Linear solvation-energy relationships: solvolytic reactions of t-butyl bromide and t-butyl iodide in hydroxylic solvents

Abstract

Solvent effects on the solvolytic reactions of Bu^tBr and Bu^tl in water, and 12 monoalcohols and 10 dialcohols, from 1 to 5 carbon atoms, have been analysed in terms of linear solvation energy relationships. The experimentally determined rate constants, at 25 °C, are well correlated through equations of the form log k=a₀+a₁g(η)+a₂E_T^N+a₃C where g(η) is a function of the refractive index, E_T^N is the normalized Dimroth and Reichardt parameter and C is the solvent cohesive pressure. The correlation analysis revealed significant information on the solvent–solvent–solute interactions. It is also shown that results are in good agreement with previous analysis using different approaches and other sets of solvents.