Os (VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in L-Proline by Sodium Periodate (NaIO4) in Alkaline Medium

Authors

  • Dr. Amrita Srivastava  Department of Chemistry, University of Lucknow, Lucknow, Uttar Pradesh, India
  • Madhu Gupta  Chemical Laboratories Feroze Gandhi College, Raebareli, Uttar Pradesh, India
  • Dr. Sheila Srivastava  Chemical Laboratories Feroze Gandhi College, Raebareli, Uttar Pradesh, India

Keywords:

Kinetics, Os(VIII), Oxidation, Proline, Sodium Periodate, Alkaline Medium.

Abstract

The present paper deals with the kinetic and mechanistic investigation of Os(VIII) catalyzed oxidation of proline by sodium periodate (NaIO4) in alkaline medium in temperature range 300C to 450C. The experimental result shows a first order kinetics with respect to Os[VIII] and [Periodate] while positive effect with respect to substrate i.e., Proline was observed. The reaction showed negative effect for [OH-]. Negligible effect of [HgOAc)2] and ionic strength of the medium was observed. The reaction is carried out in presence of mercuric acetate as a scavenger. The reaction between sodium periodate and proline in alkaline medium shows 2:1 stoichiometry. The values of rate constants observed at different temperatures (30 to 450C) were utilized to calculate the activation parameters. A mechanism involving the complex formation between catalyst, substrate and oxidant has been proposed. L-glutamic acid has been identified as main oxidation product of the reaction chromatographically and spectroscopically. Based on kinetic data, reaction stiochiometry and product analysis of the reaction a feasible mechanism has been proposed. The rate law has been derived from obtained kinetic data.

References

  1. D.L. Nelson., M.M. Cox, Lehninger Principles of Biochemistry, 4th ed., W.H. Freeman and company, New York, 2007.
  2. C. V. Hiremath, T.S. Kiran, S.T. Nandibewoor, Os(VIII)/Ru(III) catalyzed oxidation of aspirin drug by a new oxidant, Diperiodatoargentate(III) in aqueous alkaline medium: A comparative kinetic study, J. Mol. Catal., A., 248 (2006) 163-174.
  3. V.C. Seregar, C.V. Hiremath, S.T. Nandibewoor, Mechanism of oxidation of L-proline by aqueous alkaline diperiodatoargentate (III): Decarboxylation and dehydration, Z. Phys. Chem., 220 (5) (2006) 615-629.
  4. B. List, R.A. Lerner, C.F. Barbes, Proline-catalyzed direct asymmetric aldol reactions, J. Am. Chem. Soc., 122 (2000) 2395- 2398.
  5. A.K. Das, Coord Chem., 213 (2001) 307-325.
  6. S. Srivastava and R. Patel, World Journal of Pharmacy and Pharmaceutiacal Sciences., Volume 3, Issue 9 (2014) 365-371.
  7. K. Vijayasri, j. Rajaram, J.C. Kuriacose, Ruthenium(III) catalyzed oxidation of 1-phenylethanol and substituted 1-phenylethanols by phenyliodosoacetate, J. Chem. Sci., 95 (1985) 573.
  8. F. R. DUK,. J. Am. Chem. Soc., 69 (1974) 3054.
  9. G. J. Buistc, A. Bunton, W. C. P. Hipperson, J. Chem. Soc. (B) (1971) 2128.
  10. L. Maros, I.Molnar-Perel, E. Schissel and V. Szerdahelyi, J. Chem. Soc. Perkin Trans., 11 (1980) 39 .
  11. G. Dahlgre and dK. Reed, J. Am. Chem. Soc., 71 (1967) 1380.
  12. M. P Rao, B. S. Sethuram and, N. N.Rao, J. Indian Chem. Soc. 57 (1980) 149.
  13. D. Rao, M. Sridevi , P. Vani , Indian journal of applied research, Volume: 3 (2013) Issue: 5.
  14. J. Mendham, R.C. Denney, J.D. Barnes,M.J.K. Thomas, Vogel’s Text Book of QuantitatiVe Chemical Analysis, 6th ed.; Pearson Education: Delhi, India, 2003; p 466.
  15. S.M. Tuwar, S.T. Nandibewoor, J.R. Raju, Osmium(VIII)/ Palladium(II) Catalysis of Cerium(IV) Oxidation of Allyl Alcohol in Aqueous Acid, Trans. Met. Chem., 16 (1991) 430-434.
  16. F. Feigl, Spot Tests in Organic Analysis; Elsevier: New York, 1975.
  17. D.L. Nelson, M.M. Cox, LehningersPrinciples of Biochemistry,4th ed.; Freeman and Company: New York, 2007.
  18. K. Wilson,J. Walker, J., Practical Biochemistry, 5th ed.; Cambridge University Press: Cambridge, UK, 2005.
  19. M. Devendra, Y.K. Gupta, Kinetics and Mechanism of the Osmium(VIII)-Catalysed Oxidation of Phosphite by Hexacyanoferrate(III) Ion in Aqueous Alkaline Media., J. Chem. Soc., Dalton Trans. (1977) 1085-1089.
  20. B. Sethuram, Some Aspects of Electron Transfer Reactions Involving Organic Molecules, Allied Publishers (P) Ltd., Mumbai, India, 2003.
  21. J.k. Laidler, Chemical Kinetics, 3rd ed.; Pearson Education Ptc. Ltd.: New Delhi, India, 2004.
  22. S.K. Upadhyay, M.C. Agrawal, M. C., Kinetics of Oxidation of Os(VIII)-Catalysed Oxidation of Some R-Amino Acids in the Presence of Excess of Ferricyanide, Indian J. Chem. ,15A (1977) 709-715.
  23. N. Sutin, The Kinetics of Inorganic Reactions in Solution, Annu. ReV. Phys. Chem., 17 (1966) 119-172.
  24. M. Lancaster, R.S. Murray, The Ferricyanide-Sulphite Reaction, J. Chem. Soc., A (1971) 2755-2758.
  25. M. Martinez, M. Pitarque,R.V. Eldik, Outer-Sphere Redox Reactions ofCoIII(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) 2665-2671.
  26. R. S. Shettar, M.I. Hiremath, S.T. Nandibewoor, Kinetics and Mechanistic Study of Ruthenium(III) Catalysed Oxidative Decarboxylation of L-proline by Alkaline Heptavalent Manganese (Stopped Flow Technique), Electron. J. Chem. 9 (2005) 91-100.
  27. S.K. Upadhyay, Osmium(VIII) Catalysed Oxidation of D-Proline by Hexacyanoferrate(III), Int. J. Chem. Kinet., 15 (1983) 669-671.

International Journal of Scientific Research in Science, Engineering and Technology

Downloads

Published

2017-08-31

Issue

Volume 3, Issue 5, July-August-2017

Section

Research Articles

License

Copyright (c) IJSRSET

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

[1]
Dr. Amrita Srivastava, Madhu Gupta, Dr. Sheila Srivastava, " Os (VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in L-Proline by Sodium Periodate (NaIO4) in Alkaline Medium, International Journal of Scientific Research in Science, Engineering and Technology(IJSRSET), Print ISSN : 2395-1990, Online ISSN : 2394-4099, Volume 3, Issue 5, pp.362-371, July-August-2017.