Compensation effect in reactions between trans-4,4'-dinitrostilbene oxide and arylsulfonic acids

Abstract

The effect structure and temperature have on the rate and free activation energy of reactions between trans-4,4'-dinitrostilbene oxide and Y-substituted arylsulfonic acids YC₆H₄SO₃H in a mixture of dioxane with 1,2-dichloroethane (7: 3 vol/vol) at 265, 281, and 298 K is studied. It is found that as a result of the nonadditivity of the joint effect of substituents Y and temperature on the rate of the process of oxirane ring opening, the cross reaction series exhibits isoparametric properties in the aspect of enthalpy–entropy compensation. This allows the experimental determination of an isoparametric point with respect to the constant of substituent Y (σ_Y^IP= 0.52), in which activation entropy ΔS^≠ = 0 and free activation energy ΔG^≠ do not depend on temperature (ΔG^≠ = ΔH^≠), and to conduct the transition through this point with inversion of the order of the effect temperature has on the value of ΔG^≠ as a result of reversing the sign of ΔS^≠: in the series Y (σ_Y) = 4-OCH₃ (–0.27), 4-CH₃ (–0.17), H (0), 4-Cl (0.23), and 3-NO₂ (0.71), the values of ΔS^≠ (J/(mol K)) are–140,–119,–85,–42, and 44, respectively. The possibility of using isoparametric points as quantitative mechanistic criteria is demonstrated.