Table of Contents Author Guidelines Submit a Manuscript
Journal of Chemistry
Volume 2013, Article ID 186168, 8 pages
http://dx.doi.org/10.1155/2013/186168
Research Article

Kinetics and Mechanism of meso-Tetraphenylporphyrin Iron(III) Chloride Catalysed Oxidation of Indole-3-Acetic Acid by Peroxomonosulphate

Department of Chemistry, Sona College of Technology, Salem 636 005, India

Received 1 December 2011; Revised 28 June 2012; Accepted 24 July 2012

Academic Editor: Guochuan Yin

Copyright © 2013 Durairaj Kungumathilagam and Kulanthaivel Karunakaran. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Mechanistic study on meso-tetraphenylporphyrin iron(III) chloride (TPP) catalysed oxidation of indole-3-acetic acid by peroxomonosulphate (oxone) in aqueous acetonitrile medium has been carried out. The reaction follows a first order with respect to both substrate and oxidant. The order with respect to catalyst was found to be fractional. The order of reaction with respect to catalyst varies with a concentration of catalyst. Increase in percentage of acetonitrile decreased the rate. The reaction fails to initiate polymerization, and a radical mechanism is ruled out. Activation and thermodynamic parameters have been computed. A suitable kinetic scheme based on these observations is proposed. Significant catalytic activity is observed for the reaction system in the presence of TPP.

1. Introduction

Oxidation of indole-3-acetic acid (IAA) has received much attention because of the involvement of the indole derivatives in significant biological processes. They have anti-inflammatory [1, 2], tumor growth inhibitor [1, 2], antiviral, antitubercular, antibacterial, antiallergic, and psychotropic activities [3]. Oxidation of indole-3-acetic acid by dioxygen [4], Ce(IV) [4], 1,4-phenanthroline-manganese(II) complexes [5], hydrogen peroxide, persulphate, N-chlorosuccinimide, and sodium hypochlorite was reported [6]. Chlorophyll-sensitized photooxidation [7], peanut peroxidase [8], horseradish and tobacco peroxidase [911] catalysed oxidation of IAA have been studied.

The catalytic properties of the transition metal porphyrins are due to the fact that an oxotransition metal porphyrin intermediate is formed, which can transfer the oxygen atom to a substrate or can accept an electron from the substrate [12]. In the field of oxidation catalysed by transition metal porphyrins, the oxygen transfer step is the crucial step, and from an experimental point of view a lot of attention has been devoted to the nature of the oxotransition metal bond [13]. Groves and coworkers [14] described the use of meso-tetraphenylporphyrin iron(III) chloride (TPP) in combination with the lipophilic iodosylbenzene, first used in vivo by Ullrich and Staudinger [15], for the epoxidation of olefins, and the hydroxylation of alkanes.

Although the oxidation of certain substituted indoles such as 2,3-dialkyl indoles by peroxodisulphate, peroxomonosulphate, peroxomonophosphoric, and peroxodiphosphoric acids has been already reported in the literature [1618], the lack of kinetic and mechanistic investigation on TPP catalysed oxidation of IAA by peroxomonosulphate (oxone) instigated us to carry out this work.

2. Experimental

2.1. Materials

Indole-3-acetic acid, oxone, and TPP (Sigma Aldrich) were used as such. All the other chemicals and solvents used were of analytical grade (Merck, India). All the solutions used in the study were made by using doubly distilled water. All the reagents were prepared freshly and used in the reaction. All the reactions were carried out in a thermostat and the temperature was controlled to ±0.1°C.

2.2. Kinetic Measurements

The kinetic studies were carried out in aqueous acetonitrile medium under pseudo-first-order conditions. The reactions were performed by maintaining a large excess of [IAA] over [oxone] in the temperature range of 293–333 K. The reaction mixture was homogeneous throughout the course of the reaction. The reaction’s progress was monitored for at least two half-lives by iodometric estimation of unchanged oxidant at regular time intervals. The rate constants ( ) were evaluated from the slopes of linear plots of log[titre] versus time.

2.3. Stoichiometry

Solutions of IAA containing an excess of oxone were kept overnight at room temperature. By titrimetric estimation of the concentration of oxone consumed and assuming that all the IAA taken had reacted, the stoichiometry of IAA : oxone was found to be 1 : 2.

2.4. Product Analysis

A reaction mixture containing slight excess of oxone, IAA, TPP, and acetonitrile-water mixture was kept aside at room temperature for a day, so that the substrate was completely converted into product. The mixture was extracted with ether. A resinous mass was obtained in the ether layer which is treated with acetone and then with methanol. The final product was obtained from the alcoholic solution and identified by UV-Visible absorption spectra ( ) at 437 nm (Figure 6). The above product was also reported in the oxidation IAA by peroxomonosulphate [19].

2.5. Data Analysis

Correlation studies were carried out using Microcal origin (version 6) computer software. The goodness of the fit was discussed using the correlation coefficient, , in the case of simple linear regression and in the case of multiple linear regressions.

3. Results and Discussion

Factors influencing the rate of TPP catalysed oxidation of IAA by oxone such as [IAA], [oxone], [TPP], [H+] and dielectric constant have been studied. Rate and activation parameters were evaluated.

3.1. Effect of [IAA]

A constants [oxone], [TPP], [H+] and fixed percentage of acetonitrile, kinetic runs were carried out with various initial concentrations of indole-3-acetic acid, which yielded rate constants whose values depended on [IAA]. The pseudo-first-order rate constants ( ) thus obtained were found to increase with [IAA] over a range of [IAA] used 0.6–1.4 × 10−2 mol dm−3 (Table 1).

tab1
Table 1: Pseudo-first-order rate constants for the TPP catalysed oxidation of IAA by peroxomonosulphate.

The plot (Figure 1) of versus log[IAA] is linear with a slope of 0.91 showing that the reaction is first order in [IAA]. The plot (Figure 2) of 1/[IAA] versus is linear with negligible intercept on the rate ordinate, giving the proof that the mechanism for the oxidation process is not of Michaelis-Menten type.

186168.fig.001
Figure 1: Plot of versus log[IAA] for TPP catalysed oxidation of IAA by peroxomonosulphate in acetonitrile medium.
186168.fig.002
Figure 2: Plot of versus 1/[IAA] for TPP catalysed oxidation of IAA by peroxomonosulphate in acetonitrile medium.
3.2. Effect of [Oxone]

The kinetics of TPP catalysed oxidation of indole-3-acetic acid has been studied at various initial concentrations of the oxidant, [oxone] ( to  mol dm−3) and at fixed concentrations of other reactants. The plot of log [oxone] versus time yields a straight line. The pseudo-first-order rate constants, , are calculated at various initial concentrations of the oxidant and are constant indicating a first order dependence of rate on oxone (Table 1).

3.3. Effect of [TPP]

A constants [IAA], [oxone], [H+], and fixed percentage of acetonitrile, kinetic runs were carried out with various initial concentrations of [TPP], which yielded rate constants whose values depended on [TPP]. The pseudo-first-order rate constants ( ) thus obtained were found to increase with [TPP] (Table 2) over a range of [TPP] used (2.0–40.0 × 10−8 mol dm−3). A linear plot was obtained between and log[TPP] (Figure 3(a)) with a slope of 0.48, indicating that the order of the reaction with respect to catalyst (a) [2–20 × 10−8 mol dm−3] was fractional. Another linear plot was obtained between and log [TPP] (Figure 3(b)) with a slope of 1.47, indicating that the order of the reaction with respect to catalyst (b) [22–40 × 10−8 mol dm−3] was also fractional. The order of reaction with respect to catalyst varies with a concentration of catalyst. It clearly reveals that the reaction follows different mechanism at low (Scheme 1) and high concentrations of catalyst (Scheme 2). It is also noticed that higher concentration of catalyst exhibits an activation towards the reaction progress reaching a maximum value of 6.76 at catalyst concentration of 40 × 10−8 mol dm−3. Also the catalytic activity of catalyst substantially exceeds in higher concentration due to more active centres which interact mutually with one another leading to the formation of bimetallic and multimetallic active centers which has more catalytic activity than monometallic ones of catalyst in lower concentration [20].

tab2
Table 2: Effect of catalyst concentration on the reaction rate at 303 K.
186168.sch.001
Scheme 1: Probable mechanism for the low concentration of meso-tetraphenylporphyrin iron(III) chloride catalysed oxidation of indole by peroxomonosulphate.
186168.sch.002
Scheme 2: Probable mechanism for the high concentration of meso-tetraphenylporphyrin iron(III) chloride catalysed oxidation of indole by peroxomonosulphate.
186168.fig.003
Figure 3: Plot of versus log[catalyst] showing the effect of catalyst concentration (a) 2–20 × 10−8 mol dm−3; (b) 22–40 × 10−8 mol dm−3 on reaction rate.
3.4. Effect of [H+]

The reaction rates measured with various [H+] (8.0–40.0 × 10−2 mol dm−3) were found to be the same (Table 3). Such kinetic behavior indicates the nonexistence of any protonation equilibrium with respect to both oxone and IAA in the experiment.

tab3
Table 3: Effect of [H+] concentration on the reaction rate at 303 K.
3.5. Effect of Dielectric Constant

In order to determine the effect of dielectric constant (polarity) of the medium on rate, the oxidation of IAA by peroxomonosulphate was studied in aqueous acetonitrile mixtures of various compositions (Table 4). The data clearly reveal that the rate increases with decrease in the percentage of acetonitrile, that is, with increasing dielectric constant or polarity of the medium and leads to the influence that there is a charge development in the transition state involving a more polar activated complex than the reactants [2124], a neutral molecule [IAA], and a mononegative ion ( ) suggesting a polar (ionic) mechanism.

tab4
Table 4: Effect of dielectric constant on the reaction rate at 303 K.
3.6. Test for Free Radical Intermediates

No polymer formation was observed when a freshly distilled acrylonitrile monomer was added to the deaerated reaction mixture indicating the absence of free radical intermediates.

3.7. Rate and Activation Parameters

The effect of temperature was studied in the range of 293 K–333 K and the results were shown in (Table 5). The Arrhenius plot of versus (Figure 4) was found to be linear. The value of energy of activation ( ) was found to be 11.56 kJ mol−1 K−1 and  kJ mol−1,  J K−1 mol−1,  kJ mol−1. The large negative value of entropy of activation obtained is attributed to the severe restriction of solvent molecules around the transition state.

tab5
Table 5: Effect of temperature on the reaction rate.
186168.fig.004
Figure 4: Plot of versus 1 showing the effect of temperature on reaction rate.
3.8. Mechanism

Peroxomonosulphate exists [25] as in solution. Although many peroxy anions are effective nucleophiles. is very weak nucleophiles [26, 27]. Inspite of the fact that free radicals can arise from the facile homolysis of the oxygen-oxygen bond [28], an ionic mechanism is favoured in certain reactions involving oxidations by peroxides. In the present investigation no observed polymerization in the presence of acrylonitrile rules out a free radical process. Generally, the enhancement of the electrophilic activity of peroxide will minimize the importance of undesirable free radical pathways, resulting in a mixture of products [29].

The first step is the formation of a complex between oxone and TPP. This complex immediately decomposed and showed that =O is in agreement with the literature study [30]. This =O may further react with the IAA to form a complex (Figure 5) at 534 nm, which would give the product in the next step (Figure 6). This type of product was already reported [19]. The oxygen transfer step is associated with large negative value of entropies of activation and significant enthalpies of activation. The catalytic activity of TPP is significant, and this conversion exhibits fractional order. The order of the reaction varies with the concentration of catalyst [20]. It has value 0.48 for the catalyst concentration of 2–20 × 10−8 mol dm−3 and has value 1.47 for the catalyst concentration of 22–40 × 10−8 mol dm−3 (Table 2). It clearly reveals that the reaction follows different mechanism at low (Scheme 1) and high concentrations of catalyst (Scheme 2). Though the reaction mechanism is different in low and high catalyst concentrations, the final product obtained is similar in low and high catalyst concentrations. This was confirmed by UV-Vis spectra shown in (Figures 6 and 7). In accordance with the above observations and stoichiometry of the reaction, the following reactions are involved to constitute the most probable mechanism of the reaction at low and high concentrations of catalyst (Schemes 1 and 2).

186168.fig.005
Figure 5: UV spectrum showing formation of intermediate complex at 534 nm between IAA and =O.
186168.fig.006
Figure 6: UV spectrum showing the formation of product at 437 nm in low catalyst concentration after the decomposition of intermediate complex at 534 nm.
186168.fig.007
Figure 7: UV spectrum showing the formation of product at 432 nm in high catalyst concentration after the decomposition of intermediate complex at 534 nm.

4. Conclusion

In conclusion, meso-tetraphenylporphyrin iron(III) chloride has been proven to be an excellent catalyst for the oxidation of IAA by oxone. The kinetic and thermodynamic parameters for the TPP catalysed oxidation of IAA by oxone were determined, and the reaction scheme was proposed. The thermodynamic data obtained supported the proposed mechanism.

References

  1. M. Amir, N. Dhar, and S. K. Tiwari, “Synthesis and anti-inflammatory activity of some new indole and indazole derivatives,” Indian Journal of Chemistry B, vol. 36, no. 1, pp. 96–98, 1997. View at Google Scholar
  2. J. Bergman, E. Koch, and B. Pelcman, “Reactions of indole-3-acetic acid derivatives in trifluoroacetic acid,” Tetrahedron Letters, vol. 36, no. 22, pp. 3945–3948, 1995. View at Publisher · View at Google Scholar
  3. A. S. Shyadligiri and G. S. Gadaginamath, “Chemoselectivity of indole dicarboxylates towards hydrazine hydrate : part II—synthesis and antimicrobial activity of (oxadiazolyl/pyrrolyl/triazolyl) phenyl/furylmethoxyindole derivatives,” Indian Journal of Chemistry B, vol. 34, no. 12, pp. 1059–1065, 1995. View at Google Scholar
  4. J. F. Harrod and C. Guerin, “Aqueous ferric chloride as a model for peroxidase in the catalysed autoxidation of indole-3-acetic acid,” Inorganica Chimica Acta, vol. 37, pp. 141–144, 1979. View at Publisher · View at Google Scholar
  5. R. Pressey, “Oxidation of indoleacetic acid by 1,10-phenanthroline—manganese complexes,” Journal of Molecular Catalysis, vol. 70, no. 2, pp. 243–246, 1991. View at Publisher · View at Google Scholar
  6. R. L. Hinman and J. Lang, “Peroxidase-catalyzed oxidation of indole-3-acetic acid,” Biochemistry, vol. 4, no. 1, pp. 144–158, 1965. View at Google Scholar · View at Scopus
  7. J. L. Koch, R. M. Oberlander, I. A. Tamas, J. L. Germain, and D. B. S. Ammondson, “Evidence of singlet oxygen participation in the chlorophyll-sensitized photooxidation of indoleacetic acid,” Plant Physiology, vol. 70, no. 2, pp. 414–417, 1982. View at Publisher · View at Google Scholar
  8. I. G. Gazaryan, T. A. Chubar, E. A. Mareeva, L. M. Lagrimini, R. B. Van Huystee, and R. N. F. Thorneley, “Aerobic oxidation of indole-3-acetic acid catalysed by anionic and cationic peanut peroxidase,” Phytochemistry, vol. 51, no. 2, pp. 175–186, 1999. View at Publisher · View at Google Scholar · View at Scopus
  9. I. G. Gazaryan, L. M. Lagrimini, G. A. Ashby, and R. N. F. Thorneley, “Mechanism of indole-3-acetic acid oxidation by plant peroxidases: anaerobic stopped-flow spectrophotometric studies on horseradish and tobacco peroxidases,” Biochemical Journal, vol. 313, no. 3, pp. 841–847, 1996. View at Google Scholar · View at Scopus
  10. J. Ricard and D. Job, “Reaction mechanisms of indole-3-acetate degradation by peroxidases,” European Journal of Biochemistry, vol. 44, no. 2, pp. 359–374, 1974. View at Publisher · View at Google Scholar
  11. I. G. Gazarian, L. M. Lagrimini, F. A. Mellon, M. J. Naldrett, G. A. Ashby, and R. N. F. Thorneley, “Identification of skatolyl hydroperoxide and its role in the peroxidase-catalysed oxidation of indol-3-yl acetic acid,” Biochemical Journal, vol. 333, part 1, pp. 223–232, 1998. View at Google Scholar · View at Scopus
  12. B. Meunier, “Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage,” Chemical Reviews, vol. 92, no. 6, pp. 1411–1456, 1992. View at Publisher · View at Google Scholar
  13. J. Larsen and K. A. Jorgensen, “A facile oxidation of secondary amines to imines by iodosobenzene or by a terminal oxidant and manganese or iron porphyrins and manganese salen as the catalysts,” Journal of the Chemical Society, Perkin Transactions 2, no. 8, pp. 1213–1217, 1992. View at Publisher · View at Google Scholar
  14. J. T. Groves, T. E. Nemo, and R. S. Myers, “Hydroxylation and epoxidation catalyzed by iron-porphine complexes. Oxygen transfer from iodosylbenzene,” Journal of the American Chemical Society, vol. 101, no. 4, pp. 1032–1033, 1979. View at Publisher · View at Google Scholar
  15. V. Ullrich and H. J. Staudinger, in Biological and chemical aspects of monooxygenases, K. Bloch and O. Hayaishi, Eds., p. 235, Maruzen, Tokyo, Japan, 1966.
  16. R. Ghamen, C. Carmona, M. A. Munoz, P. Guardado, and M. Balon, “Oxidation of 2,3-dimethylindole by peroxophosphates,” Journal of the Chemical Society, Perkin Transactions 2, no. 10, pp. 2197–2202, 1996. View at Publisher · View at Google Scholar
  17. C. Carmona, M. Balon, M. A. Munoz, P. Guardado, and J. Hidalgo, “Kinetics and mechanisms of the oxidation reactions of some 2,3-dialkylindole derivatives by peroxodisulfate and peroxomonosulfate anions,” Journal of the Chemical Society, Perkin Transactions 2, no. 2, pp. 331–335, 1995. View at Publisher · View at Google Scholar
  18. M. Balon, M. Munoz, P. Guardado, J. Hidalgo, and C. Carmona, “Direct evidence on the mechanism of the oxidation of 2,3-dimethylindole by inorganic peroxo anions,” The Journal of Organic Chemistry, vol. 58, no. 26, pp. 7469–7473, 1993. View at Publisher · View at Google Scholar
  19. G. Chandramohan, S. Kalyanasundaram, and R. Renganathan, “Oxidation of indole-3-acetic acid by peroxomonosulphate: a kinetic and mechanistic study,” International Journal of Chemical Kinetics, vol. 34, no. 10, pp. 569–574, 2002. View at Publisher · View at Google Scholar
  20. J. Vohlidal, A. Hollander, M. Jankalkova, J. Sedlacek, and I. Sargankova, “Kinetics and mechanism of the phenylacetylene metathesis polymerization catalyzed with WOCl4/Ph4Sn in benzene,” Collection of Czechoslovak Chemical Communications, vol. 56, no. 2, pp. 351–367, 1991. View at Publisher · View at Google Scholar
  21. K. J. Laidler, Chemical Kinetics, Tata McGraw-Hill, New Delhi, India, 1965.
  22. F. Ruff and A. Kucsman, “Mechanism of the oxidation of sulphides with sodium periodate,” Journal of the Chemical Society, Perkin Transactions 2, no. 5, pp. 683–687, 1985. View at Google Scholar · View at Scopus
  23. S. P. Meenakshisundaram and R. M. Sokalingam, “Nonlinear hammett relationships in the reaction of peroxomonosulfate anion (HOOSO3-) with meta- and para-substituted anilines in alkaline medium,” Collection of Czechoslovak Chemical Communications, vol. 66, no. 6, pp. 897–911, 2001. View at Publisher · View at Google Scholar
  24. S. P. Meenakshisundaram, M. Selvaraju, N. M. Made Gowda, and K. S. Rangappa, “Effect of substituents on the rate of oxidation of anilines with peroxomonosulfate monoanion (HOOSO−3) in aqueous acetonitrile: a mechanistic study,” International Journal of Chemical Kinetics, vol. 37, no. 11, pp. 649–657, 2005. View at Publisher · View at Google Scholar · View at Scopus
  25. M. S. Ramachandran, T. S. Vivekanadam, and V. Arunachalam, “Kinetics of oxidation of carbonyl compounds by peroxomonosulfate. Acetaldehyde, propionaldehyde, and butyraldehyde,” Bulletin of the Chemical Society of Japan, vol. 59, no. 5, pp. 1549–1554, 1986. View at Publisher · View at Google Scholar
  26. C. A. Bunton, H. J. Foroudian, and A. Kumar, “Sulfide oxidation and oxidative hydrolysis of thioesters by peroxymonosulfate ion,” Journal of the Chemical Society, Perkin Transactions 2, no. 1, pp. 33–39, 1995. View at Publisher · View at Google Scholar · View at Scopus
  27. D. M. Davis and M. E. Deary, “A convenient preparation of aqueous methyl hydroperoxide and a comparison of its reactivity towards triacetylethylenediamine with that of other nucleophiles: the mechanism of peroxide bleach activation,” Journal of the Chemical Society, Perkin Transactions 2, no. 4, pp. 559–562, 1992. View at Publisher · View at Google Scholar
  28. J. A. Kerr, “Bond dissociation energies by kinetic methods,” Chemical Reviews, vol. 66, no. 5, pp. 465–500, 1966. View at Publisher · View at Google Scholar
  29. Z. Zhu and J. H. Espenson, “Kinetics and mechanism of oxidation of anilines by hydrogen peroxide as catalyzed by methylrhenium trioxide,” The Journal of Organic Chemistry, vol. 60, no. 5, pp. 1326–1332, 1995. View at Publisher · View at Google Scholar
  30. X. T. Zhou, H. B. Ji, and Q. L. Yuan, “Baeyer-Villiger oxidation of ketones catalyzed by iron(III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen,” Journal of Porphyrins and Phthalocyanines, vol. 12, no. 2, p. 94, 2008. View at Publisher · View at Google Scholar