25716-02-3Relevant academic research and scientific papers
Nucleophilic substitution reactions of 2-norbornyl arenesulfonates with anilines
Oh, Hyuck Keun,Joung, Eun-Mi,Cho, In Ho,Park, Young Sook,Lee, Ikchoon
, p. 2027 - 2038 (2007/10/03)
The kinetics and mechanism of the nucleophilic substitution reactions of exo- and endo-2-norbornyl arenesulfonates with anilines are investigated in methanol and acetonitrile at 60.0°C. Rate constants for three distinct competing processes, solvolysis ks
Application of Mechanistic and Transition-State Indicators to endo and exo-2-Norbornyl Arenesulfonates. Definition of a new Mechanistic Indicator
McManus, Samuel P.,Smith, Maurice R.,Shankweiler, Jean M.,Hoffman, Robert V.
, p. 141 - 148 (2007/10/02)
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.
