Photocatalytic Oxidative Bromination of 2,6-Dichlorotoluene to 2,6-Dichlorobenzyl Bromide in a Microchannel Reactor

Photocatalytic oxidative benzylic bromination with hydrobromic acid (HBr) and hydrogen peroxide (H₂O₂) is a green process for the synthesis of benzyl bromides, but suffers from the risk of explosion when performing it in a batch reactor. This disadvantage could be overcome by running the reaction in a microchannel reactor. In this work, a green and safe process for the synthesis of 2,6-dichlorobenzyl bromide (DCBB) was developed by conducting selective benzylic bromination of 2,6-dichlorotoluene (DCT) with H₂O₂ as an oxidant and HBr as a bromine source in a microchannel reactor under light irradiation. The reaction parameters were optimized, and the conversion of DCT reached up to 98.1% with a DCBB yield of 91.4% under the optimal reaction conditions.