Reaction of vicinal dihalopolyfluoroalkanes with sodium azide

Vicinal dihalopolyfluoroalkanes react readily with nucleophilic reagents to form the products of the replacement of one halogen by a nucleophilic residue. These reactions have been studied with F/sup -/ anion and C-, O-, and S-nucleophiles as examples. The present work studies the analogous reaction with the azide anion. When vicinal dibromopolyfluoroalkanes and related compounds react with NaN/sub 3/ in DMF, N-methylpyrrolidone, or hexametapol, halogen is replaced by an azide group, and ..beta..-halopolyfluoroalkyl azides form. The reaction of vicinal dihalopolyfluoroalkanes and related compounds with sodium azide causes replacement of halogen by an azide group probably by an ionic cleavage-addition chain mechanism. Nucleophilic azidobromination of fluoroolefins has been carried out by the action of sodium azide and bromine. These reactions were used to synthesize new ..beta..-halopolyfluoroalkyl azides.