MRC  Vol.2 No.4 , October 2013
Kinetic and Mechanistic Study of Oxidation of Piperazines by Bromamine-T in Acidic Medium
Abstract: Oxidations of piperazine, 1-methylpiperazine and 1-ethylpiperazine by bromamine-T (BAT) in buffered acidic medium have been kinetically studied at 303 K. The reaction shows a first-order dependence of the rate each on [BAT]0 and [piperazine]0, and an inverse fractional-order dependence on [H+]. The additions of halide ions and the reduction product of BAT, p-toluenesulfonamide, have no effect on the reaction rate. The variation of ionic strength of the solvent medium has no influence on the rate. Activation parameters have been evaluated from the Arrhenius and Eyring plots. A common mechanism consistent with the kinetic data has been proposed for all piperazines. The protonation constants of substrates have been evaluated. The Hammett linear free-energy relationship has been observed for the reaction with ρ = ?0.5 indicating that the electron-donating groups enhance the reaction rate by stabilizing the transition state. An isokinetic relationship observed shows β = 368 K indicating the dominance of enthalpy factors on the reaction rate.
Cite this paper: Chandrashekar, B. Venkatesha, S. Ananda and N. Gowda, "Kinetic and Mechanistic Study of Oxidation of Piperazines by Bromamine-T in Acidic Medium," Modern Research in Catalysis, Vol. 2 No. 4, 2013, pp. 157-163. doi: 10.4236/mrc.2013.24021.

[1]   W. R. Maynard Jr., “Gravimetric and Infra-Red Spectrophotometric Determination of Piperazine,” Journal of the Association of Official Analytical Chemists, Vol. 42, 1961, pp. 610-612.

[2]   G. L. Crenshaw and R. J. Shaver, “Down to Earth,” Dow Chemical Company, Michigan, 1956.

[3]   L. S. Goodman and A. Gilman, “The Pharmacological Basis of Therapeutics,” 2nd Edition, Macillan Company, New York, 1956.

[4]   R. M. Ioset, “Personal Communication,” Dow Chemical Company, Midland, Michigan, 1961.

[5]   T. J Mc Nair, F. A. Wibin, E. T. Hoppe, J. L. Schmidt and F. A. de Peyster, “Antitumor Action of Several New Piperazine Derivatives Compared to Certain Standard Anticancer Agents,” Journal of Surgical Research, Vol. 3, No. 3, 1963, pp. 130-136.

[6]   V. A. Mikhalev, M. I. Dorokhova and N. E. Smolina, “Prospidine and Some Other Derivatives of Steropoly Piperazine,” Meditsinskaia promyshlennost’ SSSR, Vol. 17, No. 1, 1963, pp. 17-20.

[7]   W. O. Foye and D. H. Kay, “Antiradiation Compounds III. N-2-Mercaptoethylpiperazines” Journal of Pharmaceutical Sciences, Vol. 51, No. 11, 1962, pp. 1098-1101.

[8]   A. Jouve, A. Grass and R. Benyamine, “Hemodynamic Studies during Angina Pectoris,” Vie Med., Vol. 44, 1963, pp. 115-120.

[9]   K. K Aravindakshan and K. Muraleedharan, “Kinetics of Non-Isothermal Decomposition of Polymeric Complexes of N,N’-Bis(dithiocarboxy)piperazine with Iron(III) and Cobalt(III)” Thermochimica Acta, Vol. 159, 1990, pp. 101-107.

[10]   M. M. Campbell and G Johnson, “Chloramine T and Related N-Halogeno-N-Metallo Reagents,” Chemical Reviews, Vol. 78, No. 1, 1978, pp. 65-79.

[11]   K. K. Banerji, B. Jayaram and D. S. Mahadevappa, “Mechanistic Aspects of Oxidations by N-Metallo-NHaloarylsulfonamides,” Journal of Scientific & Industrial Research, Vol. 46, 1987, pp. 65-76.

[12]   F. Ruff and A. F. Kucsman, “Oxidation of Dialkylsulhides with BAT in Alkaline Buffer Solutions,” Journal of the Chemical Society, Perkin Transactions II, 1990, p. 1075.

[13]   D. S. Mahadevappa and Puttaswamy, “Kinetics of Oxidation of Aliphatic Ketones with Bromamine-T in Acid Medium,” Bulletin of the Chemical Society of Japan, Vol. 61, No. 2, 1988, pp. 543-547.

[14]   K. S. Rangappa, H. Ramachandra, D. S. Mahadevappa and N. M. Made Gowda, “Osmium (VIII) Catalyzed Kinetics and Mechanism of Indoles Oxidation with Aryl-NHaloamines in Alkaline Medium,” International Journal of Chemical Kinetics, Vol. 28, No. 4, 1996, pp. 265-274.<265::AID-KIN4>3.0.CO;2-T

[15]   Puttaswamy and R. Ramachndrappa, “Ruthenium(III) Catalyzed Oxidation of Substituted Ethanols by Sodium N-Bromo-p-Toluenesulfonamide in Hydrochloric Acid Medium,” Transition Metal Chemistry, Vol. 24, No. 3, 1999, pp. 326-332.

[16]   C. G. R Nair and P Indrasenan, “New Redox Titrants in Non-Aqueous or Partially Aqueous Media—VI1: Potentiometric Determinations Using Dibromamine-T and Some Further Applications of Dichloramine-T,” Talanta, Vol. 23, No. 3, 1976, pp. 239-241.

[17]   M. S. Ahmed and D. S. Mahadevappa, “Bromamine-B as a New Oxidimetric Titrant,” Talanta, Vol. 27, No. 8, 1980, pp. 669-670.

[18]   R. M. C. Dawson, D. C. Elliott, W. Elliott and K. M. Jones, “Data for Biochemical Research,” 3rd Edition, Oxford Science Publications, 1986.

[19]   D. S. Mahadeveppa and N. M. Made Gowda, “Estimation of Glutathione with Chloramine-T and Dichloramine-T,” Talanta, Vol. 22, No. 9, 1975, pp. 771-773.

[20]   E. Bishop and V. J. Jennings, “Titrimetric analysis with chloramine-T—I: The status of chloramine-T as a titrimetric reagent,” Talanta, Vol. 1, No. 3, 1958, pp. 197-212.

[21]   D. S. Mahadevappa and Rangaswamy, “Physico Chemical Properties of Chloramine-T. II. Conductometric study of the Interaction of Chloramine-T with Chromium(III), Aluminium(III) and Iron(III) Solutions,” Revue Roumaine de Chimie, Vol. 22, 1977, pp. 1233-1241.

[22]   F. F Hardy and J. P. J Johnston, “The Interactions of N-Bromo-N-Sodiobenzenesulphonamide (Bromamine-B) with p-Nitrophenoxide Ion,” Journal of the Chemical Society, Perkin Transactions II, No. 6, 1973, pp. 742-746.

[23]   R. D Gilliom, “Introduction to Physical Organic Chemistry”, Addison Wesley, London, 1970, p. 144.

[24]   L. P. Hammett, “The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives,” Journal of the American Chemical Society, Vol. 59, No. 1, 1937, pp. 96-103.