Reaction of fluoroolefins with sulfur chlorides in hydrogen fluoride–boron trifluoride system

The reaction of tetrafluoroethylene (1), perfluorovinyl ether (3), hexafluoropropene (5), and 2-H-pentafluoropropene (7) with sulfur chlorides in anhydrous HF/BF3 system has been studied. The reaction with S2Cl2 at 40–100 °C produces a mixture of the corresponding di- and trisulfides along with smaller amounts of sulfenyl- and thiosulfenyl chlorides. In case of 7 the use of BF3 catalyst results higher yields and selectivity of the process under milder conditions. The reaction of 5 and SCl2 in HF/BF3 at 100 °C is selective, gives (CF3)2CFSCl, isolated in 65% yield.