Organophosphorus chemistry. Part IX. Reaction of dimethyl- and bis(trifluoromethyl)-phosphines with olefins

Abstract

Dimethyl- and bis(trifluoromethyl)-phosphines react smoothly with olefins under u.v. irradiation to give products R¹₂PR²(R¹= CF₃, R²= Et, Prⁿ, Buⁿ, CHMeEt, or CF₂·CHF₂; R¹= Me, R²= Et, CF₂·CHF_2′ or CF₂·CHFCI) which are in accord with a free-radical mechanism in which the phosphino-radical R¹₂P attacks the olefin to give the most stable intermediate radical.

The tertiary phosphines containing the (CF₃)₂P group readily liberate fluoroform almost quantitatively with aqueous base, but those containing the Me₂P group are more resistant to hydrolysis.