Abstract
An operationally simple method for synthesis of benzimidazole and 3H-imidazo[4,5-c]pyridine from o-phenylenediamine or pyridine-3, 4-diamine and N,N-dimethylformamide (DMF) in the presence of hexamethyldisilazane (HMDS) as a reagent is described. To evaluate the scope of application of this reagent, it was also used to prepare benzothiazole, 1H-perimidine, and benzoxazole, which was successful for benzothiazole and 1H-perimidine but benzoxazole was not formed. This reaction complies with the principles of green chemistry as it does not use toxic solvents, transition metals, or strong acids. The products are obtained in moderate to excellent yields.
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References
Alaqeel SI (2017) Synthetic approaches to benzimidazoles from o-phenylenediamine: a literature review. J Saudi Chem Soc 21:229–237. https://doi.org/10.1016/j.jscs.2016.08.001
Austen SC, Kane JM (2001) A short synthesis of the parp inhibitor 2-(4-trifluoro-methylphenyl) benzimidazole-4-carboxamide (NU1077). J Heterocycl Chem 38:979–980. https://doi.org/10.1002/jhet.5570380427
Bansal Y, Silakari O (2012) The therapeutic journey of benzimidazoles: a review. Bioorgan Med Chem 20:6208–6236. https://doi.org/10.1016/j.bmc.2012.09.013
Bhatnagar I, George M (1968) Oxidation with metal oxides—II: oxidation of chalcone phenylhydrazones, pyrazolines, o-aminobenzylidine anils and o-hydroxy benzylidine anils with manganese dioxide. Tetrahedron 24:1293–1298. https://doi.org/10.1016/0040-4020(68)88080-9
Ding S, Jiao N (2012) N,N-Dimethylformamide: a multipurpose building block. Angew Chem Int Ed 51:9226–9237. https://doi.org/10.1002/anie.201200859
Gadekar LS, Arbad BR, Lande MK (2010) Eco-friendly synthesis of benzimidazole derivatives using solid acid scolecite catalyst. Chin Chem Lett 21:1053–1056. https://doi.org/10.1016/j.cclet.2010.03.038
Gao X, Yu B, Mei Q, Yang Z, Zhao Y, Zhang H, Liu Z (2016) Atmospheric CO2 promoted synthesis of N-containing heterocycles over B (C 6 F 5) 3 catalyst. New J Chem 40:8282–8287. https://doi.org/10.1039/C6NJ01721E
Grigorjeva L, Liepinsh E, Razafimahefa S, Yahorau A, Yahorava S, Rasoanaivo P, Wikberg JE (2014) Semisynthesis of libiguin a and its analogues by trans-lactonization of phragmalin. J Org Chem 79:4148–4153. https://doi.org/10.1021/jo500318w
Iemura R, Kawashima T, Fukuda T, Ito K, Tsukamoto G (1987) Synthesis of benzimidazole derivatives as potential H1-antihistaminic agents. J Heterocycl Chem 24:31–37. https://doi.org/10.1002/jhet.5570240107
Iwahi T, Satoh H, Nakao M, Iwasaki T, Yamazaki T, Kubo K, Imada A (1991) Lansoprazole, a novel benzimidazole proton pump inhibitor, and its related compounds have selective activity against Helicobacter pylori. Antimicrob Agents Chemother 35:490–496. https://doi.org/10.1128/AAC.35.3.490
Kattimani PP, Kamble RR, Meti GY (2015) Expedient synthesis of benzimidazoles using amides. RSC Adv 5:29447–29455. https://doi.org/10.1039/C5RA00021A
Ke Y, Zhi X, Yu X, Ding G, Yang C, Xu H (2014) Combinatorial synthesis of benzimidazole-azo-phenol derivatives as antifungal agents. Comb Chem High. https://doi.org/10.2174/13862073113166660058
Kidwai M, Jahan A, Bhatnagar D (2010) Polyethylene glycol: a recyclable solvent system for the synthesis of benzimidazole derivatives using CAN as catalyst. J Chem Sci 122:607–612. https://doi.org/10.1007/s12039-010-0095-7
Liu J, Guo C, Zhang Z, Jiang T, Liu H, Song J, Han B (2010) Synthesis of dimethylformamide from CO2, H2 and dimethylamine over Cu/ZnO. Chem Commun 46:5770–5772. https://doi.org/10.1039/C0CC00751J
Mahajan T, Dhimant K, Kapse G, Hugar M (2013) ZnCl2-SiO2 catalyzed solvent free synthesis of benzimidazole derivatives under microwave irradiation. J Appl Chem 2:50–54
Maryanoff BE, Ho W, McComsey DF, Reitz AB, Grous PP, Nortey SO, Gardocki JF (1995) Potential anxiolytic agents. Pyrido [1, 2-a] benzimidazoles: a new structural class of ligands for the benzodiazepine binding site on GABA-A receptors. J Med Chem 38:16–20
Menteşe E, Bektaş H, Ülker S, Bekircan O, Kahveci B (2014) Microwave-assisted synthesis of new benzimidazole derivatives with lipase inhibition activity. J Enzyme Inhib Med Chem 29:64–68. https://doi.org/10.3109/14756366.2012.753880
Nagawade RR, Shinde DB (2006) BF3· OEt2 promoted solvent-free synthesis of benzimidazole derivatives. Chin Chem Lett 17:453–456
Nakano H, Inoue T, Kawasaki N, Miyataka H, Matsumoto H, Taguchi T, Satoh T (1999) Synthesis of benzimidazole derivatives as antiallergic agents with 5-lipoxygenase inhibiting action. Chem Pharm Bull 47:1573–1578
Nale DB, Bhanage BM (2015) N-substituted formamides as C1-sources for the synthesis of benzimidazole and benzothiazole derivatives by using zinc catalysts. Synlett 26:2835–2842. https://doi.org/10.1055/s-0035-1560319
Ruiz VR, Corma A, Sabater MJ (2010) New route for the synthesis of benzimidazoles by a one-pot multistep process with mono and bifunctional solid catalysts. Tetrahedron 66:730–735. https://doi.org/10.1248/cpb.47.1573
Ryabukhin SV, Plaskon AS, Volochnyuk DM, Tolmachev AA (2006) Synthesis of fused imidazoles and benzothiazoles from (hetero) aromatic ortho-diamines or ortho-aminothiophenol and aldehydes promoted by chlorotrimethylsilane. Synthesis 2006:3715–3726. https://doi.org/10.1055/s-2006-950289
Sajjadifar S, Mirshokraie SA, Javaherneshan N, Louie O (2012) SBSA as a new and efficient catalyst for the one-pot green synthesis of benzimidazole derivatives at room temperature. AJOC 2:1–6. https://doi.org/10.5923/j.ajoc.20120202.01
Sammaiah B, Sumalatha D, Reddy GS, Rajeswari M, Sharada L (2012) Cadmium chloride (CdCl2): a mild and efficient catalyst for the synthesis of benzimidazoles. IJIC 3:11. https://doi.org/10.5923/j.ajoc.20120202.01
Shaikh KA, Patil VA (2012) An efficient solvent-free synthesis of imidazolines and benzimidazoles using K4 [Fe(CN)6] catalysis. Org Commun 5:12–17
Sharghi H, Asemani O, Khalifeh R (2008a) New one-pot procedure for the synthesis of 2-substituted benzimidazoles. Synth Commun 38:1128–1136. https://doi.org/10.1080/00397910701863657
Sharghi H, Asemani O, Tabaei SMH (2008b) Simple and mild procedures for synthesis of benzimidazole derivatives using heterogeneous catalyst systems. J Heterocycl Chem 45:1293–1298. https://doi.org/10.1002/jhet.5570450506
Sharghi H, Hosseini-Sarvari M, Moeini F (2008c) Copper-catalyzed one-pot synthesis of benzimidazole derivatives. Can J Chem 86:1044–1051. https://doi.org/10.1139/v08-153
Siddiqui N, Andalip SB, Ali R, Afzal O, Akhtar MJ, Azad B, Kumar R (2011) Antidepressant potential of nitrogen-containing heterocyclic moieties: an updated review. J Pharm Bioallied Sci 3:194–212. https://doi.org/10.4103/0975-7406.80765
Sondhi SM, Singh N, Kumar A, Lozach O, Meijer L (2006) Synthesis, anti-inflammatory, analgesic and kinase (CDK-1, CDK-5 and GSK-3) inhibition activity evaluation of benzimidazole/benzoxazole derivatives and some Schiff’s bases. Bioorgan Med Chem 14:3758–3765. https://doi.org/10.1016/j.bmc.2006.01.054
Srinivasulu R, Kumar KR, Satyanarayana PVV (2014) Facile and efficient method for synthesis of benzimidazole derivatives catalyzed by zinc triflate. GSC 4:33
Tonelli M, Novelli F, Tasso B, Vazzana I, Sparatore A, Boido V, Giliberti G (2014) Antiviral activity of benzimidazole derivatives. III. Novel anti-CVB-5, anti-RSV and anti-Sb-1 agents. Bioorgan Med Chem 22:4893–4909. https://doi.org/10.1016/j.bmc.2014.06.043
Tong Y, Bouska JJ, Ellis PA, Johnson EF, Leverson J, Liu X, Przytulinska M (2009) Synthesis and evaluation of a new generation of orally efficacious benzimidazole-based poly (ADP-ribose) polymerase-1 (PARP-1) inhibitors as anticancer agents. J Med Chem 52:6803–6813. https://doi.org/10.1021/jm900697r
Trivedi R, De SK, Gibbs RA (2006) A convenient one-pot synthesis of 2-substituted benzimidazoles. J Mol Catal Chem 245:8–11. https://doi.org/10.1016/j.molcata.2005.09.025
Venkateswarlu Y, Kumar SR, Leelavathi P (2013) Facile and efficient one-pot synthesis of benzimidazoles using lanthanum chloride. Org Med Chem Lett 3:3–7. https://doi.org/10.1186/2191-2858-3-7
Yang X, Zhang S, Qiu Z, Tian G, Feng Y, Xiao FS (2004) Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media. J Phys Chem B 108:4696–4700. https://doi.org/10.1021/jp0380226
Yang XY, Chen LH, Li Y, Rooke JC, Sanchez C, Su BL (2017) Hierarchically porous materials: synthesis strategies and structure design. Chem Soc Rev 46:481–558. https://doi.org/10.1039/C6CS00829A
Zhu J, Zhang Z, Miao C, Liu W, Sun W (2017) Synthesis of benzimidazoles from o-phenylenediamines and DMF derivatives in the presence of PhSiH 3. Tetrahedron 73:3458–3462. https://doi.org/10.1016/j.tet.2017.05.018
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We are grateful to the Shahid Bahonar University of Kerman for the financial of this research.
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Mostafavi, H., Islami, M.R., Ghonchepour, E. et al. Synthesis of 1H-1,3-benzimidazoles, benzothiazoles and 3H-imidazo[4,5-c]pyridine using DMF in the presence of HMDS as a reagent under the transition-metal-free condition. Chem. Pap. 72, 2973–2978 (2018). https://doi.org/10.1007/s11696-018-0540-5
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DOI: https://doi.org/10.1007/s11696-018-0540-5