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Proceedings of the Chemical Society, Vol. 12, No. 166 |
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Proceedings of the Chemical Society, London,
Volume 12,
Issue 166,
1896,
Page 113-118
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摘要:
Issued 2/6/1896, PROCEEDINGS 01' THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. No. 166. Session 1895-96. May 21st, 1896. Ah. A. G. Vernon Harcourt, President, in the Chair. 91r. Thomas B. Case was formally admitted a fi'ellow of the Society. Certificates were read for the first time in favour of hlessrs. John Henry Garrett, Cheltenham ; Leon Felix GolJstsnd, 12, Quai Anglais, St. Petersbourg ; Alfred Griffiths Greenmay, Llandrindod Wells, N. Wales ; Ernest George Hill, Muir College, Allahabad ; Joshua Arthur Hughes, Abercam, Monmouthshire ; Herbert E. Law, 1526, Vallego Street, Ssn Francisco ; Asutosh Mitra, Kashniir ; Samuel Thomas Skelton, 13, Derby Street, Ramsbottom, near Kan-chester Mi.. J. Morrow Campbell is reinstated as a FelIow.The following papers were read :-'69. '' The diphenylbenzenes. I. Metadiphenylbenzene." By Frederick D. Chattaway, M.A., and R. C. T. Evans. Three isomeric diphenyl benzenes, C,H4(CsH5),,are possible, but up to the present only two compounds having this formula. are known, paradiphenylbenzene, and the so-called isodiphenylbenzene. The constitution of the former is established, as it has been obtained from paradibromobenzene, and yields on oxidat ion paradiphenyl-carboxylic acid and terephthalic acid ;the constitution of the latter is still doubtful. The authors have undertaken the synthesis of ortho- and meta- diphenylbenzene, and this paper contains an account of the first part of the investigation, 114 When benzene vapour is Ied through a red hot tube tube, a niix-ture of hydrocarbons is obtained, and from the portion distilling at temperatures near 400" paradiphenylbenzene and the so-called iso-diphenylbenzeue have been isolated.This Intter, on oxidation, yields chiefly a mixture of benzoic, I)aradiphenylcai.boxylic, :~nd terephthalic* acids. No conclusion as to its constitiition can be drawn from this, altliougli the fact that its iriono~)l.omo-derivatlveyields, on oxids dt',1011, an acid which, on reduction, yields diphenylmetscnrboxYvlic acid, shows that thc pheriyl groups probably occupy nieta positions. Haring obtained met:Ldicblorobenzene in large amount, ttie authors have sgnthesised from this metadipheriylbenzeiie, which proves to be identical with the iaodiphenyl benzene obtained from benzene.The hydrocarbon was obtained by the action of melted sodium on a niix-tnre of metac~ichlorobenzeieand chloro\;enxene dissolved in boiling xylene. It is easily sepamted from the other products of the actioii by fractional distillatiou. Metadiclilol.o7ueiizeiic appears to liave very slight action on benzene iii the preseiice of anhydrous aluminium chloride, and the hpdro- caybon cannot be prepared in tltis way. Metadiphenylbenzere is a colouvless srtbstance, easily dissolved by ordinary solvents, and crystallising in star-shaped groups of fine needles. It melts at 84", and boils at about 369" under a pressure of 766 mm. Its composition and molecular weight, determined by Raoult's method, using benzene as a solvenh, agree very closely with tl~ose required by the formula c6H3(C,H,),. "70.'' Derivatives of camphoric acid." By F.Stanley Kipping, Ph.D., D.Sc. The paper contains an account of numerous derivatives of cam-phoric acid which have been prepared f i*oiu .rr-bromocamphoric acid, and some of which have been briefly described in previous notes (Proc., 1895, 148,33 ; 151,88 ;157,210) ; the formation, properties, and relation to one ancther of all these substances are explainecl on the basis of Bredt's formula €or camphoTic acid. The lactonic monocarboxylic acid, CloHI,O4(ni. p. 1G5"), which is produced when an aqueous solution of sodium slr-bromocampborate is boiled, is derived from tr.ans-.rr-hydroxgcamphol.ic acid, CloH,,O (m.p. 131°), whereas the more stable isoineride (m. p. 2%') is the lactone of a cis-.rr-hydroxycarnphoric acid, which seems riot to exist except in the form of a salt. These lactonic acids are named trans- p-camphanic acid and cis-z--camphanic acid I-espectively, in order to recall the fact that they are isomeric with, and closely related to, the w-camphanic acid, which is derived from w-bromocamphoric acid (Trans., 1896, 69, 61). 115 Trans-rr-cai,~rlLalzicadLydride, C20H260j,crystalliscs in prim s of indefinite melting point ; the isomeric mzhgdyide of the cis- acid crys-tallises in plates or prisms, melting at 1ti4-165°. ~~'asLs-7;-camn~hutza?~zide, is obtained when nietliy lic CgHl3O1*Ci3*NH2, 7;-bromocamphorate(m.p. 114-115') is treated with aqueousamnionia ; it crystallises from aqueous ammonia in transparent octahedra, ad melt's at 114-115'. Neethylic cis-rr-cainyIaanate crystallises iii prisms melting at 75'. LU-Hydroxy-cis-.rr-comphaiiicacid, CloH,,O,, prepared by oxidising cis- z--camphariic acid with potassium permanganate, separates from water in transparent, hydrated prisms, mid melts at 264-265'. z~-acetozy-cis-rr-ca~~~pkai~icacid, CloH,,O,(OAc), is formed wheli the hydroxy-acid is heated with acetgl chloride ; it crystallises well, and melts at 123-124O. n--acetoxgcanzphoricanhydride, C12H1605,prepared by treating trans- z--hydroxycamphoric acid with acetyl chloride, crystallises in mono-symmetric plates, and melts at 86-87' (at 89-90' on re-heating).When trans-a-caiiipliaiiic acid or 7.r-hydroxycamphoric acid is oxidised with nitric acid, it is converted quaiititstively into a tri-carboxylic acid of the composition CloH,,Os (m. p. 196'), which is iiamed ti-nns-cun~photi.icai.boxylic acid; this substance crystallises from water in massive orthorliombic pyramids, and is extremely stable towards ordinary oxidising agents ; its formation from r-hydroxycamphoric acid shows that the latter substarice contains the group -CH,*OH, and consequently the rr-substituent in all these a-derivatives has displaced hydrogen from a methyl group. trawcanzphotricarboxy lic cdiycli-icle, C10H1205,forms monosymme- tric crystals and melts at 253-254". Two isomeric lactones are formed when trans-camphotricarboxylic acid is treated with bromine and amorphous phdsphorus at 100' and the product then warmed with water; these compounds have the composition CloHI2O6,and are both derived from a rw-dihydroxy-campliotrical.boxylis acid of the composition CloH140,.The one (/3-lactone) cr~stallises in six-sided plates, and melts at 220' ; the other (-1-lactone) crystallises in flattened needles of indefinite melting point, and is formed from the isomei-ide by heating the latter with allislis and then acidifying.cis-canz~hotyicarbolL.yZicacid, CloH1,O, is obtained as a salt when the ti*niis-acid is fused with potash ; it crystallises in massive trans- parent prisms, and has no definite melting point, owing t9 the eaw with which it is converted into its anhydride.cis-caiiip;"Lu~i.ic~~i.~o~~~l~ccinhythide, C,,H,,O,, is formed when the trniis-acid is lieated aloiie or with cbaueiitw,tccl sulpliuric acid ; it 116 ci-ystsllises from beuzeuo in prisms which cflloresce in tlic air aiid melt at 220”. *7L “On some substances which exhibit rotatory power both in the liquid and crystalline states.” By William Jackson Pope. Although a very large number of organic substances are known which in the liquid or amorphous condition rotate the plane of polarisation of a polarised ray passing through them, veyg few ci-ystnlline substances are known which exhibit this same property ; a still snialler numbel-of substances are known which exhibit circular polarisation both in the amorphous and crystalline condition.Substances which exhibit circular polarisation when amorphous very frequent.ly crystallise in those crystalline sub-systems in which enantiomorphisin is possible, losing during the process of crystal-lising the power of circularly polarising light ; during crystallisa- tion, the latter property is in some way compensated for by thc crystalline structure, which has neither planes nor a centre of sym-metry. Thc exact connection between the crystalline form and optical activity of circularly polarising substances is as yet by no ineans settled, and any yeinarkable cases of ciytallisattioiiof such active substances consequently possess great importance. Two substances only, viz., matico camphor and rubidium tartrate, :we known which possess the power of circularly polarising light in both the amorphous and crystalline states.The author iiow describes a third case, that of cis-rr-camphanic acid, which crystal- lises in t’he pyramidal hexagonal system ; when viewed between crossed nicols, the hexagoiial optic axial picture is seen to be of the peculiar appearance chamcteristic of circularly polarising hexagonal crystals. The crystals are strongly pyroelectric, and are laxorotatory, the specific robation being thus of tlie same sigii as that of the amor-phous or dissolved substance. Although so few cases of the occurrence of true ciidar polarim-tion in both amorphous aiid crystalline states are known, a large nunibel-of optically active substances are known, the crystals of which do, in parts, exhibit circulay polarisation.The latter pheiio- loenon is, Iiowever, due to more or less coniplicated twinning; it is iiot a result of the actual molecular structure of thc crystal, but of tlie superposition of tliiii Iaminze of the ciystal. These cases should consequently iiot be considered as true examples of the occurrence of circular polarisation in the two statea. Circular polarisation caused by the piling up of thin plates of biaxial crystals at definite angles to each other has beeii demonstrated by Reusch, who arranged clcavage flakes of mica oiic on tlic other iu n, definite sense, tlie o1,tic axial plltiics of ally picce beiiig at Ciuo to those of the two 117 plates in contact with it ; the resulting pile is uniaxial and circularly polarising. A very beautiful example of this kind of circular polari- sation is found in the hydrated crystals of the optically active trans- camphotricarhoxylic acid (see preceding paper) ; this substance crp tallises in six-sided plates which simulate hexltgonal symmetry, but are really composed of six sect80rs of an orthorhombic crystal.At the edges of the plat,es, where rio overlapping of the scctors occurs, tbe bisxial interference figure of the orthorhombic crystal can be seen, whilst in the centre of the plate, where the sectors meet and overlap, the optic axial plane of’ eacii sector being at 60” with those of its two neighbours, a uniaxial interference figurc is seen and circular polarisation is observed.The crystals of this substance thus afford a very sirikiiig imitation of Reusch’s circularly polarising piles of mick plates. *72. “ Dimethoxydiphenylmethane and some of its hornologues.” ByJohn E. Mackenzie, Ph.D.,B.Sc. This compound was prepared by the action of sodium rnethylate 011 Iwnzophenone cliloride according to the equation (C,U,),CCl, + ;2N;tOCH, = (C,H,),C(OCH,), + 2NaC1. The cliloride W~Sadded to the alcoholic solution of the sodium metliylate, and a,tfter i.caction had taken place, tlie nholc was heated in a water bath for t fi o hours. ‘Clich sii bstancc 1%as obixilied pui-e by i~eci~~-stallisatiorifrom alcohol, t iick 3 icbld being 81 per cent. of tlie calculated. The crystals are perfectly colourless arid odour-less, melt at 106.5--107” aid boil at 28t3--290° without deconipo-sitioii. ‘l’liey are easily soluble in ether, hot inetliyl and ethyl alcohols, and benzenc, but less so in the cold, iiisolnble in water.The substance is volatile with steam. It is uiiaffectecl by alkalis, but is decomposed by acids, forming bcnzoplirnone. lu a desiccator over sulphnric: acid it loses ether. Diethoxydiplieiiylnietliane (C:,H,):C( OC,H,), is prepared similarly. Yield 8.5per cent. of tIie cdculated. The colourless crystals melt at 51*5--r>P. Ths solubility aud general L~ehaviourare similar to the methoxy-cornpouri d. Dibeirzoxydiplienylniethaue (C6€15)2C(OC7H7)2is prepared sirniilarly, except that the mixture of chloride and the sodium derivative of the alcohol is heated to 205-210O.The crystals melt at 104--105O, and decompose when distilled. Tiq- deliquesce on exposure to air. They are easily dissolved by the ordinary solvents when hot, with difficulty when cold. 118 ADDITIONS TO THE LIBRARY. I. By Piwchase. Gadolin, Axel. Abhandlung iiber die Herleitung aller Krystsllo- grapbischer Sgsteme mit ihreii Unterabthcilungen aus Einem Ein-zigen Prinzipe. 92 pp., with 26 figures and 3 tables. Leipzig 1896. 8vo. (Oatwnlil’s Klassiker der Exakten Wissenschaften. 75). KirchoE, G., und Bunsen, Itt. Chemische Analyse durch Spectral- beobachtungen. 134 pp., with 2 tables and 7 figures. Leipzig 1895. 8vo. (Osttvald‘s Klassiker der Exakteii Wissenschaften.72). 11. Doiiatioizs. Lawes, Sir John Bennet, F.R.S., aid Gilbert, Sir J. Henry, F.R.S. The Rothamsted Experiments : being an Account, of some of thc Results of the Agricultural Investigations conducted at Rothamsted in the Field, tlie Feeding Shed, and the Laboratory, over a period of 50 years. viii +354 pp. London 1595. Prom the Auihors. ramphlets. Pearce, Richard. Sonic Kotcs on the Occurrence of ITrsninite in Colorado. (Read before tk e Colorado Scientific Society, iu Denver, Septem- ber 9, 1895.) From the Author. Seyewetz, A.? and Sisley, P. Chemie des MatiAres Colorantes Artificielles. Vol. I, viii+l51 pp. ; Vol. 11, 153-336 pp. Paris 1896. 8vo. From tlie Authors. RESEARCH FUND, A meeting of the Research Fund Committee will be held in June. Applications for grants, accompanied by full particulars, should be sent to the Secretaries before June 8th. At the next meeting on June 4th, the following papers will be read :-“ The magnetic rotation of organic substances with especial reference to benzenoid conipounds.” By Dr. W. H. Perkin, F.R.S. “Note on santalal and some of its derivatit-es.” By Alfred C. Chapman and H. E. Burgess.‘‘Monoiiitroguaiacol.” By Professoi. Meldola, F.R.S. HABBISON AND SONS, PBINTEBS IN ORDINARY TO HER XAJESTY, ST. MARTIN’S uzsc.
ISSN:0369-8718
DOI:10.1039/PL8961200113
出版商:RSC
年代:1896
数据来源: RSC
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