Aminolysis of 2,4-dinitrophenyl and 3,4-dinitrophenyl 2- thiophenecarboxylates: Effect of ortho-nitro group on reactivity and mechanism

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 % H2O/20 mol % dimethyl sulfoxide at 25.0 °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±) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., pKa < 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 k2/k-1 ratio but larger k1 than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller k1 value found for the reactions of 1.