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Proceedings of the Chemical Society, Vol. 29, No. 422 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 422,
1913,
Page 367-385
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摘要:
[Issued 3@/12/13 PROCEEDIXGS OF THE CHEMICAL S0 C IE’TY. Vol. 29 No.422. Thursday, December l8th, 1913, at 8.30 p.m.: Professor W. H. PERKIN,LL.D., F.R.S., President, in the Chair. Reference was made to the death, on December 4th, 1913, of Mr. Christer Peter Bandberg, of Westminster, who was elected a Fellow on March 3rd, 1870. Messrs. H. F. Tayler, A. 0. Blackhurst, V. Lefebure, C. J. Dickenson Gair were formally admitted Fellows of the Chemical Society. Certificates were read for the first time in favour of Messrs.: Ethelbert William Blair, B.Sc., 70, Fountayne Road, Stoke Newington, N. Richard Charles Denington, 69, Dover Road, S. Wanstead, N.E. John Garth, 170, St. Thomas’s Road, Preston. Ivan Richard Gibbs, B.A., University Hall, 3, Moors’ Gardens, Chelsea, S.W.Theophilus Harper, 39, Camden Street, Belfast. William Pawson Robson, B.A., Ph.D., 78, Rolland Street, Cape Town. Chandra Bhusan Roy, M.A., Patna College, Moradpore, P.O., Bankipore. M. R. Viswanatha Tyer, 50, Prem Chand Bural Street, Bow- Bazar, Calcutta. 368 The PRESIDENTannounced that, at the request of the Inter- national Committee on Physico-Chemical Nomenclature, the Council invited criticism of the symbols recently suggested by the Inter- national Association of Chemical Societies. For these symbols Fellows were referred to the Proceedings, Vol. 29, p. 333, and were requested to forward any suggestions to Professor A. Findlay, University College, Aberystwyth, before February 28th, 1914. The announcement was also made that, in order to give Fellows more frequent opportunity of meeting informally, the Rooms of the Society would be opened on January 15th, 1914, at 8 p.m., when the President and Council would be glad to meet the Fellows of the Society.Smoking will be permitted, and light refreshments will be provided. Fellows were also invited to exhibit apparatus or specimens of interest and to show experiments; those willing to do so were requested to communicate with the Secretaries before the Monday previous to the Meeting. Of the following papers, those marked * were read: “330. ‘(Absorption of gases by celluloid.” By Victor Lefebure. An absorption of gases by celluloids of a magnitude comparable with the sorption of gases by some charcoals has been observed by the author, and the chief points already established are as follows.The effect is reversible. It is not chemical, in that no compound with a very low or with a moderately large dissociation pressure is formed, assuming that such compounds would not form solid solutions with the celluloid. It is common to all the kinds of celluloid examined, but almost vanishes when a precipitate of celluloid constituents is substituted for film celluloid. The property is recovered by the refilmed precipitate. Again, it is not exhibited by the two chief constituents of the celluloid, camphor and nitro-cellulose. Finally, the effect increases with lowering of temperature and raising of pressure, and in general nature resembles a case of sorption.The quantitative experiments which have been carried out are concerned with time, diffusion, and equilibrium. The equilibrium experiments yield isotherms of the type given by previously examined sorption effects. The time experiments, yielding curves representing rates of sorption, indicate the possibility of a develop- ment of surface within the celluloid mass, and probably near to the external visible surface. The diffusion experiments have merely established the fact of diffusion through films. 369 DISCUSSION. Professor DONN-~Nwished to congratulate the author on the excellent way he had carried out the work. He thought that Mr. Lefebure's paper was the first investigation of that nature on a semi-solid colloidal film.The great rapidity of the initial absorption of the carbon dioxide by the celluloid, and the fact that the speed of absorption increased much more rapidly (per unit of weight of celluloid) than the increase of apparent (external) surface of the film, showed that in the mass of the celluloid or perhaps in the neighbourhood of the surface there was a very finegrained macro-porosity into which the gas could rapidly penetrate and be adsorbed, Diffusion of the gas into or through molecular pores was simply what one called solu- tion, and, so far as one knew, solution phenomena in semi-solid gels were relatively slow at the temperatures at which Mr. Lefebure had worked. Solution and diffusion in the ordinary sense probably also occurred in the case of the celluloid films, and accounted for the later portions of the velocity curves.Very little was known concerning the macro-heterogeneity of the camphor-nitroceliuiose system, but Mr. Lefebure's work was an important contribution to the subject. Mr. W. P. TIREAPERpointed out that it was possible to vary the porosity of structureless cellulose filaments within wide limits by varying the strain under which they were dried at tho time of manufacture. It might be possible to utilise this in determining the effect of porosity on the adsorption of gases by this material, and in this way confirm, or otherwise, some of the conclusions arrived at by the author. From this point of view it was strange that the precipilated cellulose gave a lower result, as it would certainly expose a considerable surface to the gas, and be relatively porous."331. gL Aromatic compounds obtained from the hydroaromatic series. Part 111. Bromoxylenols from dimethyldihydroresorcin." By Arthur William Crossley and Nora Renouf. In continuation of the work, of which a preliminary note has appeared (P., 1912, 28, 332), the following rearrangements of hydroaromatic to aromatic substances have been established : (1) Under the influence of alcoholic potassium hydroxide 370 dibromodimethylcyclohexenone (11) gives 5-bromo-o-3-xylenol (I) melting at 84O and 4 :5-dibromo-o-3-xyleno1 (111)melting at 97O : (1.) (11.) (111.) (IT.) (2) Heat causes the elimination of hydrogen bromide from dibromodimethylcyclohexenone, with production of 5-bromo-o-3-xylenol and 6-bromo-0-4-xylenol (IV) melting at 103O.(3) Bromine acts on bromodimethylcyclohexenone (V) to yield, in the first place, a mixture of hydroaromatic substances, which on heating loses hydrogen bromide to give 5-bromo-o-3-xylenol and 6-bromo-o-4-xylenol : C(CH,), C(CH,), H,C/\C H, H,C/\CHB~BiC(\/CO Ur V\/( '0 CH CBr (".) (VI.) (4) Tribrornodimethylcyclohexenone (VI) under the influence of heat or alcoholic potassium hydroxide yields 4:5-dibromo-0-3; xylenol and other bromoxylenols, which, up to the present, it has not been found possible to separate in a pure state. *332. The equilibrium of dilute hydrochloric acid and gelatin." 6i By Henry Richardson Procter.The author referred to a previous paper (Roll. Chem. Bezhefte, 1911, 2, 243), in which it was shown that the swelling of gelatin in dilute acids, and the amount of acid absorbed, can be explained on the current hypothesis of chemical affinity and osmotic pressure. Precise mathematical expressions for these relations were now given, and it v~asshown that the two basic affinity-constants of gelatin being known, together with molecular weight, and a small correction for original alkalinity, its whole behaviour with regard to dilute acids can be prognosticated. The mathematical relations are quite general and applicable to other amphoteric proteins and other acids and their salts, and all the concentrations in the jelly were shown to be mathematical functions of the concentra- tions of the equilibrium-acid only, and not dependent on the chemical character of the protein.Gelatin appears to be diacid as a base, with hydrolysis constants K,=0.0013, K,=1.05, and an 371 approximate molecular weight of 839, leading to the formula C,,R,,Ol,Nl,.Some difficulties in the applications of the electrometric method to colloidal equilibria were mentioned, and it was pointed out that in consequence of surface-potentials the ionic concentrations measured with the concentration-cell in colloid solutions are not those of the colloid solution itself, but of the acid or other solution with which it would be in equilibrium. Suggestions were made with regard to the probable colloidal structure of protein jellies and solution.A graphic geometrical method was described for dealing with all such equilibria as depend on the “equality of products.” DISCUSSION. Professor DONNANthought that the methods of investigation employed by Professor Proctor were the right ones, and would lead him eventually to a solution of his problems. He observed that the author inclined to the view taken by Arrhenius in his work on immunity, namely, to treat the pheno- mena as cases of molecular equilibrium, without much reference to adsorption and colloidal aggregation and disaggregation. Nevertheless in his (Professor Donnan’s) opinion both series of phenomena occurred, and must be taken into account. He would refer Professor Proctor to the work of two Italian investigators, an account of which was to be found in the Nernst F estscJi rift .”33. ‘I Researches on residual affinity and co-ordination. Part I. Metallic acetylacetones and their absorption spectra.” By Gilbert T. Morgan and Henry Webster Moss. An examination of the absorption spectra of fourteen metallic acetylacetones in alcoholic solution showed that, with the exception of the chromium compound, all these substances exhibit a well-marked absorption band in the ultra-violet. Chromic acetylacetone showed a band of this character, but in addition a well-defined band toward the red end, probably due to the metallic radicle. Comparative experiments were made on the volatility of scandium and thorium acetylacetones under the ordinary and under 8-10 mm.pressure. “334. ‘(Ionisation and the law of mass action, Part 11. The osmotic data in relation to combined water.” By William Robert Bousfield. It was shown by reference to the figurea for sucrose that the osmotic data can be brought into accurate conformity with the gas 372 equation by taking account of the combined water. The osmotic pressure equation, vapour-pressure equation, and freezing-point equations then present themselves in the following forms : 0.P. equation PjB’e (h-n) = i V.P. ,, p 6p/p (h-n)=k Y.P. ,, A/P’ (h-rL) = i, where h is the total number of molecules of water per mol. of solute and n is the number of combined molecules of water per mol. of solute.DIscusSION. Professor DONXANthought that there were some misconceptions in the paper. There was absolutely no a priori reason to “expect” the equation PV=Z$T to hold for more concentrated solutions. The general theoretical osmotic equation for solutions of any strength was now well known. If,however, there was practically no volume or energy-change on solution, this equation, as was well known, reduced to a simple form for solutions of any concen- tration. If solrztion occurred, then, of course, in relatively con-centrated solutions allowance had to be made for it. The calculations of Mr. Bousfield might serve to show that after this allowance had been made aqueous solutions of sucrose of very considerable concentration approximated to the “ simple ” behaviour referred to above.In Professor Donnan’s opinion this suggestion had been made by previous authors. 335. “ Chemical examination of sarsaparilla root.” By Frederick Belding Power and Arthur Henry Salway The material used for the present investigation consisted of grey Jamaica sarsaparilla root, such as is recognised by the British Pharmacopeia. The root was found to contain a small amount of an enzyme, which slowly hydrolysed amygdalin. An alcoholic extract of the root yielded, besides a little essential oil, the following definite compounds : (i) a crystalline glucoside, sarsasaponin, C,,H,,O,,,,7H,O, which, on hydrolysis, is resolved into sarsasapogenin, C,,H,,O,, and dextrose; (ii) sitosterol-d-glucoside (phytosterolin), C,,H,O, ; (iii) sitosterol, C,,H,,O ; (iv) stigma-sterol, C,,H,,O ; (v) a new crystalline dicarboxylic acid, sarsap’c acid, C,H,O, (m.p. 305O), which yields a dimethyl ester, C8H806, melting at 121O; (vi) dextrose; (vii) a mixture of fatty acids, consisting of palmitic, stearic, behenic, oleic, and linolic acids. The alcoholic extract contained, furthermore, it small quantity of a substance which possessed the characters of cetyl-d-glucoside, and 373 a considerable quantity of potassium nitrate was aIs0 present. The amount of resinous material was equivalent to about 1-25 per cent. of the weight of root employed. It has now been shown that Jamaica sarsaparilla root contains but one definite saponin glucoside, namely, sarsasaponin, and it is considered probable that the “parillin ” of previous investigators was a mixture of sarsasaponin and a phytosterolin.It has also been definitely ascertained that the so-called “smilacin ” (‘I smila-saponin ” of v. Schulz) is not a homogeneous substance, but contains a relatively small proportion of sarsasaponin, together with amorphous material. 336. ‘(Metallic derivatives of acetylacetone and acetyl mesityl oxide.” (Preliminary note.) By Gilbert Thomas Morgan and Henry Webster Moss. Series 1.-With the exception of copper, the metals of the first vertical series of the periodic classification yield somewhat unstable derivatives with acetylacetone. Lithium acetylacetone, -a colourless, crystalline mass, decomposed -when dissolved in the ordinary organic media, the solutions assuming a yellow colour. Caesium acetylacetone, a colourless, crystalline mass soluble in water or alcohol, was much less stable than the preceding com-pound.Silver acetylacetone, obtained as a white, crystalline precipitate, rapidly darkened on exposure, with liberation of silver; it is sparingly soluble in water; the solution rapidly deposited a silver mirror. The blue copper acetylacetone yielded a green additive compound with quinoline. Series 2.-Zinc acetylacetone, formerly described as a yellow substance, was obtained in colourless, acicular prisms, soluble in hot water or alcohol. Its cadmium analogue was much less sohble. Serzes 3.-Scandium acetylacetome, melting after sublimation at 187--187.5O, crystallised from benzene in colourless, tabular prisms, or from chloroform in square plates.It was prepared by the interaction of scandium nitrate, acetyl- acetone, and ammonia. The molecular weight determined by the ebullioscopic method corresponded with the above formula. Comparative experiments made with yttrium, erbium, and thorium indicate that the acetylacetones of scandium and yttrium 374 (the two rare earth metals of least atomic weight) do not under similar experimental conditions yield additive ammonia compounds comparable with those obtained from acetylacetones of the rare earth metals of higher atomic weight. Series Ci.---Vanadyl acetyl mesityl oxide, vo[<o--c(&pc 1312,..,O.C(C H ) prepared by the interaction of vanadyl sulphate, acetyl mesityl oxide, and ammonia, crystallised from light petroleum in grass- green leaflets.Other metallic derivatives of acetyl mesityl oxide are under examination ; they are characterised by their ready solubility in organic solvents, including light petroleum. 337. L( Constitution of the ortho-diazoimines. Part IV. Isomeric benzenesulphonyl-3 :4-tolylenediazoimides." By Gilbert Thomas Morgan and Godfreg Edward Scharff. 3-Nitro-p-toluidine and 4-nitro-m-toluidine (m. p. 111-112°), the latter base prepared from either m-cresol, m-toluidine, or diacetyl-2 :5-tolylenediamine, were converted respectively into the isomeric 4-be~ize~zesulphonyl-3:4-tolyleneariamineand 3-benzene-sulphonyl-3:4-tolylenediamine. These acylated ortho-diamines yielded the corresponding isomeric diazoimides, 4-b enzenesulphonyl- 3 :4-t07yle?~ediazoimide and 3-benzenesulpiionyl-3:4-tolylenediaso-imide : IJ NTT N TT nT,,N:N ' ' * * ' * ' * 3 -.c H <--Ilf*SO,Ph ...3 N.N ........4 a-Isomcride 8-Isomeride (m.p. 118-119"). (in. p. 150-151"). The a-isomeride is a more soluble, labile modification, which on prolonged boiling in solution changes almost completely into the less fusible, more sparingly soluble, stable /3-isomeride. 338. Organic derivatives of silicon. Part XXI. The condensation products of diphenylsilicanediol." By Frederic Stanley Kipping and Robert Robison. The study of the four condensation products of diphenylsilican4 diol previously described (Kipping, T., 1912, 101, 2125) has been continued in order to ascertain the conditions under which each is formed.375 The results seem to show that diphenylsilicone, SiPh,O, the analogue of benzophenone, is not prodiiced by the dehydration of diphenylsilicanediol, and that the closed-chain compound, 81Ph,<z>SiP h,, is not formed by the dehydration of anhydrobisdiphenylsilicanediol. In the presence of piperidine, solutions of diphenylsilicanediol and of anhydrobisdiphenylsilicanediolboth give tetra-anhydrotetra- kisdiphenylsilicandiol, and probably also some trianhydrotris-diphenylsilicanediol. Dianhydrotrisdiphenylsilica.nedio1 may be obtained by carefully hydrolysing trianhydrotrisdiphenylsilicanediol with alkali in ethereal acetone solution; it is very rapidly converted into trianhydrotrisdiphenylsilicanediol in methyl-alcoholic solution in the presence of a little hydrochloric acid.Trianhydrotrisdiphenyl-silicanediol is also formed when anhydrobisdiphenylsilicanediol is treated with a methyl-alcoholic solution of hydrochloric acid, but the reaction takes place slowly. l‘rianh ydro te trak isdiphe.nylsilicanedio1, HO*SiPh,.0.SiPh,*0.SiPh2*O*8iPh,.0H, the most complex open-chain condensation product so far obtained, may be prepared by very cautiously hydrolysing the tetra-anhydre derivative with sodium hydroxide in chloroform solution ; it melts at 127O, and is easily converted into the tetra-anhydro-derivative by traces of sodium hydroxide in alcoholic solution.339. The absorption spectra of sulphurous acid and sulphites.” (Preliminary note.) By Robert Wright. While comparing the absorption spectra of various acids with their salts, it was found that whilst the absorption of sulphurous acid is characterised by a band in the ultra-violet, the sodium salt exhibits only general absorption. It is thought that t.his is most probably due to a difference in structure between the acid and its salt, additional evidence in favour of this view being the fact that whilst the acid has the properties of a moderately strong acid, its salt suffers hydrolysis in aqueous solution, thus behaving like a derivative of a weak acid. A parallel case is to be found in the behaviour of chromic acid and its salts, where a strong acid differs in visible colour from its salts, the latter also being hydrolysable. 340.‘I An adiabatic calorimeter.” By Francis William Gray. The author described a water mantle, the temperature of which can be altered at will to prevent radiation inwards to or outwards from the calorimeter. The temperature is raised by pumping water from a hot bath through a flexible copper tube immersed in the water of the mantle. The temperature is lowered by passing tap- water through the same flexible copper tube, or, if necessary, by pumping water from it cold bath through the flexible tube. The flow of water is controlled by a system of two T-tubes and four taps.With this apparatus any rate of rise or fall of temperature likely to be required in thermochemical work can be obtained. A turbine stirrer is used for the mantle water. 341. ‘IThe distillation of coal in a vacuum.” By Maurice John Burgess and Richard Vernon Wheeler, An account was given of distillations of coal in a high vacuum at low temperatures, and the apparatus used described. The gaseous products of distillation only were discussed in detail, the liquid products being dealt with in a subsequent paper. The sequence of events when coal is gradually raised in tempera- ture in the absence of air was described, and it was shown that of part of the coal substance a decomposition point occurs at about 350j. Fractionation of the gases by means of liquid air and solid carbon dioxide dissolved in ether was stated to have enabled propane and butane to be isolated, and the presence of pentane established by explosion analysis.342. ‘‘The composition of coal.” By David Trevor Jones and Richard Vernon Wheeler. An account was given of an examination of the liquid products of distillation of coal in a vacuum at low temperatures, from which conclusions were drawn regarding the composition of the ‘‘ resinous substances ” that form part of the coal conglomerate. A description was given o€ the various compouiids contained in the oils obtained, which consisted largely of unsaturated (ethylenic) hydrocarbons, naphthenes, paraffins, phenols (chiefly cresols and xylenols), and homologues of naphthalene.Benzene, anthracene, and solid aromatic hydrocarbons were stated to be absent. The presence or absence of free hydrocarbons in any quantity in coal was discussed, and an hypothesis put forward to account 37 7 for the rapid formation of paraffins, naphthenes, etc., on distilling coal at low temperatures, It was suggested that such hydrocarbons must be present in the coal substance in such a, manner that whilst, in a Bense, structurally complete, some change in their state, such it9 can be produced by moderate heating, must take place before they can be set free. This hypothesis, particularised for the case of the paraffins, assumes their existence in coal as alkyl groups attached chemically to another non-alkyl group, R-H, the paraffin being in what can be termed a “bound” condition, as a component part of a molecule represented by the general formula R€€-C,H2n+l.The rapid die tillation of free ” paraffins from these bound ” molecules when coal is decomposed thermally was then explained according to the following scheme : RH-CnH,n+, ---f R + CnHp+Z, or RH-CnH2n+1 +R+CnlHgn,+z+Cn2H2??g With certain modifications the hypothesis was used to explain the appearance of naphthenes, olefines, and naphthalene homologuea in coal distillates. 343. isoMelamine.” (Preliminary note.) By Hans Krall. Four isomerides of melamine are theoretically possible : hT NH N Ei NH /\ /\ /\ /\NH,*g Y-KH, XH,*$ 7:NH NH:? 7:NH NH:Q F:NH NN NN NH N NH NH Only one of these, usually assumed to be (I), is known.Two series of alkylmelamines are known, and are usually assumed to be derived from (I) and (IV). During an investigation of the action of heat on guanidine salts, a second melamine has now been obtained; it is probably formed by the polymerisation of cyan-amide in its carbodi-imide phase, NH:C:NH, and may be assumed for the present to be the hitherto unknown isomelamine (IV). When guanidine carbonate is heated for three hours at 180°, the residue consists of a mixture of ammeline and a substance which analysis shows to be isomeric with melamine. The former is readily dissolved by cold aqueous sodium hydroxide. 378 isoMelami?ze crystallises from water in ill-defined crystals, quite unlike the characteristic prisms of its isomeride.The two sub- stances can be crystallised side by side from the same solution, so that the difference is constitutional, and not merely crystallc-graphic. isoMelamine gives rise to a chloride, nitrate, and sulphate of melamine, so that strong acids cause isomerisation. The true acetate can be obtained from which alkalis regenerate unaltered isomelamine. Alkalis do not affect the constitution, but they induce hydrolysis more rapidly than with the normal isomeride. At about 260° the compound decrepitates, and passes into the more stable form. Both compounds are being further studied. 344. ‘LFluorone derivatives. Part 11. Resorcinol-benzein.” By Frank George Pope. Resorcinol-benzein, as prepared by Doebner’s method, consists essentially of 3-hydroxy-9-phenylfluorone.Confirmation of this result was shown by its conversion into the sodium and barium salts, and by the preparation of the acetyl derivative, whilst by the action of phosphorus pentachloride it yields 3 :6-dichloro-9-phenylxanthonium chloride identical with the product of the reaction between 3-hydroxy-9-phenylfluorone and phosphorus penta- chloride. The different varieties of resorcinol-benzein as described by H. v. Liebig (J. p.Chem., 1912, [ii], 85, 97, 241) were not obtained, neither were the anhydro-compounds described by the same author in 1908 (ibid.,78, 534). ‘L345. The relation between viscosity and chemical constitution, Part VIII. Some homologous series.” By Albert Ernest Dunstan, Ferdinand Bernard Thole, and Percy Benson.The authors have continued their work on the additive nature of log .viscosity, and have examined the viscosity of ninety-three compounds drawn from the homologous series OF the fatty acids, alcohols, ethyl and methyl esters of the fatty acids, and esters of methylethylcarbinol, hexan-8-01, heptan-B-ol, octan-8-01, and undecan-j3-ol. They find in each series that log. viscosity is additive within limits, but that the CH, differences vary with (1) association, (2) magnitude of the group to which the growing chain is attached, (3) molecular weight, (4) temperature. 379 346. Non-aromatic diazonium salts. Part 111. 3 : 5-Dimethyl-pyrazole-4-diazonium salts and their azo-derivatives.” By Gilbert T. Morgan and Joseph Reilly.4-Amino-3:5-dimethylpyrasole dihydrochloride, can be diazotised quantitatively to a stable, very soluble diazonium chloride, which has been characterised by conversion into the moderately soluble platinichloride (I) and the sparingly soluble aurichloride (11): (1.) (11.) Addition of sodium azide to the acid solution of diazonium chloride determines at once the liberation of diazo-nitrogen and the production of 4-trzazo-3 :5dzmethylpyrazole, a distinctly basic compound, which is precipitated only on neutralising the solution with sodium carbonate. 3 : 5-Dimethylpyrazole-4-diazonium chloride is even more stable than the corresponding salt from diazotised 4-aminoantipyrine ; it is not readily decomposed by boiling aqueous potassium iodide, and its capacity for azecoupling is retained after treatment with alkali carbonates, hydroxides, thiocyanates, and cyanides.3 :Ei-Dimethylpyrazole-4-azo-~-naph~holdissolves very sparingly in aqueous alkali hydroxides, but is insoluble in water. is3 :5-Dlmethylpyrazole-4uzo-~-naphthylamine a pale orange-brown base. 347. The relative activities of certain organic iodo-compounds with sodium phenoxide. Part IV. The influence of the solvent.” By David Segaller. The velocity-coefficients of the reaction between sodium phenoxide and ethyl and propyl iodides have been measured with the view of studying the influence of the solvent in this reaction.The following solvents were employed : methyl alcohol, ethyl alcohol, propyl alcohol, isobutyl alcohol, isoamyl alcohol, and acetone. It was shown that there is no connexion in this reaction between the dielectric constant of the solvent and the influence of the latter on tho rate of the readion. The influence of the medium is very large, the velocity-coefficient in acetone solution being more than one hundred times as large as that in isoamyl alcohol solution. 380 348. “The polysulphides of the alkali metals. Part I. The polysulphides of sodium.” By Alexander Rule and John Smeath Thomas. An investigation has been made of the action of sulphur on alcoholic solutions of anhydrous sodium hydrosulphide prepared by the method previously described by one of the authors (T., 1911, 99, 558).A vigorous reaction takes place between sulphur and the hydrosulphide in alcoholic solution, with the evolution of hydrogen sulphide and the formation of polysulphides. Using amounts of sulphur corresponding with the di-, tri-, tetra-, penta-, and a possible hexa-sulphide, and concentrating the solution, a solid product was obtained, but only when the proportions of hydrosulphide and sulphur for the tetrasulphide were used was the product homogeneous. It consisted of the pure anhydrous tetra- sulphide, which is a brownish-yellow substance, crystallising in well- defined cubes. Below the proportions for the tetrasulphide, mixtures were obtained which contained unchanged hydrosulphide.At the penta- sulphide stage the solid product is a mixture of the tetrasulphide and sulphur, whilst above that stage there is some indication of the separation of a higher polysulphide. The course of the reaction and the probable nature of the substances present in solution before evaporation of the latter was determined by estimating the amounts of hydrogen sulphide evolved when varying amounts of sulphur were used in the reaction. Anhydrous eodium disulphide was also obtained by reducing solutions of the tetrasulphide with metallic sodium. It is a bright yellow, micro-crystalline powder, less soluble in alcohol than the tetrasulphide. 349. Nitro-acids derived from 2 : 3-dimethoxybenzoic acid and 4-methoxyphthalic acid.” By John Cannell Cain and John Lionel Simonsen.5-iyitro-2: 3dimethoxybemzozc acid was prepared by nitrating 2 :3-dimethoxybenzoic acid and also by nitrating 2 : 3-dzmethoxy-toluene and oxidising the 5-nitro-2 :3-cFzmethoxytolz~ene formed. 6-Nitro-2 : 3-dimethoxybenzoic acid (Wegscheider and Klemenc, Monntsh., 1910, 31,709) was synthesised as follows : 3-Hydroxy-o-tolyl methyl ether on nitration yields 5 :6-dzt~ztro-3-hydroxy-o-tolyl methyl ether, which on methylation and reduction gives 2-nztro-5 : 6-dzrnetlio~;y-m-toZz~zdz~ie.On elimination of the amino-group the resulting 6-nitro-2 :3-dimethoxytoluene furnishes, on oxidation, ths required acid. The nitration of 4-methoxyphthalic acid yields a mixture of 3-and 5-7Uitro-4-methoxyphthaZicacids, which can readily be sepax- ated.The former was also synthesised by oxidising 1-nitro-2-naph- thy1 methyl ether, and the latter by oxidising 5-nitro-4-methoxy-o- xylene. 350. ‘(The p-nitrobenzoates of borneol and isoborneol.” By George Gerald Henderson and Isidor Morris Heilbron. In the course of investigations on the action of oxidising agents on camphene and on bornylene, the authors have more than once had some difficulty in deciding whether an alcohol present among the oxidation products was borneol or isoborneol. It is troublesome to obtain these compounds in a state of purity by crystallisation alone, and such of their hitherto described derivatives as are well characterised and easily prepared, for example, the hydrogen phthalates, melt at the same or very nearly the same temperatures.The authors therefore sought for some derivative of borneol and isoborneol by means of which the alcohols could be more easily distinguished from each other, and ultimately found that the p-nitrobenzoates, which can be prepared and purified without difficulty, meet this requirement. For the preparation of the p-nitrobenzoates the following method gives good results : The calculated quantity of pnitrobenzoyl chloride is added to a solution of the alcohol in ten to fifteen times its weight of pure pyridine, and the reaction, which starts immedi- ately, is completed by warming the solution for an hour or two on the water-bath. The pyridine is then removed by cautious addi- tion of dilute sulphuric acid, the flask being kept cool during this operation by immersion in ice-water, and the precipitated p-nitro- benzoate is collected, washed with dilute sulphuric acid and with water, dried, and crystallised from alcohol.Usually one crystallieac tion is sufficient. Borneol p-htrobenzoate, N0,.C,H,*C0,*C,,H,7, crysballises from alcohol in minute, lustrous, colourless plates, which melt at 137O. It is sparingly soluble in cold alcohol, readily so in the other common organic solvents, and insoluble in water : 0.472 gave 19.1 C.C. N, (moist) at 13O and 754 mm. N=4.74. C,,H2104N requires N =4.62 per cent. isoBorneoZ p-nitrobenzoate separates from alcohol in fine, colour- less needles, which melt at 129O. In solubility it closely resembles the corresponding borneol ester : 0.559 gave 22.5 C.C.N, (moist) at 12O and 760 mm. N=4*78. C17Hz104N requires N =4.62 per cent. 382 The ultra-violet absorption spectra of these esters were found to be identical, each compound, in M/10,000-solution, showing a shallow band with head at l/h3080. The esters are readily hydrolysed when heated with dilute aqueous sodium hydroxide under reflux. The liberated alcohols were dis- tilled in a current of steam, collected, dried, and crystallised from light petroleum. The purified borneol was found to melt at 208O and the isoborneol at 217O; the melting point of the former is the same m,but that of the isoborneol three degrees higher than, that formerly recorded. 351.‘, The identity of the supposed p-2 : 5-dimethylpiperazine.” By William Jackson Pope and John Read. The authors have continued the examination of the substances described as a-and p-2 :5-dimethylpiperazine, and now show that the behaviour of the p-isomeride can only be explained on the assumption that it is cis-2 :#’-dimethylpiperazine ; it is further concluded that the a-compound is trans-2 : 5-dimethylpiperazine. 352. ‘‘ Oxidation of the anhydrides of 1: l-dihydroxydinaphthyldi-alkylmethanes.” (Preliminary note.) By Hemendra Kumar Sen-Gupta. This investigation has been undertaken with the object of ascer-taining the constitution of some of the condensation products of a-naphthol with ketones, as also of synthesising some naphtha-xanthone derivatives.The anhydride of p-1:I-diIiydrozydinaphthy2-CHpropanr, Uli3>O<CIOHt>C)3 yields, on oxidation by chromic acid, CH, 1u (1 two products, namely, (i) an orange compound, C24H1603,crystal-lising in thin, soft needles, and melting at 287O; and (ii) a golden- yellow compound, C,,H,,O,, crystallising in lozenges and melting at 245O. The latter gives on reduction a dz~ydrozy-derivative, C,,HI8O3 (m. p. 252-253O) ; its diacetyl derivative crystallises in needles and melts at 241-242’. The anhydrade of y-1 : l-dihydroxy-dmaphthylpn tare, Et>C<F:$:>O, similarly yields a deep red Et compound crystallising in plates and melting at 221O. The constitu- tions of these products are being studied. 353. “The relation of nranous salts to thorium.” By Alexander Fleck.If the electrons expelled in radioactive change arise from the same part of the atom in which the electrons governing electro- chemical change of valency exist, it should follow that the chemical properties of the uranous and thorium ions are identical. Byreducing a mixture of thorium and uranyl salts by nascent hydrogen and then treating the reduced liquid fractionally with a precipitant, it was found that although the properties of thorium and uranium in the quadrivalent condition are very similar, yet there is a distinct difference in their chemical nature, and they can be separated from one another by fractional precipitation. In carry- ing out the examination of their properties it was necessary that the precipitation, filtration, and other operations should be performed without air coming in contact with the reduced liquid.As a result of these experiments the conclusion was drawn that the electric charges on the a-and &particles must arise from the nucleus of the atom, and that electrons may be added to or with-drawn from the external ring of electrons, thereby increasing or diminishing the valency of the atom. 354. (‘The system : xylene-alcohol-water.” By Alfred Holt and Norman Murray Bell. The authors have determined the data of the varying miscibility of xylene, alcohol, and water at different temperatures, also the position of the tie-lines which give the composition of the conjugate solutions. The extent to which xylene is separated from its solution in alcohol by the addition of water has also been examined, as also th2 composition of mixtures of the three liquids which possess the same specific gravity.355. Interaction of glycerol and oxalic acid.” * By Frederick Daniel Chattaway. The explanation usually given in the texbbooks of the reactions occurring when glycerol and oxalic acid are heated together, and commonly employed in the laboratory preparation of formic acid and of ally1 alcohol, is fundamentally incorrect. The true explanation is the obvious one. The oxalic acid acts on glycerol as it does on other alcshols, and produces an acid and * This paper was read at the meeting on December 4th, 1913. 384 a normal oxalate.The former, like all such compounds, is unstable at a slightly elevated temperature, and decomposes when this is reached into carbon dioxide and monoformin. The fresh oxalic acid added displaces the formic acid from the latter, and the cycle of operations repeats itself. The more complicated reaction which goes on when the first product of the interaction of glycerol and oxalic acid is rapidly heated, untii evolution of carbon dioxide ceases and then at a much higher temperature recommences with simultaneous production of allyl alcohol, is the decomposition at the high temperature of the normal ester, which is produced from the acid ester by a repetition of the ester formation, into carbon dioxide and allyl alcohol. The main reactions concerned in the production of formic acid and of allyl alcohol should therefore be formulated, thus: FH2-0*CH0 $!H*OH yH?.Off COzH ~H!2*0*C0*C02H .,-? CH,.OH FH*OH dozH yH*OH CH,*OH -+ CH;OH 1%FH,*O.FO CH-0-CO * and not as is at, present invariably done.385 The next Ordinary Scientific Meeting will be held on Thursday, January 22nd.,1914, at 8.30 p.m., when the following papers will be communicated : ‘,Crystals of organic compounds, coloured blue by iodine.” By G. Barger and W. W. Starling. .. Organic derivatives of silicon. Part XXII. The siliconic acids.” By C. J. Meads and F. S. Kipping. “The mutual solubility of formic acid and benzene and the system : benzene-formic acid-water.” By A. J. Ewins. .‘The preparation and properties of pure formic acid.” By A. J. Ewins. ‘‘ Loose compounds of cholesterol with barium methoxide.” By E. Newbery. ‘. A study of the vapour pressure of nitrogen peroxide.” By A. C. G. Egerton.
ISSN:0369-8718
DOI:10.1039/PL9132900367
出版商:RSC
年代:1913
数据来源: RSC
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