The chemistry of vinylphosphine chalcogenides. Part 2. Some nucleophilic and electrophilic additions

Abstract

Diphenylvinylphosphine oxide (3) is inert to peroxy-acids, although it can be converted with N-bromoacetamide into 1-bromo-2-hydroxyethyldiphenylphosphine oxide (8). The reactions of the latter compound with bases are described. The phosphine oxide (3) with methanolic alkaline hydrogen peroxide gives a stable dialkyl peroxide (11) With aqueous alkaline methanol, the phosphine oxide (3) is converted into bis-1,2-(diphenylphosphinoyl)ethane (7), a compound also isolated from the reaction of 2-hydroxyethyldiphenylphosphine oxide (2) with butyl-lithium and bromine.

Diphenylvinylphosphine sulphide (5) does not react with hydroxide or hydroperoxide anion, but is converted in aqueous alkaline methanol into 2-methoxyethyldiphenylphosphine sulphide (13). The phosphine sulphide (5) also undergoes Michael-type addition of t-butoxide anion.