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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 35, Number 8
BKCSDE 35(8)
August 20, 2014 

Kinetic Study on Aminolysis of 4-Nitrophenyl Nicotinate and Isonicotinate: Factors Influencing Reactivity and Reaction Mechanism
Min-Young Kim, Minah Shin, Ik-Hwan Um*
Aminolysis, Brønsted-type plots, Field effect, Solvent effect, H-Bonding interaction
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 H2O containing 20 mol % DMSO at 25.0 oC. The Brønted-type plots for the reactions of 7 and 8 are linear with βnuc = 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.).
2443 - 2447
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