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Effect of Nonleaving Group on the Reaction Rate and Mechanism: Aminolyses of 4-Nitrophenyl Acetate, Benzoate and Phenyl Carbonate

Title
Effect of Nonleaving Group on the Reaction Rate and Mechanism: Aminolyses of 4-Nitrophenyl Acetate, Benzoate and Phenyl Carbonate
Authors
Um I.-H.Park H.-R.Kim E.-Y.
Ewha Authors
엄익환
SCOPUS Author ID
엄익환scopusscopus
Issue Date
2003
Journal Title
Bulletin of the Korean Chemical Society
ISSN
0253-2964JCR Link
Citation
vol. 24, no. 9, pp. 1251 - 1255
Indexed
SCI; SCIE; SCOPUS; KCI WOS scopus
Abstract
Second-order rate constants have been determined spectrophotometrically for the reaction of phenyl 4-nitrophenyl carbonate with a series of primary amines in H 2O containing 20 mol % DMSO at 25.0 °C. The Brønsted-type plot is linear with a β nuc 0.69 ± 0.04, which is slightly smaller than the β nuc values for the reactions of 4-nitrophenyl acetate (β nuc = 0.82 ± 0.03) and benzoate (β nuc = 0.76 ± 0.01), indicating that the reaction proceeds through a tetrahedral zwitterionic intermediate T ±. The carbonate is more reactive than the corresponding acetate and benzoate. The changing Me (or Ph) to PhO has resulted in a decrease in the β nuc value without changing the reaction mechanism but an increase in the reactivity. The electronic effect of the substituent in the nonleaving group appears to be responsible for the enhanced reactivity of the carbonate compared with the corresponding acetate and benzoate.
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자연과학대학 > 화학·나노과학전공 > Journal papers
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