Rate constants for reaction of 1,2-dimethylimidazole with benzyl bromide in ionic liquids and organic solvents

The rate constant for the Menschutkin reaction of 1,2-dimethylimidazole with benzyl bromide to produce 3-benzyl-1,2-dimethylimidazolium bromide was determined in a number of ionic liquids and molecular organic solvents The rate constants in 12 ionic liquids are in the range of (1.0-3.2) x 10(-3) L mol(-1) s(-1) and vary with the solvent anion in the order (CF3SO2)(2)N- < PF6- < BF4- Variations with the solvent cation (butylmethylimidazolium, octylmethylimidazolium, butyldimethylimidazolium, octyldimethylimidazolium, butylmethylpyrrolidinium, and hexyltributylammonium) are minimal. The rate constants in the ionic liquids are comparable to those in polar aprotic molecular solvents (acetonitrile, propylene carbonate) but much higher than those in weakly polar organic solvents and in alcohols. Correlation of the rate constants with the solvatochromic parameter ET(30) is reasonable within each group of similar solvents but very poor when all the solvents are correlated together. Better correlation is obtained for the organic solvents by using a combination of two parameters, pi* (dipolarity/polarizibility) and alpha (hydrogen bond acidity), while additional parameters such as delta (cohesive energy density) do not provide any further improvement. (C) 2004 Wiley Periodicals, Inc.