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Proceedings of the Chemical Society, Vol. 9, No. 126 |
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Proceedings of the Chemical Society, London,
Volume 9,
Issue 126,
1893,
Page 161-170
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摘要:
Issued 13/6/1893. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 126. Session 1893-94. June lst, 1893. Dr. Armstrong, President, in the Chair. Messrs. T. L.Baker, J. Addyman Gardner, James Mason, Robt. G. Grimwood aiicl Reginald B. Brown were formally admitted Fellows of the Society. The certificate of Frank Browne, Government Civil Hospital, Hong Kong, was read for the first time. Of the following papers those marked ’* were read :-*25. ‘I Azo-compounds of the ortho-series.” By R. Meldola, E. M, Hawkins and F. B. Burls. The constitution of the orthazo-compounds is still an unsolved problem owing to the coatradictory results obtained by different investigators using cliff ePeiit methods. The evidence in some cases points to the hydrazone formula and in others to the azo-formula, represented in the case of the azo-p-naphthols respectively by X*NH*N:C,H,:O and X*N2*CloH6*OH.The compounds may really be isodynamic, but their acetyl and benzoyl, &c., derivatives, which were first investigated by one of the authors and G. T. Morgan (0.8. Trans., 1880, 114), can hardly be thus regarded. The best evidence in favour of the hydrazone formula was furnished by Goldschmidt and Brubacher (Bey., 1891, 2300), who obtained acetanilide and benzanilide by reducing the acetyl and benzoyl derivatives by means of zinc dust and acetic acid in alcoholic solntion ; these products are not obtained when stannous chloride is used as the reducing agent, a fact which was made known in 1889 in the paper referred to and which has been confirmed in the present investigation, 162 In repeating Goldschmidt and Brubacher's work with the acetyl derivatives of ortho-and para-tolueneazo-P-naphthol, the authors have found that acetamido-@naphthol is also one of the products of reduction, and in the case of a number of other acetyl derivstives this compound is found to be a normal product of reduction.Thus, in the case of an acetyl derivative of the form X*N2*CloHs*OCzH30or X.N(C2H,0)*N:C,oH6:0,four products are always obtained when zinc dust and acetic acid is the reducing agent, viz. :-X*NH-C2H30, CloH6(NH*C2H30)~OH/3,X*NH2and CloH6*NH2*OH/3.The quantity of aceta,mido-/%naphthol is very small in the case of the acetyl deri- vative of benzenea,zo-/3-naphthol, a fact which accounts for this product having been overlooked by Goldschmidt and Brubacher.As the number of methyl groups in X is increased, the quantity of acetamido-p-naphthol increases, the acetyl derivative of pseudo-cumeneazo-P-naphthol giving about 9.2 per cent. of this product when reduced by zinc dust and acetic acid in the manner described. The following azo-compounds and their acetyl derivatives have been isolated and characterised in the course of the investigation :-p-Tolueneazo-/3-naphthol Red prisms, m. p. 99'. (acetyl derivative) p-Chlorobenzeneazo-p-naphthol Flat needles or leaflets, red, m. p. (acetyl de rivat i ve) 133". Pseudocnmeneazo-&naphthol . . . Bronzy prisms or bright scarlet needles, rn.p. 163-164". Other acetyl derivatives have been prepared, but used immediately for reduction for reasons explained in the paper. The acetyl deriva- tive of beneeneazo-f3-naphthol has been reduced under various condi- tions, and is always found to give a small quantity of acetamido-P-naphthol except when stannous chloride is used, when the chief product appears to be either a naphthylphenyl or a naphthylphenyl- amine derivative. The latter will be made the subject of a special investigation. Even when zinc dust and chlorliydric acid were used as reducing agents, acetamido-&naphthol was obtained, but the quantity of acetanilide is in this case insignificant, the chief products being amido-p-naphthol and aniline. The authors conclude that the formation of acetamido-&naphthol on reduction is destructive of Goldschmidt and Brubacher's evidence in favour of the hydrazone formula for the ortho-azo-compounds. The simultaneous formation of acetanilide, acettoluide, &c., and acetamido-P-naphthol cannot be explained by either azo- or hydr- azone formula alone, but if it be assumed that an intermediate product of the nature of an anhydro-compound is formed, the pro-duction of these compounds is accounted for.It is shown in the paper 163 that the same anhydro-compound would be produced whether the acetyl group were attached to nitrogen or oxygen in the original compound, so that the question of the constitution of the ortho-azo- compounds still remains an open one.Further experiments on the reduction of the acetyl and benzoyl derivatives of other ortho-azo-corn- pounds are in progress. *26. “ The production of a fluorescein from camphoric anhydride.” ByJ. Norman Collie, Ph.D., F.R.S.E. Last year the author proposed a formula for camphoric acid of the succinic type (Bey., 25, 1116). Up to that date no fluorescein had been prepared from camphoric anhydride, and it had even been stated that this anhydride did not form such a compound (J. E. Marsh, C.X. Trans., 1891, 651) ; it therefore seemed necessary to institute further experiments to obtain an explanahion of this apparently anomalous behaviour of camphoric anhydride. The author finds that under suitable conditions camphoric anhydride is without difficulty converted into a fluorescein, the best results being obtained by heat-ing one molecular proportion of the anhydride with two molecular proportions of resorcinol to about 180” C.with a relatively small amount of zinc chloride. The resulting fluorescein, (C,,HzzO,), is a reddish-brown powder, which, when dry, has B greenish lustre. It dissolves in alkalis, affording a pink coloured solution, and exhibits in dilute aqueous solutions a beaut.if ul green fluorescence. When sulphuric acid is employed iii its preparation, the yield of fluorescein is small, the chief product being R brown compound which dyes cotton mordanted with alumina a pink colour. The author finds that isopropylglutaric anhydride also furnishes a fluorescein, so that t’he production of a fluorescein from camphoric acid does not afford evidence which can be made use of in deciding whether the acid is a compound of the succinic or of the glutaric tYPee %27.“Researches on the terpenes.111. The action of phosphoruspentachloride on camphene.” By J. E. Marsh and J. A. Gardner. The authors describe the results of the further study of the action of phosphorus pentachloride on camphene. When these substances are allowed to interact without heat being applied, a mixture of camphene hydrochloride and a chlorophosphonic derivative of the formula CloH,,PCla is obtained. On treatment with water, the latter compound is converted into a mixture of acids which, together with the camphene hydrochloride, forms a syrupy mass, from which the 164 acids are separated by fractionally extracting with a solution of sodium carbonate. After further purification by means of suitable solvents, two well characterised isomeric camphenephosphonic acids of the formula CloH15POsH2 were obtained.a-Canaphenephos~honic acid, crystallised from dilute alcohol, has a composition represented by the formula 2C,,H,,P0,H2 + H,O. It is characterised by its insolubility in ether and ready solubility in chloroform ; when heated at 100" it loses the elements of two molecules of water. The anhydrous acid melts at 184". The acid is monobasic. The sodium salt crystallises from water or alcohol; the barium salt forms an almost insoluble crystalline precipitate.p-Camphenephosphcnic acid, crystallised from dilute alcohol, has the composition CloH,5POsK2.It does not lose weight when heated during several' hours at loo", but on prolonged heating it turns brown, melts, and loses weight. It is readily soluble in ether, but insoluble in chloroform; it melts at 170". The acid is monobasic. The sodium and ammonium salts have been prepared. The a-and /?-acids further differ in rotatory power. When pre- pared from camphene having a rotatory power of -60", the specific rotatory power of the a-acid was [a]D = -llYo, aiid that of the @acid -71'. When the mixture of phosphorus pentachloride and camphene is heated, a crystalline compound of the Formula ClOHl4PCl3is obtained, which has been previously described (C.X.Trans.,1891, 652). When subjected to the action of a solution of sodium carbonate, this compound yields a sodium salt of the formula CloH14C1POzNaH + 5H20. The corresponding barium salt is soluble in water, and crys- tallises with three molecular proportions of water. The acid -is an oil. On oxidation by potassium permanganatc in alkaline solution, it is converted into the corresponding chlorocampher~epJ~osph~nicacid, CloH,,P03Hz.This may be crystallised from benzene; it melts at 178", undergoing decomposition. When a mixture of camphene with a larger excess of phosphorus pentachloride is heated, and the product is hydrolysed, the same chlorocamphenephosphonic acid is obtained, together with an isomeric acid. The sodium salts of all these phosphonic acids are acted on by bromine, the phosphonic gyoup appearing in solution as sodium phosphate, brominated derivatives of camphene being produced which are under investiga- tion.On oxidation by nitric acid, chlorocamphenephosphonic acid yields camphoic acid. On fusing chlorocamphcncphosphonic acid with potash, a very small quantity of a crystalline volatile sub- stance was obtained. “28. ‘‘The composition of a specimen of jute fibre produced in England.”By Andrew Pears,jun. The author succeeded in securing a normal growth of the jute plant (Corchorus capsular&) in a <‘ hot house ” of average temperature 65”F. The stems, 5 feet in length, and branched, were cut down after maturation of the seed, which has since been germinated for growth during the current year.The stem-fibre was separated after retting in tepid water, and was exhaustively investigated. It showed the characteristic behaviour of lignocelluloses, but with important varia- tions in degree ; the most marked difference observed was in ultimate composition, the carbon percentage being only 43 as against 46-47 in the normal fibre. From the results given in full in the paper, it is shown that the factors of lignification induce variations in chemical composition, within wide limits, at the same time that the general constitutional type is preserved. Lignification may, in fact, be regarded as a gradual passage from “ saturated ” to “ unsaturated ’’ compounds, and as the result of the splitting off of water and carbon condensation, the specimen in question representing the earlier phases of such transition or evolution.28. “Note on the combination of dry gases.” By W, Ramsay, F.R.S. Mr. H, Brereton Baker has stated in his recent note that when dry ammonia is mixed with dry hydrogen chloride, these gases do not combine to form ammonium chloride ; I mould, therefore, call attention to a statement to the same effect by Dr. Sydney Young and myself in a paper on “ Evaporation and dissociation,” published in the PhiE. Trans.,1886, Part I, p. 89. After describing the behaviour of ammonium chloride at 280” in a modified Hofmann’s vapour-density tube, we state :-‘‘ When the tube cooled, a permanent gas remained, which exerted a pressure of 18.3 mm.As a very long time was allowed, so as to make certain of no further rise (of pressure) when the ammonium chloride was heated, the presence of this gas cannot be accounted for by a gradual decomposition of the ammonia, for we have shown (J. Chem. Soc., 1884, 88) that ammonia begins to de-compose only at 500°, eren when hydrochloric acid is absent. It might, however, to some extent be due to the action of hydrochloric acid onmerdury. On inclining the tube, this gas formed a bubble of considerable size at the top. Water was introduced, and almost complete absorption occurred. It appears certain then that gaseous hydrogen chloride and ammonia, when perfectly dry, combine very slowly.’’ These cxpetiments were made in order to measure the vapour pressure of ammonium chloride; hence there was always a large excess of solid chloride present.It appears, therefore, that even in presence of the associated solid compound, the gaseous constituents may remain in presence of each other without combining. I was noh so successful as Mr. Baker has been in preventing the: combination of nitric oxide and oxygen. Even a,fter a bulb of nitric oxide cont aining several grams of phosphoric anhydride-itself con-tained in a bulb of oxygen in which there was a considerable quantity of the anhydride-had been left during three months, on breaking the thin-walled inner bulb, a red colour was at once seen. I cannot but conclude that some substance other than water vapour may also have the power of effecting such combination ; unless, indeed, it be con- tended that such a lengthened exposure to phosphoric anhydride does not completely dry the gases. 30.“Ortho-, para-and peri-disulphonic derivatives of naphthalene.”By Henry E. Armstrong md W. P. Wynne. In a previous communication, dealing with the results oE the examination of a large number of disulphonic acids (these Proceed- ings, 1890, 133) attention was drawn to the ‘‘ ‘ invincible objection ’ of two sulphonic radicles to remain in either contiguous or para- or peri-positions ” relatively to one another when disulphonic acids arc formed by the action of sulphuric acid either on naphthalene or on the chloro-, amido- or liydroxy-naphthalenes. Further investigation has failed to supply a single exception to this rule, and it is noteworthy that of the known disulphonic acids only two-the No.I1 a-naphthyl-aminedisulphonic acid of Dahl & Co.’s German Patent No. 41957 (Zoc. cit., p. 125), and the minor product of the sulphonation of potassium 2 : 3’-chloronaphthalenesulphonate(206. cit., p. 132)-contain the two sulphonic radicles relatively in the positions 1: 2‘, the favoured positions being 1: 4’,2 : 4’,2 : 2’ and 2 : 3‘, the position 1:3 being taken up only in the case of sulphonation products of certain /3-chloro- and p-amido-naphtha1 enesulphonic acids. Moreover, while the number of naphthalenedisulphonic acids obtainable, either by the sulphonation of naphthalene or by eliminating the NH, radicle from naphthylaminedisulphonicacids amounts to six, it is very significant that only two naphthylaminetrisulphonicacids-the 1 : 3 : 2‘-and 1: 3 : 3’-derivatives-can be obtained by sulphonating riaphthalene, and that the only trisulphonic acids obtained by sulphonating the naphthols and naphthylamines contain their sulphonic radicles rela- tively in one or other of these positions.While preparing the final account of our Seven years’ investigations, 167 we endeavoured in various ways to prepare the missing acids con- taining the sulphonic radicles in the positions which are avoided in all products of direct sulphonation, so that their behaviour towards sulphonating agents might be studied in order that the explanation of this remarkable law of substitution might be given.While engaged in these experiments, we learnt with great satisfaction from Dr. C. Duisberg that a process had been devised in the laboratory of the Farberfabriken vormals F. Bayer & Co., of Elberfeld which had enabled them to prepare all the acids we were in search of, and with that courtesy which is characteristic of German chemical manufac- tmers, Dr. Duisberg at once communicated their methcd to US, SO that we might proceed to study the various acids from the scientific side. The process consists in displacing the amido-group in a naplithyl- amine derivative by SH and oxidising the resulting thio-derivative by means of alkaline permanganate ; the thihydride is prepared by Leuckert’s method (J.pr.Chem. [2], 41, 218) by submitting the diazo-compound prepared from the amine to treatment with potassium xanthate and hydrolysing the resulting xanthate. The thihydride thus formed being unstable in presence of oxygen, the corresponding disulphide is usually obtained. The process is described in the German Patent Anmeldung I?. 6099, C1. 22, of the Farbenfabriken vorm. Friedr. Bayer & Co., Elberfeld, in which an account is given of three new disulphonic, seven new trisulphonic and two tetrasulphonic acids of naphthalene. With no more information before us than is afforded by the specification, we have been able without the slightest difficulty to prepare the various acids, and we have nothing to add to the admirable description given in the specification-a striking illustration of the character of the German chemical patent literature of the day.Ip the present note only three new disulphonic and one new tri- sulphonic acid are referred to ; the remaining acids will be described in a later comniunication. On treatment with phosphorus penta- cliloride, thc 1 : 1’-and 1 : 2-acids yield products which apparently are the corresponding anhydrides. This behaviour is of interest as an extension of the observations made in V. Meyer’s laboratory on the formation of anhydrides of disulphonic acids of thiophen, It is remarkable that the R-acid, in which there are two contiguous P-sulph- cnic groups, has not been found to yield an anhydride. JK~the first instance, we availed ourselves of the method to pre- pare from the (Badische) 1 : 2’-P-naphthylaminesulphonicacid the 1 : 2‘-naphthalenedisulphonic acid previously discovered by us (these Proceedings, 1890, 125).The product is identical with that obtained from Dahl’s No. I1 a-naphthylaminedisulphonic acid, and thus an independent proof is afforded of the somewhat remarkable constitu- tion which we have assigned to this acid. 168 1 : 1'-Naphthalenedisulphonicacid was prepared from the Schollkopf 1 : 1'-a-naphthylaminesulphonicacid kindly placed at our disposal by the Actiengesellschaft fur Anilinfabrikation, Berlin. The correspond- i11g potassium naphthalenesulphidesulphonate, (cloH6s*so~~)~4-I&o, crystallises in very small, pale yellow scales, sparingly soluble in cold water.Potassium 1 :l'-iaapl~thalenedisulphonate,CloH6(S0,K),+ H20, crystallises in well-defined, four-sided scales, sparingly solublc in hot water ;what appears to be the corresponding anhydride crystal-hes in small, rhomboidal, probably monosymmetric plates, melting at 227", which are sparingly soluble in hot benzene, more soluble in hot xylene and acetic acid. 1 : 2-Naphthalened.isulphonic acid was obtained from the Landshoff and ateyer 1: 2-a-naphthylaminesulphonicacid. The corresponding potassizcm nn~hthaleneszL~hideszc~horzate(C,oH6S*S03K)2+ ~HzO, crystallises in pale yellow granules consisting of microscopic prisms sparingly soluble in cold water. Potassium 1 : 2-izaphthalenedisulpl~-onate, CIOH~(S03K), 5 $H,O, crystallises from water in very soluble, prismatic tables ; what appears to be the corresponding adydride crystallises from benzene, in which it is tolerably soluble, in elongated, striated prisms melting at 198". 1 : $-NaphthaZenedisuZp~o~icacid was prepared from nnphthionir: acid. The corresponding potassium napht?zaZe:/,esulrphides~~~~onate (CIOH~S*SO&>,+ SH20, crystallises from water in easily soluble, pale yellow, microcrystalline granules.Potassium 1 : $-naphthule?ze-disukhonate, CloH6(s03K), + 14H20,crystnllises from water in small, readily soluble needles ; the corresponding chloride, CI0H6(s0$1)2, crgstallises from benzene, in which it is readily soluble, in fonr-sided, monosymmetric plates showing an optic axis just beyond the edge of the microscope field : this melts at 160".2 : 2' :3'-Naphthalenet,.isu~lzonic acid was obtained fsom 2 : 9' : 3-/3-naphthylaminedisulphonicacid (amido-R-acid). The correspond-ing potassium naphthalenesulphidedisulphonate [CloH5S(SO,K)?]z + 5H20, crystallises from water in finely striated, prismatic forms having a beautiful, velvet-like appearance. Potassium 2 :2' :3'-.napht1za-lenetrisulphonate, CIoH,(SOAK),+ 3Hz0, crystallises from water in small, microcrystalline, spherical aggregates ; the corresponding chloride, CloH5(S02C1),, crystallises from benzene, in which it is tolerably soluble, in long, flat, probably monosymmetric plates show- ing longitudinal striations, melting at 200'. The method of substituting the SO,H radicle for NH, has been extended to the chloro-/3-naphthylaminesulphonicacids, and in particular to the 1: 2 :2'-or "No.3 " acid, with the object of corn-paring the product with the a-chloronaphthalene-2 : 2'-disulphonic acid obtained from Ah's a-nitronaphthalene-2 :2'-disulphonic chlor- 169 ide, to which Cleve attributes a, like constitution (Bey., 25, 2490). We take this opportunity of stating that further investigation has shown that, contrary to our previously expressed view (cj. these Proceedings, 1890, 135), the No. 2 and No. 3 acids have an inde- pendent origin. By the discovery of the disulphonic acids here described, we are now placed in possession of nine of the ten possible acids. We have previously characterised the ten possible dichloronaphthalenes and the two homonucleal trichloronsphthalenes (these Proceedings, 1890, 76, 77) ; me have now all but completed the study of the remaining twelve trichloronaphthalenes, having converted them into sulphonic acids, &c., in order that it may be possible to characterise them beyond question.80 soon as the few remaining comparisons are completed, a detailed account of the investigation will be submitted. Experiments are being carried out in the Central Institution laboratory by one of us with t,he object of determining, by means of the xanthate method, whether in the case of other hydrocarbons orthodisulphonic acids can be obtained which can exist in presence of sulphonating agents-the statements on record being far from satisfactory, and in some cases contradictory.31. "Supplementary notes on madder colouring matters." ByE. Schunck, Ph.D., F.R.S., and L. Marchlewski. Many years ago (Phil. Trans., 1853, 72) one of the authors described under the name of rubiadin a yellow colouring matter oh- tained from madder. It is now shown that madder contains a glucoside of this substance, the preparation and properties of which are described. The glucoside crystallises in yellow needles melting at about 270". On acetylation by Liebermann's method, it yields a pentacetyl derivative. On treatment with baryta water, it yields a dark red lake, one hydrogen atom being displaced by barium. On hydrolysis, it is converted into rubiadin and ordinary dextrose, Cz,H2009 + HzO = CxB1o04 + CtJ3nOs.Rubiadin crystailises in lustrous, yellow needles melting at 290". It very closely resembles purpuroxanthin, and is probably the corre- sponding derivative of meth ylant hracene. 32. "The constitution of rubiadin glucoside and of rubiadin." ByL. Marchlewski. It is pointed out that of the five hydroxyl groups in rubiadin, one is phenolic, inasmuch as the glucoside yields dark red coloured mono- metallic derivatives ; further, it is contended that probably glucose always exists in glucosides in the form of an anhydride of a hepta- 1.70 hydric alcohol ; a formula is assigned to the glucoside based on these arguments. Assuming that rubiadin is derived from the same (p) methyl-anthracene as emodin, &c., it is pointed out that there are still three possible formuh if rubiadin be regarded as a meta-dibydroxyanthra-quinone-one homo- and two hetero-nucleal.By heating a, mixture of symmetrical metadihydroxybenzoic acid, paramethylbenzoic acid and snlphuric acid at 110”,the author has obtained a substance of the same composition and closely resembling rubiadin, but melting at 267”. At the next meeting, on June 15th, there will be a ballot for the election of Fellows, and the following papers will be read :-‘‘ Contributions to our knowledge of the aconite alkaloids. VI. Conversion of aconitine into isaconitine.” By Professor Dunstan and F. H. Carr. “ VII. Modifications of aconitine aurichloride.” By Professor Dunstan and H. A. D. Jowett. “ Properties of strong solutions.” By S. U. Pickering, F.R.S. ‘‘Notes on the stereoisomerism of nitrogen compounds.” By S. U. Pickering, F.R.S. “ New methods of analysis.” By I)r. J. Clark. “ Studies on citraziiiic acid.” By W. J. Sell and T. H. Eesterfield, And other papers. HARRISON AND SONS. PBINTEES IN ORDINARY TO HER MAJESTY. ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8930900161
出版商:RSC
年代:1893
数据来源: RSC
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