The reactions of tetraphenyldiphosphine with alcohols

Abstract

The reactions of diphenylphosphino radicals (Ph₂P˙) produced by the action of heat or ultraviolet light on tetraphenyldiphosphine, with alcohols have been investigated. In general, the primary products are diphenylphosphine and alkyl diphenylphosphinite. Benzylic alcohols also give either the corresponding hydrocarbon and diphenylphosphinic acid or the corresponding ketone. These reactions involve the apparent abstraction of hydrogen from the O–H, rather than from the α-C–H bond, of alcohols. The results are rationalised in terms of initial attack of the diphenylphosphino radical on the oxygen of the alcohol.