Benzylic Bromination-Acetoxylation of Toluenes by Bromide Ion Catalyzed Thermal Decomposition of Peroxydisulfate in Acetic Acid in the Presence of Acetate Ions

Article abstract of DOI:10.1021/jo00231a017

Side-chain bromination and acetoxylation of alkylaromatics by halide ion induced decomposition of potassium peroxydisulfate in acetic acid have been studied by product analysis techniques.Catalytic amounts of lithium bromide in the presence of sodium acetate were found effective in promoting benzylic bromination, followed by conversion to the corresponding benzyl acetates by reaction with acetate.The reaction is interpreted to take place by the redox and free-radical chain mechanism involving bromine atoms (ρ = -1.38 vs. ? ⁺ for substituted toluenes).In competiti ve experiments, benzyl and 4-nitrobenzyl acetates were found lees reactive than the corresponding toluenes in acetic acid with the couple S2O8^2-/Br^- but more reactive in carbon tetrachloride with N-bromosuccinimide.