yellow precipitate permanent in the air, but decomposed when heated to 100° in a moist state; dried several days over sulphuric acid, 0·5380 gramme gave 0.1000 metallic platinum. Found..... The formula (C1, H20 CI NO2, HCl), PtCl requires 18 The codeia salt requiring per cent. 18.60 18.81 19.50 From these numbers it appears that the new base is formed from codeia by the replacement of an atom of hydroxyl by one of chlorine, thus H, N If codeia be regarded as being formed on the mixed type H, O' H2O' then the H.N new base may be looked upon as formed on the mixed type HCI ; and, using Professor Foster's nomenclature* for these types (viz. oxynitride and chloronitride respectively), codeia would be oxycodide, and the new base chlorocodide; but until further investigation affords some knowledge of the nature of the radicals occurring in codeia and morphia, it would be premature to attempt to give rational formulæ for these bases. The following Table (p. 86) exhibits the comparative reactions of solutions containing 1 per cent. of the hydrochlorates of morphia, codeia, apomorphia, and chlorocodide respectively. The physiological action of chlorocodide appears to be much less marked than that of apomorphia. Doses of grain of the hydrochlorate taken internally and grain injected subcutaneously produced no appreciable effect; Dr. Gee is now engaged in studying this subject. § 2. Action of Hydrochloric Acid on Chlorocodide. When the hydrochlorate of this base is sealed up with eight to fifteen times its weight of strong hydrochloric acid and heated to 140°-150° for three hours, the tube is found, after cooling, to contain a layer of liquid chloride of methyl floating at the top: the tarry contents of the tube, when dissolved in water and precipitated by bicarbonate of sodium, yield, on shaking up the ethereal extract with a few drops of hydrochloric acid, a copious supply of crystals of hydrochlorate of apomorphia; these, when drained from the mother liquors, washed with cold water, and recrystallized, had all the physical properties of the hydrochlorate of apomorphia from morphia, gave the same qualitative reactions, and produced the same physiological effects, and gave the following numbers on analysis after drying at 100°: : (I.) 0.3090 gramme, burnt with lead chromate, gave 0 7595 carbonic acid and 0.1740 water. (II.) 0-4030 gramme, burnt with lime, gave 0·1910 silver chloride. * Watts's Dictionary, vol. iv. p. 124. Apomorphia.. Dark purple amethyst Dark blood-red colour. Dark blood-red colour. Dark blood-red colour. White precipitate decom coloration. posed on boiling with blood-red coloration. Phosphate of Sodium. Apomorphia.. White precipitate readily Very strong solutions cause codeia to crystallize out slowly after some hours. White precipitate White precipitate sosoluble in excess; solu- slighly soluble in excess. luble in excess; solution soon decomposes. White precipitate. White precipitate. White precipitate. tion soon decomposing. Chlorocodide White precipitate diffi- White precipitate White precipitate White precipitate. White precipitate. cultly soluble in excess. slightly soluble in excess. slightly soluble in excess. Morphia Stronger solutions give a Stronger solutions give Stronger solutions give a white precipitate scarcely soluble in excess. a white precipitate insoluble in excess. crystalline precipitate insoluble in excess. Codeia 100.00 C17H17 NO2, HCI 303.5 Hence the reaction which takes place is C13 H20 CI NO2=CH, C1+C1, H2, NO2. 18 17 17 11.72 It is worthy of notice that this reaction probably takes place gradually, while that whereby apomorphia and chloride of methyl are formed direct from codeia appears to occur suddenly, thereby bursting the large majority of sealed tubes used: this never occurred with chlorocodide. § 3. Action of Water on the Hydrochlorate of Chlorocodide. When the hydrochlorate (obtained by dissolving the base freed from codeia &c. by the process previously described in as small an excess of hydrochloric acid as possible) is sealed up with ten to fifteen times its weight of water and heated for three hours to 130°-140°, it splits up into hydrochloric acid and hydrochlorate of codeia, no gas whatever being formed. during the reaction. C1 H20 CI NO2, HCI+H,O=HC1+C, H, NO,, HCl. 18 18 21 In two experiments the amount of free hydrochloric acid thus formed was estimated by titration with a solution of carbonate of sodium, and after subtraction of the small amount due to the excess of hydrochloric acid in the original liquid (estimated in the same way), was found to amount respectively to 9 and 10 per cent. of the hydrochlorate employed, the theoretical amount according to the above equation being 103; the amount of undecomposed chlorocodide was found to be very small, the liquid resulting from the digestion giving but a minute precipitate with carbonate of sodium. The filtrate from the carbonate-of-sodium precipitate was extracted with ether, and the ethereal solution obtained shaken with a few drops of hydrochloric acid; an oily liquid was thus obtained, which on standing several hours deposited crystals; these, when drained from the mother liquors and recrystallized, had the character of hydrochlorate of codeia, and gave the following numbers after drying in an ordinary water-bath till constant in weight. As crystallized hydrochlorate of codeia is stated to lose one-fourth of its water of crystallization at 100°, a sample was prepared by dissolving codeia in hydrochloric acid and recrystallizing the product; after drying in the same water-bath it was also burnt as a comparison (III.). (I.) 0.3110 gramme of hydrochlorate of codeia from chlorocodide gave 0.6595 carbonic acid and 0·2015 water. (II.) 0.2790 gramme of the same, burnt with lime, gave 0 1090 silver chloride. (III.) 0.3460 gramme of hydrochlorate of codeia made from codeia gave 0.7360 carbonic acid and 0.2300 water. C18 H21 NO,, HC1+2 H, O 371.5 10000 A portion of the regenerated hydrochlorate of codeia was precipitated by caustic potash and crystallized from benzole; after drying at 120° it yielded these numbers. 0.3325 gramme, burnt with oxide of copper and oxygen, gave 0.8795 carbonic acid and 0.2185 water. The influence of mass upon chemical reactions is well illustrated by the inverse reactions taking place between codeia and hydrochloric acid in excess, and chlorocodide with water in excess. C18 H20(HO)NO2+HCl=H HO+C18 H20 Cl NO2 2 C18 H20 C1 NO2+H(HO)=HC1+C18 H20(HO)NO2. The codeia employed in the foregoing experiments forms part of a second supply kindly given to us by Messrs. M'Farlane of Edinburgh. § 4. On the Crystalline Form of Chloride of Apomorphia. Prof. Miller has kindly determined the crystalline form of the chloride of apomorphia, which we here annex. Chloride of apomorphia. Prismatic: 001, 101 = 29° 26'-5; 100, 1 10 = 56° 48'5. Simple forms:-e, 101: m, 110. Angles between normals to the faces : No cleavage observable. e e'.. 58° 53' m m'..66 23 .. m' The crystals are small, the length and breadth of one of the largest being 0.9 and 0.22 millimetres respectively. V. "On the Action of Cyanogen on Anthranilic Acid." By P. GRIESS, F.R.S. Received June 29, 1869. * 10 Some time ago I pointed out the action which takes place when cyanogen gas is passed into an alcoholic solution of amidobenzoic acid. The principal product of this reaction is, as I have shown, a yellow compound of cyanogen and amidobenzoic acid of the formula C, H ̧(NH1)O2, 2CN, which separates in large quantities as soon as the alcoholic solution of amidobenzoic acid is nearly saturated with cyanogen. When anthranilic acid, a body isomeric with amidobenzoic acid, is submitted under the same condition to the same reagent, a totally different reaction takes place. In this case the solution remains either perfectly clear, or only traces of a similar yellow compound are precipitated. By allowing the alcoholic solution of anthranilic acid, saturated with cyanogen, to stand for several days, the acid is almost entirely converted into a new compound of the empirical formula C1, H2N2O2; two other new compounds (an acid and an indifferent body) are at the same time formed. It is worthy of remark that none of these compounds are isomeric with any of the bodies which by the same process are formed from amidobenzoic acid. Each of them belongs to a perfectly different type. I propose on this occasion to treat only of the principal product of the reaction, viz. the compound C, H, N, O,. It is prepared in the following manner. An alcoholic solution of anthranilic acid is saturated with cyanogen gas and left to stand for about eight days. The alcohol is then evaporated at a low temperature, and the crystalline residue washed several times with dilute solution of carbonate of ammonia, by which any traces of the new acid (one of the by-products of the reaction) are removed. It is then further purified by recrystallization from alcohol with the addition of a little animal charcoal. The indifferent body already referred to, which is very little soluble in alcohol, is thus separated. The new compound, C1, H1, N, O,, is then obtained in the form of white acicular crystals, which are very little soluble in boiling water, but dissolve readily in boiling alcohol and ether. It fuses at 173° C., and can be distilled in small quantities without undergoing decomposition. Its formation may be expressed as follows:: 10 10 2 10 10 2 C, H, NO, +2CN+C, H, O=C,, H,, N, O,+CHN+H, O. 2 10 10 2 2 Anthranilic Cyano- Alcohol. New compound. Hydro- Water. gen. cyanic According to this equation, alcohol as well as anthranilic acid and cyanogen take place in the reaction. Confirmatory experiments which I have made show that the compound in question is really an ether. 10 10 2 Action of Hydrochloric Acid upon the Compound C1, H1, N, O,.-Ordinary hydrochloric acid dissolves this body, and when cold does not act upon it. On boiling, however, speedy decomposition sets in and a new * Zeitschrift für Chemie. New series, vol. iii. p. 533, and vol. iv. p. 389. |