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http://dx.doi.org/10.5012/bkcs.2007.28.2.220

Aminolyses of 2,4-Dinitrophenyl 2-Furoate and Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism  

Um, Ik-Hwan (Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
Chun, Sun-Mee (Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
Akhtar, Kalsoom (Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
Publication Information
Bulletin of the Korean Chemical Society / v.28, no.2, 2007 , pp. 220-224 More about this Journal
Abstract
Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.
Keywords
Aminolysis; Nonleaving group; Yukawa-Tsuno plot; Rate-determining step; Reaction mechanism;
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