Substituent Effects on the Reaction Rates of Hydrogen Abstraction in the Pyrolysis of Phenethyl Phenyl Ethers

We report reaction profiles and forward rate constants for hydrogen abstraction reactions occurring in the pyrolysis of methoxy-substituted derivatives of phenethyl phenyl ether (PhCH2CH2OPh, PPE), where the substituents are located on the aryl ether ring (PhCH2CH2OPh-X). We use density functional theory in combination with transition-state theory, and anharmonic corrections are included within the independent mode approximation. PPE is the simplest model of the abundant β-O-4 linkage in lignin. The mechanism of PPE pyrolysis and overall product selectivities have been studied experimentally by one of us, which was followed by computational analysis of key individual hydrogen-transfer reaction steps. In the previous work, we have been able to use a simplified kinetic model based on quasi-steady-state conditions to reproduce experimental α/β selectivities for PPE and PPEs with substituents on the phenethyl ring (X-PhCH2CH2OPh). This model is not applicable to PPE derivatives where methoxy substituents are located on the phenyl ring adjacent to the ether oxygen because of the strongly endothermic character of the hydrogen abstraction by substituted phenoxy radicals as well as the decreased kinetic chain lengths resulting from enhanced rates of the initial C−O homolysis step. Substituents decelerate the hydrogen abstraction by the phenoxy radical, while the influence on the benzyl abstraction is less homogeneous. The calculations provide insight into the contributions of steric and polar effects in these important hydrogen-transfer steps. We emphasize the importance of an exhaustive conformational space search to calculate rate constants and product selectivities. The computed rate constants will be used in future work to numerically simulate the pyrolysis mechanism, pending the calculation of the rate constants of all participating reactions.