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PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 27. No.382. Thursday, February 16th, 1911, at 8.30 p.m., Professor HAROLD B. DIXON,M.A., Ph.D., F.R.S., President, in t'he Chair. Messrs. S. Judd Lewis and Walter N. Haworth were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Samuel James Manson Auld, D.Sc., Ph.D., 65, Margery Park Road, Forest Gate, E. Arthur Stewart Bowyer, M.Sc., The Woodlands, Chelford. Cecil Reginald Crymble, B.Sc., 7, Upper Crescent, Belfast. Oliver Statham Douse, B.Sc., Fern Bank, Glossop. Alfred Henry Finniss-Wieldon, 446, Currie Road, Durban, Natal, S. Africa. Henry Francis Harwood, M.Sc., Ph.D., Erlesdene, Park Road, Hale. Thomas Riley Lucas, No. 3 Cantonments, Vizianagram, Madras, India.Roney Forshaw Messervy, 73, Blenheim Crescent, W. John Lawrence Robinson Pastfield, B.A., Olivevale, St. Thomas, Exeter. Richard Garnet Penney, 40,Duesbery Street, Hull. Robert Wright, M.A., Lauriston, Derryvolgie Avenue, Belf ask.. The PRESIDENTannounced that the Conncil had recommended the following gentlemen as Honorary and Foreign Members, and that a ballot for their election would be held at the next Ordinary Scientific Meeting of the Society: Prof. Dr. Eugen Bamberger (Zurich). Prof. Giacorno Ciamician (Bologna). Prof. Dr. Paul Heinrich Ritter von Groth (Munich). Prof. John William Ma-llet (Virginia). Prof. Dr. Walther Nernst (Berlin). It was stated that the following changes in t,he Officers and Council were proposed by the Council : President to retire.-Prof. H.B. Dixon. Vice-presidents to retire.-Dr. J. J. Dobbie and Prof. F. S. Kip ping. Ordinary Members of Council to retire.-Mr. J. L. Baker, Dr. G. T. Beilby, Dr. J. T. Hewitt, and Dr. H. R. Le Sueur. ,4 s President.-Prof. Percy F. Frankland. As Vice-Presidents who have filled the ofice of President.-Prof. H. E. Armstrong, Prof. A. Crum Brown, Sir William Crookes, Sir James Dewar, Prof. H. B. Dixon, Dr. A. G. Vernon Harcourt, Prof. R. Meldola, Dr. H. Muller, Prof. W. Odling, Sir William Ramsay, Prof. J. Emerson Reynolds, The Right. Hon. Sir Henry E. Roscoe, Sir Edward Thorpe, and Sir William Tilden. A s 5"rertszcrer.-Dr. Alexander Scott. As Hon, Secretaries.-Prof.Arthur W. Crossley and Dr. C,. T. Morgan. A s Foreign Secretary.-Dr. Horace T. Brown. As Vice-Presidents.-Dr. G. T. Beilby, Dr. J. N. Collie, Dr. M. 0. Forster, Prof. A. Liversidge, Prof. W. J. Pope, and Prof. J. Wa1ker. A .s Xezo Ordinary Members of CounciZ.-Mr. W, R. Bousfield, Mr. C. F. Cross, Mr. A. R. Ling, and Dr. H. Marshall. Dr. V. H. Veley, Dr. F. B. Power, and Prof. J. Millar Thomson were elected Auditors to audit the Society's accounts. I The PRESIDENTannounced that Mr. G. H. Gabb had presented to the Society a portrait of Dr. John Jeffries, from the pastel by John Russell, R.A. 39 A ballot for the election of Fellows was held, and the following were subsequently declared elected : Solonion Farley Acree, William Joseph Chetwynd Horne.James Allan, 11.A., B. Sc. Bernard Grindrod Hougli. Edward Anderson. Reginald Hurst. Albert Ashe. William Alfred Jenkin. John Ewart Trounce Barhary. Ernyst Graham Lams, R.A. Joseph Bate. Jaincs William McBain, RI.A., Ph.D. Joseph Mayson Blnckburn. John Watterson Miller. Walter Norman Bnrbridge. Walter Roman Monre. John Fishcr Carmichael, H. Sc. Harold James Page. Harold Christopher, R. Sc. Edward Partington. Morris Cutner, B. Sc. Cyril Jarnes Peddle, M.Sc. James Edward A. Devlin. Frank Henry Plews. Harold Edgar Dryden. Henry Stanley Raper. James Furnival Eardlcy. Robert Vincr Stanforrl, M.Se., Pl1.D. Robert Leonarcl Emerson, A. E., Rf. D. George Doiiglas Snmmers. Xichael Augelo Fielding. David Thomson, KA., B.Sc.P1i.D. William Temple Gardner. William L)enham Yerschoyle. Evan Dalton Griffiths, B.Sc. Bertie James Waygood. Arthur Bennett Hall. Ian Gordon Sellar Wink. Charles Herbert Hampshire, B. Sc. Edward Escott Wood. Henry George Alan Harding. Charles Fnrsdon Yates. Of the following papers, those marked * were read : "40. Different methods of applying the Qrignard reagents." By Harold Davies and Frederic Stanley Hipping, Attention was drawn to the fact that in many of the syntheses which involve the use of a Grignard compound, the preliminary p'reparation of an ethereal solution of this reagent is quite unnecessary, because the desired result may be attained by Barbier's method. It was shown by examples that tertiary alcohols may be obtained by mixing a ketone (not acetone, however) or an ester with an alkyl or aryl halogen compound, and then adding the mixture to magnesium in presence of ether ;the formation of hydro-carbons (diphenyl, dibenzyl) as by-products, which is often a source of much trouble in using the magnesium aryl halogen compounds, is thus avoided. The method has been previously adopted in pre- paring certain silicon compounds (Trans., 1908, 93,2006 ; 1909, 95,306), and, as was shown, may also be employed in the synthesis o€ alkyl derivatives of tin.DISCUSSION. Dr. ALEX. MCKENZIE referred to the preparation of the Grignard reagent from an aryl halide in the ordinary manner, when the main reaction is accompanied by the secondary reaction, XR 4-RMgX =R*R+MgXz; thus diphenyl was formed during the preparation of magnesium phenyl bromide.Such hydrocarbons were not always readily separated from the reaction products, but the extent of their formation might be lessened by the device suggested by Schmidlin, who recommended the use of an excess of magnesium amounting to from twice to thrice the calculated quantity. "41, ''Molecular assooiation and its relationship to eleotrolgtic dissociation. 'The molecular complexity of halogen-containing compounds." By William Ernest Stephen Turner. The investigation was undertaken with the object of defining the conditions under which molecular association of halogen-containing compounds takes place, and to test whether such association could be attributed to the possession by the halogen atom of latent or residual valencies.The experimental work involved the exami- nation, in indifferent solvents, of about sixty different substances, and information concerning other substances was collected from different sources. More than a hundred substances of different, types, including salts, were inspected in the complete review. The question of the molecular complexity of salts was approached through the halogen salts of organic nitrogen, oxygen, and sulphur bases, many of these salts being found soluble in chloroform. The information then obtained was applied to the metallic salts. The chief conclusions were : 1. Molecular association of chlorine-containing compounds only occurs when the compound is electrically active, that is, is either an electrolyte or a conducting medium.2. The degree of association in chloroform of the salts of organic bases is very high, the association factors ranging in different salts from about 1.5 to 12, in solutions which seldom exceed 10 per cent. Chlorides were always least, and iodides most associated. When salts of similar bases are compared, the degree of association decreases with the mass of the base. 3. With metallic salts, the iodides are least associated, and chlorides most. In salts derived from allied metals, the degree of association decreases with increase of the atomic weight, and in- creases with the electropositive character of the metal. 4. Molecular association is the complement of electrolytic dis-sociation.Substances dissociated in ionising media are associated in different solvents. 5. Latent valencies do not give rise to association, at least directly. It is better to view association in connexion with the electrical properties of the substance. Discus SION, Sir W. RAMSAYdrew attention to the fact that possibly chloro- form as a solvent mighb exert “latent valencies,” or “residual valencies,” due to the possibility of chlorine acting not merely as a monad, but as a triad. He also added that the main objection to the idea of “molecular compounds ” was that molecules, as such, could not conduct; that molecules did not act as carriers of electricity: that property belonged exclusively to ions.Hence valency must be a property of ions, not of molecules, if there was any truth in the hypothesis that valency is due to the transit of electrons from one atom to another. Dr. PHILIPdrew attention to the fact that the molecular weight of ethyl alcohol in benzene, calculated from cryoscopic observations on 12 to 15 per cent. solutions, was four or five times the normal value, whereas the association factor of pure ethyl alcohol was about 3. He asked if Dr. Turner could offer any explanation of this difficulty. Mr. TURNERstated, in reply to Sir William Ramsay, that the possible combination of solvent and solute had been considered, but no evidence had been obtained during the investigation that such combination occurred. Moreover, in all cases, so far as the author was aware, combination between solvent and solute resulted, not in raising, but in lowering the molecular-weight values.In reply to Dr. Barger, he considered that the use of pyridine as a solvent in the determination of molecular weights was objection- able for two reasons. It had a fairly high dielectric constant, and it combined with the solute. With reference to Dr. Philip’s question, the author could offer no plausible suggestion why alcohol should be so much more associated in benzene solution than in the liquid state. In reply to Dr. Senter, Mr. Turner stated that the molecular complexities quoted of the haloid salts of the alkali metals were calculated by Walden by means of a formula which was free from the objections raised against the original Ramsay and Shields’ formula. The results were also in accord with values obtained by a second method not involving a measurement of surface tension.”42. ‘a-p-Hydroxy-m-met hoxyphenylethylamine, and the resolution of a-p-hydroxyphenylethylamine.” By Charles Watson Illloore. The author has prepared a-p-hydrozy-rn-methoxyphenylethylamime by the reduction of 4-hydroxy-3-methoxyacetophenoneoxime.The base is found to have a slight action on the blood pressure. The hgdrochloride and the benzoyl derivatives have also been prepared and characterised. a-pHydroxyphenylethylamine was prepared by Tutin, Caton, and Hann (Trans.,1909, 95, 2113), and was shown (Zoc. cit.) to exert an action on the blood pressure similar to, although much less than, epinephrine.Since the base contains an asymmetric carbon atom, it was considered of interest to ascertain whether the, optically active bases, obtained by its resolution, would differ in physiological activity, as in the case of the d-and Z-epinephrines (Cushny, Pharm. J., 1909,82,56), and the d-and E-hyoscyamines (Cushny, J. PhysiOZ., 1904, 30, 176). The base has been resolved by means of its d-camphorszclphonate, although only the salt of the lzvorotatory base has been obtained in a pure condition. Optically pure benzoyl derivatives have, however, been obtained from both the stereo-isomeric bases. The effect on the blood pressure of the I-and dl-bases has been determined, but no difference in physiological activity was observed.43. ‘(The formation and reactions of imino-compounds. Part XV. The production of imino-derivatives of piperidine leading to the formation of the PP-disubstituted glutaric acids.’I ByFerdinand Bernard Thole and Jocelyn Field Thorpe. It was shown that almost quantitative yields of the BB-disub- stituted glutaric acids can be obtained by condensing cyanoacet- amide with ketones in the presence of piperidine or alkali hydroxide. The irninepiperidones which are initially formed decompwe under the action of strong acids, yielding the substituted glutaric acids (compare Yroc., 1910, 26, 295). 44. “The interaction of copper and nitric acid in presence of metallic nitrates. Part 11.” By Edward Henry Rennie and William Ternent Cooke.The authors find that whereas in previous experiments at 59O and with 2N-acid, potassium nitrate had apparently no effect, and rubidium and csesium nitrates a retarding effect on the dissolution of copper in dilute, nitric acid, all these nitrates have either an accelerating or retarding effect according to the conditions of temperature and concentration. With the same concentration of acid, and with potassium nitrate, the lower the temperature the less is the acceleration (it often becomes retardation), whereas the higher the temperature, the greater is the acceleration. With the same temperature, increase of concentration of acid tends to lessen acceleration. These statements seem also to hold good with rubidium and miurn nitrates.The authors also find that the effect of the increase of volume of acid due to the solution in it of considerable quantities of nitrates is a factor not to be over-looked, inasmuch as it obviously diminishes tho concentration of the acid, and of nitrous acid or other products formed during the reaction. They conclude that these fresh results tend to confir’m the opinions expressed by them in their previous paper (Trans., 1908, 93,1162). 45. ‘‘The mechanism of Doebner and von Miller’s quinaldine synthesis.” By Humphrey Owen Jones and Percy Edwin Evans. Doebner and von Miller’s well-known synthesis of quinoline derivatives from an aldehyde and an aromatic mine by heating with hydrochloric acid is represented by the equation: C6H5*NH2+ 2CH,*CHO =C,,HgN+ 2H20+ H2 in the simplest case.The molecule of hydrogen is used up mainly in reducing some of the aldehyde. During the examination of the aldol bases, R*NH42HMe-CH2-CEtO, formed from m4-xylidine and similar mines (Jones and White, Trans., 1910, 97, 632), the transformation of these into quinoline derivatives by heat, or by acids in the cold was studied, and was found to take place without perceptible evolution of gas. The aldol bases cannot be reduced by nascent hydrogen, and the change was therefore further examined. It was found that no gas was evolved, and that the transformation of the aldol base from m-4-xylidine at 140--250° is represented by the following equation : 2C,H3M%*NH*CHMe*CH,-CH0=CgH,Me3N+ C9H8M%N+ 2H20. The change is practically quantitative, equimolecular quantities of 2 : 6 : 8-trimethylquinoline (m.p. 45-46.> and 2 : 6 : 8-trimethyl-tetrahydroquinoline (m. p. 50-51°, b. p. 260-261O) being produced. Similar results have been obtained with ptoluidine. The syn-thesis of these quinoline and tetrahydroquinoline derivatives can be effected in this way, namely, by isolat,ing the intermediate 44 aldol base and heating it, much more cleanly and economically than by the usual method. 46. A synthesis of derivatives of phenothioxin.” By Thomas Percy Hilditch and Samuel Smiles. The ethers of p-cresol and p-chlorophenol sulphoxides show the normal reactions of the thionyl group in sulphuric acid solution, whilst the corresponding hydroxy-sulphoxides do not.This abnormal behaviour is due to the formation of the cyclic pheno- thioxin derivatives, for example : which have been isolated. The general character of the phen* thioxin group was discussed. 47. ‘‘The nitration of acetylbenzoin and of stilbenediol diacetates.” By Arthur Gordon Francis and Charles Alexander Keane. Acetylbenzoin, on nitration with fuming nitric acid at Oo, yields a monomitm-compound, which is also obtained when the nitration is carried out at -15O in acetic anhydride solution by means of nitre and sulphuric acid. It forms alpst colourless leaflets, melt- ing at 125O (uncorr.). It is sparingly soluble in et*her or light petroleum, readily so in chloroform, acetone, or benzene, and some- what less soluble in boiling 90 per cent.alcohol. When oxidised with sulphuric acid and potassium dichromate, it yields molecular proportions of acetic acid, benzoic acid, and p-nitrobenzoic acid. It has thus the following structure: NO,-C,H,* CH( OAc)*CO*C6H,. (1) (4) Hydrolysis with acids or alkalis yields, not nitrobenzoin, but condensation compounds, which are under further investigation. Both a-stilbenediol diacetate (melting point 153O) and /3-stilbene- diol diacetate (melting point llOo), on nitration at -15O in acetic anhydride solution with nitre and sulphuric acid, yield benzoin mononitrate and a small quantity of a substance, possibly nitro- benzoin, melting at 188O, whilst 6-stilbenediol diacetate is at the same time partly converted into the a-compound. No benzoin nitrate is formed at Oo or at -25O.Benzoin mononh-ate, C6H,*CH(OoN0,).COoC,H,, crystakes from 90 per cent. alcohol in brilliant white plates, melting at 167O (uncorr.). It is very sparingly soluble in ether or light petroleum. On hydrolysis with potassium hydroxide, it yields benzoin and potassium nitrate, and on heating with concentrated nitric acid benzil is formed. 45 48, ‘‘Experiments on the formation of 4(or 5)-P-aminoethylgly-oxaline from histidine.” By Arthur James Ewins and Frank Lee Pyman. It has been found that by heating histidine (monohydrochloride) with (a) concentrated hydrochloric acid, (6) dilute (20 per cent.) sulphuric acid, and (c) potassium hydrogen sulphate in closed vessels at 265-270°, a maximum yield of 20 to 25 per cent.of the theoretical amount of the base, 4(or 5)-/3-aminoethylglyoxaline (formed from histidine by removal of carbon dioxide), can be obtained. At temperatures below 240° no formation of the base takes place, whilst at 240-25Oo the main product, of the reaction is racemic histidine. By directly heating histidine above its melting point, only very small amounts of the base are produced. Somewhat better results were obtained by fusing the monobenzoyl derivative of histidine at about 240° in a vacuum and subsequently hydrolysing the reaction product. Some new salts of racemic histidine, or 4(or 5)$-aminoethyl-glyoxaline, and the dipicrate of natural histidine were described, 49.“The dissociation of cupric bromide, and some forms of glass manometer.” By Colin Gyrth Jackson. Three varieties of glass manometer were described, whereby it is possible to measure pressures of vapours in contact with no other material. Values of the dissociation pressure of cupric bromide at a series of temperatures were given, and their connexion shown to be adequately represented by an equation involving the constancy of the heat of dissociation, the applicability of the simple gas laws to bromine under the conditions of the experiment>, and the first and second laws of thermodynamics. 50. The determination of the dissociation pressures of hydrated salts by a dynamical method.” By James Xiddick Partington. An account was given of experiments on three hydrates, in which ths dissociation pressures have been measured by a dynamical method.The results were shown to be in agreement with the view referred to in a previous communication (this vol., p. 12) 51. ‘(The influence of conjugated linkings on general absorptive power. Part I. The absorption spectra of some benzene derivatives.” By Cecil Reginald Crymble, Alfred Walter Stewart, Robert Wright, and William Gerald Glendinning. An examination of the absorption spectra of twenty-eight benzene derivatives (supported by a similar investigation of about the same number of aliphatic and alicyclic substances) has shown that it is possible to trace some connexion between the chemical structure of an unsaturated carbon compound and its general absorptive power.Of two isomeric substances containing two or more double bonds, the compound the molecule of which contains the longest chain of conjugated linkings appears to have the greater power of general absorption in the region of the spectrum above that in which any absorption band makes its appearance. In the case of two isomeric substances like atropic and cinnamic acid, the isomeride, which contains what Thiele terms crossed double bonds ” (for example, atropic acid), will have less absorptive power than the isomeride which contains a simple conjugated system of linkings, such as occurs in cinnamic acid. It was pointed out that this rule will furnish additional assistance in the determination of the constitn- tions of terpenes containing two double bonds the relative positions of which are difficult to ascertain.52. “The optical properties of acids containing three hydrocarbon residues directly attached to an asymmetric carbon atom. Part I. The synthesis of P-phenyl-P-methylvaleric acid and of as-methylethylsuccinic acid.” By John Kenneth Harold Inglis. Compounds containing an asymmetric carbon atom might be expected to be very stable when subjected t,o the action of racemising agents. In order to investigate this question, P-phenyZ-P-methylvaleric acid, CMePhEt*CH,*CO,H, has been prepared, but as the substance is a liquid, and its salts are difficult to crystallise, it is not a suitable substance for this purpose.as-Methylethyl-succinic acid, however, is crystalline, and can be obtained fairly easily by the method used by Higson and Thorpe (Trans., 1906, 89, 1467). Methyl ethyl ketonecyanohydrin condenses with the sodium derivative of cyanoacetic ester to give a liquid boiling at 165O/ 19.5 mm., which has the formula C,,H,,O,N,. This 1iqi;id gives as-methylethylsuccinic acid on hydrolysis. The acid has been resolved by crystallisation of its quinine salt. 47 ADDITIONS TO THE LIBRARY. I. Donations. Bedgrove, Herbert Sfianley. On the calctilation of thermo-chemical constants. pp. viii + 102. London 1909. (Recd. 19/1/11.) From the Author. Redwood, Xir Bowton. Petroleum. A treatise on the geographical distribution and geological occurrence of petroleum and natural gas ; the physical and chemical properties, production, and refining of petroleum and ozokerite ;the characters and uses, testing, transport, and storage of petroleum products ; and the legislative enactments relating thereto; together with a description of the shale oil and allied industries ;and a full bibliography.2 vols. pp. xxxii + 1064. ill. London 1906. (Rscd. 25/1/11,) From the Author. Richter, Victor von. Trait6 de chimie organique. Edited by R. Anschutz and G. Schraeter. Translated into French by 11. Gault. Vol. I. pp. xxiv+886. Paris 1910. (Recd. 24/1/11.) From the Publisher : M. Ch. BCranger. 11. By Purchase. Allen, Avred Henry. Commercial organic ansllysis. Vol. IV. 4th edition. Edited by W.A. Davis and Samuel X. Sadtler. pp. viii +466. ill. London 1911. (Recd. 21/1/11.) Dictionary (An Iexplanatory) of the apparatus and instruments employed in the various operations of philosophical and experimental chemistry. With seventeen quarto copper-plates. By a Practical Chemist. pp. vii + 296. London 1824. (Recd. 20/1/11.) Gmelin, Leopold, and Kraut, K. Handbuch der anorganischen Chemie. 7th edition. Edited by Friedheim, C., and Peters, Franx. Vol I., etc. Heidelberg 1905 +Refmencs. 111. Pamphlets. Clacher, William. The manufacture of carbons. (From the Electrical Review, I911, 68.) Gabb, George Hugh, A recently-discovered portrait of Dr. Jeff ries, by J. Russell, R.A. (From the Connoisseur, 1911, 29.) Xeldola, Raphael.Evolution : Darwinian and Spencerian. The Herbert Spencer Lecture. . . 1910. pp. 44. Oxford 1910. Philippine Islands. The mineral resources of the Philippine Islands. With a statement of the production of commercial mineral products during the year 1909. pp.-81. ill. Manila 2910. 48 Qneensland. Report of the Agricultural Chemist for the year ending 30th June, 1910. pp. 23. ill. Brisbane 1910. Seidell, Atherton. The solubilities of the pharrnacopaeial organic acids and their salts. pp. 98. Washington 1910. Taffanel, J. Abstract of the reports of the French coaldust experiments condiicted at the LiGvin Experimental Station, 1907-10. Abstracted and translated by the ‘‘Colliery Guardian.” pp. 82. ill. London 1910. Zenneck, J. Die Verwertung des Luftstickstoffs mit Hilfe elektrischen Flnmmenbogens.pp. 29. ill. Leipzig 1911. At the next Ordinary Scientific Meeting, on Thursday, March 2nd, 1911, at 8.30 pm., there will be a ballot for the election of Honorary and Foreign Members, and the following papers will be communicated : ‘(Potassium cupricarbonates.” By S. U. Pickering. “ Studies in the camphane series. Part XXIX. A new phenyl- hydrazone of camphorquinone.” By M. 0. Forster and A. Zimmerli. ‘(Synthesis of dipeptides of lauric acid with glycine, alanine, valine, leucine, and asparagine.” By A. Hopwood and C. Weizmann. “ Fluorone derivatives.” By F. G. Pope and H. Howard. (‘The constituents of Tl‘ithariu snmnifera.” By F. B. Vom7er and A. H. Salway. ECLAY A&D SQNR, ETD., BREAD ST. HILL,E.C., AUD BUNBAY, WFFOLL;

ISSN:0369-8718    

DOI:10.1039/PL9112700037

出版商:RSC    

年代:1911

数据来源: RSC