The oxidation reaction of isomenthol with trichloroisocyanuric acid (TCICA) was systematically investigated in acidic medium to understand its kinetics, reaction mechanism, and overall reactivity. The study was carried out under pseudo-first-order conditions by maintaining a large excess of isomenthol relative to TCICA, allowing accurate determination of the reaction rate. The progress of the oxidation reaction was monitored kinetically, and the obtained data revealed that the reaction follows first-order kinetics with respect to TCICA and fractional-order kinetics with respect to isomenthol concentration. The influence of hydrogen ion concentration was also examined, and the observed increase in reaction rate with increasing acidity confirmed that the oxidation proceeds through an acid-catalyzed pathway. To further understand the reaction mechanism, the effect of temperature on the reaction rate was studied over a suitable temperature range. The activation parameters, including activation energy, enthalpy, entropy, and Gibbs free energy of activation, were determined using the Arrhenius and Eyring equations. The calculated values provided valuable information regarding the energetic requirements and feasibility of the oxidation process. Based on the kinetic observations and activation parameters, a plausible reaction mechanism involving the formation of an intermediate complex between isomenthol and TCICA, followed by a rate-determining oxidation step, is proposed. The mechanistic interpretation is consistent with the experimental findings and explains the observed dependence of the reaction rate on substrate and acid concentrations. Overall, this study provides new insights into the oxidation behavior of cyclic secondary alcohols with N-halo oxidants and contributes to a better understanding of their reaction pathways, kinetic characteristics, and potential applications in synthetic and industrial organic chemistry.

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1. Cotton FA, Wilkinson G, Murillo CA, Bochmann M. Advanced inorganic chemistry. New York: John Wiley & Sons; 1999.
2. Atkins P, De Paula J, Friedman R. Physical chemistry: Quanta, matter, and change. Oxford: Oxford University Press; 2014.
3. March J. Advanced organic chemistry: Reactions, mechanisms, and structure. New York: Wiley; 1985.
4. Sheldon RA, Kochi JK. Metal-catalysed oxidations of organic compounds. New York: Academic Press; 1981.
5. Corey EJ. The logic of chemical synthesis. Ripol Klassik; 1991.
6. Tiwari A, Prabhu DV, Parbat HA. A kinetic and thermodynamic study of oxidation of selective alcohols using chromium-based reagents and silver nanoparticle catalyst: A spectrophotometric approach. Asian J Chem Sci. 2025;15(3):68–81.
7. Silva TF, Martins LM. Recent advances in copper catalysed alcohol oxidation in homogeneous medium. Molecules. 2020;25(3):748.
8. Müller DS. Synthesis and applications of alkenyl chlorides (vinyl chlorides): A review. Beilstein J Org Chem. 2026;22(1):1–63.
9. Jain H, Panday D. Oxidation of secondary alcohols by isoquinolinium dichromate in non-aqueous medium: A kinetics study. Rasayan J Chem. 2023;16:2034–41.
10. Hoover JM, Stahl SS. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols. J Am Chem Soc. 2011;133(42):16901–10.
11. Yang C, Farmer LA, Pratt DA, Maldonado S, Stephenson CR. Revisiting the reactivity of the dismissed hydrogen atom transfer catalyst succinimide-N-oxyl. J Am Chem Soc. 2024;146(18):12511–8.
12. Anastas PT, Zimmerman JB. The United Nations sustainability goals: How can sustainable chemistry contribute? Curr Opin Green Sustain Chem. 2018;13:150–3.
13. Bingham M, Pradhan TR, Bhattacherjee D, Alkahtani R, Kavanagh P, Wirth T, et al. Revealing the mechanism of TEMPO-hypervalent iodine(III) oxidation of alcohols. J Am Chem Soc. 2026;148(8):8852–62.
14. Tiwari A, Prabhu DV, Parbat HA. A kinetic and thermodynamic study of oxidation of selective alcohols using chromium-based reagents and silver nanoparticle catalyst: A spectrophotometric approach. Asian J Chem Sci. 2025;15(3):68–81.
15. Tojo G, Fernández M. Oxidation of alcohols to aldehydes and ketones: A guide to current common practice. Boston (MA): Springer US; 2006.

The oxidation reaction of isomenthol with trichloroisocyanuric acid (TCICA) was systematically investigated in acidic medium to understand its kinetics, reaction mechanism, and overall reactivity. The study was carried out under pseudo-first-order conditions by maintaining a large excess of isomenthol relative to TCICA, allowing accurate determination of the reaction rate. The progress of the oxidation reaction was monitored kinetically, and the obtained data revealed that the reaction follows first-order kinetics with respect to TCICA and fractional-order kinetics with respect to isomenthol concentration. The influence of hydrogen ion concentration was also examined, and the observed increase in reaction rate with increasing acidity confirmed that the oxidation proceeds through an acid-catalyzed pathway. To further understand the reaction mechanism, the effect of temperature on the reaction rate was studied over a suitable temperature range. The activation parameters, including activation energy, enthalpy, entropy, and Gibbs free energy of activation, were determined using the Arrhenius and Eyring equations. The calculated values provided valuable information regarding the energetic requirements and feasibility of the oxidation process. Based on the kinetic observations and activation parameters, a plausible reaction mechanism involving the formation of an intermediate complex between isomenthol and TCICA, followed by a rate-determining oxidation step, is proposed. The mechanistic interpretation is consistent with the experimental findings and explains the observed dependence of the reaction rate on substrate and acid concentrations. Overall, this study provides new insights into the oxidation behavior of cyclic secondary alcohols with N-halo oxidants and contributes to a better understanding of their reaction pathways, kinetic characteristics, and potential applications in synthetic and industrial organic chemistry.

🔒 This is a subscription article

Full text is available to subscribers and institutional members. Please choose an option below to access it.

1. Cotton FA, Wilkinson G, Murillo CA, Bochmann M. Advanced inorganic chemistry. New York: John Wiley & Sons; 1999.
2. Atkins P, De Paula J, Friedman R. Physical chemistry: Quanta, matter, and change. Oxford: Oxford University Press; 2014.
3. March J. Advanced organic chemistry: Reactions, mechanisms, and structure. New York: Wiley; 1985.
4. Sheldon RA, Kochi JK. Metal-catalysed oxidations of organic compounds. New York: Academic Press; 1981.
5. Corey EJ. The logic of chemical synthesis. Ripol Klassik; 1991.
6. Tiwari A, Prabhu DV, Parbat HA. A kinetic and thermodynamic study of oxidation of selective alcohols using chromium-based reagents and silver nanoparticle catalyst: A spectrophotometric approach. Asian J Chem Sci. 2025;15(3):68–81.
7. Silva TF, Martins LM. Recent advances in copper catalysed alcohol oxidation in homogeneous medium. Molecules. 2020;25(3):748.
8. Müller DS. Synthesis and applications of alkenyl chlorides (vinyl chlorides): A review. Beilstein J Org Chem. 2026;22(1):1–63.
9. Jain H, Panday D. Oxidation of secondary alcohols by isoquinolinium dichromate in non-aqueous medium: A kinetics study. Rasayan J Chem. 2023;16:2034–41.
10. Hoover JM, Stahl SS. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols. J Am Chem Soc. 2011;133(42):16901–10.
11. Yang C, Farmer LA, Pratt DA, Maldonado S, Stephenson CR. Revisiting the reactivity of the dismissed hydrogen atom transfer catalyst succinimide-N-oxyl. J Am Chem Soc. 2024;146(18):12511–8.
12. Anastas PT, Zimmerman JB. The United Nations sustainability goals: How can sustainable chemistry contribute? Curr Opin Green Sustain Chem. 2018;13:150–3.
13. Bingham M, Pradhan TR, Bhattacherjee D, Alkahtani R, Kavanagh P, Wirth T, et al. Revealing the mechanism of TEMPO-hypervalent iodine(III) oxidation of alcohols. J Am Chem Soc. 2026;148(8):8852–62.
14. Tiwari A, Prabhu DV, Parbat HA. A kinetic and thermodynamic study of oxidation of selective alcohols using chromium-based reagents and silver nanoparticle catalyst: A spectrophotometric approach. Asian J Chem Sci. 2025;15(3):68–81.
15. Tojo G, Fernández M. Oxidation of alcohols to aldehydes and ketones: A guide to current common practice. Boston (MA): Springer US; 2006.