115-05-9Relevant academic research and scientific papers
Effective Charge Development in Ester Hydrolysis Catalyzed by Cationic Micelles
Al-Awadi, Nouria,Williams, Andrew
, p. 2001 - 2004 (2007/10/02)
Reaction of hydroxide ion with substituted phenyl laurates is catalyzed by micelles containing CTAB (cetyltrimethylammonium bromide).The observed rate constants for ester consumption obey a Michaelis-Menten-like rate law, kobsd = (kOHKeq + kOHcat)/(Keq + ), where kOHcat is the second order rate constant for reaction of hydroxide ion with micelle-bound ester, Keq is a partition coefficient for dissociation of ester from the micelle-bound ester, and kOH is the second order rate constant for reaction of free ester with hydroxide ion.The value of the parameter Keq is independent of the nature of the substituent on the ester.The ratio kOHcat/Keq represents the free energy change from ester in aqueous solution to the transition state of the ester reaction in the micellar pseudophase.The dependence of log kOHcat/Keq on the pKa of the leaving phenol obeys a linear Bronsted equation with β1g = -0.51, and log kOH obeys a linear Bronsted equation with β1g = -0.56.Since both Bronsted parameters refer to catalyzed and uncatalyzed reactions starting from the same standard state (aqueous solution), the effective charge in the transtition state of both reactions is almost the same.The microscopic medium is thus similar for both cases, consistent with the COOAr moiety's residing in an aqueous-like region of the pseudophase in the catalytic process.
