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Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, NBS, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured νmax. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and β,ρs, values.
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