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Proceedings of the Chemical Society, Vol. 17, No. 243 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 243,
1901,
Page 235-248
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摘要:
Zssuecl 10/12/01 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARTEL?. Vol. 17. No.243. EXTRAORDINARY GENERAL MEETING. Erratum in Proceedings, No. 242, p. 208, line 11 (and line 9 of the Circular Letter which accompanied it), for “the words ‘the Council,’ ” read ‘‘ khe last words ‘the Council,’ ” in accordance with text of Requisition printed on pp. 208-209, December 5th, 1901. Mr. C. E. GROVES,F.R.S., Vice-president, in the Chair. Messrs. George Harker and T. G. Donnan were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Harry Burrows, The Green, Southgate, N. ; Kenneth Macomb Chance, Lawnside, Edgbaston ;William Clifford, 1, Avondale Road, Wolver- hampton; John Kemp Smith Dixon, Gothic House, Birstall, nr.Leeds ; Alfred Vincent Elsden, Storrington, Pul borough, Sussex ; Lewis Eynon, 57, Darenth Road, Stamford Hill, N.; Frederick Ferrand, 13, Torrington Street, Hopwood, Heywood ; John Oliver Ferrier, Colombo, Ceylon ; George Frederick Holdcroft, 253, Oxford 236 Street, Manchester ; Frank Sturdy Sinnatt, Glenside, Church Lane, Moston, Manchester ; Lyon Viccars Turner, Crescent Lodge, St. John’s, S.E. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected :-Messrs. Frederick T. Allen, B.Sc. ; Arthur Baker ; Thomas Thorne Baker ; Walter Craven Ball, B.A. ; Andrew Russell Bennett ; Harding Bickford ; Henry Boyers ; William Burton, B.Sc. ; William Cormack ; Samuel Irwin Crookes ; Frank Crossley , John Howard Davidson, B.Sc. ; Francis Davis ; Robert English ; Henry Wippell Gadd ; T.K. Gajjar, M.A., B.Sc. ; Hermann Charles T. Gardner ; Edward Gillman ; William Peer Groves, B.A. ; Herbert Blackmore Hammond ; Herbert Harding ; Edwin Hobson ; Beresford Ingram, B.A. ; J. S. Jameson ; Charles H. Johnson, M.B., Ch.M. ; Walter Henry Jollyman ; James David Kettle, B.Sc. ;J. Bruce-Kingsmill, M.A., B.Sc. ;Alfred Tabois Larter ; Albert W. D. Leahy; Peter Macdonald; Charles K. Millard, M.D., D.Sc. ; Edward Holl Miller ; Christian Muller ; Herbert Simpson Newbould ; Albert Edward Parkes ; Walter Herbert Pay ; Charles James Tomlin Pollitt ; Rowland Samuel Potter ; Charles Leonard Royle ; John Henry Rgffel, B.A., B.Sc.; Allan Sandford ; George Charlton Scott ; Edward Charles Sherwood, M.A. ; Norman Smith, B.Sc. ; Robert Stephenson, jun., B.A. ; William Henry Templeman; Harold Foy F. Varley; Frank Wade; Morton Wager; Herbert George Wallace ; Philip Lewington Whitehouse. Of the following papers, those marked * were read: *Ml. Influence of substitution on the formation of diazoamineg and aminoazo-compounds.” By (3, T. Morgan, D.Sc. The disubstituted derivatives of m-phenylenediamine having one free para-ortho-position with reference to the amino-radicles interact readily with diazonium salts, giving rise to aminoazo-compounds in almost theoretical quantities. The diamines of the general formula N*, X/-\NH, having substituents in both the para-ortho-positions\-/Y do not easily condense with diazonium salts, and the yield of amino- azo-compound is very poor.The bases of both series, however, combine with primulin diazo- tised on the cotton fibre, the diamines of the first series giving rise to reddish-brown am-compounds, whilst those of the second series furnish colouring matters having a brownish-yellow tint. Although the interaction of P-naphthylamine and a diazonium salt leads to the direct formation of an o-aminoazo-derivative containing the diazo-residue RON,-in the a-position contiguous to the amino- group, yet l-chloro-2-naphthylamine,under similar conditions, yields c1 stable diazoamines of the type /\/\-NH*N,*R. In this com-Ill \/\/pound, the azo-group has no tendency to shift into the aromatic nucleus, this transference being apparently prevented by the presence of the chlorine atom in the adjacent ortho-position. The following acyl derivatives were prepared in characterising cer- tain of the diamines employed in this investigation.Difo~myZ-4:6-diarnino-1 :3-xylene, needles, m. p. 182-183', the corresponding diacetyl and dibenzoyl derivatives, m. p. respectively at above 260' and 253"; diformyl-2 :4-diamino-l :3-xylene, m. p. 219-220°, the diacetyl derivative, m. p. above 260', and the dibenxoyl derivative, m. p. 232' ;diformyl-5-chloro-2 :4-tolylenediamine, silky needles, m. p. 1664 the benzoyl derivative, m. p. 205'. The following azo-compounds were produced in illustrating the behaviour of the two series of diamines towards diazonium salts.Benzene-5-axo-2 :4-diamino-1 :3-xylene, readily produced from 2 :4-di-amino-1 :3-xylene, brown needles, m. p. 208-209'; its diacetyl deri- vative, m. p, above 260' ; diacetylbenxene-5-axo-2:4-tolylenediamirte, m. p. 216-217'. Benzene-5-axo-4:6-diamino-1 :3-xylene, obtained with some difficulty and in small yield from 4:6-diamino-1 :3-xylene, forms deep red plates, m. p. 182-183' ;its diacetyl derivative, m. p. above 260'. p-Toluerte-5-axo-4 :6-diamino-1 :3-xslene resembles its lower homologue and melts at 165-1 66". Small yields of benzene-3-azo-5-chloro-2:4-tolylena-diumine and its p-toluene homologue are produced from 5-chloro-2 :4-tolylenediamine ;they crystallise in dark, brownish-red plates, m.p. 147' and 152' respectively ;the dibenzoyl derivative of the former azo-com pound melts at 236-2 374 Benzene-6-axo-2-chloro-3:5-tolyZenediumine, obtained in theoretical quantity from 2-chloro-3 :5-tolylenediarnineY forms orange-red, acicular prisms, m. p. 134' ;its diacetyl and dibenxoyl derivatives crystallise in orange-coloured needles, m. p. 251' and 233" respectively. 1-Chloro-2-naphthylamineyields the following diazoamines when treated with the appropriate diazonium chloride. 2-Diaxoamino-1-chloronaphthalene, CIC,oH,*N,H*C,oH,Cl, produced by the action of 238 1-chloro-2-naphthalenediazoniumchloride, crystallises in golden-yellow needles, m. p. 152'. p-Nitrobenzene-2-diazoa~nino-1-chloronaphthaZene? NO,*C,H,*N,H*C,,H,Cl, obtained from pnitrobenzenediazonium chloride and 1-chloro-2-naphthylamine, or from 1-chloro-2-naphthalenediazoniumchloride and pnitraniline, crystallises in: brownish-yellow leaflets; it melts and decomposes at 19'7-198".Its production by the two processes indi- cated shows that Kekulh's rule for the formation of mixed benzenoid diazoamines applies also to those containing naphthalene residues. The ethpl derivative, produced by the direct ethylation of the preced- ing compound, separates from benzene in hard, yellow, prismatic crystals, m. p. 193-194". Mr. EVERSHEDasked whether the primulin compounds described were only obtainable on the fibre, and if so, whether similar com-pounds could be obtained outside the fibre by using dehydrothiopara- toluidine instead of primulin.Dr. HEWITTinquired whether the author expected to obtain three distinct ethyl derivatives of unsymmetrical diazoamino-compounds, or whether the derivative obtained by alkylation would not be a mixture of the other two ethyl derivatives obtained by coupling diazotised amines with monoethylamines. Such cases had already been observed by Meldola. The earlier idea that in the benzene seriesp-azo-compounds exclusively result when the para-position is free can no longer be held to be absolutely true. Bamberger (Ber., 1900, 33,3188) has obtained small quantities of ortho-oxyazobenzene mixed with a large amount of the para-isomeride by the action of a phenyldiazonium salt solution on an alkaline solution of phenol.Dr. MORGAN, iu reply, said that the colouring matters produced from diazotised primulin mere obtained only on the cotton fibre, this re- action being employed merely as a ready means of ascertaining whether the symmetrically disubstituted diamines react with diazo-compounds. The substances prepared by the action of the simpler diazonium salts (benzenediazonium chloride and its p-tolyl homologue) on these bases have the appearance of true azo-compounds ;they are readily acetylated and benzoylated without decomposition, and withstand prolonged digestion with boiling hydrochloric acid, either in aqueous or alcoholic solutions, just like the isomeric azo-derivatives obtained from the di- aiuines, in which the diazo-residue enters the ring in a para-ortho-position with respect to the amino-radicles.230 *162. ‘(The determination of available plant food in soils by the use of dilute solvents.” By A. D. Hall and F. J. Plymen. The use of various weak acid solvents has been suggested in the analysis of soils, as dissolving out the mineral plant food which may be regarded as immediately ‘‘available ” for the crop. In order to ascertain which acid would give the most “critical” results, as judged by the known history of the soil, the authors have determined the phosphoric acid that could be extracted from nineteen different soils by a 1 per cent. solution of citric acid, by equivalent solutions of hydrochloric and acetic acids, by a saturated solution of carbonic acid and by an ammoniacal solution of ammonium citrate respectively.Seven of the soils mere from plots on the Broadbalk field, Rothamsted, which had been continuously manured in the same manner for 42 years previously ;the remaining twelve were soils of very various origin, which bad been the subject of crop experiments and of which the reaction to phosphatic manuring was well marked. In the same seven soils from the Broadbalk field the authors determined the potash extracted by the same solvents, with the exception of ammo-nium citrate; five other soils of different origin, whose response or otherwise to potash manuring had been tested by experiment, mere also examined. Determinations were made of the phosphoric acid and potash dissolved after long digestion with strong hydrochloric acid, of the loss on ignition and of the earthy carbonates present in each soil.The acids did not attack the phosphates and potash in the same way; in the case of phosphoric acid most was dissolved by citric acid, in the case of poiash by hydrochloric acid ;water charged with carbonic acid generally dissolved less than the other solvents. Ln all cases the weak acids gave better indications of the need of the soil for special mineral manuring than was afforded by the determination of the total phosphoric acid or potash present. Though, as a rule, all the acids gave similar indications as to the relative fertility of the soils, as regards the mineral matters under consideration, certain differences exist in their modes of attack ; for example,from the soil of the Broadbalk field, which had received an annual dressing of dung for 42 years, the weak hydrochloriclacid extracted a comparatively smaller proportion of phosphoric acid than the other solvents ; hydrochloric acid again had relatively slight action on the phosphates of the nitrated plots.The strength of the acids used affected the amount of phosphoric acid dissolved, and the addition of calcium carbonate to the soil diminished the amount dissolved by citric, but not by acetic or carbonic acids. Though the differences in the rate of attack which the various acids 240 exhibit in dealing with soils of a different type are related to the vary- ing states of combination of phosphoric acid or potash in the soils, there is still sufficient likeness in the indications afforded by all the acids to negative the idea that any one acid can be found which will discriminate sharply between the ‘‘ available ” and “non-available ” mineral plant food. The authors conclude : (1) That no sharp distinction can be drawn between “available ’’ and ‘‘non-available ” phosphoric acid and potash in the soil, and that any process for determining the “available ” constituents is an em-pirical one, dependent on the strength and nature of the acid used.(2) That the weak solvents give information as to the requirements of a given soil for mineral manures of a far more trustworthy nature than that which is afforded by such a solvent as strong hydrochloric acid.(3) That of the acids examined, the 1 per cent. solution of citric acid gives results most in agreement with the recorded history of the soil, though there is evidence that the same interpretation cannot be put on results obtained from all types of soil. DISCUSSION. Dr. ARMSTRONUsaid the only way in which the method advocated could be tested was to compare the laboratory results with those afforded by field experiments such as had been made at Rothamsted; and it was remarkable how general was the agreement in that case. But he felt less happy after listening to the account given of this work with other soils : the results did not appear to be so uniformly in favour of Dr.Dyer’s method. The conditions offered by soils were obviously very complicated, and it was difficult to believe that so simple a test could afford really comparable results in all cases, especially when applied to soils varying greatly in character. But the case was one in which the decision must be based on considerable experience. Dr. Armstrong took exception to the authors’ use of curves in expressing their results, and suggested that only vertical ordinates should be plotted. Mr. T. S. DYMONDsaid that this paper was pA.rticularly interesting, as one of the soils was a London clay from the ‘‘ derelict ” grass land of Essex, from a field which manurial trials had shown to be almost devoid of available phosphoric acid. When superphosphate of lime was used, a dressing of nitrateof soda had doubled the produce of hay, while in its absence nitrate of soda failed to give any increase at all.The citric acid-soluble phosphoric acid in the top nine inches of soil amounted, as shown by the authors, to 200 lbs. per acre, while the crop was able to 241 remove no more than 2 lbs., leaving, apparently, no further available phosphoric acid in the soil. Although that quantity might be potenti- ally “available ” in the soil, it was not actually available in such land as this, until, by improving its mechanical condition, air was admitted, fermentation encouraged, and carbonic acid produced. The experiment also indicated that the acidity of the root sap of the, grasses and clovers had little, if any, effect in dissolving ‘‘available ” phosphate.Both on this ground and on the ground that the carbonic acid-soluble phosphoric acid, as shown by the authors, was much lower than the citric acid- soluble phosphoric acid, the use of carbonic acid as a solvent would appear to give a truer idea of the amount of phosphoric acid actually available. No conclusion as to the manurial requirements of such land should be drawn without also taking into account the various circum- stances favourable to carbonic acid production. Mr. F. J. LLOYDsaid that, as in the case of Dr. Dyer’s paper (PToo., 1894, 10,36), no steps seemed to have been taken to allow for the alkaline reaction of the soil. In the 200 grams used by the authors there might easily be present 4 grams OF calcium carbonate, a quantity which would materially affect the 20 grams of citric acid in 3 litres of solution, so that the soil was not really subjected to the action of a 1 per cent.solvent. Mr. HALLsaid, in reply, that the effect produced by calcium carbonate in the soil had not been overlooked. The authors had used a soil to which successive additions of 2, 5, and 10 per cent. of calcium carbonate were made before treating with the dilute ac.cl. The amount of phosphoric acid dissolved by the citric acid was diminished with each addition of calcium carbonate, but the attack of acetic and carbonic acids was practically unchanged. The diminution was not, however, proportional to the neutralisation of the acid, because neutral saline solutions themselves had a solvent effect, dissociation doubtless coming into play.There were discrepancies still to be cleared up in the results furnished by citric acid; probably as was indicated in the paper, for different types of soil different ‘limits’ would have to be taken as indicative of the need of mineral manures. *163. (6 On a method for determining smallquantities of carbonates.” By A. D. Hall, and E. J. Russell. The authors have devised an apparatus for determining small quanti- ties of carbonates in material like soil by measuring the carbon dioxide evolved. The material is placed in a small bulb, the volume of which need not be known, in which the pressure is reduced to an approximate 242 vacuum; the carbonate is decomposed by the admission of dilute sul- phuric acid, and the change in pressure thus produced is noted.Con-nection is then made with a second vacuous bulb of known volume, and the change in pressure again read. From the two changes in pressure the volume of carbon dioxide can be calculated. A know-ledge of the volume of the material is riot required, and the volume of the carbon dioxide which dissolves in the reacting liquid does not enter into the calculation since the liquid practically forms part of the un- known volume of the first bulb. Examples are given of the measurements of carbon dioxide evolved from pure carbonates in known quantity ranging from 0.13 C.C. to 11.26 C.C. 164. (6 Derivatives of gallic acid." By F.B. Power and F. Shedden. The authors have prepared and described the following derivatives of gallic acid. Ethyl di~itrodicccet?lZguZZute, C,( NO,),( C',H,O,),OH* CO,C,H,, was prepared by the nitration of ethyl triacetylgallate, m. p. 133'. It forms lemon-yellow needles, m. p. 165O. Ethyl dinitrotricccetylycc~kate,C,(NO,),(C,H,O,),* CO,C,H,, was pre-pared from the preceding compound by the action of acetic anhydride. It forms colourless needles, m. p. 145-146", which gradually become yellow. Its cold alcoholic solution gives no reaction with ferric chloride, but, on boiling, a bluish-green colour is produced. Ethyl dinitroyallate, C,( NO,),( OH),*CO,C,H,.-When an alcoholic solution of ethyl dinitrodiacetylgallate is boiled with sodium ethoxide and allowed to stand, the sodium salt of ethyl dinitrogallate was deposited as a bright red, crystalline powder. From the aqueous solution of the latter, hydrochloric acid precipitates ethyl dinitrogallate in the form of small, yellow scales which melt at 153-154'. The same com- pound was obtained by boiling ethyl dinitrodiacetylgallate with 50 per cent.sulphuric acid. Ethylmonamidogullute hydrochloride, C,H(NH,)( OH),* CO,C,H,, HC1,H,O, was obtained, together with the diamido-derivative, by the reduction of ethyl dinitrogallate with tin and hydrochloric acid. It forms white, needle-shaped crystals, which melt at 210' with decomposition. It can be precipitated from its aqueous solution by the addition of strong hydrochloric acid.Diuzoethylyullate, 0 $3, was obtained by the action C6H(OH),CO,C,H,*N of nitrous acid on ethyl monamidogallate. When recrystallised 243 from dilute acetic acid it forms fine, reddish-brown needles, which melt with sudden decomporJition at 182O. When heated with water in a sealed tube at 220° for four hours, the nitrogen is completely eliminated and ethyl gallate is produced. EthyE diamidogallate hydrochloride, C6(NH,),(OH),*C0,C,H,,2HC)l, was obtained, together with the above described monamido-derivative, by the reduction of ethyl dinitrogallate. It melts with decomposition at 197", and is very easily oxidised. It dissolves readily in water, and the solution almost immediately becomes hlue, the colour being intensified by the addition of 5t very little ferric chloride, but destroyed by an excess.165. "Note on phosphorus suboxide." By H.C. Browning, M.A. The author has investigated the following methods used to prepare so-called phosphorus I' suboxide." (i) Oxidation of phosphorus, both in the solid state and in solution, by air diluted with carbon dioxide.. (ii) Action of metals on phosphorus oxychloride. (iii) Action of acetic anhydride on sodium hypophosphite. The results obtained confirm, on t,he whole, those of Chapman and Lidbury and of Burgess and Chapman, although the author believes that the suboxide can exist under certain conditions. I'166. The bromination of trimethylruccinic acid and the inter-action of ethyl bromotrimethylsuccinate and ethyl sodio-cyanacetate." By W.A. Bone and C. H. (3. Sprankling. When trimethylsuccinic acid is heated under pressure to 130' with the calculated quantity of bromine, it is converted into the char- acteristic white bromotrimethylauccinic anhydride, m. p. 197-198'. On the other hand, if the bromination be carried out according to the Hell-Volhard-Zelinsky (phosphorus and bromine) method and the product be poured into alcohol, a mixture of the bromoanhydride and ethyl bromotrimethyLuccinacle results, from which it is difficult to obtain the latter substance in a tolerably pure state. On heating the bromoanhydride with diethylaniline, hydrogen bromide is eliminated, and on afterwards pouring the liquid into a solution of potassium hydroxide, the potassium salt of methylernedi-methylsuccinic acid, (CH,),C(CO,H)*C(CO,H):CH,, is obtained.The acid melts at 140--141", its diethyl salt boilsat 173-176" (755-760 mm.) and readily absorbs bromine and hydrogen bromide in the cold. Ethyl bromotrimethylsuccinate reacts with ethyl sodiocyanacetate 244 with the formation of the cyano-ester which on hydrolysis yields a tribasic acid, C9H1406, melting at 137-138O. This acid is not i-cam-phoronic (aup-trimethyltricarballylic)acid (m. p. 169--173”), which would have resulted had the reaction proceeded normally, thus : (CH,),<r(C02Et)*C(CH,)Br(C02Et)+ NaCH(CK)(CO,Et) = (CH3)2C( CO, Et)-C(CH,)( C0,Et)CH(CN)(C0,E t) + NaBr. Most probably the acid fis the isomeric aa-dimethylbutane act‘@-tri-cM.boxyZic acid,a view which the authors’ experiments so far justify, and its formation is explained on the supposition that ethyl bromo- trimethylsuccinate, in contact with ethyl sodiocyanacetate, loses hydrogen bromide, forming ethyl methylenedimethylsuccinate, which immediately condenses with ethyl cyanacetate as indicated by the equation : (1) (CH,),C(CO,Et)*C(CH,)Br(CO,Et) = HBr + (CH,),C(CO,Et)*C(CO,Et):CH,.(2) ((JH,),C(CO,Et)*C(CO,Et):CH, + CH,(CN)(CO,Et) = (CH,),C(CO,Et)*CH(CO,Et)*CH,*CH(CN)(CO,Et). The further investigation of the new acid is now being prosecuted. 167. 16p-Bromocamphor.” By IF. E. Armstrong and T. M. Lowry. The formation of derivatives of b-bromocamphor on decomposing by heat the sulphobromides of the Reychler series of substituted camphorsulphoriic acids has been described in a previous notice (this vol., p.217). On treating the unsubstituted sulphobromide in a similar manner, in the spring of the present year, a bromocamphor was obtained, which melted at 76O, very similar to ordinary bromo- camphor; but as the melting point of a mixture of the two sub-stances was 65O, it was clear that they were not identical. By further purification of the substance, the melting point was raised to 799 The optical rotatory power of the new compound is very different from that of a-bromocamphor, a solution in acetone con-taining 3.3 per cent. giving [a], =1S0, the corresponding value for the a-bromocamphor being 1439 Recently, larger quantities of material have been prepared, and proof has been obtained that the new bromocnmphor is the parent term of the p-series by its direct oxidation into p-bromocamphoric acid.Simultaneously with the authors, Dr. M. 0. Forster has obtained &bromocamphor by simply brominating the isomeride of camphor which he has described under the name of hydroxycamphene. A 245 direct comparison of the products from the two sources has been made, which leaves no doubt as to their identity. Dr. Forster’s observations are described independently. 168. (I P-Bromocamphor.” By M. 0. Forster. When 1-hydroxycamphene (Tn-ms., 1901, 70,644), dissolved in glacial acetic acid containing sodium acetate (14 mols.), is treated with a solution of bromine (1 mol.) in the same solvent, water pre- cipitates a new bromocamphor, which, from the fact that bromine converts it readily into P-dibromocamphor melting at 114O, must be regarded as the monobromocamphor which has the substituent ’in the unknown P-position. The bearing which this observation has upon the constitution of 1-hydroxycamphene will be discussed in a future communication./3--Bromocamphor, C,,H,,OBr, crystallises from alcohol in long, colourless, prismatic needles and separates from petroleum in trans- parent, well-formed prisms ; it melts at 78O, has [a],,= + 19O in alcohol and [a],= + 16’ in chloroform. Alcoholic potash eliminates bromine from the substance and converts it into an unsaturated acid which belongs probably to the campholenic series.The oxime crystal-lises from alcohol in lustrous, rhomboidal plates, which melt at 156’. 169. ‘‘Substituted Dihydrobenzenes. Part I.” By A. W. Crossley and H. R. Le Sueur. When 2 :6-diketo-4 :4-dimethylhexamethylene (dimethyldihydroresor- cinol) is treated with phosphorus pentachloride, both oxygen atoms are removed apparently as hydroxyl groups, giving rise to 2:6-di- c?bZoro-6 :4-dimethyZdihydrobenzene,a colourless, highly refractive liquid, CH, C*OH CH2CCl (CH,),C/-bH, (CH3)&<-(2HY boiling at 91’ at 23 mm.\-/CH C*OH CH CCl It has a faint odour of turpentine, resinifies slowly on exposure to air, and on boiling with dilute sulphuric acid is reconverted into dimethyl- dihydroresorcinol. When treated with sodium in moist ethereal solution, both chlorine atoms are replaced by hydrogen atoms and there results 4 :4-dirnethyZdihydrobenzene,a clear, colourless, mobile liquid, with a marked odour of turpentine, boiling at 111’.It is homologous with the terpenes, which it resembles in chemical be- haviour. Thus it decolorises a solution of bromine in chloroform; concentrated sulphuric acid produces a blood red colour, changing to 246 violet on standing, and with hydrogen bromide it gives a crystalline hydrohromide. Its properties are being thoroughly investigated, and other similar hydrocarbons are being prepared. 170. 6b The part played by residual affinity in the formation of sub- stitution derivatives. The orienting influence of sulphur’.” By H.E.Armstrong and E,Horton. In previous notices, it has been argued that the formation of ortho-and para-substitution derivatives from phenolic and aminic compounds is due to the attractive influence exercised by the oxygen and nitrogen respectively, and experimental evidence has been adduced which shows that if the phenolic or aminic hydrogen be displaced by hydrocarbon or acid radicles, the ‘‘activity ” of the oxygen or nitrogen is more or less diminished, if not entirely destroyed ;in other words, that the (‘resi-dual affinity ” of the negative element becomes weakened in some cases to the point of being inoperative (compare Proc., 1899, 15,176; 1900, 16,157; B.A. Report, 1899, 683). Although applied to the explanation of the formation of substitu-tion derivatives generally as far back as 1887 (Tmns., 51, 268), the doctrine of ‘‘ residual affinity ” has not hitherto received the attention it perhaps deserves in this connection; we seem to have forgotten that the conception that addition precedes substitution dates back at least to Kekule’s famous paper on the valency of carbon (1858). But now that the doctrine of residual affinity has been rediscovered in Germany by Thiele, and advocated by von Baeyer (Bey., 1901, 34, 26S6), it appears likely to become the fashion, and there is some chance that at last justice may be done to the peculiar qualities of the negative elements; the tendency at the moment to credit oxygen with full tetrad functions is proof, however, that unless care be taken the doctrine will be pushed to unwarrantable extremes.In studying the influence of residual affinity, sulphur is an element of peculiar interest deserving of far more attention than it has hitherto received ;its lethargic behaviour in benzenoid compounds is especially remarkable. To obtain further knowledge of these compounds, the authors are engaged in contrasting the thiobenzenoid ethers with the corresponding oxygen ethers. Methyl and ethyl phenylsulphides are readily sulphonated, yielding para-acids, which afford well-defined salts, &c. On oxidation by perman-ganate, the thiosulphonates are converted into corresponding sulphone- sulphonates. If an aqueous solution of the thiosulphonate be sub- 247 jected to the action of bromine,it is converted wholly into the correspond- ing sulphoxide-sulphonate ; for example, EtS*C,H,*SO,K + Br, +OH, =EtSO*C,H,*SO3H+2HBr, the bromine acting only as an oxidising agent.As it was probable that oxidatim was due to the formation of hypobromous acid, in the expectation that if this were prevented from forming, bromine would be without action, the salt was brominated in presence of muriatic acid ;under these conditions, the salt was con- verted entirely into the ortho-bromothio-sulphonate. It seems, therefore, that, if prevented from undergoing oxidation, sulphur may behave as oxygen does; but the thioether-sulphonates are far more stable than the oxygen-ether-sulphonates,as the sulpho-group is not displaced from t'hem by bromine.Mr. Lewis has ascertained that muriatic acid has, in some cases, a distinct influence on the course of change on brominating the oxygen- ether-sulphonates, and that it promotes the formation of the ortho- bromosulphonate whilst diminishing the extent to which the sulphunic group is displaced. ADDITIONS TO THE LIBRARY. 1. By Donation. Church, A. H. The Chemistry of Paints and Painting. Third edition, revised and enlarged. Svo, pp. 355. London, 1901, From the Author, Goppelsroeder, Friedrich. Capillaranalyse, beruhend auf Capillari-tats- u. Adsorptionserscheinungen, mit dem Schlusskapitel : das Empor- steigen der Farbstoffe in den Pflanzen. Mit 59 Tafeln. Svo, pp. 545. Basel. 1901. From the Author.van't Hoff, J.H. Vorlesungen uber theoretische und physikalische Chemie. Erstes Heft: die chemische Dgnamik. Mit in den Text eingedruckten Abbildungen. Zweite Auflage. Svo, pp. 251. From the Author. 11. By Purchase. Fischer, Ferdinand. Die Brenstoff e Deutschlands und der iibrigen Lander der Erde und die Kohlennoth. Mit einer graphischen Dar- stellung. Svo, pp. 107. Braunschweig. 1901. von Georgievics, Georg. Lehrbuch der Farbenchemie. Zweite Auflage. Svo, pp. 449. Leipzig und Wien. 1902. Neumann, Bernhard. Gasanalyse u. Gasvolumetrie. Mit 116 A bbildungen. 8v0, pp. 168. Leipzig. 1901. 248 Stenglein, M. Handbuch der Presshefen-Fabrikation. Erste Ab- theilung : die Apparate u. Einrichtung von Presshefefabriken, mit 251 Abbildungen.Zweite Abtheilung : das chemische u. das mikroskopische Laboratorium des Hefebrenners, mit 125 Abbildungen u. 12 Tafeln (being Nos. 61 and 62 of iBolley’s Technologie, Bd. iv, 5, 1, 2). 8v0, pp. 327, 279. Braunschweig. 1901. LIBRARY CATALOGUE. A new Catalogue of the Library, arranged under authors’ names and subjects in accordance with the system adopted in indexing the Society’s publications, is ready for the press. Fellows who desire a copy of the Catalogue, at a cost of 29. 6d., are requested to send in their names to the Secretaries not later than January 31st, 1902. If a sufficient number of names is not received, the catalogue will not be printed. MEMORIAL LECTURES, 1893-1900. Fellows can now obtain copies of the volume of collected Memorial Lectures on application to the Assistant Secretary, price 79.6d. post free. At the next ordinary meeting, on Thursday, December 19th, the following papers will be communicated : “ Corydaline. Part VII. The constitution of corydaline.” By J. J. Dobbie, M.A., D.Sc., and A. Lauder, 13.S~. (‘The relation of corydaline toberberine. The oxidation of berberine with nitric acid.” By J. J. Dobbie, M.A., D.Sc., and A. Lauder, B.8c. ‘‘The magnetic rotation of some polyhydric alcohols, hexoses, and disaccharoses.” By W. H. Perkin, sen., Ph.D., F.R.S. ‘(Stereoisomeric halogen derivatives of a-benzoylcamphor.” By M. 0. Forster and F. M. G. Micklethwait. 6‘ Is argon an elementary substance ? ” By G. Martin. :LICHARU CLAY AND SONS LIMITED LOXlJVX AND UUNOA’,
ISSN:0369-8718
DOI:10.1039/PL9011700235
出版商:RSC
年代:1901
数据来源: RSC
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