A comparative spin trapping study of the interaction of hypobromous and hypochlorous acids with tert-butyl hydroperoxide

Hypochlorite (HOCl/OCl−) and hypobromite (HOBr/OBr−) are shown to react with tert-butyl hydroperoxide with close rate constants (10.8 and 8.9 M−1 s−1, respectively). Using a spin trap α-(4-pyridyl-1-oxide)-N-tert-butyl nitrone, both reactions are shown to proceed through decomposition of the hydroperoxide yielding butylperoxyl [˙OOC(CH3)3] and butoxyl [˙OC(CH3)3] radicals in a ratio depending on the hydroperoxide concentration. Thus, like hypochlorite, hypobromite can generate free radicals in reactions with organic hydroperoxides, which can be important for intensification of free-radical processes, e.g., lipid peroxidation at the chain branching stage.