Gas phase ion chemistry of methyl acetate, methyl propanoate and their enolic tautomers. An experimental approach

Abstract From a combination of isotopic substitution, time‐resolved measurements and sequential collision experiments, it was proposed that whereas ionized methyl acetate prior to fragmentation rearranges largely into $$ {\rm CH}_3 \mathop {\rm C}\limits^ + ({\rm OH}){\rm O}\mathop {\rm C}\limits^{\rm .} {\rm H}_2 $$ , in contrast, methyl propanoate molecular ions isomerize into $$ \mathop {\rm C}\limits^. {\rm H}_2 {\rm CH}_2 \mathop {\rm C}\limits^ + ({\rm OH}){\rm OCH}_3 $$ . Metastably fragmenting methyl acetate molecular ions are known predominantly to form H 2 ĊOH together with $$ {\rm CH}_3 - \mathop {\rm C}\limits^ + = {\rm O} $$ , whereas ionized methyl propanoate largely yields H 3 CO˙ together with $$ {\rm CH}_3 {\rm CH}_2 - \mathop {\rm C}\limits^ + = {\rm O} $$ . The observations were explained in terms of the participation of different distonic molecular ions. The enol form of ionized methyl acetate generates substantially more H 3 CO˙ in admixture with H 2 ĊOH than the keto tautomer. This is ascribed to the rearrangement of the enol ion to the keto form being partially rate determining, which results in a wider range of internal energies among metastably fragmenting enol ions. Extensive ab initio calculations at a high level of theory would be required to establish detailed reaction mechanisms.