Selective hydrolysis of perfluorochloromethylsulfenyl chlorides

Abstract

Hydrolysis of the sulfenyl chlorides F nCl 3−n CSCl (n = 1,2) yields the corresponding thiosulfinates, F nCl 3−n CS(O)SCF n Cl 3−n, and thiosulfonates, F nCl 3−n CS(O) 2SCF n Cl 3−n, as stable intermediates. Selective preparation of these intermediate products is possible by variation of the reaction conditions. A new mechanism for the hydrolysis, based upon additional experiments with the newly prepared products, will be presented. Further reactions of the thiosulfinates and -sulfonates are reported. Oxidation of CF 2 ClS(O) 2SCF 2Cl, for example, gives the corresponding disulfone: CF 2ClS(O) 2SCF 2Cl ▪CF 2ClS(O) 2S(O) 2CF 2Cl 19F− and 13CNMR-data confirm the proposed hydrolyses mechanism.