Gas-phase kinetics and mechanism of diallyl sulfide thermal decomposition

The gas‐phase kinetics of diallyl sulfide pyrolysis were studied experimentally and theoretically in a static system over the temperature range 433–463 K and a total pressure of 80 Torr in a glass vessel with the free radical inhibitor cyclohexene. The experimental results show that this reaction is homogeneous, unimolecular and follows a first‐order rate law. Theoretical studies at the B3LYP/6–31G* computational level indicate that the elimination reaction proceeds through a six‐centered cyclic transition state and the reaction mechanism is concerted and non‐synchronous. Copyright © 2003 John Wiley & Sons, Ltd.