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 (kZ-PhO-) have been measured spectrophotometrically in 80 mol % H 2O/20 mol % DMSO at 25.0 ± 0.1 oC. 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° 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 ρY = 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. © 2005 KCSNET.