摘要:

SUBSTITUTED PIBIELIC ACIDS. 98 7 LXX1X.---Substituted Pimetic Acids. By A. W. CROSSLEY, B.Sc., Ph.D., Berkeley Fellow of the Owens College, and W. H. PERKM, Jun. SOME time since (Trans., 1891, 59, 818) one of us, in conjunction with Mr. Bertram Prentice, described a method of preparing aa,-di- substituted pimelic acids, which, briefly stated, is as follows. The digodium derivative of ethylic pentanetetracarboxylste is digested with the iodide of a radide (RI)? and t h u s converted into a di-deriva- tive of this ethereal salt. ( C 00 C,H,),CNa. [ CH,] ,*CNa ( COO C,H,) + 2 RI = ( C 0 0 C2H5)2 CR* [ C H,] ,.CR ( C 0 0 C,H5) + 2NaI. On hydrolysis, this salt yields the corresponding tetrabasic acid, which, when heated at abont 2C10", loses 2 mols. of carbon dioxide, forming an an,-disubstitu ted-pimelic acid.(C 00H),CR*[ CH,]& R( C 00 R) = With the object of prepariug mono. substituted pimelic acids, ex- periments were made on the action of alkj-1 haloids on ethylic pentanetetrararboxylate in the presence of only 1 mol. of sodium COOH*CHR*[CH,],*CHR*COOH + 2COp 4 ~ 25s 8 A. T. CROSSLET AND W. H. PERKIS, JUN.: efliylate; but these were not successful, as, in such cases, half of the ethylic pent'anetetracarboxylate remained uuacted on, the other half having been converted into a disnbstitution product (loc. c i f . , p. 819). In continuing the study of this subject, various modifications of the above synthetical method were tried, i n the hope of discovering some means by which not only mono-substituted pimelic acids, b u t also ax,-disubstituted pimelic acids, containing two different radicles of the type COO H.CHR*[ CH,],*CHR'.COOH, might be prepared ; this was ultimately a-comglished in se-reral ways.When trimethlrleiie chlorobromide (uvq-chlorobromopropane, CH,Cl*CH,*CH,Br) acts on the sodium derivative of ethJ-lic ethyl- malonate, ethylic ~,-cliloropropSlethyl malonate is produced, thus. (COOCpH,)2CKa*C2Hj + CH2Br-CH,.CH2C1 = (COOC,H~)2C(CpH~)~CH2*CH2*CH2Cl + KaBr, and this substance, whec digested i n alcoholic solution with the sodium deri-ratire of ethylic malonate, yields ethylic ethylpentane- tetracarboxylate, ( COOC2H5)2C ( C2€15)*C H,-CH,*CH,Cl + CHNa( COOC,H5)? = ('COOC,H j) ?C ( C2H5).CHp.C Ep*CH,*C H (C 0 OC,H5) + Na C1. On hydrolxsis, this etherea! salt j-ields a n acid, which a t 200" loses carbon dioxide, forming ethylpimelic acid.(COOHj,C(C~H,j.[CH,],*CH(COOH), = C 0 0H.C H ( C,H,) * [ C H2 2 C H2.C 00 H + 2 C 0 L. The new acid \\-as purified by first conrcrtinz it into its ethylic salt, and then, after fractionation, reconverting this into t h e acid by hydro- lysis ; the oily product was subsequently distilled under reduced pressure, when it boiled constantly a t 260-26Di" (82 mm.), b u t did not solidif7, eFen after many weeks ; it gave a cr~-stalline dinnilide, C,LH,,N,Op (m. p. 14So), however, which, although not a. Terr charac- teristic compound, might possibly serve for t h e idrnt ification of the acid. The next acid which was prepared was ethylmeth-1 3imelic acid, COOH*CE (CzHs)*r CH2],*CK(CH3).COOH. The method used in synthesising it, and which worked very well, differs in suriic respects from that described above, and is briefly as follows.In the first place, the sodium derivative of ethylic etbylnialoiiate was digested in alcoholic solution with chloromethoxypropane (Trans., 1894, 65, 596), when the following interaction took place. (COOC2H5)2CNa(C2H5) + CH2C1.CH2*CH2*OCH, = ( CO 0 C&L) pC ( GH5) CH2. CH2.C HL.O C HJ + Na C1. The methylic" methoxypropylethylmalonate obtained was con- * Br miskake, mcthjlic alcohol wos used as the solvent instead of etliplic alcoholSUBSTITUTED PIXELlC ACIDS. 989 verted into the corresponding acid by hydrolysis ; this, on distilia- tion, is decomposed, evolving carbon dioxide and forming methoxy - propylethylacetic acid.On treatment with hydrobromic acid, this methoxy-acid yields bromopropylethylacetic acid, the ethereal salt of which readily interacts with the sodium derivative of ethylic methylmalonate, yield- irig ethylic ethy lmethylpentnnetricarboxylate, thus. (CO 0 C2H,) ,CNa-CH, + CH2BsCH2-CH2-CH ( C,&) C 0 OC,H, = (COO C2H5) zC ( CH3).CH2*CH,*CH2CH (C2H j) -CO OC,H, + NaBr . Lastly, this ethereal salt, on hydrolysis, is converted into tho corresponding tricarkioxylic acid, from which, by heating at 200" arid subsequent distillation, eth~lmethylpimelic acid, COOHC H( C2H5). [C H,],*CH( CH,)-COOH, is obtained in the usual manner. This acid boiled constantly at 265-270". under a pressure af 80 mm. It remained as an oil during several week, but was put aside, and a t the end of about four months was found to have deposited crystals ; these, after repeated recry stallisation, melted a t 78'.It seems probable that this acid exists in two stereoisomeric forms ; this would account for the extreme slowness m-ith which the oily acid crystallises, and also for the great difficulty expe;.ieuced in purifying it by recrystallisation ; we propose to further invefitigate this subject, and also t o prepare several other substituted pinielic acids, some of which it. is expected will have interesting properties. Et hy Qimelic acid, The first experiments made with the object of preparing this acid were carried out as follows. Sodinm (2.3 grams) was dissolved in absolute alcohol (25 grams), the well-cooled solution mixed with carefully purified ethylic ethj1- malonate (18.8 grams) and trimethylene bromide (21 grams), and the whole heated i n a reflux apparatus for one hour, when themix- t ure was found to be neutral, The product contains a bromo-derivative, which was not analysed, but obviously consists of ethylic bromopropyleth~lmalouate, (C 0 OC,H,) ,C (C,H,>-CH,.CH,-CH,Br ; this was mixed with sodium (2.7 grams), previously dissolved in ab- in these experiments. The product, therefore, consisted of the methylic salt, an interchange of an alli-1 rttdicle haying faken place (compare Purdie and 3farsId1, Trans., 1888, 53, 391).990 A.W. CROSSLEY AXD R. H. PERKIN, JUN.: solute alcohol (25 grams), ethylic malonate (16 grams) added, and the mixture heated in a reflnx apparatus for three hours, when i t was found to be almost neutral.Water was now added, and the precipi- tated oil extracted by agitating thrice with et,her ; the ethereal solu- tion was then washed with water, dried over calcium chloride, the ether distilled off, and the residual light yellow oil submitted to careful fractionation under reduced pressure. In this way, a colonr- less oil was obtained, boiling constantly at 275" under a pressure of 75 mm., and giving, on analpis, numbers agreeing with those re- quired for ethylic ethylpentanetetracarboxylate, Found. Theory. Cl9E,,O,. C ........... 58.73 per cent. 58.76 per cent. H... ........ 8-46 ,, 8-24 ,, This oil was hydrolpsed by boiling with excess of alcoholic potash €or three hours ; the alkaline product was then diluted with water evaporated till free from alcohol, acidified, and extracted ten times with ether.On drying over calcinm chloride, and evaporating the ether, a thick, colourless oil was left ; this was heated at 200" until no further evolution of carbon dioxide took place, and then rapidly distilled under reduced pressure; nearly the whole passed over between 250" and 260" (70 mm.), and, on analysis, gave the following results. Found. Theory. C&:604. C ........... 57.82 per cent. 57-44 per cent. H . . ......... 8-75 ,, 8-31 ,, These numbers agree fairly well with those reqnired for ethylpimelic acid, COOH.CH(CzH,)*[ CHz]3*CH2*COOH, and judging from the results of subsequent experiments, there can be no doubt that it con- sisted of this acid iu a nearly pure etate. As this acid, even after long standing, showed no signs of crystal- lising (which is remarkable in consideration of the fact that pimelic acid and all its alkyl-derivatives which have hitherto been prepaid, are solids), it was assumed that this behavionr was dne to impurity, a supposition borne out by the above analyses, the rather high values for carbon and hydrogen found indicating the presence of traces of diethylpimelic acid, C OOH.CH (C2B5j* [ CH2j3-CH (C2E3,) ,COOH. The preparation of the acid wad therefore modified in the following way. Sodinm (3.6 grams), dissolved in alcohol (50 grams), was mixed with ethylic ethylmaionate (29 grams) and trimethylene chlorobro- mide (24 grams), and heated as before until neutral. Water was then added, the oily product of the reaction extracted wit*h ether, tbeSUBSTITUTED PIMELIC ACIDS, 99 1 ethereal solution well washed with water, dried over calcium chloride evaporated, and the residoal oil allowed to remain for some days over sulphuric acid in a racnnm.The analyses of this preparation gave the following results, which agree only approximately with those for ethylic chloropropylethyl- malonate (COOC,H,),C ( C2H5).C H,*CH,*CH,Ci. Found. Y--7 Theory. I. 11. W%,o,a. C1 ...... 11.43 11.52 per cent. 13.42 per cent. This oily substance was then digested with sodium ethoxide (3.6 grams sodium dissolved in 50 grams of alcohol) and ethylic malonate (24 grams) until the product was quite neutral ; water was added, the oily ethereal salt extracted as before, and purified by frac- tional distillation under reduced pressure.The greater part distilled at 270-275" (75 mm. pressure), and consisted of ethylic ethylpen- taneteiracar boxj lat e. This was hydrolysed wit'h alcoholic potash as before, and the resulting crude ethylpimelic acid, which, again, did not crystallise, purified by conversion into its ethylic salt in the following way. The crude acid was dissolved in about five times its bnlk of absolute ethylic alcohol, mixed gradually with one-third of its volume of concentrated sulphuric acid, and the mixture allowed to stand for 48 hours ; at the eud of this time it was diluted with water, the oily ethereal salt extracted with ether, the ethereal solution washed with dil Ute sodium carbonate solution, dried over potassium carbomte, evaporated, and the brownish, oily residue purified by fractionation under reduced pressure.Ethylic ethLilpinzeZute, CO (lC,H,-C H(C2H5)* [ CH,]4*COOC1H5, is a colourless, oily liquid, possessing a faint smell, and boiling at 128-200" under a pressure of 83 mm. Found. Theory. C,,H,,O,. C ........... 64-17 per cent. 63-93 per cent. H ........... 10.27 ,, 9.83 ,, This ethylic salt was hydrolysed by boiling with alcoholic potasl;, and the ethylpimelic acid formed was extracted with ether, dried with calcium chloride, and fractioned ; almost the whole passed over as a colourless 011 between 260" and 265" under a pressure of 82 mm. It gave the following results on analysis. Found. Theory. C9HI6O4. C .......... 57.76 percent. 57.44 per cent. H . .......... 8.73 ,, 8.51 ,, I n this case, also, the acid could not be made to crystallise, so that998 A.W. CROSiLEY AND W. H. PERKIN, JUN.: we must conclude either that ethylpimelic acid is an oil, or, that wlien prepared by the above methods, small quantities of impurities are present which prevent it from crystnllising. Anilide of ethylpimelic acid, CsH,*NH*CO*CH (C2H5). [ CH,] 4. CO.XH.C,H,. In order, if possible, to obtain a crystalline nnilide of this acid, by means OF which the acid might be identified, a portion of the sub- stance was digested for 20 hours in a rzflux apparatus with about four times its volume of pure aniline. The diirk colourej product was dissolved in ether, the ethereal solution well washed with dilute hydrochloric acid to remove excess of aniline, dried over calcium chloride and evaporated ; the thick, oily residue, after standing over sulphuric acid in a vacnum for a time, partially solidified.This crnde substance, after being washed with ether and crgstallised several times from benzene, was obtained as a colourless, indistinctly crystalline powder, melting at 145" ; on analysis it gave the following numbers. Found. Theory. C21H24K202. F, . C ........... 74.39 per cent. 44 55 per cent. H ......... 8.10 ,, 7-69 ,, N. .......... 8.29 .. 8-25 ,, It is readily soluble in hot benzene, alcohol, and chloroform, but only sparingly in light petroleum. Et.hy Zmethy Zppimelic acid, C OOH. CH ( C2H,) [ CH,] 3*CH (CH,) .C OOH. The method employed in the synthesis of this disubstituted pimelic acid, containing two different radicles, was somewhat different! from that used for ethylpimelic acid, and is probably applicable in the case of all similarly constituted acids.Sodium (2-3 grams) was dissolved in absolute methylic alcohol (30 grams), ethglic ethylmalonate (18.8 grams) added, and then chlosomethoxypropane (10.d grams), when a vigorous action set i n ; as soon as this had subsided, the mixture was heated in a reflus apparatus for about an hour and a half, and after diluting with water, extracting with ether, &c., as in the case of ethyiic ethyl- pentanetetracarboxylate (p. 990), was submitted to fractionation under reduced pressure, when the greater part distilled at 180" (43 mm.). On analysis it gave the following results. Found. Theory. 7-- 7 7--- 7 I. 11. C1,HzoOj. C13H2-I@j. C ....55.17 55-97 per cent. 56.89 39-77 per cent. H .... 8-34 8.64 ,, 8-62 9.33 ,,SUBSTITUTED PIMELIC ACIDS. 993 These nnmbers agree best with the formula CIlH2005? that of methylic methoxypropylethylmalonate, crr,O*[CH,],.C(C,H,)(COOCH,),, the formation of which is explained in the introduction, the slight deficiency in carbon and hydrogen being due to the €act that the oil cont>ains traces of chlorine. This methylic salt yielded the acid on hydrolpis, which was purified by fractiona.tion under ordinary pressure. The whole passed over between 240 and 255O, and a portion boiling at 250" gave the following results on analysis. Found. Theory. C8HI6O3. C ........... 59.82 per cent. 60.00 per cent. H ........... 10-47 ,, 10.00 7, Nethozyprop yZeth;/Zcrcetic acid.t: 0 OHCH ( C,H,).[ CH,] ,.OC Ha, is a thick, colourless oil, which did not solidify after standing €or two days ; when heated with hjdrobromic acid it is readily converted into bromopr~~~ylethylacetic acid, COOH.CH(C,H,)*CH,GH,.CH,Br. In order to prepare this substance the methoxy-acid was dissolved in twice its volume of fuming hjdrobromic acid, and the solution heated i n a sealed tube at 150" for two hours. On cooling, it was observed that two distinct layers had formed, and on pouring the product into water a heavy oil was deposited ; this was extract.ed by agitation with ether, the ethereal solution washed with water, dried over calcium chloride, and evaporated. The dark brown, oily acid thus obtained did not solidify, and as it could not be purified by frac- tional distillation, was directly submitted to analysis.The numbers obtained agree only approximately with those required for bromo- propylethylace tic acid. Found. TI) eory. CiH,,O,Br. Br .......... 35.27 per cent. 38.27 per cent. The acid was converted into the ethylic salt by dissolving it in ethylic alcohol, saturating the solution with hjdrogen chloride, acd, after 24 hours, pouring the product into water ; the oily layer was extracted with ether, and the ethereal solution washed with sodium carbonate solution, dried over calcium chloride, and evaporated. I n order to obtain ethylic ethylmethylpen tanetricarboxylate, COOC,H,.CH(C,H,)*[CH,]3.C(CH3)(CGOC2H5)2, the sodium com- pound of ethylic metbylrnalonate was prepared by adding ethylic inethylmalonate (17 grams) to a solution of Fodium (2 grams) iii ethylic alcohol (25 grams), ethylic bromopropylcthy lacetate (20 grams) was then added, and the mixture heated for 2$ hours in a reflux apparatus.On adding water, extracting with ether, S-c., in the usual manner, and purifjing tLe product by fractionation under994 SUBSTITUTED PIMELIC ACIDS. reduced pi-essnre, almost the whole distilled at 227-239' (6G' mm. pressare). I t gave the following results on andpis. Found. 7--7 Theory. I. 11. c,;&oo6. C ........ 62.05 61.92 per cent. 62.81 per cent. H ........ 9.86 9.31 ,, 9.09 ,, The fraction of this substance boiling at 227-230" (60 mm.) was then hydroljsed by boiling with alcoholic potash, and the free acid obtained by extracting with ether, &c , in the usual manner.On heat- ing it at 200" until no further evolution of carbon dioxide was notice- able, and purifying the residual dark brown, oily acid by distillation under reduced pces3ure almost the whole passed over at 265-270" (SO mm.). I t gave the following results on analysis. Theory. Found. COOH.CH(CH3)*[ CH2 J3-CH (C2H,)-COOH. C ........ 59.28 per cent. 59.40 per cent. H........ 9-45 ,, 8.91 ,) These numbers agree well with those required for ethplmethyl- pimelic acid, and the formula of the acid was further corroborated by preparing and analgsing the silver salt. A small quantity of the acid was neutralised with ammonia solu- tion, and a few drops of dilute silver nitrate added ; after filtration from the slight precipitate, the clear liquid was heated to boiling and precipitated by adding a large excess of silver nitrate. The white, insoluble silver salt was collected, well washed with water, and analyscd with the following results.Found. r--- 7 Tlieory. I. 11. G"H:16044b Ag.. .... 51.68 51-78 per cent. 51.92 per cent. Tbe acid remained liquid for a long time, but after standing for four months it gradually deposited crystals, and became semi-solid ; the oil was gradually absorbed when the crystals were left in contact with porous porcelain, leaving a mass of almost colourless crystals, which melted approximately at 58". By repeated recrystallisation from water, with the aid of animal charcoal, the crude product yielded a mapiticent crystalline acid, which melted at 78" and gave the following results on analysis. Found. Theory. C,,H,,O,. C ........... 59.51 per cent. 59.43 per cent. H ........... 9-10 ,, 891 ,, Ethylmethylpimelic acid crystsllises from water in large, trans- parent, glistening prisms ; it is sparingly soluble in cold water, andHOMOLOGUES OF BUTAMGTETRACARBOXYLIC ACID, ETC. 995 is deposited from the hot, concentrated aqueous solution, on cooling, :IS an oil, which crysfallises rapidly if stirred with a glass rod. The aqueous mother-liquors of the acid, on concentration, yield diff el-ent fractions of crystalline acids, which melt roughly between 60" and 75", and presumably contain a second isomeride of etbyl- methjtpimelic acid. Owing, however, to the very small quantity of maferial at our disposal, this second acid, if present, could not be isolated, and for this reason we could not recrptnllise the ethyl- pimelic ac id (m. p. 78") as often as we could have wished, and give, thereforc, the melting-point of this acid ally BY a close approxima- tion. Chemical Laboratory, Owem College, Manchester.

ISSN:0368-1645    

DOI:10.1039/CT8946500987

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

HOMOLOGUES OF BlJTAX3GTETRACARBOXYLIC ACID, ETC. 995 LXXX.-Homologues of Blcta~etetrczCa7~~oxyl~c acid c i n c l of Acllpic acid.* By UEVAK LEG, D.Sc., B.A., Bishop Berkeley Fellow of Owens College . I N T R o D u c T I o x. WHES ethylene dibromide is treated with the monosodium derivative ot ethylic malonate, the chief product is ethjlic 1 : 1-trimethglene- dicarboxglate (Perkin, Trans., 3 887,51, 1). + 2CHNa(COOEt), = YH2>C(COOEt), yH,Br CH,Br CHZ + CH,(COOEt), + 2NaBr; but, at the same time, an oil of high boiling-point is formed, which, however, constitutes only about 3 per cent. of the whole; this, on iiivestigation, was found to be ethylic butanetetracarboxylate, and its formation may be represented by the eqGation- 7 Ha*CH (C OOE t ) z + 2CHNa(COOEt), = + 2NaBr. yH2Br CH& C H29C H (C 0 0 E t ) , The fact that this substance is produced in such small quantities made its fnrther invest,igation a matter of very great difficulty; more recently, however, Professor W.H. Yerkin, jun., has found thRt the substitution of ethylenic chloride for the bromide greatly ir creases the yield of ethylic butsnetetracarboxylate. The method * Part of a thesis accepted for the degrec of Doctor of Science of the University cf London.9% LEAN : HOMOLOGUES OF BUTAh'ETETRACARBOXYLIC ACID which is now adopted for the preparation of this substance is described in a paper published in this Journal (this vol., 578). Ethylic bntanetetracarboxylate, in constitution and properties, is very closely allied to the ethereal salts of ethane-, propane-, and pen tane-tetracarboxylic acids, all of which have been investigated in detail. These ethereal salts interact with sodium ethylate, forming disodium derivatives, the sodium displacing the hydrogen atoms of the two CH groups, and giving compounds, which, if X denote the group COOEt, may be represented thus- ?"ax2 CNaX,' CH,*CNaX, cH,<CB2*CNaX2 When these sodium derivatives are treated with alkplic halojids disubstit ution derivatives are formed of the general formula+- CRX, ' CH2<CRX2 ' CHz<CH2*CRX, ' FRXz C RX, CHZ.CRX2 i n which R represents an alkylic gi-oup, the action taking place readily, except in the case of the disodium derivative of etliylic ethane- teti-acarboxylate, when it is necessary to heat the mixture at 150' (Guthzeit and Dressel, Annalew, 256, 181 ; Perkin, Trans., 1891, 59, 818 ; Baeyer and Perkin, Ber., 17, 449). On hydrolysis, these ethereal salts yield the corresponding tetra- carboxjlic acids, which lose 2 mols.of carbonic anhydride when heated a t about 200", and are converted into derivatives of succinic, glutaric and pimelic acids, of the general formuIa+-- YHRY CHRY CHz*C'HRY CHRY ' CHZ<(lHky 9 C H ~ < ~ ~ , 7 where Y represents the group COOH, just as ethylic ethane-, propane-, and pent ane- tetracarboxjlates, under similar circumstances, are converted into succinic, glutaric and pimelic acids respectively. It has already been shown by Perkin (loc. cit.) that ethylic butare- tetracarboxylate is capable of forming a disodium derivative (COOEt),CNa.CH,*CH,*CNa( COOEt),, and that this disodium de- rivative is converted by iodine into the ethereal salt of tetrametnjl- enetetracarboxylic acid, thus- vH2-CNa( COOE t, j , yH,*F(COOE t), i 2Ka1, C H,*C Na (C 0 0 E t) -t- I' = CH,-C(COOEt), but no further experiments could be instituted a t that time with the disodinm derivative, owing to the difficulty of obtaining sufficient of the ethereal salt.When, however. the method of preparation had been so improved as to make it possible to continue, in a satisfactoryAND OF ADIPIC ACID. 997 manner, the investigation of the substance, i t was thought that interesting results would be obtained by studying bhe action of alkylic haloids on the disodium derivative. In carrying out this investigation, it was found that the disodium derivative of ethylic butanetetracarboxylate is readily act,ed on by alkylic iodides or chlorides, forming am-dialkyl-substituted butane- t etracarboxjlic acid derivatives, thus- 7 H?*CNa ( C 0 OE t)z + 2RI = yHZ*CR(COOEt), + 2NaI.C H2*C Xa (C 0 0 E t ) a CH2*CR (C 0 OE t).: The action takes place as soon as the substances are brought together, generally with considerable development of heat. On the other hand, it has not been found possible to prepare mon- alkylic derivatives of butnrietetracarboxylic acid by the action on ethylic butanetetracarboxylate of 1 mol. of sodium ethylate and 1 rnol. of an alkylic haloid. On attempting to prepare ethylic monethyl- butanetetracarboxylate in this way, the product was found to consist of ethylic diethylbutanetetracarboxylate, one half of the ethylic Imtanetetracarboxylate being recovered as such.In explanation of this remarkable actioii, one must either suppose that ethy lic butane- tetracarboxylate is incapable of forming a monosodium derivative under such conditions, or that the decomposition of the monosodium derivative takes place thus- ? H,*CE t (C 00 E i.)z + ELI = + NaI. CH,* CH( COOE t)z (1 .) 7 H,*CNa (C OOE t ) 2 CH,*CH (COOE t) 2 (2.j ~H,.CEt(COOEt)z CH,.CNa(COOEt), - CH,*CH(COOEt)? 4- bHz*CH(C0OEt), - $: H2.C F: t ( C 0 0 Et) z C H,* C H ( C 0 0 E t) , CH,.CNa(COOEt)z + bH,*CH(COOEt), C H2*CE t (C 0 OE t j, + E t I = I + NaI. (3.) YH,*CE t (COOE t) CH,*CNa( CO OE t) CHz*CE t ( COOEt), Similarly, ethylic propanetetracarboxylate (Gutbzeit 2nd Dressel, AnnaZen, 256, 180, IS&), and ethjlic pentanetetracarboxylate (Perkin, Trans., 1891, 59, 847), when treated with 1 mol.of sodium ethylate and an alkylic halo'id, yield, instead of a nionalkylic derivative, a mixture of the dialkylic derivative with unchanged ethereal salt. I n the course of this inrest;gation, a detailed study has been made of the dimethyl, diethyl, dicetyl, and dibenzyl derivatives of ethylic butanetetracarboxylate. They are all solids, and crystallise with considerable facility. On hydrolysis, these ethereal salts yield the corresponding qnadri- carboxylic acids, which possess some very remarkable properties ;998 LEAX : HOMOLOGUES OF BUTASETETRACARBOSTLX ACID 0 xalic . for, although they contain four carhoxyl groups, they do not in ail mses behave as quadribasic acids.When their basicity is determined by titration with standard solution of potassium hydrate, some o f them act as bibasic acids; notably is this the case with dibenxyl- butanetetracarboxylic acid, the result being the same whether phenol- phthnlejin or litmus is med as the indicstor. In tllis connection, it is to be nofed that the silver and calcium salts of dibei17ylbntanetetra- carboxylic acid, which mere obtained, were found to have the formuh C,,H,08Ag? and C,,H,,,O,Ca + 2H,O respectively. On the other hand, dimethyl-, diethyl-, and dicetyl-butanetetracarboxylic acids, on being titrated with potassiiirn hydrate, give different results, accord- ing as phenolphthaleh or litmus i s employed a s indicator. They behave a s quadribasic acids when phenolphthaleh is used.I f , how- ever, one or two drops of litmus solution be added to the solution of these acids in potassium hydroxide, which has been rendered neutral to phenolphthalejin bF hydrochloric acid, a distinctly blue coloration is produced. On adding more hydrorhloric acid, the blue coloration chanqes gradually to red, and the solution appears to become neutral t o litmus only when sufficient hydrochloric acid is added to neutralise one half of the potassium hydroxide, which was equivalent, as shown by phenolphthaleh, to the tetracarboxylic acid present. While the salts of dimethyl- and diethyl-butanetetracarboxylic acid were quadri- basic, those prepared in the same way from dicetylbutanetetra- carboxylic acid, like those of dibenzglbutanetetracarboxylic acid, were,found to be bibasic." Acetic.Tartaric. Citric. * As regards the action of indicators. it has been shown that the quadribasic potas- sium salts of dimethyl-, diethyl. , and dicetyl-butanetetracarboxylic acid are neutral to phenolphthrtle'in but alhaline to litmus, and that, on titrating these acids, when using litmus as the indicator, the points of neutralisation are found to be very indefinite. Dibenzplbtitanetetracarboxylic acid, on the other hand. acts as D bibasic acid, both towards litmus and phenolphthaleyn. To illustrate further the difference in behaviour of indicators, reference may be made to a systeniatic investigation of the use of litmus, methvl-orange, and phenolphthaleyn as indicators, which was carried out by Smith in 1883 (Chem. Xelc's, 1883, 47, 136).The following table is com- piled from his results. - I-- I-----+--- I -- Methyl-orange.. low results very low resulta'very low results'verp low results Litmus . . . . . . . .I sharp I indefinite 1 indefinite Phenolphthalei'n sharp sharp sharp sharp indefinite Engel (Compt. rend., 1886, 102, ZSZ), too, has shown that when a solution of phosphoric acid is tritrated, it appears to be monohasic if methyl-oranEe is used ;i5 the indicator, but bibasic with phenolphthaleh, and tritasio with Poirier's solubleASD OF SDIPIC ACID. 999 When heahd at 30-210", the disubstituted biztanetet ramrboxvlic acids readily lose 2 mols. of carbonic anhydride, yielding disnb- stituted &pic acids. The study of these disnbstituted adipio acids is especially interest- in4 in view of the recenf work of Bischoff, Auwers and Victor Meyer, Zelinsky, Perkin, and others, on the isomerism of aa-disnbstituted acids in the succinic, glutaric, and pimelic series.The svmmetrical disnbstitn ted succinic acids (Leuchart, Bw.. 18, 2348 ; Zelinsky, Ber., 21, 3170 ; Bischoff and Voit, Ber., 20, 2988 ; Hell and Rothberg, Rer., 22, 66; Bischoff and Voit, Ber., 22, 389 : Bischoff and Hjelt, Ber., 21, 2089, 2097, 2102; Bischoff, Ber., 20, 2968 ; Hjelt, Rep., 20,3078 ; Bischoff and Mintz, Rer., 23, 650: Bnit- chichin and Zelinsky, Abstr., 1889,377 ; 1890, 740) are found to exist in two well marked isomeric forms ; for instance, two dimethylsuccinic acids are known, melting at, 123-124" and 192", and two diethvlsnc- cinic acids, melting at 129" and 192".The isomerism of the disub- stituted glutaric acids is, apparently. not, so pronounced as that of the disubstituted succinic acids ; of the dialkpl-glutaric acids (Zelinsky, Ber., 22, 2883 ; Bischoff, Ber., 23, 1465 ; Bischoff and Mintz, Ber., 23, 649 ; Auwers and Kobner, Ber., 24, 1933 ; Guthzeit and Dressel, Anaden, 258, 171), the diniethyl derivatives alone have been wpa- rated into two distinct modifications, melting at 102-104" and 1.28" respectively. A number of disuhstituted pimelic acids (Perkin and Prentice, Trams., 1891, 59, 818) have been prepared, but in no crrse could a separation into two isomeridas be satisfactorilg accomplished ; i t was, however, frequently noticed that the melting-points of the acids were'not so sharp as could be desired, and there is reason to believe that these acids also occnr in two isomeric forms, which are so similar in properties that, separation is a matter of great difficulty. Considerable interest-, therefore, attaches to the question of isomerism in the disubstitnted adipic acids, as these are intermediate between the glntaric and pimelic acids.It, has been found in the course of the present research that these disubstituted adipic acids invariably exist in two modifications, which usually differ from one another in a blue. He also showed that boric acid is neutral to methyl-orange, feebly acid to litmus or phenolphthalern, ond acid to soluble blue. From these instances, it appears that litmus is liable to give lower results than phenolphthalern, and in the case of litmus the final colour change is usually very indefinite.It also is evident that any knowledge of the basicity of an acid obtained by titration isonlv relative to the nature of the indicator employed, and, further, when a polybasic acid has been only partially neutralised, its acid function may be enfeebled altogether out of proportion to the amount of base which has been added to it. This raises the wider question of the basicity of polybnsic acids, and of their affinity as B function of the affinities of the gmups wh;cli they contain. (See '' Note on the Affinities of Polybasic Acids," this vol., p. 1024.)1000 LEAK : HOMOLOGUES OF BUTANETETRACARBOXPLIC ACID very marked manner in melting-point, solubility, and other physical pro pert ies. F o r instance, the dimethyladipic acids melt at 7C-72" rrnd 142", the diethyl a t 51-5:3" aild 136", the dihenzyl at 152" and 211-213".It is remarkable that the isomerism of tbese disubstituted acids is as pronounced in the adipic series as in the mc- cinic, whilst iu the intermediate glutaric series i t is much less noticeable Of these derivatives of adipic acid, the dimethJl alone have pre- viously been obtained (Zelinsky, Ber., 24, 3997), thi-oueh the hydrolysis of ethylic die-anodimethyladipate with sulphuric acid, 3s represented by the equation- y ( p 3 YH3 7 H3 CK*Y*CH2*CHZ*Y*CX + 6HzO = HY.CH,*CHz*FH + 2EtOH CUOEt COOEt COOH COOH + 2NH, + 2C0,. It is a well-known fact that whilst oxalic acid, or malonic acid and its alkylic derivatives, do not form internal arrhTdrides, the formation of an anhydride OCCUI-S readily in the case of succinic acid, and i t is exceedingly interesting that the introduction of alkylic groups much increases the tendency to form anhydrides (Bischoff and Mintz, Bey., 23,620 and 656 ; Suwers and Jackson, Ber., 23, 1614) ; for instance, dimothylsuccinic acid yields an anhydride much more readily than succinic acid, and again anhjdride formation takes place more readily in the alkylic derivatives of glutaric acid than in the case of the acid itself.Now adipic acid does not form an anhydride, but the introduction of methyl or other groups appears to increase the tendency to form an anhydride, and Manasse and Rape (Bey., 27, 1818 ; 1894) hare vcry reccntly succeeded in obtaining the anhydride of P-methjladipic acid ; i t is noteworthy that it is wry unstable, and reverts to the acid on long exposure to the air.The disnbstituted adipic acids, described in the following pages, when heated with acetyl chloride in sealed tubes, in no case gave an anhydride ; in view, however, of the work of Manasse and Rupe (7oc. tit.), it is possible that, sufficient precautions were not taken to prevent the access of moisture from the air during the working up of the product ; further experiments are in progress to decide this point. Whilst, however, no anhydride mas formed on heating the disubsti- tuted adipic acids in sealed tubes with acetyl chloride, it was found that, whether the higher-melting or lower-melting modification was employed, a partial couversion of the one into the other was effected, the product cousisting of a mixture of the two.SimilarlF, n-hen the symmetrical disubstitnted succinic acids (Bischoj'f andAND OF ADIPIC ACID. 1001 Mintz, Ber., 23, 656) are heated in sealed tubes a t 200", in each case a mixture of the two modifications of the acid is formed. A similar conversion can be effected in the case of the dimethylglutaric acids (Zelinsky and Besredka, Ber., 24, 465 ; Auwers and Kobner, Bm., 24, 1933). It remains to refer to the theories which ha-re been advanced to account for the two modifications of these symmetrical az-disnbsti- tuted dicarboxylic acids. From the close analogy between the COZI- stitntioii of a symmetrical az-dialkylsuccinic acid and that of a tartaric acid, each containing a pair of asymmetric carbon atoms, according to one view (Bischoff and Walden, Ber., 22, lS19), it has been held that any t wo isomeric symmetrical disubstituted succinic acids correspond to the two inactive taytaric acids, the one being inactive through intramolecular compensation of right- and left- handed groups, whilst the other consists of a mixture of equal quantities of the active right- and left-handed acids.I f this is so, it should be pGssible to resolve one or other of the two substituted succinic acids into tm-o wtire constituents. The chief objection which this theory bas t o meet is that hitherto in no case has this resolution into active forms been accomplished, although repeated attempts have been made in the case of the substituted succinic acids (Bischoff and Walden, Zoc.cif.). As a result of this failure, a theory has been ~ i d e l y entertained of late, which draws an analogy between the saturated molecules of two isomeric symmetrical disubstituted succinic acids and the unsatui-ated moiecules of fumaric and mde'ic acids. According to this view, it is held that whilst, in general, a singly-bound atom or group can freely rotate, yet, under some circumstances, certain saturated molecules can be fixed in different phases. Thus, it is held that the disubsti- may exist in two so-called stereo- CHR*COOH CHR8*COOH tuted succiiiic acids I chemical isomerides, of which the acid of lower-melting point usually gives an anhydride, and is therefoise called the maleino'id or cis modification, whilst the acid of higher-melting point is incapable of forming an anhydride, and is named, on that account, the fumaroid or trans-modification.These two modificatrions may be represented thus. ? I3 R+COOH R e F-COOH R-7 COOH COOH-7 .Lt H H Xaleinoyd or cis. Fumaroi'd or trans. The isomerism in question, therefore, according to this view, VOL. T4XV. 4 B1002 LEAN : HOMOLOGUES OF BUTANETETRACARBOXYLIC ACID depends on the fixation of carbon atoms united by single bonds, and the acceptance of this view involves the removal of one of the f andamental ideas of van't Hoff s theory. A third theory-known as the theory of dynamicnl isomerism-has been advanced by Bischoff (Ber., 23, 624)) but as the compounds which led him to adopt it have since been found not to exist (Auwers and Jackson, Be,.., 23, 1606), it has not met with general acceptance.It only remains to add, before proceeding to describe these derivatives i n detail, that no attempt has yet been made t o resolre any of the diallqladipic acids iiito active forms. FH2*CH(COOH)? Bictcr n e f et 1-u ca ~.toxyl ic acid, c H?.C H ( c o OH) ?' As it appeared interesting to endeavour to obtain this acid for comparison with the other tetracarboq-lic acids described in this paper, pure ethylic butanetetracarboxylate (1 mol.) was hydrolysed by boiling it for six hours with a solution of barium hydroxide (8 mols.), and the crystalline precipitate of the barium salt collected upon a filter, washed with water, and decomposed with sulphurio acid. After the slight excess of sulphuric acid had been carefully precipitated Kith barium hydroxide, the clear aqueous solution of the carboxylic acid was evaporated first on the water-bath, and then o-rer sulphuric acid ; in two daj-s, it had crystallised in part in a mass of prismatic needles.These >>-ere separated from the mo ther-liquor, spread on a porous tile, and after drying further over sulphuric acid, were found to melt gradually between 140" and 160". 0-1618 gave 0.2520 C02, and 0.0722 H,O ; C = 48.47 ; H = 4-88. CBHl,,OR requires C: == 41.03 ; H = 4.27 per cent. CiH,,06 ,, C = 44.21; Ii = 5.26 I , As the analysis appeared to indicate that a mixture of the tetra- carboxplic and tricarboxylic acids had been formed, an attempt was made to isolate the tetracarboxylic acid from the mother liquor re- ferred to above.The aqueous solution mas evaporated further notil a second crop of crystals had been deposited; the small quantity of mother liquor still remaining was poured off from this, and erapor- ated over sulphuric acid until it had completely solidified tc a porce- lain-like mass; this product was fontid to melt gradually, and erolved carbonic anhydride between 115' and 148" ; at the latter temperature adipic acid melts, being formed from the carboxylic acids by elimination of carbonic anhydrideAND OF ADIPIC ACID. 1003 0.1567 gave 02471 C02, and 0.0734 H,O ; C = 43 000; H = 5.20 per ceut. A silver salt was prepared by pouring a neutral solution of the am- monium salt into a large excess of silver nitrate solution and shaking well ; the white precipitate was collected on a filter, well mashed, and dried first on a porous tile, and then over sulphuric acid. 0.3022 gave 0.1921 silver ; Ag = 63-06.0.1074 ,, 0.0953 CO, and 0.0211 H,O ; C = 15.15 ; H = 1-36. C,H608Ag4 requires Ag = 65.23 ; C = 14.50 ; H = 0.91. C,H,O,Ag, ,, Ag = 63.40; C = 16.44; H = 1.36. It appears, therefore, that the butanetetracarboxylic acid, obtained by the hydrolysis of its ethylic salt wit'h excess of barium hydroxide, is somewhat unstable, and tends t o part with one molecule of carbonic anhydride, with formation of butanet,ricarboxylic acid. This instability of bntanetetracarboxplic acid is in accordance with the character of its homologues. Conrad and Eischoff (Annalen., 214, 71) have shown that ethanetet'racarboxylic acid on hydrolysis with potassium hydroxide gives ethanetricarboxylic acid ; Buchner (Ber., 25, 1157), however, found that the stability of the acid depends much on the concentration of the alkali, and if dilute sodium hydroxide be used, ethanetetracarboxylic acid may be isolated. Propanetetracarboxylic acid has been obtained by Kieber (Annalen, 246, 107), who found that on slightly warming the aqueous solut.ion of the acid, i t is decomposed with evolution of carbonic anhydride.The hydrolysis of ethylic butanetetracarboxylate with alcoholic potash 'has been carried out by Perkin (Trans., 1887, 51, 19), and there was evidence of a partial conversion of the tetracarboxylic acid into the tricarboxxlic acid ; Perkin and Prentice (Trans., 1891, 59, 824), when hydrolping ethyiic pentanetetracarboxylate with alcoholic potash, obtained a similar result.This mixture of butanetetracarboxylic acid and butanetricarboxglic acid is extremely soluble in water, giving a solution of intensely acid character. It is also very readily soluble in ether, and i n methylic or ethylic alcohol, b u t insoluble in benzene, toluene, or light petroleum. A neutral solution of the amrnoninm salts gives but a slight precipi- tate in the cold with barium chloride: on boiling, however, a copious white crptalline precipitate of the monobarium salts is thrown down. Calcium chloride gives no precipitate in the cold, but the calcium salts are precipitated on boiling, and dissolve again partially on cooling. Ferric chloride and copper acetate give no yrecipitats.1004 LEAN : HONOLOGUES OF BUTASETETRACARBOSYLIC ACID yH2.CNe (COOE t)2 CH,*CJle(COOEtj,' A, Ethylic Dimetl~ylbzcta.lzetetracarbo~ylate, The quantities used in the preparation of this substance were- Ethylic butanetetracarbosylate .. . . . . Sodium dissolved in 60 C.C. alcohol.. . . 4.6 ,, Methylic iodide . . . . . . . . . . . . . . . . . . . . ,, 35.0 grams 28.4 The etbylic butanetetracarboxylate wits dissolved in the sodium ethoxide, and the methylic iodide added slowly, since much heat is developed ; it was then heated on the water-bath, using a reflux con- denser, for about two hours, until it no longer gave an alkaline reaction. Water was then added, the product evaporated, extracted with ether, and the ethereal solution dried with calcium chloride. On distilling off the ether, and allowing the resiliual oil to stand some days, ethylic dimethylbutanetetracarboxylate crystallised out in beautiful prisms.It was collected on a filter, and washed with a little ether. For analysis, a portion was dried at loo", and allowed t o solidify. C = 5'7.75 ; H = 8.04. 0.1553 gave 0.3290 GO, and 0.1184 H?O. C,8H,0s requires C = 57-75 ; H = 8-02 per cent. The mother liquors from this substance, on standing, deposited a less pure product, which was used in the subsequent preparation of the dimethyladipic acids. Ethylic dimethylbutanetetracarboxylate crystallises in beautiful, thick, four-sided prisms, melts at 54", and is readily soluble in ether, methylic and ethylic alcohols, benzene, and toluene. It dissolves Peadily in m-arm light petroleum, and crystallises out again on cooling.Dirneih y 1 b 21 tanetet racaihxtJl ic acid, yH2*CMe(COOH)2 CH,*CBIe (C OOH),' Ethylic dimethylbutanetefracarboxylate is not readily hydrolpsed by barium hydroxide ; iii order to prepare the acid, the pure ethereal salt (1 mol.) was digested for three hours with an excess of a solution of pure potassium hydroxide (6 niols.) in methylic alcohol, in a flask connected with a reflux condenser. The product was evaporated nearly to dryness, mixed with w-ater, the solution again evaporated to a small bulk to remove the last traces of alcohol, acidified with hydro- chloric acid, and extracted four times with pure ether. On distilling off the ether, the dimethylbutanetetracarboxylic acid was left as a yellowish crystalline mass; this was purified by dissolTing it in a little water, and allowing the solution to eraporate slowly over sulphuric acid in a vacuum, when the pure acid gradually crystallisedAND OF ADIPIC ACID.1005 out as a mass of minut'e white needles. These were collected; dried on ill porous tile, and over sulphuric acid in a vacuum, and analysed with the following result. 0.1014 gave 0.1698 CO, and 0.0528 HzO ; C = 45.67 ; H = 5-78. C,,H,,O, requires C = 45.SO; H = 5-35 per cent. Dimethylbutanetetracarboq-lic acid is deposited as a felted mass of minute needles on slowly evaporating its concentrated aqueous solution. It decomposes at 200" with evolution of carbonic an- hydride, is readily soluble in ether and in methylic or ethylic alcohol, bnt insoluble in benzene, toluene, and light petroleum, The basicity of the acid was determined by titration with deci- normal solutions of potassium hydroxide and hydrochloric acid.0.1763 gram of substance required 0.1480 gram of KOH for neutra- lisation, phenolphthaleyn being used as the indicator : the final colour change was sharp. Aquadribasic acid of the formula CGH,,(C0OH), re- quires 0.1.507 gram of KOHtoform a salt of thef~rrnulaC,H~,(COOK)~. On adding one or two drops of litmus solution to the solution of the quadribasic salt, which was neutral as indicated by phenolphthaleyn, there was n very distinct blue coloration, which only gradually became red on running in hydrochloric acid. It appears, therefore, that dimethylbutanetetracarboxylic acid forms quadribasic salts, which are neutral to phenolphthaleln, but alkaline to litmus.Silver Sa7t, C,oH,oO,Agl.-The acid was dissolved in dilute ammonia, and the solution placed oTer snlphuric acid in a vacuum. As soon as it was only slight])- alkaline to litmus i t was poured into a large excess of silver nitrate solution in a flask, and the mixture well shaken. The white precipitate was coIlected on a filter, well washed with wItter, and dried on a porous tile and over snlphuric acid in a vacuum. Analysis proved the salt to be quadribasic. 0-1048 gave 0.0650 Ag ; Ag = 62.02. CloH,008Ag4 requires Ag = 62.60 per cent. If a solution of calcium chloride is added to a cold neutral solution of the ammonium salt no precipitate is formed, but on heating a crystalline precipitate of the calcizcm salt is thrown down.~H,*CHXe.COOH CH2*CH31e.COOH' Dime f 11 y lad iu ic n c ids, When heated with sulphuric acid, ethylic dimethylbutanetetra- carboxylate is readily hydrolysed, but at the same time it loses '2 mols. of carbonic anhydride and yields a mixture of dimethyladipic acids. The ethereal salt was therefore heated on a sand-bath in a reflux1006 LEAN : HOMOLOGUES OF RGTAKETETRXCARBOSYLIC ACID apparatus with equal parts of salphuric acid and water for about three hours. On allowing the mixture ta cool, a considerable quantity of dimethyladipic acid crystallised out. Isolation of the modijicatim. of higher-melting poid.--l'he acid which had crystallised on cooling was washed with a little water, dis- solved in a solution of sodium carbonate, boiled with animal charcoal, and filtered; the filtrate was then acidified with hydrochloric acid, and the dimethyladipic acid which separated, collected on a filter.mashed with a little water, and recrystallised from water. This acid melted at 130--135O, and 8:s it was found to be only sparingly soluble in boiling benzene, it, was digested two or three times with small quantities of boiling benzene, and the benzene solution in each case poured off as completely as possible. The acid which still remained undissolved was recrystallised from water, and dried a t 100". It was then found t o melt sharply at 142". Analysis showed it to consist of pure dimethyladipic acid. 0.1504 gave 0.1129 H,O and 0-30.53 CO, ; C = 55.36 ; H = 8-34. C,Hl,Oa requires C = 55.18 ; H = 8.04 per cent. This acid has already been prepayed by Zelinsky (Bey., 24, 3997), by the hydrolysis of ethylic dicyanodimethylndipate.Isolatiou of the modificafiosL of lower-nzeltiiLg point.-The hot benzene solutions obtained in the isolation of the modification of dime thyl- adipic acid d higher-melting point, on cooling, deposited crystals which consisted chiefly of this modificat)ion. When these were removed, and the benzene evaporated on the water-bath, a yellowish, viscid oil was obtained, which crystallised completely on cooling, and melted at 80-90". It was digested with a small quantity of cold benzene, the solution filtered from undissolved matter, and the benzene evaporated ; the crystalline residue, on being again submitted twice to the aaine treatment, left a nearly colourless crystalline mass which melted at 70-72", arid was found by analysis to consist of pure dimethyladipic acid.0.1383 gave 0.2805 COz and 0.1028 H,O ; C = 55.31 ; H = 8.26. C,H,,04 requires C = 55.18; H = 8.04 per cent. Zeliosky ( Zoc. cit.), who separated the two isomeric dimethyl- adipic acids by recrystallisation from water, gives the melting-point of this dimethyladipic acid as 74-76'.* * Since the print,ing of the thesis, Zitzing (Ber., 27, 1578 ; 1894) has described the preparation of ethylic diinethylbutanehetracarboxylate by the action of etbylenic dibromide on the monosodium derivative of ethjlic meth~lmalonate, and he has pre- pared froin it climethylbutanetetmcarboxylic acid and two diinethjladipic acids.ASD OF ADIPIC ACID. 1007 yH2*CE t ( C 0 OE t).- CH,-CEt( COOEtj2' B.Ethylic Diethylbutnuetetracnrboxylate, The following quantities xere employed in the preparation of this substance : Ethylic butanetetracarboxylate.. . . . . Sodium dissolved in 120 C.C. alcohol . 9.2 ,, Ethylic iodide.. . . . . . . . . . . . . . . . . . . ,, 70.0 grams 70.0 The ethylic butanetetracarboxylate was dissolved in. the sodium ethoxide, and the ethylic iodide added cautiously with constant cooling, as much beat is evolved; the mixture was then heated for two hours on the water-bath, using a reflux condenser, and to ensure the completion of the action a little more ethylic iodide was added, and the digestion continued for two hours longer. The product, mixed with water and evaporated to remove alcohol, gave a beautifully crystalline cake on cooling; this was separated from the mother liquor, dissolved in ether, and the ethereal solution, after being well washed with water, was dried with calcium chloride.On slowly evaporating the ethereal solution, the ethylic diethyl- butanetetracarboxylate separated in fine silky needles. For analysis, the ethereal salt was recrystallised from ether, heated in n steam-oven to fusion, and allowed to solidify. 0.1307 gave 0.2865 CO, and 0.1030 H20 ; C = 59-78 ; H = 8.76. C,,,H,O, requires C = 59.iO ; H = 8.45 per cent. Ethylic diethylbutanetetracarbosylate crystallises from ether in fine silky needles, which melt a t about 93-94". It is readily soluble in hot methylic or ethylic alcohol, and cq-stallises out, on cooling, in fine needles. i t is also readily soluble in cold benzene and toluene, and crjstallises well from hot light petroleum.H?*CE t (C 0 OH) 3 niethylb2ctanetet.l.ncclrbowyli6 ncid, CH,.CEt(COOH),' Diethylbutanetetracarboxylic acid was obtained by the hydrolysis of its ethereal salt with barium hydroxide. As this takes place witk some difliculty, the ethylic salt v-as heated with twice the theoretical amount of barium hydroxide, for two days on the sand-bath, using a reflux condenser ; dwing the action, a strong menthol-like odour was observed. When the hydrolysis was complete, the heavy crystalline precipitate of barium diet h j-lbutanete t racarbox ylate was collected, and, after being washed with a little water, was ground up, suspended in water, and boiled for two hours with a slight excess of snlphuric acid so as to set free the diethylbutanetetracarboxylic acid.The1008 LEAK : HOMOLOOUES OF BUTANETETRACARBOSPLIC ACID excess of snlphnric acid was exactly precipitated with barium hydl=- oxide, and the aqueous solution evaporated to a small bulk on the water-bath ; as the concentration proceeded, the acid crystallised in beautiful slender needles ; these were collected on a filter, n-ashecl with a little water, and spread on a porous plate. On determining their melting-point, the acid frothed up in the capillary tube, and decomposed at 207-209". After recrystallisation from water, the decomposing-point mas unchanged. For analysis, the crystals were dried at looo. 0.1442 gave 0.2619 CO, and 0*0850 H,O ; C = 49.53 ; H = 6.34. C12Hl,0e requires C = 49.66; H = 6-20.It is remarkable that dieth ylbntanetetracarboxylic acid is only sparingl-j- soluble in ti-ater, whei-eas the corresponding dimethyl- butanetetracarboxylic acid is so very readily soluble. It crystallises from its hot aqueous solution in needles, which decompose at 207-209", with evolution of carbonic anhydride ; it is soluble in ether, benzene, toluene, and light petroIeum, and readily in methylic o r ethylic alcohol. The basicity of the acid was determined by titrakion with deci- normal solutions of potassium hydroxide aiid hydrochloric acid. 0-2139 gram of acid required 0.0850 gram of KOH for neutralisa- tion, using litmus ; litmus proved, however, a very unsatisfactory indicator, as, after dissolving the acid in excess of alkali, on titrating back with hydrochloric acid, the blue t i n t changed only gradually to red.An acid of the formula C,€€l,(COOH)i would require 0.0826 gram of ROH to form the bibasic salt, C,H,4(COOH>,(COOK),. A determination was also made in which phenolphthalein was used as the indicator. 0.2114 gram of acid required 0.1656 gram of KOH for neutralisa- tion. An acid of the formula C8H14(COOH),, would require 0.1632 gram of KOH to form the quadribasic salt, C8H,4(COOK),. The solu- tion of the acid in potassium hydroxide, after it had been neutralised with hydrochloric acid a s shown by phenolphthale'in, \\-as colourecl distinct1~- blue on the addition of one or two drops of litmus solution. It appears, therefore, that diethylbutanetetracarboxylic acid, like dimethylbutanetetracarboxylic acid, forms yuadribasic salts, which are neutral to phenolphthaleh, but alkaline to litmus, the bibasic salt being neutral t o litmus.SiZcer saZt, C,,H,,O,Ag,.-This was prepared exactly in the manner described on p. 1005, but i t was found impossible to analyse it by ignition in a combustion furnace OF in a crucible, as it decomposes with a rapidity which is almost explosire. The silver was therefore estimated as silrer chloride. Analysis proved the salt to be quadri- basic.AND OF ADIPIC ACID. 1009 0.1180 gave 0.0935 AgCl ; Ag = 59.57. C,,H1608Ag2 requires Ag = 42-86 per cent. Cl,H1408Ag4 ,, Ag = 60.17 per cent. The silver salt decorYposes slowly on exposure to light. Calcium salt, ClZHl4O8Ca2 + 5H,O (?).--If calcium chloride is added to a cold neutral solution of ammonium diethylbutanetetra- carboxylate there is no precipitate, but, on boiling, a white micro- crystalline precipitate of the calcium salt is at once thrown down ; this was collected on a filter, and dried on a porous plate.For analysis, the salt was dried by exposure to the air for four days. As the quantity available for analysis w-a s veyy small, it was impos- sible to determine the water of crystallisation accurately. An estima- tion of the calcium proved the salt to be tetrabasic, and indicated that it probably contains 5 mols. of water of crystallisation. Heated at l50", the calcium salt lost more than 15 per cent. in weight, through the elimination of a portion of its water of crystallisation. It did not decompose when heated to 160".0.1083 gave 0.0630 CaSOl ; Ca = 17.11. CV2HI6O8Ca requires Ca = 12.19. C12H1408Ca, + 5 H,O requires Ca = 17-54 ; H,O = 19.53 per cent. $lH,.CHEt*COOH C H,. C HE t - C 0 0 H ' Diet 7) yladipic acids, In order to prepare these acids, the pure diethylbutanetetracarb- oxylic acid was heated in an oil-bath at 210" until the evolution of carbonic anhydride had completely ceased. On cooling, the product solidified to a brownish crystalline cake. Isolation of the modijicatioiz oj* h i g h e r - m e l t i q poiiit.-This brownish, product was digested with boiling water, filtered while hot, and allowed to cool, when R considerable quantity of diethplndipic acid crystallised out in fine white ueedles ; this, when separated from the mother-liquor, and dried on a porous plate, was found to melt at 122-129" ; after three more crystallisations the crystals melted sharply at 136", and the melting-point was not altered by further crystallisation.An analjsis proved it to be pure diethyladipic acid. 0.1503 gave 0.3257 CO, and 0-1178 H,O ; C = 59.10 ; H = 8.70. C,oH,80, requires C = 59.40 ; H = 8-92 per cent. liolation of the rnodzlficatioii o.f lower-melting point.-This proved to- be a matter of greater difficulty. The aqueous mother-liquors, ob- tained in the isolation of the acid melting at 136", were extracted three times with ether, and the ethereal solution evaporated; the yellowish oils residue after R time deposited a few stellate groups of1010 LEAN : HOJIOLOGUEr> OF BUTANETETRACARBOSYLIC ACID crystals, and at the end of two days the oil had completely solidi- fied.A small portion, after dyying on a porous plate, was found to melt at 55-103". The solubilities of this crude product, and of the pure acid melting at 136", in various solvents, were then carefully compared, and it was found that the former was readily soluble in cold benzene, whilst the acid melting at 136" was only sparingly soluble in boiling benzene. Accordingly, the crude acid melting at 55-105" was ground up and digested with cold benzene, and the solution filtered from a small quantity of undissolved acid, which, after drying, melted at 130-132". The benzene solution eraporated on the water-bath, yielded a yellowish viscid mass, which crystallised when exposed over sulphuric acid in a racuum; it melted at 45-60' after it had been left on a porous plate for a time.The product was again digesLed with cold benzene, and the solution worked up in the same manner; on ikepeating the process, using little more than its own volume of benzene, a crystalline mass was finally obtained which melted at 45-46'. As the acid had still a yellowish tint, an attempt was made to purify it by means of the calcium salt. The acid x-as therefore digested with a large volume of lime water, and after carbonic anhydride had been passed through the solution, the filtrate was concentrated until the greater portion of the calcium salt had crystallised, arid only about 2 C.C. of yellowish mother- liquor were left. The crystalline salt was collected on a filter, and washed with a little cold water.To obtain the pure diethyladipic acid, the calcium salt was dissolred in water, decomposed with hydro- chloric acid, and extracted with ether; the ethereal solution when dried over anhydrous calcium chloride, eraporated, and exposed in a vacuum over snlphuric acid, left a colourless oil which gradually solidified to a mass of characteristic stellate groups of acicular cry- stals melting at 51-53'. For analysis, the acid was heated to fusion in a steam-oven, and allowed to solidify. 0.1218 gave 0.2631 CO, and 0.0987 H,O ; C = 58.91 ; H = 9-00. CloH,,O, requires C = 59-40 ; H = 8.92 per cent. Properties of t h e Diethytad+& acid melfiwg at I3G".-This acid crystallises in six-sided prisms of the following form.AND OF ADIPIC ACID. 101 1 The silver salt, C,,,HI6O4AgZ, was formed by dissolving the acid in slight excess of ammonia, and, after removing this excess by eva- poration over snlphnric acid, adding excess of silver nitrate solution, when the silver salt was thrown down as a voluminous white precipi- tate.This was collected on a filter, washed with water, and dried first on a porous plate, and then over sulphuric acid in a vacuum. 0.1644 gave 0.0848 Ag ; Ag = 51.58. C,,HI6O,A~ requires Xg = 51.92 per cent. The caZcium sall, C10H1601Ca 4- 2H20, was also prepared by dissolv- i n g the acid in a large quantity of water, adding excess of calcium hydroxide, and boiling the solutioa ; the excess of calcium hydroxide was removed by passing carbonic anhydride through the solution, which was again boiled, filtered, and evaporated on the water-bath ; as the concentration proceeded, calcium diethyladipate crystallised out in beautiful white prisms.I t was dried by exposure to the air for five days. 0.3155, on drying rtt 150°, lost 0.0398 H,O; the auhydrous salt so obtained gave 0.1613 CaS04; H,O = 12.61 ; Ca = 15.03. CloH,,O,Ca + 2H20 requires H20 = 13.04 ; Ca = 14-49 per cent. Unfortunately too little of the salt was left to allow of a second analysis. The calcium salt is rery sparingly soluble in water. Properties of the Dielhyladiyic acid meltiwg about 51--53".-This acid crystallises after fusion in large sub-octahedral masses, com- posed of interlacing needles, of the following form. The formation of the cnl(*izciit salt has already been described. It is more soluble in water than the calcium salt of the isomeric acid, which melts at 136".The silver salt, CloH1604Ag2, mas formed by the double decomposition of the aqueous solution of the calcium salt with silver nitrate solution ; the precipitate, after being well washed, was dried on a porous plate and in a vacuum over sulphuric acid. 0.2450 gave 0.2535 CO,, 0.0852 HZO, and 0.1276 Ag ; C = 28-22 ; CI,,H,,O,Ag2 requires C = 2384 ; H = 3.84 ; Ag = 51.92 per cent. H = 3.86; Ag. = 52-07.1012 LEAN : HOMOLOGUES OF BUTAXETETRACARBOSTLIC ACID The solubility of the two modifications of adipic acid in various solvents may be conveniently recorded in tabular form. Solvent. Ether . . . . . . . . . . . Methylic alcohol.. Ethglic alcohol . . . Benzene . . . . . . . . . Toluene. .. . . . . . . . Light petroleum . . Water.. .. .. .. .. Solubilities of the two diethyladipic acids. Diethyladipic acid melting a t 136'. Readily soluble in the cold. Readily soluble in the cold. Readily soluble in the cold. Very sparingly soluble ; soh- ble in a large qiiantity of boiling benzene, and preci- pitated in minute needles on cooling. Sparingly soluble in the cold ; reaciil? soluble in hot toluene, and partially pre- cipitated in crystals on cool- ing. Insoluble men on boiling. Soluble in much cold water; crystallises from a little hot water on cooling. Diethyladipic acid melting a t 51-53'. Readily soluble in the cold. Readily soluble in the cold. Readily soluble in the colci. Readily soluble in the cold. Readilp soluble in the cold- Soluble with difficulty om boiling, and partiall:- pre- cipitated in very minute needles on cooling.Readily soluble in the cold. Attempt fo pi-epare Etliy l i c SToiiethlllbz~fanetetmcccl-Eo,z.2/late, CH2*CE t (C OOE t)z 7 H2.C H (C 0 OE t ) 2 In this communication, the preparation of several disubstituted derivatives of ethylic butanetetracarboxylate is described, and it appeared of interest to ascertain whether monosuhstituted deriva- tives would be obtained if the monosodium derivative of this sub- stance mere employed. The following quantities were tdie11- Ethplic butanetetracarboxylate . . . . . . Sodium dissolved in 30 C.C. alcohol . . . Etbylic iodide. . . . . . . . . . . . . . . . . . . . . 35.0 grams. 15.6 2.3 ,, ,, The etb ylic buta~etetracarboxylate was dissolved in the sodium ethoxide, and the ethylic iodide added gradually ; a t first there was little evolution of heat, but, on shaking.the mixture became quite hot. It was heated on the water-bath for 2+ hours, using a reflux condenser, the product evaporated on the water-bath, water added, and the evaporation repeated. The residue was then extractedASD OF -4DIPIC ACID. 101 3 three times with ether, the ethereal solution washed with water, de- hydrated with calcium chloride, and the ether evaporated first on t,he water-bath, and finally by exposure in a vacuum. I n this way, about 35 grams of a yellowish oil were obtained, which deposited about 10 grams of ci-ystals ; these were separated from the mother- liquor by filtration with the pump, and freed from oil by spreading upon a porous plate.The product melted a t 92-93', and after repeated crystallisation from methylic alcohol the melting point re- mained constant at 93-94". On analysis, it proved t o be ethylic &ethylbut anetetracarboxylat e, co~~esponding with i t in me1 ting-point, crystalline form, and every other respect. 0.1641 gave 0.3601 COe and 0.1246 H,O ; C = 59*84; H = 8-43. CI,H,,O, requires C = 57.75 ; H = 8.02. C,,H,,O, 7 , C = 59.70; €3 = 8.4.5 per cent. It is evident, therefore, that the main product of the action was the diethyl-, and not the moiiethyl-derivative of ethylic butanetetra- carboxylat e. To determine the nature of the 25 grams of yellowish oil from which -the ethylic diethylbutanetetracarboxylate had crystallised, and which should consist, if the above conclusion is correct, of unchanged ethylic butanetetracarboxylate, together with a certain amount of its diethyl derivative in solution, the oil was hydrolysed with barium hydroxide.The 25 grams of oil were boiled with a concentrated solution of 75 grams of barium hydroxide for two day8 ; a slight excess of sulph- uric acid was then added to liberate the organic acids, and the filtered solution extracted 20 times with ether. The lasi; 15 extracts mere worked up together, and, after evaporating the ether, gave a nearly-colourless oil, which crystallised on standing. This product was heated at 210" in an oil-bath until the evolution of carbonic anhydride had ceased, and the residual dark-coloared oil, which solidified on cooling, after being spread on a porous plate, was dis- solved in a little hot water, and allowed to evaporate slowly over sulphuric acid ; the colourless crystalhe deposit lvhich formed W&S collected, and dried over sulphuric acid.It melted at 148", and consisted of pure adipic acid, as is shown by the following analysis. 0*1&1 gave 0.2613 GO, and 0.0901 H,O ; C = 49.45 ; H = 6.94. It appears, therefore, that, under the conditions employed, ethylic monethylbutanetetracarboxylate is not formed, the interaction, on the contrary, giving rise to e thplic diethylbutanctetracarboxylate, one half of the ethylic butanetetracarboxylate remaining unchanged. C,H,,-,O, requires C = 49.31 ; H = 6.86 per cent.1014 LEAN : HOMOLOGUES OF BUTANETETRACARBOSTLIC' ACID CH2.C (CicH,) (C OOE t)z CH*2C (C,,H,) (COOE t)z' C.Ethylic D~cetytbutanetetracarbc,x?lEate, I The following quantities were used in the preparation of t h i s sn bstance , Ethylic butaiietetracarboxylnte . . . . . . Sodium dissolved in 120 C.C. alcohol . . 4.6 ,, Cetylic iodide.. . . . . . . . . . . . . . . . . . . . ,, 35.0 grams. 76.0 The ethylic butanetetracarboxylate was dissolved in the cold solu- tion of sodium ethoxide, the cetj-lic iodide added cautiously, and the mixture well shaken ; no appreciable rise of temperature occurred ; the mixture was then heated for six hours on the water-bath, using a reflnx Condenser. After cooling and standing orer night, a consider- able quantity of a crystalline pan-der had separated. The contents of tbe flask were mixed with water, gently heated on the water-bath to remove alcohol, and then extracted four times with ether.The ethereal extract was washed with water, dried with calcium chloride, and the ether distilled off, when about 60 grams OF a dark oily liquid remained ; this, after some days, deposited a considerable quantitj- of a yellowish, soap-like mass, which was separated from the oil by aid of the pump, spread upon a porous plate, and crystallised once o r twice from light petroleum. The ethylic dicetylbutanetetracarb- oxylate was thus obtained pure in glistening white crjstals. For analysis, the crystals were heated to 100". 0.1092 gave 0 2908 COz and 0.1117 HzO ; C = 72.62 ; H = 11.i-36, CpeH,,Oe requires C = 72.54; H = 11.33 per cent. Ethylic dicetylbutanetetracarboxylate crystallises from light re- trolenm in small, four-sided plates, which melt a t 69.5".It is readily soluble in ether, benzene, and toluene, and in hot light petroleum, glacial acetic acid, and rnethylic or ethylic alcohol; on cooling, it crystallises again from all these solvents. To prepare this acid, piire ethylic dicet~-lbutanetetracarboxyl~~te (1 mol.) was digested for about four hours with an excess of a solution of pure potassium hydroxide (6 mols.) in hetbylic alcohol, in a flask connected with a reflux condenser. After standing over night, a quantity of potassium dicetylbutanetetracarboxylate had crystal- lised out; this was ccllected, dissolved i n hot water, and acidified with hydrochloric acid, when dicetylbuOanetetracarboxylic acid sepa- rated as an oil, which, on cooling, solidified to a hard, white, non-AND OF ADIPIC ACID.1015 crystalline cake. To free the acid from traces of potassium chloride, the cake was kneaded with a little water, extracted with ether, and the ethereal solution washed with water. After remora1 of the ether by evaporation, and drying by exposure in a vacuum over sulphnric acid, pure dicetylbut'anetetracarboxylic acid was obtained as a beautiful, white, non-crystalline mass. It was found necessary t o follow the above method, starting with pure material and utilising only the purest products, in order to prepare p i r e dicetylbutanetetra- carboxylic acid, as no solrent was found by means of which the crude acid could be purified by crystallisation. On analysis- 0-0990 gave 0.2552 CO, and 0 1007 H,O ; C = 70.30; H = 11-li.C,HirOa requires C = 70.38 ; H = 10.85 per cent. A further quantity of dicstylbutanetetracarboxylic acid, snfficientlF pure for subsequent operations, was obtained from the crude dark- coloured oily product, referred to as being obtained in the course of the preparation of pure ethTlic dicetylbutanetetracarboxylate. After hydrolysis of the oil with alcoholic potash, water was added, and the alcohol removed by evaporation on the water-bath. On cooling, almost the whole of the potassium dicetylbutanetetracarboxylate separated as a yellow saponaceous mass, which was freed from cetylic iodide, cetylic alcohol, cetene, and other impurities, by repeatedly digesting it with ether until it became almost colourless. The free acid obtained from this potassium salt was an almost colourlesa mass. Dicetylbntauetetracarboxylic acid is a white soap-like body, which has not been obtained in a crystalline form.It does not possess a, sharp melting-point, melting gradually between 80" and YO", and when heated to 150", decomposes with rapid evolution of carbonic anhydride. It is readily soluble in benzene, toluene, light petroleum, ether, and glacial acetic acid, insoluble in w&ter, and concentrated hydrochloric and hydrobromic acids. It is readily soluble in cold ethylic alcohol, bnt in methylic alcohol its solubility varies extra- ordinarily within a very small range of temperature. Thus, whereas at 23", 100 grams of methylic alcohol will dissolve 4.2 grams of the acid, at 19" only 1.9 grams of the acid are retained in solution.The basicity of the acid was determined by titration with d&- normal solutions of potassilm hydroxide and hydrochloric acid. 0.2141 gram of substance required 0.0701 gram of ROH for neutralisation, phenolphthalein being used as the indicator. A quadribasic acid of the formula CA0H7,Oe would take 0.0703 gram of KOH to form the quadribasic salt C,,H7,(COOKj,. On adding 1 or 2 drops of litmns solution to the solution of the qnadrib&c101 6 LEAN : HOVOLOGUES OF BUTANETETRACARBOSYLIC ACID salt, which was neutral as indicated by phenolphthale'in, a very distinct blue coloration appeared, which only gradually became red as hydrochloric acid was run in. It appears, therefore, that dicetylbntanetetracarbosylic acid, like diethyl- and dimethyl-butanetetracarboxylic acids, forms quadribnsic salts, which are neutral to phenolphthalexn, but alkaline to litmus.Salts of ~icetylbiita?ietef~.nca~.boxylic acid.-In connection with the results obtained when determining the basicity of the acid, it appeared of interest t o examine some of its salts. Calcizcnz saZt, C1,Hi2OaCa.-The acid was dissolved in dilute ammonia, and the excess of ammonia removed by et.aporation, until the solution was but very slightly alkaline to litmus; excess of calcium chloride was then added, and the mixture well shaken. The white precipitate, collected on a filter, mashed with water, and dried on a porous plate, was freed from a trace of colouring matter by crystallising it from boiling ethylic alcohol, from which it separated in needles.For analpis, the salt was dried in the air for six days. (1.) 0.3176 gave 0.0462 CaS04 ; Ca = 4.31. (2.) 0.2887 ,, 0.0424 ,. ,, 4-32. (3.) When heated at loo", the calcium salt slow-ly loses weight, becoming slightly viscid, and undergoes slow decomposition, so that it niay possibly contain water or alcohol of crystallisa- tion. CAoHi20,Cct requires1Ca = 4-83 per cent. I t thus appeam that the calcium salt which is formed under the above conditions is bibasic. It is insoluble in water, somewhat readilp soluble in ether, but only sparingly in ethl-lie alcohol. Silr-er salt, C40Hiz0,Ag2.-The solution of the ammonium salt, Toitich was neutral as indicated by litmus, mas poured into excess of silver nitrate solution, and the mixture well shaken. The insoluble silver salt which was thromx down was collected on a filter, well washed, and dried on a porous plate and over sulphuric acid.0.1068 gave 0.0260 silver; Ag = 24.34. The silver salt formed nnder the move conditions appears, there- It is unstable, and quickly blackens on exposure C,,H,,O,Ag., requires Ag = 24.11 per cent. fore, t o be bihasic. t o light. Pure dicetylbutanetetmcarboxylic acid was heated in an oil-bath at 205O unhil carbonic anhydride was no longer evolved ; on cooling, aAND 01' ADIPIC ACID. 1017 mther brown, non-crystalline cake was formed. With the exception of ether and methylic and ethylic alcohols, it is sparingly solable in the usual solvents ; in niethylic or ethylic alcohol it is readily soluble on warming, separating again in an amorphous form on cooling; consequently the purification and isolation of the two isomeric clicetyladipic acids is a matter of some difficulty.It was found advantageous to purify the mixture of the isomeric acids by digestiorl with ethylic alcohol and animal charcoal ; after filtration, an almost colonrless product separated on cooling, which melted gradually between 30" and 40". Isolation of the motlrjicafio?A of h i g h e ~ meZtiug-point.-The product melting at 30-40" was dissolved in hot ethylic alcohol, and the mass which separated on cooling, after drying on a porous plate and by exposure over sulphuric acid in a vacuum, mas found to melt at 38-42' ; on repeating this treatment, a substance was obtained which melted at 41-43", and subsequent recrystallisation did not raise the melting-point.I. 0.1208 gave 0.3420 CO, and 0.1355 H,O ; C = 77.21 ; H = 12-46. 11. 0.12227 ,, 0.3490 ,, 0.1380 H,O ; C = 77.54; H = 12.49. C4,H,,04 requires C = 77-53 ; H = 12.62 per cent. From the results of the analysis, it appeared that the substance melting at 41-43" was not a dicetyladipic acid, but its ethylic salt, formed by the repeated solution of the acid in hot ethylic alcohol, and .this was rendered the more probable by its behaviour on hydrolysis. To obtaiu the acid itself, the ethereal salt was hydrolysed with alcoholic potash ; the alcohol was evaporated on the water-bath, hydrochloric acid added, and the product extracted with ether ; after washing the ethereal solution with water, the ether was evaporated on the water-bath, and the aThite mass obtained xas dried by ex- posure over sclphuric acid in a vacuum ; the melting-point, namely, 40-43", was scarcely altered, but analysis proved it to be dicetyl- adipic acid.0.1138 gave 0.3203 COz and 0.1267 H,O ; C = 76.76 ; H = 12-37'. C,,H,,O, requires C = 76.77 ; H = 12.46 per cent. IsolafioiA Qf the modCjicatiou r$ lozcei* ~nt.ltisLg-point.-In the isola- tion of the modification of higher melting-point, the substance melting at 3O-4Oo, obtained by heating dicetyl butanetetracarboxylic acid at 210", was dissolved in hot ethylic alcohol ; the mass which separated on cooling melted at 38-42", but the mother liquor, on standing a day o r two, deposited a second crop, which was found to melt at 33-38°. The mother liquor from this was concentrated, and on standing deposited a third crop, melting at 29-343; this was VOL.LXV. 4 c1018 LEAN : HOMOLOGUES OF BUTAXETETRACARBOSTLlC ACID dissolved in a small quantity of alcohol, and the solution, after a time, deposited a pure white amorphous substance, which, when dried, melted a t 32-34". On analysis- 0.1491 gave 0,4188 CO, and 0.1675 H,O ; C = 76.65 ; H = 12.48. C,H,,Oa requires C = 76.7'7 ; H = 12.46 per cent. It is noteworthy that the lower-melting dicetyladipic acid, unlike the modification of higher melting-point, does not appear to form an ethereal salt when repeatedly dissolred in ethylic alcohol, though it is more readily soluble in the latter. YH,*C(C,H,)(COOEt), D. Ethylic Dibeii~ylbzrtnizetetrncar.liolu?llate, CH,*C: (C,H,)( COOEt),' The quantities used in the preparation of this substance were, Ethylic butanetetracarbosylate .. . . . . 35.0 grams. Sodium dissolred in 60 C.C. alcohol . . . Benzylic chloride . . . . . . . . . . . . . . . . . . 4.6 ,) ,, 30.0 The ethylic butanetetracarboxylate was dissolved in the cold solu- tion of the sodium ethoxide ; the benzylic chloride was then cautiously added, and the mixture after shaking became perceptibly warm. The whole was then heated on the water-bath for about two hours, using a reflux condenser to complete the action. The contents of the flask were mixed with water, and distilled with steam until the alcohol and excess of benzylic chloride mere removed ; on cooling, the crystals which gradually separatzd were collected, washed with a little water, and dried on a porous plate.They were then dissolved in ether, the ethereal solution washed with water, dehydrated with anhydrous potassium carbonate, and the ether evaporated until the dibenzyl-derivative began to separate. On standicg, a plentiful crop of small white crystals of pure ethylic dibenzylbutanetetracarboxylate was obtained ; on analysis, 0.1934 gave 0.4830 CO, and 0.1282 H,O ; C = 68.09 ; H = 7.34. C30H3808 requires C = 68.44; H = 7.22 per cent. Ethylic dibenzylbutanetetracarboxylate crystallises in small four- sided tabular crystals. It is readily soluble in boiling methylic or ethylic alcohol, froni x-hich it crystallises on cooling. It is somewhat more sparingly soluble in ether and in light petroleum, from both of which it crystallises on cooling.It dissolves in warm benzene, but does not separate out on cooling. When crystallised from ethylic- alcohol, it melts at 126-127O.AND OF ADPIC ACID. 1019 YH2.C (C7H;) (C 00 H)2 Dibeizzylbzctaiaetet,.aca,.boxylic acid, CH2*C ( C,H7) (C 0 0 H)2* This acid is formed by the hydrolysis of ethylic dibenzylbntane- tetracarboxylate with alcoholic potash. About 36 grams of the pure ethereal salt (1 mol.) were heated for two hours on the water- bath with a solution of 24 grams of potassium hydroxide (6 mols.) in methylic alcohol, in a flask connected with a reflux con- denser. After cooling, and standing over night, a considerable quantity of potassium dibenzylbutanetetracarboxylate separated in the cyystalline form; the alcoholic solution was filtered off, and worked up independently.The crystalline potassium salt was dissolved in water, and concentrated hydrochloric acid added, when the dibenzylbutanetetracarboxylic acid separated in a semi-solid state, and after standing for a short time solidified to a hard white crystalline cake. This was separated from the mother-liquor, washed with water, dried on a porous plate, and purified by repeated crystallisation from 75 per cent. acetic acid, until the melting-point was constant. It was found necessary to crystailise the acid six or seven times. For analysis, the acid was dried on a porous plate, heated at 100" in an air-bath, and finally placed over potassium hydroxide in a, vacuum, to ensure the removal of traces of acetic acid, which were retained somewhat persistently.I. 0.1491 gave 0.3477 CO, and 0.0763 H,O ; C = 63-59; H = 5.68. 11. 0.1483 ,, 0.3450 ,, 0.0754 H,O ; C = 63.44; H = 5.64. 111. 0.1591 ,, 0.3727 ,, 0.0773 H,O; C: = 63.88; H = 5-39. C,,HEI,?0, requires C = 63.77; H = 5.31 per cent. A further quantity of less pure acid was obtained from the alco- holic mother-liquors previously referred to above ; these were mixed with water, and after evaporating on a water-bath until free from alcohol, concentrated hydrochloric acid was added, when the di- bsnzylbutanetetmcarboxylic acid separated as a heavy oil ; this, when extracted with ethzr, kc., in the usual way, left the acid as a thick brownish oil, vhich did not solidify, even aft>er standing for days over sulphuric acid in a vacuum. This crnde acid was, however, sufiiciently pure for conversion into dibenzyladipic acids as described in the next section.Dibenzylbutanetetracarboxylic acid crystallises from dilute acetic acid in beautiful white plates, which, on exposure over potassium hydroxide in a vacuum, slowly lose weight, apparently from loss of acetic acid of crystallisation ; after heating for a few minutes at loo", the acid melts at 166-167", with evolution of carbonic anhydride. 4 c 21020 LEA4N : HOMOLOGUES OF BUTANETETRACARBOXYLIC ACID Heated at 100-105", it is very slowly converted into dibenzyladipic acids. It is readily soluble in cold ether, and in methylic 01- ethylic alcohol, also in hot benzene or toluene, and more sparingly in light pet)roleum, from which it ciystallises on cooling. I t is soluble in hot acetic acid, and crystallises out partially on cooling, but much more completely on the addition of water, as it is very sparingly soluble in water. The basicyty of the acid was determined by titration with decinor- ma1 solutions of potassium hydroxide and hydrochloric acid.0.1800 gram of the acid required 0.0486 gram of KOH for neutra1- isation, as indicated by litmus. An acid of the formula C,,H,,(COOH), would take 0.0974 grain of KOH to form the quadribasic salt, or 0.0487 gram of KOH to form the bibasic salt. A determination was also made in which phenolphthale'in =as used as the indicator. 0.2389 gram of the acid required 0.05'78 gram of ]<OH for neutralieation, as indicated by phenolphthaleln ; OIJ adding a drop or two of litmus to the colourless solution, it was coloured distinctly blue, and two or three drops of NjlO hydrochloric acid were necessary to render the solution neutral to litmus.An acid of the formula C1,H,,(COOH), mould require 0.0646 gram of KOH to form the bibasic salt CISHI,( COOHj,(COOS)z. Whilst, therefore, phenolphthaleh and litmue did not give nbso- lutely identical results, i t appears that dibenzylbutanetetracarbosylic acid tends to forin neut'ral bibasic salts. Salts of Diberizylbufaneteti.ncai.boz y lic acid .-In view of the res ut t obtained on titrating the acid, it was thought advisable to examine Some of its salts, in order to determine whether these were bibasic or quadribasic. Calcizcnz XQZ~, C2?H,,08Ca + 2H,O.-About 2 grams of the acid were boiled with excess of calcium hydroxide, and %he excess of lime precipitated by passing R stream of carbonic anhydride through the solution ; the product was boiled and filtered, and the gltrate evapo- rated to a small bulk.The calcium salt which orystaJlised out was collected in a filter, and dried on a porous plate. For analysis, the salt was dried by exposure to the air for six days. 0.3689, on heating at 110" till constant, lost 0.0286 YzO ; HzO = 7-75. 0.2838 salt gave 0.0788 CaSOj; Ca = 8.1 7. CzzHzoOsCa + 2H20 requires Ca = 8-25 ; H,O = 7.37 i)er cent. The calcium salt, which is formed in the above manner, appears therefore to be bibasic, crystallising probably with 2Hz0. I t loses its water of crystallisation very slowly over sulphuric acid in a vacuum; when heated at 15Go, it gradually decomposes.Si1z.e~ SnZt, CzzHaOsd,a,.-Excess of silver nitrate solution wasAND OF ADIPIC ACID. 1021 added to a neutral solution of the calcium salt The white pre- cipitate was collected on a filter, well washed with wate,', and dried on a porous plate and finally over sulphuric acid. Analysis proved the salt to be bibasic. 0.4038 gave, on ignition, 0.1389 silver ; Ag = 34-40. The same silver salt is obtained on precipitating a neutral solution of the ammonium salt with silver nitrate solution ; it is somewhat soluble in water, and decomposes readily when exposed to the light. CBH,,OsAg, requires Ag = 34-55 per cent. Q H,* C H ( CiHT) .C OOH CH,.CH( CiHi) *COOH Dibenzylndipic acids, The impure oily dibenzylbutanetetracarboxylic acid (p. 1019) was heated in an oil-bath at 200" till all evolution of carbonic anhydride had ceased ; on cooling, the impure dibenzyladipic acid solidified to a crystalline cake.The purification of this crude product, and the separation of the isomeric acids, is a somewhat difficult matter, and is best effected by means of their barium salts. About 14 times the theoretical quantity of barium hydroxide was dissolved in a con- siderable quantity of water, and boiled with the crude dibenzyl- adipic acids for 24 hours. As the barium salts thus formed remain dissolved if the solution is sufficiently dilute, the hot liquid was filtered, and a current of carbonic anhFdride passed through the solution to remove the excess of barium hydroxide. The solution was filtered, the precipitated barium carbonate washed repeatedly with water, and the colourless filtrates concentrated on the water-bath until about one-half of the barium salts present had crystallised out.The glistening white plates thus obtained were rapidly filtered from the mother-liquor (the barium salts are less soluble in hot water than in sold), dissolved in water, and concentrated hydrochloric acid added, when the dibenzyladipic acids were throim down as a white, microcrj-stalline precipitate ; this --as collected on a filter, washed with a little water, and dried on a porous plate ; the melting- point was fonnd to be 190-210". After recrystallising three times from glacial acetic acid, a crop was obtained which melted at 207-211" ; the mother-liquors were concentrated to a small bulk, and the acid which crystallised out again removed ; the filtrate was then heated to boiling, and diluted with hot water until a cloudiness began to appear ; on cooling, crystals were formed, which melted at 153-163".The solubilities of the two crops melting at 207-211" and 153-165" respectively were then compared in several solvents, arid it was found that the one melting at 207-211" was practically insoluble in boiling toluene, whilst that melting at 153-165" dig1022 LEAN : HOMOLOGUES OF BUTANETETRACARBOXYLIC ACID solved readily, and in large measure crysta,llised out again on cooling. To isolate the modification of dibenzyladipic acid of higher melting- point, the crop melting at 207-211" was digested with boiling toluene, and the undissolved acid collected on a filter, washed, and dried; on repeating this process several times, the final product melted constantly a t 211--213". Analysis proved it to consist of pure dibenzyladipic acid. 0.1440 gave 0.3893 CO, and 0.0892 H20 ; C = 73-73 ; H = 6.88. C,H,04 requires C = 73-62 ; H = 6-75 per cent. To isolate the modification of lower melting-point, the product melting at 153-165" was reci-ystallised twice from toluene and then orice from dilute acetic a,cid, when the acid was obtained in beautiful, colonrless prisms melting sharply at 152". It gave the following numbers on rmalysis. 0-1494 gave 0.4028 CO, and 0-0913 H,O ; C = 73.53 ; H = 6.79. C,H,,O, requires C = 73.62 ; H = 6-75 per cent. The mother liquor from the barium salts of the t w o acids gave a much larger quantity of the modification of lower melting-point. Properties of the dibeiizyladipic acid meliing at 211-213".-This acid is deposited from its glacial acetic acid solution in clusters of diamond-shaped crystals of the following form. The siirer salt, C20H2(rOJAg2, which is very stable, was prepared fram the ammonium salt in the same way as the other silver salts (p. 1011). It gave the following numbers on analysis. 0.2056 gave 0.0821 silver ; Ag = 39.93. C,,H,,0aAg2 requires Ag = 40.00 per cent. Properties of t h e dibeiizyladipic acid rnelfiiig af 152".-This acid crystallises from dilute acetic acid i n six-sided prisms of the follow- ing form.AXD OF ADIPIC ACID. 1023 The silver salt, CzoH200aAg2, was prepared in the same way as the 0.2620 gave 0.1049 Ag on ignition. It is somewhat soluble in hot water, and blackens rapidly on ex- The so7~diZity of the two dibenzyladipic acids in Farions solvents other silver salts, and analysed with the following result. Ag = 40.03. C201&,,04Ag2 requires -4g = 40.00. posure to light. may be conveniently recorded in tabular form. I Solubilities of the two dibenz-laclipic acids. I Solrents. I I Dibenzyladipic acid Dibenzgladipic acid ' melting at 211-213O. 1 melting at 152'. Ether ............ Methylic alcohol . . Benzene .......... Toluene .......... Ethylic alcohol.. .. Soluble in the cold. Soluble in the cold. Soluble in the cold. Insoluble. Only slightly soluble on boil- ing. Light petroleum ... 1 Insoluble. Water.. .......... 1 Insoluble. Glacial acetic acid.. 1 Very sparingly soluble in t,he 1 cold; on boiling it dis- solves readily, and on cool- [ ing crystallises out again. I Readily soluble in the cold. Readily soluble in the cold. Readily soluble in the cold. Soluble on heating; the acid is not precipitated on cooling. Readily soluble on warming; on cooling the acid crystal- lises out again. Insoluble. I nsolii ble. Readily soluble in cold naetic acid; it is precipitated in a errstallhe form on adding water. It will be seen from the above table that the two dibenzyladipic acids differ markedly in their degree of solubility in benzene, toluene, and glacial acetic acid ; the acid melting at 152' being much the more soluble of the two. The author desires particularly to thank Professor W. H. Perkin, jun., for the fruitful suggestion which led to this research, and for the encouragement which was given whilst it was in progress. Orgaiiic Laboratory, Ozcens Col Zege, Mancher fe r .

ISSN:0368-1645    

DOI:10.1039/CT8946500995

出版商:RSC    

年代:1894

数据来源: RSC

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1024 Heat prodttced on neutralisatioii of acids. I LXXX1.--Note on the Afinitiils of Polybnsic Acids. By BETAS LEAS, D.Sc., B.A. 1 s t NaOH.. ............ 2nd SaOH.. ........... 3rd KaOH ............. LIEBIG, in 2838, after a study of a number of organic acids, laic1 down as the criterion of polybasicity the capability of forming salts with different metallic oxides. The theory of polybasic acids was further deT-eloped by Laurent and Gerhardt, and later by Wurtz and Keknl6, and, as a result of their labours, the basicity of an acid has been regarded as determined by the number of stages in which the hydrogen can be displaced, or, in other words, by the number of salts it can form with a specified monad metal. Jlore recently the researches of Thornsen and Ostwald have furnished other methods by which the basicity of acids can be determined, and in other ways have enlarged our knomledge of this class of compounds.It is here desired to call attention to facts .irhich shox that the affinity of a polybasic acid is a complex function of the several affinities of all the groups contained within its molecule. I n the first place, it is to be obserred that the thermal effects of the interaction of the first, second, &c., equivalents of a base with an acid, are not necessarily the same-on the contrary, they are, in general, different. The follom-ing instances may be quoted from Thomsen’s work. Sulphuric. Oxalic. Succinic. Phosphoric. 14,750 13.850 12.400 14.850 16,650 14,460 11,750 12.250 ---- ---- - - 6,960 -LEA?;: THE AFFINITIES OF POLYBASIO ACIDS.1025 1st EOH.. ............. 2nd EOH.. ............ heats of neutralisation of the first and second molecules of a base with the molecules of bibafiic acids of the oxalic acid series, the pro- duct being the solid salts. H e obtained the following results. Osalic. Malonic. Snccinic. Sulphuric. - - 31.280 27,870 26.260 47,800 24.690 20,700 21,150 33,600 The particular point of importance in these obserrations is that in every case the second molecule of the base liberates Zess heat than the first, whilst in measurements of the heat of neutralisation in aqueous solution the reverse was frequently observed by Thomsen. Massol pointed out that whilst the heat developed on neutralisinq formic acid by potassium hydroxide is 25,800 units ,\-hen the solid salt i5 formed, oxalic acid, which may be regarded as a carboxylic derivative of formic acid, has more than twice as great a heat of neutralisation, as though the tn-o carboxyl groups effect a mutual strengthening of one another.It is seen from the above table that, --hen one of these carboxyls is neutralised, the acid salt acts like formic acid, and has almost the same heat of neutralisation. The results, then, a t which he arrived, Massol attributed to a reciprocal action between the acid groups--an action which is less in degree in uialonic and succinic acids, in which the carboxyl groups are farther apart from one another. Berthelot, in a note to Massol's paper, pointed out that the greater developmeut of heat by the fir5t molecule of base is a necessary con- sequence of the fact (-47.2,~.Cliim. Phys. [;], 4, 130) that a bibasic acid interacts with its own normal salt forming an acid salt with development of heat, Reverting now to the researches of Ostwald and his collaborateurs on the electrolqtic conductivity of carboxglic acids, many facts are Monobasic acids.+ Bibasic acids.+ I Formic acid.. ............ 0.0214 Acetic ................ 0.00180 Propionic acid ............ 0,00134 Butyric .............. 0 *00149 T-aleric .............. 0.00161 Hesglic .............. 0.00145 Osalic acid ............ 10 . Xulonic acid ........... 0.171x Succinic ............. 0'00665 Glutaric ,! ........... 0 *00475 ddipic ............. 0'00371 Pimelic ,, ........... 0.00357 * Ostwald, Zed. physikal. Chejn. (1889), 3, 174.t Ostwald, laid. (1889), 3, 271. Bethmann, itid. (1890), 5, K I ~ .1026 LEAN : THE AP'FINITIES O F POLYBhSIC ACIDS. found which have significance in the present connection. The table (p. loS5) has been drawn u p to show the relations between the 6 ' dissociation constants " of organic acids of the acetic and oxalic acid series. Assuming that the " dissociation constants *' of acids are a measure of their attinities, it is seen at once that as the homologous series are ascended the aEnity of the acid decreases, and that by introducing a second carboxyl group into a monobasic acid the affinity of the acid is in every case more than doubled, indicating a mutual strengthening influence of the two carboxyls on one another, and it is also seen that this influence decreases in extent as the distance between the two groups is increased.Such an increase in the affinity of one carboxyl group by the introduction of another is parallel to the increase which is effected in phenol by the introduction of chlorine atoms or nitro- groups. The in%uence of the introduction of alkyl groups i n t o bibasic acids of the oxalic acid series has been studied by Bethmann (Zeit. plysikal Chem., 1890, 5, 403), Walden (ibid., 1892, 8, 433), and Walker (Trans., 1892, 61, 696). The following tables of " dissociaticn con- stants" hare been compiled from their papers. Methyl- ................ Ethyl-.. ................ Benzyl- ................ Propyl- ................. 0'086 Dimethyl-, ............. 0'076 0.12i Diethyl- ............... 0'74 0 '151 Dibenzyl- ..............4 '1 - 0 '113 Diproppl- .............. Succinic acid, 0.00665. --------- I Anti- I Paw- ---- Xethgl- .......... Ethyl-. ........... Propyl- .......... Benzyl- .......... Dimethyl-, ......... Diethyl- ........... Jlethylbenzgl- ...... Ethglbenzyl- ........ 0 '0086 0.0086 0 '0089 0 '0091 0 '0122 0.0204 0.0245 0.0343 - 0 a219 - 0 '0261 Methyl-. .......... Ethyl-.. .......... 0 9052 Dimethyl-. ......... 0.0053 0 .On55 - Diethyl- ........... 0 '0055 0.0056 ...... 0.0069 M e t h ~ l p r o p ~ l - - Glutaric acid, 0 Q0475.LEAS: THE AFFINITIES OF POLYBASIC ACDS. 1027 Dimethyl-+ ......... Diethyl-. ........... Dibenzyl- .......... Dipropyl- .......... Pimelic acid, 0 90357. 0 '00339 0.00345 0 -0032 0 '0048 Although there are some irregularities which require explanation, the figures in the above tables bring out clearly the fact that an in- crease in the Conductivity of a bibasic acid is effected by the introdnc- tion of alkyl groups, and the heavier the group the greater is its influence.The benzyl group on account of its mass, but probably more by reason of its acid character, appears to have an especial in- fluence on the conductivity. Further, as the distance between the two carboxyls is increased, the effect of the introduction of alkyl groups is diminished. In view of the relations which have already been brought out, it is of great interest to compare the constants of tetracarboxglic acids with those of the corresponding dicarboxylic acids. The ouly cases which appear to have been investigated hitherto are the dimethyl- and diethgl-derivatives of pentarietetracarboxylic acid ; in each case, as Walker has found, the affinity of the acid is enormously increased by the close proximity of the two carboxylic groups a t either end of the molecular chain.I I I Pimelie acid. Peutanetetncarboxylic Ratio. acid. Dimethgl- .......... V '00339 0.37 Diethjl- ............ 0 -00345 1 : 109 1 : 608 I I I The new dialkyl-derivatives of adipic acid and of butanetetm carboxylic acid, described in the preceding paper, are now in the hands of Dr. J. Walker. Other facts recorded in the preceding paper also have a bearing on the present subject. It was found that the quadribasic potassium salts of dimethyl-, diethyl-, and dicetyl-butanetetracarboxylic acids are alkaline to litmus, and the indefinite character of the final colonr change showed that long before the tbeoretical quantity of alkali had been added, the acids had been almost completely neutralised ; and, further, the neutral silver and calcium salts of dicetyl- and dibenzyl-butanetetracarboxylic acids were found to be bibasic.This fact, apparently so anomalous, is in measure understood on * The dialkylpimelic acids hare not been separated into trro modifications.1028 SUDBOROUGH : CHLORINATION O F A h W E . recalling that in the tetracarboxylic acids there are two carboxyl groups attached to one carbon-atom at either end of the molecular structure, thus Such a juxtaposition of negative groups me have seen enormously increases the afhity of the acid, but so soon as a bibasic salt is formed, for instance COOH KOOC > C R ~ C H , - C H , - C R < ~ ~ ~ ~ , the strengthening influence of one carboxyl on another no longer exists, and instead we have the influence of the group COOK on the group COOH, with the result that the salt although dicarboxylic has little or no acid action. When R is the alkyl group methyl or ethyl, the bibasic salts have a slight acid action, andquadribasic salts were obtained; whereas when R is the hearier group, benzyl or cetyl, it was not found possible to prepare quadribasic salts. The facts which have been adduced show clearly that the chemical activity of a polybasic acid is a complex function of the affinities of the several groups which it contains, and that the influence of one or more groups cannot be removed without affecting those of the rest, The chemical character in fact of an element o r group of elements within a molecule depends not alone on itself, but also on the nature and position of those in the vicinity of which it is found. The Oweus College, Jlanchester.

ISSN:0368-1645    

DOI:10.1039/CT8946501024

出版商:RSC    

年代:1894

数据来源: RSC

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1028 SUDBOROUGH : CHLORINATION O F A h W E . LXXXII.--CMorincct 1‘0)~ of d d i n e . By J. J. SUDBOROL-GH, B.Sc., Ph.D. FOR the continuation of the work on the “esterification ” of aromatic. acids, which Professor Victor Meyer and I have been carrying on during the past year (Ber., 27, 510 and 15SO), it was of importance. t o obtain the symmetrical 2 : 4: 6-trichlorbenzoic acid [COOH = 13,. and it seemed probable that this acid might be prepared from symmetrical trichloraniline in the same way as 2 : 4 : 6-tribromobenzoic. acid is from symmetrical tribromaniline. TTichZoraniline.-Accordin,o to Beilstein, 2 : 4 : 6-trichloraniline has only been obtained in small quantities, first by A. W. I-. Hofmann (Annulen, 53, 35), by the action of chlorine cjn aniline-the amount obtained was so small that it merely sufficed for one analysis-andSUDBOROUGE : CHLORINATION OF AXILIPU7E.1029 afterwards by Wenghoffer (J.pr. Chem. 621, 16, U O ) , by the action of sulphnryl chloride on aniline. Attempts to obtain substitution products of aniline by the action of chlorine in the presence of water proved fruitless, as, in all cases, even with chlorine water at OD, the aniline was oxidised, with pro- duction of green colouring matters. By acting on a solution of aniline in carbon bisulphide, a fair amount of the trichlorinsted derivative was obtained, but usually coloured green. The best method appears to be to work with a solution of aniline i n chloroform. 50 grams of aniline were dissolved i n 500 grams of chloroform, and the solution, without any external cooling, was satn- rated with dry chlorine.After several hours, the liquid became semi-solid, from separation of the hydrochlorides of aniline and of its chlorinated derivati-oes, and as soon as the solution smelt strongly of chlorine the solid product was collected and rapidly dried on porous plates; about 90 grams of the mixed hydrochlorides mere thus ob- tained, from which the trichloraniline was separated by extracting the mass with cold water ; the hydrochlorides of aniline, monochloraniline and dichloraniline are dissolved, whilst the trichloraniline hydro- chloride is decomposed and the base set free. The crystalline residue was a little discolonred and melted at 75" ; when purified by sublima- tion on the water-bath, it formed long, colourless, silky needles, melting at 77.5".On analysis, the following result was obtained. Theory. Found. C1 .. . . . . . . 54.19 per cent. 54-18 per cent. I n order to see what other snbstitut'ion products were formed, the aqueous filtrate from the trichloraniline was distilled in a current of steam, and the distillate rendered alkaline by caustic potash. By this means, a small quantity of colourless needles was obtained. These melted at 63", and proved to be 2 : 4-dichloraniline. Theory. li'ound. C1 .. . . < . . . 43-82 per cent. 43.46 per cent. The residue was then rendered alkaline and again submitted to steam distillation, the oil which passed over being extracted with ether and then fractionated. The portion which passed over above 200", on cooling, deposited large, prismatic crystuls, which, after sublimation, melted at 69-70", and, on analysis, proved to be para- chloraniline.Theory. Found. C1 . . . . . . . . 27-84 per cent. 27.46 per cent.1030 SUDBOROUGH : CBLORlNATION OF AWILINE. From 50 grams of aniline I have thus obtained- 30 ,, 2 : 4 : 6-trichloraniline. 2 9 9 2 : 4-dichloraniline. 5 ., parachloranilir,e. and 20-30 ,, aniline recovered. I n other experiments, as much as 50 per cent. of the theoretical yield of trichloraniline was obtained, and, no doubt, the yield can be made much greater. 2 : 4 : 6-!Z'rdchZo~-obenzoic acid, C6H,C1,*COOH. To prepare this acid, symmetrical trichloraniline mas (without purification) diazotised, and then slowly added to a hot solution of cnprous potassium cyanide to convert it into the nitrile ; the product, which was very dark coloured.and mixed with unaltered trichlor- aniline, was hydrolysed by heating with excess of concentrated hydrochloric acid a t 200". The acid, isolated i n the same manner as the corresponding brom- inated acid (Ber., 27, 512), was purified by recrystallisation from boiling water. It forms long. prismatic needles, melts a t 160°, and is readily soluble in alcohol, ether, chloroform, and, to some extent, in boiling wat,er. 0.2000 gave 0.3798 AgCl ; C1 = 46.98. C7H2C13*COOH requires Cl = 47.22 per cent. This acid, like all the other symmetrically tri-su bstituted benzoic acids, yields no " ester " when dissolved in alcohol and saturated with dry hydrogen chloride. 2 : 4 : 6-TrichZo~obenzoyt c7tZmide, C6H2C1,*COC1 [COCI : Cl, = 1 : 2 : 4 : 61.This is readilF obtained by the action of phosphorus pentachloride (1 mol.) on the trichlorinated acid (1 mol.). It is a colourless oil, which boils at 275" and has a pungent odonr, resembling that of benzoyl chloride. 0.3060 gave 0.7090 AgCl ; C1 = 57.33. C,H,Cl,-COCl requires C1 = 58.19 per cent. This chloride is characterised by its remarkable stability ; when boiled with a large excess of water for 10 minutes, st trace only of hydrochloric acid was found in the solution, showing that practically no decomposition had taken place. The acid chloride was also heated on the water-bath with methylic alcohol, and, on evaporating t h e alcohol, an oil was left which, on analysis, proved to be the original chloride, and not methylic trichlorobenzoate.ELECTH~XOTIVE FORCE OF ALLOYS IN A VOLTAIC CELL. 1031 The extraordinary stability of this acid chloride suggests the pos- sibility that all acid chlorides of the general formula R : COCl : R = 6 : 1 : 2 are extremely stable substances, and not readily decomposed by water or alcohol, just as the corresponding acids do not form " esters " under the usual treatment. The Owens College, Nanchest er.

ISSN:0368-1645    

DOI:10.1039/CT8946501028

出版商:RSC    

年代:1894

数据来源: RSC

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ELECTH~XOTIVE FORCE OF ALLOYS IN A VOLTAIC CELL. 1031 LXXXIII.-77w Eloct?.omotiz:e E’orcc of Alloys in CL Voltaic Cell. By A. P. LAURIE, &LA. 0s former occasions, I have brought before the Society (Trans., 1889, 65,677) the results obtained in testing the E.M.F. of alloys in voltaic cells with the view of throwing further light on their constitution. Briefly, the method can best be explained by taking an example. If we place a plate of copper and a plate of zinc in a solution, we shall get an EMF. between the zinc and copper which can be mea- sured on a Thomsoii electrometer; if, on the other hand, we sub- stitute a copper plate for the zinc there will be practicallyno E.M.F. between copper and copper. If we now attach a small piece of zinc to the surface of one of the copper plates beneath the liquid we shall again get approximately the E.M.F. between zinc and copper, and if we suppose that the zinc, even if present in minute quantities, was mixed with the copper throughout its mass, itt wouid polarise the copper plate, and the compound plate would give an E.M.F.approximately the snme if it consisted of zinc alone. If, however, the zinc had entered into combination with the copper, i t would no longer be able to polarise the copper plate, and we should be dealing with a new metal instead of ft mixture of two metals. Furthermore, if zinc forms such a compound with copper, it may be expected to have a definite composition, and consequently, if the proportion of zinc present in this plate is gradually increased, we should expect to reach a point at which the copper was saturated with zinc, and any additional zinc being merely mixed with the metallic compound would cause a r abrupt rise in the E.M.F.I have shown i n former papers that such an abrupt rise takes place in the case of the zinc-copper alloys, the discontinuity in the curve representing the E.M.F. occurring at a point corresponding to an alloy of the formula CuZn,. I n the case of the copper-tin allojs, the discontinuity occurs at Cu3Sn. On comparing this result with the measurement of the1032 LAURIE : THE ELECTROMOTIVE FORCE electrical resistances of the copper-tin alloys by Professor Lodge and Professor Roberts-Ansten, a confirmation of the view that Cu,Sn is a compound is obtained. As is well known, Matthiessen obtained four types of curves as the result of his measurements of the electrical resistance of alloys.First he found that in certain alloys the conductivity was propor- xiooal to the amount of each metal present, the curve being a straight line joining the conductivity of the two metals. In the second t-pe of curve, the conductivity rapidly diminislled on the addition of only a small quantity of the metal having the lower conductivity, and then became practically a straight line join- ing the cur\-e representing the metal of lower Conductivity. I n the third type of curve, the electrical conductiritg diminished (rapidly on the addition of a smsll quantity of either metal to the other, thus producing a U-shaped curve. In all these cases there is, as Matthiessen truly points out, no indication of the formation of a compound, the changes in conductivity being brought about by such small traces of the metals that we must regard it rather as a case of allotropic modification.There was, however, another form of curve which he obtained ill the case of the gold-tin alloys in which discontinuities occurred in the case of intermediate mixtures of the metals, the curve having the form of a W, and he suggested that the two minimum points and the maximum point represented three different compounds between gold and tin. It is, howevel-, I think, equally open to 11s to regard these results as Seing due t o the forma- -tion of a single compound of the percentage composition correspond- ing to the maximum point of the curve, and to suppose that the two portions of the curve on each side of the maximum point are similar ‘to tile U curves obtained in other cases, the compound behaving like a new metal.In the case of the copper-tin alloys referred to above, Lodge aBd Roberts-Austen hare found a maximum point 4corresponding to the alloy Cu3Sn. In the case of the gold-tin alloys, I have already shown that a, discontinuity occurs in the curve of E.1I.F. at the percentage com- position AuSn which corresponds with the maximum point in Xatthiessen’s curve of electric conductivity, and that in the case of the tin-lead, tin-cadmium, zinc-lead, tin-zinc, and lead-cadmium a11oys which Matthiessen regards merely as mixtures, there is no indication of the existence of a compound, the E.M.F. rising in each case on the acidition of a small quantity of the more positive metal, As, therefore, the resuits obtained by this new method have so far agreed with those obtained by measuring the electrical conductivity of the alloys, I thought it as well, before using the method for ex- ploring new regions, to apply i t systematically to each of the groupsOF ALLOYS IN A VOLTAIC CELL.1033 of alloys which are given in Matthiessen’s paper on the electric con- ductivity of alloys (Trans. Roy. SOC., 1860, vol. 150, p. 161). The number of groups of alloys of which he determined the electrical conductivity in this paper is 19; I have already published the re- sults of my examination of the E.N.F. of six of these, leaving 13, and now add a considerable number of fresh results. These can be divided into tmo groups, namely, those which, on the introduction of 2 per cent.to 3 per cent. of the more positive metal, give a t once the full E.M.F. due to that metal, and those which show a gradually increasing E.M.F. as more and more of the more positive metal is added, approximating to a maximnrn on the addition of some 20-30 per cent. In no case has a discontinuity heen discovered such as that obtained in the case of the gold-tin, copper-tin, and copper- zinc alloys, thus confirming by my method Matthiessen’s conclusion that in the case of these alloys, with the exception of gold-tin, nothing in the way of chemical corcbination takes place. These results, together Iyith those already published, include 16 of the 19 alloys described by Matthiessen, the silver-tin and gold-copper allojs being excluded, as, owing to some cause which I have not yet been able to discorer, the readings obtained with these alloys and metals were so very irregular that I do not feel justified in publish- ing them until I hare discovered the source of these irregularities ; there was no indication, however, of the existence of a compound in the case of these alloys.With reference t o the two groups of alloys, namely, those giving an immediate high E.M.F., and those which give a gradually rising one, there is no sharp dividing line, as it is rather a difference of degree than difference of kind ; nor do the two groups correspond exactly with Mat thiessen’s two groups, namely, alloys which are merely mix- tures, and alloys which produce an allotropic change.It is furthermcre to be noted that whilst careful repetitions of the measurements a1wa-j-s result in a ainiilar curve being obtained, the readings will not be exactly the same in each case for an alloy of the same percentage composition. This is, I think, to be expected if we consicler these results as due to something corresponding to the case of an aqueous solution of a salt. It is easily understood that on the solidification of such a solution, the conditions will not be precise]F the same on any two separate occasions, or in t-n-o different parts of the alloy, and consequently the E.N.F. obtained must differ slightly for different preparations of the alloy. The method employed has been to prepare small samples of the alloys from approximately pure metals, and, by means of a Thornson quadrant electrometer, to test the EMF.in voltaic cells of various construction against that of a standard Daniel]. I shall first give the TOL. LXV. 4 D1032 LAURIE : THE ELECTROMOTIVE FORCE results obtained with those alloys in which the full E.M.F. is given as soon as a small quantity of the more positive metal has been added. Bismuth and Tin. The cell used consisted of a solution of stannous chloride around the tin plate, and of common salt around the bismuth plate, the two solutions being sqmrated by a plug of filter paper in a narrow glass tube. Under these conditions there was a slight E.M F. of 0.07 volt between bismuth and bismuth, but this does not affect the results. The E.M.F.s obtained were as follows.The results given are the means of three or four readings, the alloys being cleaned and scraped between each observation. Tin is positive to bismuth. Tin against bismuth .......................... 0.119 volt. 0.119 Alloy (tin 5 p. c., bismuth 95 p. c.) against bismuth ,, ,, (tin 50 ,, bismuth 50 ,, ) ,, 7 , 0.119 ,, Hisnzuth and Lead. In this case, the bismuth was i n common salt, and the lead in :e paste of lead chloride. Lead is positive to bismuth. Lead against bismuth ......................... 0.139 1-olt. 0.134 Alloy (lead 5 p. c., bismuth 95 p. c.) against bismuth ,, Bismitth a d Ziuc. In tbis case, both metals were immersed i n a single solution of Zinc against bismuth.. ....................... Alloy (5 p- c. zinc, 95 p. c. bismuth) against bismuth This result is slightly lower, showing that there is nc sharp line coinmon salt.@iY2 volt. 0.758 ~, between the allojs in this group and in the next. Bisnzzith a d Gold. These alloys were tested in a solution of common salt. Alloy (gold 95 p. c., bismuth 5 p. c.) against gold. Bismuth against gold.. ....................... 0.41.7 volt. 0-412 ,, Bismuth and Silver. Bismuth in common salt; silver siirrounded by a paste of silI-er Silver against silver.. ........................ Bismuth against silver.. ...................... 0.102 ,, Alloy(974 p. c. silver, 2$ p. c. bismuth)against silrer ,, chloride. Bismuth is positive to silver. 0.036 volt. 0.112OF -4LLOF'S IK A VOLTAIC CELL. 1035 Gold and Silrer. Both in a solution of common salt. Silver is positive to gold.Silver against gold ........................... Alloy (95 p. c. gold, 5 p. c. silver) against gold. .. 0-117 volt. 0.219 ,, Cadmium and Zinc. Both in a solution of common salt. Zinc against cadmium.. ....................... ,411oy ( 5 p. c. zinc, 9.5 p. c. cadmium) against cadmium Zinc is positive to cadmium. 0.239 volt. 0.216 ,, Antimony and Tin. These metals were tested in a solution of common salt, Tin is positive to antimony. Tin against antimony.. ....................... Alloy (5 p. c. tin, 95 p. c. antimony) against antimonr To this list must be added the former determinations of tin-lead, zinc-lead, zinc-tin, and tin-cadmium. We next come to the alloys which shorn a gradual rise of E.M.F. as the more positive metal increases in amount. The first examined were the lead-antimony alloys ; several different samples of these were prepared and tested, using different types ot \-oltaic cells.0.211 Folt. 0.188 ,, Antinzony and Lead. The readings were taken with both the alloy and the antimony in a cell of sodium chloride. E.M.F. I. Sntimong containing 4.76 per cent. lead-antimony 0.123 volt. 7, Y 7 9-05 ,, 7 :, 0-169 ,, 7 7 7, 16% ), 7 ., 0.215 ,, 7 7 7 13.4 ,, ., 0.182 ,, Antimony against lead. ....... .-. 0.246 ,, The readings given in I1 were taken with a fresh set of alloys, also in a single cell of sodium chloride. E.M.F. 11. Antimony containing 4.74 per cent. lead-antimony 0.057 volt. 7 9 7 : 9.209 ,, Y 7 3 9 0.112 ,, 7, 7 9 13.03 ,, 2 ) 7 7 0.1349 ? 7 7 , 7 7 17.03 ,, , 77 0.155 7 7 Antimony against lead ..........0.207 ,,1036 LAURIE : THE ELECTROMOTIVE FORCE The set of readings, 111, taken with the same set of alloys as in 11, only with the antimony in an inner cell containing antimony chloride, and the alloy in an outer cell containing sodium chloride, gave the following results. 111.-Antimony against antimony. .................. E.M.F. 0.285 rolt. Antimony containing 4-74 per cent. lead-antimony 0.358 7, 77 7 9.209 ,, , .) 0.415 ,7 7, ), 13.03 ,) ., 0.434 ), 7 9 7 7 1i.03 ,, 9 .) 0.475 ,) Antimony against lead.. ...... 0-494 7 , The set of readings, IV, taken with the same alloys undsr the same conditions as before, except that the alloys were in an outer cell of potassium nitrate, gave the following results. 1V.-Antimony against antimony.. .................E .M .F . 0.259 volt. Antimony containing 41-74 per cent. lead-antimony 0.342 ,7 9 7 $ 7 9.209 1, . 7 7, 0.386 9 7 9 7 ,, 13-03 , 7 7 7 ), 0.413 ,. 9 9 7 7 17-03 ,, ,? .? 0-415 ), ,4ntimony against lead ........ 0-456 ,) I n V, we have the same set of alloys read again with the alloy in an outer cell of magnesium sulphate. V.-Antimony against antimony.. .................. E.M.F. 0.254 volt. Antimony containing 4-74 per cent. lead-antimony 0-2903 ,, 7 7 7 7 9-209 ., .) .) 0 342 ), 7 , 13.031 7 7 ,, ,, 0.386 :, 7 7 7 17.03 7 7 ., ,) 0.435 ,, Antimony against lead. ......... 0.451 . 7 It will be noticed that in each of these tables the E.3l.F. rises rapidly in a continuous curve. The following are further examples of a gradually rising E.1I.F. Lead aid Gold.These alloys were tested in a solution of common salt. Lead against gold ............................ Lead is positive to gold. 0.523 Tolt. Alloy ( 5 p. c . lead, 95 p. c. gold) against gold .... 0-353 .. ), (7 p. c. lead, 93 p. c. gold) 7 7 .... 0-461: .. ,) (10 p. c. lend, 90 p. c. gold) ,, .... 0.317 ..OF -4LLOTS IN -4 VOLTAIC CELL. 1037 Lead and Silver. These met(a1s were tested in common salt. Lead is positive to silver. Lead against silver.. .......................... 0.505 volt. 0.406 Alloy (lead 5 p. c., silver 95 p. c.) against silver. .. >, ,, (lead 15 p. c., silver 85 p. c.) . . . . . 0.486 ,, In the former paper (Eoc. cit.), the E.M.F. obtained between cad- mium and lead is given as being 0.322 rolt, whilst an alloy with 3 per cent. cadmium gave 0.264.This seems to show that this alloy belongs to the present group, and I hare, therefore, tested its E.M.F. again in a solution of common salt. ,, (lead 10 p. c., silver 90 p. c.) . . . . . 0.441 ,, Cadmium and Lead. Cadmium is positive to lead. Cadmium against lead. ........................ Alloy (5 p. c. cadmium, 95 p. c. lead) against'lead . . 0.197 volt. 0.176 ,, t h u s showing a slight increase of E.M.F., which, however, disappears on amalgamating the alloy, so that this alloy can probably be placed in the first group. The copper-silver alloys I have not experimented on, and, as already stated, satisfactory results were not obtained with gold-copper and silver-tin. These results, including 15 of Xatthiessen's alloys and one other alloy, namely, bismuth-zinc, confirm in each case his conclusion that, in these alloys no compound of the metals exists.I have also repeated the former measurements of the tin-gold alloys, nsing a solution of common salt in place of the solutions formerly used. The results indicate the existence of a gradually rising E.M.F., suggesting some heat of solution, as well as the abrupt rise of E.31.F. which marks the passage over the compound. Gold and Tiw. Tin against gold.. ............................ Alloy (10 p. c. tin, 90 p. c. gold) against gold ..... ,, >, 26 7 7 :7 '28 Y , 7 , :34 7 7 ,, 36 ,, .................. ., 40 ,, .................. >, 50 ?, (23 p. c . tin) against gold.. ................ 9 7 .................. 3 - .................. 17 .................. 7 , 7, 7 7 ..................0.435 volt. 0.191 ,, 0.261 :, 0.266 ,, 0.311 ,, 0-297 ,, 0.311 ,, 0-396 ,, 0.428 ,,1038 LAURIE : THE ELECTRONOTlVE FORCE thus indicating a gradual rise of E.M.P. up to the 36 per cent. alloy when a sudden rise of nearly one-t,enth of a volt takes place on passing this point. The results of amalgamating these gold-tin alloys is somewhat curious. In both the copper-tin and the copper-zinc alloys the com- pound was not affected by amalga,mat;on ; but in the case of tin-gold the amalgamation breaks up the compound, the result being a gradual rise of E.M.F. throughout the series of alloys. Tin aiLd Gold Amalgamated. Tin against gold .............................. Alloy ( 5 p. c. tin, 9.5 p. c. gold) against gold ..... .. 10 3, qainstgold.................. 7 ) 23 .) .................. ,l 26 - 7 7 7 .................. ,? 34 3 , .................. >, 36 9 7 77 .................. ,, 40 ., .................. 7 7 5 0 :, >. .................. ?, 7 7 0.492 volt. 0.270 9 ) 0.290 .) 0.280 ., 0.310 ., 0.320 7 , 0.s40 ,. 0.330 .: 0-360 ., This curve has not been investigated beyond this point. This result suggested the possibility of dispiacing one metal in the compound by another, and I accordingly decided to try and displace the tin in the copper-tin alloy by zinc. The results obtained cer- tainly indicate that t h i s takes place. The copper-tin alloy contained 35 per cent. of tin, which is a little less than tbat necessary to form a compound between copper and tin, and pave an E.M.F. against copper of 0.057 volt.To this the same weight of zinc as there was vopper in the alloy was added, and the triple alloy gave an E.M.F. against copper of 0.259 volt, whilst tin against copper gave 0.272 volt, and zinc against copper gave 0.840 volt, and an alloy of zinc 50 per cent. with copper 53 per cent. against copper gave 0.098. Con- sequently the E.M.F. obtained from the triple alloy agreed closely with that obtained from tin, but was much below that obtained from zinc, indicating that the zinc had combined with the copper and turned out the tin. If the results obtained by Matthiessen and others as to the existelice of compounds between metals are examined, it will at once be evident that there is no apparent explanation of why certain rnehds do, and other do not, combine, nor do the results bear any obvious relationship to Mendelkeff’s table. It is remark- able, for instance, that two metals like lead and zinc do not combine, and it occurred to me as a possible hypothesis that iheseOF ALLOTS IS A VOLTAIC CELL. 1039 results might be due to the dissociation of the compound at the tern- perature of fusion of the metals. I only mention this possible expla- nation to point out that I have been unable to obtain any evidence of its correctness. I find that alloys of lead and zinc which have been lowered iii melting point by the introduction of bismuth or mercury, still indicate the presence of free zinc, showing that lowering the melting point does not enable the zinc and lead to combine; the explanation, therefore, must be sought elsewhere. The inyestigation of this question seems to me important, as we do not know a t present how many of the elements will combine two and two, aucl investigation of a sufficient rumber of alloys should finally lead to some conclusions from which a law of combination among the elements might be derived.

ISSN:0368-1645    

DOI:10.1039/CT8946501031

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

INDEX OF AUTHORS' NAMES. T R A N S A C T I O N S . 1894. And also t o such papers as appeared in the Proceedings during the Session 1893-1894 (Nos. 128-141 ; November, 1893, t o July, l894), but not in Transact,iom (marked PROC.). A. d l l h u s e n , F. E. See S. Ruhemann. Armstrong, H. E., presidential ad- dress, 336. - the action of bromine on azobenz- ene-a correction, PROC., 1893, 206. - the origin of colour. X. Coloured hydrocarbons, PROC., 1893, 2%. A r m s t r o n g , H. E., and A. Lap- w o r t h , the interaction of acid clilor- ides and nitrates, PBOC., 1893, 265. A r n o l d , J. O., and A. A. Read, the chemical relations of carbon and iron, 788. -1 ston, Miss E., and W. Ranisag, the molecular formuh of some liquids as determined by their molecular sur- face energy, 167.B. Bailey, G-. H., stability of the oxides considered in relation to the periodic law, 315. - volatilisation of salts during erspo- ration, 445. Baker, H. B., influence of moisture on chemical change, 611. Bicket, J. H., obituary notice of, 382. Bossi, A. L. Boyd, D. R., reduction of paratoluene- azodimethglaniline, 879. B r s u n e r , B., fluoroplumbates and free fluorine, 393. Brown, A. J., the specific character of the fermentative functions of yeast cells, 911. See W. R. D u n s t s n . Brown, J. T., obituary notice of, 382. Burch, G. J., and J. W.I)odgson, the action of concentrated acids on certain metals when in contact with each other, PBOC., 1894, 84. VOL. LXV. C. Carnell, W. C. Carr, F. H. Cavallo, W. C h a t t a w a j , F. D., preparation of /3-chloronaphthalene, 875.- note on 8-mercurydinaphthyl and ,B/3-dinaphthjIy 877. C h a t t a w a y , F. D.,andW.H.Lewis, phenylnaphthalene. Part 11. 8-Phe- nylnaphthalene, 869. Clarke, F. 0. H., obituary notice of, 383. Collie, J . N., a new method of produc- ing carbon tetrabromide, 262. Collie, J. N., and H. R. L e Sneur, salts of dehydracetic acid, 254. Cook, E. H., effect of heat on iodates and bromtltes. Part I. Potassic iodate and bromate, 802. See A. G. P e r k i n . See S. C. Hooker. See W. R. D u n s t a n . See J. J. Hummel. Cope, F. Crossley, A. W., and W. H. P e r k i n , jun., substituted pimelic acids, 987. -- the products of the action of fused potash on camphoric acid, PROC., 1894, 65. D. DaTidson, W. B. Da -r i e s, R. H.. obituary notice of, 384.Deeley, R. M., the oxides and the Dent, F. See A. S m i t h e l l s , DenTsr, J., note on the viscosity of solids, PROC., 1894, 136. Divers, E., and T. HIaga, oximido- sulphonates or siilphazotates, 523. Dobbie, J. J., and A. L a u d e r , COT- daline. Part 111. Oxidation witll potassium permangunate, 57. Dodgson, J. W. See G. J. Burch. See F. R. J a p p . periodic law, 106. 4 E1042 INDEX OF AUTHORS. Dougal, Mrs. M. D., a specimen of early Scottish iron, 744. D u n s t a n , W. R., and A. L. Bossi, formaldoxime, PROC., 1894, 55. D u n s t a n , W. R., and F. H. Carr, contributions to our knowledge of the aconite alkaloyds. Part IX. The effect of heat on aconitine and some of its derivatives. Formation of pyrwoni- tine, 176. -- contributions to our know- ledge of the aconite alkaloi’ds.Part A. Further observations on the con- version of aconitine into isaconitine and on the hydrolysis of aconitine, 290. D u n s t a n , W. R., and T. S. Dymond, the isomerism of ths parafinic ald- oximes, 206. -- the reduction products of nitro-compounds, P R O ~ . , 1894,139. Dunstan, W. R., and E. G o u l d i n g , the action of methylic iodide 011 hvdroxylamine, PROC., 1894, 138. D u n s t an, W. R.,and E. F. H a r r i s o 11, contributions to our knowledge of the aconite alkdoyds. Part VIII. On picraconitine, 174. Dur:stan,W.R.,andH.A.D. J o n - e t t , the action of iodine and of methjlic iodide on aconitine, PROC., 1894, 96. D u n s t a n , W. R., and C. 31. Lux- more, the properties of a-benzald- oxime and some of its derivatires, PEOC., 1893, 253. D y e r , B., on the analytical determina- tion of probably arailable ‘‘ mineral ” plant food in soils.(Illustrated bT- examination of the permanent barley soil of Hoos Field, Rothamstead), 115. Dymond, T. S. See W. R. Dunstan. Dyson, G., and A. H a r d e n , on the combination of chlorine with capbon monoxide under the influence of light, PROC., 1894, 165. - E. E a s t e r f i e l d , T. H., and W. J. Sell, Part 11, See also IT. J. st,udies on citrazinic acid. 28. Sell. EasterPield, T. I€. F. F e n t o n , H. J. H., the oxidation of tartaric acid in presence of iron, 899. F o r s t e r , M. 0. See W. A. T i l d e n . F o s t e r , W., obituary notice of, 385. F r a n k l a n d , P. F., and J. Mac- g r e g o r, the maximum moleculai.deT-iation in the series of the ethereal salts of active diacetylglyceric acid, 760. -- observations on the influence of tempemture on the optical nctiritv of organic liquids, 760. G. See J. E. Marsh. Gale, S., obituary notice of, 386. G a r d n e r , J. A. Goodwin, W., and W. H. P e r k i r , jun., B-2-dimethylglutaric acid, See W. R. D u n s t a n . PROC., 1894, 64. Goulding, E. H. Haga, T. See E. D i r e r s . Hanes, E. S . H a n n a p , J. B., new uolatile com- pounds of lead sulpliide, PROC., 1894, 113. -- the interaction of sulphide with oxide of lead, PROC., 1894, 151. H a r d e n , A. See G. Dyson. H a r r i s o n , E. F. See IT. R. Dun- s t a n . Hnworth, E., and W. H. P e r k i n . jun., synthesis of pentamethylene- carboxrlic acid, hesaniethglenecarb- oxylic acid (hexahydrobenzoyc acid) , and azelaic acid, SF.-- hexamethylene dibrornide and its action on sodium and on ethylic sodiomalonate, 591. -- 1 : 2-pentamethylenedicsrb- osylic acid, 978. H e a t o n , C . W., obituaT notice of, 386. Hercock, C. T., and P. H. Neuille, freezing points of allojs in which the solvent is thallium, 31. -- the freezing points of triple alloys, 65. H o l t , W., and TV. E. Sims, oxidation of the alkali metals, 432. Hooker, S. C., preparation and proper- ties of bromolapachol, 15. - the synthesis of lapachol, PROC., 1893, 259. Hooker, S . C., and W. C. Carnell, conversion of ortho- into para- and of para- into ortho-quinone derivatives, and the condensation OF aldehydes with 8-h~drosy-a-naphthnquinone, 76. See R. Meldola.INDEX OF AUTHORS.1043 Hooker, 5. C.,and J.G. W a l s h , jun., conversion of ortho- into para- and of para- into ortho-quinone derivatives. 11. Dinaphthyldiquinone, 321. Hooker, S. C., and E. Wilson, con- version of oi-bho- into para- and of para- into ortho-quinone derivatives. Part 111. The hydrosimes of the lapachol-group, 717. Hummel, J. J., and W. Cavallo, the colouring matter of the Indian dye- stuff Tesu, PEOC., 1894, 11. Hummel, J. J. See also A. G. P e r k i n. J. Jackson, D. H., note on hyponitrites, J a c k s o n , H., observations on the nature of fluorescence, 734. J a p p , F. R., and W. B. D a t i d s o n , interaction of benzil and benzylamine in presence of zinc chloride, PROC., 1894, 49. J a p p , F. R., and T. S. Murray, pre- paration of 2’ : 3’-diphenylindoles from benzo’in and primary benzenoi’d amines, 889.J o n e s , H. C., the results of measure- ments of the freezing points of dilute solutions, PROC., 1894, 101. See W. R. D u n - stan. PROC., 1893, 210. J o w e t t , H. A. D. K. K i n g z e t t , C. T., the aerial oxidat,ion of terpenes and essential oils, PBOC., 1894, 51. K i p p i n g , F. S., the formation of the hydrocarbon “ truxene” from phenyl- propionic acid and from hgdrindone, 269. - a-hydrindone and its derivatires. Part I, 486. -the action of aluminium on heptylic chloride, PBOC., 1893,208 ; 1894, 60. - the conyersion of a-hydrindon- oxime into hydrocarbostyril, PROC., 1893,240. K i p p i n g , F. S., and W. J. P o p e , the preparation of sulphonic derivatives of camphor, PBOC., 1894, 163.-- dextrorotatory camphor sul- phonic chloride, PRO~., 1894, 164. L. Lapworth, A. See H. E. Arm- 8 t Yon g. L s u d e r , A. L a u r i e , A. P., the E.M.F. of alloys in a voltaic cell, 1030. Lean, B., homobgues of butanetetra- carboxylic acid and of &pic acid, !w5* - notes on the a5nities of polybasic acids, 1024. Leibius, A., obituary notice of, 388. L e i c e s t er, J., the interaction of quin- ones with metanitraniline and nitro- paratoluidine, PROC., 1893, 215. See J. J. Dobbie. L e S u e u r , H. R. See J. N. Collie. Lewis, W. H. See F. D. C h a t t n - way. L i n d e r , 5. E., and H. P i c t on, solution and pseudo-solution, PROC., 1894, 166, 167. See W. B. D u n - s t a n . Iiuxmore,-C. M. M. XacDonald, G. W., and 0. Masson, a product of the action of nitric oxide on sodium ethylate, 944.&lacGregor, J. See P. F. Brank- l a n d . McKillop, Mrs. See W. H. P e n d l e - bury. McLeod, H., note on the liberation of chlorine during the heat,ing of potassie chlorate and manganic peroxide, 202. Xarchlewski, L. See E. Schunck. Marsh, J. E., a sulphate of oxamide, Marsh, J. E., and J. A. G a r d n e r , researches on the terpenes. IV. phosphorus-derivatives of camphene, 35. -- derivatives of camphene con- taining haiogens, PRO~., 1894, 57. Mason, A. T., and G. R. Winder, interaction of benzylamine and ethrlic chloracetate, 187. -- condensation products of benzylamine and several benzeno’id alkalo’ids, 191. Masson, 0. Donald. X e l d o l a , R., and E. S. Hanes, azo- compounds of the ortho series, 834. -- notes on meta-azo-com- pounds, PRO~., 1894,140.Meldola, R., and F. Southerden, azoparacresol-derivative9, PBOC., 1894,118. U i l l a r , J. H. PBOC., 1894, 58. See G. W. Mac- See W. A. Tilden. 4 E 21044 INDEX OF AUTHORS. Mills, C., studies on the structure of azobenzene. The action of bromine on azobenzene : production of tetra- bromobenzidine, 51. M i t c h e l l , C. A., analysis of water from the Zem-Zem well in Mecca, PROC., 1893, 245. Murray, T. 5. See F. R. J a p p . N. See C. T. Heycock. S e v i l l e , F. H. P. €',pars, A., jute fibre produced in Eng- land, 4'70. P e n d l e b u r y , W. H., and Mrs. Ylc- Killop, the interaction of hydrogen chloride and potassium chlorate, PROC., 1893, 211. Perkin, A. G., and F. Cope, derira- tives of anthraquinone. Part 111.842. P e r k i n , A. G., and J. J. Hummel, colouring and other principles con- tained in mang-koudu, 851. -- the colouring principles of Tentilago Madraqataaa, 923. P erkin, W. H., sen., the magnetic rota- tion of hydrogen chloride in different solvents : and also of sodium chloride and chlorine, 20. - the magnetic rotations of some of the derivatives of fatty acids con- taining halogens, also of acetic and propionic acids, phosgene, and etliylic carbonate, 402. - the magnetic rotation of com- pounds supposed to contain acetj-l, or to be of ketonic origin. Part 11, 815. P e r k i n , W. IF., jun., the cis- and trans-modifications of 1 : %tetra- inet~ylenedicarboxylic acid and of 1 : 2-pentamethylenedicarboxylic acid, 572. - derivatives of tetramethylene, 950. P e r k i n , W.H., jun., and G. RBvay, synthesis of indene, hydrindene, and &me of their derivatives, 228. See also A. W. Crossley, '8. Goodwin, and 32. E a w o r th. P i c k e r i n g , S. U., examination of some recent freezing point determin- ations, 293. P e r k i n , W. H., jun. Picton, H. See S. E. Linder. P l i m p t o n , R. T., and M. W. T r a v e r s , metallic derivatives of acetylene. I. Mercuric acetylide, 264. Pope, W. J. See F. S. K i p p i n g . R. Ramsay, W. See also Niss E. d s t o n . Read, A. A., behaviour of the mow stable oxides a t high temperature:, 313. Read, a. A. Reray, G. R i c h a r d s o n , A., action of light on Rodger, J. W. Ruhemann, S., and F. E. A l l h u s e n , formation of pyrroline-derivatives from aconitic acid, 9.See aiso J. 0. A r n o l d . See W. H. P e r k i n , jun. oxalic acid, 450. See T. E. Thorpe. S. Sak u r a i , J., constitution of glpcocine and its derivatives, PROC., 1894, 90. Schunck, E., and L. M a r c h l e w s t i , notes on madder colouring matters, 182. Sell, W. J., and T. H. E a s t e r f i e l J , studies on citrazinic acid, 828. S e l l , W. J. See also T. H. E a s t e r - f i e l d . Sirus, W. E. S m i t h , C., the natural oxycelluloses. - note on the estimation of furfurtd, Sin i t 11, E. A., notes on the cupellation S m i t h , S. I., obituary notice of, 388. S i n i t h e l l s , A., and F. D e n t , the structure and chemistry of the cyano- gen flame, 603. See W. H o l t . 472. 479. of bismuth silver alloys, 622. Southerden, F. See R.Meldola. Sudborough, J. J., chlorination of aniline, 1028. T. Thorpe, T. E., the mineral waters uf Cheltenham, 7'72. Thorpe, T . E., and J. W. Rodger, the supposed relation between thc solubility of a gas and the viscosity of its solvent, 782. Thudichum, J. L. W., the action of benzoic chloride on urine in presence of alkali: formation of benzoic de-INDEX OF AUTHORS. 1045 riratives of urochrome, PROC., 1893, 238. Tilden, W. A., and M. 0. F o r s t e r , action of nitrosyl chloride on unsatu- rated compounds, 324. T i l d e n , W. d., and J. H. M i l l a r , note on the action of nitrosjl chloride on amido-derivatives of benzenoyd lq-drocarbons, PBOC., 1894, 53. T i t h e r 1 e y, A. W., sodium, potassium, and lithium amides, 504. T r a v e r s , M. W. See R. T.Plimp- ton. Truman, E. B., apparatus for the es- traction for analysis of ga3es dissolred in water and other liquids, 43. Tu t t on, A. E., connection between the atomic weight of contained metals and the crptallograpbical characters of isomorphous salts: a crystallo- graphical study of the normal sul- phates of potassium, rubidinm, and cesium, 628. T y n d a l l , J., obituary notice of, 389. V. V e l e I , V. H., the inertness of quick- lime. Part 11, 1. W. W a1 k e r, J., the boiling points of homo- logous compounds. Part I. Simple and mixed ethers, 193. - the boiling points of homologous compounds. Part 11, '7.25. - note on the constitution of gljco- cine, PEOC., 1894, 94. Walsh, J. G., jun. 9 o o k er. W i l s o n , E. W i n d e r , G. R. See S. C. See S. C. Hooker. See A. T. Mason.

ISSN:0368-1645    

DOI:10.1039/CT8946501041

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

INDEX OF SUBJECTS. T R A N S A C TI 0 N S. 18 9 4. And also to such papers as appeared in the Froceedings during the Session 1893-1894 (Nos. 128-141 ; November, 1893, to July, 1894), but not in Transactions (marked PROC.). A, Acenaphthylene, action of nitrosyl - colour of, PBOC., 1893,206. - constitution of, PROC., 1893, 20’7. Acetaldehyde, condensation of, with 8-hydroxy. a-naphthaquinone, 82. Acetaldoxime, action of acetic anhy- dride on the isomeric forms of, 213, 815. - action of phosphorus pentachlo- ride on the isomeric forms of, 216, 218. -- action of phosphorus trichloride on the isomeric forms of, 220. - isomeric forms of, 209. Acetamide, action of phosphorus penta- dcetanilide, action of nitrosyl chloride Acetic acid, brom-, magnetic rotation -- - chlor-, magnetic rotation of, -- dibrom-, magnetic rotation - - dichlor-, magnetic rotation -- magnetic rotation of, 405, -- tribrom-, magnetic rotation - - trichlor-, magnetic rotation Acetic anhydride, magnetic rotation of, Acetic chloride, action of, on silver Scetofomaldoxime, PROC., 1894, 57.Acetyl, magnetic rotation of compounds chloride on, 327. chloride on, 219. on, PBOC., 1884, 60. of, 406, 408, 425. 403, 421. of, 406, 408, 425. of, 405, 414, 422. 414, 421. of, 406, 426. of, 405, 414, 422. 824. nitrate, PBOC., 1893, 256. supposed to contain, 815. Acetylacetone, magnetic rotation of i i mixture of, with acetic achydride, 824. Acetyl-a-benzaldoxime, crystallisation Acetylbenzenazo-p-cresol, p-clilor-, Acetylbenzene-P-azo-a-naphthol, and it 5 dibromo derivative, 840.Acetylbenzoylaconine, 291. Acetylene, metallic derivatives of, Acetylethylalizarin, 186. Ace t ylmethylpurpuroxanthin , 184. dcetyl-a-naphthalenazo-15-naphtho1, Acetyl-/3-naphthaleneazo-~-naphthol, Acetjl-m-nitrobenzeneazo-p-cresol, 838. dcetglrubiadin, 184. Acid, C,E,06, obtained by the oxidatioii of tartaric acid in presence of iron. 899. Acid chlorides and nitrates, interaction Acids, fatty, normal, boiling points of. --- boiling points of ethereal - polybasic, a5nities of, 1024. Aconine, action of heat on, 181. - formula of, 292. Aconite alkalo’ids, 154, 1’76, 290. Aconitic acid, formation of pyrroline Aconitine, action of iodine and methylic. - and some of its derivatives, effect - conversion of, into isaconitine, - hydrolysis of, 290. Of, PBOC., 1893, 255.PROC., 1894, 119. 264. 838. 836. Of, PROC., 1893, 255. 729. salts of, ‘725. derivatives from, 9. iodide on, PBOC., 1894, 96. of heat on, 176. 290.NDEX OF Aconitine, iodo-, PEOC., 1894, 97. - periodide, PBOC., 1894,s. - salts, action OP heat on, 181. Sdipic acid, homologues of, 995. Aldehydes, benzeno'id, condensation - condensation of B-1ipJroxy-n- -- normal, boiling points of, 734. Aldoximes, formation of, by the reduc- tion of aliphatic nitro-compounds, PROC., 1894, 139. products of, 191. naphthaquinone, 76. -- para5inic, isomerism of the, 206. -4lizarin, monalkyl ethers of, 185. dlizarin-p-carboxylic acid, 847. - -- nitro-, 848. Alkali metals, oxidation of, 432. Alkyl chlorides, boiling points of, dlkylaminee, normal, boiling points of, --Lllocrotonic acid, action of nitros-1 -illoye, behariour of, in a roltaic circuit, - electromotive force of, in a roltaic -replacement of one metal by - triple, freezing points of, 65.;111~lacetylacetone, magnetic rotation of, 817, 825. - refractire and disperske power of, 819, 827. Alumina, behariour of, a t high teni- peratures, 314. - phosphorescence of, in a Facuum, 737. iluminium-gold-tin alloys, freezing points of, 74. Amidoazobenzene, metanitro-, PXOC., 1894, 141. Amines, benzeno'id, nction of nitrosIl chloride on, PROC., 1894, 59. Ammonia and hjdrogen chloride, in- fluence of moisture on the combination of, 614. Anmoniurn chloride, influence of mois- ture on the action of lime on, 612. -- influence of moisture on the dissociation of, 615. - hyponitrite, PXOC., 1893, 210.- oximidosulphonates, 558. dmylenic nitrosochloride, 325. hylidenedihydroxynaphthaquinone, dnetho'il, action of nitrosyl chloi-ide on, dnhydrobishydrindone, 495. -- brom- 497. dnhgdrodiglutaric acid, 831. 732. 733. chloride on, 328. 1031 : PROC., 1894, 145. cell, 1031. another in, 1038. up-anhydride of, 84. 330. UBJECTS. 1047 Aniline, action of nitrosyl chloride on, - chlorination of, 1028. - 2 : 4 : 6-trichloro-, 1028. Anilines, substituted, nction of nitrosyl chloride on, PROC., 1894, 60. Anniversary meeting, 336. dnthraquinone, deriratires of, 842. p- An t hraquinonecarboxy lic acid, sul phonation of, 844. Antimonic anhydride, behaviour of, a t high temperatures, 314. Antimony-lead alloys, E.M.F. of, in a galranic call, 1035. Antimony-tin alloys, E.M.F. of, in a voltaic cell, 1035.bsenious sulphide, solutions of, PBOC., 1894,166. Atomic weight of contained metals and the crystallographical characters of isoniorphous salts, relation between, 628. PROC., 1894, 60. Azelaic acid, synthesis of, 86, 92. Azobenzene, action of bromine on, 51, - conversion of, into tetrabromo- - In-nitro-, PROC., 1894, 143. - m-nitramido-, PROC., 1894, 141. - ?n-niti.o-p-iodo-, PROC., 1894, 142. - perbromide, 54. - structure of, 51. - tetrabromo-, PBOC., 1893, 206. m-Azo-compounds, PROC., 1894, 140. Azo-compounds of the ortho-genes, Azo-p-cresol derirntives, PBOC., 1894, 53; PEOC., 1893, 206. benzidine, 54. 834. 118. B. Balance sheet of the Chemical Societ?, from March 16, 1893, till March lti, 1894, 380. Balance sheet of the Research Fund, from March 16,1893, till March 16, 1894,381. Barium carbonate, phosphorescence of, 736.- chloride freezing points of solu- tions of, 311. - oxide, behariour of, at high tem- peratures, 314. - oximidosulphonates, 559. - potassium oximidosulphonates, - sodium oximidosulphonates, 560. Benzaldehjde, condensation of, with - condensation of, with B-hydroxy- 561. benzplamhe, 191. u-naphthaquinone, 79.1048 INDEX OF SUBJECTS. a-Benzaldoxime, action of alkq-1 halo’ids on, PBOC., 1803, 265. -- action of hydrogen chloride, bro- mide, and iodde on, PRO~., 1893, 254. - and its derivatives, properties of, PBOC., 1893, 253. - crystallisation of, PBOC., 1893,263. - sulphate, PBOC., 1893, 295. p-Benzaldoxime, dihydrofluoride, PROC., - sulphate, PBOC., 1893, 255. Benzeneazo-p-cresol, bromo-91z-nitro-, 839.- p-chloro-, PBOC., 1894, 118. - dibromo-, PROC., 1894, 118. - ethyl ether. m-nitro-, 839. Benzeneazodimethylaniline, reduction Benzeneazo-a-naphthalene, nz-nitro-, Benzene-8-azo-a-naphthol, 835. - ethyl ether and its nitro-cleriva- - dinitro-, 840. Benzeneazophenol, m-nitro-, PBOC., Benzidine, acetylation of, 55. - tetrabromo-, acetylation of, 56. - - constitution of, 56. -- conversion of azobenzene into, 54.. Benzile and benzylamine, interaction of, in presence of zinc chloride, PROC., 1894,49. Benzoic acid, 2 : 4 : 6-trichloro-, pre- paration of, 1030. Benzoio chloride, 2 : 4 : 6-tricliloro-, 1030. Benzo‘in, preparation of 2’: 3 ’ d - phenjlindoles from, by the action of primary benzeno’id amines, 889. 1803,254. - m-nitro-, 838.of, 882. PROC., 1894, 141. tire, 841. 1894,143. Benzoylaconine, 291. Benzoylformaldoxime, PBOC., 1894, 57. Benzglamidoacetic acid, 189. Bemylamine, and benzeno’id aldehydes, condensation products of, 191. - and benzile, int,eraction of. in presence of zinc chloride, PROC., - and ethyrlic chloracetste, interitc- “ o-Benzyleneindene,” 494. Benzylglycocine, 189. Benzylidenebenzylamine, 191. Benzy lidenedihy droxynaphthaquinone, - a@-anhydride of, 81. 8-Benzylidene-a-hydrindone, 498. - dibromide, 499. Benzyllophine, PEOC., 1894, 49. 1894,49. tion of, 187. 79. Bismuth, freeezing points of alloys of. p oxide, be’nariour of, a t high tem- Bismuth-cadmium-gold allop, freeziug Bismuth-cadmium-silver alloys, frerz- Bismuth-gold alloys, E.31.F. of, in a Bismuth-silreralloys, cupellation of,624.Bismuth-silrer alloys, E.M.F. of, in :i Bismuth-tin alloys, E.M.F. of, in n Bismuth-zinc alloys, E.M.F. of, in LI Boiling points of ethereal salts of nor- -- of homologous compound^, -- of homologous simple and Bromates, effect of heat on, 802. Bromine, liquid, molecularxeight of,l69. Butane, 1 : 3-dibromo-, 962. Butanetetracarboxylic acid, 1002. I_- homologues of, 995. Butea fyondosa, colouring matter of tlie flowers of, PBOC., 1894, 11. Butyric acid, a-bromo-, magnetic rota- tion of, 410, 429. -- asp-trichloro-, magnetic rota- tion of, 410, 423. in thallium, 32, 34. pemtures, 314. points of triple, 69. ing points of, 73. voltaic cell, 1034. voltaic cell, 10G4. voltaic cell, 1034. voltaic cell, 1034. mal fatty acids, i 2 5 . calculation of the, 193, 725.mixed ethers, 194. C. Cadmium, oxide, behariour of, a t Iiigli Cadmium-gold-bismuth alloys, freezing Cadmium - gold-lead alloys, freezing Cadmium-gold-thallium alloys, freezing Cadmium-lead alloys, E.W.F. of, in :I Cadmium-eilver-bismuth alloyre, f reeziii g Cadmium-silrer-lead allojs, freezing Cadmium-sil-rer-thallium aUo~s, freez- Cadmium-silver-tin alloys, freezing Cadmium-zinc allogs, E.M.F. of, in a Csesium potassium and rubidium sul- temperatures, 314. points of, 69. points of, 66, 67. points of, 70. voltaic cell, 1037. points of, 73. points of, 72. ing points of, 72. points of, 71. voltaic cell, 1035. phatee, comparative cr~stallography of, 628.INDEX OF SUBJECTS. 1049 Cse-sium potassium and rubidium sul- phates, cornparatire optical characters of, 697.---- volume relations of, 649. - sulphate crystallography of, 64J. -- optical properties of, 674. Calcium oxide, action of chlorine on, 2. -- and ammonium chloride, in- fluence of moisture on the interaction of, 612. -- and sulphuric anhydride, in- fluence of moisture on the interaction of, 611. -- behmiour of, at high tem- peratures, 314. -- inertness of, 1. -- phosphorescence of, 736. - oximidosulphoiratep, 563. - sulphide, phosphorescence of. 737. Camphene, action of chlorine on, in presence of alcohol, PROC., 1894, 58. - action of phosphorus pentachloride on, 35, 37. - bromo-, PEoc., 1894, 57. - chloro-, PBOC., 1894, 5'7. - halogen derivatives of, PROC.. - phosphorus-derivatives of, 35.. a-Camphenephosphonic acid, 35. @Camphenephusphonic acid, 38.C'amphenephosphonic acids, action of halogens on the sodium salts of, 42. -- action of heat 3n the sodium salts of, 41. Camphor, action of bromine on, PEOC., 1894, 57. - dibromo-, a new, PBOC., 1894, 164. - preparation of sulphonic-deiiva- tives of, PEOC., 1894, 163. C'amphoric acid, products of the action of fused potash on, PBOC., 1894, 65. C'amphorsulphonic bromide, PROC.. 1894, 164. -- bromo-, Paoc., 1894, 16-1. -- dextrorotatory, PRO~.. 1894, - chloride, dextrorotatory, PROC., C'aprjlene, action of nitrosyl chloride Carbamide, freezing points of solutions Carbon and iron, chemical relations of, - bisulphide, combustion of, in ox?- - tetrabromide, new method of pro- 1894,57. 165. 1894,164. on, 326. of, 307, 308. 788. gen, 616. ducing, 262. Carbonic oxide, combination of, with chlorine irnder the influence of light, PBOC., 1894, 165.Cellulose8 and oxycellulosea. atmo- spheric oxidations of, 476. - oxy-, deoxidation of, 478. -_ -- hydrolTsis of, 4.78. -- natural, 472. Cerium dioxide, behaviour of, a t high temperatures, 311. Chelteaham, mineral waters of, 772. Chemical change, influence of moisture Chlorine, action of, on lime, 2. - and hjdrogen, influence of mois- ture on the interaction of, 612. - liberation of, during the heating i t mixture of potassium chlorate and manganese peroxide, 202. - magnetic rotation of, 27. Cinnamaldehyde, condensation of. with Cinnamene, w-nitro-, action of nitrosjl Cinnamic acid, action of nitroql chlor- Citrazinamide, preparation of, from - reduction of,with sodium amalgam, C'itrazinic acid, 28, 828.-- conversion of diammoniuni -- dinitro-, 833. -- nitration of, 831. -- sulphonation of, 834. Citrazinyl alcohol, 30. Citrazinylhydrobenzdn, 31. Cohaltosocobaltic oxide, behariour of, Colour, the origin of, PBOC., 1895, 206. Colouring principles of T-entilGgo mn- Corjdalic acid, 62. Corydaline. Part 111. 57. - distillation of, with zinc dust, 65. - oxidation of, with potassium per- manpiate, 57. Corydahnic acid, 59. -- action of hydrogen iodide OD, 62. Crotonic acid, action of nitrosyl chloride on, 388. Crystallographical characters of iso- morphous salts, connection between the atomic weight of contained metals and the, 628. Cuminaldehyde, condensation of, with P-hydroxy-a-naphthaquinone, 85. Cpnogen, flame, structure and chemis- try of the, 603.OD, 611. B-hydrox1-a-naphthaquinone, 85. chloride on, 327. ide on, 329. ethjlic citrazinate, 29. 29. citrate into, 28. a t high temperatures, 314. draspntano, 923.1030 INDEX OF SUBJECTS. D. Dehydracatic acid, salts cf, 254. Deviation, molecular, of ethereal salts of active diacetylglyceric acid, 750. 1)incetyladipic acids, 1016. Diacetylbutanetetracarboxylic acid, 1014. Diacetylglyceric acid, active, the maxi- mum molecular deviation in the series of the ethereal salts of, 760. -- influence of temperature on the rotatory power of ethereal salts of, 765. Dibenzyladipic acids, 1021. Dibenzylbutanetetracarboxglic acid, Dibenzyl- a y-diacipiperazine, 130. Dibenzyllophinium chloride, PROC., Didymium, oxide, behariour of, at high Diethyladipic acids, 1009.Diethylbutanetetracarboxjlic acid, 1007. aa’-Diglutaric acid, 830. Dihydropentenecarboxplic acid, bromo-, Dihjdropentenedicarboxvlic arid, 983. Dihydrotetrenecarboxjlil acid, bromo-, Dihydrotetrenedicarboxjlic acid, 975. -- bromo-, 978. - anhydride, 977. DihjdroxFdiketopyridine, amido-, 833. - nitro-, 832. ww,-Dihydroxphexane, 598. Di hydroxymethjlanthraquinone from Dihydroxytetraniethylenedicarboxylic Dimethylacetjlacetone, magnetic rota- Dimethylacrjlic acid, PEOC., 1894, 64. Uimethjladipic acids, 1005. Dimethylaniline, action of nitrosyl Dimethylbutanetetracarboxylic acid, &Dimethylglutaric acid, PBOC., 1894, - anhydride, PEOC., 1894,65. Dirnethylpropanetricarboxjlic acid, PBOC., 1894, 65. ,@-Dinttphthyl, 877. Uinaphthyldiquinone, 321. Diphenylamine, action of nitrosyl chlo- 2’ : 3’-Diphenjlindole, preparation of, 2’ : 3’-Diphenylindoles, preparation of, 1019.1894,49. temperatures, 314. 981. 969. mang-koudu, 863. acid, 972. tion of, 816, 824. chloride on, PROC., 1894, 60. 1004. 64. ride on, PROC., 1894, 60. 892. from benzoih and primary benzeno’icl amines, 889. 2’ : 3’-Diphenyl-a-naphthindole, 896. - compound of, with acetone, 897. - compound of, with diethyl ketone, - compound of, with methyl ethyl 2’ : 3’-Diphenj1-/3-naphthindole, 897. - compound of, with acetone, 898. 2’ : 3’-Diphenyl-o-toluindole, 893. - compound of, with acetone, 895. 2’ : 3’-Diphenyl-p-toluindole, 896. - compound of, with acetone, 896. Disodimicie, non-existence of, 507. Dissociation of ammonium chloride, in- - of nitrogen tetroxide, influence of 897.ketone, 897. fluence of moisture on, 615. moisture on, 616. E. ElaYdic acid, action of nitrospl chloride Electrical discharge, influence of mois- -- separation of mixed gases by, - repulsion in solutions, PROC., Electromotive force of alloys in a ~ o l - Elements, oxides of, and the periodic Emodin methyl ether, 925, 934. --- nitro-, 934. --- tetranitro-, 935. - tetranitro-, 925, 935. Ethers, simple and mixed, boiliiig points Ethoxypropane, chlor-, 596. Ethylenic bromide, action of, on soda- Ethylic alcohol, freezing points of solu- - anhydroanilaconitate, 12. - benzylamidoacetate, 188. - bromacetate, magnetic rotation of, - a-bromobutyrate, magnetic rota- - a-bromopropionate, magnetic rota- - butanetetracarboxjlate, prepara- - carbonate, magnetic rotation of, - chloracetate and benzylamine, in- on, 329.ture on, 621. 619. 1894,167. taic cell, 1030. law, 107. of homologous, 193. mide, 522. tions of, 307, 308. 406, 418,427, 430. tion of, 410, 429. of, 410, 429. tion of, 578. 405, 421. teraction of, 187.ISDES OF SUBJECTS. 1051 Ethylic chloracetste, magnetic rotation - chlorocarbonate, magnetic rotation - a-chlorocrotonate, magnetic rota- - chloroformate, magnetic rotation - a-chloropropionate, magnetic rota- - dehy dracetate, 261. - diacetylbutanetetracarboxy late, - dibenzylbutanetetracarboxylate, - dibromacetate, magnetic rotation - dibromotricarballjlate, action of -- action of baryta on, 10. -- preparation of, 9. - dichloracetate, magnetic rotation - diethjlacetoacetate, magnetic rota- - diethy lbutanetetracarboxgla te, - dmethylacetoacetate, magnetic ro- -- dimethylbutanetetracarboxylate, - dimethylpropane tricarboxyT-late, - - magnetic rotation of, 821, -- refractive and dispersive - ethylbutanetetmcarbosplate, at - - ethylpimelate, 991.- heptane- up,-tetracarboxylate, -- synthesis of, 104. - iodacetate, magnetic rotation of, - a-isobromobutpate, magnetic ro- - octane-w,w,-tetracarboxylate, 600. -- action of sodium ethoside - phenylpyrrolonedicarboxylate, 13. - salts of normal fatty acids, boiling - tribromacetate, magnetic rotation -- trichloracetate, magnetic rotation - aa@-trichlorobutyrate, magnetic - trichlorolactate, magnetic rotation of, 406,414, 418, 423. of, 405, 420. tion of, 412, 424. of, 4.05, 420. tion of, 409, 428. 1014. 1018. of, W, 418, 427,430.aniline on, 11. of, 406, 414, 418, 423. tion of, 823, 827. 1007: tation of, 816, 823, 827. 1004. PBOC., 1894, 65. 826. power of, 823, 828. tempts to prepare, 1012. 104. 408, 428, 431. tation of, 412, 430. and iodine on, 601. points of, 726. of, 406, 418, 428, 430. of, 406, 414, 418, 423. rotation of, 410, 424. of, 409, 4%. Ethylidenedihgdroxynaphthaquinone, -aB-anhydride of, 83. Ethylmethylpimelic acid, 992. Ethylpimelic acid, 989. -- anilide of, 992. Eugenol, action of nitrosyl chloride on, - ethylic ether, action of nitrosyl Emporation, volatilisation of salts 82. 331. chloride on, 331. during , 445. F. Fermentative functions of yeast cells, Ferric oxide, behayiour of, a t high tem- Fluorine, density of, 401. Fluorplumbates, 393. Fluorplumbic acid, 399.Formaldoxime, PROC., 1894, 55. - bromide, PROC., 1894, 56. - chloride, PBOC., 1894, 56. - iodide, PROC., 1894, 56. Formulae, molecular, of some liquide, as determined by their molecular surface energy, 167. specific character of, 911. peratures, 324. Freezing point determinations, 293. - points of alloys in which the sol- -- of dilute solutions, PROC., -- of triple alloys, 65. Zurfural, estimation of, 479. tent is thallium, 31. 1894, 101. G. Gas, supposed relation between the solubility of a, and the viscosity of its solrent, 782. Gases dissolTed in water, apparatus for the extraction for analysis of the, 4. - mixed, separation of, by the electric discharge, 619. Germination, formation of oxycelluloses during, 476. Gljceric acid, effect of temperature 011 the optical activity of ethereal salts of, 161.Olycocine and its derivatives, constitu- tion of, PROC., 1894, 90, 94. Gold, freezing points of solutions of, in thallium, 33. Gold-aluminium-tin alloys, freezing points of, 74.I052 ISDEX OF SUBJECTS. Gold-bismuth alloys, E.M.F. of, in a Gold-cadmium-bismuth alloys, freezing Gold-cadmium-lead allop, freezing Gold-cadmium-thallium alloys, freezing Gold-lead alloys, E.M.F. of, in a voltaic Gold-silver alloys, E.M.F. of, in a rol- Gold-tin alloys, E.X.P. of, in a yoltaic voltaic cell, 1034. points of, 69. points of, 66, 67. points of, 70. cell, 1036. taic cell, 1035. cell, 1037. H. Heat, latent, of fusion Gf thallium. 35. Heptabenzoylruberythric acid, 186. p-Heptoyltoluene, PROC., 1894, 60. Heptylic chloride, action of aluminium chloride on, PBOC., 1893,208 ; 1894, 60.Heptylic diacetylglycerate, active, 751. Heptpl-p-toluidine, PBOC., 1894, 61. Hexabenz o y lrubery thric acid, 1 S7. Hexahydrcibenzoic acid, spntheais of, Hexamethylene glycol, 598. HexamethylenecarboxFlic acid, synthe- Hesamethylenic &bromide, 691, 599. -- action of, on ethJ-lic sodio- malonate, 591, 599. -- action of sodium on, 591, 599. Hexylene nitrosochloride, 326. Homologous compoiinds, calculation of Hydracetylace t one, magnetic rot at ion - refractiye and disperske power of, Hydrindene, action of bromine on, 230. - and some of its deriratires, syn- - ethyl ketone, 243. -- ketoxime, 244. - methyl ketone, 140. -- lietoxime, 241. - phenyl ketone, 245. - preparation of, 248. Hydrindenecarbosylamide, 136.Hydrindenecarboxylic acid, 233. -- tetmbromo-, 237. -- anilide, 136. - chloride, 235. IIFdrindenedicarboxjlic acid, prepara - 86,103 j i, 366. sis of, 86, 103. the boiling points of, 193, 725. of, 819, 825. 820, 828. thesis of, 228. t ion of, 232. Hydrindeneethylcarbinol, 244. HydrindeneethFlcarbinyl acetate, 245. Hydrindenemethylcarbinol, 242. Hydrindenemethylcarbinyl acetate, 14.3. a-Hydrindone and its derivatives, 4SO. - brom-, 500. - condensation products of, 495. _- dibrom-, 501. - dichlor-, 503. - formation of the hydrocarboii - isonitroso-, 492. - nitro-, 495. -- preparation of, from phen-lpro- pionic chloride, 454. - properties of, 4-88. Hydrindonehydrazone, 493. a-Hgdrindoneoxime, 489. - conrersion of, into hjdrocarbostj- ril, 490. Hydrocarbons, coloured, PBOC., 1893.206. Hydrocarbostyril, conversion of a a - h j - drindoneoxime into, PBOC., 1893. 244). Hydrogen and chlorine, influence of moisture on the interaction of, 612. - chloride and ammonia, inhence of moisture on the combination of. 614. -- and potassium chlorate, inter- action of, PRO~., 1893, 211. -- freezing points of solutions of, 308. -- magnetic rotation of, in rariow solvents, 20. - peroxide, formation of, from oxalic acid, under the conjoint action of light and oxygen, 453. truxene from, 269, 278. Hydroquinolietopyridine, 830. m-Hy droxganthraquinone -B-carbosylic Hydroxybeozaldehpdcs, condensation o-Hydroxjbenzylidenebenzylamine, 192. p -IIydroxjbenzFlidencbenzylamine, HydroxThydrolnpochol. bmm-, 19. - hydroxime, 721. Hj-droxplamine, action of methj-lir iodide on, PROC., 1894, 138.HFdroxylamines, substituted, formation of, by the reduction of aliphatic nitro-compounds, PBOC., 1894, 139. b-Hydroxy-a-naphthaquinone, conden- sation of aldehydes with, 76. H~droxytetramethylene, 960. - action of bromine on, 961. Hyponitrites, PEOC., 1893, 210. - preparation of, PBOC., 1893, 210. acid, 846. of, with benzylamine, 192. 192.LDES OF SUBJECTS. 1053 I. Indene and some of its derivatives - brom-, 253. - preparation of, from hydrindene- Indenecarboxylic acid, 138. Indium oxide, behaviour of, at high Iodates, effect of heat on, 80%. Iron, an early Scottish, 744. - and carbon, chemical relations of, Isaconitine, action of heat on, 181. - and picraconitine, identity of, - conversion of aconitine into. 290. Isobutyraldoxime, action of phosphorus Isocrotonic acid, action of Oitrosjl chlo- Isosafrole, action of nitrosyl chloride on, synthesis of, 228.carboxylic acid, 246. temperatures, 314. 788. 176. pentacldoride on, 226. ride on, 328. 332. J. Jute fibre, produced in England, 470. K. a-Ketohgdrindene, -488. Ketone formed by the action of alum- inium chloride on heptylic chloride, PBOC., 1893, 209. Ketonic origin, magnetic rotation of compoimds supposed to be of, 815. L. Lapachol, bromo-, preparation and pro- - hydroxime, '720. - synthesis of, PBOC., 1893, 559. Lapachol-group, hFdroximes of, 717. a-Lapachone, it=-bromo-, 18. - hydroxime, 723. p-Lapachone, nS-bromo-, 1s. - hydroxime, 723. J,ead acetohydroxy oximidosulphonates, - ammonium oximidosulphonates, - freezing points of solutions of, - oxide, behaviour of, a t high tem- - oximidosulphonates, 566.perties of, 15. 869. 871. in thallium, 32, 35. peratures, 314. Lead potassium oximidosulphonates, basic, 569. - sulphide, interaction of, with lead sulphate and oxide, PBOC., 1894, 151. -- new T-olatile compounds of, PRO~., 1894, 113. - tetrafluoride, 399. Leacl-antimony alloys, E.X.F. of, in il voltaic cell, 1035. Lead-cadmium alloys, E.X.F. of, in n Toltaic cell, 1037. Lead-cadmium-silT-er alloys, freezing point of, 72. Lead-gold alloys, E.M.F. of, in a voltaic. cell, 1036. Lead- gold-cadmium alloys, freezing point of, 66, 67, 68. Lead-silver alloys, E.M.F. of, in a rol- taic cell. 1037. Light, action of, on oxalic acid, 450. - combination of carbonic oxide with chlorine under the influence of, PROC., 1894, 165.Lime, action of chlorine on, 2. - and aminonium chloride, influence of moisture on the interaction of, 612. - and sulphuric anhydride, influencc of moisture on the interaction of, 61 I. - inertness of, 1. - phosphorescence of, 736. Liquids, molecular formula of some, 8s determined by their molecular surface energy, 167. - organic, influence of temperature on the optical actirity of, 760. Lithamide, preparation, properties, and composition of, 517. Lithium chloride, magnetic rotation of, 26. - oxidation products of, 443. M. Xadder colouring matters, 181. Magnesium-silver couple, action of strong acids on, PBOC., 1894, 85. Magnetic rotation of acetic and propionic acids, phosgene and ethFlic carbonate, 4Q2 * -- of chlorine, 27.-- of compounds supposed to contain acetyl, or to be of ketoaic origin, 815. -- of halogen deriratires of the fatty acids, 302. -- of hydrogen chloride in dif- ferent solvents, 20. -- of lithium chloride, 26.1954 INDEX OF SUBTECTS. Magnetic rotations of sodium chloride, Mang-koudu, coiouring and other prin- - dyeing properties of, 868. Manures, estimation of available phos- phoric acid in, 162. Mercuric acetylide, 265. Mercury-B-dinaphthyl, 877. Metals in contact with one another, action of concentrated acids on, PBOC., 1894, 84. 25. ciples from, 851. Methoxypropane, chlor-, 597. Methoxypropylethylacetic acid, 993. Methylaconitine, PBOC., 1894, 97. Methylalizarin, 185. Methylaniline, action of nitrosyl chlo- 5-Methyl-4’-dimethylamidodj phenyl- -- behaviour of, with benzile, -- - behaviour of, with nitrous -- behaviour of, with salicJ-l- -- decomposition of, with hydro- Methylenediisonitrosamine, 949.Methylic acetoacetate, magnetic rotation - a-bromopentamethylenecarboxyl- - chloracetate, magnetic rotation of, - dibromo te trame thylenedicarboxyl- - dihydrotetrenedicarboxylate, 974. - dimethplacetoacetate, magnetic ro- - hydrindeiiecarboxylate, 234. - salts of normal fatty acids, boiling points of, ‘725. - cis-tetramethylenedicarboxylate, 583. Methylpentylethvlene, action of nitrosyl chloride on, 326. Methylpropylethylene, action of nitrosyl chloride on, 325. Molecular deviation, maximum, in the series of the ethereal salts of active diacetylglyceric acid, 750. - formulae of some liquids as deter- mined by their molecular surface energy, 167.Molvbdic anhydride, behaviour of, a t high temperatures, 314. Morindin from Mang-koudu, 867. Morindone from Mang-koudu, 867. ride on, PROC., 1894, 60. methane, 2-amido-, 883. 886. acid, 887. aldehyde, 883. chloric acid, 888. of, 816, 823, 826. ate, 101. 408, 424. ate, 967. tation of, 816, 823, 826. N. Naphthalene, @-broino- and 8-chloro-, action of, on benzene, in presence of aluminium chloride, 874. - B-chloro-, action of chlorobenzene and sodium on, 871. -- preparation of, 875. a-Naphthaleneazo-@-naphthol, 837. @-Nsphthaleneazo-@-naphthol, reduction of the acetyl-derivative of, 836. @-Naphthaquinonehydrazone, 839. a-Naphthol ethyl ether, trinitro-, 841. - trinitro-, 842. @-Naphthol, action of, on benzene in presence of aluminium chloride, 874.a-Naphthylamine, trinitro-, 841. Naphthylhydrazines, action of nitrosyl chloride on, €’ROC., 1894, 60. Nickelic oxide, bebaviour of, a t high temperatures, 314. Niobic anhydride, behaviour of, a t higli temperatures 314. Nitrates, action of acid chlorides on, PEOC., 1893, 255. Nitric acid, freezing points of solutions of, 309. -- molecular weight of l i p i d , Nitric oxide, action of, on potassium, -- action of, on sodium, 443. - - action of, on sodium ethoxide, 941. -- and oxygen, influence of moisture on the interaction of, 613. Nitric peroxide, influence of moisture on the dissociation of, 616. Nitro-compounds, aliphatic, reductioll products of, PROC., 1894, 139. Bitrogen oxides, red, action of, on potas- sium, 440. - tetroxide, influence of moisture on the dissociation of, 616.Nitrosyl chloride, action of, on unsatn- Kitrous oxide, action of, on potas- -- action of, on sodium, 443. 169. 440. rated compounds, 324. sium, 438. 0. Octylene, normal, action of nitrosvl Octylic diacetylglycerate, 752. Oils, essential, aerial oxidation of, Ole’ic acid, action of nitrosyl chloride on, chloride on, 326. PROC., 1894, 51. 329.INDEX OF SUBJECTS. 1055 Omicholin, PBOC., 1893, 239. Optical actirity of orgltnic liquids, in%u- Organic-compounds, viscous flow of, Oxalic acid, action of light on, 450. Oxamide, sulphate, PROC., 1894, 58. Oxides, behaviour of the more stable, a t high temperatures, 313. - of the elements and the periodic law, 106. - stability of, considered in relation to the periodic law, 314. Oximidosulphonates, 523.- and sulphazotates, identity of, - behaviour of, when heated, 542. - constitution of, 538. - hydrolysis of, 541. Oxycelluloses, atmospheric oxidations of, - deoxidation of, 477. - hydrolysis of, 478. - natural, 472. Oxygen and nitric oxide, influence of moisture on the interaction of, 613. Ozone, in%uence of moisture on the formation of, from oxygen, 617. ence of temperature on , 760. PBOC., 1894,136. 535. 476. P. Paraffins, normal, boiling points of, A’-Pentamethenylcarboxylic acid, 101. Pentamethylenecarboxylic acid, anilide -- dibromo-, 102. -- synthesis of, 86, 98. -- a/?2-tribromo-, 982. - chloride, 99. Pentamethylenediamine hydrochloride, 1 : 1-Pentamethylenedicarboxylic acid, 1 : 2-Pentamethylenedicarboxylic acid, - - cis- and tf-am-modifications -- dibromo-, 980.cis-Pentamethglenedicarboxylic acid, -- anhydride, 587. - phenyliloide of, 589. trans-Pentamethglenedicarbosylic acid, - anhydride, 985. Periodic law and the oxides of the -- stability of the oxides con- 730. of, loo. action of silver nitrite on, 94. 96. 978. of, 572. 590. 586. elements, 106. sidered in relation to the, 314. Phenanthrene, action of nitrosyl chlo- Phenazine from thymoquinonediortho- Phenol, freezing points of solutions of, - liquid, molecular weight of, 168. Phen-j-lchloropropylenehydrindone, 486. Phenylhydrazine, action of nitrosy1 P-Phenylnaphthalene, 869. - synthesis of, 870. Phenylnaphthalenes, 869. Phenylpropionic acid, formation of the - chloride, preparation of, 484. Phenylpyrrolonedicarboxylic acid, mon- Phosgene, magnetic rotation of, 404, Phosphorescence, observations on the Phosphoric acid, estimation of probably -- estimation of probably avail- -- freezing points of solutions Phosphorus, molecular weight of liquid, Picraconitine, 1’74.- and isaconitine, ideiit,ity of, 176. Pimelic acids, substituted, 987. Piperidine, nitrol-, 325. Plant food in soils, mineral, analytical determinations of probably available, 115. Platinum, freezing point of solutions of, in thallium, 34. Plumbates, fluor-, 393. Plumbic acid, fluor-, 399. Potash in soils, estimation of probably Potassamide, action of nitrosyl chloride - action of, on inorganic oxides, 519. - preparation, properties, and com- Potassium, action of dry air or oxygen - action of nitric oxide on: 440. - action of nitrous oxide on, 438.- action of the red oxides of nitrogen on, 440. - carbonate, freezing points of solu- tions of, 311. - chlorate and hydrochloric acid, interaction of, PBOC., 1893,211. and manganese dioxide, liberation of chlorine during the heating of a mixture of, 202. ride on, 327. nitranilide, PEOC., 1893, 216. 307. chloride on, PROC., 1894, 60. hydrocarbon trusene from, 369, 277. amide of, 13. 420. nature of, 734. available, iu manures, 168. able, in soils, 116. of, 308, 309. 172. available, 115. on, 521. position of, 511. on, 434, --1056 INDEX OF SUBJECTS. Potassium chlorate, effect of heat on - - influence of moisture on the - chloride, freezing points of solu- - fhoroxyperplumbate, 394. -- fluorplumbate, 394. - hydroxide, freezing points of soln- - iodate, effect of heat on, 806,811.- iodide, decomposition of, on expo- sure to air and light, 804. -- liberation of iodine from, by the action ofweak acids, 804. - melting point of, 433. - nitride, non-existence of, 512. - oxidation products of, 432. - oximidcsulphonate nitrate, 551. -- preparation of, 524. - oximidosulphonates, 54’7. - rubidium and ccesium sulphates, compai-atim cryshllographp of. 628. ---- comparative optical characters of, 697. ---- volume relation3 of, 649. - sodium oriniiclosulphonate chlo- ride, 551. -- oximidosulphonotes, 551. -- sulphata, crystallography of, 634. -- freezing points of solutions -- optical properties of, 666. l’ropionaldosime, action of phosphorus - action of phosphorus pentachloride - isomeric forms of, 221. Propionic acid, a-bromo-, magnetic rota- - - magnetic rotation of, -103, Propjlethylacetic acid, bromo-, 993.Propylic salts of normal fatty acids, Pseudosolution and solution. PROC., Purpurin-B-carboxyljc acids, 848. Pyraconine, composition and propertied - salts of, 180. Ppraconitine, 177. - hydrolysis of, 179. - salts of, 178. Pvrroline-deriratives, formation of, il-om aconitic acid, 9. 8 14. decomposition of, 617. tions of, 310. tions of, 310. of, 311. trichloride on, 225. on the isomeric forms of, 224. tion of, 410, 429. 421. boiling points of, 726. 1894,166,167. of, 180. Q- Quicklime, inertness of, 1. Quinhydroketopyridine, reduction of, 828. Quinone-derivatives, conversion of ortho- into para- and of para- into ortho-, 76, 321, 717. Quinonedi-m-nitranilide, PROC., 1893, 216.Quinonedi-p-nitrotoluidide, PROC., 1893, 216. Quinone-nt-homofluorindene, PROC., 1893, 216. Quinone-m-nitranilide, FROC., 1893, 216. Quinone-p-nitrotoluiciide, PROC., 1893, 216. Qninones, interaction of, with m-nitr- aniline and nitro-p-toluidine, YROC.: 1893, 215. R. Root sap, experiments on the aciditp of, Rotation, molecular, of ethereal salts of Rotatory power of organic liquids, Ruberjthric acid, benzoyl-deriratives of, Rubiadin, constitution of, 182. Rubidium caesium and Dotnssium sul- 127. diacetylgl y ceric acid, ’I 55. effect of temperature on, ’760. 186. p hates, compaiatir e Ass t,allogrsplig- of. 628. ----- comparative optical ---- volume relations of, - sulphate, crystallography of, 63s. -- optical properties of, 680. characters of, 697. 649.S. Safrole, action of nitrosyl chloride on, 332. Salicylddehyde, condensation of, m-it11 /+hjdroxy-a-naphthaquinone, 86. Salts, coagulative power of, on arsenious sulphide solutions, PSOC., 1894, I6b. - ethereal, of normal fatty acids, boiling points of, 725. - isomorphous, connection between the atomic weight of contained metals and the crystallogaphical characters of, 628. _I solid, viscous flow of, PROC., 1894, 136. - Tolatilisation of, during erapora- tion, 445. 3ebacic acid, synthesis of, 600.INDEX OF SUBJECTS. 1057 Silrer, freezing points of solutions of, in - hpponitrite, PBOC., 1893, 210. Silrer-bismuth alloys, cupellation of, --- E.M.F. of, in a voltaic Silrer-cadmium-bismuth alloys, freezing Silver-cadmium-lead alloys, freezing Silrer-cadmium-thallium allojs, freez- Silver-cadmium-tin alloys, freezing Silver-copper couple, action of strong Silrer-gold alloys, E.X.F.of, in a rol- Silrer-lead alloys, E.3l.P. of, in ;I 1-01- Silver-magnesium couple, action of Sodamide, action oE ethylenic broiiiidc' - action of ethylic iodide on, 521. -- action of nitrosyl chloride 011, 321. - action of, on inorganic o d e * , - prepamtion, properties anit c'oiu- Sodium, action of dry air or oq-gen on, - action of nitric oxide on, 443. - action of nitrous oxide on, 4-43. - action of strong sulphuric acid on, - carbonate, freezing points of solu- - chloride, freezing points of solu- -- magnetic rotation of, 25. - ethoxide, action of nitric oxide on, - hgdroxide, freezing points of soln- - hypmitrite, PROC., 1893, 210. - influence of contact with another metal on the action of strong sulphu- ric acid on, PBOC., 1894, 86.- nitride, non-existence of, 507. - oxidation products of, 4.40. - oxide, action of ammonia on, 510. - oximidosulphonates, 546. -- preparatioo of, 324. Soils, determination of the probably available mineral plant food i n , 115. - viscosity of, PBOC., 1894, 136. Solubility of a gas, and the viscosity of its solrent, supposed relatioa between. 782. TOL. LSV. thallium, 33. 622. cell, 1034. points of, 73. points of, 72. ing points of, 72. points of, 67, 71. acids on, PROC., 1894. 84. taic cell, 1035. taic cell, 1037. strong acids on, PROC., 1894, 8.5. on, 522. 319. position of, 504. Ml . PBOC., 1894, 86. tions of, 311. tions of, 306, 308, 309. 944. tioils of, 310. olution and pseudo-solution, PROC., 1894, 166,167.lolutions, dilute, results of meawre- ments of the freezing points of, PROC., - electrical repulsion in, PROC., ltannic oxide, behaviour of, a t liigli jtilbene, action of nitrosyl chloride 011, krontium oxide, behaviour of, a t high - oximidosulphonates, 365. Sugar, cane-, freezing points of solu- tions of, 307, 308. julphazotates, 523. - and oximidosulphonates, identity hlphuric acid, freezing points of soh- tions of, 306, 308, 310. -- molecular weight of liquid, 17c. - anhydride and lime, influence of iiioisture on the interaction of, 611. 1894,101. 1894,167. tsmperatures, 314. 327. temperatureg, 314. of, 535. T. J h t d i c anhydride, behaviour of, :t T d a r i c acid, oxidation of, in presence Temperat#ure, influence of, on the optical Terpenes, 35.- atrial oxidation of, PBOC., 1894, 31. TCSU, coloriring matter of the Indian dye-stuff, PROC., 1894, 11. Tetramethylene, bromo-, 961. - chloro-, 953, 964. - derivatires of, 9 3 . - iodo-, 964. -- action of quinoline on, 91;s. Tetramethylenearnine, 959. Tetramethylenecarboxylamide, 957. Tetramethglenemrbosylic acid, &-t ri- Tetramethylrnedicarboxylamide, 584. 1 : 2-Tetrztmethplenedicarboxylic acid, cis- and trans-modifications of, 552- ri.s-Tetr-methylenedicItrboxy1ic acid, 582. high temperatures, 314. of iron, 893. actixity of organic liquids, 760. bromo-, 973. clibromo, 965. -- - --- action of alkalis on, - - - action of potassium --- action of silver oside 969. iodide on, 978. on, 972. 4 F1055 ISDES OF SUBJECTS. tram-Tetramethylenedicarboxylic acid, -- phenylimide of, 584.cis-Tetramethylenedicarboxylic enhj- __.- dibromo-, 968. --- action of dimcth! hni- line on, 971. .)I-- action of quinoliiic on, 971. i : 1 : 2 : 2-Tetramethylenetctracar- boxylic acid, 580. Thallium, freezing point of alloys in which the solvent is, 31. - latect heat of fusion of, :35. Thallium-cadmium-silver allo~-s, frcez- Thallium-gold-cadmium nllo~-a, frec.c.iiig Thymoquinone-o-methjlpheiiazinc., Thymoquinonedi-o-nitranilide, I'xoc'., Thymoquinonedi-p-nitrotoluididc, Tin-aluminium- gold allop, f recz in g points of, 74. Tin-antimony allogs, E.M.F. of, in a voltaic cell, 1035. Tin-bismuth alloys, E.3I.F. of, in a voltaic cell, 1034. Tin-cadmium-silver allogs, freezing points of, 71. Tin-gold alloys, E.X.F. of, in a voltaic cell, 1037. Titanic anhydride, bchariour of, a t high temperatures, 314. p-Tolueneazo-p-cresol, ncet: lation and reduction of, PROC., 1894, 118. ~-Tolueneazodimeth~-l~~ii1i1~Cy prepma- tion of, 880. - reduction of, 9%. Trihydroxy-a-methjhatliranolc, iuono- methFl ether of, 936. Trihydroxy methylanthraquinone nictlijl ether, 862. Trihydroxy-a-methylant hraquinonc, monomtehyl ether of, 933. Trimethylhydroxylamine and its salts, Paoc., 1894, 139. Truxene, action of nitric ncId 011, 288. - action of nitrobcnzene oii, 2S6. - dibromo-, 287. - formation of, froin phen~llwopioiiic - molecular weight of, 183. - oxidation of, 283. Tuugstic anhydride, behariour of, at Turpentine, Russian, aerial oxidation of, 585. dride, 581. ing points of, 72. points of, 70. PROC., 1893, 216. 1893, 216. PROC., 1893, 216. acid and from hydrindone, "9. high temperatures, 314. PBOC., 1894, 51. u. Unsaturated compounds, action of nitrosyl chloride on, 324. 1-rank anhydride, behaviour of, at high temperatures, 314. Urea, freezing points of solutions of, 307, 308. Urine, action of benzoic chloride on, in presence of alkali, PILOC., 1893, 238. Crochrome, formation of benzoic-deri- vatives of, PROC., 1893, 238. C-romelanin, Paoc., 1893, 239. 1-ropittin, Paoc., 1893, 239. V. Vanadic anhydride, behaviow of, at Ventilagin, 940. Yentilago madraspntana, colouring Viscosity of solids, PROC., 1894,136. Voltaic cell, electromotive fome of high temperatures, 314. principles of, 923. alloys in, 1031. W. Water, appamt,us for the extraction for aoaljsis of the gases dissolved in, 43. - from the Zem-Zem Well in Xecca. PROC., 1893, 245. -- rapow, theory of the influence of. on chemical action, 618. Waters, mineral, of Cheltenham, 772. \\-ax from mang kondu, 867. - from Ventilugo madraspafnrin, 923. Y. Yeast-cells, specific character of the fermentatire character of, 911. Z. Zinc ch, -1e, freezing points of solu- - oxide, behaviour of, at high tern- Zinc-bismuth alloys, E.M.F. of, in a Zinc-cadmium alloys, E.M.F. of, in a Zirconiuui dioxide, behariour of, at tions of, 11. peratures, 314. yoltaic cell, 1034. voltaic cell, 1035. high temperatures, 314.

ISSN:0368-1645    

DOI:10.1039/CT8946501046

出版商:RSC    

年代:1894

数据来源: RSC