1971 Volume 44 Issue 10 Pages 2815-2820
The reactions of aryl thiocyanates (I) with alcohol in the presence of cyanide ion were found to give alkyl aryl sulfides (III). The intermediate was isolated in the case of p-tolyl thiocyanate with methanol at 0°C and was determined to be O-methyl S-p-tolyl thioiminocarbonate (IIa) on the basis of NMR and IR spectral studies. The treatment of IIa with the cyanide ion afforded methyl p-tolyl sulfide (IIIa) in a high yield. When a mixture of an equimolecular amount of O-methyl S-p-tolyl thioiminocarbonate (IIa) and O-ethyl S-p-chlorophenyl thioiminocarbonate (IId) was treated with sodium cyanide in ethanol, all the anticipated sulfides—methyl p-tolyl sulfide (IIIa), p-tolyl sulfide (IIIb), methyl p-chlorophenyl sulfide (IIIc) and ethyl p-chlorophenyl sulfide (IIId)-—were isolated. The mechanistic route, which involves the addition of alcohol to aryl thiocyanate, and the dissociation of the resulting O-alkyl S-aryl thioiminocarbonate (II) into aryl mercaptide ion and aryl cyanate, was proposed.
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