Mechanism of Reactions of Thiols and Bisulfides with Dihaloalkanes:A Quantum-Chemical Study

摘要

The potential surfaces of the reactions of thiols and disulfides with haloalkanes in the gas phase and with participation of a hydrizine molecule were studied quantum-chemically.The stereoelectronic characteristics of the prereaction complexes and reaction products were studied.The transition states were localized.The four-center reaction mechanism is preferable.The increased activation barrier in exchange of thiols with chloroalkanes is the major factor responsible for formation of unsymmetrical chlorinated sulfides.