Reactivity of Inorganic α-Nucleophiles in Acyl Transfer in Aqueous and Micellar Media: IV. Peroxyhydrolysis of Acyl Derivatives in Organized Microheterogeneous Systems1

Abstract

The micellar effects in the perhydrolysis and base-catalyzed hydrolysis of 4-nitrophenyl esters of phosphoric, phosphonic, and toluenesulfonic acids in organized microheterogeneous systems based on dicationic [Gemini surfactant AlkIm⁺–(CH₂)₃–Im⁺Alk∙2Br^–, where Alk = C₁₂H₂₅ or C₁₄H₂₉ (GS)] and monocationic (AlkIm⁺CH₃∙Br^–, where Alk=C₁₂H₂₅ or C₁₄H₂₉) surfactants have been analyzed. The reagent concentrations have been found to be the main factor responsible for micellar catalysis. The hydroperoxide α-effect defined as the ratio of the second-order rate constants of perhydrolysis and base-catalyzed hydrolysis is preserved and, depending on the nature of the surfactant and the substrate, may reach ~ 100.