R A K S m PORPHYROXINE. 456 XXXIV. -Poiphyroxine. By JKTENDRA NATH RAKSHIT. THE ethereal extract obtained in the estimation of morphine in opium by the process described by the author (Analyst 1918 48, 320) left a viscid brown crystalline residue on evaporation which when dissolved in dilute acid always gave a solution becoming more and more purple on stirring or heating. Previous authors do not agree regarding the composition of this colouring matter ; Merck in 1837 prepared from opium a substance containing its coleuring matter and called it porphyroxine ; Hesse remarked (Annate?t 1870 153 47) that the substance prepared by the former investigator was a mixture of several alkaloids one of which is meconidine and another probably rheadine. The same author (Annalen SuppZ.1864-1865 4 50) noted that Merck's porphyr-oxine agrees with rheadine in method of preparation properties, and composition. It was thought desirable to investigate whether therie is any alkaloid that may be correctly called porphyroxine in Indian opium The alkaloid now isolated was very likely a con-stituent of what Dey (Pkarrn. J. 1882 [iii] 12 397) obtained on evaporation of the ethereal extract prepared by shaking an aqueous solution of opium made alkaline with sodium carbonate or ammonia and apparently also of what Merck called porphyroxine. Considering these facts and that the alkaloid gives a purple sdu-tion with dilute acids resembling porphyry the name porphyroxine may reasonably be retained. The alkaloid isolated is fairly readily soluble in water in which respect only it resembles papaverine codamine narceine and codeine but its other properties are in striking contrast with them; the solutions sf the base or its salts are strongly laevorotatory it does not sublime like codamine and unlike codeine the aqueous solution of its hydrochloride gives a white or pale yellow precipitate with ammonia.Prepration.-Twenty parts of Indian opium powder and nine parts of freshly slaked lime were triturated in a mortar for five minutes then 100 parts of water were added gradually during one hour the trituration being continued. The solution was filtered and the filtrate shaken with an equal bulk of ether for ten m i n u h in a separator. The ethereal layer was then filtered into another separator containirig some dry lumps of calcium chloride shaken for five minutes allowed to settle the ethereal solution decanted, filtered and evaporated on a water-bath.A pale yellowish-brown, VOL cxv. 456 RAKSHIT PORPHYROXINE. soft crystalline residue was obtained which when rubbed with a spatula on a porcelain plate for three to four hours became a dry powder. One hundred grams of this powder were heated with 200 C.C. of light petroleum until the solvent boiled briskly the whole was shaken for fifteen minutes heated again to boiling and the petroleum decanted as completely as possible the insoluble residue being carefully excluded. This process of extraction was repeated five times 100 C.C. of petroleum being used each time and finally the contents of the flask were collected dried and powdered.Ten grams of this powder were triturated with 100 C.C. of 10 per cent. hydrochloric acid gradually added during half an hour and then with 100 C.C. of water gradually added during another hour, and filtered quickly the residue being washed with a little dilute hydrochloric acid. To the filtrate was added a saturated solution of sodium hydrogen carbonate a thin layer of ether being kept on the surface of the liquid and the latter was stirred until the addi-tion of a further quantity did n o t produce any effervescence. After remaining for half an hou'r for the complete separation of the pre-cipitate this was collected and washed with distilled water. The filtrate measuring about 500 c.c. was shaken with 50 C.C. of chloro-form for fifteen minutes the chloroform removed and the process of extraction was similarly repeated thrice with 30 25 and 25 C.C.of chloroform respectively. The chloroform extracts were mixed together filtered the bulk of the solvent was distilled off and the residue dried slowly on the water-bath; it. was then kept overnight in a desiccator. Sometlimes the substance formed a soft viscid, crystalline mass but generally a pale brownish-yellow viscid varnish which on rubbing with a spatula against the side of the basin for an hour became a crystalline pink powder. Five grams of this powder were heated on a water-bath with 100 C.C. of light petroleum (b. p. 100-120O) just to boiling the mixture was then shaken for fifteen minutes with a rot'atory motion heated again to boiling and the petroleum decanted through filter paper the undissolved residue being carefully excluded.The residue in the flask was again twice extracted similarly with 80 and 60 c.c., respectively of light petroleum care being always t'aken not t o inelt the substance thus causing the extraction to be incomplete. The successive petroleum extracts were collected and allowed to evaporate when the base cryst,allised in groups of radiating, shining pale yellow prisms which were carefully separated from a thin film of non-crystalline residue powdered and dried in a desic-cator. Several samples from different preparations were analysed, the results of one only being given below RAKSHIT PORPHYROXTNE. 457 0.2950 gave 007530 COz and 0.1854 H20. 0.253 , 10-6 C.C.N (moist) a t 340 and 750 mm. N=4.36. CI9H&,N requires H = 6.99 ; c= 69.30 ; N = 4-26 per cent. Porphyroxine f o m s pale yellow or white transparent prisms nlelting a t 134-135O to a clear transparent straw-coloured liquid which solidifies on cooling. It is a non-deliquescent substance appreciably soluble in water giving a strongly alkaline solution ; it is readily soluble in dilute acids acetone carbon disulphide, chloroform or glacial acetic acid moderately so in benzene carbon tetrachloride methyl or ethyl alcohol toluene or ethyl acetate, sparingly so in amyl alcohol ether light petroleum ammonia or barium hydroxide and almost insoluble in aqueous sodium hydr-oxide potassium hydroxide or lime water. When its dilute mineral acid solutions are kept exposed to air they assume a fine pink porphyry colour.The base has a strongly alkaline reaction towards cochineal methyl-orange and litmus but has no action on phenolphthalein. Iodine solution gives an orange precipitate with the aqueous solution of the base and a brick-red precipitate with its dilute hydrochloric acid solution. Mayer's reagent gives a white precipitate with its aqueous solution and the usual pale yellow one with its dilute hydrochloric acid solution. Colour reactions of the base are often vitiated by the presence of a small quantity of impurity and the following reactions were observed with a sample specially prepared by recryst'allising three times from petroleum. It gives a red colour with concentrated sulphuric acid a grass-green with concentrated sulphuric acid and a small quantity of potassium dichromate a pale yellow with concentrated nitric acid and ail orange with concentrated hydrochloric acid ; a brownish-red pre-cipitate is obtained on adding ferric chloride t o its sulphuric acid solution and when fused with potassium hydroxide it becomes brown and gives off a strongly alkaline vapour without becoming charred.0.2540 made up to 50 C.C. with chloroform gave a-4-1° (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] -139.90. The hydrochloride crystallises from water in prismatic needles. It is a stable salt and on heating softens atl 140° and melts a t 155O t o a clear pale yellow liquid which does not solidify quickly on cooling: C=69.46; H=6*98. 0.1168 gave 0.0460 AgCl. C1=9.7. C,,H,,O,N,HCl requires CI = 9.7 per cent.It is a non-deliquescent crystalline stable substance readily soluble in water chloroform methyl or ethyl alcohol or glacial acetic acid sparingly so in amyl alcohol or carbon disulphide and T 458 RAKSHIT BORPHYROXINE. almost i ~ s o h b l a in acetone benzene carbon tetrachloride ethyl a&tate ether light petroleum or toluene. 0.2920 made up to 50 C.C. with water gave &-4.0° (Ventzke) iii a 2-dcm. tube at 3 2 O whence [a] - 1 1 8 * 8 O . The pJati?tichZoSde separates from a fairly concentrated aqueous solution as a bright ochreous crystalline powder. Fouend Pt = 18.0. (C~,E,04N,HC1),PtC14 requires Pt = 18.2 per cent. When kept in a steam-oven for a long time it slowly swells up and decomposes forming a dark brown spongy mass.It darkens aA 1 8 8 O and melts and decomposes a t about 2 0 4 O . The aurichtoride was obtained as a greyish-yellow amorphous precipitate which decomposed wit'hin an hour while remaining in the mother liquor. The hydro bromide crystallism in fine white needles which melt at 148-150O to a pink liquid: 0.3367 gave 0.1555 AgBr. Br=19*7. CI9H2,0,N,HBr requires Br = 19.5 per cent. It becomes slightly pink after two or three days and is readily soluble in water methyl or ethyl alcohol or glacial acetic acid, sparingly so in acetone chloroform or ethyl acetate and insaluble in amyl alcohol benzene carbon disulphide carbon tetrachloride, ether light petroleum or toluene. 0.4209 made up to 50 C.C. with water gave a - 4-4O (Ventzke) in a 2dcm.tube a t 3 2 O whence [a] - 9 0 ~ 6 ~ . The hydrdodide was obhined as a pale brown powder which melts and decomposes a t 1 1 5 O . The salt once separated from its aqueous solution is very sparingly soluble in water and therefore in the analysis the silver iodide was precipitat'ed from its alcoholic solution : 0.1560 gave 0-8200 AgI. I=28*3. C,&,O,N,HI requires I=27.8 per cent. It is readily soluble in methyl or ethyl alcohols very sparingly so in water acetone chlorofarm ethyl acetah or glacial acetic acid and insoluble in amyl alcohol benzene carbon disulphide, carbon tetrachloride ether light petroleum or toluene. 0.3120 made up to 50 C.C. with alcohol gave a-2-8O (Y&ke)in a 2-dcm. tube a t 3 2 O whence [a] - 7 7 . 8 O . The sulphate separated from water in p d e pkk radiating plates wk& when washed with a mixture of equal pasts of absolute alcohol and sther melted a t 193O to a pink liquid with slight decompoeititm RA3SHIT BORPHYROXINE.459 0.5120 gave 0.1794 &SO,. S=4.8. It is readily soluble in carbon tetrachloride chloroform &by1 alcohol or toluene and almost insoluble in acetone amyl alcohol, benzene carbon disulphide ethyl acetate ether or light petroleum, 0.5600 made up to 50 C.C. with water gave a- 7*2O (Ventzke) in a 2-dcm. tube a t 32O whence [a] -111.4O. The phosphate did not crystallise from water but was obtained as a powder which melted a t 1 1 7 O t-o a pale brown transparent liquid : (C,gH,0,N)2,H2S0 requires S = 4.3 per cent. 0.4312 gave 0.1175 Mg,P,07.P=7.6. This salt quickly absorbs moisture when left exposed t o a damp atmosphere and becomes viscous. It is readily soluble in water, alcohol methyl alcohol or glacial acetic acid sparingly so in chloroform ethyl acetate or ether and insoluble in acetone amyl' alcohol benzene carbon disulphide carbon tetrachloride light petroleum or toluene. 0.5390 made up to 50 C.C. with water gave a - 6.1* (Ventzke) in a 2-dcm. tube a t 32" whence [a] - 9 8 - 2 O . The nitrate crystallises from water in voluminous fine leathery Lablets melting a t 1 2 2 O to a transparent pink liquid. An attempt was made to determine the nitratic nitrogen by the Crum-Prank-land met'hod but as soon as sulphuric acid was mixed with a solu-tion of 0.1367 grain of the iiitlrate in the nitrbmeter a blood-red coloration was at once produced and only 1.0 C.C.of moist nitric oxide was evolved a t 3 5 O and 750 m. The percentage of nitratic nitrogen thus found is only 0-38 whilst that required for C,,H,,O,N,HNO is 3.80 per cent. Moreover duplicat,e analyses did not always agree and the nascent nitric acid reacts with the alkaloid before it does with mercury: C,,H,O,N,H,PO requires f = 7.3 per cenf;. 0.1965 gave 0.4240 C 0 2 and 0.1090 H20. C,,H,,O,N,HNO requires C = 58.2 ; H = 6.1 per cent. It is readily soluble in water chloroform methyl or ethyl alcohol glacial acetic acid acetone or carbon disulphide sparingly so in benzene carbon tetrachloride ethyl acetate ether or toluene, and insoluble in amyl alcohol or light petroleum. 0.6835 made up t o 50 C.C.with water gave a-9.1° (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] -115.4O. The acetate was obtained as a pale brown transparent viscid varnish : C=58.7; H=6.1 460 RAKSRIT PORPHYROXINE. 0.2780 gave 0.6610 cko and 0.1920 H,O. C,,H2,04N,C,H,0 requires C = 64.8 ; H = 7.0 per cent. It is readily soluble in water chloroform methyl or ethyl alcohol or glacial acetic acid sparingly so in acetone or ethyl acetate and insoluble in amyl alcohol benzene carbon disulphide, carbon tetrachloride ether lightt petroleum or toluene. The oxalate crystallises from water in long pale yellow pris-matic crystals which darken and melt atn 182O with effervescence : 0.1670 gave 0.0492 CaC,O,. C,gH2,04N,C2H,0 requires C,H,O = 21.48 per cent. It is fairly readily soluble in water methyl alcohol or glacial acetic acid sparingly so in acetone ether or ethyl alcohol and insoluble in amyl alcohol benzene carbon disulphide carbon tetra-chloride chloroform ethyl acetate light petroleum or toluene.0.9340 made up to 50 C.C. with water gave a-12*3O (Ventzke) in a 2-dcm. tube a t 32O whence [a] -114.2O. The citrate is an amorphous yellowish-white powder which melts a t 82-85O to a t.ransparent pale brown liquid: 0.1135 gave 0.2680 C02 and 0.0735 H,O. (ClgH,,04N),C,H60 requires C= 64.1 ; H = 6.4 per centl. It is appreciably hygroscopic readily soluble in water methyl or ethyl alcohol or glacial acetic acid sparingly so in acetone, amyl alcohol carbon disulphide chloroform or ethyl acetate and insoluble in benzene carbon tetrachloride ether light petroleum, or toluene.0.1595 made up to 50 C.C. with water gave a-2-O0 (Ventzke) in a 2-dcm. tube atl 32O whence [a] -108.6O The tartrate is a pink crystalline powder which melts at 116-118O to a pale brown transparent liquid : 0.1080 gave 0.2475 CO and 0.0650 H,O. (@,,H230,N)IC4H,0 requires C= 63.4 ; H = 6.4 per cent. It is somewhat hygroscopic readily soluble in water methyl or ethyl alcohol or glacial acetic acid sparingly so in amyl alcohol, benzene carbon disulphide chloroform or ethyl acet'ate and in-soluble in acetone carbon tetrachloride ether light petroleum or toluene. 0.1635 made up to 50 C.C. with water gave a-1*8O (Ventzke) in a 2-dm. tube a t 32O whence [a] -95.5O'. The picrate is a bright yellow crystalline powder which becomes brown a t 1 7 1 O and melts a t 198O: 0.1158 gave 0.2258 CO and 0-0510 H,O. ( 2 ~ 6 4 . 8 ; H=7*6. C2H204 =,20*72. C=64*3; H=7*1. C=62*5; H=6*6. C=53.2; H=4-8. C1,H,,O,N,C,H,O,N3 requires C = 53.7 ; H = 4.7 per cent COAGULATION OF METAL SULPHIDE HYDROSOLS. PART I. 461 It is a non-deliquescent crystalline powder readily soluble in acetone chloroform methyl or ethyl alcohol glacial acetic acid, or ethyl acetate sparingly so in water amyl alcohol benzene or carbon disulphide and almost insoluble in carbon tetrachloride, ether light pet,roleum or toluene. 0.2658 made up t o 50 C.C. with water gave a - 1 - 5 O (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] - 4 9 ~ 9 ~ . OPIUM FACTORY, C AZIPUR INDIA. [Received October 31& 191S.