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Kinetic Study on Aminolysis of 4-Nitrophenyl Isonicotinate in Acetonitrile: Effect of Amine Basicity on Reactivity and Reaction Mechanism
- Kinetic Study on Aminolysis of 4-Nitrophenyl Isonicotinate in Acetonitrile: Effect of Amine Basicity on Reactivity and Reaction Mechanism
- Shin, Minah; Kim, Min-Young; Um, Ik-Hwan
- Ewha Authors
- SCOPUS Author ID
- Issue Date
- Journal Title
- BULLETIN OF THE KOREAN CHEMICAL SOCIETY
- 0253-2964; 1229-5949
- vol. 35, no. 7, pp. 2130 - 2134
- Aminolysis; 4-Nitrophenyl isonicotinate; Energy profile; Stepwise mechanism; Catalysis
- KOREAN CHEMICAL SOC
- SCI; SCIE; SCOPUS; KCI
- A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of k(obsd) vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate T-+/- and its deprotonated form T-). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield T- from T-+/- by a second amine molecule) is absent. The Bronsted-type plots for Kk(2) and Kk(3) (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with,beta(nuc) = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.
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