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Vol. 33 No. 5 (2021): Vol 33 Issue 5, 2021

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Brønsted Acid Catalysis in the Oxidation of Purine Based Alkaloids by Mn(VII) in Aqueous Acetonitrile and Sodium Fluoride Medium: A Kinetic Approach

https://doi.org/10.14233/ajchem.2021.23142%20
A. Ramakrishna Reddy
Department of Chemistry, JNTUH College of Engineering, Hyderabad-500007, India
Bhooshan Muddam
Department of Chemistry, Maturi Venkata Subba Rao Engineering College, Nadergul, Hyderabad-501510, India
A. Sambashiva Rao
Department of Chemistry, Maturi Venkata Subba Rao Engineering College, Nadergul, Hyderabad-501510, India
K.C. Rajanna
Department of Chemistry, Osmania University, Hyderabad-500007, India
A. Panasa Reddy
Department of Chemistry, Osmania University, Hyderabad-500007, India
M. Thirumala Chary
Department of Chemistry, JNTUH College of Engineering, Hyderabad-500007, India

Corresponding Author(s) : K.C. Rajanna

kcrajannaou@yahoo.com

Asian Journal of Chemistry, Vol. 33 No. 5 (2021): Vol 33 Issue 5, 2021

Abstract

Brønsted acid (HClO4, H2SO4) catalyzed Mn(VII) oxidation of purine alkaloids such as caffeine, theophylline and theobromine in aqueous acetonitrile and sodium fluoride medium revealed first order kinetics in both [(Mn(VII)] and [Alkaloid] at constant acidity and temperature. Sodium fluoride was added to the reaction mixture in order to avoid/suppress auto catalytic reaction due to the generation of Mn(III) and Mn(IV) species during the course of Mn(VII) oxidations in acidic solutions. An increase in the Brønsted acids (HClO4, H2SO4) concentration accelerated the rate of oxidation. Rate enhancements observed here in are analyzed by Zucker-Hammett, Bunnett and Bunnett-Olsen criteria of acidity functions. On the basis of observed Bunnett-Olsen criteria of acidity functions, the most plausible mechanism has been proposed with the involvement of water molecule in the slow step (as proton transferring agent).

Keywords

Mn(VII) oxidation Purine alkaloids Zucker-Hammett Bunnett Bunnett-Olson acidity functions Brønsted acid catalysis
Ramakrishna Reddy, A., Muddam, B., Sambashiva Rao, A., Rajanna, K., Panasa Reddy, A., & Thirumala Chary, M. (2021). Brønsted Acid Catalysis in the Oxidation of Purine Based Alkaloids by Mn(VII) in Aqueous Acetonitrile and Sodium Fluoride Medium: A Kinetic Approach. Asian Journal of Chemistry, 33(5), 1051–1057. https://doi.org/10.14233/ajchem.2021.23142
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