Chitosan supported bimetallic Pd/Co nanoparticles as a heterogeneous catalyst for the reduction of nitroaromatics to amines

Document Type : Research Paper

Authors

Department of Nanochemistry, Nanotechnology Research Centre, Urmia University, Urmia, Iran

Abstract

A new bimetallic nanocomposite of chitosan was prepared. Pd and Co nanoparticles were deposited on chitosan to produce a new heterogeneous recyclable catalyst for use in the bimetallic catalytic reduction reaction. The catalyst was characterized with common analysis methods for nanocomposites including Energy Dispersive X-Ray Spectroscopy, X-Ray Diffraction pattern, Thermal Gravimetric Analysis, Flame Atomic Absorption Spectroscopy and Scanning Electron Microscopy, and applied in the reduction reaction of nitroaromatics using NaBH4 at room temperature. The bimetallic system gave good results compared to each of the applied metals. Various aromatic amines and diamines were used in the reduction reaction. The aromatic amines were obtained as the sole product of the reduction reaction with 15 mol% Pd and 12 mol% Co during 2h. This reaction had some advantages such as mild reaction conditions, high yield, green solvent, and a recyclable catalyst. Also, the recovered catalyst was applicable in the reduction reaction without a significant decrease in the activity for up to six times.

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Main Subjects


[1] Chandrappa, S., Vinaya, K., Ramakrishnappa, T.,Rangappa, K. S. (2010). An efficient method for aryl nitro reduction and cleavage of azo compounds using iron powder/calcium chloride. Synlett, 2010(20), 3019-3022.
[2] Kelly, S. M., Lipshutz, B. H. (2013). Chemoselectivereductions of nitroaromatics in water at room temperature.Organic letters, 16(1), 98-101.
[3] Wienhöfer, G., Sorribes, I., Boddien, A., Westerhaus, F., Junge, K., Junge, H., Beller, M. (2011). General and selective iron-catalyzed transfer hydrogenation of nitroarenes without base Journal of the American chemical society, 133(32), 12875-12879.
[4] Yuste, F., Saldaña, M., Walls, F. (1982). Selective reduction of aromatic nitro compounds containing Oand
N-benzyl groups with hydrazine and raney nickel. Tetrahedron letters, 23(2), 147-148.
[5] Ram, S., Ehrenkaufer, R. E. (1984). A general procedure for mild and rapid reduction of aliphatic and aromatic
nitro compounds using ammonium formate as a catalytic hydrogen transfer agent. Tetrahedron letters, 25(32), 3415-3418.
[6] Di Gioia, M. L., Leggio, A., Le Pera, A., Liguori, A., Napoli, A., Perri, F., Siciliano, C. (2005). Determination by gas
chromatography/mass spectrometry of pphenylenediamine in hair dyes after conversion to an imine derivative. Journal of chromatography A, 1066(1), 143-148.
[7] Larock, R. C. (1989). Comprehensive organic transformations, VCH Publishers Inc., New York.
[8] Kabalka, G. W., Varma, R. S. (1991). Reduction of nitro and nitroso compounds. Comprehensive organic synthesis, 8, 363-379.
[9] Sudarjanto, G., Keller-Lehmann, B., Keller, J. (2006). Optimization of integrated chemical–biological degradation of a reactive azo dye using response surface methodology. Journal of hazardous materials, 138(1), 160-168.
[10] Gowda, S., Abiraj, K., Gowda, D. C. (2002). Reductive cleavage of azo compounds catalyzed by commercial
zinc dust using ammonium formate or formic acid. Tetrahedron letters, 43(7), 1329-1331.
[11] Kumará Verma, P. (2012). Zinc phthalocyanine with PEG-400 as a recyclable catalytic system for selective reduction of aromatic nitro compounds. Green chemistry, 14(8), 2289-2293.
[12] Sharma, U., Kumar, P., Kumar, N., Kumar, V., Singh, B. (2010). Highly chemo‐and regioselective reduction of
aromatic Nitro compounds catalyzed by recyclable S. Keshipour et al. Copper (II) as well as Cobalt (II) phthalocyanines. Advanced synthesis and catalysis, 352(11‐12), 1834-1840.
[13] Stiles, M., Finkbeiner, H. L. (1959). Chelation as a driving force in synthesis. A new route to α-nitro acids and α-amino acids. Journal of the American chemical society, 81(2), 505-506.
[14] Suchy, M., Winternitz, P., Zeller, M. (1991). Heterocyclic compounds, U.S. Patent, US5266554A.
[15] Junge, K., Wendt, B., Shaikh, N., Beller, M. (2010). Iron-catalyzed selective reduction of nitroarenes to anilines using organosilanes. Chemical communications, 46(10), 1769-1771.
[16] Downing, R. S., Kunkeler, P. J., Van Bekkum, H. (1997). Catalytic syntheses of aromatic amines. Catalysis today, 37(2), 121-136.
[17] Corma, A., Serna, P., Concepción, P., Calvino, J. J. (2008). Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics. Journal of the American chemical society, 130(27), 8748-8753.
[18] Blaser, H. U., Steiner, H., Studer, M. (2009). Selective catalytic hydrogenation of functionalized nitroarenes: an update. ChemCatChem, 1(2), 210-221
[19] Burke, S. D., Danheiser, R. L. (Eds.). (1999). Oxidizing and reducing agents. Chichester: Wiley.
[20] Satoh, T., Suzuki, S., Suzuki, Y., Miyaji, Y., Imai, Z. (1969). Reduction of organic compounds with sodium borohydride-transition metal salt systems: Reduction of organic nitrile, nitro and amide compounds to primary amines. Tetrahedronletters, 10(52), 4555-4558.
[21] Yoo, S. E., Lee, S. H. (1990). Reduction of organic compounds with sodium borohydride-copper (II) sulfate system. Synlett, 1990(07), 419-420.
[22] Wu, F., Qiu, L. G., Ke, F., Jiang, X. (2013). Copper nanoparticles embedded in metal–organic framework MIL-101 (Cr) as a high performance catalyst for reduction of aromatic nitro compounds. Inorganic chemistry communications, 32, 5-8.
[23] Guo, F., Ni, Y., Ma, Y., Xiang, N., Liu, C. (2014). Flowerlike Bi 2 S 3 microspheres: facile synthesis and application in the catalytic reduction of 4-nitroaniline. New journal of chemistry, 38(11), 5324-5330.
[24] Osby, J. O., Ganem, B. (1985). Rapid and efficient reduction of aliphatic nitro compounds to amines. Tetrahedron letters, 26(52), 6413-6416.
[25] Németh, J., Kiss, Á., Hell, Z. (2013). Palladium-catalysed transfer hydrogenation of aromatic nitro compounds—an unusual chain elongation. Tetrahedron letters, 54(45), 6094-6096.
[26] Obraztsova, I. I., Eremenko, N. K., Simenyuk, G. Y., Eremenko, A. N., Tryasunov, B. G. (2012). Bimetallic catalysts for the hydrogenation of aromatic nitro compounds. Solid fuel chemistry, 46(6), 364-367.
[27] Thatte, C. S., Rathnam, M. V., Pise, A. C. (2014). Chitosan-based Schiff base-metal complexes (Mn, Cu, Co) as heterogeneous, new catalysts for the β-isophorone oxidation. Journal of chemical sciences, 126(3), 727-737.
[28] Shaabani, A., Boroujeni, M. B., Sangachin, M. H. (2015). Cobalt-chitosan: Magnetic and biodegradable heterogeneous catalyst for selective aerobic oxidation of alkyl arenes and alcohols. Journal of chemical sciences, 127(11), 1927-1935.
[29] Keshipour, S., Shojaei, S., Shaabani, A. (2013). Palladium nano-particles supported on ethylenediamine-functionalized cellulose as a novel and efficient catalyst for the Heck and Sonogashira couplings in water. Cellulose, 20(2), 973-980.
[30] Shaabani, A., Keshipour, S., Hamidzad, M., Seyyedhamzeh, M. (2014). Cobalt (II) supported on ethylenediamine-functionalized nanocellulose as an efficient catalyst for room temperature aerobic oxidation of alcohols. Journal of chemical sciences, 126(1), 111-115.
[31] Keshipour, S., Shaabani, A. (2014). Copper (I) and palladium nanoparticles supported on ethylenediamine‐functionalized cellulose as an efficient catalyst for the 1, 3‐dipolar cycloaddition/direct arylation sequence. Applied organometallic chemistry, 2(28), 116-119.
[32] Keshipour, S., KalamKhalteh, N. (2016). Oxidation of ethylbenzene to styrene oxide in the presence of cellulose‐supported Pd magnetic nanoparticles. Applied organometallic chemistry, 30(8), 653-656.
[33] Shaabani, A., Keshipour, S., Hamidzad, M., Shaabani, S. (2014). Cobalt (II) phthalocyanine covalently anchored to cellulose as a recoverable and efficient catalyst for the aerobic oxidation of alkyl arenes and alcohols. Journal of molecular catalysis A: Chemical, 395, 494-499.
[34] Keshipour, S., Adak, K. (2016). Pd (0) supported on N-doped graphene quantum dot modified cellulose as an efficient catalyst for the green reduction of nitroaromatics. RSC advances, 6(92), 89407-89412.
[35] El-Hout, S. I., El-Sheikh, S. M., Hassan, H. M., Harraz, F. A., Ibrahim, I. A., El-Sharkawy, E. A. (2015). A green chemical route for synthesis of graphene supported palladium nanoparticles: A highly active and recyclable catalyst for reduction of nitrobenzene. Applied catalysis A: General, 503, 176-185.
[36] Piña, S., Cedillo, D. M., Tamez, C., Izquierdo, N., Parsons, J. G., Gutierrez, J. J. (2014). Reduction of nitrobenzene derivatives using sodium borohydride and transition metal sulfides. Tetrahedron letters, 55(40), 5468-5470.
[37] Pogorelić, I., Filipan-Litvić, M., Merkaš, S., Ljubić, G., Cepanec, I., Litvić, M. (2007). Rapid, efficient and selective reduction of aromatic nitro compounds with sodium borohydride and Raney nickel. Journal of molecular catalysis A: Chemical, 274(1), 202-207.
[38] Setamdideh, D., Khezri, B., Mollapour, M. (2011). Convenient reduction of nitro compounds to their corresponding Amines with promotion of NaBH4/Ni(OAc)2.4H2O system in wet CH3CN. Oriental journal of chemistry, 27(3), 991-996.