Alkaline hydrolyses of N-alkyl-2,4-dinitroacetanilides

Abstract

The alkaline hydrolysis in protium and deuterium oxides of N-alkyl-2,4-dinitroacetanilides (alkyl; methyl and hydrogen) proceeds via the rate-limiting formation of a tetrahedral intermediate, which decomposes to give products with water (k₂ process) and hydroxide catalysis (k₃ process), the latter process being predominant. Solvent isotope effects for both processes are ca. 3.0 (60 °C). Breakdown of the tetrahedral intermediate proceeds by two pathways with the transition states involving C–N bond breakage to give a hydrogen-bonded anilide ion intermediate.