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XXI.—On the Compounds of Ethyl-, Propyl-, Butyl-, and Amyl- Thetines

Published online by Cambridge University Press:  14 March 2016

E. A. Letts
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Extract

Compounds of Ethyl-Thetine.—In the course of the investigations, the results of which are recorded in the preceding paper, Professor Crum Brown and I observed that sulphide of ethyl, like sulphide of methyl, forms a crystalline compound with bromacetic acid. This we called hydrobromate of diethylthetine, in conformity with the system of nomenclature we had proposed for such bodies—

Owing, however, to the extremely deliquescent nature of the substance, we did not at the time subject it to a closer examination, but devoted our attention to the methyl compound and its derivatives. The following are the results of an examination which I have since made of the hydrobromate of diethyl-thetine and its derivatives: —

Hydrobromate of Diethyl-Thetine.—50 grms. of sulphide of ethyl and 70 grms. of bromacetic acid were shaken together. The acid slowly dissolved, occasioning a fall of temperature in so doing from 20–14°. After about half an hour's standing, the mixture grew warm, and deposited a slightly brown, oily liquid. The reaction was very much less intense than in the case of the methyl compound, when the sulphide of methyl actually boils and the mixture has to be cooled to prevent loss of product.

Type
Research Article
Information
Earth and Environmental Science Transactions of The Royal Society of Edinburgh , Volume 28 , Issue 2 , 1878 , pp. 583 - 624
Copyright
Copyright © Royal Society of Edinburgh 1877

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References

page 583 note * “Proceedings” viii. 220, 385.

page 583 note † Equi-molecular quantities of the two substances require, for 50 of sulphide of ethyl, 77 of bromacetic acid; the sulphide of ethyl was therefore slightly in excess.

page 585 note * Chloro-platinate of dimethyl-thetine crystallises with 2 molecules of water and has the composition expressed by the formula 2(C4H9SO2Cl), PtCl4, 2H20.

page 586 note * The specimen employed was from Kahlbaum of Berlin.

page 586 note † Equimolecular quantities require for 6·5 of bromacetic acid 5·6 of propyl sulphide.

page 588 note * These represent equimolecular quantities.

page 591 note * Chum Brown and Blaikie, “Proceedings,” vol. ix. pp. 565, 712.

page 592 note * Considerable pressure was observed on opening the tube.

page 592 note † Heintz, “Ann. der Chem. u. Pharm.” cxxxvi. 214, and cxlv. 49.

page 592 note ‡ Thioglycollic acid may be compared both with glycocoll and diglycol-amidic acid, as in each of these substances the nitrogen is partly saturated with hydrogen and partly with glycolyl. The properties of thioglycollic acid, however, point to a stronger resemblance to diglycol-amidic acid than to glycocoll.

page 595 note * This change, when observed under the microscope, was very curious. The acetate of lead first occasioned the precipitation of warty masses, which dissolved of their own accord, and from the solution groups of needles shot out.

page 595 note † Schulze, , “Jenaische Zeitschr.” i. p. 470 (1864)Google Scholar; ‘Bull. Soc. Chim.” v. p. 130 (1866)Google Scholar.

page 596 note * The above experiments were made before those described on pp. 612–617 on the action of hydrocarbon sulphides on bromacetic acid, which go still further to establish an analogy between the action of ammonia on bromacetic acid and the action of hydrocarbon sulphides generally, on the same substance, and also before the experiments on the action of sulphide of methyl on iodacetic ethyl ether, which led to the discovery of methyl-thioglycollic acid. It is quite possible that the latter substance is formed along with thiodiglycollie acid when hydrobromate of dimethyl-thetine is heated, and that in the above experiments it remained in the residue of the non-volatile products after the latter had been extracted with ether (product A). At the time the experiments were made however, this residue was taken to be impure thiodiglycollic acid, and was only roughly examined to ascertain the presence of that substance. It is also possible that it was dissolved with the thiodiglycollic acid by the ether, and formed the oily liquid which saturated B3 after the ether had been evaporated off. The experiment, therefore, needs repeating.

page 597 note * I have found this form of apparatus exceedingly convenient, not only for storing up gases, but also for absorbing ammonia, hydrobromic acid, &c. It is especially useful for this purpose in determining ammonia.

page 600 note * The disengagement of hydrobromic acid in considerable quantity, before alluded to as occurring when this salt is heated, points to a different decomposition from either of these, the nature of which I have not as yet ascertained. A disengagement of hydrobromic acid also occurs when bromacetic acid is heated with sulphide of ethylene. Perhaps the reaction is similar in both cases.

page 601 note * “Proceedings,” vol. viii. p. 508Google Scholar.

page 602 note * Muspratt, , “Ann. d. Chem. u. Pharm.” lxv. 260Google Scholar.

page 603 note * Sayzeff, , “Ann. der Chem. u. Pharm.” cxliv. 152Google Scholar.

page 604 note * Muspratt obtained this salt from ethyl-sulphurous acid, which he prepared by acting on sulphocyanate of ethyl with concentrated nit.ric acid. (Muspratt, , “Annalen. d. Chem. u. Pharm.” lxv. 253, 254Google Scholar.)

page 604 note † Equal vols, of strong nitric acid of the laboratory and water.

page 610 note * Thiodiglycollate of ethyl has been studied by Schulze, E. (“Jenaische Zeitschr.” i. 472, 477, 1864)Google Scholar, who states that it may be prepared by the action of hydrochloric acid on an alcoholic solution of thiodiglycollic acid, and probably also by treating monochloracetic ether with sulphide of ammonium. According to Schulze, it is a colourless liquid, boiling with slight decomposition at 240–250° C., and has a feeble ethereal odour. Wishing to prepare some of the ether for purposes of comparison, I treated chloracetic ether with sulphide of potassium, and obtained a liquid which boiled constantly at 161–163° C., and which did not appear to suffer any decomposition when distilled. It possessed, however, all the properties of thiodiglycollic ether, and yielded thiodiglycollic acid by saponification with potash—precipitation with acetate of lead, and decomposition of the resulting lead salt by sulphuretted hydrogen.

page 618 note * “Proceedings,” 1873–1874, p. 220Google Scholar.

page 620 note * Wislicenus, J., “Zeitsch. für Chem.” 1865, p. 625Google Scholar, mentions a compound of thioglycollic ethyl ether and corrosive sublimate, to which he assigns the formula C4H7SO2. HgCl. No doubt the compound obtained as above would have a similar composition.

page 621 note * Cahours, , “Comptes Kendus,” lxxxi. (1875) 1164Google Scholar.