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.