摘要:
Tsssicscl 2311211 898 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIEX. No. 201. Session 1898-9. December 15th, 1898. Professor Dewar, F.R.S., President, in the Chair. Mr. H. P. Bell was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. Stuart Blofeld, 4, Camden Gardens, West Kensington Park, W.; Bertram H. Bowles, 53, Dunsmure Road, Stamford Hill, N.; Thomas John Cheater, 6, Boutflower Road, Wandsworth Common, S.W. ;George Ward Hedley, 2, St. Luke’s Villas, Cheltenham ; Harold Octavius Knight, Westfield Villa, Barton-on-Humber ;Dudley Northall-Laurie, 56~,Pall Mall, S.W. ; James McCracken, 580, Govan Road, Govan, N.B. ; John O’Sullivan, ’742, Nicola Street, Vancouver City, B.C.; Arthur Lee White, 29, Huron Road, Upper Tooting, S.W. The following papers were read :-147. u The interaction of ethylic sodiomalonate and me~ityl oxide.’’ By Arthur W. Crossley. Attempts to prepare dihydrocamphoric acid synthetically have so far proved unsuccessful (Tram., 1898, ’73,23). Isobutylene dibromide does not condense with ethylic sodiomethylmalonate, nor mesityl oxide with ethylic sodiomalonate, in the expected manner. The thick, oily product obtained in the latter case cannot be distilled in a vacuum without partial decomposition ;when hydrolysed with alcoholic potash, it yields a dibasic acid, C16H2404,which crystallises from acetone in colourless, transparent, lustrous prisms belonging to the monosym- metric system, and melts at 148--148*5O, the upper part of the capillary tube becoming covered with a red film.The ethylic salt sep rates from light petroleum in thick, transparent, lustrous prisms, which usually are twinned and apparently belong to the monosym- metric system, It melts at 59-5-60’, boils at 252’ in air without 248 decomposition, and, on hydrolysis, yields the original acid. The silver salt crystallises from water in feathery needles. Sodium amalgam is without action on the acid. Bromine readily converts it into a dibromo-derivative, Cl6HQ4O4Br2 or C,6H2,04Br2, which crystallises from dilute alcohol in colourless, glistening leaflets containing 2H20,and melts with slight decomposition at 171O. On treatment with hydrogen bromide, a dihydrobromide, C16H2604Br2,is obtained, which crystallises in transparent prisms, melts at 169O with decomposition, and is reconverted into the acid, C,,H,,04, by inter- action with alcoholic potash.The acid is readily oxidised by alkaline potassium permanganate in the cold, and when the product is treated with chromic acid, an acid melting at 89’ is obtained. It is hoped that a study of its oxidation products mill give some clue to the constitution of the substance, 148. “The interaction of ethylic malonate and acetylene tetra- bromide in presence of sodium ethoxide.” By Arthur W. Crossley, This investigation was undertaken in the hope that ethylic disodio- malonate and acetylene tetrabromide would interact according to the equation, C2H,Br, + 2Na2C(C‘O,Et), = (CO,Et),C:CH* CH:C(CO,Et), + 4NaBr, as the product, on hydrolysis and subsequent heating, should yield muconic acid, CO,H* CH:CH*CH:CH*CO,H, from which tetra- bromadipic acid could be prepared for the purpose of investigating its behaviour with weak alkalis.The reaction does not take place as expected, and is of a complicated nature, the two main products being tribromethylene, CHBr:CBr2, and tetrethylic acetylenetetracarboxylate; during its progress acetylene is given off, and tarry products are also formed from which no definite chemical compound could be isolated. The acetylene tetrabromide used was prepared from acetylene generated from calcium carbide by the action of water, and purified by Willgerodt’s method (Ber., 1895, 28,2108). It boiled at 151O under 54 mm.pressure, and was a clear, colourless, highly refractive liquid. 0.1548gave 0.3353 AgBr. Br =92.18. C2H,Br, requires Br =92.48 per cent. Acetylene tetrabromide‘( 1 mol.) was added to a mixture of sodium (2 mols.) dissolved in absolute alcohol and ethylic malonate (2 mols.), and after the violent reaction had somewhat moderated, the whole was heated on a water bath for 14 hours. Water was added to the resulting dark, reddish-green, feebly-acid product, and the whole extracted with ether, On washing the ethereal extract with water, 249 the greater portion of the red colouring matter (from which the tarry products alluded to were obtained) was removed, and also a small quantity of a green solid containing sodium and organic matter.When boiled with acids, this green substance partially dissolved, forming a red solution, which was again turned green by addition of an alkali; but the amount was too small for investigation. On dis-tilling the residue from the dried ethereal extract, fractions were obtained boiling at 65-80' and at 225-230° under 47 mm. pressure ; and not more than 0.5C.C. passed over between these limits. The fraction boiling at 65-80' under 47 mm. pressure contained tribromethylene, CHBr:CBr,. This clear, colourless, heavy liquid, amounting to 63 per cent. of the total ethereal extract, was repeatedly fractionated at the ordinary pressure, and nearly the whole passed over between 164-166'; the residue, when heated above this tem- perature, gave off bromine and hydrogen bromide, and consisted probably of some unchanged acetylene tetrabromide.On analysis the fraction boiling at 164-166' gave the following numbers. 0.3410 gave 0.7251 AgBr. Br =90.47. CHBr:CBr2requires Br = 90.56 per cent. The substance was further characterised by converting it into penta- bromethane by the direct addition of bromine. The resulting solid crystallised from alcohol in long, white, glistening needles melting at 55-55.5'. 0.2656 gave 0.5887 AgBr. Br=94-31. CHBr,. CBr, requires Br = 94.1 1 per cent. The fraction boiling at 225-230' under 47 mm. pressure con-tained tetrethylic acetylenetetracarboxylate. This fraction solidified almost completely.It was spread on a porous plate, and then purified by recrystallisation from light petroleum boiling at 60-SO', from which it separated in long, white, silken needles melting at 75-76'. 0,1518 gave 0.2936 CO, and 0.0940 H,O. C =52.76 ; H = 6.87. (C0,Et)2CH-CH(C02Et), requires C =52.83, H = 6.91 per cent. Although the conditions under which the reaction was carried out mere varied to some extent, the same results were always obtained. 149. "Derivatives of camphoric acid. Part 111." By F. Stanley Kipping, D.Sc., F.R.S. This paper contains an account of the preparation, properties, and transformations of a number of compounds which have been obtained from ?r-bromocamphoric acid, and is a continuation of previous work ('l'rans., 1896,69, 913 ;Kipping and Pope, Trans.,1897, 71, 963).250 nw-Dibromocamphoric acid, rut-dibromocamphoric anhydride and 7r-bromocamphanic acid have been already briefly described (Proc., 1895, 11,211). wir-Chlorobromocamphoricanhydride, G,Hl2ClBr<~~>O, is obtained by treating r-bromocamphoric acid with phosphorus pentachloride, and then passing chlorine into the product heated at 100'. It crys-tallises in large, orthorhombic prisms melting at 214-215O, and resembles the corresponding dibromo-compound in ordinary properties. wlr-Chlorobromocamphoricacid, C,Hl,CIBr( CO,H),, can be prepared by heating its anhydride with concentrated nitric acid ;it is a colour-less, crystalline compound melting at about 197", and is very like the dibromo-acid in all respects.When wr-chlorobromocamphoric anhydride is boiled with dilute acetic acid, it is converted into a wbromocamphanic acid, identical with the compound melting at 176-177", obtained by the decom- position of rw-dibromocamphoric anhydride. Methylic Ir-bromocumphanate, CO,Me*C,H12B~~o, is easily ob-tained from the corresponding acid by the ordinary methods ;it crys-tallises in orthorhombic prisms, melts at S7--SS0, and dissolves freely in most of the ordinary organic solvents. .Ir-Brornocmphanamide, NH2*CO*C8H1,Br<(?',, is produced when 0 rrw-dibromocamphoric anhydride is left in contact with aqueous sm-monia, and can also be prepared from methylic lr-bromocamphanate in a similar manner; it crystallises in transparent needles melting at 161-162'.The action of alkalis on aw-dibromocamphoric anhydride results in the formation of hydroxy-cis-lr-camphanicacid (I'rccns., 1896, 69, 913), but when the anhydride is heated with an aqueous solution of silver nitrate, it is partly converted into the 7-lactone of hydroxycamphotri- carboxylic acid (loc. cit.); the last-named compound is also formed when r-bromocamphanic acid is boiled with an aqueous solution of silver nitrate. 150. "Synthesis of @P-trimethylglutario acid," By W. H. Perkin, jun., and J. F. Thorpe. This acid, which is especially interesting on account of the fact that Balbiano (Ber.,1895, 28,2161) obtained it by simple reactions from camphoric acid, may be prepared synthetically in the following way.Ethylic cyanacetate is digested in alcoholic solution with sodium ethylate and ethylic dimethylacrylate, and the product, 251 which contains the sodium compound of ethylic a-cyano-P@%methyl-glutarate, CO,Et(CN)CNa*CMe,* CH,* CO,Et, is treated with methylic iodide. The resulting ethylic a-cyano-app-trimethylglutarate, CO,Et(CN)CMe*CMe,* CH,* CO,Et, a colourless oil boiling at lSlo under 25 mm. pressure, yields on hydrolysis app-trimethylylzctarimime, CH --GOCMe 2<CH&e.CO>NH, which crystallises in long needles and melts at 126O. aPP-Trimethylglzcta?.ic acid, .CO,H* CHMe*CMe,*CH,*CO,H, is obtained from this imide by heating with hydrochloric acid at ZOOo; it melts at 88O, gives an anhydride melting at 82", and an arnilic mid melting at 150°, and is, in all its properties, identical with the acid obtained from camphoric acid by Balbiano.151. '4 Hydrolysis of methylic and ethylic y-cyanoacetoacetates and their derivatives. Part I." By W. Trevor Lawrence, A preliminary account is given of the results obtained in an investigation which had for its primary object the preparation of unsymmetrically disu bstitu ted ethylic acetonedicarboxylates, but has led to the discovery of a new series of acids. Methylic y-cyanodirnethylacetoacetccte, CN*CH,*COOCMe,* CO,Me, is the chief product of the interaction of methylic y-bromodimethylaceto- acetate with potassium cyanide in ethereal solution. Itboilsat 126-1 28O under 18 mm. pressure. On treatment in ethylic alcohol solution with dry hydrogen chloride, it yields an oil, CO,Et*CHCl~CO*CMe,*CO,Et, which boils at 146-150' under 40 mm.pressure, and when hydrolysed with concentrated hydrochloric acid is converted into aa-dimethyl- P-hydroxyglutaconic acid. Sodium amalgam does not reduce the nitrile under the varied conditions employed, but converts it into dimethylmalonic acid. Methylic 7-cyanodimethylacetoace tate is hydrolysed rapidly by concentrated hydrochloric acid, and converted quantitatively into a substance which is regarded provisionsliy as aa-dimetli~lLP-hydrox?/-ghtaconic acid, CO,H* CH:C(OH)*CMe,* CO,H, although several of its reactions are difficult to explain if the formula adopted is correct. Thus, the compound remains unchanged on boiling with sulphuric and with nitric acids, is not affected by potassium permanganate at 60°, and gives no coloration with ferric chloride.The acid crystallises from water in prisms, melts at 214O, and distils at 245O. The hydrogen silver salt, C7H,0,Ag, and the corresponding copper and zinc salts have been obtained. The artiline salt melts at 122O. The dimethylic salt, CO2Me*CH:C(0H)*CMe2*CO,Me, crystallises in needles, melts at 104O, and boils at 285'. The acetyl derivative melts 252 at 1369, and the benxoyl derivative at 208'. When the acid is treated with phosphorus pentabromide and t.he product poured into methylic alcohol, the methylic salt of a bromo-derivative is obtained which, on hydrolysis with hydrobromic acid, yields aa-dimethylglutaconic acid.aa-Dirnethylglutaconic acid, CO,H* CH:CH*CMe,*CO,H, is also ob-tained by the reduction of dimethylhydroxyglutaconic acid with hydriodic acid at 130' in sealed tubes. It crystallises from water in prisms, melts at 148', and is not reduced by sodium amalgam in the cold. The following compounds have also been prepared :-Ethylic y-bromo-methylet~ylacetoucetate, CH,Br*CO*CMeEt*CO,Et, boiling at 164' under 75 mm. pressure ; ethylic y-cyanomethylethylacetoacetate, CN*CH,*CO*CMeEt*CO,Et, boiling at 158' under 35 mm. ;aa-methyl-ethyFP-hydroxyglutaconicacid, CO,H* CH:C(OH)*CMeEt-CO,H, melt-ing at 164";ethylic y-bvomodiethylacetoacetute,CH,Br*CO*CEt,* CO,Et, boilingat 180' under 100mm. pressure ;ethylic y-cyccrtodiethylucetoacetale, CN*CH,*CO*CEt,* CO,Et, boiling at 158" under 75 mm.pressure ; aa-diethyl-P-hydroxyglutaconic acid, C0,H.C.H:C(OH) CEt,. CO,H, melting at 159'. Different results are obtained by the hydrolysis of these nitriles by means of sulphuric acid and of methyl alcoholic potash; moreover, the products of the reduction of the hydroxyglutaconic acids with hydriodic acid differ with the conditions ; the author is engaged in investigating these reactions, as well as the behaviour of the y-nitriles of ethylic acetoacetate and its derivatives generally. ADDITIONS TO THE LIBRARY. I. Donations. Fresenius, H. Geschichte des chemischen Laboratoriums z u Wiesbaden wahrend der zweiten 25 Jahre seines Bestehens. 4to. Pp. xx + 128, with a frontispiece and 2 plans, 1.p.Wiesbaden 1898. From the Author, van't Hoff, J. H. Leqons de Chimie Physique. Premiere Partie. La Dynamique (Thimique. Traduit par M. Corvisy. 8vo. Pp. 263. Paris 1898. From the Publishers. Mitchell, A. H. Quantitative Practical Chemistry. Part I., Elementary Stage. Pp. 70. Part II., Advanced Stage Quantitative (Volumetric) and Qualitative Analysis. Pp. 76. Reading. 1898. From the Author, Williams, C. W. The Combustion of Coal and the Prevention of Smoke Chemically and Practically Considered. Part the First. Yp. xii + 158 + xxvi. 8vo. London and Liverpool. Second edition, 1841. (With a volume of plates.) From Prof. Meldola. Williams, C. W. Plates illustrative of the Combustion of the Gaseous Portion of Coal, and of the Modes by which it may be effected in Furnaces, Lithographed in colours by George Smith and Co.14 plates (7 folding), Liverpool 1841. From Prof. Meldola. 11. By Purchase. Boltzmann, Ludwig. Vorlesungen uber Gastheorie. I. Theil. 8vo. Pp. viii + 204. Leipzig 1896. (In progress.) Classen, A. Handbuch der analytischen Chemie. I. Theil Qualitative Analyse. Funfte, vermehrte und verbesserte, Auflage. 8vo. Pp. xii + 242. Stuttgart 1896. (In progress.). Maercker, M. Handbuch der Spiritusfabrikation. Siebente, voll- standig neubearbeitete Auflage. Mit 216 in den Text gedruckten Abbildungen. Pp. xxiv + 783. Berlin 1898. Meyer, Victor, und Jacobson, Paul. Lehrbuch der organischen Chemie. Zweiter Band. Erste Abteilung.Pp. i + 320. Leipzig 1895. Zweiter Abt. 8vo. Pp. 321-576. Leipzig 1896. (In progress.) Neumann, Bernhard. Theorie und Praxis der aralytischen Elek- trolyse der Metalle. 8vo. Pp. viii + 224. Halle a.-S. 1897. Neumeister, R. Lehrbuch der physiologischen Chemie mit Be- riicksichtigung der pathologischen Verhaltnisse. Zweite Auflage. Pp. xviii + 927. Mit 1 lithographischen Tafel. Jena 1897. Schafer, E. A. Text-book of Physiology. Vol. I. Pp. xviii + 1036. London 1895. Tschirch, A., und Oesterie, 0. Anatomischer Atlas der Pharmakog- nosie und Nahrungsmittelkunde. Erste Abteilung. Tafel 1-40. 4to. Pp. iv + 174. Leipzig 1896. (In progress.) Pamphlets. Baker, R, T., and Smith, H. G. On the Essential Oil and the presence of a Solid Camphor or Stearoptene in the ‘‘ Sydney Pepper- mint,” Eucalyptus pipevita, Sm.(Read before the Royal Society of N.S. Wales, August 4, 1897.) -On the “Stringybark” Trees of N.S. Wales, especially in regard to their Essential Oils. Part I. (Read before the Royal Society of N.S. Wales, July, 1898.) Borns, H. Die Elektrochemie im Jahre 1897. (Reprinted from Chemisehen Industrie), Pp. 75. Berlin 1898. From the Author. Fairley, Thomas. On the Water Supplies of Yorkshire. (Reprinted from the Journul of the Fed. Inst, of Bvewing, 1898,) 254 Fischer, F. Chemische Technologie an den Universitaten und technischen Hochschulen Deutschlands. 8vo. Pp. 54. Braun-schweig 1898. Fresenius, H. Zur Erinnerung an R. Fresenius. 8vo. Pp. xviii, With a Portrait.Wiesbaden 1897. Fresenius, Th. W, Ueber die Entwickelung der analytischen Chemie in den letzten 50 Jahren. 8vo. Pp. 16. Wiesbaden 1898. Hintz, Ernst. Ueber Gasgluhlicht. 8vo. Pp. 45. Wiesbaden 1898. Mathews, J. A. The Action of Nitriles upon Aromat,ic Acids. Easton 1898. Spring, W. Sur la cause de l’absence de coloration de certaines eaux limpides naturelles. Bruxelles 1898. NOTICE TO AUTHORS. As the Proceedings go to press on the Monday after each ordinary Meeting of the Society, the announcement of papers for the next Meeting cannot be made in this publication unless the papers are in the hands of the Secretaries by noon on that day. At the next meeting, on Thursday, January 19th, the following papers will be communicated. ‘‘Researches on moorland waters. I. Acidity.” By W. Ackroyd.‘‘a-Ketotetrahydronaphthalene.” By F. Stanley Kipping, D.Sc., F.R.S., and Alfred Hill. RICHARD CLAY AND SONS, LIMITED LOXDQN AND EUWCAY.
ISSN:0369-8718
DOI:10.1039/PL8981400247
出版商:RSC
年代:1898
数据来源: RSC