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

Adil I Hosein; Xavier F Le Goff; Louis Ricard; Andrew J M Caffyn

doi:10.1021/ic102063e

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

Inorg Chem. 2011 Feb 21;50(4):1484-90. doi: 10.1021/ic102063e. Epub 2011 Jan 12.

Authors

Adil I Hosein¹, Xavier F Le Goff, Louis Ricard, Andrew J M Caffyn

Affiliation

¹ Department of Chemistry, The University of the West Indies, St. Augustine, Trinidad & Tobago.

PMID: 21226476
DOI: 10.1021/ic102063e

Abstract

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. Hydrolysis gives the corresponding (perfluoroalkyl)phosphonous acids. Oxidation of the phosphonous acids with H(2)O(2) produces (perfluoroalkyl)phosphonic acids in 60-78% overall yields, based on the corresponding perfluoroalkyl iodide. The X-ray crystal structures of the toluidinium salts, [MeC(6)H(4)NH(3)](2)[C(2)F(5)PO(3)] and [MeC(6)H(4)NH(3)][C(8)F(17)P(O)(2)OH], are reported.