摘要:

11 54 PERKIN : AZO-BENZENE DERIVATIVES OF PHLOROGLUCINOL. CIX. -Axo-benxen e Derivatzves of Phlorogl ucinol. By ARTHUR GEORGE PERKIN, F.R.S.E. ALTHOUGH the behaviour of resorcinol towards diazobenzene and allied substances has received considerable attention, the reactions of phloro- glucinol in this respect have been but little studied. Previous work in this direction has shown that the latter yields azo- and disazo- derivatives although with the same reagent both azo- and disazo-deriva- tives have not as yet been obtained. For instance, by treatment with diazobenzene sulphate i n aqueous solution ( Weselsky and Benedikt, Ber., 12, 226) preferably in the presence of sodium acetate, phloro- glucinol-disazobenzene is formed, but no corresponding monazo-compound appears to be capable of production in this way.Phloroglucinol- disazobenzene corresponds therefore to the isomeric azobenzene-resor- cinols in that they respectively represent the simplest products obtainable from these phenols under similar conditions. As is well known, resorcinol also forms isomeric disazobenzene derivatives, and considering the coiistitution of phloroglucinol, it seemed reasonable to expect that the latter would yield a higher or trisazo-derivative. The study of this subject suggested itself during the investigation of disazo- benzenemaclurin (Trans., 1895,933), and the main results of this paper were worked out at that time. As was to be expected, the reactive ca- pacity of various substituted diazobenzenes with phloroglucinol showed considerable dissimilarity, and further work in this direction seemed desirable.No convenient opportunity has as yet been found for this purpose, but as the presence of a free hydroxyl group in phloroglucinol- disazobenzene (Trans., 1897, 187) has rendered the capacity of this phenol to form trisazo-derivatives more obvious, it was felt that it would be better to communicate the results already obtained to the Society. P~Zoi.ogZucinoZ-tric~~obenxe.ne. -To a solution of phloroglucinol in dilute sodium carbonate, excess of a solution of diazobenzene sulphate was added; the deep-red precipitate t,hus obtained was insoluble in dilute alkali, and it could not, therefore, be the disazo-compound,PERKIN : RZO-BENZENE DERIVATLVES OF PHLOROGLUCINOI~. 1155 After being collected, washed, and dried, it was purified by cautiously diluting a hot nitrobenzene solution with boiling alcohol, the crystals which separated on cooling being collected and washed with alcohol.0.1339 gave 0,3217 CO, and 0,0517 H,O. 0.1230 ,, 21.2 C.C. nitrogen a t 24' and 762 mm. N= 19.46. C,H,O,(C,H,N,), requires C: = 65.75 ; H = 4.1 1, N = 19.1 7 per cent.. The formation of this substance from phloroglucinol in the presence of aqueous sodium carbonate is apparently not dependent on the quantity of diazobenzene sulphate present, for if this be added in the proportion of only one or two molecules to one molecule of phloro- glucinol, the trisazo-compound is formed, a portion of the phloroglucinol being unacted on. As is to be expected, the trisazo-compound also results from the action of diazobenzene sulphate on an alkaline solution of phloroglucinol-disazobenzene. C= 65.52 ; H = 4.29.0,2900 gave 49 C.C. nitrogen at 16' and 740 mm. It is obtained as a glistening mass of fine needles, having usually a beetle-green lustre; i t does not melt below 300°, but when rapidly heated above this temperature, decomposes with evolution of a cloud of black vapour. Its crystallisation is facilitated by the addition of a t'race of acetic acid to the hot nitrobenzene solution before ,dilution with alcohol. As stated above, it is insoluble in cold alkali solutions and contains no hydroxyl groups, those originally present in the phloroglucinol having assumed the ketonic form from their ortho- position relatively t o the azo-groups. Sulphuric acid dissolves it with R deep crimson coloration.PlLZo?.ogZucinoZ-oi.thotrisuxoanisoZ, prepared in a similar manner froni phloroglucinol and orthodiazoanisol, was purified by crystallisation from nitrobenzene. N = 19-17'. Theory requires N = 19.17 per cent. 0.1513 gave 0.3356 CO, and 0.0593 H,O. 0.1445 ,, 20.2 C.C. nitrogen at 18" and 762 mm. N = 16.19. C,H,O,(C,H,N,*OCH,), requires C = 61.36; H = 4-54; N = 15.90 per cent. Attempts were made to prepare from phloroglucinol the correspond- ing disazo-compound by the substitution of sodium acetate for sodium carbonate solution. The product in each case was, however, the above trisnzo-derivative, although analysis indicated i t s contamination wit11 a trace of a lower azo-compound. C = 61-03 ; H = 4.35. 0.1420 gave 18.8 C.C.nitrogen a t 17" and 758 mm. Theory requires N = 15.90 per cent. Phloroglucinol-trisazoanisol crystallises from nitrobenzene in the form of long, glistening, maroon-coloured needles which are slightly N = 15.32. 4 1 21156 GARDNER AND COCKBURN: ACTION OF iridescent and do not melt below 300". With sulphuric acid, it forms a deep violet blue liquid, and is but slightly attacked by nitric acid (sp. gr. 1.5) with gradual production of a deep violet-red solution. ~h~o~~og~uc~no~-d~scczobenxene-axometan~t~~oben~ene.-~he formation of phloroglucinol-trisazobenzene from the corresponding dieazobenzene- compound as shown above suggested the possibility of introducing two different azo-groups into phloroglucinol. The above compound is readily prepared by the addition of a diazometanitrobenzene sulphate t o an alkaline solution of disazobenzene-phloroglucinol.By the cautious addition of boiling alcohol to a solution of this substance in hot nitro- benzene, it separates in a crystalline condition. 0.1085 gave 19.4 C.C. nitrogen at 22' and 760 mm. N = 20.25. C,H,O,(C,H,N,),(C,H,N,* NO,) requires N = 20.28 per cent. As thus obtained, i t forms a dull red, glistening mass of fine needles melting at 290' with decomposition, readily soluble in boiling nitrobenzene, almost insoluble in alcohol. With sulphuric acid, it yields a deep scarlet liquid. Further work will, if possible, be carried out at a later date with the object of studying the reactive capacity of the various substituted diazobenzenea with this phenol. That this varies considerably is shown above and also from the work of previous investigators ; thus, whereas phloroglucinol in sodium acetate solution combines with two molecules of diazobenzene, with orthodiazoanisol, under similar conditions, a trisazo-derivative is formed ; further, according to Stebbins (J. Arner. Chem. Xoc., 2, 240), and Weselsky and Benedikt (Ber. 12, 226), phloroglucinol-parazobenzenesulphonic acid, CGH,O,( C6H,N,* SO,H), and isomeric phloroglucinol-parazophenols, C,H,03(C,H4N,* OH), can readily be obtained. CLOTHWORKERS' RESEARCH LABORATORY, DYEING DEPARTMENT, YORKSHIRE COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT8977101154

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

1156 GARDNER AND COCKBURN: ACTION OF CX.-Action of Phosphorus Pentachloq*ide oya Fen- chone. By JOHN ADDYMAN GARDNER, M.A., and GEoRaE BERTRAM COCKBURN, B.A. FENCHONE and fenchene are usually considered to be anaiogous to camphor and camphene in their behaviour, and on this supposition chemists have based various formulae for fenchone, which dependPHOSPHORUS PENTACHLORIDE ox PENCHONE. 1157 somewhat on their views as to the constitution of camphor. The ground for this analogy is a comparison of the properties of fencholenic and campholenic acids, fenchylamine and bornylamine, &c. (Wallacb, Acnmlelz, 1892, 269, 356), and the change of fenchone and camphor into isomeric cymenes (ibid., 1893,275,157). It seems to us, however, that before the exact relationship between fenchone and camphor can be expressed symbolically, a much more elaborate comparison of the behaviour of these substances must be made.I n order to contribute to this, we have investigated the action of phosphorus pentachloride on fenchone. By the action of phosphorus pentachloride on camphor in the cold, Marsh and Gardner (Trans., 1897, 71, 288), obtained two isomeric forms of chlorocamphene hydrochloride, C,,H,,CI,, both of which, on saponification, yielded the same chlorocamphene. Fenchone under similar conditions is acted on very much more slowly, and the pro- ducts of the action are different, for on pouring into water to get rid of the excess of phosphorus pentachloride and oxychloride, we obtained a crystalline compound of the formula CloHl,CIPO(OH),, which we name chlorofenchenephosphonic acid, an oil consisting of unchanged fenchone, and a substance containing chlorine, probably chlorofenchene, CloH,,C1.The reaction probably takes place according to the follow- ing equations- C10H160 + Pel, = CIoH16Cl, + Poc1, = CloHl5C1 + Hcl+ Pocl,. CloH15Cl + PC1, = C, ,Hl,CIPCl, + HCl. CloH14C1PCI, + 3H,O = C1,H1,C1PO(OH), + 4HC1. Fifty grams of fenchone, b. p. 190-191”, m. p. 6-’i’’,and specific rotatory power [a],, = 61O 58’, were mixed with 200 grams of phosphorus penta- chloride in a flask closed with a calcium chloride tube, and allowed to stand at the ordinary temperature for six weeks. A very slow reaction took place with a very gradua,l evolution of hydrogen chloride. After the evolution of the gas had, to all appearance, ceased, the pro- duct was poured into a large quantity of ice and left overnight. The oil obtained in this way was taken up with ether, dried, and allowed to stand, when crystals of chlorofenchenephosphonic acid slowly separated.Afterthe separation of crystals had ceased, the oil was shakenupwithvery dilute sodium carbonate solution, when a further quantity of the substance was obtained in the form of sodium salt. A small quan- tity more was also obtained from the water into which the phosphorus compound had been poured, on extracting it with ether. The total amount of acid obtained from 50 grams of fenchone was about 7 grams, corresponding with a 14 per cent. yield. For this purpose, it was exactly neutralieed with a dilute solution of caustic The acid was purified by conversion into the sodium salt.115s ACTION OF PHOSPHORUS PENTACHLORIDE ON FENCHONE.soda, evaporated to dryness, the residue dissolved in absolute alcohol, and ether added until the solution became somewhat turbid ; on stand- ing, the salt crystallised ont in white, needle-shaped crystals. It was then dissolved in a small quantity of water, acidified with hydrochloric acid, extracted with ether, and the residue left on evaporating the ether was crystallised several times from water, in which it was only sparingly soluble, and finally from acetone. It was thus obtained in white, crystalline plates melting a t 196'. It was very soluble in ether, alcohol, chloroform, and benzene. On analysis, the acid gave the following figures :- I. 0.2002 gave 0.3502 CO, and 0.1 199 H,O.11. 0.2528 ,, 0,4429 CO, and 0.1459 H,O. 111. 0.3606 ,, 0,2065 AgCl. IV. 0,2174 ,, 0.0951 Mg,P,O,. I. I I. Found. Calc. for C,,H,,C!lPO(OH),. Carbon ............ 47.70 47.78 47-92 Hydrogen , . . , . . 6.65 6.41 6-38 Chlorine ......... 14.17 - 14.13 Phosphorus ...... 12.21 - 12.37 The specific rotatory power [a], = 7" 56' in alcoholic solution. The saturating power of the acid was determined by titrating it with caustic soda solution, using phenolphthalein as indicator; with an aqueous solution of the alkali, the results were in all cases about 2 per cent. too low, but by working in alcoholic solution very satisfactory results were obtained 0.5458 gram of acid required 9.2 C.C. of alkali (I C.C. = 0.01 1 gram sodium). Calc. amount of sodium req1iir.d by 100 gram of Cl,Hl,CIPO(OH),.Found. 18.36 18-54 The insoluble lead salt, prepared from lead nitrate and the sodium 0.4365 gave 0.2876 PbSO,. C,oH,,CIPO,Pb requires P b = 45.3 per cent. The barium and copper salts are also insoluble, and may be prepared from the sodium salt by precipitation ; these salts are soluble in mineral acids, but are reprecipitated unchanged on adding an alkali. The copper salt bears a close resemblance in colour and appearance to copper phosphate. The silver salt can also be obtained as a dirty white pre- cipitate by adding concentrated silver nitrate solution to a strong solu- tion of the sodium salt, It is slightly soluble in hot water and behaves with acids like the copper salt. salt, gave the following figures on analysis :- Pb = 44.94.SPRANKLING : KETOLACTONIC ACID AND ITS HOMOLOGUES.1159 The oil left after the extraction of the phosphonic acid consists of a mixture of fenchone with a substance containing chlorine; on dig- tilling it under a pressure of 20 mm., it could be separated, without decomposition, into two fractions,’the lower boiling a t 90-95’, and the higher a t 120-125’. The lower fraction, which consisted of fenchone, distilled at 188-1 90’ under the ordinary pressure ; from its amount it was evident that less than 50 per cent. of the original fenchone had re- acted with the pentachloride. The fraction of higher boiling point contained chlorine, the amount of which was determined by Carius’ method. 0,2518 gave 0.1699 AgC1. It probably consists mainly of chlorofenchene, and on treatment with concentzated sulphuric acid gave off hydrogen chloride. On treat- ing the black product with water and distilling in steam, an oil came over which smelt of geraniums, and reacted with pentachloride of phos- phorus, although not vigorously. The quantity of chlorofenchene at our disposal was, however, too small for purification, and we are a t present engaged in preparing it in quantity, in order t o purify it and compare its reactions with those of the chlorocamphene obtained in a similar way. C1= 16.7 CloHl,Cl requires C1= 20.8 per cent. CHEMICAL LABORATOILY, ST. GEORGE’S HOSPITAL.

ISSN:0368-1645    

DOI:10.1039/CT8977101156

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

SPRANKLING : KETOLACTONIC ACID AND ITS HOMOLOGUES. 1159 CXL- Ketolactokc Acid mad its Homologzces. By CHARLES H. G . SPRANKLING, B.Sc. Lond. SONE years ago, Young (Trans., 1883, 172) found that, on heating P-ethylic acetosuccinate, alcohol mas removed, and the residue, on hydrolysis with dilute hydrochloric acid, yielded, in addition to a-ethyl- P-acetopropionic acid and a small quantity of ethylsuccinic acid, a crystalline acid which had the empirical formula C,H,,O,; this he termed ketolactonic acid and from it he obtained three barium salts : (1) By neutralisation with barium carbonate. (2) By the action of barium hydroxide in the cold. (3) By the action of barium hydroxide at looo. From the composition of these salts, he concluded that the consti- tutional formula of ketolactonic acid was probably1160 SPRANKLING : KETOLACTONIC ACID AND ITS HOMOLOGUES.the barium salts (2) and (3) being derived respectively from the acids, COOH*yH CO CH, and YH2* CO*CH, COOH*CH*C,H5 COOH*CH* C,H, As the ketolactonic acid has not been further investigated, Pro- fessor Young suggested that I should repeat his experiments, and also endeavour to obtain homologues of the acid by similar reactions. COOC,H,- YH*CO*CH, COOC,H,* CH*C,H, I. Ethglic P-Et?~gZacetosuccirlzate, This salt was prepared by the action of sodium ethoxide and ethylic acetoacetate on ethylic a-bromobutyrate in the manner described by Young (Zoc. cit.). I n order to obtain, if possible, a larger yield of Young’s ethylketolactonic * acid, the acetosuccinate was heated for a considerable time, and after being distilled, during which the boiling point rose considerably, it was hydrolysed by boiling with dilute hydro- chloric acid for about 12 hours.The crystals which separated on cool- ing after recrystallisstion melted at 1$8-l’79° (181’ Young). On evaporating the ethereal extract of the mother liquors and placing the residue (chiefly a-ethyl-/3-acetopropionic acid) in ice for a week, more of the ketolactonic acid, melting at 180°, was obtained. I. 0.2530 gave 0*5190 C0,and 0*1375 H,O. C=55.95; H=6*07. 11. 0.1190 ,, 0.2485 CO, ,, 0,0665 H,O. C=56*95; H = 6 . 2 1 . C,H,,O, requires C = 56.47 ; H = 5.89 per cent. The total weight of recrystallised acid obtained was 5.1 grams. The action of barium carbonate, and of cold and hot barium hydroxide on the acid gave rise to the barium salts Ba(C,H,O,), , BaC,H,,O(COO),, and Ba(C,H,,O*COO),, thus confirming Young’s results.When the aqueous solution of the first barium salt was allowed t o evaporate spontaneously, the crystals contained 5H,O (Young’s pro- duct, deposited from a hot solution, contained 2H,O). The salt was dried at 130’ and analysed. Ba = 28.61 per cent. Ba(C,H,O,), requires Bn = 28.84. H,O=15.92 ,, 6H20 ,, H,O = 14.41. The second barium salt is exceedingly unstable. It was, however, obtained in a nearly pure state by evaporating its aqueous solution * As lower homologues of the acid were prepared, a difficulty of nomenclature arose, and Professor Pittig (in whose laboratory the original work on the ethylic compound was done) agreed that it woald be desirable to use the name ketolactonic acid for the simplest one, so that Young’s crystalline acid will be called “ethyl- ketolactonic acid ” in this paper.SPRANKLING : KETOLACTONIC ACID AXD ITS HOMOLOGUES.I161 to dryness in a vacuum over sulphuric acid. A small quantity of barium carbonate remained admixed with the product, and was esti- mated separately. 0.0685 gave 0.0502 BaSO, tbe barium carbonate present 0.0002 BaSO,. Hence by the action of barium hydroxide in the cold, the unsatu- rated lactone ring is broken down, and the salt of an unstable dibasic acid, C,H,,O(COOH),, is formed. The barium salt, obtained by the action of barium hydroxide on ethyl- ketolactonic acid at loo', agreed in all respects with that described by Young. Ba = 43.28 per cent.BaC,H,,O, requires Ba = 42.41 per cent. Ba = 32.37 per cent. Ba(C7Hl,O,), requires Ba = 32.39. a-EtJqZ-/3-cbcetopropionic Acid. The acid obtained from the original hydrolysed solutions as a gummy oil, after being boiled wit,h barium hydroxide to decompose any ethylketolactonic acid, was recovered from the barium salt and submitted to fractional distillation ; ultimately 5.6 grams of lactone were obtained, boiling between 240" and 250'. This was purified by boiling it with water and barium carbonate to remove unaltered acid, and then extracting it from the solution by agitation with ether. The portion distilling a t 217-221" was left over sulphuric acid for a day, and then analysed. 0,1602 gave 0.3915 CO, and 0.1200 H,O. It was therefore nearly pure.XoZu6ility of the Unsuiurated Lactone in Vate~.-The lactone, when shaken with water, formed a n emulsion at the ordinary temperature, but, on warming, the solution rapidly cleared at about 97'; also on cooling in ice, it cleared a t about 2O. It is therefore more soluble in water a t 100' and at 0' than a t intermediate temperatures, and Young's observation, made with a mixture of this lactone with its next homo- logue, is thus confirmed. C = 66.73 ; H = 8.33. C7HloO2 requires C = 66.66 ; H = 7-99 per cent. In the formation of the ethylic ethylketolactonate from ethylic P-ethylacetosuccinate by elimination of alcohol, it has been assumed that the reaction takes place according to the equation If that is so, no ethylic ketolactonate should he formed if the hydrogen in the ECH group, marked *, is displaced by an alkyl group.1162 SPRANKLZNG : KETOLACTONIC ACID AND ITS HOXOLOGUES. It was found by Young, however, that neither by using methylic acetoacetate nor by the action of sodium ethoxide and methylic iodide on ethylic /3-ethylacetosuccinate, could a product free from un- altered ethylic P-ethylacetosuccinate be obtained.Analogous experiments, in which ethylic iodide was employed instead of methylic iodide, I also found to yield negative results as regards the formation of a ketolactonate, although large quantities of ethylic ethylsuccinate were formed. COOC,H,* FH* COGH, COOC,H,* CH* CH, 11. P-Methylic Acetosuccinate, Seventy grams of ethylic a-bromopropionate was heated for some time with potassium iodide and alcohol.A mixture of 51 grams ethylic acetoacetate and 8.9 grams of sodium dissolved in alcohol was added, and the liquid heated till neutral (20 hours). During the first fractionation, the thermometer was very constant at about 242-244', but, on redistilling, alcohol was given off, and the boiling point rose as by the following table. I----- I - - -190" ' 8 grams 1 10 grains 190-220 4 $ 9 1 8 2 ) 220-240 1 11 ) ) j 5 ) ) 240-245 29 ), 9 ) ) 245-255 1 10 ,) 12 9 ) 255-270 9 3 1 I 26 7 ) I Hence the decomposition of the ncetosuccinate into alcohol and ethylic niethylketolactonate takes place much more readily than in the case of the ethyl compound; the hydrolysis was also much more rapid, being complete in about 6 hours. The product, after recrystnl- lisation from alcohol melted at 176'.C = 53.21 ; H = 4.87. 11. 0.0877 ,, 0.1709 CO, ,, 0,0415 H,O. C=53.33 ; H=5*26. I. 0.2239 gave 0.4438 CO, and 0.0985 H,O. C7H,0, requires C = 53%4 ; H = 5.12 per cent. The yield in this case was very much better, amounting to 8.9 grams of recrystallised methylketolactonic acid. This acid, like the ethyl derivative, gave three barium salts, which were prepared in the manner already described. The first barium salt (from BaCO,) was much more soluble than the ethyl derivative. It was dried at 100-1220', and analysed.SPllANKLING : KETOLACTONIC ACID AND ITS HOXOLOGUES. 1163 I. 0,2134 gave 0.1103 BaSO,. Ba=30*38. 11. 0.0731 ,, 0.0379 BaSO,. Ba = 30.50. The second salt (from barium hydroxide in the cold) was even more I. 0.0580 gave 0,0392 BaSO, and 0.0053 BaSO, from the barium 11.0*1000 gave 0 0697 BaSO, and 0.0056 BaSO, from the carbonate. Ba(C7H704)2 requires Ba = 30.64 per cent. unstable than that of ethylketolactonic acid. carbonate. Bn = 45.10. Ba = 44.27. BaC7H,05 requires Ba = 44.33 per cent. Hence the barium salt of the dibasic acid, C,HsO(COOH),, is formed. The third salt (by the action of barium hydroxide at 100') gave Ba= 34.67. 11. 0.2219 ,, 0.1301 Ba80,. Ba=34*47. The salt is therefore that of the monobasic acid, C,H,O*COOH. I. 0.2479 gave 0.1462 BaSO,. Ba(C,H,O,), requires Ba = 34.68 per cent. a- M e thy 2-P - ace t opr opionic Acid. By extracting the hydrolysed solution and filtrate with ether as before, 19 grams of a-methyl-P-acetopropionic acid, mixed with methyl ketolactonic acid were obtained.After the latter (m. p. = 176-176.5") had crystallised ouk, the oil was treated in the manner described on p. 1160 ; the lactone thus obtained boiled at 210-214". I. 0.0807 gave 0.1890 CO, and 0.0523 H,O. C=63*87; H=7-22. II. 0.0920 ,, 0.2156 CO, ,, 0.0594 H,O. C = 63.90 ; H= 7.17. CG-H,,O, requires C = 64.28 ; H = 7.14 per cent. The lactone is formed according to the equation Solubility.--The lactone was much less soluble in water than that obtained from a-ethyl-P-acetopropionic acid, but exhibited the same peculiarity, namely, it was more soluble at 0" and 100' than a t inter- mediate temperatures. COOC,H,* FH* CO-CH, COOC,H,*CH* CH'(CH,),' I I I. Etlqlic P-lsopropylacetosuccincde, One hundred and thirty-t'wo grams of ethylic a-bromisovalerate, CH(CH,),*CH.Br*COOC2H5, ivas heated with a mixture of 14.4 grams1164 SPRANKLING : KETOLACTONIC ACID AND ITS ROMOI~OGUES.of sodium dissolved in absolute alcohol, and 82 grams ethylic aceto- acetate for 7 days, when it became nearly neutral. The product was then treated as usual. Fractionation gave the following results. A. R. C. D. E. F. Temperature. -170" 170-1 90 190-200 200-210 210-240 240-260 1. 16 grams 16 9 9 25 Y , 27 9 9 24 J 9 I 11* 1 The boiling point was therefore considerably lower than that of any of the corresponding compounds; this was probably due to the presence of unaltered ethylic a-bromisovalerate (b. p. 186O), and possibly also of a little ethyl ic isopropylsuccinate. Each fraction, except A, was then heated for about 6 days (a very little alcohol was given off in all cases except F).After hydrolysis, crystals appeared in D, E, and F, but not in B or C ; these after recrystallisation from benzene and light petroleum melted at 115-1 16'. (Kachler, Ann., 169, 168, and Hlasiwitz and Grabowski, Ann., 145, 205, give 114O as the melting point of isopropylsuccinic acid prepared from camphoric acid.) 0.1443 gave 0.2765 CO, and 0.0983 H,O. The barium salt was obtained as an amorphous powder. 0.2142 gave 0.1685 BaSO,. These results show that the acid is isopropylsuccinic acid, CH( OH,),. CH (COOH)* CH,COOH. This acid gave no precipitate of barium carbonate on boiling with excess of barium hydroxide. On adding calcium chloride to a solution of the barium salt and warming, a white, amorphous precipitate of the calcium salt was formed.On boiling the original hydrolysed solutions with excess of barium hydroxide, only very slight precipitates were obtained, showing that an isopropylketolactonic acid had been formed, but in very slight amount. The benzene and light petroleum mother liquors from which the isopropylsuccinic acid had crystallised were evaporated, and the acid C = 52.21 ; H = 7.57. C7H,,0, requires C = 52.50 ; H = 7.50 per cent. Bn = 46.60. C7H,,0,Ba requires Ba = 46.44 per cent.SPRANKLING : HETOLACTONIC ACID AND ITS HOMOLOGUES. 1165 residue converted into the barium salts, and analysed after drying at 120'. 0-1 400 gave 0.0894 BaSO,. Ba = 38.03 per cent. Barium isopropylketolactonate requires Ba = 27.23 per cent. ,, isopropylsuccinate ,, Ba= 46.44 ,, The barium salt was regenerated and treated with silver nitrate, when a white precipitate was formed, which proved to be chiefly silver isopropylsuccinate.The mother liquors from this solution pos- sibly contained silver isopropylketolactonate ; the acid from this, on being boiled with excess of barium hydroxide, gave a distinct precipi- tate. This was collected and weighed, and from the result it was calculated that the quantity of isopropylketolactonic acid formed would not exceed 3 per cent. The filtrate from the barium carbonate gave an amorphous barium salt. 0.1519 gave 0-07SO BaSO,. Ba = 30.65. Barium a-isopropy 1-P-acetopropionate, -tSit(C,H,,O,),, requires Ba = 30.38 per cent. Owing to an accident, the aqueous solutions from which the iso- propylsuccinic acid had crystallised were lost, and the a-isopropyl-P- acetopropionic acid, which they probably contained, could not there- fore be further investigated.IV. Ethylic Acetosuccinute, COOC,H,*~H*CO* CH, COOC,H,* C H, Et hylic sodace toace t a te was first prepared by treating et hvl ic aceto- acetate, 113 grams, with 19.95 grams sodium dissolved in alcohol; after cooling, 145 grams ethylic bromacetate was added. The condensation was exceedingly rapid, much heart being developed, and the whole of the sodium bromide separating out in about 5 minutes; no external heating was required, as the solution mas quite neutral after that time. On fractionation, the following results were obtained. A. B. C. D. E. F. Temperature. I I. I 11. 1 111. I -I------ - I- I -190" 190-240 240-260 260- 270 270-280 280-30011 66 SPRANKLTNG : KETOLACTONIC ACID AND ITS HOMOLOOTJES.The boiling point would therefore appear to lie between 260' and 270'. The fraction D was then heated for some time; alcohol was eliminated, and the residue distilled between 225' and 290'. The hydrolysis was performed with very dilute hydrochloric acid and was complete in 45 minutes, but no crystals appeared, either on cooling or after extraction with ether ; the ketolactonic acid appeared to be an oil. A portion of the ethereal extract was treated with barium carbonate as usual ; the salt obtained was a deliquescent, gummy mass, which became brittle on cooling. After drying a t 100-120', it was analysed. I. 0.3555 gave 0.2011 'BaSO,. Ba= 32.93. 11. 0.7267 ,, 0.4016 BaSO,.Ba=32*85. Ba(C,H,O,),. Ba = 32.69 per cent. The acid liberated from the salt did not crystallise. After heating a t 100" andleaving it in a vacuum over sulphuric acid for a short time, it was analysed. I. 0.1649 gave 0.3039 CO, and 0.0611 H,O. C=50.2$; H=4-12. 11. 0,3726 ,, 0.6908 CO, ,, 0.1483 H,O. C=50*56 ; H=4*39. C,H,O, requires C = 50.70 ; H = 4.22 per cent. A second portion of the acid was then treated with a slight excess of barium hydroxide in the cold, the excess being removed in the usual way, and the filtrate evaporated in a vacuum. The amount of barium carbonate which separated during the evaporation was negligible. I. 0-2782 gave 0.2138 BaSO,. Ba= 45.85. 11. 0.5448 ,, 0,4225 BaSO,. Ba=46*18. BaC,H,O, requires Ba = 46.44 per cent. A third portion of the acid was heated with a slight excess of barium hydroxide ; barium carbonate began t o be precipitated at about 80-85', and after boiling for 5 minutes the decomposition was complete. The barium /3-acetylpropionate (levulinate) was left as a deliquescent gum, which was dried at 120' and analysed.I. 0.2439 gave 0.1515 BaSO,. Ba = 37.00. 11. 0.4453 ,, 0.2776 BaSO,. Ba = 37.12. Ba(C,H70,j, requires Ba = 37.32 per cent. GENER ALI SAT I o NS. 1. Action of Brominc~ted EtIqEic Salts o n Zthylic ~odc6cetoacetate.-The The rate Condensation was very rapid with ethylic bromacetate. diminishes rapidly with rise of molecular weight.RPRANRLING : KETOLACTONIC ACID AND ITS HOMOT,OGUES. 1167 Approxima:e time reqnired. Ethylic bromacetate .................................5 minutes. , , a-bromopropionate ........................ 10 hours. ,, a-bromisovalerate ........................... 7 days. 2. Action of Heat on Alkylic Acetosuccincr$es.-The removal of alcohol with the formation of a ketolactonate is most rapid with methylic acetosuccinate, the rate diminishing very rapidly as the methyl is replaced by ethyl and isopropyl groups respectively. Ethylic aceto- succinate itself gives up alcohol much more rapidly than the ethyl derivatives, but apparently less rapidly than the methyl derivative. .. a-bromobutyrate ........................... 20 hours. Approximate time required. less than 4 days. Ethylic acetosuccinate ........................ ,, methylacetosuccinate ............... on distillation. ,, ethylacetosuccinate ..................5 days. ,, isopropylacetosuccinate ............ about 6 days. 3. Rate of Hydrolysis of Ethylic Ketolactonntes, dc., with Dilute Hydi-0- chloric Acid-The members of the series are not quite comparable in this case, for ethylic acetosuccinate was completely converted into ethylic ketolactonate, whilst the substituted ethylic acetosuccinates were only partially converted into the corresponding ethylic ketolactonates. Neglecting this difference in composition, the rate of hydrolysis diminishes with rise of molecular weight. approximate time required. Ethylic acetosuccinate ........................... 45 minutes. , , P-methylacetosuccinate ............... 6 hours. ,, P-ethylacetosuccinate . . . . . . . . . . . . . . . . . . 12 hours. ,, P-isopropylacet'osuccinate ............about 2 days. 4. Pvoducts of Hydrolysis of U+talte?*ed Etlzylz'c Acetosuccin(ttes,- By the hydrolysis of the ethylic ketolactonates, the corresponding acids are formed, and the other acids obtained by the hydrolysis of the mix- ture of ethylic ketolactonates and unaltered acetosuccinates are in all probability derived from the latter. Leaving these, the ketolactonic acids, out of account, the only acid obtained by the hydrolysis of ethylic P-methylacetosuccinate was a-methyl-P-acetopropionic acid, no indication of the presence of methyl- succinic acid having been observed. I n the case of ethylic P-ethylacetosuccinate, the chief product is a-ethyl-P-acetopropionic acid, but Young, after removing this acid by reduction and conversion into the lnctone, was able to show that a small quantity of ethylsuccinic acid was left unacted on by the sodiiim amalgam.1168 SPRANKLTNG : KETOLACTONIC ACID AKD ITS HOMOLOGUES.By the hydrolysis of ethylic P-isopropylacotosuccjnate, isopropyl- succinic acid is obtained in large quantity. As the aqueous solution from which the crystals separated was lost, it is impossible to say how much a-isopropyl-/I-acetopropionic acid was formed, but the quan- tity was certainly relatively smaller than in the case of the lower homologues. As the ethylic acetosuccinate itself was completely con- verted into ethylic ketolactonnte, only ketolactonic acid was obtained by hydrolysis. It appears, then, that by the hydrolysis of the alkyl derivatives of ethylic acetosuccinate with hydrochloric acid, more and more of the alkyl derivatives of succinic acid are formed, and less and less of the alkyl derivatives of acetopropionic acid. Constitution of the Acids. The simplest ketolactonic acid has the empirical formula C,H,O, and the constitution (I), The next one would have the graphic formula (11), and would be The fmmntion of the ketolactonic ethers from the acetosuccinic ethers termed methylketolactonic acid, and so on for the others. may be represented generally as below. COOC,H,*y H COO CH, COOC,H,* CHR = COOC,H,*C<~~~$~>CO + C,H,*OH, and the three barium salts are in each case derived from the acids, I. 11. 111. R representing in each case an alkyl group (or hydrogen). In conclusion, I tender Dr. Young my sincere thanks for the kind way in which he has given me his advice and assistance whenever required. UNIVERSITY COLLEGE, B~ISTOI,.

ISSN:0368-1645    

DOI:10.1039/CT8977101159

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

PERKIN AND THORPE : SYNTHESIS OF i-CAMPHORONIC ACID. 1169 CXIL-Synthesis of i- Camphoronic A.cid. By WTLLIAM HENRY PERKIN, jun., and JOCELYN FIELD TIIORPE. AMONG the reactions which, up to the present, have thrown light on the constitution of camphor, its oxidation by means of nitric acid has probably yielded by far the most valuable results. Laurent (Annulen, 1837, 22, 135) first showed that, camphoric acid was formed during this process, and Kachler (Annrden, 1871, 159, 302) first isolated camphoronic acid from the products of the oxidation ; subsequently, Roser (Bey., 1885, 18, 3112) obtained camphanic acid (hydroxy- camphoric acid) from the mother liquors which remain when the camphoric and cnmphoronic acids have been separated. Since camphoric acid may be converted into camphanic acid by careful oxidation (Balbiano, Rend.Bcc. LLincei, 1893, ii, 240), whilst cam- phanic acid itself, by treatment with nitric acid or chromic acid, yields considerable quantities of camphoronic acid (Bredt, Ber., 1835, 18, 2989; Koenigs, Bev., 1893, 26, 2337), i t is evident that these three acids represent, as Bredt has pointed out, distinct stages in the decom- position of the camphor molecule ; the oxidation of camphor may conse- quently be represented thus : Camphor. + Caniphoric acid. + Cainphanic acid. 4 Camphoronic acid. C10H160 '1 OHl6'4 ClOHlGO, C9H1406 Camphoric acid has been obtained from camphor by Claisen and Manasse (Aianalen, 274, 86) by a second very interesting method. These chemists converted camphor into isonitrosocamphor, C,H14<(?:NoH, by the action of amylic nitrite and sodium methoxide ; co by subsequently treating this substance with nitrous acid, they discovered camphorquinone, CsH14<X(?, an interesting substance which, when digested with a solution of potash in methylic alcohol, is slowly oxidised (probably by the oxygen of the air) to camphoric acid, This series of reactions indicates that camphoric acid is very closely related to camphor, and, indeed, it is usually supposed that the former is derived from the latter by the oxidation oE the group -CH,*CO- to two carboxgl groups, the relationship being well understood from the formulae Camphor.VOL. LXXL.1170 PERKIN AND THORPE: SYNTHESIS OF Many experiments have been made with the object of determining the constitution of camphoric acid, and many formuls have been sug- gested for this substance ; but it is hardly likely that its constitution will be definitely established until the acid has been prepared syn- thetically.In the meantime, chemists have also been busily engaged in endeavour- ing to discover the constitittion of camphoronic acid, as, if the consti- t u t i o n of this acid, which cotitains only one carbon atom less than camphoric acid, could be defiuitely settled, very Important dedtwtions coultl ohviously be made w i t h regard to the constitution of caruphoric: acid, and of camphor itself. K tuh1r.r (Annuleu, 1873, 169, 186), who first obtained camphorcmic acid i n a pure state, corihidered the acid to be a hjdroxydihasic acid, C,H,,O,, crystallising with 1H,O, and he suggested the following f o r u u h as best expressing its constitution : H2 /"\ \C/ H2 H2f: R*GH(OH)*COOH H,C C*COOH Kissling (Inaug.Diss. Wurxburg, 1878) first showed that camphoronic acid had the formula C,H,,O,, and both he and Xeyher (Inaug. Diss. Leipxig, 1891) considered the acid to be a hydroxyketodicarboxylic acid of the formula CH(CH,),* CH(COOH)*CO*CH,* CH(OH)*COOH. Bredt (Annalen, 1884, 226, 249-261) it was who, as the result of a careful investigation of the salts of camphoronic acid, first clearly showed that the acid was tribasic ; and further, as the acid distilled under diminished pressure without decomposing, he concluded that the three carboxyl groups must be attached to three different carbon atoms, otherwise, if any two carboxyl groups were attached to the same carbon atom, the acid would be a substituted malonic acid, and like this acid loose carbon dioxide at high temperatures.Bredt, at that time, thought it possible that the constitution of camphoronic acid was represented by one of the following formulae, of which he considered I the more probable: CH,*(iH*CH, CH,* $IH* CH, I. CH,--C-- H, I I. CH-- CH-- CH, bOOH bOOH COOH 6OOH 6OOH bOOH B-Isopropyltricarballylic acid. a-Isopropyltricnrballylio acid. Subsequently, Collie (Ber., 1892,25,1116) arrived at the second formula for camphoronic acid,.from the consideration of a new constitution for&CAMPHORON TC ACID. 1171 camphor which he had suggested, but this formula was clearly proved to be incorrect by Kolner and von Meyenburg (Bey., 1891,24,2899), who prepared a-isopropyltricarballylic acid synthetically, and showed that its properties were quite different from those of camphoronic acid.The next important step, which had a direct bearing on the question of the constitution of camphoronic acid, was the discovery by Bredt and Helle (Bey., 1885, 18, 2990; 1893, 26, 3049) that this acid, when distilled under the ordinary pressure, is slowly but almost completely decomposed with formation of trimethylsuccinic acid, isobutyric acid, and other products. Since the formation of trimethylsuccinic acid in this way is a n indication that camphoronic acid probably contains the group COOK. C(CH,),d(CH,)*COOH, Bredt proposed the formule COOH. C(CH,),* C(CH,)(COOH)* CH,* COOH for camphoronic acid, and represented the series-camphor, camphoric acid, camphanic acid, and camphoronic acid-in the following way : CH,-CH-CH2 I CH2-YH* COOH CH,-C( CHJ CO CH,-C(CH,)*COOH Camphor.Camphoric acid. I $VH3)2l I 7(CH3)2 CH,--C- COOH COOH FOOH CH,-C( CH,)-CO CH,-C( CH,)*COOH Caniphanic acid. Camphoronic acid. I ?(CH,), I I ?(CH:J2 Q bringing out very clearly the relationship which exists between them. Recently Tiemnnn (Ber., 1895, 28, 1089) suggested a modification of Bredt’s formula as the probable constitution of camphor, and was thus led to represent the above series in quite a different may. (CH,),C -- YH- CH, (CH,),C -- FH* COOH I p 2 I 1 YH, CH,* CH-CH-CO CH,~H-CH-(:OOH Camphor. Caniphoric acid. 1 CH 0 I COOH (CH3),C-- YH-QO (CH,),C: -- FH- COOH CH,* CH-C I> -GOOH CH3* CH-COOH Camphanic acid.Camphoronic acid. It is remarkable t h a t Tiemann shonld have suggested a formula for camphoronic acid which contains the group -CH(COOH),, especially when it is borne in mind that this acid may be distilled without loss of carbon dioxide at 200° under reduced pressure, a behaviour which is shown by no other derivative of malonic acid. I n order to get over 4 1z 21172 PEREIN AND THORPE: SYNTHESIS OF this difficulty, Tiemann assumes that csmphoronic acid, when heated, is converted into an anhydro-acid of the formula CH,*YH*C(CH,),* YH* COOH co-0-co 9 and that this acid is stable at high temperatures. But, as was pointed out by one of us (Proc , 1896, p. lS9), com- pounds of this nature when heated lose carbon dioxide in the same way as derivatives of malonic acid ; for example, carbobutyrolactonic acid, YH2 CH2* ?*’ ‘‘OH, decomposes a t comparatively low temperatures 0-- co quite readily into butyrolactone and carbon dioxide, but a still better example is given by Bredt (Anncden, 1896,292, 130) in ethylmethylcar- boxyglutaric acid, COOH- CH(CH,),* CH,* C(C,H,)(COOH), (Bischoff, Bey., 1891,24, lOSO), the formula of which is closely related toTiemann’s formula for camphoronic acid, and which, when heated a t 166*5O, melts with evolution of carbon dioxide.I n order, however, t o bring still further evidence against Tiemann’s formula camphoronic acid was heated under conditions which pre- cluded the possibility of the formation of the anhydro-acid, namely, in solution in water at 230°, and still no decomposition could be detected, the acid being recovered quite unchanged on evaporating the solution (Perkin, Zoc.cit.). Subsequently, Bredt (Annalen, 1896, 292, 131) showed that the tri- ethylic salt of camphoronic acid does not react with sodium, as it would be expected t o do if it contained the group -CH(COOC2H5),. Whilst, then, it had been shown that Tiemann’s formula was incor- rect, it still remained to prove definitely the correctness of Bredt’s formula, and the most satisfactory way of doing this seemed to be to prepare an acid of this formula synthetically, and to compare the synthetical acid with that obtained from camphor. The first experiments on this subject were instituted by Dr. Bone and one of us, and the method which was then tried was the follow- ing.Ethylic bromotrimethylsuccinate, COOC,H,= C(CH,),* CBr(CH,)* COOC,H,, was first prepared by brominating trimethylsuccinic anhydride and treating the bromo-anhydride thus obtained with alcohol. This ethereal salt was then digested in alcoholic solution with ethylic sodiomalonate, when it was expected that the following reaction would take place. COOC,H,* C(CH,),* CBr(CH3)*COOC2HB + CHNa(COOC,H,), = COOC,H,* C(CH,),* C(CH,) (COOC,H,)- CH(COOC,H,), + NaBr. The ethereal salt thus formed should, on hydrolysis and elimination of carbon dioxide, yield camphoronic acid,i-CAMPHORONIC ACID. 1173 COOH. C(CH,),* C(CH,)(COOH)* CH(COOH), - CO, = COOH- C(CH,),* C(CH,)(COOH). CH,* COOH. The product of this reaction, after hydrolysis and subsequent heating at 18Q0, mas carefully investigated, but it did not appear t o contain camphoronic acid, As, however, we were at that time not sufficiently well acquainted with the method of isolation of small quantities of camphoronic acid, we are again investigating this reaction, and hope soon to be able to communicate the results of our experiments to the Society.Several other reactions which seemed likely t o yield camphoronic acid were subsequently investigated, but also without success, until ultimately the method which is described in this paper was devised and found on trial to give the desired result. E thy1 i c P-lqdyox y - aa p- t9.i me t h y lg lu t am te , COOC,H,* C(CH,),* C(OH)(CH,)* CH,* COOC,H,, was prepwed by two different reactions which left no doubt as to its constitution, namely, the action of zinc on mixtures of (I) ethylic acetoacetate with ethylic bromisobutyrate, and (11) ethylic dimethyl- acetoacetate with ethylic bromacetate." I n both cases, an ethereal salt boiling at 165' (30 mm.) was obtained; this consisted for the most part of ethylic hydroxytri- methylglutarnte, but mixed with varying quantities of ethylic trimethylglutaconate, COOC,H,* C(CH,),* C( CH,):CH* COOC,H,, the latter being produced by the elimination of water from the hydroxy- compound, either during the condensation, or more probably during the subsequent fractionation of the ethereal salt under reduced pressure.Since, then, the products from the two reactions represented above are identical, there can be no doubt as to the constitution of the compound used as the starting point in this synthesis.When ethylic hydroxytrimethylglutarate, obtained by either of these methods, is hydrolysed with dilute hydrochloric acid, P-hydroxy-aup-trimethyl- glutaric acid, COOH- C(CH,),* C(OH)(CH,)* CH,. COOH, melting a t 128' is produced, together with small quantities of trimethylglutaconic acid, COOH- C(CH,),* C(CH,):CH* COOH ; if, however, concentrated hydrochloric acid is employed, the product of the reaction consists almost entirely of the latter acid. Boiling with alcoholic potash decomposes ethylic hydroxytrirnethylglutarate with formation of acetic and isobutyric acids. * Compare Trans., 1896, 69, 1463.1174 PERKIN AND THORPE: SYNTHESIS OF Ethylic hydroxytrimethylglutarate is readily acted on by phosphorus pentachloride with formation of ethylic chlorotrimethylglutarate, COOC2H,*C(CH,),*CC1(CH,)*CH,*COOC,HF, boiling at 139' under 20 mm.pressure; this has been obtained in a pure condition only on one or two occasions, as usually it contains varying quantities of ethylic trimethylglutaconate, which, as stated above, is present in the hydroxy- ethereal salt prepared by the methods adopted. Ethylic bromo- trimethylglutarnte, prepared in an analogous ' way, boils at 1 60° (35 mm.). If either the chloro- or bromo-derivative is heated with potassium cyanide and alcohol at 160' for 1 2 hours, ethylic cyano- trimethglglutarate, COOC,H,* C( CH,),* C( CN)(CH,)*CH,* COOC,H,, is obtained as a colourless oil which distils approximately a t 170-175O (25 mm.) ; this, like the bromo- and chloro-derivatives, always contains varying quantities of ethylic trimethylglutaconate, so much of the latter sometimes being present that it must evidently be produced by the action of the potassium cyanide on the halogen ethereal salt. When the cyano-ethereal salt is hydrolysed by boiling with hydro- chloric acid, and the product allowed to cool, large quantities of trimethylglutaconic acid separate ; and the amount is usually so considerable that we are forced to tho conclusion that some of i t must be formed by the elimination of hydrogen cyanide during the hydro 1 y sis.If now the crystals of trimethylglutaconic acid are removed by filtration, and the filtrate, after being rendered strongly alkaline with ammonia, is mixed with barium chloride, no precipitate is produced in the cold, but, on boiling, a small quantity of a sparingly soluble barium salt separates; this has been proved to be the barium salt of i-camphoronic acid, the synthesis of the acid having taken place thus : COOC,H,*C(CH,),*C(CH,)(CN)*CH,*COOC,H, + HCI + 4H20 = COOH*C(CK,),*C(CH,)(COOH)*CH,*COOH + NH,CI+ 2C2H,*OH.Aschan (Bey., 1S95, 28, 16 and 224), who has so carefully examined camphoronic acid, has shown that this acid is capable of existing in three well-defined modifications, namely, as d-, I-, and i-camphoronic acid. d-Camphovonic acid,* produced by the oxidation of d-camphor and of d-camphoric acid, melts a t 156O, dissolves in 6 parts of water at 20°, and is Izvorotatory, [ u ] j = - 26.9. 1-Cwmphoronic acid, which was isolated by Aschan from the residues * As ordinary camphoronic acid is derived from the oxidation of d-camphor and d-camphoric acid, i t appears to us that, although it happens to be lzevorotatory, i t niust nevertheless be called d-camphoronic acid ; the relationship between these substances being somewhat similar to that of d-glucose and d-fructose, the latter receiving the prefix d in spite of its powerful Izevorotatory action, owing to its belonging to the same class as a?-glucose.For this reason me have taken the liberty of reversing the prefixes d and 1 used by Aschan.~-CAMPHORONIC ACID. 1175 obtained i n the preparation of I-camphoric acid from I-borneol, melts a t 158-159°, dissolves in 6 parts of water a t 20°, and is dextrorotatorp, the value [a ]j = + 3'7.05 corresponding exactly with the reverse value of the d-acid.i-Camphoronic acid was prepared by Aschrtn by mixing solutions of equal proportions of the d- and I- acids; it differs from the active acids in being much less soluble in water (1 part requires 27 pai.ts of water at 20°), in crystallising in much better defined crystals, and in melting at a somewhat higher temperature, namely, about 172'. Thanks to the kindness of Dr. Aschan in sending us a small sample of his inactive acid, we were enabled to compare its properties with those of the synthetical acid obtained by us, the result proving that the two acids are identical, the following points being perhap3 especially worthy of notice. (1) Both acids crystallise from water in hard, transparent prisms, which, when examined under the microscope, are seen t o be identical in form.(2) Both acids when heated side by side on the same thermometer soften at about 3 67" and melt at 169-1'72", moreover, no alteration in the melting poiDt could be observed when they were mixed in eqiial proportions. (3) A solution of either acid in water, after the addition of excess of ammonia, gives no precipitate with barium chloride in the cold, but OR warming a very sparingly soluble barium salt separates, closely resembling barium sulphate in appearance. (4) When heated with acetic anhydride under the conditions de- scribed in the experimental part of this paper, both acids give the same anhydrocurnphoronic acid, melting a t about 1 36-1 3'7". (5) An aqueous solution of the synthetical acid was examined by Dr.CV. H. Perkin, sen., and found to be inactive. There can be no doubt that the synthetical acid is i-carnphoronic acid, and this synthesis proves conclusively that csmphoronic acid must, as was first suggested by Bredt (Bey., 1893, 26, 3049), have the con- stitution of a trimethyltricarballylic acid of the formula (CH&y-- qCH,J-p2 COOH COOH COOH. It is very unfortunate that, for reasons stated above, the yield of camphoronic acid obtained in this synthesis should be small, so small, indeed, as to necessitate the employment of large qiiantities of material in order to prepare a few grams of the acid. I n order to determine whether an independent worker would get the same result as we had done, we requested Mr. Hodgson, a student of Owens College, t o repeat from the commepcement the whole of our experiments on the synthesis1176 PERKIN AND THORPE: SYNTHESIS OF and isolation of camphoronic acid, and he prepared in the course of his repetition of our work about 2 grams of the pure synthetical acid.We are much indebted to Mr. Hodgson for so kindly placing his time (nearly 4 months) at our disposal, and for the skill with which he carried out this very difficult piece of experimental work. During the course of the above synthetical experiments, a consider- able quantity of trimethylglutaconic acid had accumulated, and this we have very carefully investigated, and with very interesting results. Trimethylglutaconic acid, COOH. C(CH,,),* C(CH,) : CH* COOH, al- though unsaturated, is scarcely attacked in the cold by alkaline per- manganate, and its solution in chloroform does not decolorise bromine except on long standing, when dibromotrimethylglutaric acid, COOH*C( CH,); CBr( CH,)* CHBr DCOOH, melting at 1 6 9 O , is produced.Sodium amalgam appears t o have no action on the solution of the acid in caustic soda even on boiling, and, indeed, great difficulty was experienced in reducing the acid at all ; ultimately, however, this was accomplished by repeatedly treating the acid in boiling alcoholic solution with sodium." aap-~~imetlzylglutaric ucid, obtained in this way, is a beautifully crystalline substance which melts at 1 1 2 O and shows all the properties of a substituted glutrtric acid: i t is an acid of more than ordinary interest for the following reasons.In 1894, Balbiano (Berichte, 1894, 27, 2133), by the oxidation of camphoric acid with permanganate a t the ordinary temperature, obtained a crystalline acid of the formula C,H,,O,, the constitution of which, after very careful examination, he now (Bericlh, 189'7, 30, 1908) ex- presses by the formula COOH. C(CH,)*C (CH,),. CH COOH I I I I-.--- 0- This acid on reduction with hydriodic acid is converted into a mono- basic lactone acid of the probable formula * This extraordinary stability of trimethylglutaconic acid seems to suggest that there is a possibility of the constitution of the acid being represented by a formula different from that given above. In the elimination of water from hydroxytrimctliyl- glutaric acid or its ethereal salt (or of hydrogen chloride or bromide from the corresponding chloro- or bromo-derivative), it is possible that the change may take place thus with formztion of a trimethylene derivative CH,CH, OH CH, CH, CH, CH, \/ \/ \/ \/ COOH* C----C*CH2*COOH=H,O + COOH*C--C*CH,*COOH If the acid, called by us trimethylglutaconic acid, should prove to have the constitu- tion represented by the latter formula, it would be easy to understand i t s stability towards permangnnate, bromine, and reducing agents.Z-CAMPHORONIC ACID.1177 FH(CH,)*C(CH,),- 7H9 COOH co 0 and this, on further reduction, yields a trimethylglutaric acid, which Balbiano assumed to have the formula COOH* CH(CH,)*C(CH,),* CH,* COOH, since this acid, on oxidation, yields act-dimethylsuccinic acid, COOH*C( CH,),.CH,* COOH. This decomposition is no doubt best explained on the assumption that this trimethylglutaric acid has the formula given to it by Balbiano, but on the other hand the aap-trimethyl acid, COOH* C(CH,),* CH(CH,)*CH,* COOH, might also yield aa-dimethylsuccinic acid on oxidation, and therefore, in order t o determine the constitution of Balbiano's acid, it was neces- sary to synthesise either the aap- or the ap/3-trimethylglutaric acid, and directly compare the synthetical acid with the acid from camphor. In view of the great interest attaching to Balbiano's work, we have carefully studied our au~-trimethyIglutaric acid, and we find that, when pure, this acid melts at 11 2', that it gives an anhydride melting at 39O, and an ulnilic acid melting at 155'. Balbiano's trimethylglutaric acid, on the other hand, melts at 88-89', gives an anhydride melting a t Sl", and an anilic acid * melting, not quite sharply, at 149-150'.From this, it is evident that Balbiano's acid is isomeric with our aap-trimethylglutaric acid, and it must therefore be, as its discoverer suggested, the app-acid, COOH* C(CH,)*C(CH,),* CH,. COOH. During the course of our experiments on the reduction of trimethyl- glutaconic acid, we found that this acid, when treated in boiling amylic alcohol solution with sodium is, curiously enough, not reduced, but is converted into a most beautifully crystalline substance of the formula C8Hlo03. This compound crystallises from water unchanged, but it is, nevertheless, the anhydride of a dibasic acid, since it gives, with aniline, an anilic acid, C,H,,(COOH)*CO .NH* C6H5(m.p. 138') and this, when heated, is readily converted into the corresponding anil, melting at 148'. * This aS8-trimethyZgZz~taranilic acid had not been described, and we prepared it for comparison with our isomeric anilic acid by dissolving 0.7 gram of the an- hydride of Ralbiano's acid in benzene, adding 0.7 gram of aniline and allowing the mixture, which became very warm, to stand. The crystals which separated were collected, recrystallised from dilute methylic alcohol, and the glistening, crystalline mass, which melted approximately at 149", was analysed with the following resnlt : C,,H1,NO, requires N =5'63 per cent. 0.1117 gram gave 5.4 C.C. nitrogen a t 17" and 760 mm. N=5'60.1178 PERKIN AND THORPE: SYNTHESIS OF The anhydride, which we have named iso-trimethyZgEutucorLic ccnhy- chide, dissolves in boiling potash solution, and if the solution be cooled t o 0' and acidified with hydrochloric acid, the corresponding iso-tri- nzethylglutuconic acid is obtained. At its melting point (133'), this acid is converted into its anhydride with elimination of water, and the ease with which the anhydride is formed is shown by the fact that if the aqueous solution of the acid is boiled, the anhydride, and not the acid, separates on cooling.It seems probable that trimethylglutaconic acid and iso-trimethylglutaconic acid like fumaric and maleic acids, or mesaconic and citraconic acids, are stereoisomeric. The similarity in constitution between the two latter acids and the glutaconic acids becomes very clear from an examination of the following formuke.COOH* g*CH, CH,* E*COOH He C*COOH H* C-COOH (cis) Citraconic acid. (tmns) Mesaconic acid. COOH* C(CH,),* SGH, CH,* G*C(CH,),*COOH H* C*COOH H* C*COOH (tvans) Triinetl~ylglutaconic acid. (cis) Go-Trimethylglutaconic acid, The cis-modification of trimethylglutaconic acid would, like maleic and citraconic acids, readily yield an anhydride, but it is certainly remarkable that the formation of this anhydride should take place so very easily, the only analogous case being that of xeronic acid (diethylmaleic acid), an acid which is in many respects very similar t o iso-trirnethylglutaconic acid in its properties. We are a t present engaged in a further investigation of the tri- methylglutaconic acids with a view of determining whether, and under what conditions, they may be converted int,o one another.EX P E R I M E N T A L. Condensation of Etlqlic Dimethylacetoucetccte with Etlqlic Bromacetatc in the presence of Zinc. Formation of Ethylic asp- Trimethyl-P-hpdi*oxy- glutarate, COOC,H,- C(CH,),*C(OH)(CH,)*CH,* C00C2H,. After numerous experiments, it was found t h a t this condensation could best be carried out in the following way. Ethylic dimethylacetoacetate (50 grams) mixed with ethylic brom- acetate (50 grams) is heated in a reflux apparatus on a water bath until the mixture has reached the temperature of 90-95'; a small quantity of zinc" (about 1 gram) is then added, and the flask shaken * In order that this reaction may proceed satisfactorily, the zinc used mast be thoroughly cleaned, that is, it must be quite free from grease and oxide ; with this object, commercial zinc turnings are first passed through a sieve to remove the~-CAMPHORONIC ACID.1179 vigorously until the metal has almost dissolved; another gram of zinc is then added and the process continued until the metal is only very slowly attacked; excess of zinc is now added and the whole heated on the water bath for 10-12 hours. The addition of the zinc * to the hot mixture of ethylic salts in this experiment should be carefully carried out, as otherwise a very violent action may set in, in which case there is a great decrease in the yield owing to overheating and loss of the bromethylic salt by evapora- tion and decomposition.The product consistsof a brown, viscouszinc compound containing large quantities of unchanged zinc. On adding dilute sulphuric acid (I : l o ) , the zinc compound is decomposed and st brown oil separates which is extracted by three successive treatmentsmith ether, the ethereal solution is washed at least six times with dilute sulphuric acid, then with water, dried over potassium carbonate, and the ether distilled off. It is most important that the ethereal solution should be thoroughly and repeatedly washed with dilute sulphuric acid, as insufficient mashing always yields a product containing zinc salts and which decomposes on subsequent distillation, On distilling the oil under reduced pressure (30 mm.), LZ large quantity of a fraction of low boiling point is first obtained consisting largely of unchanged ethylic dimethylacetoacetate, the thermometer then rises rapidly to 160°, the crude condensation product passing over between this temperature and 180°, leaving a small quantity of substance of high boiling point.On refractionation, the bulk distils a t 160-170° (30 mm.). The fraction distilling a t 165' (30 mm.) gave the following results on analysis. 0.1430 gave 0.3056 CO, and 0.1140 H,O. C = 58.69 ; H = 8.92. 0.1278 ,, 0.2752 CO, and 0.1041 H,O. C = 58.60 ; H = 9-05, C,,H,,O, requires C = 58.54 ; H = 8.94 per cent. The substance prepared in this way is a colourless, moderately limpid liquid with a peculiar smell, and consists for the most part of ethylic t~imetlLyl?tydroxygl utarate. COOC,H,* C(CH,),* C(OH)(CH,)*CH,*COOC,H,. I t appears, however (see p.1173), always to contain some ethylic sup- trimet hy lglutaconat e, COOC,H,* C( CH,), C( CH,) : CH* COOC,HI,, coarser particles, and well washed, first with water, then with hot dilute soda, again with water, and lastly with very dilute hydrochloric acid and water. Finally, the zinc is dried by treatment with alcohol and ether, and subsequent heating in a steam oven. * In some cases, no action takes place for a long time, the zinc being only very slowly attacked, whilst in others, apparently under exactly the same conditions, the zinc dissolves a t once, with considerable rise of temperature. The yield of con- densation product is undoubtedly more eatisfactory when the reaction proceed3 quietly.1180 PERKIN AND THORPE: SYNTHESIS OF produced probably by elimination of water during distillation ; some- times it contains traces only of the unsaturated ethereal salt, whilst a t other times large quantities are present.aa p- Tr ime thy I-P-h y &*ox yg Zu taric Acid, COOH. C(CH,),* C(OH)(CH,)*CH,* COOH. When ethylic trimethylhydroxyglutarate is digested with alcoholic potash, it is entirely split up into acetic and isobutyric acids, but if carefully boiled with dilute hydrochloric acid (3 acid : 1 water) for about 10 to 12 hours, hydrolysis ensues without appreciable decom- position ; on cooling, a small quantity of trimethylglutaconic acid, COOH. C(CH,),* C(CH,):CH* COOH (p. 1 lSZ), separates in the crystal- line state. On allowing the mother liquor from these crystals to evaporate to dryness over potash in u vacuum desiccator, an acid mas obtained which, after recrystallisation from a mixture of ethylic acetate and light petroleum, gave the following results on analysis.0.2134 gave 0.3936 00, and 0.1421 H,O. C,H,,O, requires C = 50.52 ; H = 7.36 per cent. This acid is evidently trimetl~yl~y~roxyglutaric acid, produced by the direct hydrolysis of the ethereal salt ; it crystallises in well-defined, colourless prisms, melts a t 128O, and is readily soluble in water and in most solvents except light petroleum. C = 50.30 ; H= 7.4. Ethylic aap-Trimet~yI-p-chloroglzctarate, COOC,H,* C(C'H3),*CC1(CH,)*CH,* COOC,H,. This ethereal salt was prepared by gradually adding phosphorus pentachloride (25 grams) to ethylic trimethylhydroxyglutarate (25 grams) contained in a flask connected with a long tube to lead off the hydrogen chloride produced during the action.The pentachloride rapidly attacks the oil, and a vigorous reaction takes place with considerable rise of temperature and evolution of much hydrogen chloride ; after about an hour, and as soon as the pentachloride has entirely disappeared, the reaction is completed by heating for 15 minutes on the water bath. The product is now carefully poured into ice cold alcohol, the alco- holic solution, after some time, is mixed with water, the oily deposit extracted with ether, and the ethereal solution well washed with water and dilute sodium carbonate. After drying over calcium chloride and distilling off the ether, crude ethylic trimethylchloroglutarate is ob- tained as a slightly yellowish oil, which is somewhat unstable, as on distilling it under the ordinary pressure, hydrogen chloride is eliminatedi-CAMPHORONIC ACID.1181 with production of ethylic trimethylglutaconate ; under diminished pressure (20 mm.), however, it passes over unchanged a t 139" as a colourless oil. On analysis, it yielded the following numbers. 0.2010 gave 0.1935 AgCI. C1= 13.39. C,,H2,C10, requires C1= 13.42 per cent. The action of phosphorus pentachloride on ethylic trimethylhydroxy- glutarate has been carried out in a variety,of ways and under various conditions, but only on rare occasions has the product been found to contain the theoretical amount of chlorine as in the case given above. Frequently the oil has contained only 7-8 per cent.of chlorine, whilst on one occasion it was almost free from halogen, and was found on examination to consist of almost pure ethylic trimethylglutaconate. This unpleasant behaviour, which very much retarded the progress of this research, may be explained by the unsuspected presence of large quantities of ethylic trimethylglutaconate in some of the samples of crude ethylic trimethylhydroxyglutarate used, and also by the elimina-. tion of hydrogen chloride from the product of the reaction during distillation, this being due possibly to the presence of moisture and other impurities. The elimination of hydrogen chloride from ethylic trimethylchloro- glutarate undoubtedly takes place very readily; it was found, for ex- ample, impossible to reduce it even when ice-ccld alcoholic hydrogen chloride and zinc dust were employed as the reducing agent; the temperature was never allowed to rise above 0", but notwithstanding these precautions the product consisted entirely of ethylic trimethyl- glutaconate.Ethy Zic aap- Trimethyl-,& bromog Zutccrute, COOC,H,* C( CH3),* CBr(CH,)*CH,*COOC,H,. This is prepared in a precisely similar manner to the chloro-derivative just described, namely, by the gradual addition of phosphorus penta- bromide (52 grams) to ethylic trimethylhydroxyglutarate (25 grams), and subsequently heating the product for a short time on the water bath. It was isolated, exactly as in the case of the chlorinated compound, RS a yellowish oil (28 grams) which distilled with slight decomposition at about 145' (1s mm.).0.2542 gave 0.138 AgBr. Er = 23.12. C,,H,,BrO, requires Br = 25.23 per cent. The percentage of bromine in the various samples of this brom- ethereal salt which were prepared during the course of this research varied considerably, although not nearly to the same extent as in the1182 PERKIN AND TBORPE: SYNTHESIS OF case of the corresponding chlorinated ethereal salt ; it appears, there- fore, that the former is more stable than the latter, and this was borne out by subseqiient experiments with these compounds. aap-T~wimetl~~lglutuconic Acid, COOH- C(CH,),* C(CH,):CH* COOH. During the course of this investigation, this acid has been prepared by a variety of methods, of which the following may be described. I. By the Nydvolysis of Ethylic TyimethyZhyd~.oxyglutcc?.ccte.--It has already been mentioned (p. 1180) that this ethereal salt, when treated with alkalis, does not yield the corresponding acid, but is split up into acetic and isobutyric acids; if, however, the hydrolysis is carried out by boiling with concentrated hydrochloric acid until the oily ethereal salt has disappeared, the solution on cooling deposits crystals of tri- met h y lglutaconic acid.After recrysfallisation from water, this acid was readily obtained pure, melting at 148’. 0,1663 gave 0,3378 CO, and 0.1061 H,O. ‘C= 55.31 ; H= 7.08. O,H,,O, requires 0 = 55-SO ; H = 6.97 per cent. 11. By the Action of Diethykaniline on Ethylic Tyimethylbromo- glutarate.-In this experiment, the brominated ethereal salt (23 grams) mixed with diethylaniline (50 grams) was heated to gentle ebullition in a reflux apparatus for about an hour.The dark coloured product, when cold, was mixed with excess of dilute hydrochloric acid, extracted three times with ether, and the ethereal solution, after being well washed with dilute acid, was dried over potassium carbonate and1 evaporated; the oily residue, on being submitted to two fractiona- tions under reduced pressure, passed over almost entirely a t 160-165” (30 mm.), and consisted of nearly pure ethylic trimethylglutaconate. as the following analysis shows. 0.1390 gave 0.3210 CO, and 0.1140 H,O. C,,H2,0, requires C = 63.1 6 ; H = 8.77 per cent. The results of the hydrolysis of this ethereal salt with alcoholic potash were not very satisfactory, the acid obtained being contaminated with some sticky substance which rendered it difficult to purify.It is far better to boil it with hydrochloric acid until the oily drops have disappeared ; on cooling, crystals of trimethylglutaconic acid separate and can be readily purified by a single crystallisation from water. C = 62.98 ; H = 9.11. 0*1110 gave 0.2279 CO, and 0*0710 H,O. C = 55.95 ; H = 7.10. C,H,,07 requires C = 55.80 H = 6.97 per cent.&CAMPHORONIC ACID. 1183 Alcoholic potash appears t o act on ethylic trimethylchloro- or bromo- glutarnte in somewhat the same way as diethylaniline, since in both cases considerable quantities of trimethylgliitaconic acid are formed. 111. By the Action of Zinc Dust o n Xthplic TrimetiLylchloroglutarate. -This method, which is a rather curious one t o employ in obtaining an unsaturated acid, gives such a good yield of trimethylglutaconic acid that it was usually employed in preparing this substance. Ethylic trimethy lchloroglutarate (25 grams) dissolved in absolute alcohol (100 grams) was sdturated with hydrogen chloride, and about 20 &rams of zinc dust was then gradually added to the well cooled solution ; when all h t d dissolved, the product was poured into water and extracted three times with ether.The ethereal solution, after being thoroughly washed with water and with dilute sodium carbonate, was dried over anhydrous potassium carbonate, evaporated, and the residual almost colourless oil purified by distillation under reduced pressure (30 mm) ; almost the whole passed over between 160" and 165O, the distillate consisting of nearly pure ethylic trimethylglutaconate con- taining evidently, at the most, only a trace of ethylic trimethyl- glutarate. 0.2204 gave 05113 CO, and 0,1733 H,O.C,,H,,O, requires C = 63.15 ; H = 8-77 per cent. On hydrolysing this ethereal salt with hydrochloric acid as before, the oily drops disappeared after 12 hours' boiling, and on cooling a large quantity of a crystalline acid slowly separated. This, after being collected and recrystallised from water, was analysed and found to be trimethylglutaconic acid. C = 63.27; H= 8.76. 0*1510 gave 0.3074 CO, and 0.0948 H,O. C,H,,O, requires C = 55.80 ; H = 6-97 per cent. ~~1irnetl~yEgEut~conic ncid is sparingly soluble in cold water, but dissolves readily in boiling water, and separates on cooling in well- defined, lustrous plates which melt at 148".It is remarkable that its solution in sodium carbonate does not decolorise permanganate except on long standing; bromine also acts only very slowly on the acid, with ultimate formation of trimethyldibromoglutaconic acid, COOH- C( CH,),. C(CH,)Br*CHBr*COOH. (see next section). Salts of Tvirneth$glutccconic Acid. The siluerr. salt, C,H,,Ag,O,.-This is obtained as a white precipitate on adding silver nitrate to a slightly alkaline solution of the ammonium salt 0.21'70, on ignition, gave 0.121 1 Ag. C = 5559 ; H = 6.97. Ag = 55.85. C,H,,Ag,O, requires Ag = 55.87 per cent.1184 PERKIN AND THORPE : SYNTHESIS OF The most characteristic salt of this acid is the copper scdt which separates from the neutral solution of the ammonium salt on the ad- dition o€ copper acetate, as a bright blue, crystalline precipitate which is sparingly soluble in water.This salt, which is useful in separating trimethylglutaconic acid from other acids, yields the acid in a beauti- fully pure condition when decomposed with sulpharetted hydrogen. Trimethylglutaconic acid dissolves in acetyl chloride, but without formation of an anhydride, the solution, even after boiling for some time, depositing the unchanged acid on evaporation. On the other hand, prolonged boiling with acetic anhydride gives rise t o the forma- tion of an oil boiling at about 160-170' (30 mm.) ; this is a t present under examination. aap-T~inaet?~?lZ-alP-dibron~oglutccric Acid. COOH*C(CH,),-C(CH3)Br* CHBr COOH.Bromine acts only very slowly on trimethylglutaconic acid dissolved in chloroform, but on long standing it is gradually absorbed with forma- tion of the dibromo-acid above mentioned. I n preparing it, excess of bromine was added to a solution of the unsaturated acid in chloro- form and the mixture left for some weeks, during which time a quantity of crystals of the dibromo-compound had separated. The colourless crystals were washed with chloroform and analysed. 0.2901 gave 0,2433 AgBr. C,Hl2O4Brz requires Br = 48.19 per cent. T.rimetliyZdibronLogZut~~ric acid melts and decomposes at about 169O ; it is readily soluble in ether, alcohol, acetone, and ethylic acetate, less so in carbon bisulphide and chloroform, and almost insoluble in benzene and light petroleum.It is readily decomposed by boiling with aqueous silver nitrate solution, with separation of silver bromide. Br = 48.10. i~o-~rimet?~?/ZgZutuconic Anhydride. It has already been stated that trimethylglutaconic acid is only re- duced with great difficulty, and in investigating this subject, we on one or two occasions experimented on the action of sodium and boiling amylic alcohol on the acid, and with very remarkable results. The pure unsaturated acid (5 grams) was dissolved in amylic alcohol (600 c.c.), the solution heated to boiling, and then sodium (10 grams) added as rapidly as possible, When all the sodium had dissolved, the product was mixed with water, the amylic alcohol separated, and the aqueous solution boiled until the odour of amylic alcohol was no longer perceptible.The concentrated solution of the sodium salt was then acidified and extracted with ether, when a substance melting ati-CAMPHORONIC ACID. 1185 145-149" was obtained, which consisted chiefly of the unchanged acid. However, in subsequent experiments where the above process of reduc- tion was repeated five times with the same substance, a product was isolated from the sodium salt which melted a t 94-97', and on re- crystallisation from water at 107O. The analysis gave the following results. 0*10S1 gave 0.2470 CO, and 0.0660 H,O. C = 6231 ; H = 6.79. 0*1201 ,, 0,2734 CO, ,, 0.0733 H,O. C = 62.13 ; H= 6.83. C,H,,O, requires C = 62.33 ; H = 6.50 per cent. This substance, which is an anhydride, and which we propose t o name iso-trimethylglutaconic anhydride, crystallises from water un- changed ; i t is insoluble in dilute solution of sodium carbonate, but dissolves slowly on boiling, and on carefully acidifying the cold solution, it deposits needles of the corresponding acid (see next section).The anhydride crystallises from acetic anhydride unchanged, and sepa- rates from a mixture of benzene and light petroleum in magnificent, glistening plates. iso-Trimethylglutaconic anhydride was subsequently obtained in considerable quantity in an experiment instituted with the object of preparing ethylic trimethylbromoglutarate (p, 1 l S l ) , but in which by accident the wrong proportions of the materials were used. Ethylic trimethylhydroxyglutarate (50 grams) was mixed with phos- phorus pentabromide (40 grams), and the mixture heated for 6 hours on the water bath ; the product, when cold, was poured into alcohol, without allowing the temperature t o rise above 30°, water was then added, and the oily precipitate extracted with ether.After washing the ethereal solution well with water and dilute sodium carbonate solution, and evaporating the ether, a brownish, oily residue was left, the greater part of which distilled between 175" and 185' (35 mm.). The distillate, after being left in a n ice chest for a few days, deposited a large quantity of crystals; these were collected with the aid of the pump and crystallised from benzene and light petroleum. The product consisted of pure iso-trimethylglutaconic anhydride melting a t 107". 0.1356 gave 0.3088 CO, and 0.0822 H,O. C = 62.11 ; H= 6.73.0.1394 ,, 0.3197 CO, ,, 0.0846 H,O. C = 62.60 ; H=6.73. C1,Hl,,O, requires C = 62-33 ; H = 6-50 per cent. The oily filtrate from these crystals, on distillation, boiled at 15s-165' under a pressure of 25 mm. ; it contained large quantities of bromine, and apparently consisted of ethylic trimethylbromogluta- rate. VOL, LXXI. 4 L1186 PERKIN AND THORPE: SYNTHESIS OF iso-Trinzet7LylgluCncona~il~c Acid, C,,H17N0, = C,H,,<COOH CO*NH* C,H,. In order to prepare this substance, the pure anhydride was dissolved in benzene and the solution mixed with aniline ; very little rise of temperature took place, but on standing for a few days crystals gradually separated. These, when collected and recrystallised from warm dilute methylic alcohol, formed colourless needles.0.1627 gave 8.2 C.C. nitrogen a t 14' and 758 mm. N = 5.91. C,,H17N0, requires N = 5.67 per cent. Trimethylglutaconanilic acid melts at about 138' with rapid decom- position and formation of the corresponding anil. This is readily obtained by heating the anilic acid to boiling for a few minutes and recrgstallising the residue from dilute methylic alcohol, when it separates in long, colourless needles melting at 148O. 0.1418 gave 7.2 C.C. nitrogen at 15' and 760 mm. N = 5.96. C,,H,,NO, requires N = 6.11 per cent. iso-~rimethylglzttaconic Acid. This acid could not be prepared by the action of water on the anhydride, as the latter is not acted on by water in the cold, and on boiling, although the anhydride dissolves, it separates again on cooling unchanged.If, however, the anhydride be boiled with excess of aqueous potash, and the solution after cooling to 0' be acidified with dilute hydrochloric acid, the acid will gradually separate as a woolly mass of very fine needles, which, after collecting by means of the pump, wash- ing with ice-cold water, and drying on porous porcelain at the ordinary temperature, gave the following results on analysis. 0,1372 gave 0.2830 CO, and 0.0916 H20. C = 56.25 ; H = 7-42, 0.1522 ,, 0.3117 GO, ,, 0.0996 H20. C=55.90; H=7.28. C,Hl,O, requires C = 55.81 ; H = 7.00 per cent. iso-Trimethylglutaconic acid if rapidly heated melts a t about 133", with evolution of aqueous vapour and formation of the anhydride. It is readily soluble in alcohol, ether, or warm water, moderately so in cold water, and although it is possible to recrystallise the acid from water, the aqueous solution must not be boiled, otherwise the anhydride crystallises out on cooling.~-CAMPHORONIC ACID.l l S 7 Salts of iso-Trinzethylglutccconic Acid.-The silvev salt, C,IClo Ag,O,,, separates, on the addition of silver nitrate to tho neutral solution of the ammonium salt, as a white, amorphous precipitate which, after washing well, and drying first on a porous plate and then at loo", gave the following results on analysis. 0.2539 gave, on ignition, 0.1424 Ag. The neutral solution of the ammonium salt shows the following behaviour with reagents. Burium chloride gives a t first no precipitate, but after a fern minutes a beautifully crystalline barium salt separates in four-sided plates which are very sparingly soluble even in boiling water.Calcium chloride gives at once a microcrystalline Precipitate which is very sparingly soluble in boiling water. Copper ucetute gives no immediate precipitate even on boiling, but the solution, if left, gradually deposits a beautifully crystalline, copper salt ; the crystals under the microscope are deep blue, but not well defined. Ag= 56-08, C,H,,Ag,O, requires Ag = 55.87 per cent. aap- T!rimeth2/ZgZuturic Acid, COOH C( CH,), CH( CH,) C H, CO OH, On account of the interest attaching to the isolation and identifica- tion of this acid, which has already been noticed in the introduction to this paper, we made numerous experiments with the object of prepay- ing it from ethylic trimethylhydroxyglutarnte, but in performing this apparently simple experiment we met with quite unexpected difficulties.We, in the firat place, endeavoured to reduce the hydroxy-ethereal salt directly by heating it with fuming hydriodic acid, and as this failed, we next tried the action of various reducing agents on ethylic triniethyl- chloroglutarate and on the corresponding bromo-derivative, but in all cases we obtained either trimethylglutaconic acid or uninviting oily prbducts. The results of these experiments seemed t o point to the reduction of trimethylglutaconic acid as the only way of preparing tri- methylglutaric acid, but it was a long time before a suitable reagent could be found for this purpose. Sodium amalgam has no action on the unsaturated trimethylgluta conic acid, even when the acid is boiled with a large excess of tl:c amalgam, and heating with hydriodic acid converted the acid into dark coloured, oily substances which could not be purified.Sodium and boiling amylic alcohol gave rise to a very remarkable result, iso- trimethylglutaconic anhydride being produced, as explained on p. 1 184. The right reducing agent was, however, a t length found in sodium and boiling ethylic alcohol, and the method which we adopted for preparing trimethylglutaric acid was the following. 4 ~ 21188 PERKIN AND THORPE: SYNTHESIS OF Five grams of trimethylglutaconic acid was dissolved in 200 C.C. of absolute alcohol and the solution boiled in a reflux apparatus on a sand bath; 20 grams of sodium was then added through the condenser tube as rapidly as possible. When all the sodium had disappeared, the product was dissolved in water, evaporated until free from alcohol, acidilied, and the acid extracted several times with ether.The ethereal solution was then evaporated, and the residue reduced again exactly as before. After the whole process liad been repeated five times, the acid was extracted with ether, when, on evaporating the solvent, the residue solidified almost completely. The crystalline mass thus obtained melted at 80-95', and it was found necessary to recrystal- lise it a great many times from water before the melting point rose to 1 1 2 O , which appears to be the correct melting point of asp-trimethyl- glutaric acid. 0,1280 gave 0.2584 CO, and 0.0938 H,O. C,H,,O, requires C = 55.17 ; H = 8.05 per cent.au/3-Trimethylglutaric acid, is very readily soluble in water and most organic solvents, but separates readily from its aqueous solution on saturating it with hydrogen chloride. Salts oj Trimethylglutaric Acid. -The silver salt, C,H,, Ag,O,, was obtained in the usual manner as a white, sparingly soluble precipitate, and on analysis, the details of which have unfortunately been lost, gave the correct results. A neutral solution of the ammonium salt shows the following behaviour with reagents. Lead acetate produces no precipitate in the cold, but, on boiling, a characteristic, heavy, white precipitate separates. Mercuric chloride gives no precipitate with cold moderate dilute solutions, but, on warming, a heavy, yellowish-white, insoluble salt separates.Merculrous nitrate gives, at once, a heavy white precipitate, whieh dissolves on warming, and separates again as the solution cools. C = 55-08 ; H = 8.14. Anhydi-ide ofaa~-~rinaet?~ylgluta~ic Acid, OH,* CH<~~CW,),.co>O. co This anhydride was prepared by heating the acid to boiling for some time and then distilling the product. The distillate was dissolved in ether, the ethereal solution rapidly shaken with sodium carbonate solution, dried over calcium chloride and evaporated, when the residue, kept overnight in an ice-chest, solidified completely ; this anhydride, purified by recrystallisation from light petroleum, was obtained in fine, colourless prisms; it melts at 39', and dissolves in boiling water with re-f ormation of trimethylglutaric acid,~-CAMPHORONIC ACID.1189 0.2107 gave 0.4774 CO, and 0.1443 H,O. C = 61.78 ; H= 7.61. C,H,,O, requires C = 61.53 ; H = 7.62 per cent. aap-Trimethylglzctarccnilic Acid. C14H19N03 = C,H,*NH* CO*C(CH,),* CH(CH,)*CH,* COOH (1). On adding aniline to a solution of trimethylglutaric anhydride in pure benzene, a crystalline precipitate of the anilic aeid is at once produced. This, after being washed with a little benzene and purified by recrystallisation from dilute alcohol, was obtained in lustrous plates melting at 155'. 0.2060 gave 10 C.C. N, a t 18' and 773 mm. C,,H19N03 requires N = 5.63 per cent. Trimethylglutaranilic acid is readily soluble in most organic solvents, and its general behaviour corresponds closely with that of other known anilic acids of the glutaric series.It dissolves in sodium carbonate solution, but when heated, it does not readily yield the corresponding anil, in fact, small quantities of the anilic acid, if rapidly heated, distil almost without decomposition. On hydrolysis, the anilic acid is decomposed with some difficulty into aniline and trimethylglutaric acid, N=5*70. Ethylic aap-Trimethy1-/3-cyanogZuta;l.ate, COOC,H,*C(CH,),* C(CN) (CH3)*CH,*COOC,H,. The preparation of this substance and its subsequent conversion into i-camphoronic acid were found to be problems of such experimental difficulty as to necessitate more than a year's work before the desired result could be accomplished. I n the first series of experiments, ethylic trimethyl-P-chloroglutarate (p. 1180) was treated with pure potassium cyanide, with or without alcohol and other solvents, at temperatures up to loo', but even when the constituents had been heated together for 12 hours at that tem- perature the product was found to contain only traces of nitrogen.A similar result was obtained when the corresponding bromo-deriva- tive was substituted for the chlorinated compound in the same series of experiments, and a variety of experiments in which very carefully purified, neutral, donble cyanides, such as KCN,AgCN; 2KCN,Zn(CN),; 2KCN,Hg(CN),, were used instead of the slightly alkaline potassium cyanide, also gave negative results. Ultimately, however, the desired cyanide was obtained in the following comparatively simple manner. Ethylic-asp-trimethyl-p-chloroglutarate (22 grams) was heated in a sealed tube with pure potassium cyanide (10 grams) and a little alcohol for 6 hours at 150-160'.The dark-coloured product mas mixed with1190 PERKIN AND TIIORPE: SYNTHESIS OF water, extracted with ether, and the ethereal solution, after separation from a considerable quantity of dark brown insoluble matter, was dried Over calcium chloride, filtered, and the ether distilled off. In this way, a brown oil was obtained which distilled for the most part a t 170-180' (30 mm.), and gave the following result on analysis. 0.1850 gcave 6.3 C.C. nitrogen a t 15' and 760 mm. C',,H,lNO, requires N = 5.48 per cent. This oil contained, therefore, about 73 per cent. of ethylic cyano- trimethylglutarate, but the percentage of nitrogen was found to vary very considerably in different preparations.This is, of course, due, in the first place, to the fact, already noticed on p. 1181, that the ethylic trimethylchloroglutarate employed always contains some, and often a considerable quantity of, ethylic trimethylglutaconate ; it is also due, in a less deg;ee, to the fact that, during the heating with potassium cyanide, a certain amount of the chlorinated ethereal salt appears to be converted into ethylic trimethylglutaconate by elimination of hydrogen chloride. Unfortunately, the boiling points of the cyano-compound, and of the ethylic t,rimethylglutaconate lie so close together, that separation cannot be effected by fractional distillation ; but the presence of the unsaturated ethereal salt is of no great importance in the synthesis for which the cyano-compound was employed.N = 4.02. Synthesis of i-Cccnaphoi-onic Acid (a@-Trimethyltricarballylic Acid), COOH- C(CH,),* C(CH,)(COOH)*CH,* COOK. When the mixture of ethylic trimethylcyanoglutarate and ethylic- trimethylglutaconate, obtained as described in the previous section, is digested in a reflux apparatus with concentrated hydrochloric acid, it is gradually hydrolysed, and after about 16 hours the oily layer disappears almost entirely. If now the liquid be allowed to stand in an ice chest f o r 24 hours, practically the whole of the trimethylglutaconic acid present crystallises out, which is fortunate, since the presence of this acid greatly interferes with the isolation of the camphoronic acid. The filtrate from these crystals, which contains the camphoronic acid, is made distinctly alkaline with ammonia, cooled, mixed with an excess of a strong solution of barium chloride, and filtered from any slight precipitate which may have formed.If, now, the filtrate be heated on n water bath and subsequently to boiling, the whole of the camphoronic acid is precipitated in the form of a n exceedingly sparingly soluble barium salt. This salt is collected by means of the pump, well washed, and decomposed with the calculated quantity of dilute sulphuric acid ; the filtrate from the barium sulphate, if concentrated and allowed to stand iu an ice-chest, deposits beautiful, colourless, transparent prismsi-CAMPHORONIC ACID. 1191 melting at about 158-1 60° ; after recrystallisation, however, the melting point rose to about 16S0,* decomposition occurring a t the same time.The results of the analysis agree with those required by camphoronic acid, 0.1 258 gave 0.2276 CO, and 0.0766 H,O. C = 49.34 ; H = 6.58. 0.1294 ,, 0'23.18 CO, ,, 0.0766 H,O. C=49.38 ; H=6.57. C',H,,O, requires C = 49.50 ; H = 6.40 per cent. This acid is much less soluble in water than ordinary d-camphoronic acid, and crystallisos in much more definite crystals ; i t was further. characterised by converting it into the following derivatives, which were carefully compared with the corresponding derivatives obtained from a small quantity of i-caniphoronic acid which Dr. 0. Aschail kindly sent us, and which had been prepared I y crystallising together equal quantities of the d- and I-acids. i-A~zh~~~ocnnziul~orolzic Acid, C,H,,O,.-As the result of experiments with d-camphoronic acid, i t was found that, in cases like the present, where only very small quantities of substance are available, the con- version of camphoronic acid into the corresponding anhydro-acid is best ttccomplished as follows.The finely powdered substance is boiled, in a reflux apparatus, with a large excess of acetyl chloride until i t has entirely dissolved, which is iisually the case in about half an hour: the acetyl chloride is then evaporated off on the water bath, and the residue allowed to remain over solid potash in R vacuum desiccator until it has completely solidified. The product is then dissolved in a small quantity of boiling benzene, which had previously been carefully dried by repeated dis- tillation over sodium, and the solution allowed to stand overnight.The crystals of the anhydro-acid which separate are collected, washed with a little benzene, and dried a t looo. The anhydro-acid obtained from synthetical i-camphoronic acid in this way began to soften slightly a t 13S-133~1", and melted suddenly at 136-137O.t 0.12S-i gave 0.3541 CO, and 0-0'706 H,O. C,H,,O, requires c' = 54-00 ; H A 6.00 per cent. The anhydro-acid, prepared from A schan's i-camphoronic acid under the same conditions, could not be distinguished from the synthetical substance, and as the former has not previously been described, i t was also analysed. * The melting point of cainphoronic acid depends very inuch on the conditions observed during the deterniination ; this has also been noticed by Aschan. t It is not improbable that this melting point may be somewhat too low, but the amount of snbstance a t our disposal was so siiiall t l i n t we could not subject it to further crystallisation.C = 54-03 ; H = 6.1 1.1192 PERKIX AND THORPE: SYNTHESIS OF 0.1322 gave 0.2610 CO, and 0.0'71 8 H,O. i-Campi'to~~oizn.lzilic m i d , C15H1,K0,.*-This was obtained by treating anhydrocamphoronic acid with aniline, parallel experiments being made both with our synthetical acid and with Aschan's acid, the conditions observed being exactly the same in both cases. The anhydro-acid mas dissolved in hot benzene in a test-tube, the bulk of the benzene was then boiled away, and the cold, supersaturated solution mixed with rather more than the requisite quantity of aniline.The clear solution becomes warm, then suddenly turbid, and deposits either a mass of colonrless crystals or an oil which rapidly solidifies on rubbing with a glass rod. The crystals mere washed with benzene, drained on a porous plate, and dried a t loo", they then melted a t about 140". This substance is not very easy to purify by recrystallisation, but if it is dissolved in a little hot alcohol, and the solution is then mixed with about three times its bulk of benzene, the anilic acid gradually separates in colourless crystals which melt at about 149' with decomposition. The anilic acid prepared from synthetical i-camphoronic acid gnre tlie following results on analysis. 0.0580 gave 2.44 C.C. nitrogen a t 16" and 763 mm. CI5H,,NOj reynires N = 4-77, i-Camphoronauilic acid, prepared from Aschnn's i-camphoronic acid, hnd the same melting point and properties as the synthetical substance.0.1022 gave 4.4 C.C. nitrogen a t 20' C. and 754 mm. C, ,HI,NO, requires N = 4.57 per cent. C = 53.8.1, ; I3 = 6.03. C,H,,O, requires C = 54.00 ; H = 6-00 per cent. N = 4.85. 1?c= 4-88. C'oizdewation of Ethylic Acetoacetate with h'tlqlic a-Bronzisobutyrate in presence of' Zinc. Second SptlLesis of Ethylz'c aap-l'1.imetl~?/lli~~roz!/- glutcwate, COOC',H,)* C'(CH,),* C(OH)(CH:;)*CH,*COOC,H,. As already stated in the introduction, this condensation was investi- gated i n order to prove the constitution of the ethylic trimethyl- hydroxyglutarnt,e used in this research. The experiment was carried out in a manner precisely similar to that with ethylic dimethylaceto- +.d-Caiiiphoronanilic acid. - I n order to determine the conditions for preparing tlic aiiilic acid from i-camphoronic acid, experiments were, in the first place, made with the d-acid, and by using the above inethod considerable quantities of d-camphoroii- anilic acid were prepared. This coruponnd, which has not been previously described inelts, after recrystallisation, a t 147-148", and closely resembles the i-modification in its properties. 0.112 gave 5 C.C. nitrogen a t 24" and 754 iim. K=5'dO. C,,H,,NO, requires N=4*77 per cent.Z-CIAMPHORONIC ACID. 1193 acetate and ethylic bromacetate already described. The bromo-ether (84 grams) was mixed with ethylic dimethylacetoacebate (58 grams), and the zinc gradually added to the hot mixture, the same precautions being observed as in the previous case, great care being taken to prevent the temperature rising too high, as, unless this is done, a most violent action sets in and the yield of product is then very small.The product, treated exactly as described on p. 1179, gave an oil boiling a t 160-170O (30 mm.). 0.1775 gave 0.3828 CO, and 0.1722 H,O. C,,H,,O, requires c! = 58.53 ; H = 8.94 per cent. As will be shown below, this ethereal salt is identical with the con- densation product obtained by the action of zinc on a mixture of ethylic dimethylncetoacetate and ethylic bromacetate, and both products, therefore, must consist of ethylic aap-trimethyl-,f3-hydroxyglutarate The yield obtained with the bromacetate is as much as 20-25 per cent.of the theoretical, whilst if ethylic bromisobutyrate is employed the yield hardly ever rises above 8-10 per cent. of the theoretical. This appears to be clue to the fact that zinc acts more readily on ethylic bromisobutyrate than on ethylic bromacetate, and when the former is employed large quantities of product of low boiling point are obtained. These oils, on refractionation under the ordinary pressure, were readily separated into two fractions, namely, a very large one, 110-125", consisting of a mixture of ethylic isobutyrate and ethylic methylacrylate, CH,:C(CH,)*COOC,H,, and a fraction, 1 i0-185° consisting of unchanged ethylic acetoacetate. Experiments mere now made with the object of proving that the compound produced by the condensation of ethylic acetoacetate and et hylic bromisobutyrate is identical with that obtained by the con- densation of ethylic dimethylacetoacetate with ethylic bromacetate, and in order to do this the same derivatives were prepared from the former product as have already been described as resulting from the latter. When treated mith phosphorus pentachloride or pentabromide, the con- densation product from ethylic bromisobutyrate yielded halogen deriva- tives identical in boiling point and other properties with those described on pp. 1180 and 1181. Both the chloro- and the bromo-derivative, on treatment with zinc and subsequent hydrolysis (see p. 1 183), yielded trimethylglutaconic acid melting at 148". C=58*82; H=S.90. On analysis, this gave the following result. 0*3091 gave 0,4265 CO, and 0.1302 H,O. From this acid, on reduction with sodium and alcohol, &up-trimethyl- C = 56.63 ; H = 6.92 C8H,,0, requires C = 55-81 ; H = 6.97 per cent.1194 PERKIN : YELLOW COLOURING MATTERS OBTAINED FROM glutaric acid (m. p. 1 1 2 O ) was prepared, and its identity proved by analysis and by converting it into its anhydride (m. p. 39') and into its anilic acid (in. p. 155'). These experiments prove conclusively the identity of the two con- densation products. In preparing large quantities of the condensation product from ethylic bromisobutyrate and ethylic acetoacetate, me found it con- venient to distil off the oil of low boiling point formed during the con- densation, and t o reserve the residue until a considerable quantity had accumulated, before purifying it by fractionation. On standing, this crude product deposited a small quantity of a solid substance ; this was collected, washed with ether to free it from oil, and the sparingly soluble crystals were recrystallised from boiling alcohol. The substance was thus obtained in the form of magnificent, long needles, closely resembling asbestos in appearance, but the quantity at our disposal was so small that only one analysis could be cmried out, and this gave us no clue as to i t s constitution. 0.1214 gave 0.2768 CO, and 0.0538 H,O. C,,H,,O, requires C = 61-85 ; H = 5.1 5 per cent. This substance melts at 169' and dissolves in soda, forming a bright yellow solution, the colour of which disappears on boiling ; on acidify- ing the colourless solution with hydrochloric acid, it deposits an oil. It is nearly insoluble in ether, but dissolves readily in alcohol, especi- ally on warming, and the solution gives an intense violet coloration with ferric chloride. C = 62-28 ; H= 5.38. Owms COLLEGE, MANCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT8977101169

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

1194 PERKIN : YELLOW COLOURING MATTERS OBTAINED FROM c1XIII.- Yelloio Colouring iMattem obtained f;l*on% Bhus rhocla~zthemu, Rwberis oetncnsis, a d Ruqnex obtztsijobiws. By ARTHUR GEORGE PERKIN, F.R.S.E. Rims rl~odacnthemn. Tim R. rlhodccnthentcc, or yellow cedar, a tree growing to the height of 70 or 80 feet, is indigenous to the northern part of New South Wales. Through the kindness of Mr. Henry Smith, of the Technological Museum, Sydney, about 21bs. of chippings from the stem of this tree were avaiIable for investigation these were of an orange-brown colour, and contained some yellow mordant dye-stuff. Owing to the liberality of Prof. Henry Trimble, of Philadelphia, material has been obtained for an investigation of the colouringRHUS RHODANTHEMA, BERBERIS OETNENSIS, ETC.1195 matters present in various species of rhus, and a preliminary examina- tion of these indicates that it is in the leaves alone that any appreciable quantity of colouring matter is -to be found, This makes the yellow cedar more interesting for comparison with Rhus Cotinus (young fustic), the only other member of this species which, so far as I am aware, contains a colouring matter in the stem, The finely ground wood of the cedar was extracted with boiling water, the extract treated with lead acetate, and the dull yellow precipitate, after being collected and washed, was run, in the form of a thin cream, into boiling dilute sulphuric acid, and the clear liquid, separated from the lead sulphate, extracted with ether. The extract, when evaporated, left a yellow, somewhat viscid residue, and this, on being boiled with water, gave a solution which, on cooling, deposited the colouring matter as a pale yellow precipitate ; this was collected, washed (the filtrate, A, being reserved for examination), and purified by crystallisation from dilute alcohol.0.1241 gave 0.2855 CO, and 0.0405 H,O. C = 62.74 ; H = 3.61. C,,H1,06 requires C = 62.93 ; H = 3.49 per cent. It crystallises in glistening, yellow needles soluble in alkalis with a yellow colour, and yielding, in alcoholic solution, with lead acetate, an orange-red precipitate, and, with ferric chloride, a dark green coloration. The acetyl compound, prepared in t'he usual manner, formed colourless needles melting at 196-1 98'. 0.1210 gave 0.2701 CO, and 0.0450 H,O.For the production of the corresponding benxoyl derivative, it was digested with 5 parts of benzoic anhydride at 170° for 2 hours. The solution, after treatment with acetic acid, was poured into alcohol, and the precipitate purified by crystallisation from a mixture of chloroform and alcohol. It was obtained as a glistening mass of colourless needles melting a t 181-182O. c! = 60.86 ; H = 4.13. C15H606(C,H,0), requires C = 60.79 ; H = 3-92 per cent. 0.1220 gave 0.3272 CO, and 0,0440 H,O. On fusion with alkali, the colouring matter yielded two crystalline products, readily identified as protocatechuic acid and resorcinol. The colouring matter of Rhus rhodccnfhema is therefore $set&, a fact fully borne out by an examination of its dyeing properties. The GZucoside.-The aqueous filtrate (A) from the colouring matter evidently contained a second substance, being of a somewhat viscid nature and of a deep yellow colour.In order to remove the last C = 73.14 ; H = 4.00. cl,H,06(C7H,0), requires c = 73-50 ; H = 3.70 per cent.1196 PERKIN : YELLOW COLOURING MATTERS OBTAINED FROM traces of fisetin, salt was added, the viscid Precipitate formed removed by filtration, and the filtrate, after treatment with sodium hydrogen carbonate, was extracted two or three times with ethylic acetate and the extract evaporated. The brown, viscid residue, dissolved in boiling acetic acid and diluted with water, gradually deposited crystals ; these were collected, drained upon a tile, and purified by repeated crystal- lisation from water until colourless.The substance was dried at 110' and analysed. 0.1046 gave 0.2297 CO, and 0,0430 H,O. C = 59.S9 ; H = 4-56. C,,H,,O,, requires C = 60.18 ; H = 4.45 per cent. It crystallises in glistening needles readily soluble in boiling water and dyeing mordanted calico shades closely resembling those obtained from fisetin itself. With ferric chloride in aqueous solution, it gave a green coloration, and with lead acetate a pale yellow precipitate readily soluble in acetic acid. When heated, i t melted and decomposed at 215-217'. I n order to ascertain whether this substance was a glucoside, i t was boiled with dilute sulphuric acid for several hours ; a small quantity of a yellow precipitate having the properties of fisetin separated, but a considerable portion remained unattacked.This pre- cipitate separated from the acid liquid on long standing, and its melting point was found to be identical with that of the untreated substance. The only known glucoside of fisetin is that named fustin, C58H46023, which was isolated from Rhus Cotinus by Schmid (Ber., 1886, 19, 1753); this occurs in the plant in the form of a tannin compound which is readily decomposed by acetic acid into fustin and gallotannic acid. The description given by him of its appearance and properties closely agrees with those possessed by the substance described above, although its percentage composition, C = 62.70, H = 4.14, is somewhat higher. According t o the correct formula for fisetin, fustin must now be represented as C,GH,,O,,, C = 63-34, H = 3-81 per cent., if as sur- mised by Schmid, it yields rhamnose when decomposed by acids.This glucoside is evidently peculiar, yielding as i t should 2 mols. of colouring matter and but 1 mol. of the sugar, and differs from other glucosides of the quercetin group, not only in this respect, but also by its extreme stability towards acid. To determine, if possible, whether the yellow cedar glucoside was distinct from fustin, the filtrate from the lead precipitate was examined, this being the source from which Schmid obtained his glucoside when examining R. Cotinus. For this purpose, it was concentrated, saturated with salt, filtered, the filtrate extracted with ethylic acetate, and the extract evaporated. The viscid residue, when dissolved in boiling aceticRHUS RHODANTHEMA, BERBERIS OETNENSIS, ETC.1197 acid and diluted, gradually deposited crystals, which, after purification, melted at 215-217°, and evidently consisted of the product described above. A second treatment with hot acetic acid, and subsequent crystallisation from water, effected no further purification, so that i t appeared evident that it was not contaminated with any tannin compound, although, judging from Schmid’s investigation of R. Cotinus and the detection of gallic acid (see below), such may reasonably be expected to exist in the yellow cedar. On analysis, it gave numbers agreeing with those previously obtained. C = 60.21 ; H = 4.00. 0.1019 gave 0.2250 C02 and 0.0367 H,O. C,6H3001, requires C = 60.18 ; H = 4.45 per cent. The extreme stability of this glucoside towards acid, and the small quantity available, rendered an identification of the sugar impossible.A like difficulty was experienced by Schmid in his examination of fustin, and that this yielded rhamnose is but a suggestion of his, based upon the production of this sugar from quercitrin. The above results render it very probable that the yellow cedar glucoside is not fustin. I n appearance, it was colourless and homo- geneous throughout, and if impure it is remarkable that the distinct preparations described above should contain exactly the same amount of impurity. Certainly the amount of crude substance available was small, and when purified as completely as possible by crystallisation sufficed only for the experiments noted above, but this had all the characteristics of a pure substance.Its decomposition by acids into fisetin and rhamnose (2) can be represented-thus. C36H3001f3 + 2H,o = 2C1fjH1006 f C6H1,06* Gallic Acid.-The bicarbonate of sodium solution from which the glucoside had been removed with ethylic acetate (page 1196) was neutralised with acid, extracted with ether, and the extract evaporated; the crystalline residue, after purification, was obtained in colourless needles melting a t 239-240Owith evolution of gas. An aqueous SO~U- tion gave a blue-black coloration with ferric chloride. Further tests revealed its identity with gallic acid, this evidently having been pro- duced as a result of the decomposition of gallotannic acid existing in the plant by the sulphuric acid employed during the isolation of the colouring matter.Attempts will be made to procure, if possible, the leaves of this tree for examination. It has been previously shown that the colouring matter contained in the leaves of R. Cotinus is apparently myricetin, Cl5TZlOO8, whereas that in the stem is known to be fisetin, Cl5Hl0O,. It would be interesting to see if the R. rhodunthema leaves also have a similar relation to the wood,1198 PERKIN : YELLOW COLOURING MAPTERS OBTAINED FROM Dyeing PT*operties.-These experiments were carried out in the usual manner, employing woollen cloth mordanted with aluminium, chromium, tin, and iron. The shades given by the yellow cedar are slightly weaker and differ considerably from those given by R. Cotinus, although both contain the same colouring matter. Young fustic... , . . Reddish-brown. Orange. Orange-yellow. Brown-olive. Yellow cedar ... ... Yellowish-brown. Brownish-yellow, Golden yellow. Olive. This difference is probably due to varying amounts of a brown Chromium. A luminium. Tin. Iron. extractive matter, which is contained in both plants. Berberis Oetnensis. A sample of the root of thiv plant was forwarded to me for chemical examination by Mr, Gennadius, the Director of Agriculture in Cyprus, in the hope that, flourishing as it does in the island, it might possess some commercial value as a dye-stuff. In appearance, the plant closely resembles Berberis vulgaris, the root being of a hard, woody nature and internally of a distinct yellow colour. The finely ground sample was extracted with boiling alcohol, and the orange-brown extract treated with lead acetate solution as long as a colourless precipitate was formed, this being removed by filtration.The concentrated filtrate, when poured into dilute hydrochloric acid, gave a sticky, yellow precipitate which increased on standing; this was collected, dissolved in water, and after removal of a wax-like product by means of ether, the solution was boiled, and treated with one-tenth of its volume of hydrochloric acid. On cooling, long, orange-coloured needles gradually separated, which, after purification by recrystallisa- tion from dilute hydrochloric acid, were converted into the platino- chloride, and analysed in tbe usual manner. 0.1426 gave 0,2315 CO, and 0.0435 H20. 0.3277 gave, on ignition, 0.0595 Pt. (C,,H,7N0,),H2PtCI, requires C = 44.47 ; H = 3.33 ; Pt = 18.02 per cent.The substance was evidently berberine platinocbloride, its identity being corroborated by a comparison with berberine platinochloride pre- pared from other sources. By the above method, 100 grams of root yielded 0.64 gram of the pure hydrochloride. Dyeing Properties.-An aqueous extract of this root dyes wool and silk a yellow shade, without the use of a mordant, the tint being some- what duller than that given by pure berberine hydrochloride. With cotton, mordanted with tannin, a dull yellow is obtained, but ordinary mordanted calico was not dyed, indicating that this root contained only basic colouring matter. The strength of this dye-stuff was approximately C = 44-27 ; H = 3.39. Pt = 18.15.RHUS RHODANTHEMA, BERBERIS OETNENSIS, ETC.11 99 equal to 1 per cent. of berberine hydrochloride. As a colouring matter, the use of berberine has been practically discontinued, so that the tinctorial properties of this root have but little commercial value. Possibly it may be useful as a source of berberine for medicinal purposes. Rumex obtusifolitcs. In a previous communication (Trans., 1895,67, 1084), it was shown that the leaves of Polygolzum cuspidaturn contain a yellow colouring matter, present, however, in such minute quantity that sufficient raw material could not be procured for its investigation. It naturally suggested itself, however, to test, in this respect, the dyeing property of the common dock, a member of the closely allied Rumex family, and it was at once evident that the perianths encircling the seeds" of this plant contained traces of some yellow colouring matter.Two kilos. of this product were extracted with boiling water, and the extract on being treated with lead acetate solution gave a dull grey precipitate having a faint yellowish tinge. This was collected, washed, suspended in boiling water, decomposed with sulphuric acid and allowed to settle, the clear brown liquid being decanted from the lead sulphate. From this solution, ether extracted a small amount of a brown, viscid product which from its dyeing property evidently contained the colouring matter ; it was, therefore, suspended in water, treated with excess of sodium hydrogen carbonate solution, again ex- tracted with ether, and the extract evaporated.On treating the residue with water, a brownish-orange precipitate separated, and in order to purify it, it was converted into the acetyl compound, the latter, after repeated crystallisation from alcohol being obtained in colourless needles melting a t 189-191'. The pure colouring matter regenerated from the acetyl derivative, in the usual manner, separated from its hot solution in dilute alcohol as glistening, yellow needles. Its dyeing pro- perties and general reactions left no doubt as to its identity with quercetin. The amount occurring in the material employed was ex- ceedingly minute, seeing that from the 2 kilograms but 0.1 gram of pure colouring matter was isolated. It is possible that, if gathered earlier in the season, a larger yield of quercetin might be obtained, for this specimen was collected about 'the middle of September, and had been previously subjected to much rain. As is well known, the roots of various species of the rumex family contain methylanthra- quinone derivatives, for example, chrysophanic acid, emodin, &c., and the existence of quercetin in the same class of plant is interesting. * That the seeds themselves yielded no colouring matter appeared evident, as after long boiling with water they still possessed the same hard, impermeable appearance as before this treatment.1200 YOUNG AND CLARK : NAPHTHYLCARBAMIDES. Experiments carried out with the madder plant (Rubia tinctoTiu) in- dicate that the leaves and green stems contain a yellow colouring matter in moderate quantity. This I hope shortly to investigate. CLOTHWORKERS’ RESEARCH LABORATORY, DYEING DEPARTMENT, YORKSUIRE COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT8977101194

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

1200 YOUNG AND CLARK : NAPHTHYLCARBAMIDES. CXIV. 4 i a p h t h y lead arnides. By GEORGE YOUNG, Ph.D., and ERNEST CLARK. a-N~~?~thylcarbumide, C,,H7* N H* CO NH,, THIS substituted carbamide has been previously described by Schiff (Ann., 151, go), who prepared it by passing the vapour of cyanic acid into a solution of a-naphthylamine in dry ether, and by Pagliani (Gaxx., 9, 30), who obtained it by heating naphthylamine hydrochloride with carbamide at 150-1 70" ; neither method, however, is convenient, and the latter, even under the most favourable conditions, yields principally dinaphthylcarbamide. Beilstein, quoting Schiff, states that the action of potassium cyanate on naphthylamine sulphate yields nothing but ordinary urea. We have found that if an aqueous solution of potassium cyanate be slowly added to a solution of a-naphthylamine hydrochloride in water,* naphthylcarbamide separates as a white, flocculent precipitate. When prepared in this manner, the product contained small amounts of unchanged naphthylamine, which were removed by treating it with cold dilute hydrochloric acid and subsequent digestion with benzene.The yield of pure a-nnphthyl- carbamide was over 95 per cent. of the theoretical, 0.1662 gave 0.4327 CO, and 0.0823 H,O. The solubilities of the substance agreed with those previously des- cribed. It was easily soluble in alcohol and ether, slightly soluble in benzene and boiling water, almost insoluble in cold water. Schiff and Pagliani both state that a-naphthylcarbamide decomposes at about 250" without previous fusion. On heating our preparation in a capillary tube, we observed that it softened at about 210', became perfectly solid again a few degrees higher, and finally decomposed between 270' and 280'.On repeating the experiment, we found that, * a-Naphthylamine hydrochloride is said to be very easily soluble in water As we did not find it so, we,determined the solubility and found C = 71.00 ; H = 5-50. C,,H7*NH*CO*NH, requires C = 70.95 ; H = 5.37 per cent. (Watt's Diet.). it to be 3.7670 grams in 100 C.C. of water at 20".YOUNG AND CLARK : NAPHTHYLCARBAMIDES. 1201 if the temperature were raised sufficiently rapidly, complete fusion took place a t 2 1 3-2 1 4 O , followed by resolidification below 2 18O. This behaviour is explained, as is shown below, by the conversion of the mono- into the di-naphthylcarbamide which melts when pure a t 284-286'. This change takes place rapidly at the melting point of mononaphthy Icarbamide, but also, although more slowly, below that temperature, so that if the substance be not too quickly heated the greater part of the mononaphthylcarbamide has already undergone 3hange before its melting point is reached.A specimen of a-naphthyl- carbamide prepared by Pagliani's method showed exactly the same behaviour. a-Di~~3hthyZcar~am~de, C,,H,*NH* CO *NH- Cl0H7. When a-mononaphthylcarbamide was heated in an oil bath at a tem- perature slightly above' its melting point, a considerable evolution of ammonia took place, and the residue, after being washed with dilute caustic soda to remove cyanuric acid, was recrystallised from amylic alcohol; it was then obtained in delicate, white needles, which darkened slightly on exposure to air.0.1481 gave 0.4380 CO, and 0.06'73 H,O. C,,Hl6N2O requires C = 80.76 ; H = 5.1 2 per cent. a-Dinaphthylcarbamide is insoluble in water, fairly soluble in boil- ing amylic acetate, less so in boiling amylic alcohol, and only very sparingly in boiling ethylic alcohol. After repeated recrystallisation from amylic acetate, the white needles melted a t 284-286'. The melting point of a-dinapht hylcarbamide has been previously given as 270'. C = 80.65 ; H = 5.04. a-Acety ZnaphthyZccvrbcide, C,,H,*NH- GO *NH* CO*CH,. This derivative, prepared by the action of acetic chloride on a-naphthylcarbamide, crystallised from dilute alcohol in stellate clusters of delicate, white needles which melted to a clear liquid a t a14-215".0,1464 gave 0.3668 (70, and 0.0722 H,O. C,,H,,N,O, requires C = 68.42 ; H = 5.26 per cent. a-Acetylnaphthylcarbamide is freely soluble in hot alcohol and ben- zene, moderately so in the cold solvents and almost insoluble in light petroleum. In preparing this compound, a small amount of a substance melting a t about 160° was obtained ; this was probably u-acetylnaphthyl- nmine. C = 68.33 ; H = 5.47. The amount was not sufEicient for analysis. VOL. LXXI. 4 M1202 YOUNG AND CLARK : NAPHTHYLCARPAMIDES. The brown product, obtained by heating a-naphthylcarbamide with benzoic chloride, was well washed with boiling 50 per cent. alcohol and recrystallised from boiling absolute alcohol, from which it separates in delicate, white needles.It sintered slightly a t 2374 and melted a t 243-2435'. 0.1 729 gave 0,4717 GO, and 0*0760 H20. a-Benzoylnaphthylcarbamide is insoluble in water, and moderately soluble in boiling alcohol. The alcoholic washings, on cooling, deposited a substance which melted at 154"; the figures obtained on analysis showed this to be a-benzoylnaphthylamine, the melting point of which is given as 156O by Worms (Ber., 1882, 15, 1814). C = 74.40 ; H = 4.88. C,,H,,N,O, requires C = 74-48 ; H = 4-82 per cent. 0.1562 gave 0.4735 CO, and 0.0747 H,O. C = 82.49 ; H = 5.31. C,,H,*NH* co'c,H, requires c = 82.59 ; H = 5.26 per cent. P-Naphthylcarbamide, C,,H7*NH*CO*NH,. This substituted carbamide has previously been described by Cosiner (Bey., 1881, 14, 62), who prepared it by heating P-naphthylamine hydrochloride with urea.We have prepared the /3-naphthylcarbamide by adding potassium cyanate to an aqueous solution of P-naphthyl- amine hydrochloride; it then separates as a bulky, white preci- pitate, and on recrystallisation from dilute alcohol forms small, white, feathery needles. 0.192'7 gave 0.5011 CO, and 0.0953 H,O. Our preparation agreed in its solubilities with those described by Cosiner, being easily soluble in hot alcohol and water. Cosiner gives the melting point of /3-naphthylcarbamide as 287O, the substance having previously softened a t about ZOOo. We observed the behavionr on heating to be similar to that of a-naphthylcarbamide ; when slowly heated in a capillary tube, it softens and shrinks at slightly over 200°, but at some degrees higher resolidification takes place accompanied by a considerable increase in volume, and the substance finally melts a t about 287'.If, however, the temperature of the capillary tube be raised sufficiently rapidly, complete fusion of the P-naphthylcarbamide takes place at 213-215O. The explanation, as in the case of the a-naphthylcarbamide, is that the conversion of the C = 70.92 ; H = 5-49. C,,H,,N,O requires C = 70.95 ; H = 5-37 per cent.YOUNG AND CLARK : NAPHTHYLCARBAMIDES. 1203 mono-substituted carbamide into the symmetrical di-substituted deri- vative takes place rapidly at a temperature slightly below the melting point of the former. P- Dinaphthylcaybamide, C,,H,*NH* CO *NH* C,,Hp P-Naphthylcarbamide was heated at its melting point in an oil bath until the evolution of ammonia ceased, and after washing the product with dilute caustic soda and boiling alcohol, it was recrystallised from amylic acetate; it separated as a mass of feathery needles having a slight creamy tinge and melting at 289-290'.The melting point of P-dinaphthylcarbamide is given by Huhn (Bey., 1886, 19, 2406) as 293O, and by Ekstrand (Ber., 1887, 20, 1360) as 286'. 0,1562 gave 0.4618 CO, and 0.0724 H,O. /3-Dinaphthylcarbamide is fairly soluble in hot amylic acetate, It is only slightly soluble in C=80*63; H=5.15. CzlHl6N2O, requires C = 80.76 ; H = 5.12 per cent. amylic alcohol, and ethylic acetate. other solvents. P-Acetylnaphthylcarbccmide, C, ,H,*NH*CO*NH* CO*CH,. This derivative was prepared by the action of acetic chloride on P-naphthylcarbamide. It is insoluble in cold water, and only very slightly soluble in boiling water, but easily in boiling alcohol or benzene.It forms microscopic needles melting a t 202-202.5°. 0,1725 gave 0.4321 CO, and 0.0838 H,O. C1,H1,N20, requires C = 68.42 ; H = 5.26 per cent. I n this preparation, a small quantity of a substance was obtained which crystallised from hot water in needles melting a t about 130°, and which was probably P-acetylnaphthylamine. The quantity was too small for analysis. C = 68.31 ; H, 5.39. P-Benxoyl.n~pJ~t?~ylca~bumide, C,,H,*NH* CO *NH*CO*C,H,. The product obtained by acting on P-naphthylcarbamide with ben- zoic chloride was washed with hot 60 per cent. alcohol so long as the washings gave a deposit on cooling. This deposit was soluble in benzene and alcohol, and melted at 162-163', and analysis proved it to be P-benzo yln aph t h y lamine. 0.1856 gave 0,5616 CO, and 0*0887 H20. The residue, insoluble in warm 60 per cent. alcohol, was recrystal- C = 82.52 ; H = 5.31. C1,H1,NO requires.C = 82.59 ; H = 5.26 per cent.1204 OBITUARY NOTICES. lised from absolute alcohol. at 219-220O. formula C,,H,*NH*CO*NH*CO*C,H,. It formed small, white needles melting On analysis, figures were obtained agreeing with the 0.1622 gave 0.4415 CO, and 0.0715 H,O. C = 74.28 ; H = 4.90. C18H,,N,0, requires C = 74.48 ; H = 4.82 per cent. UNIVERSITY COLLEGE, SHEFFIELD.

ISSN:0368-1645    

DOI:10.1039/CT8977101200

出版商:RSC    

年代:1897

数据来源: RSC

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1204 OBITUARY NOTICES. 0 B I T U A R Y NOT I C E S . MARSHALL HALL, late Captain in the Royal East Middlesex Militia, born in London on February 6th, 1831, was the only child of Dr. Marshall Hall, the eminent physician and physiologist. H e was educated at Eton and at Caius College, Cambridge, and was sub- sequently called to the Bar, although he never practised as a barrister. I n early youth, he showed a strong liking for scientific pursuits, especially chemistry and mineralogy, his skill in the use of the microscope being of great service to him, especially in his mineralogical investigations. This love of science determined the future course of his life. He contributed several papers, both to the Geological and the Mineralogical Society, and was one of the founders of the latter.He was an ardent mountaineer, and made numerous Alpine excursions in his early days, whilst later on he devoted much time to the study of glaciers; at the international Geological Congress held in Zurich in 1895, he succeeded in getting a committee appointed for a com- parative study of the variations of glaciers in all parts of the globe, he himself being nominated the representative of Great Britain and the Colonies on the committee. He spent much of his time in Switzer- land, residing there with his family from 1878 to 1884, studying the interesting geological and glacial problems which in that country everywhere present themselves. The scientific dredging cruise off the coasts of Spain and Portugal, which he made in 1870 in his yacht “Norna,” in company with Mr.Edward Fielding and Mr. Savile-Kent, is well known. He died suddenly at his residence at Parkstone on April 14th, 1896. He was elected a Fellow of the Chemical Society in 1866; he was also a Fellow of the Geological Society, a member of the Royal Microscopical Society, the Agricultural Society, the Mineralogical Society, the Alpine Club and numerous other societies. HENRY A. MOTT died last year at his residence in New York. He was born at Staten Island in 1852, and graduated at the School ofOBITUARY NOTICES. 1205 Mines, Columbia College, in 1873. He was Professor of Chemistry in the New York Medical College for women, official chemist to the Medico-Legal Society, and well known as an expert in Medical Jurisprudence. A t one time, he acted professionally for the United States Government in examining food products for the Indian Depart- ment.TETSUKICHI SHIMIDZU, M.E., one of our Japanese Fellows, died at Chicago from phthisis on May 8th, 1896, in his 33rd year, after a year’s illness. His father, a sak6 brewer in Mino (Japan), sent him to Tbkya in 1873, when he was only 9f years old, to be educated at the High School there, founded by Mr. Fukuzawa, the leader in education in Japan on European lines. Two years later, he entered the Preparatory School for the Imperial College of Engineering, under English teachers, matriculated in 1877, and in 1883 took the College degree, Master of Engineering, with special distinction, in the subject of Applied Chemistry. For two years he was one of the Instructors in Chemistry in the College of Engineering, and during that time devoted himself to original research, contributing to the Chemical Society, in conjunction with Dr.Divers, the following papers : ‘‘ On Calcium Hydrosul- phides ” ; “Magnesium Hydrosulphide Solution and its Use in Chemico- Legal cases as a Source of Hydrogen Sulphide ” ; “Reactions of Selenious Acid with Hydrogen Sulphide, and of Sulphurous Acid with Hydrogen Selenide ” ; ‘ I The Specific Action of a Mixture of Sulphuric and Nitric Acids on Zinc in the Production of Hydroxylamine”; “ On the Constitution and Reactions of Liquid Nitric Peroxide ” ; “ On the Action of Pyrosulphuric Acid on certain Metals ” ; and “Mercury Sulphites and the Constitution of Sulphites.” Jointly with the same chemist, he was also author of a note in the Chenzical News on the “ Red Sulphur of Japan.” In 1885, he entered the Department of the Japanese Government for Agriculture and Commerce, as Chemist, and as Examiner in the Patent Office of that Department ; and during the six and a half years in which he filled these offices received various marks of the appreciation in which his abilities and services were held.At this time he took an active part in the affairs of the Tbkyii Chemical Society, and also became Secretary of the Japan Society of Engineers, an influential body in matters relating to engineering and technology. His geniality and activity made him fill this position with exceptional success. Early in 1892, he resigned his appointments in the Government service in order to join his friend, Mr.J. Takamink (also one of our Fellows), in America, and established there a factory of Japanese fsrrnents, for use in the manufacture of diastase and alcohol more1206 OBITUARY NOTICES. economically than by malting and ordinary yeast fermentation. The manufacture, protected by several patents (see J, Xoc. Chem. Ind., 14, 55), has attained comparatively large proportions, and Mr. Shimidzu was fully occupied in perfecting the machinery and processes up to the time of his last illness. It was in December, 1886, that he was elected a Fellow of the Chemical Society, a year after he had become a Member of the Society of Chemical Industry. His father died while be was a student. His cheerful, unselfish, and in every way amiable disposition endeared him to many.He was an only child and was unmarried. E. D. WILLIAM HENRY WALENN was born in London, January7th, 1828, and died at his residence, 9, Carleton Road,Tufnell Park, on September 20th, 1896, after a long and painful illness. He was trained as an engineer at the works of Messrs. Cottam, and received part of his education at University College, London, where he studied mathematics under Professor De Morgan. He was one of the earliest abridgers of specifi- cations to the Patent Office, beginning under the then Comptroller, Mr. Woodcroft, for whom he compiled the Series of Abridgments relating to ‘‘ Electricity and Magnetism,” “ Photography,” and other subjects. I n 1866, his book, Little Experiments for Little Chemists,’’ was pub- lished, and in it was given a new process for depositing brass upon zinc.I n 1871, he contributed a paper to the Philosophical Magazine, (( On Solutions for Depositing Copper and Brass by means of Electric Force,” and about the same time he conducted some experiments for the Government in electro-deposition of copper upon the bottom of an iron ship. Between 1868 and 1880, several mathematical papers of his on ‘‘ Unitates,” and methods of checking calculations by means of these,.were published in the P l d Mag. Mr. Walenn was known among his friends as a man always ready aud willing t o aid any in- quirer after scientific truth, whether in his favourite study of mathe- matics, or in the many branches of physics and chemistry with which he was familiar. He became a Fellow of th.e Chemical Society in 1866, and of the Institute of Chemistry soon after its establishment.He was also a member of the Physical Society. THEODOBE GEORGE WORMLEY, M.D., Ph.D., LL.D., Professor of Chemistry and Toxicology in the Medical Department of the Uni- versity of Pennsylvania, died at his home in Philadelphia, January 3rd, 1897, after a comparatively short illness.OBITTJARP NOTICES. 1207 Dr. Wormley was born in Wormleysburg, Pa., on April lsh, 1826. His collegiate education was received at Dickinson College, but he left before the completion of his course in order to study medicine at the Philadelphia Medical College, from which institution he graduated in 1849. I n 1852, he was called to the chair of chemistry and natural sciences at Capital University, Columbus, Ohio, which he held until 1865, and was also Professor of Chemistry and Toxicology in Starling Medical College from 1854 to 1877. On the resignation of Professor Robert E.Rogers in 1877, he was called to the chair of chemistry and toxicology in the medical department of the University of Pennsylvania, which position he held until his decease. During 1867-1875, Dr. Wormley was State Gas Commissioner of Ohio, and in 1867-1874 chemist to the Ohio Geological Survey. The degree of Ph.D. was conferred on him by Dickinson College, and that of LL.D. by Marietta, both in 1870. He was appointed a member of the Centennial Medical Commission having in charge the arrangements for the International Medical Congress of 1876, to which he was a delegate, and he delivered an address before that body on Medical Chemistry and Toxicology. In 1862-1864, he edited the Ohio Medical und Surgicul Journal, and during the years 1859-1863, he published a series of papers in the Chemical News on the chemical reactions of various toxic alkaloids and other organic and inorganic poisons. H e was the author of '' Methods of Analysis of Coals, Iron Ores, Furnace Slags, Fire Clays, Limestones, and of Soils " (1870) ; contributed reports to the Geological Survey of Ohio (lS71), and numerous scientific papers to various 'journals, but his most notable work was the '' Microchemistry of Poisons " (New York, 1867). Dr. Wormley was a member of the American Philosophical Society and of other scientific societies. He was elected a Fellow of the Chemical Society.ia 1885. F. B. P.

ISSN:0368-1645    

DOI:10.1039/CT8977101204

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NAMES. TRANSACTIONS. 1807. And also to Proceedings of the Session 1896-1897, Nos. 169 to 182, Nov., 1896--June, 1897 (marked P.). Annable, Henry. See George Young. Armstrong, Eenry Edward, notes on nitration, P., 1896, 230. Armstrong, Henry Edward, and William Alfred Davis, 3’-bromo-B-naphthol, P., 1896, 230. Armstrong, Henry Edwurd, and William Palmer Wynne, studies on the consti- tution of tri-derivatives of naphthalene. No. 16. Conversion of chloronaphtha- lenedisulphonic acids into dichloro. naphthalenesulyhonic acids, P., 1897, 152. Armstrong, Henry Edward, and William Palmer Wynne, conversion of 1 : 1‘- into 1 ; 4‘-dichloronaphthalene by hydrogen chloride. The products of hydrolysis of 1 : l’-dichloronaphthalene-3-sulphonic acid, P., 1897, 154. Baton, Emily (Alicia), and John Norman Collie, oxidation products of ay-di- methyl-a-chloropyridine, 663 ; P., 1897, 89.B. Baker, Jt6lian Levett. See Arthur Bobert Ling. Ball, John, on the circumstances which affect the rate of solution of zinc in dilute acids, with especial reference to the influence of dissolved metallic salts, 641 ; I?. 1896, 235. Bentley, William Henry, and William Henry Perkin, jun., the reduction of xylic acid, of paraxylic acid, and of methylterephthalic acid, and the pre- paration of methylterephthalic acid and methylisophthalic acid, 157 ; P., Bevan, Edward John. See Charles Frederick Cross. VOL. LXXI. 1896, 79. Blake, Xobert Frederick. See Edmund Albert Letts. Bolam, Herbert William, on the hydro- lysis of ethylic dicarboxyglutaconate, P., 1896, 184.Bone, William Arthur, and John Cannell Cain, the explosion of acetylene with less than its own volume of oxygen, 26 ; P., 1896, 176. Bone, William Arthur, and David Smiles Jerdan, the direct union of carbon and hydrogen, 41 ; P., 1896, 175. Brooke, Arthur. See Henry Lloyd Snape. Brown, Horace T., George %arris Morris, and James Hill Millar, experimental methods employed in the examination of the products of starch-hydrolysis by diastase, 72 ; P., 1896, 241 ; discussion, P., 244. specific rotation of mal- tose and of soluble starch. 109 ; P., 1896, 242 ; discussion, P., 244. relation of the specific rotatory and cupric-reducing powers of the products of starch-hydrolysis by diastase, 115 ; P., 1896, 243; dis- cussion, P., 244. the solution-density and cupric-reducing power of dextrose, levulose, and invert-sugar, 275 ; P., 1897, 4.Brown, Horace T., and Spencer Umfre- ville Pickering, thermal phenomena attending the change in rotatory power of freshly prepared sdutions of certain carbohydrates, with some remarks on the cause of multirotation, 756 ; Y., 1897, 129 ; discussion, P., 131. -- thermochemist of carbohy- drate hydrolysis, 783 ;y., 1897, 130 ; discussion, P., 131. --- --- 4 N1210 INDEX OF AUTHORS. Bull, Benjamin Samuel, on 8-oxycellu- lose, 1090 ; P., 1897, 168. C. Cain, John Cnnnell. See William Arthur Bone. Caldecott, WilliamArtRttr, on the decom- position of iron-pyrites, P., 1897, 100. Calvert, ITnrry Thornton. See Jtelizu Berend Cohen. Carr, Francis Howard. See Wyndham Rowland Dunstan. Chattaway, Frederick D., and Henry Potter Stevens, hydrolysis of perthio- cyanic acid, 607; P., 1897, 87; dis- cussion, P., 88.-- reduction of perthiocyanic acid, 833 ; P., 1897, 149. Clark, Ernest, See George Young. Cockburn, George Bertram. See John Addymnn Gardner. Cohen, JulizuBered,and Harry Thornton Calvert, the action of nitrogen trioxidc and tetroxide on alcohols, 1050; P., 1897, 166. Cohen, Jteliies Bcycnd, ant1 William Hudson Harrison, the action of nitro- gen tetroxide on ortho- and para- nitrobenzylic alcohols, 1057 ; P., 1897, 166. -- the action of aromatic amines on diacetyltartaric anhydride, 1060; P., 1897, 167. Collie, John Norman, production of pyri- dine derivatives from ethylic 8-amido- crotonate, 299 ; P., 1897, 43; dis- cussion, P., 44. - a space formiila for benzene, 1013 ; P., 1897, 143 ; discussion, P., 145.Collie, Joha Normaw See also Emily Alicia Aston, Arthur Lapworth. Cook, Ernest H., note on a method for determining melting points, P., 1897, 74. Crompton, Holland, the theoryof osmotic pressure and the hypothesis of electro- lytic dissociation, 925 ; P., 1897, 109 ; discussion, P., 112. - *molecular rotations of optically active salts, 946 ; P., 1897, 111 ; discussion, P., 112. - heats of neutralisation, of acids and bases in dilute aqueous solution, 951 ; P., 1897, 111 ; discussion, I>., 112. Cross, Charles Frederick, Edward ,Joh?i Bevan, and Clazed Smith, the carbo- hydrates of the cereal straws, 1001 P., 1897, 150. lrossley, Arthur William, note on Wechsler’s method €or the separation of fatty acids, 580 ; P., 1897, 21. D.Iavis, William Alfred, derivatives of nitro-&naphthols, P., 1896, 231. - morphotropic relations of b-naph- tho1 derivatives, P., 1896, 233. lavis, William AIfred. See also Henry .Edward Armstrong. leeley, R. Af., the periodic law, P., 1896, 185. lewar, Jarnos. See Henri loissan. lixon, Augustus Edward, halogen sub- stituted acidic thiocarbimides, and their derivatives ; a contribution to the chemistry of thiohydantoins, 617 ; P., 1897, 6. lixon, Harold Baily, and Edward John Russell, explosion of chlorine peroxide with carbonic oxide, 605 ; P., 1897, 99, discussion, P., 100. lobbie, James Johnstone, and Fred. Mars- den, corydaline, part V., 657 ; P., 1897, 101. hotson, Fredcrick William. See 1Villian~ James Sell. Dunstan, Wyndhccm Rowland, and Francis Howard Carr, contributions to our knowledge of the aconite alkaloids.Part XIV., on pseudaconitine, 350 ; P., 1895, 151. Danstan, Wyndhanz Rowland, and Ernest Ooulding, action of alkyl haloids on aldoximes and ketoxinies, 573 ; P., 1897, 76. Durrant, Reginald G., the action of hydroxen peroxide and other oxidising agents on cobaltous salts in presence of alkali bicarbonates, P., 1896, 244. Dymond, Thomas S., and Frank Hughes, format,ion of dithionic acid by the oxidation of sulphurous acid with potassium permanganate, 314 ; P., 1897, 42 ; discussion, P., 42. E. Edwards, William Buckland. See Frederic Stanley Kipping. Evans, Clare de Brereton., studies on the chemistry of nitrogen : enantiomor- phous forms of ethylpropylpiyerido- nium iodide, 522 ; P., 1897, 64.- researches on tertiary benzenoid amines, XI., P., 1806, 234.INDEX OF AUTHORS. 1211 F. Fenton, Henry Johsa Eomtwia?t, a new synthesis in the sugar group, 375 ; P., 1897, 63. Findlay, AZexander. See Francis Robert JalW Forster, Martin Onslow, camphoroxime, part I., conversion of camphoroxime into niethylcamphoriinine and into camphenylnitramine, 191 ; P., 1897, 21. - camphoroxime, part I I., the ethers of camphoroxime, 1030; l'., 1897, 165. Fortey, Emily C., hexanaphthene and its derivatives. Preliminary note, P., 1897, 161. Francis, Francis E. , the dinitrosamines of ethyleneaniline, the ethylenetolui- dines and their derivatives, 422 ; P., 1897, 63. Frankland, Percy Faraday, Pasteur memorial lecture, 683 ; P., 1897, 79. Frankland, Percy Faraclny, and Thomas Slater Price, the amyl (secondary butylmethyl) derivatives of glyceric, diacetylglyceric and dibenzoylglyceric acids, active and inactive, 2 5 3 ; P., 1897, 9.French, FTilliam, studies on the inter- action of highly purified gases in the presence of catalytic agents, P., 1897, 52. Friswell, Richard John, on the proper- ties of nitrobenzene, 1010 ; P., 1897, 147, 148 ; discussion, P., 149. - the action of light on a solution of nitrobenzene in concentrated sulphuric acid, P., 1897, 148. a. Gardner, John Arldynaan, and Gcoyge Bertram Cockburn, action of phospho- rus pentachloride on fenchone, 1156 ; P., 1897, 173. -- preliminary note on the oxi- dation of fenchene, P. , 1897, 137. Gardner, John Addyman. See also Janaes Ernest Marsh.Gilles, William Setten, and Frank Fool'ster Renwick, further note on lretopinic acid : pinophanic acid, P., 1897, 64. -- 6-ketopinic acid and camphoic acid, P., 1897, 158. Gladstone, John Hall, and FVcidter Hib- bert, the molecular refraction of dis- solved salts and acids. Part 11. 822; P., 1897, 141; discussion, P., 142. Gioulding, Ernest. See Wyaclham Rozoland Gray, Thomas, the isomeric dibromethyl- Green, Aythzsr George, constitution and Dunstan. enes, 1023 ; P., 1897, 140. colour, P., 1896, 226. H. Hake, Henry Wilson, further experiments on the absorption of moisture by deli- quescent substances, €'., 1897, 147. Hall, (Capt.) Marshall, obituary notice of, 1294. Hambly, Frederick Jolm. See Jantcs Walker. Hanes, Edgar X. See Arthur R. McConnell. Harcourt, Augxstus Gcorge Vernon, presidential address, 592 ; P., 1897, 80.- a few thoughts on the question whether the changes which matter undergoes are different in their natnre, Harrison, William Hudson. See Jdiz6s Bcrend Cohen. Hartley, Walter Noel, and Hugh Ramage, the wide dissemination of some of the rarer elemeiits and the mode of their association in common ores and niinerals, 533 ; P., 1897, 11. -- on the spectrographic analysis of some commercial samples of metals, of chemical preparations, and minerals from the Stassfurth potash beds, 547 ; P., 1897, 46 ; discussion, ibid., 48. Hemmy, A . X. See Sie'qfried Ruhe- mann. Henderson, George Gerald, and Matthew Arehibald Parker, the action of bromo- diphenylniethane on ethylic sodioaceto- acetate, 676 ; P., 1897, 119. Hewitt, John Theodore, T.S. Moore, and A . E. Pitt, derivatives of phenetol- azo-phenols, P., 1897, 157. Eewitt, John Theodore, and Frasik G. Pope, the condensation of chloral with resorcinol, part II., 1084; P., 1897,167. Keycock, Charles Thomas, and Francis Henry Neville, the freezing points of alloys containing zinc and another metal, 383 ; P., 1897, 60 ; discussion, P., 62. X-ray photographs cf solid alloys, P., 1897, 105. Hibbert, Waltev. See John Hall (+lad- stone. Holland, Thomas €€. , crystallography of the monhydrated mercurous nitrite, 346 ; P., 1896, 218. 595 ; P., 1897, 81. -- 4 ~ 2I212 INDEX OF AUTHORS. Hughes, Frank. See Thomas S. J. Dymond. Jackson, Percy G. See John Jams Sudborough. Japp, Francis Robert, supposed condensa- tion of benzil with ethylic alcohol: a correction, 297 ; P., 1897, 48.Japp, Francis Robert, and Alexander Findlay, phenanthrone, 1115 ; P., 1897, 169. Japp, Francis Robert, and George Druce Lander, synthesis of pentacarbon rings, Part I. Anhydracetonebenzil and its homologues, 123 ; P., 1896, 107. -- synthesis of pentacarbon rings. Part 11. Condensation of benzil with acetonedicarboxylic acid, 139 ; P., 1896, 109. - - reduction of desyleneacetic acid and the constitution of Zinin's pyroamaric acid, 154 ; P., 1896,109. Japp, Francis Bobert, and Thomas Smith Murray, synthesis of pentacarbon rings. Part 111. Condensation of benzil with levulinic acid, 144; P., 1896, 146. Japp, Francis Robert, and Alfred Tingle, ammonia and phenylhydrazine deriva- tives of as-dibenzoylcinnamene (anhy- dracetophenonebenzil), 1138 : P., 1897, 170.Jenkins, Henry C., and Ernest A . Smith, the reactions between lead and the oxides of sulphur, 666; P., 1897, 104 ; discussion, P., 105. Jerdan, David Smiles, a new synthesis of phloroglucinol, 1106 ; P.,1897, 168. Jerdan, David Smiles. See also William Arthur Bone. Jowett, Hooper Albert Diekinson, some gold salts of hyoscine, hyoscynmine, and atropine, 679 ; P., 1897, 136. K. gay, Sydaey A. Kipping, Frederic Stank y , dimethylketo- hexamethylene, P. , 1896, 247. Kipping, Frederic Stanley, and TVilliarn Buckland Edwards, preparation of dimethylketohexamethylene, and es- periments on the synthesis of di- methylhexamethenylmalonic acid, P. , 1896, 188. Xipping, Frederic Stanley, and William Jacksom Pope, optical inversion of camphor, 956 ; P., 1897, 132.- - derivatives of camphoric acid. See James Walker. Part 11. Optically inactive derivatives, 962 ; P., 1897, 133. Ripping, Frederic Stanley, and William Jackson Pope, racemism and pseudo- racemisin, 989 ; P., 1897, 135 ; dis- cnssion, P., 136. Kipping, Frederic Stanley. See also Arthur Lapworth, William Jackson Pope, Cecil Revis, L. Lander, George Drzm See Francis Robert Japp ; Thomas Purdie. Lapworth, Arthur, and John Norman Collie, production of some nitro- and amido-hydroxypicolines, 838 ; P. , 1897, 146. Lapworth, Arthur, and Trederic Stanley Kipping, sulphocamphoric acid and other derivatives of camphorsulphonic acid, 1 ; P., 1896, 215. Lawrence, William l'remr, a synthesis of citric acid, 457 ; P., 1897, 65. Lean, Bevan, and Frederic H.Lees, in- teraction of ethylenic chloride, ethylic malonate and sodium ethoxide, 1062 ; P., 1897, 160. Lees, Frcderic I% Letts, Edmzind Albert, and Bobert Frede- rick Blake, on Pettenkofer's method for determining carbonic anhydride in air, P., 1896, 192. Linder, 8. Ernest. Ling, Brthw Robert, and Julian Lev& Baker, action of diastaseonstarch, 111.) 508 ; P., 1897,3 ; discussion, P., 4. Littleton, Fannie T., note on the heat of formation of the silver amalgam Ag,Hg,, P., 1896, 220. Liversidge, Archibald, presence of gold in natural saline deposits and marine plants, 298 ; P., 1897, 22. - the crystalline structure of gold and platinum nuggets and gold ingots, 1125 ; P., 1897, 22. Lloyd, Lorenzo 1;. See John J. Sud- borough. Lowry, T. M., note on stereoisomeric di-derivatives of camphor, and on nitrocamphor, P., 1897, 159.Lumsden, John 8. See Beoan Lean, See Harold Picton. See James Walker. M. McConnell, Arthur H., and Edgar S. Hanes, researches on the oxides of cobalt. Cobalt dioxide or cobaltous anhydride, cobaltous acid and co- baltites, 584 ; p., 1897, 62.INDEX OF AUTHORS, 1213 lallet, John William, note on the con- stitution of the so-called “ nitrogen iodide,” P., 1897, 55. Marsden, Fred. See James Johnstone Dobbie. Marsh, James Ernest, and John Addyman Gardner, researches on the terpenes, VII. Halogen derivatives of camphor and their reactions, 285; P., 1896, 187. -- production of camphenol from camphor, P., 1897, 137. Martin, H. W. See Arthur George Perkin. Matthews, Francis Edward, apparatus for “steam distillation,” 318 ; P., 1897, 18.Millar, Jc6mes Hills. See Horace T. Brown. Moore, 2’. S. See John Theodore Hewitt. Morria, George Harris. See also Horace T. Brown. Mott, Henry Augustus, obituary notice of, 1204. Xurray, Thomas Smith. See Francis Robert Japp. Myers, Henry C., monochlorodipar- aconic acid, 614 ; P., 1897, 100. N. Neville, Francis Henry. See Charles Thomas Heycock. P. Parker, itlatthew Archibald. See George Gerald Henderson. Pasteur, Lo~cis, memorial lecture on, 683 ; P., 1897, 80. Perkin, Arthur George, derivatives of malcurin, part II., 186; P., 1897, 6 . - apiin a i d apigenin, 805; P., 1897, 53, 138. - the yellow colouring principles of various tannin matters, 1131 ; P., 1897, 170. - azobenzene derivatives of phloro- glucinol, 1154 ; P., 1897, 172.- yellow colouring matters obtained from Rhw rhodanthema, Berberis octnensis, and Rumex obtusifolius, 1194 ; P., 1897, 198. Perkin, Arthur George, and H. 77. Mar- tin, rhamnazin, 818 ; P., 1897, 139. LI- derivatives of cotoin and pliloretin, 1149 ; P., 1897, 171. Perkin, William Henry, J U ~ . , sulpho- campliylic acid ( C9HI4SO5) with re- marks on the constitution of cam- phoric acid and camphoronic acid, p., 1896, 189. Perkin, William Henry, jun., and Jocelyn Field Thorpe, synthesis of i-camphoronic acid, 1169 ; P., 1897,72. Perkin, William Henry, jun. See also William Henry Bentley. Pickering, PercivaZ Spencer Umfreville. See Eorace T. Brown. Picton, Harold, and S. E’mest Linder, solution and pseudo-solution. Part 111. The electrical convection of certaiti dissolved substances, 568.Pitt, A . E. See John Theodore Hewitt. Pope, Frank G. See John Theodore Hewitt. Pope, William Jackson, the localisation of deliquescence in chloral hydrate crystals, P., 1896, 249. - the refraction constants of crystal- line salts. A correction, P., 1897, 11. Pope, William Jackson, and Frederic Stanley Kipping, ‘‘ enantiomorphism,” P., 1896, 249. Pope, William Jackson. See also Fred- eric Stanley Kipping. Price, Thomas Slater. See Percy Frank- land. Purdie, Thomas, and 6. Druce Lander, preliminary note on the action of alkyl iodides on silver malate, P., 1896, 221. R. Itamage,Hugh. See Walter Noel Hartley. Ramsay, William, preseutation of Long- staff medal to, 591 ; P., 1897, 80. Ray, Prafulla Chandra, the nitrites of mercury and the varying conditions under which they are formed, 337; P., 1896, 217.- mercury hyponitrites, 348 ; P. 1896, 217. -on the action of sodium hyponi- trite on mercuric solutions, 1097. - on a new method of preparing mercuric hyponitrite, 1105. - the interaction of meixurous nitrite and the alkyl iodides, P., 1896, 218. Rayleigh, John William Strutt (Lord), observations on the oxidation of nitro- gen gas, 181 ; P., 1897, 17 ; dis- cussion, P., 18. Renwick, Frank Forster. See Pillianz Settcn Gilles. Rettie, Theodore, compounds of metallic hydroxides with iodine, P., 1896, 178. Revis, Cecil, and Frederic Stanley Kipping, derivatives of a-hydrindone, 238 ; P., 1896, 229.1214 INDEX OF AUTHORS. Revis, Cecil, and Frederic Stanley Kipping, “ a-bromocamphorsulpholac- tone,” P., 1896, 247.Bodger, James Wyllie. See Thomas Edward Thorpe. Ruhemann, Siegfried, contributions to the knowledge of the &ketonic acids, part 111.) 323 ; P., 1897, 52. Ruhemann, Siegfried, and A. S. Hemmy, contributions to the knowledge of the &ketonic acids, parts 1V. and V., 329, 334 ; P., 1897, 53, 64. Russell, E’dward John. See Harobcl Baily Dixon. Scott, Alexander, the atomic weight of carbon, 550 ; P., 1897, 70 ; discus- sion, P., 71. -- a new series of mixed sulphates of the vitriol group, 564 ; P., 1897, 71 ; discussion, P., 71. Sell, William Jarncs, and Frcdcrick William Qootson, studies on citrazinic acid, part V., 1068 ; P., 1897, 167. Shenstone, William Ashwell, observa- tions on the properties of some highly purified substances, 471; P., 1897, 2 ; discussion, P., 3.Shimidzu, Tetsukichi, obituary notice of, 1205. Smith, Claud. See Charles Frederick Cross. Smith, Ernest A. See Zenry C. Jenkins. Snape, Henry Llo!id, magnesium nitride as a reagent, 526 ; P., 1897, 50. Snape, Hcnry Lloyd, and Arthur Brooke, Laurent’s amarone, 528 ; P. , 1897, 51. Sonstadt, Edward, the oxidation of ferrous sulphate by sea water, and on the detection of gold in sea water, P., 1896, 236. Spiller, John, the platinum silver alloys ; their solubility in nitric acid, P., 1897, 118. Sprankling, Charles H. Q., ketolactonic acid and its homologues, 1159 ; P., 1897, 173. Stevens, Henry Potter. See Frederick D. Chattaway. Sudborough, Joh7b Jumes, researches in the stilbene series, I., 218 ; P., 1897, 19. Sudborough, John Jcmes, Percy G.Jackson, and Lorenzo L. Lloyd, di- ortho-substituted benzoic acids, part 111. , hydrolysis of substituted benz- amides, 229 ; P., 1897, 20. T. Thomas, George L. See 8ydney Young. Thorpe, Jocelyn Field. See William Henry Perkin, jzm, Thorpe, Thomas Edward, the so-called hydrates of isopropylic alcohol, 920 ; P., 1897, 150. Thorpe, Thomas Edward, and James W’yllie Rodger, the viscosity of mix- tures of miscible liquids, 360; P., Tingle, Alfred. See Francis Robert Titherley, Arthur TT., sodanride and soiiie of its substitution derivatives, 460; P., 1897, 45. - rubidamide, 469 ; P., 1897, 46. Tutton, Alfred Edwin, the refraction constants of crystalline salts, 235 ; P., 1897, 10. - connection between the crystallo- graphical characters of isomorphous salts and the atomic weight of the metals contained.A comparative crystallographical study of the normal selenates of potassium, rubidium, and cesium, 846; P., 1897, 115; discus- sion, P., 118. 1897, 49. JSPP. V. Vernon Earcourt. See Harcourt. W. Walenn, William Hewy, obituary notice of, 1206. Walker, James, and Frederick JoJm Hambly, electrical conductivity of diethylammonium chloride in aqueous alcohol, 61 ; P., 1896, 246. Walker, James, and Sydney A. Kay, velocity of urea-formation in aqueous alcohol, 489 ; P., 1897, 75. Walker, James, and John S. Lmsden, dissociation pressure of alkyl- ammonium hydrosulphides, 428 ; P., 1897, 48. Wildermann, illeyer, Dalton’s law i n solution (molecular depression of mix- tures of two non-electrolytes, 743 ; P., 1897, 19. - experimental verification of van% Hoffs constant in veiy dilute solution (law of molecular depression), 796 ; P., 1897, 139. Williams, Jliss Katherine I., the corn- position of cooked fish, 649 ; P., 1897, 88 ; discussion, P., 89. Wormley, Theodorc George, obituary notice of, 1206. Wynne, William Palmcr. See Henry Edward Armstrong.INDEX OF AUTHORS. 121 5 Y. Young, George, oxidation of phenylsty- renyloxytriszole, 31 1; P., 1897, 53. - note on the formation of diacetani- lide, P., 1897, 156. Young, George, and Henry Annable, formation of substituted oxytriazoles froin phenylsemicarbazide, 200 ; P. , 1896, 246. Young, George, and Ernest Clark, naph- thylcarbamides, 1200 ; P. ,1897, 199. Young, Sydney, the vapour pressures, specific volnmes, and critical constants of normal pentane, with a note on the critical point, 446 ; P., 1897, 58 ; discussion, P., 59. Young, Sydney, and George L. Thomas, some hydrocarbons from American petroleum, I., normal aud iso-pentane, 440; P., 1897, 5 8 ; discussion, P., 59.

ISSN:0368-1645    

DOI:10.1039/CT8977101209

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

INDEX OF SUBJECTS. J. BRUCE. F. H. CARR. A. W. CROSSLEY, M.Sc., Ph.D. T. EWAN, B.Sc., Ph.D. M. 0. FORSTER, Ph.D. TRANSACTIONS. 1897. And also t o Proceedings of the Session 1896-1897, Nos. 169 t o 182, Nov., 1896--June, 1897 (marked P.). J. S. HALDANE, M.A., M.D., F.R.S. P. A. E. RICHARDS. L. J. SPENCER, M.A. J. F. THORPE, Ph.D. A. Acacia atechu, the composition of catechu from (PERKIN), 1136. Acetaldehyde, formation of (COHEN and CALVERT), 1051. action of water on, of ammonia and water on, aud the thermal values for its hydration (BROWN and PICKER- ING), 775. Acetaldoxime, action of methylic iodide and bromide and of ethylic iodide on (DUNSTAN and GOULDING), 577 ; P., 1897, 76. Acetamide,action of sodamide On(T1THER- LEY), 467 ; P., 1897, 46. chlor-, action of phenylallylthio- carbimide on (DIXON), 632 ; P,, 1897, 8.m- and p-Acetamidohydroxydiphenyl- triasole (YOUNG and ANNABLE), 209, 212 ; P., 1896, 246. 1 : 2-Acetamidomethoxynaphthalene, its behaviour towards SO,Cl,, and its 3’-bromo-derivative (D QVIS), P., 1896, 232. 1’ : 2-Acetamidomethoxnaphthalene (DAVIS), P., 1896, 231. Acetanilide, chlor- and brom-, action of thiourea on (DIXON), 626; P., 1897, 6. Acetic acid, brom-, condensation of ethylic salt, with ethylic dimethyl- acetoacetate (PERRIN and THORPE), 1178 ; P., 1896, 72. Acetic acid, brom-, ethylic ralt, action of ethylic sodioacetoacetate on (SPRANKLING), 1166; P., 1897, 173. action of zinc and ethylic oxalgl- acetate on (LAWRENCE), 458 ; P., 1897, 65. chlor-, ethylic salt, action of ethylic acetoacetate on (RUHEMANN and HEMMY), 329.action of aa-phenylmethylthio- urea and of o-tolylthiourea on (DIXON), 623, 631 ; P., 1897, 8. Acetic chloride, chlor-, action of lead Acetoacetic acid, ethylic salt, action of ethylic chloracetate on (RUHE- MANN alld HEMMY), 529. condensation of, with ethylic a-bromisobutyrate (PERKIN and THORPE), 1192 ; P., 1896, 72. Acetoacetic acid, sodio-, ethylic salt, action and rate ofaction of ethylic bromacetate a-bromobutyrate, bromopropionate and bromiso- valerate I( SPRANKLING), ,1160- 1167; P., 1897, 173, 174. action of, on bromodiphenyl- methane and bromotriphenyl- methane (HENDERSON and PARKER), 676 ; P., 1897, 119. thiocyanate OD ( DIXON), 620. 1 : 2- Acetonaphthalide, 3’-bromo- (DAVIS), P., 1896, 232. Aceto-a-naphthylcarbamide (YOUNG and CLARK), 1201 ; P., 1897, 199.INDEX OF SUBJECTS.1217 Acetone, freezing points of dilute aqueous 1897, 139. influence of, on the rate of formation of carbamide (WALKER and KAY), 506 ; P., 1897, 76. Acetonedicarboxylio acid, reduction of (BOLAM), P., 1896, 184. ethylic salt, action of ethylic a-chloro- crotonate on (RUHEMAKN), 327 ; P., 1897, 52. condensation of, by means of sodium (JERDAN), 1107 ; P., 1897, 168. Acetonylmalic acid, crystallography of ( RUHEMANN), 324. Acetophenone, from hydrolysisof methyl- acetophenoxime hydriodide (DUX- STAN and GOULDING), 579, Acetophenoneoxime, action of methylic and ethylic iodides on, and of methylic iodide in presence of sodium methoxide (DUNSTAN and GOULDING), 580. Aceto-p-toluidide, chlor- (DlxoN), 629. Acetoxime, sodium derivative of (TITHER- LEY), 461 ; P., 1897, 45.action of methylic bromide and iodide and of ethylic iodide on (DUNSTAN andGorJL~ING),577,579; P. ,1897,77. Acetoxydiphenyltriazole, rn-nitro- (YOUNG and ANNABLE), 211 ; P., 1896, 246. 3-Acetoxyphenyl-m-tolyltriazole (YOUNG and ANNABLE), 214; P., 1896, 246. Acetylalkylsuccinic acids, alkylic salts, action of heat on (SPRANKLING), 1167 ; P., 1897, 174. Acetylallylenedicarboxylic acid, ethylic salt, and the action of aniline on it (RUHEMANN), 326 ; P., 1897, 52. Awtylapigenin dimethyl ether and diethyl ether, preparation of (PERKIN), 812, 815 ; P., 1897, 138. Acetylazobenzene-cotoin, properties of (PERKIN and MARTIN), 1150; P., 1897, 172. Acetylcamphoroxime (FORSTER), 1040 ; P., 1897, 165. Acetylisocinnamenylmandelic acid (JAPP and LANDER), 138; P., 1896, 107.Ace t y ldime t hylb u t yr ic acid, semicarb - azone (W. H. PERKIN, jun. ), P., 1896, 191. a-Acetyl-8-diphenylpropionic acid and its ethylic salt (HENDERSON and PARKER), 676, 677 ; P., 1897, 119. Acetyldiphenyltriazole, p-nitro- (YOUNG and ANNABLE), 206 ; P., 1896,246. Acetylene, formation of, from carbon and hydrogen BONE and JERDAN), 55 ; P., 1896, 175. SOlUtiOnS Of( WILDERMANN), 800; P., Acetylene, action of the electric arc on (BONE and JERDAN), 60 ; P., 1896, 177. behaviour of an aqueous solution of, toxards bromine (GRAY), 1027 ; P., 1897, 140. explosion of, with insufficient oxygen (BONE and CAIN), 26; P., 1896, 176. a Bunsen burner for (MUNBP), P., 1897, Acetylene, brom-, behaviour of, towards hydrogen bromide (GRAY), 1029; P., 1897, 140.8-Aoetylnaphthylcarbamide (YOUNG and CLARK), 1203 ; P., 1897, 199. Acetylosyritrin (PERKIN), 1133. Acetyl-p-phenetolazophenol ( HEWITT, MOORE and PITT), P., 1897, 159. Acetylphloretindisazobenzene ( PEBKIN and MARTIN), 1152. Acetylphloroglucinolazobenzene, pro paration of (PERKIN), 190. i3-Acetyl-a-isopropylpropionic acid (SPRANKLING), 1165. Acetyl-8-isopropylsuccinic acid, ethylic salt (SPRANKLING), 1168. Acetylsuccinic acid, ethylic salt and methylic salt (SPXANKLINO), 1162, 1165. molecular refraction of, and the action of ammonia, aniline, phenylhydrazine and of bromine on (RUHEMANN and HEMMY), 329, 332 ; P., 1897, 53. phenylhydrazone of, and action of heat on (RUHEMANN and HEMMY), 332. Acetylsuccinic acid, y-brom-, ethylic salt, and the action of heat on (RUHE- MANN and HEMMY), 333; P., 1897, 53.Acetyltartranilide, preparation of (COHEN and HARRISON), 1060. Acetylthiocarbimide, brom-, action of p - t oluidine methylaniline and benzylaniline on (DIXON), 629. chlor-, and the action of aniline o- toluidine, p-toluidine; methylaniline and benzylaniline on (DIXON), 620, 621, 629 ; P., 1897, 8. Acid, C,H,,O, from chlorodiparaconic acid, by the action of sodium amalgam (MYERS), 616, 617. C1,H100SBr2, methylic salt of, ob- tained from the condensation pro- duct of ethylic acetonedicarboxylate (JERDAN), 1112. C1,H,,O8, obtained by the action of sodium on ethylic acetonedicarb- oxylate, methylie and ethylic salts of 103. (JERDAN), 1111 ; P., 1897, 168.1218 INDEX OF SUBJECTS. Acid, C,,H,,N05, from the action of hydriodic acid on corydic acid (DOBBIE and MARSDEN).663 : P., , , 1897, 101. C,,H,,NO,, from the oxidation of corvdic acid (DOBBIE and MARS- DE;), 663 ; P.’1897, 102. Acids, fatty, separation of mixtures of (CROSSLEY), 580 ; P., 1897, 21. q-Aconine, properties of, and its salts ( DUNSTAN and CARR), 357 ; P., 1895, 154. +-Aconitine, extraction of, from A . ferox roots, effect of heat on it, its hydroly- sis, its properties, and its salts (DUNSTAN and CARR), 351, 352, 356, 358 ; P., 1895, 154. crystallographic character of (POPE), 352. Aconitum ferox, the alkaloids of (DUN- STAN and CARE), 351; P., 1895, 154. Acridine dyes, oxidation of leuco-com- pounds of (GREEN), P., 1896, 226. Address, Presidential (HABCOURT), 592 ; P., 1897, 80. Adipic acid, ethylic salt, from interaction of ethylic sodioinalonate and ethylenic chloride (LEAN and LEES), 1067 ; P., 1897, 161.Agarobilla, composition and dyeing pro- perties of (PERKIN), 1137 ; p., 1897, 170: Aluminium, commercial, composition of (HARTLEY and RAMAGE), 547 ; P., 1897, 47. Aluminium alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 389 ; P., 1897, 61. Aluminium salts, spectroscopic analysis of (HARTLEY and RAMABE), 548 ; P., 1897, 47. Aluminium oxide (alumina), composition of (HARTLEY and RAMAGE), 547 ; P., 1897, 47. Aluminium minerals and ores, composi- tion of (HARTLEY and RAMAGE), 538 ; P., 1897, 12. Amides of alkali metals, melting points of (TITHERLEY), 470. Ammonium iodide, refractive power of, when dissolved in ethylic alcohol (GLADSTONE and HIBBERT), 827 ; P., 1897, 142.hydrosulphide, dissociation pressure and heat of dissociation of (WALKER and LUMSDEN), 432 ; P., 1897, 48. i-Amylic alcohol (isobutylearbinol), dis- covery of (PASTEUR LECT.), 705. Amylic alcohol (sec-butylcarbinol, m e - thyZethyZcarbiizcarbino2) racemisation of (FRANKLAND and PRICE), 255. Anhydracetonebenzil and the action of acetic anhydride on it (JAPP and LAN- DER), 130 ; P., 1896, 107. Anhydracetonebenzilcarboxylic acid ( J ~ i ~ ~ a n d LANDEE),140 ;pa, 1896,107. Anhydracetophenonebenzil. See Di- benzoylcinnamene. a-Anhydrobenzillevulinic acid, its ba- rium salt, and the action of hydroxyl- amine on (JAPP and MURRAY), 146 ; P., 1896, 146. a- and P-Anhydrobenzillevulinic acids, action of permanganate on (JAPP and MURRAY), 148.8-Anhydrobenzillevulolactone ( JAPP and MURRAY), 148 ; P., 1896, 146. i-Anhydrocamphoronic acid (PERKIN and THORPE), 1191 ; P., 1896, 73. Anhydro-oxalaconitic acid, triethylic salt (RUHEMANN and HEMMY), 336 ; P., 1897, 64. Aniline (phnylasnine), freezing points of dilute aqueous solutions of (WILDERMANN), 800 ; P., 1897, 139. action of sodamide on (TITHERLEY), 464 ; P., 1897, 45. oxidation of, by chromic acid (COLLIE), 1022. Aniline-blue, electrical convection of, in solutions (PICTON and LINDER), 571. Acisic acid from the hydrolysis of apige- nin dimethyl ether (PERKIN), 81 4 ; P., 1897, 138. Anncal General Meeting, 591 ; P., 1897, 80. Anthrax, inoculation for, and bacillus of (PASTEUR LECT.), 735, 740; P., 1897, 80. Apigenin, preparation, properties, con- stitution, derivatives, and decompo- sition products ; action of nitric acid on (PERKIN), 806, 817 ; P., 1897, 54, 138.comparative dyeing experiments with (PERKIN), 818 ; P., 1897, 138. dimethyl ether and diethyl ether, prc- paration and properties of, and their acetyl derivatives (PERKIN), 815; P., 1897, 138. Apigenin, dibrom- (PERKIN), 808 ; P., 1897, 54. Apium petroseliusn, the glucoside from (PERKIN), 805 ; P., 1897, 53. Argon, separation of, from the atmo- sphere (RAYLEIGH), 184; P., 1897, 18. Arsenic trisulphide, electrical convection of, in solutions ( PIVTON and LINDER), 571. B-Asparagine, pseudoracemism of (KIP- PING and POPE), ZOO1 ; P., 1897, 136.INDEX OF SUBJECTS. 1219 i-Aspartic acid, synthesis of (PASTEUR Association, molecular, and rotatory power of optically active corn- pounds (CKOMPTON), 950 ; P., 1897, 111.dielectric constant, dissociating power, and osmotic pressnre, con- nection of (CROMPTON), 943 ; P., 1897,110. and heats of nentralisation of acids and bases (CROMPTON), 951 ; P., 1897, 111. Asymmetric carbon atoms, superposition of the optical effects of (FRANKLAND and PRICE), 266 ; P., 1897, 9. Atmospheric air, carbonic anhydride in (LETTS and BLAKE), P., 1896, 192. Atomic weight of carbon (SCOTT), T., 550 ; P., 1897, 70. Atropine, auribroniicle, and hydrobromide gold chloride, the formation and pro- perties of (JOWETT), 681. Azine dyes, oxidation of Ieuco-corn- poundsof (GREEN), P., 1896, 226. Azonium dyes, oxidation of leuco- compounds of (GREEN), P., 1896, 226. LECT.), 704. B. Balance Sheet of the Cheniical Society, March 27th, 1897, 600.of tho Research Fund, March 27th, 1897, 602. Barium, occnrrence of, in common minerals (HARTLEY and RAMAGE), 533 ; P., 1897, 11. chloride, refractivo powers of solid and dissolved (GLADSTONE and HIBBERT), 825. Beer, researches on (PASTEUR LECT. ), 727 ; P., 1897, 80. Benzaldehyde, formation of (COHEN and CALVEET), 1051 ; P.: 1897, 166. from caniphoroxime benzylic ether (FORSTER), 1032 ; P., 1897, 165. action of ammonium cyanide on (SNAPE and BROOKE), 529 ; P., 1897, 51. action of magnesium nitride on, (SNAPE), 527 ; P., 1897, 50. condensation of, with phenylazocarb- amide (YOUNG and ANNABLE), 201 ; P., 1896, 246. Benzaldehyde, o-nitro-, preparation of (COHEN and HARRISON), 1058 ; P., 1897, 166. estimation of, by phenylhydrazine (COHEN and HARRISON), 1059.m-nitro-, acid obtained in preparation of ( COHEN and CALYERT), 1056. Benzaldehyde, m- andp-nitro-, oxidation of the condensation product of, with phenylsemicarbazide (YOUNG and ANNABLE), 205 ; P., 1896, 246. p-nitro-, formation of (COHEN and HARRISON), 1058 ; P., 1897, 166. Benzaldehydephenylhydrazone, 0- and p-nitro- (COHEN and HARRISON), 1058. Benzamide, action of sodamide on (TITHERLEY), 468 ; P., 1897, 46. Benzamide, 0-, m-, and p-bromo-, 2 : 4, 2 : 6-, and 3 : 5-dibromo-, hydrolysis of (SUDBOROUGH, JACKSON, and LLOYD), 232 ; P., 1897, 20. 3 : 5-dibronio-, and 2 : 4 : 6- and 3 : 4 : 5-tribromo-, preparation and properties of (SUDBOROUGH, JACK- SON and LLOYD), 230 ; P., 1897,20. (SUDBOROUGH, JACKSON and LLOYD), 231; P., 1897, 21.Benzamidohydrindene (REVIS and KIP- PING), 251 ; P., 1896, 229. Benzene, formation of, from hexn- aaphthene (FORTEY), P., 1897, 162. a space formula for (COLLIE), 1013; P., 1897, 143. viscosity of mixtures of carbon tetra- chloride and (THORPE and RODGER), 362 ; P., 1897, 49. Benzene, di-substitution derivatives of (COLLIE), 1018. tribromo-, from bromacetylene (GRAY), 1029 ; P., 1897, 140. chloro-, nitration of (COLLIE), 1020 ; P., 1897, 144. nitro-, colour and spectrum of vapour of (FRISWELL), 1013; P., 1897, 148. freezinv and boiling points o!, spec& gravity of solid and liquid (FRISWELL), 1011 ; P., 1897, 148. coloration of a solution of, in sul- phuric acid by the action of light (FRISWELL), P., 1897, 148. chlorination of (COLLIE), 1019 ; P., 1897, 144.Benzil, prepar.etion of (SUDBOR~UGH), 219 ; P., 1897, 19. Benzo-a-naphthylcarbamide (YOUNG and CLARK), 1202 ; P., 1897, 199. Benzonitrile, 2 : 4 : 6-t.ribromo- (SVD- BOROUGH, JACKSON, and LLOYD), 230 ; P., 1897, 21. 2 : 4 : 6-trichloro- (SUDBOROUGH, JACK- SON, and LLOYD), 231 ; P., 1897, 21. Benzophenylsemicarbazide, the two probable isomerides of (YOUNG awl 2 : 4 : 6-trichloro- ANNABLE), 202 ; P., 1896, 246.1220 INDEX OF SUBJECTS. Benzoyl, nitro-, probable identity of, with a-nitrobenzylic alcohol (phenyl- nitrocarbinol) (COHEN and CALVERT), 1055 ; P., 1897, 166. Benzoylacetic acid, ethylic salt, action of cthylic a-chlorocrotonate on (RUHE- MANN), 327 ; I?., 1897, 52. Benzoylazotide and its dry distillation (SNAPE and BROOKE), T., 529 ; P., 1897, 51.Benzoyl-8-butylenedicarboxylic acid, etliylic salt (RUHEMANR), 327 ; P., 1897, 52. Benzoylcamphoroxime,( FoRsTER), 1041 ; P., 1897, 166. 8-Benzoylcinnamic acid (desylenecceetic acid) and its reduction (JAPP and LANDER), 133,155 ; P., 1896,107,109. B-Benzoylnaphthylcarbamide (YOUNG and CLARK), 1203 ; P., 1897, 199. Benzoyloxydiphenyltriazole, ~ n - and p - nitro- (YOUKG and ANNABLE) 207, 211 ; P., 1896, 246. Benzoyloxyphenyls tyryltriazole, (YOUNG and ANNABLE), 216 ; P., 1896, 246. 3-Benzoyloxyphenyl-m- tolyltriazole (YOUNG and ANNABLE), 214; P., 1896, 346. Benzoyl-o- and -p-phenetolazophenol (HEWITT, MOORE, and PITT), P., 1897, 157. 8-Benzoyl-13-phenylpropionic aoid (desyl- acetic acid) (JAPP and LANDER), 136, 155 ; P., 1896, 107, 109. Benzoylsuccinic acid, ethylic salt, and the action of ammonia on it (RUHE- MANX and HEMMY), 333, 334; P., 1897, 53.Benzylamine, formation of (COHEN and CALVERT), 1054 ; ( DELI~PINE), A., i, 394. Benzylglutaconic acid ( BOLAM), P., 1896, 185. a-Benzylhydroxylamine, from camphor- oxime benzylic ether, platinochloride (FORSTER), 1039 ; P., 1897,165. Benzylic alcohol, action of nitrogen tetroxide on (COHEN and CAL- VERT), 1052 ; P., 1897, 166. a-nitro- (phenylnitrocnrbinol) (CO- HEN and CALVERT), 1054 ; P., 1897, 166. o- and p-nitro-, action of nitrogen tetroxide on (COHEN and HAR- RISON), 1057 ; P., 1897, 166. nitrite, preparation of ( COHEN and CALVERT), 1050 ; P., 1897,166. Benz ylideneaminoh ydrindene ( REVIS and KIPPING), 251 ; P., 1896, 229. Benzylidenic nitrosate ( COHEN and CALVERT), 1055 ; P., 1897, 166.Benzylprop ylene te tracarboxy lic acid, ethylic salt, action of alkalis on (BOLAM), P., 1896, 184, 185. Berberine,, occurrence of, in Berberis Oetnensis (PERKIN), 1198 ; P., 1897, 198. Berberis Oetnensis, occurrence of berberine in (PEBKIN), 1198 ; P., 1897, 198. Beryllium sulphate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 824. Bismuth, occurrence of, in common minerals ( HAHTLEY and RAM AGE), 533 ; P., 1897, 11. Bismuth alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 390 : P.. 1897. 61. Bittern, gold in ~LIVERSIDGE), 298 ; P., 1897, 22. Blende, composition of (HARTLEY and RAMAGE), 540 ; P., 1897, 13. Boilingpoint of normalpentane (YOUNG), 446 ; P., 1897, 58. Borneol, behaviour of, towards phos- phorus trichloride and bromine (MARSH and GARDNER), 286 ; P., 1896, 187.Bromine, action of highly purified, on nierciiry (SHENSTONE), 485 ; P., 1897, 2. Butane te tracarboxylic acid, eth ylic salt, action of sodium ethoxide on (LEAN and LEES), 1067 ; P., 1897, 161. aacyButanetricarboxylic acid (adipo- carboxylic acid), ethylic salt (LEAN and LEES), 1065 ; P., 1897, 161. aaa,-Butanetricarboxylic acid, sodio-, ethylic salt, action of ethylic iodide on (LEAN and LEE^), 1065. Butyric acid, a-bromo-, action of ethylic sodioacetoacetste on (SPRANKLING), 1160 ; P., 1897, 173. Butyric bromide, a-bromo-, action of lead thiocyanate on (DIXON), 635. iso-Butyric acid, bromo-, ethylic salt, condensation of, with ethylic aceto- acetate (PERKIN and THORPE), 1192 ; P., 72.Butyrolactonecarboxylic acid ( BOLAM), P., 1896, 184. Butyrylthiocarbimide, -a-bromo-, and the action of aniline, and of o-toluidine on (DIXON), 635 ; P., 1897, 9. C. Zadmium, occurrence of, in common minerals (HABTLEY and RAMAGE), 533 ; P., 1897, 11. hdmium alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 387 ; P., 1897, 61.INDEX OF SUBJECTS. 1221 Cadmium hydroxide, precipitation of iodine along with (RETTIE), P., 1896, 178. Cmalpina brevifolia and C. coriaria, composition of the fruit of (PERKIN), 1137 ; P., 1897, 170. Caesium, selenate, crystallography and physical propertiev of ( TUTTON), 846 ; P., 1897, 115. Calcium, occurrence of, in common mine- rals (HARTLEY and RBMAGE), 583 ; P., 1897, 11. i-cis-s-Camphanic acid, comparison of, with the active acid (KIPPING and POPE), 983 ; P., 1897, 133.trans-s- Camphanic acid, crystallographic comparison of, with the inactive acid (KIPPING and POPE), 973 ; P., 1897, 133. trans- and cis-s-Camphanic acids, race- mic anci pseudoracemic ( KIPPING and Camphene, behaviour of, towards phos- phorus trichloride and bromine (MARSH and GARDNER), 287 ; P., 1896, 187. derivatives, crystallography of (MIERS and BOWMAN), 293. dichloride, from camphor (MARSH and GARDNER), 288 ; P., 1897, 187. Camphene, tribromo-, and its a- and 8- tribromides (MARSH and GARDNER), chloro-, and its a- and B-hydrochlorides (MARSH and GARDNER), 288, 289 ; P., 1896, 187. and its behaviour toward con- centrated sulphuric acid (MARSH and GARDNER), P., 1897, 137. Camphenylnitramine, from camphor- oxime (FORSTER), 197; P., 1897, 21.Camphoic acid, from the oxidation of ketopinic acid (GILLES and REWWICK), P., 1897, 158. Campholenonitrile, from the ethers of camphoroxime (FORSTER), 1031. cis-Camphopyric acid, from oxidation of fenchene (GARDNER and COCKBURN), P., 1897, 137. Camphor, optical inversion of ( KIPPING and POPE), 956 ; P., 1897, 132. behaviour of, towards phosphorus tri- chloride and bromine, and towards phosphorus pentachloride (MARSH and GARDNER), 285, 288; P., 1896, 187. Camphor, a-bromo-, behaviour of, towards phosphorus trichloride and bromine (MARSH and GARDNER), 286 ; P., 1896, 187. POPE), 990. 285-287 ; P., 1896,187. Camphor, inactive T-bromo-, and T- chloro-, melting points and race- mism of (KIPPING and POPE), 996. aa-chlorobromo-, stereoisomeric forms (LOWRY), P., 1897, 159.nitro-, birotation of (LowRY), P., 1897, 160. nitrobromo-, reduction of (LOWRY), P., 1897, 160. Camphoric acid, constitution of (W. H. PERKIN, jun.), P., 1896, 191. Camphoric acid, i-s-bromo-, crystalline form of anhydride (KIPPING and POPE), 969 ; P., 1897, 133. s-chloro- and its anhydride (LAP- WORTH and KIPPING), 15 ; P., 1896, 216. i-s-chloro- and its anhydride (KTPPING and POPE), 967 ; P., 1897, 133. Camphoric anydride, w-bromo-, race- misni of (KIPPING and POPE), 999. active and inactive T-bromo-, melting points of (KIPPING and POPE), 996. Camphorimine, from camphoroxime benzyl ether (PORSTER), 1032 ; P., 1897, 165. i-Camphoronanilic acid (PERKIN and THORPE), 1192. Camphoronic acid, behaviour of, a t high temperatures (W.H. PERKIN, jun.), P., 1896, 192. synthesis of (W. H. PERKIN, jun., and THORPE), P., 1897, 73. i-Camphoronic acid, synthesis of, and its nnilic acid (PERKIN and THORPE), 1169, 1192 ; P., 1896, 72. Camphoroxime, behaviour of, towards bromine (FORSTER), 1045. behaviour of, towards methylic iodide, nitric acid, nitric peroxide, and potassium permanganate (FORSTER), 191 ; P., 1897, 21. hydrobromide, platinochloride,methyl, ethyl, benzyl ethers, acetyl and benzoyl derivatives (FORSTER), 1030, P., 1897, 165. i-Camphoroxime (FORSTER), 1048 ; P. , Camphorsulpholactone, a-bromo- ( REVIS Camphorsulphonic acid, a-bromo-, oxida- tion of animonium salt (LAPWORTH and KIPPING), 7 ; P. , 1896, .215. chlorides and bromides, active and inactive, melting poiiits and psuedo- racemism of (KIPPINGand PoPE),996.trans-Camphotricarboxylio acid and anhydride, raceniic and pseudoracemic KIPPING and POPE), 990. i-trans-Camphotricarboxylic anhydride, crystalline form ( KIPPING and POPE), 985 ; P., 1897, 133. 1897, 166. and KIPPING), P., 1896, 247.1222 INDEX OF SUBJECTS. trans-Camphotricarboxylic anhydride, melting point and raceniism of (KIPPING and POPE), 996. a-Camphylic acid, chloride, anilide, ethylic salt, dibromide, dihydro- bromide, and bromo-derivative of (W. H. PERKIN, jun.), P., 1896, 189, 190. B-Camphylic acid, and its dibromide, hydrobromide, bromo-, and iso-bromo- derivatives (W. H. PERKIN, jun.), P., 1896, 190. iso-8-Camphylic acid, and its chloride, anilide and ethylic salt (W. H. PERKIN, jun.), P., 1896, 190. Carbamide, (uTecG) velocity of formation of, from aiuinonium cyaiiate dissolved in aqueous alcohol (WALKER and KAY): 489 ; P., 1897, '75.influence of glycerol, cane-sugar, glycol, methvlic alcohol. and acetone on the rate 6f formatiok of (WALKER and KAY), 506 ; P., 1897, 76. freezing points of dilute aqneous soh- tions of (WILDERMAXN), 802 ; P., 1897, 139. freezing points of solutions of mixtures of resorcinol, cane-sugar, dextrose, and alcohol with ( WILDERMANN), 750 ; P., 1897, 119. Carbimidoglycolide, thio- (Dioxythi- nzole) (DIXON), 632 ; P., 1897, 8. Carbon, preparation of pure (BONE and JERDAN), 45 ; P., 1896, 61. atomic weight of (SCOTT), 55C; P., 1897, 70. direct union of, with hydrogen (BONE and JERDAN), 41 ; P., 1896, 175. Carbon tetrachloride, viscosity of mix- tures of benzene and (THORPE and RODGER), 362 ; P., 1897, 49.Carbon monoxide (carbonic oxide) and hydrogen, mutualactionof, athigh temperatures (BONE and JERDAN), 52. explosion of mixtures of chlorine peroxide and (DIXON and RUSSEL), 605 ; P., 1897, 99. Carbon dioxide (carbonic nnlzydride), estimation of, by PETTENKOFER'S method (LETTS aiid BLAKE), 1896, P., 192. Carbon bisulphide, viscosity of mixtures of methylic iodide and (THORPE and RODGEE), 367 ; P., 1897, 50. Oarbotetrinic acid, ethylic salt (RUHE- MANN and HEMMY), 333; 53. Carnallite, gold in ( LIVERSIDGE), 299. Carvone tribromide, pseudorscemism of (KIPPING and POPE), 1000 ; P., 3897, 136. P., 1897, Carvoxime, density of the active and inactive fornis of ( KIPPING and POPE), 999 ; P., 1897, 136. Catechu, colouring matters of, from dif- ferent sources (PERKIN), 1135.Celluloses, hydrolysis of pure, and fer- nientation of the hydrolytic products (Cnoss, BEVAN, and SMITH), 1005; P., 1897, 150. Change, chemical and physical, identity of different kinds of (HARCOURT), 595. Chloral hydrate, deliquescence of crystals Chlorine, pure, preparation of, by the electrolysis of silver chloride (SHEN- STONE), 479 ; P., 1897, 2. action of sunlight and of the silent electric discharge on highly purified (SHENSTONE), 486, 487 ; P., 1897,2. action of highly purified, on mercury (SHENSTONE), 485 ; P., 1897, 2. Hydrochloric acid (hydrogen chloride), refractive power of, when dissolved in methylic , ethylic, amylic, and octylic alcohol, ethylic and amylic ether (GLADSTONE and HIBBERT), 827; P., 1897, 142.Chlorine peroxide, explosion of mixtures of carbonic anhydride ant1 (DIXON and RUSSEL), 605 ; P., 1897, 99. Chloroform, viscosity of iirixtures of ethylic ether with (THOEPE and RODGER), 370 ; P., 1897, 50. action of magnesium nitride on (SNAPE), 527 ; P., 1897, 60. Chromium occiirrence of, in common minerals (HARTLEY and RAMAGE), 533 ; P., 1897,ll. double sulphate of zinc and (SCOTT), 568 ; P., 1897, 71. Chrysin monomethylic ether, dyeing property Of(PE1tKIN and MARTIN),^^^. Cinnamaldehyde, oxidation of the con- delisation product of, with phenyl- semicarbazide (YOUNG and ANNABLE), 215 ; P., 1896, 246. iso-Cinnamenylmandelic acid, and its acctyl derivative ( JAPP and LANDER), 135, 138 ; P., 1896, 107. Citrazinic acid (2 : 6-dihydroxypyridine- 3-carbox1~lic acid), action of phosphorus pentachloride and phosphorus oxy- chloride on (SELL and DOOTSON), 1068 ; P., 1897, 167. Citric acid, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 824.ethylic salt, synthesis of (LAWRENCE), 458 ; P., 1897, 65. Cobalt, occurrence of, in common mine- rals (HARTLEY and RAMAGE), 533 ; P., 1897, 11. Of (POPE), P., 1896, 249.INDEX OF SUBJECTS. 1223 Cobalt, action of hydrogen peroxide on solutions containing (DURRANT), P., 1896, 244. Cobalt dioxide (MCCONNELLand HANES), double sulphate of copper, nickel, and Cobaltic salts (DURRANT), P., 1896, Cobalt ores and minerals, composition of (HARTLEY and RAMAGE), 541 ; P., 1897, 13. Colloids, dissolved, electrical convection of (PICTON and LINDER), 568. Colour, relatioil of o- and p-quinonoicl structure to (GREEK), P., 1896, 226.Colouring matters, o- and p-quinonoid structure in (GREEN), P., 1896,226. relationship of vegetable, to accom- panying tannins ( PERKIN), 11 37. Colpoon comnp-cssum, (Osyris compressa, Fusnnus compre.~sus, Thpsiwn Coi!poo?i), leavesof,used as a substitute for sumach (PERKIN), 1132. Copper, occurrence of, in common mine- rals (HARTLEY and RAMAOE), 533; P., 1897, 11. Copper alloys with ziuc, freezing points of (HEYCOCK and NEVILLE), 419; P., 1897, 61. Capric chloride, refractive power of, when diwolved in ethylic alcohol (GLADSTONE and HIBBERT), 827 ; P., 1897, 142. sulphate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 825. double sulphates of iron, nickel, zinc, magnesium, manganese, cobalt, and (SCOTT), 565 ; P., 1897, 71.Corydaline, action of nitric acid on (DOBBIE and MARSDEN), 657, 658 ; P., 1897, 101. nitrate, properties of (DOBBIE and MARSDEN), 657 ; P., 1897, 101. Corydaline, optically inactive (DOBBIE and MAKSDEN), T., 660. Corydic acid, properties of, salts of, and its behaviour with hldriodic acid (DOBBIE and MARSDEN), 662 ; P., 1897, 101. Cotoin, constitution of, and its acetyl derivatives (PERKIN and MARTIN), 1149, 1152 ; P., 1897, 172. Cotoinazobenaene, and its acetyl deriva- tive (PERKIN and MARTIN), 1150; P., 1897, 172. Cotoinazo-o- and-p-toluene ( PERKIN and MARTIN), 1150 ; P., 1897, 172. Critioal pressure and critical volume, of normal pentane (YOUNG), 448; P., 1897, 58. 586 ; P., 1897, 62. (SCOTT), 567 ; P., 1897, 71.244. Critical temperature, behaviour of sub- stances near the (YOUNG), 453; P., 1897, 68. of normal pentane (YOUNG), 448 ; P., 1897, 58. Crotonic acid, a-chloro-, ethylic salt, action of ethylic benzoylacetate and of ethylic acetonedicarboxylate on (RUIIEMANN), 324, 327 ; P., 1897, 52. Crystalline and dissolved salts, refractive powers of (GLAD ST ONE and HIBBERT), 823 ; P., 1897, 141. structure of externally compensated and optically active forms of a sub- stance (KIPPING and POPE), 992 ; P., 1897, 135. Crystallographic characteristics of peudoracemic substances ( KIPPING and POPE), 994 ; P., 1897, 136. Crystallography of caesium, potassium, and rubidium selenates (TUTTON), 852, 857, 859 ; P., 1897, 115. of hydrated mercurous nitrite (HOL- LAND), 346 ; P., 1896,218.Enantiomorphism (POPE and KIPPIKG), P . , 1896, 249. Optical axes of caesiurn, potassium, and rubidium selena es (TUTTON), 874, 881, 887 ; P., 1 7, 116. Selectire delique cence in chloral hydrate (POPE), ., 1896, 249. q-Cumene (1 : 3 : 4-tri ethylbenzene), oxi- dation of (BENTL P and PERKIN), Cyanamide, sodium derivative of (TITHERLEY), 460 ; P., 1897, 45. Cyanogen :- Perthiocyanic acid, its hydrolysis with water or strong sulphuric acid, and its oxidation (CHATTA- WAY and STEVENS, 607, 611, 612, 613 ; P., 1897, 88. reduction of (CHATTAWAY and STEVENS), 834 ; P., 1897, 150. Cyanomaclurin, diazobenzene deriva- tive of (PERKIN), 187 ; P., 1897, 5. 161 ; P., 1896, 79. 1 D. Dehydrocorydaline and its salts (DOBBIE and MARSDEN), 658 ; P., 1897,101. reduction of (DOBBIE and MARSDEN), 660.Deliquescence of salts in moist air (HAKE), P., 1897, 147. selective, of crystals of chloral hy- drate (POPE), P., 1896, 249. Density, heat of fusion, and melting point, connection between ( CROMP- TON), 929 j P., 1897, 110.1224 INDEX OF SUBJECTS. Density of amylic glycerates, diacetyl- and dibenzoyl-glycerates (FRANK- LAND and PBICE), 268. of mixtures of liquids (THORPE and RODGER), 360 ; P., 1897, 49. of normal pentane, liquid, and gaseous (YOUNG), 449 ; P., 1897, 58. of potassium, rubidium, and caesium selenates (TGTTON), 868 ; P., 1897, 116. of mixtures of .isopropylic alcohol with water (THORPE), 924 ; P., 1897, 150. of racemic and pseudoracemic sub- stances (KIWING and POPE), 999 ; P., 1897, 136. of deliquescent salts, determination of the (TUTTON), 865.Deoxybenzoin (phenyl benzyl ketwne), from desyleneactic acid and alco- holic potash (JAPP and LANDER), 157. preparation of, and action of phos- phorus pentachloride on (SUD- BOROUGH), 218, 219 ; P., 1897, 20. Desylacetic acid. See 8-Benzoyl-p- Desyleneacetic acid. See 8-Benzoyl- Dextrose (d-glucose, gyape-sugar), heat of transformation of the a- into the B- variety (BROWN and PICKER- INO), 757 ; P., 1897, 129, 130. heat of dissolution of (BROWN and PICKERING), 769. freezing points of dilute aqueous solu- tions of (WILDERMANN), 800, 803 ; P., 1897, 139. freezing points of solutions of mixtures of carbamide and (WILDERMANN), 751 ; I?., 1897, 119. anhydrous, solution-density of (BROWN, MORRIS, and MILLAR), 78, 276 ; P., 1896, 242, 1897, 14.anhydrous, cupric-reducing power of (BROWN, MORRIS, and MILLAR), Diacetanilide, preparation of (YOUNG), P. 1897, 156. Diacetyl-m-aminohydroxydiphenyltri- azole and Diacetyl-p-aminohydroxy- diphenyltriazole (YOUNG and ANN- ABLE), 208, 212 ; P., 1896, 246. d- and i-Diacetylglyceric acids, 1- and i-amylic salts, rotatory power of (FRANKLAND and PRICE), 257, 262, 265 ; P., 1897, 9. Diacetyltartaric anhydride, action of aniline on (COHEN and HARRISON), 1060 ; P., 1897, l67. Diazobenzene, action of, on natural colouring matters (PERKIN), 187. phenylpropionic acid. cinnamic acid. 279, 284 ; P., 1897, 4. Dibenzamide, production of, from dib benzoylcinnamenimide ( JAPP and TINGLE), 1145 ; P., 1897, 170. a8-Dibenzoylcinnamene (anhydmceto- phenonebenzil, benzoylstyrene), modifi- cation of the formula of (JAPP and TINGLE), 1138 ; P., 1897, 170.Dibenzoylcinnamenimide, reduction of ; oxidation of ; conversion of, into di- benzamide (JAPP and TINGLE), 1145 ; P., 1897, 170. d- and i-Dibenzoylglyceric acids, 1- and i-amylic salts, rotatory power of (FRANKLAND and PRICE), 258, 262, 266 ; P., 1897, 9. Dibenzoylstyrene. See Dibenzoyl- cinnamene. Dicamphylic acid (W. H. PERKIN, jun. ), P., 1896, 189. Dicarboxyglutaconio acid (methenyllbis- malonic acid, propylenetetra-carboxylic acid), ethylic salt action of alkalis and of acids on (BOLAM), P., 1896,184. Dicyanodiamide, from. perthiocyanic acid (CHATTAWAY and STEVENS), 613. Diethylammonium chloride, electrolytic conductivity of (WALKER and HAM- YBL), 61 ; P., 1896,246. Diethylaniline, pentabromo- (EVANS), P., 1896, 235.as-Diethylcarbamide, rate of formation of (WALKER and KAY), 506. Dihydro-a-camphylic acid (W. H. PER- 2 : 4-Dihydroxydiphenylacetic lactone (HEWITT and POPE), 1086. a8-Drhydroxy-aB-diphenylglutaric acid (JAPP and LANDER), 133 ; P., 1896, 107. Dihydroxymaleic acid, action of heat on aqueous solutions of (FENTON), 375 ; P., 1897, 63. 4 : 6-Dihydroxy-2-methylpyridine, 5- amino- and 5-nitro- (LAPWORTH and COLLIE), 840, 842 ; P., 1897, 146. Dimethylacetoacetic acid, ethylic salt, condensation of, with ethylic brom- acetate (PERKIN and THORPE), 1178 ; P., 1896, 72. Dimethylammonium hydrosulphide, dis- sociation, pressure, and heat of dis- sociation of (WALKER and LUMSDEN), 433 ; P., 1897, 48. Dimethylaniline, tetrabronio- (EVANS), P., 1896, 235.Dimethylaniline-o-salphonic acid (EVANS), P., 1896, 234. aa-Dimethylglutaric acid (pentanedicarb oxylic acid) from 8-camphylic acid (W. H. PERKIN, jun.), P., 1896, 191. KIN, jUIl.), P., 1896,190.INDEX OF SUBJECTS. 1225 1 :3-DimethylcycZohexane (dimethylhexa- methylmae), broitiide of (KIPPING and EDWARDS), P., 1896, 189. 1 : 2-Dimethyleyclohexane-4-carboxylic acid (hexnhydro-p-xylic mid) and its chloride anilide, ethylic salt, and bronio- and dibromo-derivatives (BEmLm and PERKIN), 161, 169, 170, 171 ; P., 1896, 79. acid (hexahydroxylic acid) and its anilide and ethylic salt; bromo-deriva- tive, and its ethylic salt (BENTLEY and PERKIN), 173 ; P., 1896, 79. 1 : 3-Dimethylcyclohexanone-2 (dinzethyl- ketohcxamethylene) ( KIPPING and EDWARDS), P., 1896, 188.oxime and semicarbazone ( KIPPING), acid (tctrahydro-p-xyZie acid) and its ethylic salt ( BENTLEY and PERKIN), 157, 172 ; P., 1896, 79. Dimethylketohexamethylene. See Dimeth ylcyclohexanone. Dimethylpimelic acid (heptamdicarb- oxylic acid), formation of ( KIPPING and EDWARDS), P., 1896, 188. 2 : 4-Dimethylpyridine( Zutidine), chloro-, oxidation of (ASTON and COLLIE), 653 ; P., 1897, 89. a-chloro- (COLLIE), 309; P., 1897, 43. 2 : 4-Dimethylpyridine-3-carboxylic acid, metallic and ethylic salts of (COLLIE), 306 ; P., 1897, 43. ms- Dimethylsuccinic acid (Gobutanedicar- boxylic acid), from sulphocamphylic and 8-camphylic acids (W. H. PER- KIN, jun.), P., 1896, 189. Dimethyl-o-toluidine, tctrabromo- (EVANS), P., 1896, 235. 1 : 2 : 5-Dimethyl-o-toluidine-m-snlpho- nic acid, nction of bromine on (EVANS), P., 1896, 235.a- and 8-Dinaphthylcarbamides (YOUNG and CLARK), 1201,1203; P., 1897,199. mDioxyphenylcoumarin, acetyl deriva- tive of the iriethylic ether of ( PERKIN and MARTIN), 1149. Diparaconic acid, chloro-, and the action of sodium amalgam on (MYERS), 614, 616 ; P., 1897, 100. Dipentene, tetrahromidc, densities of active and inactive forms of (KIP- PIXG and POPE), 999. hydrochloride nitrolanilide, pseudo- racemisni of (KIPPING and POPE), 1000; P., 1897, 136. 8-Diphenanthrylamine ( JAPP and Diphenylamine, action of sodamide on 1 : ~-DimethylcycZohexane-4carbosylic P., 1896, 248. 1 : 2-Dimethylcyclohexene-4carboxylic FINDLAY), 1124 ; P., 1897, 169. (‘rITHERLEY), 465 ; P., 1897, 45. VOL LXXI. By-Diphenylbutyric acid ( JAPP and LAXDEB), 156.By-Diphenyl-y-butryolactone (JAPP and LANDER), 156 ; P. 1896, 109. Diphenylcarbamide, from aniline and etliylic acetosuccinate (RUHRMANN and HEMMY), 331. Diphenylcrotolactone (JAPP and LAN- DER), 136, 156 ; P., 1896, 107. 2’ : 3’-Diphenyleneindole (JAPP and FINDLAY), 1124 ; P., 1897, 170. s-Diphenylethane (dibeazyl), chloro- clinitro- (SUDBOROUGH), 223 ; P., 1897, 20. Diphenylfumaric acid ( JAPP and LANDER), 142 ; (JAPP and MURRAT), 152. Diphenylmaleic acid(JAPP and LANDER), 132, 142 ; P., 1896, 107. Diphenylmaleic anhydride ( JAPP and MURRAY), 152. Diphenylmethane, broxuo-, action of ethylic sodio-acetoacetate on (HEN- I?., 1897, 119. 8-Diphenylmethyl ethyl ketone, and its oxime and semicarbazone (HENDERSON and PARKER), 677, 678 ; P., 1897,120.1 : 2 : 3-Diphenylmethylcyclopentane (JAPP and MURRAY), 153. 1 : 2-Diphenlcyclopentane (diphenyl- pentamethylene) (JAPP and LAFDER), 131 ; P., 1896, 107. Diphenylcyclopentanone ( JAPP and LANDER), 131, 141 ; P., 1896, 107. Diphenylcyclopentenonethyloic acid, and its silver salt arid oxinie (JAPP and MURRAY), 151 ; P., 1896, 146. 6-Diphenylpropionic acid ( HENDERSOX and PARKER), 677. Disazobenzeneapigenin, the properties of (PERKIR), 808 ; P., 1897, 54. Dissociation and decomposition (HAR- COURT), 597. Distillation, apparatus for automatic steal11 (hfATTHEWS), 318 ; P., 1897, 18. fractional, of volatile liquids, appar- atus for (YOUNG and THOMAS), 440 ; P., 1897, 58. n -Di-?n-tolylpiperazine (FRANCIS), 42 6, 427. Dividivi, composition and dyeing pro- perties Of(PEBKIN), l i 3 7 ; p., 1897,170.DERSON and PARKER), 676, 677 ; E. ELECTROCHEMISTRY :- Conductivity of solutions, connection of freezing point and (CROMPTOB), 942 ; P., 1897, 110. 4 01226 ELECTROCHEMISTRY :- INDEX OF SUBJECTS, Conductivity of aqueous and alcoholic solutions of diethylanimoniuin chloride (WALKER and HAYBLY), 61 ; P., 1896, 246. Dielectric constant, dissociating power, and molecular association ( CROMP- TON), 943; P., 1897, 110. Electric discharge, silent, action of the, on pure chlorine (SHEN- STONE),486 ; P., 1897, 2. Electrical convection of dissolved col- loids (PICTON and LINDER), 568. Electrical furnace for heating glass apparatus (SHENSTONE), 478 ; P., 1897, 3. Electroysis, of water exposed to the atmosphere (RAYLEIGH), 181 ; P., 1897,17.Electrolytic dissociation (CROMPTON), 941 ; P., 1897, 110. and optical activity (CROMPTON), 946 ; P., 1897, 111. and heats of neutralisation of acids and bases (CROMPTON), 951 ; P., 1897, 111. Elements, connection between the heats of fusion, densities, and melting points of the (CROMPTON); 932 ; P., 1897, 110. Ellagic acid, occurrence of, in various tanning materials, and dyeing pro- . perties of (PERKIN), 1137 ; P., 1897, 170. Ellagitannic acid, occurrence of, in various tanning materials ( PERKIN), 1137. Enantiomorphiam (POPE and KIPPING), of optically active crystals (POPE aiid Epsomite, spectroscopic analysis of (HARTLEY and RAMAGE), 550; P., 1897, 47. Ethane, hexmhlor-, action of magnesium nitride on (SNAPE), 527 ; P., 1897, 50. 3-E thox y-1 : 5-diphenyltriazole, m- ui tro- and p-nitro- (YOUNG and ANNABLE), 210 ; P., 1896, 246. 2-Ethoxynaphthalene7 crystallography of derivatives of (DAVIS), P., 1896, 233. dibrom-, tribrom-, 3’ : l-broniamino-, 3’ : l-bromonitro- (DAVIS), P., 1896, 232.P., 1896, 249. KIPPING), P., 1896, 249. 3-Ethoxy-l-phenyl-5-styryltriazole 3-Ethoxy-l-phenyl-5-m-tolyltriazole (YOUNG and ANNABLE), 216 ; P., 1896, 246. (YOUNG and ANNABLE), 214; P., 1896, 246. 3-Ethoxy-l-phenyltriaeole 314 : P.. 1897. 53. (YOUNG), 3-Ethoxy-1-phenyltriazole-5-carboxylic acid, ethylic salt of, and amide (YOUNG), 312 ; P., 1897, 53. Ethylacetoxime, periodide of, and hydro- lysis of (DUNSTAN and GOULDING), 5i9. a-Ethyl-B-acetylpropionic acid ( SPRANK- LING), 1161. 8-Ethylacetylsuccinic acid, ethylic salt (SPRANKLING), 1160 ; P., 1897, 173.a-Ethyladipic acid (hexmedicarboxylic acid) (LEAN and LEES), 1067 ; P., 1897, 161. Ethylamine, action of potassium 011 (TITHERLEY), 463 ; P., l897., 45. Ethylammonium hydrosulphide, dis- sociation, pressure, and heat of dis- sociation of (WALKER and LUMSDEN), 433 ; P., 1897, 48. a-Ethylbutane-aaa,-tricarboxylic acid (hexxnnetricnrboxylic acid) and its ethylic salt (LEAN and LEES), 1065, 1066 ; P., 1897, 161. Ethyldeoxybenzoin, action of phosphorus pentachloride on (SUDBOROUGH), 218 ; P., 1897, 20. Ethyldibenzoin, a correction (JAPP), Ethylene, dibrom- (symmetrical) froni acetylene and bromacetylene (GRAY), 1027 ; P., 1897, 140. a-dibrom-, from vinylic tribromide (GRAY), 1025 ; P., 1897, 140. Ethyleneaniline, p-dinitroso-, and its hydrochloride (FRANCIS), 423 ; P., 1897, 63.Ethylenedibenz ylidenediphenylene- p-tetramine and its hydrochloride (FRANCIS), 424. Ethylenedibenzylidenedi-o- tolylene- p-tetramine and its hydrochloride (FRANCIS), 426. Ethylenediphenylene-p-tetramine and its hydrochloride (FRANCIS), 423 ; P., 1897, 63. Ethylenedisalicylidenediphenylene- p-tetramine and its hydrochloride (FRANCIS), 424. Ethylenedi-o-tolylene-p-tetramine and its hydrochloride (FRANCIS), 425 ; P., 1897, 64. Ethylenedi-?1z-tolylene-p-tetramine (FRASCIS), 427 ; P., 1897, 64. Ethylene-o-tolnidine, its dinitrossmiiie aud p-clinitroso-derivative (FRANCIS), 425 ; P., 1897, 64. Ethylene-m-toluidine, preparation of, and its hydrochloride and dinitros- aniine (FRAKCIS), 426, 427 ; P., 1897, 64. 297 ; P., 1897, 48.ISDES O F SUBJECTS. 1227 Ethylene-p-toluidine diiiitrosaniiiie (FRANCIS), 428 ; I?., 1897, 64. Ethylenic glycol, influence of, on the rate of forniatiou of carbarnide (WALKER and KAY), 506 ; P.1897, 76. Ethylic alcohol, freezing points of solu- tions of niixtures of carbamide with (WILDERMANN), 752 ; P., 1897, 119. influence of, on the rate of formation of carbamide (WALKER and KAY), 506 ; P., 1897, 76. Ethylic ether, viscosity of mixtures of chloroform with (THORPE and RODGER), 370 ; P., 1897, 50. Ethylic iodide, action of mercurous nitrite on (RAY), P., 1896, 218. Ethylidenesuccinamide, amino-, and action of potash on (RUHEMANN and HEMMY), 331. Ethylpiperidine and its picrate (EVANS), 524 ; Y., 1897, 64. Ethylpropylpiperidonium iodide, and its enantiomorphous crystals (EVAXS), 524 ; P., 1897, 64.Ethylstilbene, chlordibrornicle, and di- chloride (SUDBOROUGH), 227 ; p., 1897, 20. B-chlor- (SUEBOROUGH), 218, 226 ; P., 1897, 20. Ethylsulphuric chloride, action of lead thiocyanate on (DIXON), 640. Ethylthioglycollic acid (a-thiobz~tyric acid) (DIXON), 637 ; P., 1897, 9. F. Fenchone, behaviour of, towards plios- phorus trichloride and hromine (MARSH and GAKDKEK), 286 ; P., 1896, 187. beiiavionr of, towards phosphorus pentachloride ( GARDNER and COCK- BURN), 1157 ; P., 1897, 173. Fenchonephosphoric acid, chloro- sodium, lead, barium, copper salts ( GARDNER and COCKBURN), 1157 ; P., 1897, 173. Ferment, butyric, effect of oxygen 011 ( PASTEUR LECT. ), 714. lactic, nature O f (PASTEUP. LEC'l'. ), 712. Fermentation, chetnicsl theory of (PASTEUR LECT.), 725; P., 1897, 79.acetic (PASTEUR LECT.), 721. alcoholic (PASTEUR LECT.), 712. hctyric (PASTEUR LECT.), 714. lactic (PASTEUR LECT.), 712. Fisetin, occiirreiice of, in .Ehi~s CO~L,LUS niid Id. rhodnnthcvicc (yellow cedar), (PEIWIS), 1195, 1197 ; P., 1897, 198. Fish, coinposition of cooked (WILLIAMS), 649 ; I?., 1897, 88. Plachrric. See Silkworm diseaws. Fluorine, liquefaction of, and i)i operties of iicluid ( BIoissAiN and DEWAH), P., 1897, 175. Food, composition of cooked fish used as (WILLIANS), 649 ; P., 1897, 88. Formaldehyde, formation of (C'OHBS and CALVEKT), 1051. Formaldehyde, thio-, from the action of hydrogen sulphide on the hydro- lytic products of cellulose (CROSS, BEVAN and SMITH), 1006. Formaldoxime, action of methylic iodide and bromide on (Duh-s~ss aud GOULDING), 575 ; P., 1897, 76.niethiotlide, and the action of heat on it ; its hydrolysis, and reduction (DUXSTAX and GOULDISG), 676, 576, 577. Formamide, action of sotlamide on Formic acid, barium, calcium, and stroll- tiuni salts, iefractive powers of solid and dissolved (GLADSTONE and HIBBERT), 825. Fowl cholera, investigation of (PA~TEUR LECT.), 739. Freezing point, of solutions, iiifiueiicse of niolecular associatiou on (CROMP- TOX), 928 ; P , 1897, 110. in dilute solutions, niolecular depre>- sion of the (WILDERMAM), 796 ; P., 1897, 139. of solutions containing two substances ('rITHXRLEP), 466 ; P., 1897, 46. (J\71LDERhfANN), 745 ; P., 1897, 119. of solutions of volatile substances (CKOMPTON), 937 ; P..1897, 110. of alloys of zinc with aiiother metal (HEYCOCK and NEVILLE), 383 ; P., 1897, 60. Fumaric acid, chloro-, ethylic salt, action of ethylic sodiomethylaceto- acetate on (RUHEMANN), 324, 325 ; P., 1897, 52. action of ethylic sodio-oxalacetate on (RUHEMANN and HEMMY), 335 ; P., 1897, 64. Furfuraldehyde (furfttro2) aiiioun ts of, produced by hydrolysing various celluloses(CRoss, REVAK anclSnrITH ), 1005. influence of fermentation 011 (CROSS, BEVAN and SMITH), 1007. Furfuroids, constitution of (CEOSS, BEVAN and SMITH), 1001 ; P., 1897, 151. 4 0 21228 INDEX. OF Furnace, eiectric. for heating delicate glass ’apparatus (SHENSTOGE), 478 ; P., 1897, 3. Fustin, formula of (PERILIN), 1197. G. Galactic acid, calcium salts, raceniism of ( KIPPIXG and POPE), 999.Galena, composition of (HARTLEY and RAMAGE), 542 ; P., 1897, 13. Gallium, occurrence of, in common minerals (HARTLEY & RAMAGE), 533 ; P., 1897, 11. Gallnuts, composition and dyeing pro- perties of (PERKIN), 1137 ; p., 1897, 170. Gallotannic acid, occiirrence of, in Rhus rhodnnf7zenza (PERKIN), 1197. d-Glucose. See Dextrose. Glucoside, C,,H,,O,,, occurring in Xhus rhodunthema (PERILIN), 1196 ; P., 1897, 198. Glutaconic acid (propylenedicarboxylic acid), prepnration of ( BOLAM), P., 1896, 184. d- and i-Glyceric acids, I - and i-amylic salts, rotatory power of (FHANKLAND and PRICE), 256, 261, 264; P., 1897, 9. Glycerol produced in alcoholic fennenta- tion (PASTEUR LECT.), 713. inflnence of, on the rate of fornistion of carbamide (WALKER and KAY), 506 ; P., 1897, 76.Glycollic acid, thio- (DIXON), 630 ; P., 1897, 8. Glycollic aldehyde from dehydroxy- maleic acid, its oxidation, the action of heat and the action of phenylhydr- azine on it (FENTON), 375; P., 1897, 63. Glyoxal, osazone of (FENTON), 375. Gold in natural saline deposits and marine plants (LIVERSIDGE), 298 ; P., 1897, 22. presence of, in sea-water, and a method for its detection (SONSTADT), Y., 1896, 238. nuggets and ingots, crystalline struc- ture of (LIVERSIDGE), 1125 ; P., 1897, 22. origin of (LIVERSIDGE), 1125, P., 1897, 22. Gold alloys with sodium, structure of (HEYCOCK and NEVILLE), P., 1897, 105. \i i t h zinc, freezing points of (HEYCOCK and NEVILLE), 419 ; P., 1897, 61. Grape eugar. See Dextrose. 3UBJ ECTS. Gulonic lactonee, melting points and racemism of (KIPPING and POPE), 997.Haematites, composition of ( HARTLEY aud RAXIAGE), 536 ; P., 1897, 12. Hemoglobin, clectricel convection of, in solutions ( PICTON and LINDER), 571. 1 : 2 : 3 : 4-Hemipinic acid from oxidation of‘ corydic acid (DOBBIE and MARS- 1 : 2 : 4 : 5-Hemipinic acid (nzetahe?nipinic acid) from oxidation of corydic acid (DOBBIE and MARSDEN), 664. Hexahydro-xylic acids. See Dimethyl- cyclohexanecarboxylic acids. Hexanaphthene, from American petro- leum, identity of M ith cycZo-haxane (FORTEY), P., 1897, 161. cyclo-Hexane (hexnn~ethylene, hexnnaph- thene), and its di-, t r f - , and tetra- chloro-derivatives (FORTEY), P., 1897, 161. Hofmann’s violet,electrical convection of, in solutions (PICTON aiid L I N D E R ) , ~ ~ ~ . Hydantoic acids, thio- nomenclature and constitution of (DIXON), 633, 637 ; P., 1897, 9.Hydantoins, thio-, nomenclature of (DIXON), 637 ; P., 1897, 9. Hydrazobenzene, sodium derivative of Hydrindene, amino-, and its salts, and benzoyl derivative (REVIS and Kmr- ING), 250 ; P., 1896, 229. a-Hydrindone, derivatives of, and its oxidation with nitric acid (REVIS arid KIPPIXG), 238 ; P., 1896, 229. bromo-, oxidation of (REVIS and KIPPING), 242 ; P., 1896, 229. iso-nitroso-, alkali derivatives of (REVIS and KIPPING), 248 ; P., 1896, 229. a-Hydrindoneazine (REVIS and KIPPING), a-Hydrindone-oxime, action of mineral acids on (REVIS and KIPPING), 248 ; P., 1896, 229. a-Hydrindonesemicarbazone (REVIS and KIPPING), 241. a-H ydrindonylbromh ydrindone ( REVIS and KIPPING), 243 ; P., 1896, 229. Hydrocarbon, C14H12, from camphor- oxime benzyl ether (FORSTER), 1032 : P., 1897, 165.Hydrogen, direct union of, with carbon (GONE and JERDAN); 41 ; P., 1896, 175. DEN), 664 ; P., 1897, 102. (‘rITHERLEY), 462 ; P., 1897, 45. 248 ; P., 1896, 229.TNDEX OF SUBJECTS. 12.29 Hydrogen, reaction of, with carbon monoxide at high temperatures (BONE and JERDAN), 52. influence of platinum on the combina- tion of oxygen with (FRENCH), P., 1897, 52. p-Hydroxyacetophenone from the decom- position of apigenin (YERKIN), 810 ; P., 1897, 138. Hydroxyanthraquinone dyes, oxidation of leuco-compounds of (GREEN), P., 1896, 226. p-Hydroxybenzoic acid, from the de- composition of apigeuin ( PERKIN), 810 ; P., 1897, 138. ethylic salt, from hydrolysis of apigenin diethylether (PERKIN), 815.Hydroxycamphene (ea~nphenol) (MARSH and GARDNER), 290 ; P., 1896,137,187. Hydroxycamphorsulphonic acid, di- bromo-, and its lactone and bromide (LAPWOIITH and KIPPISG), 19 ; P., 1896, 215. o-Hydroxydiphenylacetic lactone (HEWITT and POPE), 1086. 3-Hydroxy-1 : 5-diphenyltriazole, 772- amino-,p-amino-,w -nitro-, and p-ni tro-, and their acetyl and benzoyl deriva- tives (YOUNG and ANXABLE), 205, 207, 209,211 ; P., 1896, 246. Hydroxyindonylhydrindone ( REVIS and KIPPING), 247 ; P., 1896, 229. Hydroxymethylcoumalin and the action of methylic alcohol and hydrochloric acid on i t (RUHEMANN), 326. Hydroxyisonicotinic acid, chloro- (SELL and DOOTSON), 1073 ; P., 1897, 167. 3 -Hydroxy- 1 -phenyl-5-s tyryloxytri- azole, and its benzoyl derivative (YOUNG and ANNABLE), 215; P., 1896, 246.oxidation of (YOUXG), 31 1 ; P., 1697, 53. and its acetyl and benzoyl derivatives (YOUNG and ANNABLE), 212; P., 1896, 246. Hydroxytriazoles, formation of, from phenylsemicarbazide (YOUNG and ANNABLE), 200 ; P., 1896, 246. B-Hydroxy-aaB-trimethylglutaric acid, ethylic salt, synthesis of (PERKIN and THORPE), 1178 ; P., 1897, 72. Hydroxytriphenylpyrrolone, hydrolysis of, and production of benzilic and benzoic acids (JAPP and TISGLT”), 1146; P., 1897, 171. Hyoscine auribromide and hydrobromide gold chloride, formation and proper- ties of (JOWETT), 679, 680 ; P., 1897, 136. 3 - Hydroxy- 1 - p heny 1 - 5 - s t yr yl t r iaz ole, 3-Hydroxy-l-phenyl-5-m-tolyltriazole, Hyoscyamine hydrobromide gold chla- ride, the formation and prop9rties of (JOWETT), 681 ; P., 1897, 136.I. Indamine dyes, oxidation of leuco-com- pounds of (GREEN), P., 1896, 226. Indigo, electrical convection of, i n solu- tions (PICTON and LINDER), 571. Indigo dyes, oxidation of leuco-com- pound of (GREEN), P., 1896, 226. Indium, occurrence of, in common mine- rals (HARTLEY ’ and RAMAGE), T., 533; P., 1897, 11. Indonylbromhydrindone ( EEVIS and KIPPING), 245 ; P., 1896, 229. Indophenol-dyes, oxidation of leuco- compounds of (GREEN), P., 1896, 226. Iodine, electrical convection of, in solu- tion (PICTON AND LINDER), 571. aetion of highly purified, on mercury (SHENSTONE), 485 ; P., 1897, 2. precipitation of, together with metallic hydroxides (RETTIE), P., 1896, 178. Ferric chloride, refractive power of, when dissolved in ethylic alcohol or ethylic acetate (GLADSTONE and HIBBERT), 827; P., 1897, 142.hydroxide, electrical convection of, in solutions ( PICTON and LINDER), 571. Ferrous sulphate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 825. double sulphates of copper, zinc, manganese, and (SCOTT), 565 ; P., 1897, 71. Iron ores, composition of ( HARTLEY and RAMAGE), 534 ; P., 1897, 12. Steel-rails, composition of ( HARTLEY and RAMAGE), 548 ; P., 1897, 47. Iron :- K. Kainite, gold in (LIVERSIDGE), 299. spectroscopic analysis of ( HARTLEY and R.AMAGE), 549 ; P., 1897, 47. Ketohydrindene. See Hydrindone. Ketolactonic acid and its hoinologues (SPRANKLING), 1159 ; P., 1897, 173. Ketolactonic acids, ethylic salts, rate of hydrolysis of (SPRANKLING), 1167 ; P., 1897, 174. Ketonic acid, C,H,,O,? from the oxida- tion of B-camphylic acid, and its seniicarbazone (W.H. PERKIS, jun.), P., 1896, 191.123" IXDEX OF SUBJECTS. d-Ketopinic acid (GILLES and RESWICI;), P., 1897, 158. i-Ketopinic acid, its oxidation, and its oxime and bromo-derivative (GILLES Kieserite, spectroscopic analysis of ( HAKTLEY and RAMAGE), 550 ; P., 1897, 47. atld RENWICK), P., 1897, 65. L. Lactic acid (inactive ctlzylidenelnctic m i d ; a-hydrozyppl.opiontic acid), separation of, into its active coni- ponents (PASTEUR LECT.), 693. Lactone, Cl2HIOO7, obtained by action of sodiam on ethylic acetonedicarboxylate, arid its hydrolysis (JERDAK), 1110, 1113 ; P., 1897, 168. Lactose (milk-sugar), heat of transfor- ination of the u- into the &variety (BROWN and PICRERING), 767 ; l'., 1897, 129, 130.heat of dissolution of (BROW'S and freezillg points of dilute aqueous solu- tions of ( WILDERMANN), 802 ; P., 1897, 139. Lead, occurrence of, in common minerals (HARTLEY and RAMAGE), 533 ; P., 1897, 11. reaction of lend snlphate and of sul- phurous anhydride with (JENKINS and SMITH), 671, 6 7 2 ; P., 1897, 104. Lead alloy with zinc, freezing points of (HEYCOCK and NEVILLE), 394; P., 1897, 61. Lead sulphide, action of oxygen on heated (JEXKIKS a i d SMITH)^ 666 ; I>., 1897, 104. reaction of lead sulphate with ( J m - KIKS and SAIITH), 669 ; P., 1897, 104. Lecture, memorial : Pasteur (FRASK- Levulose (d$rmtow, f m i t s z i y n r ) , heat of transformation of the u- and the 765 ; P., 1897, 129, 130. heat of dissolution of (KROWX and PICICERING), 769.anhpdrons, solii tion-density and cupric- reducing power of (BROWN, MORRIS and MILLAR), 277, 210, 284 ; P., 1897, 4. Levure lactique (PASTEUR LECT.), 712. Limonites, coinposition of (HARTLEY and RAMAGE), 536 ; P., 1897, 12. Liquids. miscible, viscositj- of nlixtures of i I ' H O R P E and RODGER), 360 ; F., 1897, 49. PI CR ERIKG) , 769. IAKU), 683 ; P., 1897, 79. &variety (BROWN arid PICKERING), Liquids, volatile, apparatus for the fractional distillation of (YOUNG and TrronrAs), 440 ; P., 1897, 58. Lithium, chloride, refractive power of, when dissolved in ethylic and propylic alcohols (GLADSTONE and lIIBBERT), 827 ; P., 1897, 142. Longstaff medal, Presentation of, to I'KOF. RAMSAY, 591 ; Y., 1897, 80. Luteolin, triethylic ether (PERKIN), 191 ; (HERZIG), A,, i, 94.(PERKIN), 191. trimethylic ether, formation of Lutidine. See 2 : 4-Dimethylpyridine. 4- Lutido B tyril (2 : 4-dimeth y Lp y ~ i d o i i c ) (COLL~E), 307 ; P., 1897, 143 ; (ASTON and COLLIE), 653 ; P., 1897, 89. ~-Lutidostyril-fi-carboxylic acid and its etliylic salt (COLLIE), 310 ; P., 1897, 43. M. Maclurin, derivatives of ( P E R I C I ~ ) , 186 ; P., 1897, 5. Maclurinazobenzene, constitution of (YEILKIN), 186 ; P., 1897, 5. Magdala red, electrical convection of, in solutions ( PICTON and LINDER), 571. Magnesium alloys with zinc, freezing points of (HEPCOCIC and NEVILLE), 395 ; P., 1897, 61. Magnesium hydroxide, precipitation of iodine together with (RETTIE), P., 1896, 178. nitride, action of benzaldehyde, of chloroform, and of hexachlorethane (SB~LPE), 527 ; P., 1897, 50.snlpliate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 825. copper snlphate (SCOTT), 567 ; P., 1897, 71. Magnetites, composition of ( HARTLEY and RAMAGE), 538 ; P., 1897, 12. Malic acid, silver salt, action of isopro- pylic ioaide and ethylic iodide on (PURDIE and LANDER), P., 1896, 221, 222. ethylic salts, optical activity of (PUP,- DIE and LANDER), P . , 1896, 221, 222. isopropylic saIt (PURDIE and LANDER), P., 1896, 221. i-Malic acid, synthesis of (PASTEUP. LECT.), 704 ; P., 1897, 79. Malonic acid, formation of (JERDAN), 1108. Malonic acid, sodio-, action of ethylenic chloride on (LEAN and LEES), 1062; l'., 1897, 161.INDEX 0 1 Yalonyl-B-butylenetricarboxylic acid, ethylic salt, and the action of am- monia on it (RUHEMASX), 327, 328 ; P., 1897, 52.Yaltodextrin-a, C36Hfi2031, from action of diastase on starch, and the action of diastase on it (LING and BAKER), 510, 514 ; P., 1897, 3. Maltodextrin-B, identity of with Prior’s achroodextrin III., and the action of diastme on it ( LING and RAKER), 510, 517 ; P., 1897, 3. iso-Maltosazone, from action of yrheiiyl- hydrazine acetate on a mixture of mal- tose and inaltodextrin-B (LIKG and BAKER), 511, 519. Maltose, specific rotation of (BROWN, MOHP,IS and MILLAR), 110 ; P., 1896, 242, 243 ; (LING and BAKER), 512 ; P., 1897, 3. heat of transformation of the a- into the !-variety (BROWK and PICKEILIKG), r64 ; P., 1897, 129, 130. heat of dissolution of (EROWK and PICKERIKG), 769. freezing points of dilute aqueous solu- 1897, 139.anhydrons, solution-density of ( BROWN, l!ORRIS and RfILLAR), 77 ; P., 1896, 242. cupric-reducing power of (BROWN, MORRIS and MILLAR), T., 99, 100 ; P., 1896, 242 ; (LISG and BAKER), 512; P., 1897, 3. isolaltose, its probable composition and thc action of brewery yeast on it, its cupric-reducing and specific rotatory powers (LIXG and BAKER), 511, 513 ; 520, 521. Manganese, occurrence of, in corninon minerals ( HARTLEY and RANAGE), 533; P., 1897, 11. donble sulpliates of copper, iron and (SCOTT), 567 ; P., 1897, 71. Manganese ores and minerals, composi- tion of (HARTLEY and RAirAGE), 539 ; l’., 1897, 12. Manometer with fused silver chloride (SHENSTOSE), 486 ; P., 1897, 3. Medal, Longstaff, presentation of, to PROF. RAMSAY, 591 ; P., 1897, 80. Melting point, a method of determining (COOK), P., 1897, 74.of racemic and psendoracemic snb- stances (KIPPISG and POPE), 994 ; P., 1897, 136. Memorial lecture : Pasteur (FRANC- LAPITD), 683 ; P., 1897, 79. Menthone, behaviour of, towards phos- phorus trichloricle and bromine ( MARSH and GARDSER), 286 ; P., 1896, 187. tions O f (WILDERMAXN), 802 ; P., SUBJECTS. 1231 Mercury, purification of (SHENSTOKE), molecular association in liquid (CROMP- action of high]? purified chlorine, bromine, andiodineon (SHENSTONE), 485 ; P., 1897, 2. Mercury alloy with silver, heat of formation and specific heat of (LrTrLE- TON), P., 1896, 220. Mercuric salts, constitution of (Riiu), hyponitrite (RAP), 349, 1097, 1105 ; sulphate, basic (RAY). 1098. Mercuroso-mercuric nitrites (bmic) ( R ~ Y ) , 341 ; P., 1896, 218.Mercurous nitrates ( R ~ Y ) , 342 ; P., 1896, 218. nitrite, hydrated, crystallography of (HOLLAND), 346 ; P., 1896, 218. nitrites and liyponitrites (RAY), 337, 348 ; P., 1896, 217. Yesitylacetamide (SUDBOROUGH, JACK- SON and LLOYD), 232 ; P., 1897, 21c- Yesitylformamide (SUDBOROUGH, JACK- SON and LLOYD), 233 ; P., 1897, 21. Methane, formation of, by direct union of carbon and hydrogen {BONE and JERDAN), 51, 55; P., 1896, 175. action of the electric arc on (BONE and JERDAN), 59 ; P., 1896, 177. 1 : 2-Methoxyacetonaphthalide, 3‘-bromo- (DAVIS), P., 1896, 233. 2-Methoxynaphthalene, cystallography of derivatives of (DAVIS), P., 1896, 233. I-amino-, 3’-amino, 1’-amino- and its acety! derivative, 3’ : 1 -bromamino-, 1-nitro-, l’-nitro-, 3’-nitro-, 1 : 1’- dinitro- and 1 : 3’-dinitro- (DAVIS), P., 1896, 231, 232.Methylacetaldoxime, and its hydrolysis (DUNSTAN and GOULDING), 577 ; P., 1897, 77. Yethylacetoacetic acid, sodio-, ethylic salt, action of etliylic chlorofumarate on (RUHEMANN) 325 ; P., 1897, 52. Methylacetophenoxime, hydriodide of, and its hydrolysis (DUNSTAK and GOULDING), 579. a-Methyl-B-acetopropionic acid (SPRANKLING), 1163. Methylacetoxime, periodide of, and its hydrolysis (DUNSTAN and GOULDING), 578; P., 1987, 77. Methylamine, hydrochloride, h ydriodide, and platinochloride ( DUNSTAN and GOULDIKG), 576, 578. Methylcamphorimine, hydrochloride, hy- driod ide, met h iodide, platin ochloride, picrate, chromate, niercnrichloride, Iter- bromide (FORSTEP,), 193 ; P., 1897, 21. 483 ; I’., 1897, p. TON), 933.1103. P., 1896, 217.1232 INDEX OF SUBJECTS. P., 1897, 89. Methylpyridinetricarboxylic acid, from Methyldeoxybenzoin, action of phos- phorus pentachloride on (SUD- BOROUGH), 218 ; P., 1897, 20. Methylene-blue dyes, oxidation of leuco- compounds of (GREEN), P., 1896, 227. Methylformaldoxime, hydriodide of, and the action of heat on an aqueous solu- tion of it (DUNSTAN and GOULDING), 575 ; P., 1897, 76. acid(?iiethyltctrahzJdroterc~~tlzalic midl and its methylic salt (BENTLEY and PERKIN), 178 ; P., 1896, 79. B-Methylhydroxylamine, from formal- doxinie methiodide (DUNSTAN and GOULDING), 577. Methylic alcohol, influence of, on the rate of formation of carbamide (WALKER and KAY), 506 ; P., 1897, 9 6. Methylic iodide, viscosity of mix- tures of carbon bisulphide with (THOHPE and RODGER), 367 ; P., 1897, 50. Methylmannosides, melting points and racemisni of (KIPPING and POPE), 997. 2-lethylisonicotinic acid, 6-chloro-, and its salts (ASTON and COLLIE), 656; P., 1897, 89.Methylparaconic acid, dichloro-, ancl the action of barium hydroxide on (MYERS), 614 ; P., l897? 100. trichloro-, action of acetlc acid and zinc dust on (MYERS), 614 ; P., 1897, 100. Methylisophthalic acid [Me : (COOH)2~ 1 : 2 : 41, preparation of, and its methyllc salt (BENTLEP and PERKIN), 175, P., 1896, 79. 4-Methylpicolinic acid, 2-chloro-, and its salts (ASTON and COLLIE), 655 ; 1-Methylcyclohexene-2 : 5-dicarboxylic 3-Naphthalenesulphonic acid, 1 : l‘d- chloro-, potassium salt, chloiide, amide ( ARMSTRONG and WYXNE), 1’. , 1897, Afovzcs timtorin, niaclurin from ( PERKIN), 186 ; P., 1897, 5.Mucor nizscedo, fermentation by ( PASTEUR LECT.), 728. Mycodcrmn nceti (PASTEUR LECT.), i21. Myricetin, occurrence of, in the leaves of Rhzss Cotinus (PERKIN), 1136, 1197 ; P., 1897, 170. Myrobalans, composition and dyeing properties of (PERKIN), 1137 ; P., 1897, 170. oxidation of corydic acid - (DOBBIE _ _ and N. 155. Naphthalene, space formula for (COLLIE), 1017. Naphthalene, 1 : 1’-dichloro-, conversion of, into 1 : 4’-dichloronaphthalene (ARMSTRONG and WYNNE), P., 1897, 154. 1 : 2’-dichloro-, from 1 : 1’ : 3-dichloro- naphthalenesulyhonic acid (ARM- STHONG and WYNNE), P., 1897,155. 1 : 2 : 1’-trichloro-, behaviour of, to- wards concentrated hydrochloric acid (ARMSTRONG and WYNNE), P., 1897, 15G. 2 : 3‘ : 1’-trichloro-, and 2 : 4’ : 2’-t~i- chloro- (ARMSTRONG ancl WYNNE), P.. 1897, 153.Naphthalene-1’ : 3’-disulphonic acid, 2-chloro-, conversion of’ the chloride of, into 2 : 3’ : 1’-trichloronaphthalene (ARNSTROSG and WYNNE), P., 1897, 153. Naphthalene-4‘ : 2’-disulphonic acid, 2-chloro-, conversion of chloride into 2 : 4’ : 2’-trichloronnphthalene (ARM- STROSG and WYNNE). P.. 1897, 153. MARSDEN), 664 ; J?., 1897, 102. - 225 .1 ; 18?7?.20- 7 . . . 7 In--- Methylstilbene, chloro-, its constitution, and dibromide (SUDBOROUGH), 2‘-Naphthalenesulphonic acid, 2 : 4‘4%- chloro-, barium and potassium salts, chloride, amide ( ARMSTROXG and ^. WYNNF) -- . ._’ ’- P., 1897, - - 153. . _ - I , -. p3Iloro-, ana its olabrornlue (DUD- BOROUGH), 218, 224 ; P., 1897, 20. Methylterephthalic acid, preparation of, and its methylic salt (BENTLEY and PERKIN), 175 ; P., 1896, 79.Methyltetrahydroterephthalic acid (1 -methylcyclohexene-2 : 5-dicarbox!~lic acid) and i t s methvlir. salt (BENTLEY Y‘-napntnalenesulpaonic acid, a : ~‘-62- chloro-, and its potassium salt, chloride, and amide (ARMSTRONG and WYNNE), P., 1897, 153. a-Naphthalenesulphonic acids, effect of heat on (COLLIE), 1022. &Naphthol, nitration of (ARMSTRONG), P.. 1896. 281). ana rmtKm), i i u ; r., NYO, i Y. cryswiograpny 01 uerivatives 01 Methylt@oglycollic ._ %id_ _(~.2h~olactic I - - - (DAVIS), - - - P.: 1896, 233.. . acid) (UIXON), 634 ; Y., 1887, 8. Methyl-violet, electrical convection of, in solutions (PICTON and LINDER), 571. &Naphthol, I-bromo-, nitration of 3’-bromo-, snlphonation of (ARMSTRONG (ARMSTRONG), P., 1896, 230.and DAVIS), P., 1896, 231.INDEX OF SUBJECTS. 1233 B-Naphthol, I: 3’-dibronio-, conversion of, I Nitroso-compound, from camphoroxime 3’-bromo-l-nitro- (ARMSTRONG and a-Naphthylamine, action of sodainide on (TITHERLEY), 465 ; P., 1897, 45. B-Naphthylamine, yellow compound ob- ’ into 3’-brorno-B-naphthol (ARM- I (FORSTER), 199 ; P., 21. STRONG and DAVIS), P., 1896, 230. DAVIS), P., 1896 231. 0. Obituary notices :- Capt. Marshall Hall, 1204. tnined by action of diacetyltar- Henry A. Mott, 1204. taric anhydride on (COHEN and ‘ Tetsukichi Shimidzu, 1205. HARRISO~), 1061 ; P., ‘1897, 167. 3‘ : l-bromonitro-, acetyl derivative (DAVIS), P., 1896, 232. l-nitro- (DAVIS), P., 1896, 232. a- and B-Naphthylcarbamides and their acetyl and benzoyl derivatives (YOUNG and CLARK), 1200, 1202 ; P., 1897, 199. Nickel, occurrence of, in common mine- rals (HARTLEY and RAMAGE), 683 ; P., 1897, 11.Nickel alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 403. Nickel sulphate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 824. double sulphates of copper, cobalt and (SCOTT), 566 ; P., 1897, 71. Nickel ores and minerals, composition of ( HARTLEY and RAMAGE), 541 ; P., 1897, 13. iso-Nicotinic acid, 2 : 6-dichloro-, its acid chloride, amide, and ethylic salt, and its conversion into citr- aziuic acid, and the action of am- monia 011 it (SELL and DOOTSON), 1075, 1076 ; P., 1897, 167. tetrachloro-, its chloride, amide, and ethylic salt, and its conversion into trichloramino- and dichlorodiamino- pyridine (SELL and DOOTSON), 1078, 1080, 1083 ; P., 1897, 167. iso-Nicotinic acids, chloro-, conversion of, into chloropyridines and chlor- sminopyridines (SELL and DOOTSON), 1081 ; P., 1897, 167.Nitratine, gold in (LIVERSIDGE), 299. Nitration, notes on (ARMSTRONG), P., 1896, 230. Nitric acid, Nitric peroxide. See under Nitrogen. Nitrogen oxidation of ( RAYLEIGH), 181, 185; P., 1897, 17. Nitrogen iodide (MALLET), P., 1897, 55. Nitric peroxide, preparation of (COHEN molecular association in liquid Nitric acid, refractive power when dissolved in amplic nitrate or nitro- benzene (GLADSTONE and HIB- BERT), 828 ; P., 1897, 142. and CALVERT), 1052. (CROMPTOX), 934. William Henry Walenn, 1206. Theodore George Worr?iley, 1206. (Edema, malignant, bacillus of ( PASTEUR LECT.), 737 ; P., 1897, 80.Optically active crystals and enantio- morphism (POPE and KIPPING), P., 1896, 249. Orcinol, condensation of, with chloral (HEWITT and POPE), 1085. Osmotic pressure, association theory of (CROMPTON), 925 ; P., 1897, 109. Osyritrin, a glucoside from CoZpoon com- pressurn, its properties, hydrolysis, and its acetyl derivative (PERKIN), 1134 ; P., 1897, 170. Oxalacetic acid, ethylic salt, action of zinc and ethylic bromacetate on (LAWRENCE), 458 ; P., 1897, 65. Oxalacetic acid, sodio-,ethylic salt,action of ethylic chlorofumarate on (RUHE- MANN and HEMMY), 335; P,, 1897, 64. Oxazine dyes, oxidation of leuco-com- pounds of (GREEN), P., 1896, 226. Oximes, action of alkyl iodides on (DUNSTAN and GOULDING), 573 ; P., 1897, 76.B-Oxycellnlose, preparation of, nitration of, benzoate of (BULL), 1092-1095 ; P., 1897, 168. Oxygen, influence of platinum on the combination of, wit11 hydrogen (FRENCH), P., 1897, 52. Oyster shells, gold in ( LIVERSIDGE), 298 ; P., 1897, 22. Ozone, influence of moisture on the formation of (SHENSTONE), 472 ; P., 1897, 2. P. Pasteur memorial lecture ( FRANKLASD), 683 ; P., 1897, 79. Pasteurisation (PASTEUR LECT. ), 724 ; P., 1897, 80. Pentacarbon rings, synthesis of (JAPP and LANDER), 123 ; P., 1896, 107. Pentacetylmaclnrin anhydride (PER- KIN), 186 ; P., 1897, 5. Pentane, normal, vapour pressures spe- cific volumes, and critical constants Of (YOUNG), 446 ; P., 1897, 58.1234 INDEX O F SUBJECTS. iw-Pentane, physical constants of Phenylethylthiohydantoin (DIXOX), ( I ~ O T r ~ ~ ~ n d T r i o n r A S ) , 445; P.,1897,58.’ 636 ; I?., 1897, 9. Pentanes, separation of, from Aniericun Phenylhydrazine, action of sodamide on petr’oleuin (YOIJNG and THOMAS), I (TITHERLEY), 461 ; P:, 1897, 45. 440 ; P., 1897, 58. sodium derivative of (TITHEIILEP), Pentoses, relationship of, to yeast l’., 1897, 151. Periodic system of the elenients (DEELEY), P., 1896, 185. Persian berries, the constitnen ts of ( P ~ r e ~ r r ; and MARTIN),, 819 ; P., 1897, 139. Petroleum, Amcrican, separation of pen- tanc and iso-pntane from (YOUXG and Phenanthraquinone, behaviour of, towards hydriodic acid (JAYP and FISDLAY), 1118 ; P., 1897, 169. Phenanthrone (JAPP and FISDLAT), 1115 ; I’., 1897, 169. B-Phenanthrylamine, hydrochloride (JAW and FISDLAY), 1123 ; P.1897, 169. /3-Phenanthrylic acetate (JAPP and FIXDLAT), 1122 ; P., 1897, 169. oxidc, and its picrate and methylic drrivative (JAPr and FINDI,AP), 1119 ; I?., 1897, 169. iso-Phene thylmandelic acid (J AI’P and LANDER), 137 ; l’., 1896, 107. o- and p-Bhenetolazophenols, hydro- chlorides, acetyl, benzoyl and benzene- sulphonic derivatives (HEWITT, Phenol, freezing point of dilute aqueous solutions ot (WILDERMANE), 800 ; l’., 1897, 139. sodium derivative of, oxidation of by fused caustic soda (COLLIE), 1022. Phenol, .m-nitro-, nitration of (COLLIE), 1022. Phenylallylthiocarbimide, action of chloracetamideon (DIXON), 632 ; l’., 1897, 8. Phenylallylthiohy dantoin ( DI xos ), 6 32, 633 ; P., 1897, 8. Phenylazocarbamide, condensation of, with benzaldeliyde ( YOUXG and AXNAELE), 201 ; P., 1896, 246. Phenyl benzyl ketone.See Deoxy- benzoin. Phenylbenzylthiohydantoin (DIXOK), 631 ; l’., 1897, 8. Phenyl-up-dibromopropionic acid, pseudoracemimi of (KIPPIXG and POPE), 1001 ; P., 1897, 136. Phenyldimethyl thiohydantoin ( D I XOY ) , 635 ; P., 1897, 9. 5-p-Phenylenebis-3-hydroxy-l-phenyl- triazole (Yorrsa arid AKNABLE), 217 ; l’., 1896, 246. (CROSS, 1:EVAS and SMITH), 1008 ; TITOhlAh), 440 ; P., 1897, 58. RIOORR, and PITT), P., 1897, 157. 461 ; P., 1897, 45. Phenylhydrazone, CI8Hl6O6N2,, from the condensation product of etliylic actonedicarboxglate (JERDAS j, 1113. 1 -Phenyl-3 -me thyl-fi-pyrazolone-4- acetic acid aiid its ethylic salt (RUIIE- Phenylmethylthiohydantoin, its cousti- tution, and the action of baryta water on it (Drsoh-), 629, 630 ; P., 1897, 8.aa-Phenylmethylthiourea, action of ethylic monochloracetate on (DIXON), 631 ; P., 1897, 8. Phenylnitrocarbinol. See Benzylic alco- hol, a-nitro-. Phenylsemicarbazide, benzoyl derivative of, the two probable isonierides of (Yousc and ASKABLE), 202 ; P., 1896, 246. oxidation of the condensation products of, with w- and p-nitro-benz- aldehyde, with nz-toluic aldehyde, with cinnamaldehyde, and with terephthalic aldehyde (YOUKG and ANSABLE), 203 ; l’., 1896, 246. Phenylsulphonic chloride, action of lead thiocyanate on (DIXOK), 640. Phenylthiocarbimide, from plienyl thio- hydantoin and carbon b i d p h i d e (DIXOS), 628 ; P., 1897, 7. Phenylthiocarbimidoglycolide ( DIXON), 626 ; l’., 1897, 7. Phenylthiohydantoin, its constitution, and the action of hydrochloric Acid and of carbon bisnlphide on (DIXON), Phloretin, constitution of, and its acetyl derivative ( PERKIX and NARTIS), 1152, 1153.Phloretindisazobenzene and its acetyl derivative ( PERKIN and MARTIN), 1151 ; P., 1897, 172. Phloretindisazo-o-toluene and -11-toluene (PERKIX and MARTIS). 1151, 1152 ; P., 1897, 172. Phloroglucinol, from tlie decomposition of apigenin (PERKIN), 809 ; P., 1897, 54, 135. synthesis of (JERDAS), 1108; P., 1897, 168. identification of (JERDAX), 1114. Phloroglucinolazobenzene, melting point and acetylisation of ( PERKIN), 189, 190 ; P., 1897, 5. Phloroglucinoldisazobenzeneazo-nz- nitrobenzene (A. G. PERKIN), 11% ; P., 1897, 173. M A X 3 alld HEMMY), 332 ; P., 1897, 63. m i , 626, 628, 629; P., 1897, 7.1NUE;X Or' Phloroglucinol-o-trisazoanisol and tris- azobenzene (A.G. PERKIS), 1154, 1155 ; Y., 1897, 172. YHOTOCHENISTRY :- Light, Pction of, on highly purified chlorine (SHENSTONE), 487 ; 1'. , 1897, 2. coloration produced in a solution of tiitrobenzene i n sulphuric acid on rxposure to (FRIswELL), P., 1897, 145. Rontgen rays, photographs of gold- sodiunl alloys ( HEYCOCK and NEVILLE), P., 1897,-105. Rotatory power, of aniylic glycerates, diacet ylgl ycerates and dihe II zoyl- glycerates (FRANKLAYD and PRICE), 253 ; P., 1897, 9. of salts containing the same active group (CROMY~OY), 946 ; P., 1897, 111. Multirotation, cause of ( RROWN and PICKEKING), 769 ; P., 1897, 130. Refraction of dissolved snhstances, iiifliience of the nature of the solvent on the (GLADSTOKE and HIBBEI~T), 826 ; P., 1897, 142.of potassium, ruhidinni, and czsiiim sclenates in solution (TVTTOK), 911 ; P., 1897, 117. of potassium sulphate in solution (TUTTON), 913 ; P., 1897, 117. of crystalline salts (TUTTON), 235 ; P., 1897, 10; (POPE), P., 1897, 11. of salts in the crystalline and dis- solved states (GLADSTONE nnd HIBBERT), 823 ; P., 1897, 141. Refractive index of casium, rubi- dium, and potassium selenates (TTJTTON), 876, 881, 888; P., 1897, 116. Spectroscopic analysis o f aluininium C O ~ ~ O I I I I I ~ S , steel, and Stassfurth minerals ( HARTLEY and RAMAGE), 547 ; P., 1897, 46. of conimon ores atilt miiierals (HARTLEY and RAMAGE), 538 ; P., 1897, 11. Phthaleins, oxidation oflenco-componnds of (GREEN), P., 1896, 226. y-Picoline (4-methziZpyridilte), pcnta- chloro- (SELL and DOOTSON), 1080 ; P., 1897, 16i.Pinene, hydrobromide, behaviour of, towards phosphorus trichloride and bromine (MARSH and GARDXER), 287 ; P., 1896, 187. d-Pinene, behnvionr of, towards phos- phorous trichloride and bromine (MARSH and GARDKER), 287; P., 1896, 187. Pinophanic acid, silver salt ( GILLES and EENWICK), P., 1897, 65. Plants, marine, gold in ( LIVERSIDGE), 298 ; P., 1897, 22. Platinum, nuggets, crystalline structure of (LIVERSIDGE), 1129; P., 1897, 22. Platinum alloys with silver, solubility of, in nitric acid (SPILLER), P., 1897, 118. with zinc, freezing points of (HES- COCK and NEVILLE), 421. Polymerisation. ( HARCOUILT), 595. Pomegranate, rind composition and dyeing propeyties of (PERKIN), 1137 ; P., 1897, 170.Porcelain, permeability of, to furnace gases (ROSE and JERDAN), 43 ; P., 1896, 61. Potassium, occurrence of, in common iriiuerals (HARTLEY and KAMAGE), 533 ; P., 1897, 11. Potassium cobaltite (MCCOXXELL and HASKS), S S i ; P., 1897, 62. pernianganate action on sulphurous acid of' (DYMOND and HUGHES), 314 ; P., 1897, 42. hydrogen phosphate, nitrate and di- chromate, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 824. selenate, crystallograpliy and physical properties of (TUTTON), 846 ; P., 1897, 115. tliiocyanate, action of sulphuric acid on (CHATTAWAY and STEVENS), 61 0 ; P., 1897, 87. Presidential address (VERNON HAR- COURT), 592 ; P., 1897, 80. Propaldehyde, formation of (COHEX and CALVEI:~'), 1051. Propionamide, action of sodatnide on (TITHERLET), 467 ; P., 1897, 46.Propionic acid, a-homo-, ethylic salt, ac.tion of ethylic sodio-acetoacetate on (SPRANKLING), 7162 ; P., 1897, 173. Propionic bromide, a-homo-, action of lead thiocyanate on (DIXON), 633. P r opionylthiocarbamide, a-bromo-, and action of aniline and o-toluidine, methylaniline, and benzylaniline on (DIXON), 633, 634, 635; P., 1897, 8. iso-Propoxysuccinic acid, isopropylic salt ( PURDIE and LANDER), P., 1896, 221. Go-Propylic alcohol, hydrates of (THo~wE), 920 ; Y., 1897, 150. Protocatechuic acid, from the action of sodium hydroxide on apigenin (%I:- Klh'), 811 ; l'., 1897, 138. Pzcnicrc Gmnatuin, composition of the friiit rind of (PERKIN), 1137 ; P., 1897, 170.1236 INDEX OF SUBJECTS. Pyridine, space formula for (COLLIE), 1018. derivatives, production of, from ethylic 8-aminocrotonate (COLLIE), 299 ; P., 1897, 43.Pyridine, 2 : 3 : 5 : 6-tetmchloro- and pcntachloro-, dichloramino- and tri- chloramino- (SELL and DOOTSON), 1081, 1082, 1083 ; P . , 1897, 161. Pyrites (iron pyrites), composition of (HARTLEY and RAMAGE), 542 ; P., 1897, 13. the decomposition of (CALDECOTT), P. , 1897, 100. Pyro-+-aconine and Pyro-#-aconitine (DUNSTAN and CARR), 358 ; P., 1895, 154. Pyroamaric acid, See By-Diphenyl- butyric acid, Pyronetricarboxylic acid, ethylic salt (RUHEMANN and HEMMY), 336, P., 1897, 64. Q. Quercetin, from Gambier catechu and Acacia catechu (PERKIN), 1135. occurrence of, in Bumex obtusifolius ( P ~ I c I N ) , 1199 ; P., 1897, 198. production of, by hydrolysis of osyri- trin (PERKIN), 1133. QtLercus Bgilops, composition of the fruit of (PERKIN), 1137; P ., 1897,170. Quercm infectoru6, con] positioil of gall - nuts of (PERKIN), 1137; P., 1897, 170. Quinoline-dyes, oxidation of leuco-com- pounds of (GREEN), l'., 1896, 226. Quinone (benzoquinoize), preparation of (FRANCIS), 423 ; P., 1897, 63. o- and p-Quinonoid structure in colour- ing matters (GREEN), P., 1896, 226. R. Babies, protective inoculation for (PAS- Racemism and Pseudoracemism (KIP- PING and POPE), 989 : P., 1897, 135. Besorcinol, freezing points of solntions of carbamide and (U'ILDERJIANN), 750 ; P., 1897, 119. condensation of chloral with ( HEWITT and POPE), 1084 ; P., 1897, 167. Rhamnazin, constitution, dyeing pro- perties, decomposition of by alkalis, and tetramethylic ether (PERKIN and MARTIN), 819-821 ; P., 1897, 139.Bhodanic acid, from phenylthio- hydantoin and carbon bisulphide (UIXON), 628 ; P., 1897, 7. TEUR LECT.), 742 ; P., 1897, 80. Bhus Cotinus, the composition of catech from (PERKIN), 1136 ; P., 189'7, 170. the colouring matter and glucoside of (PERKIN), 1196, 1197 ; P., 1897, 198. Ahus rhodantlzeina (yellow c e d a ~ ) , occur- rence of fisetin in (PERKIN), 1194; P., 1897, 198. Rhus tinctoyia, colouring matter of (PERKIS), 1120 ; P., 1897, L98. Rock-salt, gold i n (LIVERSIDGE), 298 ; spectroscopic analysis of ( HARTLEY and carbinol) hydrochloride, electrical con- vection of, in solutions (PrcTox and LINDER), 571. Rubidium, occurrence of, in common minerals ( HARTLEY ancl RAMAGE), 533 ; P., 1897, 11. action of ammonia on (TITHEHLEY), 469 ; P., 1897, 46.Rubidamide, ancl the actiori of heat, of water, and of acetoxime on it (TITHKRLEY), 469 ; I?., 1897, 46. di-Rubidammonium, and the action of heat on it (TITHERLEY), 469. Rubidium selenate, crystallography and physical properties of (TUTTON), 846 ; P., 1897, 115. Rumex obtusifolius, occurrence of querce- tin in (PERKIN), 1199 ; P., 1897, 198. P., 1897, 22. RAMAGE), 550 ; P., 1897, 47. Rosaniline (triarninodiplzeizyltolyl- S. Saffranine dyes, oxidation of leuco-com- pounds of (GREEN), P,, 1896, 227. Salicylic acid, sodium salt of, formation of (COLLIE), 1022. Salts, crystalline, refractive powers of (TUTTON), 235 ; P., 1897, 10. Selenium, estimation of,iri alkali selenates (TUTTON), 848. Shellac, electrical convection of, in emul- sions (PICTON and LINDER), 571.Siderites, composition of ( HARTLEY and RAMAGE), 539 ; P., 1897, 12. Silicic acid, electrical convection of, in solutions (PICTBN and LINDER), 571. Silkworm diseases ( PASTEUR 1,ECT. ), 733 ; P., 1897, 80. Silver, occilrrence of, in common mine- rals (HARTLEY and RAMAGE), 533 ; P., 1897, 11. in natural s;iline deposits and marine plants (LIVERSIDGE), 298 ; P. , 1897, 22. ingots, crystallirie structure of (LIVER- SIDGE), 1130 ; P., 1897, 22.INDEX OF Silver-alloys with platinum, solubility in nitric acid (SPILLER), P., 1897, 118. with zinc, freezing points of (HEYCOCK and NEVILLE), 407 ; P., 1897, 61. Silver amalgams, heat of formation and specific heat of ( LITTLETON), P., 1896, 220. Silver hydroxide, electrical convection of, i n solutions (PICTOK and LIXDER), 571.Sodium, occurrence of, in common mine- rals {HARTLEY and RAMAGE), 533 ; P., 1897, 11. Sodamide, action of ethylic iodide, of ethylenic dibromide, chlorobenzene, quinondichlorimide, carbon hexa- chloride, aniline, diphenylamine, 8-naphthylamiue, formamide, acet- aniide, propionamide, and benzamide on (TITHERLEY), 460-467 ; P., 1897, 45, 46. Sodium alloys with gold, structure of (HEYCOCK aiid NEVILLE), P., 1897, 105. Sodium, relative quantities of dextro- and 1;evo-crystals deposited from op- tically active solutions of (POPE and KIPYING), P., 1896, 249. nitrate, refractive powers of solid and dissolved (GLADSTONE and HIB- Solanaceous alkaloids, gold salts of the Solubility of racemic and pseudoracemic substances ( KIPPING and POPE), 998 ; P., 1897, 136.of potassium, rubidium, and cmium selenates in water (TUTTON), 850; P., 1897, 115. Solutions, Dalton’s law in (WILDER- MANN), 743 ; P., 1897, 119. influence of molecular association on the properties of (CROMPTON), 925 ; P., 1897, 109. molecular depression of freezing point in dilute (WILDERMANN), 796 ; P., 1897, 139. of colloidal substances, electrical convection in (PICTON and LIEDER), 568. of electrolytes, molecular association theory of’ the properties of (CROMP- dpontaneous generation ( PASTEUR LECT.), 716 ; P., 1897, 79. Staphylococcz6s pyogenes, discovery of (PASTEUR LECT.), 737 ; P., 1897, 80. Starch, electrical convection of, in soln- tions (PICTON and LINDEI~), 571. action of diastase on (LING and BAKER), 508, 513 ; P., 1897, 3. BERr), 824.(JOWETT), 679 ; P., 1897, 136. TON), 941 ; P., 1897, 110. IUB JECTS. 1237 Starch, hydrolysis of, by diastase, experi- mental methods used in the estima- tion of the solid products from the solution-density, and limits of accu- racy in the methods used (BROWN, MORRIS and MILLAR), 72, 99, 100, 106 ; P., 1896, 241, 242. hydrolysis of, by diastase products of, determination of specific rotatory power of; relation of [ ~ ] j to [ uID, and of sp. rot. power and cupric-reducing powers, cupric-reducing power of, and solution densities of (BROWN, MORRIS and MILLAR), 79, 84, 90, 94, 115 ; P., 1896, 242. thermochemistry of hydrolysis of, by malt extract, takadiastase,saliva, and pancreatin (BRoWNand PICKERING), 785 ; P., 1897, 130. soluble, specific-rotation of (BROWN, MORRIS and MILLAR), 114 ; P., 1896, 243.solution-density of (BROWN, MORRIS and MILLAR), 78 ; P., 1896, 242. S tassfur t h i te, spectroscopic analysis of (HARTLEY and RAMAGE), 550 ; P., 1897, 47. Stilbene (s-dipheizy Zethyleite), preparation of (SUDBOROUGH), 221. dibromide, preparation of (SUD- BOROUGH),. 221. Stilbene? dibromo-, chloro-, chlorobromo- and dinitro- (SUDBOROUQH), B-chloro-, preparation of, and its di- bromide and dichloride ( SUD- BOROUGH), 220, 221, 222 ; P., 1897, 20. Straw, barley, fermeiitation of the hydro- lytic products of (CROSS, BEVAN and SMITH), 1007. Streptococcus pyogenes, discovery of (PASTEUR LECT), 737 ; P., 1897, 80. Strontium, occurrence of, in common minerals ( HARTLEY and RAMAGE), 533 ; P., 1897, 11. Substance, C,,H,,O,,, from feirnen tatioii of isomaltose, and osazone of (LING and BAKER), 521 ; P., 1897, 3, 4. C16H,,02, from iso-cinnamenylman- delic acid on heating (JAPP and LANDER), 135 ; P., 1896, 107.C,,H,,O,, from anhydracetonebenzil- carboxylic acid on oxidation (JAPP and LANDER), 143. C,,H1,O,(N0OH), from a-anhydro- benzillevulinic acid and hydroxyl- amine (Jam and MURRAY), 149. C28H1803 from the oxidation of phen- anthrone (JAPP and FINDLAY), 1121 ; P., 1897, 169. 218-223 ; P., 1897, 20.1238 INDEX OF SUBJECTS. Substance, C28Hp2K2, fkom dibenzoylcin- naniene and phenylhydrazine, ile- structive distillatioil of (JAW and TINGLE), 1148 ; P., 1897, 171. C34H2402, from anhydracetonebenzil and acetic anhydride (JAPP and LANDER), 130 ; P., 1896, 107. C48H38N405, from aiihydracetonebeiizil carboxylic acid and phenylhydrazine, ( J a r u and LAXDER), 143 ; P., 1896, 109. Succinic acid produced in alcoholic fermentation(PA8TEUR LECT.), 713. Sucrose (saccharose, ca?~c-sugar), heat of dissolution of ( BP~OJVN and PICK- EKING),. 769. heat of inversion of, by invertase 1897, 131. heat of transformation of the a- into the 8 - variety (BROWN and PICKERING), 768. freezing points of solutions of mixtures of carbamide and (WILDERMANN), 750 ; P., 1897, 119. influence of, 04 the rate of formation of carbamide (WALKER and KAY), 506 ; P., 1897, 76. Sugar, C,H,,O,, from action of heat on glycollic aldehyde (FENTON), 376 ; I’., 1897, 63. Sugar, invert-, anhydrous, solutioii - density and cupric-reducing power of (BROWN, MORRIS, and MILLAR), 278, 280 ; P., 1897, 4.Sulphanilic acid, actioii of bromine on (EVANS), P., 1897, 235. Sulphocamphoric acid, its salts, and anhydride, and bromide aiid chloride of the latter ( LAPWORTH andliIPIJING), 8 ; P., 1896, 216. Sulphocamphylic acid, fusion of, with potash (W. H. PERKIN, jun.), l’., 1896, 189. Sulphur, electrical convection of, in solutions (PICYON and LINDEK), 571. Sulphurous anydride, reaction of lead with (JENKINS and SAIITH), 672 ; P., 1897, 104. Dithionic acid, formation of, by the oxidation of sulphurous acid by potassium perniangnriate (DYMOND aiid HUGHES), 314 ; P., 1897, 42. Sumach, South African, conipositioii of, and amount of catechcol-tanniii in ( PERKIN), 11 32 ; P., 1897, 170. Swine measles, inoculation for (PASTZUR Sylvite, gold in (LIVERSIDGE), 298 ; P., 1897, 22.spectroscopic aiialysis of ( HARTLEY and RAMAGIC), 550 ; P., 1697, 47. (BROWN aiid PICKEILING), 792 ; P., LECT.), 740 ; P., 1897, 80. T. Tachyhydrite, spectroscopic analysis of (HARTLEY and RAYAGE), 5 5 0 ; P., 1897, 47. Tannin glucoside, froin South African sumach (PEBKIN), 1132. Tannins, rclationship of, to accompanying colonring matters (PERKIN), 1137. Tap, vacuum, improved (SHESSTONE), 480 ; P., 1897, 3. cl-Tartaric acid, refractive powers of solid and dissolved (GLADSTONE and HIBBERT), 824. fermentation of (PAsrEult LECT. ), 697. &Tartaric acid (mesotartaric acid), forma- tiou of (PASTEUR LECT.), 702. Racemic acid, formation of, froni dextro- and Izvo-tartaric acid resolution of, by means of the quinicine and ciiichonicine salts (PASTEUR LPCT.), 694.ammonium salt of, fermentation of sodium ammonium salt, separation of, into active forms (PASTEUK LECT.), 688. Tartaro-S-naphthyl-amide and -anil (COHEK aiid HAI~RISON), 1062. Terephthalaldehyde, oxidation of the coiideiisation product of, with phenyl- semicarbazide (YOUNG and ANNABLE), 217 ; P., 1896, 246. Ter?t~inalia chcbicln, composition of the unripe fruit of (PERKIS), 1137 ; P., 1897, 170. Tetracet-ethylenediphenylene-p- tetr- amide (FRANCIS), 424. 2 : 4 : 2’ : 4’-Tetrahydroxydiphenylacetic acid, barium and zinc salts of 1897, 168. lactone o f ; its molecular weight, and acetyl, benzoyl, and sodium deriva- tives (HEWITT and POPE), 1084, 1087, 1089 ; P., 1897, 168. Tetrahydro-pxylic acid (1 : Z-climethyZ- cyclohezei~e-4-cnrbozylic acid) and its ethplic salt (B3r;TU’TLEY and PERKIN), 157, 172 ; P., 1896,.79.Tetrahydroxylic acid (1 : 3-climethyl- cycloheze uc-4-earboxylic acid) and its ethylic s d t (BENTLEY and PERXIN), 161, 173, 175 ; P., 1896, 79. Tetraphenylazine (Larwent’s A?iinroiie), preparation of, from beiizaldehyde and magnesium nitride (SNAPE), 528 ; P., 1897, 50. Tetraphenylenefurfuran ( JAPP and FINDLAY), 1120 ; P., 1897, 169. (PAYTEUK LECT.), 690. (pAS‘TEUR LEOT.), 697. (HEWITT and POPE), 1089 ; P.,INDEX OF SUBJECTS. 1239 Thallium, occurrence of, in eonimon minerals (HARTLEY and RAXAGE), 533 ; P., 1897, 11. Thallium alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 395 ; P., 1897, 61. THERMOCHEMISTRY :- Heat, specific, of silver .amalgam Heat of fusion, connection of melting point, density and (CKOMPTON), 929 ; P., 1897, 110. of zinc (HEYCOCK and NEVILLE), 403 ; P., 1897, 61.Dissociation pressure of alkylamnio- nium h ydrosulphides (WALKER and LUMSDEN), 428 ; P., 1897,48. Thermochemical data, for acids and bases in dilute aqueous solution and electrolytic dissociation 111. of alkylammonium hydrosulphides (WALKER and LUXISDEN), 439 ; P., 1897, 48. of formation of carbamide from am- monium cyanate (WALKER and KAY), 508; P., 1897, 76. of silver anialgarn (LITTLETON), P. , 1896, 220. of the hydrolysis of starch by vegetable and animal diastase, and of cane-sugar by invertase (BROWN and PICKERING), 783 ; P., 1897, 131. Heat of solution of dextrose, maltose, levnlose, milk-sugar, and cane-sugar (BROWN and PICKERING), 769. Thiazine-dyes 2nd Thiazole-dyes, oxida- tion of lenco-compounds of (GREEN), P., 1896, 226.Thiourea, from action of sulyhuric acid on potassium thiocyanate (CHATT- 1897, 88. action of chloracetanilide on (DIXON), 626 ; P., 1897, 6. Tin, ingots, crystalline structure of (LIVERSIDGE), 1130 ; P., 1897, 22. Tin alloys with zinc, freezing points of (HEYCOCK and NEVILLE), 392; P., 1896, 61. Tin ores, composition of (HARTLEY and RAMAGE), 541 ; P., 1897, 13. Tolane, and its dibroinide, preparatioii &chloride, cis and tram forms of (SUD- .m-Tolualdehyde, oxidation of the con- densation products of, with phenyl- semicarbazide (YOUSC, and ASNABLE), 313 ; P., 1896, 246. (LITTLETON), P., 1896, 221. (CROMPTON), 951; P., 1897, AWAY alld STEVEKS), 611, 612 ; P., of (SUDBOROUGH), 221. BOROUGH), 222.Toluene, nitration of (FRISWELL), Y., p-Toluidine, yellow coinpouull obtained by action of diacetyltartaric anhy- dride on (COHEN and HAKRISON), 1061 ; P., 1897, 167. sodium derivative of ('TITHERLEY), 465 ; P., 1897, 45. o-Tolylethylthiohydantoin and action of alkali on (DIXON), 636 ; P., 1897, 9. o-Tolylmethylthiohydantoin and actioii of alkali on (DIXON), 634; P., 1897, 8. o-Tolylthiocarbimidoglycolide, from o- tolylthiohydantoin (DIXON), 623 ; P., 1897, 8. o-Tolylthiohydantoin, constitution of, and action of hydrochloric acid 011 (DIXON), 622, 625 ; P., 1897, 8. o-Tolylthiourea, action of ethylic chlor- acetate on (DIXON), 623 ; P., 1897, 8. Triacetylmaclurinazobenzene, produc- tion of (PERKIN), 188 ; P., 1897, 5. Triacetylphloretylcoumaiin ( PERKIS and MARTIN), 1151 ; P., 1897, 172.Tribenzoylapigenin, the properties of Triethylluteolin. See Luteolin triethylic other. 4 : 5 : 6-Trihydroxypicoline and its salt,. (LAPWORTH and COLLIE), 843 ; P., 1897, 146. aaS-Trimethylglutaconic acid (hcxyllcnc- dicarboxylic acid), and its silver, copper, and ethylic salts ( PERKIX and THORPE), 1182 ; P., 1897, 72. iso-Trimethylglutaconic acid, and its silver, barium, calcium, and copper salts, anhydride, anilic a d , anil (PERKIN and THORPE), 1184. ua8-Trimethylglutaric acid (kccat~cdi- carbozylic acid;, silver, lead, mercury salts, anilic acid, anhydride ( PEIXIS and THORPE), llS7; P., 1897, 7 2. 8-bromo-, ethylic salt (PEKKIX . ~ n d THORPE), 1181. a- and B-dibronio- (PERIilll' and THORPE), 1184. 8-chloro-, ethylic salt (PERKIX and THORPE), 1180 ; P., 1897, 73. 8-cyano-, ethylic salt (PERKIN and THORPE), 1189 ; P., 1897, 73. Trimethylluteolin. See Luteolin trimethyl ether. 2 : 4 : 6-Trimethylpyridine and its salts (COLLIE), 308 ; P., 1897, 43. aaS-Trimethyltricarball ylic acid( hcxanc- diccwboxylic acid), synthesis of ; iden- tity of, with camphoronic, aci(1 (W. H. PERKIX, jiiiir., and THOKPE), P., 1897, 73. 1897, 145. (PERKIN), 809 ; P., 1897, 54.1240 INDEX OF SUBJECTS. Triphenylmethane, bromo-, action of, on ethylic sodioacetoacetate and ethylic sodiomalonate (HENDERSON and PARKER), 676 ; P., 1897, 119. Triphenylmethane colours, oxidation of leuco-compounds of (GREEN), P . , 1896, 226. 1 : 3 : 4-Triphenylpyrazole ( JAPP and TIXGLE), 1148 ; P., 1897, 171. 2 : 3 : 5-Triphenylpyrroline,formation of, from dibenzoylcinnanienimide, and its oxidation (JAPP and TINGLE), 1146 ; P., 1897, 171. U. Unyarica gainbier, the coniposition of catechu from ( PERKIN), 1135. V. Valeraldehyde, formation of (COHEN and CALVERT), 1051. iso-Valerie acid, a-bromo-, action of etliylic sodioacetoacetate on (SPRANK- LING), 1164; P., 1897, 173. Valonia, composition and dyeing pro- perties of (PERKIN), 1137 ; p., 1897, 170. Vanillic acid from the hydrolysis of rhamnazin (PERKIN and MARTIN), 820 ; P., 1897, 139. Vanillin froni the hydrolysis of rham- nazin (PERKIN and MARTIN), 820; P., 1897, 139. Vapour pressures of normal pentane (YOUNG), 448 ; P., 1897, 58. Velocity of formation of carbamide from ammoniuni cyanate dissolved in aqueous alcohol (WALKER and KAY), 489 ; P., 1897, 75. of carbamide in presence of glycerol, cane-sugar, glycol, niethylic alcohol, and acetone (WALKER and KAY), 506 ; P., 1897, 76. Velocity of solution of zinc in acids i n presence of salts (BALL), 642; P., 1896, 235. Veratric acid (dinzethylprotomtechuic acid), formation of, from hydrolysis of aconitine (DUNSTAN and CARR), 356 ; P., 1895, 154. Veratryl-+-aconine, properties of, and its salts (DUNSTAN and CARR), 356; P., 1895, 154. Vinegar, manufacture of (PASTEUR LECT.), 721. Vinylic tribroniide, behaviour of, towards sodium ethoxide (GRAY), 1024 ; P., 1897, 140. Virus, attenuation of ( PASTEUR LECT. ), 739. Viscosity of mixtures of liquids (THORPE and RODGER), 360 ; P., 1897, 49. Volume, molecular, of potassium, rnbi- dium, and caesium selenates (TUTTON), 870 ; P., 1897, 116. W. Water vapour, influence of. on the forms- tion of ozone (SHENSTONE), 472 ; P., 1897, 2. Water, Sea, presence of oyidising agents (iodates) and gold in (SONSTADT), P., 1896, 236. Wechsler’s method for separating fatty acids, criticism of (CROSSLEY), 580 ; P., 1897, 21. Wine, diseases of (PASTEUR LECT.), 723. X. Xylic acid, reduction of, and separation of, from p-xylic acid (BESTLEY and PERKIN), 157, 161 ; P., 1896, 79. p-Xylic acid, reduction of ( BENTLEY and PERKIN), 157 ; P., 1896, 79. p-Xylyl methyl ketone, oxidation of (BENTLEY and PERKIN), 180; P., 1896, 79. Y. Yeast, multiplication of, in a saccharine solution (PASTEUR LECT.), 729. effect of oxygen on fermentation by (PASTEUR LECT.), 728. Z. Zinc, influence of dissolved salts on the rate of solution of, in acids (BALL), 642 ; P., 1895, 235. Zinc alloys with other metals, freezing points of (HEYCOCK and NEVILLE), 383 ; P., 1897,60. Zinc hydroxide, precipitation of iodine along with (RETTIE), P., 1896, 178. double sulphates of iron, coppel’, chromium, and (SCOTT), 566 ; P., 1897, 71.

ISSN:0368-1645    

DOI:10.1039/CT8977101216

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

INDEX OF SUBJEC’I’S. 1241 ERRATA. VOL. LXIX. (TRANS., 1896). Line 8” for “litmus ” rend “ phenolphtlialein.” 8 9 9 t , , , ‘ ‘ lacmoid paper. ” 17” after “acid” iitscrt “ t o lacmoid aper.” Page 1612 1640 1665 Page 78 80 83 100 101 101 VOL. LXXI. (TRANS., 1897). Line 2 for “ were ” read ‘‘ was.’’ 8 y y (‘ absolute ” r e d “ anhydrous.” s t 0.17657, rend ‘( 100 x 0.1765 >, ___-- l9 ’’ 0.6016 0’6016 ’ 28 ,, “ 2’047 9’ reat c c 100x2‘047 , 1’371 7; 5 *0798‘ 1.3717 x 5.0798 A c A C 114 23 & 24 ,, “ [ a ] j 3 . and [a]js.8” ~ c n d “ [a]j3.8G and [ a ] j 3 , 6 . 402 7 ,, “ We have (No. 2) ” rccccl ‘( We have not.” 423 6” ,, “ NH,*C,H,*NH*C,H,’NH*CGH,,4HCl ” rcnd 573 head line for “ ALKALOIDS ” rend “ IIALOIDS.” ‘‘ NH; C,H,*NH* C,H,*NH* C,H,* NH2, 4 HCI. ” ? 7 5“ ,, (‘ benzalcloxinie ” rend “ benzaldehvde.” 574 16 ,, “oxime” rend “ketone or aldehyde ” 578 i} ,, C ‘ A ~ I 9’ red ( 6 I.” ? > ” 1111 1112 ,, li} ,, “ (CH,),CN(CH,)O,HI,I, ” wad “(CH3),CN(CH3)0,HI,I. li*} for “ C,2Hl,05(OH)(COOCH,) ” rcnd “ C,,H,,05(OH)(COOCH3).” 23 ,, “ C,,H,Br,O,(OH)(COOCH,) ” ,, “ Cl,H,Br,05(~H)(COOCH3).“ $ 9 2for “C,,Hl,0,(OH)(COOC,H5)” rend “C,,H,,05(OH)(COOC,H,).” 4 P

ISSN:0368-1645    

DOI:10.1039/CT8977101241

出版商:RSC    

年代:1897

数据来源: RSC