Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Aminolyses of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Furoates: Effect of ortho-Substituent on Reactivity and Mechanism

  • Um, Ik-Hwan (Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Akhtar, Kalsoom (Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
  • Published : 2008.04.20
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Abstract

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dintrophenyl 2-furoate (2) with a series of secondary alicyclic amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide (DMSO) at 25.0 ${^{\circ}C}$. The Bronsted-type plot exhibits a downward curvature for the aminolysis of 2, which is similar to that reported for the corresponding reactions of 2,4-dintrophenyl 2-furoate (1). Substrate 2 is less reactive than 1 toward all the amines studied but the reactivity difference becomes smaller as the amine basicity increases. Dissection of the second-order rate constants into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but slightly larger $k_1$ value than that of 1. Steric hindrance has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1, since the ortho-substituent of 1 would inhibit the attack of amines (i.e., the $k_1$ process).

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