S-Trifluoromethyl esters of thiocarboxylic acids, RC(O)SCF3

S-Trifluoromethyl esters of different types of thiocarboxylic acids have been prepared in moderate to excellent yields from halide substitution reactions of the corresponding acid chlorides and tetramethylammonium trifluoromethylthiolate. C6F5C(O)SCF3 undergoes a surprising rearrangement on attempted isolation to give 4-CF3SC6F4C(O)F, which was converted into the corresponding acid.