Phenoxazine: A Privileged Scaffold for Radical-Trapping Antioxidants

-phenoxazine (37 °C). The reactivity of the latter compound is the greatest of any RTA ever reported and is likely to represent a reaction without an enthalpic barrier since log A for this reaction is likely ∼8.5. The very high reactivity of most of the phenoxazines studied required the determination of their kinetic parameters by inhibited autoxidations in the presence of a very strong H-bonding cosolvent (DMSO), which slowed the observed rates by up to 2 orders of magnitude by dynamically reducing the equilibrium concentration of (free) phenoxazine as an H-atom donor. Despite their remarkably high reactivity toward peroxyl radicals, the phenoxazines were found to be comparatively stable to one-electron oxidation relative to diphenylamines and phenothiazines (E° ranging from 0.59 to 1.38 V vs NHE). Thus, phenoxazines with comparable oxidative stability to commonly used diphenylamine and phenothiazine RTAs had significantly greater reactivity (by up to 2 orders of magnitude). Computations suggest that this remarkable balance in H-atom transfer kinetics and stability to one-electron oxidation results from the ability of the bridging oxygen atom in phenoxazine to serve as both a π-electron donor to stabilize the aminyl radical and σ-electron acceptor to destabilize the aminyl radical cation. Perhaps most excitingly, phenoxazines have "non-classical" RTA activity, where they trap >2 peroxyl radicals each, at ambient temperatures.