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Proceedings of the Chemical Society, Vol. 18, No. 257 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 257,
1902,
Page 235-242
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摘要:
fssueti 9/12/02 PROCEED IN G 8 OF THR CHEMICAL SOCIETY. Vol. 18. No. 257. Thursday, December 4th, 2902. Dr. W. H. PERKIN,F.R.S., Vice-president, in the Chair, Mr, J. H. Ryffel was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. : Cousins, Francis George, Queen's Road, London, N. Elford, Archibald Sefton, B.A., 9, Keble Road, Oxford. Huyin, Moung Tha, B.A., 18, Mercers Road, London, N. Kemp-Welch, Maurice, Parkst one, Wey bridge, Surrey. Sibley, Samuel Edward, 3, Rutland Road, Ilford. Turner, Duncan, Elmbank, Broomhouse, near Glasgow. 236 A ballot for the election of Fellows was held, when the following were declared duly elected :-John Frederick Alder. 1)ouglas A. XacCallnni. Alfred Edward Beanes.Williain Mann, B. Sc. Herbert Blair. Juhn Marsh. John A. H. Brincker, B.A., N.B. Joseph William Mellor, D. Sc. Vernon Seymour Bryant, B. A. John Price Millington, R. A., R. Sc. Thomas Burnell Carmichael. Reni Madhav Mnkerjee. Charles Cockle. John Phelps, B.A. James Justinian Drought. Richard Piibratn, Ph. D. A.Edgar Leeder Edlin, B. A. Guy Dnnstan Ricketts, &I. Sidney Robert Edminson, B.Sc. George Archibald Park Ross, 31.13. Walter Henry Edwards. John Williain Sampson. George Felix Dudbridge Green. Duncan Simpson. Wilfrid Russell Grimwade, B. Sc., Robert Walter Sindall. Edward Gumersall. Leonard Smith. David Vincent Hollingworth. John Seabury Smythe, B.Sc., Ph.D. Alfred Holt, jun., R. A. Edgar Stansfield, B.Sc.Arthur Francis Hoskiug. Walter F. Sutlierst, Ph.D. Clements F. V. Jackson. George Sutherlaiiti Thornson. Douglas Kennedy Jardine, B.Sc. Henry Letheby Tidy, B.A. John Petty Leather. Thomas Edward Wallis, R. Sc. Prank Austin Lidbury, 31. Sc. William Carter White. Ernest Liotard. Lyndoii Wilson. Thomas Stratford Logan. Of the following papers, those marked * were read : “173. “The specific heats of liquids.” By H. Crompton. It is assumed that when heat is applied to a liquid, if there is no change in its molecular composition, (1) there is an increase in the kinetic energy of the molecules, (2) internal work is done within each molecule, (3) there is a diminution in the attraction of the molecules for one another, (4)some external work is done.The last quantity is neglected in considering the specific heat, and the first and second changes are taken to have the same effect on the specific heat of the liquid and on that of its vapour, so that together they make up the specific heat at constant volume of the vapmr. At any absolute temperature T,the molecular heat at constant volume of the vapour C, = 2.96 + 0~0002!45~~v~2’1og.rt,where n is the number of atoms in the molecule, and Mvb is the molecular volume of hhe liquid at the boiling point. The molecular attraction is regarded as measured by the difference between the latent heat of condensa- tion of the vapour and the heat evolved on simply compressing the vapour into the volume of the liquid without causing a change of 237 state.This attraction is assumed to become zero at the critical temperature and to increase regularly with the fall in temperature from the critical point downwards. At the absolute temperature T, the change in the attraction is therefore dA/dT= (L-RZ~logVo/~,)/(Tk-T), in which L is the latent heat of condensation, R the constant of the gas equation, &, and oo the volumes of the vapour and liquid respec- tively, and 7j,the absolute critical temperature. It follows from the above that the molecular heat of the liquid is Cf=C, + dA/dT, and the author showed that the molecular heats of liquids thus calculated agree fairly with those observed, except where molecular association occurs in the liquid. *174.6L The constitution of enolic benzoylcamphor," By 116. 0. Forster. From the production of camphorquinone by oxidising benzoyl- camphor with chromic acid and with mercuric acetate, it is concluded that the enolic modification of benzoylcamphor has the constitution C,H,,<boC:CC1 C,H, ? obtained fromPhenylchlorometl~ylenecc~~p~or? enolic benzoylcamphor and phosphorus pentachloride, melts at 100' and its rotation [ = -217" ; the alcoholic solution gives no colora-tion with ferric chloride. Aniline converts it into aniZi.lzophelzyZ-rnethylenecamphor and,C29H30N2,sulphur-yellow plates m. p. 117-1 18'; the acetyl derivative, C,,H,,ON,, melts at 166". When phenylchloromethylenecamphor is heated with alcoholic ammonia in sealed tubes at 150-170°, a base having the formula C17H,,0N is produced.This melts at 170°, its rotation [ = + 180.2' ; it gives an intense blue coloration with ethereal ferric chloride ; the picrate melts at 157O and the benzoyl derivative at 99-100'. On heating enolic benzoylcamphor with ammonium formate in sealed tubes at 200-220', another base, also having the formula C17H,,0N, is formed. It melts at 118-119°, its rotation [aJD= + 235.2' : it gives no colour with ferric chloride; it does not combine with benz- aldehyde or benzoyl chloride, but yields apicrate which does not melt at 250', and a bromo-derivative, C17H2,,0NBr5,orange-red plates, m, p. 173". Enolic benzoylcamphor is reduced in alkaline solution by sodium amalgam, yielding benzylidenecamphor and benzylcamphor.Potassium permanganate oxidises it to a mixture of benzoic and camghoric acids, 238 whilst potassium ferricyanide gives rise to a compound having the formula C,,H,80, and m. p. %lo,its rotation [a],= + 270*4° ;it does not react with ferric chloride, and is insoluble in alkalis, *175. Isomeric benzoyl derivatives from isonitrosocamphor.” LL By M. 0. Forster. When isonitrosocamphor is treated with benzoyl chloride in presence of sodium hydroxide, two compounds are produced each having the empirical formula CI7Hl9O,N. The cornpound from which isonitrosocamphor can be regenerated by hydrolysis, crystallises from alcohol in large, yellow prisms melting at 105-106’; it is readily soluble in petroleum, and its rotation[.ID = + 145.6O in cbloroform, The isonitrosocamphor obtained from this derivative has the rotation [.ID = +221*9O, and yields the two new substances on benzoylation.The compound which accompanies the above-mentioned derivative, although isomeric with it, does not give rise to isonitrosocamphor on hydrolysis ;it is scarcely soluble in petroleum, and crystallises from alcohol in colourless, lustrous lamime melting at 136’ and its rotation [a],= + 126.9’ in chloroform. Alcoholic potash resolves it into a mixture of benzoic and cyanolauronic (a-camphornitrilic) acids. *176. (LAction of phosphorus haloids on dihydroresorcins. Part I. Dimethyldihydroresorcin.” By A. W.Crossley and H,R.Le Sueur. Phosphorus trichloride react,s with dimethyldihydroresorcin, giving 5-chZoro-3-keto-1:1-dimethyZ-A4- tetru?ydi*obenxene, Cl\le2<CH,.cclCH,-Co>CH, 1 a colourless liquid boiling at 109O (14 mm.), and also small quantities of an anhydride of diniethyldihydroresorcin, (C,H,,O),O, melting at 99~5~. Phosphorus oxychloride gives the same chloroketone, and phosphorus tribromide the corresponding bromo-compound, C,HI10Br, which boils at 129O (25 mm.). When phosphorus pentachloride acts on dimethyldihydroresorcin, 3 :5-dichloro-1 : I-dimethyl-A2‘ ‘-dihydrobenzene (Trans., 1902, 81, S26) and 3 :5-dichloro o-xylene (Trans., 1902, 81, 1533) are obtained. By the action of phosphorus pentabromide on dimethyldihydro-resorcin, bromodimethyldihydroresorcin is first formed, and the pro-ducts of the action of the phosphorus bromides on this compound have been investigated.With phosphorus tribromide there is obtained a mixture of mono- and di-bromoketodirnethyZt&w,?qdrobenxene, the latter, 239 having tho formula C,H,,0Br2, melts at 96"; and a liquid which on treatment with bromine is converted into a tribromoxybenol which melts at 176-1775". By the further action of bromine the above dibrornoketone is converted into tri-and tetra-bromoketodinzethyl-tetrahydrobenxeae, which melt respectively at 106' and 11s". These latter substances are also produced by the action of phosphorus pent:r- bromide on bromodimethyldihydroresorcin. The action of phosphorus pentabromide on dimethyldihydroresorcin is one which is largely influenced by the conditions under which the experiments are carried out.The following products of the reaction have been isolated : bromodimetbyldihydroresorcin, tribromoketotetra-hpdrobenzene, a bromoxyleiaol, C,H90Br, melting at 83*5--54O, a di-byomoxylenol nielting at 96.5', and two tribronioxylenols melting at 176-1 77.5" and 182-183" respectively. 177. The absorption spectra of metallic nitrates. Part 11." By W. N. Hartley, D.Sc., F.R.S. The substances examined were aqueous solutions of the nitrates of fifteen metals, and of nitric, sulphuric, and !hydrochloric acids, and alcoholic solutions of ethyl and lithium nitrates. Metals which exhibit characteristic absorption bands show varia- tions in the positions and intensities of these bands which appear to be dependent upon the molecular weights of the salts in solution.Equivalent quantities of csrtain metals exhibit the same absorption spectra whether in strong or dilute solution, and, in certain cases, through a great range in dilution. A dilute solution of silver nitrate transmits a longer range of spectrum than a strong solution containing the same quantity of sdt. The effect of dilution on nitric acid of sp. gr. 1.42 is the reverse of that observed in the case of silver nitrate. There is a remarkable difference between the constitution of ethyl nitrate on the one hand (whether undiluted or in dilute alcoholic solu- tion), and that of solutions equally dilute of inorganic nitrates on the other. The effect of raising the temperature of the solutions is simply to intensify the absorption spectrum as if a stronger solution at a lower temperature had been used.Although evidence of what may be regarded as ionic dissociation is afforded by the spectra of dilute solutions of the inorganic nitrates, yet the spectra themselves are not alike, as they would be if the salts were completely resolved into NO, and metallic ions ; the evidence is just as favourable to the view that some of the salts are resolved into nitric acid and the corresponding base. In the case of esters, like ethyl nitrate, the conditions are entirely different, as the molecule is clearly not dissociated, there being no evidence of the -NO, group in the compound. Views in explanation of the facts observed were put forward.178. “The constitution of the products of nitration of meta-acetoluidide.” By J. B. Cohen and H. D. Dakin. The authors show that the nitro-derivative of nz-acetoluidide obtained by Beilstein and Kuhlberg (Annalen, 1871, 158, 348) contains the nitro-group in the para-position with respect to the amido-group, and not in the ortho-position as stated by Limpricht (Bei-., 1885, 18,403). The substance was successively converted into 2-chloro-6-nitrotoluene and 3-chloro-4 :6-dinitrotoluene. By fractional crystallisation from alcohol of the products of nitration, a nitro-derivative which had hitherto escaped observation mas separated, which proved to be 4-nitro-3-acetylaminotoluene. On hydrolysis it gave a base identical with the 4-nitro-3-aminotoluene obtained by Staedel and Kolb (Anncden, 1890, 259, 224) by the action of ammonia on 4-nitro-nt-cresol ethyl ether.179. (( The action of metallic thiocyanates upon carbonyl chloride.” By A. E. Dixon. When carbonyl chloride dissolved in toluene is allowed to stand in contact with excess of finely divided sodium, potassium, barium, mercury, or lead thiocyanate, interaction gradually occurs with forma- tion of metallic chloride, and a substance possessing the general chemi- cal characters of a thiocarbimide, but giving, under certain conditions, the reactions of a thiocyanate. It has recently been pointed out by the author that tautomerism of this kind often occurs among the so- called ‘‘ thiocyanates ’’ of electro-negative radicles (Trans., 1901, 79, 541).The interaction may be represented thus : COC1, + Pb(SCN), = PbCI, + CO(NCS),, but it does not take place quantitatively, isopersul- phocyanic acid and pseudo-sulphocyanogen and occasionally other products being formed. Heating to about 100” greatly accelerates the change, but even after thirty hours not more than one-third of the carbonyl chloride employed is converted into thiocarbimide, and much remains unchanged. Hitherto, all attempts to isolate carbonyldithiocarbimide in a pure state have failed, but its solution interacts with alcohol and with nitrogenous bases, yielding additive products. Only one molecule of ethyl alcohol could be caused to unite with one of dithiocarbimide ; the resultant hemi-thiourethane, SCN*CO*NH*CS*OEt, 241 was obtained in pale yellow prisms melting at 141-142'.It is insolu-ble in cold water, but decomposes when heated with water to near the boiling point, carbon dioxide and thiocyanic acid being formed. By combination with aniline, compounds having either the formula SCN*CO*NH*CS*NHPhor CO(NH*CS*NHPh),,can be obtained, according to the conditions. The former, carbonyEtiLiocarbimidophenyl-thiocarbarnide, crystallises from alcohol in brilliant, pearly leaflets which melt at 172O, then quickly resolidify, and now melt at 223'. It is insoluble in cold water, but gradually dissolves on boiling, becoming hydrolysed, carbon dioxide being evolved, whilst thiocyanic acid and phenylthiourea remain dissolved : SCN*CO*NH*CS*NHPh+H20= CO, +HSCN +CSN,H,Ph.Carbonyldiphenyldithioccwbarnide, CO(NH*CS*NHPh),, separates from alcohol in vitreous prisms which melt at 166' and are insoluble in boiling water, Both phenylated derivatives, as well as the hemi-thiourethane, are readily desulphurised by silver salts and by an alkaline lead solution. Attempts to produce hsrni-or complete thiourethanes by adding carbonyl chloride to potassium or barium thiocyanate in alcoholic soIution were unsuccessful ; the chloride first interacted with the alcohol, yielding ethyl chlorocarbonate, which, with the metallic thiocyanate, gave carboxycthylthiocarbimide, and this latter, combin- ing with another portion of the alcohol, formed finally Doran's carb-oxyethylthiourethane (Tram., 1896: 69, 334) or diethyl iminothio-dicarbonate, EtO* CO*NH*CS*OEt, The following compounds were also described : Cccrbonylthiocarbimidoparatolylthiocarbamide, SCN*CO.NH-CS*NH*C,H,.-Pearly leaflets melting at 182O, resolidifying at once, and now molt- ing at 237'. In general properties, this and the naphthyl compound mentioned below closely resemble the phenyl homologue. Caybonyl-di-o-tolyldithiocctrbamide, ~O(~H*CS*NH*C,H?),.-M.p. 172' has properties similar to those of the corresponding diphenyl compound. Carbonylthiocai~bimiclo-a-nap~~tl~ylt~iocarbarnide, SCIN*CO*NH.CS*NH*C,,H?, is a yellowish powder, m. p. 182O, resolidifying at once and then melt- ing at 222'. Carbonylthiocarbimido~l~~~y~b~n~ylthiocarbamide, SCN*CO*NH*CS*NPhBz. -Prepared from benzylaniline, it formed long, vitreous prisms having a faint yellow tinge, and melting with effervescence at 180O.When boiled with water it slowly undergoes hydrolysis, carbonic anhydride being evolved, thiocyanic acid passing into solution, and aa-phenylbenzylthiourea,NH,*CS*NPhBz, being left, 242 LIBRARY CATALOGUE. The Library Catalogue will be ready for issue in the course of a few days, price 2s. 6d., post free to Fellows. Remittances should be made to the Assistant Secretary, Chemical Society, Burlington House. At the next ordinary meeting, on Wednesday, December 17th, at 5.30 p.m,, the following papers will be communicated. “A reagent for the detection of carbamide and of certain other nitrogen compounds.” By H. J. H. Fenton. ‘‘The rate of decomposition of diazo-compounds. Part. 11. Diazo-compounds of the naphthalene series.” By J. C. Gain and F. Nicoll. “The state of carbon dioxide in aqueous solution.” By J. Walker. “The qualitative separation of arsenic, antimony and tin.” By J. Walker. “The hydrates and the solubility of barium acetate.” By J. Walker and W. A. Fyffe. 6‘ cis-and trans-ap-Dimethylglutaric acid and the separation of the cis-and trans-forms of substituted glutaric acids.” By J. F. Thorp0 and W. J.Young. RlCLIAttD OLAY AND UQNS, LIYIIED, LONDON AND BUNG*\
ISSN:0369-8718
DOI:10.1039/PL9021800235
出版商:RSC
年代:1902
数据来源: RSC
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