title: Evidence for the HOOO(-) anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products.
abstract: Low-temperature ozonation (-78 degrees C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.
authors.affiliation: Department of Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, P.O. Box 537, 1000 Ljubljana, Slovenia. bozo.plesnicar@uni-lj.si
authors.forename: Bozo
authors.initials: B
authors.lastname: Plesnicar
authors.forename: Janez
authors.initials: J
authors.lastname: Cerkovnik
authors.forename: Tell
authors.initials: T
authors.lastname: Tuttle
authors.forename: Elfi
authors.initials: E
authors.lastname: Kraka
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer
mesh_terms: D000838:Anions; D003080:Cold Temperature; D004148:Dioxolanes / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010087:Oxides / Q000737:chemistry*; D010126:Ozone / Q000737:chemistry*
chemical_list: D000838:Anions; D004148:Dioxolanes; D004952:Esters; D010087:Oxides; D010126:Ozone