Synthetic, Mechanistic, and Structural Studies Related to 1,2,4-Dithiazolidine-3,5-dione

Reaction of O-ethyl thiocarbamate (4) with (chlorocarbonyl)sulfenyl chloride (5) gives 3-ethoxy-1,2,4-dithiazolin-5-one (2) and 3,5-diethoxy-1,2,4-thiadiazole (3), with the relative amounts of 2 and 3 formed depending very much on the solvent (e.g., diethyl ether favors 2; chloroform favors 3). The effects of added base, order of addition, concentration, and temperature were also studied. Mechanisms for the observed transformations have been proposed and are supported by the characterization of relatively unstable acyclic intermediates, e.g., formimidoyl(chlorocarbonyl)disulfane 8, symmetrical bis(formimidoyl)disulfane 10, and ethoxythiocarbonyl imidate 11, which are obtained under alternative conditions. Compound 2 is converted with concentrated aqueous hydrochloric acid upon short reflux to 1,2,4-dithiazolidine-3,5-dione (1), rearranges upon prolonged melting to give principally N-ethyl-1,2,4-dithiazolidine-3,5-dione (13), and is desulfurized with various trivalent phosphorus compounds to yield O-ethyl cyanate (15) plus carbonyl sulfide. X-ray crystallographic structures of 1 and 2 have been solved; the planarity and aromatic character of these molecules help to explain some of their reactions.