magnesium methyl iodide -protoberberine; (b) tetrahydro-berberine, -coptisine, on coptisine chloride, followed by reduction, differs -palmatine, -.¿-berberine, -.¿-coptisine, -berberrubine, from tetrahydroworenine, worenine is most probably -worenine, -papaverine, 8-methyltetrahydroberberine, 13-methylcoptisine. dMaudanosine, 6 : 7-dimethoxy-l-m : p-dimethoxy- For the synthesis of tetrahydro-ifi-berberrubine (III), benzyl-1 : 2 : 3 : 4-tetrahydroisoquinoline; (c) crypto rn- p. 181° (ethyl ether, m. p. 131°), vanillin is converted pine, protopine, hydrastinone (6 : 7-dimethoxy-l- by way of the azlactone, keto - 2 - methyl -1 : 2 : 3 : 4 - tetrahydroisoquinoline); m. p. 191° (which on hydro (d) hydrastine, narcotine, narceine; (e) papaverine lysis yields a-benzamido-4- and its methoehloride; (/) hydrastinine, cotarnine, hydroxy - 3 - methoxycin- berberine, coptisine, worenine; Class II (structure namic acid, m. p. 210°; cf. analogous with II) : (a) ajjomorphine, bulbocapnine, Sugii, A., 1921, i, 346), into dicentrine, ¡.sodicentrine (domesticine methyl ether); 4 - hydroxy(b) thebaine; - 3 - m ethoxy (c) morphine, - codeine, sinomenine, phenylpyruvic acid, which dihydrosinomenine, dehydrosinomeninc. The groups by condensation with ethyl (a, b, c, etc.) within the two main classes indicate chloroformate and oxidation with hydrogen peroxide closely similar spectra. C. H ollin s. 1096 BRITISH CHEMICAL ABSTRACTS.— A. Synthetical experiments in the isoquinoline Vni. The synthesis of tetrahydroprotoberberme group. VII. Synthesis of 3 :11-dimethoxy- (I) (X = H ), the parent substance of the alkaloids hi protoberberinium salts. VIII. Synthesis of the palmatine-berberine series, has been effected by protoberberinium salts. S. N. Ch a k r a v a r t i, a group of reactions similar to those described above. R. D. Ha w o r t h , and W. H . P e r k in , jun. (J.C.S., The very poor yields obtained hi the two stages 1927, 2265—2274, 2275— 2281).—VII. The influence where ring closure is involved are ascribed to the of methoxyl groups on the ease of synthesis of alkaloids absence of the methoxyl groupings. 1-Benzyl - of the berberine type has been investigated by the 1:2:3: 4-tetrahydroisoquinoline (cf. Forsyth, Kelly, preparation of 3 : 11 - dimethoxytetrahydroproto - and Pyman, A., 1925, i, 1167) [sulphate, +5H 20, berberine (I, X =O M e). m - Mcthoxyphcnyl - (3 - m - + H 20, m. p. 191° (decomp.)] from l-benzyl-3 : 4-di- hydroisoquinoline (sulphate, m. p. 216°) reacts with anhydrous formic acid to give the N -formyl derivative. This compound when treated with phosphorus oxy chloride under strictly defined conditions yields dihydroprotoberberine (not isolated), which is reduced with zinc dust and hydrochloric acid to tetrahydro- protoberberine (I), m. p. 85° (hydrochloride, m. p. 232°; m-cthoxypJienyhlhylamide, an oil, obtained by con hydriodide; picrate, m. p. 151°). Compound (I) is densation of [3-m-methoxyphenylethylamine and oxidised by alcoholic iodine in the presence of sodium TO-methoxyphenylacetie acid (or the corresponding acetate to a periodide, from which protoberberinium chloride) yields, when heated with phosphorus oxy- iodide (II) (X = H ), m. p. 232°, is obtained (chloride, chloride, 6-methoxy-l-(3'-meihoxybenzyl)-3 : 4-dihydro- +4H20, +0-5H20 ; picrate, m. p. 192— 193°). Treat isoquinoline, an oil (picrate, m. p. 155°). The sulphate ment of protoberberinium chloride with hot aqueous of this base is reduced by zinc and sulphuric acid to potassium hydroxide yields oxyprotoberberine, m. p. 6-methoxy-l-(3'-methoxybenzyl) -1 : 2 : 3 : 4 -tetrahydro- 102°, and dihydroprotoberberine (not isolated). With isoquinoline, an oil (hydrochloride, in. p. 192°; sulphate; methyl iodide, tetrahydroprotoberberine gives the picrate, m. p. 148°). Condensation of the tetrahydro- a- and fi-methiodides, m. p. 210° and 230— 232°, base with formic acid affords the ~N-formyl derivative respectively (methochloride). The methiodide with and when heated with phosphorus oxychloride, this methyl-alcoholic potassium hydroxide gives anhydro- undergoes ring closure in what is presumed to be methyltetrahydroprotoberberine (III) (X = H ), an oil the £>ara-position to give 3 : 11 -diinethoxy dihydro (hydrochloride, hydrated, m. p. 234— 235°), also pro protoberberine, m. p. 130° (hydrochloride, +4H 20 ; duced by the action of silver hydroxide on the hy dr iodide] picrate, m. p. 232°). Reduction of this quaternary salt. This anhydro-compound is un base with zinc dust and sulphuric acid yields 3 : 11- changed when boiled with methyl alcohol or chloro dimethoxytelrahydroprotoberberine (I), m. p. 111° form or when heated with dilute hydrochloric acid. [ihydrochloride; hydriodide, m. p. 205°; picrate, m. p. M. Cl a r k . 139—140° (decomp.)]. Addition of iodine to a boil Manufacture of derivatives of cinchona alka ing alcoholic solution of (I) in the presence of sodium loids. C. F. B o e h r in g e r and S o e h n e , etc.— See acetate gives a periodide from which is obtained B ., 1927, 828. 3 : ll-dimethoxyprotoberberinium iodide (II), m. p. Conversion of palmatine into its cryptopine 242° (chloride, m. p. 200° and +3H 20 ; picrate, m. p. analogue (cryptopalmatine). R. D. H a w o r th , 238°). Treatment of the chloride with hot potassium J. B. K o e p f l i, and W. H . P e r k in , jun. (J.C.S., hydroxide solution yields a mixture of 3 : 11-dimethoxy- 1927, 2261— 2265).— Tetrahydropalmatine (I) forms oxyprotoberberine, m. p. 143°, and 3 : 11-dimethoxy- an a-methiodide, m. p. 230°, and a less soluble ¡3-meth dihydroprotoberberine, separated by extraction of iodide, m. p. 266° (decomp.), which are converted the latter compound with dilute hydrochloric acid. into methiodides [a, syrupy; (3, m. p. 250° (decomp.)]. When (I) is heated with methyl iodide it gives a The methochlorides or methiodides when treated mixture of a-3 : 11 -dimethoxytetrahydroprotoberberin- ium methiodide, m. p. 224° (a-methochloride), with OMe OMe the (3-methiodide, m. p. 245° (decomp.) [fi-metho- /N o M e CH2 chloride, m. p. 245° (decomp.)]. Treatment of the /CH, / K y (i d mixed methochlorides with alcoholic potassium hydr (L) x "\CH' , oxide yields anhydro-3 : 11-dimethoxytetrahydrober- berine (III) (hydrochloride, m. p. 236°), an oil which q jj is unchanged by boiling / v 2 a with chloroform or aque- with methyl-alcoholic potassium hydroxide give X / Y x^H—/ NX ous alcohol but decolor- anhydromethyltetraliydropahnatine B (II), m. p. 115— L /N M e \ / ises bromine hi chloro- CH CH’CF ^orm solution or acid (HI.) 2 permanganate. Base (III.) V ° % chV (IV.) (III), together with some 3: W-dimethoxytetrahydroprotoberberiniummetho- ’Ach/?\>’ A 3H/VCHa carbonate, m. p. 216°, is the only base obtained 2 Me CH2 ^ Me CH2 by the action of silver hydroxide on the mixed 116° [hydrochloride, m. p. 210° (+ H 20, decomp.)]- ap-protoberberinium salts. The methohydroxide, obtained by the action of ORGANIC CHEMISTRY. 109’] silver hydroxide on the methiodide, when evaporated anhydride and sodium acetate into diacetylyohimbine in a vacuum yields a mixture of this compound with m. p. 183° (hydrochloride, 3H20, [a}§ —7-5°), and ar a?ihydromethyltetrahydropalmatine A (III), m. p. 131— amoiphous monoacetylyohimbine, m. p. about 150‘ 132°. The latter, oxidised with perbenzoic acid in (chloroaurate, blood-red, m. p. 170°), indicating the chloroform, is converted into the amine oxide [hydro presence of a secondary nitrogen atom. Oxidatior chloride, m. p. 198—200° (decomp.)], from which with mercuric acetate produces a mercury derivative cryptopalmatine (IV), m. p. 148— 150°, is obtained but neither this nor the demercurated oxidation pro by warming with hydrochloric-acetic acid. duct was obtained crystalline. The latter on reduc C. H o llin s. tion gives the original dextrorotatory yohimbine, Alkaloids of Corydalis cava. IX. Constitution together with a sparingly soluble isomeride, 1 -yohim of corycavine and corycavamine. E. Sp a t h and bine, m. p. 253—254° (hydrochloride, [ajg —27-22°) H . H olte r (Ber., 1927, 60, [5], 1891— 1898; cf. von The alkaloid reacts with bromine water to give mono- Bruchhausen and Stippler, this vol., 683).— Cory and di-bromoyohimbines, described by Barger and cavine is reduced to dihydroeorycavine and the latter Field, the analyses agreeing with C21H2S03N2Br,HBi substance is converted into the quaternary iodide, and C21H2402N2Br2,HBr, respectively. Ring scission C2iH2204NI, m. p. 296— 297° (corr.), which, when of yohimbine cannot be effected by treating the heated at 260°/0-01 mm., gives a mixture of bases in methiodide, m. p. 249— 250°, or the methochloridc 50% yield separable by means of their hydrochlorides with sodium hydroxide or amalgam and alcohol. into two stereoisomeric substances, C20H19O4N, m. p. Yohimbine is reduced by sodium and alcohol to 140° and 203°, respectively. Removal of the methyl- yohimbyl alcohol, m. p. 202°, or +2H aO, m. p. 148— enedioxy-groups from the base of m. p. 140°, followed 149° (hydrochloride, [a]L2 +37-5°). The ring in by exhaustive méthylation of the tetrahydxoxy-base yohimbyl alcohol is extremely stable, since the meth thus produced with diazomethane, affords dl-meso- iodide, m. p. 215°, is unaffected by alkalis, the metho- corydaline, m. p. 162— 163°, whilst similar treatment chloride by sodium amalgam and alcohol, and the of the base of m. p. 203° gives ¿Z-corydaline, m. p. methiodide on distillation gives methyl and yohimbyl 135— 136°. The results show that corycavine has alcohols. Cyanogen bromide reacts with yohimbine, the structure of corydaline if its protopine-like con giving 70% of yohimbine hydrobromide, [a]g +52-22°, stitution is taken into account and confirm in its and an amorphous substance, m. p. 70— 80°, [a]'£ essentials the formula (I) proposed by Gadamer and -26-61°. It is concluded, therefore, that yohimbine von Bruchhausen. The authors, however, prefer the contains a tetrahydroqumoline ring (cf. von Braun, ketonic form (II) in analogy with other protopine A., 1907, i, 899; 1917, i, 169; 1918, i, 185). S. Co f f e y . o / Preparation of homatropine. F. C h em n itiu s €H 2 be obtained crystalline. Treatment with alcoholic ative, but yields no phenylhydrazone, oxime, or semi- potassium hydroxide furnished neoline (hydrobromide carbazone; 2 : 2-carbonyldi-indole, m. p. 198°; and darkening at 198°, sintering at 200°, m. p. 205°) 1 : 1-carbonyldi-indole, m. p. 245°. In contradiction together with benzoic and acetic acids. to the statement of Majima and ICotake (A., 1923, i, S. Co f f e y . 150), the formation of indole- 1-carboxylic acid by Alkaloid trichloroacetates. Use of trichloro the action of carbon dioxide on magnesium indolyl acetic acid in toxicology. G. F lo re n ce (Bull. Soc. iodide in ethereal or anisole solution (A., 1911, i, 486) chim., 1927, [iv], 41, 1097— 1100).— Trichloroacetates is confirmed. T. H. P o p e . of the following have been prepared : aniline ( + H 20), Mechanism of the Grignard reaction in the o-toluidine (+ H aO), p-toluichne (+ H 20), strychnine indole series. R. M a jim a and T. H o sh in o (Proc. ( + 3H20), brucine (+3H20), morphine (+3H20), Imp. Acad. Tokyo, 1927, 3, 339—341).—When mag codeine (+ 2 H 20), quinine ( -f 4H20), quinidine nesium indolyl iodide reacts with an alkyl (or acyl) (+ 4 H 20). They are well-defined, crystalline salts halide, the active halogen of the latter first removes decomposing in boiling aqueous solution to the the magnesium iodide group, and, the free indolyl alkaloid, chloroform, and carbon dioxide. The solu ■lt radical immediately changing to the bilities of the salts in water are given, and are such ' form (I), the alkyl group enters the as enable their easy separation from coagulated x x 3-position. In warm solutions a albumins. Crystalline salts could not be obtained similar course is followed in the from cocahie, nicotine, atropine, and cinchonine. reaction with a carbonyl-containing H . B u rto n . ' ■' compound, and, after hydrolysis in Alkaloids of the animal kingdom. M. Sc iie n c k this case, an aldehyde group remains in the 3-position. (Z. angew. Chem., 1927, 40, 1081— 1086).—A sum In the cold, however, the tautomeric change to (I) does mary of recent work. not take place with sufficient rapidity, and the aldehyde Derivatives of o-aminophenylarsinic acid. H. group assumes the 1-position. B. W. A n d e r so n . B urton and C. S. G ibson (J.C.S., 1927, 2387— 2388). Position occupied by acetatomercuric groups, —When either o-ethylaminophenylarsinic acid, m. p. Hg-OAc, in anilines having in the nucleus a 128— 129° [?i?£ro.so-derivative, m. p. 160° (decomp.)], halogen group or a hydrocarbon residue. I. or its acetyl derivative, m. p. 187— 188° (silver salt), L. V ecch iotti (Gazzetta, 1927, 57, 485—497).— is reduced by sulphur dioxide in alcohol-hydrochloric Previous results (cf. Jackson and Peakes, A., 1908, acid-iodine solution, arsenic is eliminated from i, 523; Schoeller and Schrauth, Ber., 1912, 45, the molecule. 4-Nitro-2-aminodiethylaniline (hydro 2812; Vecchiotti, A., 1924, i, 957) show that when, chloride, m. p. 205—206°; benzylidene derivative, in a substituted aniline, the meia-position to the m. p. 97—98°), prepared by reduction of 2 : 4-di- amino-group is occupied by a halogen atom or a nitrodiethylaniline with ammonium sulphide, is con- hydrocarbon residue, the action of mercuric acetate verted by the Bart reaction into 3-nitro-Q-diethyl- gives rise to a monomercuri-compound in which the atninophenylarsiriic acid, m. p. 195— 196° (decomp.), acetato-mercuric group always occupies the para- which is convertible normally into 3-nilro-6-diethyl- position to the amino-group and to a dimercuri- aminophenylarsenious chloride [3-nitro-Q-diethylamino- compoimd having the two mercuri-groups in the ;phenyldichloroarsine\, m. p. 143— 144°. M. Cl a r k . 2 : 5- or, more usually, in the 4 : 6-positions. 9-Methylcarbazole-3-arsinic acid and its re Treatment of ?w-chloroaniline in alcoholic solution duction products. H. B u r to n and C. S. Gib so n with aqueous-alcoholic mercuric acid gives: (1) (J.C.S., 1927, 23S6—23S7).— 3-Amino-9-methylcarb- 4-Acetatomercuri-3-chloroaniline, NH2-C0H;1Cl-Hg-OAc, azole has been converted by the usual procedure into m. p. 155°; the corresponding hydroxymercuri-com 0-methylcarbazole-3-arsinic acid, m. p. above 300°, pound, decomp. 210°, chloromercuri-compound, de 9-methylcarbazole-3-arsenious chloride, m. p. 121— comp. 202°, acetyl derivative, m. p. 205°, and mercury 122°, and 2315—2317).—Detail improvements are described (Biochcm. Z., 1927, 187, 307— 314).—Tyrosine and in the preparation of lead tetraphenyl from lead tryptophan, when forming part of a protein molecule, chloride and magnesium phenyl bromide (cf. Pfeiffer are oxidatively destroyed when irradiated both in and Truskier, A., 1904, i, 544). F. G. W il lso n . diffused daylight (in presence of a sensitiser) and Effect of alkali, acid, and enzymes on proteins, with the mercury lamp, the destruction not being as peptones, polypeptides, 2 : 5-diketopiperazines, rapid, however, as when these acids are free. Addi and related compounds. E. A bderhalden and tion of alkali increases the action and of formalde H. Mahn (Z. physiol. Chem., 1927, 169, 196— 222). hyde accelerates the attack on tryptophan. — Experiments similar to those carried out previously P. W. Clutterbuck. on silk peptone (Abderhalden and Schnitzler, this Catalytic hydrogenation of hsemateric acid vol., 686) have been made with elastin. A solution and hsemin. A. P a p e n d ie c k (Z. physiol. Chem., has been obtained by heating dried defatted powdered 1927, 1 6 9 , 59— 63).—Hsemateric acid in acetic acid elastin with iV-hydrochloric acid for 5— 6 hrs. at solution is catalytically hydrogenated (cf. A., 1926, 70— 75° and in some cases by the action of pepsin 631) to a porphyrin not distinguishable from meso- in acid solution. The hydrolysis of the dissolved porphyrin. The maximum amount of hydrogen elastin by Ar-hydrochloric acid and by iV-sodium absorbed is equivalent to 6 atoms of hydrogen per hydroxide at various temperatures has been followed mol. of hsemateric acid; no decolorisation occurs. by Sorensen “ formol ” titrations or by Willstatter’s Mesoporphyrin solutions absorb hydrogen irregularly, methods, and by measurements of the optical rotation and are not decolorised. Appreciable hydrogenation of the peptone solution and its copper salts. The of hacmin occurs in acid solution with the formation hydrolysis of dipeptides and anhydrides by various of mesohsemin and mesoporphyrin. In alkaline amounts of acid and alkali at different temperatures solution, approximately 6 atoms of hydrogen are has been measured by amino-nitrogen determin absorbed per mol. of hsemin, but spectroscopical ations ; it is found that certain polypeptides are not examination reveals no mesohsemin. hydrolysed by iV-hydrochloric acid at the ordinary A. W o rm all. temperature, but are attacked by iV-sodium hydroxide Determination of active hydrogen in haemin, under similar conditions. The bearing of these results in some of its derivatives, and in pyrroles. II. on the theories of protein structure is discussed and H. F isch er and E. W a l te r (Ber., 1927, 6 0 , [7i], the conclusion is reached that linkings other than 1987— 1995; cf. A., 1926, 630).—Determinations are those of polypeptide and 2 : 5-diketopiperazine nature recorded of the number of atoms of active hydrogen per molecule of the following substances, using the are present. A. W ormall. method of Zerewitinov (A., 1907, ii, 509; 1908, i, Blood pigments. VII. Behaviour of pros 593; 1911, i, 101) as modified by Flaschentrager (A., thetic groups in different solvents. F. H a u r o - 1925, ii, 999). The results are expressed in paren w it z (Z. physiol. Chem., 1927, 169, 235—262).— theses after the name of the compound : bis-(3-carb- Spectrophotometric measurements of the spectra of ethoxy-2 : 4-dimethyl-5-pyrryl)methane (2-11); bis- hsemin, mesohsemin, dimethylmesohsemin, and aetio- (3-earbethoxy-2 : 4-dimethyl-5-pyrryl)methene (1-13); hsemin and the corresponding hsemocliromogens have bis - (4 - carbethoxy -2:3- dimethyl - 5 - pyrryl)methane been made in the presence and absence of pyridine (1-94); bis-(4-carbethoxy-2 : 3-dimethyl-5-pyrryl)- and cyanides. The spectrum of hsemin in pyridine methene (0-81); bis-(2-bromo-4-carbethoxy-3-methyl- differs significantly from that of hseinochromogen, 5-pyrryl)methane (1-01); bis-(2-bromo-4-carbethoxy- The preparation of trimethyl hsematin from methyl- 3-methyl-5-pyrryl)methene (1-08); product of the hsematin and methyl sulphate results in the change : condensation of benzaldehyde with 3-acetyl-2 : 4-di- CIO — >- CH'C(OMe) in the unsaturated side-chain, methylpyrrole (2-21); bis-(5-carbethoxy-3-((3-methyl- the Fe-OH grouping not being methylated. In all malonic ester)-4-methyl-2-pyrryl)methane (5-3); ethyl the solvents used, the chlorine atom of hsemin chloride 5-carbethoxy-2 : 4-dimethyl-3-pyrryl-(3-methylmalon- dissociates as the anion, and in acid solution the ate (2-31); ethyl 2 : 5-dimethyl-4-ethyl-3-pyrryl-(3- coloured residue behaves as cation. In alkaline solu methylmalonate (1-7); ethyl malonate (1-1); tri- tions both hydrogen and chlorine are dissociated, phenylmethyl chloride (—); cycZopentadiene (0-86); even with a preparation esterified at both carboxyl ethyl ¡3 - methoxymethylmalonate (0-95); hsemin groups. Thus hsemin contains a third acid group (3-02—5-11 according to temperature); dihydro- (cf. this vol., 1092). Hydrogen cyanide is not bound hsemin (4-06— 4-49); m&sohsemin ester, by hacmin in the same way as chlorine, bromine, C3gH40O4N4FeCl (2-1); aetiohsemin (1-64— 1-98); iso- or hydroxyl groups. The action of hydrogen cyanide aetiohaemin (2-37); protohsemin (4-82, 4-68); copro on hsemin chloride is similar to that of pyridine or porphyrin ester (3-82, 4-46); ¿socoproporphyrin ester aniline; the coloured portion of the compound be (4-22, 4-3); p-wocoproporphyrin ester (3-72); setio- haves, however, as cation with pyridine or aniline porphyrin (2-03, 2-09); protoporphyrin diester (1-93); and as anion with hydrogen cyanide. Pyridine isosetioporphyrin (4-08,4-32); 1:3:5: 7-tetramethyl- resolves haemoglobin into globin and pyridine-hsemo- 2:4:6: 8-tetraethylporphin (2-1); 2:3:6: 7-tetra- chromogen, oxyhaemoglobin into the same products methyl -1 : 4 : 5 : 8 - tetraethylporphin (2-05, 2-2); together with oxygen, and methsemoglobin into 1:4:5: 8-tetramethyl-2 : 3 : 6 : 7-tetraethylporphin globin and pyridine-oxyhsemin. The constitution of (2-1); coproporphyrin ester (synthetic) (4-32); iron the different hsemins is discussed. A. W o rm all. complex salt of tetramethylhsematoporphyrin (5-82); Effect of irradiation on the tyrosine and uroporphyrin ester (9-46); i.souroporphyrin ester tryptophan contained in protein. F. L ie b e n (7-37). From the results, it appears that either the 1100 BRITISH CHEMICAL ABSTRACTS.— A. experimental material is insufficient to allow deduc has not previously been isolated directly from a tions with regard to the constitution of the blood protein hydrolysate. G. A. C. G ough . pigments or that the porphyrins and hsemins are able Determination of organic material by oxid to unite with hydrogen in such a manner that pro ation with chromic acid. T. VON Fellenberg duction of methane ensues with Grignard’s reagents, (Biochem. Z., 1927, 1 8 8 , 365— 391).— An attempt to particularly in the presence of pyridine. Possibly extend the use of Bang’s micro-determination of fat the Zerewitinov method is not applicable to complex by combustion with dichromate and sulphuric acid unsaturated systems. H. W r e n . to a large number of organic substances gives the Pyridine-hcemins. A. H a m s ik (Z. physiol. Chem., following results. Formic acid yields quantitatively 1927, 169, 64— 72).—-From a solution of hsemin carbon dioxide, acetic acid is not attacked, wdiilst chloride in pyridine, ether slowly precipitates large with propionic and butyric acids more oxygen is crystals and it is suggested that a pyridine-hsemin used than is required to convert them into acetic chloride compound has been formed. These crystals acid. Higher fatty acids give very complex results. become much smaller when washed with ether or Malic, tartaric, and citric acids give carbon dioxide alcohol and hsemin chloride is regenerated. Hsemin quantitatively. Oxalic acid is not attacked and acetate forms a partly crystalline similar precipitate succinic acid onty slightly so. Soluble carbohydrates which, with ether and alcohol, yields a mixture of and polyhydric alcohols are oxidised quantitatively, oxyhsemin and oxyhsemin anhydride. This accounts but ethyl, propyl, and isobutyl alcohols form one for the high iron content of hsemin acetate prepar molecule of acetic acid and dimethylethylenecarbinol ations (cf. Küster and Gerlach, A., 1922, i, 596) and forms two molecules. Benzoic acid is oxidised quan their incomplete solubility in pyridine. Hsemin titatively and salicylic acid almost so. Glycine and formate, acetate, oxalate, and sulphate, but not alanine are scarcely attacked, whilst tyrosine is hsemin chloride, decompose when heated in pyridine- oxidised almost completely. Proteins give different chloroform solution, giving oxyhsemin and oxy- values, the smallest being that of gelatin (glycine-rich). hiemin anhydride. A. W o rm all. The method is adapted for determination of alcohol in acetic acid and of methyl alcohol mixed with a small Blood pigments. VI. Relation between amount of ethyl alcohol. P. W. Clutterbuck. heemin, hsemochromogen, and porphyrin. F. Determination of phenylacetylene. F. H e in H a u r o w itz (Z. physiol. Chem., 1927, 91— 101; 1 6 9 , and A. M e y e r (Z. anal. Chem., 1927, 30— 31).— cf. this vol., 686).— Porphyrins can be converted into 7 2 , Phenylacetylene is precipitated from an alcoholic the corresponding hsemins by ferrous or ferric salts solution as its copper compound by an ammoniacal in presence of acetic acid, but with butyric and valeric solution of cuprous chloride. The precipitate is acids ferrous iron only is introduced. It is concluded filtered into a glass Gooch crucible, washed with that in the acetic acid solution a reduction occurs water, alcohol, and ether, and dried in a vacuum which is not effected primarily on the ferric salt, over concentrated sulphuric acid. This determin but probably on a loose intermediate compound of ation can be checked by treating the precipitate with iron and porphyrin. Hsematin is not formed on a solution of ferric ammonium sulphate in dilute acidification of a solution of hsemochromogen in sulphuric acid, and titrating the ferrous sulphate absence of oxidising agents. Hsemin chloride in formed with permanganate. The error is less than pyridine solution can be reduced to hsemochromogen 1%. F . S. H aw k in s. by sodium in the absence of oxygen or compounds containing oxygen, and the hsemochromogen formed Volumetric determination of hydroxyl groups contains 40 per mol. The formulae of porphyrin and in organic compounds. V. L. P e t e r so n and hsemin are discussed in relation to the active hydrogen E. S. W est (J. Biol. Chem., 1927, 74, 379— 383).— atoms present and the combination of bi- or ter- Hydroxyl groups in sugars and other organic com valent iron. A. W o r m a ll. pounds may be determined by heating the compound with a known amount of acetic anhydride and Electrodialysis of proteins. W. P a u li (Bio- pyridine until acetylation is complete, dilution of the chem. Z., 1927, 1 8 7 , 403— 409).— A reply to Dhere reaction mixture with water, and titration of the (this vol., 423). P . W. Clutterbuck. excess acetic acid. C. R. H a rin g to n . Phosphorus nucleus of ovovitellin. S. P o s t e r - Determination of isopropyl alcohol in presence n a k and T. P o s t e r n a k (Compt. rend., 1927, 1 8 5 , of acetone, and of methylethyl ketone in presence 615— 617; cf. this vol., 273, 582).— ßj-Ovotyrin, of sec.-butyl alcohol. H. A. C a ssa r (Ind. Eng. C72H 144° 78N24P 12. is hydrolysed by boiling 25% Chem., 1927,19, 1061— 1062).— Rapid determinations hydrochloric acid to phosphoric acid (12 mols.), of isopropyl alcohol i n presence of acetone are effected pyruvic acid (1-6 mols.), histidine (0-7 mol.), arginine by quantitative oxidation of the alcohol to acetone (0-62 mol.), lysine (0-75 mols.), Z-serine, [aj'g —6-67° with chromic acid solution and back-titration of the (7-9 mols.), and ammonia (4-9 mols.). The ammonia excess of chromic acid. The acetone is determined by and pyruvic acid are probably produced by deamin Messinger’s method (J.S.C.I., 1 9 2 0 , 2 8 0 a ), applying ation of part of the serine, and when allowance is a correction of 1—2% for the isopropyl a lc o h o l made for this, serine and phosphoric acid appear in present, sec.-Butyl alcohol may be determined in almost equimolecular amounts. Hydrolysis of ßr ovo- presence of methyl ethyl ketone by this method, tyrin with 15% sulphuric acid affords polypeptides but for the determination of methyl ethyl ketone with N : P ratios of 1-1— 1*3 together with phosphoric Messinger’s method gives high results and a modific acid, serine, and its deamination products. Serine ation thereof is suggested. R. B r i g h t m a n . BIOCHEMISTRY. 1101 Determination of diacetyl and acetylmethyl- present, even in small quantities, the ethereal solu carbinol. C. B. v a n N ie l (Bioehem. Z., 1927, 187, tion shows a vivid, red fluorescence. The red colour 472— 478).— A slight modification of the usual method is not given by carotin or xanthophyll. It is sug for determination of diacetyl and acetyl methyl- gested that this reaction might be utilised in separat carbinol as nickel dimethylglyoxime is described. ing the two components of chlorophyll (cf. Willstatter P. W. Clu tte r b u c k . and Hug, A., 1911, i, 393), since on treating a methyl- Determination of the methoxyl content of alcoholic solution of crude chlorophyll with light volatile substances in dilute aqueous solutions petroleum, the latter shows a gradually increasing containing aldehydes. K. W ie sl e r (Z. angew. fluorescence, whilst the fluorescence of the alcoholic Chem., 1927, 40, 975).—The ordinary Zeisel method solution gradually diminishes. S. Co f f e y . for the determination of the methoxyl group fails in the presence of aldehydes but good results are ob Determination of selenium in organic com tained by the following modification: The solution pounds. E. H. S h a w and E. E. R e id (J. Amer. is mixed with freshly-precipitated silver oxide and Chem. Soc., 1927, 49,' 2330—2334).— The sample distilled to two thirds its volume, the distillate being (0-2—0-4 g.) is mixed writh sucrose (0-4 g.), potassium collected in a second distillation flask containing nitrate (0-2 g.), and sodium peroxide (14 g.), the 10 c.c. of hydriodic acid (d 1-96). The latter flask mixture covered with a thin layer of sodium peroxide, is heated gently on the water-bath and is provided and the whole burnt in the Parr bomb in the usual with a reflux air condenser connected at its upper manner. The mass is dissolved in water and the end to a small washing flask containing a suspension solution boiled, cooled, acidified with hydrochloric of red phosphorus in water, whence the vapours pass acid, filtered, and diluted to 350 c.c. The selenium into a measured volume of 0-liV-alcoholic silver is then precipitated (a) by adding 200 c.c. of hydro nitrate. Carbon dioxide is passed through the chloric acid, heating the mixture not quite to the apparatus throughout the determination. The de b. p., and passing in a rapid stream of sulphur dioxide, posited silver iodide is collected and weighed as usual. or (b) by adding 50 c.c. of hydrochloric acid and 3 g. A. R. P o w e l l . of potassium iodide, and gently boiling the mixture, Detection of chlorophyll by means of the with replacement of evaporated water, until the excess analytical quartz lamp. P . W. D a n c k w o r t t and of iodine is volatilised. The selenium is collected on E. Pi'AU (Arch. Pharm., 1927, 265, 560— 562).— a Gooch crucible, washed with alcohol and water, Small quantities of powdered drugs or tinctures are and dried at 110— 120°. The greatest errors recorded treated with water and ether and the mixture is in 25 analyses are +0-17% and —0-33%. illuminated by the quartz lamp. If chlorophyll is F. G. W il lso n . Biochemistry. Regulation of respiration. IX. Relation of Effect of asphyxia on blood. J. B. Collip tissue acidity and blood acidity to volume flow (Trans. Roy. Soc. Canada, 1927, [iii], 21, V, 151).— of blood as illustrated by haemorrhage and Asphyxia produces a slight but definite increase in re-injection. A. B . H er tzm a n and R. G ese ll the serum-calcium and in the inorganic phosphorus (Amer. J. Physiol., 1927, 81, 563— 578).— The changes content of the blood, and a decrease in blood-_pn in acidity of the circulating arterial and venous blood of from 0-15 to 0-35 of a unit. H . D. K a y . were determined by the manganese dioxide electrode Micro-determination of carbon dioxide in and checked by the hydrogen electrode. Haemorrhage blood and other solutions. Efficiency of paraffin elicited increased alkalinity of the arterial blood and in preventing loss of carbon dioxide. D. R aefel increased acidity of the venous, decreased oxygen (J. Biol. Chem., 1927, 74, 839— 849).— An apparatus consumption, and increased pulmonary ventilation. is described in which the carbon dioxide in a small Reinjection reversed all these changes. The import amount of liquid is liberated and aspirated into ance of volume flow of blood and acidity in the control standard barium hydroxide solution, the excess of of the normal acid-base equilibrium is emphasised. which is then titrated with the aid of a micro-titration R. K. Ca n n a n . syringe. The method is applicable to determination Effects of respiratory gases on density of of 0-1—0-5 c.c. of carbon dioxide with a maximum blood and other fluids. W. F. H am ilto n and error of ± 2 % . The loss of carbon dioxide from H. G. B a r b o u r (J. Biol. Chem., 1927, 74, 553— normal blood-serum kept under liquid paraffin does 556).—Dissolution of carbon dioxide in water, alkaline not exceed 2% in 24 hrs., although in presence of salt solution, blood-serum, and whole blood increases higher concentrations of carbon dioxide the loss may the density of these liquids, the increases being in be 10%. C. R . H a r in g to n . ascending order of magnitude owing to the effect of chemical reactions in causing the increase of volume Oxidation processes in blood-serum. T. R. per c.c. of carbon dioxide to be progressively less. P arsons and W. P arsons (Bioehem. J., 1927, 21, In the case of oxygen, the dissolution of which in whole 1194— 1205).— In the presence of certain oxidising blood is accompanied by actual diminution in volume, agents such as potassium ferricyanide and potassium the effect on the density is very much greater. permanganate, human blood-serum absorbs oxygen C. R. H a r in g to n . at the rate of about 0-25 c.c. per c.c. per hour when 1102 BRITISH CHEMICAL ABSTRACTS.— A. shaken with air at the ordinary temperature. The metrically with a standard. The method is accurate same effect is observed in the presence of ferric salts to 0-5 mg. for 10— 15 mg. in 100 c.c. in alkaline solution, but not with ferric salts in acid Ch em ica l A bstr a c ts. solution nor with dichromate at any reaction. Ex Effects of dialysis and of ether extraction on traction with ether reduces the rate at which the diffusibility of calcium in human blood-serum. serum will absorb oxygen in this way, but this can R. P. L oeb and E. G. N ichols (J. Biol. Chem., 1927, be restored in some measure by the re-addition of 74, 645— 649).— Normal human blood-serum, the the extracted material, provided that this is recovered same serum dialysed until free from calcium, and by evaporation of the ether extract in an oxygen-free the same serum extracted with ether, were dialysed atmosphere. The oxidisable substances are precipit under similar conditions against calcium chloride ated completely by full saturation with ammonium solution; in all cases the equilibrium concentration sulphates, partly by half saturation, and scarcely at of calcium attained in the serum was higher than all by one third saturation with ammonium sulphate. expected from the Donnan equilibrium, the deviation The substances primarily responsible for the effect being greatest in the serum extracted with ether and are therefore most probably lipins. S. S. Z il v a . least in the dialysed serum. The view is therefore Action of essential oils on the formation of supported that un-ionised compounds of calcium with methsemoglobin. E. D essem o n te t (J. Pharm. protein account for the unequal distribution of calcium Exp. Ther., 1027, 31, 377— 386).— The formation of attained on dialysing blood-serum against water. methsemoglobin in a mixture of defibrinated blood C. R. H a r in g t o n . and various essential oils has been studied. Oils Free sugar of the blood-plasma. E. J. Big- containing eugenol, safrolo, isosafrole, linalool, aneth- w o o d and A. W uillot (Bull. Soc. chim., 1927, ole, anisole, and carvcnc induce the formation of 9, S67— 883).—When blood-plasma or -serum is methsemoglobin within 24 hrs., whilst menthol, incubated with yeast for I— 1 hr., the reducing power thymol, borneol, oil of cloves (eugenol-free), methyl of the deproteinised fluid, determined by the method salicylate, and camphor produce no reaction. It is of Hagedorn and Jensen (cf. A ., 1923, ii, 265, 440) therefore suggested that this property of the alcoholic does not completely disappear, but becomes approxim constituents of essential oils depends on the presence ately constant at a value corresponding with 0-0— of unsaturated side-chains and on the position of 0-03% of' dextrose. The residual reducing power of the etliylenic linkings. No relation between velocity the scrum of rabbits, dogs, and man is on the average of formation of methsemoglobin and degree of un 13-3%, 13-5%, and 14-3%, respectively, of the saturation has been detected in carvene, carvone, original reducing power. The total sugar of the pinene, vanillin, and cineole. There appears to be a cerebrospinal fluid is on the average 67% of that of definite pressure of oxygen specific for linalool, for the blood, but the fermentable sugar of the cerebro carvene, and for pinene, at which the formation of spinal fluid is 75% of that of the blood. Conclusive methsemoglobin is an optimum. E. A. L tjnt. evidence as to the nature of the non-fermentable reducing material was not obtained, but the possibility Calcium and potassium content of the blood. that it may be uric acid has been excluded, although E. K y l in (Acta med. Scand., SuppL, 1927, [xix], uric acid may be responsible for the abnormally high 1— 112).—The normal calcium content of the blood is values obtained in cases of nephritis. 10-6— 12-0 (average 11-13) mg. % ; below 21 years the W . O. Ive r m a c k . average is 11-6 mg., and above 41 years 10-83 mg. % . Blood-sugar. III. Non-dextrose of blood- The regulation of the calcium content is hormonal. filtrates. B. Sjo ll em a (Biochem. Z., 1927, 188, The normal potassium content of the blood is 18—24 465— 474).—Further investigations (cf. this vol., 476, (average 20-7) mg. % ; in pathological conditions 789) of the non-dextrose reducing substances of blood the calcium content is usually diminished and the show that when blood-filtrates are shaken with potassium content increased, but in diabetes high charcoal and acetic acid the ergothioneine and gluta blood-calcium values are observed. The response of thione present cause no appreciable error in the the human organism to adrenaline is largely dependent blood-sugar determination with ferricyanide. Both on the potassium : calcium ratio. dextrose and the non-dextrose reducing substance Ch em ica l A b st r a c t s . reduce ferricyanide but little when the pa is smaller Calcium content of blood-serum of rat. A. T. than 9-5. Dextrose remains completely in solution Cam eron and J. E. W illiam son (Trans. Roy. Soc. when both trichloroacetic and tungstic acids are used Canada, 1927, [iii], 21, V, 139— 145).— The calcium as précipitants, but a non-dextrose reducing substance content of the serum of the normal white rat (on a is precipitated by the former, but not by the latter. mixed diet), determined during summer or winter, Ergothioneine (0-1%) is not precipitated by tri shows an average value corresponding with that of chloroacetic acid. Sulphur determinations of the other mammals, but with greater individual variations. fractions show that blood-corpuscles contain other No difference for sex is observable. Values deter non-dextrose reducing substances than ergothioneine mined in late spring are definitely lower (average and glutathione. An adaptation of the Folin-Wu 2 mg. lower) while still showing about the same method is given for determination of dextrose in degree of variation. H. D. K a y . blood-filtrates. P. W. Cltjtterbuck. Determination of calcium in blood and urine. J. S. Sh a r p e (Edinburgh Med. J., 1926, 33, 27— 30). T otal sugar of b lood and urine. M. R. E v erett, —The cloudiness produced by ammonium oxalate in H. A. Sh o e m a k e r , and F. Sh e pp a r d (J. Biol. Chem., a protein-free solution in glycerol is compared nephelo- 1927, 74, 739— 759).—The low results obtained by BIOCHEMISTRY. 1103 Folin and Berglund (A., 1922, ii, 400) for the total sugar Action of hirudin on thrombin. J. 0. W. of blood and urine were due to the interfering effect of B a r r a tt (J. Physiol., 1927, 64, 47— 53).— From the hydrochloric acid used in the hydrolysis, and of determinations of the amounts of thrombin inactiv silicates in the sodium hydroxide employed for neutral ated wrhen solutions of varying concentrations of isation, on the subsequent colorimetric determination. thrombin and hirudin are mixed, it is concluded that Satisfactory results are obtained by hydrolysis with the reaction is of the same type as that of a weak sulphuric acid and neutralisation with potassium acid with a wreak base. R. K . Ca n n a n . hydroxide free from silica. C. R. H ar in g to n . Determination of catalase in blood and animal Plasma-proteins of normal dogs. C. W. M a t tissues. E. G a g a r in a (Bioehem. Z., 1927, 188, th ew (J. Biol. Chem., 1927, 74, 557— 560).—The 284).—A claim of priority over Golzov and Jankovsky blood-plasma of normal dogs contains, on the average, (this vol., 689 ; cf. J. Exp. Biol. Med., 1926, 7, 33). 0-45% of fibrin, 4-64% of albumin, and 2-12% of P. W . Clu t t e r b u c k . globulin. For any one animal the figures remain Immunological behaviour of mucoids. J. H. practically constant. C. R. H a r in g to n . L e w es and H. G. W ells (J. Infect. Dis., 1926, 40, Effect of hydrogen-ion concentration and pro 316).—Various mucoids from eggs and blood are tein concentration on the osmotic pressure of antigenic although less so than most other proteins serum-proteins. J. M a r r a c k and L. F. H e w it t of equal solubility. The ovomucoids from goose and (Bioehem. J., 1927, 2'1, 1129— 1140).— The osmotic duck eggs were the most closely related to each pressure of serum-proteins rises with increase of pa other, as were also the hen and guinea-fowl mucoids. to an extent which is less than that calculated for Seromucoids from sheep, ox, and dog blood wrere ideal solutions if the compound of protein and base easily distinguishable from one another and showed is fully dissociated. The activity coefficients of anions but little relationship to the ovomucoids. are slightly reduced by the presence of protein in Chem ical A b str ac ts. solution. The excess of diffusible ions in the protein Isolation of substances with immune pro solution, due to the Donnan effect, and deviations perties. A. L o cke and E. R. M a in (J. Infect. Dis., from the state of ideal solution cause the osmotic 1926, 39, 848).— Diphtheria antitoxin was purified pressures of proteins not to bear a linear relation to by isoelectric fractionation of the Ramon toxin- the protein concentration. It is not necessary to antitoxin precipitate. These preparations contain suppose that proteins in solution occupy a greater 0-0005—0-0015 mg. of nitrogen per antitoxin unit, bulk than they do when dry (cf. Verncy, A., 1926, have the anaphylactogenic character of horse-serum 856). S. S. Z il v a . protein, and are injured by boiling as well as by ageing. Chem ical A bstr acts. Role of tissues in maintaining acid-base Composition of blood and tissues of foetal calf. equilibrium of blood. I. Effect of isolated J. B. Collip (Trans. Roy. Soc. Canada, 1927, [iii], muscle-tissue. II. Effect of hind-leg prepar 21, V, 147— 150).— Very high values for serum- ation. M. G. B a n u s and L. N. K a t z (Amer. J. calcium and inorganic phosphorus are found, partly Physiol., 1927, 81, 628— 643, 644—649).— !. Appar due to asphyxia. Whole blood shows a higher non atus is described for the perfusion of isolated organs protein nitrogen figure than does serum, although with oxygenated non-acapnic blood under controlled the urea values for the two fluids are almost identical. conditions. The gastrocnemius of the dog was per Foetal serum has a low protein content. Amniotic fused with blood rendered acid by addition of hydro fluid shows great variation in the calcium content, chloric acid and the changes were observed in the which is apparently unrelated to the blood-calcium Pa, chloride content, and carbon dioxide-combining value. The fœtal heart-musele shows a relatively power at constant carbon dioxide tension. No high glycogen content which diminishes writh the age measurable exchange of chloride or alkaline radicals of the foetus. The glycogen content of the skeletal occurred between blood and tissues, and it is con muscle, on the contrary, increases with the age of cluded that at constant carbon dioxide tension under the fœtus. H. D. K a y . the experimental conditions muscle does not increase Mechanism of the Golgi black reaction [of the buffering power of the blood. animal tissues]. A. M o sc h in i (Arch. Farm, II. When the hind-leg was perfused there was sperim. Sci. aff., 1927, 43, 97— 114).— Chemical some increase in the p n and carbon dioxide-combining theories of this reaction, the development of a black power of the blood, but no change in the chloride-ion colour in sections which have been treated with concentration. The nature of this buffering effect potassium dichromate solution, kept for a few days, of some of the tissues of the hind-leg is unknown. and treated with a silver nitrate solution, and of the R. K . Ca n n a n . modified reaction, in wrhich the second reagent applied Distribution of nitrogen in the blood and is mercuric chloride, followed by ammonia or other urine of the turtle. F . H . W il e y and H . B. L ew is reagents, are discussed. It is suggested that, by the (Amer. J. Physiol., 1927, 81, 692— 695).— Determin reducing action of the tissue, potassium chromite is ations of the distribution of the nitrogen of the formed, and that this reacts with reagents subse blood, urine, and tissues of the turtle (Chrysemys quently applied. E. W . W ig n a l l . pinta) are reported. The turtle excreted consider ate amounts of both urea and uric acid, so that, as Colloid chemical and morphological study of regards nitrogen metabolism, it is intermediate chromosomes. Y. K u w a d a and T. Sa k a m u r a between mammals and the reptiles of arid regions. (Protoplasma, 1926, 1, 239—254). R. K . Ca n n a n . Chem ical A b str ac ts. 1104 BRITISH CHEMICAL ABSTRACTS.----A. Iron content of animal tissues. 0. A. E l v e h - the bile and blood of normal and jaundiced animals je m and W. H. P e terso n (J. Biol. Chem., 1927, 74, further confirm their identity. R. K. Ca n n a n . 433— 441).— Iron is determined directly in a sample Surface energy of some physiological fluids. of tissue and in a duplicate sample to which a known I. N . V e d e n s k i (Biochem. Z., 1927, 188, 270— amount of iron has been added; if the recovery of 278).— Physiological fluids may be surface-inactive the added iron in the second case be not quantitative, (urine, gastric juice), surface-active (blood, milk, the determination is repeated after preliminary re bile, saliva), or may hold a mean position (aqueous moval of phosphates (ef. A., 1926, 443). Figures are humour, cerebrospinal fluid). The total surface given for the iron content of various tissues of the energy of surface-active liquids shows a maximum ox and for that of the spleen, liver, and kidney of at a definite temperature, but of surface-inactive different animals; the latter organs are rich in iron liquids does not changc with temperature. The as compared with the other tissues. surface tension of the less surface-active physiological C. 11. H a r in g t o n . liquids decreases directly with the temperature, but Chemical composition of brain. II. G. V. that of the surface-active liquids changes according Stu ck er t (Cordoba Medica, 1927, 2, 13— 19).— to a typical curve. The total surface energy of milk Data are given for the chemical composition of the shows a sharp increase at 60°. cerebrum, medulla oblongata, and cerebellum of P. W. Clu tte rbu c k . ox-brain. No marked differences exist in respect Measurement of colloid-osmotic pressure in of their content of total lipins, proteins, and soluble biological fluids. A. K ro g h and F. N akazaw a extractives. The individual lipins occur in different (Biochem. Z., 1927, 188, 241—258).— Two simple proportions. For example, the cerebellum contains methods, each requiring 0-3— 0-5 c.c. of liquid, are twee as much phosphatide as the medulla oblongata, described for the determination of colloid-osmotic the difference being attributed chiefly to lecithins pressure and are used for human, horse, and frog and kephalins. The medulla oblongata is rich in serum, human urine, etc. The methods are accurate fats and fatty acids. G. W. R o bin so n . to within 10 mm. pressure of water. The results are not affected by changes in salt concentration Preparation of kephalin. P. A. L e v e n e and from 0-5 to 1-5% and of from 7 to 8, but at a I. P. R olf (J. Biol. Chem., 1927, 74, 713— 714).— Practical details are given for the preparation of lower j)a the pressure decreases. Carbonic acid does not exert any specific effect on the colloid-osmotic kephalin from brain. C. R . H a r in g t o n . pressure. The latter decreases more quickly on Iodine content of the thyroid gland of various dilution than the colloid concentration. Curves breeds of ox and its relationship to the condition showing the relationship of the pressure per cent, of these glands. T. v o n F e l l e n b e r g and H. and the percentage protein are ahnost linear and may P a c h e r (Biochem. Z., 1927, 188, 339— 364).— Of be used for the investigation of pathological sera. 80 ox thyroid glands examined, the weight varied Addition of caffeine does not affect the colloid- from 8-7 to 130-4 g., the lower values relating pre osmotic pressure of serum. P. W. Clutterbuck. dominantly to the English shorthorn variety and A m ylase content of dog saliva and the influence the heavier to the Swiss and Austrian (brown, of diet. O. G a l e h r (Fermentforsch., 1927, 9, 224— Simmental, etc.) varieties. The relative iodine con 227).—In view of the conflicting reports as to whether tent is not directly related to the weight of the dog’s saliva contains a diastatic enzyme, investigations gland, the brown and shorthorn varieties having a have been made on the saliva of three dogs which higher iodine content than the heavier glands. The have been fed almost exclusively on carbohydrates absolute iodine content generally increases with for several months and that of three control dogs fed increasing weight. The colloid content and size of on a carbohydrate-free diet. It is found that dog follicle is correlated rather with the iodine content saliva has no “ dextrinase,” but contains very small than with the weight of gland. It was not possible, amounts of a “ polyamylase. ” The amount of this however, to establish a definite race variation or diastase secreted bears no relationship to the diet variation due to origin and condition. and no increase of the starch-splitting activity occurs P. W. Cl u t t e r b u c k . during long carbohydrate feeding. A. W o r m a l l . Enzym es of the om entum . J. M. G o ld b er g Influence of diet on the inorganic constituents (Biochem. Z., 1927, 188, 475— 4S0).— Enzymes pos of hum an saliva. G. W . C la r k , J. S. S h e ll, J. B- sessing proteolytic, lipolytic, and faint amylolytic Josephson, and M. E. S t o c k le (Dental Cosmos, actions are detected in the omentum of dogs. 1927, 69, 500—513, 605— 617).—The acid-base P. W. Cl u t t e r b u c k . balance of the ration had little influence on the Ultra-violet absorption spectra of certain ability of adults to retain bases. Diets contammg physiological fluids. M. C. R e in h a r d (J. Gen. green foods increased the retention of calcium, Physiol., 1927, 11, 1—6).—Ultra-violet absorption phosphorus, sulphur, and nitrogen. There is no curves are given of human bile, saliva, pericardial relationship between the quantity of an elemen fluid, urine, and haemoglobin. W. 0 . K e r m a c k . ingested or retained and the quantity in the circu - Spectrophotometric determinations of purified ating blood or resting saliva, or between the concen bilirubin. C. S h e a r d , F . C. M a n n , and J. L. trations of inorganic constituents in the blood an B ollm an (Amer. J. Physiol., 1927, 81, 774— 781).— in the saliva. The concentration of inorgaiiic phos Spectrophotometric comparison and tests of the phorus was 4— 5 times as great in the saliva as m solubilities of purified bilirubin and the pigment in blood-plasma. Ch em ical A bstracts. BIOCHEMISTRY. 1105 Gastric digestion. Relation of volume, accurate results and possesses no advantage over the hydrogen-ion concentration, and buffer capacity simple extraction with ether. of the test meal to the gastric contents. W. A. P. W . Cl u tte rbu c k . Sta n d ish , G. R. Co w g ill, and A. T. Shohl (Amer. Proteases of urine. II. Proteolytic action J. Physiol., 1927, 81, 696— 706).—The amount of of urine in protracted starvation and with experi gastric juice varies with the volumo and concen mentally increased protein catabolism. 0. tration of the meal. The p¡¡, of the gastric contents P eczenik (Fermentforsch., 1927, 9, 166— 191; cf. remains nearly constant at a value of about 4 through A., 1926, 1275).—After prolonged starvation the out the meal. The buffer capacity of the stomach urine of the rat, guinea-pig, and cat has a proteolytic contents likewise remains fairly constant after an action which varies with tho type of food administered initial rise. R. K. Ca n n a n . before the fast. Rats which are starved after a long Constituents of sweat, urine, and blood. III. meat diet- give a urine which has strong peptic and Urea. G. A. T a l b e r t , J. R. F in k l e , and S. S. tryptic activities, and the protein usage, as deter K atsu k i (Amer. J. Physiol., 1927, 82, 153— 156).— mined by the total nitrogen of the urine, is much Tables are given of the urea-nitrogen found in the higher than with rats which are starved after a milk blood, urine, and sweat of 17 subjects. diet. After injection of protein (caseinogen and R. K. Ca n n a n . milk), during prolonged starvation, and under experi Chlorine and sodium in the milk of mammals. mental influences which lead to an increased cell L. B arteie and E. D ufilho (Compt. rend., 1927, disintegration, protein derivatives pass into the 185, 613— 615; cf. B., 1926, 644).—The milk of circulation and cause secretion of pepsinogen. women contains 1-162 g. of chlorine per litre on the A. W orm all. 6th day of lactation. This value rises to a maximum Distribution of protein in blood in experi of 1-349 g. on the 12th day and falls to 0-923 after mental anaemia. M. B o d a n s k y , S. W. M orse, 9 months, at M'hich time the milk contains 0-154 g. V. C. K ie ch , and R. B. B ram kam p (J. Biol. Chem., of sodium per litre. Whilst the amount of chlorine 1927, 74, 463— 471).—Figures are given for the seems to be large during the colostral period, sodium distribution of the various protein fractions in dogs’ does not appear in considerable amounts until the blood-serum, classified by the method of Howe (A., 45th day. Other elements than sodium are in 1922, ii, 172). More than half of the protein obtained combination with the chlorine, since the milk of from the red blood-corpuscles by haemolysis can be mares, which contains 0-568— 1-207 g. of chlorine per salted out within the limits of precipitation of tho litre, contains only traces of sodium. globulins. In anaemia induced by administration G. A. C. Gotjgh. of acetylphenylhydrazine, the albumin : globulin ratio Urinary acidity. Electrometric titration of of the serum decreased, whilst tho content of fibrinogen, euglobulin, and tho protein fraction pre- urine. S. M o rg u lis and W. R. H am sa (J. Biol. Chem., 1927, 7 4 , 851— S61).— Urine is titrated electro- cipitable by 0-75J/-sodium sulphate increased. metrically against a buffer solution of pa 7-4, using C. R. H arington. the quinhydrono electrode. Much lower values for Pernicious anaemia. III. Contrast of the the acidity of the urine are thus obtained than by chloride contents of corpuscles and plasma in tho method of titration with phenolphthalein as pernicious anaemia and other conditions. A. T. indicator, owing to the increasing buffering capacity Camebon and M. E. F oster (Canad. Med. Assoc. J., of urine as the reaction becomes more alkaline than 1927, 17, 670— 675).—The plasma-chlorine values in the anaemias are normal; cell-chlorine values in Vn 7-4. C. R. H arin g to n . pernicious anaemia are low, but in secondary anaemia Determination of acetone in urine. G. K l e y e r are high. Both plasma- and cell-chlorine values are (Pharm. Ztg., 1927, 72 , 1262— 1263).—Details are low in diabetes and other conditions where increase given for carrying out adapted Rothcra and the of blood constituents requires osmotic compensation, more delicate Reichardt and Frommer-Emilewicz and in acute intestinal obstruction. (salicylaldehyde) tests. P. W. Clutterbuck. Chemical A bstracts. Nitrogenous constituents of hen urine. R. E. Glycolysis in leucaemic blood. H . L. Schmitz. Davis (J. Biol. Chem., 1927, 74, 509— 513).—A and E. C. Glover (J. Biol. Chem., 1927, 74, 761— technique is described for the collection of hen’s 773).—In normal blood the rate of glycolysis is 15-— urine without contamination with faeces. In such 23 mg. % per hr. and is independent of the initial urine there was found, on the average, total nitrogen concentration of dextrose. In cases of myelogenous 100 mg. %, of which 62-9% was uric acid, 10-4% leucaemia rates of glycolysis of 18—84 mg. % per hr. carbamide, 17-3% ammonia, and 8-0% creatinine. were observed, with an approximate parallelism C. R . H a r in g to n . between the rate of glycolysis and the leucocyte Salicylsulphonic acid as a protein reagent. G. count. In lymphatic leucaemia, tho rate was not R oche (Pharm. Ztg., 1927, 72, 1263).—A claim of increased. Addition of potassium cyanide to the priority as the first to suggest the use of sodium blood accelerates glycolysis markedly in myelogenous salicylsulphonate as a test for protein in urine. leucaemia and slightly in lymphatic leucaemia, but is P. W. Clu t t e r b u c k . almost without effect in normal blood. Determination of quinine [in urine] by Hart C. R. H arin gton. mann and Zila’s method. I. A . Sm or od in c ev Cerebral and cardiac glycogen and muscular A. N. A d ov a (Biochem. Z., 1927, 188, 279— lactic acid in adrenalectomised rats. B. A. ¿oá). This method (A ., 1918, i, 328) does not give H oussay and P. M azzocco (Rev. Soc. Argentina 1106 BRITISH CHEMICAL ABSTRACTS.----A. Biol., 1927,3, 491—500).— Extirpation of the adrenals Diagnostic value of the diastatic enzyme of in rats is without marked effect on cardiac and the urine. L. Ivreyberg (Norsk Mag. Lsegeviden- cerebral glycogen or on muscular lactic acid and skap., 1926, 2 4 , 992— 1003).— Acute diseases of the lactacidogen. The increase in muscular lactic acid pancreas and salivary glands arc usually accompanied after 1 min. tetanisation is greater than in the controls. by a considerable rise in the diastatic index of the The excess of lactic acid disappears within 5 min., urine. The normal index (number of c.c. of 1 in 103 slightly more rapidly in the rats deprived of their starch solution transformed by 1 c.c. of urine) ranges adrenals than in the controls. between 4 and 64. Chemical Abstracts. G. W . R o bin so n . Experimental lead hsematoporphyria. H. Fate of sugar in the animal body. VII. L ie b ig (Arch. exp. Path. Pharm., 1927, 1 2 5 , 16— Carbohydrate metabolism of adrenalectomised 28).—The administration of lead by mouth or intra- rats and mice. C. F. Cori and G. T. Cori (J. Biol. peritoneally to rabbits causes them to excrete Chem., 1927, 74, 473— 494).— In adrenalectomised haematoporphyrin in the urine and fasces. The rats, a starvation period of 24 hrs. caused almost origin of the pigment appears to be in the bone- complete disappearance of glycogen from the liver marrow and it is not secreted in the bile as is the case and a marked fall in the blood-sugar, the glycogen in sulphonal poisoning. A method is given for the of the muscles remaining unchanged. Administration determination of haematoporphyrin in the urine and of dextrose to such animals resulted in normal faeces. W. O. Kermack. synthesis of glycogen, although the rate of absorption Chemical nature of the serum-globulin of of the dextrose was slower than in the normal animal. the hsematoporphyrin rabbit. M. K om atsu The relationship between dextrose oxidised and con (J. Bioehem. [Japan], 1927, 7 , 19—26).—The verted into glycogen after administration of dextrose nitrogen: sulphur ratios of normal serum-albumin and to adrenalectomised rats with and without insulin -globulin of rabbits are 9-94 and 20-5, respectively. was similar to that previously observed for normal The sulphur content indicates that the globulin, which rats (A., 1926, 1271); further, the effect of insulin show's an increase of 50% in haematoporphyrin rabbits, in decreasing the liver-glycogen of normal fasting retains its normal chemical constitution. mice was observed also in adrenalectomised mice. Ch em ica l A bstracts. These effects of insulin are therefore to be regarded as Blood-chemistry in leprosy. II. Alkali re specific to this hormone and are independent of the serve. E. M. P aras (Philippine J. Sci., 1927, 33, effect of adrenaline. C. R. H a r in g to n . 155— 167).—The Van Slyke method for the determin Calcium metabolism in diabetes. E. K y l in ation of carbon dioxide capacity has been performed (Acta Med. Scand., 1927, 66, 197—206).—In diabetes on 110 specimens of blood-plasma from cases of of pancreatic origin the blood-calcium is high, falling leprosy classified as follows : (a) leprosy without after injection of insulin with elimination in the complication; (b) lepra reaction without alkali urine. Ch em ica l A b strac ts. treatment; (c) lepra reaction with alkali treatment; (e) leprosy with tuberculosis; (e) leprosy with nephritis; Acid production in diabetes. M. O d in (Acta (/) leprosy with miscellaneous complications such as Med. Scand., Suppl., 1927, X V III, 1—573).— In mild malaria, anaemia, osteoarthritis, etc. The mean diabetes the carbon dioxide capacity of the blood value obtained for the normal healthy adult was (C), the total acid excretion, and the pR of the urine 70 vol.-% of carbon dioxide. The following results are normal, but there is increased acetonuria; in have been obtained respectively: (a) no significant severe diabetes C is generally low. The total acidity variation from the normal mean, mean value for of the urine is less when C is less than 30 vol.-% than 41 cases 67-9; (b) no significant variation, mean when it is 30— 39 vol.-%. In coma, 0 is always below value for 19 cases 66-5; (c) characteristic indications 30 v o l.-% ; when it is below 25 vol.-% there is always of alkalosis in some cases, mean value for 16 cases coma. During coma there is a rise in the blood-sugar 75-7; (d) no significant variation, mean value for 7 value. The urinary acid and acetone excretion often cases 72; (e) significant reduction, mean value for decreases during coma. Coma due to lack of insulin 8 cases 61; (/) significant reduction, mean value for is ascribed to a lag in the production of ammonia. 19 cases 59-6. There appears to be no correlation A fat-vegetable diet causes G to rise, until the urine between the alkali reserve, and the duration, type, or actually becomes alkaline. (Edema is considered to stage of the disease. E. A. L u s t . be due to an excessive value of O. Changes in the value of C, the total acidity and p a of the urine Identity of urinary albumin. L. F. H ewitt following a meal have been followed for normal and (Bioehem. J., 1927, 2 1 , 1109— 1111).—Purified diabetic subjects. The effects on acid production of albumins excreted in the urine of patients with varying the diet have also been investigated. chronic nephritis or albuminuria of pregnancy have been isolated, purified, and examined for their Ch e m ic a l A b st r a c t s. Cholesterol content of the blood-plasma as rotatory power and dispersion. They do not differ in an index of progress in insulin-treated diabetics. these respects from serum-albumin. S. S. Z ilva. I. M. Rabinowitch (Canad. Med. Assoc. J., 1927, 17, Kidney phosphatase. II. The enzyme in 171— 175).—The blood-lipin is a better index of the disease. R. T. B r a in and H. D. Kay (Bioehem. J.. course of diabetes than is the 'blood-sugar. An 1927, 2 1 , 1104— 1108).— B oth in c h r o n i c nephritis m increased blood-cholesterol value is not compatible man and in acute experimental nephritis in rabbi s with an improvement in pancreatic function. the phosphatase activ ity of the renal tissue is marked y Ch em ica l A b str a c ts. reduced. S. S. Z ilva . BIOCHEMISTRY. 1107 Prevention of tetany by oral administration 296).—The administration of chitose to the dog, hen, of ammonium chloride. W . F. W e n n e r (Amer. frog, and rabbit leads to the excretion in the urine of J. Physiol., 1927, 81, 612— 619).— Oral adminis small amounts of hydroxyinethylpyromucic acid, the tration of ammonium chloride prevents and cures maximum yield being 6-3% of the chitose administered. tetany in parathyroidectomised dogs. Its action That hydroxyinethylpyromucic acid is one of the main is due, probably, to an increased acidity of the blood products of metabolism of chitose appears improbable, and consequent rise in serum-calcium. however, since feeding with hydroxymethylfurfur- R. K. Ca n n a n . aldehyde results in the excretion of 66-7% of the acid Decreased nitrogen secretion during preg as hydroxymethylpyromucic acid. Chitonic acid nancy. S. St e f a n c s ik (Magyar Orvosi Arch., 1927, and chitaric acid yield no hydroxymethylpyromucic 28, 156— 160).—Accumulation of urea in the liver acid in these feeding experiments. The preparation does not occur. Use of amino-acids by the foetus of hydroxymethylpyromucyl chloride (5-hydroxymethyl- accounts for the low concentration of these substances fumn-l-carboxyl chloride), b. p. 120°/9 mm., hydroxy- in the blood. Chem ical A bstr acts. methylpyrorrmcic acid, m. p. 167° (uncorr.), and Theory of muscle contraction with X -ray hydroxymethylpyromucylglycina, diffraction patterns from relaxed and contracted 0H-CH2-C4H20-C0-NH-CH2-C02H, is described. muscles. J. H. C la r k (Amer. J. Physiol., 1927, A. WORMALL. 82, 181— 194).— It is suggested that lactic acid Behaviour of isoquinoline in the animal production leads to contraction by reason of an organism. M. T a k a h a sh i (Z. physiol. Chem., abrupt conversion of the substance in the anisotropic 1927, 169, 297—299).—After subcutaneous injection bands from the liquid crystal into the solid crystal of isoquinoline, the methylated compound has been state. It is shown that under the influence of slight isolated in small quantities from the urine of the dog increases in acidity the myelin forms of ammonium and the hen, but not of the rabbit. A. W ormall. oleate contract with the formation of acicular crystals. Detoxication of benzoic acid in man. J. L. X-Ray diffraction patterns of relaxed and contracted B r akefield (J. Biol. Chem., 1927, 74, 783—785).— muscles show two distinct differences. In the con After administration of 5—6 g. of benzoic acid to tracted state the zones, representing first, second, and human subjects, more than 90% was recovered from third order reflexion from equidistant molecular the urine as hippuric acid; a trace of free benzoic, planes, show a fairly well-defined ring at the edge and but no benzoylglycuronic acid was detected. an increase in diameter. These differences suggest an C. R . H arington. approach to a microcrystalline state. The distance Utilisation of calcium of spinach. L. Mc between the molecular planes is 9-5 A. in the relaxed L aughlin (J. Biol. Chem., 1927, 74, 455—462).— and 8-5 A. in the contracted muscle. The distances Storage of calcium in adult women was not impaired probably refer to the widths of the molecules forming when 70% of the total intake of this element was the equidistant planes. R. K. C annan. supplied in the form of spinach. Dextrose and salt solutions recovered from C. R . H arington. Thiry-Vella loops. H. L. W h ite and J. R a b in o - Growth and reproduction on synthetic diets. witch (J. Biol. Chem., 1927 , 74, 449— 454).— Solu II. G. A. H artw ell (Biochem. J., 1D27, 21, 1076— tions of dextrose in water or dilute sodium chloride 1086).—Three generations of rats have been reared were introduced into loops of the intestine of dogs with on a synthetic diet of butter, caseinogen, potato starch, a Thiry-Vella fistula; after removal of the solution no salt mixture, marmite, and distilled water. The mutarotation was observed. Slight differences which substitution of cod-liver oil for butter in this diet were sometimes observed between the reducing power produces less good growth and causes sterility. and rotatory power of such solutions were accounted Synthetic diets are described which produce good for by entrance into the solution from the gut of non- growth in young rats, but cause inability of the young reducing lcevorotatory or non-dextrose reducing sub to be born and consequent death of the doe. The stances. The results of Hewitt and Pryde (A., 1920, dietary requirements of the rat vary at different i, 508, 648) were therefore not confirmed. phases of its existence. S. S. Zil v a . C. R. H a r in g to n . Physiology of reproduction in birds. XXII. Effect of p H on the respiratory exchange of Blood-fat and -phosphorus in the sexes. 0. the muscle of the frog. M. Gomel (Atti R. Accad. R iddle and F. H. B urns (Amer. J. Physiol., 1927, Lincei, 1927, [vi], 5, 808—-812).— The respiratory 81, 711—724).—During the ovulation cycle in exchange in the muscle of the frog has been determined female ring-doves there is a notable increase in the between the values p u 9-1 and 3-0, using Jarisch’s fat and lipoid phosphorus of the blood. The relation and Mcllvaine’s solutions for the buffering medium, of the ovary to this increase is discussed and the flight differences in the values obtained are reported, question of sex inequalities in fat metabolism reviewed. out m both cases the maximum respiratory exchange R . K . Can nan. akes place at pn 7-1. The use of Mcllvaine’s solution Nitrogen equilibrium and nitrogen balance. rings about a more rapid decrease in the respiratory Experiments with rye bread. A. P utter (Z. exchange below pH 5-3 than the use of Jarisch’s Biol., 1927, 86, 317—344).—A discussion, based on so ution. Variations in the respiratory quotient are experimental evidence, of the preliminary conditions also observed. E. A. L u n t . necessary for the attainment of suitable basal con v fT'lral1' compounds derived from sugars. J. ditions for feeding experiments. Experiments on nitrogen equilibrium in which these conditions are not ^ arashima (Z. physiol. Chem., 1927, 169, 278— 1 1 0 8 BRITISH CHEMICAL ABSTRACTS.----A. fulfilled give too high values for the nitrogen adminis carbon dioxide, the last stage is the addition of a tration with which equilibrium is reached. molecule of carbamide to the pyrimidine nucleus. W. R obson . The two reactions are biologically irreversible. In Role of the lungs in intermediary nitrogenous the invertebrates no species can form uric acid from metabolism. I. Total and residual nitrogen purines which cannot convert it into allantoin except content of arterial blood and of blood from the those which do not contain it and those which form it right heart in the normal animal and after from acyclic compounds. Ch em ical A b str ac ts. intravenous injections of serum. II. [With S! Purine metabolism. III. Basal metabolism R rasso vitz k a j a . ] Residual nitrogen content of and purine content. IV. The nuclear-plasmic the defibrinated blood flowing to and from the ratio in dogs in carbohydrate and protein feeding isolated lung. A. M. T s c h a k n y (Biochem. Z., and in starvation. R. T r u s z k o w s k i (Biochem. J., 1927, 188, 372—377 ; 378— 380).—I. In dogs, the 1927,21,1040— 1046,1047— 1053).— III. The chemical arterial blood flowing from the lungs contains much nuclear-plasmic ratios of whole rats and guinea-pigs less residual nitrogen than the blood flowing to the differ little from one another. The values obtained lungs" from the right heart. This decrease is still for purine- and total nitrogen and for the nuclear- greater after injection of serum. Some of the residual plasmic ratios of liver and of skeletal muscle of rats, nitrogen is therefore retained by the lung. rabbits, dogs, horses, and cattle vary within wide II. Experiments with the isolated organ confirm limits, but are in no way connected with the basal the view that nitrogen accumulation takes place in the metabolism of the animals in question. The purine lung. P. W. Cl u t t e r b u c k . content of animals cannot therefore be identified with the intensity of the metabolism. Amino-nitrogen in the egg of Botnbix mori. IV. The total nitrogen and purine contents of the M. T ir e l l i (Arch. Farm, sperim. Sci. all., 1927, 43, liver of the dog are respectively 43 and 47% higher 115— 128).— The determination by Monzini (Ann. R. when the animal is fed on meat than when carbo Staz. Bac. Padova, 1921, [v], 43, [2]) showed that the hydrates are consumed. The nuclear-plasmic ratio amino-nitrogen in the eggs of the silkworm moth of the liver tissue in meat-fed dogs is almost the same increases during incubation, but in a slight and as on a carbohydrate diet. The total solids of the transient amount. It is now found that tho amino- skeletal muscle of dogs fed on meat are 14% higher nitrogen is greater in the fresh or hibernated eggs than than on carbohydrate diet. The total nitrogen and in those which have been incubated, in which the purine contents of skeletal muscle are respectively values oscillate, decreasing during the first phase and 35 and 49% higher in dogs fed with meat than in subsequently increasing. Variations in the nitrogen those fed on carbohydrates. The nuclear-plasmic in eggs of the “ yellow native ” and “ white Chinese ” ratio of skeletal muscle in meat-fed dogs is slightly moths, and of crosses, are discussed. higher than that found in carbohydrate feeding. In E . W . W ig n a l l . starvation, the nuclear-plasmic ratio of the liver is Influence of fat and carbohydrate diets on 10% above normal, whilst that of skeletal muscle is uric acid of blood. V. J. H a r d in g , K. D. A l l in , unchanged. These experiments do not support the and B. A . E agles (J. Biol. Chem., 1927, 74, 631— view of protein storage. S. S. Z elva. 643).—The increase in the uric acid of the blood, previously observed (A ., 1925, i, 604) to result from Metabolism of sulphur. XIII. Effect of a diet rich in fat, is accompanied by decreased ex elementary sulphur on growth of white rat. cretion of uric acid. During the normal puerperium G. T. L e w is and H. B. L e w is (J. Biol. Chem., 1927, the uric acid of the blood is not increased by a diet 74, 515— 523).— Addition of flowers of sulphur to a low in protein and rich in carbohydrate, although in diet deficient in cystine was not only u n a b le to the puerperium following toxaemia such diets do replace the latter, but also caused actual retardation cause an increase in the uric acid. of growth, when given in small amounts. Addition of C. R. H a r in g t o n . larger amounts of sulphur, even in presence of an Metabolism of uric acid in the living animal. adequate supply of cystine, caused toxic effects, V. S. J. P r z y l e c k i (Arch. int. Physiol., 1926, 27, presumably due to formation of hydrogen sulphide in 159—202).— The invertebrates are classified (a) the intestine. C. R. H a r i n g t o n . according as they excrete (or contain) uric acid, or Role of lipins in biology and immunology- not (uricopositive, uriconegative), and (6) according L. S u r a n y i (Magyar Orvosi Arch., 1927, 28, 125"- as they decompose uric acid, or not (uricolytic, 137).— It is suggested that lipins, and especially uricostatic). Uidike the higher vertebrates, certain cholesterol, play an important part in the n e u tr a lis invertebrates lack purine oxydases, whilst others ation of the normal products of assimilation, whether readily oxidise endogenous or exogenous purines to poisonous or not, and probably in their t r a n s p o r t and uric acid. The decomposition, with vertebrates and elimination. Chemical Abstracts. invertebrates, of uric acid by uricase proceeds only in the^ presence^ of oxygen, and terminates with Effect of fasting on the urine of steers. T.M. allantoin. The invertebrates do not contain allan- Ca r p e n t e r (Amer. J. Physiol., 1927, 81, 519 551).-- toinase. Some can synthesise uric acid from acyclic Comparative analyses are reported of the urine o compounds; the invertebrates cannot decompose steers before, during, and after fasting periods o allantoin, alloxan, dialuric acid, or barbituric acid to from 5 to 14 days. R- K. Cannan. urea or ammonia. Whilst the first stage in tho K inetics of the sw elling of cells and tissues- catabolism of uric acid involves the elimination of J. H. N o rth ro p (J. Gen. Physiol., 1927,11, 43—o >■ BIOCHEMISTRY. 1109 —The rates of swelling of Arbacia eggs and of slices of sugar. Also when given to depancrcatised dogs it carrot and potato conform to the formulæ previously- causes a decrease in the concentration of sugar in tlio developed (of. this vol., 825) for the increase in volume blood and in the urine. The hyperglycccmic action of a gelatin solution within a collodion membrane and of galegine is antagonised by ergotamine. When for the swelling of blocks of gelatin. galegine and ergotamine are administered together, W . 0 . K erm ack. hypoglyesemic convulsions may be produced in the Influence of external osmotic pressure and rabbit and the dog. W. 0. K erm ack. disturbance of the cell surface on the perme ability of Spirogyra for acid dyes. G. W . Scartii Physico-chemical causes of the behaviour of (Protoplasma, 1926, 1, 204— 213).—The cells of the phenol-camphor medicament. P. G u n th e r Spirogyra are normally highly impermeable to acid and M. P eiser (Z. pliysikal. Chem., 1927, 128, 189— dyes, the permeability increasing with the osmotic 202).—The fact that an equimolecular mixture of pressure of the medium in which the dye is applied. phenol and camphor does not exert any corrosive It is suggested that the permeability is regulated by action on the mucous membrane of the mouth cannot an organised film on the surface of the cytoplasm. be attributed to compound formation, since f.-p. Chem ical A bstracts. curves for phenol-camphor mixtures indicate only Permeability of living cells. VII. Effects of the existence of an extremely loose compound, and light of different wave-lengths on the penetration the densities and refractive indices of the mixture are of 2 : 6-dibromophenolindophenol into Valonia. very nearly additively constituted of those of the M. M. B rooks (Protoplasma, 1926, 1, 305— 312).— components. A distribution of the phenol between Between 300 and 700 y. the amount of 2 : 6-dibromo the camphor and water in favour of the camphor phenolindophenol penetrating the sap of Valonia phase is not a possible explanation, for addition of a from a 0-000351f-solution in sea-water increased as the little water to a mixture containing 15 mols. % of wave-length decreased. Ch em ical A bstr ac ts. camphor causes the separation of a solid which is nearly pure camphor. With the mixture used Bioelectrical phenomena. W. J. V. Oster- medicinally, however, addition of a little more water hout (J. Gen. Physiol., 1927, 11, 83— 99).— A dis results in the appearance of a third phase, consisting cussion of bioelectrical phenomena preliminary to the of an approximately 1-3% aqueous solution of publication of experimental results. The advantage phenol. The efficacy of the mixture is therefore due of using single large cells as of Valonia and Nitella is to the addition of water causing the deposition of emphasised. W. 0. K er m ac k . finely-divided and nearly pure camphor with sub Properties of radiation-substances with weak sequent formation of an aqueous solution of phenol irradiation. H. Zwaardemaker (Proc. K. Akad. which has a bactericidal but not a corrosive action. Wetensch. Amsterdam, 1927, 3 0 , 420— 422).— Per R. Cu th ill. fusion of a heart with Ringer’s solution deficient in Phenylalanine series. IX. Pharmacological potassium causes its action to cease, but on irradiation action of hexahydrophenylalanine and hexa- the beat recommences after a latent period of \— 1 hr. hydrotyrosine, and of the related amine and The perfusion liquid is then capable of regenerating its derivatives. E. W aser (Arch. exp. Path. the beat of another heart which has been similarly Pharm., 1927, 125, 129—139).—The pharmacological treated but not irradiated. The active substance has activity of the following compounds has been not been isolated, but is soluble in alcohol, stable investigated; hexahydrophenylalanine, hexahydro- when the solution is heated, and adsorbed by charcoal tyrosine, and the hydrochlorides of their ethyl esters; and magnesium silicate; it may be dialysed and is hexahydrophenylcthylamine hydrochloride; hexa- ultrafilterable, but does not appear to lower the hydrotyramine hydrochloride, iV-methylhexahydro- surface tension of water. H. F. G illb e . tyramine hydrochloride and OxV-diacetylhexahydro- tyramine. Their toxicity and their action on the Relationship between structure and action of pupil, heart, respiration, intestine, and temperature cardiac glucosides. W . A. J a c o b s and A. H o f f are small, but hexahydrophenylethylamine, hexa- mann (J. Biol. Chem., 1927, 74, 7S7— 794).—Satur hydrotyramine, and Af-methylhexahydrotyramine ation of the double linking associated with the lactone markedly raise the blood-pressure. group in the cardiac glucosides reduces, but docs not W . 0 . K erm ack. abolish, the physiological activity, which is therefore Preparation of dibismuthyl monosodium a property of the molecule as a whole. Cymarin, on citrate. W. F. vo n Oettin gen, Y. I sh ik a w a , and hydrogenation, gave dihydrocymarin, C30HÎGOg,H2O, T. Sollmann (J. Pharm. Exp. Ther., 1927, 31, 353— m. p. 128° and 190°, [a]fj +17-8° in pyridine, of which 360).—Dibismuthyl monosodium citrate has been the toxicity was 1/16 of that of cymarin. Ouabain prepared by dissolving monobismuthyl citrate in gave dihydro-ouabain, C30H48O12, m. p. 105°, [a]S sodium hydroxide. The formation of a pure product "7.4"4°^in water; toxicity 1/23 of that of ouabain. depends on the final pa of the solution, which should Bigitoxin^yielded dihydrodigiloxin, m. p. 202—204°, not exceed 7*6, and on the amount of alcohol used to KB +2-4° in pyridine. C. R. H a r in g to n . precipitate the dibismuthyl salt. The therapeutic Pharmacology of galegine. H. M ü ll e r and ad v a n t a g e s claimed for this substance over the bismuth (Arch. exp. Path. Pharm., 1927, 125, citrates now in use are that, prepared in this way, the j . . )•—Galegine raises the blood-sugar when bismuth content is constant, the substance is stable Administered to rabbits or when given in large doses in aqueous solution, and can be readily sterilised. 0 dogs, but small doses given to dogs lower the blood- E. A. L u n t. 1110 BRITISH CHEMICAL ABSTRACTS.— A. Colloidal lead phosphate for use in cancer affinity for carbon monoxide was determined in tho therapy. F. B isch off and N. R. B latiierwick case of tho moth. Its affinities differ in different (J. Pharm. Exp. Ther., 1927, 31, 361— 375).— species and perhaps in different , tissues. The toxic Colloidal lead phosphate is prepared by adding sodium effect is not due to any impurities in the gas. phosphate solution to a hot solution of lead chloride S. S. Z il v a . in water containing 4% of gelatin. When administered Nitrogenous metabolism in experimental sub thus it is relatively non-toxic to rats and rabbits, acute arsenic and antimony poisoning. E. and it does not affect the fragility of red blood- P r ib y l (J. Biol. Chem., 1927, 74, 775—781).— corpuseles (human) in vitro. The rate of excretion Subacute poisoning of rabbits with sodium arsenite by the rabbit of lead given as phosphate is the same and with antimony potassium tartrate causes an as that for lead administered in other forms. Ionic increase in the non-protein nitrogen of the blood, lead, buffered with serum containing enough phosphate which is more marked in the case of the arsenite and to react completely with the lead, is also non-toxic. is chiefly due to an increase in carbamide nitrogen. E. A. L unt. In the urine, there is an increase in the total nitrogen Synthetic medicináis. II. Theory of lax excreted. C. R . H arin gton . atives. H. P. K a u f m a n n .— See this vol., 1075. Inhibitory effect of metallic salts on bacterial Physiological action of two disulphones. A. growth. I. Silver salts. P. H. A n dresen R í:csei (Biochem. Z., 1927, 188, 405—408).— Butyr- (Dansk Tids. Farm., 1927, 16, 471— 489).—In a one diethylsulphone, with tadpoles, is, with respect medium containing peptone, the amount of ionic to concentration 20 times and with respect to time silver required to inhibit bacterial growth cannot be 30 times as active as sulphonal and the animals determined exactly, since the ionic concentration of recover twice as quickly. q/cZoHexanone diethyl added silver does not remain constant. If, however, sulphone is 10 and 20 times as active, respectively, as to a synthetic medium containing aspartic acid and a sulphonal and the animals recover more quickly. mixture of inorganic salts sodium thiosulphate is A larger concentration acting for a shorter time is added, a culture fluid is obtained which on the addition less injurious than a more dilute solution for a longer of silver nitrate displays a definite and constant time. With guinea-pigs the lethal dose is about silver-ion concentration for at least 48 hrs. at 37° 1 g. per kg. body-veight and tho narcotic dose is (silver-ion concentration measured electrometrically). very near this. This substance is also powerfully In such a medium, at pu 7-2 growth of B. coli is antipyretic. P. W. Clu t t e r b u c k . prevented at an Ag' as low as 0-16 x 10”u . Similar Localisation of veronal and phenylethyl- and di- minimum inhibiting values were found for certain allyl-barbituric acids in the brain (the problem other bacteria, which, in absence of silver, grow ox sleep). E. K e e se r and J. K ee se r (Arch. exp. readily in this medium. The silver-ion concentration Path. Pharm., 1927, 125, 251— 256).—Phenylethyl- is the governing factor in growth inhibition and, barbituric acid, veronal, or diallylbarbituric acid no matter how much total silver be present in the when injected intravenously into rabbits could be medium, the ionic concentration must bo maintained recovered from the thalamus and corpus striatum, at or over the above minimum to ensure complete but not from the great hemispheres, the mesence inhibition. H. D. Ka y . phalon, the cerebellum, the pons, or the medulla Antagonism of glucosone and cyanides in vivo. oblongata. W. 0 . K e r m a c k . A. H y n d (Biochem. J., 1927, 21, 1094— 1101).—In Utilisation of carbohydrate in the non-diabetic the case of mice and rats, a subcutaneous injection of organism. II. Respiratory exchange after ad dextrose or of dextrose plus insulin affords no pro ministration of carbohydrate under the influence tection against toxic action following either tho of adrenaline and substances with adrenaline subsequent subcutaneous injection of either alkali or like action (pituitary extract, ephedrine, and methyl cyanide or of the inhalation of gaseous hydro “ ephetonine " [synthetic (/¿-ephedrine]). A. gen cyanide. Glucosonc, on the other hand, exerts a L u b lin (Arch. exp. Path. Pharm., 1927, 125, 229— definite antagonistic action towards cyanides in 241).—Adrenaline, pituitary extract, and particularly these circumstances, but is less efficient than cystine. ephedrine and “ ephetonine ” retard the conversion The previous, or simultaneous, intravenous adminis of carbohydrate into fat, a process which the authors tration of glucosonc or of dextrose plus insulin consider is favoured by the action of insulin. appears to be protective against the intravenous W. 0 . K e r m a c k . injection of alkali cyanide into rabbits, but the Carbon monoxide as a tissue poison. J. B. S. results obtained are somewhat variable. S. S. Z ilv a . H a l d a n e (Biochem. J., 1927, 21, 1068— 1075).— The movements of a moth and the germination of Effect of ethyl cyanide and ethyl carbylamine cress seed are inhibited by carbon monoxide. The on biological oxidations. O. H. E merson and J. v\. greater the partial pressure of oxygen the more carbon B u c h a n a n (J. Pharm. Exp. Ther., 1927, 31, 387— monoxide is required. Rats living on oxygen dis 392).— In solutions of the same molar concentration solved in their blood under pressure in presence of ethyl carbylamine is a more powerful depressant sufficient carbon monoxide to combine with almost of the oxygen consumption of Planaria dorotocephala all their haemoglobin are killed by the addition of and P. maculata than ethyl cyanide; its action is more carbon monoxide. It is concluded that cells similar to that of potassium cyanide. E. A. Lunt. contain a catalyst of oxidation which is poisoned by Purification of malt amylase. E. Glimm and carbon monoxide (cf. Warburg, A., 1926, 1277). Its W. S omm er (Biochem. Z , 1927, 188, 290— 32o).- BIOCHEMISTRY. 1111 A method is described depending on a charcoal Isolation of diastase from human urine. P. treatment of dilute solutions of diastase (Merck) R ostock (Fermentforsch., 1927, 9, 192— 194).— after 3 days’ aseptic autolysis (in presence of The urine of subjects with acute pancreatic necrosis toluene) at 40°. The original diastase solution is specially suitable for the preparation of diastase, contained 9% of carbohydrate (erythrodextrin) and since the diastatic value is very high in this condition 8% of total nitrogen, readily reduced Folding’s and trypsin and lipase are absent. By dialysis of tho solution, gave strong ninhydrin and peroxidase urine under sterile conditions and subsequent drying (with benzidine-hydrogen peroxide) reactions, and at 37°, a preparation has been obtained which is had an amylase value of 0-2—0-5. The amylase thirty times as active as the most active commercial filtrate obtained after 3 days’ aseptic autolysis of preparation (Merck). A . W orm all. this solution at 40° followed by treatment twice with animal charcoal was water-clear, had amylase Liver diastase. E. F. L esser (Bioehem. J., content 5-8, nitrogen content only 3-8%, was free 1927, 21, 1128).—Polemical against Eadie (this vol., from reducing carbohydrates, and gave a very faint 482). About two thirds of the liver diastase is ninhydrin reaction. adsorbed on the surfaces of the cell and is therefore Amylase may be adsorbed by aluminium hydroxide unable to act on the liver glycogen. This applies also and eluted without loss by means of secondary to tho parotid gland of the mouse. S. S. Z il v a . phosphate solution, 50% of inactive material being Coagulation of egg-yolk by pancreatic diastase. separated. Adsorption by stannic acid separated E. L agrange (Arch. int. Physiol., 1926, 26, 347— 70% of inactive material, but elution from kaolin, 361).—Pancreatic juice contains a vitellinase which and still more so from stannic acid, caused considerable is more sensitive than lipase to the reaction of tho inactivation of the enzyme, these acid colloids precipitate; its action is prevented by sodium separating the enzyme from its protective agent. fluoride. Chemical A bstracts. Adsorption on gelatinous zinc phosphate succeeded Influence of thorium-X on the activity of only in presence of 20% alcohol, and since the con emulsin. A. M attbert (Compt. rend., 1927, 185, version into crystalline phosphate took some time, 669—671).—Tho total radiation of thorium-X in most of the amylase became inactivated. After concentrations down to 0-05 y per c.c. of liquid, saccliarification of starch, amylase is completely accelerates the action of emulsin on amygdalin, adsorbable from the maltose complex and elutablo. whilst at higher concentrations the reaction is moro Amylase may be heated for a considerable time at and moro, and with 12 y per c.c. completely, inhibited. 50° without injury and remains adsorbable, but is At the latter concentration [5- and y-rays have only a no longer elutablo from the adsorbate. slight effect, and tho effect above must therefore bo P. W Clu tte r b u c k . due to the a-radiation (cf. A., 1925, i, 737; 1926, 759; Taka-diastase. K. N is h ik a w a (Bioehem. Z., this vol., 483). P. W . Clutterbuck. 1927, 188,386— 404).—The optima for the follow ing enzymes of taka-diastase arc : for amylase, 6-8— Amygdalase, gentiobiase, gentianase. K. 7-2, for tryptase (hydrolysis of gelatin) 7-7— 8-3, JOSEL’HSON (Z. physiol. Chcm., 1927, 169, 301— (hydrolysis of fibrin) 8-2— 8-6, and for the milk- 304).—Tho relationship between these enzymes is clotting enzyme 5-2— 6-7. Trypsin, diastase, lipase, discussed and it is considered that no definite con and milk-clotting enzyme aro adsorbed by fibrin clusion can yet be reached as to the identity of from a taka-diastase solution and may be eluted eentianase with amygdalase or with gentiobiase. under suitable conditions by dilute acids and alkalis fa A. W ormall. or by allowing tho fibrin-enzymo complex to react Specific action of plant enzymes. Ill- Con with starch solution, when both diastase and trypsin ditions of action of leaf salicinases. A. V. pass into solution. If taka-diastase is heated for B lagoveschenski and N. I. Sossiedov (Bioehem. J., 10 min. at 65°, the amylase is considerably inactivated, 1927, 21,. 1206—1210).—A definite optimal hydrogen- to a greater extent in presence of sodium or potassium ion concentration exists for the action of salicinases chlorides than in distilled water. Inorganic and from various species of Populus and Salix. Different organic calcium salts havo a protective action on plants contain various amounts of the enzyme. amylase, but barium and magnesium salts are much Salicinase is present in Gossypium hirsutum ; the moro injurious. The same applies to tryptase, but enzyme is therefore not confined to tho Salicaceee. the heat action is much more injurious. Zinc is S. S. ZlLVA. mjurious to amylase and zinc and copper to trypsin, Action of carbon monoxide on certain oxidising but iron, nickel, cobalt, and copper are without enzymes. M. D ixo n (Bioehem. J., 1927, 21,1211 effect on amylase. Amylase is inactivated by 1215).—Carbon monoxide has no inhibitory effect on mercuric chloride and reactivated by adding the the aerobic oxidation of aldehyde or hypoxantlnne corresponding amount of sodium cyanide. Trypsin by tho milk oxidase, or of succinic acid by the succm- is similarly inactivated, but requires more cyanide oxidaso of muscle. Its action thus differs from that or reactivation. In taka-diastase there is also of cyanide, which strongly inhibits the latter reaction. S. ZlLVA. present a phenoloxidaso which oxidises only di- o. yuroxybenzeno derivatives (dihydroxyphenyialan- Peroxidase. V. Mathematics of the enzyme lne and pyrocatechol) and is without action on action. H. W. B an si and H. U cko ; ^rosine. Under suitable conditions, taka-diastase Chem, 1927,169, 177—195; cf. this vol., 377).— lhe onvcrts fibrinogen into fibrin. oxidation of pyrogallol by peroxidase proceeds P. W. Clutterbuck. according to the equation u—Jet where u is 1112 BRITISH CHEMICAL ABSTBACTS.— A. change in time i, i is a constant, and 1/a tho Influence of some poisons on the serum- exponential factor. The calculated values with lipase of warm-blooded animals. A . K t t d r j a v - varying amounts of enzyme, hydrogen i^eroxido, z e v a (Fermentforsch., 1927, 9 , 139— 145).—In and pyrogallol, and with variations in tho pa and general, the serum-lipase of tho carnivorous animal temperature, agree very well with tho experimental (cat and dog) is more readily inhibited by atoxyl results. The factor a is constant for one enzyme than is that of the herbivora, the rabbit, however, preparation with variations in the amount of enzyme being an exception. Of these animals, the cat, dog, and pyrogallol, and, within certain limits, the con and rabbit are most sensitive to arsenic. Quinine centration of hydrogen peroxide; it is influenced inhibits most strongly the serum-lipases of the dog, chiefly by alterations in p a and temperature, being sheep, and cow, and the lipase of the horse, hen, and increased by a rise in temperature and a rise in Ca. pigeon to a less extent, whilst it has very little action The values for a usually lie between 1 and 2, but in the case of the guinea-pig, cat, and rabbit. No with an excess of hydrogen peroxide and a pn below relationship can be traced between tho sensitivity 4-5 the value rises above 2. The decrease in velocity of the lipases to quinine and tho type of food eaten. observed during the course of the oxidation is duo Morphine exerts little inhibitory action on serum- to adsorption of the enzyme on the purpurogallin lipase except with the dog, whilst strychnine has formed, and removal of this product from a reaction even less influence. The sensitivity of the serum- mixture, in which the reaction has ceased, leads to a lipases to morphine and strychnine cannot be resumption of the oxidation. Hydrogen peroxide correlated in any way with the type of food or with inhibits the action of poroxidase only if present in tho general sonsitivity of the animal to the poison. high concentrations. A modification of Willstatter’s A. W o r m a l l . scheme is suggested for tho reactions between hydrogen Specificity of proteolytic enzymes. E. W a l d - peroxide and peroxidase, resulting in the formation s c h m i d t -L e i t z , W . G r a s s m a n n , and H. S c h l a t t e r of an active additive product which gives up oxygen (Ber., 1927, 6 0 , [B], 1906— 1909; cf. A., 1926, 323).- and an inactive product which is dissociated into Enzymic hydrolysis of triglycine, dZ-alanyldiglycine, free peroxidase and hydrogen peroxide under tlio tetraglycine, dMeucyltriglycine, pentaglycino, I- influence of tho substrate. A. W o r m a l l . leucyltriglycyl-Z-tyrosinc, hcxaglycine, and Meucyl- heptaglycine by intestinal erepsin and pancreas- Action of tyrosinase on tyrosine. H. S. R a p e r trypsin activated by enterokinaso has been investig (Fermentforsch., 1927, 9 , 206— 213).— The mechanism ated. Lengthening of the peptide chain, for of the oxidation of tyrosine by tyrosinase is discussed example in glycylglycine or leucylglycino by intro (cf. A., 1926, 977; this vol., 278). The first product duction of further glycyl residues up to the octapeptldo, is 3 : 4-dihydroxyphenylalanine, which is then oxidised is without influence on the specificity of the enzyme, to tho corresponding quinone; an intramolecular whereas tho conversion of leucyltriglycine into leucyl- change results in the production of 5 : 6-dihydroxydi- triglycyltyrosine is accompanied by a qualitative hydroindole-2-carboxylic acid, which is then oxidised change in the specific action, since the peptide is to the corresponding quinone (red compound). This hydrolysed by trypsin but not by erepsin. The quinone yields 5 : 6-dihydroxyindoIo and 5 : 6-di- nature of the amino-acid component is therefore of hydroxyindole-2-carboxylic acid, the precursors of primary importance, but the effect of lengthening melanin. From tho nitrogen content of melanin the chain is shown by comparison of the hydrolysis (A., 1925, i, 473) it is possible that each molecule of of le ucyl tri glycyl tyrosine and glycyltyrosine. dihydroxyindole oxidised to melanin takes up one Tho observation that peptides can be hydrolysed atom of oxygen and loses two atoms of hydrogen, by pancreatic trypsin renders unnecessary the formal and that condensation occurs with the formation distinction between the proteases proper, including of colloidal amorphous melanin. Tho results do not trypsin, and the peptidases. H. r e n support tho view that melanin production is due to W . the oxidation of a pyrrole derivative formed from Specific adaptation of polypeptidases, k. tyrosine. A. W o r m a l l . A b d e r h a l d e n and E. S c h w a b (Fermentforsch., Purification of lactic acid-forming enzyme of 1927, 9 , 252— 263).—Various polypeptide derivatives muscle. 0. M e y e r h o f and K. M e y e r (J. Physiol., have been subjected to the action of polypeptidases, 1927, 6 4 , xvi).—The muscle extract is brought to and the nature of tho substrate grouping responsible pu 5 with acetate buffers, thereby precipitating the for the affinity for the corresponding enzyme is protein and enzyme. Subsequent elution with considered. cZZ-Leucyltyramine is hydrolysed by tho phosphate solution effects dissolution of the enzyme erepsin of intestinal and pancreatic press juices, with some protein. After a repetition of this process but not by yeast maceration juice. The secondary the activity had increased more than tenfold, and base, iminodiisohexoyltyramine, is hydrolysed by the may bo further increased by adsorption on aluminium yeast juice only, whilst tho phenylcarbimides o hydroxide prepared by Willstatter’s method. The phenylalanine, leucine, and glycinc aro unattackec co-enzyme and phosphoric esters are removed during by these juices. Pancreatin hydrolyses benzoyl-a - the purification so that boiled muscle extract must leucylglycylglycine and benzoyl-rfZ-alanylglycylglycine be added to obtain glycolysis. Besides enzyme and (cf. Imai, A ., 1924, i, 92i). Tyramine is^ con co-enzyme a hydrolysable ester is necessary. This densed with a-bromoisohoxoyl bromide to give c appears to be a hexosediphosphate. On purification ot.-bromoisohcxoyllijramine, m. p. 113°, and this, w e tho enzyme becomes more stable and may be pre heated with ammonia in a sealed tube at olH served for several days. R. K. C a n n a n . 70°, yields dl-leucyltyramine, decomp, about 11», 1113 and the secondary baso iminodiiaohexoyltyramine, and W. R. W ooldridge (Biochem. J., 1927, 21, NH[CH(C4H0)-CO-NH-CH2-CH2-C6H4-OH]2. 1224r—-1251; cf. this vol., 280).—The action of various A . WORMALL. organic and inorganic reagents on tho enzymic Behaviour of cZI-alanyl-S-aminovaleric acid activity of B. coli has been studied. The evidence and dl-leucyl-S-aminovaleric acid towards poly obtained militates against tho hypothesis that tho peptidases. E. A bderiialden and J. H ar tm an n activity of surfaces is due to their adsorption of (Fcrmentforsch., 1927, 9, 199—205).—dZ-a-Bromo- specifically activc molecules. On tho other hand, propionyl bromide is condensed in an alkaline solution the results support the conception of “ active centres ” with 8-aminovalcric acid to yield dl-a-bromopropionyl- •in tho mechanism of enzyme action. This view is S-aminovaleric acid, m. p. 112°, which is converted developed from the theory previously advanced by the action of ammonia into dl-alanyl-S-aminovaleric (Quastel, A., 1926, 434) that dehydrogenations of acid, m. p. 162°. Similarly, 8-aminovaleric acid substrate molecules are induced by electric fields condensed with c/i-a-bromisohexoyl bromide yields which characterise these “ active centres.” dl-u.-bromisoJiexoyl-8-aminovaleric acid, m. p. 75—76°, S. S. Z il v a . which with ammonia gives dl-leucyl-8-amimvaleric The equation of alcoholic fermentation. A. acid, m. p. 164—-165°. The two dipeptides, rfZ-alanyl- H arden and F. R. H en ley (Biochem. J., 1927, 21, and cZi-lcucyl-8-aminovalcric acids, unlike cZZ-lcucyl- 1216—1223; cf. Harden and Young, A., 1906, i, glycine, are not hydrolysed by yeast maceration juice. 470).—Tho reaction which occurs when a mixture A . WORMALL. of a hexose and an inorganic phosphate is fermented Behaviour of i-leucylglycyl-f-tyrosine and by ycast-juice or zymin (yeast treated with acetone) (Z-leucylglycyl-l-tyrosine towards yeast macer has been re-examined and the amounts of carbon ation juice, pancreatic juice, and intestinal juice. dioxide, hexosemonopkosphatc, and hexosediphos- E. A bderiialden and N. Schapiro (Fermcntforsch., phato produced have been determined. The ratio 1927, 9, 234— 237).—These enzyme solutions acting carbon dioxide/total phosphorus csterified is on tho on Z-leucylglycyl-Z-tyrosine in a phosphate buffer average 0-9, indicating that if Harden and Young’s solution at p n 8 for 24 hrs., eliminate Z-tyrosine, which equation bo taken as correct, about 10% of the has been isolated in the pure condition, whilst Z-leucine, phosphorus is esterified without evolution of carbon glycine, and Z-leucylglycine are also formed. No dioxide. The product of this csterification is probably action occurs with cZ-leucylglycyl-Z-tyrosine. d-a- a monophosphate. Tho ratio carbon dioxidc/di- Bromoisohexoylglycyl-Z-tyrosino is condensed -with phosphate is on the averago 2-3S, but varies con glycyl-Z-tyrosino to give d-a-bromoisohexoylglycyl-l- siderably in individual cases. The fact that this tyrosine, an oil, which when treated with ammonia ratio is almost invariably somewhat greater than the yields l-leucylglycyl-l-tyrosine, [a]„—30-9°. d-Lcucyl- value 2 required by Harden and Young’s equation glycijl-l-tyrosine, [a]jJ-(-32-80, is prepared in a similar suggests that the diphosphate is originally produced manner with the intermediate formation of 1-a- in accordance with the equation, but that a part of bromisohexoylglycyl-l-tyrosine, an oil. it is subsequently partly hydrolysed with formation A . W orm all. of a monophosphate. Tho ratios carbon dioxide/ Structure and enzyme reaction. I and II. monophosphate and monophosphate/diphosphate are The systems urea-urease-charcoal and poly- highly variable and show no definite relations. saccharide-amylase-charcoal. S. J. P r z y l e c k i, S. S. Z il v a . H. N iedzwiedzka , and T. M ajewsici (Biochem. J., Alcoholic fermentation by yeast-cells under 1927, 21,1025— 1039).— In the system urea-eharcoal- various conditions. VIII. E. A bderiialden urease the enzyme is almost quantitatively adsorbed, (Fermcntforsch., 1927, 9, 195—198; cf. A., 1923, i, whilst the substrate remains almost entirely in 519).—Experiments have been carried out to deter solution. The velocity of enzymic reaction in this mine whether ultra-violet light has any influence on system is almost the same as in the absence of the alcoholic fermentation. Irradiated ergosterol, the adsorbent and is unaffected by the addition of alcoholic extract of irradiated yeast, and irradiated narcotics. Propyl or butyl alcohol docs not remove yeast maccration juice have no significant influence. the enzyme from the adsorbent to any appreciable A. W ormall. extent. In tho system amylase-charcoal-glycogen Influence of natural and synthetic thyroxines or -dextrin the enzyme and much of the substrate on alcoholic fermentation. E. A bderiialden (50—75%, according to the quantity of charcoal (Fermcntforsch., 1927, 9, 243—245).—Thyroxine has present) are adsorbed. In this case tho velocity a varying influence on the fermentation of dextrose of hydrolysis is considerably lower than in the absence by bottom yeast in a phosphate buffer solution at of an adsorbent, and narcotics can remove the sub pa 4-5—6-5; usually a definite acceleration is obtained, strate, but not the enzyme, from tho charcoal to a but often there is no effect or even a very slight peat extent. This reduction in tho velocity of inhibition. Natural thyroxino and synthetic hydrolysis is duo to spatial separation of enzyme thyroxine give identical results with tho same yeast. and. substrate. If the effective concentration of tho A. W ormall. substrate be taken into consideration, the law of mass Alcoholic fermentation of solutions of dextrose action is followed in enzyme reactions in a hetero in water exposed to the radiation of a quartz de F azi geneous medium. S. S. Z il v a . mercury vapour lamp. R. (Atti R. Accad. Lincei, 1927, [vi], 5, 901-905; cf. this vol., Experiments on bacteria in relation to the 592).—Aqueous dextrose solution, prepared immedi mechanism of enzyme action. J. H. Q uastel ately after the water used has been exposed to tho 1114 BRITISH CHEMICAL ABSTRACTS.— A. radiation from a quartz mercury vapour lamp, is bacterial residue amounting to 2902 g. ; the alcohol- fermented by yeast appreciably moro rapidly than cther extract was separated into ether-soluble and one prepared with untreated water. Suspension of water-soluble fractions, the former yielding 253-1 g. the yeast for a time in the irradiated water also of phosphatidcs and 240 g. of fat, and the latter 12-5 g. enhances the speed of fermentation, but treatment of basic substances and 33-9 g. of a polysaccharide. of a highly impure or enfeebled yeast with tho The phosphatides, on further purification, yielded irradiated water may result in a considerable lessening 138-3 g. of a fraction having N 0-4%, P 2-3%, m. p. in the velocity of fermentation. T. H. P o p e . 210°. On hydrolysis with dilute acid, this gave palm itic acid 30-5%, oleic acid 12-8%, a liquid saturated 1 ‘ Acclimatisation ' ' of fresh culture-yeasts to acid, C20H,10O2, 20-9%, dextrose 13-9%, a sugar acid galactose. H. v o n E u l e r and B. J a n sso n (Z. 13-8%, and glycerophosphoric acid 5-4%. No choline physiol. Chem., 1927, 169, 226—234).—Top yeast was found, the nitrogen being apparently present as E and bottom yeast H, previously suspended for long ammonia. The acid C20H40O2 was separated by frac periods in a galactose solution containing phenol, do tional crystallisation of the benzyl-t/i-thiocarbamide not acquire the power to ferment galactose. In salt, m. p. 143— 144°, into an optically inactive contrast to earlier experiments (Euler and Nilsson, fraction and one having [a]» +3-54°. The sugar A., 1925, i, 866), a low phenol concentration, sufficient acid gave with phenylhydrazine, in the cold, a sub to prevent any detectable increase in cell count, but stance, m. p. 194— 195°. C. R. H arin gton . not sufficient to prevent fermentation of dextrose, is maintained throughout. Similarly experiments Soluble specific substance of pneumococcus. on the fermentation of galactose by fresh bottom V. Aldobionic acid from specific polysaccharide yeast II at 38° fail to prove that “ acclimatisation ” of type III pneumococcus. M. H eidelberger can occur without new formation of yeast-cells. and W. F. G o ebe l (J. Biol. Chem., 1927, 74, 613— “ Acclimatisation ” to galactose is concerned with the 61S).—The aldobionic acid obtained by hydrolysis of zymase and not with the co-zymase, since “ acclim the specific polysaccharidc of pneumococcus (cf. this atised ” dried bottom yeast washed free from co vol., 77), on oxidation with barium hypoiodite, gave zymase ferments galactose on the addition of co-zj'masc a dicarboxylic acid, C10H13O9(CO2H)2, calcium salt, [a]D —7-5° ; this compound gives the naphthoresorcinol from untreated yeast. A. W o rm a l l. test and yields tho same amount of furfuraldehyde, Pigment produced by ChromobacteriUm vio- on distillation with hydrochloric acid, as the original laceum . J. R e il l y and G. P y n e (Bioehem. J., 1927, aldobionic acid. Further, on hydrolysis with hydro- 2 1, 1059— 1064).— Tho organism was grown in bromic acid in presence of bromine the aldobionic acid nutrient lactose broth, filtered, and extracted at yields saccharic acid. The aldobionic acid must there 50° with alcohol at reduced pressure. The pigment fore be a compound of dextrose and glycuronic acid was precipitated from tho alcoholic solution by the combined in glucosidic linking through the aldehyde addition of water. The formula C50H59O15N5 is group of the latter. C. R. H arington. suggested. One fifth of the total nitrogen is removed Soluble specific substance of Friedlânder’s by the action of nitrous acid. S. S. Z il v a . bacillus. IV. Hydrolytic products of specific Auto-elimination of ammonia in bacterial carbohydrate of type A Friedlânder’s bacillus. cultures. A. B e r th e lo t and G. A m o u r e u x (Bull. W. F. G o eb e l (J. Biol. Chem., 1927, 74, 619—629).- Soc. Chim. biol., 1927, 9. 932— 934).— Cultures of On hydrolysis of the specific polysaccharide from B. proteus vulgaris which normally develop an alkaline Fricdlander’s bacillus type A with sulphuric acid, reaction as the result of the production of ammonia there was obtained an aldobionic acid, C^H-igOjo, do not do so in presence of magnesium sulphate and which is a glucosidic compound of dextrose and alkali phosphate, since the ammonia is then eliminated glycuronic acid of tho same type as and isomcnc from the solution as ammonium magnesium phosphate. with the acid obtained similarly from the specific W. 0 . K e r m ac k . polysaccharide of pneumococcus type III (cf. preceding Production of acetylmethylcarbinol by Clos abstract). C. R. H arington. tridium acetobutylicum. P. W. W il s o n , W. H. Action of free chlorine on micro-organisms. P et e r se n , and E. B. F r e d (J. Biol. Cliem., 1927, F. D ie n e r t and P. E t r il l a r d (Compt. rend., 19i7, 74, 495;—507).—In butyl alcohol fermentation by the 1 8 5 , 621— 623).—The concentrations of free chlorine above organism, acetylmethylcarbinol is regularly required to sterilise aqueous suspensions of micro produced in maximum amounts of 0-3—0-4 g. per organisms, containing about 106 per c.c., vary con litre, the production occurring simultaneously with siderably, e.g., B. coli, 0-1; B. subtilis, 1-0 mg. per that of acids and acetone. The amount of acetyl litre. Occasionally 4— 5 times these concentrations methylcarbinol is increased by addition of phosphates are required to sterilise the suspensions c o m p le te y. and decreased by protein; the effect of such modi Agitation of the mixture increases tho efficiency o fications in the medium on the production of acids the disinfectant since extraneous organic mat er and of acetone is less marked. 0. R. H a r in g t o n . shields tho organisms to some extent. By J ujV Separation of lipin fractions from tubercle ment of the concentration of free chlorine it is possi bacilli. Phosphatide fraction of tubercle bacilli. in some eases to obtain a pure culture froni a nuxc culture. G. A. C. Gough. R. J. A n derson (J. Biol. Chem., 1927, 74, 525— 535, 537—551).—Tubercle bacilli (3868-5 g.) were extracted Functions of the adrenal cortex and mechan with a mixture of ether and alcohol and then with ism of biological oxidations. A. vo n “ J j chloroform. The latter removed 427 g. of wax, the G y ô rg yt (Magyar Orvosi Arch., 1927,2 8 ,138 l )■ BIOCHEMISTRY. I I 15 Some biological oxidations require a hydrogen activ 1093). Glucosimine, glucose ureide, glucosamine ation as well as an oxygen activation. In the plant hydrochloride, or chitose cannot relieve the symptoms the oxygen-activating system has the character of a caused by insulin. S. S. Z il v a . phenoloxidasc. An aromatic substance which is oxidised by the phenoloxidase to a quinone is also Mechanism of the insulin effect on carbo present; the quinone is reduced again, thus acting hydrate metabolism. H . P h illips (U.S. Naval catalytically as a hydrogen carrier. In certain plants Med. Bull., 1927, 25, 309—314).—Cohnheim’s, Col- there is a second reducing aromatic substance acting lip’s, and the y-glucose theories are discussed. as a catalyst in tho oxidation system. An analogous _ Chemical A bstracts. substance is present in the adrenal cortex. Effect of cobalt on insulin hypoglycaemia in Chem ical A bstracts. rabbits. N. R. B la th er w ick and M. Sa h y u n Effect of the parathyroid hormone on gastric (Amer. J. Physiol., 1927, 81, 560—562).— Contrary secretion. II. Calcium content of gastric juice. to Bertrand and Maeheboeuf (A., 1926, 869), it is W. C. A ustin and S. A . M atth ew s (Amer. J. Physiol., found that cobalt is without appreciable influence on 1927, 81, 552— 559).— The calcium content of pure insulin hypoglycemia in rabbits. R. K . Can n a n. gastric juice (dog) is 5— 6-5 mg. %. It does not vary Food requirements for growth of the rat. I. greatly during parathyroid hypercalcajmia. Growth on diet of purified nutrients. L. S. II. K . Ca n n a n . P almer and C. K en n e dy (J. Biol. Chem., 1927, 74, Application of the axolotl metamorphosis 591—611).—Normal growth was not obtained in rats reaction to the assay of thyroid gland hormones. (kept from access to their faeces) on a diet of purified B. M. Z a v a d o v s k y and E. V. Z a v ad o v sk y (Endo caseinogen, dextrin, agar, and salts, with butter fat crinol., 1926,10, 550— 559).— The average velocity of and wheat embryo extract as sources of vitamins-^4 metamorphosis of axolotls varies directly with the and -B ; some hitherto unrecognised factor must concentration of thyroxine solution (0-1— 0-001 g. per therefore be necessary for the growth of these animals. litre) to which the animals are exposed. C. R. H arington. Ch em ical A bstracts. Phosphorus and calcium metabolism on de Regulation of the production of insulin. I. ficient diets. I. Action of ultra-violet light. Dextrose as the hormone liberating insulin. II. Action of cod-liver oil. III. Changes of E. Grafe and F. M e y t h a l e r (Arch. exp. Path. phosphorus or calcium content of the diet. P. Pharm., 1927, 125, 181— 192).— From a study of the Schultzer (Biochem. Z., 1927,188, 409—426, 427— blood-sugar curves obtained after administration of 434, 435—447).—I. The action of ultra-violet light on dextrose by injecting it into the femoral and pan- the phosphorus and calcium metabolism of young rats creatieo-duodenal arteries, evidence is adduced indicat on various diets is investigated. On a non-rachitic ing that the secretion of insulin by the pancreas is diet deficient in phosphorus and vitamin-!?, the rats the result of direct stimulation by dextrose. lost in weight, and irradiation considerably increased W. 0. K erm ack . phosphorus retention. On a rachitic diet deficient in Behaviour of sugars foreign to the body under phosphorus, irradiation caused increased phosphorus the action of insulin. I. Effect of insulin on and calcium retention due to greater absorption, and the degree of assimilation of various sugars. the rachitic changes declined. Acid-soluble phos P. B asch and L. P o l l a k . II. Resorption of phorus returned to normal and serum-calcium rose sugars injected intraperitoneally under the above normal. On a diet deficient in calcium, irradi influence of insulin. L. P o lla k (Arch. exp. Path. ation caused considerable phosphorus and calcium Pharm., 1927, 125, 89— 101, 102— 128).—I. Insulin retention and serum-calcium returned to normal. does not appear to influence the permeability of the II. Investigation of the effect of 12 days’ treat kidneys of the rabbit to dextrose. On tho other hand, ment with cod-liver oil on the phosphorus and calcium it markedly increases tho tolerance of the animal metabolism of young rats on the above diets showed towards dextrose, less towards laevulose, very slightly that cod-liver oil had the same effect as ultra-violet towards galactose, and not at all towards mannose, light both in respect to phosphorus and calcium sucrose, and lactose, when these sugars are adminis retention and to acid-soluble phosphorus and serum- tered intravenously. calcium. II. When Ringer solution is injected into the III. The phosphorus and calcium metabolism of peritoneal cavity of a rabbit, the blood-sugar con young rats is investigated on diets the phosphorus centration of the peritoneal fluid gradually becomes and calcium contents of which are changed during the equal to that of the blood. The rate at which the experiment. Addition of phosphate to a diet rich in process occurs does not appear to be influenced by calcium and relatively poor in phosphorus causes insulin, except in as far as insulin influences the increased phosphorus retention due to greater absorp Wood-sugar concentration, and it is probably depen tion and an increased calcium retention due to dent on simple diffusion. The rates of absorption of lessened excretion of calcium in the urine. Excretion dextrose, kevulose, and galactose, but not those of of calcium in the faeces increased somewhat, acid- mannose and lactose, when these sugars are intro soluble phosphorus increased, and serum-calcium duced into the peritoneal cavity are increased by the remained unchanged. Decreasing the calcium carb action of insulin. W. 0. K erm ack. onate content of the same diet caused an increase of both phosphorus and calcium retention, due to Effect of certain sugar derivatives on insulinised increased reabsorption. Serum-calcium remained Clu tterbuck. imce- A. H y n d (Biochem. J., 1927, 21, 1091— unchanged. P. W. 1116 BRITISH CHEMICAL ABSTRACTS.----A. Physiological equilibrium in plants. III. Gymnocladus dioica have, respectively: moisture, Connexion between the course of absorption of 5-98%, 11-41%; ash,3-85%,3-18%;protein (N x 6-25), soil nutrients and their movement in plants. 32-30%, 6-50%; crude fibre, 2-01%, 21-12%; free A. R ippel (Bioehem. Z., 1927, 187, 272—282).— invert-sugar, 0, 3-56%; sugar by inversion, 12-06%, With Helianthus it is shown that the course of absorp 18-95%; pentosans, 5-67%, 17-29%; and starch tion of soil nutrients corresponds with their mobility (diastase), 13-32%, 18-91%. Light petroleum ex ha the plant. Absorption of readily mobile elements tracts 19-27% from the seeds, 0-41% from the pods. such as nitrogen, potassium, and phosphor us accelerates For ether the corresponding figures are 19-29% and the formation of dry substance, whilst absorption of 1-24%, and for 95% alcohol, 49-00% and 42-05%. less mobile elements such as calcium, sulphur, The oil obtained by ether extraction of the ground magnesium, and silicon has a much smaller or no seeds deposits a small amount of solid when kept. effect. It seems possible that in the young plant, the It is practically odourless, with a bland taste, and has former, and with increasing age, the latter type of di0 0-9219; n20 1-4769; iodine value (Hanus) 137-5; absorption is favoured. P. W. Clu tte r b u c k . saponif. value 191-03; Reichert-Meissl value 0-44; Nature and metabolism of sugars in Iris. H. acid value 0-39; acetyl value, 11-35; unsaponifiable Colin and A . A ugem (Compt. rend., 1927,185, 475— matter, 1-28%; soluble acids (as butyric acid %), 478).—The sugars occurring in three varieties of 0-83; insoluble acids, 93-93% (iodine value 132-0); Iris at various seasons have been investigated. unsaturated acids (corr.), 89-74% (iodine value 145-0); C. W. G ib b y . and saturated acids, 4-86% (iodine value 3-4, before Enzymic hydrolysis of tui'anose. M. B r id e l correction). The oil contains the glycerides of oleic and T. A ag aard (Compt. rend., 1927, 184, 1667— acid (37-41%), linoleie acid (56-37%), saturated acids 1669).—Prom the action of various enzymes on (probably stearic and palmitic acid, with a small turanose it is inferred that this substance is a glucoside amount of arachidic acid) (5-08%), whilst a phytosterol, of lsevulose, and moreover that the constitution of m. p. 165— 166°, was obtained from the unsaponi P . W illson. turanose may require revision. W. R obson . fiable material. G. Extraction of asperuloside from Gallium Relative proportions of potassium and sodium verum , L. Probable presence of the glucoside in plants. G. B e r t r a n d and D. I. P erietzeanu in Rubiaceai. H . H&r is s e y (Compt. rend., 1927, (Compt. rend., 1927,184,1616— 1618).—In terrestrial 184, 1674— 1675).—A method of extraction of this plants the ratio K/Na is distinctly higher than unity. glucoside is described, together with a table showing The ratio, however, is extraordinarily variable, the results of trial extractions on other members of fluctuating from 3 in the case of the mallow to more this family. W. R obson . than 1000 in the elder. In marine plants, preliminary Allantoic acid in the leaves of Acer pseudo- figures yield ratios also greater than unity. platanus. R. F osse and A. H ie u l l e (Compt. rend., W . R obson. 1927,184, 1596— 1598).— The dixanthy 1allantoic acid Accuracy obtainable by repetition of simple obtained hy the addition of xanthhydrol to extracts measurements. A. K r o g h (J. Biol. Chem., 1927, of the leaves of Acer pseudoplatanus (cf. A., 1926, 548), 74, 393— 407).—The maximum accuracy obtainable followed by crystallisation of the crude product from in making simple measurements is given by the pyridine, is not derived entirely from the allantoic acid average of ten readings, further repetition serving no in the extract. It appears that the extract contains good purpose. This conclusion is reached both from some uroxanic acid, the xanthyl derivative of which statistical considerations and from the practical suffers decarboxylation on crystallisation and is con execution of such operations as the measuring of the verted into dixanthylallantoic acid. The uroxanic thickness of needles and cover slips and the use of the acid, together with carbamide, has been directly polarimeter; in the latter connexion, the degree of accuracy claimed by Lundsgaard and Holboll (A., isolated from the extract. G. A. C. G o u gh . 1925, i, 1494; 1926, S61) could not be substantiated. ¡¿-Ephedrine from Chinese Ephedra. B. E. C. R. H arington. R ead P en g and C. T. (Chinese J. Physiol., 1927, 1, Methods. VIII. L. P in c u s s e n . D eterm in 297— 304).— Both Chinese and Swiss Ephedra contain ation of total sulphur in urine and in organs. A. both i/r-ephedrine and ephedrine. The solubility of K o n a r sk y (Bioehem. Z ., 1927, 187, 398—402).- ^-ephedrine hydrochloride in chloroform is 53 times as A method is described for the determination of great as that of ephedrine hydrochloride, and this sulphur in organic substances, tissue, and urine. difference is utilised in the separation of these alkaloids. P. W . Clutterbuck. It is suggested that this difference in solubilities and Ceruleomolybdate determination of phos the inability of a small excess of ammonia to liberate phates. B. E. Gil b e r t and J. B. Sm ith (J. Biol. tho bases from these salts may account for the many Chem., 1927, 74, 223—229).— In the method of erroneous statements concerning the occurrence of Deniges (A., 1920, ii, 770) the presence of high con these alkaloids and also for the low assay results centrations of acid inhibits the development of colour; reported. W. R obson . in such cases, therefore, it is necessary to employ a Kentucky coffee nut tree seed-oil. C. B a r k e n - standard of the same acidity as the unknown solution. bu s and A. J. Z im m erm an (J. Arner. Chem. Soc., The coloured compound formed in the reaction appears 1927, 49, 2061— 2064).—The seeds and pods of to be colloidal. C. R. H a r i n g t o n . NH’ P- 135°- The gives 2 : 4 : 6( ^-triacetatomercuri-m-iodoaniline, m. p. products of the interaction of carbonyl chloride and 190° (decomp.). T. H. P o pe . magriesylindole are : 3 : 3-carbonyldi-indole, Preparation of lead tetraphenyl. H . G il m a n C17H12ON2, m. p. 280°, which forms a silver deriv and J. R obinson (J. Amer. Chem. Soc., 1927, 49,. ORGANIC c h e m i s t r y . 1099