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Bulletin of the Korean Chemical Society v.30 no.9, 2009년, pp.1939 - 1945   SCI SCOPUS
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N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

Puttaswamy    (Department of Chemistry, Central College Campus, Bangalore University   ); Shubha, J.P.    (Department of Chemistry, Central College Campus, Bangalore University  );
  • 초록

    Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl $O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$ , and a fractional- order dependence on $[H^+]$ . Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$ O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.


  • 주제어

    Pyrazines .   Oxidation kinetics .   Bromamine-B .   Acid medium.  

  • 참고문헌 (46)

    1. Campbell, M. M.; Johnson, G. Chem. Rev. 1978, 78, 65 
    2. Murthy, A. R. V.; Rao, B. S. Proc Indian Acad. Sci. 1952, 35, 69 
    3. Banerji, K. K.; Jayaram, B.; Mahadevappa, D. S. J. Sci. Ind. Res. 1987, 46, 65 
    4. Brenner, D. H. In. Synth. Reagents 1985, 6, 9 
    5. Gowda, B. T.; Mahadevappa, D. S. J. Chem. Soc. Perkin Trans. II 1983, 323 
    6. Geethanjali, A. Synlett. 2005, 18, 2857 
    7. Kolvari, E.; Ghorbani-Choghamarani, A.; Salehi, P.; Shirini, F.; Zolfigol, M. A. J. Iran. Chem. Soc. 2007, 4, 126 
    8. Puttaswamy.; Mahadevappa, D. S.; Rangappa, K. S. Bull. Chem. Soc. Japan 1989, 62, 3343 
    9. Ananda, S.; Jagadeesha, M. B.; Puttaswamy.; Venkatesha, B. M.; Vinod, T. K.; Gowda, N. M. M. Int. J. Chem. Kinet. 2000, 32, 776 
    10. Shashikala, V.; Rangappa, K. S. J. Carbohyd. Chem. 2002, 21, 219 
    11. Puttaswamy.; Jagadeesh, R. V. Appl. Catal. A: Gen. 2005, 292, 259 
    12. Meenakshisundaram, SP.; Markkandan, R. Indian J. Chem. 2005, 44A, 71 
    13. Usha, K. M.; Gowda, B. T. J. Che. Sci. 2006, 118, 351 
    14. Vasudha, A. M. Structureal Aspects of Pseudoaromatic Compounds; University of Poona: Poona, 1966; p 10 
    15. Andrew, J. T.; Mottaram, D. S. Flavor Science: Recent Developments; Woodhead Publishing: Great Britain, 1996; p 202 
    16. Fennema, O. R. Food Chemistry; Marcel Dekker: The Ohio State Univer., Colombus, Ohio, 1996; p 741 
    17. Brown, D. J. The Pyrazines; John-Wiley Interscience: New-York, 2002; p 77 
    18. Borg-Karlson, A. K.; Tengo, J. J. Chem. Ecology 1980, 6, 827 
    19. Joule, J. A.; Mills, K. Heterocyclic Chemistry; Wiley-Blackwell: New-York, 2002; p 194 
    20. Craig, E. M.; Garth Pews, R. J. Org. Chem. 1977, 42, 1869 
    21. Nobuhiro, S. J. Org. Chem. 1978, 43, 3367 
    22. Seizaburo, O.; Akira, K.; Tsuneo, K.; Fumihiko, U. Chem. Pharm. Bull. 1971, 19, 1344 
    23. Elina, A. S.; Musatova, I. S.; Syrova, G. P. Khim. Getero. Soed. 1968, 4, 725 
    24. Klein, B.; Berkowitz, J. J. Am. Chem. Soc. 1959, 81, 5160 
    25. Langmuir, V. K.; Laderoute, K. R.; Mendonca, H. L.; Sutherland, R. M.; Hei, T. K.; Liu, S. X.; Hall, E. J.; Naylor, M. A.; Adams, G. E. Int. J. Radiat. Oncol. Biol. Phys. 1996, 34, 79 
    26. Hei, T. K.; Liu, S. X.; Hall, E. J. Br. J. Cancer. Suppl. 1996, 7, 57 
    27. Ahmed, M. S.; Mahadevappa, D. S. Talanta 1980, 27, 669 
    28. Morris, J. C.; Salazar, J. A.; Wineman, M. A. J. Am. Chem. Soc. 1948, 70, 2036 
    29. Puttaswamy.; Nirmala Vaz. Transition Met. Chem. 2003, 28, 409 
    30. Akerloff, G. J. Am. Chem. Soc. 1932, 54, 4125 
    31. Bishop, E.; Jennings, V. J. Talanta 1959, 1, 197 
    32. Hardy, F. F.; Johnston, J. P. J. Chem. Soc. Perkin Trans II 1973, 742 
    33. Pryde, B. G.; Soper, F. G. J. Chem. Soc. 1962, 1582 
    34. Narayanan, S. S.; Rao, V. R. S. Radio Chim. Acta 1983, 32, 211 
    35. Subhashini, M.; Subramanian, M.; Rao, V. R. S. Talanta 1985, 32, 1082 
    36. Collins, C. J.; Bowman, N. S. Isotope Effects in Chemical Reactions; Van Nostrand Reinhold, New York, 1970; p 1267 
    37. Kohen, A.; Limbach, H. H. Isptope Effects in Chemistry and Biology; CRC Press: Florida, 2006; p 827 
    38. Moelwyn-Hughes, E. A. The Kinetics of Reaction in Solutions; Clarender Press: Oxford, 1947; p 374 
    39. Benson, S. W. The Foundations of Chemical Kinetics; McGraw-Hill: New York, 1960; p 19 
    40. Frost, A. A.; Pearson, R. G. Kinetics and Mechanism; Wiley: New York, 1961; p 135 
    41. Laidler, K. J. Chemical Kinetics; Tata Mc Graw-Hill: New Delhi, 1995; p 211 
    42. Amis, E. S. Solvent Effects on Reaction Rates and Mechanisms; Academic Press: New York, 1966; p 1672 
    43. Gilliom, R. D. Introduction to Physical Organic Chemistry; Addison- Wesley: London, 1970; p 144 
    44. Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 96 
    45. Exner, O. Coll. Czech. Chem. Commun. 1964, 29, 1094 
    46. Exner, O. Pro. Phy. Org. Chem. 1973, 10, 411 

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