Chapter 1 Kinetics of Electrophilic Aromatic Substitution

Abstract

This chapter focuses on electrophilic aromatic substitution and reviews the literature published prior to 1969. In general, kinetics studies fall into two classes: those aimed at determining the reaction mechanism and those that utilize the reaction to determine substituent effects in electrophilic aromatic substitution. The chapter also discusses the kinetic evaluation of complex formation. Kinetic studies are of little value to determine the extent of complex formation in the reaction path of electrophilic substitution. Unless the formation of the complex is rate-determining, the kinetic form is independent of complex formation. In addition, the influence of complex formation on reaction rates only comes from the factors that lead in the first place to complex formation. Substituent effects are inadequate for showing the extent of complex formation; however, when they indicate similar effects on substitution and complex formation, they provide evidence that the latter is a pathway of the former.