Computational insights on the structure of transition states and intermediates of the Boyland-Sims Oxidation reaction

The Boyland-Sims Oxidation reaction uses an alkaline solution of peroxydisulfate salt to convert arylamines o-aminophenols. long-standing mechanism involves a nucleophilic attack by the amine leading formation arylhydroxylamine-O-sulfonate intermediate, which then rearranges arylamine o-sulfate. on peroxide oxygen has been questioned Marjanović et al. who have proposed nitrenium ion intermediate as reactive species rather than uncharged amine. It challenged variety experimental observations. We present here new computations at high-level density functional theory (B3LYP/6-311++G**) model both and pathways in series aromatic amines. In this study, energetics intermediates mechanisms are computed for aniline, 2,4-dinitroaniline, N,N-dimethylaniline. To further support reaction, calculations were performed find transition states involved mechanisms. state revealed two possible energetically feasible rearrangement Our results indicate that oxidation reactions proceed via predicted earlier.