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2,6-Di-tert-Bütilfenolün Çeşitli Oksidantlarla [5,10,15,20 Tetrakis(4 karboksifenil)porfirinato]kobalt(II) Katalizörlüğünde Oksidasyonu

Bu çalışmada 2,6-di-tert-bütilfenolün (DTBP) çeşitli oksidantlarla [5,10,15,20-tetrakis(4-karboksifenil)porfirinato]kobalt(II) ([CoTCPP]) tarafından katalizlenen oksidasyonu araştırılmıştır. Oksidant olarak potasyum peroksimonosülfat (okzon), tert-bütilhidroperoksit (ButOOH) veya hidrojen peroksit (H2O2) kullanılmış ve reaksiyonlar hacimce %10-15 su içeren metanol çözeltilerinde oda sıcaklığında yürütülmüştür. Oksidasyona substrat, katalizör ve oksidant derişimlerinin etkileri incelenmiştir. Reaksiyon ürünleri gaz kromatografisi-kütle spektrometresiyle (GC-MS) belirlenmiş ve ürünlerin ve reaksiyona girmemiş DTBP miktarları gaz kromatografisi (GC) ile elde edilen kromatogramlardaki pik alanlarından belirlenmiştir. DTBP oksidasyonunda oksidant olarak okzon ve ButOOH kullanıldığında [CoTCPP] katalitik aktivite göstermiştir. H2O2 varlığında ise [CoTCPP] katalitik aktivite göstermemiştir.

Anahtar Kelimeler:

tetrakis(4-karboksifenil)porfirinato, kobalt(II), 2, 6-Di-tert-bütilfenol, Oksidasyon

Oxidation of 2,6-Di-tert-Butylphenol Catalyzed by [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]cobalt(II) in the Presence of Various Oxidants

In this study, the oxidation of 2,6-di-tert-butylphenol (DTBP) catalyzed by [5,10,15,20-tetrakis(4-carboxylphenyl)porphyrinato]cobalt(II) ([CoTCPP]) in the presence of various oxidants has been investigated. Potassium peroxymonosulfate (Oxone), tert-butylhydroperoxide (ButOOH) or hydrogen peroxide (H2O2) were used as oxidants and the reactions were carried out in 10-15% (v:v) of water-methanol solutions at room temperature. The effects of the concentration of the substrate, catalyst and oxidant on the outcome of the reactions were investigated. The products of the reaction mixtures were identified using GC-MS and the amounts of the products and unreacted DTBP were determined from the peak areas on GC chromatograms. [CoTCPP] showed catalytic activity in the oxidation of DTBP when Oxone or ButOOH was used as oxidant. No catalytic activity of [CoTCPP] was observed when the oxidant was H2O2.

Keywords:

Oxidation, [tetrakis(4-carboxyphenyl)porphyrinato, cobalt(II), 2, 6-Di-tert-butylphenol,

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[1] X. Y. Wang, R. J. Motekaitis, and A. E. Martell, "Metallotetraphenylporphyrin-catalyzed oxidation of 2,6-di-tert-butylphenol," Inorg. Chem., vol. 23, pp. 271-275, 1984.
[2] M. T. Hassanein, S. S. Gerges, M. A. Abdo, and S. H. El-Khalafy, "Studies on the oxidation of 2,6-di-tert-butylphenol by molecular oxygen catalyzed by cobalt(II) tetraarylporphyrins bound to cationic latex," J. Porphyr. Phthalocya., vol. 09, pp. 621-625, 2005.
[3] B. Meunier, "Metalloporphyrin-catalysed oxygenation of hydrocarbons," Bull. Soc. Chim. Fr., pp. 578-594, 1986.
[4] F. P. Guengerich and T. L. Macdonald, "Chemical mechanisms of catalysis by cytochromes P-450: a unified view," Acc. Chem. Res., vol. 17, pp. 9-16, 1984.
[5] W. Sokol, “Uptake rate of phenol by pseudomonos putida grown in unsteady state” Biotech. Bioeng., vol. 32, 1097-1103, 1988.
[6] F. Cavani, G. Centi, S. Perathoner, and F. Trifirò, Sustainable Industrial Chemistry: Principles, Tools and Industrial Examples: John Wiley & Sons, 2009.
[7] R. A. Sheldon, I. Arends, and U. Hanefeld, Green chemistry and catalysis: John Wiley & Sons, 2007.
[8] E. I. Solomon, U. M. Sundaram, and T. E. Machonkin, "Multicopper oxidases and oxygenases," Chem. Rev., vol. 96, pp. 2563-2606, 1996.
[9] N. Kitajima and Y. Moro-oka, "Copper-Dioxygen Complexes. Inorganic and Bioinorganic Perspectives," Chem. Rev., vol. 94, pp. 737-757, 1994.
[10] R. Bernini, E. Mincione, M. Barontini, G. Fabrizi, M. Pasqualetti, and S. Tempesta, "Convenient oxidation of alkylated phenols and methoxytoluenes to antifungal 1, 4-benzoquinones with hydrogen peroxide (H2O 2)/methyltrioxorhenium (CH3ReO3) catalytic system in neutral ionic liquid," Tetrahedron, vol. 62, pp. 7733-7737, 2006.
[11] A. Pui and J.-P. Mahy, "Synthesis, characterization and catalytic activity of halo-methyl-bis(salicylaldehyde)ethylenediamine cobalt(II) complexes," Polyhedron, vol. 26, pp. 3143-3152, 2007.
[12] A. Pui, I. Berdan, I. Morgenstern-Badarau, A. Gref, and M. Perrée-Fauvet, "Electrochemical and spectroscopic characterization of new cobalt(II) complexes. Catalytic activity in oxidation reactions by molecular oxygen," Inorg. Chim. Acta, vol. 320, pp. 167-171, 2001.
[13] J. J. Bozell, J. O. Hoberg, and D. R. Dimmel, "Catalytic oxidation of para-substituted phenols with nitrogen dioxide and oxygen," Tetrahedron Lett., vol. 39, pp. 2261-2264, 1998.
[14] M. Hassanein, M. Sakaran, and S. Shendy, "Oxidation of 2,6-Di-tert-butylphenol by dioxygen catalyzed by tetrasodium phthalocyaninatocobalt(II) tetrasulfonate in aqueous micellar media," J. Iran. Chem. Soc., vol. 7, pp. 128-133, 2010.
[15] H. Türk and Y. Çimen, "Oxidation of 2,6-di-tert-butylphenol with tert-butylhydroperoxide catalyzed by cobalt(II) phthalocyanine tetrasulfonate in a methanol–water mixture and formation of an unusual product 4,4′-dihydroxy-3,3′,5,5′-tetra-tert-butylbiphenyl," J.Mol. Catal. A: Chem., vol. 234, pp. 19-24, 2005.
[16] Y. Çimen and H. Türk, "Oxidation of 2,6-di-tert-butylphenol with tert-butyl hydroperoxide catalyzed by iron phthalocyanine tetrasulfonate in a methanol–water mixture," J. Mol. Catal. A: Chem., vol. 265, pp. 237-243, 2007.
[17] H. Turk and W. T. Ford, "Autoxidation of 2, 6-di-tert-butylphenol in water catalyzed by cobalt phthalocyaninetetrasulfonate bound to polymer colloids," J. Org. Chem., vol. 53, pp. 460-462, 1988.
[18 W. T. Ford, R. Chandran, and H. Turk, "Catalysts supported on polymer colloids," Pure App. Chem., vol. 60, pp. 395-400, 1988.
[19] X. Y. Wang, R. J. Motekaitis, and A. E. Martell, "Metallotetraphenylporphyrin-catalyzed oxidation of 2, 6-di-tert-butylphenol," Inorg. Chem., vol. 23, pp. 271-275, 1984.
[20] F. R. Longo, M. G. Finarelli, and J. B. Kim, "The synthesis and some physical properties of ms-tetra(pentafluorophenyl)-porphin and ms-tetra(pentachlorophenyl)porphin," J. Heterocyc. Chem., vol. 6, pp. 927-931, 1969.
[21] R. F. Pasternack, L. Francesconi, D. Raff, and E. Spiro, "Aggregation of nickel(II), copper(II), and zinc(II) derivatives of water-soluble porphyrins," Inorg. Chem., vol. 12, pp. 2606-2611, 1973.