The thermal decomposition of dimethyl disulphide has been stitdied in the gaseous state by a static method. The primary reaction, which follows a reproducible induction period, produces one mole of methyl rnercaptan per mole of disulphide, together with a product of low volatility believed to be a thioformaldehyde polymer:There is also a competing reaction producing a large quantity of hydrogen sulphide. 'The remaining volatile products, hydrocarbons of two or more carbon atoms (believed to be chiefly ethylene), free sulphur, polysulphides, and carbon disulphide are formed either by the latter reaction or by the extensive decomposition of products. The decomposition is catalyzed by hydrogen sulphide, and more strongly by the complete reaction mixture. A mechanism is proposed for the main reaction.The present investigation was undertaken as a contribution to our fragmentary understanding of the mechanisms of reactions i~lvolvi~lg the carbonsulphur bond system in organic sulphur compounds. The C-S-S-C bond system of dimethyl disulphide was of special interest. Little is known about the thermal deconlposition of the alkyl disulphides, although the thermal decompositio~l of aryl disulphides has received some study. The work of Schonberg, Mustafa, and Askar (10) suggests that diphenyl disulphide dissociates a t the S-S bond into two free aryl thial radicals. In an early investigation Otto and Rossing (8) found that on distillation a t atmospheric pressure diamyl disulphide (b.p. 248" C.) gradually decomposes into sulphur or sulphur-rich substances and a tarry residue. Bezzi (3) reported that dioctyl disulphide decomposes a t its boiling point of 190" C. a t 15 mm. Faragher, Morrell, and Comay (7) found that decomposition of vaporized naphtha solutio~ls of various alkyl disulphides a t 496" C. produces the corresponding alkyl mercaptan, hydrogen sulphide, free sulphur, alkyl sulphides, thiophenes, and saturated and unsaturated hydrocarbons.In some preliminary experiments in this laboratory it was found by Patrick (9) that dimethyl and diethyl disulphides decompose above 300" C. yielding co~nplex pressure-time curves. The homogeneous decomposition of dimethyl disulphide was found to produce large amounts of mercaptan and hydrogen sulphide.
E X P E R I M E N T A L
ReagentsT h e dimethyl disulphide, obtained from Eastman I