ORGANOPHOSPHORUS CHEMISTRY. PART 21. INSERTION OF OLEFINS INTO P-CF3 BONDS

Article abstract of DOI:10.1016/S0022-1139(00)81516-X

Tris(trifluoromethyl)phosphine and ethylene reacted efficiently under u.v. irradiation to give 3,3,3-trifluoropropylbis(trifluoromethyl)phosphine in good yield.With vinyl fluoride, vinylidene fluoride, and propene the reaction was regioselective rather than regiospecific, and the yield of 1:1 adduct was low.In these reactions, and in those with vinyl chloride, but-1-ene, and hexafluoropropene, in which only traces of 1:1 adduct could be detected, the bulk of the olefin and of the phosphine was recovered, and numerous by-products consistent with radical intermediates were identified.With propyne, 1,1,1-trifluoro-3-bis(trifluoromethyl)phospino-cis-but-2-ene was obtained in moderate yield, but no reaction occured between the phosphine and either but-2-yne or hexafluorobut-2-yne.Tris(trifluoromethyl)phosphine oxide did not form an adduct with ethylene, tetrafluoroethylene, or propyne.Bis(trifluoromethyl)phosphine and dimethylphosphine both reacted readily under u.v. irradiation with 3,3,3-trifluoropropene, the phosphinyl radical attacking the terminal carbon in each case.