Kinetic Study on Alkaline Hydrolysis of Y‐substituted Phenyl X‐substituted Benzenesulfonates: Effects of Changing Nucleophile from Azide to Hydroxide Ion on Reactivity and Transition‐State Structure

Kinetic Study on Nucleophilic Displacement Reactions of Phenyl Y‐Substituted Phenyl Carbonates with 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene: Effects of Amine Nature on Reaction Mechanism

“…Furthermore, a β lg value of –0.48 is too large or too small for reactions reported previously to proceed through a stepwise mechanism with formation of T ± being the RDS ( e.g ., β lg = –0.3 ± 0.1) or with breakdown of T ± being the RDS ( e.g ., β lg = –0.9 to –1.9) . However, the current β lg value is typical for reactions reported previously to proceed through a concerted mechanism ( e.g ., β lg = –0.51 for reactions of Y‐substituted phenyl 4‐nitrobenzene‐sulfonates with OH – 13a and for those of Y‐substituted phenyl diphenylphosphinates with HOO − , 13b and β lg = –0.64 for those of Y‐substituted phenyl benzoates with C 2 H 5 O − in anhydrous ethanol) 13c . Thus, it is proposed that the current reactions proceed through a concerted mechanism on the basis of the linear Brønsted‐type plot with β lg = –0.48.…”