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Published online by Cambridge University Press: 17 January 2013
In pursuing the investigation of the crystalline constituents of opium, which formed the subject of a previous communication to this Society, I have succeeded in obtaining from the same mother liquor which formed the raw material of my previous researches, a considerable quantity of papaverine, the base recently detected by Merck, and of meconine, the indifferent crystallizable substance discovered by Couerbe in the year 1830. The former was encountered quite unexpectedly in the precipitate from which narcotine and thebaine were prepared by the process described in the first series of these researches. The latter was only obtained after many fruitless trials, in which I was induced to persevere by the desire of comparing it with the substance discovered by myself among the products of the decomposition of narcotine by nitric acid, and described under the name of opianyl. The composition of that substance, as determined by my analyses, approximates very closely to that of meconine; and though the formula assigned to the former is double that obtained by Couerbe from his analysis of the latter, the sole reason for adopting the higher atomic weight was, that the mode in which opianyl was obtained by the decomposition of narcotine, afforded satisfactory grounds for establishing its true constitution.
page 198 note * Merck has published only one nitrogen determination of papaverine, giving 4·75 per cent., which greatly exceeds the calculated number. I have observed the same tendency to give an excess, having in one experiment obtained as much as 4·66. The only mode of explaining this anomaly, was by supposing that the base carried down a small quantity of the ammonia which had been used to precipitate it. In order to ascertain whether this opinion was well-founded, a quantity thrown down by potash was analysed, and the results are those of the second determination.
page 202 note * Edinburgh New Philosophical Journal, vol. 1., p. 103.
page 205 note * Although the salts of papaverine are highly crystallizahle and sparingly soluble, the presence of resinous impurities in the opium fluid has a remarkable tendency to prevent their separating in the crystalline form; and we see that in this instance a certain quantity of the base had even resisted precipitation by ammonia. It is probably the same peculiarity which prevents its appearing as an impurity in the hydrochlorate of morphia, prepared by the process of Robertson and Gregory. The hydrochlorate of papaverine is less soluble than the hydrochlorate of morphia, and a priori we should expect it to be the first substance to deposit from the concentrated fluid, yet the commercial hydrochlorate of morphia does not contain a trace of it, the whole being retained in the mother liquor.
page 205 note † Annales de Chimie et de Physique, 2d Series, vol. 1., p. 347.
page 205 note ‡ Ibid., vol. lix., p. 140.
page 205 note § Ibid., vol. lviii., p. 157.
page 214 note * Quarterly Journal of Chemical Society, vol. vi., p. 125.
page 215 note * Annalen der Chemie und Pharmacie, vol. lxxvii., p. 207.
page 215 note † Ibid., vol. lxxxii., p. 320.
page 217 note * Annalen der Chemie und Pharmacie, vol. lxx., p. 71.