Reaction of dimethyl sulfoxide with chlorothiolformates, hydrogen chloride, hydrogen fluoride, and hexafluoroisopropanol

Dimethyl sulfoxide reacts with phenyl chlorothiolformate according to the stoichiometry:[Formula: see text]p-Chlorophenyl and tert-butyl chlorothiolformate appeared to react in a similar manner. The 1:1 hydrogen chloride adduct Me2SO:HCl was characterized by elemental analysis and proton and carbon nmr. A cryoscopic molecular weight determination of the adduct Me2SO:HOCH(CF3)2 showed it to be monomeric at low concentrations but associated at higher concentrations, suggesting a monomer–dimer equilibrium. The 1:2 adduct Me2SO:2HF is formed by the addition of anhydrous HF to dimethyl sulfoxide.