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 (C) 2003 John Wiley Sons, Ltd.