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.

Reaction of perfluoroalkyl grignard reagents with phosphorus trihalides: a new route to perfluoroalkyl-phosphonous and -phosphonic acids.

The reaction of perfluoroalkyl Grignard reagents with phosphorus(III) halides was explored. In the process a new convenient, one-pot, high yield method for the synthesis of (perfluoroalkyl)phosphonic acids has been developed. Perfluoroalkyl Grignard reagents react with phosphorus trichloride or phosphorus tribromide to form (perfluoroalkyl)phosphonous dihalides.