Unimolecular decomposition of chemically activated methylallylether

Abstract

AbstractThe unimolecular decomposition of chemically activated methylallylether (MAE) formed by the cross combination of methoxymethyl and vinyl radicals was studied in the gas phase. The experimentally determined rate constant was found to be 1.11 × 108 sec−1 at 9.6°C for the decomposition of MAE into propene and formaldehyde. The decomposition of MAE via the six‐center retro‐“ene” type transition state is analyzed by using the RRKM unimolecular reaction theory. For the molecular parameter assignments of energized MAE, a model which contains one internal rotational mode is supported, and MAE decomposition is characterized by a tight complex model. The best agreement between experimental and theoretical results was found when a critical energy of 40.1 kcal/mol was used.