Kinetics and mechanism of aminolysis of phenyl acetates in aqueous solutions of poly(ethylenimine)

Article abstract of DOI:10.1021/jo9514681

Second-order rate constants (k_n) for the aminolysis of some phenyl acetates with poly(ethylenimine) (PEI) were obtained in a pH range 4.36-11.20 at 25 °C in 1 M KC1. Linear Bronsted-type plots (log k_n vs pK_N of PEI) were found for less reactive esters 2-nitrophenyl acetate, 4-acetoxy-3-chlorobenzoic acid, and 4-acetoxybenzenesulfonate with slopes of 0.92, 0.99, and 0.82, respectively. Curved plots were obtained for 3-acetoxy-2,6-dinitrobenzoic acid and 4-acetoxy-3-nitrobenzene-sulfonate, which are consistent with a stepwise reaction. The most likely mechanism involves the existence of a tetrahedral intermediate (T^±) and a change in the rate-determining step from its breakdown to its formation when the basicity of the polyamine increases. A semiempirical equation was used to calculate the values of limiting slopes of the plots (0.9 and 0.1 for both esters) and pK_N at the center of the curvature of the plots (p-K_N° = 7.94 and 9.02, respectively). The values of pK_N° are lower than those estimated for the aminolysis of the same esters with simple monomeric amines (pK_n° > 11) because of a better leaving ability of the aryl oxide ion from the tetrahedral intermediate when amino groups of PEI instead of simple amines are involved. Estimation of the pK's of the reactive intermediates and of the microscopic rate constants for the proton transfer from T_± to PEI or from PEIH⁺ to T^± indicates that either base or acid catalysis is unimportant in the aminolysis of these esters by PEI.