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http://dx.doi.org/10.5012/bkcs.2012.33.2.519

Alkali-Metal Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Benzoate and Benzyl 2-Pyridyl Carbonate: Effect of Modification of Nonleaving Group from Benzoyl to Benzyloxycarbonyl  

Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
Kang, Ji-Sun (Department of Chemistry and Nano Science, Ewha Womans University)
Kim, Chae-Won (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University)
Lee, Jae-In (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.2, 2012 , pp. 519-523 More about this Journal
Abstract
A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.
Keywords
Metal ion catalysis; Ethanolysis; Electrophilicity; Nucleofugality; Transition state;
Citations & Related Records
Times Cited By KSCI : 12  (Citation Analysis)
Times Cited By Web Of Science : 6  (Related Records In Web of Science)
Times Cited By SCOPUS : 6
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