Journal of Organic Chemistry p. 141 - 148 (1988)
Update date:2022-08-05
Topics:
McManus, Samuel P.
Smith, Maurice R.
Shankweiler, Jean M.
Hoffman, Robert V.
We have mechanistically classified endo- and exo-2-norbornyl arenesulfonates by using two common probes: the effect on rate of added thiourea and rate correlation in aqueous ethanol and trifluoroethanol.Interestingly, the exo isomer is improperly classified by each of these probes because of medium-dependent ion-pair return.In search of better mechanistic indicators, pseudo-first-order solvolytic rates and products have been determined for a series of endo- and exo-2-norbornyl arenesulfonates.Using these and literature data, we have compared these substrates with others by plotting α-deuterium isotope effects against β1gMe values determined for a series or arenesulfonates in the same or a similar solvent.The use of this type of plot as a heuristic method for distinguishing k8 and kΔ substrates is discussed.Finally, our product studies are consistent with the involvement of solvent-seperated ion pairs in the solvolysis of 2-norbornyl arenesulfonates.Different alcohol-ether product ratios for the isomeric esters in consistent with dual pathways for product formation with the endo substrates.
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