Effect of Ionic Liquids on the Menschutkin Reaction: An Experimental and Theoretical Study

摘要

The effect of ionic liquids (ILs) on the Menschutkin reaction between N-methylimidazole and benzylhalides has been investigated. Hammett correlations have been used to obtain information on the reactionmechanism of benzyl chlorides in ionic and molecular solvents. The solvent effects on this reaction havebeen examined using both multiparameter linear solvation energy relationships and theoretical calcula-tions. These latter have been performed using a supermolecular approach, i.e., the IL is represented by anexplicit ionic pair, IP. Two possible different reaction pathways have been obtained changing the positionof the IL-IP with respect to the reagents. It is hypothesized that inside the IL the Menschutkin reaction ofbenzyl chloride with N-methylimidazole can follow different reaction pathways by considering theinfluence of dynamic heterogeneity in ionic media on the time scale of the lifetime of a transition state.