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Proceedings of the Chemical Society, Vol. 6, No. 84 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 84,
1890,
Page 75-94
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摘要:
Issued 31/5/1890. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 84. Session 1890-91. May 15th, 1890. Dr. W. J. Russell, F.R.S., President, in the Chair. Mr. James Hamilton was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. Charles F. Branson, Eenley Lodge, Macaulay Road, Clapham Common ; John Huchinson Edwhrd, 117, Stockport Road, Manchester ; Arthur R. Haslam, Ph.D., 64, Rathgar Road, Dublin ; John Robert Johnson, 16, Oxford Street, Liverpool ; Patrick Kelly, 43, Lennox Street, Dublin ; Thomas Parker, M.I.C.E., Wolverhampton ; Richard James Redding, Royal Laboratory, Woolwich Arsenal ; Frederick Smith, Johannesberg, Transvaal, South Africa. The following were elected Fellows of the Society :-James Robert Appleyard ; William Henry Blake ; James Rear Colwell ; S.Sydney Monckton Copemnn, M.A., 3I.B. ; Andrew Fair- grieve ; G. H. Findlay ; Jobn Archyll Joues ; Oliver Kirk ; Robert Walter Oddy ; William Tate. The following papers were read :-36. " Diethylphosphorous acid " By T. E. Thorpe, F.R.S., and Barker North, Associate of the Normal School of Science. The authors describe the mode of preparing this compound and its properties. It is obtained by adding alcohol, drop by drop, to phos- phorous oxide contained in a, vessel surrounded with ice and salt. It is a colourless, mobile liquid, possessing a peculiar penetrating 76 alliaceous smell. Its vapour is poisonous, and even small quantities produce headache and nausea.It boils at 184--185', and has the 15.5"relative density 1.0749 at -. It interacts with water forming4 alcohol and phosphorous acid, and is converted by bromine into ethyl bromide and metaphosphoric acid. 57. " The homonucleal trichloronnphthalenes." By Henry E. Armstrong and W. P. Wynne. I :2 : 3-Tr~chZoronnphthaZelae.-The compound prepared by Faust and Saame from a-chloronaph tlialene tetrachloride has been shown by Widman to be this modification, the proof being that it affords nitrotrichlorophthalic a,cid on oxidation with nitric acid ; the authors have obtained it from a novel source-by the action of phosphorus pentachloride on Zincke and Kegel's @-dichloro-P-naphthol (Berichte, 1888,3385). This naphthol-derivative is found to crystallise in aggre- gates, such as Zincke and Kegel describe, of long, prismatic needles springing from a common centre-m.p. 76-77"; also (a) in fairly large aggregates composed of characteristic short, stumpy prisms- m. p. 76-75'" ; and (b) in very long, slender, flat, transparent needles melting at 66", and on refusion at 74". In no case was a higher melt- ing point than 77" observed. Zincke and Kegel, however, give 81" as the melting point of the substance ; and it is noteTborthy, therefore, that the authors find the melting point of trichloroke tonaphthalene to be 92-93', instead of 96", and that one of them, in conjunction with Mr. Rossiter, has found that the various chloro-derivatives of P-naphthol described by Zincke and Kegel uniformly melt at temperatures about 4" lower than stated by these chemists ; it may also be mentioned that a similar discrepancy is to be noted in the case of a recent paper of Clausius (Berichte, 1890,517), who specially calls attention to the fact that he finds the melting point of 2 : 2'-di-hydroxynaphthalene to be 4" higher than previously observed.ap-Dichloro-/3-naphthol exchanges its hydroxyl for chlorine when distilled with the theoretical quantity of phosphorus pentachloride at 240-250". The resulting trichloronaphthalene crystallises from alcohol, in which it is sparingly soluble in the cold, either in long, very slender needles or in radiate aggregates OP flat needles ; it melts at 81". It is but little acted on when heated at 100" with H,S04, but is readily sulphonated when digested with four times its weight of acid containing 10 per cent.SO3foil an hour at 100". The bnriam salt of the acid, (C10H4C13S03)BBa,+ 3+H20, crystallises in small, spberical aggregates, and is sparingly soluble in water ; the potassium salt, C10H4C13S03K, is very soluble in water, but sparingly soluble in 77 alcohol, from which it crystallises in minute, anhydrous needles. The chloride, CIoH4Cl3*SO2Cl,crystallises from benzene, in R hich it is very soluble, in small, prismatic needles ; from petroleum spirit, in which it is sparingly soluble, in small, flat, slender needles ; and from acetic acid in white aggregates of very small needles; it melts at 182". The amide could not be obtained crystalline : it melts at 296".The chloride was hydrolysed by prolonged heating with concentrated muriatic acid at 260" : the regenerated trichloronaphthalene crystal- lised from alcohol in long, slender needles melting at 81". 1 :2 :$-TrichZoronu~hthuZene.-This modification was first prepared by Cleve, who most accurately described its properties (Berichte, 1888,893),from dichloralphanaphthol ; the authors prefer to prepare it from dichloralphanaphthylamine. It melts at 92". When sulphonated, either by means of the theoretical quantity of SO,HCl, or by heating with twice its weight of H2S04at 100" for one hour, it yields an acid which when dissolved in water forms a viscid solution -in this respect resembling the acid obtained by sulphonating 1: 4-dichloronaphthalene. The barium salt (CloH4C13S03)2Ba + 3H,O is very sparingly soluble in water, and crystallises in fluffy masses of very small, slender needles ; the potassium salt C,H,C'l,SO,K is extremely soluble in water, but sparingly soluble in alcohol, from which it crystallises in anhydrous, short, slender needles.The chloride CloH4Cl.3S0,C1crystallises from benzene in tufts of long, slender needles ; from petroleum spirit, in which it is sparingly soluble, in long, slender needles ; and from acetic acid in slender, flat needles ; it melts at 157-158". The amide crystallises from alcohol in tufts of short, slender needles, and melts at 235". The chloride was hydrolysed with considerable difficulty, requiring prolonged heating at 260-265" with concentrated muriatic acid : the resulting tri-chloronaphthalene crystallised from alcohol in tufts of slender, flat needles melting at 92".38. "The ten isomeric dichloronaphthalenes and the sulphonic acids and trichloronaphthalenes derived therefrom." By Henry E. Armstrong and W. P. Wynne. Whereas, theoretically, only ten dichloronaphthalenes arc possible, twelve have actually been described. Nine of these are already proved to be definite substances, and their constitution may be re-garded as well established (cj. these Proceedings, 1888, 104; 1889, 34,48) ; these nine include the three possible ax-, the four possible &-and the two possible hetero-&3-compounds. Of the r:maining fhree, one-the so-called a-dichloronaphthalene (m.p. %')-has been shown by the authors to be non-existent, and to consist of the (fl\A( M. p. = 67.5'. c1 c1fYI w M. p. = 82". c1ii^lX" M. p. = 106.5'. M. p. =119'5'. C l M c1 HI M.\A/p. = 114'. /\AClIllclv\/ M. p. = 135'. 78 aa-Dichloronaphthalenes. c1 c1 S02C1, m. p. = 132'. M. p. = 669 SOzNHz,m. p. = 244'. SOzC1, m.p. = 114". M. p. = 131'. SO2NHZ,m. p. = 228'. c1 c1 80zC1, m. p. = 139 -5'. M.p. = 103'. S02NH,, m.p. = 204'. pp-Dichloronaphthalenes. S c1 S02C1,m. p. = 142". M. p. = 109.6O. SO2NH2,m. p. = 268'. S02C1, m. p. = 178". -SOzC1, m. p. = 163.5'. M. p. = 91". S02NH2,m.p. = 218'. A/\Cl-Ill c1vy S02Cl, m. p. = 136O.M. p. = 113O. B02NH2,m. p. = 269". 79 ap-Dicldoronap hthalenes. c1 c1 c1 ,iyio'A\/'\/ \ M. p. = 35". S02C1, m. p. = 104'. S02NH2,m. p. = 217.0 c1 M. p. = '78.5". c1 S02C1,m. p. = 167'5O. S02NH2,m.p. = 190". - I l lclv\/DL p. = 91". c1 c1 c1 S02C1, m. p. = 148 -5". M.p. = 103". S02NH2,m. p. = 272". BA c1A clfl\ 3 IJ"lC1 M.\/vclS02C1, m. p. = 121O. p. = 113". S02NH2,m. p. = 228". c1 c1 M.p. = 62.543%". S02C1,m. p. = 118". M.p. = 66". S02NH2,m. p. = 226". c1 c1 c1 A/\ /v\ cl\/v -c1I \/ i)\Cl M. p. = 48". S02C1, m.p. = 151". M.p. = 66". SOnNHn.m.D. = 216". 1:3-(m. p. 61") and 1 :4-(m. p. 68') modifications (these Proceedings, 1888, 106). A second is undoubtedly also non-existent, viz., the " K-dichloronaphthalene" (m.p. 94"),which, according to Claus (Ber., 1882, 314), is obtained by the action of phosphorus pentachloride on the a-naphtholsulphonic acid prepared by sulphonating a-naphthol dissolved in acetic acid. The several monosulphonic acids formed from a-naphthol, however, correspond to one or other of the nine recognised dichloronaphthalenes, and on this ground alone the pro- duction of the tenth, and-it is to be supposed-only possible, modification in such a manner appears impossible : even if the facs be left out of account that homo-PP-dichloronaphthalene-the only modification required in addition to the nine above specified in order to complete the list-cannot be prepaTed from akpha-naphthol. Aiaphthol is converted, with exceptional facility, into the 1: 2 :4-disulphonic acid, and the corresponding trichloronaphthalene melts at 92", which is very nearly the melting point of Claus's compound ; the authors, therefore, have little doubt that the substance described by Claus as K-dichloronaphthaleIie was in reality 1 : 2 : 4-trichloro-naphthalene.The only remaining modification to be considered is the L-dichloro- naphthalene (m. p. lZO"), first prepared by Leeds and Everhard by heiting naphthalene tetrachloride with silver oxide, and which was subsequently separated by Widman from the product of the action of alcoholic potash on the tetrachloride; until it was discovered that a-dichloronaphthalene was a mixture of the 1: 3-and 1 : 4-corn-pound, the authors were inclined to think that perhaps this modifica- tion was impure c-dichloronaphthalene (cf.B. A. Report, lSSS), but the necessity for this assumption occasioned by the existence of the a-compound having been removed, it appeared highly probable that the L-compound was the homo-PP-modification ; and this proves to be the case, the authors having succeeded in obtaining asubstance with all the properties ascribed by Leeds and Everhard and by Widman to 4-dichloronaphthalene by a novel method which places its constitution beyond all doubt, viz., by partially reducing 1 : 2 : 3-tri-chloronaphthalene. The existence of a complete series of ten isomeric dichloro- naphthalenes may, therefore, now be regarded as established. No fewer than eight of these have been discovered by Cleve and his pupils ; all who study the subject must be led to admire the work of the Swedish chemists and to recognise the influence which it has exercised.In order to characterise the various dichloronaphthalenes, and also to determine the manner in which constitution affects the course of chemical change in the case of naphthalene-derivatives, the authors 81 have sulphonated the ten modifications, and have converted the resulting sulpho-acids into tricbloronaphthalenes. A brief account of the results is now given, details with reference to the composition of the salts, &c., being reserved for afull communication. To avoid the possibility of the occurrence of secondary changes induced by the presence of water, chlorosulphonic acid was through-out employed as the sulphonating agent instead of sulphuric acid, and sulphonaiion was effected by adding slightly less than the theoretical quantity of this agent to a 10 per cent.solution of the dichloro- naphthalene in dry carbon bisulphide ; the carbon bisulphide was subsequently removed by distillation on a water-bath, the acid dissolved in water and the solution steam-distilled to free it froni unattacked dichloronaphthalene and traces of carbon bisulphide, and finally filtered to remove the small proportion of insoluble, non-volatile compound (sulphochloride or sulphone) always formed. az-Dichloronaphthal enes. (1.) 1:4-DichZoro~nphthalene.-On sulphonation, this yields a practically uniform product, a very small proportion of an isomeric acid of undetermined constitution being simultaneously formed.The chZoride of the acid, CI,H,Cl,S02C1, crystallises from benzene, in aggregates of slender, prismatic needles melting at 132" ; the amide is sparingly soluble in cold alcohol, crystallising in tufts of very slender, long needles melting at 244". The corresponding trichloro-naphthalene crystallises in tuits of slender needles, which, on stand- ing, undergo conversion into opaque, white aggregates melting at 66" (cf. these Proceedings, 1890, 18). The sulphochloride undergoes hydrolysis when heated wit'h concentrated muriatic acid at 260- 265" ; the pure dichloronaphthalene thus obtained crystallised from alcohol in long, narrow, slender ribbons melting at 67.5".(2.) 1: l'-DichZoronaphthaZen~was prepared by Attsrberg's method (Bey., 1876, 1732) from P-dinitronaphtlialene. The sulphonation product consist,s of a single acid, the chloride of which crystallises from petroleum spirit in minute aggregates melting at 114"; the amide crystallises from alcohol in tufts of small, slender needles melting at 228". The corresponding trichloronu~l~tAaZenecrystallises from alcohol in very long, slender needles melting at 131". (3.) 1: 4'-DichZo~onaphtl~aZeneyields two acids on sulphonation ; one of these is formed in small quantity only, and has not been com- pletely examined, The chief product yields a chloride which crystal- lises from benzene in aggregates of long, flat, thin, narrow plates melting at 139.5" ; the amide crystallises in small, prismatic aggre- gates melting at 204".The corresponding trichloronaphthdene 82 crystallises from alcohol in long, slender needles melting at 103". On hydrolysing the acid at 260-265" with concentrated muriatic acid, pure 1 :4'-dichloronaphthalene was obtained, which crystallised from alcohol in short, flat, thin scales melting at 106.5". ap-Dic~loronaphthnlsnes. (4.) 1:2-Dichloronaphthalene is found to yield a mixture of an U-and a P-sulphonic acid, the former constituting about two-thirds of the product. The chlorides of the two acids require to be mechanically separated after crystallisation from benzene. a-Acid.-The chloride crystallises from benzene, in which it is very soluble, in large, prismatic forms melting at 104' ; the amide crystal-lises from alcohol in tufts of small, slender needles and melts at 217".The corresponding trichZoronuphthaZene crystallises from alcohol in short, flat needles melting at 78*h0. On hydrolysis with concentrated muriatic acid at 230",the chloride gave pure 1: 2-dichloronapbthalene melting at 35". /I-Acid-The chloride of the @-acid is less soluble in benzene, and crystallises in aggregates of small prisms melting at 167" ; the amide crystallises from dilute alcohol in short, slender, white needles melt- ing at 190". The corresponding trichZoronaphthaZene crystallises from alcohol in slender needles and melts at 91". On hydrolysis with concentrated muriatic acid at 260-5365', the p-chloride gave pure 1:2-dichloronaphthalene melting at 35".(5.) 1: 3-Dichloronaphthalene.-On sulphonation this yields a mix- ture of an a-and a &acid, the former constituting about four fifths of the product. The chZoride of the @-acid crystallises from benzene in well-defined prisms melting at 148.5",and crystallographically identical with those of the chloride of Widman's dichloronaphthalene-a-sulphonicacid ; the amide is sparingly soluble in alcohol and crystallises in flocks of microscopic needles melting at 272". The corresponding trichzoro-nuphthalene crystallises from alcohol in long, slender, flak needles melting at 103". On hydrolysis with concentrated muriatic acid at 230", the a-chloride gave pure 1 : 3-dichloronaphthalene, which crystallised in long, slender ribbons melting at 61".The P-acid, although the minor product of sulphonation, constitutes the sole product when the sulphonation product is heated in a dry atmosphere at 160" for 18 hours. Its ch7oride is very soluble in benzene and crystallises best from a mixture of benzene and petroleum spirit in long, narrow, four-sided prisms melting at 121" ; the anzide crystallises from alcohol in tufts of short, very slender needles, and melts at 228". The corresponding trichloronaphthalene is sparingly holuble in hot alcohol and crystallises in short, slender needles melt- ing at 113". On hydrolysis with concentrated muriatic acid at 260-265") the /%chloride gave pure 1:3-dichloronapllthalene melt- iug at 61°.(6.) 1: Z'-Dichlorona~hthaZeneyields an almost uniform product OR Hulphonation, the proportion of isomeric acid formed being very small. The chloride of the chief product crystallises from benzene in trans-parent, slender, flax needles which rapidly became opaque on exposure to the air, and then melt at 118"; the amide is sparingly soluble in alcohol and crystallises in narrow, slender ribbons melting at 226". The corresponding trichloronap hthaZene crystallises from alcohol in slender, flat needles which, on standing in the solrent, became opaque and melted at 66". On hydrolysis with concentrated muriatic acid at 230", the chloride gave pure 1:2'-dichloronaphthalene, which crys- tallised from alcohol in small, crystdliue aggregates melting at 62.5". The synthetical 1: 2'-dichloronaphthalene, prepared by Erdmann's method, was found to melt slightly higher, viz., at 63-63.5".(7.) 1 : 3'-DichZoronaphthalene yields an uniform product on sul-phonation. The chZoride of the acid crystallises from benzene in magnificent prisms and melts at 151"; the nmide crystallises from alcohol in long, slender needles melting at 216". The corresponding trichloronaphthalene crystallises from alcohol in slender, Bat needles which become opaque on standing in the solvent and melt at 66". On hydrolysis with Concentrated muriatic acid at 230") the chloride gave pure 1: 3'-dichloronaphthalene, which crystallised from alcohol in long, slender ribbons melting at 48".pp-Dichloronaphthalenes. (8.) 2 : 3-Dichloron~phthclene. To prepare this modification a solution of 1: 2 : 3-tlrichloronaphthalene in alcohol heated at 60-70" is treated with one and a half times the theoretical qusntityof 2 per cent. sodium amalgam during one hour ;the L-dichloronaphthalene is purified by fractional steam-distillation and fraciional cry stallisation from alcohol. It crystnllises in the manner described by Leeds and Ever-hard and by Widman, in thin, lustrous scales, and melts at about 120". On sulphonation it yields a product containing an a-acid and probably a @-acid, the former constituting the chief product. The &-chloride crystallises from benzene in lustrous, slender, narrow ribbons melting at 143"; the arnide is sparingly soluble in alcohol and crystallises in aggregates of small, slender needles melting at 268".The corre- sponding trichloronaphthalene crystallises from alcohol in long and very slender needles, and melts at 109.5". On hydrolysis with con- 84 centrated muriatic acid at 230°, thea-chloride was found to yield pure 2 : 3-dichloronaphthalene, which crystallised from alcohol in the characteristic thin scales melting at 119.5". Isomeric Acid.-The salts of this acid have not yet been obtained in quantity sufficient for analysis. The chloride is very soluble in benzene and crystallises in opaque, hemispherical aggregates melting at 178"; on hydrolysis with concentrated muriatic acid at 260-265", it gave 2 :3-dichloronaphthalene melting at 119.5".There can be little doubt that this acid has the constitution [Cl, : SOsH = 2 : 3 : 2'1. (9.) 2 :2'- DichZoronaphthalene yields an almost uniform product on sulphonation, the proportion of isomeric acid formed being yery small. The chloride of the chief product cryst;tllises from benzene in well-formed, elongated prisms, and melts at 163.5' ; the arnide crys- tallises from dilute alcohol in tufts of long, slender needles, and melts at 218". The corresponding trichloronaphthalene crystallises from alcohol in minute plates and melts at 90-5-91". On hydrolysis with concentrated niiiriatic acid at 260--265", the chloride gave pure 2 :9'-dichloronaphthalene, which crystallised from alcohol in large, thin laminae melting at 114".(10.) 2 :3'-Uic~Zo~onaphthaZencaffords an almost uniform sulpho- nation product, the proportion of isomeric acid formed being small ; the chZoride of the chief product crystallises from benzene in radiate groups of long, slender, prismatic needles melting at 136" ; the arnide is sparingly soluble in alcohol and crjstallises in small aggregates of prismatic needles melting at 269". The corresponding trichZ0s.o-maphthaZeiae is sparingly soluble in alcohol and crystallises in small, slender needles melting at 113". On hydrolysis with concentrated muriatic acid at 230J, the chloride gave pure 2 : 3'-dichloronaphtha-lene crystallising from alcohol in long narrow, ribbons melting at 135". It is noteworthy that the chlorides OP the 6-sulphonic acids require prolonged heating at a higher temperature than those of the a-acids to effect their hydrolysis ; and that on distillation with phosphorus pentachloride they give a smaller yield of trichloronaphthalene.In the table on pp. 78-79, the formulte of the dichloronaphthalenes are given in the first column, those of the acids into which they are converted on sulphonation we given in the second, and the third comprises the trichloronaphthalenes obtained from the dichloronaph- thalenesulphonic acids. The evidence on which the constitution of the tri-derivatives here given is based has been incidentally given in previous papers (cf. these Proceedings, 1889, 48 ; 1890, 11),and will be snmmarised in a forthcoming account of the trichloronaphtha- lenes.85 39. “The chlorides of naphthalene and its derivatives, and the manner in which they are decomposed by alkalis.” By Henry E. Armstrong and W. P. Wynne. It being established that t-dichloronaphthalene is the homo-p/j-moditication, it follows that naphthalene tetrachloride affords the three theoretically possible dichloronaphthalenes : HC1 c1 C1 ” Hbl The 1:3-compound is produced in largest, the 2 :3-in smallest, quantity. Hitherto it has always been supposed that, the dichloride which is the initial product of the interaction of naphthalene and chlorine decomposes only in one way, yielding a-chloronaphthalene ; the authors find that /%chloronaphthalene is also produced. They have been led to this discovery by further study of the isomeric acid obtained in small quantity together with 1:4-chloronaphthalene-sulphonic acid from a-chloronaphthalene by Armstrong and William- son (cf.these Proceedings, 1886, 233; B. A. Report, 1887) : this acid proves to be identical with that obtained on sulphonating /3-chlo- ronaphthaleue. In like manner, ihe secondary product obtained by Armstrong and Williamson from bromonaphthalene is derived from /3-bromonaphthalene, which is present in ordinary bromonaphthalene even after considerable fractionation. The proportion of /3-compound produced is but small in either case. This recognition of the presence of the p-compound in bromonaphthalene affords an explanation of Jolin’s observation that the sulphonation product of bromonaphtlla-lene contains an acid convertible into 2 :3‘-dibromonaphthalene.The manner in which chlorine acts on derivatives of naphthalene, as well as that in which the resulting chlorides decompose, becomes of special interest now that Bamberger’s researches have shown how very differently the a-and fi-derivatives behave when hydrogenised ; in the course of their experiments the authors have had occasion to collect a number of data bearing on this question, having re-examined the action of chlorine on the two chloronapht$alenes and the two monosulphochlorides. In each case, chiefly one tetrachloride is formed, and this decomposes chiefly in one way, the amount of sub-sidiary products in either case being relatively small; the exact nature of these subsidiary products has yet to be determined, and can- not be ascertained until considerable quantities of material have been operated on, and a more exact knowledge of some of the trichloro- naphthalenes has been obtained. The results of their own and previous observations are summarised in the following table :-Chief product of action Chief chloride.of potash on chloride. c1 c12 c1iyI /’d\ HC1 /-/\ c1-1 1 lHCl -w\’;&lJC1 31. p. = 81’. HCl c1 HC1 c1 The influence of the subst.ituent both as affecting the addition of chlorine and the elimination of hydrogen chloride is especially note- worthy. It will be seen that the sulphochlorides behave alike, but the two chloronaphthlenes dissimilarly towards chlorine, and that each compound decomposes in a manner peculiar to itself on treatment with alcoholic potash.40. “Isomeric change in the naphthalene series. No. 6. The influence of position in determining the nature of the isomeric change in the case of the chloronaphthalenesulphonic acids.” By Henry E. Armstrong and W. P. Wynzie. Arnell, in an “academic treatise” (Bidrag till Kannedom om Nuftalins Chlorsulfonsyror; Upsala,lSS9), in which a valuable summary is given of all that was known of the subject at the time of its pub-lication, states that when a-chloronaphthalene is sulphonated by means of sulphuric acid it yields both the 1:4-and the 1:4’-derivative, the latter forming a large proportion of the product when the sul-phonation is effected at an elevated temperature (160O) The forma- %ionof the l : 4‘-acid when sulphonation was effected by means of chlorosulphonic acid was overlooked by Armstrong and Williamson, but the experiments which they made on the effect of heating the initial product (these Proceedings, 1887,145) led them to believe that the 1:4-acid was converted into the 1:4'-isomeride.Further study of the subject has shown that the 1 : 4'-acid is obtained in small quantity when a cold solution of a-chloronaphthalene is sulphonated by means of S03HCI, the product being heated only for a short time on the water-bath to remove the bisulphide; and that if the product be heated at about 150" during 5-6 hours, almost complete conversion into the 1:4'-acid is effected.It is therefore not improbable t,hat the 1: 4-acid is the only immediate product of sulphonation, and that the small quantity of the isomeride obtained at low tempera- tures is due to the occurrence of isomeric change at the moment of interaction. The fact that the a-chloronaphthalene-derivativeundergoes change into the more symmetrical aZp7~a-isomeride, while 2 : lf-/3-chloro-naphthalenesulphonic acid is converted in a similar manner into the more symmetrical Beta-isomeride, appears to be noteworthy as indi- cating a tendency to a final state of symmetry, thus- On reference to the tables at pp. 78-79, in which the constitution of the acids formed on sulphonating the ten dichloronaphthalenes is indicated, it will be observed that in some cases an a-and in some cases a 6-sulphonic acid is formed, or a mixture of both.The suthors are of opinion that the cc-acid is always initially produced ; in some cases this is so unstable that it spontaneously passes over into the p-isomeride and escapes observation, while in others it is partially preserved. They base this conclusion on the fact that in all cases hitherto studied in which both acids are formed it is possible to con- vert the a-into t'he @acid by heating. Thus I :2-dichloronaphthalene affords about two-thirds x-and one-third /3-acid, but when the product is heated the latter is practically the sole product (cf. B. A.Report, 1889). In like manner the product of initial sulphonation from 1:3-dichloronaphthalene contains about one-fifth /3-acid; but if this be heated at 160" during 18 hours complete conversion into the P-isomeride is effected.It is noteworthy that the position ultimately taken up by the SO,H radicle appears to he determined by the beta-chlorine- atom, thus- Cl ,filA,.’ 88 (\,44 s,y)iy‘i -\A/\/\/ \A/S The p-snlphonic acids are probably the most “ degraded ” products, and from this point of view the further study of the behaviour of the 1: 4’-~-chlorosulphonic acid and of the 1: 1’: 4-rr-dichloro-sulphonic acids as well as that of the 2 :1‘-and 2 :4’43-and 2 : 3-and 2 : 3‘-pp-dichlorosulphonic acids will be of special interest, in order to ascertain whether or no the determining factor is the tendency of the molecule to acquire a configuration which most nearly approaches symmetry.41.“A third naphthaquinone.” By R. Meldola, F.R.S., and F. Hughes. In preparing monobromindone by the action of fuming nitric acid on dibrom-a-naphthol (Proc., 1890, 57), a small quantity of a bye-product is obtained which remains undissolved in alcohol on treating the crude indone with this solvent ; a sufficient quantity of this sub- stance has been obtained by the authors to enable them to identify it as a new naphthaquinone. The pure substance forms slender, pale yellow needles, having no distinct melting point, but blackening about 220’. It is not reduced by sulphurous acid solution, but by treatment with zinc-dust and acetic acid it is converted into a dihydr- oxynaphthalene crystallising in whitish needles which become slate- coloured on exposure to the air and have no definite melting point but darken about 205”.The dihydroxynaphthalene has all the pro- perties of a phenol, and is readily reconverted into the quinone by oxidation. Its diacetyl-derivative fuses at 226-227”. On oxidation with alkaline permanganate it affords 1:2 : 3-hydroxyphthnlic acid, C6H,(@H)(COOH), (m. p. 194-197”), and hence the authors con- clude that the quinone is the unknown peri-derivative :-0-0 iyiW The formation of this quinone during the oxidation of dibrom-a-naphthol by nitric acid cannot at present be explained; the authors suggest that in the bromination of a-naphthol a, minute quantity of peri-monobrom-r-napht.ho1 is produced, and that, this is converted into the quinone by the action of nitric acid.Experiments to test this explanation are in progreps. DiscussroN. Dr. ARMSTRONGsaid it appeared to him that, regarding the quinones as diketones, four true quinones could not be derived from naphtha- lene; the new compound described by the authors either had the constitution indicated by the formula which they had suggested, 0-0 /\/\I ,or it was a keto-compound of higher molecular weight, viz., 1 .=/-\=/-\=,\-/ \-/ : judging from its properties, this lattero=(_)=<)=o explanation appeared the more probable. It would, perhaps, be possible to decide this question by means of the Raoult method.The com- pound was of a novel type, and was one of great interest. The speaker also expressed the opinion that t,he formula assigned to the bromindone anilide which Professor Meldola had exhibited (Chem. Xoc. Trans., 1890, 399) did not satisfactorily account for its colour. Dr. QUIXCKEdrew attention to Graebe a'nd Veillon's experiments on the oxidation of acenaphthalene and his own on nitroperinaphtha- quinone; he thought that the compound obtained by the former chemists was the qzinone now described by Professor Meldola and Nr. Hughes. Mr. GROVES,in reference to Dr. Armstrong's statement that the new substance was not a true quinone, remarked that the same had been said of P-napthaquinone at the time of its discovery; it was a quinone notwithstanding.The new quinone, certainly, like di-naphthlyl-/I-diquinone, was very sparingly soluble in most solvents : but, on the other hand, it could easily be obtained in well-formed crystals, whilst the diquinom was a crystalline powder. Professor MELDOLAstated that the limitation of the term qninone to such compounds as could be represented as diketones was quite arbitrary, and he thought it justifiable to apply the name to all four dioxy-derivatives of naphthalene indicated by theory. It was for a long time undecided whether the quinones were peroxides or di-ketones, and even now the question could not, in his opinion, be regarded as definitely settled. He did not think the alternative formula suggested by Dr.Armstrong was more probable than their own, but the decision of the question by Itaoult's method would be attempted, although he feared the extreme insolubility of the corn- 90 pound in most solvents would interpose great practical difficulties. The objection raised ‘against the formula of bromindone anilide was of too general a nature to be met, especially in the absence of any alternative suggestion. He was not aware that any chemical formula could be written so as to account for the colour of an organic com- pound. It was well known that all the anilides of quinones were highly coloured bodies, and the formula proposed was the only one which satisfactorily represented the formation and properties of the compound in question. With respect to Dr.Quincke’s observation, Professor Meldola expressed his acquaintance with the work referred to, and stated that reference had been made to it in their paper (Chem. SOC.Trans., 1890, 398). The compound described by Graebe and Veillon had had the formula C24H,A0,ascribed to it by those authors (Ber., 1887, 659). 42. “The relative antiseptic powers of isomeric organic com-pounds.” By Thos. Carnelley, D.Sc. Aberdeen, and W. Frew, Dundee. The authors have determined the relative antiseptic powers, in reference to ordinary aerial micro-organisms, of a number of isomeric organic compounds, more particularly di-derivatives of benzene, with the object of investigating the influence of atomic arrangement on this property. A table of results is given which indicate that, so far as the com- pounds which have been tried are concerned (and with the exception of the hydroxybenzoic acids), para-compounds are more antiseptic than the corresponding ortho- and meta-compounds.On the whole, compounds containing the carboxyl-group are comparatively weak, while phenols and nitro-compounds are relatively strong antiseptics ; paranitrophenol being, with the exception of a-naphthol, the most powerful of any of the compounds tried. These results entirely accord with those of Walcott Gibbs and Hare, who have recently investigated the poisonous action of di-derivatives of benzene On dogs. 43. “Note on the preparation of pyrocatechol.” By W. H. Perkin, Jun., Ph.D. The veqr high price of pyrocatechol renders it desirable to discover improved methods of preparing it; the author has, therefore, studied the action of iodhydric acid on guaiacol, which is easilyprocured at a moderate cost.He finds that an almost theoretical yield of pyro-catechol may be obtained by boiling guaiacol with a fuming solution of hydrogen iodide ; details are given in the paper. 91 44. ‘‘ Benedikt’s acetyl values.’’ (Second notice.) By J. Lewkowitsch, Ph.D. THE results quite recently brought forward by the author (these Proceedings, 1890, 72) were so unexpected that it was determined to verify them by examining other fatty acids : capric, lauric, and cerotic acids were therefore acetylated in the manner previously stated. The approximate purity of the acids used was ascertained by determining the quantity of caustic potash required for their saturation.Capric Acid.-The acid value was found to be 318.65, while theory requires 326.2. The acetylated product gave an acid value of 176.4, and a saponification value of 350 4; consequentIy an acetyl value = 174. Lauric Acid.-The acid value found was 273.02, the theoretical value being 280.5. The acetylated acid gave an acid value = 161.5, a saponification value = 293.99; its acetyl value therefore was 132.49. Cerotic Acid.-The acid value found was 128.4; theory indicates for C26H5202141.6 (or for C2,H6,O,136.8). The acetylated cerotic acid gave an acid value = 73.87, a saponification value = 242.1 ; so that the ncetyl value was 68.23.From the approximate coincidence o€ the acetyl value of capric acid (174) with the acid value of the acetylated acid (176*4), it might be inferred that the acetylated capric acid contains one acetyl- group, but an acid of the formula CloHl,O2*C2H,Ohas a theoretical acid value of 262. Similarly the value for a mono-acetyl derivative of lauric acid would be 231, and that for a mono-acetyl derivative of cerotic acid 228 (resp. 124). (The same formuls would apply to mixed anhydrides of acetic acid and capric acid, &c.) It was easy to decide whether the action of acetic anhydride on fatty acids affected the COOH group of the latter, for in that case an alcohol of the CnHn+20series ought not to become acetylated. The author experimented on cetyl alcohol, which was treated with acetic anhy-dride.The acid value of the resulting substance was-as is to be expected--niZ; the saponi6cation ralue found was 192.65. As a substance of the formula C,6H330.C2H30has theoretically a saponifi-catioii value = 198, it is evident ihat simply etherisation of the cetyl a,lcohol has taken place. It was therefore to be supposed, as the mixed anhydrides of the higher fatty acids and acetic acid could not have been formed, that by the interaction of acetic anhydride and the higher fatty acids the anhydrides of the latter had been produced-taking palmitic acid as an example-according to the following equation :-2Cl,jH310.0H+ (C,H,O),O = (C1sH310)20+ 2C2H-I,0*OH.In that case the quantities of caustin, potash required by the equation 92 (CI6H3,O),O + 2KOH = 2C,sH3,O.OK + H,O ought to agree with the saponificatim values found.The following table gives the quan- tities of caustic potash required by theory, in milligrams, compared with the quantities actually used in the above experiments :-NO~.wt. Theory. Expt. Capric anhydride (C,oH~,O),O .. . .. 326 344 350.4 Lauric anhydride (CI,H,,O),O. . . .. 242 294 293.99 Palmitic anhydride (C16H3,0),0.... 494 227 226.13 Stearic anhydride (C18H,sO)20..... 550 204 221.18 Oleic anhydride (C18H,,0),0 ...... 546 205.4 242 Considering the approximate purity of the acids used, the theo- retical values agree very well with the experimental values ;and it may be pointed out that with pure material it would be easy by this method to determine which is the formula of cerotic acid.In the light of this explanation, the “ acid values ” found for the products of the interaction of acet,ic anhydride and fatry acids lose every quantitative meaning ; these ralues have only been found as the “ acetylated ” acids were dissolved in cold absolute alcohol for titration with potash, which hydrolysed at once the anhydrides, hydrolysis ceasing only when a limit is reached which depends on the quantity of alcohol present, and the nature and dilution of the standard solution-in some experiments half normal soda, in others decinormal potash. Had the substances been shaken up with water (hot water does not decompose them), in the first drop of potash falling into the mixture the pink colour would have appeared at once, or very soon when the limit for tlie system of substances was reached.It is hardly necessary to state that experiments carried out, in this direction fully bear out the correctness of the anthor’s conclusions. Thus the interaction of KOH or NaOH and the anhy- drides in aqueous solution affords an elegant illustration of that class of actions which require a measurable time for their completion. The anhydrides Gf the higher fatty acids are now within easy reach, as they can be prepared in a very short time by means of acetic anhy- dride. ADDITIONS TO THE LIBRARY. I. Donations. The Elements of Laboratory Work : a course of Natural Science, by A.G. Earl. London 1890. From the Publishers. Systematic Tests for Soluble Salts, Bases, and Acids, by A. A. Sutherland. London 1889 (Pa,mphlet). From the Author. 93 The Principles of Chemistry and Molecular Mechanics, by G. Hinrichs. Davenport, U.S.A., 1874. From Hy. Bassett, Esq. Annual Report of the Medical Officer of the Local Government Board for the Year 1888. From Dr. Buchanan. A Guide to the Literature of Sugar, by H. L. Roth. London 1890. From the Publishers. Histoire des parfums et hygihne de la toilette, par S. Piesse. Qdition Franqaise, par F. Chardin-Hadancourt et H. Massignon et G. Halphen. Paris 1890. Chimie des parfums et fabrication des savons, par S. Piesse. fidition Fmnqaise, par F. Chardin-Hadan-court et H.Massignon et G. Halphen. Paris 1890. From C. H. Piesse, Esq. Geographical Survey of New South Wales :-1. Geology of the Vegetable Creek Tin-Mining Field, by T. W. E. David. 460. Sydney 1887. 2. Mineral Products of New South Wales, by H. Wood: Notes on the Geology of New South Wales, by C. S. Wilkinson; and Description of the Seams of Coal worked in New South Wales, by J. Mackenzie. &o. Sydney 188i. 3. Paheontology I.-The Tnvertebrate Fauna of the Hawkesbury- Wianamatta Series of New South Wales, by R. E-lheridge, Junr. 4to. Sydnev 1888. Annual Report of the Department of Mines, New South Wales, for the Year 1887. From the Secretary for Mines. United States Geological Survey :-Seventh Annual Report for 1885-6, by J.W. Powell. Washing-ton 1888. Monographs, Vol. XIII. Geology of the Quicksilver Deposits of the Pacific Slope, by G. F. Becker. 4to. Washington 1888. Monographs, Vol. XIV: Fossil Fishes and Fossil Plants of the Triassic Rocks of New Jersey and Connecticut Valley, by J. S. Newberry. 4to. Washington 1888. Bulletin. Nos. 48-53. Washington 1888-9. From the Directer OF the SurveF. Grundlagen der Chemie, von D. Mendelejeff; iibersetzt von L. Jaweiii und A. Thillot. From Prof. Mendelejeff. Las Aguas Minerales de Chile, poi*L. Darapsky. Valparaiso 1890. From the Author. 11. By Purchase. De la loi du contraste simultan6 des couleurs, et de l’assortiment des objets colorks consid6rk d’aprhs cette loi, par E. Cherreul ; avec un introduction de H.Cherreul. &o. Paris 1889. 94 Die 3fikro-organismen der Giihrungsindustrie, von A. Jorgenseii. 3te Aufl. Berlin 1890. Trait6 pratique des rnati&res colornntes artificielles derides du go-ildronde houille, par A. M. Villon. Paris 1890. Gasaualytische Methoden, von W. Hempel. 2te Auflnge. 1890. ConfQrences fstites au laboratoire de M. Friedel. Paris 1889. RESEARCH FUND. Fellows desiring grants are requested to forward their applic a t’ions to the Secretaries in order that they may be considered at the nest meeting, early in June. At the next meeting, on June 5th, the following papers will be read :-“Note on the preparation of pure crystalline copper for spectroscopic work.” By Mr. C. C. Duncan. “The action of ethylic osalnte on camphor.” By Dr. Bishop Tingle. ‘’ The structure of cycloid hydrocarbons.” By Dr. Armstrong. ‘‘ Studies on the constitution of tri-derivatives of naphthalene.” No. 4. By Dr. Armstrong and Mr. Wynne. EARSISON IND SONS, PRINTEPS IN ORDINARY TO HER MAJESTY, ST. NABITIS’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8900600075
出版商:RSC
年代:1890
数据来源: RSC
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