title: Photooxidation of Di-tert-butyl Malonate in the Presence and Absence of Nitrogen Dioxide.
abstract: The rate constant for the reaction of di-tert-butyl malonate (DTBM) with chlorine atoms in the gas phase was measured using cyclohexane and pentane as references. The measurements lead to a value of (1.5 ± 0.1) × 10-10cm3molecule-1s-1. The subsequent photo-oxidation mechanism of DTBM in the absence and presence of nitrogen dioxide was investigated. The main carbonated products identified in the first case were acetone, formic acid, carbon monoxide, and carbon dioxide. The addition of nitrogen dioxide lead besides to the formation of (CH3)3CC(O)OONO2and (CH3)3CONO2. The proposed photo-oxidation mechanism was supported both experimentally and computationally. The results reveal that the (CH3)3COC(O)CH2C(O)OC(CH3)2O•radical formed reacts according to two competitive reactions: decomposition to yield acetone and (CH3)3COC(O)CH2C(O)O•radical 55 ± 2%, and migration of the H atom of the methylene group to the terminal oxygen atom 40 ± 3%.
authors.affiliation: Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC) CONICET - Departamento de Fisicoquímica, Facultad de Ciencias Químicas (Universidad Nacional de Córdoba), Ciudad Universitaria (X5000HUA), Córdoba, República Argentina.
authors.forename: Diana
authors.initials: D
authors.lastname: Henao
authors.affiliation: Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC) CONICET - Departamento de Fisicoquímica, Facultad de Ciencias Químicas (Universidad Nacional de Córdoba), Ciudad Universitaria (X5000HUA), Córdoba, República Argentina.
authors.forename: Walter
authors.initials: W
authors.lastname: Peláez
authors.affiliation: Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC) CONICET - Departamento de Fisicoquímica, Facultad de Ciencias Químicas (Universidad Nacional de Córdoba), Ciudad Universitaria (X5000HUA), Córdoba, República Argentina.
authors.forename: Gustavo A
authors.initials: GA
authors.lastname: Argüello
authors.affiliation: Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC) CONICET - Departamento de Fisicoquímica, Facultad de Ciencias Químicas (Universidad Nacional de Córdoba), Ciudad Universitaria (X5000HUA), Córdoba, República Argentina.
authors.forename: Fabio E
authors.initials: FE
authors.lastname: Malanca