Current time in Korea 11:29 Apr 26 (Fri) Year 2024 KCS KCS Publications
KCS Publications
My Journal  Log In  Register
HOME > Search > Browsing(BKCS) > Archives

Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 31, Number 9
BKCSDE 31(9)
September 20, 2010 
 
Title
 Metal Ion Catalysis in Nucleophilic Substitution Reaction of 4-Nitrophenyl Picolinate with Alkali Metal Ethoxides in Anhydrous Ethanol
Author
 Yeon Ju Hong, Song I Kim, Ik Hwan Um*
Keywords
 Metal ion catalysis, Ion pair, Ethanolysis, Electrophilicity, Nucleofugality
Abstract
 Pseudo-first-order rate constants (kobsd) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, M+ = K+, Na+ and Li+) in anhydrous ethanol at 25.0 ± 0.1 oC. The plot of kobsd vs. [EtOM] exhibits upward curvature regardless of the nature of M+ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased kobsd values when 18-crown-6-ether (18C6, a complexing agent for K+ ion) is added in the reaction medium. Dissection of kobsd into kEtO- and kEtOM (i.e., the second-order rate constant for the reaction with dissociated EtO- and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3 ~ 17 times more reactive than dissociated EtO-. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which M+ ion increases the electrophilicity of the reaction site. Interestingly, Na+ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high Na+ ion selectivity.
Page
 2483 - 2487
Full Text
 PDF

How to access to the WOL for The Bulletin of the Korean Chemical Society ?

The Bulletin of the Korean Chemical Society will be co-published with Wiley-VCH from 2015 towards. The online version of the Journal will thus be available on Wiley Online Library, Wiley(-VCH)'s global online platform.

KCS members can get a free online access to the Bulletin of the Korean Chemical Society in WOL.

Close