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

✍ Scribed by G. Ronco; R. Guyon; P. Villa

• Publisher: John Wiley and Sons
• Year: 1988
• Tongue: German
• Weight: 982 KB
• Volume: 71
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19880710320

✦ Synopsis

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

The solvolysis of a series of I-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, (direct products formation) and k,, (hydrogenium bridged ion formation as tertiary carbocdtion or products precursor). The intrinsic properties of solvent and the aryl suhstituant electronic effects only affect the total solvolysis rate and the respective contributions of k , and k,, processes. Comparing the observed and calculated kinetic isotope effects of D-C(2) allows one to conclude that no step can he called 'rate-determining step' but that the steps following ionisation have a prcponderent effect on the total solovolysis rate.