Manipulating Solute Nucleophilicity with Room Temperature Ionic Liquids

• Published in: Journal of the American Chemical Society 2004-09, Vol.126 (37), p.11549-11555
• Main Authors: Crowhurst, Lorna, Lancaster, N. Llewellyn, Pérez Arlandis, Juan M, Welton, Tom
• Format: Article
• Language: English
• Subjects: Chemical reactivity; Chemistry; Exact sciences and technology; Organic chemistry; Reactivity and mechanisms
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja046757y

In this work we report the effect of ionic liquids on a class of charge-neutral nucleophiles. We have studied the reactions of nbutylamine, di-nbutylamine, and tri-nbutylamine with methyl p-nitrobenzenesulfonate in [bmpy][N(Tf)2], [bmpy][OTf], and [bmim][OTf] (bmpy = 1-butyl-1-methylpyrrolidinium; bmim = 1-butyl-3-methylimidazolium) and compared their reactivities, k 2, to those for the same reactions in the molecular solvents dichloromethane and acetonitrile. It was shown that all of the amines are more nucleophilic in the ionic liquids than in the molecular solvents studied in this work. Comparison is also made with the effect of ionic liquids on the reactivity of chloride ions, which are deactivated in ionic liquids. The Eyring activation parameters revealed that changes in the activation entropies are largely responsible for the effects seen. This can be explained in part by the differing hydrogen-bonding properties, as shown by the Kamlet−Taft solvent parameters, of each of these solvents and the formation of hydrogen bonds between the solvents and the nucleophiles.