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Oxidation of Tranexamic Acid by Bromamine - T in HCl Medium Catalyzed by RuCl3: A Kinetic and Mechanistic Approach

Author Affiliations

  • 1Acharya institute of Technology, Soldevanahalli, Hesarghatta Road, Bangalore-560090, Karnataka, INDIA
  • 2Department of Chemistry, Jyoti Nivas College, Koramangala Industrial Layout, Bangalore - 560095, Karnataka, INDIA

Res.J.chem.sci., Volume 2, Issue (7), Pages 7-15, July,18 (2012)

Abstract

Kinetics and oxidation of tranexamic acid (TX) [trans -4-(aminomethyl) cyclohexanecarboxylic acid] by sodium -N- bromo -p- toluenesulphonamide (bromamine – T or BAT) in hydrochloric acid medium using RuCl3 as catalyst at 303K have been studied. The rate was first order in [BAT]o, fractional order in [TX], first order in RuCl3, fractional order in [H+] and [PTS].Addition of NaCl and NaBr did not affect the rate of the reaction which indicates that the rate of the reaction depends only on[H+]. Variation of ionic strength did not affect the rate of the reaction indicating that non – ionic species are involved in the rate limiting step. Dielectric effect is positive. Rate increased with increase in temperature from 293K to 323K. From the linear Arrhenius plot, activation parameters were computed. Addition of reaction mixture to aqueous acryl amide solution did not initiate polymerization, showing the absence of free radical species. Oxidation products were identified. Protonated oxidant H2O+ Br is the reactive species which reacts with the substrate. Based on kinetic results, reaction stoichiometry and oxidation products, a suitable mechanism have been proposed.

References

  1. Usha Joseph, Ramachandrappa R. and Pushpa Iyengar., Kinetics of Oxidation of Pioglitazone by Chloramine – T in HCl medium- A mechanistic Approach, International Journal of Universal Pharmacy and Life Sciences., 2(2), 85(2012)
  2. Puttaswamy, Ramachandrappa R and Made Gowda N. M., Kinetics and Mechanism of Rurhenium(III) catalyzed oxidation of Secondary Alcohols by Bromamine – T in Hydrochloric acid solutions, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry.,32(7),1263(2002)
  3. Puttaswamy and Shubha J.P., Kinetics and mechanism of sodium N -halo--toluenesulfonamides oxidation of diclofenac in alkaline medium, AIChE Journal.,55, 3234 (2009)
  4. Diwya, Ramachandrappa R. and Pushpa Iyengar., Kinetics and Mechanism of oxidation of Miglitol by Bromamine –T (BAT) in HCl medium using RuCl as catalyst, J. Chem. Pharm. Res., 4(3), 1676(2012)
  5. Ramachandrappa R, Diwya, PushpaIyengar., Kinetic and mechanistic studies on the oxidation of Voglibose by Bromamine – T in HCl medium, RJPBCS.,3(1), 837(2012)
  6. Nair C.G, Lalithakumari R and Senan P.I.,Bromamine-T as a new oxidimetric titrant, Talanta., 25, 525 (1978)
  7. Puttaswamy and Jagadeesh R.V., Mechanistic Studies of Oxidation of Thiols to Disulfides by Sodium -Chloro-toluenesulfonamide in an Alkaline Medium:A Kinetic Approach, Ind. Eng. Chem. Res., 45(5), 1563(2006)
  8. Rangaraju P. R., Venkatesha T.V. and Ramachandrappa R., Kinetic and mechanistic studies on the Oxidation of Tinidazole by Bromamine – T in HCl medium, RJPBCS., 2(4), 947 (2011)
  9. Sonawane Vilas Y, Mechanistic study of chromium (VI) catalyzed oxidation of benzyl alcohol by polymer supported chromic acid, Res. J. Chem. Sci.,1(1), 25-30 (2011)
  10. Reynolds J.E.F. and Prasad., The Pharmaceutical Press, 31st edn, London. (1996)
  11. Gennaro A. R., In: Remington; The Science and Practice of Pharmacy, 20 th edn, Philadelphia (2000)
  12. Puttaswamy, Anu Sukhdev and Shubha J.P., Palladium(II) –catalyzed oxidation of tranexamic acid by bromamine – B in alkaline medium and uncatalyzed reaction in acidmedium: A study of kinetic and mechanistic chemistry, Journal of molecular catalysis., 332(1-2), 113-121 (2010)
  13. Rangappa K.S, Mahadevappa D. S. and Gowda.B.T., Some Analytical Applications of aromatic Sulphonylhaloamines: Estimation of Indigocarmine by Chloramine – B, Bromamine – T and Dibromamine – T, Microchem.J.,26, 375-386 (1981)
  14. Akerloff G., Dielectric Constants of some Organic Solvent- Water mixtures at various temperatures, J. Am. Chem. Soc.,54, 4125 (1932)
  15. Ramachandrappa R, Puttaswamy, Mayanna S.M. and N. M., Made Gowda., Kinetics and Mechanism of Oxidation of Aspirin by Bromamine – T, N- Bromosuccinimide and N- Bromophthalimide, International Journal of Chemical Kinetics.,30, 6 (1998)
  16. Feigl F., Spot tests in organic analysis, Elsevier, Amsterdam, 156 (1966)
  17. Vogel A.I. Text Book of Practical Organic Chemistry,thEdition, London (1989)
  18. Amis E.M., Solvent effects on reaction rates and mechanism.,Academic Press, NY (1966)
  19. E.A. Moelwyn- Hughes., Kinetics of Reaction in Solutions: Calender Press: Oxford; Physical Chemistry, 2nd EditionOxford University Press, London (1947)
  20. Pyrde B.G. and Soper F.G., The interaction of anilides and hypochlorous acid, J. chem. Soc., 1582 (1926) ; ibid 1510 (1931)
  21. Morris J.C., Salazar J.A. and Wineman M.A., Equilibrium studies on Chloro Compounds : The Ionization Constant of N- Chloro – p- toluenesulphonamide, J. Amer. Chem. Soc., 70, 2036 (1948)
  22. Bishop E. and Jinnings V.J., Titrimetric Analysis with Chloramine – T : The status of Chloramine – T as a Titrimetric Reagent, Talanta., 197 (1958)
  23. Backhouse J. R., Dwyer F.D. and Shales N., Chemistry of Ru(IV) Potential of the Quadrivalent/ Trivalent Ru Couple in HCl, Proc. Roy.Soc., 83, 146 (1950)
  24. Cotton F.A. and Wilkinson G., Basic Inorganic Chemistry, rd Edition., John Wiley and Sons, 83, 146 (1995)
  25. Davfokratova T., Analytical Chemistry of Ruthenium, Academy of sciences: USSR, 54 (1963)
  26. Griffith W.P., The Chemistry of Rare Platinum Metals., Inter Science, New York 141 (1967)
  27. Puttaswamy and Ramachandrappa R., Ruthenium (III) –catalyzed oxidation of amides by sodium N - bromobenzenesulphonamide in hydrochloric acid : a kinetic and mechanistic study, Transition Met. Chem24, 52 (1999)
  28. Vinod Kumar C.H, Shivananda K.N., Rajenahally V. Jagadeesh and Naga Raju C., Ruthenium complex catalyzed oxidative conversion of aliphatic amines to carboxylic acids using bromamine-T: Kinetic and mechanistic study, J.Mol.Cat. A., 311, 23 (2009)
  29. Hardy F.F. and Johnston J.P., The Interaction of N- Bromo – N- Sodiobenzenesulphonamide(Bromamine – B) with p- Nitrophenoxide Ion, J. chem. Soc., Perkin tran II, 742 (1973)
  30. Reichardt C., Solvent and Solvent Effects in Organic Chemisty,rd edn (2003)