Reaction of silver(I) fluoride with perfluorocarbonyl compounds: Reexamination of a valuable route to perfluoroalkoxy compounds.

Martin A. Walker, Taylor A. McCarty and David L. Hoffman

The reaction of silver(I) fluoride with hexafluoroacetone or a perfluoroacyl fluoride generates a species equivalent to a silver(I) perfluoroalkoxide. This may be alkylated in high yield with alkyl halides such as iodomethane or p-bromobenzyl bromide to produce alkyl perfluoroalkyl ethers, which are finding increasing application as environmentally benign fluids. This process was described some years ago in the patent literature, but it has remained obscure, yet we have found it to be simpler and milder than the usual method using cesium fluoride. We also examined the reaction of the silver(I) perfluoroalkoxide equivalent with other electrophiles such as perfluoroalkyl iodides, sulfonyl chlorides and chlorosilanes. Our investigation of the scope and limitations of the reaction demonstrates the value of this approach to perfluoroalkoxy compounds.