74. Solvolysis Mechanism of cis- and trans-2-Arylcyclopentyl p-Toluenesulfonates. Subsequent Step in cis-2-Arylcyclopentyl p-Toluenesulfonate Solvolysis

Article abstract of DOI:10.1002/hlca.19880710320

The solvolysis of a series of 1-deuteriated, 2-deuteriated, and undeuteriated cis-2-arylcyclopentyl p-toluenesulfonates in HCOOH, AcOH, and EtOH has been studied.We have shown that the classical secondary carbocation arising from substrate ionisation undergoes two concurrent processes, namely k_c (direct products formation) and k_ip (hydrogenium bridged ion formation as tertiary carbocation or products precursor).The intrinsic properties of solvent and the aryl substituent electronic effects only affect the total solvolysis rate and the respective contributions of k_c and k_ip processes.Comparing the observed and calculated kinetic isotope effects of D-C(2) allows one to conclude that no step can be called 'rate-determining step' but that the steps following ionisation have a preponderent effect on the total solvolysis rate.