Kinetics and mechanism of the reaction of Δ3-phospholens with diethyl peroxide

Abstract

A kinetic study of the reaction of Δ³-phospholens with diethyl peroxide in a variety of solvents (cyclohexane, tetrahydrofuran, and acetonitrile) is reported. The kinetic order, solvent effect, activation parameters, and lack of inhibitory effect by galvinoxyl lead to the proposal of a rate-determining biphilic attack of the phospholen on the peroxide followed by a fast fragmentation of the intermediate phosphorane to trans,trans-hexa-2,4-diene and a diethyl alkyl (or aryl) phosphonite.