title: Ab initio study of the decomposition of 2,5-dimethylfuran.
abstract: The initial steps in the thermal decomposition of 2,5-dimethylfuran are identified as scission of the C-H bond in the methyl side chain and formation of β- and α-carbenes via 3,2-H and 2,3-methyl shifts, respectively. A variety of channels are explored which prise the aromatic ring open and lead to a number of intermediates whose basic properties are essentially unknown. Once the furan ring is opened demethylation to yield highly unsaturated species such as allenylketenes appears to be a feature of this chemistry. The energetics of H abstraction by the hydroxyl radical (and other abstracting species) from a number of mono- and disubstituted methyl furans has been studied. H-atom addition to 2,5-dimethylfuran followed by methyl elimination is shown to be the most important route to formation of the less reactive 2-methylfuran. Identification of 2-ethenylfuran as an C(6)H(6)O intermediate in 2,5-dimethylfuran flames is probably not correct and is more likely the isomeric 2,5-dimethylene-2,5-dihydrofuran for which credible formation channels exist.
authors.affiliation: Combustion Chemistry Centre, National University of Ireland, Galway, Ireland. john.simmie@nuigalway.ie
authors.forename: John M
authors.initials: JM
authors.lastname: Simmie
authors.forename: Wayne K
authors.initials: WK
authors.lastname: Metcalfe
mesh_terms: D005663:Furans / Q000737:chemistry*; D006801:Humans; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D015394:Molecular Structure; D013816:Thermodynamics
chemical_list: D005663:Furans; C051224:methyl radical; C030011:carbene; D017665:Hydroxyl Radical; C029060:2-methylfuran; C037555:2,5-dimethylfuran; D008697:Methane