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Proceedings of the Chemical Society, Vol. 20, No. 276 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 276,
1904,
Page 35-44
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摘要:
Issued 21/2/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 20. No.276. Wednesday, February 17tli, 1904. Professor W. A. TILDEB,D.Sc., F.R.S., President, in the Chair. Mr. E. R. Bug& was formally admitted a Fellow of the Soziety. ertificates were read for the first time in favour of Messrs. William Barbour, KA., B.Sc., Grove Villa, Waltham Cross. R. H. Durward Benn, Westmount, Montreal, Canada. Ellis Clayton, 6, Spring Hurst Road, Saltaire. Percy Kent Le May, 6, Lothair Viilas, Hatfield, Herts. Franklin E. Itobertson, Hardera Road, Peckham, S.E. Thomas G. Shacklady, Addiscombe Villas, Cliffe-at-Hoo, Kent. It was announced that the following changes in the Officers and Council were proposed by the Council : As Tyeasurer : Dr. A. Scott, F.R.S., vice Dr.H. T.Brown, F.R.S. As Secretary : Dr. 31. 0. Forster, vice Dr. A. Scott, F.R.S. As Vice-presidents : DF. H. T. Brown, F.K.S., and Prof. H. 33. Dixon, F.R.S., vice Prof. H. McLeod, F.R.S., and Prof. H. A. llliers, F.R.S. As Ordinary Xembers of Conncil : Dr. Bernard Dyer, IMr. A. D. 36 Hall, Dr. A.. Lapworth, Prof. J. M. Thomson, F.R.S., vice Dr. M. 0. Forster, Mr. S. U. Pickering, E.R.S., Dr. J. A. Voelcker, and Prof. J. Walker, F.R.S. Dr. L. T. Thorne, Dr. G. T. Moody, and Dr. J. Wade were elected to audit the Society’s accounts. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected : John Prest Ackroyd, B.Sc. Bernard Middleditch, B.A. Allan Baguley, B.Sc. ,Jack Percival Montgomery.Charles Thomas Bennett. Benjamin L. Murray, B.S. Alicli Cole Benson. Thomas S. Patterson, Pi1.D. George Edward P. Broclericli, B. Sc. Bertram Yrentice, PIi.D., D.Sc. Alfred Denys Cowper. JatindranDth Sen, h1.R. Julien Drugman, Ph. D. Alfred Shrubsole. Nevi1 Norton Evans. Raymond Louis Siau. James Rocheid Forrest. Samuel John Smith. George Fry. Henry Ernest Stevenson. Robert Gamler, 31.Sc. Frederick Henry Streatfeild. Am Ghose. Charles Herbert Thompson, Harry James Glover. Hubert Thompson, B.Sc., John Augustus Goodson. Alfred Tingle, B.Sc., Ph. D. John Monteath Guthrie. William Wood Underhill. Leo Frank Gntlmann, Ph. D. Leon Edward Walling. Alfred Henry Hoit. Francis Langston Watt. Cyril Douglas McConrt. Charles Edward Whiteley.Francis D’Oyley Mears, Jun. William Henry Woodcock. Of the following papers, those marked * mere read : *24. ‘(Observations on some intramolecular and originally rever- sible changes extending over prolonged periods of time.” By Richard John Friswell. The question of the limitation of chemical action to a certain range of temperature was discussed in the light of W. R. Grove’s experiments on the dissociation of water by heat, described in the Bakerian Lec- ture (Phil. Trcms., 1847, 137, l), and of recent experiments at very low temperatures, and it was pointed out that, as a rule, reactions are hastened by elevation of temperature, and hence their course has been less studied than their products. Reference was made to V.Meyer’s labile hydrogen atom, and some results obtained by the author and A. G. Green (Trans., 1885,47,917; 1886, 49, 746) were discussed. It is suggested (1) that the labile condition is not confined to hydrogen, (8)that the constitution of a 37 compound is only relative and exists only so long as the substance is submitted to a certain definite stress, (3) that different stresses develop dissimilar constitutions, and that therefore the constitution of a compound depends on its environment. Experiments on the changes occurring during very long periods of time were described, these consisting in the slow appropriation by nmino- azobenzene base from a solution of aniline hydrochloride of sufficient hydrochloric acid to saturate itself; this reaction was shown to occur even in the presence of much free aniline, and the variations due to changes of temperature were described.These and analogous experiments are held to justify the arguments as to the effects of stress on the successive disruption of the molecules of aniline hydrochloride and aminoazobenzene hydrochloride. Preparations illustrating the above-descri bed experiments were ex hibit ed. DISCUSSION. Dr. MORGANsuggested that the interaction occurring between aniline hydrochloride and aminoazobenzene might be explained in terms of the ordinary theories of chemical equilibrium. Aniline hydrochluride, in aqueous solution, undergoes dissoci-ation, and attains a state of equilibrium which may be repre-sented approximately by the equation C,H,~NH,Cl~C,H,*NH, +HCl.This equilibrium is disturbed by the introduction of aminoazobenzene, because this base forms a sparingly soluble hydrochloride and thus gradually abstracts the free acid from the solution. Excess of aniline hinders this change owing to the fact that, being itself a product of the dissociation of the soluble hydrochloride, it reverses the foregoing balanced reaction, in accordance with the law of mass action, thereby decreasing the amount of available hydrochloric acid. Dr. HEWITTasked whether the proof of the existence of a diazonium salt in an acid solution of diazoaminobenzene during the period of isomerisation to aminoazobenzene did not depend on the coupling properties of such a solution; if so, the demonstration is not con- clusive, since it has been known for years that diazoamino-compounds couple with phenols even in the absence of acids.One of the earliest known cases of this reaction was discovered by Heumann and (Economides, who obtained benzeneazophenol from diazoaminobenzene and phenol (Ber., 1887, 20, 373). In reply to Dr. Hewitt, Mr. FRISWELLsaid that a full account of the evidence for the presence of diazobenzene chloride in the solution during t.he conversion of the diazoaminobenzene into aminoazobenzene would be found in the papers published in conjunction with Prof. A. G. Green (Zoc. cit.). Shortly, it consisted in treating the separated solution with phenols and amines, whereby known azo-dyes were produced and identified.In reply to Dr. Morgan, he had no objection to make to the ex-planation based on the suggested tendency to dissociation of aniline hydrochloride in aqueous solution. He had endeavoured to overcome this tendency by the addition of free aniline, but this only delayed the abstraction of the acid by the aminoazo-base, and, in his opinion, furnished additional evidence in favour of the stress hypothesis which he had advocated. *25. “Note on a magnesium oxybromide.” By George William Fraser Holroyd. An ethereal solution of magnesium phenyl bromide, obtained by Grignard’s method (A~LN. Phys., 1901, 24, 437), when saturated CJLZ‘WL with acetylene and left in a stoppered vessel for several days, deposited clear, colourless crystals having the form either of octohedra or of combinations of the octohedron and cube.The yield of crystals was about 4grams from 50 grams of bromobenzene. The volume of the solution before passing the acetylene was 220 c.c., and 52 grams of bromobenzene were employed. The acetylene, dried with phosphorus pentoxide, was passed through successive portions of 30 C.C. of this solution, thecurrent of gas being continued for about 4 hours, and the flasks being kept for 2 or 3 days or longer before removing the crystals which are gradually deposited. The ethereal solution diminished to about two-thirds of its original volume during the saturation with acetylene. The crystals, which vary considerably in size when obtained from distinct preparations, are hygroscopic and very soft ; they were not recrystallised for analysis, but rapidly dried on filter paper, scraped with a sharp nickel spatula, and analysed as quickly as possible. 0.1037 gave 0.1391 AgSr.Br =53.00. $,0.0894 0.048 MgSO,. Mg= 10.86. CsH2,0,Br,Mg2requires Br =52.86 ; Mg = 10.49 per cent. The substance is decomposed by water, heat being generated during the reaction ; magnesium hydroxide is precipitated, and ether is set free. The ether was estimated by introducing n crystal into a eudiometer standing over mercury ; dry oxygen and two drops of water mere then added successively, the apparatus was surrounded by a steam jacket and an electric spark passed through the gaseous mixture. The carbon dioxide produced was measured by caustic potash absorption, after 39 decomposing any magnesium carbonate present by the addition of three drops of dilute sulphuric acid.0.0221 gave 8-44C.C. CO, ;Mg,Br,,C,H,,O, requires 8-73C.C. CO,. Oxygen used = 13.34 C.C. ;Mg,Br,,C,H,,O, requires 13.1 C.C. oxygeii. The analyses point to the formula Mg2Br,*OH,2(C,H5),0,and the substance doubtless owes its origin to the action of small quantities of water on the magnesium phenyl bromide, C6H5MgBr+ H,O =C,H, -t-MgBrOOH, the magnesium oxybromide then combining with ether and magnesium bromide ; the latter is always a by-product of the action of bromobenzene on magnesium in ethereal solution, the acetylene serving merely to evaporate the ether. Zelinsky (Chem.Centr., 1903, ii, 277), by the interaction of magnes-ium, iodine, and ether, obtained a compound to which he assigns the formula and the compounds MgBr2,3(C,H5>,0,and MgBr,,(C2H5),0, have also been produced. Zelinsky considers that these compounds play the deof catalysts in the formation of the mixed organo-magnesium compounds. The compound obtained by the author is evidently related to these products, and should perhaps be represented by the formula “26. “The arrangement in space of the groups combined with the tervalent nitrogen atom.” By Frederic Stanley Ripping and Arthur Henry Salway. The Hanhsch and Werner hypothesis regarding the tervalen t nitrogen atom indicates the existence of enantiomorphously related isomerides in compounds of the type NR,R,R,, and one of the objects of this investigation was either to isolate, if possible, such isomerides or to demonstrate their non-existence.Since an externally compensated acid chloride may be used for the detection of asymmetry in bases where the asymmetry is due to it carbon atom (Kipping and Hall, Trans., 1901, 79, 444), it seemed probable that, if tervalent nitrogen compounds were asymmetrical, their asymmetry could be detected in like manner, but no evidence of the existence of isomerides mas obtained on examining the products of the interaction of dl-benzylmethylacetyl chloride with methp !aniline, p-toluidine, benzylaniline, and phenylhydrazine. p-Toluidine and 40 benzylaniline also gave negative results with optically active benzyl- methylacetyl chloride.Although the introduction of one centre of asymmetry failed to afford separable isomerides, it seemed highly probable that the introduction of a second centre of asymmetry would give a satisfactory result if enan tiomorphously related derivatives of tervalent nitrogen were really capable of existence. The products from d-benzylmethylacetyl chloride and I-menthylamine, cl-hydrind- amine, I-methylhydrindamine, and I-phenylethylnmiiie, however, re-tained their uniform character after fractional crystallisation. These results indicate that the three radicles, together with the tervalent nitrogen itself, are situated in one plaiie ; that two of the radicles are symmetrically arranged with respect to the third, and that in all probability this is true of any two, that is to say the whole arrange- ment is the most symmetrical one possible.The substituted amides derived from the interaction of benzyl-methylacetyl chloride and the foregoing inactive and active bases mere described. Assuming that the isomerism of the syn- and anti-forms of oximes is structural and represented by the formule R>C:NOH andR, R>C<xH, the latter structnre, since it contains an asymmetric carbon atom, should exist in enantiomorphously related forms, and the introduction of an optically active acid chloride should produce two non-enantiomorphously related separable isomerides. The action of benzylmet bylacetyl chloride on benzoinoxime was studied, but instead of the desired acyl derivative, the following products were obtained: benzil, benzoin, benzaldehyde, benzonitrile, ammonium chloride, hydrogen chloride, and benzylmethylacetic acid, together with a compoilnd melting at 126O.Attempts to obtain a benzyl-methylacetyl derivative from a-benzaldoxime were also unsuccessful, decomposition taking place with the formation of benzonitrile. Benzoyl chloride interacts normally with benzoinoxime, giving henxoinoxime benzoccte, CHPh(OH)*CPh:NOBz, which crystallises from alcohol in leaf-like plates melting at 165-166". Benzoylbenzoinomiine, CHPh(OBz)CPh:NOH, prepared by treating benzoylbenzoin with hydroxy Ianiine, crystallises from alcohol in globular clusters melting at 148O.dl-Benzylmethylacetyl chloride gives, with dl-hydrindamine, two isomeric dFbenzylmethylacetohydrindamides, which can be easily separated; these two compounds melt at llO-lllo and 119~5~ respectively, and their formation affords proof of the asymmetry of the hydrindamine molecule. d-Benzylmethylacetyl chloride and dl-hydrindamine give a mixture 41 of the isomeric amides dAdB and dAZB, from which the derivative of the cl-base is easily isolated ; the enantiomorphously related com-ponents of &-a-phen ylethylamine may be separated in a similar manner, the compoond, CH,Ph*CHMe*CO*NH*CHMePh,of the I-base being easily isolated. 27. ‘‘The esterification of r-mandelic acid by menthol and borneol. ’’ By Alexander McKenzie.The results recorded in this research deal with tho method of resolving i-compounds devised by Rlarckwald and the author (Ber., 1899, 32, 3130; 1900,33,305; 1901, 34, 469. Compare Walden, Ber., lS99, 32,2703; E. Fischer, Ber., 1899, 32,3617). When v-mandelic acid was heated with 2-borneol, the unesteri6ed acid was lzvorotatory, whilst the mixture of esters yielded a laevo-rotatory acid. When I-bornyl dE-mandelate mas submitted to fractional hydrolysis, a laevorotatory acid was obtained from the initial hydrolysis, and an inactive acid from the final hydrolysis of the residual esters by an excess of alcoholic potassium hydroxide. d-Mandelic acid was isolated from the dextrorotatory acid obtained from the initial hydrolysis of I-menthyl dl-mandelate.Z-Menthyl c2l-mandelate can yield either a dextrorotatory or a lzvorotatory acid from the initial fractional hydrolysis according to the amount of alkali used. I-Menthyl dZ-mandelate boils at 225O under 30 mm. pressure and melts at 85-86’ ;it has [CL]~-$4~2~(c=10.890) in ethyl-alcoholic solution ; it is partially racemic, and is not resolved into I-menthyl cl-mandelate and I-menthyl I-mandelate when repeatedly crystallised from light petroleum at the temperature of the laboratory, Potassium I-mandelate is completely racemised when heated with a large excess of potassium hydroxide in aqueous or ethyl-alcoholic solution. 28. ‘‘Certain organic phosphorus compounds.” By Augustus Edward Dixon. In pursuing the study of the interaction of phosphorus halides with metallic thiocyanates (Trims., 1901, 79,541), the author has now succeeded in isolating phosphorus and phosphoryl ‘I thiocyanates ” respectively.Phosphorus trithiocganate, P(CNS),, obtained from phosphorus trichloride and dry ammonium thiocyanate in presence of benzene, is an almost colourless oil boiling at 163’ under 15 mm. pressure, and having a sp. gr. 1.487 at 15~5~.When treated with water, a portion was quickly hydrolysed, forming phosphorous and thiocyanic acids ; 42 the remainder was hydrolysed exceedingly slowly, but otherwise no material difference in properties or composition was observed between this residue and a distillate not subjected to the action of water. Phosphoryl trithiocyanate, PO(CNS),, obtained from phosphorus oxychloride, is a clear, pale yellow, highly refractive oil, boiling at 1'75" under 21 mm.pressure, and completely hydrolysed by cold water into phosphoric and thiocyanic acids, together with some isoper-thiocyanic acid, resulting from the interaction of these products ;it has a sp. gr. 1.520 at 13.5". These substances not only behave as thiocyanates, but also, to some extent, manifest the properties of thiocarbimides, being freely de- sulphurised by alkaline salts of lead and silver; they unite spontaneously with aniline, &c., fixing either one or three molecular proportions, according to the amount presented, to form amorphous solids, insoluble in cold water. The additive products are readily hydrolysed by contact with hot water, yielding in all cases ap-proximately one molecular proportion of monosubstituted thiourea ; a little hydrogen sulphide is evolved, but otherwise the rest of the contained sulphur appears as thiocynnic acid.Certain tests which have been employed to distinguish betweea thiocyanates and thiocarbimides (such as treatment of the alcoholic solution with sodium, or the action of thioacetic acid) cannot be safely accepted as final where acyl thiocyanates are concerned, all the latter so far examined being tautomeric in the sense that, under suitable conditions, they can behave as thiocarbimides to a greater or less extent if their power in this direction is measured by their capacity to fix aniline in the form of an immediate derivative of normal phenylthiocarbamide.The study of these supposed tautomeric phenomena is being continued. 29. "Note on the relation between the chemical composition of some organic substances and the density of their solutions." By Charles Edward Fawsitt. The density of aqueous solutions of different salts in equivalent quantities is an additive property, and the principal relations are given by Valson's Law of Moduli. The relation of density in solutions of organic compounds (feeble electrolytes or non-electrolytes) to chemical composition or constitution is not yet so fully understood. The author, in continuing an investigation on the amides (Proc. Boy. Xoc. Edin., 1904, 25, 51), has measured the demity of aqueous solutions OF a number of amides at 25O, when the solutions contained the gram-molecular weight of the substance dissolved in one litre The densities of urea, methylurea, and as-dimethylurea solutions are 1.0155, 1.0137, and 1.0107 respectively; n comparison of these num-bers with those obtained by Kanitz (Zeit.physikal.Chem., 1897, 22, 336) for ammonia, methylamine, aud dimethylamine, namely, 0.9932, 0.9886, and 0,9856, shows that the differences for the corresponding numbers are fairly close to one another. The densities of solutions of acetamide, propionamide, and butyr- amide are 1.0040, 1.0028, and 1.0006. The values obtained for acetic, propionic, and butyric acids by Reyher (Zeit. phpsikal. Chenz., 1888,2, 744) are 1.0084, 1.0066, and 1.0040, and show a similar relationship.From these results, it will be seen that the density of such solutions is to a great extent an additive property, but constitution also plays some part, because isomeric substances give different values. ri30. The so-called ‘ hydrocellulose.’ ” By Arthur Landauer Stern. When cellulose is exposed to the action of dilute acids under certain conditions, the tenacity of the fibres is destroyed, and it falls to a powder which has been called hydrocellulose, and stated to have the e mpirical formula C,,H,,O,,. It is now shown that when the above reaction takes place, in- stead of a gain in weight, as theory indicates, there is invariably a loss, and that a small amount of soluble matter is formed, a portion of which, in all probability, is d-glucose.The elementary composition of the powder is also shown to be identical with that of cellulose, the previous statements bearing on this point being founded on faulty experimental methods. A hydrabed cellulose is not formed under these conditions, but a hydrolysis takes place similar to that undergone by other carbo- hydrates under comparable conditions. 31. ir Isomeric change of diacylanilides into acylaminoketones.” By Frederick Daniel Chattaway. When the diacylanilides are heated in presence of hydrogen chloride or zinc chloride, intramolecular rearrangement takes place and the isomeric acylaminoketones are produced thus : NH*COR NH*COR /\ and Iqcori-+ I/\/ \/COR 44 Such isomeric changes as have been studied follow an exactly similar course to that of other analogous transformations in which atoms or groups of atoms pass from the nitrogen into an ortho-or para-position in the ring.The introduction of a second acyl group into the nucleus has, however, not yet been effected (compare Proc., 1902, 18, 173 ; 1903, 19,50, 5’7, 106, 124). 32. (‘Intramolecular rearrangement in derivatives of the aromatic aminoketones.” By Frederick Daniel Chattaway. The acyIchloroamino-derivatives of the aromatic ketones readily undergo the intramolecular rearrangement characteristic of substituted aromat,ic chloroamines in which the halogen linked to the nitrogen changes place with a hydrogen atom attached to the ring in an ortho- or para-position. The conditions necessary for the transformations to t,ake place were indicated, and a series of new aromatic chloroarnino- ketones with their acyl derivatives was described.ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the Election of Officers and other business will be held on Wednesday, March 23rd, at half-past five o’clock in the afternoon. At the next Meeting, on Thursday, Mttrch 3rd, 1904, at 8 p.m., the following papers will be communicated :-“Chemical dynamics of the alkyl iodides.” By K. A. Burke and F. G. Donnan. ‘‘The constitution of phenolphthalein.” By A. G. Green and A. G. Perkio. “8-Ketohexahydrobenzoic acid.” By W. H. Perkin, jun. “Photochemically active chlorine.” By C. H. Burgess and D. I;. Chapman.‘‘The separation of p-crotonic acid from a-crotonic acid.” By R.S. Norrell and A. E. Sellars. R. CLAY AND SONS, LTD., BREAII ST. HILL, E.C.> AND BUSGAY, SCGFOLB.
ISSN:0369-8718
DOI:10.1039/PL9042000035
出版商:RSC
年代:1904
数据来源: RSC
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