Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Carbonates

  • Kim, Song-I (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Hwang, So-Jeong (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Jung, Eun-Mi (Department of Chemistry, Sangmyung University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • Received : 2010.05.20
  • Accepted : 2010.05.27
  • Published : 2010.07.20
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Abstract

Second-order rate constants $(k_{OH^-})$ have been measured spectrophotometrically for alkaline hydrolysis of Y-substituted phenyl phenyl carbonates (2a-j) and compared with the $k_{OH^-}$ values reported previously for the corresponding reactions of Y-substituted phenyl benzoates (1a-j). Carbonates 2a-j are 8~16 times more reactive than benzoates 1a-j. The Hammett plots correlated with $\sigma^-$ and $\sigma^o$ constants exhibit many scattered points, while the Yukawa-Tsuno plot results in excellent linear correlation with $\rho$ = 1.21 and $\gamma$ = 0.33. Thus, the reaction has been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little. However, one cannot exclude a possibility that the current reaction proceeds through a forced concerted mechanism with a highly unstable intermediate.

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