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Proceedings of the Chemical Society, Vol. 10, No. 143 |
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Proceedings of the Chemical Society, London,
Volume 10,
Issue 143,
1894,
Page 211-220
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. No.143. Session 1894-95. November 16th, lS94. Dr. Armstrong, President, in the Chair. Mr. A. E. Tanner was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. John Melrose Arnot, The Bally Paper Mi!ls, Calcutta ; Edward Elliott, Messrs. Reckitt & Sons, Hull ; Harry Harris, The Pulo Brani Smelt- ing Works, Singapore ; Richard Ernest Kenynn, Ashville College, Harrogate ; George Holman Kingdon, B.A., Taddyforde House, Rxeter ; Alexander Macb’arlane, Pait Street, Ancoats, Manchester ; Arthur Marshall, 65, Fairholme Road, West Kensington, W. Of the following papers, those marked *, were read. %64. Sulphonic derivatives of camphor. Part 11.” By F. Stanley Kipping, Ph.D., D.Sc., and William J.Pope. fn this paper the authors describe the sulphonic bromides and chlorides of crtmphor, bromocam phor, and chlorocamphor which have been referred to in previous notes (Proc., 1894, 163, 164). The be-haviour of dextro-rotatory camphorsulphonic bromide has now been fully examined, and presents many features of interest. Dextro-rotatory camphorsulphonic bromide, C,,H1,0*S02Br,is ob-tained in large orthorhombic octahedra, the crystallographic COH-stants of which approximate very closelp to those of dextro-rotatory camphorsulphonic chloride (Trans , 1893, 548). The axial ratios of these suIphonic derivatives are as follows. C,,H,,O~SO,Cl a : 2, : c = 0 9980 : 1: 1.0368 C‘~~H,,O.SO,BVa : b : c = 0.9816 : 1 ; 1.0249; 212 The substances are iherefore isoniorphous, and consequently possess the same constitution.The sulphonic chloride almost invariably cry- stallises in tetrahedra, which, however, exhibit the positive and negative henii-octahedid forms ; the hemiliedral character of this substance is thus placed beyond doubt. The sulphonic bromide, ou the other hand, usually crystallises in orthorhombic octahedra, which, from their geometrical form, would seem to be holohedral. The com- plete analogy between the bromide and chloride is demonstrated, however, by the fact that the bromide crystallises in tetrahedra on varying the conditions of crystal1isat)ion. A careful crystallographic comparison of the octahedral and tetrahedl*al forms of the sulphonic bromide showed conclusively that the difference bdtween them is only one of habit, and is not due to a diffei-ence between their crystalline structures.The inactive campliorsulphonic bromide which the authors have prepared has even less of the characteristics of a definite racemic modification than the corresponding sulphonic chloride. In the latter case %he non-racemic nature of the compound could not be demonstrated; in the case of the sulphcnic bromide, the evidence against the existence of a true racemic modification is much more definite. By crgstallising tlie inactive sulphonic bromide from cthylic acetate solution it may be partially resolved into the two opposit'ely active constituents. Further, the solution deposits large butterfly-shaped twin crystals ; on examining these, the two wings are found to consist of the two oppositely active modifications.The hvo- and dextro-isomerides therefore twin together witholat forming a true racemic modification. "65. ''Halogen derivatives of camphor." By F. Stanley Kipping, Ph.D., D.Sc., and William J. Pope, Seven new halogen derivatives of camphor have been obtained by heating the sulplionic chlorides and bromides, which are described in the preceding and in other papers, at temperatures below 200" ; the following is a list of the compounds thus prepared. Dextrorotatory chlorocamphor, C,,H,,OCl ; inactive chlorocamphor CloHI5OCI. Dextrorotatory byomoc Lmphor, C,,H,,OBr ; inactive bromoczmpbor, CloH,50Br.Dichlorocamphor, C,,H,,OCl,. Dibromo-camphor, C,,H,,OBr,. Chlorobi~oriiocaniphoi~,Cl,,Hl,OCIBr. The bromochlorocamphor, which is doubtlcsb produced on heating bromooamphorsulphoiiic: chloridc has iiot yet been obtained in a state of purity, owing to the fact that secondary changes occur dnring its formation, giving rise to 'ct somewhat complex product. The dihalogen derivatives, and some of the monoMogcn dwira tivev, notably the optically inactive hromocnmphor, are very well characterised substances, aud have been examined crystallographic- ally ; very interesting cases of dimorphism and of polymorphism have also been met with, and have been carefullp studied. "66. "Dimethylpimelic acid." By F.Stanley Kipping, Ph.D., D.lc.In preparing 2 : 6-diacetylheptane, for the purpose of studying its behaviour on reduction (Trans., 1893, 63, 111), the author and Mackenzie obtained, as a bye-product, an acid of the composition C9H1604,which, judging from its method of formation, was to be re- garded as ad-dimetiiylpimelic acid, CO,H.CHMe[CH,],-CHMe-CO,H. This acid, after careful purification, was obtained in well defined crystals, melting at 80-81" (Trans., 1891, 59, 569). A short time after the publication of this paper a dimethylpimelic acid, having, doubtless, the same conslitution as the compound just, mentioned, WES prepared by Perkin and Prentice (Trans., 1891, 59, 818), and also by Zelinsky (Ber., 24, 3997) ; in both cases, however, the melting point differed from that given by the author and Mac- kenzie. Perkin and Prentice found the melting point to be 74-76", and, being cognisant of the earlier observations, they repeatedly re- crystallised their acid, but without effecting any change ; Zelinsky, who appears to have overlooked the paper by the author and Mackenzie, gave the melting point as 71-73', and having obtained at the same time an oily acid of the composition C9HI6O5,he suggested that the latter was a, stereoisclmeric form of the crystalline acid.These statements having thrown some doubt on the accuracy of the observations made by the author and Mackenzie, and the whole matter being in an unsatisfactory condition, the aa'-dimethylpimelic prepared by the hydrolysis of ethylic dimethyldiacetylpimelate was again examined.The crude crystalline product began to soften at 52-58", and usually liquefied completsly at about 70" ; when repeatedly recrystal- lised the melting point gradually rose, and finally an acid melting zt 80-81" was obtained in a state of purity; this acid was identical with that (m. p. S0-81°) previously described. The crystalline fractions of lower melting point were found to have the same composition as the pure acid melting at 80-81", a fact which indicated the presence of a stereoisomeric form, but all attempts to isolate such a compound by fractional crystallisation were unsuc- cessful. Portions melting from .55 to 70' were therefore treated with phosphorus pentachloride and aniline successively, aid the products submitted to careful fractional crystallisation ;in this way two anilides were isolated, one melting at 183-184', the other at 154-155", and on analysis both gave results agreeing with those required by the ani1id e, NHPh*C0 CHXle* [CH, ]3-CHAle-C0*NHPh .On hjdrolysis they both gave an oily acid, which was ultimately obtained in well-defined crystals ; the acid from the anilide of liigher melting point was identical with the compound melting at 80-81", whereas the product from the anilide melting at 154-155" was the sought for stereoisomeride, and melted at 74-5-75". aa'-Dimethylpimelic acid, like the lower members of the series, exists therefore in two physically isomeric modifications, but the two forms are so similar in properties that their separation is not easily accomplished. It seems probable that the acid described hy Perkin arid Prentice is identical with the modification melting at 74.5-75', but the melting point given by Zelinsky leaves the nature of his acid quite un-certain."67. "Hexahydro-s-toluic acid." By Williax Goodwin and W. H. Perkin, jun., F,R.S, Some time since one of US, in conjunction with P. C. Freer (Trans., 1888,53,ZOS), prepared methylhexamethylene carboxylic acid (hexa- hydro-o-toluic acid) from the product of the action of methylpenta-methyleneclibromide on the sodium derivative of ethyl malonate, and described it as a colourless oil boiling at 235-236". Recently Markownikoff has studied the reduction products of o-toluic acid, obtained by treating a boiling solutioii of the acid in amyl alcohol with a large excess of sodium, and has isolated a hexahydro-o-toluic acid, which boils at 240', and solidifies on cooling, the melting point of the pure acid being 41".This wide difference in the properties of the sjnthetical acid and the acid obtained by reduction made it desirable to reinvestigate the whole subject, with a view of determining t8he reason of the isomerism, and in order to do this we have prepared considerable quantities of both the acids, and carefulIy re-examined their properties, with the result that we find that the two acids are undoubtedly isomeric ; the synthetical acid does not solidify at -lo", whereas Markownikoffs acid solidifies at ordinary temperatnres with the greatest ease.The anilides of the t>wo acids also differ in a marked manner, as the anilide of the spthetical acid melts at 66", that of Markownikoff's acid at 140'. hu esamination of the formula of hexabydro-o-toluic acid at owe reveals the fact that this acid can exist in two stereoisomeric forms. PH2\ PH\CH, HC-CH, CH, CHSC-H 1 I I I CHo HC-COOH CH, HC-COOH \C/ \CH/ H2 Cis-form. Trans-fom. and if appears that the two acids mentioned above are in reality the two stereoisomeric forms of hexahydro-a-toluic acid. This view is not improbable, siiice Baeyer and Raasow (Aranaleu, 282, 140) hare shown that the somewhat analogously constituted p-phenylhesahydrobenzoic acid, C6H5*CH<CH,.CH2cB2'cHz>CH~COO€Z, can be obtained in a cis and trans form.In spite of a number of experiments, we have not succeeded in transforming the one modification into the other, probably because, owing to the low melting point of the solid acid, it would be exceed- ingly difficnlt to isolate it from admixture with the liquid acid. *68. "The addition of the sodium derivative of ethylic malonate to ethylic trimethylenedicarboxylate." By W. A. Bone, Ph.D., and W.H. Perkin, jun., F.R.S. If a inixt ure of ethylic trimethylenedicarboxylatewith the sodium derivative of ethylic maloiiste be digested in alcoholic solution a sodium compound is formed, which, when decomposed with acids, yields ethylic butane tetracarboxylate ; additions having taken place thus, with disruption of the trimethylene ring, (C00CzH5)2.CH CH?.CHz*CH(C00C2H5)2. Similarly, when the sodium derivative of ethylic methylmalonate is employed in this reaction, ethylic methylbutanebetracarboxylateis formed (b. p. 210-250" (55 mm.)). This ethereal salt on hydrolysis yields the corresponding te trabasic acid, which at 200" loses 2 mols. of carbon dioxide, and yields rnethyl- aadipic acid, COOH*CH(CHz)*CH,*CH,~CH,*COOH,colourless, crystalline substance which inelts at 64O. and is excessively soluble in water. "69. 'I The reduction of chlorides of organic acids." By W. H. Perkin, jun., F.R.S.,and J. J. Sudborough, B.Sc. The authors bave found that aldehydes and alcohols may be readily prepared from acid chlorides by acting on these in moist ethereal solution with sodium, the yield obtained, especially in the case of the chlorides of the fatty acids, being satisfactory.The following substances have been obtained by this method. n-Butyl aldehyde and n-butyl alcohol from n-bu tyryl chloride. Isoamyl aldehyde and isoamyl alcohol from isovaleryl chloride. Benzyl alcohol from benzoyl chloride. o-Tolyl alcohol from o-toluic acid chloride. This reaction is being carefully inuestigated in order to determine in what directions it is applicable, arid with the object of finding the exact conditions for obtaining the best yields. 70. "WEthyl methyl propionic acid, C,H5CH(CH3)CH2400H." By W. H. Bentley, B.Sc. This acid, which is required for some experiments in connection with the fusion of camphoric acid with potash, has not been de- scribed.Its preparation and properties form the subject of the present paper. Mct.hyl ethyl ketone was reduced by sodium in moist ethereal solution, and thus converted into methyl ethyl carbinol. This, when treated with iodine and phosphorus, yielded secondary butyl iodide, CH3*CHI*CH2*CH3,which has been prepared by de Luynes (BZ. 2, 3), who obtained it from erythritol by the action of hydriodic acid, and by Wurtz (AnnuZen, 152,23), by the addition of hydriodic acid to rLornial butylene. It boils at 117-118". Ethyl secondary butyl malonate is formed when this iodide re- acts with the sodium derivative of ethyl malonate. It distils at, 228-231", and when hydrolysecl yields the corresponding dibasie acid, which on distillation is decomposed, with the formation of @-methyl ethyl prop ionic acid, C,H,CH (CH,) *CH2*CO0H.The pure acid boils at 196", and possesses properties similar to those of the higher fatty acids. In order to facilitate its identification, the following derivatives were prepared. EthyZ saZt, C5Hll*C00C2H5a colourless oil, boiling at 157--158". Anilide, C5H11.CO*NH*CsH5,crystallises from light' petroleum in silky needles, m.p. 78". p-Tohide, C5H11*CO*NH*C7H7,melts at 75-76". lli 71. “The alkaloids of Corydalis cava. CorybulLine.” By James J. Dobbie, M.A., D.Sc , and Alexander Lauder. This alkslo’id is obtained from the commercial corydaline supplied by Schuchardt of Gorlitz, by either of the following methods.(1.) The crude material is dissolved in hydrochloric acid, and the solution mixed with excess of soda, which throws down the corydaline only. The filtrate is then saturated with carbon dioxide, when the corybulbine separates out. (2.) The crude corydsline is repeatedly exhausted with hot alcohol, wliicli dissolves out the greater part of the corydaline. The residue iu dissolved in a large quantity of boiling alcohol, from which the corybulbine separates on cooling as an exceedingly fine crystal-line powder. It is purified by conversion into the hydrochloride, which, after repeated recrj stallisation from water, is decomposed by ammonia. Corybulbine is nearly insoluble in water, solulJe with difficulty in methyl and in ethyl alcohol, and insoluble, or nearly so, in ether.It dissolves readily in carbon bisulphide, chloroform, and hot ben-zene. It is also soluble in solutions of the caustic alkalis. An alcoholic solution of the alkaloid rapidly reduces a warm solution of silver nitrate. When heated, corybulbine softens at %loo,but does not melt till 238-240”. A solution of the alkaloid in chloro- form is dextro-rotatory. Corgbul bine has the formula CzlH,,NO,. The hyJrochloride, C21H25N04*HCl,is obtained in clusters of prismatic needles by dis- solving the alkalo‘id in hot dilute hydrochloric acid. This salt is remarkable for the difficulty with which it dissolves in water. The acid sulphate, C2,H2,NO4-HzSO4, is prepared in the same manner as the hydrochloride. It dissolves with difficulty in hot water, from which it slowly separates on cooling, in long prismatic crystals.The platinochloride, (C,,H,,N04),H,PtC1,, is thrown down as a pale yellow precipitate on adding platinum chloride to a solution of the hydrochloride in water containing a little hydrochloric acid. The methiodide, C,,H,NO,*CH,I, a pale yellow, crystalline sub- stance, is prepared hy digesting the alkaloid with a mixture of absolute alcohol and methy! iodide. When acted on with a concentrated solution of hydrogen iodicie, one molecular proportion of corybul bine gives three molecular pro-portions of methyl iodide. 218 72. “Corydaline. Part IV.” By James J. Dobbie, M.A., D.Sc., and Alexander Lauder.When subjected to the action of nascent chlorine, corydalino forms a monochloro-derivative C22H2sClNOa, which crystallises from water in flat,prismatic crystals. The specific rotation of corgdaline has been found to be +311”. Oxidation with Potassium Pemaanganate.--The authors have ex-amined the mother-liquor of corydalinic acid, and have obtained from it several new oxidation prodncts. The mother liquor is neu-tralised with ammonia and precipitated with lead acetate. On) decoinposing the lead precipitate with sulphuretted hydrogen and concentrating the solution, a little corydalinic acid first separates out ; a mass of crystals then sioa-ly deposits which consists chiefly of hemi-pinic acid identical with that obtained from narcotine, mixed with n small quantity of a nitrogenous acid which has not yet been investi- gated.The mother liquor filtered from the lead precipitate slowly deposits crystals of a neutral sixbstance haying the formula C,,H,,NO,. which contains two met hoxy-groups, and is probably an oxy-deriva- tive of dirnethoxy-isoquinoline. The further investigation of the action of hydrogen iodide on corydalinic acid has shown that the chief product of decomposition is protocatechuic acid. The authors conclude from the results which they have obtained that corydalinic acid, C,,H,N (OCH,), (COOH),, contains both a benzene and a pyridine ring ; that by the action of hydrogen iodide the benzene ring is split off in the form of protocatechuic acid, whilst the nitrogenous ring is broken up into ammonist and the non-nitro- genous corydalic acid described in a former paper.The appearance of hemipinic acid amongst the products of the oxidation of cory-daline would be accounted for by the oxidation of the benzene ring of corydalinic acid. The analysis of the neutral cornpound shows that two of the methoxy-groups are attached to the pyridine ring of cory-dalinic acid. It is therefore probable that corydaline is a,n alkalo’id of the same type as papaverine, narcotine, and hydrastine, containing an isoquinoline and x benzene nucleus, but of simpler constitution than these alkaln’ids, inasmuch as the two nuclei appear to be united directly to one another and not through an intervening carbon-atom.73. “Attempts to estimate sulphur compounds in the atmosphere.” ByWilliam H. Oates, 1851 Exhibition Science Scholar, Firth College, Sheffield. The paper contains an account of attempts made to estimate the total amount of sulpliur compounds present in the atniosphere of SheKeld. Various forms of apparatus and different oxidihing agents, such as hydrogen peroxide, sodium peroxide, iodine, and potassium per-manganate, were tried, but in none of the experiments was it conclusively proved that all the sulphur compounds present in the air were oxidised and ret'aiued by the apparatus used. The results of the determinations tend to show that the amounts of sulphur compounds present in the air, which have been previously published, are considerably too low, and that none of the forms of apparatus used in the experilnerits described are capable of yiclding correct results.At the next meeting, on Thursday, December 6th, there will be :t hallot for the election of Fellows, and the following papers will be read :-“ The relative behaviour of chemically prepared and of atmospheric liquid nitrogen.” By Professor Dewar, F.R>.S. “ The use of the globe in the study of crystallography.” By J. Y. Buchanan, F.R.S. “ The latent heat oE fusion.” By Holland Crompton. “ New Method of preparing dihydyoxgtartaric acid.” By H. J. H. Feuton. ‘. Essential oil of hops.” By A. C. Chapman.
ISSN:0369-8718
DOI:10.1039/PL8941000211
出版商:RSC
年代:1894
数据来源: RSC
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