Pulse radiolysis and product analysis of 1,1-diphenyl-ethylene and related compounds in methanol

Abstract
Pulse radiolysis of 1,1-diphenylethylene (DPE) in methanol in the presence of oxygen, as well as of 1,1-diphenyl-2-chloroethylene (DPE-2-Cl), 1,1-diphenyl-1-chloroethane (DP-1-Cl-Et) and 1,1-diphenyl-2-chloroethane (DP-2-Cl-Et) in methanol saturated with argon, was performed. The products formed under pulse-radiolysis conditions were also analysed. Spectroscopic and kinetic data of the corresponding transients are presented. The reaction rate constants determined in methanol are k(e s+ O2)=(2.0 ± 0.1)× 1010 dm3 mol–1 s–1, k(e s+ DPE-2-Cl)=(1.1 ± 0.1)× 1010 dm3 mol–1 s–1, k(e s+ DP-1-Cl-Et)⩽ 1.5 × 1010 dm3 mol–1 s–1, k(e s+ DP-2-Cl-Et)=(1.3 ± 0.2)× 1010 dm3 mol–1 s–1, k(H + DPE-2-Cl)=(2.0 ± 0.6)× 1010 dm3 mol–1 s–1, k(H + DP-1-Cl-Et)⩽ 8 × 109 dm3 mol–1 s–1, k(H + DP-2-Cl-Et)⩽1 × 108 dm3 mol–1 s–1. It has been established that the solutes are primarily attacked by e s and H, whereas the CH2OH species (or O2) react with the intermediates thus produced. Reaction mechanisms consistent with the spectroscopic and kinetic data are presented.

This publication has 0 references indexed in Scilit: