α‐Distonic ions as transient species in the reactions of metastable alkyl benzoate radical cations

The key intermediates to the fragmentation of metastable methyl and ethyl benzoate radical cations are α‐ and β‐distonic isomers of the molecular ions. The α‐distocic isomers are also formed by fragmentation of longer chain alkyl benzoates, but may not be long‐lived, stable species. Rearrangement of the α‐distonic ions prior to fragmentation can take place, but (re)formation of the benzoate molecular ions does not occur.