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Proceedings of the Chemical Society, Vol. 6, No. 79 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 79,
1890,
Page 29-34
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摘要:
Issued 12/3/1890 PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 79. Session 1889-90. Narch 6th, lS90. Dr. W. J. Russell, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Nessrs. Joseph Barker, 8, St. James’s Street, S.W. ; Charles Ridgeway Beck, 181, High Street, Burton-on-Trent ; David Corrie, Nobel’s Explosives Company, Polmont Station, N.B. ; Andrew Cowan Holbom, B.Sc., 10, West Garden Street, Glasgow ; Herman Lescher, 61, Egeyton Gardens, South Kensington ; Henry de Mosenthal, 220, Winchester House, Old Broad Street, E.C. ; James S. H. Walker, 304, Morning-side Road, Edinburgh. The followiiig were elected Fellows of the Society :-Frederic Alfred Anderson, B.Sc., Percival Babington, G. Russell Beardmore, M.D., Richard Berncastel, Bertram Blount, Robert Frederick Blake, Henry Herbert Bunting, William Burton, Paul Alexander Cobbold, *John Dennant, Frank Gossling, John Charles Jackson, John S.Lumsden, Alfred E. Macintyre, Frederick Mills, Ira Xoore, John Myles, Robert Ricliard Rothwell, Edward Sergeant, DL.l>., Basil Williain Valentin. The President announced that the senior Secretatry would attend the meeting to be held in Berlin on March the llth, to cclebmte the 2.5th anniversary of Professor KekulB’s benzene theory, and would pesent the following address from the Society :-“ The President amd Council of the Chemical Society, on behalf of British Chemists, desire to offer to Professor August Kekulk their warmest congratulations on the occasion of the Twenty-fifth An- niversary of the promulgation of his theory of the Constitution of Aromatic Compounds.'( The influence which the felicitous conception of Benzene as n closed chain has had on the development of chemical theory, the im- petus which it has imparted to the study of the intricate problems of isomerism among the derivatives of this and similar compounds, and the guidance which it has afforded in an industry of such magnitudr and importame as that of the Coal Tar Colours, is universally re-cognised; and it is with special pleasure that the countrymen of Faraday, the discoverer of Benzene, recount these benefits while paying honour to their author. " This theory found the chemistry of even the immediate derivatives of benzene an almost untilled field; it has transformed it into a fertile province, to which have been anncxed regions the very existence of which was unknown."May it long be permitted to you, Professor KekuG, whose work has been so full of suggestion and inspiration, to remain witness to the benefits which continue to flow from your fruitful generalisa- tion." The following papers were read :-16. " Some crystalline substances obtained from the fruits of rarious species of Citrus." By William A. Tilden, T).Sc., F.R.S., and Charles R. Beck. The authors have examined the solid matters which are deposited from freshly extracted oils of limes, lemons, and bergamot made by hand. The substance from oil of limes (C. Zhnettn), after purification by repeated crystallisations from alcohol contaiiiing a little potash, forms small, pale-yellow needles, united in tufts, which melt at 121-122'.It is proposed to name this substance Zimettin. It is neither an acid nor a glucoside. It is not acted on by acetyl chloride or by phenylhydrazine. Analysis leads to the formula C16H1406. When submitted to the action of bromine it affords a tribrorno-derivative, C16H11B~g06,which crystallises in colourless scales. When boiled with a concentrated solution of soda limet bin loses an acetyl-group, yielding a substance very similar to itself in appearance and pro-perties, C14Hll(OH)Oa. When fused with potash it yields phloroglucol and acetic and formic acids. Essence of lemon yields a substance similar to limettin in appear- ance, though the crystals are more lustrous and melt at 116".Con-cordant analyses lead to the formula CIIHlAO6,which contains 2C less than the formula of limettin. Be~gamot yields a crystalline compound differing from both the preceding. It forms colourless, distinct prisms melting at 270-2171'. 31 The examination of this substance will be continued when a supply of material has been obtained. These substances are entirely distinct from the compounds which, under the names of aurantiin, hesperidin, limonin, have been obtained by other chemists from various fruits of the orange and lemon tribe. The two former of these are glucosides. Hesperidin has been shown to be a derivative of phloroglucol, and in its origin is probably connected with the siibstance described under the name limettin in this paper.17. " Reduction of a-diketones." By Francis R. Japp, F.R.S., and Felix Klingemann, Ph.D. Benzil was boiled for a few minutes with fuming iodhydric acid, and after removal of the iodine the product was distilled under re- duced pressure : an excellent yield of deoaybenzo&z was obtained. Phenanthraquinone, subjected to the same treatment, yielded the so-called phenanthrone, which Lachowicz, who prepared this compound by the reduction of dichlorphenanthrone (from phenanthraquinone and phosphorus pentachloride), regarded as the deoxybenzo'in of phen-Q,iH*y0anthraquinone, CJL*CH, ' the aiithors, however, conclude that it is a phenol, viz., ?6H4'fi(oH), as it is not acted on by phenylhydrazine,CCH,.CH and when heated with acetic anhydride forms an acetyl-derivative (m.p. 76-77'). When Lustgartea's test for @naphthol (shaking the solution in caustic potash with chloroform) is applied to it, like P-napthol, it affords a strong Prussisn blue coloration, the colouring matter separating in blue needles with a coppery lustre. This inter- action is to be further studied. By boiling phenanthraquinone with acetic acid, to which a small quantity of strong iodhydric acid together with some amorphous phos- phorus had been added, ~rLonacety~henanthraquilzol, Ci,H,( 0H) (0CJ&O), was Obtained, identical with the compound prepared by Klinger (Annalen, 249, 138) by the direct interaction of aldehyde and phen- anthraquinone in sunlight.By distilling acetylphenanthraquinol under reduced pressure, two compounds were obtained : a substance which distilled over, and which crystallised from benzene in red plates, melting at 155",giving on analysis, C, 84.0, H, 4.7 per cent. ; and a second substance, which sublimed into the neck of the flask, condensing in the form of needles, melting at 295-297", and giving figures agreeing with the formula C2sH160. The authors obtained a compound which they believe to be identical with this by heating acetylphenanthraquinol with concen-trated chlorhydric acid at 200-210" ; it is possibly tetraphenyzene-furfzcram, 96H,'g-c'cI I I H'; the last-mentioned mode of formation being CGH,*C CwCGH, \/0 analogous to that in which lepiden (tetraphen-ylfurfuran) is obtained from benzoin. 18."Studies on isomeric change, No. TV. Halogen-derivatives of quinone (first notice)." By Arthur R. Ling. The experiments of Hantzsch and of Nietzki have proved, in opposition to those of Levy, that the " anilic '' acids are paradi- hydroxy-derivatives, and Hantzsch and Schniter have shown that an isomeric change occurs when paradichloroquinone is brominated, the product being metadichlorometadibromoquinone. The author has made several attempts to prepare paradichlorodibromoquinone, but hitherto unsuccessfully ; in so doing he has obtained results which confirm Hantzsch and Schniter's conclusion. Metadichlorodibromoquinone is formed on brominating paradi- chloroquinone or diacetylparadichloroquinol in acetic acid solution, also by the chlorination of paradibromoquinone, t8heisomeric change apparently occurring in the first and last mentioned cases at the ordinary temperature.By brominating diacetylparaciichloroquinol dissolved in carbon tetrachloride in the presence of a trace of iodine, a diacetpldichlorobroroquinol has been obtained, which melts at 260-270" ; this may, however, be a mixture of isomerides. Metadichlorobromoquinone is obtained by brominating metadi-chloroquinone, and also together with the paradichloro-derivative by brominating paradichloroquinone. It forms yellow plates which do not show a sharp melting point (175-180") ; it is sparingly soluble in cold alcohol, easily in boiling.On treatment with potash it yields chlorbromanilic acid. The quinol formed by reducing it with sul- phurous acid separates from chloroform in white needles melting at 133",sparingly soluble in cold water or in chloroform but easily in the boiling liquids. On acetylation it yields a diacetyl-derivative which crystallises from alcohol in white needles melting at 174-180". Paradichlorobromoquinone is formed together with its isomeride on brominating paradichloroquinone. It is somewhat more soluble in the ordinary solvents than its isomeride, and melts at 158-159". On treatment with potash it.yields chloranilic acid. Paradichlorobromoquinol crystallises from water in long, trans-parent, monohydrated needles which melt at 124-126" ; they easily 33 lose their water, becoining opaque, and then melt at 132-135@ Recrystallised from chloroform, the substance melts at 135.5": it possesses about the same solubility in all the solvents tried as its isomeride.Hence ihe two cannot be separated by crystallisation. On acetylatjon it yields an acetyl-derivative, which crystallises in silky needles melting at 158-159", sparingly soluble in cold dilnte nlcohol, but easily in boiling. When paradichlorobromoquinone is brominated at the ordinary temperature, a product is obtained which may perhaps contain para- dichlorodibromoquinone, since on treatment with potash it affords a mixture of chlorobromanilic and bromanilic acids. In this way the author hopes to succeed in isolating paradichlorodibromoquinone.19. "Note on a phenylic salt of pheriylthiocarbamic acid." By Augustus E. Dixon, M.D. When heated together in equimolecular proportions at lM-150°, phenol and phenylthiocarbamide int'eract forming phenylic phenyl-thiocarbamide, NHPhGSOPh, but the yield is very small; this salt forms octahedral crystals resembling sulphur in appearance, melting at 150". 20. " Contributions to the chemistry of thiocarbamides. Inter-action of benzyl chloride and of allyl bromide with thiocarbamide, phenyl- and diphenylthiocarbamides." By Emil A. Werner. An account is given of the first part of an investigation of the action of benzyl chloride and allyl bromide on thiocarbamide and its different phenylated homologues.After reviewing the results already obtained by Claw, Bernthsen and Klinger, and Will and Rathke in the same direction, the following compounds are described :-C6HloN2S*HCl,m. p. 174",and the base C,H,,N,S, m. p. 88", from benzyl chloride and thiocarbamide. C,,H,~N,S.HCl, m. p. 112",and the base C14H14N2S,m. p. 81-82", from benzyl chloride and phenylthiocarbarnide. C,,H,,N,S*HCI, m. p. 152-153", and the base C20H,,N2S,a viscid liquid, from benzyl chloride and diphenylthiocarbamide. C4H8N2S*HBr,m. p. 84",from allyl bromide and thiocarbamide ; the base could not be isolat>ed in a pure state. CIoH,&,S.HBr, a viscid liquid, from allyl bromide and phenyl thiocarbamide; the base forms a syrupy fluid which is rery unstable.m. p. 170-171", and the base CI6Hl6NZS, C16H16N2S*HBr7 m. p. 57", from allyl bromide and diphenyl thiocarbxmide. 34 The decomposition of the bases by dilute sulphuric acid at 170" (Will's reaction) is studied, and it is shown that the primary thio- carbamide-derivatives behare in a different manner to the homo-logues. Characteristic mercuro-chlorides possessing somewhat similar pro-perties have been obtained from the several compounds: the corn- pound C8H,,N2S*HC1*HgCl2 may be taken as an example ; it melts at 112",and at 136"decomposes with loss of a molecular proportion of HC1 and simultaneoiis alteration in the position of the alkyl-group (benzyl) . The sulphates and picrates of the bases are described, and in the case of the compound C4H8N2S*HBr, from C3H,Br and CSNzH4,a chromium alum has been obtained, (C4H,NZS)$rz(S0,),.24H20.Benzyl thiocarbamate (CONH2*SC7H7)and bcnzyl phenylthio- carbamate (CONHCsH5*8C7H7)were incidentally prepared : both compounds combine with two molecular proportions of AgNO, ; the resulting products are immediat,ely decomposed by ammonia in accordance with the equation : NH2-CO*S*C7H7+BAgNO, + 2NH3 = CO(NH2)Z + AgSCTH, + AgN03 + NHANO,. ANNIVERSARY MEETING. The anniversary meeting will be held at Four o'clock in the After- noon of Thursday, March 27th next. It is arranged that, in the evening of the same day, the Fellows and their friends will dine together at the Whitehall Rooms, Hbtel M8tropole (entrance in Whitehall Place).Dinner will be on the table at seven for half-past seven o'clock. Fellows intending to be present are particularly requested to giye notice by means of the post-card which they have received for the purpose not later than Saturday, March 22nd. Price of dinner, including wine, One Guinea. It is proposed to hold a special meet'ing of the Society on Thursday, May 8th, for the exhibition of new interesting apparatus or specimens. Fellows who desire to exhibit objects are requested to communicate with the Secretaries. At the next meeting, on March 20th, Professor Judd, F.R.S., will deliver a lecture on the evidence aforded by petrographical research of the occurrence of chemical change under great presswes. HARBlSON ANY SONS, PRINTERS IN ORDIBARY TO HER MAJESTY, BT. 36AETIN'S LANE.
ISSN:0369-8718
DOI:10.1039/PL8900600029
出版商:RSC
年代:1890
数据来源: RSC
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