Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetic and Theoretical Studies on Pyridinolysis of 2,4-Dinitrophenyl X-Substituted Benzoates: Effect of Substituent X on Reactivity and Mechanism

  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Kim, Eun-Hee (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Im, Li-Ra (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Mishima, Masaaki (Institute for Materials Chemistry and Engineering, Kyushu University)
  • Received : 2010.07.06
  • Accepted : 2010.07.26
  • Published : 2010.09.20
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Abstract

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 2,4-dinitrophenyl X-substituted benzoates (X = 4-MeO, H and 4-$NO_2$) with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plots exhibit downward curvature (e.g., $\beta_2$ = 0.89 ~ 0.96 when $pK_a$ < 9.5 while $\beta_1$ = 0.38 ~ 0.46 when $pK_a$ > 9.5), indicating that the reaction proceeds through a stepwise mechanism with a change in rate-determining step (RDS). The ${pK_a}^o$, defined as the $pK_a$ at the center of Br${\o}$nsted curvature, has been analyzed to be 9.5 regardless of the electronic nature of the substituent X in the benzoyl moiety. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that $k_1$ is governed by the electronic nature of the substituent X but the $k_2/k_{-1}$ ratio is not. Theoretical calculations also support the argument that the electronic nature of the substituent X in the benzoyl moiety does not influence the $k_2/k_{-1}$ ratio.

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