title: Quantum chemical study of the thermal decomposition of o-quinone methide (6-methylene-2,4-cyclohexadien-1-one).
abstract: o-Quinone methide (o-QM), or 6-methylene-2,4-cyclohexadiene-1-one, has been identified as an important intermediate in lignin and alkyl benzene combustion, and the thermal decomposition of o-QM is therefore relevant to the combustion of transportation fuels (which contain toluene) and of biomass and low-rank coals (which contain lignin). We present a comprehensive reaction mechanism for the unimolecular conversion of o-QM to the reaction intermediates tropone and fulvene, calculated using theoretical quantum chemical techniques. Enthalpies of formation for all reactants, products, and intermediates are calculated using the CBS-QB3 theoretical method. Transition states are determined with the CBS-QB3 method, which we use to obtain rate constants as a function of temperature from transition-state theory, with Wigner tunneling corrections applied to hydrogen-shift reactions. Barrier heights are also calculated with the BB1K density functional theory (DFT) method for thermochemical kinetics. Reaction pathways are identified leading to tropone (which rapidly decomposes to benzene + CO) and to fulvene + CO, via initial hydrogen transfer to 2-hydroxyphenylcarbene and via ring opening to 1,3,5,6-heptatetraen-1-one, respectively. Quantum Rice-Ramsperger-Kassel (QRRK) theory analysis of the reaction kinetics indicates that the dominant reaction pathway is formation of tropone via 2-hydroxyphenylcarbene; the formation of fulvene + CO via initial ring opening constitutes a secondary pathway, which becomes more important with increasing temperature. Our calculations, using BB1K barrier heights, yield the rate equation k(T) [s(-1)] = 2.64 x 10(14) exp(-35.9/T [K]) for o-QM decomposition, which is in relatively good agreement with the experimental rate equation. Calculations provide an apparent activation energy of 71.3 kcal mol(-1), versus 67.2 kcal mol(-1) from experiment.
authors.affiliation: Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, USA.
authors.forename: Gabriel da
authors.initials: Gd
authors.lastname: Silva
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Bozzelli
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry; D018533:Biomass; D003031:Coal; D005579:Fossil Fuels; D006358:Hot Temperature; D045563:Indolequinones / Q000737:chemistry*; D008031:Lignin / Q000737:chemistry; D008956:Models, Chemical; D011789:Quantum Theory
chemical_list: D001555:Benzene Derivatives; D003031:Coal; D005579:Fossil Fuels; D045563:Indolequinones; C068040:quinone methide; D008031:Lignin