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Palladium(II) Catalysed Oxidation of l-proline by Heptavalent Manganese in Aqueous Alkaline Medium: A Free Radical Intervention and Decarboxylation

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Abstract

The kinetics of palladium(II) catalysed oxidation of l-proline by permanganate in alkaline medium was studied spectrophotometrically. The reaction between permanganate and l-proline in alkaline medium exhibits 2:1 stoichiometry (KMnO4: l-proline). The reaction is first order with respect to [MnO −4 ] and [Pd(II)], an apparent less than unit order in [alkali] and zero order in [l-proline] under the experimental conditions. Reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Addition of reaction products did not affect the rate significantly. A mechanism involving the intervention of a free radical generated by l-proline has been proposed. The reaction constants involved in the mechanism were evaluated. The activation parameters with respect to the slow step of the Scheme were evaluated and are discussed.

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References

  1. R. Stewart, in K.B. Wiberg (ed.), Oxidation in Organic Chemistry, Part A, Ch. 1. Academic Press, New York, 1965.

  2. A.J. Fatiadi (1987) Synthesis 106 85 Occurrence Handle10.1055/s-1987-27859

    Article  Google Scholar 

  3. D.G. Lee, E.J. Lee and K.C. Brown, Phase Transfer Catalysis, new chemistry, catalysts and applications, ACS symposium series No. 326, American Chemical Society, Washington DC, 1987, p. 82.

  4. D.G. Lee, in W.S. Trahanovsky (Ed.), Oxidation in Organic Chemistry, Part D. Academic Press, New York, 1982, p. 147.

  5. J. F. Perez-benito and D.G. Lee, J. Org. Chem., 52, 3239 (1987); L.I. Simandi, M. Jaky, C.R. Savage and Z.A. Schelly, J. Am. Chem. Soc., 107, 4220 (1985).

  6. R. Stewart K.A. Gardner L.L. Kuehnert J.M. Mayer (1997) Inorg. Chem. 36 2069 Occurrence Handle10.1021/ic961297y

    Article  Google Scholar 

  7. M. Jaky, I.V. Kozhevnikov and E. Hoft, Int. J. Chem. Kinet., 24, 1085 (1992); S.A. Farokhi and S.T. Nandibewoor, J. Chem. Res., (S) 451 (2003), (M) 801 (2003).

  8. D.S. Mahadevappa, K.S. Rangappa, N.N.M. Gowda and B. Thimmegouda, Int. J. Chem. Kinet., 60, 589 (1986); K. Bal Reddy, B. Sethuram and T. Navaneeth Rao, Indian J. Chem., 20A, 395 (1981).

    Google Scholar 

  9. M.K. Mohanti and D. Laloo, J. Chem. Soc. Dalton. Trans., 311 (1990).

  10. K. Balreddy, B. Sethuram and T. Navaneeth Rao, Indian J. Chem., 20A, 395 (1981); R.B. Chougale, G.A. Hiremath and S.T. Nandibewoor, Polish J. Chem., 71, 1471 (1997).

  11. B. List R.A. Lerner C.F. Barbas (2000) J. Am. Chem. Soc. 122 395

    Google Scholar 

  12. J. Szammer, M. Jaky and O.V. Germasimov, Int. J. Chem. Soc., 24, 145 (1992); M. Jaky, I.V. Koozhenikov and E. Hoft, Int. J. Chem. Kinet., 24, 1055 (1992).

  13. L.I. Simandi, M. Jaky and Z.A. Schelly, J. Am. Chem. Soc., 22, 193 (1985); P.L. Timmanagoudar, G.A. Hiremath and S.T. Nandibewoor, Pol. J. Chem., 70, 1459 (1996).

  14. I.S. Ahmed C.J. Mohammad (1985) Int. J. Chem. Kinet. 11 813 Occurrence Handle10.1002/kin.550110802

    Article  Google Scholar 

  15. G.P. Tikhonova and S. Bovkovets, Russ. J. Inorg. Chem., 23, 1687 (1978); S.M. Tuwar, S.T Nandibewoor and J.R. Raju, Indian J Chem., 29A, 235 (1990).

  16. R.T. Mahesh, M.B. Bellakki and S.T. Nandibewoor, J. Chem. Res.,13 (2005)

  17. A.G. Sykes, H. Gemeleus and A.G. Sharpe (ed.), Advances in Inorganic and Radio Chemistry, 1967, Vol. 10, p. 153.

  18. W.M. Latimer (1959) Oxidation Potentials EditionNumber2 Prentice- hall New Jersey 343

    Google Scholar 

  19. G.H. Jeffery J. Bassett J. Mendham R.C. Denney (1996) Vogel’s Textbook of Quantitative Chemical Analysis EditionNumber5 ELBS Longman Essex, UK 371

    Google Scholar 

  20. A. Carrington and M.C.R. Symons, J. Chem. Soc., 3373 (1956).

  21. W.M. Latimer (1959) Oxidation Potentials EditionNumber2nd edit Prentice- hall New Jersey 328

    Google Scholar 

  22. F. Feigl and V. Anger, Spot Tests in Organic Analysis, Elsevier, New York, 1975, p. 195 and 197.

  23. L.J. Bellamy (1958) The Infrared Spectra of Complex Molecules EditionNumber2 Methuen and Co. Ltd London 133

    Google Scholar 

  24. V.I. Shlenskaya A.A. Biryukov (1966) Russ. J. Inorg. Chem. 11 28

    Google Scholar 

  25. D.R. Lide (Eds) (1992) Hand Book of Chemistry and Physics Chemical Rubber Publishing Company London 8–51

    Google Scholar 

  26. I.M. Kolthoff, E.J. Meehan and E.M. Carr, J. Am. Chem. Soc., 75, 1439 (1953); A.A. Frost and R.G. Pearson, Kinetics and Mechanism, Wiley Eastern Private Ltd, New Delhi, p. 367.

  27. R. Chang (1981) Physical Chemistry with Applications to Biological Systems MacMillan New York 326

    Google Scholar 

  28. W.K. Wan, K. Zaw and P.M. Henry, Organometallics, 7, 1677 (1988); B.I. Nabivanets, L.V. Kalabina and L.N. Kudritskaya, Russ. J. Inorg. Chem., 16, 1736 (1971).

  29. S.A. Chimatadar, S.B. Koujalagi and S.T. Nandibewoor, Transition Met. Chem., 26, 241 (2001); B.P. Sinha and H.P. Mathur, Z. Phys. Chem. (Leipzig), 246, 342 (1971).

  30. F.M. Moore and K.W. Hicks, Inorg. Chem., 14, 413 (1975); K.W. Hicks, J. Inorg. Nucl. Chem., 38, 1381 (1976).

  31. K.A.K. Lott and M.C.R. Symons, Discuss. Faraday Soc., 29, 105 (1960); M. Jaky, M. Szeverencyi and L.I. Simandi, Inorg. Chim. Acta. 186, 33 (1991).

  32. M.R. Kembhavi A.L. Harihar S.T. Nandibewoor (2000) Oxid. Commun. 23 304 Occurrence Handle1:CAS:528:DC%2BD3cXks1ymu7g%3D

    CAS  Google Scholar 

  33. R.G. Panari R.B. Chougale S.T. Nandibewoor (1998) Pol. J. Chem. 72 99 Occurrence Handle1:CAS:528:DyaK1cXhsFCgsr0%3D

    CAS  Google Scholar 

  34. R.G. Panari R.B. Chougale S.T. Nandibewoor (1998) J. Phys. Org. Chem. 11 448 Occurrence Handle10.1002/(SICI)1099-1395(199807)11:7<448::AID-POC23>3.0.CO;2-A Occurrence Handle1:CAS:528:DyaK1cXmt1aktLk%3D

    Article  CAS  Google Scholar 

  35. E.S. Lewis (1974) Investigations of Rates and Mechanisms of Reactions EditionNumber3rd edit Wiley New York 415

    Google Scholar 

  36. O. Exner, Coll. Czech. Chem. Commun., 29, (1964) 1094; O. Exner, Coll. Czech. Chem. Commun., 37, 1425 (1972).

  37. J.E Leffler (1955) J. Org. Chem. 20 1202 Occurrence Handle10.1021/jo01126a009 Occurrence Handle1:CAS:528:DyaG2sXosVSj

    Article  CAS  Google Scholar 

  38. M.R. Kembhavi A.L. Harihar S.T. Nandibewoor (2000) Oxid. Commun. 23 304 Occurrence Handle1:CAS:528:DC%2BD3cXks1ymu7g%3D

    CAS  Google Scholar 

  39. S.A. Chimatadar A.K. Kini S.T. Nandibewoor (2005) Inorg. React. Mech. 5 231 Occurrence Handle1:CAS:528:DC%2BD2MXhtlegsbk%3D

    CAS  Google Scholar 

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  1. P.G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580 003, India

    Veeresh C. Seregar, Chanabasayya V. Hiremath & Sharanappa T. Nandibewoor

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  1. Veeresh C. Seregar
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  2. Chanabasayya V. Hiremath
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Correspondence to Sharanappa T. Nandibewoor.

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Seregar, V.C., Hiremath, C.V. & Nandibewoor, S.T. Palladium(II) Catalysed Oxidation of l-proline by Heptavalent Manganese in Aqueous Alkaline Medium: A Free Radical Intervention and Decarboxylation. Transition Met Chem 31, 541–548 (2006). https://doi.org/10.1007/s11243-006-0029-x

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