[KSCI] Korea Science Citation Index Service

http://dx.doi.org/10.5012/bkcs.2014.35.8.2443

Kinetic Study on Aminolysis of 4-Nitrophenyl Nicotinate and Isonicotinate: Factors Influencing Reactivity and Reaction Mechanism

Kim, Min-Young (Department of Chemistry and Nano Science, Ewha Womans University)
Shin, Minah (Hana Academy Seoul)
Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)

Publication Information

Bulletin of the Korean Chemical Society / v.35, no.8, 2014 , pp. 2443-2447 More about this Journal

Abstract

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$ . The Br ${\o}$ nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

Keywords

Aminolysis; Br ${\o}$ nsted-type plots; Field effect; Solvent effect; H-Bonding interaction;

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Times Cited By KSCI : 3 (Citation Analysis)

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