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Proceedings of the Chemical Society, Vol. 7, No. 93 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 93,
1891,
Page 23-28
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摘要:
Issued 4/3/1891 PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 93. Session 1890-31. February 19th, 1891. Dr. W. J. Russell, F.R.S., President, in the Chair. Certificates mere read for the first time in favour of Messrs. Walter Johnson Cooper, High Street, Mitcheldean, Gloucester ; Charles F. Forshaw, LL.D., D.Sc., Bmclford, Yorks ; Jolun Alfred Fostei., Royal Naval College, Greenwich ; Claude Hooper Baker, 4,Westbxiik Terrace, Gibson Street, Hillhead, Glasgow ; William L. Hiepe, Ph.D., 21, Acornl, Street, Manchester ; F. Stanley Kipping, Ph.D., D.Sc., 7, Milboriie Grove, South Kensington ; Charles hinsworth Mitchell, 27, Farnley Road, South Norwood ; Percy Morrice Randall, 3, Belsize Park Gardens. Messrs. Hollaiid Crompton, R. H. Davies and Bernard Dyer were appointed by the meeting to audit the Treasnre1”s accounts. The following were clnly elected Fellows of tlie Society :-Messrs.John Charles Aydaris ; Henry Austin Appleton ; Charles Norrish Aclams, ISi1.h. ; Jdhn Frederick Blooiiiey ; Clayton Beadle ; Robert John Brown ; Thomas Byriie ; Artliur Cole, B.A. ; Arthur Colefsx, B.A., Ph.D. ; Cliarles Henry Corbett ; Hendrie Thoinas Donorail ; Robert Bond Greaves ; Ernest F. Hooper ; Frederick William Harrold ; lloses William Jones ; Henry Charles Jenkins ; Frederick Herbert Moore ; Reginald !Porn Mwrshall ; Edgar J. Millard ; William Morley Martin ; Arnold JVhitatkeY Oxford ; Jlichael Samuel Pickeriiig ; William Jackson Pope ; Toni Kirke Rose ; R. Stockclale ; Matthew Carrington Sykes ; Herbert D.Shaw ; R. Greig Sinith ; Kenelm Edward Symes : Howard C. Suc~6; A. H. Tapp ; E’redcrick William De Telling, B.A.; David Wilkinsoii ; Thomas M. W-j-att; Stephen Newcornbe Welliiigtoii ; Dr. W. Will. The following papers mere read :- 24 9. " The action of reducing agents on ax'-diacetylpentane. Syn-thesis of diniethyldihydroxy heptamethylme." By F. Stanley Kipping, Ph.D., D.Sc., and W. H. Perkin, Jun., Ph.D., F.R.S. On reducing ad-diacetylpentane, COAle*[CH,],*COMe (Trans., 56, 330), dissolved in moist ether, with sodium, it is converted into a colourless liquid of the composition C9Zls02. The method of prepara-tion, properties and some derivatives of this reduction product are described in the paper, and also various experiments made with the object of determining its constitution.The authors' investigations have shown that the reduction product must be regarded as a dimethyldihydroxyheptnmethylene of the con- CH2GH2*$J(0.H)*CHsstitntioii CH2< CH,*CH,*C(OH)*CH3. This conclusion is based on the following considerations :-The reduction product is formed by the addition of two atoms of hydrogen to diacetylpentane, and may, therefore, theoretically have the consti- tution represented by one of the following formulE :-CH2*CH,*CO*CH, CH,*CH,.~(OH)*CH3 1. CH~<CH,.CH,.CH(OH).C~:, -11-CH,< CH,-CH,*C(OH)-CH,' As in the one case the compound would be an open-chain ketone alcohol (For~nulaI), and in the other a dihydroxy-derivative of a closed carbon chain (Formula II), it is comparatively easy to ascer- tain which of the two formulae represents the constitution of the compound.(1.) The reduction product does not combine with hydroxylamine, or with phenylhydrazine. (2.) It yields a diacetyl derivative of the composition C,,H,,O, with acetic anhydride. (13.) Phosphorns pentabromide converts it into a clibromide of the composition C,H,,Bi;. (4.)It is not acted on by such reducing agents as zinc and chlorh~dric acid, sodium amalgam, or sodium and alcohol, (5.) On reduction with hydrogen iodide, it is converted in to a hydrocar.bon of the composition C,H,,. These facts, the autliors think, are sufficient to warrant the conclu- sion that the reduction product is a climethyldihydroxyheptaniethyl-ene of the constitution given above.Di,nethyId.ihydroxyh~ptapnptli~lene,C9HI8O2,is a thick, colourless liquid, boiliiig at '201" (180 mm.) ; it is only sparingly soluble in cold water, but miscible with alcohol, ether &c. in all proportions, The sodizcnz derivative, C,HI7O2Na + H2G,is R colourless, semi-crystalline, very deliquescent compound. Uii?teth?lldihrornoheptnnzeth~lene,C9H,,Br2, prepared by treating the dihydroxy-compound with phosphorus pentabromide in chloroform solution, is a thick, colourless oil. 25 Dimelhylh~ydroxyiodoF,e~tamethylene,C19H,,01,is formed when the glycol is heated with hydrogen iodide ; it is a colourless liquid, with a pleasant, sweetish smell. Dimethyzheptarnethylene diacetate, C,H,,( OAc),, is obtained when the dihydroxy-compound is boiled with acetic anhydride ; it boils at 199-202” (65 mm.) and is readily hydroljsed by dilute soda.DirnethyZh~~tametlzyZei.Le,C,H,,, is obtained in the form of a colour- less, mobile oil when dimethyldihydroxyheptamethylene is heated with hydriodic acid and amorphous phosphorus ; it boils at 153-154” and has an odour very like that of light petroleum. D~SCUSSION. Dr. ARMSTRONGand Dr. COLLIEboth drew attention to the possible formation of a hexa.methylene compound by reduction of the diketone diacetylpentane, and asked what evidence other than synthetical esta- blished the const’itution of the reduction product. Dr. KIPPING,while admitting that at present there was no such evi- dence, contended that the formation of a hexamethylene compound was altogether improbable.10. “The osmotic pressures of salts in solution.” By R. H. Adie, M.A This paper contains tlie experimental results of an investigation of the osmotic pressures of salts in solution by direct observation, by the method of Pfeffer. The results are arranged under five headings. 1. Boyle’s Law applied to solutions.-The observations are plotted out with osmotic pressures for ordinates and concent’rations (in terms of gram molecules per litre) for abscissae. The salts observed were potassium and sodium nitrates, potassium iodide, potassium sulphate, potash alum, potassium ferrocjanide and cobalticyanide and a few others. The results obtained show that the osmotic pressures do not vary directly as the conceiitrations, but take a definite curved form, approaching Ostwald’s line of 110 dissociation at two points, and receding from it elsewhere.Potash alum gives the nearest approach to a straight line of tlhe salts examined. 2. Charles’s Law applie; to solutions.-Only one experiment yielded any result, and that was confirmatory of the correctness of applying Charles’s Law to solutions. 3. Influence of bases on osmotic pressures.-No definite in%uence can be attributed to the base, except that the salts of some bases, e.g., soda, appear to be more readily dissociated by water than those of others, e.y., potash. 4.Influence of acids ow osmotic pressures.-In the case of inorganic acids, no very definite influence can be detected ; though the equiva- Ients of the salts of monobasic acids give iii general higher osmotic pressures than those of the salts of dibasic acids.In the case of organic acids, an increase in the molecular weight of homologous acids increases the osmotic pressure, and a ring nucleus gives a higher osmotic pressure than an open chaiD. 5. Avogndq-0’s Law applied to salts in solution.-The author examines and compares the differences between the observed results and those calculated on the assumption that Avogadro’s Law applies to salts in solution, and snggests that they may be due, as in Crookes’ hypothesis, to t,he existence of simple and complex molecules in solution, as well as to the formation of water compounds in the solution.This hypothesis does not appear to require so large a modification of ordinal-y chemical ideas as that of Ostwald and Arrhcnins. 11. “A direct comparison of the physical constants involved in the determination of molecular weights by Raoult’s method.” ByR. H. Adie, M.A. In this paper, t.he author tries to connect the constants of Raoult’s method of determining molecular weights of a substance in solution with those ascertained by direct observation of the osmotic pressure of the same solution. Also, by the same method of Rnoult, to connect’ the osmotic pressure with the gaseous pressure of any substance in solution. The substances chosen are potassium iodide and ammonia. The solutions of potassium iodide and ammonia are compared by meaiis of the lowering of tbe freezing point, and thcn the osmotic pressures of the same solutions of potassium iodide are given.The author sho-ivs that the constants obtained by the two methods do not agree, and suggests an hypothesis to explain the same, which is given above. DISCUSSION. Mr. PICKERINGsaid that the numerous results brought forward by Mr. Adio could not fail to be of value. They seemed toafford fresh proof of the irregularities almcst invariably shown by the properties of solutions, where, according to the physical t,heory, there shcjuld be nothing but retgularity and uniformity. It was to be regretted that the deterininations had not been pushed further into the region of dilute solutions, for it was here that some of the most surprising irregularities existed, and it was here that the existence of such must tell most strongly against any purely physical theory.MY.Adie had touched on one of the most fundamental objections to the present phjsical theory of solutioc-the existence of osmotic pressure-for this is due to the impermeability of a membrane to the dissolved substance ; and how can it be contended that if the molecules of the 27 latter were single, ancl still more if they were dissociated into ions, they cannot get through holes which the water molecules have no difficulty in threading ? 12. “Derivatives of piperonyl.” By Frederick 11.PeiIkin. The author describes the results of experiments made with the object of determining the constitution of the compound Cl0H9NO, obtained by his brother from berberine (Trans,, 1890, 992), a know-ledge of which was essential to the determination of the nature of this alkaloid ; two formula would account for the properties of the sti bstance, viz.:-The second of these is found to be applicable to the substance in question. In the present paper, the author describes the preparation of the compound represented by the first formula from pipmonal. On heating a mixture of ni tropiperonal, acet,ic anhydride and sodium acetate, an acid was obtained identical with that formed on nitrating the piperonylacrylic acid of Lorenz. On reduction with ferrous sulphate, this nitro-acid is converted into the corresponding amido- acid, but when zinc or tin and muriatic acid is used, the anhydro- derivative of the amido-acid is obtained.The nct’ion of bromine on piperonylacrylic acid is described, ancl also the formation of a benzoin-like compound from piperonal and potassium cyanide. 13. “Studies on the constitution of tri-derivatives of naphthalene, No. 9. Andresen’s p-naphthylaminedisulphonic acid.” By Henry 3:. Armstrong and W. P. Wynne. According to Schultz (Bey., 23, 77), napbthalexe-1 :3‘-disulphonic acid on nitration yields a mixture of several nitronaphthalenedi- sulphonic acids. The chief product on reduction gives the so-called a-naphthylamine-c-disulphonicacid [NH, :S0,H :SO,H = 1’:1:3’;21. Armstrong and Wynne, these €’roc., 1890,151 of the Germ.Pat. 45776. Of the other acide, the production of which has been also noted by Bernthsen (Bey., 23, 3088, footnote), one yields on reduction, according to Schultz, a &naphthylaminedisulplionic acid. As this was the first instance in which the format,ion of a beta-nitro-acid by the nitration of a naphthalenesulphonic acid had been observed, the attention of the authors was directed to the determination of its constitution, and through the liberality of the Actiengesellschaft fur Anilinfabrikation a considerable supply of the material remaining after the separation of the greater part of the 6-acid was placed at 28 their clisposal for examination. After separation from the associated acids, and coinpnrisori with a specimen of the pnre Andresen acicl received from Dr.Schultz, the smido-acid was analysed by tlie hydrazine and Satncimeycr methods already described. When redncecl by the hydrazine method, it gave naphthalene-1 :3'-disulphonic acid, which was characterised by means of its chloricle, C,,,H,(SO,Cl),, melting at 127", ancl the derived 1 :3'-dichloroiiaphtjhalenemelting at 48". On treatment by the Sandmeycr process, it mas converted into a chloronaphthalenedisulphonic acid, the chloride of which, C1,H,CI( SO,Clj,, crystallisecl from benzene in radiate groups of flat needles melting at 174", and on distillation with PCl, yielded 1: 3 : 3'-trichloronaphthalene melting at 80.5". This acid, conse-quently, was identical with that obtained by the authors by snlphon-atiiig 2 :2'-P-chloronaphthalenesidphonicwith 20 per cent.anhydiu- sulphuric acid (these Proc., 1890, 133). As a further poof of the identity of the two compounds, the ch loronaphthalenedisulphonic chloride derived from the Andresen acid was hydi-oljsecl by heating with dilnte sulphnric acid at 250-270" for several hours, with the result that .~-chloronaphthalene melting at 59.5" was obtained. Com-bining these resnlts, it follows that the Andresen acid is a /3-iiaphthyl-amiiiedisulplioiiic acid of the constitutioii- The salts of this 2 :4:%'-p-naphtiiylamiaeclisulphoiiicacid, anc3 the mode of separation froiii the other naplithylarninesulphoiiic acicls coiitained in the mixture, will he described when the examination of the nitration product of naphthalene- 1 : 5'-disulphonic acid has been completed. At tlie next meeting, on March Gtli, the following papers will be raac1:-"Chloro- and bromo-derivatives of naphthol and naphthylamine." By Dr. Armstrong and E. C. Rossiter. ''The crystalline form of the calcium salt of optically active glyceric acid." By A. 3.Tut,ton. ''Fernientations induced by tlie Pwuiimcoccus of Friedlaeatler." By Prof. H. I?. Frankland, A. Stanley xiid W. Frew. HAHKISOX AKD SOKS, PHISTERS IN ORDINARY TO HIEXNAJESTY, ST.NARTIR'S IAKE.
ISSN:0369-8718
DOI:10.1039/PL8910700023
出版商:RSC
年代:1891
数据来源: RSC
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