Palladium(II)-catalyzed oxidation of tranexamic acid by bromamine-B in alkaline medium and uncatalyzed reaction in acid medium: A study of kinetic and mechanistic chemistry

Tranexamic acid (TA) possess antifibrinolytic properties and finds extensive applications in pharmaceuticals. Its oxidation-kinetic study is of much significance in understanding the mechanistic profile of TA in biological systems. In this context, a systematic kinetic study of palladium(II) (Pd(II)) catalyzed oxidation of TA by sodium N-bromobenzenesulfonamide or bromamine-B (BAB) in alkaline medium and uncatalyzed reaction in perchloric acid medium at 303 K was investigated. In acid medium, the reaction exhibits a first-order dependence of rate on [BAB]o and less than unity order dependence on [TA]o. The reaction rate shows inverse less than unity order dependence with respect to [H+]. In alkaline medium, the reaction shows first-order dependence on both [BAB]o and [Pd(II)] and zero-order with respect to [TA]o. The order with respect to [OH−] is less than unity. Activation parameters have been evaluated. The oxidation reactions are nearly 10-fold faster in acid medium in comparison with alkaline medium. In alkaline medium, the Pd(II) catalyzed reactions are about 6-fold faster than the uncatalyzed reaction. Further, the catalytic constant (KC) has been calculated at different temperatures and activation parameters with respect to Pd(II) catalyst have also been evaluated. The conjugate acid C6H5SO2NHBr and the anion C6H5SO2N−Br of BAB have been postulated as the reactive oxidizing species in acid and alkaline media, respectively. The proposed mechanisms and derived rate laws are in agreement with the observed kinetics.

Tranexamic acid (TA)–bromamine-B (BAB) redox system obeys rate laws (1) and (2) in acid and alkaline media, respectively.Figure optionsDownload high-quality image (66 K)Download as PowerPoint slideResearch highlights▶ The present research investigation is the first report on the TA–BAB redox system from the kinetic and mechanistic points of view. ▶ The stoichiometry and oxidation products of TA by BAB in acid and alkaline media are the same, but their kinetic characteristics are different. ▶ Reactions of TA with BAB are 10-fold faster in acid medium in comparison with alkaline medium. ▶ Pd(II) catalyzed reactions in alkaline medium are found to be 6-fold faster than the uncatalyzed reactions.