A Kinetic Study on Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Z-Substituted-Phenoxides: Effect of Modification of Nonleaving Group from Benzoyl to Phenyloxycarbonyl on Reactivity and Reaction Mechanism

Abstract

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Zsubstituted-phenoxides (k Z-PhO −) have been measured spectrophotometrically in 80 mol % H 2 O/20 mol % DMSO at 25.0 ± 0.1 o C. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Brønsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with β nuc = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with σ o and σ -constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ρ Y = 1.51 and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-ClPhO -is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

Reactions of Aryl 5‐substituted‐2‐Thiophenecarboxylates Promoted by 4‐Z‐C6H4O−/4‐Z‐C6H4OH in 20 mol % DMSO(aq). Effect of Nucleophile on Acyl‐Transfer Reaction

“…Earlier, Um et al . reported that the β nuc values for the reactions of 4‐nitrophenyl phenylcarbonate and 4‐nitrophenyl benzoate with aryloxides in 20 mol % DMSO(aq) were 0.54 and 0.72, respectively . This outcome has been interpreted with the concerted mechanism.…”