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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 33, Number 10
BKCSDE 33(10)
October 20, 2012 

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
Se-Won Min, Min-Young Kim, Ik-Hwan Um*
Nonleaving group, Phenolysis, Brønsted-type plot, Yukawa-Tsuno plot, Concerted mechanism
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 % H2O/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 βnuc = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with σo 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.
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