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Proceedings of the Chemical Society, Vol. 13, No. 185 |
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Proceedings of the Chemical Society, London,
Volume 13,
Issue 185,
1897,
Page 231-234
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摘要:
IBsued 11/12/1897. PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY TBE ISI'ECRETARIEX. No. 185. Session 1897-8. December 2nd, 1897. Professor Dewar, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. Charles Edward Brittain, B.Sc., 11, Highfield, Scarborough ; William Arthur Caldecott, B.A., Box 1891, Johannesburg, S.A.R. ;John Cooper, B.Sc., 20, Derwentwater Road, Gateshead ;Frederick Cowling, Clay Cross, near Chesterfield ; Wilbraham T. A. Edwards, Reduit, Mauritius ; Frederick Gilderdale, 3, Havelock Street, Newcastle ; William Setten Gilles, Coniston, Cedars Road, Beckenham ; William Hobson 1slills, B.A., Jesus College, Cambridge ; Frank Forster Renwick, Glengall, Woodford Green, Essex ; William Colebrook Reynolds, 64, Lydford Road, Paddington, W.;Andrew Jamieson Walker, B.A, Kilycadden, Killygordon, Co. Donegal ; Ernest Charles M'eismuller, 30, Pepys Road S., New Cross, S.E. The following were duly elected Fellows of the Society :-John Ball, 'Ph.D. ; William Ball ; Alec. Alfred Beadle ; Richard Oxley Burland, J.Y. ; Alexander McLean Cameron ; Alexander Clarkson ; Frank Collingridge, B.Sc. ; James Murray Crofts, B.A. ; John Daniel1 ; Andrew James Dixon, F.I.C.; Oscar Guttmnnn, F.I.C. ; Robert Hamilton ; John Harger, B.Sc., Ph.D. ; James Walter Horseman; Charles Kelly; Tom Lemmey, B.A. ; James Scott Maclaurin, D.Sc. ;Alan Macmullen, B.A. ; Charles Jodrell Mansford, B.A. ; Edward Masters ; John A. Mathews, MA., 1M.Sc. ; Philip George Gregory Moon ;James Charles Philip, B.Sc., Ph.D.;Alexander Eerguson Reid ; Ernest Henry Roberts ; Edward Sydney Simpson, B.E. ; Robert Francis Wood Smith ; Thomas Southern, Junr. ; Frederick William Steel ;Michael Edmund Stephens ;George Xtubbs ; Edward Howard Tripp, Ph.D. ; John Scriven Turner ; Framjee Khurshedjee Viccajee ; Percy John Vinter, MA. ; Arthur James While ;Francis Samuel Young, M.A. 2 32 The PRESIDENTcalled the attention of Fellows to the fact that, although according to the Council regulations no paper could be an- nounced which had not been received, it was open to any Fellow to make a communication at a meeting of the Society in the event of there being available time, provided that he handed a written state- ment to the Secretaries of the essence of his communication.In answer to a question from Dr. HAKE, said that the PRESIDENT the appearance of such communications in the Proceedings would be subject to the editorial discretion of the Secretaries, and that when presented as full papers they would come before the Publication Com- mittee in the usual way. The following papers were read :-"124. " The representation of the isomeric benzene hexachlorides by Collie's space-formula." By Francis Edward Matthews, Ph.D. This paper discusses Collie's space-formula for benzene from the point of view of the halogen hex-addition compounds. The formula is shown to explain the existence of two isomeric hexachlorides satis- factorily, and the following formulze are proposed for these com-pounds :-Icx I4 a-Compound.8-Compound. These formule likewise explain the differences in stability towards alcoholic alkalis. The a-substance, containing the chlorine in the ortho-position to, and on the same side of the carbon nucleus as the hydrogen-atoms with which it is :,removed in the form of hydrogen chloride, is readily decomposed ; the P-substance, in which the hydrogen and chlorine are on opposite sides of the nucleus, has much greater stability, The remainder of the paper discusses the formation of benzene di-derivatives from mono-derivatives, and it is maintained that their formation is best explained by assuming the previous forms- tion of unstable oi*tho-addition-compounds instead of unstable meta-compounds, as Collie has suggested.DISCUSS~ON. Dr. WYNNEasked whether any explanation could .be given of the formation of 1 : 2 : 4-trichlorbenzene from the benzene hexachlorides by the action of alcoholic potash. The usually accepted formulze for benzene gave no clue to the reason for the production of unsymmetri- cal derivatives in such cases, and he was unable to see that the formuh now proposed mere more satisfactory in this respect. Dr. LAPwoRTrr pointed out that the author’s statement as to the impossibility of explaining the production of two different hexachlorides from benzene by means of any formula prior to Collie’s, appeared to need qualification. It is easily seen that Kekulh’s formula represents several stereoisomeric substances, as each ‘‘ doubly bound ” pair of carbon atoms may form a fumaroid or maleoid combination.Taking into consideration the circumstance that, for a number of reasons, the formula must be considered as a labile one, the positioiis of the ethylenic ancl single linkings being supposed to alternate, it is not impossible that, under the conditions of interaction of chlorine and benzene, the latter may react in the form of two or more of it,s possi- ble dereoisomers. The addition of chlorine to a pair of carbon atoms doiible bound as in funiaroid compounds would, of course, afford :L trans-clichloro-derivative, whilst a cis-dichloro-compoiuid would result if the original combination were of the maleoid type. Kekulk’s formula therefore, woulcl appear to afford a perfectly satisfactory explanation of the production of more than one benzene hexachloride.Mr. E. J. PARRYasked if Dr. Matthews had any experimental evidence for assigning the symmetrical formula to the a-hexachloride, ancl the nnsymmetrical to the P-compound. If the explanations of subst8it,ution offered by Collie and the author were correct, there should certainly be twice as much ortho- as para-dichlorbenzene pro- duced when chlorbenzene is chlorinated. Further, he coulcl not understand why, if these explanations were correct, the nitratioii of chlorbenzene should give ortho-and para-compounds whilst the chlorination of nitrobenzene, or the nitration of nitrobenzene, should yield me ta-compounds.Dr. MATTHEJVS,in reply, stated that it had always seemed to him a remarkable fact that 1: 2 :4-trichlorbenzene alone was produced by the action of alkalis upon the benzene hexachlorides. He had made several attempts with large quantities of material to isolate the syni-metrical modification, but always without result. The formation of the 1:2 :4-compound could, however, be easily explained, either by Kekulh’s or Collie’s formula. With regard to Dr. Lapworth’s remarks, the formulz. proposed above accmnt for the production of two and not of a greater number of isomerides which might be expected if these hexachloricles were regarded as cis-and trans-modifications ; whilst certain properties of the com- pounds do not seem to harmonise with the idea that they are stereoisomerides. The anbwer to Mr.Parry’s questions are contained in the paper itself, the difference in stability of the two hexachlorides towards alkalis is explained by assuming that hydrogen chloride is more redly removed from atoms in the ortho-position and on the same side of the carbon nucleus than from those in which these conditions do not obtain. Hence the above formuh. were assigned. “125. ‘‘Compounds of piperidine with phenols.” By Otto Bosenheim, Ph.D., and Philip Schidrowitz, Ph.D. With a view of obtaining substances of the general formula (CGH~G-,))(C,H~~:N),,which seemed to be of interest on account of their relation to the phenylenediamines and polyamines, the authors studied the action of piperidine on phenols and their derivatives in the presence of dehydrating agents.Although so far unsuccessful in this direction, a series of addition products in the nature of salts was observed, in which piperidine acts as the base, and the phenol as the acid. They are well crystallised compounds, easily obtained by the interaction of their components, usually in ethereal solution. They are resolved into their constituents by strong acid or alkalis. M. Oechsner de Coninck (C. R.,1897, 124, 563) describes a number of colour reactions obtained by the action of piperidine and other bases on phenols in dilute aqueous solution, but has apparently not observed the formation of the addition compounds described in the paper. The influence of the number and position of the oxy-and nitro- groups in the phenols on the additive capacity of the piperidine mole- cule was studied, but no general rule could be deduced.The following compounds were analysed, and are describeJ in the paper : Compounds of piperidine (1mol.) with pyrocatechol (2 mols.), guaiacol (2 mols.), ;hydroquinone (1 mol.), pyrogallol (1 mol.), vanil- lin (1 mol.), 0-and pdrophenol (1 mol.), picric acid (1 mol.), 1 :2 :4-dinitronaphthol (1 mol.). Phenol, p-chlorphenol, resorcinol, phloroglucinol, m-nitrophenol, and a-and p-naphthol did not furnish crystalline compounds. KEKULE MEMORIAL LECTURE. The Kekuld Memorial Lecture will be delivered by Professor F. R. Japp, LL.D., F.R.S., at an extra meeting of the Society on Wednesday, December 15th, at 8.30 p.m. At the next meeting, on December 16th, the following papers will be read. The authors of those marked with an asterisk have announced their intention of being present. * ‘‘Stereochemistry of unsaturated compounds. Part I. Esteri-fication of substituted acrylic acids.” By J. J. Sudborough, Ph.D., D.Sc., and Lorenzo L. Lloyd.* ‘’ Formation and hydrolysis of esters.” By J. J. Sudborough, Ph.D., D.Sc., and Martin E. Feilmann, B.Sc. * “A new method of determining freezing points in very dilute solution.” By M. Wilderman, Ph.D. RICHARD CLAY AND SONS, LIMITED, LONnON AND BUNCAY.
ISSN:0369-8718
DOI:10.1039/PL8971300231
出版商:RSC
年代:1897
数据来源: RSC
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