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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 34 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 34,
1887,
Page 29-37
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 34. Session 1886-87. March 3rd, 1887. Dr. Hugo Miiller, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. James Warne Chenhall, Churston, near Brixham, Devon ; George Collar, B.A., 28, Sterndale Road, West Kensington Park, W. ; Hugh Gordon, 3, Courtfield Gardens ; David Lloyd Howard, Rectory Manor, Wal- thitmstow ; Edward Rawlins, Burley Road, Leeds ; Louis H. Schubart, 201, West 125th Street, New York. The following were elected Fellows of the Society :-Messrs. Cecil Howard Cribb, Leonard Dobbin, Joseph F. Geisler, Edgar Hall, Alexander Hay, Thomas A. Hedley, John S. Jackson, George McGowan, Gerald T. Moody, Joseph W. O'Connor, Henry D. Richmond, Arthur H.F. Ruppel, W. Scrutton, Henry Lloyd Snape, B.Sc., Arthur Stanley, Henry Wa.llis. The following papers were read :-18. " Tartaric and Racemic Acids and the Magnetic Rotatory Power of their Ethyl Salts." By W. H. Perkin, Ph.D., F.R.S. The author has very carefully determined and compared certain physical properties of the diethylic salts of ordinary tartaric and racemic acids, prepared by the usual method by saturating the alco- holic solution of the acid with hydrogen chloride. Both boil at 232-233" (corr.) under a pressure of 197 mm. They have the same relative density, vie. :-15"Diethjlic tartrate.. d--= 1.20972 d-25" = 1.20189.15" 25" 2 5" ,, racemate.. d15" = 1.20983 d-2-= 1.20214.15" 25" 30 They have also the same mean molecular magnetic rotatory power, me.:-Diethylic tartrate at 14.8' = 8.766 ,, racemateat 15.5 = 8.759 It may therefore be concluded that the racemate is a mixture of the two tartrates. Racemic is distinguished from tartaric acid by crystallising with 1 mol. proportion of water; the author finds that silver racemate, like the tartrate, is anhydrous. In preparing silver tartrate, he obtained an acid salt, CaH5Ago6*H20,crystallising in well-defined monoclinic prisms, measurements of which by Professor Haushofer are given. An acid silver racemate atppears also to exist, but is much less soluble than the tartrate, and the crystals are small. The relative densities of aqueous solutions of the two acids were determined, using (a)a solution containing 8.333 per cent., and (b) a solution containing 25 per cent., the latter being supersaturated in the case of racemic acid ; the results are-(a*> @.) Tartaric acid solution..d-15" = 1.03703 d-1.5-3"=1.12346.15" 15" Racemic acid solution.. d-15" =1.03712 d-15.3" =1.12398.15" 15" The relative densities of the solid acids were also determined :-Racemic acid, CaH6O6*H,O..d-"" - 1.6873.4" 99 ,, dehydrated ...... = 1.7782. Tartaric acid.. ................ = 1.7594. These results, the author considers, point to the conclusion that on dissolving in water racernic acid separates into the two tartaric acids, only a small quantity remaining unchanged. He is of opinion that the water is present in crystallised racemic acid as such ; and he finds that if the hydrated acid be crystallised from absolute alcohol, well-defined anhydrous crystals are obtained much less solublethan tartaric acid in alcohol.19. "Anhydracetonebenzil." By Francis R. Japp, F.R.S., and Cosmo Innes Burton, B.Sc. Anhydracetonebenzil (formerly dehydracetonebenzil), C17H140?,was originally prepared by Japp and Miller (Trans., 1885, 27) by tlie 31 condensation of benzil with acetone under the influence of caustic potash; they concluded that it contained a closed chain formed by the interaction of the acetone with the lateral chain of the benzil. The authors adduce further evidence in support of this view. Anhydracetonebenzil reacts with phenylhydrazine, forming the compound CI7HI4O(Nd%*C6H,)(slender, yellow needles, melting at 197"), which is not altered by heating with excess of phenylhydr-azine.By boiling anhydracetonebenzil for a few minutes with iodhydric acid it is deprived of an atom of oxygen, and yields a compound, C17H140 (colourless prisms from alcohol ; m. p. 110"). This reacts with phenylhydrazine, forming Cl7Hl4(N,H*C6H,),which crystallises from alcohol in rosettes of short, yellow needles, melting with decom- position at 170-180". Fuming iodhydric acid and amorphous phosphorus at 130" convert anhydracetonebenzil into a hydrocarbon, C17H18, which crystallises from alcohol in colourless, long, flat needles, melting at 47",and dis- tilling under ordinary pressures with partial decomposition at 305" (uncorr.). The authors regard this hydrocarbon either as diphenyl- pentamethylene (1, 2), or as phenylbenzyltetramethylene (1,1).It is not reduced to C17H20 by the action of the hydriodic acid at a higher temperature, as it would be if it were an unsaturated open-chain compound-diphenylamylene. By reduction with tin and hydrochloric acid in alcoholic solution anhydracetonebenzil is converted into a compound, C31H3402, very sparingly soluble in alcohol, from which it crystallises in lustrous, minute rhomboidal plates, melting at 187-188". When boiled with sulphuric acid diluted with twice its volume of water, 2 mols. of anhydracetonebenzil part with 2 mols. of water, and unite, forming a compound, C,4H2402,which crystallises from benzene in two forms-one with, the other without benzene of crystallisation.This substance melts with decomposition at 195-200", evolving exaky one molecular proportion of carbonic oxide, according to the equation C34H24Oz = C33H240 + CO. The compound C,H2,0 crystal-lises from benzene in small plates of the formula C,H240,CsH6,which, after expelling the benzene, melt at 162-163'. It reacts with phenylhydrazine, yielding C33Hz4(N2H*C6H,)(pale -yellow, slender needles, very sparingly soluble in alcohol ; m. p. 250"). In this respect it differs from its parent compound, C&fz*Oz, which does not react with phenylhydrasine. Anhydracetonebenzil, when treated with concentrated alcoholic chlorhydric acid in the cold, is converted into a compound, C17H13C10, which crptallises from alcohol in flat needles with a silky lustre (m.p. 128"). When this compound is heated with alcoholic ammonia at looo, it yields the condensation product C34H240z(m. p. 195-200") already described. When oxidised with dilate nitric acid, anhydracetonebenzil yields chiefly benzoic acid, together with paranitrobenzoic acid, oxalic acid, bend, and a small quantity of a neutral nitrogenous substance crys- tallising in needles (m. p. 264"). The authors have also commenced the study of the reactions of anhydracetophenonebend, C22H,,02(Japp and Miller, Trans., 1885,36), which wits not supposed by its discoverers to contain a closed lateral chain. This compound appears to react both with 1 and with 2 mols.of phenylhydrazine, but neither of the derivatives thus formed could be obtained free from the other. When boiled with fuming iodhydric acid, it is transformed like anbydracetonebenzil, parting with an atom of oxygen, and yielding a compound, CZ2Hl60(long flat prisms from alcohol ; m. p. 92-93'). With alcoholic chlocbydric acid in the cold anhydracetophenonebenzil behaves like anhydracetonebenzil, forming a compound, C22'E[16C10, which crystallises from alcohol in colourless, slender needles, melting at 115". 20. " Condensation Compounds of Benzil with Ketones." By the same. In order to ascertain whether the reaction in which anhydracetone- benzil and anhydracetophenonebenzil are formed (see foregoing note) is of general application, the authors have examined the action of benzil with various homologues of acetone.Caustic potash of sp. gr. 1.27 was used as the dehydrating agent. In every case 1 mol. of benzil was found to react with 1 mol. of the ketone, eliminating 1mol. of water. The intermediate additive compounds, the forma- tion of which was observed in the case of the reactions of benzil with acetone and acetophenone (Japp and Miller, Trams., 1885, 21 and 34), were not isolated. The following compounds, which for purposes of nomenclatur6 are assumed to be true homologues of anhydracetonebenzil, have been prepared :-,Methyl-anhydracetonebenzil,C18HL80,. From methylethylketone and bend. Colourless thin prisms from alcohol ; m. p. 179".DimethyZ-anhydracetonebenxiZ,C19H,02. From diethylketone and benzil. Colourless rhomboidal plates from alcohol ; m. p. 150". EthyZ-anhydracetonebenz~Z,CI9Hl8O2. From me thylpropylketone and benzil. Colourless minute needles from alcohol ; m. p. 156". Amyl-anhydracetonebensiz, C22H2402. From methylhexylketone and benzil. Tufts of colourless slender silky needles from alcohol ; m. p. 150.5". 33 21. “ Constitution of Glycosine.” By Francis R. Japp, P.R.S., and E. Cleminshaw, M.A. Debus sliowed (Phil. Trans., 148, 209) that glyoxal reacts with ammonia according to the two equations- I . .. . . 3C,H,O, + 4NH3 = N4(C,H3)iV3 + 6HzO. Glyoxal. Glycosine. TI . . . . . 2CzH20, + 2NH3 = C3H4Nz + CHZOZ + 2HzO. Glyoxal. Gtlyoxaline. Formic acid.Radziszewski (Bey., 15, 1495) has suggested that the second of these reactions occurs in two stages. In the first stage, 1 mol. of glyoxal is hydrolysed, yielding formic aldehyde and formic acid ; in the second, the formic aldehyde reacts with another mol. of glyoxal and 2 mols. of ammonia, forming glyoxaline. Interpreting this second stage by the light of the condensations of dicarbonyl-compounds with aldehydes and ammonia studied by one of the authors, glyoxaline would receive the formula \CH (Japp, Trans., 1883, 17).CH-NH This formula is in keeping with the reactions of the compound and has found general acceptance. It occurred to the authors t’hat the second of the above reactions in which glycosine is formed, might in like manner be iiiterpretedas belong- ing to the class of dicarbonyl-aldehyde-ammonia condensations, glyoxal being both a dicarbonyl-compound and an aldehyde. It would only be necessary to assume that, of the 3 mols.of glsoxal takiiig part in the reaction, one has the function exercised by the aldehyde in such condensations, whilst the other two act as dicarbonyl-compounds. On this assumption the reaction would occur according to Equation I1 (Trans., 1884, 672) of the general reactions of this class, save that in tlie present case, as the aldehyde is a dialdehyde, the molecular pro-portions of the other reacting substances are doubled :-CHO 21 + CHO-CHO + 4HN3= CHO Glyoxal as dicai*bonyl-compo~~nd. Glyoxal as aldehyde. CH-NH CH-NdI1 \CdNH-YF %--CH + 6H,O.Gly cosine, 34 The glyoxal molecule of aldehyde function reappears as an oxalic acid residue in the formula of glycosine ; the two glyoxal molecules of dicarbonyl function I-eappear in the form of two unsaturated groups -CH CH-(comp. Trans., 1884, 673). In this respect the reaction would belong to the numerous class involving mutual oxidation and reduction between similar molecules, to which class the aldehydes furnish the largest contingent. If the foregoing view is correct, it should be possible to sub-stitute, in the foregoing reaction, for the two gl-yoxal molecules of dicarbonyl function, two diketone molecules containing the group CO*CO. Thus, by the action of ammonia on a mixture of bend and glyoxal, a tetraphenyZglycosine should be formed :-C6H,*CO CHO PhmC-NH+ 4NH, = I I \C*C/*NH-t*Ph+ 6H,O.C6H5.A* + AH0 Ph*C---N’ %-C-Ph This was found to be the case. Tetraphenylglycosine, prepared by the above method, crystallises from alcohol in long, very slender, silky needles, C,,H22N4,C2Hs0,which readily part with their alcohol of crys- tallisation. It melts above 300”. It forms unstable salts. Debus formulates glycosine as a tertiary amiiie on the quadruple ammonia-type (see reaction I). The formula above suggested differs from this in containing two imido-groups. In order to prove the presence of two displaceable hydrogen-atoms, the authors heated glycosine with benzyl chloride, and obtained dibenxylglycosine, C6K4N,(N*C7H7),,which crystallises from alcohol in oblique plates melting at 145”.The authors have also prepared some new platinichlorides of glyco-sine. In addition to the diacid salt, C&&&f&PtCI6, described by Debus, they have obtained a naonncd salt, (C6H6N4)2H,PtC16,the existence of which was suspected by Debus, and a tetracid saZt, CbH6N4(H2PtC16)2,the latter being of the three that which is most readily prepared in a pure state. A suggestion regarding the constitution of glycosine, similar to that here developed, has been thrown out by Wallach. He says (Bey., 16, 545, footnote) :-“ Glycosine probably stands in the same relation to glyoxaline as dioxalethyline to oxalethyliiie.” It is to be remarked, however, that dioxalethyline appears to be deri~ed from an isoineride of glycosine, in which the two glyoxaline complexes are united at a different point.22. “Diphenylglyoxaline and Methyldiphenylglyoxaline.” By Francis R. Japp, F.R.S. The author received from Mr. W. Palmer Wynne a small quantity 35 of a base, melting at 218", obtained together with imabenzil, bend- imide, and benzilam by dissolving benzil in warm methylated spirit and saturating the solution with ammonia. This base remained in the last mother-liquors. The author failed to obtain it on substituting pure alcohol for methylated spirit. An attempt was then made to prepare it, employ-ing methylated spirit; but the only basic substance obtained was methyldiphenylglyoxaline (m. p. 235"), showing that the spirit contained aldehyde. An old specimen of wood spirit was then used.A new base was then obtained, which was deposited from alcohol in crystals not unlike those of Mr. Wynne's base, but melting at 22'7". This proved to be dipherzylglyoxaline, formed by the condensation of formaldehyde, contained in the wood spirit, with bend and ammonia. The crystals differ in form according as they are deposited from hot or from cold alcohol-the latter form only resembling that of Mr. Wynne's base. Analysis of Mr. Wynne's base gave figures intermediate between those required for diphenylglyoxaline and methylglyoxaline. A mixture of these compounds in molecular proportions was therefore allowed to crystallise from alcohol. The solution deposited crystals indistinguishable from those of Mr.Wynne's base, and, like these, melting at 218". Finally, Mr. L. Fletcher has established the identity by crystallographical measurements. The hydrochlorides of the mixed bases also crystallise together in forms identical with those of the hydrochloride of Mr. Wynne's base. 23. '' Dehydracetic Acid." By W. H. Perkin, Jun., Ph.D. It is known that if dehydracetic acid, CBH804, be treated with alkalis it is decomposed principally into acetic acid, carbonic anhydride and acetone, a small quantity of malonic acid also being formed. The author finds, however, that in the first place dehydracetic acid is converted into two molecules of acetoacetic acid, C8H80d+ 2Hz0 = 2CH3.CO*CH2*COOH. Dehydracetic acid reacts with phenylhydrazine and with hydroxylamine, forming the compounds C7H803(N2H*CsH,) and C,H803(N*OH); and it therefore contains a carboxyl-group.The fourth oxygen-atom (not counting tlhe carboxyl-group) is present neither as CO nor as OH, and the author therefore proposes the formula C*CO CH-COOH The action of aniline on methylic dehydracetate, in the author's opinion, is such as to prove the correctness of this expression, two substances, methylic 1?kenyldimethyl~yridine cnrboxylate and phenyldi-metl~ylppyridone,being formed, which are both pyridine-derivatives, VlZ :-C*CO*C*CO,CH, CHG0.C H It II and II IICH3*C*NPh*C*CH, CH,*C*NPh*C*CH, An interesting synthetical proof of the correctness of the formula assigned to dehydracetic acid has lately been given by Conrad and Guthzeit (Ber.,20, 154).24. “ The Colouring Matter of Drosera Whittakeri.” By Professor E. H. Rennie, M.A., D.Sc. The author’s attention was drawn to the presence of a red colour- ing matter in the tubers of the above-mentioned Drosera, which grows plentifully on the hills near Adelaide, South Australia, by Professor Tate. On inquiry he ascertained that Mr. Francis, of Adelaide, had extracted the colouring matter by means of carbon bisulphide, and had found that it was volatile, and that beautiful tints could be produced with it on silk by means of various mordants, but had not continued the investigation. To separate the colouring matter, the tubers were heated with hot strong alcohol.After dis-tilling off the spirit, a little water was added and the precipitated colouring matter was then dried and sublimed; the product was a mixture of two substances differing in solubility in boiling alcohol and acetic acid. The less soluble was obtained in small brilliant red plates, canoe-shaped under the microscope, which melted at 192-193”. Analysis gave numbers fairly agreeing with those required by the formula CllH805,which may represent a trihydroxy-methylnaphtha-quinone. The reactions of the substance, in so far as they could be studied with the small quantity of material at disposal, serve to support the view that it is thus constituted. The second substance was finally obtained in needles, quite different in appearance from the red plates, though to the eye of much the same colour. Under the microscope single cryst’als seemed yellow, but wherever they over-lapped the colour appeared deep orange to red.It fused at 164-165”. Analysis gave numbers fairly agreeing with the formula G,H*Oa. 25. “Further Notes on the Di-haloid Derivatives of Thiocar-bamide.” By George McGowan, Ph.D. The author bas succeeded in obtaining dithiocarbamide dibromide in beauhiful large rhombic crystals, by the action of bromine on an 37 aqueous solution of thiocarbamide. At the ordinary temperature it is quite stable. By the further action of bromine on an aqueous solution, this dibrornide is converted into carbamide, or, more pro- bably, in the first instance into cyanamide, bromhydric and sulphuric acids being produced at the same time. Sulphuretted hydrogen acts on dithiocnrbamide dichloride, (CSN,H4),C12,in alcoholic solution, producing thiocarbamide hydro- chloride, CSN,H4*HC1, and sulphur.All attempts to prepare the dicyanide, (CSN2N4CN)2,have failed. From the results of a number of experiments with dieerent cyanides on thiocarbamide and its dichloride, the author concludes that pr+ bably the dicynnide is formed, but immediately breaks up, the sepa- rated sulphur being taken up by the excess of cyanide present and thiocyanate formed. At the next meeting, on March 17th, there will be a Ballot for the Election of Fellows, and the following papers will be read:- “ The Action of Heat on Nitrogen Peroxide.” By Dr. A. Richard- son. “ The Formation of Naphthalenesulphonic Acid by means of Sul-phuric Anhydride.” By Dr. Armstrong and W. P. Wynne, B.Sc. HAltRlSON AND SONS, PRINTERS IN ORDINAlEY TO HER MAJESTY, ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8870300029
出版商:RSC
年代:1887
数据来源: RSC
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