Reactions of polyfluoroalkylsulfenyl chlorides with phenols

Polyfluoroalkylsulfenyl chlorides thiolate phenol and its ortho- and meta-substituted derivatives regiospecifically at the para-position in the absence of a catalyst and of a hydrogen chloride acceptor. Ortho thiolation occurs with significantly greater difficulty in the para-substituted phenols, and is only possible with the strong electron-donor properties of the substituent. Polyfluoroalkylthiolation of phenols is rendered more difficult with the increase in the steric impediments at the sulfur atom of the sulfenyl chloride and the volume of the substituents by the OH group of the phenol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1619–1625, July, 1991.