摘要:

ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c. for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *.acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide. * From bottom.___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c.for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide.* From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c.for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide.* From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c. for (----,,yntl ‘‘ Calcdnted.Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide.* From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c.for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide.* From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL.LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c. for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02.” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide. * From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893). Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL.LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c. for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02.” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide. * From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.ERRATA. VOL. LXIII (TRANS., 1893).Page Line 761 T63 between lines and 4’ insert “ 60. Ueber Isodnlcit.’ BEI.., 11, 1197.” 763 18* delete “ during his absence in England.” line 4” f o r ‘‘ 60.” read “ 61.” 64 so 333 323 530 535 336 >, > ? 548 364 367 568 371 634 c;ii 7 ill VOL. LXV (TRASS., 1894). 12* fo,. ‘‘ a TelloKijh, crystalline nlnss ‘’ ,*erCd ‘* crj-atdhhg in fine: white 15 12 15 8 s* fop “ Claus so decided ’’ read “ Clam hrtd SO decided.” 3* for “ thery” read (‘ theory.” needles.’’ f o r ‘‘ corydalic acid ” rend ‘‘ corgdalhic acid.” f o r “ 230”” read “ 2133.” f o r “ 01414 ” read “ 0.1341 .” for “ sulphammonates ” read “ sulpliammonate.” 19” for “ methyl-orange 11” for “ IdentitT ” read “ Unitj.” 11 18 &c. for (----,,yntl ‘‘ Calcdnted. Rawhig.” read “ rosolic acid.” for “ acid of hydrogen salts ” mad *. acid 01- hydrogen d t s . ” “ Raschig. Calculated. Found. 3* for “ alkaline ” read “ alkali.” -,* for ’’ potassium salts ” rend ‘* potassium salt.” 8 7 11 17” f01* “ K, s d t ” read “K5 salt.” 3 f02. ” hydroxy-lead ’’ read “ hydrosp-lead salt.” 8 for “ near ” read “ slight.” 19” for ‘‘ (XHJ ” read “ (NH&.” 14* for “ these three crops ” read ‘* t h e e crop?.” 6 and 15, f o r “ brachypinacoid ” relrd ‘* macropinacoid.” 5 * for “molecular dispersion ” read “ xolecular refraction.” .3 for ‘* extremely soluble ” read “ extremely soluble :’ for “ as ’’ read ‘6 Of.” for “ the two” read (‘ two.” The numbers for (‘ Sulphu1- 1y shorrlcl be 16-50, 16.61, 3.ud 16-73; those @yen are for sulphur trioxide. * From bottom. ___ -- - - - _ - - hlARXISON ASD 8068, PBISTEBS IN ORDIKABY TO HER MAJESTY, ST. MAETIN’S LANE.

ISSN:0368-1645    

DOI:10.1039/CT89465FP001

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

9 II.-Fvrmation of Pyrroline Derivatives from Aconitic UCid. By S. RUHEMANN, B.D., M.A., and F. E. ALLHUSEN, B.A., Jesus College. THE experiments described in this paper are a continuation of the work on the conversion of fatty acids into pyridine derivatives, which has been the subject of several communications to this Society and to the Berichte. It may be pointed out that the transformation cf ethylic acetylcitrate and of ethylic aconitate into citrazinamide was the starting point of the enquiry, and we hare resumed the stady of aconitic acid with the object of further testing the view as to the constitution of pyridine deduced from the formation of the amide of dihydroxyisonicotinic acid, and of examining more carefully the substances which have been obtained from it., and which were de- scribed some time ago (Beer., 20, 3369 ; 21, 1247).The result of the experiments now recorded is the transformation of aconitic acid into pvrroline derivatives, brought about by the action of aniline on the et,hereal salt of dibromotricarballylic acid, obtained by combining ethylic aconitate with bromine. The aconitic acid was prepared by Hentzschel's method (J. pr. Chem., [ Z ] , 35, ZOS), which gave even a better yield than that indicated by the author; its ethereal salt, prepared in the usual manner, was then transformed into ethylic dibromotricarballylate in the following manner." 6.7 grams of bromine (a little more than the required quantity) were added in portions to a solution of 10 grams of ethylic aconitate in 20 grams of carbon tetrachloride, contained in a bottle, surrounded by cold water, and exposed to strong sunlight.The rapidity with which the halogen is taken up was found to depend on the intensity of the light, combination being complete in some of the experi- ments after 40 minutes, whilst in others an honr's exposure was required. In all cases, hydrogen bromide was formed, the amount increasing in proportion to the diminished intensity of the light. On some occasions, when part only of the bromine had been added to the mixture, and on account of absence of bright sunlight the opera- tion could not be completed the same day, dense fumes oE hydrogen bromide were evolved on opening the bottle, and the absorption of the remaining bromine was much delayed. After the carbon tetra- chloride and the small excess of the halogen had been distilled off on I owe the directions for the preparation of the ethereal salt of dibromotricarb- allylic acid to Mr. A.Michael, and I gladly avail mjself of this opportunity of expressing my thanks to h i m . 4 . R.10 RUHEMANN ASD ALLHUSEN : FORMATION OF the water bath, the residual yellow oil was heated in a vacuum at 150°, in order to remove the remainder. The ethylic salt t.hus ob- tained, amounting to 15 grams (theory requires 16.2 grams), was not distilled, as this causes it to undergo partial decomposition. Its density was 1.5354 at 21"/21" ; a n analysis was made of the addition product, purified in the manner described. 0.3730, by Carius' method, gave 0.3367 AgBr. Br = 38.41. C3HIBr,(COzEt), requires Br = 38.28 per cent.Action of Baryta on Ethylic Dibromotricarballylate. This action was studied with the object of displacing the halogen in the etbylic salt by hydroxyl groups, thus converting it into hydroxycitric acid, the acid which Pawolleck (Annalen, 178, 157) obtained by the action of lime on chloraconitic acid, the product of the addition of hypochlorons acid to aconitic acid. I t wm found, however, that under the influence of baryta the salt underwent decomposition, yielding barium bromide and the barium salts of oxalic acid and succinic acid. The ethylic salt was heated on a sand bath, with excess of an aqueous solution of barium hydroxide, in a flask attached to a reflux condenser ; the reaction took place very readily, the oil gradually disappeared, and a yellow precipitate was formed, which mas collected and washed with hot water until the liltrate was almost free from bayium.This precipitate consisted for the most part of barium oxalate, as was proved by an analysis of the acid obtained from it. The filtrate was freed from barium by dilute sulphnric acid, the solntion concentrated, and the crystals which separated as the solution cooled were washed with concentrated hjdrochloric acid and recrystallised from water. They were proved to be succinic acid by the ordinary tests, and by analpis of the acid and of its silver salt. The formation of oxalic and succinic acids from ethylic dibromo- tricarballylate by the action of baryta might be supposed t o involve the formation first of hydroxycitric acid, which then undergoes de- composition, as indicated by the equation VH(OH)*COOH F(OH)-COOH = YOoH + ~Hz*CooH C H2.C OOH COOH CHa-COOH' The fact, however, tha.t hydroxycitric acid is formed from chloro- citric acid by boiling it with lime water renders this explanation improbable, and leads to the view that baryta removes hydrogen bromide from the salt, and that the resulting bromaconitic acid,PYRROLINE DERIVATIVES FROM ACONITIC ACID.11 $Br*COOH Y*COOH undergoes decomposition as follows. , is transformed into hydroxyaconitic acid, which finally C H2.C 00 H fi(OH)*COOH C,*COOH + H20=FooH + I C H2* COOH CH2*COOH COOH CH,=COOH' This view is supported by the behavionr of one of the products formed by The Action of Aniliite on Ethylic Dibromtricarballylate. It was found that aniline acted on the ethylic salt a t the ordinary temperature with development of heat, and, after about an hour, aniline hydrobromide separated.The action, however, took place more readily on heating a mixture of the ethylic salt with an excess of aniline on the water bath, and was completed after an hour's diges- tion. The aniline hydrobromide was filtered off, washed with ether, and the excess of aniline extracted from the dark brown, ethereal iiltrate by shaking it with dilute sulphuric acid. On distilling off the ether, a dark, viscous oil remained, from which needles separated after standing several hours in a vacuum over sulphuric acid ; these were collected, washed with a little ether, and frequently recrysfal- lised from the same solvent, when colonrless needles were obtained, veig soluble in alcobol, and melting a t 87-88'.The substance was dried in a vacuum over sulphuric acid, and analysed. 0.2220 gave 0.1140 H20 and 0.5170 CO,. C = 63.50 ; H = 5.7. 0.2500 ,, 0.1288 ,, ,, 0.5845 ,, C = 63.74; H = 5.7. 0.2595 ,, 10.5 C.C. of moist nitrogen at 18" and 765 mm. N = 4.7. ClsH,,NOs requires C = 63.37 ; H = 5.61 ; N = 4-62 per cent. This compound, as shown below, is to be regarded as ethylic anhydroanilaconitate, and its constitution is expressed by one of the formuh The filtrate from this substance, after removal of the ether, was a dark brown, viscons mass from which no crystals separated even after several weeks. On attempting to distil it in a yacuum, decomposition fook place at a temperature above 300°, the mass charred, and a liquid passed over having a distinct cyanate odour; the distillate partially solidified to a mass of colourless crystals which, after re-12 RUEEMA" AND ALLHUSEN: FORMATION OF crystallisation from hot alcohol, melted at 235", and was recognised as diphenylcarbamide. 02495 gave 28.8 C.C.moist nitrogen at 19" and 760 mm. N = 13.26. CO(NH*C6H5), requires N = 13.20 per cent. If, however, the above-mentioned viscous, brown product was heated to a temperature of 250-260", a small quantity of colonrless crystals of diphenylcarbamide came over, whilst the liquid remain- ing in the flask solidified to a brown, crystalline mass. This, on crystallisation from alcohol, gave yellowish plates insoluble i n ether, but soluble in hot spirit.This substance melted at 181°, and, on analysis, gave numbers which agree with the formula CI6H1,No5. I. 0.2025 gave 0.1060 H20 and 0.4715 CO,. C = 63-50 ; H = 5.81. 10 C.C. moist nitrogen at 18" and 744 mm. N = 4.84. CvH,,NO, requires C = 63.37 ; H = 5.61 ; N = 4.62 per cent. It is isomeric with the substance melting at 87-88' (p. 11) ; its 11. 0.2330 ,, constitution, as shown below, may be represented by the symbol CO OC,H,. f-f R COOC2H5*C C-OH . v N*CGH5 The compound appears, therefore, to be a derivative of pyrroline, namely, ethylic phenylpyrrolonedicarboxylate. Bthylic Anhydroanilaconitate. The formula assigned to this substance (p. 11) are both in ac- cordance with the behaviour of the compound towards ammonia and alkalis. When lef5 in contact with concentrated ammonia, it was gradually dissolved, and, on adding hydrochloric acid to the solution, it became turbid, and the original substance separated in colourless needles melting at 87-88'.The ammoniacal solution, no doubt, contains the ammomium salt, E<COONH4, and the acid salt formed on acidifying then loses water, and the original snb- stance is reproduced. On boiling the substance with concentrated potash in a flask attached to a reflnx condenser, it dissolved, but zn oil soon separated, and was identified as aniline. Tbis action agrees with the formulm assigned to eihylic anhydroanilaconitate. The same decomposition takes place on heating the ethereal salt with baryta ; the products are aniline and a precipitate consisting of the barium salts of oxalic and succinic acids.The latter of these a cids was isolated, and identified by its reactions and by an analysis. NH.CeH5 COOC?H,*CH,.C*COOC,H,PYRROLINE DERIVATIVES ETEtOJI ACONITIC ACID. 13 The action of potash or baryta on ethylic anhydromilaconitate may be represented as follows. c<T*c6HH" (0H)COOH + CsH,*NHa. I I co q*COOH + 2H,O = $I*COOH CH,* C 0 OH C H2*C 0 0 H The hydroxyaconitic acid, however, simultaneously takes up molecule of water, and is resolved into oxalic and snccinic acids. Ethylk Phen y l p yrrolonedicarboxylate probably owes its formation to the presence of ethylic anilidoaconitate, c<COOC,H,, in the filtrate from the substance melt- C 0 0 C2H6* C H,*6*CO OC,H, ing at 87-88". This compound may be regarded as the first product of the interaction of aniline and ethylic dibromotricai-ballylate, which then loses one molecule of alcohol yielding either ethylic anhydro- anilaconitate or ethylic phenylpyrrolonedicarboxylate. That the view expressed above with regard to the constitution of the latter salt is correct is rendered probable by the change it undergoes when heated with ammonia and potash.Action of Amnntonia.-Strong aqueous ammonia dissolves the com- pound when left in contact with it for several horns, and a blood-red liquid is formed which gradually deposits red crystals, readily soluble in water. On adding hydrochloric acid to the red solution, however, the colonr disappears, and a yellowish precipitate is thrown down which is almost insoluble in water and in alcohol, and decomposes without melting when heated.I t was purified by dissolving it in ammonia, reprecipitating with acid, and washing with water. The substance was dried at 100" and analysed. I. 0.2230 gave 0.0835 H,O and 0.4815 COP C = 58-88 ; H = 4-16. 24 C.C. moist nitrogen at 18" and 753 mm. N = 11-58. C12Hl,,N204 requires C = 58.52 ; H = 4.06 ; N = 11.38 per cent. The results of the analyses indicate that this compound is the acid amide of phenylpyrrolonedicarboxylic acid. Its behavionr character- ises it as such, and its constitution will be represented by the formula COOH. C C*OH or by CONH2G C*OH. It ia readily dis- NH*CsBs 11. 0.2370 ,, COpyTH2.ff-gHz COOH #-#H \/ N*CsH5 \/ N°C6H5 solved by alkalis, and is precipitated unchanged on the addition of mineral acids. If boiled with potash, however, ammonia is evolved, and the alkaline solution then yields a precipitate of pyrrolonedi- carboxylic acid on the addition of an acid.14 PTRROLINE DERIVATlVES FROM ACONITIC ACID.Action of Potash on the Ethereal Salt.-The presence of a hydroxyt group in the ethereal salt follows from the fact that the pyrroline derivative is soluble in dilute alkalis, and that it is precipitated un- changed from the solution on adding an acid. If, however, the soln- tion is boiled with strong potash f o r about 30 minutes in a flask attached to a reflux condenser, hydrolysis takes place, and, on acidi- fying and cooling, almost colourless needles separate ; these are slightly soluble in cold and fairly easily in boiling water. The ethereal salt is also hjdrolysed by heating it with water for several hours, the yellow plates of the salt gradually disa,ppearing, and being replaced by colourless needles.These melt at 227", but decompose, On analysis, numbers were obtained which agree with those required bythe formula C0OH.C C-OR. COOH*g-EH \ / I. 0.2090 gave 0.0715 H20 and 04475 CO,. C = 5836 ; H = 3.80. 12-5 C.C. moist nitrogen at 16" and 755 mm. N = 5.82. 11. 0.2493 ,, C,2HJY0, requires C = 58.30; H = 3-65 ; N = 5.67 per cent. On heating pyrrolonedicarboxylic acid with lime, an oil having n distinct odour of pyrroline is formed ; this gives the characteristic test,, colonring fir-wood red, after it has been moistened with hydro- chloric acid. We intend to further study this acid and the pyrrolone formed from it. The behaviour of eihylic dibromotricarballylate with etbylic sodium malonate was found to be similar to that of the ethereal salts of bromomalonic acid and its homologues (Ruhemann, Ber., 26, 23563.To 1.2 grams of sodium, dissolved in 20-30 grams of absolute alcohol, were added 7.7 grams of ethylic malonate, and then 10 grams. of the ethereal salt of the dibromo-acid. Action readily took place, and was completed by heating for about 30 minutes on the water bath. On adding water, an oil separated, which was dissolved by agitation with ether, and the ether removed bg distillation. On standing over night, the oily residue deposited colourless needles, which, after recrystallisation from dilute alcohol, melted at 76'. 0-2150 gave 0.1345 H,O and 0.4175 CO,. C = 52.91 ; H = 6-95. CI,H,08 requires C = 52.83 ; H = 6.91 per cent. This substance is ethylic ethanetetracarboxylate, (C 00 C2E5) ,CH.CH( C 0 0 C,H,),, which Conrad and Bischoff (Annulen, 214, 68) obtained from ethylic chlormalonate and ethylic sodiomalonat e.PREPARAnON AND PROPERTIES OF BRONOLAPACHOL. 15 The filtrate from ethylic ethanetetracarboxylate consisted chiefly of ethylic malonate and aconitate ; their separation was effected by frac- tional distillation in a vacuum. The portion boiling between 184" and 186" under a pressure of 25 mm. was analysed. 0.2090 gave 0.1350 HzO and 0.4280 C02. Action takes place, therefore, according to the equation C = 55.84 ; H = 7-17'. C,,H,,06 reqnires C = 55.81 ; H = 6.97 per cent. - yHBr*COO C2H, - CHNa(Coo C2H5)z 4- C 0 0 C,H5*CH2*CBr*C 0 0 C2H5 CH( CO OC2H,), #H.COOC,H, CH( C0OC2H5), i- COOC2H5*CH2*C.COOCaH5 2NaBr + I I n conclusion, we express our best thanks to Mr. A. F. Shoycr, of Trinity Hall, for the help he has given us, more especially at the be- ginning of this work. Gonville and Caius College, Cambridge.

ISSN:0368-1645    

DOI:10.1039/CT8946500009

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

PREPARAnON AND PROPERTIES OF BRONOLAPACHOL. 15 111.-Prepuration a id Properties of Bromolcipctcl~ol. By SAMUEL c. HOOKER. IN my researches on the constitution of lapachol and its deril-atipes, I have shown that these substances are of peculiar interest, ot\-ing to the changes which readily occur in the quinone group, some of the componn& being derivatives of a-naphthaqninone, and some, deriva- tives of @-naphthaquinone. In order to furnish further examples of these changes, and in the hope of subsequently being able to formulate some general rules regarding them, I have prepared the compounds described in this paper. The preparation of dibromo-P-lapachone was described in a paper. recently presented to the Society (Trans., 1893, 63, 424) ; this com- pound, which can he readily obtained in comparatively large quanti- ties by following the directions there given, has furnished the material for this investigation.In a previous communication, I discussed at length the reconversion of bromo-,%lapachone into lapachol (Trans., 1852, 61, 615). I have EOW found that dibromo-p-lapachone may be, in like manner, readily converted into bromolapachol. The preparation of bromolapachol in this indirect manner is the more interesting because i t has so far proved impossible to obtain a simple bromine derivative of lapachol by the direct action of bromine.16 HOOKER : PREPARATION AND PROPERTIES I have previously called attention (Trans., 1892, 61, 621) to the Tery remarkable change which 13-lapachone undergoes in contact with concentrated hydrochloric acid, being fhereby quantitatively con- verted into a-lapnchone.It was also shown at the same time that a-lapachone can be quantitatively reconverted into /3-lapachone by merely dissolving it in concentrated sulphuric acid. Similar changes occur with the bromolapachones described in this paper. The relation hetween these compounds is shown in the following formulae. ~r-Bromo-~-lapachone.# nz-Bromo-a-lapachone. mz-Bromo-B-lapachone is an orange-red compound which melts a t about 205" ; it interacts very readily with orthotoluylenediamine yielding a yellow azine. nS-Brom-a-lapacbone is a pale yellow snbstance which fuses at 172*5-173*5". 0 On boiling with dilute aqueous alkalis, both cornpounds are readily converted into the same bromhydroxyhydrolap-achol, EXPERIMENTAL PART.0 To prepare bromolapachol, 10 grams of finely-powdered dibromo- p-lapachone are moistened with a 10 per cent. solution of sodium hydr- oxide: and very thoroughly ground to a paste; the quantity of the alkaline solution is then gradually increased until 100 C.C. in all have been used, t,he mixing being continned so as to insure entire freedom from lumps. The solution with the substance in suspension is then transferred to a small flask, 10 grams of zinc dust are added, and the flask is loosely corked, and slightly agitated at intervals during an hour, after which it,s contents are rinsed out and diluted with about * This compound is isomeric with the bromo-6-lapachone preViOUdy described (!ham, 1892, 61, 638), obtained by the action of bromine on lapachol. I hare added bhe prefix rtx to its name for purposes of distinction, intending to wnvq by the same that the bromine is situated in the naphthalene ring, but that ita exact position has yet to be determined.OF BROXOLAPACHOL.17 1500 C.C. of water. The zinc dust is separated as completely as pos- sible by decantation, and the diluted solution is then oxidised by drawing air through it by means of an ordinary filter pump. When the oxidation, which usually takes some hours, is complete, the solution is of a rich claret colour, and can be readily filtered off from the green, orange, and other particles in suspension. The solution should remain absolutely bright after filtration: if it passes through the filter paper with difficulty, or if a film forms over its surface, the oxidation is incomplete and should be continued.When thoroughly oxidised, the solution is poured" into an excess of dilute hydrochloric acid, and the resulting light yellow precipitate is washed and dried. Bromolapachol is thus obtained in a pure form, the yield being 6 grams. The reactions involved in its formation are precisely similar to those concerned in the reconversion of bromo-P-lapachone into lapachol (Tmns., 1892, 61, 615 and 642), and need no further explanation here. Bromolapachol may be obtained crystallised in leaflets very closely resembling lapachol, by boiling the substance, as a.bove obtained, with a quantity of alcohol insufficient to dissolve it. When a larger quantity of alcohol is used and the substance passes entirely into solution, it is redeposited, on cooling, in very characteiistic, golden scales, which reEemble flattened needles.The substance, crystallised from alcohol, gave the following figures on ad-jwis. 01570 e v e 0,3218 CO, and 0606 HzO. 0.1679 ,, 0.0975 AgBr. Br = 24.71. C1J313Br03 requires C = 56.07 ; H = 4.04 ; Br = 24.92 per cent. Bromolapachol can be reconverted into dibromo-p-lapachone by the action of bromine. The change corresponds precisely to the forma- tion of bromo-/3-lapachone from lapachol (Trans., 1892, 61, 639). 1 gram of bromolapachol dissolved in 35 C.C. of chloroform was added t o 0.5 gram of bromine in 15 C.C. chloroform. After standing a few minutes, the chloroform was distilled off from a water bath, and the residue dissolved in 10 C.C.of boiling alcohol ; dibromo-/I-lapachone began to crystallise out almost immediately; 0.95 gram was obtained.+ Bromolapachol dissolves in concentrated sulphnric acid forming * Not vice versd, or the precipitated bromolapachol will enclose considerable quantities of its undecomposed zinc salt. t The mother liquor was allowed to stand for some time ; it sloml~ deposit& yellow needles in small quantity, beSeved to be the previously described compound, 2C,,HI3Br3O3,HBr (Trans., 1893, 63, 433), which it resembled in appearance aa well as in its properties, as far 8 s the small quantity obtained rendered comparison possible. It melts at 170-171". C = 55-90; H = 4-28. VOL. LXV. c18 an intensely precipitated HOOKER : PREPARATION AND PROPERTIES orange-red solution, from which 12~-bromo-/3-Iapachone is on adding water.Tbis compound is formed by the action of concentrated sulphnric acid on bromolapachol, on bromhydroxyhydrolapachol, and on n”-brorn-a-lapachone ; in all three cases the conversion occurs quan- titatively. It is most conveniently prepared by dissolving 5 grams of bromolapachol in 25 C.C. of concentrated sulphnric acid, and pour- ing the solution into a, relatively large volume of water; bromo-p- lapachone separates in a crystalline condition, and, when well washed, is pure enough for most purposes. For analysis, it was crystallised from alcohol. C = 56-48 ; H = 4-64. I. 0.1815 gave 0.3759 CO, and 0.0758 HzO. fII. 0.1864 ,, 0.3832 ,, ,, 0.0736 ,, C = 56.06 ; H = 4.38. 111. 0.1212 ,, 0.0716 AgBr. Br = 25.13.ClaH13Br0, requires C = 56.07 ; H = 4.08 ; Br = 2492 per cent. n~-Bromo-/?-lapachone separates from alcohol in orange-red needles, which slowly darken on exposure to diffused daylight. It melts and decomposes at about 205” when the temperature is rapidly raised, and at lower temperatures when more slowly heated. It dissolves in most of the organic solvents without difficulty, although it is in most cases considerably less soluble than p-lapachone, which it closely resembles in appearance as well as in its reactions. It is converted by hjdrogen bromide or chloride into nZ-brom-a-lapachone, and by boiling aqueous alkalis into bromhydroxyhydrolapachol. nx-Bromo-P-lapachone combines very readily with orthotoluylene- diamine, in acetic acid solution, giving a yellow azine which dissolves i n concentrated snlphuric acid, forming an intensely violet solution.0 nx- B rom-a-lapachone, (?) Br This compound can be readily obtained by the action of hydrogen bromide on the corresponding Plapachone, It is most conveniently prepared as follows. 4 grams of ?zx-bromo-(3-lapachone, free from large crystals o r lumps, are immersed i n 120 C.C. of a solution of * I a m indebted to Mr. Ellwood Wilson for this combuslion.OF BROMOLAPACHOL. 19 hydrogen bromide, sp. gr. 1.49. The acid is then slowly heated, being finally kept at a temperature just. below its boiling point, until the orange crystals have disappeared and entirely given place to yellow ones, a change which soon occurs. When the solution is cold, it is diluted with water, and the compound is collected and thoroughly washed.It may be further purified by crystallisation from alcohol, in which it is not very soluble. 0.2039 gave 0.4180 CO, and 0.0765 H,O. 0.1463 ,, 0.0875 AgBr. Br = 25.45. nZ-Brom-a-lapachone crystallises from alcohol in pale yellow scales or plates which melt at 172-5-173-5". If the compound is dissolved in concentrated sulphuric acid, and the solution, after standing aboui 15 minutes, is poured into an excess of water, the isomeric nZ-bromo-/?-lapachone is obtained as an orange, crystalline precipitate. ns-Brom-a-lapachone is converted by boiling aqueous alkalis into bromhydroxyhydrolapachol. A 2 per cent. solution of sodium hydr- oxide is conveniently used for the purpose, the boiling being con- tinued until the greater part of the compound, which should be finely pdverised, is dissolved. The filtered alkaline solution is acidified with acetic acid, and bromhydroxyhydrolapachol is a t once precipi- tated in a crystalline condition. C = 55.90; H = 4-16. CISHl&3r03 requires C = 56-07 ; H = 4.04; Br = 24.92 per cent. 0 This compound may be most conveniently obtained by the action of a 2 per cent. solution of sodium hydroxide on nz-bromo-/?-lapachone, the directions above given for the conversion of nz-brom-a-lapachone into the same compound being followed. After crystallisation from absolute alcohol, bromhydroxyhydrolapachol gave the following re sulta on analysis. 0.2715 gave 0.5260 COz and 0.1082 H,O. C = 52-83 ; H = 4.42. 0.1997 ,, 0.1096 AgBr. Br = 23.35. ClaH,Br04 requires C = 53.09; 3 = 4.42; Br = 23.59 per cent. Bromhydroxyhydrolapachol separates from alcohol in two forms. It is sometimes obtained as golden leaflets or scales, and sometimes as dense crystals, which, when deposited slowly, attain considerable size. It melts at 164.5-165.5", and is readily converted into nz-brom-p-lapachone by concentrated sulphuric acid. c 2

ISSN:0368-1645    

DOI:10.1039/CT8946500015

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

20 IV.-The Magnetic Rotation of Hydyogen Chloride in dz$erent Solvents: and also of Sodium Chloride, Lithium Chloride, and of Chlorine. By W. H. PERKIN, Ph.D., F.R.S. FOUR years ago I gave an account of observations on the magnetic rota- tions of solutions of the hydrogen compounds of the halogens (Trans., 1889, 55, 702, &c.), showing that in aqueous solution the rotations of these compounds yaried with the concentration, and that t-he numbers obtained were smaller when very little water was used than when much was present. It was of interest, therefore, t o examine these compounds in the absence of water, but as it was not possible to work with the liquefied gases, for want of suitable apparatus, a neutral solvent had to be found, which was not easily acted on by these substances.Many liquids were tried, but generally they were either not sufliciently good solvents, or they were acted on by these powerful agents. At last, a trial with isoamyl oxide, or ether, showed that it not only dissolved an appreciable quantity of hydrogen chloride, bnt was scarcely acted on by it, even after many days, and a solution of the gas in this solvent was consequently employed. It could not be used, however, with hydrogen bromide and iodide, as it is attacked by them too readily. The rotation for hydrogen chloride given by this solution was much lower than that yielded by any of even its strongest aqueous solutions, approximating to the value estimated from compounds of the fatty series, and only a little more than half that given by dilute aqueous solutions.Dr. H. Jahn (Ann. Phys. Chem., 43,280), however, has questioned the correctness of my results, and has suggested that when isoamyl oxide is saturated with hydrogen chloride, a change occurs involving the formation of isoamyl chloride and alcohol, and, therefore, that the product I examined was a mixture of these compounds, and not a solution of hydrogen chloride as I had stated. In a recent inaugural dissertation by Dr. Schonrock, describing experiments undertaken at the suggestion of Dr. Jahn, this point is again referred to, and elaborate calculations are made to see whether Dr. Jahn’s hypothesis can be reconciled with my results. Dr. Schonrock considers that, if I had made certain errors in my measure- ments decting the second decimal place of the specific rotations I gave, my results would not be inconsistent with Jahn’s hypo- thesis, remarking that “in the face of these results i t must be admitted that the assumption of the decomposition of amyl ether by hydrogen chloride is in no way opposed to Perkin’s observations.”Tl€E MAGNETIC ROTATION OF HYDROGFX CHLORIDE.21 An account is then given of what is called a special investigation on this subject, of which I need say but little, except that measurements are described made with a solution of hydrogen chloride said to contain 1.0841 per cent. of hydrogen chloride, 1.2193 of amyl chloride, and 1.0079 of amyl alcohol ; from which Schonrock actually ventures to calculate the molecular rotation of hydrogen chloride, and finrllly remarks, " Hydrogen chloride, therefore, turns the plane of polarisa- tion to an equal extent, both in water and in amyl ether" (Zeit.physikal. Chenz., 11, 773-776). The influence of experimental errors on the measurements of dilute solutions cannot have been brought under the notice of Dr. Schonrock, because if he had considered the subject he certainly would not have measured either this or the other very dilute solutions to which he refers in his dissertation. In a paper on the magnetic rotation of sulphnric and nitric acids, &c., I have drawn attention to this subject (Trans., 1893, 63, 58). I have lately made further experiments with solutions of hydrogen chloride in isoamyl oxide. If, in the saturation of this liquid, the hydro- gen chloride be free from air, and the passage of the gas be discon- tinued when it commences to bnbble through unabsorbed, the amount taken up can be pretty closely found by weighings made before and after the experiment. The accurate determination of the free acid is, however, of the simplest character, consisting in merely fransfer- ring a weighed quantity of the solution to a stoppered bottle con- taining water, and titrating with caustic soda solution, In the following table, the results obtained by direct weighings and by titrating solutions made at different temperatures are compared.The results given by the weighings are slightly lower than the othem, but this is only what might be expected, and is caused by loss of the solvent by evaporation. Temperature at which absorption occurred. by weighings.by titration. Per cent. of HC1 Per cent. of HC1 0" 18-61 18-70 5 16.78 17.04 9 16.28 16-26 13 15-05 15.40 15 14.59 14.91 25 11.27 11.58 These results show that very little, if any, action takes place; otherwise the titrations would give lower results than the weighings, but other evidence on this point will be found further on. In the case of the solutions given above, the saturation was not carried out so far as to be quite complete, but the results show that isoamyl oxide behaves like an ordinary solvent, the amount of hydrogen chloride absorbed increasing as the temperature is reduced.22 PERKIN: THE MAGNETIC ROTATION It is scarcely necessary to say that in preparing a solution of hydro- gen chloride in isoamyl oxide, it is better to do so at a temperature several degrees above that at which t'he solution is to be wed, so that it may not give off gas and change in composition, during the observa- tions.Of course, such soln tions require very careful manipulation whilst being examined; it would never do, for example, to pour them from one vessel to another. I have again determined the magnetic rotation of hydrogen chloride in isoamyl oxide. The solution was prepared at 13", and contained 1441 per cent. of dissolved gas = HCi + 1.372C,oH2,0. Density : d 4"/4", 0.8366 and d 9"/9", 0.8323. Magnetic rotation : t. Sp. rotation. Xol. rotation. 9.3" 1.0398 17.584 Less C1,H,O (11.168 x 1.372) = 15.323 Mol. rotation of HC1 = 2.261 These numbers correspond very closely with those previously ob- tained, namely, 2.211 and 2.265.A solution containing 14-8 per cent. of hydrogen chloride, after it had been made three days, was freed from hydrogen chloride by washing first with water, and subsequently with dilute alkali, and the amyl oxide was then quantitatively examined for isoamyl chloride ; for this purpose rather large quantities mere used-6 and 7 grams-and to decompose any chloride it might contain, the liquid was heated in a sealed tube with alcohol and sodium ethylate at 120-130" (the chloride is decomposed at 100" by this reagent). After the alcohol and isoamyl oxide had been removed, the saline solution was neutralised with nitric acid, and titrated with decinormal solution of silver nitrate. Two determinations were made, and gave 0.0071 and 0.0058 per cent., so that the extent to which action took place between isoamjl oxide and hydrogen chloride during three days' contact is so small that it can be ignored, so far as the magnetic rotation is concerned.I have found that chemical action does very slowly take place if a solution of hjdrogen chloride in this solvent is kept in a warm place, an aqueous layer containing hydrogen chloride separating after the lapse of several months. The above solution containing 14.41 per cent. of hydrogen chloride, examined three weeks after its preparation, mas found to contain 14-29 per cent. of hydrogen chloride. It had been kept at a temperature of from about 6" to 12". I may here mention that I have made a few quantitatire experi- ments with hydrogen bromide and isoamyl oxide. A solution wasOF HTDROQEN CHLORIDE IN DIFFEREXT SOLVENTS.23 prepared which wa,s found by direct weighing to contain 36.5 per cent. of the gas; at the end of ten hours, however, this gave, on titration, only 32.1 per cent. of hydrogen bromide. A second solution, containing 45-7 per cent. of bromide, at the end of 12 hours, contained only 39.3, and,after 36 hours, 31.1 per cent., showing that interaction takes place too rapidly in this case to allow of this solvent being used for measurements of the magnetic rotation of hydrogen bromide as previously mentioned. While experimenting on the preparation of chlorides from alcohols and hydrogen chloride, I had occasion to notice how small an amount of chemical change appears to take place unless a, dehydrating agent be also present, or the temperature be considerably raised, and it occurred t o me that it might be useful to make a few experiments in connection with this subject, to ascertain whether the formation of chlorides really took place at ordinary temperatures ; and if so, at what rate.For this purpose, isoamyl alcohol, kept at about loo, w a ~ slowly saturated with hydrogen chloride ; weighings being made before and after the saturation. The titrations of this solution agreed closely with the numbers given by the weighings, being slightly higher, as in the case of the isoamyl oxide solutions. After keeping for a week and' again titrating, practically the same numbers were obtained, so that it is evident scarcely any chemical action had taken place, the product being simply a solution of hydrogen chloride in isoamyl alcohol.Experiments were then made with ethylic alcohol with the following r eault s. Ethyl alcohol taken ............. Weight of solution .............. Percentage of hydrogen chloride Hydrogen chloride absorbed.. .... according to weighings. ........ Percentage found by t,itrat,ion .... Two days after preparation ....... Five days 3, Seven days ....... ....... 99 19-566 grams 12.142 ,, 31.708 ,, 38.29 per cent. 35-45 ,, 38.46 ,, 38.27 ,, 38-08 ,, From these results, it is evident that with this alcohol also chemical change takes place with remarkable slowness, and it was, therefore, thought worth while to examine the magnetic rotation of hydrogen chloride both in isoamyl alcohol and in ethyl alcohol. Two different solutions in isoamyl alcohol were examined ; they gave the following results.SoZution 1.-This contained 28.03 per cent. of dissolved gas = HCl + 1-065C5H,,O.24 PERKIN: THE MAGNETIC ROTATION Density : d 4"/4", 0.9356; d 8"/8", 0.9326. Magnetic rotation, average of 40 readings : t. Sp. rotation. MoI. rotation. 7-5" 1-2403 9.617 6-329 3.288 Less C,H,,O (5.943 x 1.065) = Mol. rotation of HCl = Solution 2.-This contained 25.45 per cent. of dissolved gas = Density d 4"/4", 0-9281 ; d 9"/9", 0.9244 Magnetic rotation, average of 32 readings : - HC1 + 1'215C5H12O. t. Sp. rotation. Mol. rotation. 8%" 1.2189 10.505 7.320 Less Ca,,O (5.943 x 1.215) = Mol. rotation of HC1 = 3.285 The average of these closely concordant results is 3.286. The solution containing 25.45 per cent.of hydrogen chloride when first prepared, after being kept for three weeks at a temperature of frcm about 6" to 12O, contained 25.32 per cent. Only one solution of hydrogen chloride in ethyl alcohol has been examined ; it gave the following results. This contained 40.04 per cent. of the dissolved gas = HC1 + Density : d 4"/4", 09897 ; d S"/S", 0.9863. Magnetic rotations, average of 64 readings : 1.1 88 C,H,O. t. Sp. rotation. Mol. rotation. 7.75" 1.2991 6.668 3.305 Less C2H60 (2.780 x 1.188) = 3.365 This number is slightly higher than that obtained with the isoamyl alcohol solution, but only by 0.083, and this may be parti- ally due t o the presence of the trace of water which is usually found in alcohol even when carefully dried (the density was 0.7967 a t 15"/15"), aqueous hydrogen chloride having a high rotation.Solutions of hydrogen chloride in both liquids were examined to see whether they contained any appreciable amount of chlorides. The isoamyl alcohol solution was treated in the same manner as the isoamyl oxide solution, the hydrogen chloride being removed, and the remaining alcohol heated in a sealed tube at 120-130" with alcohol and sodium ethylate, &c. Two determinations mere made, and gave 0.0062 and 0.0058 per cent. of chlorine, so that practicallyOP HYDROGEN CHLORIDE IN DIFFERENT SOLVENTS. 25 in these solutions, which were three days old, no change capable of influencing the rotation had taken place. The examination of the ethyl alcohol solution for ethylic chloride was not so simple as the foregoing.The following method was adopted : 34 grams of a freshly-prepared solution containing 32.37 per cent. of hydrogen chloride was taken and diluted with its own bulk of water; the product was nearly nentralised with sodium hydrate, and then rendered alkaline with sodium carbonate ; after this it was distilled in an apparatus provided with a fractionating column until about 30 C.C. had passed over. All these operations were performed in an apparatus provided with one exit only, and this was guarded with a potash bulb containing alcohol to absorb any ethyl chloride that might otherwise escape. The distillate and alcohol from the bulbs were mixed and heated with sodium hydrate in sealed tube at 100" for about two hours (ethyl chloride is quickly decomposed under these conditions).The chlorine found in the saline solution by this process amounted to only 0.00054 per cent. ; therefore, ethyl alcohol can be saturated with hydrogen chloride without any appreciable chemical change taking place, and from the results previously given it is seen that combination afterwards proceeds but very slowly with the lapse of time. The isoamyl oxide used in the foregoing experiments was obtained from Kahlbanm; it had scarcely any permanentl rotation, but when saturated with hydrogen chloride it produced a slight rotation t o the left. The permanent rotation of the isoamyl alcohol, on the other hand, was reduced to about one-third by satmating with hydrogen chloride, which is much more than ca2 be accounted for by the increase in volume due to the gas absorbed.The magnetic rotation of hydrogen chloride dissolved in these alcohols lies between that of its rotation in isoamyl oxide and in water, thus : Diff. Rotation of aqueous solution (20 p. c.) . Rotation in alcohols (average). . . . . . . . Rotation in isoamyl oxide (average) . . 4.412) 1.086 3.326 2*245} 1.081 That the alcoholic solution should give lower results than the aqueous is only what might be expected from analogy, as I have found that diethylamine hydrochloride and ammonium iodide (Trans., 1889, 55, 714, 720, 744) and other compounds behave in the same manner when dissolved in this liquid. Sodizcm Chloride.-As I have examined sodium chloride in the dry state as rock salt, and also in aqueous solution, this seems to be a suitable occasion to give an account of the results, so that a compari-26 PERKTN: THE MAGNETIC ROTATION son may be made between the hydrogen and sodium compounds of chlorine.The column of rock salt examined was 136 mm. long. Density : d 6"/6" = 2.1675. Magnetic rotation : Although almost perfectly transparent when viewed with the polariscope, the rock salt did not show such distinct changes as transparent fluids do, owing, it is believed, to the presence of an extremely minute quantity of selenite, or some other crystalline sub- stance, but by taking a considerable number of readings errors from want of sharpness were no doubt overcome. It was examined on two occasions, 50 readings being made each time ; the following are the averages : t. Sp. rotation. Mol. rotation.15-0" 2.7168 4.073 16.0 2.7269 4.088 Entire average.. 15.5" 2.7213 4.080 The solution of sodium chloride employed contained 26.174 per cent. ; its composition was therefore NaCl + 9.166Hz0. Density: d 10°/lOo = 1.2028 ; d 20"/20" = 1.1995. Magnetic rotation, average of 32 readings : t. Sp. rotation. Mol. rotation. 15.5" 1.3769 14.234 Less OH, = 9.166 - ~~- Mol. rotation of NaCl = It will be seen from the above results that there is an analogy between the rotation exhibited by sodium chloride and hydrogen d o r i d e in aqueous solution, and when water is absent, inasmuch as in both cases the aqueous solution gives the higher results. In the presence of water, sodium chloride, however, does not increase in rotation t o nearly the same extent as hydrogen chloride does.H. Becqnerel, who also has measured the rotation of rock salt, as well as of chloride of sodium in solution, has found that the latter gives the higher numbers. From the rotation of rock crystal, a .value for sodium is obtained by subtracting from it that of chlorine as found in organic chlorides, namely, 1.733 ; this gives 2.347, a number considerably higher than that estimated from the solutions of the sodium salts of the fatty acids or the inorganic acids containing oxygen. Lithium Chloride.-This salt being very soluble, it is possible to examine it in very concentrated, as well as in dilute, solutions, and the results obtained are interesting, inasmuch as the strong solutions 5.068OF HPDROGEN CHLORIDE IN DIFFERENT SOLVENTS. 27 give lower results than the dilute.Three different solutions were ex- amined, about 64 readings being made wit'h each. I. LiCl + 11. LiCl + 3.213 mols. OH, : d 15"/15", 1.3066 ; d 20"/20", 1.3059. 7.411 mols. OH, : d 15"/15", 1.1575 ; d 25"/25", 1.1568. 111. LiCl + 11.760 mols. OH, : d 15"/15", 1.10649; d 25"/25", 1.10600. Magnetic rotation : t . 8p. rotation. 3101. rotation. I. 19" 1.7294 7.379 Less OH, = 3.213 4.166 Mol. rotation of LiCl = 11. 23.2" 1.41 70 11.970 Less OH, = 7.411 4.559 -- 3101. rotation of LiCl = 111. 17.4" 1.2877 16.440 Less OH, = 11.760 4.680 -_ - 3101. rotation of LiCl = These results therefore show that aqueous solutions of this salt behave in an analogous manner to solutions of hydrogen chloride. These results were referred to in the "Proceedings," 1890-91, p.142. Chlorine.-This is probably the only element of its class that it will be possible to measure in a satisfactory manner by the method at present in use, as both bromine and iodine are so strongly colonred that light will not penetrate through a layer sufficiently thick-to afford trustworthy results, either in the case of the pure substance or of a sufficiently strong solution. H. Becquerel, how- ever, who attempted to measure bromine, using the red light of the lithium flame, obtained a number which gives a high value for this element. I n the case of chlorine, it would have been best to examine it in the liquid condition, but at present I have no convenient ar- rangement for this purpose ; therefore a suitable solvent for the gas had to be found. The best for this purpose is carbon tetrachloride, which at about 13" dissolves snfEcient to form a 10 per cent. s o h - tion. The determination of the amount of chlorine taken up by the solvent was made by introducing a weighed quantity of the solution into a bottle containing potassium iodide, and titrating with sodium thiosulphate. Two solutions were examined. 1. Contained 10.29 per cent. of chlorine; composition = C1, + Density : d 4"/4", 1.6085 ; d 10°/lOo, 1-5973. 4.02CC1,.28 EASTERFIELD AND SELL ON CITRAZINIC ACID. Magnetic rotations, average of 190 readings made on four diil'erent occasions : f. Sp. rotation. Mol. rotation. 7.1" 1.2866 30.760 26.460 C1, = 4.300 Less CCl, (6.582 x 4.02) = 11. Contained 9.88 per cent. of chlorine; composition = C1, + Density : d 4"/4", 1.6093 ; d 9"/9", 1.5998. Magnetic rotation, average of 72 readings : 4.d04C C1,. f . Sp. rotation. Mol. rotation. 8.2" 1.2858 32.058 27.670 Less CCl, (6.582 x 4.20-4) = C1, = 4.388 The average number for the molecular rotation of chlorine from the above is 4.344. If the atomic value be taken as half this, it will be 2.172. This result is higher by 0.439 than the value found for this ele- ment when in combination, as in propylic chloride, in which case it is 1.733. At the same time, it is a much lower value than that calculated from the rotation of a dilute solution of hydrogen chloride (4.154 about).

ISSN:0368-1645    

DOI:10.1039/CT8946500020

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年代:1894

数据来源: RSC

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28 EASTERFIELD AND SELL ON CITRAZINIC ACID. V.-Studies on Citraxinic acid. Part 11. By T. H. EASTERFIELD, MA., and W. J. SELL, M.A., F.I.C. Conrersion of Diammonic Citrate into Citrazinic acid. SO many methods have been described for the conversion of " an- hydro "-citric into citrazinic acid derivatives, that we have been led to investigate the action of heat on the ammoniuui salts of citric acid, with the object of directly preparing citrazinic acid. Behrmann and A. W. Hofmann (Bey., 17, 2688) have, indeed, attacked this problem, but were unable to obtain definite results, probably because their experiments were carried out a t too high a temperature. Sabanin and Lasknomky (Zeit. anal. Chem., 17, 74) have shown that when ammoniacal solutions of citric acid are heated, in sealed tubes, at 110-120" during seveid hours, and subsequently exposed to the air, a blue-green colour is gradually developed, and we find that, if a solution of diammonic citrate is heated on the water bath for several days in an open dish, and then allowed to cool, it behaves in a similarEASTERFIELD AND SELL ON CITRAZNIC ACID.29 manner. This development of colonr, on exposure, is, however, shared by cold dilute ammoniacal solutions of citrazinic acid, and led us to suppose that a slow condensation of citric t o citrazinic acid had occurred, even under this gentle treatment. When the action was slightly forced, by heating the citrate of ammonia at 130" for three hours in an open vessel placed in an air bath, a considerable quantity of citrazinic acid (about 6 per cent.of the citric acid taken) was formed, but, at temperatures above 160: no citrazinic acid could be isolated. The acid produced in this way always showed a rather high per- centage of nitrogen ; after treatment with potash and animal charcoal, it was identified as citrazinic acid by the fluorescence of its alkaline solutions, its behaviour with a warm solution of potassic nitrite, and by an analysis. 0.1287 gave 0.0395 H,O and 0.2202 CO,. 0.1571 ,, 12.7 C.C. dry nitrogen at 11" and 760 mm. N = 9.62. This is the simplest condensation of citric acid into a pyridine derivative which has been hitherto described. Preparation of Citrazinamide f r o m Ethylic Citrazinate.-Though it could scarcely be doubted that citrazinamide is, in reality, the amide of citrazinic acid, it seemed desirable to check this conclusion by preparing the amide from an etihereal salt of the acid.Ethylic citrazinate was heated with an excess of strong ammonia at 120-130", f o r two hours in a sealed tube ; a crystalline substance was formed which, after recrystallisation from dilute ammonia, was recognised by its appearance and a nitrogen determination, as the anhydrous ammonium salt of citrazinamide described by us in a former paper. 0.1347 gave 28.4 C.C. dry nitrogeu a t l2"and 764 mm. N = 25.01. CsHJVz0,,NH3 requires N = 24.55 per cent. C = 46-63; H = 3.40. Cke[,NO, requires C = 46-45 ; H = 3.23 ; N = 9.03 per cent. Reduction of Citratinamide by Sodium Amalgam-Emil Fischer (Ber., 23, 933) has pointed out that, whereas amides of the benzenoid series are readily reduced to alcohols by the action of sodium amalgam, those of the aliphatic series undergo no such reduction, and the recent work of Max Marx (Annakm, 263, 249-259), and more par- ticularly that of Arthur Hutchinson (Trans., 1890, 57, 957), has em- phasised the correctness of Fischer's statement.As far as we are aware, no experiments have yet been made with the object of finding out whether amides of the pyridine series would behave as fatty, or as benzenoid compounds, on reduction. In the case of citrazinamide, reduction readily takes place in alkaline solution, citrazinyl alcohol being one of the chief products ; and as in the case of some benzeno'id30 EASTERFIELD AND SELL ON CITRAZINIC ACID. amides, a small quantity of a hydrobenzoin is simultaneously formed.These experiments may, therefore, be regarded as yielding additional evidence of the benzenoid habitns of the derivatives of pyridine. 10 grams of citrazinamide were dissolved in a small quantity of caustic soda solution and diluted to 200 C.C. ; the solution was then reduced with 29 per cent. sodium amalgam, of which 215 p m (rather more than 4 atoms of sodium) were required. During the early stages of reductmion, the liquid darkened considerably, but, towards the end of the process, it became of a light amber colonr. As soon as an escape of hydrogen showed that the reduction was complete, the liquid was acidified with dilute sulphuric acid, and the small quantity of resinous matter which separated was filtered off and neglected.On concentrating the solution to about one-quarter of its bulk, and allowing it to cool, a brown substance separated in minute spherules, subsequentIy identified as a hydrobenzoin (see below) ; the solution was then neutralised with ammonia, poured into 10 times its volume of methylated spirit, and, after filtration from the moist sulphates, the spirit was distilled off. The solution, thus left, was acidified with hydrochloric acid and evaporated to a small bulk in a vacuum over sulphuric acid and potash; the crystalline sub- stance which was deposited was then dissolved in a small quantity of hot water, from which it separated, on cooling, in clusters of almost colourless prisms. Analysis agrees with the supposition that it is citrazinyl alcohol, formed according to the equation CsH4302*C:ONHz + 2H2 = CsH4NO2.CHz.OH + NH,.The crystals contain 1H20, which they do not lose in a vacuum a t the ordinary temperature, but do so readily at 100". After two recrystallisations, the substance melted at 158" without under- going decomposition. 0.1635 gave 0.0830 H,O and 0.2695 CO,. 0.1539 lost 0.0174 H,O and gave 11.4 C.C. dry nitrogen at 770 mm. CsH7N03,H20 requires C = 45.28; H = 5.66; N = 8.80; H,O = Another specimen gave C = 45.07 ; H = 5.44 ; N = 9.12 per cent. C = 44.95 ; H = 5.64. and 12". 11.32 per cent. H,O = 11.30; N = 8.88.HEYCOCK AND NEVILLE: FREEZNQ POINTS OF ALLOYS. 31 The aqueous solution of the alcohol is very acid to litmus paper, and gives a precipitate with ammoniacal nitrate of silver ; if this pre- cipitate is dissolved in a drop of ammonia, and the solution warmed, a silver mirror is formed.Citrazinyl alcohol dissolves easily in hot water, comparatively sparingly in cold water, but readily in a i d or alkaline solutions, ethyl and methyl alcohol, acetone, and ethylic acetate. I n ether, benzene, chloroform, and light petroleum, it is either very sparingly soluble, or insoluble. The yield was about 16 per cent. of the amide employed. vH(OH)-yH(OHj C C /\ /\ Citrazinyl Hydrobenzoiiz, Hv QHz Hv HZ H0.C CO HO*C CO It has been mentioned that, during the preparation of citrazinyf alcohol, a substance consisting of brown sphernles was obtained ; this dissolves readily in hot water, much more sparingly in cold water, and its aqueous solution reddens blue litmus ; it is very soluble in alkalis, and is reprecipitated on the addition of a mineral acid. When analysed, it gave numbers which agreed with those required for a hydrobenzoh of the above formula ; the yield of the compound was very small, and we have been unable to make further experiments with it. Different specimens ga-re the following analytical resnlh. 0.1374 gave 0.0523 HzO and02615 (30,. C = 51.9; H = 4-22. 0.1135 ,, 0.0425 ,, ,, 0.2114 ,? C = 50.8; H = 4-14. 0.1192 ,, 9.7 C.C. dry nitrogen a t 11" and 758 mm. N = 9.67. 0.1135 ,, 9-6 C.C. ,, ,, 10" and 7T0 mm. N = 1023. Uniz ersity Lab m a f ory , (C,HaNO,*CHOH)~ requires C = 51.42; = 4.20; N = 10.00 per cent: Cambridge.

ISSN:0368-1645    

DOI:10.1039/CT8946500028

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年代:1894

数据来源: RSC

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HEYCOCK AND NEVILLE: FREEZNQ POINTS OF ALLOYS. 31 VL-Freezing Points of Alloys in which the Solvent is Thallium. BY C. T. HEYCGCK and F. H. NEVLLE. Ox account of the costliness of thallium, as mmpared with the solvents we have hitherto used, these experiments were conducted On 8 small scale, about 60 grams of thallium being employed in each series.32 HEYCOCK AND NEVILLE : FREEZING POINTS The small quantity of solvent obliged us to use a Geissler ther- mometer with a small bulb and a much less open range than those we usually employ. The experimental errors were from this cause greater than in most of our work with tin, lead, and cadmium as solvents, but we think the results are in the main trustworthy. The thallium was procured from Messrs. Johnson and Matthey, and when estimated with permanganate, as in Crookes' Select Methods, gave a content of at least 98 per cent.of thallium. The behaviour of bismuth when dissolved in thallium (see curve, below) probably points to impurities in the thallium, for the curve repro- duces the phenomena oE a triple alloy.? From the fact that the maximum freezing point reached was 303.7" it follows that the freezing point of pure thallium is not lower than this temperature (see Trans., 1891, 59, 936). As we expected from the result of dissolving thallium in lead (Trans., 1892, 61, 910 and 914), the behaviour of lead in thallium is anom- alous. It will be seen from the tables (pp. 33-35) that the addition of lead to thallium raises the freezing point. The case is analogous to that of antimony in tin and silver in cadmium.An infusible sub- Freezing points of Thallium containing Bismuth. 300" 290" 280' 270' 260" 250" 250' 240" XW" I'SW Freezing points of Thallium containing Bismuth. The numbers on the top and left side refer to the left-hand portion of the curve, those a t the bottom and right side to the right-hand portion of the curve. lead, a little mercury, and traces of other metals. t An analysis of the thallium shows that it contains a considerable quantity ofOF ALLOYS IN WHICH THE SOLVEXT IS THALLIUM. 33 stance separates from the solution of lead and thallium in such quantity as to interrupt the experiment. This may be a compound or may be, as F. W. Knster suggests for antimony and tin, the mixture solidifying isomorphonsly (Zeit. physikal.Cherra., 12, 508), but on the latter hypothesis we should expect the atomic rise to be much smaller. The latent heat of fusion of thallium has, so far as we know, not been directly determined. We were, therefore, unable to apply Van't Hoffs formula for the purpose of calculating the atomic fall. But the agreement of the observed atomic falls caused by gold, silver, and platinum makes it pretty certain that the average of these is the true atomic fall. We can therefore use this number to calculate t,he latent heat of fusion of thallium. TABLE I.--Silver in Thallium. Total weigh of thallium. Total weight of silver present. 0 0 -122 0 -244 0 '480 0 %84 0 975 0 -880 Atoms of silver per 100 of thallium. 0 0 -385 0 -571 1 *517 2 -160 2 -4& 2 -780 Freezing point of solution.302 -26" 299 -83 297 -46 292 -7 1 289 -09 288 '33 288 '35 TABLE IL-Gold in Thallium. Geissler Thermometer. Atomic fall. ~~ Atomic fall. Total weight of thallium* present. 0 0 '218 0 -505 0 -835 1 '387 1 -925 2 -373 3 -063 3 -616 4-193 0 0 371 0 -859 1 *a0 2 -359 3 -274 4 -036 5 -208 6 -149 7 -130 301 '30° 298 -76 295 -75 292 -22 286 -33 280 -71 276 -20 272 -59 267 -17 261 -38 6 *85 6 -46* 6 -39* 6 -35+ 6 *29* 6 -22 5 '51t 5 5 5 5 -60 t The sudden decrease in this atomic fall, followed by a slow reeovery, snggests VOL. LXV. D the possibility of an experimental error.34 HETCOCK AND NEVILLE: FREEZING POINTS OF ALLOYS. TABLE III.-PEatinum in !l%ullium. Total weight of platinum. -I-- 0 0 -066 0 *252 0.488 0 '805 1 '307 I 1.527 Weight of thallium.-- 60 '32 64, -63 70 -96 9 9 Y ? 9 , ?? Atoms of platinum per 100 of thallium. 0 0 -106 0 -372 0 *720 1 -188 1,930 2 -255 Freezing point of solution. 301 -95" 301 -41 299 -65 a7 '39 294 * 55 291 '11 291 -16) Atomic fall. 5 -08t 6 -19* 6 '33* 6 '23f aturated Selecting those atomic falls of the metals, gold, silver, and plat- inum, which are marked with an asterisk in the preceding tables, we find that the mean fall produced by one atomic weight of a foreign metal in 100 atomic weights of thallium is 6-31' centigieade. If X is the latent heat of an atomic weight of thallium and T its freezing point on the absoiute scale, we have h = 0*02T2/6.31. 'fleiglit of thallium used. 60 Total weight of bismuth present. 0 0 -187 0-489 1 '637 2 -556 3 -653 5 *664 6 -805 8 -358 9 -740 10 -898 7 .2 -786 13 -889 16 -211 18 -115 20 -107 22 -416 24 -388 26 -090 29 *269 34 -338 39 -764 43 -157 Atoms of bismuth per 100 of thallium. 0 0 -307 0 -801 2 -513 4 -181 5 -992 9 -266 11 -130 13 -674 15 -933 17 -830 20 -915 22 T20 26 -518 29 -634 32 %?O 36 -669 39 -895 42 -682 47 -880 56 -175 65 '030 70 -590 Freezing point of solution. 301 -18" 301 -29 301 -41 301 -18 300 -59 299 -39 3b2 -30 303 4.9 303 -68 302 -57 301 -06 297 -56 294 -98 288 *89 283 -38 277 -35 271 -25 264 -08 258 -95 2,iO -4.3 237 -75 225 -08 217 -30 t The platinum dissolves easily at; the melting point of thallium.PHOSPHORUS DERIVATIVES OF CAMPHENE. 35 301 *lBO 301 -49 301 -90 302 -99 306 -48 Weight of tballium present. 62 -398 -- Y 7 3 1 Y Y 7) ----- 0 2 -09 2 -41 2 -26 2 *05 TABLE V.-Lend in Thallium. 0 0 -094 0 -189 0 -508 1 *634 0 0 -148 0 -299 0 -802 2 -580 , The thermometer could not be adjusted on account of a lump of solid which did not melt a t 350'. It, is pretty certain that a compound of lead and thallium separates out. Assuming the observed freezing point of thallium, 301", to be correct, T is 574 and the latent heat of fusion of 1 gram of thallium is 5-12 calories. This is somewhat less than that of lead, which is given by Person as 5-37. We must again express our thanks to Mr. C. T. R. Wilson, of Sidney College, for his care in carrying out many of the experiments in this paper.

ISSN:0368-1645    

DOI:10.1039/CT8946500031

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年代:1894

数据来源: RSC

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PHOSPHORUS DERIVATIVES OF CAMPHENE. 35 VII.-Rusecwches o n the Terpenes. IV. Phosphorus Derimtives of Camphene. By J. E. MARSH and J. A. GARDXER. PHOSPHORUS pentachloride acts on camphene in a manner different from that in which it acts on organic substances generally. In ardinary cases, chlorine is substituted for hydrogen, hydroxyl, or oxygen ; but, in the case of camphene, the group PCla is substituted for hydrogen. The action appears to be in some respects similar to that which Anschutz and Moore observed as occurring between phos- phorus pentachloride and salicylic acid (Amer. Chem J., 10, 296). Excess of the pentachloride was used, and in this case not only was chlorine substituted for the acid hydroxyl, but the hydrogen of the phenolic hydroxyl was also displaced by PC14, the compound of the formula COC1.C6H,.0PC1, thus produced being converted by water into an acid of the formula COOH*C6H,*O-P0,H,.I n like manner, the compounci of the formula C10H15*PC14 obtained from camphene is converted by water into an acid of the formula There is, however, a considerable difference in the nature of the The salicylic derivative is CioHi,*PO3z- products obtained in the two cases. D 236 33ARSE AXD GARDNER: formed at a high temperature, and can be distilled in a vacuum, whereas the camphenephosphoric chloride is formed at the ordinary temperature, and is decomposed at loo", and if it be distilled in a vacuum it yields a new compound of the formula CIJIl,PCI, (Trans., 1891, 59, 652). This compound has been prepared in the pure state, but hitherto we have been unable to separate the compound of the formula Cl,H,,.PClr from the substances with which it is mixed.Its existence has been inferred, however, from the compounds ob- tained by the action of water. The compound of the formula Cl,-,H,,PC1, is converted by water into a new acid of the formula, Another action occurs when camphene is moderately heated with a large excess of phosphorus pentachloride, resulting apparently in the formation of a compound of the formula ClJtl4PCI5 or ClJ€lrCl*PC14. On subjecting this t'o tbe action of water, an acid of the formula CloHl,CI.PO( OH)r is produced, which is also obtainable by the oxidation of the above-mentioned phosphinic acid, Cl,H,,C1-P( OH),. The acid of the formula CloH16*P0 (OH),, which we call camphenephosphonic acid, exists in several isomeric forms, differing in rotatory power according to the nature of the isomeric camphenes from which they are obtained ; and even the same cam- phene yields two distinct isomeric acids, differing in solubility, melting point, rotatory power, and also in chemical properties. The chlorocamphenephosphonic acid also exists in two isomeric forms when derived from the same camphene, differing in solubility, in melting point, in rotatory power, and in the amounts of combined water.We find that the sodium salts of these acids are decomposed by bromine water, phosphoric acid being separated. Cm&C1*P( OH),. Campheizes of Various Origin. Camphene varies much in rotatory power, this property being influenced partly by the mode of preparation and partly by the rotatory power of the turpentine used.We pro- pose to consider in another paper the relations between the rotatory power of camphene and that of the turpentine from which, it is obtained. I n other respects, the properties of camphene, what- ever the rotation, seem to be the same. The part,icnlar actions studied in this paper seem to take place in exactly the same manner whatever camphene is employed, and to yield products identical in every respect except in regard to rotatory power. The description of the general course of the changes applies equally well to camphenes from all sources, and it is only when we have to characterise the different products more exactly that we shall have to take into account differences in rotatory power.PHOSPHORUS DERIVATIVES OF CAMPHENE.37 Adwn of Pitosphorts Pentachloride on Camphene. When 5 parts of camphene is mixed with 8 parts of phos- phorus pentachloride in a. mortar, the two solids form a thin cream, slight heating being observed, but no appreciable evolution of hydro- gen chloride. After a short time, the mixture sets to a hard solid mass; this is mixed with water, or, better, with ice in excess, and allowed to stand, when a clear, oily, cdourless liquid is formed which sinks in the excess of water. After a time a further action occurs, the oil darkening in colonr, and the whole becoming hot. The syrupy liquid is then fractionally extracted with a solution of carbonate of soda as long as anything is dissolved, camphene hydro- chloride being finally left, and from this camphene may be obtained by heating with aniline.The soda extractions contain the sodium salts of two camphenephosphonic acids, and from the sohtion the acids may be precipitated partly in a crystalline and partly in a syrupy state by the addition of hydrochloric acid. The acidified extracts, as well as the original solution from which the syrup separated in the h s t instance, are shaken up with ether to extract the dissolved phosphonic acids. Separation of the Phosphowic acids.-The two phosphonic acids are separated from one another by means of ether, which dissolves only one of them, leaving the other as a white, felted mass of crystals. The acid which is insoluble in ether we call a-, and the soluble acid p-camphenephosphonic acid.The latter is yecovered from the ether either by evaporating the ether or by shaking up the ethereal solu- tion with dilute caustic soda, and precipitating the acid by adding hydrochloric acid. It is obtained in a crystalline form, but is usnally mixed with some syrupy matter which has not been investigated. This syrupy matter is best removed by means of benzene, in which it is readily soluble, the crystals scarcely at all. Both the acids are purified by crystallisation from dilute alcohol, being dissolved in strong alcohol, a.nd water added to the hot solution; the a-acid crystallises most readily, the other more slowly, giring largeel. crystals. The two acids are further distinguished by their behavioiir with chloroform ; in this case, however, it is the 13-acid which h i n - soluble, whilst the a-acid readily dissolves.Not infrequently in the first extraction of the acid by sodium carbonate in accordance with the method above described, the sodium salt of the a-acid crystallises out, and the acid itself may then be obtained directly from the purified sodium salt. a- Camphenephosphonic acid, 2CIoH,,*YO,H2 + H,O. This acid crystallises from dilute alcohol in colourlees, light, fluffy needles, insoluble in ether, but soluble in alcohol, benzene, and chloro-38 NARSH AND GARDNER: form. above formula. Analysis : The air-dried acid has the composition represented by the I. 11. Calculated. Carbon.. . . . . 53.61 53.51 53.33 per cent. Hydrogen,. . . 8.21 8.19 8-00 ,, When dried at loo", it loses 2H20, leaving the anhydro-acid Water lost after 12 honrs (also after 24 hours) heating at 100'.[ C,a,,*PO(OH)-j,O. Found 7.97. Calculated 8.00 per cent'. Analysis, after heating at 100" : Found. Calculated. 57.96 per cent. I ? I. Carbon.. . . . . 58.11 58.31 Phosphorus.. 14.96 - 14.97 ,, Hydrogen.. . . 7-97 7-93 7.70 ,, When dried in a desiccator, or in a vacuum, the acid quickly loses one molecule of wat'er, and afterwards very slowly gives up the second molecule. Calculated. r - - L - 1 mol. H,O. 2 mob. HzO. Loss after 24 hours.. . . 4.2 p.c. - - 4.00 - ,) 48 ,, .... 5-8 ,? ,, several days. 7-56 ,, - 8-00 Substance dried in a vacuum 24 hours. Calculated for 14.35 per cent. Found. Cl,Hl,*PO,H,. 14.32 Phosphorus . . . . . . The air-dried acid begins to melt at about 160°, but the melting point is not constant.The anhydro-acid melts at 184'. p- Camphenep hosphonic acid, CloH15*P03H2. This acid crystallises from dilute alcohol in large, colourless crystals, needles several cenbimetres in length having been obtained ; it is soluble in ether, but insoluble in chloroform and benzene. When heated at loo", it does not appreciably lose weight (less than 2 per cent. after several days) ; but, after prolonged heating during several weeks, it was found to liquefy and darken in colour ; after three weeks, it had lost 37 per cent., and the syrupy residue contained phosphoric acid. The acid melts at 167", but decomposes.PHOSPHORUS DERIVATIVES OF OAMFHENE. 39 Analysis : Found. T-h- 7 I. Ir. 1x1. CloB15-~03~2~ Carbon 55.5 per cent. .......55-29 55.4 55.32 Phosphorus.. .. 14.42 - - 14.35 y, Calculated for Hydrogen. .... 7.97 7.8 8.2 7.8 91 Sodium a- Camphenephosphonate, CloHI,*PO,HNa + 4H20.-ThiS salt is obtained from the acid and sodium carbonate. It is produced either when one or two equivalents of carbonate of soda are used for each equivalent of acid. It is soluble in alcohol and in water, and was crystallised both from water and from dilute alcohol. When heated at looo, the salt loses its water of crystallisation, 2 mols. of the salt losing 9H20 and leaving the salt of the anhydro- acid. Found. Calculated. Loss of water. .... 259 26.1 per cent. Analysis of crystallised salt : CloH,,-P03HNa + 4H20. Carbon. .......... 38.69 38-71 per cent. Hydrogen ........ 7-90 7.74 y, Analysis of dried salt : (C,*H,,P02W20.Carbon .......... 51.96 52.4 per cent. Hydrogen ........ 6.64 6.55 ), The salt was also analysed by conversion into sodium metaphos- A weighed quantity of the anhydro-salt wits heated with NaPO, ........... 43.8 44.4 per cent. Sodium B- Camphenephosphonate, C,,,H1,*PO3NaH + 5H,O.-This salt, like the preceding, is obtained, whether one or two equivalents of sodium carbonate be used for each equivalent of acid. It crystal- lises from water in colourless, unctuous plates, and is soluble, though with difficulty, in alcohol. phate. nitric acid and ignited. Analysis of crystallised salt : Found. Calculated. Carbon .......... 36.43 36.58 per cent. Hydrogen.. ...... 8.15 7.93 ,, Phosphorus ...... 9.74 10-0 ), The salt WM also analysed by converting it into sodium meta- phosphate.Found. Calculated. NaP03 .......... 30.37 31.1 per cent.40 MARSH AND QARDNER: On heating at 100": and also in a vacuum, the salt loses marly the whole of its water of crystallisation. But the last traces are difficult to remove at a temperature below that a t which the Ralt itself under- goes decomposition. Loss of water : Calculated for 5 mole. H20. In a vacuum.. .... 25.9 27.4 per cent. At 100" .......... 26.56 Phosphorus in dried salt : Found 12.62. Calculated 13.0 per cent. AmmoltirLrn a-Camphenephsphomuzte, CIOH15*P03H*NHd.-This salt was prepared by dissolving the acid in strong ammonia and evapo- rating to dryness. It is very soluble in water, and was precipitated from the aqueous solution, in the form of light, feathery crystals, by adding alcohol and ether.On analysis, it gave Found. Calculated. Nitrogen ........ 6.4 6.0 per cent. Crystanised from water, it gave Found. Calculated. Nitrogen ......... t5.9 7 6-0 per cent. It is difficult to tell, without further investigation, whether this salt is a derivative of the hydrated, or of the anhydro-, acid, there being such a slight difference in composition. Ammonium /3-Camphenephosphonate, CloH1~*P0,H~NH4.-The acid was dissolved in ether and the salt precipitated by passing dry am- monia into the solution. On analysis, it gave Found. Calculated. NH, ............ 7.78 7.26 per cent. This salt was less soluble in water than the preceding. Crystallised from water, it gave Found. CaldSLted. Nitrogen ......... 6.65 6.0 per cent. Barium a- Camphenephosphonate, (Cl,H,5*P02)2Ba0.-This salt was prepared by adding baryta water t o the acid. It is very slightly soluble in water, and crystallises from hot water, on cooling, in voluminous, wool-like masses.It is also obtained by precipitating the ammonium salt with barium chloride. Analysis of the dried salt: Found. CalCUhtecL Barium .......... 24.33 24.9 per cent. The air-dried salt contains 5H20, corresponding to the formula (Cld&,*P02)2Ba0 + 5H20.PEOSPEORUS DFalTATIVES OF CAMPKENE. 41 Found. Calculated. Water. .......... 14.4 14.1 per cent. Zinc a-Camphenephosphonate, ( C10E:15*P02>2Zn0.-The zinc d t W R ~ obtained by adding zinc nitlate to the ammonium salt, when it was precipitated in a flocculent state, very elightly solnbIe in water. Dried in air, it is anhydrous. Analysis gave Found.Calculated. Zinc 13.75 13%3 per cent. .......... Rotatory Power. It has been already stated that the phosphonic acids derived from different camphenes differ in their rotatory power in respect of polarised light, without appreciably differing i n chemical properties. They thus present a difference in physical properties similar, in kind, to that presented by the camphenes, and by the turpentines from which they are derived. The two isomeric phosphonic acids are obtained from laevorotatory camphene, as well as from dexhrotatory camphene ; but, whereas the acids from dextrorotatory camphene are inactive, those from 1Evorotatory camphene are also laevorotatory, though to different degrees ; thns, in alcoholic solution, the a-acid has a specific rotatory power [aID = --119*, whilst the ,%acid has a, specific rotatory power of only -71" in alcoholic solution.Experiments are in progress with the object of endeavouring to separate the inactive acids obtained from dextrocamphene into their possible active constituents. For this purpose, the cinchonine salts, both of the inactive and of the active a-acids, have been prepared; they are both beautifully crystalline substances. A more detailed description of these salts is reserved for future publication, should the experiments in progress with them lead to any definite result. Action of Heat on the #odium Salts of the Camphenephosphonic an'ds. It has already been noticed that, when heated at 100" for a long time, /3-camphenephosphonic acid undergoes decomposition, the mfs- talline acid being converted into a syrupy liquid containing phosphoric acid, a considerable loss in weight taking place.Both acids also decompose at their melting points. A more detailed study has been made of the action of heat on the sodium salts of the two acids. When sodium /3-camphenepbosphonate is heated, it loses its water of crystallisation, and, on raising the temperature to about 160°, under- goes an almost quantitative decomposition kt.0 camphene and sodinnr metaphosphate. On distilling i t from an air bath at about this tem- perature, 90 per cent. of the theoretical amount of camphene was recovered. When heated on a watch glass in the air bath for several42 PHOSPHORUS DERIVATITTS OF CAMPEIENE. hours, it melted, and left 32.9 per cent.of residue, the amount calm- lated for the conversion of the crystalline salt into sodium meta- phosphate being 31.1. This residue gave the test for metaphosphonie acid, namely, coagulation of albumin, a white, gelatinous precipitate with silver nitrate, and a yellow precipitate with ammonium molyb- date. Sodium a-camphenephosphonate does not undergo decomposition so readily or so completely, 48.1 per cent. of residue being obtained, the amount calculated for the conversion of the dry salt into sodium metaphosphate being 44.9 : this occurred on heating in an open dish. When the salt was heated in a retort, neither camphene nor any distillate but water was obtained up to the temperature ZlO", but on heating at 260°, a small quantity of a semi-solid distillate resembling impure camphene was obtained, and a residue was left amounting to 75 per cent.of the dry salt. The difference in the constitution of the dry s d t s readily accounts for this difference in behaviour nnderthe influence of heat. It will be seen that sodium p-camphenephosphonate, having the formula C,,H,,*PO,HNa, can break up according to the equation CI,H,,=PO3HNa = CloH1, + NaPO,, whereas a-camphenephosphonate of sodium, having the formula (C~oHl,*P02Na),0, cannot break up into phosphate and camphene. It is probable that the greater de- composition of the latter salt when freeIy exposed to the air, so as to leave a residue containing metaphosphate, is due to the action of aqueous vapour. Hydrolysis of the Phosphonic acids.-When subjected to the action of water in sealed tubes, the salts both of the a- and of the &acids are decomposed, yielding in both cases camphene and sodium hydrogen phosphate, NaH2P04.Here again the two salts show a difference in behavionr; for while the p-salt is readily decomposed at 170°, the a-salt shows no apparent change below 1800, but is decomposed a t a temperature considerably above ZOOo. Action of Halogens on the Sodium Salts of the Pl~osphonic acids. Bromine water, chlorine, and iodine attack Eodi um p-camphene- phosphonate, seicting free phosphoric acid and yielding precipitates, that produced by bromine being very dense; a precipitate is pro- duced in this manner even in very dilute solutions. The a-salt is less readily acted on, but it, too, is decomposed by bromine and chlorine, although not by iodine. We have not j e t ascertained the nature of the organic products formed in these cases.The pre- cipitate produced by bromine is of an oily nature; in one case this oil was collect,ed, washed with caustic soda, and dried. It decom- posed on distillation. It contained over 60 per cent. of bromine, approximately corresponding to the f ormnla C,,,H,,Br, or Cl0H,,Br3.EXTRACTION OF GASES DISSOLVED IN EATER. 43 Nature of the Isomerism. From the description of the acids and their compounds given above it will be observed that the two acids may be represented as derived one from orthophosphoric acid, thus, P O E /3-Camphenephosphonic acid. l0H Phosphoric acid. the other from pyrophosphoric acid, thus, OH P O l O H LO Pyrophosphoric acid. a-Camphenephosphonic It may heuce be objected that, inasmuch as the two acids are derivatives of two different phosphoric acids, they are not strictly isomeric. On the other hand, if the difference between the acids were solely due to theiia being related one to the other as ortho- phosphoric acid is to pyrophosphoric, we should expect them to be mutually convertible into one another, or at any rate one of them convertible into the other, just as pyrophosphoric acid is convertible into orthophosphoric acid. We have not found, however, that either of the acids is convertible into the other; and though the a-acid may, under certain circumstances, take the orthophosphoric type, it is still distinct from the /3-acid. We have, therefore, to look for the cause of the isomerism in the different positions which the phosphonic grouping occupies in each case with respect to the camphene nucleus. For the explanation of this isomerism, however, we shall have to wait until the constitution of camphene has been definitely ascer- tained. acid. University Labor0 tory, Oxford.

ISSN:0368-1645    

DOI:10.1039/CT8946500035

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

EXTRACTION OF GASES DISSOLVED IN EATER. 43 VII1,-Apparatus f o r the Exts-action for Analysis of Gases dissolved in Wader a r d other Liquids. By EDGAR B. TRUMAN, M.D., F.C.S., Borough Analyst, Nottingham. THE apparatus hitherto described for this purpose may be referred to two classes. In the first, the dissolved gases are separated by boiling, and.44 TRUMAN: APPARATUS FOR THE EXTRACTION FOR carried by a long delivery tube (from which air has been expelled bv passing steam through it) into a vessel containing, and inverted over, mercury. This method is described and illustrated i n Watts’ Dictionary of Chemistry, 5, 1028 (1st edition, 1869). Fresenius’ method (Quantitative A?zalysis, 1870, 289) differs only slightly from this, as he conducts the gases given off ou boiling into a vacuous tube, these gases being subfiequently decanted into a vessel containing mercury.In the Analyst for March, 1893, there is an abstract of a paper by G. Musaio, on methods in use for determining the quantity of gas dissolved in potable waters. He obtains the gases by boiling the water in a flask completely filled by it, the gases being received into another flask filled with boiling distilled water, at the pressure of the atmosphere ; but as each increment of gas increases the pressure, and this in a flask closed by a cork, there must be liability to leakage. The connections are made by means of india-rubber corkg, and india-rubber tubes with pinch-cocks, and there are 11 junctions, all of glass and india-rubber, in any of which leakage may occur. To this class also belongs an apparatus de- scribed and figured by Bremer in Rec.Traw. Chim., ll, 278 (Abstr., 1893, ii, 432). The great disadvantage of this method is that it affords no means of estimating separately the gases given off at the ordinary tempera- t-me, and on boiling. The second class does separate the two sets of’ gases, and may be typified by M’Leod’s apparatus (J. Chenb. Xoc., 1869, 307). I n this “ apparatus for determining the quantities of gases existing in solution in natural waters,” a Torricellian vacuum is produced in the first place, and the water to be examined is driven into the vacuum ; the gases given off at 50” C. are then pumped out by a Sprengel. After the vacuum has been restored, the water is heated by means of a hot-water pipe arrangement, and the gases given off are again removed by the Sprengel.Gamgee, in his Text-book of the Physiological Chemistry of the Animal Body, 1880 (1, 196), gives. an article on the separation and determination of the gases in blood. The blood is received into a graduated burette with stopcock, which is filled with mer- cury, and communicates below with a mercurial reservoir. From the burette the blood is forced through suitable connecting tubes into the vacuous chamber of a mercurial pump. Several pumps are described-Ludwig’s, in which the vacuum is Torricellian ; Pfliiger’s, in which the vacuum is also Torricellian, but in which there is an arrangement by which the water vapour disengaged in a vacuum from the blood is at once absorbed. Alvergniat’s pump is similar to Pfliiger’s, but the barometric chamber, that is, the chamber in whichANALYSIS OF GASES DISSOLVED IN WATER, ETC.45 the vacuum is formed, ii much smaller, and therefore sooner ex- hausted. In the British Medical Journal of 18th Aupst, 1888, is an address by M'Kendrick on the gaseous constituents of the blood in relation to respiration. The pump 6gured here acts also by producing a Torricellian vacuum, and in all the pumps mentioned the gases are obtained for analysis ultimately by raising the mercury reservoir, and driving the gases through connecting tubes into suitable vessels, re- quiring, therefore, a considerable supply of mercury other than that in use with the Sprengel. These apparatus of the second class are highly complicated, and have many stop-cocks and other connections; in some of these connec- tions, for example, in the case of an india-rubber tube with pinch- cock, it must be almost impossible to complete the union without including a little atmospheric air.Iu the apparatus which I have devised I make use of the water- pump to produce a vacuum in the first place, supplementing its action by that of the Sprengel. The gases are separated into those given off at the ordinary temperatures, and on boiling, and the in- strument is very simple in its construction. It is a slightly modified form of the apparatus I showed and described at the chemical section of the British Association held a t Nottingham in September, 1893. A glass flask, A (p. 46), of 500 C.C. capacity, is joined by means of its tubular termination to a second flask, B, of 200 C.C.capacity, the connection being made by inclia-rubber tube covered by a water seal. B must have a long and evenly tubular neck to allow of the movement up and down of this water seal. IT^ the lower flask is suspended from the upper one a thermometer reading up to 150" C. A piece of slender glass rod, narrow enough to pass up the tubular end of A, and about 25 mm. in length, is narrowed in the middle, a piece of platinum wire is wound by one end round the narrowed portion, and the rod is pushed up into the flask by pushing with a stout wire, and pulling at the unattached end of the platinum wire ; the rod is fixed transversely across the lower opening of the flask, and to the dependent wire is attached the thermometer.The right- hand one communicates by means of a two-way tap, P, with a vessel, C, having a capacity of more than 50 c.c., and closed above by a well-fitting glass stopper. This vessel is graduated at 25 and 50 C.C. The two-way tap alternately makes communication between A and C, or between C and the small capillary or millimetre tube H, 30 mm. lolrg. This capillary tube should be filled from C with boiled distilled water to displace the air which it contains. The From the neck of flask A ascend two millimetre t'ubes.46 TRUMAN: APPARATUS FOR TEE EXTRACTION FOR capacity of the tube is so small that the amount of water which it contains may be neglected. Of course the water examined, when introduced at H, is diminished by that amount. If desired, the necessary correction can be made by a slight scratch above and 50 C.C.mayk, and the vessel filled to the corrections. H lengtheued by the addition of a longer tube, ZC. the 25 may beANALYSIS OF QASES DISSOLVED IN WATER, ETO. 47 The tube on the left side rises to the level of the bottom of C; it is then bent at a right angle, and, proceeding in a horizontal direc- tion, has two tubes, supplied with stop-cocks, joined on to it. The first passes upwards, and is attached by a water, or glycerine, seal to a mercury tube, D, doubled on itself above and below, as shown, and having the length, from one doubled end to another, of 880 mm. This tube is graduated in niillimetres, from 0 to 400, in two direc- tions, downwards in the open limb, and upwards in the long part of the tube, starting, in each case, from the level of the horizontal tube.This tube is filled with mercury up to the zero points; i t indicates the rate of exhaustion of the apparatus, and is also a test of leakage. The second tube, E, a little further on, passes downwards, for the purpose of attachment to a Geissler's water-pump. Still farther on, the main tube receives a stop-cock, and then bends downwards for connection with a Sprengel pump. The flask A is cooled by a covering of some porous material satn- rated with water. What is known to surgeons as Gamgee tiswe answers very well; this consists of a layer of cotton-wool, freed from fat, and enclosed between two layers of gauze. A little jacket of this material is fastened round the upper part of the flask bya thin wire, passing through a pair of eyelet holes, such as are used in the manufacture of boots.To the upper end of the tobe, forming the water-seal, is fixed an india-rnbber tube, cut out to receive the glass tube, and conveying away the surplus water from the jacket above. The thin wire that fastens together the jacket turns down to hold up the rubber tube, and so prevent kinking. If thoroughly wetted at the commencement of the operation, very little additional water is required for the purpose of keeping down the temperature. Flask B, having been separated from A, after a previous experi- ment, and emptied of its contained liquid, is secured, by a wired india-rubber connection, and water seal, to 8. The terminal tube and tube E are put into connection with the mercurial and the water pump.The liquid to be examined may be introduced into the apparatus either by the mouth of t'he vessel C, or, without access of air, by the capillary tube H. In the former case, t,he stopper of C is removed, and the two-way tap is closed to both of its communications. I n the latter case, after fillinq the space from the two-way tap to the end of A by running out boiled distilled water from C, the stopper is retained in its place, and the two-way tap is turned so that C and A communicate. The water pump is set t o work, and, with high-pressure water, the apparatus is exhausted to about 740 mm. in 10 minutes. In a trial experiment, after 10 minutes action of the Geissler, the height oE the mercurial column raised by the e-dmnstion was 738 mm.The tension48 TRUMAN: APP-QRATUS FOR THE EXTRACTION FOR of water vaponr at the temperature recorded in the lower flask, B (lSo), equals 15.5 mm., making the whole height, in a dry tube, 753.5 mm. The reading of a standard barometer at the time was 756-8, the difference being thus only 3.3 mm. When the Geissler ceases to depress the mercury, the stop-cock at E is closed, and ex- haustion is completed, in about 30 minutes more, by the Sprengel. F. J. Smitb, in Nature, 3rd August, 1893, describes and fipres a 46 Periodic Mercurial Pump,” for refilling, automatically, the Sprengel reservoir, by means of a water pump. By utilising the Geissler in this way, the labour of refilling the Sprengel bs hand is abolished. Tha.t a vacuum has been obtained, is shown by the well-known metallic click of the falling mercury in the Sprengel, and by the fact that bubbles of air cease to be given off at the end of the delivery tube: not by the mercurial tube D, as it is impossible to be certain that the temperature, and consequently the tension, of water vapour in the upper part of D is the same as in flask B, where the thermo- meter is read. The liquid to he examined for gases is then introduced by the mouth of C, in which case it is poured up to the 25 or 50 C.C.mark ; then, by cautiously making commuuication between C and H, the liquid flows into A, and then into R ; if 100 C.C. are required, this step is repeated. If, however, the filling is to be done without access of air, the tube H is allowed to dip into a beaker containing the liquid to be examined, and communication opened between it and C.In this way, the liquid is allowed to rise up to 25 or 50 C.C. ; the tap then opening the way from C to A , the conhents of C will descend into A and B, the operation being repeated, if necessary. If it is required to remove the water, or other liquid, from any depth, such as the bottom of a Winchester quart, a suitable length of glass tube of small, or capillary, bore should be filled m-ith the liquid and attached to H by india-rubber tubing. If the bore is sufficiently small, the liquid will remain, by capillary attraction, high enough to permit its being raised suficiently above the surface of the liquid to allow of its attachment to E, without admitting air. The quantity of liquid employed may vary from 100 C.C.of an ordinary drinking water to 50, 25, or 10 C.C. of a mineral or aerated water. The liquid is allowed to stand for an hour, so that gases disengaged at ordinary temperatures may come off. These ars collected by the Sprengel, and analysed in the usual way. The vacuum having been restored in this way, heat is gently applied to B, by means of a Bunsen burner. If carefully dore, there is no bumping. At first, I made use of small pieces of platinum foil t o prevent bumping, but found it unnecessary to do so. The effectANALYSTS OF GASES DISSOLVED IN WATER, ETC. 49 of heat is, by disengaging gas and lessening the vacuum, to raise the temperature of the water, or other liquid, and the tension of the vapour. At first. the water boils when it is scarcely warm; gradually the mercurial column rises in the short limb of D, the record of the thermometer increases, and the liquid gets hotter.When the readings of the mercurial tube and the thermometer remain constant, the Bunsen is removed. The gases given off by boiling are then collected by the Sprengcl, and analysed. I f ordinary pressure and boiling temperature have been attained before all the gases presumably hare been given off, the Bunsen is removed, the gases pumped out, and a second boiling is proceeded with. Practic- ally, no water passes over with the gas, if the jacket at A is kept cool, and, therefore, no error arises from solubility of the gases in thc distilled water, as is the case with some other forms of apparatus.Results obtaiqed by Jlethods described. Ratio of dissolved gases in matter by calculation at 20" C. is- 0,. ................... 28.23 3,. ................. 54.14 CO?. ................. 17.52 100~@0 Professm M'LeotL's Figures, C.C. per 100 2.01s. Grand Junction CannZ Water. 0, .......... 1.391 0.007 1.398 N, .......... 9%09 O * i ) l 1 0 620 CO, ........ 0.420 3.877 4-297 2.42 3 895 6-31 5 At 50" C. By distillation. Total. - - Ratio taking only CO, at 50" C.- .............. 24.c3 Very near to the theoretical .............. N, } figures. 0, :h72 CO, ............ 19.9 Ratio taking both quanticies of C0,- 0 2 .................... 9.8 AT: .................... 28.1 C 0 2 ................... 68.1 showing the disturbing influence of the CO, given off by boiling, which is, as the following figures show, derived from the decomposition of the calcic bicarbonate, and is not simply dissolved gas.VOL. LXV. E50 EXTRACTION OF OASES DISSOLTED IN WATER. Gases in Rain Water. At 50” C. BJ dietilhtion. Total. 0, .......... 0.671 0.014 O-fi85 N? .......... 1.348 OfU3 1.381 (30,. ........ 0.055 0.071 0.116 2.064 0.118 2.182 -- - Ratio per Total. 0 .................... 30.7 N, .................... 61.8 c02 ................... 7.5 Yrofeasor Frankland, ‘‘ Water Analysis,” 1S8S, working by Fyeseizizcs’ JIe t hod. Rain water. Deep chalk well water. O2 ............ 0.637 0.088 N?.. .......... 2.308 1944 CO,. .......... 0.128 5.520 Ratios. O2 ............ 30.7 0.373 N2.. .......... 63.0 25-948 GO, .......... 6-3 73.679 N y jgures. Nottingharn T;tTater Szipply.9th May, 1893. 16th May, 1893. r I 6 m . 60” F. Boiling. Total. Oa ........ 0.40 0.76 1-16 0.36 0.67 1-03 N2.. ....... 1.24 2.25 3-49 1-34 2.47 3-€!1 GO, ....... 0.10 0.52 0.62 0.09 0.39 0.48 A 1-74 3.53 5.27 1.79 3.53 5.32 Ratio, 9th May, for total. 0, .................... 22-0 N, .................... 66-2 CO, ................... 11.8 The water of the 16th May was titrated with decinormal acid and methjl-orange, to ascertain the amount of calcium carbonate ; and, in another quantity of the same water, after expulsion of the gases by boiling and tiltration of the water, the amount of calcium carbon- nte remaining in solution was estimated.MILLS ON THE STRUCTURE OF AZOBENZENE. 51 100,OOO parts contained /----h----- 7 Before After boiling. boiling. CaCO, .............. 9-25 7-5 = CO,.. ............ 4.07 3.3 In c.c. .............. 2060 1670 = per cent.. ......... 2-06 1.67 Difference = 0.39, which is the same figure as that obtained by measuring the CO, given off on heating. This shows that the gas given off at ordinary temperatures in a vacuum is the dissolved gas; that given off on heating is derived from the decomposition of r;he bicarbonate of calcium, CaH,(C03)?, CO, being given off in exact proportion to the CaC03 thrown down by heating. Of course, on heating under ths ordinary pressure, the usual amount of CaC03 would be thrown down, namely, all but 2 in 100,000 of water. If water containing caustic potash is heated in the manner described, and the resulting freed gases pumped out, on adding an air-free solution of pyrogallol to the flask contents, no change of tint occurs in the mixed solubions. If now air is allowed to enter, the usual darkening occurs at once. I conclude, therefore, that dissolved CO, is given off at ordinary temperatures in a vacuum, and that the oxygen is entirely driven off by boiling ; but, with respect to nitrogen, I can offer no opinion. The oxygen appears to be entirely remored by heating.

ISSN:0368-1645    

DOI:10.1039/CT8946500043

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

MILLS ON THE STRUCTURE OF AZOBENZENE. 51 IX-Studies on the 8tr.uctur.e of Axobenxene. The action of Bromine on Ax obenxene ; pyoduction uj* Tetrub I-omoben xidin e. By CHAS. MILLS, Assoc. C.G.L.I. AMONG coloured substances of simple composition, azobenzene is one of the very few which is represented by a formula of a non- quinonoid type, and moreover by a formula which cannot well be modified so as to bring this compound within the " colour rule " to which Dr. Armstrong has so persistently directed attention in recent years (Proc., March, 1888, 27 ; 1892, 101, 143, 189 ; 1893, 52, 206.) Nietzki, in the introduction to his Chemie der Organischen Farb- stofe, tails attention to the peculiarities of azobenzene in the following words : " Eine Klasse von Farbstoffen, deren Eigenschaften mit Bezng auf ihre Constitution anff allen mussen, sind die Azokorper, specie11 aber52 N U S ON TELE STRUCTURE OF MUBENZENE.ihr einfachster Reprkentant, das Azobenzol. Wahrend wir dnrch Substitution eines einzelnen Wasserstoffs in einem Benzolring, selbst wenn zwei solche Ringe durch ein zweiwerthiges Radikal verkettet werden, wenig oder gar nicht gefarbte EGrper erhalten, ist das Azobenzol eine intensiv gefarbte Verbindung nnd ein starkes Chromogen. Es liesse dieses an sich fast die Vermuthung aufkommen, dass dem Azobenzol nicht in allen Reaktionen die einfache Constitut’ionsformel C:,H,.K‘:N*C6H5 znkommt, und einzelne Thatsachen konnten hier zu weiteren Speculationem verleiten. Die grosse Leichtigkeit, mit welclier das Azobenzol, namentlich aber das daraus entstehende Hydrazobenzol, i n ein Derivat des Diphenyls, das Benzidin, ubergeht, scheint fast darauf hinzudeuten, dass Zwischen den beiden Benzolkernen eine Art von loser Bindnng vorliegt.Es liesse sich diese nur mit der Anschauung vereinigen, dass, nach Analogie der Chinone, eine Losung der doppelten Bindungen im Benzolring stattfindet. Es kame diese Auffassung in N- N !I H/\H = A H ;I llH I!H . Selbstredend mchstehender Formel zum ausdmck, a\/ v kl H gehoren derartige Formeln in das Gebiet der Hjpothese, nnd konnen nnr als Versoche, die sammtlichen FarbstoEe unter einen gemein- samen Gesichtspunkt zubringen, betrachtet werden.” N-- N quite the same objection, and is perhaps more in accordance with the marked red colour of azobenzene ; but both expressions equally fail to inspire confidence, as the mode of condensation they picture has not hitherto been recognised as occurring between t w o cycloids, and even the ortho-formula is not a satisfactory expression from Dr.Armstrong’s point of view. Under these circumstances, it appeared desirable to further study azobenzene and it,s derivatives, and, therefore, at Dr. Armstrong’s request, I undertook to examine its behavionr with bromine, a s the statements on record are in some respects remarkable ; thus Werigo has described a c0ZourZes.s tetrabromazobenzene (Annalen, 165, 200). The existence of such a compound mould undoubtedly, in a measure, serve to confirm the view that nzobenzene has not the constitution which is commonly attributed to it. My experiments shorn, however, that Werigo was in error, and t h a t the compound described by him as tetrabromazobenzene is simply tetrabromobenzidine.MILLS ON THE STRUCrURE OF AZOBENZENE. 53 Rodatz has described (Amale%, 215, 21 7) tetra- and hexa-bromazo- benzenesulphonic acids of the formulae Br Br S Br Br 8 which are of interest in connection with the question raised in this communication.The salts of the tetrabromo-acid appear to manifest properties such as derivatives of azobenzene might be expected to exhibit ; the description given of the derivatives of the hexabrom- acid is somewhat less satisfactory. I have endeavoured to prepare this latter acid, but haye not been so successful as Rodatz, and am inclined to think bhat the action is by no means so simple as is implied in his account. I therefore propose to further study the behaviour of the bromanilinesulphonic acids on oxidation with per- mangana te.H. von Reiche has described (AnnaZert, 203, 64) two azobenzene- tetrasulphonic acids formed by reducing 1 : 2 : 4- and 1 : 3 : 5-nitro- benzenemetadisulphonic acids. That prepared from the 1 : 3 : 5-acid yields colourless salts ; when it is mixed with stannous chloride, no action ig apparent, and the product resembles the parent substance ; but v. Reiche nevertheless regards this “product ” as a hydrazo- acid, as it is converted into a benzenemetadisulphonic acid by the action of nitrous acid, &c. There can be no doubt that v. Reiche never had an azobenzene derivative in his hands, and that his product was the amido-acid corresponding with the nitro- acid used.The same is, perhaps, true of the reduction product he prepared from the 1 : 2 : 4-nitro-acid, which he describes as /I-azobenzenetetrasulphonic acid ; some of the salts of this acid are spoken of as coloured, but there is no reference to colour in the case of the sulphonic chloride, and the sulphonamide is described as a yetlowish, crystalline mass. The corresponding hydrazo-acid is said to yield diazobenzenedisulphonic acid when snb- jected to the action of nitrous acid. The a-diazo-acid, according to v. Reiche, behaves in a peculiar manner with phosphorus penta- chloride, but there appears to have been no difficulty in the case of the fi-acid in obtaining a sulphonic chloride ; as amido-acids do not yield sulphonic chlorides, this latter statement is remarkable, and it will be necewary to revise von Reiche’s work.Action of Bromine on Azobemeize. Azobenzene Perbromide.-Azoben- zene, according to Werigo, readily combines with bromine, forming a highly unstable hexabromide ; it is easy to prepare this substance by following his directions, but it loses bromine with such readiness54 MILLS ON THE STRUCTURE OF AZOBEKZENE. that it must be a matter of great difficulty to satisfrtctorily determine its composition ; on exposure to air, the whole of the bromine is given off, leaving unaltered azobenzene. As it was conceivable that this perbromide might be analagous in composition to a diazoperbromide, it was added to a concentrated solution of ammonia ; but no azoimide was formed, the product consisting chiefly of unchanged azobenzene mixed with a small proportion of paradibromazobenzene, m.p. 209". With the object of preparing higher derivatives, I have made a number of experhents on the action of bromine on azobenzene in different solvents a t temperatures varying from 60" to 90" (compare Janorsky, Monatsh., 1887, 8, 49). The results show that bromine has very little action on azobenzene dissolved in either acetic acid or chloroform, most of the azobenzene being unattacked. I n the case of acetic acid, small amounts of meta- bromazobenzene (m. p. 55-56") and o-dibromazobenzene (m. p. 187") were obtained, while, on using chloroform as a solvent, y-dibromazo- benzene (m. p. 205"), o-bromazobenzene (m. p. 87"), and o-dibromazo- benzene (m.p. 187") were produced, all, however, in very small quantity. On heating azobenzene with bromine in a sealed tube at loo", a quantity of symmetrical tribromaniline was formed, the rest of the product being resin. The resistance which azobenzene opposes to the action of bromine is very striking, and it would seem that the preparation of pure hromo-derivatives by the direct action of bromine is a matter of con- siderable difficnlty. Conversion of Azobenzene into Tetra6romobenzidine.-The subs tance described by Werigo as tetrabromazobenzene was prepared by adding bromine to a hot concentrated alcoholic solution of azobenzene ; its preparation in this manner is Fery easily effected : the azobenzene is dissolved in about twice its weight of hot alcohol, and from three to four times its weight of bromine is poured down the condenser tube when the mixture is nearly boiling; very vigorous action ensues, bromine and hydrogen bromide being given off.On filtering off the solid product and well washing it with a little alcohol, a white residue is obtained. On extracting this product with boiling alcohol, a con- siderable proportion is dissolved ; this soluble portion consists of tribromaniline, m. p. 119". As the substance obtained after ex- tracting the tribromaniline agreed in its properties with the descrip- tion given by Werigo, in the first instance, I subjected it to the action of stannous chloride : the product was purified without difficulty by recrjstdlising it from boiling xylene, from which it separated in short, flat needles melting sharply at 284-286" (uncorr.).This sub- The mixture eventually becomes solid.MILLS ON THE STRUCTURE OF AZOBENZENE. 55 stance was proved by direct comparison to be identical with the tetrabromobenzidine prepared by Clam and Risler from benzidine by direct bromination (Ber., 14, 86). In the course of the experiments, I was led to notice the very clgse resemblance of the product described by werigo as tetrabromazobenzene with this tetrabromobenzidine, and therefore reexamined the crude product ; ultimately, by repeatedly recrystallising it from boiling xylene, a product indistitlguishable from tetrabromobenzidine was obtained. When impure, the substance chars before it melts, and this, perhaps, accounts for the high melting point observed by Werigo.The difference in composition between tetrabromazobenzene and tetrabromobenzidine is so slight that it is impossible to decide by analysis which compound is dealt with ; and the absence of hasic properties makes it difficult to differentiate the tetrabrom obenzid ine. The following analyses of the prodnct from azobenzene were made. Subs. 0.1885. AgBr 0.2836 Br 64.02 ,, 0.2342. ,, 0-3.527 ,, 64.08 ,, 0.1927. ,, 0.2892 ,, 63.86 Subs. 0.1226. N, 6.3 C.C. (moist) ; t. 17" ; bar. 758 mm. N 5.96. Theory for C,,H,Br,N,: Br 64-00. Acetylation of Tetrabromobenzid ine and Benzidine.-On merely boiling the tetrabromobenzidine w i t h a large excess (six times its weight) of acetic oxide, a product was obtained which was easily purified by crystallisation from benzene, from which it separated in fine needles melting at about 306" (uncorr.) ; this substance was also easily soluble in carbon disnlphide and chloroform, less easily in alcohol, ar.d insoluble in ether and petroleum spirit.The remlts of the analyses made of this substance prove it to be a tetracetate. N 5-60. Subs. 0.1343. AgBr 0.1512 Br 47-91 ,, 0.1434. ,, 0-1617 ,, 47.97 ,, 0.2670. ,, 0.3012 ,$ 4840 Subs. 0.2073. Nr 8 C.C. (moist) ; t 22" ; bar. 760. N 4.47. Theory for C,,H,Br,X2Ac, : Br 47.90 ; N 4.19. The formation of this tetrucetafe is effected with mmarkable readi- ness ; as no corresponding derivative of benzidine has been described, I subjected benzidine to the action of an excess of acetic oxide ; the diacetate, m. p. 317", was almost immediately produced, but prolonged boiling was necessary to effect further acetylation.Ultimately a product was obtained which still contained diacetate ; on boiling this with benzene, a large proportion dissolved, but sepa- rated from the liquid on cooling ; after recrystallising this product56 MILLS ON THE STRUCTURE OF AZOBENZENE. from a mixture of alcohol and benzene, it was obtained in long, silky needles melting at 21W215". Analysis shows it to be a tetmcetate. Subs. 0.1307. N2 9 C.C. (moist) ; t. 11.5" ; bar. 747 ; N 8.15. ,, 0.2804. ,, 18.8 ,. t. 11.5" ; bar. 747.4 ; N 7-94. Theory for C,,H,N,Ac, : N 7.95. Benzidine tetracetate is but slightly soluble in benzene and ether, but readily in alcohol and chloroform. It is known that tribrom- aniline is readily converted into a diacetate (Remmers, Ber., 7, 350), and Clanis and Philipson have recently described ( J .pr. Chem., [2], 43, 47-61) diacetates of 1'-bromo- and 1 : ?i'-dihromo-betanaph- thylamine ; it would seem, therefore, that the two atoms of hydrogen in the NH, group of amineil are the more readily displaced by acetyl the less basic the amine. Constitution of Tefrabromobcnzidine.--It was to be expected that benzidine would furnish a tetra-ortho-deriTatioe, and this proves to be the case. It is not easy to diazotise tetrabromobenzidine ; the method finally adopted was to dissolve i t in 15 times its weight of oil of vitriol and to gradually add four-tenths of its weight of finely- powdered sodium nitrite ; after sereral hours, the mixture was poured into 20 times its weight of cooled dehydrated alcohol, and after warm- ing the solution until gas was no longer evolved, i t was cooled and the product filtered off.The product could not be obtained in a satisfactory condition by mere recrystallisation, but it was eventually pnri6ed by partially oxidising it by boiling with a solution of chromic anhydride in acetic acid; after this treatment i t crystallised from benzene, in which i t was but moderately soluble, in white, microscopic needles melting at 189"; of this substance, 0.1723 gave 0.2753 AgBr = Br 67.99 ; the percentage of brcmirie in tetrabromodiphenyl being 68.08, there was no doubt it was this substance. A satisfactory amount of the diphengl derivative may he obtained in the manner described if the oxidation be carefully conducted. various methods of oxidising the tetrabromodiphenyl were tried, but no satisfactory results were obtained ; by boiling it with a solu- tion of chromic anhydride in acetic acid, a relatively small proportion of an acid was obtained which, after recrystallisation from alcohol,. melted at 212--213" ; as this is the melting point of dimetadibromo- benzoic acid, there is little doubt that this acid is formed by oxidis- ing tetrabromodiphenyl from tetrabromobenzidine, and that this latter compound is the tetra-ortho-derivatire. Chenzical Department, C.G.L.J. Central Technical College, Exhibition Road, S. W.

ISSN:0368-1645    

DOI:10.1039/CT8946500051

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

57 X - Coryduiine. Part 111. Oxidation with Potassium Pemnanganate. By JAMES J. DOBB~E, M.A., D.Sc., and ALEXANDER LACDER. IN a previous paper (Trans., 1892, 61, 605), we showed that coryd- aline contains four methoxy-groups ; by oxidising i t with potassium permanganate, we have obtained further light on the constitution of the alkaloid. This oxidation was carried out with small quantities of the material, about 8 grams being used for each operation ; for tvhis purpose, the alktlloYd was suspended in abont 2 litres of boiling water, and a solution of potassium permanganate added until it was no longer reduced, the liqaid in which the alkaloid was suspended being kept at the boiling point all the time: the amount of permanganate required was about 27 grams, dissolved in 2-3 litres of water.In the event of excess of potassium permangauate having been added, it was reduced by passing sulphur dioxide through the solution. The oxidation usually occupied three hours. The rednction of the per- manganate waa very rapid at first, ammonia being continuonsly evolved, but, after about three-fourths of the solution had been added, the oxidation proceeded very slowly. The corydaline employed W&B carefnlly purified by repeated recry stallisation until the melting point was constant. When the oxidation was complete, the manganese precipitate was allowed to settle, the solution filtered off, and the precipitate thoroughly washed with boiling water until the washings were no longer alkaliue to litmus paper. The filtrate was then evaporated to dryness, the organic matter extracted with absolute alcohol, the alcohol distiIIed off, the concentmted solution cautiously erapor- ated to dryness, and the residue dissolved in water.The potassium in the residue having been estimated, the amount of sulphuric acid required to convert it into potassium sulphate was added. At this stage a considerable quantity of black, tarry matter separated, and was removed by filtration; the solution was concentrated, filtered from a further precipitate of tarry matter, and the potassium snlphah in the filtrate precipitated by adding a large quantity of absolute alcohol ; the alcoholic solution was then filtered from the precipitated potassium snlphate, the latter being washed with absolute alcohol until free from organic matter.The greater part of the alcohol was now distilled off, and the remaining solution placed in a desiccator over concentrated sulpburic acid, when the solution gradually de- posited a crop of dark brown crystals of 8 nitrogenous organic mid. On concentrating the mother liquor, a further crop of crystals w s & VOL. LXY. F58 DOBBIE AND LAUDEK: O-XIDATIOY OF CORYDALTNE tained, but the separation of the last portions of the acid was rendered difficult by the presence of some of the black, tarry matter mentioned above, which-is easily soluble i n alcohol, and also, to a, slight cxtent, in hot water in presence of the acid. When the whole of the acid had been extracted, the mother liquor yielded, on evaporation, a clear, yellow, resinous mass. This residue is easily soluble in water and i n alcohol, and contains an organic acid or acids, which are precipitable by silver and lead, but we have not, aa yet, completed our examination of this product of the oxidation.The yield of crystalline acid obtained by the method dezcribed was 20 per cent. of the corydaline used. A portion of the latlter always escaped oxidation, and was recovered from the precipitated manganese ox ides. With the view of shortening the process described above, we adopted the following modification i n some of our experiments. The potassiam in tbe filtrate from the insuganese precipitate was directly neutrslised with sulphnric acid, and the potassium snlphate precipi- tated with absolute alcohol, the rest of the operation being carried ou as already described.We found, however, when this modified pro- cess was employed, that the yield of acid was greatly diminished. Various other methods of working up the oxidation products were tried, such as precipitation with silver and lead, and subsequent de- composition with hydrogen snlphide, but none of them yielded satis- factory results. The crude crystalline acid obtained by the process described above was found, on examination, to be homogeneous; it was purified by repeated crystallisation from water, in which it dissolved readily when hot, separating out again on cooling. The colonring matter was re- moved by treatment with animal charcoal, but even then the acid still retained a slight ye€low tinge; when pure, it forms flat, six-sided prisms, which have the habit of monoclinic crystals.They contairf 3H,O. The acid, dried at lOO", gave the following results on analysis. I. 0-3011 gave 0.5562 CO, and 0.1274 H,O ; C = 50.38 ; H = 4.70. IT. 02i78 ,, 0.5141 ,, ,, 0.1158 ,, C = 50.47 ; H = 4-63. 111. 0.2766 ,, 0.5094 ,, ,, 0.1203 ,, C: = 50.23 ; H = 4.1'3 IV. 0.3224 ,, 0.0691 Pt. N = 3.09. V. 0.2669 ,, 0.0529 ,, N = 2.16. VI. 0.2735 ,, 0.0567 ,, N = 2.99. The mean result of Analyses I and 111 for carbon and hydrogen, and of I V and VI for nitrogen, gives C = 5050 ; H t 4-76; N = 3.04. From these numbers we deduce the formula, C,91-I,,N0,2, which requires C = 50.11 ; H = 4.62 ; N = 3.07. The water of crptnllise-WITH POTASSIUM PERMAKGANATE. 59 tion was determined in specimens of the acid which were dried in a vacuum over strong snlphuric acid.0.6549 lost 0.0700 at 100". H,O = 20.68. 1.1365 ,, 0.1182 ,, H20 = 10.40. The mean of tbe two determinations is H,O = 10.54 per cent. C19H2,N0,2,3H20 requires H,O = 10.61 per cent. I n determining the water of crystallisation, the substance must not be heated above loo", as at higher temperatures and even on long con- tinued heating at this temperature, there is an appreciable loss of weight, owing to the volatilitly of the acid. In the second of the two estimations quoted ahove, the acid was heated at 100" for six hours and weighed; it was then heated for one hour more an& a p i n weighed, and as it was found to have lost only 0.0006 gram, the weight was taken as constant. It is freely soluble in hot, but only to a slight extent in cold, water ; it is also soluble i n methylic and ethylic alcohols, but is insoluble in ether, chloroform, benzene, and carbon bisulphide.When heated, corrd- alinic acid melts between 175" and 180", undergoing decomposition. Long before its melting or decomposing point is reached, however, the acid begins to sublime ; when heated on a large watch glass covered with a funnel, a snblimate of beautiful, silky, colourless needles is ob- tained. Their identity with corydalinic acid was proved by analysis of their silver sait and a determination of their decomposing or melting point, which was found to correspond with that of the unsublirned acid. We attempted to determine the vapmr density of the acid at a temperature sufficiently high to ensure its complete volatilisation, but we were only partially successful, owing to the fact that slight d s composition invariably accompanies volatilisation at a high tempera- ture, a small residue, insoluble in water, being left.In one deter- mination, made with Victor Meyer's apparatus, using the vaponr of boiling diphenylamine to volatilise the acid, the density found wag 252.6, the theoretical value for C19H21N01z being 227.5. The acid forms well-defined salts, most of which are suitable for analysis. Potassium SaEt.--Sn aqueons solution of the acid was neutralised with potassium hydrate, evaporated to dryness, and the residue dis- solred in water and recrystallised several times. The salt crystallid in tufts of beautiful, silky needles, and gave the following results 011 an a1 y sis.We propose the name corydalinic acid for this substance. 0.1927 gave 0,0459 K,SO,. I( = 14.44. 0.1043 j , 0*0%76 ,, K = 14-46. Cl9Hl9NOJG requires K = 14-68 per cent. F 260 DOBBIE AND LAUDER: OXIGATION OF CORYDALINE Silver Salts.-We have prepared a normal and an acid silver salt of corydalinic acid. The normal salt, C19H17NO12*Ag4, was obtained by exactly neutdising the acid with ammonia and precipitating with silver nitrate. The salt separates from a concentrated solution in the form of a thick, curdy precipitate, but from more dilute solutions in the form of a crystalline precipitate. This salt is appreciably solnble even in cold water. It was dried at loo", and gave the following results on analysis. I. 0.4826 gave 0.2333 h g . Ag = 48.34. 11. 03350 ,, 0.1640 ,, Ag = 49.10.111. 0-2684 ,, 0-1313 ,, Ag = 48.91. IV. 0.1518 ,, 0.0742 ,, Ag = 48-88. 3iean resuit of Analyses I1 and 111. Ag = 49.00 per cent. C,,H17NO12Ag, requires Ag = 48-92 per cent. The salt used for the first analysis was prepared without previously neutralisinq the acid with ammonia, and that used in number IV was prepared from corydalinic acid, which had been sublimed. The acid silver salt was prepared by adding silver nitrate to a cow centrated aqueous solution of the acid, care being taken not to add an excess of silver. The precipitate obtained is gelatinous in appear- ance, but in reality consists of a thick mass of very delicate, short needles. 052130 gave 0.0693 Ag. Ag = 32.53. 0.2457 ,, 0.0802 ,, Ag = 32.64. 0.1120 ,, 0.0361 ,, Ag = 32.23.The salt was dried at 100" and analysed. Mean result of above analyses, Ag = 32.46 per cent. Cl,Hl9NO,,Ag2 requires A g = 32.29 per cent. When the acid silver salt is carefully heated, a beautiful sublimate of short, needle-shaped crystals was obtained ; this sublimate waa proved to be corydalinic acid by taking its melting point, and testing i t with the reagents which precipitate this acid. Ba<rium Salts.-The normal salt was prepared by adding a solution of corydalinic acid neutralised with ammonia to a solution of barium chloride, so as to have the latter always in excess. The solution at first remains perfectly clear, but, 011 gently heating, crystallisation begins simultaneously at a great many different points, and the liquid sppears to fill suddenly with a mass of fine crystals which slowly subside to the bobtom of the beaker. This salt is a,ppreciablg boluble in cold water, and contains no water of crystallisation. It was dried at 100" for analysis.0-3320 gave 0.2152 BaS04. Ba = 38-12, 0.2396 ,, 0.1551 ,, Ba = 38.07. Mean result of the above analyses, Ba = 38.09. C,H,,NO,Ba, rcquires Ba = 37-82.WITE POTASSIUM PERMANGANATE. 61 An acid salt was prepared by adding barium chloride to an aqueous solution of corydalinic acid neutralised with ammonia. The precipi- tation takes place in the same mamner as that of the normal salt, but the precipitate in this case forms a very bulky jelly. The salt is slightly soluble in water, and may be obtained in the crystalline form from dilute solutions. It was dried at 100" and analysed.0.2616 gave 0.0985 BaS04. C19H,9NOlzBa requires Ba = 23.24 per cent. This was one of the first salts of corydalinic acid which we pre- pared, and as we were ignorant of the properties of the acid at the time, no special precautions were taken to obtain an acid salt. Lead Salt.-The normal lead salt was prepared by precipitating tbe acid, after neutralisation with ammonia, with excess of lead acetate solution. A white, gelatinous precipitate immediately formed which became distinctly crystalline on standing, and, when collected, aggregated on the filter paper as a compact film possessiug a magni- ficent silvery lustre. This is by far the most beautiful salt of coryd- alinic acid which we hare obtained. It coutains no water of crys- tallisation, and is only very slightly soluble in water.It was dried at 100" for analysis. Bn = 22.15. 0.2328 gave 0.1637 PbSO,. Pb = 48-01. 0.3539 ,, 0.2486 ,, P b = 47.97. Mean result of above analyses, P b = 47.99 per cent. C19Hl,N0,zPb, requires P b = 47.85 per cent. The salts of corydalinic acid show a marked tendency to assume the gelatinous condition. When great care is not taken to observe exactly the conditions under which the normal and acid salts respec- tively are formed, a compound intermediate in composition is almost invariably obtained. It is obvious from inspection of the formulze of the salts described that corydalinic acid is tetrabasic. With the view of determining whether any of the four methoxy- groups present in corydaline bad been removed by the oxidation with potassium permsnganate, we treated the acid with fuming hydrogen iodide solution by Zeisel's method, as described in our second paper on corFdaline (Trans., 1892, 61, 605). The results, although invariably somewhat low, showed conclusively that ail four metboxy-groups are still present in the acid.The following were the results obtained. 0.2373 gave 0.4599 AgI. OCH, = 25.58. 0.2633 ,, 0.5099 :, OCH, = 25.57. 0.1916 ,, 03778 ,, OCH, = 26-04. Theory for four OCH, groups in C,gH21N0, = 27-25 p. c. OCH,. 0.3068 ,, 0.5996 :, OCH, = 25.81. 39 three 9 , Y, 9 ) = 20.44 ,,62 DOBRIE AND LAUDER: OXIDATION OF CORTDALINE Corydalinic acid may therefore be represented by the formula As we have found in previous researches that Zeisel's method for determining methoxg-groups is capable of yielding very accurate results, and as we used every precaution in applying i t in this case, we are unable to account for the discrepancy between the theoretical numbers and those actually obtained, unless i t is connected with the fact that the action of hydrogen iodide breaks up the acid into several simpler compounds. C1IHt.N (0 ca3) 0 ( c 0 0 H) 4.Corydalic acid. Action of H y d r ~ g e n Iodide on Corydalinic acid.-By the action of hydrogen iodide on corydalinic acid we should expect to obtain an acid bearing the relation to corydalinic acid indicated by the following formuls. C,,H,N( 0 c H3) 4 (C 0 0 H>* C 11 H,N ( 0 H ) 4 ( C 0 0 H ) o Corydalinic acid. Corresponding hydroxy-acid. Tn reality, however, the decomposition goes much further than this.About 4-5 grams of corrdalinic acid were boiled with 130 C.C. of a fuming solution of hydrogen iodide of sp. gr. 1-70 for three hours, using a reflux condenser, which was allowed to get warm at first so that the methyl iodide might escape. The solution was allowed to stand over night, when a mass of long, slender, silky needles separated ; on concentrating the mother liquor, a further crop was obtained, but the total weight of the crystals was always less than half the weight of the corydalinic acid decomposed. The crystals were drained by aid of a filter pump until most of the hydrogen iodide solution had been removed, pressed between slightly damp filter paper, and finally heated in the water oven at 100" for several hours. After this treatment, the crystals were found to be quite free from hydrogen iodide ; they were further purified by recry stallisation from water, in which they are easily soluble.This substance is a powerful non- nitrogenous acid, and contains no water of crystallisation. It was dried at 100" for analysis. C = 44.18 ; H = 4-04. 11. 0.2432 ,, 0.3942 ,, ,, 0.0881 9 , C = 44.21 ; H = 4.03. 111. 0.2687 ,, 0.4396 ,, ,, 0.0937 ,, C = 44.62; H = 3.87. Mean result of Analgses I and 11, C = 44.19 ; H = 4.04 per cent. From which we deduce the formula C9Hlo08, which requires C = 43-90 ; H = 4.06 per cent. We shall refer to this acid for the present under the name of corydalic acid, until the further investigation of its properties, in mbich we are now engaged. has enabled us to deter- mine exactly its relation to acids of known constitution. I.0-2546 gave 0.4124 C02 and 0.0927 H20.WfTH POTASSIUM PERMARGANATE 63 Corydalic acid dissolves readily m water and in alcohol. It melts with Cecomposition at 200". When silver nit,rate is added to its con- wntrated aqueous solution, a copious white precipitate is obtained after some time ; this dissolves readily on heating with partial rednc- tion of the silver, whilst the addition of ammonia causes immediate reduction, even in the cold. Ammonia and potassinm hydrate pro- duce a pink coloration in solutions of the acid ; an alcoholic solution of potassium hydrate added to an alcoholic sointion of the acid throws down a precipitate which is white at first, but rapidly darkens, and finally becomes dirty yellowish-brown.A solution of copper acetate heated with the acid is reduced to the red oxide. With an aqueous SoIution of tlie acid, ferric chloride gives an intense, deep green coloration, which is changed to violet by the addition of ammonia or sodium carbonate, the reaction resembling in all respects that which is characteristic of the pyrocatechin derivatives. Dilute nitric acid (1 : 5), heated with a solution of corydalic acid, is reduced, nitrous fumes being evolved ; the solution thus obtained, after nen- tralisation with ammonia, gives a yellow precipitate with lead acetate, totally different in appearance from that obtained with corydalic acid. When the acid is heated with lime, a phenol is produced. Owing to its powerhl reducing properties, and to its tendency to form mixtures of acid and neutral salts, tlie preparation of the salts of corydalic acid presents special difficulties; so far, we have only succeeeded in obtaining one salt which gave satisfactory results on analysis.Lead SuZf.-When lead acetate is added to a cold aqueous solution of corydalic acid, a white, curdy precipitate is immediately thrown down. This precipitate was dried at 100" and aualjsed. 0.1568 gave 0.1447 PbSO,. Pb = 63.02. 0.1149 ,, 0.1052 ,, Pb = 62.53. Mean result of abore analyses, Pb = 62.78 per cent. CgH608Pb, requires P b = 63.11 per cent. When the acid is precipitated with lead acetate i n presence of ammonia, the precipitate contains a higher percentage of lead than the above salt, but we have not been able in t'his way to obtain 8 compound of definite composition.We found in two cases 65.97 and 66-53 per cent of lead ; (C9H50,)2Pb5 requires P b = 68.23 per cent Barium chloride produces no precipitate either in a hot. or cold solution of corydalic acid, and the addition of ammonia only causes a precipitate after boiling. The only analysis which we made of the pTecipitate obtained i n this way gave an nnsatlsfactory result. C9&08Bh requires Ba = 53.14 per cent. The etliylic salt of corjdalic acid, which is a crystalline substance, was prepared by dissolving tbe acid in absolute alcohol, and saturating Fouud 51.26 per cent.64 OXIDATION OF CORYDALINE WITH POTASSKTJX PERMANQANATE. the hot solution with gaseous hydrogen chloride. The quantity pre- pared was too small for analysis.We have not yet completed our examination of the mother liquor from which the corydalic acid was obtained, but we have ascertained that it contains a mixture of substances, amongst which is a nitro- genous compoond. The reactions of corydalic acid show that i t contains both hydroxyl and carboxyl groups, and the fact t h a t it yields a phenol wheu heated with lime shows further that it is a derivative of benzene; more- over, the analysis of the lead salts proves the presence of five atoms of displaceable hydrogen. Bemembering that the acid contains nine carbon and eight oxygen ahms, the only formula which recoti- ciles these facts with its formatian from corydalinic acid is CsH,(OH),(COOH),. As corydalic acid has all its oxygen present in methoxy- and carboxyl groups, and as the action of hydrogen iodide convert,s the former into hydroxyl groups, the simplest explanation of all the facts is that the acid formed b? the action of hydrogen iodide on coryd- nlinic acid is, as represented in the above formula, a dihydroxytri- carboxylic derivative of a partially-reduced benzene ring.Although it would be premature to speculate as to the precise constitution of corydaline, the resulcs of the oxidation with potassium permanganate have in this, as in so many other cases, given an im- portant clue. The formation of corydalinic acid from corydaline is, perhaps, most easily explained on the assumption that corydaline is a derivative of a naphthaquinoline, and that when oxidation takes place the alkalojid is broken up as in the conversion of the naphtba- quinolines into phenylpyridinedicarboxylic acids, the benzene and the pyridine ring each having attached to it two of the methoxy- groups, the carboxyl group of the pyridine r i n g and one of the carboxyl groups of the beczene ring representing the third ring of the naphthnquinoline which has undergone oxidation, whilst the remaining two carboxyl groups of the benzene ring represent the oxidation of the side chains, or fourth ring, whose loss is indicated by the removal of three atoms of carbon on oxidation.According to this view, corydalinic acid is a tetmmethosy-tetracarboxyl derivatit e of a partially-reduced phenylpyridine, from which, by the action of hydrogen iodide, the pyridine ring is eliminated together with one of the carboxyl and two of the hydroxyl groups, leaving corydalic acid.Corydaline contains a larger number of hydrogen atoms than any of the other alkaloyds of Cwydalis caca. and it is noteworthy in this connection that that part of corydaline which is represented by corydalic acid consists of a partially-reduced benzene ring.THE FREYEZING POINT OF TRIPLE ALLOYS. 65 The facts connected with the constitution of coqdaline which have been established so far are the following. I. That it contains four methoxy-groups. 11. That on oxidation with perrnanganate it yields an acid which is derived from a, nitrogenous compound having the formula 111. That this acid, on treatment with hydrogen iodide yields a non-nitrogenous acid which is a derivative of benzene. IV. That the methoxy-groups in corydaline are distributed equally between the nitrogenous and the non-nitrogenous rings. V. That some, and probably all, of the carbon atoms which are Temoved during oxidation are attached to the benzene ring. We anticipate that the investigation of the other products of oxidation, on which we have been engaged for some time, will throw further light on the problem. CI,Hl,N. Although we have not yet brought to a conclusion the investiga- tion of the action of other agents on corydaline, it may not be out of place to indicate briefly some of the results which we have ob- tained. Ozidation with Potassium Hydrate.-We have made numerous attempts to act on corydaline with fused potassium hydrate, vaqing the proportions of alkali to alkaloid, the temperature, and the length of time during which the fusion was continued, but have always found that even after prolonged heating only a small portion of the alkaIoid is affected anti1 the ternpcrature is raised to the point at which it chars and decomposes completely. Distillation with Zinc Dust.-When distilled with zinc dust, coryd- aline yields trimethylamine, phenolic products, and a thick, tarry substance ; the last,-mentioned, on distillation with steam, yields a clear, oily liquid, the greater part o€ which passes over between 224" and 236". University College of North Wales, Bangor.

ISSN:0368-1645    

DOI:10.1039/CT8946500057

出版商:RSC    

年代:1894

数据来源: RSC