摘要:

Issued 12111 jou. PROCEEDINGS OF THE CHEMICAL SOCIETY. Thursday, November 4th, 1909, at 8.30 p.m., Professor HAROLDB. DIXON,F.R.S., President, in the Chair. Xessrs. R. Muller and H. S. Wills were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Xessrs. : Arthur Fordshaw, M.Sc., 104, Holly Road, Handsworth, Birming- ham. Alexander David Gardiner, 6, Wellfield Terrace, Springburn, Glasgom. Eric John Holm yard, 7, Blanor Street, Cambridge. Francis Hugh Ping, 10, Forest Place, Whipps Cross Road, Ley tonstone, N.E. Richard Vernon Wheeler, D.Sc., British Coal Dust Experiments Committee, Altofls Colliery, Normanton. Of the following papers, those marked * were read : '6"246. The formation and reactions of imino-compounds.Part XI. The formation of 1-imino-2-cyanocyclopentanefrom adiponitrile.' By Jocelyn Field Thorpe. A method was described by which as-dicyanobutane (adiponitrile) can be completely converted into 1-imino-2-cyanocyclopentanein accordance with the scheme : DISCUSSION. The PRESIDENTasked whether, if the second cyano-group was necessary for the reaction to proceed (though it remains at the end unchanged), it did not point to a trausitory interaction between this group and the catalyst? Dr. J. I?. THORPE,in reply, said that the precise mechanism of the re:tction was htill open to question, but the nitrile group reinaining unaffected apltarently had some influence, since its presence seenied to be essential. In reply to Dr.MORGAN,lie stated that the use of piperidinc, diethylamine, arid other catalytic agents of that type did not lead to the formation of imino-compounds. In reply to Nr. BALY,Dr. Thorpe said that so far as he knew there was no chemical evidence of a hydrogen atom of the methylene group of ethyl cyanoacetate wandering to the nitrogen atom under the influence of sodium ethoxide. *247. Studies in the camphane series. Part XXVII. Camphoryl-phengltriazen (camphordiazoaminobenzene) and its bearing on the constitution of diazoamino-compounds.’’ By Martin Onslow Forster and Charles Samuel Garland. Proni a study of the compouiids derived from aminocamphor and from rnethylaminocamphor by coupling these bases with diazonium salts, the authors conclude that aliphatic-aromatic diazoamiuo-com-pounds must be represented by the expresion X*N:N*NH*C,H,,the hydrogen atom of the triazen nucleus taking up a position of superior st,ability in the neighbourhood of the phenyl group rather than that of the alkyl radicle, X.DISCUSSlON. Dr. MORGANsaid that the authors’ experiments amply justified the conclusions which they deduced in regard to the constitution of mixed aliphatic-aromatic diazoamines. With reference to mixed diazoamines containing two aryl (benzenoid) group” X and Y, he could riot, in the present state of knowledge, share Dr. Forstcr’s belief that the coupled product of diazonium salt, X*N,Cl, and aromatic aniine, Y*NH,, is entirely either X*N,*N€€*Yor X*NH-N,-T. He preferred to regard the product, formed under the ordinary ex-perimental condition5, as a mixture of these two isomeric diazoamines.The observations of Griew, Meldola, Schraube, Hantzsch, and others showed conclusively that, when a diazonium salt and an aromatic amine are dissolved together in dilute acid, a certain amount of rearrangement occurs consequent on the tuigration of diazo-nitrogen. The solution, if only feebly acid, then contains the following four reagents, cc, by c, and d (two diazo-hydroxides and two primary aromatic :&mines), produced by hydrolysis from their respective salts. 2 45 X*N,*OH Y*NH, a +--+ b X*N,*NH.Y X-NH, Y N,*OH --++ { X*NH-N,*Y1 c +--+d In the formation of the mixed diazoamine, coupling occtirs dong the lines ab and cd, with the result that the precipitated product is a mixture in which the proportions of X*N,*NH*Tand X*NH*N,*Y depend on the extent to which the migration of diazo-nitrogen has occurred.The Fame result is obtained whether one starts with X*N,CI and Y-NH, or with Y*N,Cl and X-NH,. Migration of dizizo-nitroAen occurs in either case; the same four reagents, cc, b, c, and d, becorm effective, and their interaction determines the nature of the conpled pi*oduct. Dr. J. E.THORPEpointed out that if the system of three nitrogen atoms with a double valency between two of them describwl by Dr. Forster could be considered as analogous to the system of two carbon atoms and one oxygen atom (C*C:O), as in ethyl acetoacetate, or to the system of three carbon atoms with a double valency between two of them (C*C:C), as in glutaconic acid, then any hydrogen attached to the extreme nitrogen atoms might be regarded for experi-mental piirposes as being attached to the central nitrogen atom, thiis : N-N--N in the same manner as in glutaconic acid.In no case of this kind would there be reasonable hope ol obtaining any trustworthy chemical evidence respecting the position of the hydrogen atom. Dr. FORSTERwas prepared to admit that aromatic dinzonmino-compounds, when produced in the coupling process, exposed to light., and recrystallised from hot solvents, behaved as Dr. Morgan indicated, namely, as a mixture of two isomeric diazoamines, but he attributed this to nu alteration of X*N,*NH*Yinto X*NH*N,*Y,effected by the environment, such alteration proceeding with greater facility when the attraction exerted by Y for the hydrogen in the triazen chain did not differ greatly from that exerted by X. He was led to this con-clusion principally by three circumstances.1. The numerous cases of resolution by acids upon which current, views regarding the constitution of aromatic diazoamino-compounds are based have been studied most frequently st temperatures ranging from that of the laboratory to lOO", instead of at zero or below, 2. When prepared by Dimroth's method, from arylazoimide and magnesium aryl halide, a-naphthylphenyltriazen is resolved by alcoholic hydrogen chloride below zero into a-nrtphthyldinzoninm chloride and aniline, unaccompanied by a-naphthylarnine.3. There does not appear to have been recorddd a case in which two isomeric diazo-carbamides have arisen by direct action of phenyl-carbimide on a diary1 triazen. 248. “ Dynzmics of the reaction between iodine and acetone.” By Harry Medforth Dawson and May Sybil Leslie. The physical properties of solutions of iodine in acetone are abnormal, and it has been found that this is due to a reaction iaesulting in the formation of hydrogen iodide and one or inore iodoacetnnes. At the ordinary temperature the reaction takes place fairly rapidly, but is incomplete, indicating thqt the change is reversible. In order to elucidate its mechanism, the authors have made measure- ments of the velocity of the resction, the rate of change being diminished by dissolving the reacting substances in various inert solvents.In aqueous solution, the reaction proceeds much more nearly towards completion than it does in carbon tetrachloride, benzene, nitrobenzene, methyl alcohol, or methyl acetate. On the other hand, the velocity of the change in neutral solution appears to be milch slower in water than it is in the other solvents wed. A detailed examination of the reaction in aqueous solution has shown that in presence of acids the rate of disappearance of the iodine is constant when the acetone is present in relatively large excess. In solutions acidified with sulphuric mid, the velocity is proportional to the concentration of the acid and also to that of the acetone.If no foreign acid is added, an autocatalytic effect is observed, due to the hpdrogen iodide formod during the reaction. 249. Studies in phototropy and thermotropy. Part I. Aryl-idene- and naphthylidene-amines.” By Alfred Senier and Frederick George Shepheard. In a recent paper, the authors described a series of Schiff’s bases (salirylidene-amines), one of which, namely, salicylidene-nz-to!uidine, was found to be highly phototropic (Tmns., 1909, 95, 441). The investigation has now been extended to the study of a number of other salicylidene-amines and related compounds, and five compounds, including saIicylidene-m-toluidine,which exhibit phototropy have been prepared.Early in this investigation it was observed that many OF the coloured bases becarrie deeper in colour on heating, and that this change, like phototropy, was reversible. The whole of the compounds in qiieetion were then subjected to an examirntinn to obtain further evidence, if possible, of this property. Their colour changes were noted (1) between the ordinary temperature and a temperature just below their melting paints, and (2) between the ordinary temperature and that of solid carbon dioxide. This led to the interesting fact that most of the compounds exhibit this phenomenon, which has long been known, in isolated instances, among inoi.ganic subatances. This reversible change of colour the authors propose to term tltemzotropy. Whilst it is possible that phobobropic and thermotropic isomerism may be explained by intramolecular rearrangement, as is generally supposed, it seems more probable, bearing in mind that the substances affected are solids, that it depends on different modes of aggregation of the ordinary molecules which may be supposed to be grouped together in the probably much more complex molecules of solids.250. “The action of mercaptans on acid chlorides. Part I. Oxalyl chloride ; the mono-and di-thio-oxalates.” By Humphrey Owen Jones and Hubert Sanderson Tasker. The following esters of dithio-oxalic acid have been prtapared by the action of oxalyl chloride on the corresponding mercnptans or their metallic derivatives. PILeny? dithio-oxalate, n sulphur-yellow solid, melting at 119-12Oo, and tlistilling unclecomposed.Xethyl cliiY~io-oxakcte, pale yellow prisms, melting at 82*5--83.5O. Et?hyl dithio-oznlnte, yellow prisms, melting at 27-27*5”, and distilling at 235’. PropgZ dithio-oxakate and ccmyl dithio-oxalate, yellow liquids, the former dis-tilling at 15S0/15mm., and the latter at 206”/19 mm. On boiling these esters with an alcoholic solution of potassium hydrosulphide, the mercapt’an is set free, and potassium dithio-oxcdate, (KSCO),, separates as a white, crystalline powder. This salt can be used as a delicate test for nickel or cobalt, owing to the formation of a complex potassium nickelo-or cobalto-thio-oxalate, which is intensely coloured. The nickel salt is less stable towards potassium cyanide and strong acids than the cobalt salt, so that by adding potassiiim cyanide the colour of the nickel salt can be destroyed before that of the cobalt salt, and in this way 10 per cent.of cobalt can be detected in the presence of 90 per cent. of nickel. The colour of the nickel and cobalt salts can be seen readily at dilutions of 1 in 40,000,000 on looking through 25 cm. of solution. 251. “The action of mercaptans on acid chlorides. Part 11. The acid chlorides of phosphorus, sulphur, and nitrogen.” By Hubert Sanderson Tasker and Humphrey Owen Jones. Phosphorus trichloride reacts with phenyl rnercaptan or its metallic derivatives to give triphenpl trithiophosphite as stated by Schwarze j 248 phosphoryl chloride siwilm~ly gives trip henyl trithiophosphate, melting at 115' (Schtvarze gave the melting point as 72", and this mas cor-rected by Michaelis).Sulphuryl chloride in the cold gives a deep yellow colour, probably due to the formstion of an ester, which disappears with the formation of phenyl disulphide and the evolution of sulphur dioxide. Thionyl chloride also gives a yellow colour in the cold, but this again disappears quickly ; phenyl disdphide is formed and sulphur dioxide is evolved, but the possible new oxide of sulphur, SO, is not formed. Numerous experiments were made to discriminate bet ween the two following equations to represent this reaction : 8C6H,*SH+ 4SOC1, =SHCl + 2x0, + 3(C,H,*S), +(C(jH,)2S4 4C,H5*SH+SOC1, =(C6H,*Y),+ (C,H,),S, + H,O + 2HCI.It was found that both reactions seem to take place simultaneously, but that the mnin reaction appears to be represented by the first equation. Nitrosyl chloride reacts readily with mercaptans in the cold; hydrogen chloride is evolved, and brilliant red colours are produced (probably due to the formation of esters of thionitrous acid), which gradually di*appear with the evolution of nitric oxide and tho forma-tion of alkyl disulphide. The same colour is produced by the action of the chloride on the mercaptides. When nitrosyl chloride is treated with an alkyl mercaptan at a low temperature (solid carbon dioxide and ether), a small quantity of hydrovylarnine hydrochloride is always formed. 252. LL The colouring matters of the flowers of Hibiscus sabdariffa and Thespasia lampas." By Arthur George Perkin, The flowers of the Hibiscus sccbdarzfa yielded 0.36 per cent.of a mixture of three yellow colouring matters, the mnin constituent of which, C,,Hl,O,, crystallising in yellow needles, gives an acetyl deriv-ative, C1,€I-1,08(C'2H,0)6,m. p. 229 -230°, and, 011 fusion with alkali, protocstechuic acid. It was identical with gossypetin present in Tndian cotton flowers (Gossypium herbccceum), the formula, C,, LI,,O,, previously given for which is now abandoned. Together with quer-cetin, the flowers yielded a, trace of a spzringly soluble new colouring matter, for which the name Itibiscetin is proposed ;this melts at about 340°, and gave a colourless acetyl compound, m.p. 238-239°. In addition to these substances, free protocntechuic acid mas also isolated. The flowers of Thespasin; lccmpas gave guercekin to tho extent of 0.6 per cent., together with 8 small quantity of free yrotoc%techuic acid. 249 253. ‘(The reduction of 4-hydroxy-o-toluic acid.” By Oscar Baudisch, Gilbert Stanley Hibbert, and William Henry Perkin, jun. By reducing 4-hydroxy-o-toluic acid with sodium and alcohol, the authors have obtaiued the four possible isomerides, namely, the two cis- and the two tr.tns-l-~nethylcyclohe~;an-i-oZ-2-carbozylicacids, of which various derivatives were described. 1-Meth~Z-A6-cycloAexen-4-oE-2-car6oxglicacid is also formed in this reaction. 254. (‘The reduction of 6-hydroxy-o-toluic acid.” By Oscar Baudisch and William Henry Perkin, jun.On reduction with sodium and alcohol, 6-hydroxy-o-toluic acid yields a mixture of cis- and trans-l -rnet~~cgclohezan-6-0~-2-carboxy~~c acid. 255. ‘‘The reduction 5-hydroxy-nz-toluic acid.” By Andrew Norman Meldrum and William Henry Perkin, jun. By reducing 5-hydroxy-m-to1uic acid with sodium and isoawyl alcohol, the authors have prepayed trans-l-?neth?/lcyclo?~exan-5-02-3-carboxylic acid. This is convex ted into the corresponding cis-ucid by distillation and hydrolysing the resulting lactone. 256. ‘‘ The reaction between potassium permanganate and manganese sulphate in acid solution.” By Anukul Chandra Sirkar and Jatindra Mohon Dntta. The authors find that in neutral or very faintly acid solution at 85’ the reaction between potassium perrnanganate and manganese sulphate is in accordance with the equation : 3MnS0, + 2KMn0, + 2H20=5Mn0, + K,SO, +3H,SO,.In solution freely acidified with sulphuric acid at S5O the reaction is practically the same as in neutral or faintly acid solution ;at 100’ the manganese dioxide which has been formed by the interaction between the permang:tnate and manganese salt is attacked by the acid of the solution, forming a certain quantity of manganese sulphate in accordance with the equation : 2Mn0, + 2H,SO, = 2MnS0, + 2H,O +0,. The manganese sulphate thus formed reacts with a further quantity of potassium permanganate, 3Mn80, + ZKMnO, +2H,O =5Mn0, + K2S0, +2H,SO,, and these two reactions occur in a cycle indefinitely, or so long as the solution remains freely acid.In solutions which were at the start neutral, a certain amount of sulphuric acid is at first produced, but this subsequently becomes used up, and thus in this case a limit IS put to the amount of perrnanganate reduced by a limited quantity of manganese salt even at 100’. This investigation offers an explanation of what might be termed the catalytic reduction of potassium permanganate in freely acid solution by either manganese salt or rmnganese dioxide. 257. “ The condensation of ketones and aldehydes with the sodium derivative of ethyl cyanoacetate. Part 11.’’ By Henry Dent Gardner, jun., and Walter Norman Haworth. An account was given of the investigation of the products formed by the condensation of ethyl sodiocyanoacetste with acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, and methyl hexyl ketone.RESEARCH FUND. A Neeting of the Research Fund Committee will be held in December next. Applications for Grants, to be made on forms which can be obtained from tho Assistant Secretary, must be received on, or before, Monday, 6th December, 1909. All persons who received grants in December, 1908, or in December of any previous year, whose accouuts have not been declared closed by the Council, are reminded that reports must be in the bands of the Hon. Secretaries not later than Wednesday, 1st December. The Council wish to draw attention to the fact that the income arising from the donation of the Worshipful Company of Goldsmiths is to be more or less especially devoted to the encouragement of research in inorganic and metallurgical chemistry.Fur thermora, that the income due to the sum accruing from the Perkin hlemorial Fuud is to be applied to investigations relating to problems connected with the coal tar and allied industries. ERRATA. 1909. P. 187, line 8, for ‘i formally elected” read “formally admitted.’’ P. 213, line 13, fbr “ 16H+2” read “16H+2pu.” At the next Ordinary Scientific Meeting on Thursday,November 18th, 1909, at 8.30 p.m., the following papers will be communicated : ‘‘ The resolution of asymmetrical derivatives of phosphoric acid.” By B. D. W. LuE and P.8. Kipping. “The configuration of tropeine and y-tropeine and the resolution of atropine.” By 85. Barrowcliff and F. Tutin. “The electromotive behaviour of cuprous oxide and cupric hydroxide in alkaline electrolytes.” By A. J.Allmand. “Note on the stereoisomeric modifications of a/3-dibromobenzyl-acetone.” &y Miss 1. Smedley. RICHARD CLAY AND SONS, LIMITED, BREAD ST. HILL, E.c., AND numAy, SUFFOLK.

ISSN:0369-8718    

DOI:10.1039/PL9092500243

出版商:RSC    

年代:1909

数据来源: RSC