Kinetics and Mechanism of Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Carbonates

Summary of second-order rate constants for reactions of Y-substituted phenyl benzoates ( 1a-j ) and Y-substituted phenyl phe-nyl carbonates ( 2a-j ) with OH – in 80 mol % H 2 O/20 mol % DMSO at 25.0 ± 0.1 o C a entry Y p K aY‐PhOH k OH‒ /M ‒1 s ‒1 12a 3,4-(NO 2 ) 2 5.42 98.9 794 b 4-NO 2 7.14 13.4 140 c 4-CHO 7.66 4.72 50.8 d 4-COMe 8.05 3.27 34.7 e 3-NO 2 8.35 5.97 - f 4-COOEt 8.503.1135.1 g 3-CHO 8.98 1.93 25.7 h 3-Cl 9.02 - 21.4 i 3-COMe 9.19 1.80 21.2 j H 9.95 0.449 7.31 a The data for the reactions of 1a-j were taken from ref. 5. rate constants ( k obsd ) were determined from the equation ln ( A ∞ ‒ A t ) = ‒ k obsd t + C . The correlation coefficient for the linear re-gression was usually higher than 0.9995. The plots of k obsd vs . [OH – ] were linear passing through the origin. The second-order rate constants ( k OH‒ ) were determined from the slope of the linear plots of k obsd vs . [OH – ]. The uncertainty in the k OH‒ values is estimated to be less than 3% from replicate runs. The