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Kinetics and Mechanism of meso-Tetraphenylporphyriniron(III) Chloride Catalyzed Oxidation of Indole by Peroxomonosulphate
Corresponding Author(s) : K. Karunakaran
Asian Journal of Chemistry,
Vol. 25 No. 8 (2013): Vol 25 Issue 8
Abstract
Mechanistic study on meso-tetraphenylporphyriniron(III) chloride (TPP) catalyzed oxidation of indole by peroxomonosulphate in aqueous acetonitrile medium have been carried out. The reaction follows a fractional order (0.57) with respect to substrate and first order with respect to oxidant. The order with respect to catalyst was found to be one. Increase in percentage of acetonitrile decreased the rate of the reaction. The added H+ did not affect the reaction rate. The reaction fails to initiate polymerization and free radical mechanism is ruled out. Activation and thermodynamic parameters have been computed. Nucleophilic attack of the ethylenic bond on the persulphate oxygen in presence of meso-tetraphenylporphyriniron(III) chloride is envisaged to explain the reactivity. A suitable kinetic scheme based on the observations was proposed. Significant catalytic activity is observed for the reaction system in the presence of meso-tetraphenylporphyriniron(III) chloride.
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- R.J. Sundberg, Indole, Kirk-othmer Encyclopedia of Chemical Technology, Wiley, New York (1995).
- R.N. Goyal and A. Sangal, Electrochim. Acta, 50, 2135 (2005).
- A.T. Al-kazwini, P. O'Neill, G.E. Adams, R.B. Cundall, G. Lang and A. Junino, J. Chem. Soc. Perkin Trans II, 1941 (1991).
- A.T. Al-kazwini, P. O'Neill, G.E. Adams, R.B. Cundall, A. Junino and J. Maignan, J. Chem. Soc. Perkin Trans. II, 657 (1992).
- S.N. Krylov and H.B. Dunford, J. Phys. Chem., 100, 913 (1996).
- W.B. Lawson and B. Witkop, J. Org. Chem., 26, 263 (1961).
- N. Finch and W.E. Taylor, J. Am. Chem. Soc., 84, 3871 (1962).
- K.S. Rangappa, D.T. Esterline, C.K. Mythily, D.S. Mahadevappa and S.Y. Ambedkar, Polyhedron, 12, 1719 (1993).
- S.P. Meenakshisundaram and N. Sarathi, Int. J. Chem. Kinet., 39, 46 (2007).
- (a) R. Somuthevan, R. Renganathan and P. Maruthamuthu, Inorg. Chim. Acta, 45, L165 (1980); (b) A. Jameel and P. Maruthamuthu, J. Indian Chem. Soc., 75, 368 (1998).
- R. Suthakaran, P. Subramaniam and C. Srinivasan, Proc. Indian Acad. Sci., 97, 555 (1986).
- R.J. Kennedy and A.M. Stock, J. Org. Chem., 25, 1901 (1960).
- B.M. Trost and D.P. Curran, Tetrahedron Lett., 22, 1287 (1981).
- R. Mello, M. Fiorentino, C. Fusco and R. Curci, J. Am. Chem. Soc., 111, 6749 (1989).
- M. Balon, M. Munoz, P. Guardado, J. Hidalgo and C. Carmona, Org. Chem., 58, 7469 (1993).
- B. Meunier, Chem. Rev., 92, 1411 (1992).
- J. Larsen and K. Anker-Jorgensen, J. Chem. Soc. Perkin Trans II, 1213 (1992).
- J.T. Groves, T.E. Nemo and R.S. Myers, J. Am. Chem. Soc., 101, 1032 (1979).
- D.S. Bhuvaneshwari and K.P. Elango, J. Indian Chem. Soc., 86, 242 (2009).
- K.J. Laidler, Chemical Kinetics, Tata-McGraw Hill, New Delhi (1965).
- F. Ruff and A. Kucsman, J. Chem. Soc. Perkin Trans. II, 683 (1985).
- S.P. Meenakshisundaram, M. Selvaraju, N.M. Made Gowda and K.S. Rangappa, Int. J. Chem. Kinet., 37, 649 (2005).
- M.S. Ramachandran, T.S. Vivekanadam and V. Arunachalam, Bull. Chem. Soc. (Japan), 59, 1549 (1986).
- D.M. Davis and M.E. Deary, J. Chem. Soc. Perkin Trans II, 559 (1992).
- J.A. Kerr, Chem. Rev., 66, 465 (1966).
- Z. Zhu and J.H. Espenson, J. Org. Chem., 60, 1326 (1995).
- X.-T. Zhou, H.-B. Ji and Q.-L. Yuan, J. Porphyr. Phthalocya., 12, 94 (2008).
References
R.J. Sundberg, Indole, Kirk-othmer Encyclopedia of Chemical Technology, Wiley, New York (1995).
R.N. Goyal and A. Sangal, Electrochim. Acta, 50, 2135 (2005).
A.T. Al-kazwini, P. O'Neill, G.E. Adams, R.B. Cundall, G. Lang and A. Junino, J. Chem. Soc. Perkin Trans II, 1941 (1991).
A.T. Al-kazwini, P. O'Neill, G.E. Adams, R.B. Cundall, A. Junino and J. Maignan, J. Chem. Soc. Perkin Trans. II, 657 (1992).
S.N. Krylov and H.B. Dunford, J. Phys. Chem., 100, 913 (1996).
W.B. Lawson and B. Witkop, J. Org. Chem., 26, 263 (1961).
N. Finch and W.E. Taylor, J. Am. Chem. Soc., 84, 3871 (1962).
K.S. Rangappa, D.T. Esterline, C.K. Mythily, D.S. Mahadevappa and S.Y. Ambedkar, Polyhedron, 12, 1719 (1993).
S.P. Meenakshisundaram and N. Sarathi, Int. J. Chem. Kinet., 39, 46 (2007).
(a) R. Somuthevan, R. Renganathan and P. Maruthamuthu, Inorg. Chim. Acta, 45, L165 (1980); (b) A. Jameel and P. Maruthamuthu, J. Indian Chem. Soc., 75, 368 (1998).
R. Suthakaran, P. Subramaniam and C. Srinivasan, Proc. Indian Acad. Sci., 97, 555 (1986).
R.J. Kennedy and A.M. Stock, J. Org. Chem., 25, 1901 (1960).
B.M. Trost and D.P. Curran, Tetrahedron Lett., 22, 1287 (1981).
R. Mello, M. Fiorentino, C. Fusco and R. Curci, J. Am. Chem. Soc., 111, 6749 (1989).
M. Balon, M. Munoz, P. Guardado, J. Hidalgo and C. Carmona, Org. Chem., 58, 7469 (1993).
B. Meunier, Chem. Rev., 92, 1411 (1992).
J. Larsen and K. Anker-Jorgensen, J. Chem. Soc. Perkin Trans II, 1213 (1992).
J.T. Groves, T.E. Nemo and R.S. Myers, J. Am. Chem. Soc., 101, 1032 (1979).
D.S. Bhuvaneshwari and K.P. Elango, J. Indian Chem. Soc., 86, 242 (2009).
K.J. Laidler, Chemical Kinetics, Tata-McGraw Hill, New Delhi (1965).
F. Ruff and A. Kucsman, J. Chem. Soc. Perkin Trans. II, 683 (1985).
S.P. Meenakshisundaram, M. Selvaraju, N.M. Made Gowda and K.S. Rangappa, Int. J. Chem. Kinet., 37, 649 (2005).
M.S. Ramachandran, T.S. Vivekanadam and V. Arunachalam, Bull. Chem. Soc. (Japan), 59, 1549 (1986).
D.M. Davis and M.E. Deary, J. Chem. Soc. Perkin Trans II, 559 (1992).
J.A. Kerr, Chem. Rev., 66, 465 (1966).
Z. Zhu and J.H. Espenson, J. Org. Chem., 60, 1326 (1995).
X.-T. Zhou, H.-B. Ji and Q.-L. Yuan, J. Porphyr. Phthalocya., 12, 94 (2008).