摘要:

J O U R N A L HORACE T. BROWN LL.D. F.R.S. J. N. COLLIE Ph.D. F.R.S. A. W.CROSSLEY D.Sc.,Ph.D.,F.R.S. BERNARD DYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.R.S. P. F. FRANKLAND Ph.D. LL.D. C. E. GROVES F.R.S. F. R. 8. OF J. T. HEWITT M.A. D.Sc. Ph.D. F. R. S. A. MCKENZIE M.A. D.Sc. Ph.D. G. T. MORGAN D.Sc. J. C. PHILIP D.Sc. Ph.D. Sir WILLIAM RAMSAY K.C. B. LL.D. A. SCOTT M.A. D.Sc. F.R.S. F.R.S. THE CHEMICAL SOCIETY. ABSTRACTS OF PAPERS ON ORGANIC CHEMISTRY. 6biior J. C. CAIN D.Sc. Ph.D. szCl?xr- @bib A. J. GREENAWAY. E. F. ARMSTRONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. W. GODDEN B.Sc. E. GOULDING D.Sc. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. H. B. HUTCHINSON Ph.D. Z. KAHAN B.Sc. L. DE KONINQH. G. D. LANDER D.Sc. F. M. G. MIGKLETHWAIT. N. H. J. MILLER Ph.D. T. H. P O P ~ B.Sc. T. SLATER PRICE D.Sc. Ph.D. E. J. RUSSELL D.Sc. S. B. SCHRWER D.Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. F. SODDY M.A. F.R.S. L. J. SPENCER M.A. R. V. STANFORD MAC. Ph. D. J. J. SUDBOROUGH Ph.D. D.Se. A. JAMIESON WALKER Ph.D. B.A. W. 0. WOOTTON B.Sc. W. J. YOUNG M.Sc. D.Sc. 1911. Vol. C. Part I. LONDON GURNEY dz JACKSON 10 PATERNOSTER ROW. 1911.RICHARD CLAY & SONS LIMITED .RUNOWICE ETREB" STWORD STREET S.E. AND BUNGAY SVFlroLy.

ISSN:0368-1769    

DOI:10.1039/CA91100FP001

出版商:RSC    

年代:1911

数据来源: RSC

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J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. AND HORACE T. BROWN LL.D. F.R.S. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. BERNARD DYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.R. 5. P. F. FRANKLAND Ph.D. LL.D. C. E. GROVES F.R.S. F. R. S. J. T. HEWITT M.A. D.Se. Ph.D. A. MCKENZIE M.A. D.Sc. Ph.D. G. T. MORGAN D.Sc. J. C. PHILIP D.Sc. Ph.D. Sir WILLIAM RAMSAY K. C.B. LL.D. A. SCOTT M.A. D.Sc. F.R.S. F.R.S. F.R. S. &biilYx Snb- Qbiiar J. C. CAIN D.Sc. Ph.D. A. J. GREENAWAY. g.Vsfxrrcfoxtl E. F. ARMSTRONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. W. GODDEN B.Sc. E. GOULDINO D.Sc. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. 2. KAHAN B.Sc. L. DE KONINGH. G. D. LANDER D.Se. H. B. HUTCHINSON Ph.D. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. S. B. SCHRYVER D.Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. F. SODDY M.A. F.R.SI L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph.D. B.A. W. 0. WOOTTON B.Sc. W. J. YOUNG M.Sc. D.Sc. E. J. RUSSELL D.SC. 1911. Vol. C. Part 11. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1911.RICXARD CLAY & SON& LIMITED 1RImWICR STREET STAMFORD STRXLT 8 E AND BUNOAY (IUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91100FP003

出版商:RSC    

年代:1911

数据来源: RSC

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INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 35 Nature of' the Decomposition of Hydrogen Peroxide by Light. A. TIAN (Complt. rend 1910 161 1040-1042).-By sub- mttting solutions of hydrogen peroxide in conductivity water t o the action of ultra-violet light from a quartz-mercury lamp the author finds that the reaction for its decomposition is a unimolecular one and proceeds in accordance with the equations H20 = H20 + 0 ; 2 0 = 0,. The decomposition by light therefore resembles that induced by catalysts and is different from the decomposition by heat which is a blniolecular reaction. Under the conditions of the experiment the t 9 . 3 3 2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. reverse action occurred to an extent not exceeding the formation of 0.00005 gram of hydrogen peroxide per litre.w. 0. w. Catalytic Decompoaition of Hydrogen Peroxide in a Homogeneous Medium. ETJGEN SPITALSKY (x Buss. Phys. Chew. Xoc 1310,42 1086-11593C).-A discussion of the nature of catalysis in which it is shown that the velocity and to some extent the direction of all oxidising-reducing actions and particularly that of hydrogen peroxide are greatly affected by the concentration of the hydrogen ions of the reacting mixture and that the condition of the latter at any given moment and whatever the concentration of the hydrogen ions can be completely defined by the effective concentration of the hydrogen peroxide at that moment. I n the catalysis of hydrogen peroxide by dichromnte there is a simultaneous reversible formation of various intermediate compounds of varying stability of which those having the least number of molecules of the hydrogen peroxide attached to the catalyst are comparatively less stable ; hence towards the end of the reaction when the concentration of hydrogen peroxide is less the velocity of the reaction is greatest.The measurements were made gasometrically the experiments being performed in Bredig and Walton’s apparatus (Abstr. 1903 ii 282) and Riesenfeld and Weich’s criticisms (Abstr. 1908 ii 951) of the gasometric method are shown to be entirely without foundation. Many of the results have already been published (Abstr. 1907 ii 338 942). Since chromic acid or the dichromate in acid solution is reduced by hydrogen peroxide to chromic oxide it was necessary in order to complete the experiments on the catalytic decomposition of hydrogen peroxide by chromates to investigate how far this process occurs ia the catalytic experiments described and what is its relation to the activity of the catalyst.I n very dilute solutions all the best ordinary methods for the estimation of chromic acid are wholly inapplicable but the following very accurate and convenient method is employed. To about 10 C.C. of a solution containing 0.0108 mol. CrO 30 C.C. of sodium hydrogen arsenate solution containing 0 004 gram-mols. NaH,AsO per litre are added then 30 C.C. of hydrochloric acid. The mixture is left for twenty minutes after which two drops of methyl-orange or indigo solution are added as indicator and the mixture titrated with an equivalent solution of potassium bromate.The method is recommended as a general one in analysis and as a more accurate and cheaper substitute for iodometric methods. I n the presence of a large excess of hydrogen peroxide chromic acid is at first rapidly reduced although the reaction is not instantaneous after which the hydrogen peroxide is catalytically decomposed under the influence of the chromium tri- and sesqui-oxides but the relative pro- portion of the two last formed finally does not alter with the con- centration or quantity of hydrogen peroxide employed the reaction being one of chemical equilibrium between the two oxides a fact which WRS confirmed by the measurement of the concentration of the hydrogen ions in various mixtures. * The fresh matter i s published also in Zeitsch. anorg.Chem. 1910 69 179-208.INORGANIC CHEMISTRY. ii. 37 Contrary to Riesenfeld’s assumption (Zoc. cit.) it is shown that the form of curves obtained for the decomposition of hydrogen peroxide in the presence of dichromate is best explained by the fact that after the reduction of the dichromate and the establishment of equilibrium between the two oxides the catalytic decomposition of the hydrogen peroxide proceeds without any further change in the catalyst or if any change does occur it is a reversible one and only depends on the con- centration of the hydrogen peroxide at the given moment. The catalytic properties of chromic acid in no way depend on its previous history and the effect of the fresh acid is identical with that of the acid after having been used several times; it is evident therefore that no irreversible changes take place.The curves and the general charac- teristics of the reaction are closely analogous to those of fermenting processes. Z . K. Catalysis of Hydrogen Peroxide. EUGEN SPITALSKY (Ber. 1910 43 3187-3201).-8 reply to the criticisms of Riesenfeld (Abstr. 1908 ii 951). It is also shown that the usual method of determining the velocity of the catalytic decomposition of hydrogen peroxide by measuring the rate at which oxygen is evolved gives the bame results as the direct titration of the hydrogen peroxide with pot a sium permangana t e. T. S. P. The Colours of Colloidal Sulphur. RAPHAEL E. LIESEGANC (Zeitsch. Clwn. l z d . Rolloide 1910 7 307-308).-1f drops of a 20% citric acid solution are placed on a thin layer of a solidified solution containing gelatin and sodium thiosulphate the precipitation of sulphur which results from the diffusion of the acid is accompanied by the development of colour effects.I n transmitted light the colour is a deep lilac-blue The colour is not due to interference but appears to be determined by the size of the colloidal particles. After about twenty-four hours the colour effects disappear and this is supposed to be due to the conversion of S into S,. H. M. D. Reduction of Phosphoryl Chloride by Hydrogen under the Influence of the Electrical Discharge. ADOLPHE BESSON aud L. POURNIER (Compt. rend. 1910 151 876-878. Comp7re Abstr. 1910 ii lZl).-When the vnpour of phosphoryl chloride mixed with pure dry hydrogen is submitted to the action of the silent electrical discharge the armatures slowly become coated with a yellow solid.If this is removed by hot water and dried in a vacuum it is obtained as an easily oxidised reddish-yellow powder having the composition P,O. It appears to be identical with the oxide obtained by the action of phosphine on phosphoryl chloride in presence of hydrogen bromide (Abstr. 1898 ii 216; 1901 ii 502) the existence of which has been questioned by other investigators. The action is stated to take place in accordance with the equation 2POC1 + 4H2 = P20 + 6HCl+ H,O. The reaction was carried out in an apparatus of fused silica- which is described in detail. The use of glass for the purpose is inadmissible w. 0 w,ii. 38 ABSTRACTS OF CHEMICAL PAPERS. Safety Explosives Employed in Mines.J. TAFFAKEL (Compt. rend. 1910 151 873-876).-It is shown experimentally that the gases formed by the detonation of safety explosives of the securite type contain a much greater proportion of carbon monoxide when the charge is enveloped in the usual paraffined wrapper than when the explosive is uncovered or wrapped in ordinary paper or asbestos. The presence of the secondary flame accompanying explosion appears to depend largely on the presence of an oxidisable envelope or of coal dust. It is not seen when asbestos paper is employed and the use of the latter therefore enables heavier charges to be fired with safety. w. 0. w. Bromo- and Hydrobromo-derivatives of Silicon. ADOLPHE BEYSON and L. FOURNIER (Compt. rend. 1910 151 1055-1057).- Four kilograms of the crude product arising from the action of hydiogen bromide on silicon at a red heat were fractionally distilled under diminished pressure.About 90% of the liquid consisted of silicon tetrabromide the remainder containing tribromosilicomethane with a small quantity of dibromosilicomethane SiH2Br2 a spontaneously inflammable liquid b. p. about 75" and probably bromosilicomethane SiH,Br b. p. 30-40". The product of the action of the silent eIectric discharge on tri- bromosilicomethane yielded on fractionation silicon tetrabromide hexabromosilicoethane colourless crystals m. p 9 5 O b. p. 265O an octabromide Si,Br8 crystals m. p. 133" a decabromide Si4Brlo m. p. 185" (decomp.) together with an uninvestigated yellow residue. Silicon tetrabromido differs from the tetrachloride in not under- going reduction when mixed with hydrogen and submitted to the silent electrical discharge.w. 0. w. The History of " Potaah I' and of its Name. EDMUND 0. VON LIPPMANN (Chem. Zeit. 1910 34 1217-1219 1226-1338 1335-1 237).-Historical. L. DE K. The Isomorphism of Potassium and Sodium Compounds. ERNST SOMMERFELDT (Zeitsch. anorq. Chenz. 1910 €39 47-51).-The question of the possible isomorphism of potassium and sodium compounds has been studied in the double sulphates blodite Na,Mg(S0,),,4H20 and leonite K2Mg(S0,),,4H,O the crystals being examined by the ultramicroscope. Crystals of blodite become turbid if containing more than 0.8% K,SO the number of particles increasing with the time whilst leonite only shows similar particles when as much as 11.6% Na,SO is present.According to Osttvald the crystallisation of a supersaturated solution is only brought about by a foreign salt if the latter is isomorphons with the salt in solution. The crystallisation of a supersaturated solution of potassium sulphate on the addition of a crystal of ammonium sulphate may be explained by the dissolution of the crystal displacing potassium sulphate. I n accordance with this explanation a readily sduble salt such as potassium iodide alsoINORGANIC CHEMISTRY. ii. 39 brings about the crystallisation of potassium sulphate. criterion may therefore sometimes give misleading results. Ostwald’s C. H. D. A Characteristic Behaviour of Alkali Phosphate. ERNST SALKOWSKI (Zeitsch. physiol. chem. 1910 69 475-478).-It was noticed that the addition of sodium hydroxide to an American meat juice caused it to set into a crystalline mass.When exposed to the air the juice deposits crystals of potassium dihydrogen phosphate and the addition of sodium hydroxide no longer causes crystallisation to occur in the liquid. W. D. H. Some New Compounds of Nitrogen and Hydrogen with Lithium. I. FRANZ W. DAFERT and R. MIKLAUZ (~ilonc6tsh. 1910 31 981-996. Compare Abstr. 1909 ii 882).-Metallic lithium com- bines with pure dry nitrogen a t the ordinary temperature amorphous lithium nitride Li,N being formed ; the presence of relatively small quantities of oxygen or hydrogen however will completely prevent the reaction. Lithium is not attacked by dry air at the room temperature. Lithium nitride has m.p. 840-845’; the fused substance rapidly attacks iron nickel copper platinum porcelain and other silicates. At 870’ i t will eat through any containing vessel. It penetrates through vesseIs of magnesia as through a filter. When heated at 220-250’ in a current of hydrogen a new com- pound trilithiumanzmoniun Li,NH is formed from the amorphous nitride. If this compound is heated above 340’ in an atmosphere of hydrogen part of its hydrogen is expelled to be absorbed again on cooling. If the temperature is raised to 480’ pure trilithiumarnide Li3NH2 is formed. This latter compound is also formed directly by the action of hydrogen OD crystallised lithium nitride which has been obtained by heating lithium a t 460’ in a current of nitrogen; the reaction is so vigorous that the amide is obtained as a fused mass.Trilitbiumammonium is an extremely hygroscopic substance evolv- ing hydrogen and ammonia under the action of water. Trilithium- amide possesses similar properties ; it is not sensitive towards light. T. s. P. Photo-Halides. 11. WILLEM REINDERS (Chem. mkekbkad 191 0 ’7 993-1005. Compare Abstr. 1910 ii 1062).-The author advances arguments in favoiir of the theory that the photo-halides are absorp- tion compounds of colloidal silver and normal halides. He does not consider that there is any evidence to support the theory that they are sub-halides. A. J. W. ‘( Ripening ’’ of Silver Halide Emulsions. RAPHAEL E. LIESEGANG (Zeeitsch. physikal Chem. 1910 75 374-377).-The increase in size of the particles of silver halides the so-called “ripening” of photographic plates may be accounted for in two ways (2) by the association of small particles a process analogous to the coagulation of colloids and (2) by the gradual increase in sizeii.40 ABSTRACTS OF CTXEMICAL PAPERS. of the larger particles a t the expense of the smaller owing to the greater solubility of the latter. The first process must be associated with a kind of diffusion which could not take place in a solidified gelatin film and the observation that ripening proceeds rapidly in such a dried film supports the latter view Further evidence in favour of this explanation is adduced. G. S. Calcium Silicates in Cement. L. Sz. SZATHMARY (Zeitsch. Kryst. Min. 1910 48 448; from Vegy6sxeti Lapok 1907 2 No. 7 and Bdnydsxuti 5s Kohdszati Lapok 1908 46 635-652).-Several calcium silicates have been prepared synthetically but some of them are probably of the nature of solid solutions.Which of these are present in cements the author leaves undecided. The calcium aluminate 2Ca0,AI,03 is probably a constituent of cement. In- cidentally the following analysis is given of [impure] wollastonite from Csiklova Hungary. SiO,. CaO. Fe,O,,. GO,. H,O. Total. 44.95 49.49 0'58 4'31 0.58 99.91 L. J. S. The Alloys of Tellurium with Cadmium and Tin. MATSUSUKE KOBAYASHI (Zeitsch. ccnorg. Chem. 1910 69 1-9; Mem. Coll. Sci. Xng. Kyoto. 1910 ii 353-363).-Mixtures of cadmium and tellurium fused in glass or porcelain tubes in an atmosphere of carbon dioxide have been submitted to thermal analysis.The freezing-point curve has a maximum at about 1041° corresponding with the compound TeCd but it is not possible to prepare this compound in a pure condition under ordinary pressure owing to the volatility of cadmium. The two eutectic points lie so near to the freezing points of cadmium and tellurium respectively as to be indistinguishable from them. The freezing-point curve of mixtures of tellurium aud tin also has a maximum at 780° corresponding with the formula TeSn. The eutectic point between this cornpound and tellurium lies at 393" and 86% Te. The compound TeSn has D 6.472 and does not form solid solutions with tin or tellurium (compare Fay Abstr. 1907 ii S80; Biltz and Rlecklenburgh Abstr. 1909 ii 1022). The thermal results are confirmed by microscopical examination.C. H. D. Falk's White Lead. JULIUS F. SACHER (Chern. Zeit. 1910 34 1261-1263. Compare Abstr. 1910 ii 712 1067).-When lead carbonate lead oxide and lead acetate are kneaded together the product is not 5PbC03,2Pb(OH)2,Pb0 but a mixture in varying proportions of normal lead carbonate and white lead. The mixtures only become white when air containing carbon dioxide has access otherwise n yellow or red colour persists. True white lead examined microscopically is always amorphous and pure normal lead carbonate is always crystalline different preparations diBering only in the size of their crystals.INORGANIC CHEMISTRY. ii. 41 The decomposition of white Iead by hydrogen snlphide ohsewed by Falk carbon dioxide being liberated is due to the presence of lead acetate the acetic acid set free decomposing a further quantity of carbonate.C. H. D. Formation of Colloidal Copper. ANDR$ RASSEKFOSSE (Bull. Acad. my. Belg. 1910 738-741).-Copper sulphate in sulphuric acid is reduced by various organic liquids forming at first probably violet cuprous sulphate and finally colloidal copper. When a few drops of alcohol are placed in a solution of copper sulphate in sulphuric acid a violet zone which gradually becomes brown is formed between the two liquid layers. On gently warming i t disappears to re-appear on cooling but a t 45' it becomes yellow. The solution is stable and is not affected by filtration or by treatment in a centrifugal machine but when submitted to an electric current deposits a deep reddish-brown granular pulverulent copper quite different from the coherent deposit obtained from a solution of copper sulphate in sulphuric acid.Similar results with some difference in details are shown when methyl alcohol ether acetone acetic acid or chloroform is added to such a solution and a solution of copper phosphate in phosphoric acid shows similar behaviour. T. A. H. Corrosion of Copper and Iron Alloys by Water Con- taining Salt and Air. Oxidation of Copper 4t High Temperatures. WILLEM P. JORISSEN (Zeitsch. angew. C'hsin. 19 10 23 2305-2306).-A specimen of delta metal from the keel of a ship which had been attacked by sea-water was found to contain 41.1% of cuprous oxide no cupric oxide being present; the zinc had completely disappeared. Cu prous oxide was also formed from copper which had been kept for two years either in sea-water or in a solutiori of sodium chloride of the same chlorine content.When copper is partly immersed in distilled water cuprous oxide is formed on the submerged part whereas cupric oxide is formed on the other part. Cuprous oxide is formed when air is continually circulated over copper heated to a temperature above that at which dissociation of cupric oxide takes place. Analyses are given of (a) a piece of iron which had been in the ground for years ( b ) iron used to protect a copper alloy in a pump from corrosion ( c ) iron used for the same purpose in a ship's condenser (d) some Dutch bronze cannons fished up from the Straits of Messina. T. s. P. Occluded Gas in Alloys of Copper. G. GUILLEMIN and B. DELACHANAL (Compt.rend. 1910 151 881-883. Compare Abstr. 1909 ii 144).-Results of analyses are given showing the total volume of occluded gas and the percentage of carbon dioxide carbon monoxide methane hydrogen and nitrogen in different specimens of brass bronze aluminium bronze phosphor-bronze and tin. Forgeable brass contains hydrogen cnrbon dioxide and carbon monoxide ; the latter predominates in unsound ingots containingii. 42 ABS'I'PACTS OF CHEMICAL PAI'ERS. blow-holes. The presence of hydrogen does not impair the mechanical properties of brass The small amount of gas in phosphor-bronze consists chiefly of carbon dioxide and hydrogen. Commercial tin contains hydrogen carbon dioxide and carbon monoxide. w. 0. w. The Tempering of Bronzes. L. GRENET (Compt. Tend. 1910 151 S70-87i).-The connexion between the temperature at which bronze is annealed after tempering and the hardness of the product appears to be the same as in the case of steel.w. 0. w. The Formation of Cuprous Iodide from the Physico- chemical Standpoint. P. P. FEDOTBEFF (Zeitsch. anorg. Chem. 1910 69 22-37).-The reaction occurring between copper and iodine in presenceof water has been studied Cu + I - CuI Z CuI + I. Equilibrium at 20" is only reached after fifteen to thirty hours' shaking. The quantity of iodide dissolved increases with the proportion of iodine. I n solutions in equilibrium with solid iodine the concentration of the dissolved iodine increases with that of the copper. Isothermals for the two systems (cuprous iodide and iodine respectively as solid phase) are drawn and it is shown that in all the saturated solutions the ratio Cu 41 is maintained.The range of composition within which cupric iodide is stable is increased by raising the temperature. Assuming that the complex ion present is I'3 the ratio 1'3/1' at 20" = 0,964. As the cation does not enter into the equilibrium the general conclusion is drawn that in aqueous solution of iodine in iodides the iodine is equally divided between the simple and the complex ions. The formula of cupric iodide in a solution saturated with iodine is Cu<' The number of complex ions increases with rising temperature. The solubility-product Cu' x I' = L = 5-06 x 10-12 (Bodlander and Storbeck Abstr. 1903 ii 607) so that K = ( C U ' * ) ~ ( I ' ) ~ / L ~ ( I ~ ) = The potential of the iodine electrode a t 20° is e = 0.900 + O-O2910g(I,)/(I')2; and of the Cu"/Cu' electrode a t ZOO e = 0.476 + 0.05 810g(Cu")/( CU').I,' 4.18 x 10-14. C. H. D. Double Sulphates formed by Lanthanum and Cerium Sulphates with the Alkali Sulphates. BARRE (Compt. Tend. 1910 151 87 1-873).-The solubility of lanthanum and cerium sulphates in aqueous solutions of potassium sodium and ammonium sulphates at different concentrations has been determined. The existence of the following double salts has been revealed by the solubility curves and confirmed by analyses La2(SO,),,K2SO4,2H2O ; La2(S04),,5K,S04 ; La,( SO,),,Na2SO4,2H20 ; La2(S0,)s,5(NH4)2S0,. C'e,(S04)3,K2S04,2H,0;2Ce2(S0,)3,3K2S04,8H,0; Ce2(S04)3,5K,S04 ; Ce,(S04),,Na2S04,2H20 ; La,(S04)3,(NH,)2S0,,2H20 ; 2La2(S04),,5(NR4)2SU ; Ce~(S04)39(NH4)~S04,sH~0 ; Ce2(S04),,5(NH4)2S04.INORGANIC CHEMISTRY.ii. 43 Lanthanum and cerium sulphates are more soluble in a solution of ammonium sulphate than in one of sodium or potassium sulphnte. w. 0. w. Nature of the Oxides Causing the Colour of Oriental Sapphires. AUGUSTE VERNEUIL (Compt. rmd. 1910 151 1063-1066).-The opinion that the colour of oriental sapphires is due to ferric oxide is based on analyses by Vauquelin Forchhammer and others. The author having previously described the preparation of artificial sapphires from fused alumina coloured by ferric and titanic oxides (Abstr. 1910 ii 212) now shows that the latter is present in the natural stones ; three sapphires of different origin being found to contain 0*03-0.058% of titanic acid.The conclusion is drawn that the colour of sapphires is due to titanium present as an oxide or as a titanate of iron. Catalytic Properties of Asbestos. P. A. TSCHEISHWILI (J. Russ. Phys. Chem. Soc. 1910 42 856-862).-An acid- solution of N'/20- potassium permanganate filtered through asbestos is reduced in each of the first eight filtrations after which it is no longer reduced on filtration. Ten C.C. loses in t h i s way 0.025 C.C. for each filtration and the results obtained are exactly the same for asbestos from various sources and whether it has only been treated with acids and water or whether it has been ignited before such treatment.* The precipitate formed on the asbestos has no catalytic influence on the reduction of the permanganate and it does not consist of manganese peroxide.It is much more convenient to use asbestos in the filtration of perman- ganate solutions and allow 0.025 C.C. as correction than to use glass wool through which a clear filtrate cannot be obtained. V. ANDSTROM (Zeitsch. anorg. Chem. 1910 69 10-21. Compare Moody Trans. 1906 89 720; Friend Proc. 1910 26 179; Idamberti and Thomson Trans 1910 9'7 2426). -Thin strips of soft iron are enclosed with water (the oxygen and carbon dioxide in which have been estimated) in flasks closed by ground stoppers sealed by mercury. After shaking for a definite time the rust formed is collected on a filter that present as an incrustation on the strips being added and the iron in the filtrate is also estimated. The quantity of iron removed by corrosion is independent of the proportion of carbon dioxide in the water and is proportional to the amount of dissolved oxygen the ratio of iron t o oxygen corresponding with Fe,O,.The dissolved portion of tho iron corresponds with Fe(HCO,),. When very little oxygen is present but the solution contains large quantities of carbon dioxide corrosion only proceeds very slowly. The results are interpreted as indicating that rusting is principally due to the action oE oxygen probably with intermediate formation of hydrogen peroxide. C. H. D. Dissociation of Ammoniacal Ferrous Chlorides and the Formation of Ferrous Nitride. FERNAND GIRARDET (Bull. Soc. chim. 1910 [iv] 7 1028-1034. Compare Lang and Rigaut Trans. 1899 '75 883; Jackson and Derby Abstr.1900 ii 59ti).-The w. 0. w. Z. K. The Rusting of Iron. These results are shown in the form of curves.ii. 44 ABSTRACTS OF CHEMICAL PAPERS. interaction of ammonia with ferrous chloride is reversible between -18O and 3509 and a study of the tensions of dissociation of the products indicates that two compounds of this type exists represented by the formuh FeC12,6NH3 and FeCI2,2NH3. The former is stable only at low temperatures. Above 350° the chloride is decomposed and ferrous nitride is formed the optimum temperature for this reaction being 480'. I n preparing ferrous nitride it is best to heat the chloride to 480a and then introduce ammonia gas. F u l l experimental details and tables of dissociation tensions are given in the original. T. A. H. Chemical Constitution of Iron-pyrites and Pyrolusite.L. BENEDEK (Zeitsch. Kryst. Min. 1910 48 447-448; from Magy. Chern. B'olySirat 1908 14 85-81).-Iron-pyrites when heated to a red-heat in an atmosphere of carbon dioxide loses kalf of its sulphur and ferrous sulphide (FeS) remains. At 300-400' in water vapour half the sulphur is also lost after which the ferrous sulphide is decomposed with the production of ferrous oxide and hydrogen sulphide. These reactions indicate in the author's opinion that the iron in iron-pyrites is ferrous. Pyrolusite (Mn02) when heated in an atmosphere of hydrogen passes first into Mn203 at 280' into Mn304 and finally into MnO. Preparation of Tantalic Acid from West Australian Fergusonite. klodium Tantalate. EDGAR WEDEKIND and W. MAASS (Zeitsch.angew. Chern. 19 10 23 2314-231 6).-A specimen oE fergusonite from West Australia contained 5422% Ta,O 1.80% Cb2.0 27.73% Y203 3.20% Ce203 and 0036% Tho and owing to t h e high tantalum content the authors have used it t o prepare tantalum pentoxide and derivatives. The acid and basic constituents were separated essentially according t o the method of Krdss and Nilson (Abstr. 1887 706) the residue then consisting essentially of tantalic columbic and titanic acids; 7.5 grams of the residue were then care- fully added to 15 grams of sodium carbonate fused in a platinum crucible after which a further 4 grams of sodium carbonate and 1.6 grams of sodium nitrate were added. The cold fusion was extracted with 750 C.C. of water filtered and left overnight; 6-4 grams of sodium tantalnte crystallised out.The finest crystals were picked out the remainder dissolved in much hot water and after cooling the tantalum precipitated as tantalic acid by means of carbon dioxide (compare Weiss and Landecker Abstr. 1909 ii 942). The tantalic acid was dried at looo mixed with a little fuming nitric acid evaporated to dryness and then converted into pentoxide by ignition. Sodium tantalate forms colourless hexagonal crystals which give an alkaline solution. Analysis gives Na,Ta,O,,,H 1 2*32H,O agreeing with Rose's empirical formula Na,Ta,0,,25H20 ; 10*5H20 are lost at lO5-1lO0 a further molecule a t 190° and the last molecule in the blow pipe. It is probably an acid sodium salt of-a tritantalic acid of L. J. S. tantalate obtained on heatingbeing a hexatantalate.T. 8. P.INORGANIC CHEMISTRY. ii. 45 Gold 'l?elhtides. GIOVANNI PELLINI and E. QUERCIGH (Atti R. Accad. Lincei 1910 [v] 19 ii 445-449).-The freezing-point curve of the system gold-tellurium has been determined the alloys being fused in an atmosphere of carbon dioxide. The curve has a single maximum corresponding with the compound AuTe melting a t 464'. There are two eutectic points at 12 and 47 atomic % Au and a t 416" and 447" respectively. There is no indication of the formation of solid solutions. The compound RuTe occurs in nature as calaverite. As such a compound is not obtained by the action of tellurium on solutions of gold salts it is probable that the mineral has been formed by a process of fusion Halogen Compounds of Rhodium. Mlle.(3. GOLOURKINE (Bull. Xoc. china. Belg. 1910,21 388-396).-Spongy rhodium readily dissolves in a solution of hydrochloric acid saturated with chlorine or in a solution of hydrobromic acid saturated with bromine giving the corresponding halogen compounds. The preparation of the bromine compounds is described. One gram of spongy rhodium is heated with 24 grams of 40% hydrobromic acid containing 7 grams of bromine in a sealed tube at SO-looo for forty-eight hours. The contents of the tube are distilled under diminished pressure the residue treated with a little water and again distilled to remove all hydrobromic acid. The bromide remain- ing is dissolved in water and the solution evaporated in a vacuum over sulphuric acid the final drying of the product being carried out in a vacuum over fused potassium hydroxide. If the spongy rhodium used contains zinc or bismuth the resulting impure bromide is reduced in a current of hydrogen ; the zinc or bismuth bromide sublimes leaving pure rhodium from which the pure bromide is obtained by the treatment already detailed. Rhodium tribromide RhBr,,%H,O is a blackish-red substance which is very soluble in water. When heated at 100-140° it loses not only water but also hydrogen bromide. With potassium hydroxide the solution gives a precipitate of the hydroxybromide Rh(OH)2Br,2H20 and from the filtrate dark red crystals of potassium rhodobromide K,RhBr5 are obtained. Potassium aodium rubidium ammonium and bccrium rhodobromides are prepared by adding a slight excess of rhodium bromide to the solutions of the bromides of the metals mentioned. The solution is evaporated to dryness and the excess of rhodium bromide extracted with slcohol leaving the rhodobromide undissolved. They possess the general formula M',RhBr5 and are readily soluble in water; most of them are dark red in colour the sodium salt being brick-red. A warm concentrated solution of potassium iodide produces a black precipitate of rhodium iodide RhI from a solution of rhodium bromide. Dilute solutions give no precipitate in the cold. C. H. D. T. S. P,

ISSN:0368-1769    

DOI:10.1039/CA9110005035

出版商:RSC    

年代:1911

数据来源: RSC

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ii. 46 ABSTRACTSc OF CHEMlCAL PAPERS. Mineralogical Chemistry - Iron-pyrites from Hungary. A. LIFFA (Zeitsch. R~yst. Min 1910 48 441-442; from Poldtnni KoxEb'ny 1908 38 276-294 405-423).-Crystallographic descriptions are given of iron-pyrites from various Hungarian localities. Crystals (penetrated by quartz) from Csunghny gave on analysis by K. Emszt Fe. As. Ni. S. SO,. Total. 45-36 trace 0.05 51 '61 2-54 99-86 L. J. S. Blomstrandine from the Urals. OTTO HAUSER and H. HERZFELD (Centr. Min. 1910 756-764).-some black crystals supposed to be aschynite embedded in pegmatite from Miask proved on analysis to be the blomstrandine of Brogger (Abstr. 1907 ii 885). Approximate goniometric measurements are given ; D 6.00 Ta,05. Cb,O,. TiO,. SnO,. WO,. ZrO,. UO,. Tho,. 1-30 15.08 34-07 0.20 trace 0.50 3.24 7.93 Y,O,.(Ce,La,Di),O,. Al,O,. FeO. MnO. CaO. MgO. PbO. ignition. Total. 26-66 4-69 1-36 1-73 0'16 1.04 0'28 0.35 0.96 99'55 The ratio of meta-columbates to meta-titanstes is here 1 1 whilst in the Norwegian mineral this is 1 2 and 1 4. Nephrite from the Ham. J. UHLIU (Jahrb. Min 1910 ii 80-103).-Small veins the largest of them 20 cm. in thickness of nephrite occur in the gabbro-serpentine rocks of the Radauthal near Harzburg. The material is pale green greyish-green or light grey but of a darker green colour (due t o enclosed chlorite) in a few strings. Under the microscope it is seen to consist of a felted mass of actinolite needles with occasional chlorite. A t times however the actinolite fibres have a parallel arrangement giving rise to a finely fibrous texture ; this (" Fasernephrit ") is the material recently described from the same locality under the name nephritoid (J.Fromme Abstr. 1910 ii 314). Analysis I of light grey material corresponds approximately with the actinolite formula Mg,Ca(SiO,) Loss on L. J. 5. HvO H20 Si02. TiO% Also3. Fe2O3. C1-203. FeO. KiO. MnO. CaO. MgO. RzO. Ka,O.(l25'). (Ign.) Total. Sp. gr. I. 56'51 0.02 1-80 - trace 4'35 0 ~ 1 3 0-OG 12-72 21 32 - - 0 2s 2.70 99.82 2.94 11. 49'170'11 6'52 0'59 - 7-07 0.07 O'SO 22.91 10'140*08 0'30 0'43 2'10 100'29 3.30 Another small vein of much the same appearance consists of a compact felted mass of pyroxene needles and scales together with some prehnite and garnet. This pyroxene gave analysis 11 agreeing approximately with the diopside formula Ca( Mg,Fe)(SiO,),.L. J. S. Zeolites from Nadap Hungary. B ~ L A MAURITZ (Zeitsch. Kryst. Nin 1910 48 439-441; from Iroldtani Kozlony 1908 38 190 231 and Ann. InX-nutur. Alusei Nation. Hurtgarici 1908 6 537-845 546-554).-Cavities and crevices in weathered andesiteMI N ERA LUG1 (? A L C H EM I S'I'RY. ii. 47 in the neighbourhood of Nadap comitat Fejdr contain the crystal- lised zeolites epistilbite (not before recorded from Hungary) heulandite chabazite and stilbite together with calcite amethyst iron-pyrites and fluor-spar. Crystallographic descriptions are given of each of these zeolites and analyses of the heulandite (I and 11) and stilbite I11 and IV) SiO,. A1,0,. Fe,O,. CaO. SrO. Na,O. K,O. Li,O. H,O. Total. I. 56.57 16.93 - 6.91 0'93 1-68 1-25 trace 16-15 100.42 11.56'71 17'30 - 7-05 0'88 1.80 1.37 trace 15.87 100.98 111. 55'79 17-03 trace 7'82 - 1'46 0'20 - 18'65 100.97 IV. 55.78 16.70 trace 7'86 - 1.56 0'26 - 18-79 100.95 L. J. S. Analyses of Hungarian Minerals. ALEXANDER VON KALRC- SINSZKY (Zeitsch. Kryst. Min. 1910 48 446-447 ; from Jcch~esbe~. k. ungarisch. geol. Anstalt for 1907 1909 294-314).-A report on the work of the chemical laboratory of the Hungarian Geologicit1 Survey includes many analyses of limestones coals and clays and the following analyses (I) of kaolinite from ICovbsz6 and (TI) of magnesite from Jolsva Loss on SiO,. Al,O,. Fe,Os. MgO. CsO. Moisture. ignition. Total. I. 48'71 35'16 1-10 0.34 1'26 3-15 10.37 100.09 MgCO,. CaCO,. FeO. H,O. Insol. Total. 11. 72'25 25'43 2'01 0'34 0'26 10029 L.J. S. Behaviour of Gabbro Magma in Fusions. XANS ANDESNER (Jahrb. Min. 1910 Bed.-Bd. 30 467-494).-Hornblendite from Kals Tyrol was used in the experiments; this is a schistose rock composed largely of hornblende together with some zoisite quartz rutile and apatite and having practically the same bulk composition as a gabbro. When fused alone the glassy product has much the characters of a basalt and under the microscope shows crystals of magnetite plagioclase and augite. I n other experiments the ampbibolite was fused with various proportions of olivine quartz tungstic acid nephelite alumina or anorthite. The microscopical structure of the products are described in detail. The minerals formed include magnetite plagioclase olivine augite nephelite spinel (picotite) and corundum ; the last two of these being produced when an excess of alumina is present.WALTER ANDRE WAHL (Zeitsch. anorg. Chem. 19 10 69 52-96).-An analytical comparison of meteoric stones and minerals with terrestrial rocks and minerals shows that the former are distinguished by containing a relatively larger proportion of oxygen. The different classes of siderolites differ principally in their state of oxidation; thus those containing only metallic iron and olivine may be derived from those containing iron pyroxene and olivine by oxidation a part of the iron being oxidised to ferrous oxide and then converting the metasilicate into an orthosilicate Fen + a(Pe,Mg)SiO + b(Fe,Mg),SiO + 0 = L. J. S. Meteorites. Fen - m + (a + b)(Fe,Mg)@Opii.48 ABSTRACTS OF CHEMICAL PAPERS. When still less oxygen is present silica is found in the form of trid ymite. The difference between enstatite-chondri tes and ordinary chondrites ix also shown to be one of the degree of oxidation. The presence of calcium sulphide in certain meteorites is explained in the same way. Chondrites of loose structure are t o be regarded as fragmentary of the nature of tuffs. The various forms of chondrulitic structure may be explained by the breaking up of a silicate magma into spray in a hot atmosphere and the crystallisation of the drops from outside inwards. The consolidation of the tuffs is brought about by heat and may be imitated artificially. The structure of the original mass is repre- sented by eucrite. Explanations are given of the other derived structures including veins and breccias. Meteoric Stone of Mern Seeland. ARISTIDES BREZINA (Jnhrb. Min. 1910 ii Ref. 207-208 ; from Danske Yidensk. Xelsk. S’kr$kr 1909 [vii] 6 (3) 113-125).-This stone fell on August 22ud 1878 a t Mern near Praesto in Seeland. Its original weight was 73 pounds. It is described as the representative of a new type ‘(veined crystalline enstatite-spheroidal-chondrite.” The con- stituents are olivine rhombic pyroxene clinoenstatite nickel-iron troilite and chromite. SiO,. A1,0,. Fe,O,. MgO. K,O. Na,O. H,O. CO,. S. Fo. 39’81 2.70 12.23 15’46 0-46 1.35 0‘06 2-47 2‘47 13.00 The iron is in part present as sulphide and of the sulphur 2.38% is liberated as hydrogen sulphide when the material is treated with hydrochloric acid. 45.20% is insoluble in hydrochloric acid. Traces C. H. D. The chemical composition is :- of phosphoric acid and manganese are present. 1,. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9110005046

出版商:RSC    

年代:1911

数据来源: RSC

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ii. 48 ABSTRACTS OF CHEMICAL PAPERS. Physiologiaal Chemistry. Putting into Action of the Human Machine JULEH AMAR (Compt. rend. 1910 151 892-894).-A subject set to do muscular work immediately on rising from lsleep showed a sudden temporary diminution in his respiratory quotient. This reached a minimum at 0.82 after four minutes from the commencement of the experiment j after four minutes' rest it had risen to 0.99 but at ,the end of four minutes' furthet exertion it fell to 0*86. The Question of the Oxidation of the Products'of Zgmin Fermentation during Respiration. LEONID IWANOFF (Biocltem. Zeitsch. 1910 28 347-349).-I?olemical .in reply to Kostytschew (Abstr. 1910 ii 148). The Isoelectric Constants of the Constituents of Blood. corpuscles and their Relationship to Haemolysis by Acids.' LEONOR MICHAELIS and DENGO TAKAHASTU (Biochem Zeitsch.1 9 10 29 439-452).-The methods employed were chose repeatedly used by w. 0. w. W. J. Y.PHYSIOLOGICAL CHEMISTRY. ii. 49 Michaelis and his collaborators in the previous investigations on pro- teins namely the determinations of the hydrogen ion concentration in which coagulation most readily takes place and the method of electrical cataphoresis. They also determined the hydrogen ion con- centration in which haemolysis takes place. The coagulation optimum for the stroma substance of all the species of blood investigated was I"'] = 1.10-5. The isoelectric constant of oxyhEmoglobin is Red blood-corpuscles in isotonic solution remain intact when [H'] = 1.10-5. On further addition of acids haemolysis takes place.On the assumption that the coagulation optimum con- centration of hydrogen ions represents the isoelectric point the conclusion is drawn that bhe haemoglobin is only hsld intact in the corpuscles when they are negstively charged. He] = 1.8 x 10-7. S. B. S. Influence of Electrolytes and Non-electrolytes on the Permeability of Red-Blood Corpuscles. MIROSLAV MICULICICH (Zeatr. Physiol. 19 10 24 523-527).-The effect was ascertained of the separate addition of a number of salts and non-electrolytes on the time of complete haemolysis of defibrinated ox-blood by urethane alcohol and saponin. The substances were added in such a concentra- tion that the resulting mixtures were isotonic with 0.97% sodium chloride. By employing different salts of the same base the anions were arraaged into a comparative group for each haemolysin in order of the length of time required for hsmolysis.I n a similar manner by using different salts of the same acid the cations were arranged into a similar group. It was found that with very few exceptions the order of grouping of both anions and cations was the same for urethane and alcohol but differed markedly in the case of saponin. This is explained by the fact that saponin brings about haemolysis in a different manner from the other two. The differences in the times of haemolysis observed with the various salts is attributed to the different influence of the electrolytes on the permeability of the blood- cells to the haemolysin. Differences were also obtained in the cases of non-electrolytes.W. J. Y Permeability of Red Corpuscles in Physiological Conditions especially to Alkali and Alkali-earths. G. GRYNS (P'roc. K. Akad. Wetenscli. Amsterdam 19 10 489 -491).-Hamburger's data and conclusions (Abstr. 1910 ii 1080) on this subject are questioned. W. D. II. The Influence of Oxidation in Living Cells according to Researches on the Red Corpuscles. OTTO WARBURG (Zeitsch. piysiol. Chem. 1910 69 452-462).-Experiments on the red corpus- cles of the goose suspended in Locke's solution confirm the views of Overton and H. Meyer on the importance of the lipoid membrane in oxidation and narcosis. The general result of the action of various reagents the solubilities of which in water and oil are given is that the occurrence of a lipoid phase influences chemical changes which diminish oxidation more than the occurrence of a watery phase.VOL. C. ii. 4 W. D. H.ii. 50 ABSTRACTS OF CHEMICAL PAPERS. Hemolysis 'by Ammonia Sodium Hydroxide and Sodium Carbonate. OSCAR GROS (Biochem. Zeitsch. 1910 29 350-366).- The relationship between the concentration OF the ammonia and carbonate and the time necessary for complete hydrolysis can be represented by the equation cm.t = k (where c = concentration t = time k = constant) in which the exponent m varies between 0.65 and 0.71. The ammonia or carbonate appears to be adsorbed by the corpuscle and the amount adsorbed regulates the rate of hydrolysis. This relation- ship only holds so long as the amount of ammonia present is large compared with that used in hzmolysis or by-reactions.When small quantities of ammonia are employed so that the time necessary for complete bsmolysis is large nearly all the ammonia is adsorbed and the rate of hsmolysis is proportional to the amount of ammonia and inversely proportional t o the concentration of blood-corpuscles. I n the case of sodium hydroxide the reaction equation is C13. t = k. It was only possible to investigate t h i s reaction in low concentrations. S. B. S. A Proof of the Presence of Toxic Substances in the Blood of Animals after Thyroidectomy. PAUL TRENDELENBURG (Biochem. Zeitsch. 1910 29 396-407).-1t has been shown by Reid Hunt (Abstr. 1905 ii 847) that mice which have been fed on thyroid gland or on blood from cases of Basedow's disease (exophthalmic goitre) are able to withstand injections of acetonitrile many times as large as the amount required to kill normal mice.A similar resistance is now obtained by feeding mice on the blood of cats from which the thyroid gland has been removed. The conclusion is drawn that this is due to the presence of toxic subatances in the blood of the cats and thus adds support to the hypothesis that the thyroid gland functions as a remover of these poisons. The Behaviour of Chlorine in Serum. W. J. Y. PETER RONA (Biochem. Zeitsch. 1910 29 501-508).-The author has employed the method originally used by him for investigating the state of sugar in the blood. H e has placed serum in dialysing membranes and surrounded them with salt solutions of varying concentrations and thereby found a con- centration which does not alter on dialysis.This concentration corresponds with the amount of free sodium chloride in the serum. From the results the conclusion is drawn that the whole of the chloride in serum is free and not united to the protein. Nevertheless the chlorine in the serum directly determined was less than t h a t found by the dialysis method. The difference although small was appreciable and the author ascribes i t to tho fact that the real concentration of chloride in the serum is greater than the apparent owing to the fact that the proteins occupy a definite volume in the serum. S . B. S. The Origin of the Hydrochloric Acid in the Gastric Tubules. MABEL P. FITZGERALD (Prpc. Roy. Xoc. 1910 B 83 56-93).-An historical account is given of the various micro-chemical tests which have been employed by many workers in order to locate the seat of formation of the hydrochloric acid of the gastric juice.PHYSIOLOGICAL CHEMISTRY.ii. 51 Although evidence connects this origin with the parietal cells of the gastric tubules hitherto no certainty of this has been attained neither has it been proved that hydrochloric acid exists in a demonstrable form in the secretion of the glands before this reaches the free surfaceof the Solutions containing potassium ferrocyanide 1 -5% and ammonium ferric citrate 2.25% were injected into rabbits and guinea-pigs and the animals killed from three to thirty hours after the first injection. 'l'his mixture readily formed Prussian blue with hydrochloric acid of a much less concentration than that contained in the gastric juice but gave no reaction with sodium phosphate or carbon dioxide.Micro- scopical sections from the stomach showed the presenca of Prussian blue in the lumina of the gland tubules and in the canaliculi in the parietal cells. Hydrochloric acid was thus shown to be already in the free state in the secretion as it appears in the canaliculi. No definite evidence was obtained of the occurrence of free hydrochloric acid in the cytoplasm of the parietal cells although a faint blue coloration occasionally observed in them seemed to indicate its presence. The source of the hydrochloric acid in the parietal cells is attributed to the chlorides which mere shown to be present in greater abundance than in the chief cells or the adjacent tissue elements.nlUC0SL. W. J. Y. Oxalic Acid Metabolism. JULIUS POHL (Zeitsch. exp. Path. 1910 '8 308-311).-The contention of Tomaszewski (Abstr. 1910 ii 425) that oxalic acid is oxidised by the animal organism is denied. Oxalic acid which was injected into dogs was recovered unchanged from the urine whilst oxalic acid was not destroyed by incubation with a paste made by grinding the liver of a rabbit. Parabanic acid was injected into a dog and was subsequently found in the urine partly unchanged and partly changed into oxalic acid. The two acids were estimated as follows a portion of the urine was boiled with ammonia to convert the parabanic acid into oxalic acid and the totdl amount of the latter determined as calcium salt. Another portion was precipitated with normal lead acetate to remove the oxalic acid and the parabanic acid in the filtrate converted into oxalic acid with ammonia and determined as such.It is suggested that parabanic acid is possibly a source of the oxalic acid normally found in the animal organism and that at an inter- mediate stage oxaluric acid is formed. W. J. Y. Protein M e t a b A s m of the Dog and the Effect of Feeding with Protein and Protein Cleavage P r o d u c t s on the Secretion of Bile with Special Reference to Time Relationships. ADAM LOEB (Zeitsch. B~ol. 1910 55 167-235).-The quantity of bile depends on the quantity and kind of protein administered; casein and gliadin are less effective than flesh. It therefore appears that i t is not formation of urea but its work in dealing with the nitrogen- free residue that causes in the liver the increase of bile formatioa.Peptone increases bile formation. The excretion of sulphur in the bile is in the first four hours after a meal about twice as great as in the next four hours The excretion of ammouia in the urine falls 4-2ii. 58 ABSTRACTS OF CHEMICAL PAPERS after a meal and is at the maximum in the night. This depends on changes in the alkalinity of the body which accompany the secre- tion of digestive juices. I n the period of digestion also relatively more acid equivalents in the form of sulphates and phosphates are excreted than in the period of rest. The fixed alkali behaves in the same way. The flow of bile somewhat elevates excretion of ammonia; in abundant protein feeding ammonia is excreted in absolutely higher but relatively lower amount.After feeding there is a decrease in the excretion of phosphates. On a protein-rich diet a greater amount of the nitrogen is excreted in the first third of the day than on a protein-poor diet ; the same is true for protein cleavage products. I n a dog with a biliary fistula nitrogenous equilibrium and even retention can be maintained on abiuretic protein products provided the nitrogen given is above the protein minimum. The excretion of “neutral sulphur” in such a dog is higher during the digestive period than during rest but the relationship of this to the sulphur in the food mils not determined. The output of sulphates on a protein-rich diet is most marked during the digestive period and this increase appears more rapidly than that of nitrogen excretion.W. D. H. Digestion and Absorption of Nucleic Acid in the Alimen- tary Canal. E. S. LONDON and ALFRED SCHITTENHELM (Zeitsch. physiol. Chem. 1910 70 10-18).-Previous work on this question has mainly consisted of investigations in vitro. The present experi- ments were carried out in vivo in dogs with fistulae. Nucleic acid is neither altered nor absorbed in the stomach but chemical changes occur in the intestine; a small amount of purine bases is liberated but the greater part of the nucleic acid is split into dialysable compounds which contain organically-united purine substances. Following Levene’s work these are nucleosides or nucleotides but they were not identified more closely The absorption of such com- pounds occurs in the lower jejunum and ileum The digestive juices contain no purine bases on a purine-free diet. W.D H. The Inhibition by Cholesterol of the Irritating Action of Oleic Acid. F. W. LAMB (J. Path. Bact. 1910 15 129).-In a study of the absorption of triolein and oleic acid in the frog’s intestine the investigation was complicated by the irritating effect of these substances; this may be obviated by mixing oleic acid with a n equimolecular amount of cholesterol. Powell White obtained similar results on subcutaneous injection of the same substances. W. D. H. The Action of Drugs on the Cerebral Vessels. WALTER E. DIXON and WILLIAN D. HALLIBURTON (Quart. J. exp. Physiol. 1910 3 316-318).-The experiments were performed on the carefully isolated brains of dogs; these were perfused with Ringer’s solution at constant pressure and the rate of outflow noted by a drop record. The cerebral blood vessels respond towards drugs in the manner similar to the pulmonary and coronnry vessels.Adrenaline,PHYSIOLOGICAL CHEMISTRY. ii. 53 pilocarpine and muscarine drugs well recognised as acting on uerve- endings cause some dilatation although they always produce marked constxiction of systemic vessels. It is probable that the dilator action is confined to the larger blood vessels and it is suggested that the action is due to an effect on vaso-dilator nerves Barium lead veratrine and pituitary extract cause some constriction the inference being that these drugs here as elsewhere act directly on muscle. The constriction with pituitary extract is slight and transient and is followed by dilatation.W. D. H. The Synthetic Formation of Amino-acids in the Liver. GUSTAV EMBDEN and ERNST SCHMITZ (Biochern. Zeitsch. 1910 29 423-428).-0n perfusion of a glycogen-poor liver with p-hydroxy- phenylpyruvic acid tyrosine could be isolated in the form of t,he dinaphthalenesulphonyl derivative and after perfusion of p-phenyl- pyruvic acid phenylalanine could be isolated in the form of a carbamic acid. Leucic acid on perfusion gave rise apparently to leucine- carbamic acid. Furthermore by simple perfusion of a glycogen-rich liver part of the glycogen appears to give rise to alanine ; lactic acid and pyruvic acid being apparently formed as intermediate products. 8. B. S. A Synthesis with Acetic Acid in the Artificially Perfused Liver.OTTO NEUBAUER and OTTO WM~BUIW (Zeitd. physiol. Chem. 1910 70 l-g).-In the artificially perfused dog’s liver if the liquid contains dLaininophenylacetic acid there is formed d-acetylarnino- phenylacetic acid [n adhition to phenylglyoxylic and I-mandeli; acids. W. D. H. Probable Function of Cholesterol in the Production of Uric Acid in the Animal Organism. F. TRAETTA-MOSCA and F. APOLLONI (Gacxoetta 1910 40 ii 368-377. Compare following abstract).-When a mixture of calf’s liver and cholesterol or phyto- sterol to which a little ammonia has been added is incubated in presence of toluene for two days uric acid is formed. Neither the liver done nor cholesterol nor putrefying liver yields any uric acid in these circumstances. When the liver has been boiled no production of uric acid from the mixture can be observed.The authors suppose that by oxidation of the cholesterol a-hydroxyisobutyric ‘acid is formed and that this combines with 2 molecules of urea to produce uric acid. The reaction is effected by ferments contained in the liver. R. V. S. Importance of a-Hydroxyisobutyric Acid in the Form- ation of Uric Acid from Cholesterol by means of Calf’s Liver. F. TRAETTA- MOSCA and GOLDA MIZZENMACHER (Gccxxettcc 1910 40 ii 378-388. Compare preceding abstract).-In confirma- tion of the hypothesis that a-hydroxyisobutyric acid is formed as an intermediate product when uric acid is producted from cholesterol and calf’s liver in presence of ammonia the authors find that when a-hydroxyisobutyric acid is mixed with calf’s liver physiological salineii.54 ABSTRACTS OF CHEMICAL PAPERS. solution and ammonia and the mixture incubated for two days in presence of toluene and chloroform uric acid is produced. The reaction proceeds better in an atmosphere of carbon dioxide than in air. When no hydroxyisobutyric acid is added smaller quantities of uric acid are formed. Urea added to the mixture does not increase the amount of uric acid produced. The ammonia seems to play a lending part in the reaction. When the liver has been previously boiled no uric acid is formed. The addition of glycerol sodium butyrate or fermentation lactic acid instead of hydroxyisobutyric acid does not lead to an increased formation of uric acid. The estimations of uric acid were effected by the Ludwig-Salkowski method.R. V. S. Differentiation of the Tryptic and Proteolytic (Autolytic) Actions of the Liver. FRIEDRICH SIMON (Zeitsch. physiol. Chem. 1910,70 65-84).-The course of digestion of various proteins under the influence of trypsin and the autolytic enzyme of the liver are compared; the points to which special attention is paid are the amounts of coagulable nitrogen uncoagulable nitrogen and ammonia a t various stages. The two enzymes manifest differences the principal one being that the digestion of the insoluble protein goes on longer in autolytic than in pancreatic digestion and there is also perhaps a temporary activity of synthetic processes noticeable in the former case. W. D. H. The Influence by Salt Ions of Autolysis. LEO BRULL (Biochem. Zeitsch.19 10 29 408-41 3)-In concentrations of N/ 1 0 the chlorides of the alkaline earths increase the autolysis more than do the salts of the alkalis in the same relative concentration. The action of calcium chloride is more marked than that of the other chlorides of the alkaline earths. Loeb's solution does not increase the rate of action. S. B. S. The Stimulating Action of Lipoids on the Action of Liver Diastase. EuaENro CENTANNI ( Biochem. Zeitsch. 1 91 0 29 389-394).-Lipoids of egg-yo1 k blood intestine etc. increaw the rate of action of the natural liver diastase from which lipoids had been removed by ether. The lipoids of the liver itself also increased the action. The activating action is not due to the reaction or to dialysable constituents and tbe activating substance is not destroyed by prolonged boiling.The dialysable lipoid substances are however also capable of reactivating the diastase of the parenchyma which had been extracted with ether. The lipoids of yeast exerted no action. S. B. S. Glycolysis. The Oxidative Destruction of Sugar by the Action of Organic Preparations. WALTHER LOB and GEORCI PULVERMACHER (Biochem. Zeitsch. 19 10 29 3 16-346).-The organic preparation which stimulated the oxidative destruction of sugar either by hydrogen peroxide or oxygen was prepared by precipitating the alcoholic extract of pancreas with iron salts (ferric or ~~W-QUF),PHYSIOLOGICAL CHEMISTRY. ii. 55 It was thought from the experiments of Minkowski and Cohnheim that the secretion by the pancreas was an active agent in stimulating the peroxydase of the iron containing blood-pigment ; hence the employment of the preparation mentioned.Its action was studied i n some detail under varying conditions. Pepsin and pancreatin digestion do not destroy the oxidative properties. It is not entirely stable to heat although different preparations vary in this respect. Amongst the sugar products isolated were formaldehyde (very small quantities) small amounts of carbon dioxide and also formic acid and poly b ydroxy-acids. Pentose mas also found in relatively large quantities. I t has not yet been determined whether similar prepara- tions other than those derived from the pancreas exert a like action. s. B. s. Physiology of Glands. ” XVI. The Internal Secretion of the Thyroid and its Formation under the Influence of Nerve-Stimulation.LEON ASHER and MARTIN FLACK (Zeitsch. Biol. 1910 55 83-166).-The internal secretion of the thyroid increases the excitability of the depressor nerve and the activity of adrenaline in raising arterial pressure. The secretory nerves of the thyroid are contained in the laryngeal (especially the superior) nerve. If these nerves are stimulated the depressor nerve action and the action of adrenaline are increased Removal of the thyroid abolishes tbe effect. Injection of iodothyrin does not produce these results but injection of thyroid extract does ; thyroid extract contains other active substances. The great elevation of blood pressure produced by a combination of an excitation of the thyroid’s secretory nerves and an injection of adrenaline does not occur when the depressor nerves are cut.The secretion of the thyroid and injection of thyroid extract have in themselves no effect on pulse or blood-pressure The bearing of these observations on Basdow’s disease is discussed. w. D. H. The Inhibition of the Action of Chemical Muscle-stimuli by Non-electrolytes. VELYEN E. HENDERSON (Zentr. Physiol. 19 10 24 5 19-523).-Non-electrolytes such as dextrose sucrose and mannitol in the presence of sodium salts were found to inhibit the exciting action of guanidine and oxalic acid on muscle. Moreover the convulsions of the muscle produced in it mixture of the stimulant and sodium chloride ceased on the addition of the non-electrolytes. The ssme results were obtained when Ringer’s solution was employed in place of sodium chloride.The action is attributed to an exosmosis of the active ions in the presence of the non-electrolyte. W. J. Y. The Inhibitory Influence of Magnesium on the Direct Excitability of Frog’s Muscle and the Antagonistic Effects of Sodium and Calcium on this Influence. DON R. JOSEPH and SAMUELJ. M E L T Z E R ( C ~ ~ ~ Zentr. 191o,ii,237; fromzent?.. Physiol. 1910 24 7-S).-Solutions of magnesium sulphate diminish the direct and indirect excitability of frog’s muscles to induction shocks. Sodium restores the direct and calcium after or together with sodium restoresii. 56 ABSTRACTS OF CHEMICAL PAPERS. the indirect excitability. If the magnesium salt is injected into the lymph sac the sodium of tho lymph prevents thelinhibition of the direct excitability and the simultaneous injection of calcium chloride restores the indirect excitability.The Influence of Different Substances on the Gaseous Exchange of the Surviving Muscular Tissue of Frog’s. 1V.-IX. TORSTEN THUNBERG (Shnd. Arch. PhysioZ. 191 0 24 23-61 62-71 72-74 75-79 80-85 86-89. Compare Abstr. 1910 ii 54 523).-The investigations were conducted on the lines of the author’s previous work. Thirty-eight organic acids were in- vestigated; although many lessen the gaseous exchange none act in the specific way namely by lessening the output of carbon dioxide which was previously found to be the result of oxalic malonic and succinic acids. Succinic acid produces the most marked effect. Various narcotics and antiseptics lessen the gaseous exchange in varying degrees without altering the respiratory quotient ; among the antiseptics phenol has the greatest and boric acid the least effect.Fumaric malic and citric acids in very small concentrations increase the amount of anoxybiotic carbon dioxide products ; the question arises whether specific enzymes are responsible for their production Potassium fluoride lessens the gaseous exchange,. and like the organic acids specially affects the substances that yield carbon dioxide ; potassium chloride bromide and iodide are indifferent substances in this relation. Potassium chlorate has no effect but the bromate and especially the iodate are toxic to muscle. The bromine compounds of succinic fumaric and maleic acids act like the dicarboxylic acids in raising the respiratory quotient ; in the metabolism of muscle these acids probably enter the muscle substance.The Chemical Conditions Neceesary for the Maintenance of the Normal Cell Structure. I. and 11. ERIK MATTEO PROCHET WIDNARK (Skand. Archiu. PhysioZ. 1910 23 421-429 ; 24 13 22). -1. Weighed portions of muscular tissue from frogs finely minced were allowed to soak in isotonic saline solutions t o which varying quantities of solutions of calcium strontium barium and magnesium chlorides were added. The loss of weight undergone by the tissue owing to this treatment was estimated. I n the case of calcium chloride the tissue undergoes its maximal loss of weight (37%) when the caIcium chloride attains the concentration of 15 millimols. per litre. Similar results were obtained with barium and strontium chlorides but the action of magnesium chloride is very much less marked.11. To account for shrinking of the cell after treatment with calcium salts it is suggested that the calcium precipitates the phosphates in the interior of the cell. No evidence of this hypothesis could however be obtained experimentally as muscular tissue from which the greater part of the phosphorus had been removed by washing with isotonic saline solution also showed loss of weight on treatment with calcium salts. Furthermore if citrates are added in addition to the calcium salts to prevent precipitation of phosphate loss of weight also took place. W. D. H. W. D. H. S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 57 The Reducing Action of the Tissues. WALTER STRASSNER (Biochm.Zeitsch. 1910,29,295-310).-The author has measured the reducing action of tissues on methylene-blue using the method of Knecht and Hibbert (titanium chloride method) for estimating the dye. The author draws the conclusion that the reducing action is due to the sulphhydryl group in the tissues in spite of the facts that heating autolysis and hydrocyanic acid diminish the reducing action. He shows however that hydrocyanic acid also diminishes the reducing action of thiolacetic acid and suggests that autoxidation or heat- ing may destroy the sulphhydryl group. Starvation phosphorus poisoning and other actions which produce fatky tissues diminish the reducing capacity of the tissues which is unaffected however by poisoning with mercuric chloride chloral hydrate and other drugs.S. B. S. The Staining of Fat by Nile-blue Sulphate. J. LORRAIN SMITH (J. Path. Bact 1910 15 53-55).-When the fat in the human tissues is neutral Nile-blue sulphate colours it red ; but if the f a t contains much fatty acid the globules take a colour compounded of blue and red in variable proportions. The blue staining of the fatty acid is due to the union of the colour base (oxazine) with the acid in the form of a soap-like compound. As a rule lipoids contain fat in a neutral form but hydrolysis readily occurs and so blue staining may be obtained. The red substance as Thorpe showed (Trans. 1907 93 324) is not present in the Nile-blue sulphate in dry powder but it appears in aqueous solutions of the dye because the oxazine base spontaneously oxidises into oxazone; in the same way it imparts a red colour to liquid neutral fat.Some confusion has arisen in the work of recent investigators as they have regarded the oxazine base and the oxazone as the same thing and in accordance with this assumption they have applied to the double staining of fat the theory of metachromatism by the base set free in aqueous solution by hydrolytic dissociation. Such conclusions are unwarranted. W. D. H. The Resorption of Choleaterol and Cholesteryl Esters. H. A. KLEIN and ADOLF MACKUS-LEVY (Biockem. Zeitsch. 1910 29 465-471).-The authors investigated the amount of cholesterol in the faeces of a dog on a fixed diet to which were added cholesterol and cholesteryl oleate. It was found that a somewhat larger proportion of the former was resorbed than of the latter.Various data are given as to the amount of cholesterol in eggs butter brain and other substances and the suggestion is made that the synthesis of cholesterol in the animal body can be investigated by estimating the amount formed in fowl's eggs when the birds are kept on diets containing varying amounts of cholesterol. The Occurrence of Deoxycholic Acid in Gall Stones. WILLIAM K~STER (Zeitsch. physiol. C'hem. 1910 69 463-465)- The occurrence of deoxycholic acid in the gall stones of oxen was regarded as probable seeing that it is so easily derived from cholic acid by reduc- tion. Evidence is adduced to show that this is the case. S. B. S. W. D. H.ii. 58 ARSTRACTS OF CHEMICAL PAPERS. The Alteration in the Excretion of Amino-acids or Sub- stances Titratable with Formaldehyde as a Cause of the Increase in the Gal.N Ratio after Great Loss of Blood. DIONYS FUCHS (Zeitsch. physiol. Chern. 1910 69 482-490).-The amount of amino-acid nitrogen in the urine (dog and rabbit) is increased by great loss of blood both absolutely and relatively to the total nitrogen. The condition does not again become normal until three weeks later. A second bleeding produces a still more marked effect. There is no special effect on ammonia excretion. The increase in the Cal. N ratio (energy quotient) is in part at least due to the rise of amino-acid excretion. W. D. H. The Influence of Prolonged Inanition on the Excretion of Amino-acids or Substances Titratable with Formaldehyde. DIONPS FUCHS (Zeilsch.physiol. Chem. 19 10 69 491-495).-1n the later stages of inanition the amount of amino-acid nitrogen in the urine rises absolutely but not relatively to the total nitrogen; the ante-mortem rise of total nitrogen is therefore not to be attributed to the increased excretion of amino-acids. Lactic acid and other fatty acids increase a t this stage and ammonia usually falls. A Yellow Substance in the Urine. L. DE JAGER (Zeitsch. physiol. Chem. 191 0 70 60-64j.-A yellow precipitate is produced in the urine by the addition of hydrochloric acid and formaldehyde. It contains neither urobilin nor urochrome but appears to be a compound of urea. The Detection and Formation of Aromatic Substances in the Body. 11. The Behaviour of Indole and Scatole in Rabbits. FERDINAND BLUMENTHAL and ERNST JACOBY (Biochem.Zeitsch. 1910 29 472-487).-To account for the presence of indole in the urine of starving rabbits which has been assigned amongst other causes to haemorrhage to delay of faeces in the intestine during starvation and consequeot putrefaction etc. the authors have tested the contents of the intestines of rabbits when fed and during starvation. They find that the tests with ether or benzol extracts of fsces are untrustworthy probably owing to extraction of urobilinogen and other causes but that satisfactory results are obtained with the Ehrlich vanillin and heliotropin read ions with the aqueous distillates from faeces. I n the case of fasting animals the contents of the large but not of the small intestine contain indole and in the case of fed animals the latter also sometimes contains phenol.After injection of indole and scatole indole substances are found in the contents of the alimentary tract. I n view of Jaffe's investigations on the supposed indole-3-carboxylic acid in normal urines the urines of fed and starving rabbits were also investigated and indole-yielding substances (obtained on distillation of the urine) were found in the urine of both but more especially in those urines in which the indican reaction was positive. S. B. S. W. D. H. W. D. H. The Oxydase Reaction in Myeloid Tissues. JOHN SHAW DUNN (J. Puth. Bnct. 1910 15 20-30).-The oxidisiag property sfPHYSIOLOGICAL CHEMISTRY. ii. 59 leucocytes was first pointed out by Vitali in 1887 when he showed that pus added to tincture of guaiacum produces a blue reaction without the addition of hydrogen peroxide ; this property is destroyed by heat.The precipitate obtained by adding alcohol to a chloro- form extract of pus has the same power so also have organs rich in granular leucocytes such as bone-marrow but not purely lymphocytic organs like lymph glands or thymus (Brandenburg). The blood in myelogenous leucaemia has the same property and as it belongs only to granular leucocytes the reaction may be used in diagnosis (E. Meyer). I n the present research i t is shown that the synthesis of indophenol from a-naphthol and p-phenylenedimethyldiamine is produced with great rapidity as shown by the microscopic examination of blood films by the polynuclear and eosinophile leucocytes fairly rapidly by hyaline leucocytes and by the myelocytes of marrow and in IeucEmic blood.It is produced less readily by basophile leucocytes but not by lymphocytes red corpuscles or by normal tissue elements with the exception of parotid and lachrymal gland epithelium. The occurrence of the reaction in large hyaline leucocytes confirms Ehrlich's view that they originate in bone-marrow. The oxidising substance exhibits considerable resistance to heat and its effects can therefore be observed in most cases in tissues submitted to the paraffin method of imbedding but i t is desirable in the investigation of the more embryonic forms of myeloid cells that unfixel films or sections should be examined also. W. D. H. The Wassermann Reaction in Rabbits Infected with the Trypanosomes of Nagana and the Effect of Treatment with Arsenophenylglycine (Ehrlich).CARL H. BROWNING and I. MCKENZIE (J. Path. Bact. 1910 15 127-128).-No safe conclusion as to the action of pathogenic protozoa can be based on the Wasser- mann reaction in t h e case of rabbits; for instance normal rabbits may give a positive reaction. This and other irregularities are fairly common in the lower animals. Arsenophenplglycine is a therapeutic agent of high efficiency in trypanosome infections in rabbits. W. D. H. The Behaviour of p-Hydroxyphenyl-lactic Acid and p-Hydroxyphenylpyruvic Acid in the Animal Body. YASHIRO KOTAKE (Zeitsch. physiol. Chem. 1910 69 409-419).-1- and dl-p- Hydroxyphenyl-lactic acids are almost completely unchanged in the body and are excreted unchanged in the urine ; p-hydroxyphenyl- pyruvic acid is almost completely destroyed.This agrees well with Neubauer's work and views on alcaptonuria. W. D. H. The Phyeiological Action of an Ergot base and of 4-p- Aminoethylglyoxaline. FRIEDRICH KUTSCHER (C'hem. Zentr. 19 10 ii 327-328 ; from Zentr. Physiol. 1910 24 163-165).-The bases precipitable by silver nitrate from extract of ergot are separable into two fractions one precipitable by ammonia and silver nitrate the other precipitable by silver nitrate and barium hydroxide. From the first fraction the picrolonate and the chloride (as hygroscopic crystals) were . *ii. 60 ABSTRACTS OF CHEMICAL PAPERS. prepared; this base gives Pauly’s diazo-reaction but not the biuret reaction. It causes lowering of the blood-pressure in rabbits heart slowing and stoppage OF respiration ; a few milligrams are fatal.I n this it differs from histidine which is physiologically inactive and from 4-/?-aminoethylglyoxaline which causes a rise of blood-pressure and is much less toxic. W. D. H. [Poisonoua Action of Sodium Chloride on Sea Urchin’s Eggs.] OTTO WARBURG (Zeitsch. physiol. Chem. 1910 60 496-497; Biochem. Zeitsch. 1910 29 414-415).-Polemical in regard to the work of Jacques Loeb and Wasteneys (Abstr. 1910 ii 1096). W. D. H. The Behaviour of Lead Compounds in the Human Stomach. THOMASON (Chent. Zentr. 1910 ii 328-329 ; from Xprecilsaccl 1910 43 325-327).-The effect of dilute (0.15 to 0.25%) hydrochloric acid on white lead and lead glaze at body temperature in the presence and absence of foods and pepsin was investigated. The percentage solubility of white lead in the stomach increases with a lessening of the food present; the solubility of lead is inversely proportional to the amount of protein and directly proportional to the amount of hydrochloric acid present. Toxicity of Some Inorganic rand Organic Arsenic Com- pounds and Tolerance to these Poisons. L. LAUNOY (Compt. rend. 1910 151 897-899).-The percentage of arsenic mas deter- mined in a number of compoundsof the element and the toxic dose for guinea-pigs found when the substances were administered by injection through the peritoneum. The following list shows the weight of arsenic in grams per kilogram of body-weight required to kill the animal in one to ten days sodium arsenate 0.006-0*012 ; sodium thioarsenate 0.00875 ; sodium thiotrioxyarsenate 0.0099 1 ; sodium cacodylate 0.091 25 ; sodium thiocacodylttte 0.07131 ; sodium methyl- arsinate 0.0254 ; sodium thiomethylarsinate 0.0256 ; atoxyl 0.0418 ; thioatoxyl 0*0221 ; acetylatoxyl 0*0481 ; acetylthioatoxyl 0.0266 ; colloidal arsenic 0.0083. It was not fonnd possible to establish tolerance to arsenic by W. D. H. prolonged administration of atoxyl in small doses. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110005048

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 60 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Biochemistry of Micro-organisms. IV. The Fermentation of Formic Acid by Bacillus Kiliense. HART%% FRANZEN and G. GHEVE (Zeitsch. physiol. Chem. 1910 70 19-59. Compare Abstr. 1910 ii 799).-Protocols are given in full to illustrate the action of the Bacillus Riliense in the fermentation of formic acid; its activity is compared with that of the bacilli previously investigated. W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 61 New Method for Detecting Reducing and Oxidising Pro- perties of Bacteria. w. H. SCHULTZE (Centr. Bakt. Par. 1910 i 56 544-55 l).-Reductase-agar is prepared as follows Concentrated aqueous sodium hydroxide is added drop by drop to 100 C.C. of boiling water containing 1 gram of a-naphthol until the latter is dissolved.On cooling more sodium hydroxide is added until the solution again becomes clear and light brown in colour The solution is then mixed with a 1% solution of p-nitrosodimethylaniline (equal vols.) filtered and mixed with about two-thirds the volume of ordinary nutritive-agar (liquid) and poured into Petri dishes. Oxydase-agar is prepared by adding a well-filtered mixture of equal volumes of 1% a-naphthol solution (prepared as described above) and 1% p-phenylenedimethyldiamins hydrochloride t o liquefied nutritive- agar (about 3 parts). As the preparation becomes blue in a few hours it must always be freshly prepared. The oxydase-agar may be employed for showing the ovidising action of liquids such as saliva etc.N. H J. M. Mobilisation of the Phosphoric Acid of Soils under the Influence of Bacteria. S. A. SEWERIN (Centr. Bakt. Par. 1910 ii 28,561-580).-The experiments were made with soil (1100 grams) to which finely-ground phosphorite (10 grams) was added. After being sterilised the soil was inoculated and kept for two months and the soluble phosphoric acid determined. During the whole time air was passed through the flasks and the amount of carbon dioxide produced estimated. As regards the production of soluble phosphoric acid the results were negative the amount of readily soluble phosphoric acid being diminished. There was a considerable production of carbon dioxide ten to twenty times as much as in sterilised soil. The disappearance of readily soluble phosphoric acid is attributed partly to its assimilation by the bacteria and partly to purely chemical changes.This does not exclude the possibility that a smaller amount of insoluble phosphoric acid may have been rendered soluble. N. H. J. M. The Formation of Trimethylamine by Bacterium pro- digiosum. D. ACKERMANN and H. SCHUTZE (Chem. Zentr. 1910 2 756 ; from Zentr. Physiot. 1910 24 210-211).-Trimethylamine can be obtained from cultures of B. p9-od~giorrum grown on potatoes. I t s parent substances are choline and lecithin. By the addition of choline or lecithin the yield of trimethylamine is increased up t o twenty-fold. Betaine has no influence. In cultures on peptone-agar no trimethylamine is formed but it occurs when cholino is added. B. vzclgatus on potatoes yields no trimethylamine even if choline is added also.W. D. H. Action of the Bulgarian Ferment on Proteins and Amino- compounds. JEAN EFFRONT (Compt. read. 1910 151 1007-1009). -The Bulgarian ferment contains an enzyme capable of effecting a more profound decomposition of casein than results from the action ofii. 62 ABSTRACTS OF CHEMlCAL PAPERS. pepsin or trgpsin. The liberation of ammonia has been demonstrated when the ferment acts on asparagine milk or Witte's yeptone in presence of calcium carbonate in the latter case the amount set free corresponding with 40% of the total nitrogen. In the author's opinion the value of the Bulgarian ferment in the treatment of gastro-intestinal disorders depends on its ability to decompose proteins rather than on the lactic acid it produces.w. 0. w. Biological Degradation of Carbohydrates. AUGUSTE FERNBACH (Compt. vend. 1910 151 1004-1006).-Starch is readily hydrolysed by Tyrozhrix tenius whether the micro-organism is present in vityo or as a maceration. The successive products are maltose dextrose and dihydroxyacetone. When the organism is cultivated in a medium containing glycerol the trio1 undergoes oxidation to dihydroxgacstone methylglyoxal and two decomposition products of the latter. namely acetic acid and formaldehyde. These are also met with in the later stages of the hydrolysis of starch and sucrose and probably arise from the action of bacterial secretions. w. 0. w. The Behaviour of Yeast Gum in Autolysis and in Alcoholic Fermentation. ERNST SALHOWSKI (Zeit. physiol.CIwm. 1910 89 466-471).-After autolysis and alcoholic fermentation yeast still contains much of the gum but quantitative experiments are not given to determine the amount which disappears. W. D. H. Chemical Disinfectants. SHERTDAN DELESPINE (J. h'oc. Chern. Ind. 1910 29 1344-1354).-The factors influencing the efficiency of a large number of substances used as disinfectants as regards (1) their power of inhibiting the activity of bacteria (2) their bactericidal action are enumerated and discussed. It is pointed out that certain substances even in minute amounts have the property of arresting the multiplication and other activities of bacteria and may be called antiseptics but that the same materials in larger quantities may kill bacteria and are then appropriately named disinfectants.Illustrations are given of substances such as mercuric chloride which may act in both ways time of exposure and concentration of solution apart from the nature and resisting power of the bacteria being the chief factors which determine whether the substance is merely inhibitory or lethal. It is well known that different bacteria show different powers of resistance towards dis- infectants and that in general the spores of a bacillus are far more resistant both to heat and to bactericidal agents than the bacillus itself but it is also the case t h a t different individuals in a pure bacillus culture exhibit different powers of resistance. A series of tests with phenol on cultures of Bucillus coli showed that younger cultures were more resistant than older ones although after some time the resistance became almost constant or diminished very slowly.The drying of Bacillus coli by exposure to air at 14-18' had little effect on its resistance to phenol until about the seventeenth day when the resistance began to diminish. The material associated withVEOEK'ABLE PHYSIOLOGY AND AGRICULTURE. ii. 63 the bacteria and the disinfectant has an important influence on the efficiency of the latter. It is shown that certain substances which when present in sufficient quantity act as disinfectants act as stimulants to the growth of bacteria when present in minute amounts. The Importance of the Temperature Factor in the Determination of the Rate of the Activity of Certain Dis- infectants. R. R. FASSON c. W. PONDER and G.SIMS WOODHEAD (J. Pc6th. Bact. 1910 15 131-133).-The experiments were made with emulsified disinfectants derived from coal-tar (cresols etc.) as com- pared with carbolic acid. Dose and time of action are important factors in estimating their activity but temperature also must be taken into account. At lower temperatures the activity of the emulsion is raised more rapidly than that of the solution but a t the higher temperatures used the activity of the emulsion is no longer increased in proportion to the increase in the activity of the carbolic acid. T. A. H. W. D. H. The Sterilisation of Chalk Waters by the Use of Minute Quantities of Bleaching Powder. G. SIMS WOODHEAD (J. Pccth. Bact. 1910 15 130-131).-The activity of bleaching powder in the destruction of bacteria of the Coli group is very great and large quantities are qiiite unnecessary.The amount of chlorine necessary to kill the whole of the non-sporulating bacilli in Cambridge water is usually one part per seven million parts of water. Various details on the method are added. W. D. H. The Disinfecting Power of Complex Organo-mercury Com- pounds. I. Aromatic Mercurycarboxglic Acids. WALTHER SCRRAUTH and WALTER SCHOELLER (Zeitsch. Ryg. Ivfect. 1910 66 497-504).-Tbe disinfecting power of a number of derivatives of sodium hydroxy-o-mercuribenzoate OH*HgmC,H4*C0,Na was compared in order to ascertain the effect of the introduction of various groups on this property. It was found that by substituting the hydroxy- group by groups having a stronger afliaity for silver such as iodine cyanogen or veronal the disinfecting power was decreased.With sulphur i t was still further decreased wbilst the power was almost entirely lost in compounds in which both valencies of the mercury were attached to the benzene ring such as in sodium mercuridibenzoate Hg(C,H,*CO,Na),. W. J. Y. The Pentosan Content OL Various Fungi. J. L. WICHERS and BERNHARD TOLLENS (J. Lundw. 1910 58 238-242).-Various fungi growing on wood were examined and found to contain pentosans and in some cases methylpentosans. The amount varied from 2.5% in Frametea odorata to 6.7% in LenxitesJEaccida ; methylpentosans were found also in Xyfavia polymorphu and Eomes fomentarius. Estimations made a t the same time by the quicker method of Boddener and Tollens (see this vol.,sii 75) always gave rather lower results.E. J. R. HENRI H~RISSEY and C. LEBAS (J. Yiiurm. Chrm. 1910 [vii] 2 490-494).-The glucoside Occurrence of Aucubin in Garrya app.ii. 64 ABSTRACTS OF CHEMICAL PAPERS. aucubin was first isolated from Aucubn jcqonicu (Abstr. 1902 i 634) and has since then been recorded by Bourdier (Th&e Paris 1908) in Plantago spp. I n the present investigation it was isolated not quite pure and in small amount from the stem and leaves of Gclrrya elliptica G. macrophylla and G. Thureti. T. A. H. The Carbohydrates of White Pepper. K. H. BODDENER and BERNHARD TOLLENS (J. Landw. 1910 58 229-231).-1t has already been shown that white peppsr in addition to its 54% of starch 1% of ethereal oil and 4 to 9% of piperin contains also pentosans and methylpentosans or at least substances that give furfuraldehyde and methylfurfuraldehyde on distillation with hydro- chloric acid.The authors have endeavoured to investigate further these pentosans but without success. The methods used for separating the piperin and the starch with its transformation products removed also the greater part of the pentosans so that the amount remaining after the final purification was too small for separation. The Root of the Kermek (Statice Plumbaginaoeae). G. POVARNIN and A. SEKQETEFF (J. Russ. Phys. Chern. ~ o c . 1910 42 1084-1034).-The root of the kerrnek (Statice Gmelini) contains tannides 15-70% sugars 2.03% soluble substances 30.1 5% non-tanning substances 14.45% water 10.76% ash 4*23% resins 0.34% some amine (probably alkaloids) a trace of gallic acid possibly some phloroglucinol and a glucotannide. Kermek and similar tanning roots should be analysed as far as possible without access of air The tanning sub- stances in the root are readily oxidised and consist of at least two tannides red and yellow which can be distinguished by the differently coloured lead calcium and barium salts ; the tannides also give charac- teristic reactions with silver and cadmium nitrates formic acid and concentrated sulphuric and hydrochloric acids.On dry distillation the tannides yield pyrogallol. Violuric acid is recommended as a reagent for the detection of basic The Death of Plants at Low Temperatures. A. A. RICHTER (Bull. Acad. Sci. St. Petersburg 1910 1251 -1260).-AspwgiZlus niger when exposed to very low temperatures ceases to evolve carbon dioxide and loses all the .properties of living protoplasm neither does it regain these a t 18-19"; but it revives rapidly at 30-34' even if it had previously been frozen at the temperature of a mixture of ether and solid carbon dioxide E. .J. R. substances in plants. 2. K. Z . R. Effect of Road Tarring on Vegetation. MARCEL NIRANDE (Compt. Tend. 1910,151,949-952. Compare Abstr. 1910 ii 884).- The vapour of hydrocarbons arising from tar or asphalt exercises an injurious action on vegetation producing blackening of the leaves characteristic of death of the protoplasm. The effects observed are not due to actual contact with particles of tar since them in common with solid hydrocarbons such as naphthalene or anthracene have very little action-when applied to plants i n the state of fine powder.w. 0. w-.VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 65 Influence of Different Volatile Substances on Higher Vegetation. HENRI COUPIN (Compt. rend. 19 10 151 1066-1067). -The author classifies forty-seven aliphatic and aromatic volatile substances into five groups according to their relative toxicity towards germinating wheat. The action of the same compound differs in intensity with different plants. The grains are more open to attack at the earlier stages of germination than when the aerial organs have attained development. w. 0. w The Presence of Arginine and Hiatidine in Soils. Pyrimidine Derivatives and Purins Bases in Soils. OSWALD SCHREINER and I ~ M U N D c. SHOREY (J Biol.Chern. 1910 8 381-384 385-393).- I n soils the products of cleavage of proteins of vegetable origin can be separated out. Those identified in the present research were argitiine and histidine in variable proportions cytosine xanthine hypoxanthine and picolinecarboxylic acid. W. D. H. Calcium or Sodium Nitrate [as Manure]. PAUL WAGNER Bisd. Zmtr. 1910 3 9 729-731 ; from 1Mitt. deut. Zanndw. Ges. 1910 St. 8 107-109).-1n field experiments with mangolds winter rye arid barley somewhat higher yields were obtained with sodium nitrate than with calcium nitrate whilst in the case of sugar beet potatoes and oats the yields were rather higher when calcium nitrate mas employed. N. H. J. M. Manurial Action of Ammonium Sulphate in Conjunction with Sodium Chloride. BERNHARD SCHULZE (Bied. Zewtr. 1910 39 731-733; from Atfdt. deut. Zandw. Ges. 1910 St. 30 452-458). -It is shown by field experiments that when sodium chloride is applied along with ammonium sulphate the manurial value of the ammonium salt becomes about equal to that of sodium nibrate. N. H. J. hf. Employment of Nitrogenous Manures for Sugar Beet. B. ERREN Fa. PRACHFELD and W. VILIKOVSKY (Bied. Zentr. 1910 39 782-783 ; from Mitt. 2andw.-botan. Versuchsstat. Tabor).-Moderate amounts of sodium nitrate increased the yield of roots whilst larger amounts oiily increased leaf production. Calcium nitrate gave almost the same results as sodium nitrate. Calcium cyanamide only increased the yield slightly and liquid manure had less effect than sodium nitrate. In moderate amounts nitrogenous manures had no or very slight injurious effect on the amount of sugar in the roots and had no effect on the amounts of non-sugars. N. €3. J. -M. 5 VOL. C. ii.

ISSN:0368-1769    

DOI:10.1039/CA9110005060

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 66 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Photochemical Reactions in Laboratory Work. KURT GEBRARD (Chern. Zeit. 1910 34 1269)-The author points out that whilst a slightly acid solution of potassium iodide in starch mucilage remains colourless in the dark it rapidly becomes coloured in the light due to liberation of iodine although in presence of a fourth substance liberation of iodine may occur more rapidly in the dark than in tho light. This and observations recorded by others (for example Gibbs Abstr. 1909 i 640 and Batik 1910 i 543) indicate that as the result of unsuspected photochemical reactions errors may often be caused in ordinary laboratory work. T. A. H. Several Acids Suitable for Use as Standards in Acidimetry. JOSEPH H. KASTLE (Amer. Chem. J.1910 44 487-493).-pNitro- toluene-o-sulphonic acid (Kastle t b i s vo!. j 30) and p-amino-o- sulphobenzoic acid and potassium o-nitro-p-sulphobonzoate (Hart Abstr. 1881 1144) are recommended as standards for use in acidimetry. The last two are anhydrous and can be thoroughly dried without risk of decomposition. p-Nitrotoluene-o-sulphonic acid although crystallising with 2H,O is a definite and very stable com- pound All these substances are stable in the air are not hygroscopic or deliquescent and give very sharp end-reactions with phenol- phthalein. E. G. Use of Metallic Potassium in Estimating the Halogens in Benzene Derivatives. C. H. MARYOTT (Arner. J. Sci. 1910 [iv] 30 378-380).-Stephanoff (Abstr. 1907 ii 50) proposed to estimate the halogens by treatment with alcohol and metallic sodium.The author did not get satisfactory results but on substituting potassium for sodium a complete reduction was effected. About 0.4 gram of the substance is placed in an Erlenmeyer flask and 7 0-15 C.C. of alcohol-benzene mixture are added (1 vol. of 98% alcohol with 2 vols. of benzene free from sulphur compounds). About ten times the theoretical amount of potassium is now added gradually in small pieces. When the action slackens two extra C.C. of alcohol are added and when the potassium has completely dissolved the whole is shaken with water. The aqueous layer is then acidified with nitric acid and the halogen is precipitated with silver nitrate as usual. L. DE I(. Estimation of Total Sulphur in Urine. W. DENTS (J. Biol. Chem. 1910 8 401-403).-Benedict7s method (Abstr.1909 ii S27) in which the oxidising agent is a mixture of copper nitrate and sodium or potassium chlorate was compared with Folin’s sodium peroxide method. The former method leads to spattering and loss due to too rapid evolution of nitrogen oxides. It can be modified and the spattering avoided by mixing the copper salt solution with sodiumANALYTICAL CHEMISTRY ii. 67 chloride and ammonium nitrate; the results then are very near to those obtained by Folin’s method. W. D. H. Benedict’s Method of Estimating the Total Sulphur in Urine. CARL L. A. SCHMIDT (J. Biol. Chem. 19 10,8,423-425. Corn pare Abstr. 1910 ii 827).-Benedict’s and Folin’s methods gave practically the same results. The presence of sugar makes no difference but albumin causes the oxidation by Benedict’s method to be violent ; it makes no difference in Folin’s method.W. D. H. Estimation of Sulphur in Organic Compounds. THEODOR ST. WARUNIS (Chem. Zeit. 1910 34 1285-1286).-0~3-0~4 Gram of the finely powdered substance is mixed in a spacious silver or nickel crucible with 10 grams of powdered pure potassium hydroxide and 5 grams of sodium peroxide by means of a silver wire. After covering the crucible with a lid the mixture is heated for some fifteen minutes in an air-bath at 75-80’ and then heated over a gradually increased flame until it has melted completely The mass is then allowed to cool and dissolved in water solution of bromine in hydrochloric acid is added and the liquid filtered and boiled to expel the excess of bromine.A blank experiment should be made to allow for any sulphate present in the reagents or sulphuric acid absorbed from the gas I n the filtrate the sulphuric acid is estimated as usual. employed. L. DE K. Estimation of Sulphur and Phosphorus. CHARLES G. L. WOLF and EMIL OSTERUERG (Biochem. Zeitsch. 1910 29 429-438).-The authors have investigated various methods for the estimation of sulphur in tissues. They show that satisfactory results can be obtained by preliminary oxidation of the organic matter and completion of this process by the reagent originally suggested by Benedict containing copper nitrate and potassium chlorate. They show also that after destruction of the organic matter and precipitation of the sulphate in this way the phosphorus can be estimated in the filtrate so that only one sample is necessary for the estimation of both sulphur and phosphorus. S.B. S. Remarks on the Iodometric Titration of Acids and Kjeldahl’s Nitrogen Estimation. R. KOEFOED (Zeitsch. physiol. Chem. 19 10 69 421-440).-Correct results are obtained by strictly adhering to the procedure given. The ammoniacal distillate is collected in a flask containing 15 C.C. of N-sulphuric acid until the total volume measures 100 C.C. When making the check 15 C.C. of the acid are diluted up to 100 C.C. with water previously boiled. Ten C.C. of 5% potassium iodide 2 C.C. of 2% starch solution (saturated with sodium chloride) and finally 4 C.C. of 4% potassium iodate are added. The iodine liberated which represents the free acid is then titrated with N/lO-sodium thio- sulphate which operation should occupy just two minutes.The author has tried the various chemicals from time to time proposed as standards including glycine and hippuric acid after con- version into ammonihm sulphate by Kjeldahl’s process. The results 5 2ii. 68 ABSTRACTS OF CHEMICAL PAPERS. agent and the sodium hydroxide solution are admitted through the which are tabulated do not differ much except those witlh glycine and hippuric acid which give somewhat higher figures. Jn most cases Kjeldahl’s original process (use of potassium perman- ganate) is recommended; in such cases where there is danger of forma- tion of piperidine rings the Gunning modification (use of potassium sulphate) is more appropriate. L. DE K. Nitrogen. MATTHEW STEEL (J.Biol. Chena. 1910 8 365-379. Error in Estimating Nitrogen in Soil. EILHARD A. ~~ITSCHERLICH and ERNST MERRES (Chem. Zentr. 1910 ii 495 ; from Landw. Jalwb. 1910,39,345-367).-1n soil sampling a sample should be taken by means of a borer from eaFh square metre ; according to the soil the error will vary from k 4 to 6%. The error due to changes during the drying of soils in the air can be avoided by adding tartaric acid. Soil extracts should be kept under carbon dioxide. N. H. J. M. Nitrometer Appendage Flasks. FRANZ MICHEL (Chem. Zeit. 1910,34 1237).-The H-vessel (see figure) which dispenses with the use of the pipettes and funnels is used as follows Tube a which for nitrogen estimations carries two marks at 25 and 50 C.C. respectively contains the alkaline hypobromite solution.Tube b also carries two walk2 of 5 and 10 C.C. respectively and is intended for the substanceANALYTICAL CHEMISTRY. ii. 69 t o be tested. The diameters of the tubes are so chosen that their length is about equal. If a solid substance such as an ammonium salt has to be tested a weighed quantity is placed in tube b. and water is addgd up to the desired mark. Liquids are introducld up t o the desired ‘mark or may be delivered from a pipette. After closing the tubes ( a with a rubber cork b with a stopcock tube) the pres- sure in both tubes is equalised as usual. To start the reaction the apparatus is inclined in such a manner that the liquid from b gradually euters a and when the effervescence has ceased the liquid is allowed to again enter b and this operation is repeated a few times.When all the liquid is once more in tube a the apparatus is placed in a horizontal position a downwards and well shaken I n this manner it is impossible for any liquid to enter the stopcock tube. L. DE K. Application of Busch’s ‘ I Nitron” Method to the Analysis of Chili Saltpetre. LEOPOLD RALILBERGER (Chem,. Zentr. 1910 ii 685 686 ; from Osterr..ung. Zeitsch. Zuckw-lnd. Landw. 19 10 39 433 -436).-Busch’s method (Abstr. 1905 ii 382) may be employed for estimating the quantity of nitrate in Chili saltpetre provided that this contains not more than the normal amount of perchlorate. IF the salt contains a large amount of perchlorate the results obtained by the process are untrustworthy. w. P. s. Analysis of Nitrates by Grandval and Lajoux’s Method.Estimation of Nitrates in Water by a Sulphosalicylie Reagent. HUBERT CARON arid DBSIRI? RAQUET (BUZZ. Soc. chim. 1910 [iv] 7 1021-1025 1025-1027).-1n the first paper the modified form of Grandval and Lajoux’s process introduced by Perrier and Farcy (Abstr. 1909 ii 344) is criticised and in the second tbe use of a solution of salicylic acid in sulphuric acid is suggested in place of phenol dissolved in sulphuric acid as a colorimetric reagent for nitrates. It is stated that the coefficients of decolorisation quoted by Fartoy (Abstr. 1909 ii 616) do not agree with those calculated from the results given in his previous paper (Abstr. 1909 ii 344). Further the dry residue from the water is liable to absorb moisture and unless this is guarded against different results are obtained by different workers for the same proportion of nitrates.The results obtained vary also with the method used in preparing the solution of phenol in sulphuric acid and the authors recommend the use of a reagent freshly prepared by dissolving 1 C.C. of the liquefied phenol specified in the Codex Fraqais in 10 C.C. of sulphuric acid. In the second paper it is pointed out that several phenolic substances dissolved in sulphuric acid give colours with nitrates and a solution of from 1 to 5% of salicylic acid in sulphuric acid is suitableii. 70 ABSTRACTS OF CHEMICAL PAPERS. for use in estimating nitrates in water. The process suggested is as follows Evaporate 10 C.C. of the water to dryness with 1 c.c of a 1% Eolution of sodium salicylate; add to the residue 1 C.C.of sulphuric acid and after mixing thoroughly for some minutes add 10 c.c of water and 10 C.C. of ammonia and compare the colour given with that furnished by a known nitrate solution similarly treated. The quantity X of nitrate in the water is given by the formula where h and h' are the respective heights of the two solutions giving the same tint in the colorirneter Y and V' the original volumes of the two solutions and P the amount of nitrate in the standard solution. T. A. H. X == Phl7~' x V'l V Estimation of Free Carbon Dioxide in Water. J. TILLMANS and 0. HEUBLEIN (Zeitsch. Nab. Genussrn. 1910 20 617-630).- Titration with calcium hydroxide solution yields trustworthy results provided that phenolphthalein is used as the indicator.Rosolic acid is quite useless for the piirpose as the hydrogen carbonates of the alkalis and alkaline earths exhibit a strongly alkaline reaction towards this indicator. w. P. s. Acid Content of Moor Water. H. STREMME ( J . pr. Chern. 1910 [ii] 82 519-520).-It is pointed out that Endell in his paper on the acidity of moor waters (Abstr. 1910 ii 1005) has worked according to the method first given by the author two years ago (Zeitsch. prakt. Geol. 1908 126). PHILIPPE BARBIER (Bull. Xoc. chim. 1910 [iv] 7 1027-1028).-The material is dissolved in the ordinary way excess of sodium acetate added and the acids neutralised by sodium hydroxide. A 10% aqueous solution of sodium hyposulphite is then added until the red coloration of the liquid just disappears.The mixture is boiled when alumina is precipitated as a dense powder which can be collected and weighed as usual Iron can be estimated in the filtrate by any of the ordinary methods. Glucina is precipitated with the alumina if present and can be separated by digesting the precipitate with ammonium carbonate solution during thirty-six hours when the alumina remains undissolved and the glucina can be recovered quantitatively by prolonged ebullition of the solution. T. S. P. Separation of Alumina and Ferric Oxide. T. A. H. Estimation of Manganese in Steel by the Volhard-Wolff Method. AUGUST KAYSSER (Chem. Zeit. 1910 34 1225-1226).- -One gram of steel is boiled with 25 C.C. of hydrochloric acid D 1.12. When solution is complete a 1 gram tablet of compressed potassium chlorate is added and the boiling continued until the odour of chlorine has passed off. The liquid is transferred t o a flask and after precipitating the iron with zinc oxide avoiding an excess the hot solution is titrated with potassium permanganate solution (1.9.gram per litre ; 1 C.C.= 0.1% of manganese in the sample). When dealing with samples rich in carbon more potassium chlorate should be used. La DE K,ANALYTICAL CIIERZISTRY. ii. 71 Method of Dissolving Tinstone. ADOLPH GILBERT (Zeitsch. ofentl. Chent. 1910 16 441-442).-Natural tinstone is much more refractory than artificial stannic oxide towards fusion with alkali. I€ 0.5-1 gram tinstone is fused with 10-154 grams of sodium hydroxide in a silver crucible a little finely-powdered wood charcoal being added (50 mg.) a reaction takes place with considerable develop- ment of heat and solution is complete in three to five minutes.The heating must be continued in order to burn off the excess of carbon. All the tin passes into solution in water iron oxide romaining insoluble. It is desirable to remove copper and sulphur by a pre- liminary roasting and extraction with hydrochloric or nitric acid. The quantity of carbon used is only a small fraction of that required to reduce the tin oxide. The reaction has been described by Burghardt (Abstr. lS90 1027) but has remained unnoticed in the literature. C. H. D. Precipitation of Vanadic Acid as Silver Vanadate and Estima- tion of Phosphoric and Vanadic Acids in the Presence of One Another. GRAHAM EDGAR (Arne?..Chem. J. 1910 44 4G7-472).- The solution of the alkali vanadate which may contain excess of alkali carbonate but no cther matters precipitable by silver nitrate is acidified with nitric acid and boiled to expel carbon dioxide. Dilute sodium hydroxide is then added t o the boiling solution until the yellow liquid turns colourless. An excess of N/lO-silver nitrate is added and then ammonia to dissolve the precipitate formed and the excess of ammonia is boiled off ; a few fragments of porous tile should be added to prevent bumping. The silver vanadate is collected on a filter and well washed and then the excess of silver is estimated in the usual manner by acidifying the filtrate with nitric acid and titrating with N/10- ammonium thiocyanate with ferric nitrate as indicator.One C.C. of silver consumed = 0.00304 grain of vanadic acid. I n the presence of phosphoric acid this is co-precipitated as tri- silver phosphate with the vanadic acid. The latter is then estimated separately by dissolving the precipitate in sulphuric acid and reducing the vsnadic acid by boiling with sulphur dioxide. The vanadium is titrated hot with N/ZO-permanganate and the phosphoric acid is found by an easy calculation. L. DE K. An Indirect Method for Estimating Columbium and Tan- talum. HARRY W. FOOTE and RALPH W. LANGLEY (Arne?.. J. &. 1910 [iv] 30 393-400).-The process is based on the great difference between the densities of the oxides of columbium (4.552) and tantalum (8.71 6 ) . When applied to the mineral stibiotantalite a sufficiency of the sample is treated with hydrofluoric acid the solution is largely diluted with water and the antimony and bismuth are removed by means of hydrogen sulphide; the precipitate is then treated further by the usual process.The filtrate is evaporated to dryness and the residue heated with sulphuric acid to expel the fluorine. After diluting with water the solution is made alkaline with ammonia and the precipitate is collected washed ignited and weighed After heating over a blastii. $2 ABSTRACTS OF CIIEMICAL PAPERS. lamp €or an hour the density of the mixed oxides is determined and their composition ascertained by referring to a table. L. DE K. A Recent Method for Separating Tantalum and Columbium. HARRY W. FOOTE and RALPH W. LANGLEY (Amer. J. Xci.1910 [iv] 30 401-402).-Weiss and Landecker (Abstr. 1909 ii 942) have stated that tantalic acid may be precipitated from its solution in sodium carbonate by means of a current of carbon dioxide; any columbic acid remains in solution and may be separated by boiling with sulphur dioxide. The authors however agree with Rose and with Ostwald that the columbium is almost completely co-precipitated with the tantalum and that therefore this process cannot be employed for their separation. L. DE K. Estimation of Both Phenol and p-Cresol in Urine. MAX SIEGFRIED and It. ZIMMERMANN (Biochem. Zeitsch. 1910,29 368-388). -The method is based on two determinations (1) the total amount of bromine required to convert the phenol and p-cresol in the liquid into tribromophenol and tribromo-p-cresol and (2) the quantity required to convert the phenol into tribromophenol and the,cresol into dtbromo-p- cresol.Since 6 atoms of bromine are necessary for the formation of either of the tribromo-compounds whilst that of dibromo-p-cresol only requires 4 atoms the quantities of phenol and p-cresol present are readily calculated from the difference between the two determinations. For the first estimation a modification of Koppeschaar's method is employed. Twenty to 30 C.C. of sulphuric acid (1 1) are added to a meamred volume of the liquid contained in a stoppered flask and a standard solution of potassium bromide and bromate (0.834 gram KBrO and 2-97 grams KBrper 1000 c.c.) is run in from a burette the liquid being continually agitated until the precipitate collects together into a mass and the liquid becomes coloured distinctly yellow.At this point the volume that has been added is noted and an eighth part of this volume is further run in. The mixture is then shaken al frequent intervals for one hour. It is then filtered through glass- wool into 25 to 30 C.C. of 5% potassium iodide solution and the iodine liberated titrated with NjlO thiosulphate. The second reaction is carried out with the same quantity of the original liquid 30 C.C. of 25% hydrochloric acid are added and the whole diluted to 500 C.C. The volume of the solution of potassium bromate and bromide required to produce a yellow coloration as previously determined is then run in the liquid being gently rotated throughout and the mixture left without shaking for fifteen minutes.Twenty-five to 30 C.C. of 5% potassium iodide are added and the flask left for one hour in front of a light. The iodine liberated is titrated with thiosulphate. The method gives good results. A new tribromo-p-cresol was obtained by the action of potassium bromide and bromate on p-cresol in the presence of hydrochloric acid and the subsequent addition of potassium iodide ; it crystallises from acetic acid in colourless needles m. p. 139'. W. J. Y.ANALYTICAL CHEMISTRY. ii. 73 An Improvement in Scherer’s Reaction for Inositol. ERNST SALKOWBKI (Zeitsch. physiol. Chem. 1910 69 478-481).-A trace of inositol is dissolved in a few drops of nitric acid a drop of 10% cal- cium chloride solution added and then a drop of 1% platinum chloride solution; the whole is carefully evaporated in a porcelain capyule.A red colour develops; on the addition of water it becomes orange ; the red returns on heating once more with a blue tinge; on stronger heating it becomes a dirty green. Performed in this way the reaction is more delicate and the colours more intense. W. D. H. A Simple Method for the Estimation of Sugar in Blood. LEONOR MICHAELIS and PETER RONA (Zeitsch. physiol. Chem. 1910 69 498).-PolemicaI against K. Moeckel and E. Frank (Ahstr. 1910 ii 1116). W. D. H. Reischauer’s Titration Process for the Estimation of Diabetic Sugar. GUSTAV OTTO GOEBEL (Apoth. Zeit. 1910,25,614-615).-into six separate test-tubes are introduced the usual quantity of Pehling’s solution and water and to each is added an increasing amount of the urine to be tested.After being heated in the boiling water-bath for fifteen minutes they are cooled rapidly shaking being avoided. They are now all tested for excess of copper in the following manner 0.5 gram of potassium iodide dissolved in a little water is added and after gentlo shaking 5 C.C. of dilute sulphuric acid (1 5). Excess of copper will be noticed by the formation of cuprous iodide and also free iodine which may be recognised by adding starch solution ; no riotice should be taken of a blue colour appearing gradually. The contents of the tube which show no excess of copper are those where about the right amount of urine has been added and serve :ts a guide for R second trial when a little less urine should be used. L. I)E K.Estimation of Sugar by Safranine. K. A. HASSELBALCII and J. LINDIIARI) (Biochem. Zeitsch. 19 10 29 41 6).-The authors in reply to Wender’s criticism (Abstr. 1910 ii 11 16) maintain that their safranine method for the estimation of sugar (Abstr. 1910 ii 905) is new in that they so elaborated the details tbnt the reaction can be used quantitatively and not merely qualitatively. S. B. S. Polarimetric Estimation of Lactose. H. DROOP RICHMOND (Ancclyst 1910 35 516-517).-0f the many substances which have been proposed for the removal of proteins previous t o the polarimetric estimation of lactose in milk that most commonly used is mercuric nitrate but the author finds that this reagent does not effect complete precipitation of all the proteins present. If the filtrate obtained from milk which has been treated with mercuric nitrate is further treated with phosphotungstic acid a somewhat voluminous precipitate is obtained and the optical activity of the solution is increased.I n the case of milk itself the difference in the polarisation before and after treatment with phosphotungstic acid is small but with dried milks and other milk products the difference may amount to several unitsii. 74 ABSTRACTS OF CHEMTCAL PAPERS. per cent. As however the use of mercuric nitrate is so convenient and involves such a small dilution the author recommends that its use be continued in conjunction with the addition of phosphotungstic acid. The milk should be treated with mercuric nitrate in the usual manner; after the addition of 5% of phosphotungstic acid and 5% of sulphuric acid (1 l) the mixture is filtered and the filtrate is examined in the polariscope.The readings observed are multiplied by 1.1. w. P. s. Estimation of Lactose in the Presence of the Commonly- occurring Sugars. JULIAN L. BAKER and H. F. E. HULTON (Analyst 19 10 35 5 1 2-5 14).-The method proposed depends on the fact that brewers’ yeast ferments such sugars as dextrose invert sugar maltose and sucrose whilst lactose is not affected. The estimation is carried out by adding about 0.5 gram of washed brewers’ yeast to 100 C.C. of a 2-3% solution of the mixed sugars allowing fermenta- tion to proceed for seventy hours at a temperature of 2 7 O then filter- ing and boiling the solution and determining its copper-reducing power.If the sugar solution is non-nitrogenous a small quantity of sterile yeast water or asparagine may be added. Lactose alone appears to be slightly attacked by the yeast. results of experiments showing that from 90-95% of the quantity present is found at the end of the fermentation process but in the presence oE other sugars the loss of lactose is much less. The fermenta.tion must not be prolonged for more than seventy-two hours as after this period of time bacteria develop the solution becomes acid in reaction and the lactose diminishes rapidly. The process is particularly suitable for the estimation of lactose in the presence of flour for instance in infants’ and invalids’ foods; when sucrose is also present it is advisable t o invert this sugar with invertase or citric acid before proceeding with the estimation of the lactose.The method is not however applicable in the case of foods,’etc. containing commercial sugars such as dextrin- maltose glucose and the like as these even after fermentation in the presence of diastase leave a residue which reduces Fehling’s solution. w. P. s. Estimation of Lactose in Milk. VITOUX (Ann. Falsljr. 1910 3 471-472).-1t is shown that the process described by Denigks (treatment of the milk with sodium metaphosphate and hydrochloric acid filtering and determining the cupric reducing power of the filtrate) yields results which agree closely with those obtained by the official (French) method of estimating lactose in milk. The latter method is however to be preferred for the analysis of milks which have been preserved by the addition of dichromate as the end-point of tbe titration with Fehling’s solution is not obscured.W. P. S. New Method for the Quantitative Estimation of Sucrose in the Presence of other Sugars. ADOLF JOLLES (Zeitsch. # a h . Genussm. 1910 20 631-638).-The method is based on the fact tbnt sugars such as arabinose rhamnose dextrose laevulose galactose mannose invert sugar maltose and lactose are rendered opticallyANALYTICAL CHEMISTRY. ii. 75 inactive when heated in dilute alkaline solution whilst sucrose remains unaffected. The reaction to some extent depends on the concentration of the sugar and alkali ; for instance a 1% dextrose solution containing sufficient sodium hydroxide to render the alkalinity of the whole approximately N/lOO becomes optically inactive after being heated a t a temperature of 37’ for twenty-four hours.The solution however then becomes acid in reaction and t o avoid this it is recommended that the solution have an alkalinity approximately N/10 and contain not more than 2% of the above-mentioned sugars; the quantity of sucrose present does not matter. Instead of heating a t 37O for twenty- four hours the mixture may be boiled in a reflux apparatus or heated in a closed flask in a boiling-water bath for thirty minutes but the lower temperature is to be preferred as the solution becomes less darkly coloured. As applied to the estimation of sucrose in wine con- densed milk etc. the details of the process are as follows A definite quantity of the sample is neutralised clarified by the addition of lead acetate filtered and the excess of lead removed from the filtrate by means of sodium phosphate.After removing the lead phosphate by filtration an aliquot portion of the filtrate is treated with a suflicient quantity of sodium hydroxide solution to render the alkalinity of the solution equivalent to N/lO and the mixture is then heated as described After cooling the solution is examined in the polariscope ; any rotation observed is due solely to sucrose and the quantity of the latter in the sample is then calculated. The results obtained by the process agree closely with those yielded by the ordinary polarimetric A Modiflcation of the Furfuraldehyde Method of Estimating Pentoaans. K. H. BODDENER and BERNHARD TOLLENS (J. Lundw. 1910 58 232-237).-1t is usual to estimate pentosans by distilling with hydrochloric acid collecting the furfuraldehyde formed and then converting this into a weighable substance by precipitating with phloro- glucinol in the cold leaving the mixture for sixteen to twenty hours.The authors find that precipitation is practically complete in a much shorter time if the mixture is heated t o 80-85O and then allowed to cool for one and a-half to two hours; bluish-green flocks are thus formed which are readily filtered and washed. The phloroglucide is not the same as is obtained in the cold the reaction being C5Ha02+ C,H60 = CllH402 + 3H20 whilst in the cold the products are C,,H,O + 2H20. The modification is not suitable if it is desired t o estimate the methyl- pentosans separately ; further (this vol.ii 63) it does not give identical results with the older method but the differences are only small. Its great value is the considerable saving of time it effects. method of estimating sucrose. w. P. s. The necessary tables are given for the conversion. E. J. R. Estimation of Starch. FRIEDRICH SCHUBERT (Chem. Zentr. 1’310 ii 658-689 ; from 0sterr.-ung Zeitsch. Zucker-lnd. Landw. 1910 39 41 1-422).-The author discusses the more important processes which have been proposed for the estimation of starch and describes the following modification of Lintner’s process for the estimation of starch in barley (Abstr. 1907 ii 823) A weighedii. 76 ABSTRACTS OF CHEMICAL PAPERS quantity of the barley is rubbed down with 25 C.C. of a 1% phospho- tungstic acid solution 75 C.C.of hydrochloric acid are then added and after the lapse of thirty minutes the solution is poured through a filter. As exactly 100 C.C. of reagents have been added to the barley there is no need to dilute the mixture to any definite volume but the optical rotation of the filtrate must be corrected for the quantity of water present in the barley and for the volume of the dissolved starch. One gram of pure starch occupies a volume of 0.49 C.C. w. P. s. Estimation of Acetaldehyde by mean8 of Pyrrole and Application of this Method to the Estimation of Lactic Acid. W. SOBOLEWA and J. ZALEWSKI (Zeitsch. physiol. Chem. 1910 69 441-451).-1oto a number of test-tubes is placed the reagent consist- ing of 5 C.C. of aqueous pyrrole and 10 C.C.of 2.2% hydrochloric acid. Into each of the tubes is introduced an increasing volume of acetaldehyde solution of known strength (about 0.25 gram per litre) and after half an hour the minimum quantity of acetaldehyde required to produce an opalescence is ascertained. This then serves as a measure for the estimation of the concentration of acetaldehyde solutions. On boiling a lactate with dilute sulphuric acid in a current of air and cautiously adding potassium permanganate 80-92% of the lactic acid is obtained as acetaldehyde which may then be estimated by the pyrrole method. L. DE K. Titanium Chloride in Volumetric Analysis. IV. Esti- mation of Quinones. EDMUND KNECHT and EVA HIBBERT (Bey. 1910 43 3455-3457).-Quinones are reduced by titanium chloride in the cold.To the solution of the quinone in cold water is added an excess of the titanium trichloride and the excess of the latter determined by titration with iron alum using potassium thio- cyanate as indicator. The titration of the quinone may also be carried out directly with the titanium chloride using methylene-blue as an indicator ; the quinone is quantitatively reduced before the methylene- blue enters into reaction and is decolorised. Analytical results are given with p-benzoquinone toluquinone and P-naphthaquinone. In a footnote it is pointed out that methylene-blue may be used as an indicator instead of potassium thiocyanate in the titration of ferric salts. T. S. P. Acids in Tan Liquors. HENRY R. PROCTER and A. SEYMOUR- JONES (J. Xoc. Chern. Ind. 1910 29 1354-1362).-The estimation of the acids present in tan liquors is of technical importance since these substances act on hide in such a way as to facilitate the absorp- tion of tannin. Such action is confined to the relatively strong acids and is not exhibited by weak acids such as the phenols and for that reason the method of estimation must discriminate between the two classes.Many methods have been devised for this purpose and in the present investigation the best known of thcm have been examined and the results obtained are discussed and criticised.AKALY TICAL CHEMISTRY. ii. 17 Among the methods available the discrimination referred to above is effected iu one of two ways (a) the tannins and other weak acids are removed by precipitation with gelatin hide powder or some similar agent and the acids iu the filtrate estimated by titration with standard alkali using a suitable indicator or (b) liquors are titrated directly with standard alkali in presence of an indicator which will react with the stronger acids only.A special case of class (a) is the “lime-water” method which depends on the fact that lime forms soluble salts with the stronger acids and insoluble salts with the tannins phenolic matters etc. the formation of a definite faint tur- bidity being taken as the end-point. The general objections to methods of class ( a ) are (1) co-precipitation of stronger acids and (2) undue dilution of the liquors. Methods of class ( b ) present as chief difficulty the selection of a suitable indicator. The authors think that the best results are obtainable with methods of group (6) and they are now engaged in the investigation of buitable indicators.The most promising resu’l ts were obtained with Congo-red ( methyl-orange (loe4) hamatein (10-1 to lO-I5) and fluorescein t o 10-7). The figures given in brackets after the name of each indicator represent the concentration of hydrogen ions at which colour change occurs. T. A. H. Separation of Saturated Fatty Acids (Palmitic and Stearic) from Oleic Aoid. PIETRO FALCIOLA (Gaxxetta 1910,40 ii 21 7-229). -See this vol. i 5. Estimation of Total Tartaric Acid by the Goldenberg Process. CHARLES ORDONNEAU (Bull. Xoc. chim. 1910 [iv] 7 1034-1041).-1n order to ascertain the effects on the analytical results obtained by the Goldenberg method for the examination of factory and commercial tartaric products of impurities likely to occur in such materials the author has applied the 1907 modification of that process (Abstr.1908 ii 237) to potassium hydrogen tartrate contain- ing known amounts of various impurities. With calcium tartrate alone the results are 3053% too low when phenolphthalein is used as indicator and 3.60% for litmus whilst with potassium hydrogen tartrate containing 5 and 10% of calcium tartrate the corresponding losses are 2.34 and 2.39% for litmus and 1.25 and 1.34% respectively for phenolphthalein but these losses are somewhat reduced by the presence of alumina although the loss dim to the presence of 5% of the latter alone is 19.35% for litmus and 8.80% for phenolphthalein. Similar errors are caused by ferrous ferric and aluminium phosphates. The errors caused by these and other substances are tabulated in the original. I n general the losses are about twice as great for litmus as for phenolphthalein and an approximation to the correct figure may be got as a rule by adding to the result obtained with phenolphthalein the difference between this result and that furnished by the use of litmus as an indicator although R further correction is needed in some cases.Phenolphthalein may be used in all cases in place of litmus if the titration is carried out at 50° after boiling and cooling the liquid. Certain of the changeb suggestedii. 78 ABSTRACTS OF CHEMICAL PAPERS. by the author have been made in the most recent form of the Golden- berg process adopted by the London Congress of Applied Chemistry (Abstr. 1910 ii 758).Detection of Hydrocyanic Acid in an Exhumed Corpse and the Stability of Hydrooyanic Acid in Presence of Putrefying Matter. WILIIELM AUTENRIETH (Ber. plmrm. Ges. 19 10 20 432-446).-It is generally assumed that hydrocyanic acid disappears rapidly in animal organisms by (1) combination with dextrose in the blood ; (2) interaction with proteins ; (3) hydrolysis to formic acid or (a) according to Ganassini (Abstr. 1904 ii 758) conversion into xanthine derivatives. The detection of the acid in a child’s corpqe which had been exhumed after forty-three days lead the author t,o investigate the stability of hydrocyanic acid in presence of decomposing matter of various kinds when it was found that although the acid disappears it does so comparatively slowly.I n a mixture of pig’s stomach intestine and pancreas (50 grams) with bitter almond water (50 grams) and water (200 c.c.) bydrocyanic acid could still be detected by the Yrussian blue guaiacum or thiocyanate tests after forty-five days and this was also the case when dilute potassium cyanide solution was substituted for bitter almond water. When the quantity of acid initially present was reduced t o 1 in 15,000 it could still be detected after thirty-six days. One part of the acid in 10,000 of cow’s blood could still be detected by the Prussian blue reaction after forty-eight days. I n a series of quantitative experiments an aliquot part of the mixture was distilled after twenty and also after sixty days and the aeid estimated by Liebig’s method.The percentages of the acid originally present found after twenty days varied from 47.7 to 87.5 and after sixty days from 41.4 to 63.3. No evidence of more rapid disappearance of the acid in presence of dextrose or proteins could be obtained and in this respect the behaviour of the acid seems to be different in the dead and living organism probably because active enzymes are present in the latter case. T. A. H. T. A. H. Influence of the Alkalinity of the Wash-Water on the Percentage of Water in Butter. W. MEYERINGH (Chem. Weeklad 19 10 7 951 -953).-Butter washed with acidified water appears t o have a lower percentage of fat than that washed with alkaline water. A. J. W. Reactions of Cyclic Amines. F. LAVILLA LLORENS (Anal.2%. Qwim. 1910 8 127-132).-The following bases give characteristic colorations when oxidising agents such as potassium permanganate potassium ferricyanide potassium or ammonium persulphate are added t o their solutions in dilute acid. Potassium permanganate is the best reagent to use a few drops of a 0.2% solution developing a coloration rapidly. Aniline greyish colour initially then more or less reddish-violet tinge which changes to a characteristic blue; this after a long time takes on a greenish hue.ANALYTICAL CHEMISTRY. ii. 79 Methylaniline gives the same indications as aniline. o-Toluidine in absence of much free acid a characteristic blue coloration distinct from that of aniline ; in presence of an increasing proportion of hydrochloric acid the colour changes to bluish-green or yellowish-grey.With acetic acid even in concentrated solution only the blue shade appears. The coloration given by aniline is nearly independent of the amount of free acid but with the toluidines and the following bases it varies greatly according t o the concentration of the acid. m-Toluidine initially reddish coloration changing to blue. p-Tohidine final coloration red. o-4-Xrylidine red colour slightly vioLet in shade. m-4-Xylidine red colour more violet than with o 4-xylidine. p-Xylidine ; red colour. a-Naphthylamine blue coloration ; P-nap?&Jamine ; greenish-grey Estimation of Urea. STANLEY R. BENEDICT (J. Bid. Chern. 1910 8 405-421).-l!he Folin method yields traces of ammonia nitrogen from creatinine rather more from uric acid and allantoin yields all its nitrogen.The method recommended is to add to the urine potassium hydrogen sulphate zinc sulphate a piece of paraffin and a little powdered pumice. The mixture is boiled to dryness and then placed in a sulphuric acid bath at 162-165' for an hour. The contents are then washed with water into a distilling flask sodium hydroxide added and distillation continued for forty minutes with standard acid. The residual acid is then titrated and the urea nitrogen calculated. W. D. H. GEOIXGES DENIGBS (Compt. reyid. 1910 151 1062-1063).-Ten C.C. of a solution of morphine or one of its salts (minimum concentration 0.03 gram per litre) are treated with 1 C.C. of hydrogen peroxide (5-12 vols.) and 1 C.C. of ammonia. After shaking one drop of a solution of copper sulphate containing 1-4% of the crystallised salt is added.On shaking again the liquid develops a colour varying from rose-pink t a intense red according to the amount of morphine present. Sparingly soluble morphine salts should be dissolved in a few drops of hydrochloric acid before dilution The reaction gives positive results with certain morphine derivatives such as apomorphine or heroine but not with codeine the baine papaverine narceine or narcotine. It has the advantage of being applicable to solutions containing organic matter such as sugar and to plant extracts. coloration only faint. vcT. a. I). New Reactions of Morphine. w. 0. w. Volumetric Estimation of Quinine in Drugs etc. JULIUS KATZ (Ber. Deut. pharm. Ges. 1910 20 316-329).-1n the method described the quinine (or cinchona alkaloids) is converted into its hydrogen salt by evaporating its alcoholic solution with an excess of hydrochloric acid ; sodium chloride is added to aid the evaporation of the excess of the acid and the quinine hydrochloride is then titrated with alcoholic potassium hydroxide solution using Pan i d s Blue asii.80 ABSTRACTS OF CHEXICAL PAPERS. indicator. The details of the process as applied to the estimation of quinine alkaloids in cinchona bark are as follows 6 grams of the dry and powdered bark are shaken for thirty minutes with 15 grams of chloroform and 5 grams of 5% sodium hydroxide solution; 1 gram of magnesia and 45 grams of ether are then added and the mix- ture is poured on a filter.Forty grams of the filtrate are evapor- ated to a volume of about 1 c.c. and the residue is rinsed into a porcelain basin with alcohol; after the addition of 10 drops of hydro- chloric acid and 0.25 gram of sodium chloride the mixture is evapor- ated to dryness. The residue after being dried for fifteen minutes in the water-oven is dissolved in alcohol 5 drops of a 0.2% Poirrier’s blue solution are added and the solution is titrated with N/lO-alcoholic potassium hydroxide solution.’ Each C.C. of the latter solution is Caution aB t o Testing for ‘‘ Saccharin ” in Sweetened Foods and Beverages. EZIO COMANDUCCI (Boll. chim. farm. 1910 49 791).-When solutions of dextrose and sucrose were extracted with a mixture of equal volumes of light petroleum and ether it was found that the residue after distilling off the ethereal liquid yielded on heating with resorcinol and sulphuric acid and subsequently treating with alkali and water a fluorescent solution the production of which has been regarded as a test for ‘‘ saccharin.” I f the ethereal extract is washed with water three or four times however the residue obtained no longer shows this reaction whilst “saccharin” would not be removed by such treatment. TAKAOHI SASAHI (Biochem.Zeitsch. 1910 29 395)-In the reaction already described (Abstr. 1910 ii 166) the iron salt concentration should not be too great. A convenient reagent is obtained by adding one drop of a 1% ferric sulphate solution to 100 C.C. of iron-free concentrated sulphuric acid. The methyl alcohol employed must be perfectly free from aldehydes S. B. 8. equivalent to 0.0162 gram of quinine. w. P. s. R.V. S. A Sensitive Reaction for Scatole. Iodometric Estimation of Antipyrine in Migrainine. C. SLEESWYK (Pharrn. Weekblud 1910 47 1282).-(‘ Migrainine ” is prepared by dissolving 90 parts of antipyrine 9 parts of caffeine and 1 part of citric acid in water and evaporating the solution to dryness on the water-bath. In order to test the commercial product the author uses the iodometric method originally proposed by Bougault and since modified by Zernik with a further modification. 1.351 Gram of iodine 2.5 grams of mercuric chloride and 1.1 gram of the sample are each dissolved in 200 C.C. of 95% alcohol ; 20 C.C. of the migrainine are then mixed with 20 C.C. of the mercuric chloride and the iodine is run in until the liquid turns yellow ; 1 C.C. of iodine = 0.005 gram of antipyrine. It is as well to check the iodine by means of pure antipyrine. The migrainine may also be dissolved in water instead of alcohol. The titration should be repeated the bulk of the iodine being added at once and the last drops more carefully ; the end- poink is then very distinct. L. DE K,

ISSN:0368-1769    

DOI:10.1039/CA9110005066

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 81 (3eneral and Physical Chemistry Recalcdlation of Atomic Refractions. FRITZ EISENLOHR (Zeitsch. plqsikal. Chent. 1910 75 585-607).-As certain factors for example optical exaltation mere not sufficiently taken into account in the older tables of atomic refrsctivities the author has recalculated the refraction for the Ha D Hp and Er lines and the dispersions Hp - Ha and Hv - Ha for a large number of non-aromatic compounds and from the results the atomic refractions and dispersions given in the accompanying table have been calculated. The experi- mental data is due mainly to Bruhl and t o Landolt and has been amplified by the author. On the basis of the new data benzene is found to show no optical anomaly. A tomic Re fractions. Ha. D. m* CH group .................. 4.598 4'615 4.668 Carbon ........................2'413 2.418 2.438 Hydrogen .................. 1 -092 1 -1 00 1 '1 15 Oxygen (in CO group) _.. 2'189 '2.211 2.247 (in ethers) ...... 1.639 1'643 1'649 Chlorine .................. 5.933 5.967 6.043 Bromine ..................... 8.803 8.865 8'999 Iodine ...................... 13.757 13.900 14.224 (in OH group) ... 1'522 1.525 1.531 Ethylene linking ......... 1 %86 1.733 1 *824 Acetylene ......... 2 -828 2 '398 2 -506 Hr 4'710 2.466 1.112 8.267 1.662 1.541 6'101 9'152 14.521 1.893 2.538 HB-TIa 0.071 0.025 0.023 0.057 0.012 0 006 0.107 0.211 0 '482 0'135 0.139 Hy-Ha. 0.113 0'056 0.029 0.078 0'019 0-015 0.168 0-340 0.775 0.200 0.171 G. S. Refraction and Magnetic Double Refraction of Solutions of the Rare Earths. G. J.ELIAS (Bey. Deut. physikal. Ges. 1910 12 956-962. Compare Abstr. 1908 ii 549).-The refractive index of an aqueous solution of neodymium nitrate has been measured for wave- lengths in the neighbourhood of the yellow absorption band. The data indicate the occurrence of slightly anomalous dispersion in this region. Preliminary observations of the double refraction produced by a solution of erbium nitrate in a transverse magnetic field are also recorded. The double refraction increases with the intensity of the magnetic field ; it is greater for blue than for yellow light and appears to be somewhat anomalous in the immediate neighbourhood of the absorption bands. No magnetic double refraction could be detected in solutions of neodymium nitrate mttnganous nitrate or ferrio chloride. The double refraction phenomena are examined theoretically.H. M D The Sequence of Chemical Forms in Stellar Spectra. SIR NORMAN LOCKYER (Proc. Roy. Xoc. 1910 A 84 426-432).-A brief account is given of recent work on the classification of stars on the YOL. c. ii cii. 53 ABSTRACTS OF CHEMICAL PAPERS. basis of spectroscopic observations and the influence of temperature on the spectra of ‘‘ chemical forms ” characterised by special molecular or corpuscular groupings. H. M. D. The Emission and Absorption of Luminous Gases from Experiments with Continuous Currents of High Intensity. WJLHELM JURGJOHANN (Zeitsch. wiss. Photochem. 19 10 9 84-1 03 105-1 29 141-1 68).-The intensity of the emission spectra obtained from nitrogen hydrogen carbon monoxide and oxygen when subjected to continuous currents in Wehnelt tubes has been measured for currents of varying intensity.I n the case of nitrogen and hydrogen the absorption was also investigated. The data for nitrogen show that the intensity of the first group of bands is proportional to the current density between 1.4 arid 12.7 amperes per square cm.; on the other hand that of the second group of bands increases more rapidly than the current density or the energy consumption. I n the case of bydrogen the variations of intensity of the spectrum do not appear to be related in any simple way with the current density or the energy consumption and the lines of the first subsidiary series behave differently according to the pressure of the gas in the discharge tube.The intensity of the red and green bands of carbon monoxide increases in a linear manner with the current density that of the blue bands more rapidly. With increasing current intensity the energy maximum is displaced in the direction of smaller wave-lengths. The conclusion drawn from these observations is that tho changes in the energy of the radiation from a luminous gas cannot be accounted for in a simple manner by the changes in the intensity of the current or by the variations in the energy consumption or yet by the corresponding changes in temperature. The Resonance Spectra of Iodine. ROBERT W. WOOD (PhpikuZ. Zeitsch. 1910 11 1195-1196 *).-Resonance spectra similar to those investigated previously in the case of sodium vapour are obtained quite readily when a large evacuated bulb containing a small quantity of iodine is subjected to the influence of white or mono-chromatic light.When. the fluorescence is excited by white light its colour is yellowish- green but a reddish-yellow fluorescence is obtained when the rays from a mercury lamp are used as the exciting agent Spectroscopic examination of the fluorescent light of iodine acted on by the mercury rays has shown that the spectrum consists of a series of i:olated lines separated from one another by intervals of about 65-70 Angstrom units. The investigation of the resonance phenomena can be carried out much more easily i n the case of iodine as compared with sodium for the fluorescence effects are developed by iodine vapour at the ordinary temperature. The Glow Discharge in Rubidium and CEesium Vapours. GEORG GEHLHOFF (Be?..Detct. physikal. Ges. 1910 12 963-969)- The phenomena accompanying electrical discharge through rubidium * and Phal. Uag. 1911 [vi] 21 261-265. H. M. D. N. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 83 and cssium vapour have been examined in a similar way to that described previously in the case of sodium and potassium (Abstr. 1910 ii 679). Discharge commences through rubidium vapour at about 120° and through cmium at 60-709 I n both cases the negative glow is at first yellowish-green in colour but a t a higher temperature rubidium exhibits a bluish-violet and caesium a sky- blue colour. The nature of the emission spectra of the negative and positive glow and the effect of the admission of small quantities of hydrogen nitrogen and air are described in detail (ccmpare following abstract).H. M. D. The Emission of the Series and Fundamental Spectra in the Glow Discharge of the Alkali Metal Vapours. GEORG GEALHOFF (Ber. Deut. physikal. Geu. 19 10 12 970-974).-The author compares the glow discharge emission spectra ol sodium potassium rubidium and caesium. Ail four metals show the lines of the principal and subsidiary series in the spectrum of the anodic glow light although i t is probable that the principal lines in the spectra of potassium rubidium and cssium are due t o the surrounding positive sheath. I n the case of sodium the spectrum of this positive column of light contains only the principal series of lines; in the case of the three other metals both principal and subsidiary series are observed although the secondary series is very faint for potassium.The negative glow spectrum of sodium shows the principal and subsidiary series whereas the corresponding spectra for the three other metals exhibit the secondary series lines and the fundamental spectrum. These relationships indicate a close relationship between the spectral emission and the atomic weight of the metal. It is assumed that the principal series lines are due t o impacts between the atoms and electrons of small velocity those of the subsidiary series t o impacts with electrons of intermediate velocity whilst the fundamental spectra are caused by impact of the atoms with high speed electrons. By taking into account the varying electropositive character of the alkali metals it is shown that various phenomena observed in connexion with the glow discharge can be satisfactorily accounted for. When the discharge tube contains both sodium and potassium vapours the positive glow and sheath exhibit the potassium spectrum.The negative glow shows the principal and subsidiary series of sodium lines and in addition the subsidiary series and the fundamental spectrum of potassium. This effect is explained in terms of the above assumption as due to the less electropositive character of the sodium. H. M. D. Absorption in Luminous Hydrogen. RUDOLF LADENBURG (Ber. Deut. physikal. Ges. 1910 12 1018-1022).-Polemical against Pfliiger (compare Abstr. 1910 ii S l l ) . H. M. 0. The Ultra-violet Absorption of Benzene. L. GREBE (Zeitsch.wiss. Photochem. 1910 9 130-140).-The absorption of ultra-violet rays by benzene in liquid and vapour form has been investigated. The spark discharge between aluminium electrodes under water was 6-2ii. 84 ABSTRACTS OF CHEMICAL PAPERS. used as a source of ultra-violet radiation and absorption spectra were obtained by means of a quartz spectrograph. I n the case of benzene vapour observations were made at temperatures ranging from 17O to 185O and the records show that this variation of temperature is practically without influence on the position of the absorption bands. The same result follows from the observations on liquid benzene at ZOO 43O and 70°. On comparing the positions of the liquid and vapour bauds it is found that the former are displaced in the direction of the visible spectrum by a nearly constant amount represented by 17 AngstrBm units.Prom experiments in ethyl-alcoholic solutions containing 0.1 and 50% of benzene respectively it is found that with diminishing concen- tration the bands are displaced in the direction of smaller wave- lengths. I n a 50% solution in ethyl ether the bands occupy the same position as in the corresponding alcoholic solution. Molecular Vibrations of Solid Substances. A. STEIN (Physiknl. Zeitsch. 1910 11 1209-1212).-0n the assumption that the mole- cules of solid substances are in vibratory movement and that the amplitudes of the vibrations are proportional to the distance between the centres of the molecules in the case of substances which have the same melting point the author deduces an expression for the relative frequencies of the molecular vibrations. This may be written in the form n,/n,= Jzz $</ Jml Vq in which rn n and v denote respectively the frequency the molecular weight and the molecular volume of a solid substance.According to the theory that the absorption of ultra-red rays is a consequence of molecular (or atomic) vibrations the values of n / r ~ ~ can be obtained from observations on the behaviour of solid substances towards ultra-red rays. From the mean frequencies of vibration of the residual rays obtained by Rubens by selective reflexion from plates of rock-salt sylvine potassium bromide and potassium iodide the values of nlln are obtained for the different pairs. On comparison of these ratios with the corresponding JG 2q/ JGl vc ratios it is found that the two series of numbers are approximately the same.A similar agreement is found by a comparison of the data for quartz and fluorspar. The values of Jm Jv are also tabulated for various series of metals having approximately the same melting points. These values indicate the existence of simple relationships for the relative magnitudes correspond very closely with simple integral ratios Influence of Substituent Groups on the Spectrum of Progressive Phosphorescence. JOSEPH DE KOWALSKI and J. DE DZIEEZBICKI (Compt. rend. 191 1 152 83-86. Compare this vol. ii 3) .-The progressive phosphorescence of the following substances has been examined at about - 190' in alcoholic solution benzoic acid the toluic acids the amino- and hy droxy-benzoic acids benzonitrile and the three toluonitriles.The wave-lengths of the principal bmdR are given. The substihent groups are found to have a marked influence on the spectrum of progressive phosphorescence ; those like H. IT. D. _ - - - H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 85 the CO,H and CN groups which extend it towards the red are termed 6‘ bathophosphic,” whilst those which prolong the spectrum towards the violet areecalled hypsophosphic. Examples of the latter are the hydroxy- and methoxy-groups ; the methyl group occupies an inter- Ultra-microscopic Observations. J. AMANN (Zeitsch. Chem. Inn. Kolloide 1913 8 11-15. Compare Abstr. 1910 ii 844),-1f strongly illuminated ultra-microscopic particles are examined by means of an ultra-microscope which is slightly out of focus the image of a particle presents the appearance of a series of concentric light and dark rings showing interference colours.With this arrangement the sparkling of the ultra-microscopic particles is much more evident than when the ultra-microscope is in focus. The sparkling effect is attributed to a variation in the amount of light reflected from a particle at different times in consequence of the irregular shape of the particle and its rotational motion. These movements are termed krypto-kinetic in order to distinguish them from Brownian motion. The phenomenon in question has also been observed in sections of yiixrtz from different sources. Solutions of potassium ferro- and ferri-cyanide under the ultra- microscope exhibit numerous large particleq. When subjected to white light LL large number of small particles suddenly appear and this so-called photo-phase is supposed to be the immediate cause of the evolution of oxygen from hydrogen peroxide when a solution of this substance is brought into contact with a previously insolated ferro- or ferri-cyanide solution (compare Weigert Abstr.1908 ii 5 ) . Observations of the colour of fluorescein under different conditions are recorded. According to these it appears that a colloidal substance may exhibit four totally different colours according to the method of illumination. H M. D. mediate position between these. w. 0. w. Micro-polarisation. EMIL FISCHER (Bey. 191 I 44 129-1 32. Compare Donau Abstr. 1908 ii 647).-The following pieces of apparatus are described 1.A small glass cylinder 20 x 7 mm. provided with a glass stopper. This is used for the preparation of small amounts of solutions of known concentration. 2. A pyknometer of the usual form but with very thick walls. so that it holds about 0.0’7 C.C. of liquid. These are of white glass 50 x 1.5 mm. and do not hold more than 1 C.C. 4. A narrow glass tube drawn out to a capillary for transferring the liquids from one vessel t o another. The light must be strong ; either incandescent gas light or the apparatus made by Schmidt and Haensch for obtaining homogeneous light from the Nernst lamp is recommended. An accurate balance is essential and very volatile solvent7 are to be avoided With tubes narrower than those described the sedimentation of the solutions does not take place. Action of Ultraviolet Rays in Accelerating Chenii cal Reactions and in Modifying a State of False Equilibrium.JEAN POUGNET (J. Pharm. Chem. 1910 [vii] 11 540-543).-Ultrs- 3. Observation tubes for the polarimeter. 3. J. S.ii. 86 ABSTRACTS OF CHEMICAL PAPERS. violet light accelerates the rate of change of plastic into rhombic sulphur of vitreous selenium into crystalline selenium and of barley sugar into the crystalline form. It also increases the velocity (I) of the transformation of potassium manganate into potassium permangan- ate ; (2) of the reaction between potassium permnnganate and oxnlic acid (3) of the inversionof sucrose by acids and (4) of the saponification of ethyl acetate by sodium hydroxide. T.S. P. Principal Types of Photolysis of Organic Compounds by Ultra-violet Light. DANIEL BERTHELOT and HENRY GAUDECFION (Compt. vend. 1910 151 1349-1352. Compare Abstr. 1910 i 349 814).-Hydrogen predominates in the gases formed when alcohols of the type CH,R*OH undergo decomposition through exposure to ultra- violet light ; the hydrocarbon R is evolved with the lower terms of the series with the higher members it remains dissolved in the slcohol. Hydrocarbons of the type R or RR’ are not formed in the case of alcohols with a branched chain but owing to the greater ease with which the lateral chain is broken methane and ethane occur in con- siderable quantity. Photolysis occurs more readily with the lower members of the alcohols aldehydes and acids than with the higher ones.Hydrogen (2 vols.) and carbon monoxide (1 vol.) are evolved from ally1 alcohol Carbon monoxide is the principal gaseous product when aldehydes are decomposed the proportion rising as the series is ascended ; hydro- carbons are also formed. Acraldehyde undergoes rapid polymerisation under the action of the light; the gas evolved contains carbon monoxide (80 vols.) carbon dioxide ( 5 vols.) hydrogen (5 vols.) and an un- saturated hydrocarbon (10 vols.). Citral gives carbon monoxide and hydrogen. Camphor forms carbon monoxide (5 vols.) and methane Acids give chiefly carbon dioxide accompanied by hydrogen and carbon monoxide with hydrocarbons in the earlier members of the series the latter diminishing as the series is ascended. (1 vol.). W. 0. W. Action of Light on Chlorophyll.P. A. DANGEARD (Compt. rend. 1910,151,1386-1388).-A simple method of demonstrating the effect of light of different wave-lengths on chlorophyll or other substances is to mix an alcoholic solution of chlorophyll with collodion and coat a glass plate with the mixture. When dry the plate is exposed to a good spectrum. After some hours colourless bands appear where action has taken place; the first band to appear corresponds with the principal absorption band of chlorophyll. w. 0. w. Canal Rays. JORANN KOENIGSBERGER and K. KILCHLING (Ber. Beut. pfiysikal. Ges. 1910 12 995-1017).-0bservntions relating to the nature and properties of canal rays are described with reference to the phenomena of dissociation neutralisation diminution in velocity and deflexion.H. M. D. HORACE H. POOLE (Phil. Mag. 1911 [vi] 21,58-62. Compare Abstr. 1910 The Rate of Development of Heat by Pitchblende.GENERAL AND PHYSICAL CHEMISTRY. ii. 57 ii 176).-New determinations of the rate of heat development from pitchblende by the former method gave as the results 8.15 6.5 and 6.2 ( x cal. per hour per gram) the last experiment which was the best agreeing well with the former determination 6.1. On the assumption that 1 gram of radium generates 110 cal. per hour the theoretical development should be 4.4. F. S. The Ratios which the Amounts of Substances in Radio- active Equilibrium Bear to One Another. HUGH MITCHELL (Phil. Mag. 1911 [vi] 21 40-42).-From the general solution of the equation giving the quantity of the nth substance in a dis- integration series after any time t the parent substance being initially free from products the correct relation between the quantities of the members of a radioactive series in equilibrium is deduced.The ratio of the number of atoms of the lzth substance to that of i t and all the preceding substances in equilibrium with it is the same as the ratio of the average life of the &,h substance to that of the parent sub- stance. The correct relation is thus A& = xn/(xI + x2 + x3 + . . . . xn) instead of A& = x,/xl as usually written. The correct relation makes no assnmption as to the relative periods of the parent and its products beyond the requirement that the parent element should be the longest- lived of the series. F. s. The Relation between Viscosity and Atomic Weight for the Inert Gases; with its Application to the Case of the Radium Emanation.ALEXANDER 0. RANKINE (PhiZ. Mag. 1911 [vi] 21 45-53).-From the temperature-coefficient of the viscosity of the inert gases Sutherland's constant C is calculated and from it the viscosities at the critical temperatures are deduced and found to be proportional to the square-root of the atomic weights for argon krypton and xenon. The value so found for helium is about sixteen times the value so calculated from its atomic weight but direct experiments by Schmitt of the viscosities of argon and helium from - 193' to + 184' have shown that whereas argon conforms to helium departs from Suther- land's equation the more seriously the lower the temperature. It is probable tbe equation fails so near to the absolute zero.The unknown critical temperature of neon calculated from the assumption that its viscosity at the critical temperature is proportional to the atomic weight and from Sutherland's equation is 6 1.l'A. Calculated from the relation that Sutherland's constant is proportional to the critical temperature it is 62.7"A. The viscosity of radium emanation a t Oo calculated from its atomic weight critical temperature and the value of Sutherland's constant which is taken as proportional to the latter is 2.13 x The molecular volume calculated from this is 16-97 times that of helium and larger than that of any other gas in the group. The deduction that the critical temperature and therefore Sutherland's constant is pro- portional to the fourth power of the true atomic radius is found to hold good strictly for all the gases except helium for which a departure is to be expected.F. S.ii. 88 ABSTRACTS OF CHEMICAL PAPERS Researches on Helium. IV. Absorption of Helium by Salts and Minerals. ARNALDO PIUTTI (Rend. Accad. Sci. Ris. Nut. Napoli 1910 [iii] 16 253-255 *).-The author finds that helium is absorbed by certain fused salts and minerals and points out the bearing which this has on the calculations of the age of rocks which have been made on the assumption that the helium contained in them has all been derived from radioactive elements. Crystals of potassium sulphate deposited in the course of a month from an aqueous solution in an atmosphere of pure helium did not absorb the gas.On the other hand antimonite borax and boric anhydride after fusion in an atmosphere of helium show the spectrum of the gas when they have been powdered in the air. I f air is passed through fused borax or boric anhydride and the fused mass then suddenly cooled by means of liquid air the solid obtained shows the spectrum of helium. No helium can be found when air has not been passed through the fused salt. The 7-Rays of Thorium and Actinium ALEXANDER S. RUSSELL and FREDERICK SODDY (Phil. Nag. 1910 [vi] 21 130-154. Com- pare Abstr. 1909 ii 460 851; 1910 ii 474).-The two types of thorium y-rays from mesothorium-2 and thorium-D resemble that of radium-C both in the ratio of the intensity of the y- to that of the /I-rays and in their penetrating power. Thorium-B gives the most penetrating y-rays known the absorption-coefficient X being from 8 to 21% less than for radium-C y-rays whereas for the mesothorium y-rays X is from 4 to 25% greater than for radium according to the experimental disposition used for the measurements.The y/P ratio for mesothorium is from 1-0 to 0.8 and for thorium-D 0.69 to 0.51 times that for radium-C. The proportion of y-rays contributed by the two thorium products in equilibrium in minerals is very similar. The y / P ratio of actinium is only from one-eighth to one-sixteenth of that of radium-C so that aotinium in this respect resembles uranium-X. The y-rays of actinium are abnormally highly absorbed by lead the absorption curve showing two sudden changes in the value of X at 0.3 cm. and 0.85 cm.whereas for zinc and aluminium the curves are exponential X being about 1.9 times that for radium-C. For lead the ratio ranges from about 8 times to about 2.2 times according to the part of the range examined and the disposition employed. Admixture of mesothorium with radium can be detected by the departure of the y-ray absorption curve in lead from the exponential form the y-rays of mesothorium being distinctly the less penetrating. Some generalisations with iegard to y-rays show that they are more allied in properties to the a-rays which precede and follow them in the series than to the /3-rays which accompany them. The penetrabilities of the y-rays from uranium-X mesothorium-2 radium-C and thorium-l) increase as the period of the product diminishes as for a-rays in general whilst the a-rays preceding and following these types of y-rays show the same increase in penetrating power as the y-rays themselves The greater the penetrating power of the yrays the less abnormal the absorption by lead as compared with other metals and the less is the hardening produced by passage through lead.* and Le Radzuczu 1911 8 13-14. R. V. S. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 89 The Ionisation of the Atmosphere Due to Radioactive Matter. A. S. EVE (Phil. Mug. 1911 [vi] 21 26-40).-The radio- active theory of the ionisation of the atmosphere is generally satis- factory but some results remain unexplained. Assuming the presence of the emanation in equilibrium with 80 x 10-l2 gram of radium per cubic metre of the atmosphere on the average the ionisation so caused by the a-rays is 1.63 ions (per C.C.per second) while thorium possibly contributes not more than one additional. From Wright’s values of tbe natural ionisation in an aluminium electroscope at Toronto on land and on the frozen surface of Lake Ontario the ionisation contributed by the y-rays from the radium in the earth isestimated to be in the free air about 2.5 which is smaller than that found in many experiments with lead-screened electroscopes and suggests that part of the penetrating radiation comes from the atmosphere. It is calculated however that the penetrating rags of the atmosphere from the emanation and its products must produce an ionisation negligible in comparison with that due to the a-rays and are one twenty-third as intense as the penetrating rays from the earth.The total ionisation of the air from all sources assuming the penetrating rays of the radium and thorium series in the earth to be equal and neglecting those from uranium and actinium is 4.35 which is some- what greater than the value normally found in c l e y weather. The fact that the ionisation over the ocean is scarcely less than over the land is the greatest objection to the radioactive theory of atmo- spheric ionisation for the amount of radium in sea-water is extremely small. It is calculated that there should be a rapid diminution of the effect due to y-rays from the earth with altitude detectable at an elevation of 100 metres while at 1000 metres the effect should be negligible I n an appendix Wulf’s results (PftysikaZ.Zeitsch. 1910 11 811) on the Eiffel tower are referred to as establishing this rapid diminution. F. S. The Radioactivity of the Leinster Granite. ARNOLD L. FLETCHER (Phil. Mag. 1911 [vi] 20 102-lll).-The whole mass of the Leinster granite covering 600 square miles contains radium the mean content being 1.7( x 10-12 gram per gram). Separate specimens showed quantities varying from 0.41 to 4-36 the specimens showing the highest and lowest amount coming from the same locality. Probably the distribution is fairly homogeneous throughout. The mica in the granite constituting about 20:k of the whole Contained about half the radium but the small quantity of thorium present did not seem to be concentrated in any constituent. One crystal of biotite showing countfess pleochroic halos and considerable radioactive darkening contained 11.87 units of radium but no thorium and in the three specimens of granite containing the most radium there was no thorium.I n ten out of twenty-three specimens the ratio between the radium and thorium was between 2.0 and 2.6 x 10-7 the mean ratio for the whole series being 2.4 x 10-7. Details are given of the methods employed including the latest form assumed by Joly’s arrangement for estimating thorium in minerals F. S.ii. 90 ABSTRACTS OF CHEMICAL PAPERS. A Spectroscopic Investigation of the Nature of the Carriers of Positive Electricity from Heated Aluminium Phosphate. FRANK HORTON (Proc. Roy. Xoc. 1910 A 84 433-449).-The value found for elm for the positive ions from heated aluminium phosphate indicates a molecular weight of the carrier of about 28 and the possibility that the molecules are either nitrogen or carbon monoxide.Two hours' heating of a platinum strip coated with aluminium phosphate generated sufficient ions t o allow of a spectroscopic examination of their nature. The spectrum was found to be the same whether the strip was heated simply or in an electric feld under conditions such that the ions would be formed and in the electrodeless ring discharge showed the lines of carbon and oxygen together with others due to mercury and hydrogen whilst in an electrodeless spectrum tube the banded spectrum of carbon monoxide was obtained. The conclusion is arrived a t that the positive ions are molecules of carbon monoxide. F. s.Relationship between Chemical Aenity and the Photo- electric Effects of Potaseium in its Compounds. ROBEBT POHL and P. PRTNGSHEIM (Ber. Deut. physikal. Ges. 1910 12 1039-1048. Compare Abstr. 1910 ii 923).-The photo-electric properties of potassium alloys have been investigated and it is shown that these are connected with the' electro-chemical properties of the metal with which the potassium is associated. A comparison of the results obtained for bismuth antimony and phosphorus alloys shows that the normal photo-electric effect of potassium is displaced in the direction of smaller wave-lengths as the metal in combination with the potassium becomes more electro-negative. The same behaviour is exhibited by the alloys of the series bismuth lead thallium mercury and gold.I n those cases in which a selective photo-electric effect can be observed this is also found to he displaced in the same direction as the electro-negative character of the second component of the alloy becomes more pronounced. A t the same time the range of wave- lengths which give rise to photo-electric activity becomes more restricted. Since the frequency of the active rays affords a measure of the velocity with which the electrons leave the molecule of the photo- electrically active substance it appears that the affinity between a metal and its electrons can be determined from observations on the wave-lengths of the raps which give rise to the photo-electric effect. H. M. D. Transference Experiments with Thallous Sulphate and Lead Nitrate. K. GEORGE FALK (J.Amer. Chem. Soc. 1910,' 32 1555-1571).-A study of the change of the transference number of tri-ionic salts with the concentration was carried out by Noyes (Abstr. 1901 ii 143) with the object of ascertaining whether intermediate ions such as KSO,' in the case of potassium sulphate and NO,Ba' in that of barium nitrate exist in appreciable quantities in solutions of such salts and the results were recorded for potassium sulphate barium chloride and barium nitrate.GENERAL AND PHYSICAL CHEMISTRY. ii. 91 Transference experiments have now been made with 0.03~V- and O'lNsolutions of thallous sulphate and lead nitrate at 25' with the aid of special apparatus. The cation transference numbers found for the thallous salt are 0.479 at 0.03Xand 0.476 at O*liV and those for the lead salt 0.487 at both concentrations.The limit of error in these results does not exceed & 0.003. The transference numbers at zero concentration as calculated from Kohlrausch's extrapolated values of t h e equivalent conductivities of the separate ions are 0.489 for thallous sulphate and 0.503 for lead nitrate and ale thus 2.5-3.2% higher than the values obtained by direct measurement a t a concentration of O.U3-0*1N. It is not certain whether this change of the traiisference number with the concentration is real. If so it might be due in the case of thallous sulphate to the presence of the intermediate ion TISO,'. I n the cace of lead nitrate however the presence of the intermediate ion N0,Ph' would probably cause a change in the opposite direction.The results of these experiments and those of Noyes (lac. cit.) on the transference values of tri-ionic salts indicate that either the inter- mediate ion is not formed to any considerable extent by the dissocia- tion of such salts up to concentrations of 0.1 or O-SN or that if it is formed its equivalent conductivity has a definite value of such magnitude as to render the transference number independent of its concentration. E. G. Method for Making Two Substances React in the Electric Arc. PAUL SABATIER (Compt. rend. 1910 151 1328).-An apparatus similar to that described by Salmon (this vol. ii 15) was employed by the author in 1899 (CongrBs Assoc. francaise I 229). W. 0. W. A New Property of the Magnetic Molecule. PIERRE WEISS (Compt. rend. 1911 152 79-81).-The niagnetic susceptibility of magnetite has been measured at different temperatures between 550' and 900° and the results plotted in the form of a curve.The conclu- sion is drawn that at certain temperatures the magnetic moment of the molecule increases by a definite aliquot portion of the magnetic moment at low temperatures and the supposition is advanced that this is due to a variation in the size of the molecule or in tha distance between the poles. w. 0. w. Use of the Magnetic Field as a m e a n s of Determining Constitution in Organic Chemistry. V. PAUL PASCAL (Bull. Xoc. chim. 1911 [iv] 9 6-12. Compare Abstr. 1910 ii 100 179).- Further evidence of the additive character of magnetic susceptibility in organic compounds is given (compare Abstr. 1910 ii 580) and the values of B (the correction which peculisrities of structure necessitate in calculating molecular suFcepti bility) are given for a number of compounds free from oxygen and chlorine.The atomic susceptibilities for the usual constituents of organic compounds are as C1= - 209.5 x 10-7 ; Br = - 319.2 x 10-7 ; I = - 465.0 x 10-7. Those for nitrogen sulphur and variously linked oxygen have been given follows H = - 30.5 10-7; c= - 62.5 10-7 ; F = - 63.0 x 10-7;ii. 92 ABSTRACTS OF CHEMICAL PAPERS. already (Abstr. 1910 ii 100). For saturated open chain hydrocarbons the value of B is nil and the molecular svsceptibility is given by the formula XM= - 10-7[n62.5 + (2n+ 2)30.5]. For a single open chain ethylenic linking B= + 57 x 10-7 and for two or more such linkings +110 x 10-7.For a double linking between two nitrogen atoms B= + 19 x 10-7 for one between a carbon and a nitrogen atom it becomes +85 x 10-7 and for two such linkings i t is + 106 x 10-7 but for a triple linking as in *CN it falls to + 8 x 10-7. The influence of the cyclopropane nucleus is B= + 75 x which is much greater than that +31 x 10-7 due to the cydohexane nucleus. Similarly for the piperidine nucleus B = + 37 x I n cydohexene derivatives B = + 72 x 10-7 and in cyclohexadiene compounds it is + 110 x 10-7. Theso cases illustrate the general ruIe that the diamagnetism of the molecule in closed chain compounds falls with increase in the number of certain kinds of double linkings present. Solutions. 111. and IV. F. SCHWERS (Zeitsch. phpsikal.Chem. 1910 75 615-620 621-627; Bull. SOC. cAim. 1910 [iv] 7 1072-1077 1077-1083.+ Carnpare Abstr. 1910 ii. 1039).- 111.-Eelationship between the Density and the Magnetic Rotation of the Plane of Polarisation of Binary Mixtures.-It is shown from the data of Sir W. H. Perkin that the ratio between the alterations of the deneity (difference between observed density and that calculated according to the mixture rule) and the alterations of the magnetic rotation (difference between observed and calculated rotation) is a constant for mixtures of the two components in any proportion. The constant 2 has a definite value for each system and when solutions of the same substance (water) in the different members of an organic series are examined 2 is found to increase with increasing molecular volume.It is shown by reference to mixtures of sulphuric acid and water and of nitric acid and water that when electrolytic dissociation occurs 2 diminishes steadily with increasing dilution. IT.-Density Befractivity and Alagnetic Rotation of Dissociating Mixtzcres.-As in the case of sulphuric and nitric acids the constants 2 for hydrochloric hydrobromic and hydriodic acids in aqueous solution also diminish on dilution. When the molecular volume is increased by substitution of iodine or bromine for chlorine the rotation constant diminishes and the refraction constant (calculated in a similar way) increases. When however the increase of molecular volume is due to an increase in the number of atoms in the molecule the effect on the coostsnt,s is the converse of that mentioned above.Electrolytic dissociation brings about an increase of the magnetic rotation of the plane of polarisation and a diminution of the refractivity with reference to the density if the latter is regarded as constant. G. S. The Isolation of Long-waved Heat Rays by Quartz Lenses. HEINRICH RUBENS and ROBERT W. ~ ' O O D (Sitxungsber. K. &ad. Wiss. Berlin 1910 1122-1137).-A method is described by means of which heat rays of wave-lengths ranging from 80p to 2 0 0 ~ Ic and BdI. Acnd. roy. Belg. 1910 850-883. T. A. H.GENERAL AND PHYSICAL CHEMI9TRY. ii. 93 Can be isolated from the rays emitted by an incandescent mantle. The rays from the mantle are passed through two quartz lenses which are suitably placed with reference to the source of light and the isolation of the longwaved rays is essentially dependent on the selective refraction of the quartz lenses The bundle of rays obtained by this method is far from homogeneous but the energy content is much greater than that of the homogeneous rays obtained by selective reflexion.By means of a radio-micrometer the distribution of energy amongst the component rays of the bundle has been examined and these measurements show a maximum intensity in the neighbourhood Observations are also recorded which show the extent t o which the long-waved rays are absorbed by various solid liquid and gaseous substances and a comparison is made between the amounts of these rays and of those obtained by selective reflexion from potassium bromide (A = SZp) which are reflected; by various substances.I n the case of rock-salt fluorspar and glass the proportion of the reflected quartz rays is in good agreement with that calculated from the dielectric constants of those substances. of A = loop. H. M. D. A Simple Automatic Stirrer for Use with the Depressi- meter. LODEWYK TH. REICHEH. (Chem. Weekblad 1910 7 1085-1087). -The author has devised an automatic stirrer for use with the depressimeter. A copper disk supported by a horizontal axle held by a clamp is connected with a jointed iron rod by means of an eccentric attachment. A horizontal arm connects the rod with the vertical stirrer. The bearing of the rod can be moved nearer to or further from the centre of the disk thus diminishing or increasing its eccentricity. The motive power is supplied by a hot air engine through a belt to the copper disk.A. J. W. Vapour Pressures of Binary Mixtures in the Light of van der Waals’ Theory. 11. PHILIPP KOHNSTAMM (Zeitsch. plqsikal. Chem. 1910 75 527-551. Compare Abstr. 1901 ii 145).-Considerable light is thrown on the vapour-pressure curves of binary mixtures by a mathematical treatment based on the introduc- tion by van der Waals of a new factor the vapour pressure of an ideal binary mixture the ‘‘ mixture assumed as uniform,” defined as follows. In the ordinary pu-diagram for a single substance the part of the isothermal joining the points on the diagram representing the gas and liquid phases is a straight line but in the case of a binary mixture the corresponding part of the diagram will be a sloping and not a horizontal line (as evaporation does not occur at constant pressure).The ‘‘ uniform mixture ” is an ideal mixture such that the line in question is horizontal as for a simple substance. By making use of the (hypothetical) critical pressures and temperatures of such mixtures a number of deductions as to the possible types of binary vapour-pressure curves are made. For the method used and the forms of the curves on different assumptions as to the relative magnitude of the factors concerned the original paper shotild bb consulted. G. s.ii ABSTRACTS OF CHEMICAL PAPERS Method for Determining the Molecular Weights of Dissolved Substances by Measurement of Lowering of Vapour Pressure. ALAN W. C. MENZIES (J. Amer. Chern. Soc. 1910 32 1615-1624).-Apparatus is described for the determina- tion of molecular weights in cases in which great accuracy is not required.It consists of an outer tube in which the solvent is boiled attached to a small reflux condenser and an inner test-tube provided with a pressure gauge-tube and a glass stopper. The side-tube from the outer tube to the condenser is of 1 cm. diameter so that the solvent may boil under the barometric pressure and is connected to the condenser by means of rubber tubing furnished with a screw-clip. When the stopper is removed atid the clip closed the vapour of the liquid boiling i n the outer tube escapes through the gauge-tube which is open at both ends into the test-tube. A narrow U-shaped side- tube connects the condenser with the lower part of the outer tube and the condensed liquid is thus returned to the outer tube without cooling the upper part of the test-tube. Both the test-tube and gauge-tube are graduated.The lower end of the gauge-tube is in the form of a bulb which is perforated by a number of holes t o distribute the vapour as it issues. The boiling solvent in the outer tube maintains at a constant temperature the test-tube which contains the solution the vapour pressure of which is being determined. The pressure is measured by the difference in the level of the liquids in the gauge-tube and test-tube. The values of K,,,=p-p' (where p is the vapour pressure of the solvent and p' that of the solution) that is the lowering of vapour pressure in mm. of boiling solvent that would be caused by the presence of 1 gram-mol.of a non-volatile solute in 1 litre of solution have been calculated for various solvents. The molecular weight can be calculated from the formula M = 1000 WKB/L Y x 760 where W is the weight of solute added L the measured lowering of the vapour pressure in mm. V the volume of the solution in c.c. and B the height of the barometer. A series of determinations carried out with this apparatus are quoted and the method is compared with ebullioscopic methods. It is sliown that within the limits of error uf observation the vapour pressures are identical whether determined by static or dynamic methods and that if any difference at all exists betKeen the vapour pressure at the b. p. as measured statically and dynamically of water and alcohol such difference does not exceed 0.01 mm.of mercury. E. G. Convenient Form of Apparatus f o r the Measurement 0 the Vapour Deneities of Easily Volatile Substances. ALAN w. c. MENzIES (J. Amer. Chern. soc. 1910 32 1624-1628).-The apparatus described is a slight modification of that recommended by the author for the determiriationof molecular weights of dissolved substances (preceding abstract). The test-tube is closed a t the lower end by the introduction of 6-8 C.C. of mercury which also serves by its rise in the gauge-tube to indicate the increase of pressure in the test-tube. T ~ Q substance the vayour density of which is to be determined isGENERAL AND PHYSICAL CHEMISTRY. ii. 95 placed in small glass bulbs each provided with a capillary which is sealed off before the final weighing.The bulb is attached to the lower end of the stopper of the test-tube by inserting the point of the capillary into a hole drilled in the stopper and wedging it in with a few shreds of dry asbestos. The hole is made in an oblique direction so that the neck of the bulb may be broken by rotating the stopper in such a way as to force the bulb against the top of the gauge-tube. I n order to obtain a constant for the apparatus a quantity of benzene sufficient to give a rise in the mercury level of about 100 mm. is weighed in a small bulb and the latter is attached to the stopper of the test-tube. A liquid of suitable b. p. is placed in the outer tube and caused to boil steadily so that its vapour surrounds the whole of the closed portion of the test-tube.As soon as the mercury in the gauge-tube has attained a constant level the stopper of the test-tube is rotated in order to break the neck of the small bulb which falls on to the surface of the mercury. The mercury instantly rises in the gauge-tube and reaches a constant level in a few seconds The rise in the mercury column is observed and a correction made by adding the amount of the slight fall of the level of mercury in the test-tube. Prom the data (1) weight of benzene taken (2) molecular weight of benzene and (3) rise of mercury in mm. the required constant K is calculated representing the rise in mm. which would be caused by the volatilisation of one gram-mol. of any substance in the apparatus a t the particular tem pera ture. The molecular weight of a substance can be calculated by means of the formula M - V K / R where li is the rise of the mercury in mm.and W the weight of substance taken. It is not suitable for temperatures above 200° but determinations are quoted which show that the method is both rapid and accurate at other temperatures. E. G. The apparatus is compact and can be easily manipulated. Fall of Temperature in Vapours of High Molecular Complexity at Small Pressures. C. VON RECEIENBERG (Zeitsch. physikal. Chem. 19 10 75 628-636).-Polemical against Hansen (Abstr. 1910 ii 827). No new facts are adduced. G. S. Critical Phenomena in Solutions under the Kardioid Ultra-microscope. W. G. VON LEPKOWSKI (Zeitsch. physikul. Chem. 19 10 '75 608-6 14).-The ultramicroscope in its latest improved form has been employed to elucidate the nature of the opalescence in binary mixtures in the critical region.The results are on the whole in favour of Donnan's theory (Abstr. 1904 ii 240) that the oFalescence is due to minute drops. A mixture of amylene and aniline critical temperature 14*%-14.5° was used for the experiments. On cooling progressively from room temperature ZOO a grey field with a clear circle in the middle was observed; at a certain point the previously clear field appeared as a rapidly agitated mass in which separate particles could not be dis- tinguished. As the temperature is further lowered (but still above the critical temperature) the flickering becomes still more pronounced theii. 96 ABSTRACTS OF CHENICAL PAPER% ultramicroscopic particles moving with enormous velocity.Suddenly relatively large drops appear and the critical temperature is reached. The phenomena appear in the converse order on warming. Particles from the small drops are projected into the bulk of the liquid with enormous velocity ; the drops become smaller and smaller and finally disappear. The remarkable observation was made that when a relatively large drop is warmed until it has disappeared and even the flickering has stopped i t reappears on cooling at the same point and with the same contours. This phenomenon occurs repeatedly on warming and cooling. It may be taken as showing that the rate of diffusion in the critical region is very small. G. S. Sublimation Apparatus. EMIL DIEPOLDER (Chem. Zeit. 191 1 35 $).-The apparatus consists of a wide glass tube sealed at the lower end and closed at the upper by a rubber cork carrying two tubes one of which serves for the entrance of air or other gas whilst tho other is attached to a wider tube which fits accurately into the outer closed tube and acts as a receptacle for the sublimate.The substance to be sublimed is contained in a small beaker placed at the bottom of the outer tube. The apparatus may be used for sublimation either at the ordinary or under diminished pressure. F. E. Therniochemical Studies of Some Binary Compounds of the Alkali and Alkali-earth Metals. ROBERT DE FORCRAND (Compt. rend. 1911 152 27-31).-The author has collated in tabular form the best existing data for the heats of dissolution and formation of the chlorides bromides iodides fluorides and oxides of calcium strontium barium lithium sodium potassium rubidium and cesium. Deter- minations of the heats of dissolution of the following anhydrous compounds were made to complete the series.The values are in Calories. Ca12 + 28.12 Lip - 1.04 RbCl - 4.50 RbBr - 5.96 RbI - 6 50 RbF + 5-80 CsCl - 4.68 CsBr - 6-73 CsI - 8.25 CsP + 8-37. The data are discussed from the point of view of Berthelot’s principle of maximum work. w. 0. w. Thermochemistry of the Silicates. EMIL DITTLER (Zeitsch. anorg. Chem. 1911 80 273-304. Compare Abstr. 1909 ii 970).- The difficulties of obtaining correct cooling and heating curves in the case of silicates owing to the suspended transformation effects are fully discussed and the precautions which must be taken are enumerated.Thermal and optical measurements on diopside from Zermatt adularia from St. Gotthard oligoclase-albite from Wilmington (Delaware) labradorite from Kiew an artificial labradorite artificial anorthite and anorthite from Pizmeda are given. Owing to the extremely small velocity of melting the absorption of heat a t the melting point is not the chief factor in the heating curve so that with different velocities of heating the melting point will occur at diBerent points in the curve. Melting point determinations on large fragments must be avoided since they are more readily super- heated than a fine powder and thus give higher results.GENERAL AND PHYSICAL CHEMISTRY. ii. 97 Geologically freezing points are more important than melting points and are generally lower than the latter owing to undercooling.The temperatures a t which cry stallisation begins to take place in various minerals are as follows artificial diopsicle 1?90-1250° ; artificial labradorite 1 230° ; labradorite from Kiew 1200-1 160' ; artificial anorthite 1310' ; anclrthite from Pizmeda 1200'. The temperatures a t which crystallisation is complete could not be determined. T. S. P. Determinations of the Law of Chemical Attractions between A t o m s from Physical Data. RICHARD D. KLEEMAN (Phil. Mag. 19 11 [vi] 21 83-102).-From data of Ramsay and Young and Mills relating to surface tension and latent heat of benzene chlorobenzene carbon tetrachloride and methyl formate and to the critical density of ethyl ether Py-dimethylbutane Pedimethylhexane isopentane n-pentane rb-hexane n-hept ane n-octane benzene cyclohexane fluoro- benzene chlorobenzene bromobenzene iodobenzene carbon tetra- chloride and stannic chloride various consequences of the mathe- matical expressions deduced in previous ptLpers are tested.F. 8. Recovery of Hammered Materials. L ~ ~ o N GUILLET (Compt. rend. 1910 151 1127-1128).-Experiments on hard and soft steel and on nickel show that complete recovery on annealing characterised by attainment of maximum length occurs in each case at 750-800". The curves showing elasticity on traction exhibit two elastic limits one constant and characteristic for the metal in the ordinary state the other variable with the temperature of recovery. The metals in this respect behave as heterogeneous materials of which only one constituent shows the effects of hammering w 0.w. Some Abnormal Temperature-coefflcients of the Molecular Surface Energy of Organic Substances. PAUL WALDEN (Zeitsch physikccl Chern. 1910 75 555-577).-According to the EotvGs- Rarnsny-Shields rule the temperature-coefficient of the molecular surface energy d [ y ( Mv)3]/dt is about 2.121 for unimolecular sub- stances for associated substances it is less and for dissociated sub- stances greater The author now finds that the coefficient in question is 6-21-5.35 for tristenrin and 5.57-4.92 for tripalmitin between 60' and 120° whereas the molecular weights according to cryoscopic determinations with a number of organic solvents are normal. The coefficient for the isobutyl ester of ricinoleic acid amounts to 3.24-3-30 between 2 3 O and 86' whilst its molecular weight is normal.The above rule therefore does not hold even approximately and the deviations appear to be the greatest for complex substances of high boiling point. The surface-tension of solutions of tripalmitin and tristearin in benzene has also been measured. The average value of the coefficient for both solutions calculated according to the mixture rule is about 2-18; the solutions therefore behave as non-associated and non-dissociated liquid systems. On the other hand two hydroxyl-free solvents with abnormally small coefficients of molecular surface energy succinonitrile and formamide VOL. C. ii. 7ii. 98 ABSTRACTS O F CHEMICAL PAPERS. have been investigated. From the results of surface-tension mc'asure- ments the coefficient for the nitrile between 80' and 100' is 0.565 indicating a moleciilar complexity of 7.27 from 100-118' it is 0.601 the complexity being 6.63.For formamide between 5' and 60° the coefficient varies from 0.638 to 0.710 corresponding with a molecular coniplexity of 6975-5.1 7. The conclusion that these two compounds are highly associated is confirmed by cryoscopic and ebullioscopic measurements. G. S. EMIL HATSCHEK (Zeitsch. Cliem. Ind. Kolloide 1911 8 34-39. Compare this vol. ii 19)-On the basis of certain assumptions relating to the form and distribution of the disperse phase in the dispersive medium the author has examined the changes which should result from the disturbance of the normal arrangement of the disperse phase as a consequence of the relative movement of juxtaposed layers of an emulsion and has deduced a relationship between the viscosity of the emulsion and that of the dispersive medium.The effect of this relative movement such as is involved in the flow of the emulsion through capillary tubes is dependent on the relative magnitudes of the surface tension and the viscosity of the disperse phase if the proportion of this is very large and a decrease in the viscosity of the disperse phase is shown to be accompanied in certain circumstances by an increase in the viscosity of the emulsion. For a disperse system of this type there is a critical velocity of displacement of juxtaposed layers a t which an abrupt change takes place in the viscosity and this velocity is determined by the rate at which the particles of the disperse phase regain their original structural form when deformed as a result of the lateral displacement of these layers.For velocities of displacement greater than this critical value the relationship between the viscosity of the emulsion and that of the dispersive medium is expressed by ql = 77 If/( v'- l) in which yr and q are the viscosities of the emulsion and the dispersive medium and f i s the ratio of the volume of the emulsion to that of the disperse phase. For velocities of displacement smaller than the critical value the mathematical treatment of the question presents difficulties but it is shown that the viscosity of the system under these conditions must be greater than for greater velocities The Viscosity of Dispersoids.H. M. D. The Phenomenon of Agglomeration in Finely Powdered Substances. M. C. SCHUYTEN (Chem. Zeit. 1910 34 1357).- A sample of pure iron powder kept for fifteen years in a well stoppered bottle which had not undergone oxidation had formed a globular mass with a peculiar goose-neck shaped excrescence. Barium sulphate prepared by mixing equivalent proportions of solutions of barium chloride and ammonium sulphate gradually formed conical excrescence reaching a length of 6-7 cm. The author ascribes these phenomena to pbysical actions. Globular Appearance of Certain Precipitates. FRIEDBICH BARDACH (Chem. Zeit. 191 1 35 33).-The globular or flocculent L. DEE.GENERAL AND PHYSICAL CHEMISTRY. ii. Y9 appearance assumed by finely divided substances such as precipitated barium sulphate etc.has been fully discussed by Quincke (Abstr. 1902 ii 200) and others who attribute the phenomenon to the action of osmotic pressure surface tension etc. The outer surface of the flocks has a characteristic appearance whilst the interior frequently exhibits a cell-like structure. w. P. s. Parallelism between the Occurrence of Cohesion and the conditions Necessary for Dyeing. AC’GUSTE ROSENSTIEHL (Bull. Xoc. chim. 1911 [iv] 9 12-18. Compare Abstr. 1909 ii 796).- A number of cases are quoted showing that the conditions under which cohesion occurs between the same or different substances are exactly analogous to those under which the dyeing of fabrics takes place and it is suggested that cohesion between dye and fabric plays the principal rAle in this operation although chemical affinity between dye and fabric may also be operative Deduction of the General Phase Theorem for Adsorption Systems. P.N. PAWLOPF (Zeitsch. physilal. Chem. 1910 75 552-554).-The form of the phase rule for a system capable of adsorption is deduced mathematically; it is similar t o that for a system in which adsorption does not occur. Condensed disperse systems capable of absorption have six kinds of variables whereas T A. H. colloidal adsorption systems are characterised by seven variables. G. S . A New Proof of the Existence of an Adsorption Equili- brium in Hydrosols. ALFRED LOTTERMOSER and P. MAFFIA (Ber. 1910 43 3613-3618).-Experimental results are recorded in support of the view that electrolytes are adsorbed by hydrosols in accordance W i t h an exponential law.Freshly precipitated ferric hydroxide was dissolved in ferric chloride solution and n portion of the electrolyte removed by filtration through collodion. The contents of the filter were then diluted with water and the solu- tion again filtered this process being repeated until a hydrosol containing relatively little chlorine was obtained. From this hydrosol a series of others were prepared by addition of varying quantities of water and each of these was then subjected to filtration through collodion. The chloride in the various filtrates was estimated and by difference the adsorbed chloride was ascertained. Denoting by c the number of millimols. of chlorine per C.C. of the filtrate and by xlm the millimols.of chlorineadsorbed by one gram of ferric oxide it is found that the experimental data can be satisfactorily represented by the equation x/m = P.cl/P in which /3 = 2-83 and l / p = 0.163 are constants. Similar results were obtained in the investigation of a ferric oxide hydrosol prepared by addition of ammonium carbonate to a solution of ferric chloride. ‘‘ Anomalous ” Adsorption. WILLIAM M. BAYLISS (Zeitsch. Chena. Id. Kolloide 191 1 8 2-4).-The so-called ‘‘ anomalous ” adsorption recently observed by Biltz and Steiner (Abstr. 1910 ii 830) can be accounted for on the basis of the author’s observations on electric H. M. D. 7-2ii. 100 ABSTRACTS OF CHEMICAL PAPERS. adQorption ” (Abstr. 1906 ii 344). I n these experiments filter- paper was the adsorbent and this becomes negatively charged in contact with water.I n consequence of this electric charge electro- positive colloids are attracted by the paper whilst electro-negative colloids are repelled. In presence of neutral salts the negative charge is ‘partly or completely neutralised by the cation and as a result the adsorption of electro-negative colloids is facilitated whilst that of electro-positive colloids is hindered. This neutral salt action ex- plains the absence of ‘‘ anomalous ” adsorption in the experiments of Biltz and Steiner when dialysed night-blue was used instead of the commercial substance. It also accounts for the approximately normal adsorption observed in the experiments in which dilute solutions of the dye were examined. H. M.D. Capillary Analysis of Colloidal Solutions. NAIMA SAHLBOM (XoZZ. Chem. BeiThefte 19 10 2 79-141).-The behaviour of colloidal solutions of it number of inorganic substances has been investigated by observations of the capillary efYects produced when long strips of filter paper are supported with the lower edges immersed in the solutions. It has been found that the positive colloids are precipitated at the surface of contact whereas negative colloids rise through the capillary network without hindrance. The precipitation of tha positive colloids is not due to chemical action but to the setting up of an E.M.F. as a consequenco of the streaming of the liquid through the capillaries ; this potential difference brings about the discharge OF the positively charged colloidal particles.If the capillaries are not sufficiently narrow the resulting E.M.P. is not large enough to give rise to complete pre- cipitation and a rise of the positive colloid is observed. A detailed examination of the phenomena observed in the case of colloidal ferric hydroxide has shown that the free acid present in an incompletely dialysed solution prevents complete precipitation. Addition of acid to a completely dialysed hydrosol has the same effect. The capillary phenomena exhibited by solutions of colouring matters are in many cases closely similar to those observed with inorganic colloids. EL M. D. Capillary Electrical Precipitation of Positive Colloids. FRITZ FICHTER (Zeitsch. Chem. Ind. Kolloide 1911 8 1-2. Compare preceding abstract).-The precipitation of positive colloids as a result of the production of electrical forces by difeusion through capillary tubes has been further examined by experiments with parallel glass plates.When a drop of a dialysed colloidal solution of ferric hydroxide is placed on one of the plates and the second plate is allowed to sink slowly on to the former i t is found that the thin layer of solution between the plates exhibits a sharply defined circular opalescent zone in consequence of the precipitation of the positive colloid. A similar phenomenon is observed with colloidal solutions of chromic oxide zirconium dioxide and thorium dioxide. With coloured solutions of basic dyes such as night-blue and methylene-blue the visible effect is still more pronounced. Prom the dimensions of the circular zone of precipitation and theGENERAL AND PHYSICAL CHEMISTRY.ii. 101 weight of the solution between the plates the critical distance between the plates requisite for the production of the precipitation can be calculated. In the case of ferric hydroxide this was found to be 0.0322 but this is very much smaller than the value (0,075 mm.) expected on the basis of experiments with capillary tubes. The much smaller value is probably due to mechanical displacement of the precipitation zone when the plates are brought together. In similar experiments with solutions of negative inorganic colloids and acid dyes no precipitation effects are observed. H. M. D. Origin of Internal Pressure in Solutions. V. POLOWZOFF (Zeitsch. physikal. Chem. 1910 75 513-526).-According t o Tammann (Innere Xrafte und Eigenschuften der Losungen; Leipzig 1907) the greater internal pressuro in a solution as compared with the pure solvent is due to attraction between solvent and solute and is of the same nature in electrolytes and non-electrolytes.Drude and Nernst (Zeitsch. physikcd. Chem. 1894 15 79) on the other hand ascribe the increased pressure at least in the case of electrolytes t o the effect of the electrostatic field of the ions (theory of electrostriction) and in accordance with this view it has been found that the complete ionisation of a mol. of a binary salt is attended by a contraction (resulting from the increase of pressure) of 13-14 C.C. In the present paper further evidence is advanced in favour of the electrg- striction theory.From observations on the density of solutions of monochloroacetic acid in different dilutions the degree of dissociation of the salt being known it is calculated that the complete ionisation of a mol. of the salt is attended by a contraction of about 10 C.C. On the other hand the apparent molecular volume of ethyl alcohol in benzene only varies slightly from dilute to very concentrated solutions although the molecular complexity greatly diminishes on dilution. This is difficult to reconcile with Tammann’s theory as an increase in the number of molecules should cause increased attraction between solvent and solute and therefore increased internal pressure and consequent contraction The data of Ritzel (Abstr. 1907 ii 740) on the compressibility of solutions of ethyl alcohol in benzene are also in favour of the view that the internal pressure does not increase on dilution.Finally it is shown by an indirect method that the dissociation of amyl acetate into amylene and acetic acid is attended by an increase and not by a diminution of volume. This is in agreement with Nernst’s theory-as no ions are concerned there can be no electrostriction. The electrostriction theory cannot of course account for the increased internal pressure caused by dissolution of non-electrolytes such as the sugars and glycerol in water ; these solutions require further investigation. G. S. Influence of Foreign Substances Dissolved in the Mother Liquor on the Faces of Crystals of Meconic Acid and on their Pseudopolychroism. PAUL GAUBERT (Compt.rend. 1910 151 1134-1 136. Compare hbstr. 1906 ii 152).-Meconic acid occurs in OrthorhQmbic hemimorphic cry staia having curved faces andii. 102 ABSTRACTS OF CHEMICAL PAPERS. showing marked double refraction [a b c = 0.613 1 0.900 ; a = 63O p= 138’1. Addition of different substances to the solution in which the crystals are growing may modify the crystalline form to a con- siderable degree ; thus picric acid produces elongation in the direction of the axis a whilst methylene-blue elongates the axis 6. The extent of elongation depends on the amount of foreign matter absorbed by the crystal. A large quantity of methylsne-blue produces hemimorphism the crystals being H-shaped. Addition of carbamide to the mother liquor causes the crystals to exhibit pseudopolychroism when viewed through a Nicols’ prism.This appears to be due to the presence of microscopic bubbles which produce partial absorption through repeated reflexion. w. 0. w. Theory of the Phenomena of Transition between Colloidal and True Solutions. P. P. VON WEIMARN (Zeitsch. Chem. Ind. Kolloide 191 1 8 24 -33).-A theoretical paper in which the author discusses the relationships be tween unsaturated supersaturated and colloidal solutions in reference to the action of the dispersive and coagulating forces. The hydrosols of slightly soluble substances are qualitatively differentiated from the corresponding unsaturated solutions by the fact that continuous condensation takes place in the former. I n accordance with this view the disperse particles are not amorphous but are characterised by vectorial structure.The forces which determine the vectorical arrangemept are peculiar to the molecules and the play of these forces is not inhibited by the excessive development of the surface which is characteristic of colloidal systems. Observations relating to the precipitatioa of supersaturated solutions of barium sulphate are cited in support of the author’s views. H. M. D. The Micellary or ‘‘ Colloidal ” State. GIOVANNI MALFITANO (Koll. Clhern. Beihrzfte 1910 2 142-212).-A theoretical paper in which the relationsbips and differences between the colloidal and crystalloidal states and between the processes of coagulation (floccu- lation) and crystallisation are examined. In part the theoretical con- siderations have reference to experimental observations publisbed previously (Abstr.1909 ii 473) on the behaviour of solutions of ferric chloride. H. M. D. The Saturation Capacity of Colloidal Compounds. WALTH~RE SPRING (Bull. SOC. chim. Belg. 1910 24 446-453 ; Arch. Sci. plt,ys. 32at. 1910 [iv] 30 561-571).-0bservations relating to the influence of saponin on suspensions of soot in water are described which seem to show that the capacity of colloidal substances to form complex aggregates is limited in a similar way to that observed in the case of chemical combination. From preliminary experiments with solutions of saponin it appears that this substance occupies a position intermediate to the colloids and crystalloids. Its solutions show the Tyndall effect and under theGENERAL AND PHYSICAL CHEMISTRY.ii. 103 influence of a current the saponin moves towards the anode ; on the other hand dialysis experiments show that it undergoes diffusion. To ascertain the influence of saponin on the durability of soot suspensions solutions containing from 7.5 to 0.0045% of saponin were shaken up with the same quantity of soot carefully freed from fatty matter by extraction with benzene and the times required for the clarification of the solutions were observed. From these data it appears that R solution containing between 3.5 and 3% of saponin is most favourable to the persistence of the suspension. If the solutions are made either slightly acid or alkaline clarification takes place in all cases very quickly and there is no optimum effect. When a current is passed through the most durable suspension the soot migrates to the anode although a pure aqueous soot suspension shows the opposite effect.This indicates the formation of colloidal aggre- gates as a result of the adsorption of saponin by the soot. The effect of saponin on the behaviour of suspensions of soot when subjected to filtration has been examined and it appears that the adsorption of the soot by other substances such as filter-paper is to a large extent prevented by reason of the formation of soot-saponin aggregates. The view that the formation of colloidal aggregates or adsorption compounds is limited by a definite saturation capacity is supported by this and a number of other observations of similar character which are described in detail.H. M. D. Colloidal Chemistry and the Phase Rule. W. P. A. JONKER (Zeitsch. Chenz. Ind. Kolloide 191 1 8 15-18).-The applicability of the phase rule to colloidal systems is discussed and the conclusion drawn that the relatively large amount of surface exhibited by colloidal substances is without influence on the nature of the equilibrium relationships from the phase rule point of view. The coaguIation of colloids is not comparable with the separation of a liquid into two layers for the former process is not accompanied by by an increase in the number of phases. Objection is taken to the introduction of surface tension as a new independent variable in the consideration of colloidal systems for surface tension is quite different in character from temperature and pressure in that its magnitude cannot be varied at will.I n reference to the connexion between the amorphous and crystal- line states it is stated that realgar is a suitable substance for experimental investigation. This can be obtained in amorphous or crystalline form by melting together equivalent quantities of sulphur and arsenic. The crystalline variety melts at 320° whereas the amorphous becomes liquid at about 130° and when heated to 350' its properties change in a continuous manner. These observations are cited as evidence in support of the view that the amorphous and crystalline forms are to be regarded as distinct phases. IT. M. D. The Equilibrium between Potassium Hydrogen Carbonate and Trihydrated Magnesium Cttrbonate. NANTY (Compt. wnd. 1910 151 1352-1354).-Polernical against Eogel (Abbtr.1886,ii. 103 ABSTRACTS OF CHEMICAL PAPERS. 121) and Buchner (Zeitsch. Elektrochern. 1908 14 63). has re-examined the conditions of equilibrium in the reaction and is unable to confirm the existence of two distinct limits of formation and decomposition for the reverse reactions at 20-30”. For the same temperature at constant pressure the actions appear to The author KHCO + MgCO,,SH,O + H,O MgC03,KHC0,,4H,0 converge towards a common limit. w. 0. w. Electron Conception of Valency. I(. GEORGE FALK and JOHN M. NELSON (J. Amer. Chena. Xoc. 1910 32 1637-1654).- Thomson’s hypothesis that each linking between the atorus of a compound is due to the transference of a negatively-charged corpuscle from one atom to the other is considered in its application to various classes of organic compounds and references to its application to inorganic compounds are quoted from the papers of Noyes (Abstr.1908 ii 349) and Ramsay (Trans. 1908,93 774). It is shown that all cases of isomerism. connected with the presence of a double bond whether between like or unlike atoms can be interpreted on the basis of the direction of the valencies (that is the direction of transference of the corpuscles) .without recourbe to spatial configurations. The theory of directive valencies is also employed to account for the existence of certain isomerides and to account for certain reactions which have not been explained previously. E. G. Stokes’s Forniula. MAX REINGANUM (Bey. Deut. pliysikal. Ges. 1910 12 1025-1038).-1n view of the frequent application of Stokes’s formula in the calculation of the diameters of small particles from observations on their velocities of movement under the influence of EG known force the author has examined the conditions under which this formula holds good.For very small particles such as the ions in gases the formula is not valid and it is shown that the determination of the dependence of the velocity of such particles on the pressure of the gas may be used as a means of ascertaining whether Stokes’s equation is applicable or not. In the use of the small metallic particles investigated by Ehrenhaft (Physikal. Zeitsch. 1910 10 318 940)) the uncorrected equation is inapplicable and the calculated diameters of the smallest particles are in consequence incorrect.On the assumption that the small particles can be regarded as elastic spheres similar to gas molecules the author deduces a new formula connecting the radii of the spheres and their velocity of movement. According to this the radius of the particles is propor- tional to the velocity whereas in Stokes’s formula the radius is proportional to the square-root of the velocity. For a given radius the new formula shows that the velocity is inversely proportional to the density of the gaseous medium but according to the older formula the density of the gas is without influence on the velocity of the particles. From the data of Ehrenhaft the dimensions of the particles calculated from the two formulm are compared. I n the case of gold and platinum the calculated values are nearly the same for the largerGENERAL AND PHYSICAL CHEMISTRY.ii. 105 particles but the author’s formula gives much smaller values for the radii when the most slowly moving particles are considered. H. M. D. Automatic Rapid Mercury Pump for High Vacua. A. BEUTELL (Chem. Zeit. l910,34,1343-1343).-With one of the author’s mercury pumps a vacuum of 0*0007 mm. can be obtained in ten minutes and one of 0.0001 mm. in twenty minutes whilst after twenty-five minutes it was impossible to measure the vacuum with a McLeod gauge. A photograph of the pump as mounted is given but no details. A Modified Separating Funnel and Washer for Heavy Liquids. HARFORD M. ATKINSON (Chem. News 1910 102 30S).- The funnel consists of an ordinary tap funnel with a second tap and short tube inserted about half-way up the side of the bulb.The Only 0.29 kg. of mercury is necessary to work the pump. T. s. P. washing liquid etc. can be washings performed without running off the heavy liquid. The drying with calcium chloride can also be carried out in the funnel. N. C. run off by this side tap and further Filtering Apparatus for Substances which are Hygroscopic or Altered by Exposure to Air. WIL- HELM STEINKOPF (Chem. Zeit. 1910 34 1358).-On the suction flask A is placed a Buchner funnel B having a ground flange the edge of which is turned upwards to prevent the lid from slipping ; the funnel is closed by means of a ground-glass lid C furaished with a neck. Into this fits the adapter B which has a tube E bent a t right angles and a side tubulus J’ into which the neck of the reaction flask G is ground.This neck is bent a t such an angle that when the bulb of the flask is turned upwards the contents liquid and pre- cipitate readily flow into D. The neck of the flask G also has a tubulus H which during the reaction proper may be connected with a reflux condenser or a gas-delivery tube but during filtering is fitted with a separating funnel containing the washing liquid. H is placed not in the-position shown in the diagram but so much to one side thatii. 106 ABSTRACTS OF CHEMICAL PAPERS. the contents will not run into it when the flask is rotated in F. To prevent moisture entering during the filtration phosphoric oxide tubes are attached t o E and to the side-tube of A leading to the pump.As the solvents used are generally ether benzene light petroleum and the like i t is advisable to place on the dry filter paper a cut and ground inverted funnel J which keeps the paper in position and also prevents any splashing of the precipitate on to the sides G€ the Biichner funnel If desired an inert gas can be transmitted through E. L. DE I(. Automatic Extraction of Aqueous Liquids by Organic Solvents of Lower Density. RICHARD KEMPF (Chem. Zeit. 1910 34 1365-l366).-The apparatus consists of a flask surmounted by two tubes placed concentrically to one another ; the vapour from the boiling ether etc. passes through the annular space between the tubes to a condenser. The condensed ether drops into a funnel tube which is placed concentrically in and reaches to the bottom of the inner tube which is closed below and contains the liquid to be extracted. A flat glass spiral is twisted round the stem of the funnel like an ascending stair and so forces the ether into intimate contact with the liquid to be extracted as it ascends through it. The ether collects on tbe surface of the aqueous liquid and flows through two openings in side of the inner tube back into the flask below. L. DE I(. Apparatus for Preserving and Measuring Poisonous Hygroscopic or Low-boiling LiqUids.wrLHELM STEINKOPF (Chem. Zeit. 19 10 34 13 19).-The liquid under investigation for example anhydrous hydrogen cyanide is directly distilled into the cylindrical vessel in which it is to be preserved. Sealed into this vessel is a narrow tube reaching down to the bottom and connected with a measuring tube through a stopcock. Another tube containing a stopcock is also sealed into the top of the vessel and by connecting this tube with a source of pressure the liquid in the vessel may be forced over into the measuring tube the various stopcocks being appropriately manipulated. The whole apparatus in made of glass. T. S. P. Aluminium Apparatus for Use in the Laboratory. HUGO MASTBAUM (Chem. Zeit. 1910 34 1319).-Condensing spirals made of aluminium tubing are very serviceable in distillations occuring in wine and brandy analyses. Boilers of the same material may also be used in the production of steam for distillations. T. S. P. A New Apparatus for the Preparation of Liquid and Solid Air for Demonstrations. MAX BAMBERGER (Oesterr. Chem. Zeit. 1910 [ii] 13 137-138).-The paper contains a sketch with description of an apparatus suitable for the production of small quantities of liquid air. It consists of two series of copper tubes and a steel flask ; the apparatus is cooled and the enclosed air subjected to a pressure of 120 atmospheres. F. M. G. M.

ISSN:0368-1769    

DOI:10.1039/CA9110005081

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

i. 101 Organic Chemistry. Formation of Hydrocarbons from Carbon Monoxide. 1,120 VIGNON (Bul!. SOC. cJLZ'WZ. 1911 [iv] 9 lS-20).-Various observers have shown that when carbon monoxide is passed over heated sodium or potassium hydroxide soda-lime or calcium hydroxide a formate is produced and that on further heating hydrogen is evolved. I n the present investigation i t is shown that with lime and carbon monoxide bet ween 350" and 400" considerable quantities of methane ethylene and hydrogen are formed and that from 400" to 600" the quantity of hydrogen increases at the cost of the hydrocarbons. The reactions taking place are probably represented by the following equations 2CO + Ca(OH) = (H*CO*O),Ca = C,O,(O),Ca + H ; 2(H*COnO),Ca + CaO = 3CaC0 + CH ; 4(H*CO*O),Cit + 2Ca0 = 6CaC0 + C,H + 2H2 and experiments in heating calcium formate or oxalate alone and mixed with lime have confirmed this explanation of the origin of the hydrocarbons.Carbon monoxide may be converted into hydrogen and hydrocarbons to the extent of 99.5% by passage over hot lime several tirnep and it is suggested that in this way illuminating gas might be freed from this toxic constituent. T -4. H. A Secondary Heptane in Roumanian Petroleum. N. COSTACHESCU (dinit. sci. Univ. Jussp 19 10 6 294-301).-The fraction of petroleum from Colibasi having b. p. 87*5-93.5" con- tains P-methj lhexane with 1 3-dimethylcyclopentano and a small quantity of isomeric heptanes. When the fraction is heated with nitric acid (D 1.4) at 60' in sealed tubes the /3-methylhexane is converted mainly into a nitw-derivative C7HI5O2N b.p. 86-S6*5"/ 21.5 mrn 1); 0.9961 n 1.43855 ; the other hydrocarbons however w. 0. w. undergo oxidation to oxalic acid and carbon dioxide. Dimorphism of Iodoform. BRUNO BARDACH (Chem. Zeit. 1911 35 11-12).-The thin yellow needles obtained previously (Abstr. 1909 i 645) by the action of iodine and potassium iodide on acetone solutions of anhydrides and anhydride-forming compounds are now found to consist of iodoform. The crystals have m. p. 12l0 and on distilling in steam or crystallising from alcohol are transformed i r t o the ordinary hexagonal form. P. B. Estimation of Active Hydrogen in Organic Compounds by means of Magnesium Methyl Iodide. TH. ZEREWITINOFF Ber. 1910 43 3590-3595. Compare Abstr. 1907 ii 509 ; 1908 i 593).-The method previously described for the determination of replaceable hydrogen atoms is applicable also to the alkaloids.Those alkaloids which contain active hydrogen react with magnesium methyl iodide at the ordinary temperature and yield methane quantitatively. VOL c. i. ii. 102 ABS!CRACTS OF CHEMICAL PAPERS When heated no additional methane is formed showing the alkaloids t o contain no amino-group. The rapidity of the method and the fact that only small quantities of substance are required are important features. A number of the commoner alkaloids were tested. Pseudo-acids from nitromethane nitroethane etc. react as if they contained one bydroxyl although the amount of methane obtained is somewhat less than the calculated but it increases on warming.The experiments were made both in amyl ether and in pyridine solution; xylene mesitylene and anisole may equally well be used. E. F. A. [Pinacolin Derivatives] Corrections. MAURICE DELACRE (BUZZ. SOC. clhim. 1911 [iv] 9 41-43).-Polemical in reply to Richard (this vol. i 6) clainiiag priority as regards the synthesis of the alcohol CMe,*CHMe*OH (Abstr. 1906 i 477) and other matters. T. A. H. Preparation of Octan-yy-dione-a-ol and its Homologues. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 227177).-The condensation of unsaturated ketones by which 1 5-diketones are obtained is a reaction about which very little is known; the diketo- alcohols now described are of technical importance in pharmacological preparations. Octan-yy-dione-a-oZ CH,*CO*CH2*CH2*CH,*CO*CH,*CH,*OH b.p. 142-143'/22 mm. a colourless odourless oil miscible with water in all proport,ions is prepared as follows methyleneacetone (Abstr. 1910 i 652) is mixed with water (15 parts) either alone or in the presence of a small quantity of potassium carbonate and allowed to remain until the odour of methyleneacetone has disappeared ; the solution is acidified with tartaric acid saturated with ammonium sulphate aud the product extracted with ether dried and fractionated when a considerable amount of butan-y-on-a-01 CH,*CO*CH,*CH,*OH b. p. 84-85'/23 mm. is also obtained. Pc-DirnetAyloctccn- yq-dione-a-ol is prepared by boiling methyl methylone-ethyl ketone with aqueous formic acid during forty t o fifty hours unchanged mettiyl methylene-ethyl ketone is removed by steam and the solution rendered alkaline whereby any fornzyldimethyl- oclandionol is hydrolysed. The product a viscous odourless colourless oil b.p. 145.5'/16 mm. 148'/18 mm. and 264-268' under atmospheric pressure can also be obtained by either boiling dimethyl- octendione (this vol. j 114) with water or by shaking i t with cold dilute formic or with sulphuric acid; the semicarbctxone has m. p. 209-2 10'. F. M. G. M. Preparation of Narcotics [Glyceryl Ethers]. 0. F. BOERRINGER and S~~HNE (D.R.-P. 226454).-Glyceryl triethyl ether is not a narcotic but when mixed alkyl residues are introduced this property is developed ; these compounds are colourless mobile fluids. Glyceryl ay-dimet?hyl P-ethyl ether C7HI6O3 b. p. 65'/20 mm. DZo 0.917 was prepared by the ethylation of the ay-dimetbyl ether in benzene solution with the neeessary quantity of sodium ethoxide andORGANIC CHEMISTRY i.103 ethyl bromide. Glyceryl ay-dimethyl P-propyZ ether C,H,,O was similarly obtained with propyl chloride ; it has b. p. 76-77'/17 mm. atid D20 0.908. Glyceryl P-methpl ay-diethyl ether C,H,,O has b. p. 75'/17 mm. D20 0.902. Glyceryl ap-dimeth$ y-ethyl ether C7H160a b. p. 49'/7-S mm. D20 0,919 was prepared from glycerol ethyl ether methyl iodide and &odium methoxide in benzene solution. Glyceryl ay-dieth?yl P-propyl ether C,,H,,O has b. p. 77-78'1' 9-10 mm. and D'O 0.882. G'lyceiyl a/3-dirnethyl y-propyl ether C,H,,C) b. p. 66-67'/9-10 mm. D20 0,910 was obtained from glycerol propyl ether b. p. 122'112 mm. D2 1.034 which was prepared by the action of sodium propoxide on glycerol monochlorohydrin.Glyceryl a-methyl /3y-Jiethyl ether C,H,,O b. p. 57"/7-S mm. D20 0.901 was prepared from glycerol naethyl etJLer b. p. 108-109"/ 8-10 mm. D20 1.1 15. Glyceryl /I-beiaxyl ay-dimethyl ether C12H,s03f has b. p. 149-150°/17-1 S mm. and D2O 1.025. Glyce~ol a-ethyl y-propyl ether b. p. 86.5'/10 mm. D'O 0,935 was prepared from the sodium derivative of glycerol ethyl ether and propyl bromide and yielded on methylation g l y e r y l /3-methgl a-ethyl y-propyl ether C,H,oO b. p. 71.5-72"/7-8 mm. D20 0.893. F. nil. Q. M. A Very Basic Chromic Acetate. ERNST GUSSMANN (ZeitsCh anorg. Chem. 1911 69 217-220).-1n the preparation of hexa- acetatotrippridinetrichromi-diacetate (Abstr. 1910 i 503) it was found t h a t the mother liquors contained a violet basic acetate Cr2(OAc),(OH),,9H20.This is best obtained as follows To a solution of 10 grams of hexa-acetatotrichromium diacetate (Abstr. 1909 i 757) in 15 grams of water are added 10 grams of pyridine and the solution heated for half a day. After separating t h e crystals of the above-mentioned diacetate of the tripyridine base the mother liquor is allowed to evaporate at room temperatuke. After several weeks the crystals are collected and washed with cold water to remove the admixed diacetate of the tripyridine base. Rapid concentration of the solution is not favourable to the formation of crystals. The violet acetate forms violet four-sided double pyramids and loses 9H,O over sulphuric acid. It readily dissolves in dilute acids giving a violet solution which makes it probable that the hydroxyl groups possess on hydroxo- and not an ol-character. In phenol it gives a normal molecular weight.It is also formed when a solution of the diacetate of the trichromium base is repeatedly evaporated or when a solution of freshly cold-precipitat ed chromium hydroxide in acetic acid is allowed t o evaporate at room temperature. A green amorphous basic acetate has also been obtained by drying the diacetate of t h e hexa-acetatotrichromium base at 100-1 loo. 1b is less basic than the violet acetate. A formula cannot be given far it a t present. T. s. P. Behaviour of Acetic Anhydride at EL High Temperature. EUQEN BAMBERGER (Ber. 1910 43 3517-3580).-According t o the author the first stage in the formation of acetone by the distillation 'I 'ti. 104 ABSTRACTS OF CHEMICAL PAPERS.of calcium acetate is the dissociation of the salt into calcium oxide and acetic anhydride which at the high temperature necessary for its production decomposes into carbon dioxide and acetone. With a view t o confirming this supposition the behaviour of acetic anhydride at high temperatures has been studied. On heating the anhydride for several hours at 290-300° small quantities of acetone a111 acetyl- acetone were found amongst the products. Whether the formation of the last-named substance is due to the direct acetylation of acetone by means of acetic anhydride or to the intermediate formation of ket en has not been determined. These experiments also support the contention of Schmidlin and Bergmann (Abstr.1910 i 816) that the first stage in the synthesis of keten from acetic anhydride (Wilsmore Trans. 1907 91 1938) consists in the decomposition of the latter into carbon dioxide and acetone. The reaction O(COMe) = CO + COMe is probably reversible but the amounts of carbon dioxide and acetone are very small when equilibrium is attained. The fact that acetone is produced in large quantity by the distilla- tion of calcium acetate is not in opposition to this view for the dissociation products carbon dioxide and acetone are continuously removed during the reaction the latter by distillation the former by union with the calcium oxide produced by the decomposition of the acetate. Various by-products obtained in the manufacture of acetone were examined for acetylacetone but no indication of its presence was obtained.F. B. Salts of a Green and of a Violet Propionatochromium Base. RUDOLF F. WEINLAND and KARL HOEHN [with &I. FIEDERER] (Zeitsch. nnoi*g. Chern. 1910 69 158-178. Compare Abstr. 1908 i 847).-Salts of the green hexapopionatotrichromiurn base Y (OH) (o*coEt)61. To prepare the dichromute propionute where Y = [Cr Y(O*COEt)(Cr20Z),H,0 2 grams of chromium trioxide are warmed with 20 C.C. of propionic acid After filtering from the undissolved chromium trioxide the solution on keeping deposits four-sided brownish-green plates of the salt i n question. Molecular weight determinations in acetophenone gave 961-801 as against 937.6. The sesquichromate propionate Y(O*COEt)( HCr0,)($CrO4) is obtained by warming chromium trioxide and chromium hydroxide in the proportion of 2 mols.of the former to 1 mol. of the latter with propionic acid. On concentrating the solution dark olive crystals are obtained. Molecular weight in acetopheaone was 753-878 as against 877.5. When a mixture of chromium trioxide and chromium hydroxide in the molecular proportion of 1 3 is dissolved in propionic acid and the solution concentrated green six-sided plates of the chyomate propionate Y(O*COEt)(CrO4),1*5H,O are obtained. It may also be obhained by dissolving 1 gram of chromium trioxide in 50 C.C. of propionic acid and concentrating the solution. When less than ten parts of propionic acid to one part of chromium (OH,),ORGANJC CHEMISTRY. i. 105 trioxide are taken and the mixture heated chromates are obtained which contain less propionic acid in the anion than the above-mentioned salts.Whether a dichromate or a lower chromate of the base is obtained depends on the time of heating ; the longer the heating the poorer is the resulting chromate in chromic acid. Whenever the dichromate propionate is recrystallised from a little water propionic acid is lost from the anion and pure sesquichromate Y(Cr0,)($Cr0,),2H20 is obtained. Even when the chromate propionates are recrystallised from a solution of propionic acid some of the latter is split off from the anion. The chloride chromute Y(Cr0,)C1,H20 is obtained as yellowish-green six-sided plates by the addition of concentrated hydrochloric acid to strong solutions of any of the above salts.The nzonopropionate Y(O*COEt),ZH,O is prepared from the chromate propionates by removing the chromic acid with lead propionate or from the chloride (Abstr. 1908 i 935) by treatment with silver propionate i t forms pale green rod-like crystals. Salts of a violet pentapropionutotrichromiurn base Y (OH) where The dipropionate Y(O*COEt) forms the starting point for the preparation of t h e other salts. It is best prepared by dissolving 1 mol. of freshly-prepared chromium hydroxide which has been washed with cold water in 3 mols. of propionic acid at the room temperature The solution is then heated in a sealed tube for five hours a t 140-160’ ; on cooling violet crystals of the dipropionate are found on the walls of the tube. After purification by a somewhat complicated method they are obtained as flat prisms which may be 1 cm.long. Molecular weight in acetophenone was 615 a s against 737.7. The nzono- pyopionate Y’(O*COEt),3H20 where Y’ = Cr,(OH) is obtained by saturating the aqueous solution of the dipropionate with sodium chloride or nitrate ; light violet crystals. The sesguipropionate Y(O*COEt)21Y’O*COEt,H,0 results on evaporating a solution of one part of the dipropionate with five parts of sodium propionate ; violet Bat prisms. The sulphatepropionate (Y O*COEt),S0,,4H20 crystallisc s i n violet plates on the addition of concentrated sulphuric acid to the saturated solution of the dipropionate. The bromide propionate Y(O*COEt)Br,4H20 forms violet prisms as also does the chloride Y’Cl,Y’O*COEt,lUH,O ; they are iorrned from the dipropionate by precipitation with concentrated hydrobromic and hydrochloric acid respectively. All t h e salts of the violet base are readily soluble in ether and chloroform; those of t h e green base are insoluble in ether.The salts of the violet base cannot be recrystallised from water. From the solution of chromium chloride hydrate CrC1,,6H20 in a solution of sodium propionate violet crystals are obtained having t h e composition Cr(O*COEt),*OH,H20. They are insoluble in ether in contradistinction t o the violet pentapropionatotrichromium salts. Y = 1 CI-,(OH)~ w 9 g [ Z 2 Y O 2 ) 7 T. S. P,i. 106 ABSTRACTS OF CHEMICAL PAPERS. Condensation of ap-Dibromopropaldehyde with Mslonic Acid. ROBERT LESPJEAU (Conapt. rend. 1910 151 1359-1361.Compare Spenzer Abstr. 1005 i 204).-a~-Dibromopropaldehyde Acts on malonic acid to form &WdmmwuaZeric acid m. p. P2S-l3O0; the ethyl ester has b. p. 160-161°/12-13 mm. Both t h e acid and the ester on treatment with zinc and alcohol furnish ethyl Ap-pentenoate CHMe:CH*CH,*CO,Et b. p. 145 -146'/760 mm. (On brominating the corresponding acid a su bslarice is obtained probably identical with ap-dibromovaleric acid. w. 0. w. The Oil and Wax of Coffee Beans. HAPI'S MEYER and ALFRED ECKEHT (Moizccfsh. 1910 31 1227-1251).-Uriroa,tsted coffee beans from which the greater part of the caffeine had boen extracted were dried powdered and digested with benzene. The oil thus obtained had a brownish-yellow colour WAS nearly odourless arid had the consistency of olive oil.On hydrolysis i t gave 21.2% of non-saponifi- able matter. For isolating the acids formed on hydrolysis it was found advisable t o saponify with lithium hydroxide solution (compare Yartheil and FeriB Abstr. 1904 i 4) but this method did not give a complete separation of saturated from unsaturated acids. The sparingly soluble lithium salts gave the following acids Carnaubic acid 10% (Sturcke Abstr. 1884 1280 ; Uarmstiidtcr and Liefschutz 1896 i 346; Dunham and Jacobson 1910 i 215); daturic acid 1-1*5% (Gerard Abstr. 1890 1396; Kreis and Hafner 1903 i 788 ; Holde Ubbelohde and Marcusson 1905 i 318) ; palmitic acid 25-28% and decoic acid 0.5%. I n order to obtain the carnaubic acid pure the least soluble fraction of the lithium salts was transformed into chloride by means of thioriyl chloride and then into ester ; the processes of conversion into lithium salt chloride and ester were repeated when the methyZ ester was obtained in the form of glistening plates m.y. 51-55' and this on hydrolysis gave the acid with m. p. 74' (not 70" or 72.5'). The lead salt has m. p. 109-110" and is soluble in toluene. The acid resembles stearic acid in many respects but its ethyl ester is not 80 soluble in alcohol. The detection of glyceryl esters of this acid in fats is readily accomplished by warming the fat with absolute alcohol and a little sulphuric acid when the sparingly soluble ethyl carnaubate mixcd with a little palmitate and stearate is deposited. JIetlqZ daturate CIGH,,*CO,Me has m. p. 30° and the magnesium Falt m. p. 137-142'.The more soluble lithium salts were converted into lead salts and the saturated and unsaturated acids separated by extraction with benzene. The acids isolated wero palmitic oleic 2% and linoleic SO% The unsaturated acids were identified by oxidation with 2% per- manganate solution in t h e cold when dihydroxystearic and sativio acids were obtained and by bromination when tetrabromostearic acid was isolated. The wax contained a small amount OF alkaloid which was removed by steam distillation and solution in glacial acetic acid. When finely divided and made into a n emulsion with potassiiim hydroxide solution the wax was oxidised by 4% permanganate to carnaubic acid and whenORGANIC CHEMISTRY i. 107 hgdrolysed with alcoholic potassium hydroxide solution a t 150-1 70° it gave carnaubic acid (50%) and a compound with the properties of a tannol.This latter has not been' obtained crystalline ; it has no definite m. p. but i s soluble in alkali solutioris and can be benzoylated. The wax is therefore a tannol resin. J. J. S. Preparation of Cfompounds of Unsaturated Acids with Aldehydes Ketones and Formic Acid. EARBWERKE YORRI. MEISTER LUCIUS Kz BRUN~NG (U.R.-P. 226222 and 226223).-It is found that unsaturated fatty acids of high molecular weight combine (in the presence of acid condensing agents) with kebones or aldehydes t o form a new series of oily compounds. The free acid may be replaced by the oil which under the experimental conditions becomes almost entirely hydrolysed. The substances employed were acetone formaldehyde acetaldehyde benzaldehyde dextrose lzevulose sucrose and maltose which were severally heated with castor oil ricinoleic acid oleic acid and cottonseed oil in the presence of either sulphuric acid zino chloride or phosphoryl chloride.The second patent states that formio acid may be employed in this reaction instead of formaldehyde and details are given of its condensation with ricinoleic acid. F. M. G . N. Preparation of Acyl Derivatives of Castor Oil [Ricinoleic Compare Abstr. 1909 i 696).-The aromatic acyl derivatives af ricinoleic acid have not previously been prepared ; it is now found that aromatic acid chlorides reacting with the hydroxyl group of the acid yield the corresponding acyl derivative ; these are usually tasteless odourless oils. The benzoyl ester vas prepared by boiling castor ail in benzene solution with bonzoyl chloride in the presence of pyridine during half an hour; the anisogl ester was obtained in a similar manner.The salicyl ester was prepared by heating castor oil and salql together a t a temperature of 200' during three hours and distilling off the separated phenol in a vacuum. Acid]. VEREINIGTE CHININFABRIKEN ZIhIMER & CO. (D.R.-P. 2261 11. F. M. G. &I. E&er Csndensations with Chloroacetic Ester. WILHELM WISLICENUS (Bey. 1910 43 2528-2533).-1n the Claisen con- densation ethyl chloroacetate can function as the ester component and also as the methylene compound. The interaction of ethyl chloroacetate ethyl oxalate and sodium ethoxide in ethereal solution yields ethyl chloro-oxalacetate CO,Et*CO*CHCl*CO,Et b.p. 150-152"/56 mm. (compare Peratoner Abstr. 1893 i 11 ; Roubleff Abstr. 1891 223) ; this forms a green copper salt and yields oxamide when treated with ammonia; at 240° it loses only half the theoretical amount of carbon monoxide ; in alcoholic solution it gives an intense red ferric chloride reaction. When equal molecular quantities of ethyl formate and ethyl chloro- acetate are introduced into a cold alcoholic ethereal solution of potaasium rpethoxide a potassium salt is formed from wbich byi. 108 ABSTRACTS OF CHEMICAL PAPERS. acidification ethyl a cicrZoroform?llacetats CHO*CHCl*Cd,Et is obtained a s a n oil giving a n intense violet ferric chloride reaction. On repeated distillation in a vacuum it is obtained i n colourless leaflets m. p.88-90°; the latter give only a faint violet coloration with ferric chloride and yield with copper acetate a green copper salt ; a f t e r fusion t8he crystalline ester gives the original intense violet ferric chloride reaction. The isomerism here exhibited has not been further investigated but there is little doubt that the liquid ester has the enolic structure 0 H*CH :CCl*CO,E t. The benxoyl derivative OBz*CH:CCl*CO,Et prepared from the above-mentioned potassium salt crystallises from alcohol in large colourless plates m. p. 90-91'. With phenylhydrazine both the ester and the potassium salt react to form the osazone of ethyl P-hydroxypyruvate CH( :N*NHPh) *C(:N*NHPh)*CO,Et (compare Will Abstr. 1892 356). The Condensation of two molecules of ethyl chloroacetate has also been effected (compare Erlenbach Abstr.1892 953) ; ethyl chloro- acetate (2 mols.) and sodium ethoxide (1 mol.) flee from alcohol are allowed t o react in ethereal solution at a low temperature; on acidifying the sodium salt thus produced ethJ a-y-dichlorouceto.ccetafe CH,Cl*CO*CHCl*CO,Et is obtained in a n impure condition. It is purified by converting it into the copper salt and decomposing this with hydrochloric acid; it forms a colourless oil with a penetrating odour b. p. 118-120"/15 mm. and solidifies on cooling m. p. lS-20° ; it gives an intense cherry-red coloration with ferric chloride and is hydrolysed by boiling with dilute sulyhuric acid to s-dichloro- acetone ; the copper salt (CH,CI*CO*CCI*CO,Et),Cu crystallises in microscopic green needles melting at 149' (decomp.) to a turbid yellow liquid.F. B. Ethyl y Chloroacetoacetate. ROBERT LESPIEAU (Bull. Soc. chim. 1911 [iv] 9 31-33. Compare Abstr. 1899 i 243; 1905 j 406 ; Picha Abstr. 1907 i 178).-Polemical with Schlotterbeck (Abstr. 1909 i 550) on the physical properties of this ester. T. A. H. Condensation of Ethyl Acetate with its Higher Homo- logues. ANDRB WAHL (Conzpt. rend. 1911 152 95-98).-1t has hitherto been found impossible to prepare P-ketonic esters by cond ms- ing ethyl acetate with its higher homologues. This condensation has now been effected by adding alternately t o the higher ester small carefully weighed portions of ethyl acetate and sodium. I n this way the formation of ethyl acetoacetate and of the compound R*CO*CHR*OK is prevented or diminished; the yield however is small 5-6% in the case of ethyl propionylacetste for the pure compound and lS-ZO% i n the case of ethyl butjyrylacetate.The latter forms a green copper derivative Cu(C8H1303) m. p. 125-1 26' ; on boiling with methyl alcohol it changes into a blue busic salt C,H,,O,*CuOMe. Ethyl butyrylacetate is converted by oxides of' nitrogen into ethyl butyiylglyoxylate CH,Et*C'O*CO*CO,Et an orange-yellow liquid b. p.ORGANIC CHEMISTRY. i. 109 87-8So/13 mm. becoming colourless on the addition of water or alcohol with which it combines ; the diketone condenses wit.h p-phenyl- en ed iam i n e for mi n g 8th y l 2 -prop yIguinoxali~ze-3- carboxylute N:yPIa C6H4<N :C*C*,Et' long needles m. p. 63-64'. w. 0. w. y-E thoxy-a-alkylacetoacetic Esters.MARCEL SOMMELET (Bull. SOC. chim. 1911 [ivl 9 33-38. Compare Abstr. 1907 i 21 10'7).- The considerable differences in the hoiling points ascribed by Isbert to the compounds he regarded as a-ethoxp butanone and a-ethoxypentanone (Abstr. 1886 1009) From those found by the author for his pre- parations of these substances has led him t o re-investigate esters having the constitution assigned by Isbert to the esters from which his ketones were prepared. The author finds that they do not correspond with Isbert's dewriptions and that on hydrolysis they furnish ketones identical with those he has described already (loc. cit.). Ethyl y - ethoxv - a - methylacetoacetate 0 Et.CH,*CO*CHMe*CO,Et Di 1.033 D;' 1.01'7 b. p. 112-114°/14 mm. 116.5-lIS*5°/19 mm.obtained by condensing ethoxyscetonitrile with ethyl a-bromopro- pionate in presence of zinc (compare Blake Abstr. 1901 i 252) is a faintly yellow liquid which reduces ammoniacnl silver nitrate in the cold and gives a violet coloration with ferric chloride. On hydrolysis with potassium hydroxide solution the ester yields a-ethoxy- butanone and with hydrazine hydrate gives a pyraxolone m. p. 1 35-13io which crystallises from boiling water. Ethyl y-ethoxy-a-ethylacetoacetate Di4 1 -0157 b. p. 125-128"/ 28 mm. similarly obtained resembles its lower homologue and on hydrolysis gives a-ethoxppentsnone and with hydrszine hydrate furnishes a pymxolone m. p. 99-99*5" which crystallises from boiling water in hard prisms. Eihyl y-ethoxy-aa-di?12ethy~(ic~toacetate D 1,065 D:' 1.047 b.p. 114-116°/17 nim. 11 1-1 1Y0/14 mm. obtained by condensing ethyl homoisobutyrate with ethoxyscetonitrile in presence of zinc is a pale yellow liquid reduces amrnoniacal silver nitrate and on alkaline hydrolysis furnishes ethozymethyl isopropyl ketone OEt*CH,*COPrp b. p. 160" (approx.) which gives a ssmicurbazone m. p. 12s-129.5'. Along with the cster there is formed i n this condensation a small quantity of a substance Cl2HI9O4N m. p. 90-9 1*5" which crystallises in needles or prisms is soluble in strong acids becomes yellow in contact with alkdi and gives no coloration with ferric chloride. Heated with alkali in a closed tube it evolves ammonia and Furnishes a trace of isobutyric acid and an unidentified oily product. T. A. H. Iso- and Hetero-poly-acids.11. Oxalato-tellurates. ARTHUR ROSENREIM and 33. W EINEIEBER (Zeitsch. anorg. Chem. 19 1 1 69 261-265. Compare this vol. ii 116) -Concentration of a solution containing molecular proportions of telluric acid and an alkali oxalate leads to the deposition of crystals of the oxtlato-tellurates. The potassium rubidium and caesium salts have the general formulai. 110 ABS'rRAC'fS O F CHEMICAL PAPERS M2C,0,,HGTe0 where M = K Rb or Cs and crystallise in stellar aggregates of needles. The effect of beat on these salts shows t h a t the water is firmly combined so that telluric acid hydrate H,TeO and not the auhydride TeO is probably contained in the complex anion. Their solubilities increase from the potassium through the rubidium to the cmiurn salt this being the opposite order to what generally obtains with salts of these metals Comparison of the solubility of the potassium salt with the solubilities of potassium tellurate and oxaliu acid shows that a great diminution in solubility has taken place pointing to complex formation.This could not be verified by conductivity measurements however owing to the hydrolysis which takes place. Homogeneous ammonium or sodium oxalato- tellurates could not be obtained T. S. P. These compounds should therefore be formulated as M2[ HGTeo,C,o,]* Molecular Rearrangenients in the Camphor Series. VI isoCampholactone WILLIAM A. NOYES and A. W. HOMBERGER (J. Amer. Chem. Soc. 1910 32 1665-1669).-1n an earlier paper (Abstr. 1909 i 133) the authors described a compound obtained by the action of nitric acid on isocampholactone which they regarded as a dilactone of the composition C,HI30,.It has now been found that this substance is in reality a nitrolactone. isoCampholautone prepared by Noyes and Taveau's method (Abstr 1904 i SO?) gave [a]? - 63.1" in an 8.8% solution in alcohol ; Noyes and Taveau found [.ID - 60.7" in a 5% solution. On heating isocampholactone with ammonium hydroxide in a sealed tube a t loo" it yields the ammonium salt of the corresponding acid m. p. 13T0 which is re-converted into the lactone when left in the air When the lactone is heated with nitric acid (D 1-27} a mixture of products is obtained the chief of which is nit.r*oisocamphoEactone NOp-C,H,,<Xo m. p. 122O b. p. 27Z0 which crystallises in needles and has -85-4O in a 5.5% solution in alcohol.A monobasic lactonic acid C,H,,O m. p. 1 3 8 O was isolated from the mother liquor which has [.ID - 4 2 ~ 0 5 ~ in a 6% solution in alcohol ; its barium salt was prepared ; the amide has m. p. 164". Aminoisocamnpholactone NH,-C,H,,<b m. p. 84" obtained by reducing nitroisocampho1;tctone with tin and hydrochloric acid forms small crystals and is decomposed by sodium hydroxide with formation of a compound m. p. 152O. CO Hydl.ozylamninoisoca~~?~oZacton~ co 0 ' OHqNH*C,HI,< I m. p. 144O prepared by treating nitroisocampholactone with zinc dust and acetic acid forms small stellate crystals is slightly basic and readily reduces Fehling's solution. When nitroisocampholactone is shaken with OBN-sodium hydroxide until completely dissolved and afterwards acidified with hydrochloricORGANIC CHEMIS'I'RY.1. 111 acid an acid C,H,O,N*CO,H m. p. 73-74' is produced ; its barium salt crystallises in needles containing 2&H20 By the action of ammonium hydroside on nitroisocampholactone the corresponding amide m. p. 96-97' is obtained. E G. Molecular Rearrangement8 in the Camphor Series. VII. Derivatives of isoCamphoric Acid ; I-Hydroxydihydro- campholytic Acid. WILLIAN A. NOYES and LUTHER KNIGHT (J. A n w . Chem. Soc. 1910 32 1669-1674).-d- and l-isoCamphoric acids are usually regarded as cis- and trans-isomerides As however the evidence of this structure does not seem altogether conclusive in the case of the latter compound the present work was undertaken in order to throw some light on the question.Assuming that iso- camphoric acid is stereoisomeric with camphoric acid a is used in this paper to denote the secondary carboxyl and /3 the tertiary carboxyl group. By boiling isocarnphoric acid with methyl alcohol and sulphuric acid the a-methyl and dimethyl esters are obt:tined. The dimethyll ester C,H14(C0,Me)2 b. p. 146"/27 mm. has D2" 1.073 D@ 1.069 and [a]g - 65.3" ; a 10% solution in alcohol has [a]" - 63%'. The a-methpl ester m. p. 88' crystallises in needles and gives [.ID - 57.9'in a lo?; alcoholic solution ; its avaide m. p. 157" crystallises in plates arid has [a] - 60.05' in a 10% alcoholic solution /3-isoCan~pi~orarnic acid C0,H*C8Hl,*CO*NH in. p. 165-166' obtained by hydrolysing the a-methyl ester amide with sodium hjdroxide crystallises in needles.When i:s sodium szlt is treated with sodium hypobromite solution ccnz~.izoisod~hydrocccnapho~~t~c acid CO,H-C,H,,*NH,,. m. p. 225-22'i0 is produced ; its hydrochloride and lead salt are described. When this acid is heated a t 250-300° it is converted into an unhgdride which furnishes R mitroso-compound m. p. 194". Jf aniinoisodihy drocampholytic acid hydrochloride is treated with a solution of sodium nitrite there are produced a hydrocarbon a lactone d-campholytic acid and l - l ~ ~ d ~ o x ~ d i i ~ y d r o c ~ ~ ~ ~ p ~ ~ o acid CO,H*C,H,,-OH m. p. 132' which forms granular crystals and gives [ u ] ~ - 70.04' in an aqueous solution containing 1.45%. The formation of this compound instead of hydroxydihydroisocnmpholytic acid which was expected renders it probable that the former is the more stable and that part of the hydroxydihydroisocampholytic acid is converted into i t by the action of the nitrous acid or else that d-campholytic acid is formed as an intermediate product and unites with water to produce I-hydroxydihydrocampholytic acid.E. G. Saccharinic Acids. HEINRICH KILIANI (Ber. 19 1 1 44 109-113).-A reply t o Nef (Abstr. 1910 i 714). The phenyl- hydrazide of a-metasaccharin has m. p. 145" as previously found and not 113-115' as stated by Nef. The trihydroxyadipic acid described by Kiliani and Eisenlohr (Abstr. 1909 i 553) is not identical with the old trihydroxy-acid; it has m. p. 159-160° whereas a mixture of the two melts a h 142-145°. The silver salt also does not crystallise in the small plates characteristic of the silver salt of the old acid The presence ofi.112 ABSTRACTS OF CHEMICAL PAPERS. a compound with a branched chain in parasaccharin has been con- firmed by reduction to a-ethylbutyrolactone and the isolation of this in the form of Chanlaroff's calcium salt 3Ca(C,Hl10,),,2H20 (Abstr. 1885 374). The yield of calcium salt however is small and large quantities of syrupy salts are formed. By oxidising parasaccharin with nitric acid t o parasaccharone (Abstr. 1904 i 975) and reducing this with hydriodic acid a small amount of n-adipic acid has been obtained. These results indicate that parasaccharin must be a mixture. Nef's parasaccharin (a-d-galactometasaccharin) does not appear to be hygroscopic whereas the author's preparations are excessively hygroscopic.The acid obtained by the oxidation of barium parasaccharinic acid is not hydroxycitric acid as stated previously (Abstr. 1904 i 976) but &tartaric acid. J. J. S. Glucodeconic Acids. L. H. PHILTPPE (Conzpt. rend. 1910 151 1366-1367. Compare this vol. i 12).-On evaporating an aqueous solution of p-glucodeconic acid a mixture of two compounds is obtained (1) the hydrated p-lactone C,,H,,O, H20 crystaltising in hemihedral needles rn. p. 135' (anhydrous m. p. 193') [a]:7-41.2'; (2) a n anhydride C20H3s021 separating in microscopic granules resern bling those of starch m. p. 216-.218' [a] about - 10'. The lactone is the chief constituent in dilute solutions whilst the anhydride pre- dominates in concentrated solutions. The p-lactone is also formed when the a-lactone is heated a t 140' in pyridine. Sodium P-glucodeconate is gummy but the barium cadmium and strychnine salts are crystalline.The P-phenplhydrazide crystalliees in needles m. p. 246' and is ten times more soluble in water than the a-compound. w. 0. w. Derivatives of Aldol and Crotonaldehyde. RUDOLF W EGSCHEIDER and ERNST SPATH (iionatsh. 1910 31 997-1029).- The authors have examined the behaviour of aldol towards acetylating agents under various conditions and find that acetylation is accom- panied by the formation of condensation products; loss of water and rupture of the aldol molecule also occur. When aldol is boiled with acetic anhydride in the presence of a little sulphuric acid ethylidene acetate and mZdoZ triacefate OAc-CHMe*CH2*CH(OAc) are produced.The latter substance is a colourless oil b. p. 138-140'/ 1 2 mm. which yields crotonaldehyde when boiled with water or alkalis; when treated with bromine in chloroform solution it is converted into bromocrotonaldehyde. Gentle acetylation of aidol with acetic anhydride and sulphuric acid in benzene or chloroform solution yields amont. st other products aldol nzonoacstute OAc*CHMe*CH,*CHO; i t is a colourless oil b. p. 87-89"/18 mm. and is also obtained by the action of acetic acid and a little sulphuric acid on xldol a t the ordinary tempeiaature. By heating aldol with acetic anhydride alone Wurtz (this Journ. 1872 808) obtained two substances which he considered to be croton-OROAKIC CHEMISTRY. i. 133 aldehyde diacetate and acetylaldol. The authors have repeated Wurtz's experiments and find that his crotonaldehyde diacetate consists of a mixture of aldol triacetate and a compound Cl2HI8O5 whilst the substance described as acetylaldol is identical with crotonaldehyde diacetate.The compound C12H1805 is probably the diacetyl deriv- ative of dialdan C,H,,O a substance obtained by Wurtz by the action of acids on aldol; i t is produced by gently acetyIating aldol with acetic anhydride and sulphuric acid either alone or in chloroform and benzene solution and also by the action of acetic and sulphuric acids on aldol at the ordinary temperature; the b. p. varies from 144-147'/13 mm. to 152-154"/12 min. according to the method of preparation but whether this variation is due to impurity or the presence of two dialdan diacetates has not been decided.The constitution of the compound is discussed and arguments advanced in favour of the formula OAc*CHMe-C H (CHO) *C H( OAc)-CH CEI Me. The following condensation products were also isolated and examined a diacetate of C12H2,,02 colourless oil b. p. 201-203°/ 10 mm. produced by acetylating aldol with acetic anhydride in the presence of a little sulphuric acid and probably having the structure a substccnce C18H,,07 $!HRle.O* CHMe CHO CH,-CH(OAC)>~<CH(O~C)*CH CHMe ' b. p. 228-233"/13 mm. obtained by the action of a mixture of acetic and sulphuric acids on aldol and represented as a monoacetyl derivative of ? OH*CHMe*CH(CHO)*CH(OH) CHBIe-- CHMe:CH*CH(OIs)>c<CH(O H)*C'H,*C HMe ' a mixture of the monoacetyl derivatives of C8H1403 and C8H160+ produced by acetylating aldol with acetic anhydride and sulphuric acid in chloroform solution Acetyl chloride reacts with aldol in benzene solution forming a-chlorocrotyl acetate CHMe:CH-CHCl-OAc b.p. 76-77'1 18 mm. ; the same substance is also produced by the addition of acetyl chloride to crotonaldehyde. When aldol is acetylated by means of acetic anhydride in the presence of sodium acetate the main product is crotonaldehyde diacetate. AZdo/phenythydraxone is obtained in an impure condition by the action of phenylhydrazine on aldol in ethereal solution ; it is a viscid oil b. p. 196"/10 mm ; the p-nitrop7~enyZhydraxone crystallises in reddish-yellow needles m. p. 109-1 1 lo with previous sintering a t 107' ; aldoloxime has b.p. 117-1 1S0/1 1 mm. Crotonalclehydep~en~Z~~ydrazone prepared by the action of phenyl- hydrazine on crotonaldehyde in alcoholic solution a t 35-42O is a yellow oil b. p. 156-158O/11 mm. (compare Trener Abstr. 1901 i 232) ; the p-nitrophenylhydrazone crystallises in brown needles m. p. 1 S4-185". The authors also describe two new condensation products of acetaldehyde. A specimen of crotonaldehyde which had been kept for three and a-half months in a closed glass vessel filled with carbon dioxide,. yielded on distillation an oil ClOHl8O4 b. p. 88-95"/16 mm. and a viscid liquid C,,H2s0 b. p. 156-161°/16 mm. It is suggestedi. 114 ABSTRACTS OF CHEMICAL PAPERS that these two substances are produced by the condensation of acetaldehyde derived from the para-aldehyde (with which the original crotonaldehyde was probably contaminated) according t o the equations Cl,Hl,Op = 5C,H,O - H,O and CI,H,,O = 8C2H,0 - 2H,O.F. B. FARBEN- FABRIKEN VORM.FRIEDR. BAYER & Co. (D.R.-P. 227176).-The methylene ketones employed in the following reactions were recently described (Abstr. 1910 i 653) ; it is now found that they polymerise readily yielding octendiones (and higher polymerides) of considerable thera- peu tic importance. A,-Octen-yr]-dio?te 11. p. 75-76'/21 mm. a colourless oil sparingly soluble in water and with a penetrating odour is prepared by the long boiling of methyleneacetone under reflux and subsequent fractional distillation of the products its semicarbuxone has m. p. 199". Pfj-DivtetlL yZ-Aa-octen-yr]-dione COMe- CHMw CH CH,*CO CMe CH is prepared in a similar manner from methyl methylene-ethyl ketone but owing to the higher temperature employed more of the higher poly- merides are simultaneously produced ; it is a colourless highly refractive oil b.p. 187-194" or 83-85"/17 mm. with pine-like odour immiscible with water and slowly decomposed by boiling at atmospheric pressure into its progenitors ; its seniioadaxone has m. p. 183". Dimethyl- octendione can also be obtained by tho slow distillation in a vacuum of P[-dimethyloctan-yq-dione-a-ol (see this vol. i 102) with a n equal weight of hydrogen potassium sulphate or by boiling it with acetic anhydride. Preparation of Octendione and its Homologues. F. M. G. M. The Influence of'. I n a c t i v e Substances on the Rotation of La3vulose.NEUMANN WENDJCR (Biochem. Zeitsch. 191 1,30 357-373). -The addition of inorganic acids to a solution of I~vulose was found in most cases to increase the specific rotation the increase varying with the degree of acidity of t h e solution. Inorganic salts as well as organic acids varied in their behaviour causing in some cases a rise in others a decrease in the rotation. Alcohols and acetone produced a marked diminution in the rotation which was proportional t o t h e amount added. W. J. Y. Mercerised Cellulose. CHARLES F. CROSS (Ber. 1911 44 153-154).-1n connexion with Miller's results (this vol. i 17) it is pointed out that bleached cotton is not a homogeneous cellulose and that by t h e action of sodium hydroxide solution the P-celluloses are dissolved.Previous heating at 90-100' renders the P-celluloses still more reactive towards alkalis. The increase in weight of tho cellulose on hydration is compensated by the loss in weight due to the removal of the P-celluloses (compare Cross and Bevan '' Cellulose," pp. 4 and 28). The author upholds the view t h a t a definite series of hydrated c?lluloses exists and t h a t these are stable within the limits 0' t o 50'. J. 3 . S. Mercsrised Cellulose. CARL G. SCRWALBE (Be?.. 1911 44 Compare preceding abstract).-Attention is drawn t o the 161-1 52.ORGANlC CHEMISTRY. i. 115 fact that during treatment with sodium hydroxide solution a portion of the cellulose is dissolved. Previous experiments (Abstr. 1908 ii 627) have shown that mercerised cellulose does not contain water (compare also Ost and Westhoff Abstr.1909 i 210). According to Liebermann (Dingler's polyt. J. 1886 1 8 1 133) an aqueous solution of rosaniline base does not dye cotton-cellulose. For behaviour of mercerised cotton towards sitbstantive dyes compare Knecht (J. SOC. Dyers 1908 24 6S) and Hiibner and Pope (.I. doc. Chem. Ind. 1904 23 401). Cellulose. 11. Hydrocellulose. H. JENTGEN (Zeitsch. angew. Chem. 1911 24 11-12 Compare Abstr. 1910 i 654).-1n support of the view that acid in the molecular condition brings about the conversion of cellulose t o hydrocellulose (compare Schwalbe Abstr. 1910 i 817) the following facts are given (1) A 1% aqueous acid solution has practically no hydrolysing effect ; (2) Methyl or ethyl alcoholic solutions act slowly and the action depends on the amount of dissociation ; (3) 1% solutions of acids in non-ionising media.hydrolyse readily. The compounds of cellulose with the molecular acids are regarded as catalysts. The hydrolysis observed by Schwalbe during acetylation is regarded as a secondary or tertiary process. J. J. S. J. J. S . Hydrocellulose. CARL G. SCHWALBE (Zeitsch. angew. Chem. 191 1 24 12-13. Compare Abstr. 1910 i S17).-Mainly polemical in reply to Jentgen (preceding abstract). Acyl Derivatives of Guanidine. WILHELM TRAUBE (Be?*. 19 10 43 3586-3590).-Guanidine interacts with the esters of monobasic acids forming simple acyl guanidines. Formylguanidine NH,*C(NH)*NH*CHO separates in crystalline granules m. p. 1'75" (decomp.). On shaking with bromine formylbromo- guanidine results ; it crystallises in almost colourless needles which decompose violently at 125'.Acetylguaniclirbe separates in colourless rhombic crystals m. p. 185' to a clear liquid; on further heating i t solidifies and the new compound after crystallisation from water has m. p. 261O. Acetyl- guanidine hydrochloride has m. p. 145" (Korndorfer found 142q Arch. Pharm. 1903 241 449). Chloroacet~lguanidir~e crystallises in slender colourless needles m. p. 125O. Tricrl~lo~oacet~lguanidine forms small colourless crystals In. p. 183' ; the hydrochlos.ide crystallises in platelets. Uenxoylguanidiue forms short colourless crystals m. p. 160' ; the bydrochloride separates i n lustrous needles m. p. 207" (Korndorfer found 210° loc. cit.). m-Nitrobenxoylguanidine crystallises in stellate needles m.p. 195-197". E. F. A. J. J. S. Complex Salts of Certain Amino-acids. LEO TSCHUaAEFF and E. SERBIN (Compt. rend. 1910 151 1361-1363).-a-Amino-acids form stable complex internal salts with certain heavy metals ini. 116 ABSTRACTS OF CHEMICAL PAPERS. this respect differing from the p- 7- and &acids which appear unable to do so. The following salts are sparingly soluble and were pre- pared in each case by boiling a n aqueous solution of the amino-acid with somewhat less than the calculated amount of purpureochromium chloride. The glycine salt Or ( \ **:zg:2)3 crystallises i n small bright red prisms; it is stable at 300° and is not decomposed by boiling with alkalis or dilute acids. ( .-NH,*ClfMe )5 has a similar c o n s t h i o n The ulunine salt Cr x0-- and shows the same properties; it crystallises in rosy needles.The aspctragine derivative Cr( C,H70,N,) is less soluble and separates in microscopic rose-violet needles. a- Aminoisobutyric acid a-arninoiso- valeric acid and leucine form similar compounds. The salts can a l e 0 be prepared but in a less pure state by boiling the amino-acids with a n aqueous ammoniacal solution oE chromic chloride. When glycine is treated in this way a basic salt is obt.rined for which the OH 00NH2*(?H2)2 is suggested. constitution ( Xz2”HG>)2Cr<OH>Cr (KO --co w 0. w. Action of Carbon Disulphide on Amino-acids. MAX SIEGFRIED and 0. WEIDENHAUPT (Zeitsch. physiol. Chem. 1910 70 152-160).-Carbon disulphide combines with amino-acids in the presence of barium hydroxide or other alkalis in much the same manner t h a t carbon dioxide does (compare Abstr.1905 ii 332 ; 1906 i 324 ; 1908 i 379) yielding dithiocarboxylic derivatives of the amino-acids; for example glycol yields a salt of CO,H-CH,*NH-CY*S H. Nost of the salts are readily soluble but when treated with benzgl chloride yield spaiingly soluble acid benzyl esters of the type C0,H*CH2*NH*CS*S*UH2Pb by means of which the dithiocarboxylic acids can be isolated with great ease. Benxyl hydrogen glycinedithiocarboxylate C,,H,,02NS2 crystallises from water in long broad colourless needles with a silvery lustre and has m. p. 165’; 100 C.C. of an aqueous solution saturated at t h e ordinary temperature contains 0.0096 gram of ester. The bavium salt ( C,,Hlo02NS2),Ba cry stalli5es from hot water in broad needles.The yield ot ester is 50% when the theoretical amount (2 mols.) of potassium hydroxide (78.6% solution) is used but falls t o nil when 1.5 times the theoretical amount is used. Benayl hydrogen dl-alunincditl~iocur~oxylnte CO,H* CHMe-N H*CS,*CH,Ph crystallises from water in Short colourless glistening needles m. p. 136’. I t s solubility a t 20’ is 0-0102. Benzyl hydrogen pheny Iglycineditl~rocarboxylute CO,H*CH,*NPh* CS,*CH,Ph crystallises from water i n slender needles m. p. 171’. Its solubilityORGANIC CHEMISTRY. i. 117 in water at 20" is 0.0038 and it is only sparingly soluble in hot water. The acid beizxyl ester of difhioca~boxyphenylarninoacetic acid CO,H* CHPh*N H*C'S,,*CH,Ph crystallises from aqueous alcohol in needles m.p. 88" ; the butiurn salt (C,,H,,O,NS,),Ba crystallises in slender needles. Banxyl hydrogen samosinedithiocarboxylute CO,H*UH,*NRle* CS,*CH,Ph crystallises from hot water in colourless needles m. p. 1 2 5 O and has solubility 0.0153 a t 20". The barium salt forms rhombs. Benxyl hydrogen as~arccgi.i.zedit~iocc~rbozyZate CO K*C,N,( CO*NH,)-NH*CS,*CH,Ph has m. p. 180° and yields a barium salt which crystallises i n slender needles. Similar compounds have not been obtained from arginine lysine histidine aspartic acid and glutamic acid ; the leucine derivative is oily. The formation of the sparingly soluble benzyl ester affords a simple method for the separation of glycine from aspartic or glutamic acids. J. J. S. Syntheses of Bases of the Sugar Group.EMIL FISCHER and KARL ZACH (Ber. 19 1 1 44 132-1 35) .-AminomethyZglucoside hydro- bromide C7H1505N,HEr is formed when triacetylmethylglucoside bromohydrin (Fischer and Armstrong Abstr. 1902 i 263) reacts wit,h ammonia a t the ordinary temperature The acetyl derivative (10 grams) is sealed up with 12-15 C.C. of solid ammonia. The temperature is allowed to rise gradually t o the ordinary temperature at which it is kept for seven days and the tube then opened after the ammonia has been again solidified. After removal of the excess of ammonia the syrup is extracted with absolute alcohol the alcohol evaporated under reduced pressure and the residue extracted with warm dry ethyl acetate which removes acetamide and leaves a mixture of ammonium bromide and the hydrobromide of the amino- glucoside; the latter is obtained from t h e mixture in a crystalline form by dissolving in a little warm methyl alcohol and adding much ethyl acetate.To remove the last traces of ammonium bromide the compound is dissolved in absolute alcohol. The yield is 56% of the theoretical. The salt has not a well-defined m. p. but melts and decomposes at about 2 0 5 O (corr.). The hydro- chloride has m. p. 315" (decomp. corr.) and [.]? -25*l0 and both salts dissolve readily in water. The free base dissolves in methyl alcohol but is precipitated as a flocculent mass on the addition of ether. When heated with N-hydrochloric acid in a sealed tube at looo the hydrochloride yields the salt of an amino-sugar. This reduces Fehling's solution b u t is not identical with glucosamine hydrochloride since i t dissolves more readily in water and concentrated hydrochloric acid and is decomposed much more readily than glucosamine by con- centrated hydrochloric acid.The osazone which it yields with sodium acetate and phenylhydrazine hydrochloride is not identical with p hen y 1 g 1 ucosazone. It has [a] - 21.2". J. J. S . VOL. c. i Ei. 118 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Double Compounds of Carbamide with Alkaline-earth Bromides. GEHE & Co. (D.R.-P. 226224).-The action of carbamide on the alkaline-earth bromides yields compounds of therapeutic value in heart complaints. Culcium bvomocaybumide m. p. 186' is prepared by heating calcium bromide (250 parts) with carbsmide (225 parts) in the presence of a small quantity of alcohol or water during three hours under a reflux condenser ; it crystallises from alcohol or ether.F. M. G. M. Preparation of Substituted Carbamic Acid Esters. VEREINIGTE CHININFABRIKEN ZIMMER St Co. (D.R.-P. 22571 2)- a-Methyl-P-tciclhloroethyZ allop?hanate C,I&O,N,CI3 prisms m. p. 186O is prepared by heating trichloroisopropyl alcohol (1 mol.) with carbamic chloride (2 mole.) on the water-bath. Yetrachloroethyl ullophanute C,I3,O3N2CI is obtained by substitut- i n g chloral for the alcohol in the foregoing preparation and allowing the mixture to remain a t the ordinary temperature during two days; it forms colourless crystals which decompose at about 1 60'. When molecular proport ions of trichloroisopropy 1 alcohol and p - e thox y - phenylcarbimide are heated together at 1 S5O ts.ichloroisopropy1 p-etIiox~~T~en?/Zcarbamc~te C,,H,,O,NCl is obtained as a syrup which after crystallisation from petroleum has m.p. 86'. Preparation of Esters of Allophanic Acid. CHEMISCHE WERKE VOBM. DR. HEINRICH BYK (D.R.-P. 236228).-Tertiary alcoholic esters which are therapeutically important are not readily prepared by the ordinary methods and allophanic tertiary alcoholic esters have not previotisly been obtained. AnayZ atlophanate CMe,Et*O*CO-NH*CO*NH colourless needles m. p. 149-150° is prepared by treating a cooled solution of ainylene hydrate in an indifferent solvent with cyanic acid and evaporating in a vacuum ; i t is sparingly soluble in water ether or benzene readily so in alcohol and is decomposed by hot alkalis.Preparation of a-Bromo-a-ethylbutyrylcarbamide. FARBEN- a-et~~ylbutycylcarbamide CBrEt,*CO*NH*CO*NH colourless tasteless odourless crystals m. p. 1 14-1 1 f0 and of therapeutic value is prepared (1) by heating a-bromo-a-ethylbutyryl bromide (obtained by the action of bromine on a-ethylbutyric anhydride) with carbamide at 100' ; (2) by the action of sulphuric acid on a-bromoethylbutyrylcyanamide (prepared from cyanamide and a-bromoethylbutyryl chloride) ; (3) from the interaction of ammonium acetat,e with phenyl a-bromo-a-ethyl- 6utyrpZcarbnrnute which forms colourless crystals and is prepared from a-bromo-a-ethylbutyryl bromide and the sodium derivative of phenyl carbarnate ; (4) by the oxidation of a-bromo-a-ethylbutyrylthiocarb- amide with potassium permanganate or (5) the direct brornination of a-eth ylbutyrylcarbamide. Calcium Cyanamide.NIKODEM CARO (Zeeitsch. angew. Chem. 19 10 23 2405-241 7).-[ With B. Scauc~]-\Vlien solutions contain F. M. G. M. F. M. G. M. FABRIKEN VORM. FRIEDR. BAYER & C O . (u. R.-P. 225710).--a-Bromo- F. 31. G. Rl.ORGANIC CHEMISTRY. i. 119 ing dicyanodiamide and silver nitrate in the mol. proportions 1 I 2 1 and 3 1 are mixed the compounds AgNO,,C,H,N AgN0,,2CpH4N4 and AgN03,3C,H4N are produced. The first of these substances is converted by sodium hydroxide into the compound C,HpN,Ag whilst the second yields a mixture of the same compound and sllver oxide. Silver dicyanodiamide decomposes when boiled first into silver cyanamide ; when the boiling is more prolonged the latter is further decomposed with production of cyanamide.Cyanamide dicyanodiamide and carbamide are estimated as follows Calcium cyanamide (7 grams) is shaken for two and a-half hours with 400 C.C. of water and the solution made up to 600 C.C. A portion of the solution (250 c.c.) is treated with ammonia and silver acetate diluted to 400 c.c. filtered and the precipitate mashed. The nitrogen (cyanamide) is then estimated by the Kjeldahl method. A part of the filtrate (300 c.c.) is boiled with potassium hydroxide diluted to 400 c.c. and the nitrogen in the precipitate (dicyanodiamide) estimated as before. A part of the filtrate (300 c.c.) is evaporated down the silver precipitated with hydrogen sulphide and the excess of t h e latter expelled by carbon dioxide.It is then diluted to 400 c.c. and t h e nitrogen (carbamide) estimated in 100 C.C. [With RICHARD JACOBY and B. SCH6CK.]-When calcium carbide is heated in absence of air with 10% sodium cyanide for three hours a t 900° nearly the whole of the cyanide is converted into cyanamide. The same change occurs when barium cyanide is heated in a current of acetylene diluted with hydrogen. [With B. Sc~ucK.]-\vhen calcium 2yanamide is heated in a current of dry carbon dioxide the carbide present is completely decompoled and the calcium cyanamide is decomposed with production of carbon. [With R. .TACOBY and B. SCH~JCK.]-AS regards the alleged production of nitrides by the action of nitrogen on a mixture of alumina and carbide it was found that neither nitrides nor cyanamide are produced at 800-1 200° products being obtained containing not more than 0 8% per cent. N st the lower temperature and generally no nitrogen a t temperatures of 1000" or more.Calcium carbide when heated with alumina in an inert atmosphere yields a black substance concaining neither calcium nor aluminium carbide. [With B. Sc~ijc~.]-Piire cyanamide can be prepared by slowly adding sodium cyanamide to well cooled strong hydrochloric acid and distilling off the water in a vacuum. The cyanamide is then dissolved in ether. It can also be obtained by adding a concentrated solution of aluminium sulphate to a n aqueous extract of calcium cyanamide. The filtrate is distilled in a vacuum and extracted with ether. Cyanamide forms colourless crystals m. p. 41-42" readily soluble in water alcohol and ether.When heated it is at onceconverted into dicyano- diamide (in. p. 2 0 4 O ) ; the same change takes place when it is exposed t o air. [With I:. JACOBY.]-T~~ temperature n t whbh nitrogen acts OD mixtures of baryta aud carbon is reduced by adding fluorides; the I,. 2i. 120 ABSTRACTS OF CHEMICAL PAPERS. action takes place at a temperature below the m. p. of the fluoride. When a mixture of barium carbonate carbon and calcium (or barium) fluoride is heated without nitrogen a t the temperatures employed for nitrogen fixation there is a production of carbide. No carbide is formed at this temperature in absence of fluoride. N. H. J. M. Preparation of Phenylnitromethane [a-Nitrotoluene] by the Action of Mercurous Nitrite on Benzyl Chloride.PARCHANAN NEOGI and BIRENDRA BIIUSAN ADHIC~RY (Zeitsch. c6nol.g. Chem.. 191 1 69 270-272).-o-Nitrotoluene is readily obtained by the inter- action of mercurous nitrite and benzyl chloride the reaction mixture being fractionally distilled under diminished pressure. The yield is much better than when silver nitrite is used. T. S. P. Preparation of Diphenylmethane and its Homologues. ERNST VON MEYER (J. pr. Chem. 1910 [ii] 82 538-540).-The hydrocarbon obtained by the action of phosphoric oxide on benzyl ethyl ether in benzene solution and regarded by Schickler as an isomeride OF stilbene is shown to be diphenylmethsne not only by the fact that it is not formed wheu light petroleum is used as the solvent but also by its oxidation to benzophenone by chromic and acetic acids and by its nitration to 4 4'-dinitrodiphenylmethnne and tetranitro- diphenylmethane.Phenyl-p-tolylmethane and phenyl-a-naphthylmethane are obtained in a similar manner by replacing the benzene by toluene and naphthalene respectively ; p-chlorodiphenylmethane is obtaiiied by using p-chlorobenzyl ethyl ether instead of benzyl ethyl ether and triphenylmethane by employing diphenylmetbyl ethyl ebher. c. s. Triphenylmethyl Chloride Diphenylcarbamyl Chloride and Cyanuric Bromide Acting as Acid Halogenides. ERNST VON MEYER (J. pr. Chem. 1910 [iiJ 82 521-538).-A compnrative study of transformations in which trjphenylmethyl chloride diphenyl- carbamyl chloride and cyanuric bromide function as acid halogenides. [With P. FiscHE~.l-l'riphenylmethyl chloride reacts with carbamide methylcarbamide and phenylcarbamide in pyridine to form s-ditri- phe4lyzmethylcccrbarif~e CO(NH*CPh,) s-triphenyZmeth?lZ~,zeth?/Zcnrb- mnide NHMe*CO*NH-CPh m.p. 263O and s-phenyltriphenylmethyl- carbunzide NHPhG0.N HOCPh rn. p. 2 4 2 O respectively and with thiocarbamide to form tl.iphenylmelhyEthiocarbccmide NH,*CS*NH*CPh m. p. 217'. Triphenylmethyl chloride reacts with potassium phthal- co imide a t 200' to form triphenyZmethylphthalimide C,H,<CO>N*CPh m. p. 172y with pyrrole and with piperidine yielding triphan.yltueth?yI- pyrrole C,NH,*CPh m. p. 258O and trii0iLenylmethyl~ipel.idine C,NH,,*CPh m. p. 153O respectively and with pyridine or yuinoline in benzene solution readily forms the crystalline additive compounds C,NH,,CPh,CI m.p. 171° and C,NH,,CPh,Cl m. p. 163" which are decomposed by water or alcohol and form intensely yellow solutions in hot pyridine. When fused with phenol or with resorcinol triphenyl- methyl chloride yields p-hydroxytetraphenylmethane and dihydroxy-ORGANIC CHEMISTRY. i. 121 tetrup~&enylmet?&ane CPh,*C,H,(OH) m. p. 268' respectively ; with mercaptans in benzene or ethereal solution however the chloride acts as a n acid chloride yielding thio-ethers triphenylmethyl methyl sulphide m. p. 105' from methyl mercaptan triphanylmethyl ethyl sulphide m. p. 125' from ethyl mercaptan and phenyl triphenylmethyl sulphide m. p. 105O from phenyl mercaptan. Triphenylmethyl chloride reacts with alcoholic p toluene-sulphinic acid a t 1 30' to'form acetaldehyde and triphenylmethnne by the decompohition of the initially formed tri- phenylmethyl ethyl ether and yields with sodium p-toluenesulphinate in benzene p-tolyZIri~hsnylmethyZsulr)hone CPh,*SO,*C,H,Me m.p. 173' which is decomposed by water into triphenykarbinol and p-toluenesul phinic acid. Triphenylmet hyl chloride reacts in ether with magnesium benzyl chloride to form triz~hennylbenzylmethane m. p. 140° with magnesium p-chlorobenzyl chloride to form triphenyl- p-c~~Zorobsnx~,lmethane m. p. 172' and with magnesium phenyl bromide to form diphenyl and triphenylmethyl the latter being obtained in the form of its peroxide. [With A. NIcoLAos.]-DiphenylcArbamyl chloride and pyridine yield an additive compound C,NH,,NPh,*COCl m. p. 107'. which forms a platinic?&wicle decomp.170' picrate m. p. 161' and iodide m. p. 182'. The formation of esters from diphenylcmbamyl chloride and alcohols only occurs very slowly ; easily however in the presence of a little alkali or potassium cyanide ; ethyl diphenylcarbamate has m. p. 72' the corresponding methyl arid isop-opyl esters 86' and 117' respectively. lbipheny lsemicai*baxide ( R-D iphe n y barbam ylphen y lh ydrazide) NHPh*N H COON Ph (ncetyl derivative m. p. 165' ; nitroso-compound m. p. 131') is obtained readily from phenylhydr azine (2 mols.) and diphenylcarbamyl chloride in benzene and is oxidised by alcoholic ferric chloride to diphenpl- ca~,bam~luxo~l~enyl NPh N*CO*KPh In. p. 1 3S0 red needles which develops a deep red coloration with conwntrated sulphuric acid. The interaction of diphenylcarbamyl chloride and aliphatic amino-acids is accomplished best by employing the latter in the form of their esters or sodium salts acetone being used AS solvents ; thus a-diphsnyl- carba~niflo)7ropio?zic acid CO H *CHMe*NK*CO*NPh m.p. 1 4 9 O is obtained from alauin e a n d u-diphen y lcar bamidohexoic mid CH,Me*[CH,];CH (CO,H)*NH*CO*NPh in. p. 52' from leiicine. E'th!/Z o-dii)henyZcarban2idobenzoc~t~ C0,Et*C,H,*NH*CO*NPh2 m. p. 1OSo obtained by heating eqiial molecular quantities of ethyl anthrxni1:tte and dipheriylcarbamyl chloride with a n excess of zinc dust R t about loo' yields the free acid m. p. 178' by hydrolysis. The halogen in diphenylcarbarnyl chloride is readily replaced by an aikyl or aryl group by the Grignaril reaction ; thus with magnesium ethyl iodide i t yieltls diphen?/lpl.ot'ionccmide m.p. 58' with magnesium propy1 bromide diphsn?l?butyrarriide m. p. 47' and with magnesium phenyl bromide diiul~s?z?/lbenzamide m. p. 176'. Diphenylcarbumyl cyanide NPh,*CO.CN m. p. 126' obtained from the chloride and an excess of potassium cyanide at 1 80-200° yields diphenylamine hydrogen cyanide and carbon dioxide by hydrolysis with alcoholici. 122 ABSTRACTS OF CHEMICAL PAPERS. potassium hydroxide; it forms an amido-oxime NPh,*CO*C(NH,):NOH m. p. 2225" with alcoholic hydroxylamine at 60-80° and is converted in alcoholic eolution into the tlhioamide NPh,*CO-CS-NH m. p. 220' by hydrogen sulphide in the presence of aqueous ammonia. {With FRAULEIN NA~~.]-Cyanuric bromide is obtained in 70-80% yield by the action of nascent hydrogen bromide on a benzene solution of cyanogen bromide. Cyanuric bromide forms cyanuric trihydrazide with 10% hydrazine cyanuric triphenylhydrazide with ethereal phenyl- hydrazine and in boiling benzene reacts ( a ) with o-chloroaniline t o form cyanuric tri-o-chloroanilide (trichlorophenylmelaarraine) m.p. 161'; (b) with 2 4-dichloroaniline to form cyanuric tri-2 4-di- chloroanilide m. p. 261"; (c) with nz-nitroaniline to form trinitrophnyl- melamine (CN),(NH*C,H,*NO,) ; (d) with a-naphthylamine to form iri-a-napl~t~~ylmelumiiae (CN)3(NH*C,oH7)2 m. p. 225"; (e) with methyl- aniline to form tripheiayltrimellyl~el~rna~e (CN),(NMePh) m. p. 1 15" ; (f) with benzylaniline to form triphen~ZtribenzyZm~elamine m. p. 1 20' ; (9) with $7-aminophenol to form cyanuric di-p-hydroxyanilide bromide (CN),(NH*C,H,*OH),Br m.p. 275' (decomp.) ; ( I t ) w i t h p-anisidine to form a correspoading anisidide (CN),(NH*C,H,mOMe),Br rn. p. 250' (decomp.) and (i) with anthranilic acid to form the substance (CN),(NH*C,K,-CO,H),Br m. p. 197'. Cyanuric bromide and carb- amide (3 mols.) at 130-140' yield ti*icarbamylmelamine m. p. above 300". Cyanuric bromide reacts in the normal way with aluminium chloride and an aromatic hydrocarbon in the presence of carbon disulphide forming substances of the type (CN),Ar,; -4r=Ph m. p. 231"; Ar-p-C,H,Me m. p. 275-276"; A r = 3 4-C6H,Me m. p. 210" ; Ar = 2 4-C,H,Me2 m. p. 155"; Ar =p-C,H,*OMe m. p. 115" ; A r = a-CIoH1 m. p. 190-200" ; the constitutions of these compounds (excluding the first) are determined by the fact that hydrolysis by hydrochloric acid at 200-220' yields p-toluic 3 4-dimethylbenzoic 2 4-dimethylbenzoic anisic and a-naphthoic acids respectively.The analogous triethyl compound (CN),Et obtained by Otto and Voigt from dicliloropropionitrile is also produced by the interaction of (CN),(NH.C6H,Cl) (CW),(NH*CO*NH,) cyanuric bromide and ethereal magnesium ethyl iodide. c. s. Triarylmethyls. v. WILHELM SCHLENK and ANNA HEGZENSTEIN (Bey. 1910 43 3541-3546. Compare Abstr. 1909 i 791; 1910 i 236 237 469).-According to the authors the sole objection t,o the hexaphenylothane formula for the colourless form of triphenylmethyl lies in the comparative stability of the closely related pentapbenylethane. Investigation of the behaviour of the latter compound in high boiling solvents shows however that the remarkable power of dissociation characteristic of " colourless " triphenylmethyl is also shared by pentaphenylethane a1 though in a less marked degree.Solutions of pentaphenylethane in anisole or ethyl benzoate on being heated rapidly t o boiling acquire the deep yellowish-brow11 colour of n hot solution of triphenylmethyl ; on quickly cooling the colourORGANIC CHEMISTRY. i. 123 diminishes to a light yellow. The solution decolorises iodine and at once becomes colourless when shaken with air ; the colour however rapidly reappears and finally vanishes only by repeated shaking with air. This behaviour SO closely resembles that of tripheriylrnethyl solutions that there can be no doubt that triphenylmethyl is one of the products of dissociation of pentaphenylethane Ph,C-I-CHPh,.The second dissociation product diphenylmethyl polymerises to tetra- phenylethane which can be readily isolated by boiling pentaphenyl- ethane in ethyl benzoate solution in an atmosphere of nitrogen. On passing oxygen through a boiling solution of pentaphenylethsne in e thy1 benzoate the diphenglmethyl is oxidisecl to tetraphenylethylene. A new method of formation of hexa-arylethanes is also described. When n concentrated benzene 'solution of molecular quantities of 4-pbenyl-triphenylmethaiie and 4-phenyl-triphenylmethyl chloride is exposed to sunlight i t acquires a reddish colour due to the formation of 4-phenyl-triphenylmethyl C,H4Yh.CPh2H + C1CPh;C6H4Ph Z C,H4Ph* CPh,* * a CPh2-C,H4Ph + HCl.The reaction is however reversible the amount of 4-phenyl- t riphenylmethyl being w r y small when equilibrium is attained. In n similar manner phenylbisdiphenylmethpl CPh(C,H,Ph) is obtained from phenylbisdiphenylmetliane and pheriylbisdipheriylruethyl chloride. Q .H Diphenylbisdiphenylene-ethane ?6R4>CPh*CPh< ' 4 on account C,HA G H A of its stability towards hydrochloric acid is produced 'In buantitative yield by exposing a concentrated benzene solution of phenyldiphenylene- methyl chloride and phengldiphenylenemothane (phenylfluorene) to Applications to Phenanthrene. PIERRE BRETEAU (Compt. !rend. 19 10 151 1368-1 369).-By passing a mixture of pherianthrene vapour and hydrogen over spongy palladium a t 160° a mixture of the tetra- and octa-hydride is obtained; when hydrogenation is carried out a t the oiatiinarg temperature in presence of palladium black suspended in cyclohexane only the tetrahydride is formed.Precipitated palladium prepared by treating a solution of the chloride in hydrochloric acid with zinc also yields the tetrahydride when brought into contact with Action of Concentrated Sulphuric Acid on Some Aromatic Nit roamin es. 11. Derivatives of Met hylanili ne Methyl- p-anisidine and Methyltoluidines. FREDSRIC EEVEBDIN (Bull. ASoc. chirn. 1911 [iv] 9 43-49. Compare Abstr. 1910 i 255).- Fiirther instances are given of tbe reduction of the nitro- to the 1,itroso-group by sulphuric acid in certain aromatic nitro-derivatives and i t is shown that this reaction explains why such nitro-derivatives respond to Liebermann's test. 3 4 6-Trinitrophenylmethylnitroamine on treatment with sulphuric acid a t atmospheric temperature furnishes picramide and some nitroso- methylpicramide (Bamherger and Miiller Abstr.1900 j 217). The latter is also produced if alcohol is used along with sulphuric acid the action of sunlight. F. 3:. Hydrogenations in Presence of Palladium. phenanthrene in alcoholic solution. w. 0. w.i. 124 ABSTRACTS OF CHEMICAL PAPERS. but in this case the principal product of the reaction is trinitromethyl- aniline. Dimethyl-p-anisidine on nitration in the cold furnishes the N-nitroso-derivative of dinitromethyl-p-anisidine m. p. 11 1-1 1 3' but with hot nitric acid gives the N-nitro-derivative m. p. 1 2 5 O which may also be obtained by the further action of nitric acid on the nitrosoarnine and conversely the latter is reproduced by the action of sulphuric acid on the nitroamine.Further when the nitroamine is heated with phenol or the nitrosoarnine is heated with hydrochloric acid dinitromethyl-p-anisidine m. p. 129O is formed. By bailing the nitroamine with sodium hydroxide solution a small yield of Weselsky and Benedikt's dinitroquinol methyl ether (Abstr. 18SL 1139) is obtained. The fact that this nitroarnine like that obtained from dimethyl-o-anisidine (Abscr. 1910 i 255) gave the Liebermann reaction led the author to examine nitroamines obtained from alkyl- toluidines and for this purpose 3 5-dinitro-o-tolylmethylnitroamine and its p-isomeride were prepared by the method described by van Romburgh (Rec.trav. chim. 1884,3 392). As secondary products in these preparat,ions some 3 5-dinitro-2-nitromethylanlinobenzoic acid and its 4-isomeride were obtained (Ahstr. 1908 i 167). These melted at 187' and 204' respectively. Both nitroamines gave Liebermann's reactiou. The first on treatment with sulphuric acid at atmospheric temperature gives Stoermer's 3 5-dinitro-o-tolylmethyl- nitrosoarnine (Abstr. 1899 i 44) but is recovered unchanged from sulphuric acid a t - 10". 3 5 -Dinitro-o-tolylmethylnitroamine with sulphuric acid at atmospheric temperature furnishes 3 5-dinitro- 2-nitromethylaminobenzoic acid (see above) and a substance cry stallis- ing in colourIess needles and decompo;ling above 300° but with sulphuric acid a t - 10' it gives the same acid with as chief product 3 5-dinitro-p-tolylmethylnitrosoamine m.p. 127-1 28' (compare van Romburgh Abstr. 1896 i 478). The Reaction of Cellulose Nitrate with Dimetbylaniline. JORANN WALTER (Zeiiech. angew. Chem. 191 1 24 62-64).-Gun- cotton and celluloid absorb dimethylaniline the colour gradually deepening through green and blue to violet. The coloration becomes darker on exposure t o light and is not removed by solvents. Strongly- coloured specimens have a n odour of phenylmethylni trosoamine. Other aromatic amines produce similar colorations but less rapidly and of less intensity. Velocities of Addition of Bromine to the I m i d e s of Some Substituted Maleinamic Acids. 11. ARNALDO PIUTTI and G. CAJXAGNI (Rend. Accad. Xci. Pis Mat. Napoli 1910 [iii] 16 255-261.Compare Abstr. 1909 i 36O).-Continuing their investi- gations on this subject the authors have measured the velocibies of addition of bromine t o the following imides (compare Abstr. 1910 i 672) hydroxyphenylmaleinimide (white form) methoxyphenyl- maleinimide (white and yellow forms) ethoxyphenylmaleinimide (white and yellow forms). The velocity is very slow in a11 these cases ; for the white imides the reaction is complete in about fifty days for the yellow forms in about seventy-five days. Since Bnuer has shown that I?. A. H. C. H. D.ORGANIC CHEMISTRY. i. 125 substance of t h i s type the power of adding on bromine diminishes with increase in the number of negative groups this forms an additional argument for assigning t o the yellow form the symmetrical formula I 1 >N*C,H,*OR.The white isomerides behave as weak bases and that is consonant with their having the constitution CH*CO CH-CO R. V. S. Preparation of Alkali and Ammonium Salts of Nitrosoaryl- hydroxylamines. OSKAR BAUDISCH (D.K.-P. 227659).-Nitroso- arylhydroxylamines a r e known but their salts have not previously been obtained; they a r e now prepared by either the oxidation of an amine or the reduction of a nitro-compound i n alkaline solution in the presence of sodium nitrite or an alkyl nitrite. Ammonium nitrosophsnyli,ydroxy?ccmin~ prepared from nitrobenzene concentrated ammonium hydroxide zinc dust and amyl nitrite crystnllises in silvery leaflets m. p. 163-1 64" and sublimes readily. The sodium salt C,H,*N(NO)*ONa and the potassium salt form snow-white needles ; the iron palt crystallises in garnet-red needles or rosettes with a blue metallic lustre; it is insoluble in water but soluble in the ordinary organic solvents; the copper salt forms dark grey crystals and has similar properties.Ammonium a-nitrosonaphthyl- hgdroxylamine colourless leaflets is rather unstable turning pink in the light; i t dissolves i n water and is converted on boiling into a-nitrosonnphthalene ; the sodium and potussium salts are colourless ; the copper salt (C10H702N2)2C~~ forms glistening bluish-grey needles insoluble in water. The formation of complex double salts of ammonium with copper nickel cobalt or iron is also discussed. F. M. G. M. Separation of p- and m-Nitro-o-anisidine. CHEMISCHE FABRIK GRIESHEIM-ELEKTRON (D.R.-P. 228357).-The nitration of aceto-o- anisidide yields a mixture of two isomeric nitroaceto-0-anisidides ; these have previously been separated by the more ready hydrolytic disso- ciation of p-nitro-o-anisidine which is precipitated by the addition of water t o a n acid solution of the mixed sulphates whilst m-nitro-o- anisidine sulphate remains in solution.It i s now found that a separation can be effected by fractional crystallisation of the mixed sulphates ; t h e mixture of m- and p-nitro- aceto-0-anisidides is hydrolysed by heating with 70% sulphuric acid and the mixture then diluted with hot water until the concentration of the sulphuric acid is reduced to 40% ; on cooling pure p-nitro-o-anisidine sulp?mte separates i n colourless crystals and the m-nitro-o-anisidine i s precipitated from the filtrate by the addition of alkali.F. M. G. M. Preparation of Phenyl Ortho-oxalatee. SCHULKE and MAYR (D.R.-P. 22623 l).-When dehydrated oxalic acid is mixed wit.h fusedi. 126 ABSTRACTS OF CHEMICAL PAPERS. phenol (2 mols.) at a temperature of about 40° and then heated to 90-100" with continual stirring pure diphmyl ortho-oxalate OPh*C(OH),*C( OH),*OPh is obtained in quantitative yield; it crystallises from acetic acid and has m. p. 126". F. M. G. M. Synthesis of Alcohols in the cycZoHexane Series. ALPHONSE MAILHE and MARCEL IXURAT (Bull. ~Soc chirn. 19 10 [iv] 7,1083-1089). -The co n d ensation of 1 -meth y lcyclob exan-3-one with various magnesium alkyl haloids has been studied and t h e alcohols obtained and some of their derivatives are described (compare Sabatier and Mail he Abstr.1906 i 254 ; Murat Abstr. 1909 i 146). l-~lethyl-3-ethylcycZohexan-3-ol Do 0.9201 D20 0.9013 n 1,459 b. p. SS"/ZO mm. obtained by condensing 1-methylcyclohexan-3-one (Abstr. 1905 i 275) with ethyl magnesium bromide is a colourless liquid with a feebly camphoraceous odour (compare Zelinsky Abstr. 1901 i 661) ; the phenylurethane m. p. 98" crystallises i n colourless prisms ; tho acetute DO 0.9493 DZo 0.9303 n 1.441 b. p. 9S-100°/ 30 mm. has a fruity odour. The alcohol is readily dehydrated yielding 1 -meth?yl-3 -ethylcycloh,exene Do 0.8366 DZ0 0.8296 n 1.454 b. p. 149-151"/760 mm. a mobile colourless liquid of pleasant odour; i t gives a greenish coloration with sulphuric acid and alcohol furnishes a nit?-osochloride m.p. 124-1 26" and on reduction yields I-met?qZ-3- eth7~lcyclohexane DO 0.8320 D20 0.S313 n 1.460 b. p. 145-146O. l-niIethy1-3-propylc~cZohexan-3-ol Do 0.9063 D15 0.896 I n 1.461 b. p. 96-98"/20 mm. is a colourless viscous liquid (Zelinsky Eoc. cit.); it yields a phenylus*ethane m. p. 112O and a n acetate DO 0-9367 1)20 0.9248 n 1.454 and h.p. 108-110"/20 mu. which is colourless and has a fruity odour. The alcohol is readily dehydrated yielding l-methyl-3-propylcyclohexene Do 0.83'75 D15 0.8302 n 1 m4.56 and b. p. 16S-171"/760 mm. which absorbs bromine and gives a yellowisb-green colour with alcohol and sulphuric acid furnishes a nits*osochloride m. p. 128-131' (decornp.) and on reduction gives 1 -methyl-3 propylcyclohexane b.p. 164-1 65O. 1 -Meth~l-3-isobutyZcycloJ~exc~n-3-ol Do 0.901 1 D19 0.8972 n 1.465 b. p. 107-109°/20 mm. is best obtained by condensing magnesium isobutyl chloride with methylcyclohexanone although the secondary reaction already described (Abstr. 1905 i 706) occurs and occasions some loss. The alcohol is viscous and dehydrates easily giving an ethyleiaic hydq-ocarbon b. p. 192-1 95" having a somewhat alliaceous od our . l-Meth~Z-3-isoarnyZcyclohexnn-3-oZ Do 0.8982 lY2 0.8856 n 1.464 b. p. 12d-I 2s0/2O mm. is a viscous colourless pleasant-smelling liqrrid; the phen,yZumthane m. p. 128O is crystalline and the acetate DZo 0.9146 n 1-457 b. p. 140°/20 mm. is a thick liquid with a pleasant odour. The alcohol on dehydration gives l-metA,p?- 3-isoarnylcyclohexesze DO 0.8301 D2O 0.8190 n 1.459 b.p. 209-21 1'1 760 mm. which gives a greenish coloration with sulphuric acid and alcohol yields a nitrosochloride m. p. 136O and on reduction furnishes l-mathyl-3-isoamylcyclohexane b. p. 205" a colourless liquid with a n odour recalling that of petrol.ORGANIC CHEMISTRY. i. 127 3-cyclo~€exyZ-l-metJ~ylcyclohexun-3-oZ Do 0.981 5 UlS 0.9685 nD 1,495 b. p. 153-155O/20 mm. is a viscous liquid of agreeable aroma yields a phen?/luyethane m. p. 141" gives an intense blue coloration with bromine in chloroform and on dehydration furnishes 3-cvclohexyZ- l-metl~yZcyclohexe?za Do 0.9634 DlS 0.9 138 n 1.492 b. p. 240'/760 mm. a mobile liquid which is scarcely coloured by sulphuric acid and alcohol but gives a nitrosochloride m. p. 142-146' which is possibly a mixture of isomericles.3-Phenyl-l-meth~Zcyclo~exan-3-ob m. p. 61° b. p. 153"/20 mm. (decomp.) crystallises i n monoclinic prisms yields a phenytuwtl~ar~a m. p. 143" and on dehydration furnishes 3-phen~l-1-methylcyclo- Iiexene DO 0.9859 1120 0,9702 n$' 1.555 and b. p. 145"/20 mm. as a colourless mobile liquid which absorbs bromine and with sulphuric acid and alcohol gives a rose-red coloration. 3-Benx~Z-l-~~et7~ylcyclohe.z.a~~-3-oZ DO 1.0032 D17 0.9873 n Z -532 b. p. 165O/18 mm. (decomp.) is a colourless liquid having a lemon-like odour and is obtained in small yields by condensing methylcycZo- hexanoue with benzyl mngnesiuni chloride the chief product being dibenzyl. 3-BenzyZ-l-~nethyZcyclohexene DO 0-9693 D20 0-9591 n 1.547 b. p. 156"/20 mm.or 271°/760 mm. is colourless and has a disagreeable odour. T. A. H. A Solid Molecular Compound of Hexamethylenetetramine and Guaiacol. E. HOFFMANN-LA KOCHE & Co. (D.R.-P. 225924).- The preparation of a hexamethylenetetraminetriguaiacol has been previously described (hbstr. 1910 i 378). A compound obtained in a similar manner and with identical properties is now found t o have tho composition of a hexamethylenetetraminediguaiacol and it is suggested that the former compound was possibly not an individual sumtance. F. M. G. Di31. Fermentation of Tyrosine to p-Hydroxyphenylethanol (Tyrosol). FELIX EHRLICH (Ber. 191 1 44 139-146. Compare A bstr. 1907 ii 384).-A 60-80% yield of p-hydroxyphenylethanol OH*C,H,*CH,-CH,*OH can be obtained by the fermentation of tyrosine with large amounts of yeast in the presence of much sugar and of nutritive salts.Small amounts of acids are also formed; these are soluble in ether and give Millon's reaction. The hydroxy-alcohol is termed iyrosol. It crystallises in long glistening needles and rods of rhombic habit; it has m. p. 93' and b. p. 310'. It has .zi bitter taste does not reduce Fehling'a solution and gives a Bordeaux-red coloration when warmed with concentrated sulphuric acid. With ferric chloride solution it gives an indigo-blue coloration and with Rlillon's reagent and also with diazobenzenesulphonic acid dark red colorations. It does not give the Piria reaction but develops an iutense yellowish- green coloration with formaldehyde and sulphuric acid. It is oxidised by alkaline permanganate solutions reacts with phosphorus penta- chloride yielding a yellow oil and also forms an oily acetj 1 derivative.The dibenzoyl derivative C22H1s04 prepared by the Schotten-Baumann method crystallises from alcohol in felted needles m. p. 11 1". The formation of tyrosol is brought about by either top or bottomi. 128 ABSTRACTS OF CHEMICAL PAPERS. yeads. It is also formed in appreciable amounts when a sterilised solution of tyrosine and sugar is inoculated with pure cultures of yeast and in small amounts during t h e fermentation of pure sugar solutions by pure yeasts. I t s formation in the latter case is due t o the autolysis of the dead yeast cells and the Formation of tyrosine which is used as nitrogenous nutritive material by the living cells and transformed into tyrosol.It is not formed in the absence of sugars. Tyrosol thus appears t o be a by-product in most processes of fermentation by yeast and is present in all fermented liquors especially in beer and wine the flavours of which are due in part to the presence of the hydroxy-alcohol. J. J. S. Preparation of Nitrobenzoic Acids from the Corresponding Nitrotoluenes. GUSTAV L~TTGEN (D.R.-P. 226225)-The oxidation of nitrotoluenes to the corresponding nitrobenzoic acids with nitric and sulphuric acids is not satisfactory; it is now found that the reaction proceeds smoothly in nitric acid solution with potassium chlorate as the oxidising agent. 2 4 6-Trinitrotoluene was dissolved in concentrated nitric acid (48 Be) and warmed to 90-95'; potassium chlorate (2 parts) was gradually stirred in the temperature being maintained meanwhile at 100-120° i pure trinitrobenzoic acid separated from the reaction mixture on cooling. P.A$. G. M. Synthesis of Compounds of the Normal Amy1 Series from Piperidine. JULIUS YON BRAUN and W. SOBECKI (Bey. 1910 43 3596-3599).-Although benzo-c-chloroamylamide derived from piperidine is very stable the corresponding benzoiodoamylamide is relatively easily reduced. It is prepared from the chloro-compound by boiling this with sodium iodide in alcohol and is dissolved in much concentrated hydrochloric and acetic acid cooled and stirred with zinc dust for a number of hours. Banzo-n-amyZc6mide separates RS an oil and is purified by dis- tillation; b. p. 208-210°/15 mm. It is readily hydrolysed to n-amylamine or when distilled with phosphorus pentachloride or pentabromide is converted into cn-amyl chloride or bromide respec- tively.To prove that the normal carbon-chain structure had remained intact the bromide was boiled with potassium cyanide and converted into the nitrile of n-hexoic acid. E. F. A. Secondary Anthranilic Acids and the Transformation of their Nitroso-derivatives into a Peculiar Class of Intensely Red Substances Soluble in Water. JOSEF HOUBEN and TH. ARENDT (Ber. 1910 43 3533-3541. Compare Abstr. 1908 i 27; 1909 i 645 794).-Previous attempts t o nitrosylate methyl dimethylanthranilate failed. The authors now find that the action of sodium nitrite and fuming hydrochloric acid on the ester yields 5-nitroso- N-methylanthranilic acid one of the methyl groups being split off from the nitrogen atom.When 5-nitroso-N-methylanthranilic acid is dissolved in sodium carbonate and shaken with acetic anhydride a red substance is formed,ORGANIC CHEMISTRY. i. 129 which is very soluble in water. Similar red products have been obtained by the action of various acid chlorides and anhydrides either in aqueous or pyridine solution on a large number of nitroso- derivatives of secondary anthranilic acids and their esters and also on quinoneoximecarboxylic acid but oiilg in one instance has the product been isolated. When 5-nitroso-N-rnethylanthranilic acid is shaken with pgridine and acetic anhydride a red solution is formed from mhicb by the addition of ether a brownish-red pyridine salt C,,H,,O,N is pre- cipitated ; the salt is very soluble in water forming blood-red solutions and melts with decomposition t o a dark red liquid.CO,H-C,H,=NH-CH;COMe prepared by dissolving anthranilic acid in the equivalent quantity of potassium carbonate and boiling the solution with chloroacetone has m. p. 169-170'; the nitrosuntine which forms white crystals m. p. 115-1 16' (decomp.) could not be transformed into 5-nitroso- N-acetonylanthrariilic acid by t h e action of hydrochloric acid ; the semicarbuxone obtained from the sodium bisulphite compound of ace tonylanthranilic acid has m. p. 240-241' (decomp.). MethylucetonyZxntiLruniZic acid CO,H*C,H,*NMe*CH,.COMe pre- pared from metl ylanthranilic acid and chloroacetone crystallises in small light grey needles m. p. 123-126'.[With L. ET~1~0E~.]-N-8cetonylanthl.anilic acid CO2H-C,H,*NH* CH ,- CNe N N €3 CO N H 2 4 - D i r ~ i t r o d i p ~ e n y l ~ t ~ ylarnine-2'-cardoxylic acid CO,H*C H4*NMe-C,H,(N0,) is obtained by boiling 4-chloro- 1 3-dinitrobenzene with methyl- anthrnnilic acid in aqueous potassium carbonate ; it forms clusters OF yellow needles m. p. 178". Action of Ethereal S a l t s on the Monosodium Derivative of Phenylacetonitrile. P. Bouiioux (Conhpt. rend. 19 10 151 1357-1359. Compare Abstr. 1910 i 623).-Ethyl benzoate con- denses with the sodium derivative of phenylacetonitrile to give a 75% yield of cyanophenylacetophenone CN-CHPh*COPIi lamellae m. p. 93-94' (compare Walther and Schickler Abstr. 1897 j 522). Ethyl carbonate in the same way forms ethyl cyanophenylacetate CN*CHPh*CO,Et b.p. 163-165"/19 mm. D17 1.085 the yield being 55?& Ethyl oxalate yields a small quantity of ethyl cyanophenyl- pyruvate. The foregoing cyano-derivatives are sufficiently acidic to be capable of titration using phenolphthalein as indicator. F. B. w. 0. w. Crystallographic Examination of Some Nitrophenylmethyl- acrylic Derivatives. FHAKCESCO RANFALDI (Bend. Accud. Xci. Fzs. Mut. Napoli 19 10. [iii] 16 225-234).-P-o-Nitrophenyl-a-methyl- acrylic acid N0,.C,H',*CH:CR~e.CO,H forms monoclinic prismatic crystals [a b c = 1.3446 1 1.4562 ; = 92"24'51"]. P-m-Nitrophenyl- a-methylacrylic acid forms colourless acicular crystals which could not be obtained in a measurable form. P-p-Nitrophenyl-a-mettiylacrylic acid forms triclinic pinacoidal crybtals [a b c = 1.2567 1 1.4602 ; a = 84'42'8'' ; /3 = 83'31'31" y = 87'35'18"].Sodium P-o-nitrophenpl-i. 130 ABSTRACTS OF CHEMICAL PAPERS. a-methylacrylate forms rhombic disphenoidal crystals [a 3 c = 1,3940 1 2.05441. K. v. s. Preparation of Glycol Monosalicylate. C. F. BOEHRINGER & SOHNE (D.R.-P. 225984. Compare Abstr. 1908 i 176).-The esterification of salicylic acid with ethylene chlorohydrin yields P-chloroethyl salicyhte OH*C,H;CO2.CH,.CB,cl which on careful hydrolysis with mild reagents gives the therapeutically valuable glycol salicylute OH*C6H;C0,*CH,*CH2*OH. The hydrolytic agents described a s suitable are (1) sodium acetate axid dilute acetic acid; (2) disodium phosphate and water or (3) sodium salicylate and water a sealed tube being employed and a temperature of 130" maintained in each case.F. &I. G . M. Pyrogenetic Decomposition of cycZoGallipharic Acid. HERMANN KUNZ-KRAUSE and PAUL MANICKE (Arch. Phuwn. 19 10 248 695-709. Compare Abstr. 1904 i 587; 1910 i 458 677),- The decomposition of cyclogallipharic acid when heated alone or with various dehydrating agents has been studied and the results correlated with those recorded in previous papers (Zoc. cit.). When heated with potassium hydrogen sulphate the acid furnishes unsaturated gaseous hydrocarbons acraldehyde cyclogallipharol and 4-hydrox y-m-xylene. Sulphuric acid is without action on cyclogallipharic acid in the cold but on heating with this reagent it is converted into the keto- anhydride of cp!ogallipharic acid at 125-130° ; a t 150-160" some cyclogallipharol is formed and a t 180' this substance is the sole product of the reaction.When heated alone the temperature being gradually raised from 130" to 250" the amounts of carbon dioxide evolved indicate that the acid undergoes the same progressive decomposition as with sulphuric acid the same stages however being reached at somewhat higher temperatures. Above 250' complete decomposition into carbon dioxide and volatile hydrocarbons takes place. I n conclusion a summary of the results recorded in this and the two preceding papers of the series is given. T. A. H. Preparation of Carvacrolphthalein. CURT EHRLICH (D.R.-P. 235983).-Cucl.~ucrolpht7~aZe~~ colourless transparent needles m. p. 246-2247" is prepared by heating phthalic anhydride ('1 part) with carvacrol (2 parts) and stannic chloride ( 2 parts) a t 100' during two hours.It is insoluble in water soluble in sodium hydroxide with a deep blue colour and compares very favourably with phenol- phthalein as a n indicator. F. M. G. I\I. Esterifhation of Unsymmetrical Di- and Poly-basic Acids. XXIII. Trimellitic Acid. RUDOLF WEGSCHEIDER HEINRICH FELIX PEKNDANNER and OTTO AUSPITZER (Uoncctsl~ 1910 31 1253-1301). -The formation of acid esters of trimellitic acid (benzene-] 2 4-tri- carboxylic acid) by diEerent methods has been studied in order t o determine whether the rules previously laid down for dibasic acidsORGANIC CHEMISTRY. i. 131 hold good. The investigation was complicated by the fact that the three carboxgl groups differ but little from one another arid therefore mixtures of acid esters are obtained by each method; these mixtures cannot be separated readily into their constituents.They do not crystallise well and several of them tend t o form mixed cryhtals. The 1 4- and 2 4-dimethyl esters crystallise extremely slowly and are usually obtained as syrups although from their con- stitutions their m. p.’s should be relatively high. The constitution of the 4-methyl ester C0,R5e*C,H,*(C02H) [(CO,H),:CO,Me = 1 2 41 follows from the fact t h a t it is formed by the addition of water to the methyl ester of the anhydro-acid CO,~f.e*C,H,:(CO),O and the constitutions of the two isomeric monomethyl esters were deterininecl by conversion in to the corresponding nmidedicarboxylic acid and then by means of bromine and potassium hydroxide transforming the amides into aminoiso- and aminotere-phthalic acids.The constitution of the dimethyl esters was determined by the elimination of carbon dioxide from their potassium salts in the presence of lime. The products formed by the esteritication of the acid both by the direct and by the catalytic method could not be obtained pure with the exception of small amounts of the 1- and 2-monometbyl esters but the fact that the syrups obtained yield appreciable amouxits of the methyl ester of anhydrotrimellitic acid points t o the conclusion that by these methods the carboxyl groups in position 4 that is the carboxyl group least affected by “steric hindrance,” is first esterified. The 1- and 2-monomethyl esters uiider similar conditions yield the 1 4- and 2 4-dimethyl esters and but little 1 %dimethyl ester.By partial hydrolysis of the normal ester with potassium hydroxide t h e 1 2-dimethyl ester is first formed and by further hydrolysis the %monomethyl ester with smaller amounts of t h e isomeric 1 -ester. By the addition of methyl alcohol to the acid anhydride both the 1- and 2-monomethyl esters are formed but at the same time the csrboxylic group in position 4 is esteri6ed to a slight extent. The mono-silver salt with methyl iodide yields mainly 1-methyl together with the 2-methyl ester and the disilver salt yields mainly 1 2-di- rnetbyl ester. These results agree on the whole with the generalisation that in the formation of acid esters from the acid by esterification or t rom neutral esters by hydrolysis steric hindrance is the determining factor whereas in the formation from the anhydride or from the acid metallic salts the relative strengths of the carboxyl groups are of first importance.Full details of the methods used for separating the mixtures obtained in each experiment are given. Methyl hydrogen isophthalate has m. p. 167-1669’ and not 126” as stated by Meyer (Monatsh. 1901 22 437). A 90% yield of triniellitic acid can be obtained by the action of nitric acid on French colophony (compare Scheder Anu. Chem. Piturm. 1874 1’72 94) provided the mother liquors are worked up. It has not been found possible t o prepare the acid from naphthol yellow-S by Ree’s method (Trans. 1886 49 510) but Schultz’ method (Abstr. 1909 i 897) gives fairly good yields if the chromic anhydride is addedi.132 ABSTRACTS OF CHEMICAL PAPERS. gradually. The m. p. depends on the method of heating; when dipped into a bath at 200° it has a. p. 215-217O in a n open tube or 239-234' in a closed tube. A 2% solution of the normal ammonium salt gives precipitates with solutions of mercuric cadmium lead ferric aluminium uranyl and silver salts. The following acid halts have been prepared C0,H~C6H3(C02Ag) slender needles from hot water ; C02Ag*C6H3(C0 H) ; C,H406Ba,H,0 insoluble in water. The l-??tonome~lzyZ ester CIOHSOB is most readily prepared from the mono-silver salt and is most conveniently separated from the free acid by precipitating the latter i n the form of its barium salt ; it may be purified by the addition of benzene to its ethereal solution and has m.p. 203*5-205*5O but frequently melts to a certain extent at 177O resolidifies at 179O and then melts at the higher temperature given. The two m. p.'s a r e probably due t o dimorphism. When mixed with the isomeric S-monomethyl ester its ni. p. is not appreciably affected. The latter ester is best prepared hy the partial hydrolysis of the 1 %dimethyl ester ; i t is sparingly soluble in water wheieas the 1-ester dissolves readily and crystallises from this medium as a colour- less powder m. p. 208'. The 4-methyl ester is most readily obtained by the addition of water t o the methyl ester of the anhydro-acid and crystallises from water in compact plates rn. p. 145-14i". The CO co anhydro-ester CO,Ne*C,H,< >0 has m.p. 94-99O is transfurmed into a syrup by the addition of a little alcohol and when kept for some time even in a desiccator yields the 4-monomethyl ester. 'l'tie 1 2-dimethyl ester CI1H,,O crybtallises from carbon tetrachloride or better from a mixture of ether and light petroleum in nodular masses of needles m. p. 115*5-117° after softening at 108'; when slowly heated above the m. p. the ester resolidifies and then has m. p. 121". It has b. p. 200°/12 mm. The 1 4- and the 2 4-dimethyl eaters are both syrups and the solution of the ammonium salt of the former gives a precipitate with concentrated solutions of copper sulpliate whilst that of the latter is precipitated even in dilute solution The trimethyl ester has b. p. 194'112 mm. (cow.) and solidifies in a freezing mixture at - 13' to a vitreous mass. The 1-amide NH2*CO*C,H3(C0,H) is obtained by heating the corre- sponding ester with a concentrated solution of ammonia in methyl alcohol at 100' for one and a-half hours then acidifying removing trimellic acid by extracting with ether and extracting several times with amyl alcohol.After removal of the amyl alcohol and iecrystal- lisiog the residue from a mixture of methyl alcohol and benzene the amide is obtained pure and has m. p. 185-186'. The isomeric 2-amide obtained by a similar method has m. p. 199-200'. The 1-amide reacts with bromine and alkali yielding 4-amino-isophthalic acid which was isolated in the form of i t s methyl ester (m. p. 130'). The 3-amide under similar couditions yields aminoterephthalic acid which was isolated as i t s methyl ester m.p. 123-126O (Cahn- Speyer Abstr. 1907 i 549 gives m. p. 133"). By the action of a methyl-alcoholic soliltion of ammonia on the a n h j dro-acid a mixture of the 1- and 3-amides is obtained. J. J. S.ORGANIC CHEMIS'L'RP. i. 133 Ring Syntheais of Pyrornellitic Acid. FRANZ FEIST (Ber. 1911 44 135-138).-Small amounts of pyromellitic acid (14% yield) are formed according to the eqiiation 2C0,Et*CH2*CH:Br*CHBr*C02Et + 8KOH = C,H2(C02K)4 + 4KBr + 4EtOH + 4H,O + H2 when ethyl up-dibromoglutarate is mixed with alcoholic potassium hydroxide solution. The acid is isolated by acidifying the potassium salt and extracting eighteen times with ether. It is accompanied by large quantities of oily impurities which can be removed by stirring with a small amount of ether i n which the impurities dissolve.The anhydrous acid has m. p. 275" and the tetramethyl ester m. p. 141.5'. T T C I Preparation of Diglycollyldisslicylic Acid. CHEMISCHE FABRIK VON FRIEDR. HEYDEN (D.R.-P. 227999).-DiylgcoZlyldi- saZicpZic [o-digZycoZZyEoxybenzoic] acid O(CH2*CO*0.C6H,*U02H)2 glistening leaflets m. p. 168-170° is readily prepared b y boiling salicylic acid (or a salicylate) in benzene solution with diglycollic anhydride in the presence of an indiffereni; base (such as pyridine); it is of therapeutic importance and compares favourably with acetyl- salicylic acid in this respect. F. M. G. M. An o-Hydroxyaldehyde of Triphenylcarbinol. AUGUST IBisTHzYcKI and MARTIN EELLMANN (Ber. 1910 43 3579-35%)- Salicylaldehyde can be condensed with benzylic acid forming 4-hydroxy-3-aldehydotriplienylacetic acid (Abstr.19 10 i 32 l) and this by the elimination of carbon dioxide is readily converted into 4- bydroxy-3-aldehydotriphenylcarbinol which is the third aldehyde of the triphenylmethane series to be described. 4- Hydroxy-3-aldehydotriphenylacetic acid prepared by the con- densation of the components in benzene in presence of tin tetra- chloride crystallises + &C7HSl in microscopic prisms or needIes m. p. 198-200' (from toluene) or in stellar aggregates of prisms +&C,H m. p. 197-198' (from benzene). The aaine N,[ :CH-CGH,(OH)*CPh2-C02HJ2 derived from the action of hgdrazine sulphate and sodium carbonate ia a yellow powder (decomp. 270-280') ; the sodium salt crystallises in slender yellow needles.The oxime crystallises in microscopic colourless needles which turn yellow at l l O o m. p. 2%' (decomp.). The semicar6~6xone forms bunches of microscopic slender prismatic needles m. p. 198-199" (decomp.). The aniline derivative is a granular yellow powder m. p. 85-86' (decomp.). Methyl 4-methoxy-3-aklehydotr~p~ennyZucetate prepared by the action of methyl sulphate iii cold sodium hydroxide solution crystallises in bunches of faintly yellow-coloured four-sided prisms m. p. 4-Benxoxy-3-aldehyclotriphenylacetic acid crystallises in concentric- ally-grouped colourless needles m. p. 195.5-1 96.5". 4-Hydroxy-3-aldehydotriphenylcarbinol (Zoc. cit.) prepared by the action of concentrated sulphuric acid on the aldehydo-acid crystallises in aggregates of light yellow prismatic plates m.p. 1213-124O decomp. at 170". The solution in concentrated sulphuric acid is 148-1 4 9'. VOL. C. i. Ii. 134 ARSTRACTS OF CHEMICAL PAPERS. orange-red; a second isomeric form could not be obtained. The acetyl derivative crystallises in reniform aggregates of colourless prisms m. p. 131-132' the fused mass being orange-yellow. The phenyl- hydruxone forms rounded aggregates of microscopic prisms decomp. 177". The ozime separates in bunches of colourless flat prisms; on heating it becomes yellow and softens at 95' becomes colourless and solid again at 102' m. p. 151' (decomp. 175'). The semicarbaxone crystallises in colourless microscopic needles which become yellow at 140' and decompose at 164' with an intense red coloration. On heating the hydroxyaldehydocarbinol in a stream of dry air in a sulphuric acid bath a t I 90-200° the anhydride 2-aldehydodiphenyl- qzcino,methnne CPh,:C,H,O*CHO is obtained as a brown powder.This darkens in colour at loo' and begins to melt indefinitely a t a somewhat higher temperature. E. F. A . Hexahydroacetophenone [cycZoHexyl Methyl Ketone] and Hexahydrobenzoylacetone. MARCEL GODCHOT (Compt. rend. 1 9 10 151 1131-1 134).-Adigic acid is the sole product of the oxidation of cyclohexyl methyl ketone by alkaline potassium perrnanganate. cyclo- Hexyl methyl ketone (Bouveault Abstr. 1904 i 61) forms an oxime b p. 145-150°/20 mm. m. p. 60'; no isomeric form wits detected. I t undergoes the Beokmann change forming acetylaminocgclohexune (hexahydrocccetnnizide) C,H,,*NHAc crystallising in needles m.p. 103' identical with the product obtained by acetylating cyclohexyl- amine. Irexaliydrohenzoylaceto~~ C,H,,*CO*CH,-COMe is obtained in the form of its sodium salt by the addition of sodium ethoxide to a mixture of cycEohexy1 methyl ketone and ethyl acetate. The diketone has b. p. 103--105'/25 rnm. D15 0.9933 and was prepared in the pure state from its copper derivative which crystallises in pale green needles m. p. 210' ; the phenylhydrazone and oxime appear to be oily. w. 0. w. Ketones Derived from 0- m- and p-Toluic Acids. JEAN B. SENDERENS (Compt. rend. 1911 152 90-92. Compare Abstr. 1909 i 286 627 ; 1910 i 11 179,489).-The under-mentioned ketones have been prepared by passing the vapour of an aromatic and an aliphatic acid over thorium oxide at 460-470'.A single distillation of the product usually suffices to yield the aromatic ketone in a state of purity. The new ketones are liquids ; their odour resembles that of citrons in the case of the ortho-compounds and of fennel in the case of the para- derivatives; the odour of the meta-compounds is not characteristic. The b. p.'s given are corrected o-Tolyl methyl ketone b. p. 211'/745 mm. D 1.0262; semicarhazone m. p. 192'. m-Tolyl methyl ketone b. p. 221'/745 mm. DS 1.0165; semicurbaxone m. p. 188' (decomp.). p-Tolyl methyl ketone b. p. 224.5'/745 mm. D! 1.0150 ; semicarbccxone m. p. 200'. o-Tolyl ethyl ket'one b. p. 224'/745 mm. D 1.0119; semicurbaxone m. p. 169'. m- Tolyl ethyl ketone b. p. 234'/745 mm. DS 1.0059; semicarbaxone m.p. 166'. p-Tolyl ethyl ketone b. p. 23S0/745 mm. D 1.0053; eeinic irbazone m. p. 180° 0-Tolyl proyyl ketone b. p. 238*5'/788 mm.,ORGANIC CHEMISTRY. i. 135 D! 0.9836 ; sm~ca~bazone m. p. 176'. m-Tolyt propyl ketm b. p. 247'1758 mm. DI 0.9882; samkarbazm m. p. 152O. p-Tolyl p o p y l ketone b. p. 261*5O/758 mm D9 0.9774; semiccrrhsona m. p. 190°. O-Tdylieopropyl ketoru b. p. 230°/758 mm. Di 0.9858; the sem&mrbazma is an oil. m-ToZyl isoFopyl ketone b. p. 238'/758 mm. D 0.9841 ; samicarbazone m. p . 120'. p-Tolyl ieopropyl ketone b. p. 243O/ 758 mm. DS 0.9778 ; serraicai*bazone m. p. 101'. o-Z'olyZ isobutyl kstolte b. p. 247*5'/758 mm. DS 0.9744 ; semicurbaxone m. p. 166'. m-TolyZ isobutyl ketone b. p. 254'/758 mm. DS 0.9712 ; semicarbazcma m.g. 172". pTolyl isobutyl ketone b. p. 259"/758 mm. DP 0.9707; semi- cwbazoite m. p. 212'. w. 0. w. Quinonee. EERMANN HAAKH (J. pr. Chem. 1910 [ii] 82 546-551).-A theoretical paper in which an attempt is made t o account for the recent numerous examples of the formation of highly. coloured additive corupounds of p-benzoquinone with inorganic acids and salts aromatic hydrocarbons and other substances. The author assumes that the comparatively feebly-coloured p-benzoquinone itself has Graebe's peroxide constitution in which the oxygen atoms have no residual affinity ; when it forms highly-coloured additive com- pounds the quinone acquires the Fittig constitution addition occurring by means of the residual affinity of the oxygen atoms. c. s. Oxonium Hydrosulphides of p-Benzoquinone.M. M. RICHTEB (Bar. 19 10 43 3599-3603).-On mixing hydropersulphide and p- benzoquinone in anhydrous solvents at the ordinary temperature a voluminous brilliantly blue compound is obtained which is labile in character and under certain conditions changes to a faintly yellow substance. The blue compound is obtained in presence of an excess of benzoquinone the yellow with an excess of hydropersulphide. The amorphous indigo-blue substance bis-p-benxopuinoneoxo!nium H H hydrotrisulphide 0 C6H, O<s.s.s>O C,H,:O decomposes at 1 1 5 O or when exposed to moisture. It dissolves in anhydrous solvents with an orange coloration but- is more or less decomposed. By the action of p-benzoquinone dissolved in carbon disulphide and potassium hydrosulphide in absolute alcohol in a stream of hydrogen pbernxoquinoneoxonium hydrosulphide 0 C6H4:O<EK is obtained as EL dark greenish-black powder extremely sensitive to traces of moisture.~risquinhy~roneoxonium hydrosulphide C,,H,,O,,S is obtained by passing dry hydrogen sulphide through a solution of quinone in formic acid It is a microcrystalline almost black powder decomp. 140'. The same compound is obtained on passing dry hydrogen sulphide over fused p-benzoquinone. Hydropersulphide does not combine with substituted quinones ; the entry of substituents particularly of strongly negative groups into t h e quinone molecule weakens the basic properties of oxygen and prevents salt formation E. F. A 1 2i. 136 ABSTRACTS OF CHEMICAL PAPERS. Constitution of Quinhydrone-like Subatances.M. M. RICHTER (Ber. 1910 43 3603-361 l).-The characteristics of oxonium salts namely simple addition of the components in their formation ready decomposition in solution or when sublimed and marked increase in the intensity of the colour are also those of the quinhydrones. It is suggested that quinhydrones phenoquinones alloxantin etc. are all to be regarded as oxonium compounds and their dissociative and colour properties are due to quadrivalent oxygen and quinquevalent nitrogen. p-Benzoquinone has been shown (com- pare Siegmund Abstr. 1909 i 109 ; Meyer ibid. i 395) to combine both with one and with two molecules of mono- and di-hydroxy- phenols. H The evidence in favour of the formula O:C,H,:O<O,C .OH for quinhydrone is discussed. Two more must be added to the characteristics of the quinhydrones already enumerated namely they are composed of quinonoid and benzenoid sections and they have the power of forming salts.The entry of substituting groups particularly those of a strongly negative nature into the quinone molecule materially lessens the basic properties of tho oxygen atom and in consequence prevents salt and quinhydrone formation. Thirteen cornpounds are enumerated of six main types which are quinb ydrone compounds of pphenylenediamine benzidine and p-benzo- quinonedichlorodi-imine. It is considered that the simple oxygen atom generally behaves as a quadrivalent atom. Preparation of N-Alkyl- and N-Arylaryl-sulphaminoanthra- quinones. FRITZ ULLMANN (D.R.-P. 227324).-By the action of alkylsulphon~mides of the general formula R*NH*SO,-R (R = alkyl or aryl ; R = aryl) on halogenated anthraquinonee condensation products are obtained.6 4 E. F. A. 1 -p Toluenesu Zphon ylphennyZaminoant?~rayu.inone CBH,<CO>CBH3*NPh*S0,. co C,H is prepared by heating together p-toluenesulphonylanilide and a-chloroanthraquinone in nitrobenzene solution in the presence of copper acetate and $odium carbonate ; i t crystallises from acetic acid in glistening yellow cryst>als m. p. 193’. 1 -p-l’oluenesuZ~honyI,rLetf~~Z~m~noanth~a~u~none yellow needles m. p. 192O is prepared in a similar manner from p-toluenesulphonylmethyl- amide and a-chloroant hraquinone. By treatment with concentrated sulphuric acid it yields a-methylaminoanthraquinone. Preparation of 6-Chloro-l-hydroxynaphthacenequinone and of 6-Chloro-1-hydroxynaphthacenequinone-4-sulphonic Acid.ANILINFAHBEN arid EXTRACT-FABHHEN VORM. J. R. GEIGY (D.R.-P. 226230).-!Che work of Weiamann and others has shown that o-1-hydroxy-P-napbthoylbenzoic acid when heated with concen- trated sulphuric acid and boric acid is converted quantitatively into 1-hydroxynaphthacenequinone (Trans. 1906,90 116 ; 1907,91 41 1 j F. M. G. 1sI.ORGANIC CHEMISTRY. i. 137 1909 93 279) ; this reaction has now been extended t o 4'-chloro-1'- hydroxy-/?-naphthoyl-o-benzoic acid (Abstr. 1910 i 746) and its sulphonic acids. 6-Chloro - 1 - T~ydroxynaphthacenequinone (annexed formula) was prepared by dissolving crystallised boric acid (6 part,s) in 80 parts of concentrated sulphuric acid (25% SO,) slowly adding the 4'-chloro - 1'-hydroxy - /? - naphthoyl- /"-vCo/'/\ benzoic acid (20 parts) and heating a t '70" until I 1 I 1 sodium hydroxide ceased to produce a yellow \/'"'\k\/ coloration.The product after cryatallisation from benzene formed long reddish-yellow needles m. p. 307' and seems not t o be identical with the 6-chloro-1-hydroxy- naphthacenequinone m. p. 290-293' (Trans. 1907 91 418). The sodium salt is insoluble in water. 6-ChZoro-1-~,ydrox~~zn~hthacenequinone-4-suZphonic acid was isolated in the form of its monosodium salt a brick-red powder by boiling with a saturated solution of sodium chloride; it is soluble in water with a yellow coloration; the disodium salt was obtained as a dark red gelatinous precipitate soluble in water with a blue coloration.OH F. M. G. M. Preparation of Alkyloxyacetyl Derivatives of M e n thole. ALFRED EINHORN (D.R.-P. 225821).-The interaction of ethoxyacetic acid and mentholcarboxyl chloride in a cooled ethereal solution yields menthol ethoxyacetate a colourless oil b. p. 144'/14 mm. The reaction is a general one €or the alkyloxyacetic acids and mentholcarboxyl halides. P. M. G. M. Preparation of Santalyl Alkylaminoacetates. FARBENFABRIKEN VOEM. FRIEDR. BAYER & Co. (D.R.-P. 226229)-It is found tbat santalyl alkylaminoacetates of therapeutic importance can be prepared by treating chloroacetylsantalol with a secondary amine. Chloroacetyl- santalol a viscous yellow oil was prepared by treating santalol with chloroacetyl chloride in the presence of pyridine or with chloroacetic acid pyridine and carbonyl chloride.This product was isolated mixed with a solution of dimethylamine in benzene and left during twenty-four hours ; the scmtaZyl dimethylaminoacetate was extracted with hydrochloric acid and on rendering the solution alkaline with sodium carbonate separated as a yellow odourless oil which hydrolyses readily with alkalis into its components. It forms well characterised salts ; the hydrochlokle crystalliees from acetone in odourless colour- less needles m. p. 154". Analogous compounds can be prepared with diethylamine or piperidine. F. M. G. M. CataIytic Reactions at High Temperatures and Pressures. XXII. Reduction of Terpenes. WLADIMIR IPATIEFF (Bei.. 19 10 43,3546-3553. Compare Sabntier and Senderens Abstr. 1901 i 459 ; Vavon Abstr.1910 i 52 400).-By reducing I-limonene with hydrogen a t 280-300' under 110-120 atmospheres' pressure using cupric oxide as the catalyst an unsaturated hydrocarbon CI0Hl8 b. p. varying from 172" t o 17Cio is obtained. The same hydrocarbon is alsoi. 138 ABSTRACTS OF CHEMICAL PAPERS. produced when copper is used but a higher temperature is necessary. Further reduction of this hydrocarbon leads to the formation of p-menthane. [With D ~ ~ c ~ u s s o ~ ~ . ] - F r e n c h I-pinene in the presence of iron is not reduced but undergoes isomerisation to dipentene. A t 265O with cupric oxide as catalyst it is reduced to a hydrocarbon C10H,8 whilst repeated reduction a t 280-290' yields a hydrocarbon C,,H, b.. p. 163-170° D20 0.7949. Similar results were also obtained with metallic copper.With nickel oxide the reduction takes place with great rapidity and at a lower temperature than with cupric oxide C,,H2 being formed. It is considered probable that the hydrocarbon C10H20 obtained from I-pinene consists of a mixture of 0- and p-menthanes. For the purpose of comparison menthane was prepared from cymene by reducing with hydrogen nickel oxide being used as a catalyst ; it had b. p. 167-170' DZo 0.8038. Peppermint Oil Prepared from Dry Leaves of Mentha piperite. J. MURAOUR (BUZZ. SOC. chirn. 1911 [iv] QJ66-67).-Dry leaves which had fallen naturally from mint plants during cultivation gave a yield of from 400 to 500 grams of oil per 100 kilos. of leaves. This oil was yellow and had an odour recalling that of Japanese peppermint oil.Two samples gave the following constants D15 0.91 1 to 0,913 aD= - 38'18' to - 40°4' solubility 1 in 1.5 to 2.5 vols. of alcohol at 80° and contained 33.16 to 40.31% of esters and 43.99 to 45.67% of total menthol. The results of examination of commercial peppermint oils indicated that some of these products consisted of true peppermint oil of French origin mixed with oil from the fallen leaves. F. B. T. A. H. Essential Oils. I. Orange Flower Oil. 11. Schinus molle Oil. G. LALOUE (Bull. Soc. chim. 1910 [iv] 7 1101-1107 1107-1 109).-a more detailed account of work already published (Abstr. 1910 i 755; 1909 i 817). Gildemeister and Stephan's observation (Abetr. 1897 i 81) that Schinus moZZe oil contains pinene and phellandrene is confirmed and there is probably also about 20% of sesquiterpenes present. Oil distilled from branches and leaves obtained a t Grasse was richer in pinene than oil from leaves and branches obtained in Algeria.HEINRICH KILIANI (Ber. 1910 43 3574-3579. Compare Abstr. 1897 i 9 I).-Seligmann (Abstr. 1903 ii 314) obtained from the juice of A. toxicaria procured from Sarawak an antiarin differing from t h a t previously described. It is now found with juice obtained from Java that two antiarins exist the new /?-form being present in the larger proportion. They differ in crystalline form melting point water of hydration and composition although there is no difference in their toxic character. a- Antiarin C2tH,20,,,4H20 crystallises in glistening plates or leaflets m. p. 220-225' P-Antiarirz C,7H3s0,0,3H,0 or C28H38010 3H20 crystallises in slender needles or bunches of columnar needles m.p. 206-207'. T. A. H. Milk Sap of Antiaris toxicaris.OBGANIC CHEMISTRY. i. 139 Emulsin is without action on either glucoside; the products of hydrolysis of /3-antiarin have not been characterised. Digitonin Digitogenic Acid and their Oxidation Products HEINRICH KILIANI (Ber. 1910 43 3562-3574. Compare Abstr. 1904 i 505).-A further study of the oxidation products of digitogenin shows that digitic acid has the composition C2sH42011. Molecular weight determinations are particularly di5cult to carry out in the case of oxidation products of digitogenic acid. It has not been found possible so to conduct oxidation as to obtain simple products of known constitution; even with ozone the chief product is an acid l o prepare digitonin German digitalis is extracted with alcohol ether tLe insoluble residue is dissolved in water the vessel placed in a bath of water at 70' a small quantity of amyl alcohol added and after inoculation the whole is allowed to cool slowly until crystallisation is complete.Digitic acid is tri basic the barium salt being (C2SH41012)2Ba3,18H20. The normal potassium salt is hygroscopic and the acid salt admixed with free acid; the calcium salt is amorphous so that neither is suitable for analysis. The by-products of the oxidation consisted of acids miscible with sodium chloride solution from which no chemical individual could be isolated and of acids insoluble in salt solution. When further oxidised with permanganate in strongly alkaline solution a definitely crystalline calcium salt C19H2s07Ca,8H20 was obtained (compare Kiliani and Baylen Abstr.1895 1 65). The acid is indefinitely crystalline m. p. 170" (decomp.). Anhydrodigitic acid when oxidised with potassium permanganate in neutral solution forms an acid C2,H,,07 crystallising in crusts of small pyramids m. p. 196-200O; the magnesium salt crystallises in needles and small pyramids. From the products of oxidation of digitog6nic acid by hot permanganate in neutral solution a new tribasic acid C,,H,,Oll has been isolated; it crystallises in leaflets m. p. 155" (decomp.). The barium salt C2sH,oOllEa,10H20 crystallises in aggregates of closely- packed needles and is strongly acid. The acid is isomeric with digitic acid.On oxidation of digitogenic acid with ozone more than 60% of an acid C2,H4,07 is obtained ; this crystallises in clusters of pyramids m. p. 2%2". A magnesium salt C2,H,,07Mp,l 1 H20 crystallises also in tiny pyramids. It has not been established in what form the two atoms of carbon are eliminated during the Oxidation. MAX GONNERMANN (Pjiiger's Archiv 1911 137 453-469).-Sinigrin is not acted on by any enzyme with the exception of myrosin. The enzymes investigated under varying conditions of solvent etc. were of both animal and vegetable origin; bacteria including those in the intestine have no effect in liberating allyltbiocarbimide. This confirms Kobert's statement. Various details E. P. A. c2!3H4007* E. F. A. Saponiflcation of Sinigrin. regarding the mode of preparation of this glucoside are given.yV. D. H.i. 140 AI3STlUCTS OF CHEMICAL PAPERS. A Saponin-Cholesterol Compound. S. YAGI (Arch. exp. Path. Pharm. 1910 64 141-146).-Ransom having shown that cholesterol inhibits the haemolytic power of saponin Windaus Found that certain saponins form additive products with cholesterol ; the digitonin- cholesterol compound for instance is crystnllisable and has the formula C82H140029 that is a combination of one molecule of each substance (C55H,4028 + C,7H,,0). Other cholesterides have been separated by the same author. The present paper gives details of the preparation and properties of another crystallisable choles t eride namely that of dioscine in which three molecules unite with two of cholesterol 3C24H,80,,2C,7H,,0 1 or 3H,O a microcrystalhe powder m.p. 223O ; this is inactive on blood corpuscles. The feeble haemolytics such as Merck's saponin sapotoxin and dioscorea-sapotoxin need about an equimolecular amount of cholesterol t o render them inactive ; half the amount leaves them still partly active ; the feeble members of the group therefore do not contain active mixed with inactive molecules. W. D. H. Action of Nitric Acid on Aloins; Production of Tetra- nitroaloe-emodin and of 2 4 6-Trinitro-3-hydroxybenzoic Acid. EUQBNE L~GER (Compt. rend. 1910 151 1128-1131 ; BuEZ. SOC. chim. 1911 9 SS-97).-It has long been known that chrys- animic acid and picric acid are amongst the products OF the action of nitric acid on the aloins. It is now shown that the production of these compounds is preceded by the formation of two other substances which are then converted into these acids by the further action of nitric acid.Tetncnitroaloe-ernodin C,,H,O,(NO,) arises from the action of nitric acid (D 1.2) on barbaloin or zsobarba,loin a t the temperature OF the water-bath. It occurs in slender golden needles m. p. about 285O with deflagrakion. On long boiling with nitric acid (D 1-32) it is converted into chrysammic acid. The mother liquor from the tetranitroaloe-emodin contains 2 4 6- trinitro-3-hydroxybenzoic acid (Griess Annalen 186 1 11'7 28) ; this crystallises from ether in almost colourless efflorescent rhombic Iamellz n1. p. 1855-186-5° (corr.). It loses carbon dioxide when heated with nitric acid and forms picric acid. Tetranitrorhein C,4H02(N02)4(0H)2*C02H is probably an inter- mediate product in the conversion of tetranitroaloe-emodin into chrysammic acid It has been isolated as short efflorescent prisms. w.0. w. Chlorophyll. X. Comparative Investigation of Chloro- phyll from Different Plants. 11. RICHARD WILLSTATTER and ALFRED O P P ~ (Annalen 19 10 3'78 1-1 8. Compare Willstatter Hocheder and Hug Abstr. 191 0 ii 150).-An examioation of the leaves of 200 species of plants has shown that the chlorophyll present is the so-called amorphous or wax-like form which yields phytol. The phaeophytin obtained from the dried leaves gives a 33% yield of phytol provided the extraction is carried out rapidly. I nORGANIC CHEMISTRY. i. 141 many cases for example grass and plantains good yields of pbytol are also obtained when a slow method of extraction is used but in others the amount of phytol isolated diminishes as length of time taken for the extraction is increased.Thus the yields OF phytol from Hermleurra spondylium are 6.0 when the extraction takes twenty-four hours 20.2 for one hour and 31.5% for three-quarters of an hour. It is evident that the chlorophyll loses its phytol when its alcoholic solution is left in contact with the plant tissues and this loss is due to enzyme action (Willstatter and Stoll next abstract). The results account for the low percentages of phytol obtained in previous experiments (Zoc. ci".) as the slow method of extraction was used. The increase observed in the amount of phytol when the dried material is kept can be accounted for by the enzyme losing its activity with age.The one consists in rubbing the leaf powder with chalk and sufficient alcohol to form a thick paste (about 1 litre per kilo. of leaf powder) leaving for five minutes filtering under pressure and washing with small amounts of alcohol. The second method consists in making a much stiffer paste 300 C.C. of alcohol for 1 kilo. of powder and placing on a percolator and using low pressures. This second metbod is the better when comparatively concentrated solutions of chlorophyll are required. The phzeophytin was obtained by the addition of oxalic acid to the extract. When chlorophyll had not undergone decomposition a fine compact precipitate of phaeophytin mixed with oxalates was obtained but if much phytol has been formed the precipitate had a voluminous coagulated appearance.Phytochlorin-e and phytorhodin-g have been isolated from the phEophytin from 125 different plant species. The amount OF phyto- rhodin-g diminishes as the boiling with the alcoholic potassium hydroxide is increased or as the concentzation of the alkali is increased. I n many cases a phytochlorin somewhat more feebly- basic than phytochlorin-e was isolated. The usual method of hydrolysis was boiling for two to three hours with 24% methyl-alcoholic potassium hydroxide using 5 C.C. of solution for 1 gram of phzeophytin. J. J. S. Chlorophyll. XI. Chlorophyllase. RICHARD WILLSTATTER and ARTHUR STOLL (Annulen 1910 3'78 18-72).-Willstatter and Oppe (preceding abstract) have shown that the conversion of amorphous chlorophyll into crystallised chlorophyll is accompanied by the elimination of a phytol group and that the change occurs when the process of extraction is slow but can be avoided by using a rapid method of extraction.It is now shown that crystallised chlorophyll contains one methoxy- and one ethoxy-group and not two methoxy- groups (Willstgtter Hocheder and Hug Abstr. 1910 ii 150) and that the amorphous chlorophyll contains one methoxy- and one phytyl group; it is proved that the change of the amorphous into the crystallised chlorophyll is a process of alcoholysis and in each stage of the change the phytol eliminated is equivalent to the ethyl alcohol Two quick methods of extraction are described.i 142 ABSTRACTS OF CHEMICAL PAPERS. entering the molecule.equation The reaction which is represented by the C,,H,*OH + C0,H*C,1H,,N411g( CO,Me).CO,Et takes place in the presence of a specific enzyme chlorophyllase which belongs to the group of esterases. Other substances of the same group for example lipsse from linseed or pancreas lipase cannot bring about the same change. The enzyme reacts slowly with pbEophytin and does not react at all with waxes of an ester nature. It is highly probable that the enzyme brings about the formation of phytyl esters in the plant. Working with methyl alcohol it has been found possible to replace the pbytoxyl groups by methoxyl (methanolysis) and in the presence of moist ether to replace the phytoxyl group by hydroxyl (hydrolysis). Lipases on the other hand produce hydrolysis but do not appear able to induce alcoholysis.The following system of nomenclature is suggested for chlorophyll derivatives the tricarboxylic acid C31H29T4Mg( CO,H) from which chlorophyll is derived is called chlorophyllan ; the monomethyl ester obtained by the hydrolysis of chlorophyll is termed chlorophyllicle ; amorphous chlorophyll is phytylchZorophylEide ; Borodin’s crystallised chlorophyll is ethylchlorophyllide ; the magnesium-free compound is termed phcceophor6ide; phaeophytin is thus phytylphccenphorbide and the compound hitherto called phaeophorbin is ethylphaeophwbide. A rapid method for the extraction of chlorophyll is described which differs somewhat from those recommended by Willstatter and Oppe (preceding abstract). It consists in moistening 1 kilo. of the leaf meal for five minutes with 0.5 litre of alcohol (96%) then spreading on a thimble and applying suction for a short time.The addition of alcohol and suction are used alternately until a further litre of alcohol has been added; in the course of twenty minutes 1 litre of solution is obtained; by washing with alcohol a further 0.9 litre of extract is obtained in thirty-five minutes more. The amount of chlorophyll in the two extracts is 80% of the total present. The solutions although dilute are purer than those obtained by the methods already described and therefore yield more phaeophytin. For the estimations of phytol the method already described (Abstr. 1910 ii 150) has been used. The amount of chlorophyll transformed into ethylchlorophyllide by means of chlorophyllase has been deter- mined both by the estimation of the phytol liberated and by determining the amount of silver iodide obtained from the product by Zeisel’s method.Details for the calculations are given. The results obtained by the two methods agree indicating t h a t the ethyl groups ent2ring the molecule are equivalent to phytyl groups removed. It is highly probable that the reaction is a direct exchange of alkyl for phytyl groups and that it does not consist in the hydrolysis of the phytyl ester to the acid and the subsequent conversion of this into the ethyl ester. The enzyme was in the form of leaf meal from which the chlorophyll had been extracted and was used whilst moist with alcohol. The reaction was most rapid when the mixture was kept well shaken and in eachexperiment the flasks were well corked in order to prevent (:0,H*C,,H,,N,n~g(C02Me)*C0,*C20H3 + EtOH = C,IH31N4(C02H)R,ORGANIC CHEMISTRY. i.143 the admission of moisture. Although the reaction mixture is non- homogeneous i t is probable that the diffusion phenomena are such that the mixture behaves as if it were a homogeneous one. The values of K however when calculated by means of the equation for a iinimolecular reaction are not constant but diminish as t increases. This is shown t o be due partly to the fact that the enzyme tends to become less active when kept for some time. With varying amounts of enzyme Schutz's rule p = K JKt holds good approximately. With chlorophyll solutions of different concentrations the amount transformed in a given time is roughly proportional to the concentration.The addition of water to the alcoholic solutions accelerates the activity of the chlorophyllase; thus the value of I l x lo3 after ten hours varies from 28 to 3'7 using 92% alcohol but with 80% alcohol K x 1013 has the values 175 166 and 80. Even in 80% alcohol the reaction is a true alcoholpsis and not hydrolysis. The activity of the enzyme is less at 35' than a t 25'; when boiled with alcohol the enzyme is gradually destroyed and in drying leaves for the preparation of the enzyme i t is necessary to avoid high temperatures. Calcium carbonate has no effect on the alcoholysis whereas magnesium hydroxide has an appreciable retarding effect. Young leaves appear to contain a smaller amount of enzyme than older ones and the amount tends to increase as the chlorophyll increases.The methylchlorophyllide obtained by using methyl in place of ethyl alcohol is formed much less readily and its isolation is rendered difficult by the readiness with which it is transformed into readily soluble derivatives. The reaction proceeds more readily in the presence of a small amount of water for example in 92% methyl alcohol but the best results are obtained by treating fresh leaves with 50-60% methyl alcohol. The product varies with the species of plant used ; that obtained from Eeruclewm C7,H7,01,N,Mg2 crystallises from ether in which it is sparingly soluble in steel-blue glistening prisms. The corresponding methylphaeophorbide C7,H7,O1,N forms glistening spindle-shaped crystals with a metallic lustre.The methyl- chlorophyllide from stinging nettles is somewhat more readily soluble in ether and crystallises in triangular and hexagonal plates. Chlorophyllide CO,Me*C,,H,,N,Mg(CO,H) may be obtained by the action of the enzyme on a moist ethereal solution of chlorophyll in the absence of alcohol. It forms green plates and is extremely unstable and is transformed readily into the isomeric magnesium phaeophorbide C0,Me*C,~H,l(C02)zMg which forms black crystals readily decomposed by acid. The synthesis of chlorophyll from chlorophyllide and phytol can be accomplishsd by means of chlorophyllase but the yields are small. Chlorophyll always appears to be accompanied by chlorophyllase ; in Soybus aucupuria Mellitis melissoph. Stachys silvitica Lamium maculatum and Herudeurn the amount of enzyme is comparatively large.The presence of the enzyme in stinging nettles grass Sambucus Aspidium Equisetum Taxua Avena and Platanus can be demonstrated by the prolonged action of the tissue on the chlorophyll extract when products are obtained which contain but little combined ph ytol. Extracts of stinging nettles and of PZatanus react with the enzymei. 144 ABSTRACTS OF CHEMICAL PAPERS. from Glxleopsi.9 or Heracleuin more readily than with their own enzymes but the alcoholysis does not proceed to completion. Under conditions which result in the complete alcoholysis of the chlorophyll of Galeopsis or Herudeurn only 66% of the chlorophyll of stinging nettles is decomposed. The chlorophyll of Herudeurn reacts only slowly with stinging-nettle meal but the rate is greater than that between stinging-nettle meal and the chlorophyll from stinging-nettle ex tract.J. J. S. Chlorophyll. XII. Phytol I. RICHARD WILLSTATTER ERWIN W. MAYER and ERNST HUNI (Annulen 1910,378,73-152. Compare Willstatter and Hocheder (Abstr. 1907 i 7S4).-Crude phytol and the distilled product are not identical but isomeric and the process of distillation appears to produce a shifting of a double linking. The two are termed respectfully a- and P-phytol. An examination of the products of oxidation shows that the a-compound has the olefine linking between carbons 5 and 6 as it yields a ketone Cl,H3,0 whereas P-phytol yields a ketone C,,H260 and contains a n olefine linking between carbons 7 and 8. The chief oxidation products isolated are the following ketones and acids.(1) Ketone C,,H,,O obtained from a-phytol by means of chromic anhydride or from the a-ozonide. (2) Ketone C,,H,,O from P-phytol by means of chromic anhydride from the P-ozonide or from the acid C14H2s02 by means of chromic acid. (3) Ketone C,,H,,O from trihydroxyphytan and chromic acid or by the action of ozone on the ketones 1 and 2. (4) Ketone C,H,,O by the action of ozone on any of the other ketones. ( 5 ) Acid C14H,,02 from a-phytol and ozone from trihydroxyphytan and chromic acid or from the ozonide of the olefine C15€€30. (6) Acid C12H2,02 from the ketone C,,H,,O and ozone from the ketom C13H,,0 and chromic acid or from the acid C14H2802 and chromic acid. (7) Acid Cl0H2,O2 from the ketone C15H,o0 and ozone and from the ozonide of the olefine C,,H,,. The first two ketones are easily obtained in a state of purity but the two lower ones are more difficult to prepare.They are all methyl ketones altbough they yield only traces of bromoform with hypo- bromite and only small amounts of methylamine by the Beckmann transformation. The presence of the acetyl group in the ketone C,,H,,O can be demonstrated by the following series of reactions C,,H27*CH(OH)*CH2*OH -+ C,,H,7*C02H. The four ketones resemble one another in physical properties. They are pale yellowish- green oils with relatively high b. p.’s and it is suggested that the compounds especially the lower members have the tautoineric enolic structure. The acids are saturated and do not decolorise bromine but react readily with permanganate.They do not crystallise and resemble phgtol in physical properties. The reduction products of phytol and also numerous esters have been prepared. a-Phytol contains the double linking in the Pa-position with respect to the CH2*OH-group as the phytenic acid obtained by oxidising with chromic acid is an up-unsaturated acid and the following structural C,,H,?*CO*CH -+ C,,H,i*CH(OH)*CH -+ C,,H2r*CH:CH -+ORGANIC CHEMISTRY. i. 145 formula is suggested CHMe,'[CH31e],*C;Me:CMe.CHMe*CHMe*CH2*OH. It is possible that a-phytol is a condensation product of isoprene 4C5H8 + H,O + 3 8 = C20H400. The formula suggested for P-phytol is CHMe,fCHMe]4*CMe:CMe*[C€lMe]2*CH2*OH. a-Phytol has DF 0.856 and ng1.46364 and P-phytol D," Oms52 and n 1.46380.It can be distilled in portions of 10-30 grams from Claisen flasks and has b. p. 203-204"/9-10 mm. Both compounds give the same iodine number. A good test for the presence of phytol for example in phaeophytin preparations is the formation of a stable colourless oil by heating for a short time with concentrated nitric acid. When the boiling is prolonged a nitrogenous acid is formed the alkaline solutions of which have an intense yellow colour. Many phytol preparations both crude and didtilled undergo autoxidation (Engler and Weissberg Abstr. 1899 i 189) when kept for several months in corked vessels. A sharp penetrating odour with an acid reaction is noticeable and the oil becomes limpid and a t the same time distinctly acid. The formation of a peroxide can be detected by Engler's method.The rate of autoxidation varies considerably with different samples and it is probable that small amounts of some impurity present in both the crude and the distilled products act as a catalyst. The acid formed. is not homogeneous and is unsaturated; the analytical numbers indicate that it may be a mixture of equal amounts of phytenic acid and a saturated acid with 10 carbon atoms. Phytyl hydq*oyen p~~thulates COzH*C,H4*C0,*C,,H,q are formed when the phytol and phthalic anhydride are boiled for five hours with benzene and can be isolated by making use OF the fact that their sodium salts are very sparingly soluble in water but are soluble in ether. The a-phytyl ester is a syrup readily soluble in most organic solvents ; it yields an oily dibromide which is unstable and a silver salt C,,H,,O,Ag in the form of minute flat prisms m.p. 119" ; the isomeric stlver P-phytyl phthalute crystallises in prisms m. p. 116'. Cetyl hydrogen p?&alute C0,H-C6H4*C0,*C1,€I, forms indefinite crystals of a waxy consistency and has m. p. 61-62' The silver salt C,,H,70 A g crystallises from benzene. Phytyl ether 0(C70H39)2 obtained by the action of concentrated sulphuric acid on a glacial acetic acid solution of the alcohol is a viscid oil sparingly souluble in glacial acetic acid or in methyl alcohol and forms a dibromide. Phytol cannot be reduced by means of sodium and ethyl or amyl alcohol but by electrolytic reduction in cold alcoholic sulphuric acid solution using platinised platinurn electrodes with a voltage of 6 and a curreut density of 3 ampere per sq.m. and an earthenware diaphragm the saturated alcohol phytanol (dihydrophytol) C,? H,,O is obtained together with the hydrocarbon phytan. Phytanol is readily prepared by reduckg phytol with hydrogen in ethereal solution using platinum- black as catalyst; a slow stream of hydrogen is passed through for about three weeks when 40 grams of phytol are used. The reduction is ruuch quicker when the hydrogen is used under slight pressure and the apparatus is shaken continuously. It is a colourless odourless oil has b. p. 20165-2020/9-5 mm. is miscible with all organici. 146 ABSTRACTS OF CHEMICAL PAPERS. solvents and is isomeric with arachyl alcohol (Haller Abstr. 1907 i 377). It forms a sodium derivative C,,H,,*ONa in the form of a viscid oil soluble in ether or light petroleum.The phenylurethane NHPh*CO*O*C20H+l obtained by the combina- tion of the alcohol with phenylcarbimide is also a thick oil. Phytanyl hydrogen phthalate C0,H*C6H,*C02*C,,H41 is a syrup and ibs silver salt C,,H,,O,Ag has m p. 1 06-106450. Phytanyl pyruuate CH,* CO*CO,*C,,H, obtained by heating the components a t 110-120° or more readily by shaking the alcohol for a long time at the ordinary temperature with five times its weight of pyruvic acid and removing the excess of acid by means of water has b. p. 219-220°/10 mm.; its aemiccwbazone C23H4703N3 cryatallises from methyl alcohol in needles m. p. 88-91'. Cetyl pyruvate has m. p. 26*5-27.5" and its semicarbazone C,,H,,O,N,. crystallises in flat prisms m.p. 140-141'. The esterification of P-phytol by means of glacial acetic acid at 155' has been studied ; at the end of one hour 3445% of the acid is trans- formed into ester but after one hundred and forty-four hours the yield has fallen to 6*9% owing to decomposition of the ester into phytndiene. Geraniol and nerol react in much the same manner with glacial acetic acid at 155". The initial rates of esterification with acetic acid a t 155' of the following unsaturated alcohols have been determined oleyl alcohol erucyl alcohol geraniol nerol cholesterol and the values obtained are smaller than those for the corresponding saturated alcohols. Erucyl ulcohol C22H440 prepared by reducing ethyl erucate with boiling amyl alcohol and sodium has b. p. 240*5-241-5°/10 mm.and forms rhombohedra1 crystals m. p. 34.5-35-5". Its dibromide C,?H,,OBr forms glistening prisms m. p. 45-45-54 When reduced with hydrogen in the presence of finely- divided platinum the unsaturated alcohol yields docosyl alcohol C,,H,,O which crystallises from chloroform in glistening prisms m. p. 71-71.5° ; the phenplurethane C,,H,,O,N crystallises from ethyl acetate in glistening prisms m. p. 86-86-5'. The percentages of acetic acid transformed into ester at 155" are the following dihydrophytol '73 ; arachyl alcohol 76.2 ; tetrahydrogeraniol 68.5. These values are lower than those given by normal alcohols. Pliytanic acid C,,H,,02 is best prepared by oxidising dihydrophytol with an acetic acid solution of chromic acid in the presence of potassium hydrogen sulphate and forms a viscid oil b. p.221"/7.5 mm. The silver salt C,,H,,O,Ag darkens a t 165" and has m. p. 177-177.5". Ths umide C,,H,,*CU*NH crystallises when its solutions in methyl alcohol or light petroleum are well cooled and has m. p. 53-53'5'. AP-l'hytenic acid C,,H,O is formed together with the kebone C,,H,,.O when phytol is oxidised with an acetic acid solution of chromic anhydride (5 atoms of 0) in the presence of potassium hydrogen sulphate. It forms a yellow oil b. p. 210-220°/11.5 mm. and has D," 0.917 and 12;' 0,893. The position of the ethylene linking is established by the readiness with which it yields a y-lactone (Abstr. 1907 i 786) when heated with sulphuric acid and water The saturated hydrocarbon phytane is most readily obtained bg reducing pfiytene with hydrogen and platinum; it is a colourlesa,ORGANIC CHEMISTRY i 147 mobile oil with b.p 169650/9*5 mm. and Df 0.803 is only sparingly soluble in cold methyl alcohol and solidifies when cooled by liquid air. In t.he preparation of phytene (Abstr 1907 i 786) a di-iodo- derivative C2,H,,T2 is obtained in the form of a heavy oil and when this is reduced with zinc dust and glacial acetic acid or with zinc dust and hydriodic acid it yields impure phytene although the two iodiue atoms are not attached to adjacent carbon atoms. Phytadiene C2,H3* is formed when P-phytol phthalic anhydride ,and benzene are heated for a day in a Babo funnel owing t o the readiness with which the phytyl hydrogen phthalate decomposes into phytadiene and phthalic acid ; it has b.p. 186-187°/13 mm. and DF 0 826 and its iodine number points t o the presence of two olefine linkings. a-Phytol ozonide prepared by passing a current of 6% ozone into a dry chloroform solution of the alcohol and then removing the chloroform under reduced pressure at 20° forms a pale green syrup with a pungent odour and dissolves readily in most organic solvents. Methyl alcohol separates the crude ozonide into an insoluble “ motoxide,” C2,H4,0,0 and a soluble oxozonide C,,H,,O,O,. The yield of the ‘‘ moloxide ” is larger the shorter the time of ozonising and i t canbe obtained crystalline by well cooling its methyl alcoholic solution. It is a n oil at the ordinary temperature and when boiled with water yields the same products and in the same amounts as the oxozonide.Tbis latter when kept for some months under reduced pressure over phosphoric anhydride yields the normal oxonide C,,H,,O,O,. The best yields of the ketone C,,H,,O are obtained when a-phytol is oxidised with a glacial acetic acid solution of chromic anhydride in the presence of potassium hydrogen sulphate. With the theoretical amount of oxygen only a small amount of the alcohol is osidised ; but with 4 to 5 atoms of oxygen t o each molecule of alcohol a 73-97% yield of ketone can be obtained. The same ketone is also formed when either of the ozonides of a-phytol is boiled with water for three hours in a reflux apparatus using 25 grams at a time. The aqueous solution has a decided acid reaction and gives the ordinary reactions for aldehydes. Tho oily product consists of the ketone together with the acid C14H2802 (3*5%) phytenic acid the hydrocarbon C15Hi(2 and a small amount of a n ether.The acids can be removed by extraction with very dilute sodium hydroxide solution and the ketone purified by dis- tillation under reduced pressure. It forms a pale yellowish-green limpid oil which turns quite colourless in the course of two t o three weeks. It has b. p. 173-174’/9 mm. and 291*8-292*4O/722 mm. and is optically inactive. The oxime C,,H,,ON is a viscid oil with b. p. 201-202°/ 10 mm. and DS 0.885 ; the sernicarbaxone C,,H,,ON crystallises from alcohol i n woll-developed prisms m. p. 64*5O and the p-nitrophenyl- hydyazone C2,Ha502N3 forms a pale yellow oil. The ketone combines with bromine in chloroform solution yielding an unstable dibromide which is probably derived from the isomeric enolic compound Many ketones for example cholestanone and methyl ethyl ketone form colourless dibromides in solution (compare also Linnemann Annalen 1863 125 307; Lippmann Zeitsch.Chem. 1869 5 29). The ketone gives negative results with the following reagents for aldehydes sodium amalgam and diazobenzenesulphonic acid beuzenesulpho-i. 148 ABSTRACTS OF CHEMICAL PAPERS hydroxamic acid pyruvic acid and P-naphthylamine. It yields a Deroxide from which the ketones Cl3H2,O and Cl1H2,O are formed by Loiling with water. The alcohol C,,H,,O obtained by reducing the ketone with sodium and alcohol is a colourless viscid liquid with b. p. 178-180"/12 mm. or 173-174@/8 mm. Di 0.848 DY 0.838 and nz 1.44912.The saturated hydrocarbon C15H32 occurs in the first fraction obtained by distilling the crude ketone under diminished pressure and is deprived of the last traces of ketone by repeatedly shaking with three times its volume of glacial acetic acid in which the ketone is readily soluble. It has b. p. 260*5-263*5O/723 mm. (corr.) or 127-130°/9*5 mm. D 0.789 Di0 0.779 and nz 1.43322 and is also formed in small quantities when the ketone is reduced with zinc dust and glacial acetic acid. The oZe$ne CH,:CH*CHMe*C,,H, obtained by the action of phosphoric oxide on the alcohol C,,H,,O at 60-7O0 has b. p. 150-152°/11 mm. or 29O0(corr.)/724 mm. Dt 0.803 and Di0 0.790 and combines readily with bromine. Its ozonide Cl5H3,O4 is a viscid oil with a pale green colour.When the alcohol C,,H3,0 is heated at 150° for an hour with phosphoric oxide or when the above olefine is heated for several hours at 130° with the anhydride a product is formed which contains a small amount of a saturated (cyclic) hydrocarbon. The ketone C,,H,,O resembles its higher homologue ; it has b. p. 168-170°/10 uim. or 288-289O/722 mm. D 0.865 D:00+348 and is optically inactive. It is not oxidised so readily as its homologue C15H300. The ozime Cl,H,,ON is a viscid oil b. p. 196-19S0/11 mm. and Uq 0.891 and the semicccrbaxone Cl,H,,ON forms slender needles m. p. 62'. A 94% yield of the ketone is formed by oxidising P-phytol with a glacial acetic acid solution of chromium trioxide in the presence of potassium hydrogen sulphate and an 82% yield by boiling P-phytol- ozonide with water.It is formed together with the acid C1,H,,O (26-33%) by oxidising the ketone Ci5H,o0 with a glacial acetic acid solution of chromium trioxide in the presence of concentrated sulphuric acid. A by-product formed at the same time is the ether O(C,,H,i)2 which has b. p. 228-233O/722 mm. and DqO.836. Z~ihydroxyp~~yt~~rLe C20H39(OH)3 obtained by converting a-phytol dibromide into the acetate and subsequent hydrolysis is a viscid oil sparingly soluble in cold methyl alcohol and when oxidised with chromium trioxide in the presence of glacial acetic and concentrated sulphutic acids yields the ketone C,,H,,O as a colourless mobile oil b. p. 16S-17Oo/8 mm. together with the acid C1,H,,02; its semi- carbazone C,,H 250N3 crystallises from alcohol in needles m.p. 68-72'. The same ketone is formed when the product obtained by the prolonged action of ozone on the ketone Cl5H3,,0 is boiled with water. The ketone C9Hl8O is a limpid oil with b. p. 16S0/10 mm. or 282O/720 mm. and has l.); 0.836. The olefine dibrornide C,,H,,Br is a yellow oil and when shaken with silver acetate and glacial acetic acid at the ordinary temperature yields the bromoacetyl derivative C15HROBrAc as a viscid oil which reacts with silver acetate at loo" yielding the diucetate and this on bydrolysis with cold methyl-alcoholic potassium hydroxide yields an Its semicadaxone has m. p. 75'.ORGANIC CHEMISTRY. i. 149 ether oE the glycol (C,,H,,*OH)O as a brown viscid oil. The ether when oxidised with chromium trioxide glacial acetic and sulphuric acids yields as intermediate product a carbony1 compound C,,H,,O and ultimately the acid C,,H,802. The same acid is also formed when the olefine ozonide is boiled for five hours with water but appreciable amounts of the ester C,H17*C0,*C,,H, are also formed.The acid C14H2*02 is a colonrless comparatively viscid oil with b. p. 1 86-188°/ 8-9 mm. DS 0.887 and DJ"" 0.870. The siZver salt C,4H2702Ag is obtained crystalline by using alcoholic solutions and has m. p. The acid C,,H,,O is a colourless odourless,viscid oil b. p. 155-1 5S0/ 11 mm. and 261°/732 mm. D 0.956 Di0 0.936 and rtg 1.45205; it decolorises permanganate in glacial acetic acid solution after a short time. The silver salt CIqH,,O,Ag,. forms a crystalline precipitate and with benzene forms colloidal solutions.The ester C9H17*C02*C,oH,I forms a colourlesP mobile oil b. p. 175-176°/11 mm. Dj 0.889 and DSo 0*808. It is hydrolysed by a cold concentrated solution of potassium hydroxide in methyl alcohol. Electrical conductivity measurements of the acid C10H2002 phytanic acid and AP-phytenic acid were made in aqueous alcoholic solution. The unsaturated acid is a better electrolyte than the saturated acid and the acid C,,H,,,O conducts better than acetic acid. A distillation flask similar to that described by Michael (Abstr. 1902 i 70) is recommended for distillations under reduced pressure. Use is made of a column of glass beads but the capillary tube for introducing bubbles of air is passed through a side-tube fused into t h e body of the flask.186-188O. J. J. S. Condensation Products of 2-Coumaranone. KARL FRIES and W. PFAFFENDORF (Ber. 1911 44,114-124. Compare Abstr. 1910 i 186; also Fries and Fink Abstr. 1909 i 42,44).-By the condensation of 2-coumarone with sodium ethoxide solution in the absence of air i t has been found possible t o obtain two isomeric compounds C10H1003. The relative amounts of the two vary with the conditions but so far it has not been found possible t o ascertain the conditions which determine the proportions. Neither compound appears t o have t'he hydroxylic structure corresponding with the acetyl derivative already described (Abstr. 1910 i 186) as they are both very sparingly soluble in alkalis. They are represented as isomeric ketones and both yield 2 1'-diketo-A'* 2-1 2'-dicoumaran (" oxindirubin," '' 1 2-bis- coumaran-indigo") when mixed with a small amount of bromine in glacial acetic acid solution. 2- Keto-1 2'-coumurancounz arone C,H4<O>CH co C<Ee->O is the chief product obtained by condensing 2-coumaranone with a hot 3% sodium ethoxide solution and is also formed by t'he hydrolysis of the acetate (Zoc.cit.). It crystallises from methyl alcohol in compact. colourless needles m. p. 1 1 6 O and its solution in concentrated sulphuria acid has a yellowish-red colour with a strong yellowish-green fluor- escence. Its solutions especially in the presence of impurities are VOL. c. i. rni. 150 ABSTRACTS OF CHEMICAL PAPERS. unstable. It yields a somewhat unstable hydrobromide in the form of light red needles and with acetic anhydride and sodium acetate yields the acetate of the tau tomeric hydroxy-compound.The isomeric 2-~eto-Al:~-dicozcmurccn C,H4<-,->C:C<2Z2>0 co is more readily soluble in acetone and crystallises from methyl alcoh61 in brilliant coppery-red plates m. p. 141'. It is decomposed when boiled for some time with methyl alcohol yields a yellowish-red hydrochloride and is most readily obtained by condensing 2-coumarone with glacial acetic acid saturated with hydrogen bromide. When either of the ketones or the ,acetate m. p. 106' is heated for eight hours at 100' with a saturated solution of hydrogen chloride in glacial acetic acid a product C,,H1604 76H4*7=$!'V is obtained which crystallises from xylene in flesh- o-s $*C,B4 coloured needles. These are not molten at 340° y6114*F 7.Q but sublime in reddish plates with a metallic lustre.()-- C=C.C,H The annexed formula is suggested. Nitric acid con- verts it into a deep black-coloured substance the acetic acid solution of which has a reddish-violet colour. By the condensation of 5-methglcoumaranone with sodium ethoxide only one product is obtained namely 2-keto-5 5'-dimetlllyl-A1:2'-di- coumaran C,,H140,. This crystallises from alcohol in yellow prisms m.p 156'(when quickly heated) and is readily oxidised to 5 :5'-dirnethyl- leuco-oxindirubin. It undergoes decomposition when heated alone or with glacial acetic acid. The product C36H2404 obtained by heating the acetate m. p. 133' (Zoc. cit.) with a saturated solution of hydrogen chloride in glacial acetic acid crystallises from xylene in pale red needles which melt above 340'.When rubbed with a little nitric mid it yields a blue-black compound which dissolves in glacial acetic acid to brilliant violet-blue coloured solutions. 2 1'-Dihydroxy-1 2'-dicoumarone (" leuco-oxindirubin ") yields a phenylhydruxone C,,H,,O,N which crystallises from glacial acetic acid in pale red needles m. p 179' and when hydrolysed with hydrochloric acid yields oxindzrubm. The acetyl derivative of 2 1'-dihydroxy-1 2'-dicoumarone ClsHleOs crystallises in glistening plates m. p. 198'; when hydrolysed mlth alkalis it yields the leuco-compound but with hydrochloric acid yields oxindirubin The phenylhydraxonte of 2 l'-dihydroxy-5 5'-dimethyl-l 2'-di- coumarone C,,H,,O,N forms xed needles m. p.163'. The oxime C,,H1,O,N crystallises from methyl alcohol in yellow needles m. p. 194' and the acetyl derivative C2,H1,05 in yellow prisms m. p. 200'. J. J. S. Oxindigo [2 %Diket~-A~:~'-dicournaran]. KARL FRIES and A. HASSELBACH (Bey. 1911 44 124-128).-So far it has not been found possible to obtain ( 6 oxindigo " by the alkaline oxidation of %coumaranone or from halogen derivatives of coumaranone (com- pare Abstr. 1897 i 424; 1901 i 9 4 ; 1909 i 44 174). Attempts to prepare the oxygen compound of the action ofORGANIC CHEMISTRY. i. 151 ammonium sulphide on p-dimethylaminoanildiketocoumaran were also unsuccessful. By the condensation of the anil derivative with 2-coumaranone in boiling xylene a product C,,H,,O,N is formed and this when hydrolysed by means of a mixture of glacial acetic and concentrated sulphuric acid a t the ordinary temperature yields amino-dimethyl- aniline and '' oxindigo." 3- Keto-2-p-dimethylanainoanilcoumara~a c,H,<~:>c N* C,H,*NMe prepared by the action of an alcoholic solution of 2-coumnranone on an alcoholic solution of p-nitrosodimethylaniline in the presence of 2N-sodium hydroxide solution at 3' crystallises from benzene in large prisms with a blue-black lustre or from alcohol in dark brown glistening needles m.p. 185'. It is hydrolysed by strong acids to p-aminodimethylaniline and o-hydroxyphenylglyoxylic acid. The condensation product C,,H,,O,N probably C H ~ ~ ~ > C ( N H . C ~ H . N M ~ ) *cH<!>c,H~ crystallises from a mixture of benzene and light petroleum in flat prisms with a bronzy lustre m.p. 203' (decornp.) after sintering at 190'. The yield is 30% of the theoretical and the product dissolves in alkali hydroxides yielding reddish-brown solutions. 2 2-Diketo- Al 'lt-clicoumaran ( "oxindigo," L 6 1 1 -dicoumarone-indigo") - . C,H,<:>C:C<(>C,H crystalliees from glacial acetic acid or from xylene in long prisms with an intense lemon-yellow colour. It has m. p. 272' after sintering a t 250° and its solution in con- centrated sulphuric acid has a yellowish-red colour. It is decomposed by alcoholic sodium hydroxide solution and even by sodium carbonate in the presence of alcohol. J. J. S. A New Thiophen Compound C,,H,S and Some of its Derivatives M. LANFRY (Compt. rend. 1911 152 92-94).- The tarry product obtained when a mixture of sulphur and naphthalene vapour is passed through a red-hot iron tube contains 0.2-0*4% of a compound crystallising in ruby-red /\ \/\/\/ I II ti ii s s reaction with sulphuric acid and I - leaflets or clinorhombic prisms.The substance has m. p. 115.5' (corr.) b. p. 345' and in composition approximates to the formula C,,H,S,.; it is supposed to be benxdzthaophen (annexed formulae). It gives the thiopheu isatin. The 6romo-derivative ClOS,H,Br4 crystallises in silky orange needles m. p. 247-248'. The tet~anztro-derivative CI,S,H2(N0,) was obtained as an orange powder decomposing a t 300°; it has well-marked acid characters and forms highly-coloured compounds with cyclic hydrocarbons. On treating benzdithiophen with hydrogen peroxide in acetic acid solution it yields in the first place a compound C,OH,O@ slender m 2i.152 ABSTRACTS OF CHEMICAL PAPERS. rose-yellow needles m. p. 130' having the properties of a p-diphenol. On further oxidation a second compound Cl,H60,S is formed; this crystallises in radiating red needles m. p. about 125'; it is insoluble in aqueous alkalis and develops no coloration with sulphuric acid and isatin. w. 0. w. Silicotungstates of Coniceine Sparteine and Atropine. MAURICE JAVILLIEB (BUZZ. Sci. Phccrm. 1910,315-320. Compare Abstr. 1899 ii 456 ; 1909 ii 45O).-Coniceine silicotungstate 1 2W0,,Si0,,2H20,4C,Hl,N + 3H20 prepared by adding potassium silicotungstate to an aqueous solution of coniceine tartrate is an amorphous substance which becomes anhydrous at 120". I t is soluble in boiling water ; 100 C.C. of water a t 15' dissolve about 0.02 gram of the salt.Sparteine silicotungstate 12 WO Si0,,2H20,3C,,H,,N2 + 7H20 is amorphous and loses 6H,O at 120'. The precipitation of this salt is visible in aqueous solutions containiog 0.0002% of sparteine and consequently may be omployed in estimating the alkaloid. Atropine silicotungstate 12 W0,,Si02,2H20,4C ,HpO,N + 4H,O be- comes anhydrous at 120". It is less easy t o obtain pure than the foregoing owing to a tendency to undergo hydrolysis. Advantage has been taken of its sparing solubility (less than 1 in 40,000) to Preparation of Alkyl Halides and Alkyl Nitrates of Tropeine a n d ScGpoleine Alkaloids. A. GERBER (D.R.-P. 228204).-&1ethy3- atropiniurn methosulphite C,7H,3~0,NMe*S03Me is prepared by heat- ing atropine with rmthyl sulphite and methyl alcohol in a sealed tube a t 100"; thepZccti.nichloi.ide (C17H2,0,NMeC1),PtCI forms orange- coloured leaflets.Atropine methobromide m. p. 220° and atropine metho- witrate are formed respectively by evaporating the foregoing com- pound with aqueous potassium bromide or with potassium nitrate ; these compounds are soluble in water or alcohol sparingly so in ether or acetone. Dihydroberberine. JOHANNES GADAMER (Arch. Pharm. 191 0 248 670-681).-Faltis' evidence for the view that the action of potassium hydroxide on berberine results in the formation of oxy- berberine and tetrithydroberberine (Abstr. 1910 i 698) is reviewed and criticised and further facts are brought forward in support of the author's opinion that in this reaction oxyberberine and dihydro- berberine are formed (Abstr.1902 i 173 555 ; 1905 i 369 ; Freund and Beck 1905 i 151). Faltis' observation that by the action of zinc and acetic acid on oxyberberine the latter is rendered colourless could not be confirmed. Dihydroberberine hydrochloride prepared as already described (Zoc. cit.) crystallises with 4H20 but readily loses 1H20 on drying in a desiccator. Dihy droberberine is less basic than teti ahydroberberine and is less easily removed than the latter from solution in ether by agitation with dilute hydrochloric acid. Tetrahydroberberine is resolved by crystallisa tion of t h e d-bromocamphorsulphonate into d- and I-canadines but repetition of a similar fractional crystallisation estimate atropine in pharmaceutical preparations.w. 0. w. F. M. G. M.ORGANIC CREMISTKY. i. 153 of dihydroberberine d-bromocamphorsulphonate (Abstr. 1902 i 1'73) showed that no resolution of this base took place although tetrahydro- berberine was again easily resolved either alone or in admixture with di hydroberberine. Dihydroberberine furnishes a rnethiodide m. p. 205O which dissolves i n water forming a yellow solution giving no precipitate with ammonia but forming a white precipitate with much sodium hydroxide the liquid a t the same time developing a violet fluorescence; the pre- cipitate is not dissolved by ether. Tetraiqdroberberine methiodide m. p. 245-250° is colourle~s and soluble with difficulty. Oxyberber- ine fornis an additive product with methyl sulphate.Dihydroberberine is more poisonous to rabbits than tetrahydro- berberine. T. A. H. Corydalis Alkaloids. V. R-Corydaline and Phenylberberine. JOHANNES GADAMER (Arch. Phurrn 19 10 248 6S1-695).-A des- cription of direct and indirect attempts made to resolve optically in- active corydaline m. p. 135O into optically active forms (Abstr. 1902 i 306; 1905 i 463). fractionation of the tartrate quinate and d-bromocamphorsulphonate were unsuccessful. Natural d-corydaline does not give a crystalline salt with the last-mentioned acid. Attempts were then made to effect the resolution of a-methyl- dihydroberberine (Freund and Beck Abstr. 1905 i 151) and to reduce the d- and l-isomerides thus obtained so producing active forms which should differ from corydaline only in containing a dioxymethylene group in place of two methoxyls and should therefore correspond with the d- and Z-corydalines and to d- and Z-mesocorydaline (compare Freund and Mayer Abstr.1907 i 633). The resolution of r-a-methyldihydro- berberirie could not however be effected and this was also the case for pheny 1 berberine. Oxyberberine treated with magnesium ethyl iodide in benzene solution with dimethylaniline as a catalyst was recovered for the most part unchanged but small quantities of methylnoroxyberberine (Faltis Ahstr. 1910 i 698) and of a non-basic substance m. p. 165-166' separating from alcohol in bright yellow crystals were obtained. Oxyberberine reacts with magnesium phenyl bromide in ether to form (1) a tertiary buse which may be either a phenyltetra- hydrober berine or diphenyldihydroberberine and (2) phenylberberine.The latter furnishes a hydrochloride m. p. 255-257' (decomp.) which separates from alcohol or water in brownish-yellow crystals. The aurichloride m. p. 215-216" (decomp.) forms long brown needles from alcohol containing hydrochloric acid. The acid sulphate softens a t 270° but does not melt even at 278" and separates from dilute sulphuric acid in compact yellow crystals. The nitrate m. p. 268-270" (decomp.) is deposited from alcohol in compact brown crystals. On reduction with zinc and dilute sulphuric acid phenylberberine hydrochloride yields phenyltetrahydroberberine m. p. 222" which [With ERNST STEINBRECHER.]-AttemptE to eff eCt resolution byi. 154 ABSTRACTS OF CHEMICAL PAPERS.separates from a mixture of chloroform and alcohol in compact almost colourless crystals and may also be obtained by reduction of phenyldihydroberberine. The latter prepared by Freund and Beck's method (Abstr. 1905 i 151) on oxidation with iodine in alcohol fur- nished isophenylberberine which gives a hydrochloride m. p. 275-278' (decomp.) separating from water in silky bright yellow crystals. The aurichloride forms reddish-brown short needles sinters a t 250° but does not melt at 280' ; along with it was produced a second gold salt m. p. 223-225' which may be impure phenylberberine aurichloride (see above) since on decomposition with hydrogen sulphide it yielded some phenylberberine hydrochloride. This phenylberberine is probably produced in the initial oxidation along with isophenylberberine. The latter on reduction yielded a varnish from which no crystalline derivative could be obtained.The relationship between phenyl- berberine and isophenylberberine is uncertain 2nd it is regarded as improbable that the difference is due to hydrogenation of a different pyridine nucleus in each case. T. A. H. Preparation of Curarine. RUDOLF BOEHM (Pjiiger's Archiu 1910 138 203-207).-The action of curare is so uncertain because commercial specimens contain other substances in addition to its most active constituent curarine. The best kinds of curare contain only 3 to 9% of this alkaloid. Very small doses of curarine produce marked results. The methods of separating i t from curare have been dealt with in extenso in the author's previous writings (Abstr.1887 1125 ; 1898 i 283) and are brieflygiven in the present paper. W. D. H. Preparation of Alkylhalogen Derivatives of Morphine Alkaloids. A. GERBEH (D.R.-P. 228247).-The halogen double salts of the alkaloids and their quaternary compounds obtained by the action of alkyl halides and methyl sulphate have been pre- viously described (Abstr. 1.905 i 542 658; 1906 i 530 877; 1908 i 452) and the work has now been extended to the products obtained with methyl sulphite. Methylrnorphinium methosulphite C17Hl,0,NMe*S0,Me is prepared by heating morphine with methyl sulphite and methyl alcohol in a sealed tube at looo and subsequently evaporating in a vacuum; the amorphous faintly coloured hygroscopic product is rendered crystalline by dissolving in absolute alcohol and precipitating with ether ; when evaporated with a saturated solution of potassium bromide it is con- verted into morphine methobromide (m.p. 260'). Jlethylrtarcotinium methosulphite has similar properties and is analogckly prepared from nircotine ; its platinichloride ( C,,H,,07NMeC1),PtCI forms small orange crystals. Methylcodeinium methosulphite methylapomorphinium methosulphite metliylthe6anium methosulphite with their respective rnethobromides were also prepared ; thebaine methobromide has m. p. 185'. F M. G. M.ORGANIC CHEMISTRY. i. 155 Strychnine and Brucine. 11. ROBERTO CIUSA and G. SCAGLIAEINI (Atti R. Accad. Lincei 1910 [v] 19 ii 501-505. Compare Abstr. 1910 i 583).-When cacothelin is suspended in water acidified with hydrobromic acid and treated with bromine water until it has all dissolved it is converted into the hydvobromide of an acid C19H2206N2,HBr,2H20 which is obtained in yellow crystals by the evaporation of the solution The free acid Cl,H220,N2,2H,0 (com- pare Hanssen Abstr.1887 505) forms scales having a nacreous lustre. It is not toxic. The platinichloride (C1,H220,N2),H2PtC1 obtained in presence of hydrochloric acid crystallises in small yellow prisms. R. V. S. Identity of Vernine and Guanosine and Notes on Vicine and Convicine. ERNST SCHULZE and G. TRrEa (Zeitsch. physiol. Chem. 1910 70 143-151. Compare Abstr. 1910 ii 645).-The pentose (compare Schulze and Castoro Abstr. 1904 ii 506) obtained by the hydrolysis of vernine yields I-arabinose-p- bromophenylosazone (Levene and Jacobs Abstr.1909 i 858) and is presumably d-ribose. A detailed comparison of vernine with Levene and Jacobs' guanosine (Abstr. 1910 i 620) has proved that the two are identical. The following formula are suggested for vicine and convicine namely The hydrolysis of vicine is represented by the equations C2?H36015NS and CX)H!?5016N69 2H20' C20H36015NS + H2° = CSH1.404NS + 2C6H1206 Dwicin. Hexoses. (2) C,H,*O,Ns + 4H2O = C,H,oOsN4 + 4NH3 and that of convicine by the equation C20H2,016N6,2H,0 + 4H20 = CsH,0,N4,2H20 + 2C,H1206 + 2NH Alloxanthin. (compare Ritthausen Abstr. 1881 1158 ; 1899 i 715). hexoses with pyrimidine derivatives. The two compounds are thus glucosides formed by the condensation of J. J. S. Indole in Coal Tar. RUDOLF WEISSGERBER (Ber. 1910 43 3520-3528).-The sodium derivative of indole C,H,<G!;>cH is obtained in the form of a brown amorphous mass m.p. 140° by heating indole with sodamide at 150-160° or with sodium at 170-180O ; it reacts with methyl iodide yielding 1-methylindole together with small quantities of 2-methylindole and 3-methylindole. On warming with benzoyl chloride in benzene solution it yields benxoylindole C6H4<gE>cH ; the latter crystallises from alcohol in compact rhombic plates m. p. 67-68O b. p. 213'/16 mm. and is readily hydrolysed by aqueous sodium hydroxide. The potassium derivative of indole is obtained as a light-coloured mass by heating indole with potassium hydroxide. The formation of the potassium compound furnishes a ready means of separating indole from coal tar.The fraction b. p. 240-260° freed from phenols and bases by shaking with alkali hydroxide and dilute sulphuric acid is heated with potassium hydroxide at 1 90-200°,i. 156 ABSTRACTS OF CHEMICAL PAPERS. the unattacked oil removed by washing with benzene and the potassium indole decomposed by water ; the separation may also be effected by means of sodium or sodamide. The crude indole may be purified by converting it into the bisulphite compound (Hesse Abstr. 1900 i 48) or into the sodium salt of indolecarboxylic acid (compare Zatti and Ferratini Abstr. 1890 i 202) by heating with sodium at 190-200" in a stream of carbon dioxide. The free acid obtained from the sodium salt by acidification loses carbon dioxide when heated in n vacuum a t 230-250° and yields indole.E. B. Preparation of Halogenindoxylic Acids and their Esters. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 226689).-The conversion by alkalis of phenylglycine-o-carboxylic acids into derivatives of indoxyl has been described (compare Abstr. 1908 i 974 1019) and it is now found that the reaction can be applied successfully to halogenated derivatives of the acid. Methyl 5 7-dichZoroindoxyZcarboxyZate C,H,Cl<-NH->C*C02Me colourless needles m. p. 1959 is prepared by boiling dimethyl 4 6-di- clr Zorophen ylglyc ine -2 - carboxy Zate m . p. 7 7-7 8O in t ol uene solution with sodium or sodium methoxide; the toluene can be replaced by other indifferent solvents. Dimethyl 6-chZoro-4-bromoplien~ZyZycie-2-carboxylate m. p. 81 - 83' (obtained from 6-chloro-4-bromopheoylglycine-2-carboxylic acid m.p. 23S0 in the usual manner) yielded on similar treatment methyl 7 - C h h ~ O - 5-brornoindoxylcarboxyZate7 C,H,CIBr<-N H->C*CO,Me long needles m. p. 203-205". Methyt 4 6-dichZorophenyZglycine-2-carboxylate colourless needles m. p. 133-134' on treatment with sodium ethoxide yielded sodium 5 7-dichloroirndoxy~carboxy~c~te a yellow powder which is readily con- verted into 5 7 5' 7'-tetrachloroindigotin by the action of air and water E. M. G. M. W H ) C W ) Betaine Formation and S teric Hindrance. ALFRED KIRPAL (.Monatsh. 1910 31 969-979. Compare Abstr. 1908 i 679).- Nicotinic isonicotinic and cinchomeronic acids interact with chloro- acetic acid in neutral solution giving almost theoretical yields of the corresponding betaines ; picolinic and quinolinic acids under the same conditions react incompletely whilst dipicolinic acid remains un- changed.The author suggests that these results may be explained on the assumption that the carboxyl group in the a-position exerts a negative influence on the nitrogen atom which therefore shows less tendency to assume the quinquevalent condition. This explanation is however not applicable to quinaldine and 2 6-dimethylpyridine both of which on treatment with chloroacetic acid do not yield betaine but are converted into their hydrochlorides ; the non-formation of betaines in these cases is referred to steric influences. isor'Vicotinic acid betaine C,H70,N prepared by heating isonicotiqiqORGANIC CHEMISTRY. i. 157 acid and chloroacetic acid in faintly alkaline aqueous solution crystallises in needles m.p. 262' (decomp.). Nicotinic acid betaine forms monoclinic prisms or octahedral crystals and has m. p. 190' (decomp.). Picolinic acid betaine crystzllises in short pointed prisms m. p. 1 6 5 O (decomp.) ; the hydyochloride has m. p. 181'. Cinchomeronic acid betuine C,H70,N forms rhombic plates m. p. 180° (decomp.). Quinolinic acid betaine C,H70,N,H2O crystallises in colourless prisms which when heated at loo" lose their water of crystallisation and carbon dioxide yielding nicotinic acid betaine ; the same decom- position also takes place on boiling its aqueous solution ; the hydro- chloride is readily hydrolysed aqueous solutions rapidly depositing the free betaine. a-Yicolinebetaine C,H,O,N prepared by heating a-picoline with chloroacetic acid on the water-bath and isolated by means of its platinichloride crystallises in colourless hygroscopic needles which turn brown at 100' and decompose at 162'; the platinichloride forms yellow prisms m.p. 212' (decomp.) ; the hydrochloride has m. p. 188' (decomp.). F. B. Derivatives of 2-Phenylquinoline. 11. ERNET MURMANN (Nonatsh. 1910 31 1303-1306. Compare Abstr. 1892 1003).- Disulphonic acids can be obtained by heating 1 -phenylquinoline with four times its weight of commercial fuming sulphuric acid on the water-bath until a test drop gives no crystals (monosulphonic acid) when heated with five drops of water and no turbidity on addition of aqueous ammonia. The mass is diluted with five times its weight of water and a small amount of monosulphonic acid separates during the course of a day.After further dilution boiling with animal charcoal and neutralising with barium carbonate crystals of a barium salt C,,H,O,NS,Ba 6 H20 in the form of long colourless needles are obtained. The culcium salt C,,H,0,NS,Ca,6H20 forms slender yeIlow needles sparingly soluble in water and the zinc salt crystallises with 5H20 in large felted needles. The filtrate from the barium salt contains an isomeric salt which is sparingly soluble in alcohol and crystallises with 12H,O. The first barium salt when fused with potassium hydroxide yields a red phenol m. p. 140-141'. J. J. S. Formation of Acyl Derivatives of Phenylhydrazine in Aqueous Solution. STEPHAN JAROSCHY (Monutsh. 1910 31 95 1-967).-The phenylhydrazides of formic acetic propionic butyric and isobutyric acids are readily formed by heating the acids with phenylhydrazine in aqueous solution.The relative velocities of formation of these hydrazides under various conditions at 100' have been investigated by estimating the amount of unchanged acid by titration with barium hydroxide With the same concentration of acidi. 158 ABSTRACTS OF CHEMICAL PAPERS. and of base it is found that the rates of formation stand in the same order as the magnitude of the dissociation constants of the acids The effect of temperature was studied in the case of the formyl derivative. Increase of temperature is accompanied by an increase in the relative velocity and the same effect is produced by increasing the concentration of the acid.The addition of a small quantity of hydrochloric acid was found to diminish the rate of formation of the acetyl derivative. The author suggests that this is to be referred to the diminution in the ionisation of the acetic acid; on this assumption the acylation is due t o the anions. F. B. Oxidation of Methyluracil. ROBERT BEHREND and KARL BTRUVE (Annalen 1910 378 153-169. Compare Behrend and Dietrich Abstr. 1900 i 120 ; Behrend and Grunewald Abstr. 1902 i 834 ; Behrend and Fricke Abstr. 1903 i 739 ; Behrend and Osten Abstr. 1906 i 309 ; Behrend and Hufschmidt Abstr. 1906 i 310 ; Hobel Abstr. 1907 i 557; Offe ibid. 645).-When oxidised with potassium ferricyanide in ammoniacal solution methyluracil yields the amide of uracilcarboxylic acid CO<NH,cMe>CH NH-CO + NH + 3 0 = co<NH*C(CO *NH,) ">CH+2H20.This appears to be the first instance recorded of the oxidation of a -CH to a -CO*NH group. The reaction does not consist in the oxidation of the methyl to a carboxylic group and the conversion of the latter into the -CO*NH group by means of ammonia as it is shown that a temperature of 240" is required for the latter reaction. It is possible that an aldehyde group is first formed and that this yields an aldehyde-ammonia -CH<gE- which is then oxidised to the -CH< group. When the oxidation takes place in the presence of potassium hydroxide the product is uracilcarboxylic acid. I n the preparation of the amide the mixture is heated a t 50-60° for five to six hours and allowed to cool when potassium ferrocyanide separates; this is removed and the filtrate heated until all the ammonia is driven off and an odour of hydrogen cyanide is noticed.The solution is filtered hot and kept for one to two days a t the ordinary temperature when methyluracil separates as octahedra or needles and in the course of a week or so the amide separates in a crystalline form. It is most readily freed from uracil by conversion into its sparingly soluble potassium derivative C,H,03N3K,2H,0 which crystallises from hot water in well-developed prisms. Its solution has an alkaline reaction. The arnide C,H,O,N H,O crystallises in small lancet- shaped plates dissolves in 110 parts of boiling water and in 2000 parts of water at 20°. When boiled with alkalis it yields uracil- curboxylic acid NH- C(CO,H) ">CH,H,O in the form of rhombic plates which lose their water of hydration at 120'.The anhydrous compound decomposes above 300' without melting. The hydrated compound dissolves in '70 parts of water at 100" and in 500 parts at IS' NH-- 0 NH2ORGANIC CHEMISTRY. i. 159 The addition of acetic acid to a solution of the carboxylic acid in potassium hydroxide solution precipitates potassium uracilcarboxykate C,H,O,N,K. The ammonium salt C,H70,N,,H,0 crystallises in small six-sided plates. The acid is identical with the product obtained by hydrolysing the ester described by Muller (Abstr. 1897 i 549). When methyluracil is oxidised with potassium ferricyanide in the presence of potassium hydroxide solution i t is best to leave the mix- ture for twenty days at the ordinary temperature and then to acidify with acetic acid when potsssium uracilcarboxylate is precipitated.It has not been found possible to oxidise the carboxylic acid with potassium ferricyanide but wibh permanganate (30) at 15’ the acid yields oxaluric and oxalic acids. J. J. S. Oxidation of a- and P-Dimethyluracils. PAUL HENKEL (Annalen 1910 378 170-18’7. Compare Behrend and Grunewald Abstr. 1902 i 834)-The oxidation of a- and P-dimethyluracils is analogous t o that of methgluracil (compare table given by Osten Annalen 1905 343 151). Methylparabanic acid can be isolated from the oxidation products of both compounds under conditions such that its formation from methyloxaluric acid is excluded. The two dimethylurscils have been transformed into corresponding a- and P-tribydroxydimethyl- dihydrouracils by Osten’s method (Abstr.1906 i 309). These hydroxy- derivatives exist in only one form whereas the corresponding tri- hydroxymethyldihydrouracil exists in two forms (Abstr. 1908 i 840). Although it has not been found possible to isolate an acetylmethylallan- turic acid by the action of alkali on the trihydroxy-derivatives it is shown that a conversion of the six-membered ring into a five-membered ring must take place under the influence of alkalis since when oxidised with permanganate in the presence of excess of potassium hydrogen carbonate the a-trihydroxy-derivative yields methylparabanic acid together with methyloxaluric acid but no trace of acetylmethylcarb- amide. Trihydroxy-/3-dimethyldihydrouracil is oxidised much less readily and under similar conditions yields s - acetglmethylcarb- amide together with methyloxaluric acid and met hylparabanic acid ; but when the solution of the hydroxy-compound is left in contact with the potassium hydrogen carbonate for twenty-four hours before the addition of the permanganate the products obtained are methylpara- bank acid and methyloxaluric acid.Acetylmethyloxaluric acid is not formed during the oxidation in the presence of the carbonate. Nitro -a-dimethyluracil (5 - nitro - 2 6 - dioxy-3 4-dimethyldihydro- pyrimidine) C 0 < ~ ~ ~ ~ ~ ~ $ 2 0 N O 2 prepared by Osten’s method (Zoc. cit.) crystallises from water in yellow plates m. p. 249-250° and when reduced by Behrend and Griinewald’s method (Zoc. cit.) yields the corresponding amino-derivative C6H902N3 in the form of yellow crystals m.p. 281-282’. Trihydroxy-a-dimethyldihydrouracil (4 5 5- trihydroxy-2 6 - dioxy- cO>C(OH) ob- 3 4-dinzet~yldihydrop~ri~zidine) CO<NMe.CMe(OH) NH- tained by oxidking the amino-a-dimethyluracil with bromine water at low temperatures crystallises when its aqueous solution is concentratedi. 160 ABSTRACTS OF CHEMICAL PAPERS. at the ordinary temperature under 4 mm. pressure and decomposes at 120O. When heated at 70-80° for fifteen minutes with ethyl alcohol which crystallises from alcohol arid has m. p. 114-llii". ' X t r o - p - dimeth-yluracil (5-nitro - 2 6 - dioxy - 1 4-dimethy2dihydro- p y r i m i d i n e ) C O ~ ~ f ~ ~ ~ ~ ~ C * N 0 2 crystallises from water in pale yeliow prisms m.p. 229-230' (decomp.) ; the corresponding amino- derivative has m. p. 256-257' (decomp.) and t~il~ydroxy-P-dimeth?/Z- dihydrouracil (4 5 5 - trihydroxy - 2 6 - dioxy - 1 4 - dimethyldihydro- co>C(OH) crystallises from dilute Bromo-P-dimethyluracil C O < ~ ~ ~ ~ ~ e > C B r is sometimes formed as a by-product ; i t has m. p. 243'. 4-Hydroxy-5 5-diethoxy-2 6-dioxy- 1 4-dinzethyldiiiydropyri~id~ne C,,H,,O,N crystallises from alcohol has m. p. 124-126' (decomp.) and dissolves in 20 parts of cold absolute alcohol. Methylparabanic acid is readily transformed into methyloxaluric acid when its alcoholic solution is made alkaline with N/5-alcoholic potash and kept for an hour. It has not been found possible to obtain either of the above- mentioned nitro-derivatives by the action of methyl iodide and alkali on nitromethyluracil. J.J. S. Action of Potassium Permanganate and of Bromine on 1 4 5-Trimethylwracil. KARL BREMER (AnnuZen 19 10 378 188-209).-By analogy with methyluracil (Abstr. 1906 i 310) i t was thought probable t h a t by the oxidation of 1 4 5-trimethyluracil with cold permanganate methylacetylcarbamide and pyruvic acid would be formed and that with warm permanganate acetyldimethylhydantoin or its oxidation products would be obtained. Actual experiment has shown that the products are the same at both temperatures using 2 atoms of oxygen ; in both cases only acetylmethylcarbamide and a syrup are formed. No trace of pyruvic acid can be detected in the syrup and the only product so far isolated from the syrup is oxalic acid.Dihydroxytrimethyldihydrouracil has been prepared by Behrend Osten and Beer's method (Abstr. 1906 i 309) but it has not been settled definitely whether the compound has the con- stitution of the uracil (I) or whether it is the isomeric acetyldimethyl hydantoin (2). NMe-- wrimidine) CO<NH.CjyJe(()H) acetic acid and decomposes at 133". I n favour of the latter formula are the facts that it is not readiG oxidised and does not appear to be affected by alkalis. Attempts to oxidise 1-phenyl-4 5-dimethyluracil were unsuccessful owing t o the slight solubility of the compound in water. Behrend and Hennicke's method (Abstr. 1906 i 314) for the preparation of thiontrimethyluracil gives a 25% and not an 80% yield. A 45-50% yield is obtained when a mixture of equivalentORGANIC CHEMISTRY.i. 161 quantities of methyl thiocarbimide and ethyl P-amino-a-methyl croton- ate is heated to 55-60' and then kept for twenty-four hours in an ice chest ; after removing the crystals the filtrate is heated to 70° and on cooling gives a further crop of crystals. The desulphurisation is accomplished most readily by heating the ,compound in a reflux apparatus with 65% sulphuric acid for about forty-five minutes at 150-160" and subsequent dilution with three times the volume of water. The yield of trimethyluracil is 80%; it crystallises from hot water and has m. p. 222-223'. 1-Phenyl-4 5-dimethyluracil C,,H,,O,N is formed when ethyl phenylcarbamidomethylcrotonate (A-bstr. 1901 i 136) prepared from ethyl p-amino-a-methylcrotonate and phenylcarbimide is hydrolysed with 5% potassium hydroxide so!ution and the solution acidified with hydrochloric acid; it has m.p. 235'. 4-B~onzo-5 -hgdrox!j-l 4 5-trimeth~WihgdrourclciI obtained by the action of water and an excess of bromine on trimethyl- uracil at the temperature of the water-bath crystallises from hot water in needles m. p. 127' after sintering a t 120'. When heated with alcohol or by itself at 95' and then at 115' it loses water and yields 4-bromo- 1 4-dimethgZ-5-methyZenedihydrouracil co<NH* NMe-- CMeBr ">C:CH which crystallises from benzene or dilute alcohol and has m. p. 195O after sintering at 170'. This unsaturated compound reacts with bromine water yielding 4-bromo-5-hydroxy-1 4-dimethyZ-5- bi*ornomethyldihydrouraciZ C O < ~ ~ ~ ~ & ~ > C ( C H B r ) * O H m.p. 150-151' after sintering at 145'. and this. when heated at v 90-100' for three hours yields 4-bronzo-1 4-dirneth&B-bron~o- meth y leltedihydrouraciZ CO< NMe--C H. CMeEr O>c CH I' in the form of well-developed needles m. p. 1 75-178' which again react with bromine water yielding 4- bronzo-5-hydroxy - 1 4-climethyl-5-dibromometl~~/ldi- hydrouracii c0<NH.CMeBr N Me-- "o>C(CHBr2)*OH as colourless crystals. DibromohydroxymethyIdihydrouracil does not yield an unsaturated compound when heated at 150'. Chlorohydroxytrimethy Idihydrouracil C,H ,0,N2CI obtained by the action of chlorine water on trimethyluracil crystallises from hot water and has m. p. 154-155'. 4-Bromo-5 -hydroxy - 1 -phenyl- 4 5 -dimeth yldih ydyouraci! has m.p. 195'. 4 5-Dihydroxy-1 4 5-trimetliyIdi~ydl.ouraciZ C7H1,0,N prepared from the bromohydroxy-compound by Behrend and Grunewald's method crystallises from water in large prisms m. p. 165O. It reacts with boiling acetic anhydride yielding an acetyl derivative C9H,,0,N m. p. 135-150' and with phenyldydrazine yields a pl~enylhydraxzde Cl3HI8O3N4 in the form of needles m. p. 155-158O after sintering at 145'. J. J. S. c PHI 3OP2 Br,i. 162 ABSTRACTS OF CHEMICAL PAPERS. Quinazolines. XXVI. Synthesis of Some Stilbazoles Hydrazones and Schiff Bases in the k4-Quinazolone Group. MARSTON T. BOGERT GEORGE DENTON BELL and CARL GUSTAVE AMEND (J. Arner. Ghem. Xoc. 1910 32 1654-1664).-1t has been shown in earlier papers (Bogert and Gortner Abstr.1909 i 679; Bogert Amend and Chambers Abstr. 1910 i 893) that derivatives of 4-qujnazolone can be easily prepared which contain a 2-methyl group and amino-groups attached t o either or both the benzene and metadiazine portions of the nucleus. A study has been made of the behaviour of these different groups towards aldehydes and the results show that with reference to their reactivity with benzaIdehyde they may be arranged in the following order (1) the 3-amino-group (in the metadiazine nucleus) ; (2) the 2-methyl group; and (3) the 7-amino- group (in the benzene nucleus). When 2-methvl- 4 - auinazolone is boiled for ten minutes with benzaldehyde it is converted into the stilbazole namely 2-styryl-4- N=$? *C€I:CHPh CO*NH quinaxolone (2-styryZ-4-hydroxyquinaxoline) C,H,< N--(? *CH:cHPh m.p. 252-253' (corr.) which forms -- or 'cH4<c( OH N colourless silky needles and yields a brorno-derivative. 2-0-lI9droxy- N=(? CH CH* C,H;OH styryl- 4 -quirzaxoZone C,H,<CO. m. p. 301' (decomp.) obtained by the action of salicylaldehyde on 2-methyl-4-quin- azolone crystallisesinminute pale yellow needles and yields bright yellow salts with hydrochloric acid and potassium hydroxide. 8-p-llydyoxy-m- N= (? CH CH C6H3( OH) OMe methoxystyryl - 4 - quinnxolone CsH4<U0.NH 9 m. p. 280' (corr.) forms minute pale yellow needles and gives dark yellow alkali salts. When 2 3-dimethyl-4-quinazolone is boiled with benzaldehyde m. p. 170" 2-st yry I- 3 -metii yZ-4-puinaaolone CGHh< (corr.) is produced which forms light yellow slender needles.3-Amino-2-methyl-4-quinazolone was prepared by the action of hydrazine hydrate on acetylanthranil (Bogert and Gortner loc. cit.). I n one experiment a compound m. p. 193" (corr.) was isolated which crystallises in prisms and is probably acetylanthrnnylcccetyliL?/draxide NHA c*C,H,-CO*NH*NHAc. The hydrazone 3-benzylideneamino-2- rnethyl-4-quinazolone obtained by boiling 3-amino-2-methyl-4-quin- azolone (1 mol.) with benzaldehyde (1 mol.) has m. p. 187' (corr.) and not 183" as stated by Bogert and Gortner (Ioc. cit.) ; its hydrochloride softens at 220° and decomposes without melting a t about 300'. When 3-amino-2-methyl-4-quinazolone (1 mol.) is boiled with benzaldehyde (2 mols.) 3-bernxy~~deneamino-~-~tyry~-~-qu~nazo~one N=$l*CH:CHPh CO*NMe N=$I *CH:CHPh C ~ H 4 < ~ 0 - 1 ; $ .~ ~ ~ ~ h 9 m. p. 155' (corr.) is obtained which forms minute nearly colourless stellate groups of crystals ; its hydrochloride does not melt below 3 0 0 O . When this substance is treated with boiling dilute hydrochloric acidORGANIC CHEMISTRY. i. I63 and the product distilled with steam benzaldehyde passes over with the distillate and 3-amino-2-styryl-4-quinazolone m. p. 164O (corr.) is obtained which cristallises in plates or broad needles and when heated with benzaldehyde is reconverted into its benzylidene derivative ; the benxoyl derivative has m. p. 195' (corr.). When 3-amino-2-methyl-4-quinazolone is heated with cinnamnldehyde salicylaldehyde or vanillaldehyde the methyl group is not affected but condensation takes place only with the amino-group.3-Cinnarnyl- ideneamino-'2-methyl-4-quinazolone m. p. 148-14 9" (corr.) forms bright yellow needles. The corresponding salicylidene derivative m. p. 1 7 1 O (corr.) crystallises in short pale yellow needles yields a bright yellow potassium salt and a hydrochloride m. p. 250' (decornp.) and is hydrolysed by hydrochloric acid or potassium hydroxide with formation of salicylaldehyde. Although the salicylidene compound refuses to condense with a second mol. of salicylaldehyde it condenses readily with benzaldehyde with forxnation of 3-salicylidenearnino-2- - N=$l *CH:CHPh m. p. 232-233' C0.N.N CH CGH,*OH' styryl-4-quinaxoZone C,H,< (corr,) which crystallises in yellow needles. 3 - Vanillyliderzeamino-2- methyl-4-quinaxolone m.p. 21 5-21 6" (corr.) forms small yellow prisms or needles and gives deep yellow salts with hydrochloric acid and potassium hydroxide. I n the case of 7-amino-2-methyl-4-quinazolone as in that of the 3-amino-derivative condensation is possible with either the methyl or amino-group or with both The amino-group however is differently situated being in the benzene instead of the metadiazine nucleus and attached to a carbon instead of a nitrogen atom. Aldehydes con- densing with the $'-amino-group should therefore yield true Schiff bases instead of hydrazones. I n one experiment a benaylidene derivative m. p. 324' (corr.) was obtained which seemed to be the Schiff base since it was hydrolysed by potassium hydroxide with formation of benzaldehyde and the quinazolone but this compound could not be obtained subsequently; its acetyl derivative has m.p. 2 74-2 7 6' (corr.). 7- Acetylcmino-2-styryl-4-quint~cxolone N=C *CH:CHPh N=~C*C6H,<Co.$JH m. p. 323-324' (corr.) obtained by boiling 7-acetylamino-2-methyl-4- quinazolone with benzaldehyde forms short colourless needles. 7-Amino-2 3-dimethyl-4-auinazolone condenses with benzaldehyde " A to form 7-arnino-2-styryl-3-methyl-4-quinaxolone N=y *CH:CHPh NH,*C6H8<C0 .NMe 9 m. p. 229*5-230° (corr.) which crystallises in yellow prisms ; its acetyl derivative has m. p. 272' (corr.). When 3 7-diamino-2-methyl-4-quinazolone is boiled with an excess of ben zalde h y de 3 7-dibenx ylideneamino-2-st yv y I - 4-quinaxolone N=C -CH:CHPh CHPh:N*C6H,<(T0. &.N:CHp) 9 m.D. 238' (corr.) is produced together with small quantities of twoi. 164 ABSTRACTS OF CHEMICAL PAPERS. other substances m. p. 196" (corr.) and 172" (corr.) which seem to be isomeric dibenzylidene derivatives. ~-~cety~ccm~no-~-be~zzy~~deneum~2-styryl-4-quinazoZone m. p. 261" (corr.) obtained by boiling 3-amino- 7-acetylamino-2-methyl-4-quinazolone with excess of benzaldehyde forms yellow needles ; its solution in alcohol has a green fluorescence. 3 7-Diacetylamino-2-methyl-4-quinazolone condenses with benzalde- hyde with formation of 3 7-diacetyZamino-3-styryl-4-quinaxoZone m. p. 283-284" (corr.). 3-Amino- 6-ace tylamino-2-methyl-4 -quinszolone condenses similarly with lenzaldehyde with production of 6-acetyZarnino-3-benzyZiJeneam~no- 2-styryZ-4-puinaxolo~e m.p. 238-239' (corr.) which forms short silky yell0 w needles. E. G. Constitution of Indirubin. I. and 11. ANDRI~ WAHL and P. BAGARD (BUZZ. Soc. chim. 1910 [iv] '7 1090-1101; 1911 9 56-83. Compare Abstr. 1909 i 330 735).-I. Maillard's objection (Abstr. 1910 i 138) to the view that the authors' new synthesis of indirubin (Abstr. 1909 i 330) supports von Baeyer's formula for this substance is based on two main contentions: (a) that proof of the formation of indirubin was insufficient ; ( b ) that molecular transforma- tion may have occurred in the reaction. I n regard to (a) it is now shown that the synthetic indirubin like commercial indirubin yields Schunk and Marchlew ski's colourless crystalline compound m. p. 204" when reduced with zinc and acetic anhydride in presence of anhydrous sodium acetate (Abstr.1895 i 288). Contention (b) implies that both oxindole and indoxyl should condense with isatin chloride to give indirubiu but actual trial shows that when the reaction is conducted in presence of pyridine to remove the hydrogen chloride formed indoxyl gives indigotin and no indirubin whereas oxindole gives indirubin as chief product. 11. m-Bromoisatin chloride condenses with oxindole to furnish a bromoindirubin which is isomeric with but different from that obtained by condensing m-bromoisatin with indoxylic acid. The production of isomerides in these two reactions can be explained easily from von Bseyer's but only with difficulty from Maillard's formula. nt-Bromoisatin chloride condenses with oxindole in benzene solution to form a bromoindirubin having the formula It forms dichroic triclinic crystals showing oblique extinction and angle ph'= 126'.Its solubility is 0.192-0.199 gram in 100 grams of acetic acid a t 2 5 O . The bromoindirubin obtained by condensing m-bromoisatin with indoxylic acid has the formula C6H4<~~>C:c<,,>NHv C,H,Br and has been prepared already by von Baeyer (Abstr. 1882 198). It forms dichroic crystals which belong to the monoclinic system and show right extinction and angleyh' = 101". Its solubility is 0.042-0,052 gram in 100 grams of acetic acid a t 25". T. A. H.ORGANIC CHEMISTRY. i. 165 Quindoline and ‘‘ Thioquindoline.” EMILIO NOELTING and 0. R. STEUER (Ber. 1910 43 351 2-351 7).-Indoxylic acid condenses with 0-aminobenznldehyde in hydrochIoric acid solution yielding quindoline (compare Fichter and Bohringer Abstr.1907 i 92; Fichter and Rohner this vol. i 85). / \ - c / m This is identical with indoline described by I I I I Schutzenberger (this Journ. 1877 ii 898). \/\/‘\/\/ By heating indigotin with an alkaline solution NH C of sodium thiosulphate Geraud (Abstr. 1879 Since the same compound is also produced by the condensation of indoxyl and isatin in alkaline solution it must be a quindolinecarboxylic acid of the annexed structure. N CO,H I 936; 1881 51) obtained a substance to which he assigned the formula C3,Hz403N4. pared by the condensation of o-nitrobenzaldehyde and indoxylic acid in aqueous acetic acid solution crystallises in red needles m. p. 217’; on reduction with zinc dust and acetic acid it yields quindoline.By condensing indoxylic acid with o-aminobenzaldehyde in the presence of a little hydrochloric acid 2-o-aminobenxyZidene-indoxyl C6H,<~~>C:CH*C,H4*NH is produced ; if the condensation is carried out in more acid solution quindoline hydrochloride is obtained. 3-Keto-2-o-rtitrobenxylidene-thionaphthen C,H4<- CO ,->C CH*C,H,*NO prepared from o-nitrobenzaldehyde and 3-hydroxythionaphthen-2- carboxylic acid i n acetic acid solution crystal- /\ c=N- \ lises from alcohol in orange-yellow needles I f I m p. 171’; on reduction it yields “thio- \/(/b‘CH-\/ quzndoline ” (annexed formula). The latter crystallises in almost colourless needles m. p. 169O and with concentra5ed acids forms yellow salts which are decomposed by water ; the hydrochloride and picrate are described.Quindoline and ‘ 6 thioquindoline ” dye tannin-mordanted wool silk and cotton pale yellow ; with quindolinecarboxylic acid the shade is somewhat deeper. J?. B. Anthraquinone-1-carboxylic Acid. FRITZ ULLMANN and WILLEM VAN DER SCHALK (Be?*. 1911 44 128-129) -Anhydro- anthrapuinone-9-h ydraxone-1 -carboxylic acid (pyridaxonanthrone) (I) obtained by the action of hydr- NH o azine hydrate on the chloride of anthraquinone-1-carboxylic acid Nj/\Co crystallises in needles which are /\/\/\ sparingly soluble in the usual I I solvents but dissolve in sodium \/v tions. hydroxide Phenylhydrazine to orange-yellow gives solu- the (1.1 (11.1 corresponding N-phmylpyridazon- anthrone. Anthraquinone- 1 -carb- S /\/\/\ ’()\,\ I I 1 GO VOL.c. 1. ni. 166 ABSTRACTS OF CHEMICAL PAPERS. oxylic acid reacts readily with hydroxplamine in the presence of sodium acetate solution yielding oxaxonanthrone (11) in the form of pale yellow needles m. p. 247'. Method for Preparing Aromatic Acylguanidines. PAUL PIERRON (Compt. rend. 1910 151 1364-1366. Compare Wheeler and Johnson Abstr. 1902 i 27).-Aromatic acylguanidines are best prepared by boiling the aromatic acylcyanamides with the hydro- chloride of an aromatic amine in alcoholic solution; thus benzoyl- cyanamide and aniline hydrochloride yield benzoylphenylguanidine the hydrochloride of which has m. p. 159'. Benxoyl-m-tolylguanidine C;H,*NH*C(NHBz):NH cryfitallises in needles or leaflets m. p. 71" ; the hydrochloride has m. p. 1709 CHPh:CH*CO*NH*C(NHPh):NH forms prismatic needles m.p. 140' ; benzoyl-$-curnidylguanidine CI7Hl90N3 occurs in prismatic needles m. p. 140-141'. On boiling acylcyanamides with o-phenylenediamine in alcoholic solution an acylaminobenziminazole is produced. The arylcyanamides do not readily undergo this condensation. Cinnamoyl-o-phnylene- guanidine [2-cinnamoylimi~oben~~minaxoZe~~ J. J. S. Cinnamoylphenylguanidine C,H,<,N~>C:N*CO*CH:CHPh crysta.llisqs in needles m. p. 262'. w 0. w. Pechmann's Isomeric Hydrazidines. HENRY L. WHEELER and TREAT B. JOHNSON (Bey. 1911 44 15l).-The authors have already shown (Abstr. 1904 i 628) that the formulse suggested by Busch and Ruppenthal (this vol. i 86) for Pechmann's hydrazidines (Abstr. 1896 i 31) namely NH,*NPh*CPh NPh and NHPh*NH*CPh:NPh are correct.J. J. S. Preparation of 4-isoValerylamino- 1 - phenyl-2 3-dimethyl- 5-pyrazolone and of 4-~-Bromoisovctl~rylamino-l-phenyl-2 3- dimethyl-5-pyrasolone. KNOLL & Co. (D.R.-P. 22701 3).-Com- pounds possessing valuable therapeutic properties are obtained by introducing isovaleryl or substituted isovaleryl residues into 4-amino- 1-phenyl-2 3-dimethyld-pyrazolone. 4-isoVnle~*ylamino-l -phenyl-2 3-dimethyl-5-pyraxolone m. p. 203' odourless and with a bitter taste is prepared by heating 4-amino- 1 -phenyl-2 3-dimet hyl-5-pyrazolone with isovaleric acid and phosphorus trichloride at 125' during half an hour treating with sodium carbonate and crystallising the dried product from benzene; its aqueous solutions give a blood-red coloration with ferric chloride.4-a-Bromoisoualerylamino-1 -phenyl-2 3-dimelhyl-5-pyrazolorns is ob- tained when a-bromoisovaleryl bromide is substituted for the isovaleric acid and phosphorus trichloride in the foregoing preparation ; it forms glistening colourless needles ra. p. 206' (decornp.) is odourless but has a bitter taste and forms crystalline salts with acids and a yellow coloration with ferric chloride. Preparation of 4-Imino-5.oximino-2 6-diketopyrimidine and its 3-Alkyl Derivative. EMANUEL MERCK (D.R.-P. 227390).-The action of nitrous acid on a hot dilute acetic acid solution of cyano- F. M. G . M.ORGANIC CHEMISTRY. i. 167 acetylmethrlcarbamide NHMe*CO*NH*C0*CH,.CN yields oximino- cyanoacet ylmethylcarbamide NHMe*CO*NH*CO*C( NOH).CN colour- less crystals m.p. 218' (decomp.). When this substance is warmed with 30% sodium hydroxide (4 parts) an orange-yellow precipitate slowly separates which on the addition of acetic acid is converted into the characteristic red crystals of 4-imino-5-oximino-2 6-diketo- 3-me th ylpyrimidine N H<gg ~ ~ ~ ~ ~ > C NH. Analogous results are obtained when cyanoacetylcarbamide is employed in the foregoing reaction ; a yellow crystalline sodium derivative separates on treatment with sodium nitrite yielding on acidification oximinocyanoacetyl- carbamide glistening colourless crystals m. p. 220° which are readily converted into the corresponding 4-imino- 5 -0ximino - 2 6-diketo- pyrimidine. The sodium hydroxide can in this reaction be replaced by sodamide sodium ethoxide or an alkylcarbamide.Preparation of Anthrapyrimidines and Anthrapyrimidones. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 225982).-The reaction between aminoanthraquinones and acid amides has been previously described (Abstr. 1910 i 445); the same result is now obtained with acylaminoanthraquinones and ammonia 1 -anthra- pyrimidone (Zoc. cit. ) having been prepared by heating aminoanthra- quinoneurethane with ammonium hydroxide at 150° ; likewise 1 4-diaminoanthraquinonemonourethane yields 4-amino-1 -ccnthra- pyrimidone brown crystals and 2-bromo-4-arnino-l-p-methykanthra- pyrimidine a brown powder is obtained from 2 4-dibromo-1-acetyl- aminoanthraquinone. A tabulated description of the following compounds with the coloure of their solutions in various solvents is given in the original 1-amino- anthraquinoneurethanc greenish -yellow crystals ; 1 -amircoanthva - quinonecarbsmide chloride orange crystals ; 1 4 -diaminoanthra - pinonemonourethane garnet-red crystals ; 4-chloro-l-ccminoanthra- quinoneurethane golden-yellow crystals ; 2 4-dibromo-1 -acetyZamino- snthraquinone brownish-jellow crystals ; 4-amino-1-anthrapyrimidone dark brown crystals.F. M. G. M. 4-Dibromo-1 2 3- triaaol-5-one-1-acetamide. TREODOR CURTIUS and ERNST WELDE (Ber. 1910 43 857-862).-The dibromo-deriv- ative mentioned previously (Abstr. 1907 i 450) is shown to be 4-dibromo-l 2 3-triaxole-5-one-l-aceramide. F. M. G. M. - C Br,*CO -N>N*CH2*CO*NH2. Its formation from the a&monium salt of 5-hydroxr-1 2 3-triazole- 1-acetamide is represented by means of the equation C H C( 0 NH,) C4H402N,Br + HBr + NH,Br and its formation from the nitroso-derivative by the equation C,H80aN5 + 2Br = C,H,O,N,Br + NOBr + NH,Br the nitrosyl bromide formed immediately yielding nitrous and hydro- bromic acids.n 2 y===-.N >C*CH,*CO*NH + 2Br2 =i. 168 ABSTRACTS OF CHEMICAL PAPERS. The dibromo-derivative crystallises from hot alcohol in colourless glistening needles m. p. 151O (decomp.) after turning brown at 120O. It changes colour when exposed to the air for several hours and then has a n odour of bromine. When boiled with dilute sulphuric acid it is hydrolysed to nitrogen ammonia glycine and dibromoglycollic acid the last of which is further hydrolysed to hydrobromic and oxalic acids. The same decomposition occum only more slowly when the bromo-derivative is boiled with water.J. J. S. Derivatives of isoUrio Acid. HEINRICH BILTZ (Bey. 1910 43 3553-3562).-1t has been shown (Abstr. 1909 i 740) that diethoxy- 4 5-diphenyldihydroglyoxalone is converted on heating at the m. p. into 5-ethoxy-4 5-diphenylisoglyoxalone. Diethoxy-1 3 7-trimethyl- uric acid might be expected to behave similarly but it does not change a t the m. p. However on boiling it in glacial acetic acid solution 5-ethoxy-trimethyEisouric acid formed. This can be crystallised from cold alcohol without change but on boiling with alcohol containing a little acid the diethoxy- derivative is regenerated. On reduction with zinc and acetic acid hydrogen is added at positions 4 and 9 that in 4 is immediately eliminated with the ethoxyl group in position 5 and trimethyluric acid is obtained 5-Er hoxytrimethylisouric acid is completely analogous to 5-ethoxy- diphenylisoglyoxalone and the conclusion is drawn that the ethoxyl group in position 4 and the imino-hydrogen in position 9 are on opposite sides of the plane of the glyoxalone ring.By the action of chlorine on trimethyluric acid in chloroform solu- tion a dichloride is first formed soluble in chloroform chlorine being added in positions 4 and 5 . This is unstable hydrogens chloride being eliminated between positions 4 and 9 and a chlorine derivative OF isouric acid is obtained y M e * C O * q O w >N& is C 0 NMe*C N CO >co. ~Me*CO*FCl*N'Me>CO -~ rMe*CO*yCL*NMe C O*NISle*CCl-NH C O*NMe-C N Alcohol converts this chloride into 5-ethoxy-1 3 7-trimethylisouric acid ; water readily converts it into apocaffeine.5-Ethoxy-1 3 7-t~imethylieouric acid forms long thin colourless needles m. p. 174-176O. 5-Methoxy-1 3 7-trimethylisouric acid crystallises in obliquely cut six-sided columnar forms m. p. 205'. 5-Chlovo-1 3 7-trimethylisouric acid separates in colourless flat needles or prisms with oblique end faces and a rectangular cross sectioq m. p. 158' (decomp.). The corresponding 5-bromo-compound could not be obtained. E. F. A. Hydroxyaeo-compounds and Ketohydrazones. I.-111. KARL AUWERS [and in part HUGO DANNEHL and A. BOENNECRE] (Annalen 1910 3'78 210-260. Compare Auwers Abstr. 1908 i 47C).-The results of previous investigations indicate that when possible the phenylhydrazones of benzoquinones and naphthaquinones undergoORGANIC CHEMISTRY.i. 169 molecular rearrangement into azo-compounds whereas with mixed azo- derivatives the reverie process takes place. Phenanthraquinonephenylhydrazone (Zincke Abstr. 1883 1 135 ; Werner Annalen 1902,321 304) when benzoylated in the presence of pyridine yields a benzoyl derivative which is identical with the product obtained by condensing phenanthraquinone with as-benzoyl- phenylhydrazine in the presence of mineral acids From the readiness with which it is hydrolysed and from the fact that when reduced with zinc dust and cold acetic acid the chief products are aniline and 9-benzoylamino-l O-hydroxyphenanthrene (87%. yield) the conclusion is drawn that the benzoyl compound is an 0-derivative + N I3,Ph.y6H4'G' N:NPh 13;'6H,*G*NHBz -+ C,H,*C* OBz C6H4' c* O H I n the condensation of phenanthraquinone with benzoylphenyl- hydrazine a wandering of the benzoyl group from nitrogen to oxygen occurs a wandering analogous to that observed in the condensation of P-naphthaquinone with benzoylphenylhydrazine. The same 0-acetyl derivative is obtained by acety lating phennn t b raq uinonephenyl- hydrazone and by condensing phensnthraquinone with as-acetyl- phenylhydrazine. This acetyl derivative is so readily hydrolysed that it is difficult to purify. The general conclusion drawn is that phenanthraquinonephenylhydrazone is 9-benzeneazo- 10-phenanthrol. 9- Benxeneaxo-lO-phenanthryl benzoate C,? HI8O2N2 crystallises from glacial acetic acid in glistening red plates m.p. 193-194'. 9-Benzoyl- amino- 10-phenanthrol C,,H,,O,N crystallises from glacial acetic acid in glistening flat needles m. p. 848-249'. 9-Benaeneaxo-lO-p~e~nthr~Z acetate C,,HI,0,N2 crystallises from light petroleum in brilliant red plates m. p. 139-140° and is hydrolysed when warmed with alcohol or acetic acid. The question as to the constitution of Khorr's 4-benzeneazo-5- keto-1-phenyl-3-methylpyrazolone has been investigated (Knorr Abstr. 1887 678; 1888 724 ; Japp and Klingemann Trans. 1888 53 519; Wedekind Annalen 1897 295 330 ; Biilow Abstr. 1899 i 355 ; Eibner Abstr. 1903 i 8'71). The siime benzoyl derivat.ive is obtained by (1) the action of benzoyl chloride on the sodium derivative suspended in dry e,ther ; (2) the action of benzoyl chloride and sodium hydroxide solution on an aqueous acetone solution of the pyrazolone; (3) the con- densation of ke tophen yl me thy1 py razolone with as-phen yl benzoy 1- hydrazine hydrochloride in dilute alcohol.It is regarded as the - ,OMe*s.N :NPh 0-benzoyl derivative X< since when reduccd-with zinc NPh*C*OBa dust and cold acetic acid it yields appreciable amounts of aniline together with benzanilide and rubazonic acid. It has not been found possible to isolate the N-bensoyl derivative of the aminohydroxy phenp lmethylpyrazole.i. 170 ABSTRACTS OF CHEMICAL PAPERS. Knorr's compound is thus a true azo-derivative and as it dissolves ,CMe*E*N:NPh Nc<NPh*C*OH ' and is 4-beazeneazo-5-hydroxy-1 -phenyl- 3-methy1pyrazoIe. When the p-phenylhjdrazone of up-diketobutyric acid is condensed with benzoglphenylhydrazine mat,er is eliminated and Knorr's azo- compound and ethyl benzoate are obtained instead of the exDected readily in alkalis it is represented by the enolic formula CMe*$XN*NPhBz L .The free hydroxy- N'NPh*CO N-benzoyl derivative pyrazole is also formed (1) when the benzoylated osazone of the diketo- butyric acid is warmed with benzene and phosphoric oxide; (2) when the /I-phenylhydrazone of ethyl ap-diketobutyrate is condensed with as- benzoyl phenylhy drazine hydrochloride in alcoholic solution both with and without the addition of sodium acetate and (3) when the dibenzoyl derivative of the osazone of the ethyl diketobutyrate is warmed with alcoholic potassium hydroxide. The methyl derivative obtained by condensing ketophenylmethyl- pyrazolone with as-phenglmethylhgdrazine must be the N-methyl ether as alkyl groups do not wander under these NeN Ph C 0 conditions.This constitution is confirmed by t,he fact that when reduced with zinc and acetic acid methylaniline is obtained but no trace of aniline. The same metbyl etker together with a small amount of the CRle*$XN*NMePh - isomeric 0-metbyl ether N<CMe'E" :Nph is formed when Knorr's NPh* C OMe azo-compound is methylated by means of methyl iodide or sulphate and alkali. When reduced the 0-metbyl ether yields appreciable amounts of aniline. The N-methyl ether is readily hydrolysed to the monomethyl derivative of ethyl diketobutyrate osazone whereas the 0-ether is not acted upon when boiled with alcoholic potassium hydroxide.The benzoyl derivative of 4-benzeneazo-5-h ydroxy- 1-phenyl-3-metb yl- pyrazole C,,H,,O?N crystallises from alcohol in long yellow glistening needles or from light petroleum in quadratic plates m. p. 137O which are readily hydrolysed when boiled wit,h 50% acetic acid. The dibenzoyl derivative of 4-amirto-5-l~ydroxy-l-phenyl-3-methyl- pyrnxole N<Nph.g.oBZ prepared by benzoylating thecorresponding amine cry stallises from dilute alcohol in colourless glistening needles ID. p. 196q and on hydrolysis yields a colourless compound m. p. 110-1 159 probably the acid NHPh*N:CMe*CH(NHBz)*CO,H which CMe*QH*NHBz when heated yields the N-benxoyl :derivative 9 m. p. 1839 Keto-1 -phenyl-3-methylpyrazolone prepared by Snchs and Barschall's method (Abstr.1902 i 504) has m. p. 121'. The mono- benzoylosctxone of up-diketobutgric acid NHPhON :CNe*C(CO,H):N*NBzPh crystallises from light petroleum in slender pale yellow needles m. p. CMe*C*NHBz NqNPh*COORGANIC CHEMISTRY. i. 171 110-11 lo and dissolves in cold sodium hydroxide solution without undergoing hydrolysis. Ethyl ap-diketobutyrate and benzoylphenyl- hydrazine yield the dibenxopEccted osaxone C32H,8~04N4 even in the presence OF an excess of ester. I t crystallises from dilute methyl alcohol in long colourless prisms m. p. 190'. Ethyl afl-diketobntyrate and phenylmethylhydrazine yield the dimethylosaxone NMePh-N CMe*C(CO,Ft):N*NMePh which crystallises from alcohol in pale yellow glistening prisms m. p. 103-104°. The phenylmEthylhydruzoiie of 4-keto-1-phenyl-3-methyl- 5-pyrazolone C17H160N4 crystallises from dilute alcohol in glistening orange-yellow felted needles m.p. 144' and is insoluble in alkalis ; the isomeric O-methyl ether forms compact yellow prisms m. p. 78". It has not been found possible to acetylate or benzoylate Graebe and Gfeller's acenaphthenequinonephenylhydraz me ( A bstr. 1893 i 657) but the benzoyl derivative C25H1602N2 can be prepared by con- densing the quinone with benzoylphenylbydrazine hydrochloride and alcohol. It crystallises in glistening orange-red needles m. p. 170° and is readily hydrolysed by cold alcoholic sodium hydroxide. When reduced with zinc and acetic acid it yields no trace of aniline and is therefore a N-benz y l derivative and the phenylhydrazone probably has the hydrazone and not the azo-structure.Acenap?ifhenequinowphenylrnethylhydvazone C19H140N2 crystallises from acetone in dark red needles m. p. 1144 and when reduced yields methylaniline and no trace of aniline. Camphorquinonephenylhydrazone cannot be directly acylated but the benzoyl derivative C23H2402N2 can be obtained by condensing the quinone with benzoylphenylhydrazine in the form of colourless felted needles m. p. 153'. This is also a N-benzoyl derivative and the parent substance a hydrazone which exists in one form only (compare Lapworth and Hann Trans. 1902 81 1514). The two N-benzoyl derivatives unlike most other N-benzoylated compounds are readily hydrolysed. The following new N-benzoyl derivatives prepared by condensing the ketones with benzoylphenyl- hydrazine are not readily hydrolysed by alkalis Ethyl acetoacetate benzoyZphenylhydi*axone C19H,,03N2 forms compact colourless quadratic crystals m. p. 144-145' and with alcoholic potash yields the benxoylphenylhydruxone of acetoacetic acid Cl7Hl6O3N2 in the form of small colourless prisms m. p. 203'. Diacstyldibenxoylosaxone C30H2602K4 crystallise's from boiling glacial acetic acid in slender needles m. p. 249" and is formed even at - 15' i n the presence of an excess of the ketone. Benzil-benxoylphenyl- hydrazone C27H2002N2 crystallises from light petroleum in slender prismatic needles m. p. 176". Baeyer and Claisen's phenylazoscetylacetone (Abstr. 1888 828) is best prepared by the gradual addition of a solution of phenyl- diazonium chloride exactly neutralised with sodium carbonate t o a cold solution of acetylacetone (1 mol.) in sodium carbonate (0.5 mol.). The benzoyl derivative (Pechmann Abstr. 1893 i 84) is most Teadily prepared by the Schotten-Baumann method; it has m. p. 160-161' is readily hydrolysed by alkalis and is sometimes accom- panied by an ismeride m. p. 134'. When reduced the benzoyli. 172 ABSTRACTS OF CHEMICAL PAPERS. derivative yields benzanilide but no trace of aniline. The compound is thus a N-benzoyl derivative and the parent substance a y-phenyl- hydrazone of py8-triketopentane and not an azo-derivative. Benzoylacetylacetone in the form of its sodium derivative reacts with a neutralised solution of phenyldiazonium chloride yielding 0-6enzeneazodiacet?/l6elzxoylmetliane NPh:N*O*CMe:CBzAc which crystallises from methyl alcohol in golden-yellow prismatic needles m. p. 77-78O. The compound is not affected when boiled with alcohol ; with cold alkalis or with an ethereal solution of hydrogen chloride it yields the phenylhydrazone of phenyl methyl triketone and when boiled with glacial acetic acid yields benzoylacetone. The reaction with hydrogen chloride is similar to that described by Dimroth and Hartmann as characteristic of 0-azo-compounds (Abstr. 1909 i 66). The azo-compound (m. p. 77-78') reacts with an alcoholic solution of P-naphthol yielding benzeneazo-P-naphthol and benzoylacetylacetone. When reduced with zinc dust and acetic acid the azo-compound yields appreciable amounts of aniline. The isomeric acetylphenylhydrazone of phenyl methyl triketone CAcBz:N*NAcPh is formed when the 0-azo-compound is boiled for four hours with toluene; it separates from alcohol in colourless crystals m. p. 15S0 and when reduced yields acetanilide but no trace of aniline. The compound is isomeric with the benzoyl derivative of phenylazoacetylacetone m. p. 160'. These results agree with Pechmann's view that the compounds derived from diazo-compounds and aliphatic ketones with the reactive -CO*CH,* group are not azo-compounds but hydrazones. Generalisations based on the constitution of N-benaoyl derivatives and the readiness with which they are hydrolysed cannot be drawn. J. J. 5. Method for Determining the Individuality or Plurality of Diastases in a Liquid. PIERRE ACHALME and BRESSON (Compt. rend. 1910 151 1369-1372).-1n order to ascertain whether a particular liquid contains one or more enzymes the authors suggest that it should be allowed t o act under identical conditions on solutions of two different substances capable of being hydrolysed by it and on a solution containing a mixture of the same two substances. If two diastases are present the action on the mixture should be the sum of the action on the two substances taken individually whilst if only one enzyme is present the action on the mixture should not exceed that on either substance alone. The results of illustrative experiments are given in tabular form. It is found that the time taken to effect hydrolysis in the three solutions is the same if two diastases are present but that when only one enzyme is acting a longer period is Chlorophyll. XI. Chlorophyllase. RICHARD WILLSTATTES and ARTHUR STOLL (Annnlen 1910,378,18-72).-See this vol. i 141. required to hydrolyse the mixture. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110000101

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

I NORG A NIC CH EM ISTRY. Inorganic Chemistry. ii. 107 Reactions in the Presence of Nickel. ( a ) Inability of Nitrogen and Hydrogen to Combine in Presence of Nickel. (6) Reduction of Oxides of Nitrogen Sulphur and Phosphorus in Presence of Nickel. PA~CH~NAN NEOGI and BIRENDRA BHUSAN ADHIC~RY (Zeitsch. anorg. Chem. 1910 69 209-214).-A mixture of nitrogen and hydrogen (1 3 or 1 6 by volume) does not give rise to the formation of ammonia when passed over heated reduced iron the temperature varying from dull to bright red heat. Similar negative results are obtained when the reduced iron is replaced by ‘pure iron wire or by ferric oxide no matter whether the gases are dried or not (compare Ramsay and Young Trans. 1884 45 93). No ammonia could be detected when the iron was replaced by reduced nickel nickel wire or electrolytic nickel.When a mixture of nitric oxide and hydrogen (1 3 or better 1 4) is passed over reduced nickel the nitric oxide is almost quantitatively converted into ammonia. The reaction begins at 300° but once it has set in the temperature may be lowered to 120’. Hydrogen sulphide is formed when a mixture of sulphur dioxide and hydrogen is passed over nickel heated to a dull red heat. The hydrogen sulphide is probably formed partly by direct reduction of the sulphur dioxide and partly by reduction of nickel sulphide formed by the interaction of nickel and sulphur dioxide. Hydrogen phosphide is produced when hydrogen is passed over a mixture of phosphoric oxide and reduced nickel at a dull red heat. T. S. P. Catalysis of Hydrogen Peroxide.ERNST H. RIESENFELD (Ber. 1911 44 147-150. Compare Abstr. 1905 ii 951).-The reaction between chromic acid and excess of hydrogen peroxide can be represented by the equation 4H2Cr,0 -i- 7H,02 = Cr2(Cr207)3 + 1 1H,O + 50,. This agrees with Spitalsky’s statement that only about 28% of the chromic acid is reduced b u t this author did not notice that all the free acid is used up. The reaction is not a catalytic process (compare Spitalsky this vol. ii 36 37). J. J. S. Raschig’s Nitrososulphonio Acid ‘‘ Blue Acid.” WILHELM MANCHOT (Zeitsch. angew. Chern. 19 11 24 13-1 4. Compare Abstr. 1910 ii 956 1055).-Mainly a reply to Xaschig (Zeitsch. angew. Chem. 1910 23 2248). Raschig’s ferric nitrososulphonate should have the ratio NO Fe = 1.5 1 whereas the actual proportion is 2 1.It is pointed out that there is no trace of evidence for the existence of a blue compound formed by the union of nitric oxide with sulphuric acid. J. J. S. Products Formed when Phosphoric Oxide Dissolves in Water. D. BALABEFF (Zeitsch. nnory. Chem. 191 0 69 2 15-2 16). -Phosphoric oxide was allowed to deliquesce over (1) 75% sulphuricii. 108 ABSTRACTS OF CHEMICAL PAPERS. acid (2) 9% sulphuric acid ; some was also thrown into water. I n the first two cases the reaction was considered to be complete when the snow-like appearance of the phosphoric oxide has disappeared. I n all cases metaphosphoric acid was the only product of reaction. After eighteen hours the metaphosphoric acid had completely changed into the ortho-acid in the last two cases. The velocity of hydration of metaphosphoric acid produced by the deliquescence of phosphoric oxide is much greater than that of the metaphosphoric acid obtained by heating orthophosphoric acid.T. S. P. Rate of Hydration of Pyrophosphorio Acid. A Correction. G. A. ABBOTT (J. Amer. Chem. /~’oc. 1910 32 1576-1577).-1n a paper on this subject (Abstr. 1909 ii 661) it was stated that the specific conductivity of a mixture of pyro- and ortho-phosphoric acids is a linear function of its composition. It has been pointed out to the author that the experimental data quoted were not consistent with this statement and it has been found that the wrong data were inadvertently given. The correct data are now recorded. Correc- tions are also given for certain typographical errors which occurred in Abbott and Bray’s paper (Abstr.1909 ii 660) on the ionisation relations of ortho- and pyro-phosphoric acids and their sodium salts. E. G. New Determinations of Some Constants of the Inert Gases. CLIVE CUTHBERTSON (Phil. Mag. 1911 [vi] 21 69-’77).- Recent determinations of (I) the viscosity at difierent temperatures and (2) the refraction and dispersion of the argon gases afford independent sets of measurements of the fraction of the volume containing the gas which its molecules actually occupy. For argon krypton and xenon the values in absolute measure so found by the two methods are of the same order and there is a constant ratio between them; the volumes calculated from the viscosity being about 1.75 times that calculated from the refractivity.For helium and neon the ratios are 3.0 times and 2.53 respectively. For oxygen and nitrogen the ratios are similar to that found for argon but hydrogen departs widely from it. For all the gases the numbers of ‘ 0 dispersion elec- trons ” in the atoms calculated from the refractivities and dispersions by means of Sellmeier’s formula bear a linear relation to the reciprocals of the radii of the spheres of action of the atoms as calculated from the viscosity. The squares of the numbers of “ dispersion electrons ” are for all the gases proportional to the radii of the spheres of action diminished by a constant equal to 0.95 of the radius of the sphere of action of helium a t 0’. The squares of the relative numbers of ‘‘ dispersion electrons ” plotted against the critical temperatures of the gases fall on a straight line passing near the origin.From this relation the unknown critical temperature of neon is calculated t o be about 4 6 O A. The radii of the spheres of action also bear a linear relation to the critical temperatures. These results suggest that the electric charges which influence dispersion control also the critical temperature and the temperature-coefficient of viscosity and show thatINORGANIC CHEMISTRY. ii. 109 Sellmeier's formula which is in the manner of its derivation tentative can be safely employed to give results comparable with thoce obtained from the kinetic theory. F. S. A General Method for the Preparation of Anhydrous Chlorides. EDOUARD CHAUVENET (Compt. rend 19 11 152 87-89.Compare Abstr. 1909 ii 53).-The method consists in heating the oxide of the metal in a slow current of carbonyl chloride at a tempera- ture varying from about 350' in the case of vanadium oxide to 650' in the case of thoria. Chlorides of the following elements have been prepared in this way vanadium tungsten tantalum titanium zirconium thorium tin barium magnesium zinc glucinum aluminium iron chromium manganese nickel uranium cerium yttrium lanthanum. An excellent yield of the anhydrous higher chloride was obtained in each instance except with tungstic oxide when the oxychloiide was formed arid in the case of titanium when a mixture of chloride and oxychloride was produced. The method is specially suitable for preparing the chlorides of the rare-earth metals Silica is not attacked by carbonyl chloride. w.0. w. The Causes of the Differences in the Action of Sodium and Potassium on Water. MANINDRANATH BANERJEE (Ckem. News 1910 102 319-380).-When the metals are throwo on water the hydrogen which is evolved is charged with the vapours OF the metals and so the motion is affected by their densities and molecular volumes and those of their oxides and hydroxides. Thus in the cme of potassium the high density and large molecular volume of its vapour counteract the motion of the hydrogen its movement is retarded the heat is not dissipated and so the gas bursts into flame. I n the case of soditim the density and molecular volume being very low the hydrogen keeps in a state of motion and does not ignite the heat being dissipated.N. c. The Miscibility of Glaserite with Sodium Sulphate and its Dependence on the Temperature. RICHARD NACKEN (Xilzungsbe?*. X. Akad. Wiss. Berlin 1910 1016-1026. Compare van't HOE and Barschall Abstr. 1903 ii 434).-From a study of the solidification of fused mixtures of sodium and potassium sulphates it has been found that the hexagonal modifications of the enantiotropic dimorphous components which separate out first form a complete series of mixed crystals. As the temperature falls these primary mixed crystals undergo transformation and the diagrammatic representation of the resulting relationships shows that the formation of the hexagonal mixed crystals which crystallise from aqueous solutions at low temperatures is confined to certain concentrations of the components.The limiting concentration on the one side is represented by glaserite Na2S0,,3K2S04 (76%K,SO,). The other limiting concentration corre- sponds with about 49%K2S04 at 180° but with fall of temperature this proportion of potassium sulphate diminishes. Crystalline forms corresponding with these limiting concentrations are obtained together with potassium or sodium sulphate when fusedii. 110 ABSTRACTS OF CHEMICAL PAPERS. mixtures containing excess of potassium or sodium sulphate respectively are allowed to cool. The relationships indicated by the concentration-temperature diagram have been supplemented by crystallisation experiments a t 60' and 34'. When the aqueous solutions contain excess of potassium sulphate glaserite and potassium sulphate are obtained.If excess of sodium sulphate is present the crystals which separate consist of sodium sulphate together with mixed crystals containing glaserite and sodium sulphate and the composition of these mixed crystals approximates towards glaserite as the temperature of crystallisation is lowered. H. M. D. Fusions of Alkali Metaboratee and Metaphosphates. H. 8. VAN KLOOSTER (Zeitsch. amorg. Chern. 1910 69 122-1 34).-The freezing-point curve of mixtures of potassium metaborate and meta- phosphate possesses two eutectics at 681' and 770' respectively the former corresponding with 90% and the latter with 30% of potassium metaphosphate. The portions of the curve between the eutectics rises to a very flat maximum extending between 50 and 60% of potassium metaphosphate. The eutectic arrest is only noticeable in the neigh- bourhood of tbe eutectics so that it cannot be used to determine the position of the maximum. Investigation of the fusions showed that free borate could be detected by Tammann's reaction (characteristic red precipitate with mercuric chloride solution) up to 55% KPO so that the composition of the compound lies between 55 and 60% KPO and is probably 59% KPO corresponding with KPO,,KBO,.Fusions of this composition give neutral solutions whereas with higher and lower percentages of potassium metaphosphnte they are re$pectively acid and alkaline. The presence of the compound KPO,,KBO is also indicated by the microscopic examination of thin sections. Between 65 and 85% potassium metaphosphate the fusions mould not crystallise solidifying to a vitreous mass.Potassium metaphosphate bas m. p. 810° and potassium metaborate melts at 947O. The freezing-point curve of mixtures of sodium metaphosphate (m. p. 610') and sodium metaborate (m. p. 966') could only be followed between 0 and 30% and between 50 and 80% of sodium metaphosphate the other mixtures solidifying to vitreous masses. The curve between 50 and 80% of sodium metaphosphnte shows a flat maximum which is probably due to the existence of the compound NaPO,,NaBO further evidence in support of the existence of which is given by chemical and optical investigations similar to those described for the potassium compounds. Conductivity measurements showed that this compound also exists in solution to some extent.Sodium metaborate and potassium metaborate give a continuous series of mixed crystals the freezing-point curve showing a flat minimum at 50% sodium metaborate. Indications of a decomposition of these mixed crystals at 522-553' were obtained in mixtures containing 40-60% of sodium metaborate. Lithium metaborate (m. p. 843') and sodium metaborate do not form a compound with each other the freezing-point curve showing a eutecticINORGANIC CHEMISTRY. ii. 111 at 650' with 52% of lithium metaborate. The miscibility i i n the crystalline condition is very limited the lithium metaborate dissolving 2% of the sodium metaborate and the latter dissolving 3% of the lithium metaborale. T. S. P. Efflorescence of Washing Soda Crystals. ALEXANDER C. GUMMING (Chern. News 1910 102 311).-The author examined a specimen of large crystals of washing soda which had been for at least twenty years in a glass case with a wooden floor.The case fitted closely but was not air-tight. It was a t first thought that the crystals now consisted of the trihydrate the existence of which had not been previously known. Further analysis however showed that the crystals consisted almost entirely of pure sesquicarbonate Na,CO,!NaHCO 2H,O. The loss of weight on the ignition of the sesquicarbonate if calculated as due entirely to water would lead to the formula for the trihydrate. I T r( Il. w. The Binary Syatems Li,O-SiO Li,SiO,-ZnSiO ZnSi0,-CdSiO Li2Si0,-LiB02. Na,SiO,-NaBO and Na,SiO,-Na,WO,. H. S. VAN KLOOSTER (Zeztsch. anorg. Clhem. 1910 69 135-157).-The binary system Li,O-SiO forms two compounds namely lithium ortho- and meta-silicate with m.p.'s 1243' and 1188' respectively ; they are only slightly miscible in the crystalline state. Lithium metasilicate forms mixed crystals with silica up to 24.3% SiO,. The existence of a n acid silicate Li,Si,O, has not been confirmed. No compound is formed in the binary system Li,SiO,-ZnSiO,. Mixed crystais exist from 0 to 7('c)% and 71(?) to 100% of lithium meta- silicate. The eutectic temperature is approximately 990° and the eutectic composition 52(?)% of lithium metasilicate. That portion of the freezing-point curve lying between 10 and 70% Li,SiO could not be determined thermally and reliance had to be placed on the optical investigation. The system ZnSi0,-CdSiO gives an isomorphous series of mixed crystals the minimum point of the curve being at 25% ZnSiO,.The optical investigation did not completely verify the results obtained thermally. I n the system Li,SiO,LiBO mixed crystals exist from 0 to 24% and 91 t o 100% of lithium metasiliaate; no compound is formed. The eutectic temperature and composition are respectively 803' and 22% Li,SiO,. No compound is formed in the system Na,SiO,-NaBO but mixed crystals exist from 0 to 5% and 96 t o 100% of sodium metasilicate. The eutectic temperature and composition are respectively 81 5" and 55% Na,SiO,. Below 1100' sodium tungstate is practically immiscible with sodium metasilicate. The two components are quite immiscible in the crystalline condition. Sodium tungstate has m. p. 700' and transition temperatures at 589' and 572". Throughout this investigation optical methods were more trust- worthy than the thermal ones for determining the compositions of the saturated mixed crystals. Zinc metasilicate has m.p. 1419'. Cadmium metasilicate has m. p. 1155'. Sodium metasilicate has m. p. 1056'. T. 5. P.ii. I12 ABSTRACTS OF CHEMICAL PAPERS. Revision of the Atomic Weights of Silver and Iodine. 11. Ratio of Silver to Iodine. GREGORY P. BAXTER (J. Amer. Chem. Soc. 1910 33 1591-16C)2).-From determinations of the value of the ratio 2Ag I,O Baxter and Tilley (Abstr. 1909 ii 225) calcu- lated the atomic weights of iodine and silver by the aid of the value 0.849943 for the ratio A g I (Baxter Abstr. 1905 ii 81 579) and found them to be 126.891 and 107.850 respectively (0 = 16).Richards and Willard (Abstr. 1910 ii 292) however have obtained a value of 107.871 for the atomic weight of silver. As it was thought possible that this discrepancy might have been due to an error in the ratio Ag I this ratio has now been re-determined. Weighed quantit,ieu of iodine were reduced to hydriodic acid by means of a solution of hydrazine. The product was diluted and treated with a slight excess of a very dilute solution of silver nitrate. The clear supernatant liquid was carefully filtered and concentrated by evaporation and the excess of silver was estimated gravimetrically as silver iodide. Three samples of iodine and several specimens of silver were employed each of which had been carefully purified The results of thirteen experiments gave an average value for the ratio A g I 0,849906 and i t is therefore considered probable that the silver iodide obtained in the earlier determinations was contaminated with occluded impurities. On combining this ratio with that of ZAg:T,O the atomic weights of silver and iodine are found to be 107.864 and 126.913 respectively (0= 16).E. G. Revision of the Atomic Weight of Calcium. I. Analysis of Calcium Bromide. THEODORE W. RICHARDS and OTTO HONIG- SCHMID (J. Amer. Chern. Soc. 1910 32 1577-1590; Monatsh. 1910 31 1203-1226).-Determinations of the atomic weight of calcium by the analysis of the pure chloride (Richards Abstr. 1902 ii 394) gave a value of 40.126 (0 = 16 ; C1= 35*455) which agrees fairly well with that obtained by Hinrichsen (Abstr.1902 ii 137). In the present paper an account is given of a further study of this constant by the analysis of calcium bromide. The calcium bromide was prepared in the following manner. Calcium nitrate was carefully purified by repeated crystallisation and was converted into the carbonate by precipitation with ammonium carbonate. The carbonate was dissolved in hydrobromic acid prepared by the action of hot platinum on a mixture of bromine vapour and hydrogen and the solution was slightly acidified and afterwards concentrated. The bromide was repeatedly crystallised in quartz vessels and was dried with special precautions and fused in a platinum boat first in a current of hydrogen mixed with hydrogen bromide and afterwards in an atmosphere of nitrogen. The salt was then dissolved in water and when necessary the solution was carefully neutralised the deviations from exact neutrality being estimated by comparison with the pure crystallised salt with the aid of methyl-red.The analysis of the bromide was effected either by determining the amount of silver equivalent to the calcium present or by weighing the precipitated silver bromide. From the results of six experiments in each way values for the two ratios CaBr 2Ag and CaBr 2AgBrIN 0 RCI A N I C CH E 1cI I ST R Y. ii. 113 were obtained which gave essentially the same value for the atomic weight 40.070 (Ag= 107.88) or 40.066 (Ag= 107.87). Two different specimens of the salt gave almost identical results. The density of fused calcium bromide was found to be 3.353 at 25”.E. G. Electro-deposition of Lead from Perchlorate Solutions. FRANK C . MATHERS (Chem. Zeit. 1910 34 1316-1318 1350-1351 ; Trans. Amer. Elektrochem. Xoc. 1910 17 261-272).-Experiments with the lead perchlorate plating and refining bath are described. The properties of lead perchlorate which are of special value in plating or refining solutions are (I) Great solubility. (2) Cathode deposits which are smooth dense and free from “treee.” (3) Ap- proximately theoretical corrosion of the anode and deposition upon the cathode. (4) Absolute stability under all conditions to which it is subjected in a plating or refining batb. (5). No polarisstion from the formation of lead peroxide on the anode. (6) Very high electrical conductivity. The bath should contain about 5% of lead 2-5% of free perchloric acid and 0.25% of peptone.A current density of from 2-3 amperes per sq. dcm. (18-2‘7 amperes per sq. ft.) may bo used. The peptone is gradually used up and after about four dLiys a quantity equal to the original amount should be added. The free acid which is very slowly neutralised by the chemical solution of the lead must be restored by treatment of a suitable portion of the solution with the right amount of sulphuric acid thus precipitating lead sulphate and leaving perchloric acid in solution. The bath gives excellent purification the cathode being about 99*9S% pure and shows no deterioration with use giving as good deposits after two months as at the beginning if the concentration acidity and the required amount of peptone are maintained. Chlorides and barium salts must be absent.A bath that has been giving good deposits will form very bad “trees” if a quantity of hydrochloric acid or some barium perchlorate is added to it. The filtrate is returned t o the bath. T. S. P. Red Lead. IV. JAROSLAV MILBBUER (Chem. Zeit. 1910 34 1341-1342. Compare Abstr. 1910 ii 294).-The oxidation of litharge to red lead in air a t 460’ follows a course similar t o t h a t already observed in the case of lead. Litharge obtained in the manufacture of nitrites is much better for this purpose than ordinary litharge; at 500” the former gave t h e same percentage of red lead after one hour as the latter after fifteen hours at 460’. Thus although 460’ is the optimum temperature for the formation of red lead the increased velocity attained at 500° gives better results.The rate at which red lead is formed is conditioned more by the origin or by the kind of lead oxide used than by the size of the particles. The percentage of red lead obtained depends on the partial pressure of the oxygen in the gas used but even with pure oxygen a t 450° it has hitherto been impossible to obtain 100% red lead. T. S. P VOL. c. ii. 8ii. 114 ABSTRACTS OF CHEMlCAL PAPERS. Studies in Tapour Pressure. VI. Quantitative Study of the Constitution of Ualomel Vapour. ALEXANDER SMITH and ALAN w. c MENZrEs (proc. Boy. 8oc. Edin. 1910 31 183-185; Amer Chem. Soc. 1910 32 1541-1555).-A review is given of previous work on the constitution of mercurous chloride vapour and it is shown that there are no experimental data in existeuce from which the proportion of dissociated (Hg i- HgC1,) t o non-dissociated molecules (HgCI) in the vapour can be deduced.An investigation has now been made based on the principle of partial vapour pressures. Determinations have been made of the vaporir pressures of mercury mercurous chloride and a mixtiire of theie substances between 360' and 400' by means of the static isoteniecope (Abstr. 1910 ii 1036 1037). The results show t h a t mercurous chloride vapour even when saturated is completely dissociated into Hg and HgCl and that molecules of the formula HgCl or Hg,CI are not present. The b. p. of mercurous chloride is 382-5' and its molecular weight when dissolved in mercury corresponds with the formula HgCl. E. G. Double Nitrates of the Rare Earths.I. Double Nitrates of the Rare Earths with the Alkali Metals. GUSTAV JANTSCH and 8. WIGDOROW (Zeitsch. unorg. Chem. 1911 69 221-231).-To prepare the double nitrates of the rare earths with the alkali metals t h s procedure generally adopted was to dissolve the oxide of the rare earth together with the necessary quantity of the nibrate of the alkali metal in concentrated nitric acid and evaporate until crystals formed. Wyrouboff's statements (Abstr. 19OS ii 385) as to the hydration of the crystals of the double nitrates of sodium potassium and cesium with lanthanum and cerium are not confirmed. The formulz of the various compounds are written so as to indicate that the rare earths are tervalent in their stable forms of combination.Lanthanum sodium nitrate [La(N O,),]Na,,H,O forms blender white needles ; D = 2.63 and molecular volume = 195.08 ; it is not completely dehydrated at 150". has D:= 2.54 and molecular volume = 281.76 ; hygrcscopic white shining crystals which lose 2H,O at 60'. Acid Eunthanum rubidium mnitrute [La(N03),]Rb,HN0,,6H20 obtained when lanthanum and rubidium nitrates are taken in the molecular proportion of 1 2 ; forms colourless plates which lose 5H20 and 1HN03 a t 120'; the resulting [La(N0,)4]Rb,H,0 is not dehydrated at 200" ; D = 2.377 and molecular volume = 270.6. When lanthanum and rubidium nitrates are taken in the molecular proportion of 1 4 lanthanum rubidium nitrate results j monoclinic crystals m. p. 8 6 O DZ = 2.497 and molecular volume = 277.1 ; it loses 4H,O on prolonged heating at 60".Lanthanum csesium nitrate [La(N0,),]Cs2,2H,0 forms small tabular crystals D = 2.827 and molecular volume = 265.5. Lunthanum thalloua nitrate [La(NO,),]TI2,4H,O forms hygroscopic crystals m. p. 72" ; Dt = 3.318 2nd molecular volume = 280.0 ; it loses 4H,O a t 100'. Cerous sodium Lanthanum potassium nitrate [La(NO,),I K,J H,O [La(N@,),]Rb 4H,O,INORGANIC CHEMlSTRY. ii. 115 nitrate [Ce(N0,)5]Na2,H,0 consists of hygroscopic slender needles which are not corupletely dehydrated at 150" ; D = 2.65 and molecular volume = 194.0. Cerous rubidium nitrate [Ce(N0,),]Rb2,4H20 has D = 2.497 and molecular volume = 277.6 ; hygroscopic monoclinic needles m. p. 70° which lose 4H,O at 60'. Cerous thaltous nitrate [Ce(NO3),]T1,,4H,O forms hygroscopic crystals m.p. 64s53; Di = 3.326 and molecular volume = 279-7 ; it loses 4H20 a t 60°. Praseodymium rubidium nitrate [Pr(N0,)5]Rb2,4H,0 green hygroscopic monoclinic crystals m. p. 69.5' ; D = 2 5 U and molecular volume = 277.4 ; it loses 4H20 a t 60°. Neodymium rubidium nitrate [Nd(N0,),]Rb,,4H20 consists of hygroscopic bright reddish-violet plates m. p. 47' ; D! = 2.56 and molecular volume = 272.3 ; it loses 4H,O a t 60". The temperature a t which the above compounds melt in their water of crystallisation falls with increasing atomic weight of the rare-earth metal. T. 8. P. A New Element Accompanying Lutecium and Scandium in Gadolinite Earths Celtium. GEORGES URBAIN (Compt. rend. 1911 152 141-143. Compare Abstr. 1907 ii 956; 1908 ii 283; 1909 ii 735).-During repeated fractionation of the nitrates in the isolation of lutecium from gadolinite earths a few drops of a mother liquor were obtained which did not crystallise.This contained a new oxide belonging to the rare earths and characterised by a magnetic susceptibility three or four times less than that of lutecia. The name celtium is given to the corresponding element and the symbol Ct assigned to it. Spectroscopic examination of the oxide showed the presence of luteciurn scandium a trace of neoytterbium and negligible traces of calcium and magnesium. The new element shows a large number of lines in the arc ; the following are very intense A = 2685.2 2765.8 3080.7 3118.6 3197.9. The chloride is somewhat more volatile than t h a t of lutecium but less volatile than scandium chloride.The hydroxide is less basic than lutecium oxide and more basic than scandium oxide Celtium either appears t o be entirely absent from xenotime or else it occurs in very faint traces. w. 0. w. Electrical Properties of Aluminium-magnesium Alloys. WITOLD BRONIEWSKI (Compt. rend. 191 1 152 85-S7. Compare Abstr. 1910 ii 128; Grube Abstr. 1905 ii 523).-From an examination of aluminium-magnesiam alloys by the electrical method already described the author comes to the conclusion that two definite compounds AlMg and Al,Mg probably exist. These form a con- tinuous series of solid solutions with one another preventing their recognition by the thermal method. The existence of the compounds A1,Mg and AlMg could not be confirmed and alloys of the metals in these proportions showed a heterogeneous structure under the microscope.w. 0. w 8-2ii. 116 ABSTRACTS OF CHEMICAL PAPERS. Formulm of Aluminium Salts. GERRIT H. COOPS (Chem. Weekblud 1910 '7 1071-10'76. Compare Coops Abstr. 1910 ii 506 ; and Olivier ibid. 507).-Polemical. A reply to Olivier. A. J. W. Colloidal Solubility of Metals in Distilled Water in Presence of Air and in a Vacuum. MARGHERITA TBAUBE-MENGARINI and ALBERTO SCALA ( A t t i R. Accad. Lincei 1910 [v] 19 ii 505-508. Compare Abstr. 1909 ii 809).-Distilled water acts on aluminium in the warm and in the presence of air and zinc and iron are attacked in the cold colloidal solutions being formed in each case. Lead and iron which alone were experimented with! yield colloidal solutions when treated with distilled.water in a vacuum. The clear solutions become turbid in air that of 'iron turning a greenish and finally a reddish colour whilst the red solution becomes milky. The colloidal iron solution when kept i n a vacuum forms black green and red deposits. Of these the red and black ones are permanent in air but the green deposit becomes red even in a vacuum. The bacteriform colloidal corpuscles of all these metals change (without passing into true solution) into the leaf-like crystals characteristic of colloidal solutions. It. v. 8. Solid Solutions of Iron and Manganese Borides. JOSEF HOFFMANN (Chem. Zeit. 1910 34 1349-1350).-The heterogeneous nature of the borides prepared by the thermite process has already been shown by optical methods (Abstr. 1910 ii 5081 and is confirmed by the chemical behnviour of the various products The composition of the saturated solutions obtained is 7 atoms of iron to 9 of boron for the iron boride and 10 atoms of manganese to 28 atoms of boron for the manganese boride. Mineral acids extract compounds such as Fe,B FeSB4 and FeB from the iron boride leaving a residue consisting mainly of Fe with a little FeB,.The soluble portions of manganese boride consist chiefly of MnB toget,her with some MnB the undissolved residue being elementary boron mixed with some higher borides. T. S. P. Iso- and Hetero-poly-acids. I. Metatungstic Acid. ARTHUR ROSENEIEIM and FRANZ KOHN (Zeitsch. anorg. Chenz. 1911 69 247-260. Compare this vol. i log).-The authors distinguish between '' isopoly-acids " and '' hetero-poly-acids." The former are compounds containing the acid anhydride and the acid hydrate of one and the same element for example the polychromates polytungstates etc. whilst the latter are compounds in which acid anhydrides of one or more elements are combined with a hydrate or salt of the acid of another element for example the phosphomolybdates etc.which have hitherto been called complex acids. According to Copaux's views of the constitution of the meta- tungstates boro- and silico-tungstates (Abstr. 1909 ii 318) the metatungstates must contain water of constitution so that they should belong to the hetero- and not to the iso-poly-acids. It order to find out how much water of constitution is contained in the meta-INORGANIC CHEMISTRY. ii. I17 tungstates the authors have prepared by double decomposition various insoluble salts since these generally do not contain water of crystal- lisation.XiZuey rnetatungstate Ag2W,0,,,3H20 forms small white crystals which lose l*lH,O a t 16U0 and 1.3H20 at 200’; 2 mole- cules of water and probably 3 are therefore firmly combined. I n t?haZZium rnetatungstate T1,W,01,,3H20 only 1 molecule of water is firmly combined. Guanidine metatungstate (CHSN,)2H,W40,3,3H,0 was obtained from guanidine carbonate and metatungstic acid as a white microcrystalline powder. Between 90’ and 150° i t loses 2H20 so that probably only 1 molecule of wat,er is firmly combined. The normal lead and mercury metatungstates although frequently mentioned in the literature could not be obtained. A solution of an alkali metatungstate gives with lead nitrate a precipitate of the double salt PbW40,3,Pb(N0,),,10H20 which loses SH20 at l l O o so that 3 molecules of water are firmly combined. From the above results combined with Friedheim’s statement (In- aug.Dissert.) that the metatungstntes of sodium barium manganese and cadmium still cont,ain 3H20 a t looo and especially since insol- uble salts are generally anhydrous the authors draw the conclusion that the metatungstates contain 3 molecules of water of constitution that is they are aquo-salts and must probably be formulated as n,[wo[~,3jq although they may be R2[WO(wo4)3] When heated at such a temperature that water of constitution is lost they are decomposed. Metatungstic acid was prepared by treating a concentrated aqueous solution of ammonium metatungstate with ether and concentrated hydrochloric (or sulphuric) acid.Of the three layers formed the lower yellow one contains the free acid together with ether and the mineral acid from which the free metatungstic acid is obtained by evaporation in a current of air. It readily euoresces ; crystals were obtained corresponding with H,W4O,,,8K2O and H2W40,,,6H20. It is quite insoluble in ether (compare Abstr. 1896 ii 477) although in the presence of a mineral acid it is possible that a molecular compound of metatungstic acid and ether is formed. I n aqueous solution it behaves as a normal electrolyte and conductivity measure- ments after the addition of varying quantities of sodium hydroxide show it to be a dibasic acid.I n absolute alcoholic Eolution it acts as a colloid. P2O) - Esters of metatungstic acid could not be obtained. The above results cannot be brought into accordance with Copaus’ formulation of metatungstic acid as H,,W,,07,,3H20 + aq. T. S. P. Atomic Weight of Vanadium. D. J. M ~ A D A M . ~ ~ ~ . (J. Amel.. Chem. Xoc. 19 10 32 1603-1 615).-The values previously obtained for the atomic weight of vanadium show considerable discrepancy and a re-determination has therefore been made by a new method. This method is based on the observation of Smith and Hibbs (Abstr. 1894 ii 455) that vanadium can be completely removed from sodium metavanadate by volatilisation in a current of dry hydrogen chloride,ii. 118 ABSTRACTS OF CHEMICAL PAPERS Five samples of sodium metavanadate were used in the experiments The apparatus employed is described with the aid of a diagram.A weighed quantity of the anhydrous salt was placed in a weighed quartz flask and was heated in 8 current of hydrogen chloride containing a little chlorine. When as much as possible of the vanadium had been removed a little water was introduced into the flask and the mixture was again heated in the current of hydrogen chloride. The whole of the vanadium was thus expelled and w residue of sodium chloride obtained. The flask and residue were weighed and the weight of the sodium chloride obtained by subtracting that of the flask. The results of five experiments gave an average value for the atomic weight of vanadium 501967 +_ 0.006 (Na = 23-00 ; C1= 35.46). This value agrees with that obtained by Prandtl and Bleyer (Abstr.19 10 ii 135) by the analysis of vanadium oxychloride. Anhydrous sodium metavanadate has D 2.79. E. G. Bismuth. LUDWIU VANINO and EMILIE ZUMBUSCH (Arch. Pharm. 1910 248 665-669).-Trials with the various methods described for the preparation of bismuth hydroxide showed that it was difficult to prepare a product free from nitrate. Good results were obtained with Thibault’s process (Abstr. 1901 ii 106) but only when a very large excess of potassium hydroxide was employed. A satisfactory preparation was obtained eventually by dissolving bismuth nitrate (20 grams) in water (100 c.c.) containing mannitol (7.5 grams) adding 50 C.C. of ice-cold potassium hydroxide solution (22 grams in 100 C.C. of water) and finally dilute sulphuric acid until the mixture was only slightly alkaline (compare Abstr.1902 i 8). Previous work by Vanino and Treubert (Abstr. 1898 ii 435 598 ; 1899 ii 428; compare Herz and Guttmann Abstr. 1907 ii 274) has shown that bismuth suboxide probably does not exist but the authors have made experiments with the process described by Jaworososki for the preparation of this substance (Pharm. Zeit. BUSS. 1896). This method consists in warming a mixture of ferrous sul phate sodium potassium tartrate and sodium hydroxide in water with basic bismuth nitrate. The brownish-black precipitate so obtained in the author’s experience was never free from iron even when the reacting ingredients were used in calculated proportions for the production OF the suboxide so that they do not regard Jaworososki’s preparation as a definite substance. T. A. H. Brown Gold. MAURICE HANRIOT (Compt. rend. 1910 151 1355-1357).-This name is given to the residue obtained when nitric acid is allowed t o act on an alloy of gold and silver containing about 20% of gold It always contains a small quantity of silver and a considerable amount of nitric acid. The latter is lost a t 175-200°; on further heating it changes colour and undergoes contraction ; at 900’ the substance evolves gas and at 1040O it melts changing into red gold. The author has measured the contraction undergone by strips of alloy containing 1-3.5% of silver on treatment with nitric acid andMINERALOGICAL CHEMISTRY. ii. 119 also the further contraction t h a t ensues on heating. Results are also quoted showing the further contraction t h a t occurs on a second and third heating. ViT. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110005107

出版商:RSC    

年代:1911

数据来源: RSC