83 



OPIUM, ALKALOIDS OF. 



OPIUM, ALKALOIDS OF. 



The crystals are in the form of colourless radiating needles, whic 

 are very readily dissipated by exposure to heat and, like the other sail 

 of morphine, are decomposed by ammonia, potash, and soda, th 

 morphine being precipitated. Acetate of morphine is slightly deli 

 quescent. 



ifeconatf of morphine, which is the natural salt existing in opium 

 does not crystallise ; it is soluble in water and in alcohol. 



Sulphate of morphine (C M H,,NO,, HO, SO, + 5Aq.) crystallises i 

 needles grouped in bundles ; it is soluble in about twice its weight o 

 water. 



Biiulphate of morphine is procured by supersaturating the neutra 

 salt with sulphuric acid ; the excess of acid is to be removed by ether 

 which does not dissolve the bisalt. 



Sitrate of morphine is obtained by dissolving the alkaloid in th 

 acid ; it assumes at first a fine deep orange colour, which afterward 

 becomes yellow, and, by the continued action of the nitric acid, oxali 

 acid is procured ; when however dilute acid is used, a neutral salt i 

 procured in the form of stellated crystals. It is soluble in 1 4 part o 

 water. 



Phosphate of morphine crystallises in cubes, or in radiating bundles 

 when the acid is in excess. 



Tartrate of morphine contains (2C M H 1S NO (1 , jjjj.+eq.), anc 

 bitartrate of morphine (C 3 ,H,,NO,, C.H.O,, + Aq.). The citrate is said 

 to be the morphine salt contained in " black drop." 



Sulphomorphide (C M H M N,0 1(1 S,) containing the elements of sulphate 

 of morphine less four atoms of water, is an amorphous substance pro 

 duced by the action of excess of dilute sulphuric acid upon morphine 

 if binozide of lead is also present a brown uncrystaUisible matter 

 termed morphelin results. 



lodomorphine 



, I s ?). Obtained on triturating together 



equal parts of iodine and morphine, or on adding iodine to solution o 

 sulphate of morphine and heating. It has a red-brown colour. 



.'/.'/< y -< ..... / /.'"<(C M H 1 ,(C,H 3 )N0 )ande^morpAme(C M H,,(C,H 5 

 NO,) are obtained as crystalline hydriodates by acting upon morphin 

 with the iodides of methyl and ethyl respectively. 



The general properties of the salts of morphine and the means o: 

 detecting their presence are as follow : when nitric acid is dropper 

 on crystallised morphine, a bright red or orange colour is the result 

 when morphine or one of ita salts is acted on by a neutral solution ol 

 gesquioxide or sesquichloride of iron, a fine blue colour is the result 

 which disappears when an excess of acid is added, and reappears when the 

 latter is saturated. Lassaigne proposes to detect the presence of the salts 

 of morphine by evaporating the suspected solution at a temperature ol 

 212 : the residue treated with alcohol dissolves the salt of morphine, 

 and probably some other matters which may have been mixed with it ; 

 by spontaneous evaporation of the alcoholic solution the salt ol 

 morphine crystallises ; from this, redissolved, ammonia throws down a 

 precipitate which is recognised to be morphine by its bitter taste, 

 alkalinity, solubility in alcohol, &c. Vegetable alkaloids as a general rule 

 combine with iodic acid to form iodates ; but when a solution of iodic 

 acid is brought into contact with morphine or its salts, the liquid 

 assumes a reddish brown colour, and exhales the peculiar smell of 

 imliin.-, the presence of which may be detected by starch. According 

 to Serullas, who proposed thin test, a grain of morphine in 7000 

 grains of water may be detected by it. 



'deine (C M H.,TfO e + 2 Aq.). Tim alkaloid derives its name from 

 i in i ! reck word xoSb), a poppy head, in allusion to its natural source. 

 It exists in opium in far smaller quantity than morphine, the amount 

 varying from two to eight parts in one thousand. Large quantities of 

 it are, however, obtained as a bye-product in the preparation of 

 morphine, and as a substitute for that alkaloid, it has of late years been 

 much used on the continent. It readily crystallises on evaporating the 

 liquors from which morphine has been precipitated by ammonia. 



Codeine crystallises in large, colourless rhombic octohcdra. It is 

 loluble in eighty parts of cold, and seventeen of boiling water, and is 

 also freely soluble in alcohol and in ether. Its solutions possess 

 powerful tcvo-rotation. 



The salts of codeine are as great in number as those of morphine, 

 and are even more readily obtained in large crystals : their constitu- 

 tion is also very similar. Iodide of ethyl combines with codeine to 

 form hydriodate of ethyl-codiine (Cj.H^C.HJNO,). Chlorine, bro- 

 mine, and peroxide of nitrogen respectively give chlorocodeine 

 (C s .H M ClNq, + 3Aq), bromocodeine (C J ,H 10 BrNO 4 +Aq.) and nitro- 

 codeine (C^H^NO.jNO,,). Tnkromocodeine (Cj.HuBr.NO,) has also 

 been obtained; and iWocorfrinefC^H^NOjjIjXbya process similar to that 

 for preparing iodomorphine. Di-iodocodeine (C^H^I^NO,) is a yellow 

 crystalline precipitate formed on adding chloride of iodine to a strong 

 solution of hydrochloiate of codeine. Cyanogen passed into a strong 

 alcoholic solution of codeine is absorbed and after a time brilliant hexa- 

 gonal plates of a new base Cyanocodeine (C^H^N.O,^ CjjH^NO,, 

 Cy,) are deposited. Cyanocodeine forms crystalline salts with acids. 



3. Thebaine (Cj.H^NO,), so called from Thebei, an ancient city of 

 Egypt, the alkaloid having probably been first obtained from Egyptian 

 opium. Pelletier thought it only an isomeric modification of morphine, 

 and hence called it fiaramorjihint. Ita position among, and the method 

 of ita separation from, the other alkaloids, have already been indicated. 

 It is not, like papaverine, precipitated from solution by subacetate of 

 lead, but on separating the lead by sulphuric acid and adding slight 



excess of ammonia; it is then thrown down, and may be rendered 

 colourless by treatment with animal charcoal and recrystallisation from 

 alcohol. 



Thebaine crystallises in colourless square plates of silvery lustre and 

 acrid, styptic taste. It is insoluble in alkalies and in water, but readily 

 so in alcohol or ether. It melts at 257 Fahr., and at a higher tem- 

 perature is decomposed ; is coloured red by sulphuric acid ; rapidly 

 attacked by nitric acid ; with acids forms salts that crystallise with 

 difficulty, or not at all ; and, finally, is very poisonous. 



4. Paparerine (C^H^NO,). This base was discovered by Dr. 

 Merck in 1848. It is separated from the lead compound already 

 mentioned, by digesting in alcohol, filtering, distilling off the alcohol, 

 treating the residue with hydrochloric acid, again filtering, evaporating, 

 and setting aside, when hydrochlorate of papaverine gradually crystal- 

 lises out. 



Papaverine occurs in confused aggregated, acicukr, white crystals. 

 It is tolerably soluble in hot alcohol or ether, but insoluble in water. 

 In contact with great excess of hydrochloric acid it separates in oily 

 drops, and collects as a layer at the bottom of the vessel, but this 

 layer gradually solidifies into a mass of crystals. Papaverine differs 

 from the other opium alkaloids in giving a blue colour with strong 

 sulphuric acid. The salts that it forms with acids are mostly difficultly 

 soluble in water, and do not appear to be very poisonous. 



5. Opianine (C OT H M N 2 O ai ). This alkaloid seems to exist only in 

 Egyptian opium, and occurs along with the morphine prepared from 

 that variety of the drug. It is less soluble in alcohol than morphine 

 and may therefore be separated by crystallisation. It forms long, 

 colourless, transparent, brilliant needles; is precipitated from its 

 solutions by ammonia as a white impalpable powder ; is insoluble in 

 water and cold alcohol, and not very soluble in boiling alcohol, the 

 solution possessing a marked alkaline reaction, powerfully bitter taste, 

 and is apparently as poisonous as an equally strong solution of mor- 

 phine. The hydrochlorate forms double salts with the chlorides of 

 platinum and mercury. Opianine is unaltered by strong sulphuric 

 acid ; is turned yellow by nitric acid ; and blood-red changing to yellow 

 by sulphuric acid containing nitric acid. It much resembles nar- 

 cotine. 



6. Jfarcotine (C 4(1 H 15 N0 14 + 2 Aq.) derives its name from the Greek 

 fKUTixiis, narcotic ; its narcotic properties are, however, far inferior 



to those of morphine. It is extracted from that part of the opium 

 that remains insoluble after exhaustion with water, by treating with 

 dilute acetic or hydrochloric acid, and precipitating the filtrate with 

 ammonia; the precipitate digested in boiling alcohol, filtered and 

 allowed to cool, deposits the narcotine in crystals. 



Narcotine occurs in opium to the extent of six to eight per cent. 

 It crystallises in colourless right rhombic prisms, inodorous, but of 

 bitter taste. It is insoluble in cold water ; only soluble in seven 

 thousand parts of boiling water ; insoluble in caustic alkalies, but 

 soluble in ether, alcohol, and the fixed and essential oils. Its alcoholic 

 solution exerts Isevo-rotation on polarised light, but dextro-rotation if 

 excess of an acid is present. It is coloured blood-red by sulphuric 

 acid containing nitric acid. By heat it fuses and gives off water, and 

 at a higher temperature than 340 Fahr. is decomposed. 



Narcotine combines with some of the acids, but the resulting salts 

 are somewhat unstable and crystallise with difficulty. The chloro- 

 ptatinate contains (C, 8 H J5 NO U , HC1, PtCl,). The sulphate is decom- 

 >osed, when boiled with dilute sulphuric acid, into a dark green 

 amorphous powder termed lulphanarcotide (C M H 4 ,N.S. 1 0, 1 ), that is to 

 say, the elements of neutral sulphate of narcotine less four atoms of 

 water : if some binoxide of lead is also present a brown amorphous 

 alkaloid termed narcetine results. 



Narcotic acid is produced as an oleaginous potash salt, on boiling 

 narcotine for some time with strong caustic potash. 



Ifumopic acid is a dark brown amorphous body formed on heating 

 narcotine in an oil bath to a few degrees above its fusing point. 



Cotarnine (C S( ,H 1J NO > -t-2Aq.) is produced when narcotine is acted 

 upon by oxidising agents. It forms starry groups of colourless 

 needles, slightly soluble in cold water, more so in hot water, insoluble 

 n potash, but soluble in alcohol, ether, and ammonia. It readily 

 iombines with acids to form salts. The hydrochlorate contains (C, 

 I,jNO,, HCl,+6Aq.), and crystallises in long silky needles. 



Opianyl (C !0 H (0 0,) (Gerhardt's hydride of opianyl (G W H,0 S , H), ac- 

 ompanics cotarnine under the circumstances just mentioned. It is 

 dentical with the meconin that exists naturally in opium. It occurs 

 n acicular crystals. Nitric acid converts into hyponitromeconic acid, 

 r nitrrimeconin. [MECONTN.] 



ApophyUic acid (C 18 H,NO e ), so called from the resemblance of its 

 rystals to those of the well known mineral apophyllite, is produced by 



e breaking up of cotarnine on prolonging the oxidation of narcotine ; 



e opianyl is also then broken up into hemipinic and opianic acids. 



Hemipinic acid (C, H 10 0,., + 4Aq.) crystallises in colourless rhom- 

 oidal prisms. It is volatile and condenses in brilliant plates. Ethyl- 

 emipinic acid contains (C JO H (I (C 4 H B ) 0,,+ 3Aq.). 



Opianic acid (C W H 10 10 ) (Gerhardt's hydrattd oxide of opianyl 



80 " H I ) * s a to ' era ^ ) 'y abundant product of the energetic oxida- 

 on of narcotine. It crystallises in small, shining, silky prisms ; is 

 ightly soluble in cold water, more so in hot water, and also in alcohol ; 



