Structure‐dependence in initial decomposition of trans‐1,2‐dimethylcyclohexyl isomers: Kinetic exploration and conformational analysis

Abstract

AbstractTo elucidate the combustion behaviors of trans‐1,2‐dimethylcyclohexyl isomers, their initial decomposition have been explored by employing quantum chemical calculations coupled with transition state theory. All conformational structures and their interconversion mechanisms were studied. Originated from distinct conformers, all accessible transition states were explicitly identified in multiple paths for H‐transfer or β‐scission, and then were carefully used in kinetic predictions. The fairly speedy conformation fairly dominates over decomposition that allows thoroughly evaluating the contribution of various conformers to the final kinetics. Conformational analysis unravels that the most favorable 1,5 H‐transfer is only feasible for one twist‐boat with radical site in axial side chain accompanied by one isoclinal methyl group. The results for β‐scissions are affected by steric energies and substituent effects remained in conformational structures. These findings facilitate to finally figure out the proper kinetic parameters for each decomposition reaction for the implication in kinetic modeling simulation.