The Oxidation of Benzyldimethylamine by Bromine

Abstract

The rates of oxidation of several substituted benzyldimethylamines by bromine in 50% aqueous acetic acid have been determined spectrophotometrically. Electron-withdrawing substituents decrease the rate of reaction with the Hammett ρ value being −0.95. The reaction is subject to general base catalysis and substitution of deuterium in the α-position decreases the rate of reaction by approximately 30%, thus indicating that the α-C—H bond is cleaved in the slow step of the reaction. All results are consistent with a mechanism which involves, in the rate determining step, loss of an α-hydrogen atom as a proton with concomitant transfer of electrons from nitrogen to the oxidant.