Preparation of chlorofluoromethylene olefins via phosphine dechlorination of dichlorofluoromethyltris?dimethylamino?phosphonium chloride

The reaction of dichlorofluoromethyltris?dimethylamino?phosphonium chloride with tertiary phosphines provides a convenient preparation of the chlorofluoromethylenetris?dimethylamino?phosphonium ylide. This ylide provides reasonable yields of chlorofluoroolefins from aldehydes, activated ketones, non-activated ketones, and activated esters. The mechanism of phosphonium salt formation was shown to involve positive chlorine abstraction from CFCl₃ by (Me₂N)₃P followed by recombination of the intermediate ion pair. Dechlorination of the resulting dichlorofluoromethyltris?dimethylamino?phosphonium chloride by triphenylphosphine gave an olefinating solution of reasonable stability. In contrast, the solution obtained by dechlorination of the phosphonium salt by tris?dimethylamino?-phosphine showed no stability.