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Proceedings of the Chemical Society, Vol. 26, No. 371 |
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Proceedings of the Chemical Society, London,
Volume 26,
Issue 371,
1910,
Page 109-120
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摘要:
Zsssued 14/5/10 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol.26. No.371. Thursday, May 5th, 1910, at 8.30 p.m., Professor Harold B. Dixon, M.A.,F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. : Middleton Henry Dand, Steyning, Sussex. John Edward Hackford, B.Sc.,15, Burford Road, Nottingham. Govind Laxman Joshi, 5, ‘Argyle Avenue, Victoria Park, Man-Chester. Frank Stevenson Long, B.Sc.,80, Tylney Road, Forest Gate, E. Walter William Reed, M.Sc., 28, South Parade, Huddersfield. John George ROSB, Government Analytical Laboratory, Cape Town. St. Clair Overbeck Sinclair, M.A., Government Analytical Labora- tory, Grahamstown, Cape Colony. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected : Georges Baume.Edwin Harrison. John Bethw-aite. William Jacob Jones, B.Sc. Rohert Benedict Bourdillon. James Kenner, Ph.D., B.Sc. Oscar Lisle Brady, B.A. Sea-Kwain Kwoh. Henry Leslie Farmer Baswell, B.A. Samuel Lamb. Ettore Cardoso, D. Sc. Frederick Charles Lewia. Thomas Patrick Cheetham. Charles Herbert Bell Longman. Herbert Edmund Clarke, B.Sc. Hubert Leslie Lucking, Ph.D. Thomas William Dickson, B. A. Horace George Mason, B.Sc. Harry Farrands, M. A. Francis Edwin Needs. Charles Samuel Garland. Knowles Preston. Harold Albert Goldsbrough. Motilal Kashalchand Shah. 110 Of the following papers, those marked * were read : “114. The correlation of rock and river-water analyses.” By Henry Stanley Shelton.The author called attention to the necessity of correlation between the analyses of rocks and of river-waters. Further remarks were added to what has already been published concerning the amount of sodium. Attention was also called to the large amount of sulphates shown in river-water analyses, and to the discrepancy between these analyses and those of the rocks which show a very minute proportion of sulphur. Some suggestions were made to analysts, with the view of explaining the discrepancy and of correlating these two departments of chemical work, DISCUSSION. Dr. DYERobserved that river-water was largely drawn from surface drainage, and that surface soil necessarily contained sulphates, for sulphur was an integral constituent of the proteins in plants.The decay of plant residues in the soil and the consumption of crops by animals on the land must constantly produce sulphates. Farmyard manure contained plenty of sulphates. Mr. J. PHELPSsuggested that the large proportion of sulphur in river-water, compared with that in igneous and sedimentary rocks, might be due to the fact that water flows through the rocks chiefly along (‘faults,” in which mineral veins, containing a much larger pro- portion of sulphur than the bulk of the rock, are frequently found; and that river beds usually followed such geological formations. Mr. SHELTONsaid that vegetation undoubtedly segregated some portion of sulphate, but it could not be regarded as an original source.Mr: Phelps’s argument rather increased the difficulty than solved it, for it would imply that, in continents which had been upheaved for prolonged geological eras, no sulphide would remain. In reply to Mr. Baly, he remarked that organo-silicic acid would decompose into organic matter and silica. The circulation of organic matter he had not considered in detail. * There were many ways in which an excess of oceanic carbonaceous matter could be returned to the land. Silica was undoubtedly deposited in large quantities over the greater part of the ocean floor. Dr. Colman’s reference to the incrustation caused in boilers in which river-water had been used was a question that could only be settled by further investigation. It was not diaputed that river-waters contained some sulphate.What proportion would account for boiler incrustation could not be deter-mined without careful quantitative analysis. 111 *115. (‘The constitution and synthesis of caoutchouc.” By Samuel Shrowder Pickles. In statements made recently by Klages and by Harries (Chenz. Zeit., 1910, 36,315), certain doubts have been expressed regarding the possibility of the polymerisation of isoprene into caoutchouc by the methods indicated by Tilden. These methods were of two characters, (1) the action of certain reagents (for example, an aqueous solution of hydrogen chloride) on isoprene, and (2) the slow spontaneous pol ymerisa tion of is0 prene itself . The latter method has been repeated by the author, and a white, rubber-like compound was produced, which gave derivatives like those obtained from natural caoutchouc, namely, the tetrabromide, (Cl,,H16Br4)z,and the nitrosite.The constitution of caoutchouc was discussed, objection being taken to the dimethylcyclooctadiene formula. Other formulae were proposed for caoutchouc and the ozonide which, the author considered, afford a better explanation of the properties and behaviour of these substances. DISCUSSION. The PRESIDENTinquired whether the author had studied the ethyl analogue of isoprene. Dr. STEVENSinquired whether the author had extracted the substance obtained with acetone. This solvent would probably dissolve out most of the impurities, leaving the caoutchouc intact.He also drew attention to a statement made by Harries, namely, that cycZo-octadiene readily polymerises when warmed, to yield a caoutchouc-like substance. In all probability a series of derivatives existed, and this would explain the fact he (Dr. Stevens) had observed that the caoutchouc obtained from different latex-bearing trees varied in physical and chemical properties, however carefully it might be purified. Dr. PICKLES,in reply to the President, stated that, of the so-called derivatives of isoprene, one had been observed to have similar properties. Kondakoff had shown that methylisoprene (&dimethyl- Aav-butadiene) underwent polymerisation to a rubber-like compound in a few months time. He (the speaker) had himself tried the experiment with dimethylisoprene (PG-dimethyl-A@-pentadiene), but this did not appear to polymerise readily.The displacement of the hydrogen atoms attached to the terminal carbon atoms of isoprene by methyl groups apparently prevented or restrained polymerisation. In reply to Dr. Stevens, Dr. Pickles said that the polymeride of isoprene, as at first precipitated, was more or less sticky. This was 112 probably due, not to resin, but to the presence of hydrocarbons other than rubber. Natural rubber mas similarly sticky and weak when first precipitated from solution in terpenes. Although Harries bad obtained a rubber-like compound from the polymerisation of octa-dimes, he had not shown that it formed additive compounds of the type CloHl,Br,.Etb yl acrylate readily polymerised to rubber-li ke compounds, but in the process the double bond disappeared. Replying to Dr. Forster, Dr. Pickles was of the opinion that, grant- ing the possibility of residual affinities causing a kind of polymerisa-tion in an unsaturated compound, those residual affinities should disappear when the compound became saturated, and therefore the bromide Cl,Hl,Br4 should be a simple chemical molecule. "116. "The constituents of the flowers of trifolium incarnatum." By Harold Rogerson. The dried flowering tops of the carnation clover (Trifolium incarnatum, LinnB), when extracted with alcohol and the resulting extract distilled in a current of steam, yielded a small amount of an essential oil, which contained furfuraldehyde, and possessed the following constants : d 20°/20'= 0.9597 ; uD -1'48' in a I-dcm.tube. The portion of the alcoholic extract which was soluble in water contained a quantity of a sugar which yielded d-phenylglucosazone (m. p. 205--206'), and from the aqueous liquid the following definite substances mere isolated : benzoic and salicylic acids in very small amount, with apparently a trace of p-coumaric acid ; pratol, Cl,Hl,O, ; quercetin, Cl,HI,07,and a new glucoside of the latter, C,,H,,01,,3H20 (m. p. 242-215'), which has been designated incarnatrin. The portion of the alcoholic extract which was insoluble in water consisted chiefly of resinous material, but from it the following com- pounds were obtained : an alcohol, C,,H,,OH (m.p. 72-74'), which had previously been obtained from the wax of the humble-bee, and which it is now proposed to designate incarnatyl C~CO~O~;hentri-acontane, C31H64;a phyt~sterol,C,~H,,O (m. p. 135-136' ;[a],,-41.7'); trifolianol, C21H,,02(OH)2(m. p. 295-300' ; [a],, -44.1°), and a mixture of fatty acids. "117. ''The triazo-group. Part XIII. Triazomethylcarbimide (tri- azomethyl isocyanate)." By Hartin Onslow Forster and Robert Ildiiller. T~iaxomet~ylcarbimide,N,*CH,-N:C:O, prepared by heating the triazoacetyl azide which arises from interaction of triazoacetlyl chloride 113 and sodium azide, boils at 44-45’/32 mm., and has sp. gr. 1*258/18’; it changes rapidly when heated into tristriaxomethyl isocyanzcrata, (NB*CH2*NCO),,which melts at 153’.PhenyZtri~zomethyZc~rb~~ide, C,H,*NH°CO*NH*CH2’N,,and triaxometh?/lcacrbccmide, N,*CH,*NR*CO*NH,, melt at 120° and 56O respectively. In all these compounds the union between carbon and the triazo-group is so weakened by association with another atom of nitrogen that hydrazoic acid may be eliminated from them by the action of water. 118. 66 The absorption spectra of nicotine, coniine, and quinoline as vaponrs, liquids, and in solution.” By John Edward Purvis. The general results of an examination of the absorption spectra of nicotine, coniine, and quinoline are : (1) N/ 1000-alcoholic solution of nicotine exhibited ap absorption band in the ultra-violet, showing its relationship to pyridine; the vapour OF nicotine showed none of the series of narrow bands found by the author in pyridine ; and liquid nicotine, like that of pyridine, showed no selective absorption. (2) N/lO-,N/lOO-,and Nj 1000-alcoholic solutions of coniine showed no bands of selective absorption in the ultra-violet, a result similar to that noticed by Hartley in solutions of piperidine; the vapour of coniine showed none of the series of bands found in the vapour of piperidine ;and liquid coniine, like liquid piperidine, was remarkably transparent.(3) N/IOOO-alcoholic solutions of quinoline exhibited tbree bands in the ultra-violet, as observed by Hartley; the vapour of quinoline had no narrow bands analogous to those found in benzene by Hartley, or to those in pyridine found by the author ;and liquid quinoline showed no bands of selective absorption.The results were compared with the previous results of the examination of the spectra of pyridine and its derivatives, and were discussed from a consideration of the constraint on the pulsations of the nucleus influenced by the side-chains and by their freedom of movement when existing as vapours, liquids, or in solution. 119. (‘Fluorones.” By Frank George Pope and Hubert Howard. Fluorone derivatives may be obtained by the oxidation of hydroxy-phenylxanthen derivatives in alkaline solution in a current of air. The betaine ortho-quinonoid structure of Rehrmann was rejected, since phenylmethylfluorone is quite insoluble in alkali, and the opinion wag expressed that Doebner’s resorcinol benzein is identical with hydroxy- phenylfluorone, as was first pointed out by Kehrmann in 190s.114 120. Ionic equilibrium in solutions of electrolytes.” By James Riddick Partington. The dilution law for solutions of strong electrolytes referred to in a preliminary note (Proc.,1910, 26, No. 365, 8) mas considered in relation to the fundamental hypothesis of the ionising effect of moving ions, and a possible method of testing this hypothesis experimentally was suggested. The formula was contrasted with others previously obtained, and was shown to be applicable to the existing data for twelve typical binary electrolytes. 121. ‘‘Sodium succinates.” By Hugh Marshall and David Bain. An examination of the sodium succinates and of the equilibrium- relationships in the system Na2C,H,0, :H,C,H,O, :H,O has been made in continuation of the work done on the potassium salts by Marshall and Cameron (Trans.,1907, 91, 1519).The only salts obtained were : NaHC4H,0,,3H,0 ;NaHC,H,O, ;Na2C,H,0,,6H20 ;Na,C,H,0,,H20. With the exception of the last-msntioned, all of these had already been described. A solubility diagram has been made for the system, with isotherms for Oo, 25O, 50°,and 75O. Although no superacid salt was isolated corresponding with the potassium salt, KH,(C,H,O,),, the results seem to indicate the formation of some such salt in solution, since the quantity of extra succinic acid which passes into solution on the addition of a given quantity of sodium succinate is, at higher tempers- tures, considerably more than can be explained by the formation of the ordinary acid salt.(The addition of the acid salt itself increases the solubility of succinic acid,) The transition points for the hydrated salts were determined dilato- metrically, and solubility curves (0-75”) for the normal salt, the acid salt, and the acid itself have been drawn. 122. (‘The formation and reactions of imino-compounds.” Part XII. The formation of imino-derivatives of cyclopentane from open-chain mononitriles.” By Alec Duncan Mitchell and Jocelyn Field Thorpe. The authors showed that the formation of the five-carbon ring through the imino-group is not confined to open-chain dinitriles, but that mononitriles having a carbethoxyl group in the &position with respect to the nitrile group also PASS readily into imino-deriv-atires of cyclopentane.Thus ethyE 2-iminocyclopentane-1:3-dicarb- 115 oxylate (I)is formed by the condensation of ethyl sodiomalonate (II) and ethyl 1-cyanocyclopropane-1 -carboxylate (HI), ethyl carbonate being formed at the same time : vH2>C(CN)*C0,Et + CHNa(CO,Et),-+CH, (III.) ('I.) 7H2*CH(c02Et)>C:NH + CO(OEt),. CH,*CH(CO,Et) (1.1 Ethyl 2-iminocyclopentane-1 :3-dicarboxylate is at once hydrolysed by hydrochloric acid, yielding ethyl cyclopentan-1-one-2 :5-dicarbmylate (IV), from which either cyclopentane (V) can be produced by acid hydrolysis, or adipic acid (VI) by the action of alkalis : 123. "New sensitive test for hydrocyanic acid." By James Moir.The author having found the guaiacum test unsatisfactory, and the phenolphthalin-copper test sometimes inapplicable, has succeeded in finding a reagent which will detect hydrocyanic acid in a dilution approaching one part in five millions of water. The test depends on the oxidation of a leuco-compound by nascent cyanogen resulting from the action of cupric copper on cyanides, but the author finds that none of the common leuco-compounds can be used. The reagent is made by adding small quantities of copper acetate and acetic acid to a warm solution of hydroccerulignone (tetramethoxy- diphenol) in a large quantity of water, digesting the mixture at 50' for a few hours, and filtering. The solution to be tested is rendered faintly acid with acetic acid (using sodium acetate also if a " strong " acid is present), and then treated with about one-quarter of its volume of the reagent.In solutions stronger than 1 in 100,000, an immediate crystalline precipitate of ccerulignone (red with purple lustre) is obtained ; with weaker solutions, a brick-red coloration, Oxidising substances must, of course, be absent, but most of them can be avoided by applying the test on paper exposed to the vapour evolved by the liquid to be tested, as in the guaiacum test. A similar reaction is given by other tetrit-substituted diphenols and by benzidine and its derivatives. Benzidine gives an indigo shade; dianisidine, bluish-green, and tolidine, a green shade.116 Although not so sensitive as hydrocarulignone, these reagents are more trustworthy and keep much better. The colours produced are all derivatives of so-called diphenoquinhydrone. 124. ‘‘Changes in volume in the formation of dilute solutions.’’ By Harry Medforth Dawson. The changes of volume which occur in the formation of dilute solutions of iodine and naphthalene have been determined for fifteen different solvents at 18’. For these fiolvents the ‘‘ solution volume ” of one gram-molecule of iodine varies from 67.2 to 50.5 C.C. ; that of one gram-molecule of naphthalene from 1255 to 112.9 C.C. If the solvents are arranged according to the magnitude of the observed volume change, an entirely different sequence is obtained according to whether the dissolved substance is iodine or naphthalene.There appears to be no connexion between the internal pressure of the solvent and the ‘‘molecular solution volume ” of the solute in the case of either of the dissolved substances, and the observed changes in volume cannot he interpreted in terms of the change in internal pressure which follows from the addition of the solute to the solventl. To explain the observations it seems necessary to admit that in many cases combination occurs between solvent and solute. 125. Deninger’s carbon monosulphide.” ‘I By Frederick Percy Dunn. In 1895 Deninger (J.pr. Chem., [ii], 51, 346) described the prepara- tion of a gas obtained by the action of iodoform on silver sulphide, wbich he assumed to be the missing carbon monosulphide.Subsequent investigation has not confirmed his supposition. Russell and Smith (Trans., 1902, 81, 1538) studied Deninger’s reaction, and obtained a reddish-yellow liquid having the characteristic odour of the alkyl sulphides, but failed to find any evidence of the existence of carbon monosulphide. At the same time their experiments gave no very precise indication as to what was the exact nature of the action of iodoform on silver sulphide. From a preliminary study of the mutual behaviour of the two substances, it appeared not unlikely that the course of the reaction was really due to the decomposition of the iodoform by heat, and that the products of this change mutually reacted or were acted on by the silver sulphide.The decomposition of iodolorm was first studied by Hofmann (Quart. Journ. Chem. Sot., 1861, 13, 65), who found that on heating 117 it for some hours in a sealed tube at 150’, and then distilling the product in a current OF steam, methylene iodide was obtained, together with a brown residue, “the nature of which appeared anything but attractive.” It was subsequently shown by Schmidt (Arch. internat. Phcwm. Therap.,1901, 8, 110) that even at the temperature of boiling water, iodoform in the presence of air evolves iodine with the simultaneous formation of the two oxides of carbon. By heating iodoform in a vacuous tube at 180’ (the temperature at which Deninger heated his materials), it was found to be resolved into iodine, methylene iodide, carbon, a trace of hydrogen iodide, a very small quantity of a hydrocarbon, probably methane, as shown by the explosion results, and possibly traces of free hydrogen.Some portion of the methylene iodide was doubtless obtained by the action of hydrogen iodide on iodoform (Lieben, Zeitsch. Chern., 1868, 4, 712). By heating either iodoform or methylene iodide with silver sulphide, the reddish-yellow liquid described by Russell and Smith was obtained. The course of Deninger’s reaction appears to be mainly as follows : methylene iodide, formed by the decomposition by heat of the iodoform, acts on the silver sulphide with the formation of methylene sulphide, probably a lower polymeride of the compound obtained by Husemaun (Annalen, 1863, 126, 294) by the action of alcoholic sodium sulphide on methylene iodide.Russell and Smith (Zoc. cit.) state with regard to the gas obtained from their experiment that “ on explosion with oxygen about 6 per cent. of sulphur dioxide was formed, accompanied by more than five times that amount of carbon dioxide; this result is completely explained by the presence of the vapours of carbon disulphide and the reddish-yellow sulphide, and indicates that in the latter compound there are four or more carbon atoms to each atom of sulphur.” This conclusion appears to be erroneous, since, as the silver sulphide and iodoform were heated in the presence of air, carbon dioxide and monoxide would be obtained (Schmidt, Zoc.cit.), together with a small quantity of a hydrocarbon, the presence of which was proved in the present experiments. Hence a, certain proportion of the carbon dioxide obtained would be due to this circumstance, The reaction between bromoform and silver sulphide was also studied, the products of the reaction being silver bromide, hydrogen sulphide, carbon, a small quantity of a solid alkyl sulphide, and a trace of free sulphur. Neither in the reaction between silver sulphide and iodoform nor in that between silver sulphide and bromoform was there found any trace of the solid polymeride of carbon monosulphide recently described by Dewar and Jones (P9*oc. Roy. Xoc., 1910, 83,A, 526). 118 126. ‘‘The resolution of externally compensated acids and bases.” By William Jackson Pope and John Read.It was shown that when the resolution of an externally coin-pensated acid (or base) is attempted by crystallisation with an optically active base (or acid), one of three different kinds of behaviour is to be observed. (1) The two salts, dBdA and dBZA, which are capable of formation, are readily separable by crystallisation, and show no tendency to form solid solutions one in the other ;in this case an easy separation is effected by the method of Pope and Peachey. (2) The two salts, dBdA and dBZA, combine to form a partially racemic compound; in this case no resolution occurs. (S) The two salts, dBdA and dBZA, form solid solutions one in the other, and separation by fractional crystallisation is slow and very incomplete.The resolution of externally compensated camphor-r-sulphonic acid by crystallisation with one-half an equivalent of strychnine, in accord- ance with Pope and Peachey’s method, was readily effected, and forms a typical instance of behaviour of the kind (1). The resolution of 1-methylcyclohexylitlene-4-aceticacid by cry stallisation with brucine is very difficult to effect, owing to it presenting a case of the new type (3). The separation by crystallisation of d-bornylamine and d-neo-bornylamine d-a-bromocamphor-r-sulphonates and of d-menthylamine and d-isomenthy lamine hydrochlorides also proved diflicult, owing to the formation of solid solutions between the two component salts of the mixture.127. “The interaction of alkyl halides and metals of the iron group.” By James Frederick Spencer and Muriel Kate Harrison. An attempt to ascertain whether metals of the sixth, seventh, and eighth groups could be caused to react with alkyl halides, after the manner of other metals (Tvans., 1908, 93,68, 1821 ; 1910, 97, 385), led to the results described below, which, although in the main negative, show that there is no tendency on the part of these metals to fqrm compounds of the type R*M“*X. Of the metals experimented with, namely, iron, cobalt, nickel, manganese, chromium, and molybdenum, only iron and nickel reacted with alkyl halides, and these only when heated in a sealed tube for several hours. The reaction between the metals nickel and iron and iodobenzene takes place very completely, with the formation of diphenyl in extremely large yields, and constitutes a very good method for the preparation of this substance.119 Nickel which has been freshly reduced from the oxide by means of hydrogen is mixed with iodobenzene out of contact with air, and heated in a sealed tube for several hours at 280’. After cooling, the contents of the tube are distilled in a current of steam, and 85 per cent. of the theoretical quantity of diphenyl is obtained. In the case of iron a similar reaction occurs at 180’, and the yield of diphenyl is 65 per cent. of the theoretical. This reaction is not general, for, with the exception of p-iodotoluene, it could not be brought about in the case of any other halogen derivative. RESEARCH FUND.A Meeting of the Research Fund Committee will be held in June next. Applications for Grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on, or before, Monday, June 6th, 1910. All persons who received grants in June, 1909, or in June of any previous year, whose accounts have not been declared closed by the Council, are reminded that reports must be in the hands of the Hon. Secretaries not later than Wednesday, June 1st. The Council wish to draw special attention to the fact that the income arising from the donation of the Worshipful Company of Goldsmiths is to be more or less especially devoted to the encourage- ment of research in inorganic and metallurgical chemistry.Further-more, that the income due to the sum accruing from the Perkin Memorial Fund is to be applied to investigations relating to problems connected with the coal-tar and allied industries. ERRATUM. PBOCEEDINQS,19 10. Page. Line. 107 16 for “Knowles, Preston,” read ‘‘ Preston, Knowles.” 120 In consequence of the death of His Majesty King Edward, the Banquet to the Past Presidents of the Society, fixed for May 26th, has been postponed, The Ordinary Scientific Meeting of the Society fixed for Thursday, May 19th, has been postponed until Thursday, May 26th, 1910, at 8.30p.m. The following papers will be communicated : “The constituents of the leaves of PPU~UBserotina.” By F.B. Power and C. W. Moore. 6‘ Mechanism of tautomeric change.” By H. T. Tizard. ,‘A new sulphide of nitrogen.” By F. P. Burt. ‘‘Volumetric estimation of manganese in manganese ores.” By H. V. Krishnayya. ‘I Reactions of copper.” By T. N. Das. ‘‘ Synthesis of 6-carboxy-3 :4-dimethoxyphenylglyoxylic acid.” By V. J. Harding and C. Weizmann. “Note on the paper by Dr. A. Slator and Dr. H. J. S. Sand on ‘The r61e of diffusion in fermentation by yeast cells.’” By H. T. Brown. “The resolution of gnoscopine (dl-narcotine). Preliminary note.” By W. H. Perkin and R. Robinsou. 6‘ The action of potassium chlorate on concentrated sulphuric acid. Preliminary note.” By S. Smith. ‘6 The products of diazotisation of the trinitrq-anisidines.” ByR. Meldola and F. Reverdin. R. OLAY Amn SONS, LTD., RRXAD ST. BILL, EX., AN]) RUNGAY. SUFBOLK.
ISSN:0369-8718
DOI:10.1039/PL9102600109
出版商:RSC
年代:1910
数据来源: RSC
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