Structure-Reactivity Relationships in Nucleophilic Reactions on Cinnamoyl Azide and Phenyl Cinnamates. Kinetic Stability of the Acyl Azide and Relative Leaving Ability of Nitrogen and Oxygen

Article abstract of DOI:10.1021/jo01303a034

The alkaline hydrolysis and aminolysis of cinnamoyl azide and aryl-substituted phenyl cinnamates and the azidolysis of the phenyl cinnamates have been studied.The positions of the rate-determining steps in the reactions are identified by the structure-reactivity relationships.The enhanced affinity of azide ion for an acyl carbon compared with its basicity is proposed to account for the observed kinetic stability of cinnamoyl azide toward alkaline hydrolysis and aminolysis.Azide ion resists expulsion from the tetrahedral intermediate more than quinuclidine derivatives but less than phenolates.This is explained in terms of the electron withdrawal as well as electron donation by resonance.