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http://dx.doi.org/10.5012/bkcs.2003.24.9.1245

Effect of Amine Nature on Rates and Mechanism: Pyridinolyses of 4-Nitrophenyl Benzoate  

Um, Ik-Hwan (Department of Chemistry, Ewha Womans University)
Baek, Mi-Hwa (Department of Chemistry, Ewha Womans University)
Han, Hyun-Joo (Department of Chemistry, Ewha Womans University)
Publication Information
Bulletin of the Korean Chemical Society / v.24, no.9, 2003 , pp. 1245-1250 More about this Journal
Abstract
Pseudo-first-order rate constants ($k_{obs}$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate with a series of pyridines in $H_2O$ containing 20 mol % DMSO. The plots of kobs vs pyridine concentration are linear up to ca. 0.1 M pyridines, indicating that the effect of self-association of pyridines with their conjugate acids are insignificant in this concentration range. The Bronsted-type plot has been obtained to be linear with a ${\beta}_{nuc}$ value 1.11, suggesting that the pyridinolyses proceed through a rate-determining breakdown of the zwiterionic addition intermediate. The pyridines studied have shown higher reactivity than isobasic primary and secondary amines toward the substrate. 1-Benzoyl-4-dimethylaminopyridinium ion, a possible intermediate, has not been detected since the rate of its hydrolysis in the reaction condition is comparable with or even faster than its formation.
Keywords
Pyridinolysis; Bronsted-type plot; Rate-determining step;
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Times Cited By KSCI : 4  (Citation Analysis)
Times Cited By Web Of Science : 8  (Related Records In Web of Science)
Times Cited By SCOPUS : 9
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