Methyl dithiochloroformate

Anhydrous Na-benzenesulfinate added in small portions at 0 during 1 hr. to a stirred soln. of methyl dithiochloroformate in dimethylformamide, and stirring continued 4 hrs. at the same temp. S -methyl S-phenyl trithiocarbonate S,S-dioxide. Y 61%. F. e. and procedure s. N.H. Nilsson and A. Senning, B. 107, 2345 (1974). 

Catalytic amounts of dichlorobis(triphenylphosphine)palladium(II), Cul, and triphenylphosphine added to phenylacetylene, methyl dithiochloroformate, and triethylamine, and the mixture allowed to react at room temp, for 15 h product. Y 90 /o. The more stable a,p-acetylenethionocarboxylic acid esters were obtained from methyl thionochloroformate. Alternatively, both classes of compd. were obtainable via the corresponding a,p-acetyleneiminoester salts. F.e.s. K. Hartke et al.. Tetrahedron Letters 20, 1073-6 (1989). 

Treatment of 2-methyl-l-penten-3-ol with phenyl chlorothionoformate leads to a 96.5 3.5 EjZ mixture of the rearranged product 1 in 67% yield308. The reaction of 2-methyl-l-penten-3-ol with phenyl dithiochloroformate gives 5-2-methyl-2-pentenyl 5-phenyl dithiocarbonate (2) in 30% yield and >99% 308. 

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