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Proceedings of the Chemical Society, Vol. 22, No. 305 |
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Proceedings of the Chemical Society, London,
Volume 22,
Issue 305,
1906,
Page 57-67
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摘要:
lTssued 23/2/06 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 22. No. 305. Thursday, February 15th, 1906, at 8.30 p.m. Professor R. MELDOLA,F.R.S., President, in the Chair. Messrs. H. B. Hartley and H. L. Tidy were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Richard Henry Beckett, B.Sc., Inval, Haslemere, Surrey. Herbert Reginald Cooper, Redington, Northwood, R.S.0. Charles Davidson, 37, Herriot Street, Pollokshields, Glasgow. Edward Gardner, 70, Parliament Hill Mansions, Highgate Road, N.W. Richard Godfrey Hamilton Garvey, 25, Park Mansions, Battersea. William Tabor Lattey, Corpus Christi College, Cambridge. Hamilton McCombie, M.A., B.Sc., Ph.D., The University, Birmingham. Thomas Jenkins Murray, Ph .D., The University, Birmingham.Edgar Gall Oliver, &LA.,Chigwell School, Essex. Lawrence George Richardson, 14, Ashgrove, Horton, Bradford. David Sommerville, B.A., RED., 3 1, Manor House, Marylebone. Foster Sproxton, B.Sc., Uplands, Alexandra Park Road, Wood Green, N. Harold Augustine Tempany, B.Sc., St. Johns, Antigua, B.W.T. It wits announced that the following changes in the Officers and Council were proposed by the Council. 58 As Vice-presidents : Prof. W. H. Perkin, jun., F.R.S., and Dr. Rudolph Messel, vice Prof. W. R. Dunstan, F.R.S., and Mr. D. Howard. As Ordinary Members of Council : Prof. W. Gowland, Dr. H. A. D. Jowett, Dr. F. E. Matthews, and Prof. A. G. Perkin, F.R.S., vice Prof.A. E. Dixon, Prof. J. J. Dobbie, F.R.S.,Dr. E. J. Mills, F.R.S., and Prof. J. M. Thomson, F.R.S. Mr. E. Grant Hooper, Dr. H. F. Morley, and Dr. H. R. Le Sueur were elected Auditors to audit the Society’s accounts. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected. George Ernest Banner. George Frederick Wesley Martin. Arthur Ernest Barker, B.A., B.Sc. Samuel Parfitt. William Edward Bell. John Parkin, M.A. Charles Frederick Polwhele Blatch- William Hughes Perkins, B.Sc. ley, B.A. John Edinund Pitman, B.Sc. Thos. Going Stoney Bogue. Harold Rogerson, M. Sc. Arthur Forbes Braid. Philip Foale Rowsell. Richard Victor Briggs. John Kirby Shrimpton. William Caldwell, M.A. Frank Smith, B.Sc.Reginald William Lane Clarke. George Stanley Talbot. Wm. Boulton Conyngharn. Percy Charles Thornton. Stephen Lewis Conrtauld, B.A. Arthur William Thorp. Thomas Harold Durrans. Ronald William Tonkin. Frederick Watkins Evans. Franklin Wilfred Walker. Hans Eduard Fierz, Ph.D. Richard Alfred Warren. Wslter Hamis Glover, Ph.D. Hardolph,Wastenays. Harry Sands Grindloy, D.Sc. Henry Edgar Watt, M.Sc. William Prince Hayworth. Elkaii Wechsler, Ph. D. Henry Carlyle Irving, B.A. Harold Joscph Wheaton. Llewellyn Thomas Jones, B. Sc. Herbert William Mills Willett. William Henry Matthews Jones. Richard Willstaetter, Ph.D. Robert Le Rossignol, B.Sc. Ernest Edwin Wolfe. John McDowall. John William Yates, B.Sc. William Mace. Of the following papers, those marked * were read : *35.‘(Cuprous formate.” By Andrea Angel. The compound described as cuprous formate by Joannis (Abslr., 1904, i, 644),having the formula (HC02)2Cu,,4NH,,~H20,should be named ammonio-cuprous formate, since it is quite different in properties from the substance prepared by dissolving cuprous oxide in an aqueous ammoniacal solution of ammonium formate under petroleum, diluting the solution with alcohol, and acidifying with 59 formic acid, when crystals are deposited which are collected in an atmosphere of hydrogen and washed with ethyl formate. Cuprous formate, (HCO,),Cu,, consists of colourless crystals which are very easily decomposed ; water immediately hydrolyses the substatice to cuprous oxide and formic acid, sodium carbonate solution decomposes it with effervescence, ammonia solution decomposes it with a slight hissing noise, and dilute sulphuric acid at once produces a precipitate of metallic copper.Dilute formic acid acts similarly, although more slowly. Moist air rapidly hydrolyses it, turning it orange-red, but in a desiccator over sulphuric acid it may be preserved apparently for an indefinite time. Owing to the ease with which the substance is decomposed, the preparation requires special precautions in regard to the strength of the solutions employed. The method of preparation may be employed, with modifications, for the production of other cuprous salts, DISCUSSION. Mr. A. VERNON said that Mr. Angel’s research arose out HARCOURT of some experiments on the gradual heating of cupric acetate in a vacuum, an account of which had already appeared in the Transactions.Both cupric acetate and cupric formate when strongly heated in a glass vessel deposit a mirror of copper on the glas3, showing that a gas containing copper has been formed. The temperature of decom-position of cuprous acetate is very near its temperature of volatilisa- fion, and neither it nor cuprous formate can be obtained, except in very small proportion, by sublimation from the cupric salt. *36. ‘‘The solubility of triphenylmethane in organic liquids, with which it forms crystalline compounds.’’ By Harold Hartley and Noel Garrod Thomas. Experiments were made on the crystallisation of triphenylme thane from a large number of organic liquids in order to see in what cases a crystalline compound is forme 1 wit,h the solvent.From benzene, tliiophen, pyrrole, and aniline solutions, it crgstallises under certain conditions with one molecule of the solvent, and a microscopic study of crystals of the four compounds has shown that they all belong to the rhombohedra1 system, forming an isomorphous series. The solubility of triphenylmethane in each of the four liquids and also in pyridine has been determined by a modification of the method devised by Kuriloff. Weighed quantities of solvent and solute are sealed in small glass tubes, and these are placed in a water-bath. By varying the temperature of the bath, two temperatures can be determined, at the lower of which the last crystal left undissolved ia 60 growing, and at the upper the same crystal is dissolving.These temperatures are usually 0.4' to 0.5' apart and their mean has been taken as the temperature of saturation. Experiments were also made on the spontaneous crystallisation of supersaturated solutions of triphenylmethane in each of the foregoing solvents by cooling solutions in sealed tubes after they had been heated sufficiently to destroy all crystalline niiclei. When the tubes were shaken during the cooling, crystallisation took place at definite temperatures. The results confirm the existence of a metastable region in which supersaturated solutions cannot crystallise spontaneously. The limit of this region where the solutions pass into the labile state and crystallise can be represented by a curve, for which Miers and Isaac have suggested the name "supersolubility curve." It runs approximately parallel t3 the solubility curve at a distance from it depending on the respective solvent and solute."37. ('The spontaneous crystallisation of supersaturated solutions." By Harold Hartley. The author discussed the different views of Ostwald and de Coppet on this subject in view of the experiments described in the preceding communication and those of Niers and Isaac (Proc., 1906, 22,9). It was shown how the difference between metastable and labile solutions might be explained from the kinetic standpoint as a result of the increased solubility of the small crystals which must be first formed in a spontaneous crys tallisation.DISCUSSION. Professor MIERSwelcomed these investigations as new examples of the importance [of the supersolubility curve, and called attention to the fact that -tll;'e authors could not have established their results without a practical knowledge of crystallography. Sir WILLIAM pointed out the analogy between the behaviour RAMSAY of crpst8allisable solution in the metastable and stable states with that of a super-heated liquid, and suggested that Mr. Hartley might derive some help by a study of such behaviour. inMr. HARTLEY, reply, said that small crystals besides being abnormally soluble must also have a lower melting point than larger individuals, and that this fact would explain the usual occurrence of superfusion. Mr.P. W. Robertson and he were just starting. to investigate the conditions under which a number of pure organic substances crystallise spontaneously, and the former had suggested that the variation of melting point with the size of a crystal 61 might explain some of the irregularities which had been observed in cryoscopic work with such solvents as thymol. Supersat’urated solu-tions did not crystallise immediately on reaching the labile state unless they were vigorously shaken ;thus the pull on the solution, which was sugges ted by Sir William Ramsay’s analogy of the continuous isothermal as necessary to start crystallisation, was actually realised in the continuous production of fresh liquid surfaces.*38. Preparation and properties of some new tropeines.” By Hooper Albert Dickinson Jowett and Archie Cecil Osborn Hann. The object of this investigation was primarily to determine whether any difference in physiological action could be observed between tro- peines containing a lactone grouping and their corresponding hydroxy- acid, similar to that recorded in the case of pilocarpine and pilocarpic acid (Marshall, J.Physiol., 1904, 31, 153). For this purpose, the tro- peines of methylparaconic, terebic, and phthalidecarboxylic acids were prepared, when it was found that both terebyl- and phthalidecarboxyl- tropeines, which produce an atropine-like effect on the heart, lose this action after a molecular proportion of alkali has been added to the base, thus showing in aqueous and alkaline solution a difference in action analogous to that observed in the case of pilocarpine.In addition to the tropeines already mentioned, the glycollyl- and protocatechyl-derivatives were prepared and the opportunity taken to test Ladenburg’s generalisation. According to this chemist, a tropeine, in order to possess mydriatic action, must contain a benzene nucleus and a fatty hydroxyl attached to the same carbon atom as that bearing the carboxyl group. It mas found that this did not strictly hold, as terebyltropeine possessed a distinct rnydriatic action. It would appear, however, that the conditions most favourable for the development of the mydriatic action in a tropeine are those stated by Ladenburg, namely, that the acyl group should contain a benzene nucleus and an aliphatic hydroxyl in the side-chain containing the carboxyl group.*39. ‘‘ Studies in asymmetric synthesis. IV. The application of Grignard’s reaction for asymmetric syntheses.” By Alexander McKenzie. The author has studied the action of magnesium propyl iodide, magnesium isobutyl iodide, and .,magnesium a-naphthyl bromide respectively on I-menthyl benzoylformate and effected in each case an asymmetric synthesis of a substituted E-glycollic acid. The influence ofthe I-bornyl as contrasted with that of the I-menthyl grouping was 62 examined by acting on I-bornyl benzoylformate with various magnesium alkyl halides ;the effect of the I-bornyl grouping was to diminish the lsvorotation of the mixture of substituted glycollic acids obtained ;thus, whilst the mixture of d-and I-atrolactinic acids obtained from I-menthyl benzoylformate and magnesium methyl iodide had [a], -9.5’ in ethyl-alcoholic solution, the mixture from I-bornyl benzoylformate under similar conditions gave [a], -1*go.A mixture of d-and I-phenylisobutylglycollic acids containing an excess of the d-acid was produced from I-bornyl benzoylformate and magnesium ikobutyl iodide, whereas the mixture was lsvorotatory when I-menthyl benzoylformate was used. Similarly, a dextrorotatory mixture of acids was produced by the action of kbornyl benzoylformate on magnesium a-naphthyl bromide. The asymmetric synthesis of d-atrolactinic acid was produced by the action of magnesium phenyl bromide on I-menthyl pyruvate.When I-menthyl acetoacetate, Ementhyl ethylacetoacetate, or I-menthyl diethylacetoacetate is submitted to the Grignard reaction, no asymmetric synthesis occurs, the first of these substances reacting in accordance with its enolic structure. A slight asymmetric synthesis was, however, detected when I-menthyl lsvulate was used. 40. ‘‘o-Cyanobenzenesulphonic acid and its derivatives.” By A. Jamieson Walker and Elizabeth Smith. Reference mas made to the work of Jesurun (Bey., 1893,26,2288) on o-cyanobenzenesulphonic chloride, and to that of Remsen and others (Ames. Chem. J., 1895, 17, 309 and 347; ibid., 1896, 18, 794 and 819) and List and Stein (Bes., 1898, 31, 1648) on ammonium o-cyano- benzenesulphonnte.The authors then described a modification of Jesurun’s method for the preparation of o-cyanobenzenesulphonic chloride and the isolation from the mother liquor of o-cyanobenxenesulphonic acid, CN*C,H;S03H, which crystallises from water in white needles melting at 279-279.5”. Its silver salt has been prepared, and the action of nitric acid and bromine on the acid investigated. Reduction of the chloride with zinc dust yields o-cyanobenxene- sulphinic acid, CN*C,H,*SO,H, which crystallises in small, white needles melting at 226.5-228O. With bromine, this acid yields two compounds melting at 156-156.5O and 172.5-173O respectively, but containing no bromine. Their constitution is still being investigated. Nitrous acid converts the suIphinic acid into a yellow solid, probably o-cyall~odibenxsulphohydroxam~cacid, N[C6H,(CN)*SO2],*OH.Heating with dilute caustic soda and subsequent acidification trans- form the chloride into a substance (m. p. 2215-223’) with the sweet taste of ‘(saccharin,” and not into the sulphonic acid. 63 41. ‘‘ The condensation of dimethgldihydroresorcin and of chloro-ketodimethyltetrahydrobenzenewith primary amines. Part 11. Diamines.-m-and pphenylenediamines.” By Paul Haas. Dimethyldihydroresorcin condenses, in alcoholic solution, with one molecular proportion of a diamine, giving an 80 per cent. yield of the compound together with a small amount of a disubstituted amine having the formula CH2-C-NH*C,H4*NH--C1---CH, 11.CMe2/ NCH CH/\CH:C(OH)/ \c(Ho):CH/ \CMe,. A better yield of the latter substance is obtained by prolonged boiling in alcoholic solution of one molecular proportion of the compound I with a second molecule of dimethyldihydroresorcin. Chloroketodi-methyltetrahydrobenzene condenses with two molecules of a primary diamine to give a hydrochloride having the following formula : CH,*C(NH*C6H4*NH2,HC1),cH.111* CMe2<CH2-C(:N*C,H,*NH,) > The corresponding base is strongly alkaline to litmus, whereas the compound I has a neutral reaction ; it cannot be made to condense further with dimethyldihydroresorcin as, owing to its strongly basic nature, it is precipitated by this substance from an alcoholic solution in the form of an insoluble resorcin salt having the formula C20H24N4~C8H1202g 42.“A modification of the volumetric estimation of free acid in the presence of iron salts.” By C.Chester Ahlum. Because of the inapplicability of indicators in the titrat,ion of free acid in the presence of iron salts, t,he author devised a modification in which the iron is removed from solution, making a titration possible. The iron is precipitated by means of sodium dihydrogen phosphate. The iron phosphates are filtered off and the filtrate titrated with standard sodium hydroxide. In the reaction of the ferric salt with the sodium dihydrogen phosphate, a definite quantity of acid is liberated, necessitating a correction in the amount of acid found in the titration.Fe,(SO,), + 2NaK2P0, = 2FeP0, + Na,F04 + 2H2SO,. Fe,Cl, + 2NaH2P0, = 2FeP04+ 2NaC1+ 4HC1. 64 The amount of acid is directly proportional to the amount of ferric iron present, the latter being estimated previous to the titration. The difference between the amount of acid found in the titration and the amount of acid equivalent to the ferric iron present gives the true amount of free acid. A table giving the results of a number of estimations of free acid in mixtures of known quantities of ferric sulphate and sulphuric acid shows a considerable degree of accuracy. Calcium, magnesium, and ferrous salts do not interfere with the estimation, and the method is applied to the analysis of natural waters containing iron salts and free acid.43. “The theory of alkaline development, with notes on the affinities of 1 certain reducing agents.” By Samuel Edward Sheppard. The author first dealt with the reactions of hydroxylamine and hydrogen peroxide respectively with silver salts, with notes on the reactions of organic reducers. It was shown that at moderate concentration one molecule of hydroxylamine reduces one molecule of silver salt, but at great dilutions two, according to the equations : 2NH2*OH+ Ag20=2Ag +N, + 3H20 ; 2NH2*0H+ 2Ag20= 4Ag + N20+ 3H20, whilst one molecule of hydrogen peroxide reduced one molecule of silver salt, probably according to the equation : 2H,02+ Ag20= 2Ag + H20+ 20, + H,, hydrogen being one of the reaction products.The bearing on the molecular condition in solution of these substances was discussed. With organic reducers, such as polyphenols and aminophenols, a peculiar case of “coupled ” reaction was examined, wherein the mutual presence of organic compound and sulphite retarded the total oxidation. The author has also investigated the dynamics of develop-ment with these reducers. 44.‘‘Resolution of 2 :3-dihydro-3-methylindene-2-carboxylicacid into its optically active isomerides.” By Allen Neville. When ethyl benzylacetoacetate is treated with concentrated sulphuric acid, 3-methylindene-2-carboxylicacid is formed, which on reduction with sodium amalgam gives 3 :3-dihydro-3-methylindene-2-carboxylic acid. This acid forms with I-ment hylamine a well-defined crystalline salt, which on crystallisation from ethyl acetate gives, after a few crystallisations, the pure salts of the d-acid and I-base.This substance crystallises in long, white needles, melts at 170°,is easily 65 soliible in all the ordinary organic media except ethyl acetate and ether, and has [.ID + 27.35' and [MID + S9.63'. On decomposing this salt, d-2 : 3-dihydro-3-methylindene-~-carboxylicacid was obtained, which crystallised in long, flat needles melting at 86'. It was insoluble in water, but soluble in all the ordinary organic media ; it gave in alcohol 1.1. + 67.28" and [MI, + 11S*4lo,and in benzene [a], + 76-86' and [MID + 135.27". The sodium, potassium, barium, silver, and lead salts and the methyl ester mere prepared.From the more readily soluble portions of the menthylamine salt, the laevorotatory acid was isolated. This was exactly similar in specific rotation and other properties to the corresponding dextro-rotatory isomeride. ADDITIONS TO THE LIBRARY. I. ~0??.4&0?%8. Aaron, C. E. Assaying. 2 vols. pp. 142, 170. ill. San Fran-cisco 1900. (Recd. 13/2/06,) From Bennett H. Brough, Esq. Baeyer, AJoZf uon. Gesammelte Werke. Herausgegeben zur Feier des siebzigsten Geburtstages des Autors von seinen Schulern und Freunden. 2 vols. pp. cxxxii + 990, 1195. Braunschweig 1905. (Recd. 13/2/06.) From the Publishers : Messrs. Vieweg & Son. Baumert, Georg, Dennstedt, M., und Voigtlander, F. Lehrbuch der gerichtlichen Chemie.Band 11. Der Nachweis von Schriftfal-schungen, Blut und Sperma. pp. x +248. ill. Braunschweig 1906. (Recd. 13/2/06.) From the Publishers : Messrs. Vieweg & Son. Bernthsen, A. Kurzes Lehrbuch der organischen Cheinie. 9th edition. Edited by Ernst Mohr. pp. xxi + 638. Braunschweig 1906. (Recd. 13/2/06.) From the Publishers : Messrs. Vieweg & Son. Crookes, Xir William. Select methods in chemical analysis (chiefly inorganic). 4th edition. pp. xxiv +738. ill. London 1905. (Recd. 10/2/06.) From the Author. The wheat problem. Based on remarks made in the presi- dential address to the British Association at Bristol in 1898. Revised with an answer to various critics. With two chapters on the future wheat supply of the United States, by C.Food Davis and the Hon. John Hyde. 2nd edition. pp. xii + 229. London 1905. (Recd. 10/2/06.) From the Author, Faust, E'dwiia Stanton. Die tierischen Gifte. pp. xiv + 248. Braunschweig 1906. (Recd. 13/2/06,) From the Publishers : Messrs. Vieweg & Son. Goppelsroeder, Triedrich. Anregung zum Studium der auf Capil- laritats-und Adsorptionserscheinungen beruhenden Capillaranalyse. pp. 239. Base1 1906. (Recd. 19/1/06.) From the Author. Ostwald, Wilhelrn. Conversations on chemistry. Part 11. The chemistry of the most important elemsnts and compounds. Au thorised translation by Stuart K, Turnbull. pp. viiif-373. ill. New York. 1906. (Recd. 30/1/06.) From the Publishers : Messrs. Wiley & Sons. Parry, Laurent. Die analytische Bestimmung von Zinn und Anti- mon.pp. 78. Leipzig 1906. (Recd. 13/2/06.) From Bennett H. Brough, Esq. 11. By Purchase. Bio-chemical Journal. Edited by Benjamin Moore and Edward Whitley. Vol. I, No. I. Liverpool 1906. (Reference.) Czapek, Triedrich. Biochemie der Pflanzen. 2 vols. pp. xv +584, xii + 1027. Jena 1905. (Recd. 13/2/06.) Moeller, Josef. Mikroskopie der Nahrungs-und Genussmittel aus dem Pflnnzenreiche. 2nd edition. pp. xvi +599. ill. Berlin 1905. (Recd. 13/2/06.) Stillman, I’homas B. Engineering chemistry : a manual of quanti-tative chemical analysis. 3rd edition. pp. xxii +597. ill. Easton, Pa. 1905. (Becd. 2/2/06.) Treadwell, F. P. Analytical chemistry. Volume I. Qualitative analysiq. Translated by TViZZianz 2’.Hall. pp. xi +466. ill. New York 1905. (Recd. 27/1/06.) Wieler, A. Untersuchungen iiber die Einwirkung schwefliger Saure auf die Pflanzen. pp. vii + 427. ill. Berlin 1905. (Recd. 13/2/06.) 111. Pamphlets. Baker, Richard T.,and Smith, Henry G. Some West Australian eucalypts and their essential oils. (From the Pharrn. J., 21, 1905.) Juritz, Charles P. The need for organised chemical research in the Cape Colony. pp. 23. Cape Town [1905]. Some notes regarding South African pharmacology. (From the Trans. X.African Phil. SOC.,16, 1905.) Smith, Ilenry G. The refractive indices, with other data, of the oils of 118 species of eucalyptus. (From the J. and Proc. Roy. SOC. N.X.Wales, 39,1905.) On the occurrence of calcium oxalate in the barks of the eucalypts. (From the J.and Proc. Roy. Xoc. AT.S. Wales, 39, 1905.) 67 At the next Ordinary Meeting, on Thursday, March lst, 1906, at, 8.30p.m., the following paper will be communicated : ''Studies of dynamic isomerism. Part IV. Stereoisonieric halogen derivat,ives of camphor." By T.M. Lowry. R. (:LAY AND YON?., LTI)., BREAD ST. HILI, K.C., AND BCNOAV, SL'TFOLIi
ISSN:0369-8718
DOI:10.1039/PL9062200057
出版商:RSC
年代:1906
数据来源: RSC
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