Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Effect of Alkali Metal Ions on Alkaline Ethanolysis of 2-Pyridyl and 4-Pyridyl Benzoates in Anhydrous Ethanol

  • Lee, Jae-In (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University) ;
  • Kang, Ji-Sun (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University) ;
  • Kim, Song-I (Department of Chemistry and Nano Science, Ewha Woman's University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Woman's University)
  • Received : 2010.08.16
  • Accepted : 2010.08.30
  • Published : 2010.10.20
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Abstract

Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

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References

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