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Proceedings of the Chemical Society, Vol. 17, No. 233 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 233,
1901,
Page 35-42
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摘要:
ltwued 27/2/1901 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDIZ’ED BY THE SECRETARIES. February Blst, 1901. Dr. ~MSTRONG,Vice-president, in the Chair. Messrs. Hugh Ramage, R. W. Cohen, and A. W. Nunn, were formally admitted Fellows of the Society. The following certificates were read for the first time :--Edward George Paul Bousfield, St. Swithin, Hendon ; Albert Ernest Dunstan, 24, Lidfield Road, Stoke Newington, N. ; Alfred James Hyder, 22, Guntoii Road, Upper Glapwn, London, N.E. ; William Henry Coutts Jemmett, Tintern, Gap Road, Wimbledon ; William Shepperson, Longfield, at. Missenden, Bucks ; Charles Edmund Shaw Slierratt, 24, Argyll Road, Normacott, Staffs. It was mnounced that the following changes in the Officers and Council were proposed by the Council : As President: Professor J.Emerson Reynolds, Sc.D., M.D., F.R.S., vice Professor T. E. Thorpe, C.B., Ph.D., D.Sc., LL.D., F.R.S. As Vice-Presidents: Professor Herbert McLeod, F,R.S., and Professor H. A. Miers, M.A., F.R.S., vice Professor G. D. Liveing, &LA., F.R.S., and Professor J. M. Thomson, LL.D., F.R.S. As Ordinary Members of Council : Dr. A. W. Crossley, Professor J. J. Dobbie, M.A., D.Sc., Dr. M. 0. Forster, and Mr. 5. U. Pickering, M.A., F.R.S., vice Professor J. Norman Collie, Ph.D., F.R.S., Mr. Gowland, Mr. C. T. Heycock, M..A.,F.R.S., and Dr. Messel. Mr. F. J. M. Page, Mr. E. W. Voelcker and Mr. A. C. Chapman were appointed to audit the Society’s accounts. Mr. F.J. Lloyd was appointed to act with the Officers and Dr 36 Chattaway, who had been appointed by the c1ounci1, in drawing up a Report to the Council on the replies which have been received to the question as to the suggested change in the day and hour of the Ordinary Meetings, Of the following papers, those marked * were read : *20, Isomeric hydrindamine mandelates and phenylchloroacet- hydrindamides.” By F.S. Kipping and H.Hall. Although many salts of d-Z-hydrindamine with different optically active acids have now been submitted to fractional crystallisation (Kipping, Trans., 1900, 7’7,861), the resolution of the base into. enantiomorphously related compounds has not yet been accomplished ; this fact, and the formation in some cases of isomeric salts which appear to be partially racemic, led the authors to try to obtain some direct evidence of the asymmetry of the base.The fractional crystallisation of d-1-hyclrindanaine d-1-manclelccte, C,HI1N,C,H,O,, was therefore undertaken in order to ascertain whether the two racemic or externally compensated salts, dBdA, IBZA, and dBZA, IBdA, could be separated, but the several fractions proved to be identical, owing possibly to the conversion of one isomeride into the other, dBdA,ZBIA 2 dBZA,/BdA. From d-2-hydrindamine and d-Z-phenylchloroacetyl chloride, however, two isomeric phenplchloroacethydrindamides,C6H,*CHCl*CO*NH*CgHg, melting at 150-151’ and 124-125’ respectively, were obtained ; in this case, the isomerides are not mutually convertible in solution, and their formation shows that the base is externally compensated.d-1-Hydrindamine d-mnndeZate, prepared from the pure d-acid, is not resolved into different fractions when it is crystallised from alcohol ; it is therefore a partially externally compensated salt, dAZB, dAdB. The hydrindamine salts derived from racemic mandelic acid and from pure d-mandelic acid respectively are indistinguishable except in optical properties ;they both melt at 139-141’, whether heated separately or mixed together in different proportions ; they have also the same, or almost the same solubility, for when a mixture of the two is fractionally crystallised, the several deposits have practi- cally the same specific rotations. It may be concluded, therefore, that the three optically different compounds, dAdB, dA4ZB,ZAIB,form isomorphous mixtures, and that 37 the salts of the active and inactive acids do not represent true par- tially racemic or racemic compounds.The use of externally compensated acid chlorides for the detection of asymmetry, and of the active chlorides for the separation of enantio- morphously related compounds, is being further investigated. "21. '(Isomeric benzylhydrindamine bromocamphorsulphonates,and some salts of d-Z-hydrindamine." By F, S. Kipping and H.Hall. Benxylhydrindarnine, C,H,*NH*C7H7,prepared by treating d-l-hydr- indainine with benzyl chloride, unites with a-bromocamphorsulphonic acid, forming a mixture of tmo isomeric salts, C,,H, 7'N,C1,H,,BrO*S0,H, which are separable by fractional crystallisation.The more sparingly soluble '' a-salt " forms transparent plates, melts at Z06-207°, and has a specific rotation [aID= +50'in ethyl alcohol. The more readily soluble ''P-salt " crystallises in ill-defined prisms, melts at 186 -187O, and has a specific rotation [a],= +51.5Oin ethyl alcohol; in chloroform, the specific rotation of the @-salt seems to be slightly greater than that of the isomeride. Both salts give an optically inactive base when decomposed with barium hydroxide solution, and they both contain an acid optically identical with ordinary d-a-bromocamphorsulphonic acid. Since they both contain an asymmetric carbon group, as well as a nitrogen atom which is directly united with ( K),(C9H,),(C7H7),and with the ion of the bromo-acid, they might be regarded as salts of the two different externally compensated bases, +c' +NV, -C -NV, and +C -NV, -C +NV,or they may be considered to be analogues of the isomeric hydrindamine bromocamphorsulphonates, &c., which have been recently described (Kipping, Trans., 1900, 77, 861). d-1-Hydrindamine d-canap~ol.su~J~onate, C,H,,N,C1,H1,O*SO,H, pre-pared from the base and Reychler's camphorsulphonic acid, like the salt obtained with d-camphor-rr-sulphonic acid, is not resolved into isomerides on fractional crytallisation ;it forms long prisms melting at 165-166", and is very readily soluble in water.d-1-Hydrindarnined-JLydroxy-cis-rr-cccmphanate, un-CSH11N,C10H1406, like the corresponding salt of I-cis-a-camphanic acid, also remains homo- geneous on fractional crystallisation ; it forms transparent prisms ( +QH,O)melting at 202-203°."22. ('Constitution of bromocamphoric anhydride and camphanic acid." By A. Lapworth and W.H.Lenton. The fact that ordinary bromocamphoric anhydride on treatment with alkalis is in part converted into lauronolic acid by loss of hydro- 38 gen bromide and carbon dioxide has led to the view that the bromine atom is in the P-position with regard to one of the carboxyl groups (Aschan, Ber., 1894, 27, 2112), as it is with P-bromo-acids that this property is almost exclusively associated. In the belief that the behaviour of the anhydride in this respecl is misleading, the nut,hors have made numerous experiments which have resulted in the following observations.Camphanic acid, on treatment with phosphorus pentabromide, is re-converted into bromocamphoric anhydride, showing that the lactonic oxygen atom occupies the position of the bromine atom in the anhydride. It is difficult to oxidise camphanic acid with any but powerful agents, and when attacked it is usually converted into camphoronic acid or its decomposition products. When its amide, however, is warmed with phosphorus chlorides it is converted into the nitrile, and this, on treat- ment with alkalis, is at once resolved into hydrogen cyanide and cam- phononic acid, which, apart from all views as to the constitution of CMe,. 70camphor, must have the structure CO,H* CMe< cH,--C H2’ Camphanonitrile is therefore the lactone of an a-hydroxynitrilic acid, CH,* $Xe-CO namely, 1 CAle, 1 , which would decompose on tre:ttment with CH; b(CN)*O alkalis in the above manner. Camphanic acid and bromocam phoric anhydride are therefore represented by the formule suggested by CH,.QMe---CCl CH,*~Me-~O Bredt,, namely, I YRfe, I and I ?Me, , and the forma- UH,* C(CO,H)*O CH,*C(Gr)*CO tion, from them, of lanronolic acid has not the significance lvhich has been attached to it. *9s. 6‘ The action of acetylchloro- and acetylbromo-aminobenzenes on amines and phenylhydrazine.” By F. D,Chattaway and K. J. P. Orton. In studying the action of nitrogen chlorides and nitrogen bromides on amines and phenylhydrazine, the authors have used the acetyl- chloro- and acetyl bromo-amino-2 : 4-dichloro benzene recently prepared by them, as these substances are readily obtained pure.The operations have generally been carried out in chloroform solution, avoiding as far as possible the presence of water. The reaction with the aliphatic amines is represented by the equation R-NH,+ C6H,Cl,*YClAc =R*NHCl+ C,H,Cl,-NHAc. The chloro-amino-derivatives thus formed can be isolated. 39 The initial reaction with the aromatic amines (anilines and tolu- idines) is similar. The halogen, however, immediately wanders from the nitrogen into the para- and ortho-positions if these are unoccupied When the hydrogen atoms in the positions 2, 4, and 6 are already substituted, no such intramolecular transformation can take place, but the halogen amino-derivatives of such anilines (as 8-trichloroaniline) are very unstable, and decompose, yielding substituted azobenzenes.The azo-formation takes place to some extent when acetylchloroamino- benzenes react with the less substituted anilines: and toluidines. Two reactions take place between phenylhydrnzine and halogen amino-compounds. The one, when phenylhydrazine is in excess, is represented by the equation 4C6H5*NH*NH,+ S(:NX) =C6H5N,+ C,H5NH, + 2C,H5*NH*NH,*HCl+ 2(:NH) ; the other, when the halogen amino-compound is in excess, by the equation C6H,NH*NH2 + 3(:NX) =C6H,X+ N, +X, + 3(:NH). In the authors’ opinion, the formation of these substances is not a result of oxidation, but depends on the intermediate formation of halogen hydrazino -derivatives.The following hitherto undescribed substances have been prepared : Aceto-4-chZoromethyZaniZine,C6H,Cl*NCH3*COCH,, m. p. 92O, white plates from petroleum ; o-chZoromsthyZnniZ~ne7C6H4C1*NH*CH,, a colourless oil, b. p. 2 I So (‘760 mm.) ; S-chZoro-5-bronzoncetnniZide, C,H,C1Br*NH*COCH3, needles, m. p. 141’ ;3-bromo-4-chZoroaceticniZide, C6H,ClBr*NH*COCH,, rhombs, m. p. 130’; 2 :4 : 6, 2’ : 4’:6’-hexcc-chloroaxobenxene, C,H,Cl,*N:N*CGH,Cl,, dark red needles, m.p. 1889 ‘6*24. The preparation of orthochloroaniline.” By F, D. Chattaway and K.J. P. Orton. The authors described a convenient method of preparing ortho-chloroaniline by the chlorination of acetanilide. The chlorination is effected by adding the calculated quantity of a strong solution of bleaching powder to a solution of acetanilide (1 part) in glacial acetic acid (3 to 4parts).Orthochloroacetanilide, which forms from 5 to 8 per cent. of the product, is partly separated from the para- derivative by fractional crystallisation from alcohol. The o-chloroaniline is finally freed from p-chloroaniline by dist*illing in steam from sulphuric acid. *26. The bacterial oxidation of formates by nitrates.” By W. C. C. Pakes and W. H. Jollyman. In previous communications the authors have described the actions of a group of bacteria upon solutions containiiig sodium formate, and 40 of another group upon solutions containing sodium or potassium nitrate.Many of the bacteria which dec.ompose the formate are also found to decompose the nitrate, such, for instance, as the B. coli communis, B. enteritidis of Gartner, and the PnetcmobcuAlus of Friedlander, each of which converts formic acid into carbon dioxide and hydr ogen, and reduces nitric to nitrous acid. If any of these bacteria be cultiviLteci in a medium containing both formate and nitrate (I per cent. of each), it will be found that no gas will be evolved. After the lapse of several days, the fluid mill be found to contain sodium hydrogen carbonate and sodium nitrite. When the medium contains an excess of sodium formate as compared with the sodium nitrate, gas is evolved which, upon analysis, proves to consist of carbon dioxide and nitrogen.When the same bacteria are cultivated in media containing d-glucose and sodium nitrate, a similar effect is produced, gas is evolved which consists of carbon dioxide and nitrogen, or carbon dioxide, nitrogen and hydrogen, the latter being found if the sugar is in excess as compared with the nitrate. The authors have not yet been able to determine whether a similar result would be obtained when the organism used did not act upon both, but they have succeeded in showing that the B. pyocycmeus (which does not decompose formate) acts in a medium containing both salts almost as if the formate were absent; they have not as yet been able to find a bacterium which decomposes formate, but which does not reduce nitrates.26. “Condensation of phenols with esters of the acetylene series. Part IV. Benzo-7-pyrone and its homologues.” By S.Ruhemann and H. W.Bausor, B.A. Ruhemann and Stapleton have shown (Tvans., 1900, 77, 1184) that phenoxyfumaric acid under the influence of concentrated sulphuric acid condenses to benzo-y-pyronemonocarboxylic acid, which, on distillation, yields benzo-y-pyrone. The authors of the present paper have applied these reactions to the cresoxyfumaric acids, and thus obtained the corresponding tolu-y .pyronecarboxylic acids and tolu-y-pyrones. 27. “The influence of solvents on the rotation of optically active compounds. 11. The influence of isobutyl alcohol and second- ary octyl alcohol (methylhexylcarbinol) on the rotation of ethyl tartrate.By T. S. Patterson. In continuation of work already published (Tmns., 1901, 79, 167), experiments were described whose object was to determine the in- 41 fluence of isobutyl and octyl alcohols as solvents upon the rotation of ethyl tartrate. It was found that both liquids lower the specific rota- tion of the dissolved active substance, the latter having the greater effect. In both cases, concentrations of distinct minimum rotation occur. This phenomenon was briefly discussed. It was also shown that ethyl tartrate in isobutyl alcohol has a molecular-solution-volume greater than that in In-propyl alcohol, but less than that in octyl alcohol, which is in agreement with the generalisation deduced from the results of the former investigation.28. ([ Influence of a heterocyclic group on optical rotation ;the ethyl and methyl salts of dipyromucyltartaric acid." By P. F.Frank-land and F.W.Aston. The authors have investigated the influence on optical rotation of the heterocyclic f urf urane group by preparing diethyl dipyromucyl- tartrate and determining its rotation. The molecular rotation, [MI: = -321.44', [ = -266*54', is, at 20°, intermediate be- tween that of diethyl di-m-toluyltartrate ([ MI',"= -306.3') and diethyl di-p-toluyltartrate ([MI: = -484.4'), and at 100' intermediate be- tween that of diethyl dibenzoyltartrate ([MI:'= -251.6') and diethyl di-m-toluyltartrate ([MI:' = -281.7'). Thus the influence of the pyromucyl radicle is similar to that of the aromatic acid, but unlike that of the fatty acid radicles, the derivatives of ethyl tartrate with two equivalents of the former being strongly lzevorotatory whilst those with the latter are more strongly dextrorotatory than ethyl tartrate itself.The pyromucyl derivative again resembles the corresponding aromatic derivatives in having its lzevorotation diminished by rise of temperature, whilst the corresponding derivatives with fatty acid radicles have their dextrorotation increased under the same circum- stances. The authors also described a novel method of continuous automatic estferification which has been advantageously employed by them in the preparation of methyl and ethyl tartrates. 42 ANNIVERSARY DINNER. It has been decided by the Council to arrange for a Dinner. of tlio Fellows of the Society and their friends on Wednesday, March 27th, 1901, the day preceding that fixed for the Annual General Meeting. Further particulars will shortly be announced. At the next meeting, on Thursday, March 7th, the following papers will be communicated : ‘(Nomenclature of the acid esters of unsymmetrical dibasic acids.” By J. J. Sudborough. “Additive compounds of a-and P-naphthylamine with trinitro-benzene derivatives.” By J. J. Sudborough.‘‘Acetylation of arylaminss.” By J. J. Sudborough. RICHARD CLAY AND SONS, LIIIITED, LONDON AND BUSGAT.
ISSN:0369-8718
DOI:10.1039/PL9011700035
出版商:RSC
年代:1901
数据来源: RSC
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