Relative reactivity of methyl iodide to ethyl iodide in nucleophilic substitution reactions in acetonitrile and partial desolvation accompanying activation

Abstract

Through the examination of empirical correlations involving activation parameters for nucleophilic substitution of methyl iodide and of ethyl iodide, nucleophiles have been classified into three series: (1) nucleophiles with two equivalent reaction sites, (2) nucleophiles with a chlorine atom in the para-position, and (3) nucleophiles with a single reaction site. Three types of partial desolvation processes accompanying activation have been deduced on the basis of these classifications. A major factor determining the relative reactivity of methyl iodide to ethyl iodide in the substitution reaction of an anionic nucleophile having a single reaction site in acetonitrile (k_MeI/k_EtI) is suggested to be partial desolvation around the nucleophilic center on going from reactant to transition-state.