Theoretical study on the pyrolysis mechanism and kinetics of β-hydroxyketones

The mechanism and kinetics for the decomposition of β-hydroxypropaldehyde, primary and secondary β-hydroxyketones, were studied by using ab initio RHF/6-31G and RHF/6-31G* methods. The activation barriers of these reactions were refined to be 39.57, 40.10, and 36.80 kcal mol^-1 at the MP2//RHF/6-31G* level, respectively. The calculated results show that each decomposition is a concerted process with hydrogen transferring and bond breaking via a six-membered cyclic transition state. The thermal rate constants of the decomposition of primary and secondary β-hydroxyketones were obtained by calculating microcanonical probability fluxes through each transition state. It is theoretically confirmed that methyl substitution at the hydroxyl carbon of β-hydroxyketones causes a small enhancement in rates. The theoretical investigations of the mechanism and the rate constants are in agreement with the experimental results.