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.