Mécanisme de solvolyse des cis - et trans-(p-toluénesulfonates) d'aryl1-2-cyclopentyle II. Etude des étapes ultérieures à l'ionisation lors de la solvolyse des cis-(p-toluénesulfonates) d'aryl-2-cyclopentyle

Solvolysis Mechanism of cis- and trans-2-Arylylopentylp- Toluenesulfonates, Subsequent Step in cis-2-Arylcyclopentyl p-Toluenesulfonate Solvolysis 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 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 substitutant electronic effects the total solvolysis rate and the respective contributions of k _c and k _ip processes. Comparing the observed and calculated kinetic isotope of D–C(2) allows one to conclude that no step can called ‘rate-determining step’ but that the steps following ionisation have a preponderent effect on the total solovolysis rate.