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Proceedings of the Chemical Society, Vol. 16, No. 217 |
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Proceedings of the Chemical Society, London,
Volume 16,
Issue 217,
1900,
Page 1-8
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摘要:
Issued 24/1/1900 P R 0 C E E D 1.N G S OF THE CHEMICAL SOCIET-Y. XDITBD BY THE XECRETARIEX. Vol. 16. No.217. January 18th, 1900. Professor Thorpe, F.R.S., President; in the Chair. Messrs. E. W. Lewis, A. J. Shelton, S. Blofield, and J. N. Goldsmith were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Frederick Nolan Baker, 3rd Royal Iniskilling Fusiliers, Mullingar, Ireland ; William Francis Cooper, Ashlyns Hall, Berkhampsted ; Alexander Findlay, Emilienstrasse lo', Leipzig, Germany ; Julius Geldard, 120 Park View Terrace, Otley Road, Bradford ; Adam Houston, Brisbane House, Bellahouston, Glasgow ;Walter A. Riley, Briinswick Lodge, Newmarket Road, Norwich ; Fred Pilkington Sargeant, Springfield Place, Leeds ; Edward Shrapnel1 Smith, 35 Botanic Road, Wavertree Park, Liverpool, E.Of the following papers, those marked * were read. "1. '(Note on nitrogen halogen compounds." By Julius Stieglitz and E. E. Slosaon. The authors point out that F. D. Chattawayand K. J. P. Orton, in their work on ''A Series of Substituted Nitrogen Chlorides, &c."(F~ans., 1899,76, 1046) have overlooked a series of papers emanating from the Kent Chemical Laboratory of the University of Chicago, in which, since 1893, results of work on the nitrogen halogen compounds in 2 various directions have been given, and a definite line of work under-taken for further investigation. In one of these papers, (( Ueber die Einmirkung von unterbromiger und unterchloriger Saeure auf Saeureanilide " (Ber., 1895, 28,3265), the preparation and behaviour of acyl-pbenyl nitrogen chlorides and bromides are discussed, and some of the compounds obtained by Chattaway and Orton described. In order to avoid future conflict, the line of work pursued by one of the authors and his students is fully outlined as centring in a study of the I' Beckmann rearrangement " of acyl-nitrogen halides and analogous bodies. Further results are given concerning the behaviour of acgl-phenyl nitrogen halides, especially towards alkalis, potassium cyanide, and zinc ethide.All of these reagents reproduce acylanilides. The pre-paration of acyl-alkyl-nitrogen chlorides and representatives of the series are described : ethy2 benxoyl nitrogen chloride, C,H,NCl*COC,H,, m.p. 535", the corresponding methyl compound is an oil. Alkalis, potassium cyanide, and zinc ethide regenerate the acyl-alkyl-amides. Further representatives of the isomeric series, the chloro (or bromo) imido-acid esters, RC(:NCl)OC,H,, &c., are given : chlovoimidoethyl metanidrobenxoate, N02C,H4C(NC1)OC,H,, m. p. 61°, the corresponding bromide melts at 71" ;the analogous cldoroimide of p-naphthoic ethyl ethw melts at 68O, the bromide at 77". These ethers are remarkably stable nitrogen halides, perhaps the most stable known. Some have been distilled without decomposition in a vacuum above 100";boiling alcoholic ammonia does not decompose chloroimidoethylraetanitro-benzoate. Although a number have been obtained in solid form, no stereoisomeric compounds, RC(:NCl)OR, have as yet been observed, such as exist in the case of the analogous benehydroximic ethers, C,H,C(:NOH)OG,H5.On treatment with zinc ethide, ethylamine derivatives are obtained. DISCUSSION. Dr. CHATTAWAYsaid he regretted that the papers mentioned had been at first overlooked. Dr. Orton and he had approached the subject from an entirely different point of view, and he did not think that their future work was likely to overlap. Professor Stieglitz and his students were moiking on the Beckmann change, while they were chiefly studying substitution, and endeavouring to show that the chlorination and bromination of anilines and anilides are not direct processes, but that nitrogen chlorides and bromides are alwaysiifirst formed, and under favourable circumstances subsequently undergo isomeric change.3 “2. ‘‘On the electrolysis of the nitrogen hydrides and of hydroxyl-amine.” By E. C,Szarvasy, Ph.D. A short account was given of the experiments of the author on the electfolysis of solutions of ammonia, hydrazine, azoimide, hydroxyl- amine, and of their salts. The experiments were carried out at different temperatures, and with varying current densities and concentrations. The conditions were determined under which ammonia, hydrazine, and azoimide, on electro-lysis, yield their two components in the proportions contained in their molecules respectively, and without the formation of any secondary products.In the case of hydroxylamine and its salts, both oxidation and reduction products were formed, no matter how the experimental conditions were varied. Many att.empts were made to prepare polymeric nitrogen by electro- lysing solutions of azoimide and its salts at very high current densities j this part of the work is still in hand, *3. ((On the relationship between the constitution of some sub-stances and the fluorescence which they exhibit.” By J. T,Hewitt, M.A.,D.Sc. Since fluorescence is the absorption of radiant energy of definite wave-length or wave-lengths and emission of the same energy after it has been reduced in vibration-frequency, one would expect to find fluorescence usually a property of substances capable of existing in tautomeric forms. As a matter of fact, the colouring matters which do exhibit fluorescence are almost without exception tautomeric, the exceptions which are known being usually snbstances for which no very great degree of purity can be guaranteed. But many substances which behave tautomerically do not exhibit well-marked fluorescence; this might well be due to the fact that in a solution in which the two tautomeric forms are in equilibrium the reaction-velocities from one form to the other are so small that a very few of the molecules have the opportunity of absorbing energy when they correspond to one and emitting it in the other configuration.The case is, however, very different when the molecule in one of its configurations is symmetrical; to pass from this to the other con- figuration, either of two displacements is necessary, equal in magni- tude, but opposite in direction.Just as a pendulum (neglecting the friction due to its support and the medium in which it vibrates) swings regularly between two extreme positions, passing at regular intervals through its lowest point, so a molecule of a substance which exhibits the kind of tautomerism characteristic of fluorescein might undergo continual and frequent change. Fluorescein itself yields derivatives, not only of a phenolic lactone, but also of a quinone-carboxylic acid. The transition from the lactone to the quinone- carboxylic form may be effected by diaplacement of either of its pheholic hydrogen atoms, the symmetry of the molecule conditioning the equality of energy necessary for displacement of either atom.Hence all the molecules will be undergoing tautomeric change con- tinuously and frequently, and energy absorbed when the molecules have one configuration will be, to an appreciableextent, emitted when they correspond to the other configuration. It is practically certain that the vibration frequency of fluorescein is different in the two states (the diethyl ethers corresponding to the two forms are quite different in the character of their absorption) and hence every oppor- tunity is offered for energy of a rapid vibration frequency to be largely transformed into energy of greater wave-length. In the case of fluorescein, the condition of a molecule may be sym- bolised in the following manner : 0 0 The greater number of fluorescent dye-stuffs conform to the theory shortly stated above ;exceptions may, however, be classed under two heads.(i) Substances having the requisite structure, but not exhibiting fluorescence. (ii) Substances exhibiting fluorescence, but not possessing the doubly symmetrical tautomeric structure considered -in the case of fluorescein. It is, however, probable that. many of the exceptions are only apparent, the fluorescent spectrum not Gaving been sutliciently examined. 4. Action of fuming nitric acid on a-dibromooamphor.” By Arthur Lapworth and Edgar M.Chapman. The authors have repeated the work of Kachler and Spitzer on the oxidation of a-dibromocamphor (Monatsh., 1883, 4, 554), and agree with them that camphoronic acid is produced, but the quantity of this substance is small, and it is difficult to separate it from homocam- 5 phoronic acid, which is present in much larger amount ; on [the other hand, they have not been able to detect any isocamphoronic acid, and conclude that Kachler and Spitzer were merely dealing with impure homocamphoronic acid. The product, to which Kachler and Spitzer gave the provisional **formula C24H33BrNiO12,appears to have been a mixture of khe substance C1,H1,N,O,, already described by the authors (Tvans., 1899, 75,SSS), with ordinary nitrobromocamphor, C,,H,,OBrNO,, produced by the nitration of monobromocamphor formed in the initial stage of the react ion, Besides the above-mentioned products and dibromocampholid, a number of other substances seem to be formed. One of these remains dissolved in the water with which the mixture is diluted, and cannot be isolated by dilution.It is obtained by extracting the liquid containing the homocamphoronic acid with chloroform, and forms a neutral oil which is not readily soluble in pure water ; it is probably a lactone. When this substance is allowed to remain with aqueous potnsh, it produces an acid having the formula C,,H,,O,, which forms magnificent, transparent crystals, is sparingly soluble in water and melts at 177". When distilled, or warmed with strong acids, it undergoes a curious molecular change, yielding an acid, C10H1202,melt-ing at 167-168', which has been identified as trimethylbenzoic acid, (C0,H :Me :Me :Me : : 1 :2 :3 :4).5. "Note on Volhard's method for the assay of silver bullion.'' By T. K. Rose, D.Sc The precautions to be observed in using the method are described, and the limit of accuracy put at 0.1 per 1000, instead of 0.25 per 1000, as stated by Van Riemsdyk. 6. '*c-Suhtitated hydroxytriazoles." By George Young, Ph,R., and Ernest Witham, B.A.,B.Sc. The authors have prepared hydroxytriazoles by two actions represented by the equations R*CH:N*NH*CO*NH,+ 0 = R~C<~"">C~OH + H,O, R.CHO +NH,. CO~N.-N CO~NH,= HN-N>C*OH + NH, + CO,. Where R is the same group, R*CqN the products of the two actions are apparently identical. c-PhenylhydroxytriaxoEe, C,H,*C,N,H,O, m.p. 321-322'. Forms two silver salts, C6H5*C,N,HO*Ag and C,H,* C,N,O*Ag,. Aceby1 derivative, C6H,*C,N,HO*C,H,O, m. p. 248'. c-Metanitrophenytyl-hydroxytriaxob, NO,*C6H4*C,N3H,0, m. p. 304". Forms two 6 silver salts, C,H5N,03Ag and C,H,N,O,Ag,. Ace tyl derivative, C,H5N,03*C,H30, m. p. 26 1-262'. C~nnccmaleiiz~curbaxorte, C,H,* CH:CH*CH:N*NH*CO*NH,, m. p. 215-216'. c-XtyrenyI-h?/d~oxytriaxoZe,C,H, CH: CH C2N3H,0, in. p. 3 1 1'. Forms two silver salts, C,,H,N,OAg and C,oH7N,0Ag,. Monoacetyl deriva-tive, C,,H,N30*C,H30, m. p. 241-5442'. Diacetyl derivative, C,,H7N3O*(C2H~O),,m. p. 137-138O. 7. "Note on the use of a mixture of dry silver oxide and alkyl halide8 as an alkylating agent." By (3.Druce Lander. Dry silver oxide and alkyl iodides have been employed in tbe preparation of the ethereal salts of alkyloxy-acids (Trans., 1890, '75, 157, 485, 754). The use of the method in the preparation of alkyl derivatives of compounds of other classes has been studied. Optically active ethyl menthyl ether has been prepared by the action of dry silver oxide and ethyl iodide on I-menthol. The optically active ether is an oil boiling at 207*5O-209.5' (uncorrected) ;d 20°/40= 0.8537 : [ u]~~" 98.32'.= -The ethyl and isopropyl ethers of benzoin are obtained by the action of silver oxide and ethyl and isopropyl iodides respectively on benzoin. The ethyl ether crystallises from light petroleum in needles melting at 68-58*5' ; compare Limpricht and Jena (Annulen, 1870, 155, 96), and Fischer (Bep., 1893, 26,2415). The isopropyl ether, of similar crystalline form, melts at 72'75O.The action of silver oxide and ethyl iodide on benzamide leads to the formation of ethyl benzimidoether. The hydrochloride melts at 119-120' with evolution of gas; compare Pinner (Ber., 1883, 18, 1654) and Tafel and Enoch (Bey., 1890, 23,103). The introduction of one ethyl group in place of hydrogen in ethyl acetoacetate can be readily effected by the aid of silver oxide and ethyl iodide, The product consists of ethyl ethylacetoacetate contain- ing, however, approximately 2 per cent. of ethyl /3-ethoxycrotonate, melting at 30°, and yielding on hydrolysis ethoxycrotonic acid which melts at 137*5O,with evolution of gas, The introduction of an ethyl group into ethyl ethylacetoacetate, and ethyl malonate by the same method is also possible, but the proportion of the ethyl homologue obtained is small, No indication could be obtained of the production of the ethyl homologue of ethoxycrotonic acid by the action of silver oxide and ethyl iodide.Ethyl acetosuccinate may be prepared by the action of silver oxide and ethyl iodoacetate upon ethyl acetoacetate. Further results and details will be given in a subsequent corn-munication. ADDTTIONS TO THE LIBRARY. I. Donations. Coppock, J. B. Volumetric analysis; specially adapted to the re- quirements of students entering for the Advanced Practical Chemistry Examinations of the Science and Art Department, also the Inter- mediate Science and Preliminary Scientific Examinations of the Uni- versity of London.London 1899. From the Author. Henderson, G. G.,and M. A. Parker, An introduction to analytical chemistry. London 1899. From the Authors. 11. By Pzcrchase. .Berthollet, C. L. Essai de statique chimique. Two vols. Paris 1803. Erdmann, H. Lehrbuch der Anorganischen Chemie. Braunschweig 1898. Lachman, Arthur. The spirit of organic chemistry, an introduction to the current literature of the subject. With an introduction by Paul C. Freer. New York, 1899. Pump!& tit. Hiortdahl, Th. Om hydrazinets sulfater og alun samt om dets bestemmelse ved overmangansur kali. Christiania 1897. From the Author.Steuart, D. S.-5. The mineral wealth of Zoutpansberg : the Mur- chison Range gold-belt (excerpt from the Trans. of the Inst. of Mining Engineers). London 1899. From the Author. Wardle, Sir Thomas. A paper on art as applied to the weaving and printing of textile fabrics. (Read before the Architeotural Asso-ciation, November 24, 1899.) From the Author. Waterhouse, J. Teachings of daguerreotype (Trail1 Taylor Memo- rial Lecture III., 1899). From the Author PROCEEDINGS OF THE ROYAL SOCIETY. A few volumesof the above may be obtained by Fellows, in the order of application, from the Assistant Seoretary, Chemical Society, Burlington House, W., at the price of 10s. per vol. Vols. 8-12, 15-24, 27, 31-45 are in stock. At the next meeting, on Thursday, February lst, 1900, the fol- lowing papers will be communicated by the authors :-“The chlorine derivatives of pyridine.Part V. Synthesis of aa’-dichloropyridine. Constitution of citrazinic acid.” By W. J. Sell, M.A., and F. W. Dootson, M.A. The formation of heterocyclic compound^." By S. Ruhemann and H. E. Stapleton. ‘6 The space configuration of quadrivalent sulphur derivatives. Methyl ethyl thetine dextrocamphorsulphonate and dextrobromo-camphorsulphonate.” By W. J. Pope and S. J. Peachey.‘‘ Nitrocamphane.” By M. 0. Forster. VICTOR MEIYER MEMORIAL LECTURE. The Victor Meger Memorial Lecture will be delivered by Professor T. E. Thorpe, F.R.S., President of the Society, on the evening of Thursday, February 8th, 1900, at 8.30. ~~ RICHARD CLAY AND SONB, IJMJTED, LONDON AND BUNQAY,
ISSN:0369-8718
DOI:10.1039/PL9001600001
出版商:RSC
年代:1900
数据来源: RSC
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