Electron spin resonance studies. Part 62. Acid-catalysed interconversion of β-hydroxyalkyl radicals: radical-cation intermediates

Abstract

Evidence is presented that isomerism of β-hydroxyalkyl radicals (e.g., the conversion of ·CH₂CMe₂OH into ·CMe₂CH₂OH) can be brought about in acid solution and that reaction occurs via the formation and hydration of a radical-cation. The reaction rates for loss of OH^–(e.g.·CHMeCEt₂OH > ·CH₂CHMe₂OH > ·CH₂CHMeOH) are correlated with the stabilities of the radical-cations as measured by the ionization potentials of the corresponding alkenes.