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Proceedings of the Chemical Society, Vol. 19, No. 261 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 261,
1903,
Page 43-52
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摘要:
PROCEEDINGS OF PHR CHEMICAL SOCIETY. VOl. 19. No. 261. \Vednesday, February 18th, 1903, Profemor J. EMERSON ,REYX'OLDS Sc,D., F.R.S., President, in the Chair. 3h. J. P. Blillington was forniallg admitted a Fellow of the Societp. Certificates were read for the ti& time in favour of Meusrs. Robert Gordon Eibby, New College, Oxford. Thomas Divine, N.R., C.M., 11, Spencer Place, Leeds, Archibald Louis Robinson, B. A,, 40, Trinity College, Dublin. Xontague White Stevens, 2, Richmond Place, London, S.W. It was announced that the following changes in the Ofticera tznd Council were proposed by the Council : As President : Prof. Tilden, F.R.S., vice Prof. J. Emersou Reynolds, F.R.S. As Treasurer :Dr. Horace T. Brown, F.R.S., vice Prof. Tilden, F.R.S.As Secretary : Prof. Wynne, F.R.S., vice Prof. Dunstan F.R.S. As Vice-Presidents :Prof. Dunstan, F.R.S., and Mr. David Howard, vice Prof. Divers, F.R.S., and Dr. Stevenson. As Ordinary Members of Council : Dr. J. T. Hemitt, Dr. C. ,4. Kohn, Dr. E.J. Mills, F.R.S., and Dr. S. Ruhemann, vice Xr. H. B. Baker, F.R.S., Dr. Chattnmay, Prof. Clomes, and Dr. Lewkomitsch. 44 Dr. Hewitt, 'Dr. Thorne, and Dr. Orton were appointed to audit the Society's accounts. IN'I'ERNATIONAL CONGRESS OF APPLIED CHEMISTRY. Ry direction of the Council, the following letter was read announcing the formation of a Joint Organising Committee in this country in connection with the International Congress of Applied Chemistry which is to be held in Berlin next June.SOCIETY INDUSTRY,OF CHEMICAL PALACECHAMBERS, 9, BRIDGE LONDON,ST.,WESTMINSTER, S.W. Februury loth, 1903. It Intei*nationaZCongress of Applied Chemistry, Berlin." DEARSIR, I am directed to inform you that at the conference held at this office on the 6th inst. and referred to in my letter of the 26th ult., the following resolutions were passed : 1. That the delegates appointed by the Royal Society, Chemical Society, and Society of Chemical Industry, to represent these Societies at the International Congress of Applied Chemistry to be held in Berlin in Julie next, agree to form the joint Organising Committee contemplated in the letter of May 30th last from the President of the Organising Committee at Berlin. 2.That the Organising Committee so formed invites the co-opera- tion of the other Learned and Industrial Societies in Great Britain, whose members are interested in Applied Chemistry. 3. That the President of the Society of Chemical Industry be requested to act as Chairman of this Organising Committee. 4. That Mr. C. G. Cresswell be requested to act as Secretary pro tom. 5. That a copy of these resolutions be communicated to Dr. Otto Witt, President of the Congress. I remain, Your obedient servant, (signed) CHAS. a.CRESSWELL. The S'ecretuq, Chemical Society. 45 The following delegates have been appointed by the Council to represent the Chemical Society at the Congress , Prof. Tilden, Prof. Dunstan, Prof. W. H. Perkin, jun., and Dr.A. Scott. Fellows of the Society who propose to attend the Congress next June are requested to send their names to the Secretaries so that they may be communicated to the Organisiog Committee in Berlin. A ballot for the election of Fellows was held and the following were subsequently declared duly elected : Gilbert John Alderton. Arthur Graham Leigh. George Henry Appleyard. Harry Percy Lewis. Edwin Rayles Atkinson. Percy George Mander, B.Sc. K. Bhaduri, M.A. Frederick O’Rrien, KSc. William Bowen. George hf ontague Pr ichard. Samuel Rrat’ibnry. Thomas Samuel, B.A. George Thomas Branch. Alfred 13. Scliolefield, B.A , R.Sc. Hubert William Bywaters, Ph. D. Samnel Edward Sibley. William Henry Cadman. Alec Bowring Steven, 13.S~. John Castell-Evans.George Malcolm Thomson. Arthur John Codling. Charles Cilbnrn. Francis George Cousins. Stanley Tolson. Benjamin Claxton Coyla. Francis Digby Toyne. Cecil Henry Desch, Ph.D., D.Sc. Duncan Tuiner. Archibald Sefton Elford, B. A. John hIello Kadniore, B. A. Robert Crosbie Farmer, M.Sc., Ph. I). Thomas Crosbie Walsh. Leonard King Hindmarsh, B.A. David John Williams. Franklin Wise Howorth. Albert WiImore. Rfoung Tha Huyin, B. A. William Wade Yeomans. Maurice Kemp-Welch, B.A. Andrew Young. M. 8.,B. Sc. Frederic Herbert Lers. Of the following papers, those marked * wero read : “24. The molecular rearrangement of ,V-substituted imino ethers.”‘I By G.D.Lander. The rearrangement of the atomic grouping *C(OR):N*into *CO*NR* may be effected catalytically (Knorr and Wheeler) or by heating (Wislicenus), and both kinds of isomerisation have been studied with some of the recently prepared N-substituted imino-ethers. Alkyl iodides prove more useful in the catalytic rearrangement than bromides or chlorides, and the isomerisation by means of iodides has been examined with the following imino-ethers : N-phenylacetimino-methyl and -ethyl, N.o-tolj1-and AT-p-tolylacetimino-ethyl,N-phenyl-benzimino-methyl and -ethyl, ,V-o-tolyl- and AT-p-tolyl benzimino-methy1 and -ethyl, N-methylbenzimino-methyland -ethyl, N-ethylbenzimino- methyl and -ethyl, and N-benzylbenzimino-methyland -ethyl.Isomerisation occurs more readily with the methyl than with the ethyl compounds, the former, for the most part, undergoing rearrange- ment at loo', a temperature at which there is very little change with the latter.The ease of transformation also depends 011 the orienta- tion of the aryl group attached to nitrogen, p-tolyl changing more easily than o-tolyl compounds. The following substituted amides which result from the isomeric change do not appear to have been previously described. Benxmethyl-o-tolylamide (m. p. 65-66') crystallises in prisms from ether and light petroleum. kenxethyl-o tolylumide melts at 71-72'. Benxmothpll-p-tolylamide and benzetl7LyZ-p-tolyZamicle form prisms me1 ting at 46-48' and 38-40' respectively. Benzmethylhenzy Zamide and beneetlqlbenzyl-amide are liquids boiling respectively at 213-214' (11 mm.) and 214-216' (12 mm.).The rearrangement by heat occurs far less readily. ,V-Phenyl-acetimino-methyl ether undergoes partial isomerisation on prolonged boiling, and considerable isomeric change of N-methylbenzimino-methyl ether was obtained after 9 hours heating at 250-270°. With N-phenylbenzimino-methylether (Bey., 1900, 33, 1470), less conclusive results mere got. With ethyl-imino-ethers, the main change produced by prolonged heating is the elimination of ethylene and regeneration of the parent amide. It is therefore doubtful whether the isomerisn- tion can be caused by simple heating. Attention was drawn to the formation of ethyl paracyanoformate, (CN*CO,Et),, from diethyl imino-oxalate, HN:C(OEt)CO,Et, by loss of alcohol and subsequent polymerisation.DISCUSSION. Dr. ORTON asked whether Dr. Lander had brought about the isomeric change of an 0-iminoether into the N-alkyl compound by use of an alkyl iodide, in which the alkyl group was not identical with the alkyl group of the iminoether. If the first stage of the change is the formation of an additive product of the alkyl iodide and the iminoether, then, if sufficient quantity of the alkyl iodide be used, a N-alkyl derivative should be obtained, which would possess the alkyl group of the a,lkyl iodide, and not that originally present in the 0-iminoether. Dr. LARDERin reply stated that he had performed an experiment in which the catalytic action of normal propyl iodide (1 mol.) on a methyliminoether had been found to yield chiefly substituted methyl- amide, the corresponding propyl compound being also produced, but to a 47 less extent, the trace of methyl iodide first formed proving more effective than the relatively large amount of higher iodide also present.*25. “The nature and probable mechanism of the replacement of metallic by organic radicles in tautomeric compounds.” ByG. D. Lander. The results of the alkylxtion of keto-enolic compounds and substituted amides by means of dry silver oxide and alkyl iodides (Trans.,1900, 77, 729 ;1901, 79, 690 ; 1902, 81, 591 ;Proc., 1901, 17,59) woredis-cussed in the light of the addition hypothesis and its modifications, and also with reference to the views on the mechanism of the replace- ment of metallic radicles in tautomeric compounds as developed by Wislicenus (Tautomerie, Ahrens-Sccmmlung, 1897, 249).The opinion was advanced that none of these hypotheses is competent to give a perfectly general eIucidation of the phenomena, and an explanation was therefore sought in the hypothesis of the display of tautomeric relationships by the compounds containing metallic radicles. In order to test the validity of silver oxide alkylation as a basis for the discussion of the mechanism of this replacement of metallic radicles, the alkylation of ethyl oxaloacetate and formophenylamide by this method was investigated ; the former yields ethyl ethoxyfumnrate on treatment with silver oxide and ethyl iodide, a result agreeing with that obtained by Nef (Annalen, 1893, 2’7’7,73) ;the latter, on methyl-ation with silver oxide, gives chiefly N-phenylforminomethyl ether, NPh:CH*OMe, together with small amounts of formophenylmethyl- amide, CHO*NMePh, and diphelnylformamidine. The production of the last two substances does not appear to have been noted in the methyl- ation of silver formophenylamide by Comstock and Icleeberg (Anter.Chern. J.,1891, 13, 514), but a control experiment showed that both are formed in their process to a somewhat greater extent than by the silver oxide methylation. Methylation of the substituted amides by means of silver oxide leads to the formation of mixtures of imino-ethers and isomeric substituted amides, ethylation of these amides under similar conditioris apparently gives rise exclusively to imino-ethers.When, however, the ethylation of acetophenylamide by means of silver oxide is conducted in a closed vessel at 1 OOO, AT-phenylacetiminoethyl ether, NPh:CMe*OEt, and the isomeric smide, NEtPh-CMeO, are both produced just as isomerides are formed in the methylation of the same amide in open vessels at the ordinary temperature or at 40-50’. N-Phenyl benziminomet hy 1 ether, NPh: CPh OMe, does not undergo isomeric change when boiled in benzene soIutioL for 4 hours with dry silver oxide and methyl iodide. “26. “The chlorine derivatives of pyridine. Part VIII. The interaction of 2 :3 :4 :5-tetrachloropyridine with ethyl sodio-malonate.” By W. J. Sell and F. W. Dootson. The chief product of the interaction of 2 :3 : 4:5-tetrachloropyridine and ethyl sodiomalonate is ethyl 2 : 3 :5-trichloropyridyl-4-malonate which, on hydrolysis, loses carbon dioxide yielding 2 : 3 : 5-trichloro-pyridyl-4-acetic acid.The latter compound is non-volatile, and when heated a little beyond its melting point, is quantitatively decoliiposed into 2 :3 :5-trichloro-4-methylpyridineand casbon dioxide. On oxida-tion with potassium permangsnate, 2 : 3 : 5-trichloro-4-methylpyridioe yields the corresponding acid, These changes may be thus represented : 3C,NHCI,*CH(CO,Et), C,NHCl;CH,*CO,Et -C,NHCI3.31e --C,NH C1 CO,H. *27. ‘‘The biological method for resolving inactive acids into their optically active components.” By A. McKenzie and A.Harden. In much of the research in this field, no attempt has been made to work with pure cultures. Hence, although the optically active products desired in certain cases mere successfully obtained,there is often doubt as to the exact organism by which the resolution had actually been effected, the object having been to obtain the pure active isomeride rather than to examine the action of any particular organism on the inactive acid, and therefore many resolutions ascribed to Penicillium ylazlczcm have probably been accomplished, not by that mould, but by bacteria with which the solution under investigation had accidentally become contaminated (compare Landolt, Bas optische Brehungs-vermogen, 1898, 63). The authors have investigated the action of Yenicillium gkaucurn, Link ; Sterigmatocystis nigya, van Tieghem ( =Aspergillus niger, van Tieghem, olim); and Aspergillus griseus, Link, and their action on racemic, dimethoxysnccinic, lactic, a-ethoxypropionic, a-propoxypro- pionic, a-hydroxybutyric, P-hydroxy butyric, glyceric, malic, methox y -succinic, ethoxysuccinic, propoxysuccinic, mandelic, methoxyphenyl- acetic, ethoxyphenylacetic, propoxyphenylacetic, a-bromopropionic, a-bromobutyric, chlorophenylacetic, and monobrornosuccinic acids and alanine were investigated.Their experiments tend to show that the mode of action of the moulds is such that the one active isomeride is attacked more readily than the other, and that the extent of the resolution depends solely on the difference of this rate of attack. The view generally held, namely, that the one isomeride is attacked whilst the other remains 49 untouched, does not appear to be correct.Two other points were kept in view, firstly, whether, from the action of organisms, any definite relationship could be established as to the configuration of the various related acids, and, secondly, whether the active products of the action of different organisms on the same series of acids show any regularity as to sign of rotation. 28. Colour changes observed in solutions of cobalt chloride.” By W.N.Hartley. A paper by Donnan and Bassett (T~ans.,1908, 81, 939) contains a reference to some work on the action of heat on the absorption spectra and chemical constitution of saline solutions, and to this (Xci.Trans. Roy. Dubl. Xoc., 1900, [vii], 263) the author takes ex- ception as being misleading in certain important particulars. The characteristic spectra of aqueous solutions of cobalt chloride saturated at 20°, as seen in wedge-shaped cells at temperatures between 23’ and 93O, differ from those of the hydrochloric acid solu- tion; the compound formed at 93-100’ in neutral solutions seems to be the dihydrate, CoCl,,ZH,O, and not the anhydrous salt. The solution in hydrochloric acid probably contains a compound of the salt with the acid, for the spectrum is peculiar, and, moreover, the anhydrous salt, which is insoluble in dry ether, dissolves in this medium when the mixture is treated with carefully dried hydrogen chloride.Pure cobzLlt sulphate may be heated to 300’ without perceptible change, and does not alter at a temperature approaching 800’. Zinc chloride added to a solution of cobalt chloride prevents the development of the blue coloration on warming ;this action may be explained by assuming the formation of a double chloride which does not give rise to the dihydrate. The changes produced by mercuric chloride on an alcoholic solution of cobalt chloride are due to the formatioil of the double cobalt mercuric chloride (Clsudet’s salt), a substance which in the solid state is particularly sensitive to changes of temperature. If the blue solution observed by Donnan and Bassett during the electrolysis of cobalt chloride is due to the formation at the anode of a complex ion, it should be possible to separate and analyse solutions containing these ions and so determiue the ratio of cobalt to chlorine.The hypothesis that hydrated salts can exist in highly concen-trated solutions and can undergo dissociation on raising the tem- perature accounts precisely for the phenomena observed not only in the case of cobalt chloride but also in that of its iodide, bromide, and the salts of other metals. 50 29. "The action of ammonia and organic bases on ethyl esters of olefinedicarboxylic and olefine-p-ketocarboxylic acids." By 6. Ruhemann. Ethyl benzylidenemalonate condenses with benzamidine to form ethyl dihydro~i~~enylr~midonecarbox~Z~t~(m. p. lSSO) according to the equation : CHPh:C(CO,Et), +CPh(NH,):NH = CHPh<:%(--h>N +C,H,O.When this compound is treated with ammonia, the ring opens and then closes, with the loss of carbon dioxide and alcohol, forming di~ydrodiphenyl~yrimido~ze CH -CO(m. p. lSOO), CHPh<NH2, Cph>N, which is also formed by the action of behzamidine on ethyl benzylidene- acetcacetate in accordance with the following equation : CH,*CO*C(C!O,Et):CH Ph +CPh(NK,):NH +C2K60= COEt NHCH2<CH"ph--sH>CPh +CH,*CO, Et = CH,<~~p~~~>CPh+CH,*C'O,Et +C,H,O. In studying the action of ammonia on ethyl esters of olefine-P-keto-carboxylic acids, it was found that both ethyl ethylideneacetoacetate and ethyl f rirylideneacetoacetate are transformed by ammonia into ethyl hydrocollidinedicarboxylate and ethyl hydrofuryllutidinedicarb-oxylate respectively.The formation of these compounds depends on the previous decomposition of the ethyl olefine-P-ketocarboxylic ester into ethyl acetoacetate and the aldehyde animonias, which, in turn, condense to form the hydrogenised pyridine derivatives. Ethyl benzylideneacetoacetate, CH,*COC(CO,Et):CHPh, behaves differently towards ammonia and yields be7ixyZideneaminoacetone, CH,*CO*C(~H,):CH*C,H~(colourless needles, m. p. 125O). This substance, on heating with acids, readily loses benzaldehyde. On carefully warming the ketone with concentrated hydrochloric acid, an insoluble chloride is produced which may be regarded as diaceto- benzylideneimide hydrochloride, NH(Chc:CHPh),,HCl.30. ('Derivatives of 2)-aminoacetophenone." By F. D. Chattawag, In the course of a study of the transformation of diacetanilide into acoto-p-aminoace tophenone under the influence of hydrogen chloride or OF zinc chloride, the following compounds have been pre- pared. They are forimed by the ordinary processes, but in the pre- paration of the nitrogen-halogen derivatives great care must be taken 51 to avoid the liberation of free halogen, otherwise substitution in the ketonic chain occurs. pAcetyZchloroamiitoacetophenoi~e, O,H,Ac*NAcC'I, colourless, pearly plates, readily soluble in chloroform, m. p. 72'; pacetgZ-bromoaminoucetoplm~one, C,H, Ac*NAc Br, J ellow, rhom bic plntes, m. p. 83' ; p-popionylaminoacetophenone, C,H, Ac*NH*COEI.,colour-less prisms, m.p. 136' ; p-propi~n~Z~?~lor~~~~~ii~oc~c~~p~no~, C6H,Ac*N(C0Et)CI, colourless plates, m. p. 42O ; p-benzoykamino-cuetophenone, C6H,hc*NH*COPh,thin, colourless plates, m. p. 205' ; p-benxoyZcl..woaminocicetop?~none, C6H,Ac*N(COPh)C'l, colourless plates, m. p. 77'. On heating, the nitrogen-halogen derivatives undergo transforma- tion with considerable decomposition ; when dissolved and warmed in acetic acid, halogen passes from the nitrogen into the ortho-position in the nucleus, whilst, if free halogen is liberated, subqtitution in the methyl group of the ketone also takes place. ADDITIONS TO THE LIBRARY. II By Purchasr. Herzberg, Wilhelm. Papierprufung. Eine Anleituug zum Uuter-suchen von Papier.2nd ed. ill. Berlin 1902. Koenigsberger, Leo. Hermann von Helmholtz, VoL I. With 3 portraits, Braunschweig 1902. Vaubel, Wilhelm. Lehrbuch der theoretischen Chernie. Vol. I. Xaterie und Energie-Nolekul und Losung. Vol. 11. Zustands-Ynderungen und chemische Umsetzungen. ill. Berlin 1903. Borchers, William. Elektro-bfetallurgie. Die Gewinnung der Metalle unter Vermittluog des elektrischen Stromes. 3rd ed. Part I. ill. Leipzig 1902. Hober, Rudolf. Physiknlische Chemie der Zelle uncl der Gexebe. ill. Leipig 1902. Hofmann, Karl. Die radioactiven Stoffe nach dem gegenmiirtigen Stande der wissenschaftlichen Erkenntnis. Leipzig 1903. Zellner, Julius. Die kunstlichen Kohlen fur elektrotechnische und elektrochemische Zwecke, ihre Hers tellung und Ptiifung. ill.Berlin 1903. Naske, Carl. Die Portland-Cement-Fabrikation.Ein Handbuch fiir Ingenieure und Cementfabrikanten. ill. Leipzig 1903. 52 ANNIVERSARY DINNER, It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hot.el Rfdtropole, at 6.30 for 7 o’clock, on Wednesday, March Sfith, 1903 (t’he day fixed for the Annual General Meeting). The price of the tickets will be One Guinea each, including wine. All applications for tickets must be received not later than Wednesday, March 18th. Tickets will be forwarded to Fellows on receipt of a remittance for the number of tickets required, addressed to the Assistant Secretary, Chemical Society, Burlington House, W.ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the Election of Officers and other business mill be held on Wednesday, March 25th, atthalf past four o’clock in the afternoon. At the next meeting, on Thursday, March 5th, 1903, at 8 p.m., the following papers will be communicated : “The mechanism of the reduction of potassium dichromate by sulphurous acid.” By H. Bassett. ‘‘The constitution of pilocarpine. Part IV.“ By H. A. D. Jowett. ‘‘ Preparation and properties of 1:4-(or 1 :5)-dimethylglyoxaline, and 1 : 3-dimethylpyrazole.” By H. A. D. Jowett and C. E. Potter. “Some analyses of “Reh,” or the alkaline salts in Indian usar land.” By E. G. Hill. “Experiments on the synthesis of camphoric acid. Part 111. Synthesis of isolauronolic acid.” By W. H. Perkin, jun., and J,F. Thorpe.‘‘ Camphor-P-thiol.” By T. M. Lowry and G. C. Donington. ‘;Isomeric change of dibenzanilide into benzoyl-o-amino-and benzoyl-pamino-benzophenones.” By F. D. Chattaway. ‘(The rate of decomposition of diazo-compounds. Part 111. The temperature-coefficient.” By J. C. Cain and F. Nicoll. EICElARD CLAY ASD SONS, L1XII‘F.D LONUOP; AND BLlNOAY.
ISSN:0369-8718
DOI:10.1039/PL9031900043
出版商:RSC
年代:1903
数据来源: RSC
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