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Proceedings of the Chemical Society, Vol. 6, No. 89 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 89,
1890,
Page 165-168
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摘要:
Issued 13112/1890. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 89. Session 1890-91. December 4th, 1890. Dr. W. J. Itussell, F.R.S., President, in the Chair. I Certificates were read for the first time in favour of Messrs. Charles Henry Corbett, Rarnard Castle ; Hendrick Thomas Donovan, Crumptoii Street, Bridgetown, Barbadoes ; Henry Charles Jenkins, Lome Villa, Iveson Road, Hampstead ; William Morley Martin, Cardrew, Redruth ; Arnold Whitaker Oxford, 8, Henrietta Street, Cavendish Square, W. ; Frederick William De Velling, High Street, Heckmondwike, Porkshire ; Herbert D. Shaw, Castle Mount, Sandal, .nrWakefield ; R. Stnckdale, The Grammar School, Leeds ; Kenelm Edward Symes, Magdalen House, Bridport, Dorset. The following were elected Fellows of thc Society :-Messrs.(fustavus Anthony Abrines ; John Thomas Brierley ; William J. Butcher ; William Waters Butler ; Frank Brownsword ; M. KelKay Uamber; Ernest Bentz ; W. E. B. Blenkinsop ; Thomas Arthur Cheetham ; Arthur William Crosskey ; Arthur William Cooke ; William L. Dudley; Thomas S. Goodwin; Alfred Henry Green; William Mahowe Heller ; John Richard Jackson ; Josepb Lunt ; Haiery C. Myers ; William Mackeay ; Thomas Smith Blurray ; William Reginald Ormandy ; James Alexander Pond ; Thomas Platts; G. H. Robertson; Ernest Henry Sainter; Thomas Steel; John Joseph Sudborough ; Charles Thomas Sprayne ; Francis Henry Tate ; George Henry Wadsworth ; Sidney Wood ; George Young. The following papers were read :-95. “The action of heat on ethylic 8-amidoorotonate.” Part I.By J. Normaii Collie, University College, London. Some years ago, whilst working wibh efhyh /3-arnidoeroton&e, the 166 author noticed tthat during its purification by distillation under IT-duced pressure a crystalline compound of the formula C,oH,,NO, = 2CsH,,N02 -NH, -C2H60was always produced in small quantities, and remained behind in the fractionating flask. This condensation product was found to be the ethylic salt of an acid C8H9N03,which from its properties was considered to be the monocarboxylio acid of a hydroxglutidine. Owing to the small qum tities obtained, the in- vestigation was carried no further. Since then, having had to work with large amounts of ethylic P-amidocrotonate, a further supply of the condensation cornpound has been obtained, and a more exact study of its derivatives has been possible.The author now finds that. the acid it3 not a hydi-oxyl derivative of lutidine, but lutidonemonocarboaylic mid, for on heating it yields carbon dioxide and lutidone or ad-di-methplpyridone. This parlial decomposition by heat of ethylic 6-amidocrotonate is therefore very similar to that which ethylic metoacetate undergoes in its conversion into dehydracetic acid during distillation :-2C,H,,O, = C,&04 + 2C2H50H. Feist in his interesting paper on dehydracetic acid (Aizizalen, 257, 253) has shown that it is easily converted into dimethylpyrone- carboxylic acid, the oxygen analogue of dimetliylpyridonecarboxylic acid :-CH3-R-0-g.CH, COOHG*CO.CH ' Dimethylpyronecarboxylic Dimethylpyridonemonocnrhoxylicacid. ethyl ether.Ethylic lutidonemonocarboxylate does not decompose wben boiled with caustic soda, but is merely hydrolysed and converted into the sodium salt of the acid ; with phenylhydrazinc and hydroxplamine it also does not form any compounds, and thus differs from dehydr- acetic acid. With bromine it forms a mono hrominated derivative, C10H12N03Bi*,and with pentachloride of phosphorus the compound C10H12N02C1. The acid obtained from the sodium salt melts at 247" C., decomposing at tbe same time into carbon dioxide and a compound which agrees in every respect with the ad-dimethyl- pyridone, C,HPNO,obtained by Haitinger from dehydracetic acid.and also by Conrad and Geutzeit by heating lut,idoxiedicarl~oxylic acid. This lutidone when heated with zinc-dust yields, according to Hnitinger, ad-dimethylpyridim boiling at 148-151" C., whilst the ad-dimethylpyridine obtained from other sources boils at 142-143" C. Conrad and Geutzeit also obtained a lutidine from this lutidone, but do not give its boiling point. The author has been able to obtain D lutidine by four different methods :-(1.) By distillation of the potassiiim salt of lutidonecarboxylic acid with excess of solid caustic potash. 167 (2.) By the prolonged action of nascent hydrogen (from tin and bydrocbloric acid) on the chIorolu tidine obtained by treating the lutidone with peiitachloride of phosphorus. (3.) By heating the clilorolutidine with zinc-dust in an atmosphere of bydrogen.(4,)By heating the chlorolutidine obtained from dehydracetic acid by Haitinger's method with zinc-dust. A11 these four methods gave a lutidine boiling at 144-145" C., md yielding a platinum salt melting at 210-212" C., the melting point found by Epstein aud Ladenburg for the chloroplatinate of ma'-dimethylpyridine. The author has also been able to compare this lutidiue with a lutidine boiling at 143-144" obtained by Professor Ramsay from bone oil, and is led to regard it as identical t'herewith. By oxidation of the lutidine from ethylic P-arnido-crotonate with potassium permanganate, a pyridinedicarboxylic acid was obtained meliing at 235" C. (corr.), which, on heating, gave pyrid- ine, showing that it was dipicolinic or ad-pyridinedicarboxylic acid.96. "The action of heat on nitrosyl chloride." By J. J. Sud-borough, B.Sc. (Lond.), and G. H. Miller. An account is given of a series of determinations of the vapoi11.- density of nitrosyl chloride, NOCI, at various temperatures. At ieriiperatures from 15" to 693", the values obtained SO nearly coincide with the theoretical value 32.67, that it is to be supposed that no dissociation takes place below about 700". At higher temperatures, the compound is no longer stable, as the folIowing numbers show :-Ternperaturc. Vapour density. 784" 31.77 796 31-36 815 31.00 928 29.00 968 27-30 985 27.00 The results show that in comparison with nitrogen dioxide, NOf, which is completely decomposed below 620", nitrosyl chloride is a highly stable compound.Kitrosyl chloride in its reactions with water behaves as the chloride of nitrous acid, and inasmuch as nitrous acid not only forms nitroso- compounds, but also hydroximes by interaction with the CH, group, nitrous acid would appear to have the formula O:N*OH, and the chloride the formula O:N*Cl. As nitric oxide and nitrosyl chloride show EO tendency to polymerise, the union which takes place between 168 NO, and NO, at temperatui-es below 140” is probably established betweeu oxygen atoms, and as only like molecules of NO, are con- cerned in the formation of nitrogen peroxide, it is unlikely that the latter has an unsymmetrical formula : the formula O:N*O-O.N:O would appear to satisfy the requirements of the caw ; this leads to the formula ON-O for the dioxide, and it may be that the instability of the dioxide is due to the unsaturated condition of the oxygen.97. “ The volumetric estimat,ion of tellurium.” By Dr. B. Brauner Hitherto only gravimetric methods have been adopted in estimating tellurium, and as they involve the use of weighed filters, the determi- nation is subject to considerable error, besides occupying much tirnta. The author describes two volumetric processes. The first is based 011 the reduction of solutions of tellurium dioxide by stannous oliloride :-TeCll + 2SnC1, = Te + 8SnC14, TeO, + 2SnC1, + 4HCl = Te + 2SnC14 + 2H,O. The tellurium compound, together with muriatic acid, is digested with excess of stannous chloride, and the excess subsequently deter- mined by iodine and thiosalphate. The second method consists in adding an excess of potassiuni dichromate solution to the solution of tellurium dioxide in muriat ic acid, the excess OF dichromate being subsequently determined by means of ammonium ferrous sulphate :-3Te0, + K2Cr20, + 8HC1 = 3Te0, + 2KCl + Cr;,Cl, + 4H,O.Results are quoted showing that the first method gives satisfactory results ; but the second does not appear to be one of practical vduv. At the next meeting, on December 18th, the following papers will be read :-bb The constitution of dehydracetic acid.” By Dr. Collie. “ The theory of dissociation into ions and its consequences.” BJ-S. U. Pickering. “ The a-and P-modifications of benzene hexachloride.” By l)r. Matthews. “ The fermentation of calcium glycerate ; an optically active glyceric acid.” By Professor P. F. Frankland and W. Frea. “ Phenuvic acid.” By Dr. Colefax. UARRISON AFD SOliS, PRINTEBS IN ORDISARY TO HER MAJESTY, Sl’. MARTIX’S LAKE.
ISSN:0369-8718
DOI:10.1039/PL8900600165
出版商:RSC
年代:1890
数据来源: RSC
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