1971 Volume 44 Issue 3 Pages 756-761
The rates of reactions of N,N-dimethylbenzylamine or its derivatives with methyl iodide in fourteen nonaqueous solvents at 30°C have been studied. The effects of the solvents on reactivities and Hammett’s ρ values have been examined. For establishing the relationship between ρ and solvent polarity, a unique solvent parameter for reactivity ξ0 was defined, which measures the relative solvent polarity in determining the order of reaction rate with respect to solvent. There is a linear relationship between ρ and ξ0, but protic and aromatic solvents show deviation from this relation in a particular way. The liner relationship provides a common basis for explaining both substituent and solvent effects. This suggests the importance of solvent reorientation accompanied by an activation process. It is argued that the hydrogen-bonded solvation of reactant amines and solvation of the leaving group are responsible for abnormal behaviors in protic and aromatic solvents.
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