REARRANGEMENT AND METHYL LOSS FROM IONIZED PROPENE OXIDE AND METHYL VINYL ETHER.

Article abstract of DOI:10.1021/ja00321a007

Molecular cations of propene oxide (a) and methyl vinyl ether (b), despite a large difference (35 kcal mol** minus **1) in their heats of formation, undergo two very similar metastable methyl loss dissociations; for both of these dissociations a and b exhibit the same kinetic energy release values and produce acetyl ions. Deuterium labeling shows that a ions undergo little direct methyl loss, but instead isomerize by ring opening and 1,4-H transfer to b. For long-lived ions of energies below the decomposition threshold, nearly complete hydrogen exchange occurs between the methyl and methylene groups.