The Dependence of Ionic Liquid Solvent Effects on the Nucleophilic Heteroatom in SN Ar Reactions. Highlighting the Potential for Control of Selectivity

Abstract

Nucleophilic aromatic substitution (S_N Ar) reactions of 1-fluoro-4-nitrobenzene using similar nitrogen and sulfur nucleophiles were studied through extensive kinetic analysis in mixtures containing ionic liquids. The interactions of the ionic liquid components with the starting materials and transition state for each process were investigated in an attempt to construct a broad predictive framework for how ionic liquids affect reaction outcome. It was found that, based on the activation parameters, the microscopic interactions and thus the ionic liquid solvent effect were different for each of the nucleophiles considered. The results from this study suggest that it may be possible to rationally select a given ionic liquid mixture to selectively control reaction outcome of an S_N Ar reaction where multiple nucleophiles are present.

Keywords: aromatic substitution; ionic liquids; kinetics; nucleophilic substitution; solvent effects.