Reactions of difluoroamino-radicals. Part IV. Addition to vinyl halides

Abstract

The kinetics of addition of tetrafluorohydrazine to vinyl halides in the gas phase are in accord with the mechanism: NF₂+ C₂H₃X = C₂H₃XNF₂*(1); C₂H₃XNF₂*= NF₂+ C₂H₃X (2); C₂H₃XNF₂*+ Mol = C₂H₃XNF₂+ Mol (3); C₂H₃XNF₂= NF₂+ C₂H₃X (4); C₂H₃XNF₂+ NF₂= C₂H₃X(NF₂)₂(5) where C₂H₂XNF₂* is an activated radical and Mol is an inert molecule. Values of k₁′, k₂′/k₃′, and k₄′/k₅′ have been found between 78 and 132° for vinyl chloride and vinyl bromide, and the Arrhenius parameters calculated. Some observations have been made with vinyl fluoride at 190°.