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Proceedings of the Chemical Society, Vol. 17, No. 237 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 237,
1901,
Page 109-116
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摘要:
188Ued 9/5/1901 PROCEEDINGS OF THR CHEMICAL SOCIET-Y. EDITED BY THE SECKEY'ARIES. VOl. 17. No.237. __-- May 2nd, 1901. Professor EMERSONREYNOLDS,Sc.D,, F.R.S., Presi- dent, in the Chair. Messrs. Storr and Talbot were formally admitted Fellows of the Society. The following certificates were read for the first time : Ormsby Gore Adams, Stawell, Victoria ; Joseph Samuel Bridges, 45, Thistlewaite Road, Clapton, N.E. ; Adolf Ludwig Ferdinand Lehmann, Bangalore, Mysore, India ; William Lowson, 83, Kyrle Road, Clapham Common, S.W. ; James Bertram Russell, 356,Padiham Road, Burnley ; Thomas Sandford, 2, Market Place, 'Ulverston ; Sitmuel Edward Sheppard, Ravensmere, Bromley Road, Catford, S.E. ; Andrew Biggam Smith, Queenstown, Cape Colony ; George William Gerald Tatam, Mercers' Hall, Cheapside, E.C.; James Whittle, 30, Bridge Street, Morpeth. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected :-Messrs. U'illiam C. Ander-son, M.A., D.Sc. ;George 'Stanfield Blake ; Edward Richards Bolton ; Edward G. P. Bousfield ; Percival J. Burgess, M.A. ; William Carter ; Ernest Clark, B.Sc. ; Thomas Kennedy Cockburn ; Eustace Codding- ton, B.A. ;Walter Stevens Crocker ;Henry Drysdale Dakin ;Raymond Dubois, K.Sc. ; William Henry Duckworth ; Albert Ernest Dunstan, B.Sc. ; Samuel Philip Fastick ; Hugh Edward Ellis ; John Vargas Eyre ; John Hanley ; John A. Harrison, B.Sc. ; Francis R. 'Henley, B.A.;Henry Herbert Higgs, B.Sc. ;Alfred James Hyder ; William 110 Henry C.Jemmett, B.A. ; Ernest Alfred Lewis ; Oscar Loewenthal ; Alex. McKenzie, M.A., Ph.D., D.Sc.; Charles Edward Kenneth Mees ; Albert John Murphy; Arthur Theodore Neil, B.A.; Edgar Neumana, B.A.,Ph.D. ; William Oldershaw ; Arthur Peacock, B.Sc. ; William Robertson ; William Hammond Robinson, M.A. ; William Shepperson ; C. Edmund Shatv Sherratt ; Samuel Slefrig, 13.S~.; Henry Eming Smith ; James Smith ; Samuel Fenton Stell ; William Henry Taylor ; Herbert Ackerman Tozer, B.A. ; Joseph De Verteuil ; George Edward Welch, B.Sc. ; Adam Storer Wylie. Professor ARMSTRONGrequested that the abstract of Professor Perkin's paper might be read, and suggested that it might he desirable to arrange for accounts to be given by persons specially selected of fhe work of authors who were unable to be present in person.Of the following papers, those marked * were read, *74. '(The synthetical formation of bridged-rings. Part I, Some derivatives of bicyclopentane." By W. H. Perkin, jun., and J. F. Thorpe. In a paper recently published, Baeyer (Re?.., 1901, 33,3771) has tleveloped a system -of nomenclatui*e for bridged-rings and their YH*YH2 derivatives. Accordin to this system, the hydrocarbon CH,< CH*CH, C(C0 H).$Ne*CO,His named bicyclopentane, and the acid Me2C<bH GO previously desc;i'ihed (Yroc,, 1900, 16, I 51) is therefore tri,mthplketo-bioyclo~~e~tccned~cccrboxy~~cIt. has already heen htat ed that tliih acid. acid, when digested with potash, is converted into an acid melting at 237", and it has since been found that the latter yield.; aii nuhydride (m.p. 96") which on distillation is converted into the anhydride (m. p. 131') of an isomeric acid melting at 181". Careful investiga-tion has shown that these acids, which 2re evidently htweoisomeric, :we not fnrfuran derivatives, as IVRS at first supposed, but are Zncto?zes of h~~methy~~yd~oxybutc6~zetri.~c~c~~~ox?/~~cccc id, C(CO,H)*r:H Ale*(JO,TI /\ Y disruption of t'he whole bicyclopeiitme ring Iiaving taken place during 111 their formation. A somewhat similar admomposition is shown by etl~yl:LlirriatI,~/lllicnrbon.:yti.i,rLeth?/lellelrzcclte, C(OO,Et)*CH(CO,Et)P=Pqll.CO,Et, (loc. cit., p. 149), which on hydrolysis with alcoholic potash yields two acids melting at 187" (not 176" as previously stated) arid 158".These acids have now been shown to be the Itrctones of the two isomeric C(CO,H)*CH,*CO,H /\dimethyl~~~droxybut~netricccrbox~l~ccccicls, Me,C 0 \\CH,-CO CH*CH,*CO,H /\ and Me,C/ 'co , the trimethylene ring having been/\0 \/CH*CO,H broken during hydrolysis ; but unfortunately so far it has not been possible to decide which formula belongs to the former and which to the latter of the two acids. Both acids on heating lose carbon dioxide, and are converted into the Znctones of two isomeric dimethyZ.yclrox?lbutanedicai.~oxyZicacids /\\CH*CH,*CO,H CH*CH,*CO,H probably Me,C /\0 and Me& OO \\ \\\O / C'H,-CO CH2 that from the acid of melting point 187' melts at lo$', and that froiii the acid of melting point 158' at 154'.During the investigation of the bicyclopentane derivatives, it became necessary to prove conclusively that ethyl dimethyldicarboxy- trimetbylenemalonate really had the constitution assigned to it above, and that it was not a tetrametliylene deiivative of the formula CH( C0,Et) Me C/ >C( CO,Et),, which was the only other possibility. \CH(CO,Et) This was done by treating the ester with sodium ethylate arid ethyl iodide, wh en it yit:1ded etiqZ diwiethyZethyZdiccwboxyt7.i methylenemidonci te, ?( CO,Et)-CEt {CO,Et), ,a colourless oil boiling at 230-232"M 2c<cH c0',Ee L (30 mm.). The formation of this ethyl derivative shows that the 112 original ester must have contained a hydrogen atom replaceable by sodium, and the tetrainethyleue formula given above is therefoie excluded.When this ethyl substitution product is digested with alcoholic potash, it yields a dibasic acid (m. p. 175') which is probably dimethyl- ethylethoxyketopentamethy2eneclicarboxylicmid, UH(CO,H)-$!EtCO,H 9H(0Et)-c 0 and there is formed, at the same time, a tribasic lactonic acid melting at 193O, which is probably the Zactone of dintethyEethyZhyd?.oxybutane-C(CO,H)*CEt(CO,H), /\ietracurboxylic mid, Mo,C 0 ,and a dibasic lactonic \\CH,-CO acid melting at also, which is proba.bly the trans-modification of dimethyZethyllr.ydi.oxybut~neti.icccl.60xyZic acid, C(CO,H)*CHEt*CO,H The corresponding cis-modification, which is obtained by the action of hydrochloric acid on the dimet hylethylethoxyketopentamethj lenedi-carboxylic acid mentioned above, melts at 1444 and gives an anhydride melting at 165'.The ease with which disruption of the trimethylene ring takes place in the formation of these lactones is very remarkable ;the only other similar case which is known is that described by Buchner and Witter (Bey., 1594, 27, 571). During the course of the investigation of the bicyclopentane derivatives, some interesting derivatives of pp-dimet~~ylglzctaricacid, CO,H*CH,*CMe,*CH,-CO,H, Lave been prepared and exainiiied, arid the results may be briefly surnmnrised as follows :-aal-Uibronzodimet~~lylglzctaricmid, CO,H*CH Br CXe,*CKBr CO,H, is obtained on treating dimethylglutaric anhydride with phmphorus pentachloride and bromine aud digesting the product with anhydrous formic acid ;it melts at 187--189O, and when treated with pyridine or boiled with water it yields the lactone of a-l~omo-al-hydroxydimetl~yl-CHBr-gluturic acid, Me,C<CH(CO,H).O yo .This melts at 169-170", gives an ethyl ester boiling at 2010 (45 mm.), and is characterised by the great stability of its bromine atom which is not removed even by 113 boiling with silver nitrate and nitric acid. Strong potash, however, converts it into the hctone of aal-dihycErozydinzeth~~g~ut~~ricmid, CH(OH)--QOMe,C<CH(Co2H).0 , which melts at 142'. During the bromination of dimethylglutaric acid, a small quantity acid, CO,H C€3 r,*CMe, CH,*CO,H, isof aa-dibro~?todiinethyZgZutu~ic formed, and this, on boiling with sodium carbonate, yields aa dihydiq-oxydimet~LyZgZutcLricmid, CO,H*C(OH),*CMe,*CH,*CO,H, which melts at 84" and behaves in many of its reactions as the keto-acid, CO,H*CO*CMe,*CH,*CO,H, containing 1molecule of water less.Thus it combines with o-tloluylenediamine, and on reduction with sodium amalgam is converted into the lactone of a-hydroxydimethylgluturic CO,H*flH*CMe,*QH,acid, 0--co , which melts at 112O, and has already been described (Tmns., 1899, 75, 56). "75. Lead silicates in relation to pottery manufacture." By T, E. Thorpe, C.B.,F.R.S.,and C. Simmonds, B.Sc. As is well known, the use of oxides and basic carbonates of lead in glazes employed by potters is attended with danger to the health of the morkpeople on account of the ready solubility of these compounds in the acids of the animal organism, Attention was drawn to the fact that lead silicates or boro-silicates, or complex silicates of lead and other metals, can be used instead of the oxides or carbonates as a means of introducing lead into the glaze. On the Continent this use of lead silicates is far more common than in England, and it is generally recognised that their employment has greatly tended to minimise the risk of lead-poisoning.This is due to the fact that the lead silicates used in the continental factories are of a high degree of insolubility so far as the lead is concerned.On examining a number of lead silicates used or proposed for use in England, it was found that many were attacked by dilute acids prnctic- ally to the same extent as the oxides or carbonates. That is, they yielded the whole, or nearly the whole, of their lead to the action of acids comparable with the acids found in the human systern-such as, for example, the hydrochloric acid of the gastric juice. Other speci- mens were more resistant, but still yielded a large proportion of their lead. On the other hand, the specimens obtained from the Continent, as well as many which have recently been produced by English manu- facturers, gave up only small quantities of lead when tested under the special conditions described. A iarge number of specimens was therefore analysed in order to 114 ascertain, if possible, to what variations in chemical composition thest differences of behaviour were due.“lie couditiori on which the insolubility of the lead depends wa. found to be, primarily, the exiaterlce of a certain ratio between thc whole of the base-oxides on the one hand, md the whole of the acid oxides on the other. This becomes eventIually referable to the hypo- thetical silicic acids from which the silicates may be considered to be derived. Eor working purposes, the relation may be more simply expressed :is sum of percentages of base oxides, expressed as PbO -___ ___~~~ sum of percentages of acid-oxides, expressed as SO,’ or, alternatively, as number of acid molecules number of base molecules’ the latter ratio being obtained by dividing the percentage of each oxide by its molecular weight, and then dividing the burn of the quotients for the acid-oxides by the sum of the quotients for the base-oxides.Provided the ratio falls within certain definite limits, the amount of lead extracted under the prescribed conditions is always small. It does not depend upon the quantity of lead in the silicate, which may have any value up to 50 or 55 per cent. The other bases usually present (lime, alumina, and alkalis) may also vary considerably, replacing one another, and also the lead oxide, within very wide limits without prejudice to the insolubility of the lead. Analyses and forniulae of a number of silicates were given, together with tables showing the dependence of the solubility of the lead in the silicates upon the ratios mentioned above. DISCUSSION.Mr. F. J. LLOYDasked whether experiments had been made using smaller quantities of solutiou than 1000 parts to 1 part of substance. The acid present in 1000 C.C. would be about seven times as much as that required to dissolve 1 gram of lead oxide. The Conditions wliicli influenced the solubility of substances in dilute acid solutions were of especial interest to agricultural chemists. He had found in some experiments that the volume of solution employed appeared to materially affect the solubility, and wished to know whether the anthors had had a similar experience during their investigation. Piof.TILDENenquired whet,lier the authors liad paid special attention to the degree of fineness of the powders submitted to the action of the acid. Some facts had already been published which seemed to show that the app:went solubility of a frit was seriously influenced by the 115 amount of trituration to which the substance had been subjected before bringing it into contact with the acid. Professor CLOWESsaid it would be of interest to know if the solvent action of acids other than hydrochloric acid had been tried, and with what results. He also asked whether the method of testing finished articles purporting to be covered with leadless glaze, by exposing them to the action of dilute hydrochloric acid for some time and examining the solution for the presence of lead, was satisfactory, and what were the best conditions for applying such a test.Mr. ELWORTHYasked whether the authors had estimated the solu- bility of the frits or glazes in salt solutions, as they were much more likely to come into contact with salt solution than with free hydro- chloric acid, especially during the preparation of food, and whether the lead dissolved from the frit existed in the solution as chloride or as a holuhle silicate. Prof. CARMODYasked whether any compari4ons liad bem nlilde between the amount of lead oxide soluble in the frit,s before and after their application. Blr. SInmioNDs, in reply, stated that an excess of acid was necessary, for otherwise misleading results were obtained ;this was dne to the curious fact that, certain kinds of lead silicate reacted with a nentral solution of lead chloride and removed the lead from solution, probably as an insoluble oxychloride.The volrime of acid selected must be sufficiently great to ensure that, there should be no very considerable weakening of its strength by the action of the various acid-neutralising constituents, of which, it should be borne in mind, there might be several besides the lead, As regards fineness of subdivision, some of the specimenc; were sent ready ground, and were stated by the manufacturers to be in the cwn- dition in which they were to he used for glazing pottery ware; thesc were tested as received.Tho other specimens were ground to an impalp-able powder in an agate mortal.. Viwious solvents had )wen experi- inented with-for example, lactic and acetic acids-but the restilts threw no greater light, on the subject than those obtained with hydro- chloric acid ; consequent,ly, the experiments mere not persisted in. Salt solution had riot been tried. 1€e did not know whether te-ting the glaze on table ware with hydrochlo~ic acid had been suggested, Ibnt in Germany there mas a provision that such ware should not give up lead when boiled for half an hour with 4 per cent. acetic acid. With reference to tho state in which the lead existed when dissolved from a silicate, whether as x le3d silicate or as lead chloride, complete malyses of several of the solutions had been made, and some small quantity of silica was always present.The lead, or n part of it, may t hereforcb, perhat’s, have dissolvccl as a basic silicate. 116 76. (‘The preparation and properties of 2 :6-dibromo-4-nitroso-phenol.” By M. 0. Forster and W. Robertson. 2 :6-Di bromo-4-nitrosophenol is produced by the action of potassium hypobromite on p-nitrosophenol dissolved in potassium hydroxide solu- tion (compare Fischer and Hepp, Ber., 1888, 21, 674) ;the potassium, metyl, and benxoyl derivatives are well defined, Dilute nitric acid oxidises the substance to 2 : 6-dibromo-4-nitropheno1, but the concen- trated acid converts it into 2-bromo-4:6-dinitrophenol. Tin and hydrochloric acid reduce 2 :6-dibromo-4-nitrosophenolto 2 :6-dibromo-4-aminophenol, of which the benxoyl derivative is well defined.77. “The chlorination of toluene.” By W. P. Wynne. In consequence of the publication of an abstract of a paper by Cohen and Dakin (p. 91), the author wishes to state that he has been, and is, engaged in a study of the chloro-derivatives obtained in chlorinating toluene under Seelig’s conditions (Trans., 1892, 61,1051). The six dichlorotoluenes, and their sulphonic acids, chlorides, and arnides, to which Cohen and Dakin refer, were prepared and examined in this connection (Zoc. cit., p. 1042 ;Wyune and Greeves, Proc., 1895, 11, 151). Moreover, the 2 :5-dichlorotoluene, which these authors state is very probably formed in presence of the mercury -aluminium couple, has been recognised as present in considerable quantity in the mixture of dichlorotoluenes obt,ained by Seclig’s method. ERRATA, Page 1,iiic 94 18 ccfttcr “place ” inswt hy turtlier dissociation.”I‘ 94 20 for ‘‘ suhvnlent ” wid “subnnivalent.” At the next ordinary meeting, on Thursday, May 16th, the following papers will be communicated :-*‘The nutrition of yeast. Part 111.” By A. L. Stern, D.Sc. “Derivatives of methylfurfurd.” By €I. J. 13. Fenton and Mish Mildred Gostling. “ The preparation and optical inversion of optically active nitrogen compounds ; dextro-and laevo a-benzylphenylallylmethylammonium salts.’’ By W. J. Pope and A. W. Harvey.
ISSN:0369-8718
DOI:10.1039/PL9011700109
出版商:RSC
年代:1901
数据来源: RSC
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