Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Thiophenecarboxylates: Effect of ortho-Nitro Group on Reactivity and Mechanism

  • Seo, Jin-A (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Chun, Sun-Mee (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • Published : 2008.08.20
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Abstract

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

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References

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