Temperature-Dependent Kinetics of the Reaction of the Criegee Intermediate CH

The kinetics of the reaction between formaldehyde oxide (CH2OO) and pyruvic acid (CH3COCOOH) has been investigated. Laser flash-photolysis-transient absorption spectroscopy measurements over the range T = 275-375 K were used to measure T-dependent bimolecular rate constants. The rate constants show non-Arrhenius behavior, initially increasing and subsequently decreasing with T. A maximum value of (21.4 ± 1.1) × 10-12 cm3 s-1 was observed at 335 K. At room temperature (296 K), the rate constant was measured to be (19.5 ± 1.2) × 10-12 cm3 s-1, which is in line with the value expected for reaction of CH2OO with a substituted carbonyl and significantly smaller than typical values for reactions with carboxylic acids. Various pathways have been characterized by ab initio calculations at the CBS-QB3 level for reaction of CH2OO with the two lowest-energy conformers of pyruvic acid, labeled Tc and Tt. Both conformers can undergo 1,3-dipolar cycloaddition reactions at either carbonyl group to form secondary ozonides via submerged barriers. The presence of an internal H-bond in the more stable Tc conformer has a significant impact on reactivity, inhibiting the alternative 1,2-addition/insertion and 1,4-addition reaction pathways involving the OH or COOH groups, respectively, that occur more readily for the less stable Tt conformer and form hydroperoxymethylpyruvate ester. The unusual T dependence of the measured rate constants is attributed to the increasing thermal population of the less stable Tt conformer at higher T, and the availability of additional reaction pathways.