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Oxidation of some catecholamines by sodium N-chloro-p-toluenesulfonamide in acid medium: A kinetic and mechanistic approach

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Central European Journal of Chemistry

Abstract

The kinetics of the oxidation of five catecholamines viz., dopamine (A), L-dopa (B), methyldopa (C), epinephrine (D) and norepinephrine (E) by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in presence of HClO4 was studied at 30±0.1 °C. The five reactions followed identical kinetics with a first-order dependence on [CAT] o , fractional-order in [substrate] o , and inverse fractional-order in [H+]. Under comparable experimental conditions, the rate of oxidation of catecholamines increases in the order D>E>A>B>C. The variation of ionic strength of the medium and the addition of p-toluenesulfonamide or halide ions had no significant effect on the reaction rate. The rate increased with decreasing dielectric constant of the medium. The solvent isotope effect was studied using D2O. A Michaelis-Menten type mechanism has been suggested to explain the results. Equilibrium and decomposition constants for CAT-catecholamine complexes have been evaluated. CH3C6H4SO2NHCl of the oxidant has been postulated as the reactive oxidizing species and oxidation products were identified. An isokinetic relationship is observed with β=361 K, indicating that enthalpy factors control the reaction rate. The mechanism proposed and the derived rate law are consistent with the observed kinetics.

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References

  1. G. Zubay: Biochemistry, 4th Ed., WCB, Boston, 1998.

    Google Scholar 

  2. J.G. Cory and T.M. Devlin: Text book of biochemistry with clinical correlations, 4th Ed., John Wiley and Sons, New York, 1997.

    Google Scholar 

  3. A.L. Lehninger, D.L. Nelson and M.M. Cox: Principles of biochemistry, 2nd Ed., CBS Publishers, New Delhi, 1993.

    Google Scholar 

  4. C.M. Lozano, T.P. Ruiz, V. Thomas and O. Val: “Determination of epinephrine, norepinephrine, dopamine and L-dopa in pharmaceutical by a photkinetic method”, Analyst, Vol. 116, (1991), p. 857.

    Article  Google Scholar 

  5. E. Pelizzetti, E. Mentasti and E. Pramauro: “Kinetics and mechanism of oxidation pathways of some catecholamines with periodic acid”, J. Chem. Soc., Perkin Trans. 2, (1976), p. 1651.

    Google Scholar 

  6. B.S. Sherigara, E.V.S. Subrahmanyam, K. Ishwar Bhat and B.E. Kumaraswamy: “Oxidation of 3-(3,4-dihydroxy phenyl)-L-alanine (L-dopa) and 3-(3,4-dihydroxyphenyl)-2-methyl-L-alanine (methyldopa) by manganese (III) in pyrophosphate media: kinetic and mechanistic study”, Int. J. Chem. Kinet., Vol. 33(8), (2001), p. 449.

    Article  CAS  Google Scholar 

  7. M.M. Campbell and G. Johnson: “Chloramine-T and related N-halogeno-N-metallo reagents”, Chem. Rev., Vol. 78, (1978), p. 65.

    Article  CAS  Google Scholar 

  8. K.K. Banerji, B. Jayaram and D.S. Mahadevappa: “Mechanistic aspects of oxidation by N-metallo-N-haloarylsulfonamides”, J. Sci. Ind. Res., Vol. 46, (1987), p. 65.

    CAS  Google Scholar 

  9. Puttaswamy, D.S. Mahadavappa and K.S. Rangappa: “Oxidation of indigo carmine by N-haloarenesulfonamides: a kinetic study”, Bull. Chem. Soc. Jpn., Vol. 62, (1989), p. 3343.

    Article  CAS  Google Scholar 

  10. U. Umeshkumar, K.C. Rajanna and P.K. Saiprakash: “A kinetic study of chloramine-T reaction with acetanilides in micellar media”, Pro. Nat. Acad. Sci. India, Vol. 65A, (1995), p. 279.

    Google Scholar 

  11. Puttaswamy, T.M. Anuradha, R. Ramachandrappa and N.M.M. Gowda: “Oxidation of isoniazide by N-haloarenesulfonamides in alkaline medium: A kinetic and mechanistic study”, Int. J. Chem. Kinet., Vol. 32(4), (2000), p. 221.

    Article  CAS  Google Scholar 

  12. R.J.D. Saldanha, S. Ananda, B.M. Venkatesha and N.M.M. Gowda: “Oxidation of psychotropic drugs by chloaramine-T in acid medium: a kinetic study using spectrophotometry”, J. Mole. Str., Vol. 606, (2002), p. 147.

    Article  CAS  Google Scholar 

  13. Puttaswamy, T.M. Anuradha and K.L. Mahadevappa: “Kinetic analysis of oxidation of dopamine by sodium N-chlorobenzenesulfonamide in perchloric acid medium: a mechanistic approach”, Indian J. Chem., Vol. 40A, (2001), p. 514.

    CAS  Google Scholar 

  14. Puttaswamy and R. Ramachandrappa: “Kinetics of dopamine oxidation by sodium N-bromo-p-toluenesulfonamide in acid medium: a mechanistic approach”, Oxid. Commun., Vol. 25 (1), (2002), p. 102.

    CAS  Google Scholar 

  15. Puttaswamy and Nirmala Vaz: “Kinetics and mechanism of ruthenium (III) and osmium (VIII) catalyzed oxidation of dopamine with bromamine-B in acid and alkaline media”, Stud. Surf.Sci. Cat., Vol. 133, (2001), p. 535.

    Article  CAS  Google Scholar 

  16. J.C. Morris, J.R. Salazar and M.A. Winemann: “Equilibrium studies on chloro compounds: the ionization constant of N-chloro-p-toluenesulfonamide”, J. Am. Chem. Soc., Vol. 70, (1948), p. 2036.

    Article  CAS  Google Scholar 

  17. G. Akerloff: “Dielectric constants of some organic solvents-water mixture at various temperatures”, J. Am. Chem. Soc., Vol. 54, (1932), p. 4125.

    Article  Google Scholar 

  18. F. Feigl: Spot tests in organic analysis, 7th Ed., Elsevier, Amsterdam, 1966, pp. 332–335, 206.

    Google Scholar 

  19. A.I. Vogel: Text book of practical organic chemistry, 5th Ed., ELBS and Longman, London, 1966, p. 1257.

    Google Scholar 

  20. T.E. Young and B.W. Babbitt: “Electrochemical study of the oxidation of α-methyldopamine, α-methylnoradranaline and dopamine”, J. Org. Chem., Vol. 48, (1983) p. 562.

    Article  CAS  Google Scholar 

  21. E. Bishop and V.J. Jennings: “Titrimetric analysis with chloramine-T: The status of chloramine-T as a titrimetric reagent”, Talanta, Vol. 1, (1958), p. 197.

    Article  CAS  Google Scholar 

  22. F.F. Hardy and J.P. Johnston: “The interactions of N-bromo-N-sodiobenzesulfonamide (bromamine-B) with p-nitrophenoxide ion”, J. Chem. Soc., Perkin Trans.2, (1973), p. 742.

  23. F.G. Soper: “The hydrolysis of the p-toluenesulfonchloroamides in water”, J. Chem. Soc. Trans., Vol. 125, (1924), p. 1899; (b) D.R. Pryde and F.G. Soper: “The interaction of anilides and hypochlorous acid”, J. Chem. Soc., (1931), p. 1510; (c) D.R. Pryde and F.G Soper: “The direct interchange of chlorine in the interaction of p-toluenesulfonamide and N-chloroactanilide”, J. Chem. Soc., (1931), p. 1514; (d) F.G. Soper and F.G. Smith: “The haloagenation of phenols”, J. Chem. Soc., (1926), p. 1582.

    Article  CAS  Google Scholar 

  24. S.S. Narayanan and V.R.S. Rao: “Chlorine isotopic exchange reaction between chloramine-T and chloride ion”, Radio. Chim. Acta, Vol. 32, (1983), p. 211.

    CAS  Google Scholar 

  25. M. Subhashini, M. Subramanian and V.R.S. Rao: “Determination of the protonated constant of chloramine-B”, Talanta, Vol. 32, (1985), p. 1082.

    Article  CAS  Google Scholar 

  26. J.E. House: Principles of chemical kinetics, Wm. C. Brown Publishers, Boston, 1997.

    Google Scholar 

  27. E.A. Moelwyn-Hughes: The kinetics of reaction in solutions, Clarendon Press, Oxford, 1947; Physical chemistry, 2nd Ed., Pergamon, New York, 1961.

    Google Scholar 

  28. S.W. Benson: The foundations of chemical kinetics, McGraw-Hill, New York, 1960.

    Google Scholar 

  29. A.A. Frost and R.G. Pearson: Kinetics and mechanism, 2nd Ed., Wiley, New York, 1961.

    Google Scholar 

  30. K.J. Laidler: Reaction kinetics, Pergamon, New York, 1963.

    Google Scholar 

  31. E.S. Amis: Solvent effects on reaction rates and mechanisms, Academic, New York, 1966.

    Google Scholar 

  32. S.G. Entelis and R.P. Tiger: Reaction kinetics in the liquid phase, Wiley, New York, 1966.

    Google Scholar 

  33. C.J. Collins and N.S. Bowman: Isotope effects in chemical reactions, Van Nostrand Reinhold, New York, 1970, p. 267.

    Google Scholar 

  34. K.B. Wiberg: Physical organic chemistry, Wiley, New York, 1964.

    Google Scholar 

  35. O. Exner: “Entropy-enthalpy compensation and anticompensation: solvation and ligand binding”, Chem. Commun., (2000), p. 1655 and references therein.

  36. M. Anand Rao, B. Sethuram and Navaneeth Rao: “Oxidation studies: Ag(I)-catalysis in oxidation of amines of amines by Ce (IV) in nitric acid: A kinetic study”, J. Indian Chem. Soc., Vol. 59, (1982), p. 1040.

    Google Scholar 

  37. Puttaswamy and D.S. Mahadevappa: “Oxidation of substituted ethanols by sodium-N-bromobenzenesulfonamide: A kinetic study”, J. Phys. Org. Chem., Vol. 2, (1989), p. 660.

    Article  CAS  Google Scholar 

  38. K.K. Senguptha, N. Bhattacharjee and B. Pal: “Kinetics and mechanism of the oxidation of neutralized α-hydroxy acids by tris(pyridine-2-carboxylato) manganese (III)”, Transition Metal. Chem., Vol. 24, (1999), p. 268.

    Article  Google Scholar 

  39. K.S. Rangappa, K. Manjunathaswamy, M.P. Raghavendra and N.M.M. Gowda: “Kinetics and mechanism of oxidation of neutral α-aminoacids by sodium N-chloro-p-toluenesulfonamide in acid medium”, Int. J. Chem.Kinet., Vol. 34, (2002), p. 49.

    Article  CAS  Google Scholar 

  40. Puttaswamy and Nirmala Vaz: “Kinetic analysis of oxidation of dipeptides by sodium N-bromobenzenesulfonamide in acid medium: a mechanistic approach”, Bull. Chem. Soc. Jpn., Vol. 76, (2003), p. 73.

    Article  CAS  Google Scholar 

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  1. Department of Post-Graduate Studies in Chemistry, Central College, Bangalore University, 560 001, Bangalore, India

    Puttaswamy, R. V. Jagadeesh & Nirmala Vaz

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  2. R. V. Jagadeesh
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  3. Nirmala Vaz
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Puttaswamy, Jagadeesh, R.V. & Vaz, N. Oxidation of some catecholamines by sodium N-chloro-p-toluenesulfonamide in acid medium: A kinetic and mechanistic approach. cent.eur.j.chem. 3, 326–346 (2005). https://doi.org/10.2478/BF02476000

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  • DOI: https://doi.org/10.2478/BF02476000

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