Fluoro-organic sulphur-containing compounds. IV. Haloalkylation reactions of polyfluorinated thiophenols with CHal(3)R compounds in the presence of AlCl3 - Synthesis and some reactions of polyfluorophenylthio derivatives of halomethanes

The haloalkylation of polyfluorothiophenols with CHal(3)R compounds (Hal=Cl , F; R=Cl, H, C6H5, C6F5) in the presence of AlCl3 has been investigated. T he reactions of polyfluorothiophenols 4-XC6F4SH (X=F, H, CH3) with CCl4 and AlCl3 lead to dichloromethane derivatives (4-XC6F4S)(2)CCl2. The reaction of pentafluorothiophenol with CHCl3 in the presence of AlCl3 gave (C6F5S)(2 )CHCl and (C6F5S)(3)CH (ratio by GLC 8:1). In the reaction of pentafluoroth iophenol with ArCX3 (Ar=C6H5, C6F5; X=Cl, Fl compounds (C6F5S)(2)CClAr (Ar= C6H5, C6F5) together with C6F5SCCl2Ar (Ar=C6H5. C6F5) are formed. Peculiari ties of these processes are considered. The hydrolysis of (C6F5S)(2)CCl2 an d C6F5SCCl2C6H5 leads to bis(pentafluorophenyl)dithiocarbonate and the S-(p entafluorophenyl) ester of thiobenzoic acid, respectively. Compounds (C6F5S )(2)CF2 and (C6F5S)(2)CClF were obtained from (C6F5S)(2)CCl2 by the action of caesium fluoride. An attempt to produce these compounds through the acti on of antimony fluorides was unsuccessful. The compounds (C6F5S)(2)CCl2, (C 6F5S)(2)CClF and (C6F5S)(2)CF2 are stable to oxidation. The reactions of (C 6F5S)(2)CF2 and (C6F5S)(2)CClF with CrO3 in acetic acid proceeded only with the formation of mono-sulphoxide. The conversion is low in the former case . (C) 1999 Elsevier Science S.A. All rights reserved.