Novel magnetic nanoparticle acid catalyst for synthesis of a facile, efficient and one-pot tri substituted imidazoles.

Document Type : Original Article


Semnan University


Modified nanomagnetic acid catalyst SiO2/Fe3O4/SO3H was synthesized in simple method and used for synthesizing 2,4,5-tri substituted imidazole by combining three components such as benzil, aldehydes and ammonium acetate of which the last component was as an ammonia source. High yield of tri-substituted imidazole without significant loss of efficiency and easy recovery by an external magnetic field and several times of reusability with less deterioration are advantages of SiO2/Fe3O4/SO3H catalyst. A large amount of acid existing on the surface of the magnetic layer leads to more activities of the catalyst and as a result, the yielding of tri-substituted imidazole increases. The acidic functioned nanomagnetic core-shell catalyst was approved as per Fourier transfer infrared (FT-IR), X-ray diffraction powder (XRD), Energy dispersive X-Ray spectroscopy (EDS), Thermal gravimetric analysis (TGA), Vibrating sample magnetometer (VSM) and transmission electron microscopy (TEM).


Main Subjects

[1] A. Wauquier, W.A.E. Va n Den Broeck, J.L. Verheyen, E. P.A.J. Janssen, Pharmacol, 47 (1978) 367.
[2] R.W. Brimblecombe, W.A.M. Duncan, G.J. Durant, J.C. Emmett, C.R. Ganellin, M.E. Parons, Int. Med. Res., 3 (1975) 86.
[3] J. Heers, L.J.J.B. , J.H. Mostmans, J. Va n Cutsem, Med. Chem, 22 (1979) 1003.
[4] Claiborne CF, Liverton NJ, N. KT, Tetrahedron Lett, 39 (1998) 8939.
[5] Zhang C, Sarshar S, Morgan EJ, Krane S, Rodarte JC, Benbatoul KD, Dixon R, M. AMM, Bioorg Med Chem, 10 (2000) 2603.
[6] Cui B, Zheng BL, He K, Z. QY, Nat prod, 66 (2003) 1101.
[7] Abrahams SL, Hazen RJ, Batson AG, P. AP, Pharmacol Exp Ther, 249 (1989) 359.
[8] Wasserscheid P, K. W, Angew Chem Int Ed Eng, 39 (2000) 37872.
[9] Bourissou D, Guerret O, Ggabbai FT, B. G, Chem Rev 100, (2000).
[10] S. I, Japn Kokkai Tokyo Koho, 117 (1989) 867.
[11] Wang, K.W.Woods, Q. Li, etal., Med.Chem, 45 (2002) 1697.
[12] J. Heeres, L.J.J. Backx, J.H. Mostmans, etal., Med. Chem, 22 (1979) 1003.
[13] R. Schmierer, H. Mildenberger, H. Buerstell, German Patent 361464, Chem. Abstr, 108 (1988) 37838.
[14] T. Maier, R. Schmierer, K. Bauer, e. al, U.S. Patent 4820335, Chem. Abstr, 111 (1989) 19494w.
[15] J.C.Lee, J.T.Laydon, P.C.McDonnell, etal., Nature, 372 (1994) 739.
[16] T. Maier, R. Schmierer, K. Bauer, etal., U.S. Patent 4820335, Chem. Abstr, (1989).
[17] M.Antolini, A.Bozzoli, C.Ghiron, etal., Bioorg.Med.Chem.Lett, 9 (1999) 1023.
[18] B. S, A. A, H. MS, Monatsh Chem, 131 (2000) 945.
[19] K. AR, R. CW, Scriven EFV (eds) Comprehensive Heterocyclic Chemistry II, 3 (1996) 77.
[20] J. FR, R. HH, Chem Ber, 15 (1882) 1268.
[21] R. B, Chem Ber 15 (1882) 1493.
[22] S. H.R., M. Ranjbar, An environmental friendly approach for the synthesis of highly substituted imidazoles using bronsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate, as reusable catalyst., J. Mol. Liq., 160 (2011) 40.
[23] M. B.F, B. A.H, Z. L, One-pot synthesis of 1,2,4,5-tetrasubstituted imidazoles promoted by nano-TiCl4–SiO2, Scientia Iranica, 19 (2012) 565.
[24] S. K.F, S. S.B, K. G.K, S. B.B, S. M.S, Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the one-pot synthesis of 2,4,5triarylimidazoles under microwave irradiation, Green Chem. Lett, 3 (2010) 27.
[25] H. M.M, B. K, O. H.A., S.H. Taheri, Synthesis of 2,4,5-triaryl-imidazoles catalyzed by NiCl4.6H2O under heterogeneous system, Mol. Catal. A: Chem, 263 (2007) 279.
[26] H. Zang, Q. Su, Y. Mo, B.W. Cheng, S. Jun, Ionic liquid [EMIM]OAc under ultrasonic irradiation towards the first synthesis of trisubstituted imidazoles, Ultrason. Sonochem, 17 (2010) 749.
[27] X.B. Wang, L. He, T.Y. Jian, S. Ye, Cyclic phosphoric acid catalyzed one-pot, four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles, Chin. Chem. Lett., 23 (2012) 13.
[28] R.S. Joshi, P.G. Mandhane, M.U. Shaikh, R.P. Kale, C.H. Gill, Potassium dihydrogen phosphate catalyzed one-pot synthesisof 2,4,5-triaryl-1H-imidazoles., Chin. Chem. Lett., 21 (2010) 249.
[29] J.N. Sangshetti, N.D. Kokare, S.A. Kotharkara, D.B. Shinde, Ceric ammonium nitrate catalysed three component one-pot efficient synthesis of 2,4,5-triaryl-1H-imidazoles, Chem. Sci, 120 (2008) 463.
[30] S. Samai, G.C. Nandi, P. Singh, M.S. Singh, l-Proline: an efficient catalyst for the one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles, Tetrahedron Lett, 65 (2009) 10155.
[31] X.C. Wang, H.P. Gong, Z.J. Quan, L. Li, H.L. Ye, PEG-400 as an efficient reaction medium for the synthesis of 2,4,5-triaryl-1Himidazoles and 1,2,4,5-tetraaryl-1H-imidazoles, Chin. Chem. Lett., 20 (2009) 44.
[32] K. M, M. P, Tetrahedron Lett, 47 (2006) 5029.
[33] K. M, M. P, B. V, G. R, Monatsh Chem, 137 (2006) 1189.
[34] N. L, A. S, K. S, Mol Catal, 266 (2007) 104.
[35] Z. EJ, M. EJ, W. TF, S. KM, M. AM, Teterahedron Lett 37 (1996) 351.
[36] D. D, W. M, J. M, Org Chem, 2 (1937) 319.
[37] D. P, G. J, B. R, C. A, D. S, F. M, F. D, H. G, H. B, H. H, K. HW, V. JP, V. JC, W. A, Z. J, Med Chem, 38 (1995) 2357.
[38] W. HH, L. YO, Z. R, P. J, Tetrahedron Lett, 43 (2002) 3351.
[39] U. AY, K. YL, Tetrahedron Lett, 41 (2000) 5031.
[40] A.K. Mohammad Bakherada, Amir H. Amina, Rahele Doostia, Zahra Aghayana, A rapid, easy, and efficient method for synthesis of 4,4'-(arylmethylene)-bis-(1H-pyrazol-5-ols), catalyzed by boehmite nanoparticles, Applied Chemistry, 11 (2017) 31.
[41] B. Sreedhar, P. Radhika, B. Neelima, N. Hebalkar, Mol. Catal. A, 272 (2007) 159.
[42] K. C. BARICK, BAHADUR, Bull. Mater. Sci, 29 (2006) 595.
[43] Muzart, Chromium-catalyzed oxidations i n organic synthesis., Chem. Rev., 92 (1992) 113.
[44] Micro- spherical SnO2/Zn2SnO4: Synthesis, heat treatment and photocatalytic efficiency for decolorization of two dye mixture in wastewater, Journal of Applied Chemistry, 11 (2016) 11.
[45] A rapid, easy, and efficient method for synthesis of 4,4'-(arylmethylene)-bis-(1H-pyrazol-5-ols), catalyzed by boehmite nanoparticles, Journal of Applied Chemistry, 11 (2016) 31.
[46] E.K. Maliheh M. Hosseini, Mitra Vahidian, Reza Bagheri, Nano perlite sulfuric acid: an inexpensive heterogeneous acid catalyst for the synthesis of 1,8-dioxo-octahydroxanthenes and tetrahydrobenzoxanthenes under solvent-free conditions, Applied Chemistry, 11 (2017) 109.
[47] S.S.S. Maryam Shoghi, One-pot three-component synthesis of substituted furan-2-one derivatives using oxalic acid dihydrate as a catalyst, Applied Chemistry, 11 (2016) 99.
[48] M.B. Behruz Maleki, Gavad Baedi, Samane Sedighashrafi, One-pot and facile synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones using nano-NiO under solvent-free conditions, Applied Chemistry, 11 (2016) 107.
[49] Y.-H.W. Li-Min Wang, He Tian, Yin-Fang Yao, Jue-Hua Shao, Bo Liu, Ytterbiu m triflate as an efficient catalyst for one-pot synthesis of substituted imidazoles through three-component condensation of benzil, aldehydes and ammonium acetate, Fluorine Chemistry, 127 (2006) 1570.
[50] B.M. S. Narayana Murthy, Y. V. D. Nageswar, DABCO as a mild and efficient catalytic system for the synthesis of highly substituted imidazoles via multi-component condensation strategy Tetrahedron Letters, 51 (2010) 5252.
[51] P.H. Saikat Das Sharma, Dilip Konwar An efficient and one-pot synthesis of 2,4,5-trisubstituted and
1,2,4,5-tetrasubst ituted imidazoles catalyzed by InCl3 3H2O, Tetrahedron Letters 49 (2008) 2216.