KINETICS AND MECHANISM OF PERMANGANATE OXIDATION OF CIPROFLOXACIN IN AQUEOUS SULPHURIC ACID MEDIUM
Abstract
The oxidation of ciprofloxacin (CIP) by permanganate ion in aqueous sulphuric acid medium at constant ionic strength (I = 0.05 mol dm-3) has been investigated spectrophotometrically at 525 nm. Order with respect to substrate, oxidant and acid concentrations were determined. Product characterization of reaction mixture indicates the formation of major product m/z 263 corresponding to dealkylation of the piperazine ring of ciprofloxacin. The piperazine moiety of ciprofloxacin is the predominant oxidative site to KMnO4. Product analysis indicates that oxidation of permanganate results in dealkylation at the piperazine moiety of ciprofloxacin, with the quinolone ring essentially intact. The reaction constants involved in different steps of the mechanism were calculated at different temperatures. The activation parameters with respect to the slow step of the mechanism were computed and thermodynamic quantities were also determined.
Keywords:
Permanganate, ciprofloxacin, sulphuric acid, oxidation, kineticsDOI
https://doi.org/10.25004/IJPSDR.2015.070214References
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27. Phillips G, Johnson BE, Ferguson J. The loss of antibiotic activity of ciprofloxacin by photodegradation. J. Antimicrob. Chemother. 1990; 26: 783-789.
2. National Research Council. The Use of Drugs in Food Animals. National Academy Press, Washington, DC, 1999, pp. 27-68.
3. Ruyz M, Perello L, Ortiz R, Castineiras A, Maichle-Mossmer C, Canton E. Synthesis, characterization, and crystal structure of [Cu(cinoxacinate) 2] • 2H2O complex: A square-planar CuO 4 chromophore. Antibacterial studies. J. Inorg. Biochem. 1995; 59: 801-810.
4. Turel I, Leban I, Bukovec N. Crystal structure and characterization of the bismuth(III) compound with quinolone family member (ciprofloxacin) Antibacterial study. J. Inorg. Biochem. 1997; 66: 241.
5. Lopez-Gresa MP, Ortiz R, Parello L, Latorre J, Liu-Gonzalez M, Garcia-Granda S, Perez-Priede M, Canton E. Interactions of metal ions with two quinolone antimicrobial agents (cinoxacin and ciprofloxacin) J. Inorg. Biochem. 2002; 92: 65-74.
6. Naik PN, Chimatadar SA, Nandibewoor ST. Kinetics and Oxidation of Fluoroquinolone Antibacterial Agent, Norfloxacin, by Alkaline Permanganate: A Mechanistic Study. Ind. Eng. Chem. Res. 2009; 48: 2548-2555.
7. Caron S, Dugger R W, Ruggeri S G, Ragan J A and Brown Ripin DH. Large-Scale Oxidations in the Pharmaceutical Industry. Chem. Rev. 2006; 106: 2943-2989.
8. Lee DG. In Trahanovsky, Oxidation In Organic Chemistry. WS (ed.) Part D Academic Press, New York, 1982, pp. 147.
9. Simandi LI. In: Patai S, Rappoport Z (ed.)The Chemistry of Functional Groups. Wiley, Chichester, Suppl. C, 1983.
10. Day MC, Selbin J. Theoretical Inorganic Chemistry. Reinhold Publishing Corporation, New York, 1985, pp. 344.
11. Hassan RM. Kinetics and mechanism of oxidation of DL-α-Alanine by permanganate ion in acid perchlorate media. Can. J. Chem. 1991; 69: 2018-2023.
12. Sen PK, Saniyal A, Sen Gupta KK. Evidence of Protonation During the Oxidation of Some Aryl Alcohols by Permanganate in Perchloric Acid medium and Mechanism of the Oxidation. Int. J. Chem. Kinet. 1995; 27: 379-389.
13. Zhang H, Huang CH. Oxidative Transformation of Fluoroquinolone Antibacterial Agents and Structurally Related Amines by Manganese Oxide. Environ. Sci. Technol. 2005; 39: 4474-4483.
14. Dodd MC, Shah AD, Gunten UV, Huang CH. Reactions of Fluoroquinolone Antibacterial Agents with Chlorine. Kinetics, Mechanisms, and Pathways. Environ. Sci. Technol. 2005; 39: 7065-7076.
15. Thabaj KA, Kulkarni SD, Chimatadar SA, Nandibewoor ST. Oxidative Transformation of Ciprofloxacin by Alkaline Permanganate – A Kinetic and Mechanistic Study. Polyhedron. 2007; 26: 4877-4885.
16. Vogel AL. Vogel’s- Textbook of Macro and Semi micro Qualitative Inorganic Analysis. John Wiley and Sons, New York, 1967, pp. 291.
17. Hubicka U, Zmudzki P, Zurmoska-Witek B, Zajdel P, Pawlowski M and Krzek J. Separation and characterization of ciprofloxacin, difloxacin, lomefloxacin, norfloxacin, and ofloxacin oxidation products under potassium permanganate treatment in acidic medium by UPLC-MS/MS. Talanta. 2013; 109: 91-100.
18. Fiegl F. Spot Tests in Organic analysis. Elsevier, New York, 1975, pp. 435.
19. Vogel AI. A Textbook of Practical Organic chemistry including Qualitative Organic Analysis. Edn 3, Longman, 1973, pp. 332.
20. Joaquin F, Perenz-Benito JF. Autocatalytic Reaction Pathway on Manganese Dioxide Colloidal Particles in the Permanganate Oxidation of Glycine. J. Phys. Chem. C. 2009; 113: 15982-15991.
21. Lamani SD, Nandibewoor ST. Oxidation of Tricyclic Antidepressant Agent, Amitriptyline, by Permanganate in Sulphuric Acid Medium: Kinetic and Mechanistic Approach. J. Thermodyn. Catal. 2011; 2: 110.
22. Bailar JC, Emeleus HJ, Nyholm R, Dickenson A FT. Comprehensive Inorganic Chemistry. Pergamon Press Ltd., New York, 1975, pp. 771.
23. Abbar JC, Lamani SD, Nandibewoor ST. Ruthenium(III) Catalyzed Oxidative Degradation of Amitriptyline-A Tricyclic Antidepressant Drug by Permanganate in Aqueous Acidic Medium . J. Solution Chem. 2011; 40: 502-520.
24. Martinez M, Pitarque M and Eldik RV. Outer-Sphere Redox Reactions [CoIII(NH3)5(HxPyOz)] (m-3) Complexes. A Temperature and Pressure-Dependence Kinetic Study on the Influence of the Phosphorous Oxoanions. J. Chem. Soc. Dalton Trans. 1996; 13: 2665-2671.
25. Walling C. Free Radicals in Solutions. Academic Press, New York, 1957, pp. 38.
26. Laidler KJ. Chemical Kinetics. Tata McGraw Hill Publication Company Ltd., New Delhi, 1976, pp. 230.
27. Phillips G, Johnson BE, Ferguson J. The loss of antibiotic activity of ciprofloxacin by photodegradation. J. Antimicrob. Chemother. 1990; 26: 783-789.
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01-03-2015
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“KINETICS AND MECHANISM OF PERMANGANATE OXIDATION OF CIPROFLOXACIN IN AQUEOUS SULPHURIC ACID MEDIUM”. International Journal of Pharmaceutical Sciences and Drug Research, vol. 7, no. 2, Mar. 2015, pp. 205-10, https://doi.org/10.25004/IJPSDR.2015.070214.
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How to Cite
“KINETICS AND MECHANISM OF PERMANGANATE OXIDATION OF CIPROFLOXACIN IN AQUEOUS SULPHURIC ACID MEDIUM”. International Journal of Pharmaceutical Sciences and Drug Research, vol. 7, no. 2, Mar. 2015, pp. 205-10, https://doi.org/10.25004/IJPSDR.2015.070214.
