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http://dx.doi.org/10.5012/bkcs.2010.31.12.3543

Metal Ion Catalysis in Nucleophilic Displacement Reactions of 2-Pyridyl X-Substituted Benzoates with Potassium Ethoxide 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)
Im, Li-Ra (Department of Chemistry and Nano Science, Ewha Womans University)
Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
Publication Information
Bulletin of the Korean Chemical Society / v.31, no.12, 2010 , pp. 3543-3548 More about this Journal
Abstract
A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.
Keywords
2-Pyridyl benzoate; Metal ion catalysis; Ion-pair; Transition state; Hammett plot;
Citations & Related Records
Times Cited By KSCI : 6  (Citation Analysis)
Times Cited By Web Of Science : 7  (Related Records In Web of Science)
Times Cited By SCOPUS : 7
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