title: Insights into the formation and isomerization of the benzene metabolite muconaldehyde and related molecules: comparison of computational and experimental studies of simple, benzo-annelated, and bridged 2,3-epoxyoxepins.
abstract: 2,8-Dioxabicyclo[5.1.0]octa-3,5-diene ("2,3-epoxyoxepin") has been postulated as an intermediate in ring-opening metabolism of benzene. Density functional theory (B3LYP/6-31G*) is employed to study the activation and reaction energies for ring-opening isomerization of 2,3-epoxyoxepin, its 4,5-benzo derivative, and its 3,6-hexamethylene derivative. The results are compared with published experimental data. The markedly different fates of these three molecules suggest a means for testing the postulated metabolic pathway.
authors.affiliation: Department of Chemistry University of New Hampshire Durham, New Hampshire 03824, USA.
authors.forename: Jessica
authors.initials: J
authors.lastname: Morgan
authors.forename: Arthur
authors.initials: A
authors.lastname: Greenberg
mesh_terms: D000447:Aldehydes / Q000737:chemistry* / Q000378:metabolism*; D001554:Benzene / Q000737:chemistry* / Q000378:metabolism*; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D003510:Cyclohexanes / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010082:Oxepins / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000447:Aldehydes; D001952:Bridged-Ring Compounds; D003510:Cyclohexanes; D010082:Oxepins; C034476:muconaldehyde; C506365:Cyclohexane; C013178:oxepin epoxide; D001554:Benzene