Oxidation of Benzyl Alcohols by Monomeric Iron Phthalocyanine Complexes: Substituents’ Effect on Their Catalytic Performance

Öz

Iron phthalocyanines tetra substituted with either electron-donating n-hexyloxy or electron-withdrawing n-hexylsulfonyl substituents were prepared and tested as oxidation catalysts for benzyl alcohol, 4-bromobenzyl alcohol, 4-methylbenzyl alcohol and 4-tert-butylbenzyl alcohol. Oxidation reactions were performed at room temperature in acetonitrile, acetone, ethanol, toluene, and the best result was obtained in acetonitrile. Oxidation of alcohols using tert-butyl hydroperoxide as an oxidant in the presence of these iron(II) phthalocyanines resulted in the production of corresponding benzaldehyde and benzoic acid. When comparing the substituent effect, the hexylsulfonyl electron-withdrawing substituted phthalocyanine complex exhibited better catalytic performance in acetonitrile for all benzylic alcohol derivatives. It showed that electron-withdrawing substituted iron(II) phthalocyanine tends to produce benzaldehydes, while electron-donating substituted iron(II) phthalocyanine produced benzoic acid. This kind of catalytic system is suitable for the oxidation of benzylic alcohols to produce benzaldehyde and benzoic acid derivatives.

Anahtar Kelimeler

• Oxidation
• Benzyl alcohol
• Iron phthalocyanine
• Catalyst

Etik Beyan

There are no ethical issues after the publication of this manuscript.

Kaynakça

1. [1]. Mamedov, E, Corberán, VC. 1995. Oxidative dehydrogenation of lower alkanes on vanadium oxide-based catalysts. The present state of the art and outlooks. Applied Catalysis A: General; 127(1-2): 1-40.
2. [2]. Ahmad, JU, Räisänen, MT, Leskelä, M, Repo, T. 2012. Copper catalyzed oxidation of benzylic alcohols in water with H2O2. Applied Catalysis A: General; 411: 180-7.
3. [3]. Kheirjou, S, Kheirjou, R, Rezayan, AH, Shakourian-Fard, M, Hashemi, MM. 2016. Selective aqueous oxidation of alcohols catalyzed by copper (II) phthalocyanine nanoparticles. Comptes Rendus Chimie; 19(3): 314-9.
4. [4]. Stanje, B, Traar, P, Schachner, J, Belaj, F, Mösch-Zanetti, N. 2018. Iron catalyzed oxidation of benzylic alcohols to benzoic acids. Dalton Transactions; 47(18): 6412-20.
5. [5]. Namboodiri, VV, Polshettiwar, V, Varma, RS. 2007. Expeditious oxidation of alcohols to carbonyl compounds using iron (III) nitrate. Tetrahedron Letters; 48(50): 8839-42.
6. [6]. Yu, Y, Lu, B, Wang, X, Zhao, J, Wang, X, Cai, Q. 2010. Highly selective oxidation of benzyl alcohol to benzaldehyde with hydrogen peroxide by biphasic catalysis. Chemical Engineering Journal; 162(2): 738-42.
7. [7]. Zhao, Y, Yu, C, Wu, S, Zhang, W, Xue, W, Zeng, Z. 2018. Synthesis of benzaldehyde and benzoic acid by selective oxidation of benzyl alcohol with iron (III) tosylate and hydrogen peroxide: a solvent-controlled reaction. Catalysis Letters; 148: 3082-92.
8. [8]. Li, Z, Xu, S, Chen, Z, Zhang, F. 2014. Photophysical and nonlinear optical properties of an azobenzene substituted zinc phthalocyanine. Optik; 125(15): 3833-6.

9. [9]. Dahlen, MA. 1939. The phthalocyanines a new class of synthetic pigments and dyes. Industrial & Engineering Chemistry; 31(7): 839-47.
10. [10]. Lo, P-C, Rodríguez-Morgade, MS, Pandey, RK, Ng, DK, Torres, T, Dumoulin, F. 2020. The unique features and promises of phthalocyanines as advanced photosensitisers for photodynamic therapy of cancer. Chemical Society Reviews; 49(4): 1041-56.
11. [11]. Şahin, Z, Meunier-Prest, R, Dumoulin, F, Kumar, A, Isci, Ü, Bouvet, M. 2021. Tuning of organic heterojunction conductivity by the substituents’ electronic effects in phthalocyanines for ambipolar gas sensors. Sensors and Actuators B: Chemical; 332: 129505.
12. [12]. Sahin, Z, Meunier-Prest, R, Dumoulin, F, Isci, U, Bouvet, M. 2020. Alkylthio-tetrasubstituted μ-nitrido diiron phthalocyanines: spectroelectrochemistry, electrical properties, and heterojunctions for ammonia sensing. Inorganic Chemistry; 59(2): 1057-67.
13. [13]. Qiu, S, Li, Y, Xu, H, Liang, Q, Zhou, M, Rong, J, Li, Z, Xu, S. 2022. Efficient catalytic oxidation of benzyl alcohol by tetrasubstituted cobalt phthalocyanine-MWCNTs composites. Solid State Sciences; 129: 106905.
14. [14]. Sorokin, AB. 2013. Phthalocyanine metal complexes in catalysis. Chemical reviews; 113(10): 8152-91.
15. [15]. Safari, N, Bahadoran, F. 2001. Cytochrome P-450 model reactions: a kinetic study of epoxidation of alkenes by iron phthalocyanine. Journal of Molecular Catalysis A: Chemical; 171(1-2): 115-21.
16. [16]. Sorokin, A, Kudrik, E. 2011. Phthalocyanine metal complexes: versatile catalysts for selective oxidation and bleaching. Catalysis Today; 159(1): 37-46
17. [17]. Yüceel, Ç, Şahin, Z, İşci, Ü. 2022. Substituent effect on iron phthalocyanines as cyclohexene oxidation catalysts. Journal of Porphyrins and Phthalocyanines; 26(06n07): 452-7.
18. [18]. Ravikanth, M, Achim, C, Tyhonas, JS, Münck, E, Lindsey, JS. 1997. Investigation of phthalocyanine catalysts for the aerobic synthesis of meso-substituted porphyrins. Journal of Porphyrins and Phthalocyanines; 1(04): 385-94.
19. [19]. İşci, Ü, Afanasiev, P, Millet, J-MM, Kudrik, EV, Ahsen, V, Sorokin, AB. 2009. Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation. Dalton Transactions; (36): 7410-20.
20. [20]. Şahin, Z, Yüceel, Ç, Yildiz, DB, Dede, Y, Dumoulin, F, İşci, Ü. 2024. Phthalocyanine vs porphyrin: Experimental and theoretical comparison of the catalytic activity of N-bridged diiron tetrapyrrolic complexes for alcohols oxidation. Molecular Catalysis; 559: 113986.
21. [21]. Cakır, V, Saka, ET, Bıyıklıoğlu, Z, Kantekin, H. 2014. Highly selective oxidation of benzyl alcohol catalyzed by new peripherally tetra-substituted Fe (II) and Co (II) phthalocyanines. Synthetic metals; 197: 233-9.
22. [22]. Aktaş, A, Acar, I, Saka, ET, Biyiklioglu, Z. 2016. Synthesis of polyfluoro substituted Co (II), Fe (II) phthalocyanines and their usage as catalysts for aerobic oxidation of benzyl alcohol. Journal of Organometallic Chemistry; 815: 1-7.
23. [23]. Aktaş, A, Acar, I, Saka, ET, Biyiklioglu, Z, Kantekin, H. 2016. Fluoro functional groups substituted cobalt (II), iron (II) phthalocyanines and their catalytic properties on benzyl alcohol oxidation. Journal of Inclusion Phenomena and Macrocyclic Chemistry; 86: 183-90.
24. [24]. Azimi, F, Poursattar Marjani, A, Keshipour, S. 2021. Fe (II)-phthalocyanine supported on chitosan aerogel as a catalyst for oxidation of alcohols and alkyl arenes. Scientific Reports; 11(1): 23769.