A study of the reaction of perfluoroalkyl Grignard reagents with phosphoryl chloride and phenylphosphonic dichloride

Perfluoroalkyl Grignard reagents react with phosphoryl halides at 78 C to room temperature to selectively produce bis(perfluoroalkyl)phosphonyl halides, which after aqueous work up, give bis(perfluoroalkyl)phosphinic acids in high overall yields. Reaction of perfluoroalkyl Grignards with phenylphosphonic dichloride gives high yields of bis(perfluoroalkyl)phenyl phosphine oxides which are readily hydrolysed to perfluoroalkyl(phenyl)phosphinic acids. The reaction of perfluoroalkyl Grignard reagents with phosphoryl chloride and phenylphosphonic dichloride has been investigated. One-pot syntheses of bis(perfluoroalkyl)phosphinic acids and perfluoroalkyl(phenyl)phosphinic acids have been developed.