Solvent Free One-Pot Synthesis of 1,2,4,5-Tetrasubstituted Imidazoles Catalyzed by Secondary Amine Based Ionic Liquid and Defective Keggin Heteropoly Acid

Pranab Jyoti Das, Jupitara Das, Munni Ghosh, Sabera Sultana

Department of Chemistry, Gauhati University, Guwahati, India.
Indian Institute of Technology, Guwahati, India.

DOI: 10.4236/gsc.2013.34A002                

Abstract

Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.

Keywords

Ionic Liquids; Keggin Heteropolyacid; Microwave; Tetrasubstituted Imidazole; Solvent Free Synthesis; Multicomponent Reaction

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	M. R. Grimmet and A. R. Katritzky, “In Comprehensive Heterocyclic Chemistry,” In: C. W. Rees, Ed., Pergamon Press, London, Vol. 5, 1984, p. 374.
[2]	D. Norwood, E. Branch, B. Smith and M. Honeywell, “Olmesartan Medoxomil for Hypertension: A Clinical Review,” Drug Forecast, Vol. 27, No. 12, 2002, pp. 611-618.
[3]	S. L. Abrahams, R. J. Hazen, A. G. Batson and A. P. Phillips, “Trifenagrel: A Chemically Novel Platelet Aggregation Inhibitor,” Journal of Pharmacology and Experimental Therapeutics, Vol. 249, No. 2, 1989, pp. 359- 365.
[4]	S. E. Wolkenberg, D. D. Wisnoski, W. H. Leister, Y. Wang, Z. Zhao and C. W. Lindsley, “Efficient Synthesis of Imidazoles from Aldehydes and 1,2-Diketones Using Microwave Irrediation,” Organic Letters, Vol. 6, No. 9, 2004, pp. 1453-1456. http://dx.doi.org/10.1021/ol049682b
[5]	J. G. Lombardino and E. H. Wiseman, “Preparation and Antiinflammatory Activity of Some Nonacidic Trisubstituted Imidazoles,” Journal of Medicinal Chemistry, Vol. 17, No. 11, 1974, pp. 1182-1188. http://dx.doi.org/10.1021/jm00257a011
[6]	J. G. Lombardino, “Pharmaceutical Imidazoles,” Ger. Offen, DE 2155558 A 19720629, 1972.
[7]	A. P. Phillips, H. L. White and S. Rosen, “Antithrombotic Triphenylimidazoles,” European Patent, EP 58890 A1 19820901, 1982.
[8]	J. Zhu, “Recent Developments in the Isonitrile-Based Multicomponent Synthesis of Heterocycles,” European Journal of Organic Chemistry, Vol. 2003, No. 7, 2003, pp. 1133-1144. http://dx.doi.org/10.1002/ejoc.200390167
[9]	R. V. A. Orru and M. de Greef, “Recent Advances in So- lution-Phase Multicomponent Methodology for the Synthesis of Heterocyclic Compounds,” Synthesis, Vol. 2003, No. 10, 2003, pp. 1471-1499. http://dx.doi.org/10.1055/s-2003-40507
[10]	D. J. Ramon and M. Yus, “Asymmetric Multicomponent Reactions (AMCRs): The New Frontier,” Angewandte Chemie International Edition, Vol. 44, No. 11, 2005, pp. 1602-1634. http://dx.doi.org/10.1002/anie.200460548
[11]	D. E. Frantz, L. Morency, A. Soheili, J. A. Murry, E. J. J. Grabowski and R. D. Tillyer, “Synthesis of Substituted Imidazole via Organocatalysis,” Organic Letters, Vol. 6, No. 5, 2004, pp. 843-846. http://dx.doi.org/10.1021/ol0498803
[12]	C. Zhang, E. J. Moran, T. F. Woiwade, K. M. Short and A. M. M. Mjalli, “Synthesis of Tetrasubstituted Imidazoles via α-(N-acyl-N-alkylamino)-β-ketoamides on Wang Resin,” Tetrahedron Letters, Vol. 37, No. 6, 1996, pp. 751-754. http://dx.doi.org/10.1016/0040-4039(95)02310-0
[13]	I. Lantos, W-Y. Zhang, X. Shui and D. S. Eggleston, “Synthesis of Imidazole via Hetero-Cope Rearrange ment,” The Journal of Organic Chemistry, Vol. 58, No. 25, 1993, pp. 7092-7095. http://dx.doi.org/10.1021/jo00077a033
[14]	T. J. Donohoe, M. A. Kabeshov, A. H. Rathi and I. E. D. Smith, “Direct Preparation of Thiazoles, Imidazoles, Imidazopyridines and Thiazolidines from Alkenes,” Organic & Biomolecular Chemistry, Vol. 10, No. 5, 2012, pp. 1093-1101. http://dx.doi.org/10.1039/c1ob06587d
[15]	B. Hu, Z. Wang, N. Ai, J. Zheng, X-H. Liu, S. Shan and Z. Wang, “Catalyst-Free Preparation of 1,2,4,5-Tetrasub- stituted Imidazoles from a Novel Unexpected Domino Reaction of 2-Azido Acrylates and Nitrones,” Organic Letters, Vol. 13 , No. 24, 2011, pp. 6362-6365. http://dx.doi.org/10.1021/ol202650z
[16]	B. H. Lipshutz and M. C. Morey, “An Approach to the Cyclopeptide Alkaloids (Phencyclopeptines) via Heterocyclic Diamide/Dipeptide Equivalents. Preparation and N-Alkylation Studies of 2,4(5)-Disubstituted Imidazoles,” The Journal of Organic Chemistry, Vol. 48 , No. 21, 1983, pp. 3745-3750. http://dx.doi.org/10.1021/jo00169a027
[17]	B. Sadeghi, B. B. F. Mirjalili and M. M. Hashemi, “BF3·SiO2: An Efficient Reagent System for the One-Pot Synthesis of 1,2,4,5-Tetrasubstituted Imidazoles,” Tetrahedron Letters, Vol. 49, No. 16, 2008, pp. 2575-2577. http://dx.doi.org/10.1016/j.tetlet.2008.02.100
[18]	R. Consonni, P. D. Croce, R. Ferraccioli and C. L. Rosa, “A New Approach to Imidazole Derivatives,” Journal of Chemical Research (Synopses), No. 7, 1991, pp. 188-189.
[19]	D. A. Evans and K. M. Lundy, “Synthesis of Diphthamide: The Target of Diphtheria Toxin Catalyzed ADP-Ribosylation in Protein Synthesis Elongation Factor 2,” Journal of the American Chemical Society, Vol. 114, No. 4, 1992, pp. 1495-1496. http://dx.doi.org/10.1021/ja00030a063
[20]	P. Schneiders, J. Heinze and H. Baumgartel, “Synthesis of 4,4’,5,5’-Tetrasubstituted Di-2-imidazolyl Derivatives, Starting Materials for the Synthesis of 1,4,5,8-Tetraazafulvalenes,” Chemische Berichte, Vol. 106, No. 7, 1973, pp. 2415-2417. http://dx.doi.org/10.1002/cber.19731060739
[21]	C. F. Claiborne, N. J. Liverton and K. T. Nguyen, “An Efficient Synthesis of Tetrasubstituted Imidazole from N-(2-Oxo)-Amides,” Tetrahedron Letters, Vol. 39, No. 49, 1998, pp. 8939-8942. http://dx.doi.org/10.1016/S0040-4039(98)02058-9
[22]	S. Narayana Murthy, B. Madhav and 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, Vol. 51, No. 40, 2010, pp. 5252-5257. http://dx.doi.org/10.1016/j.tetlet.2010.07.128
[23]	S. Kantevari, S. V. N. Vuppalapati, D. O. Biradar and L. Nagarapu, “Highly Efficient, One-Pot, Solvent-Free Synthesis of Tetrasubstituted Imidazoles Using HClO4-SiO2 as Novel Heterogeneous Catalyst,” Journal of Molecular Catalysis A: Chemical, Vol. 266, No. 1-2, 2007, pp. 109-113. http://dx.doi.org/10.1016/j.molcata.2006.10.048
[24]	M. Kidwai and P. Mothsra, “A One-Pot Synthesis of 1,2, 4,5-Tetraarylimidazole Using Molecular Iodine as an Efficient Catalyst,” Tetrahedron Letters, Vol. 47, No. 29, 2006, pp. 5029-5031. http://dx.doi.org/10.1016/j.tetlet.2006.05.097
[25]	S. Balalaie, M. M. Hashemi and M. Akhbari, “A Novel One-Pot Synthesis of Tetrasubstituted Imidazoles under Solvent-Free Conditions and Microwave Irradiation,” Tetrahedron Letters, Vol. 44, No. 8, 2003, pp. 1709-1711. http://dx.doi.org/10.1016/S0040-4039(03)00018-2
[26]	S. Samai, G. C. Nandi, P. Singh and 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, Vol. 65, No. 49, 2009, pp. 10155-10161. http://dx.doi.org/10.1016/j.tet.2009.10.019
[27]	S. Balalaie and A. Arabanian, “One-Pot Synthesis of Tetrasubstituted Imidazoles Catalyzed by Zeolite HY and Silica Gel under Microwave Irradiation,” Green Chemis- try, Vol. 2, No. 6, 2000, pp. 274-276. http://dx.doi.org/10.1039/b006201o
[28]	M. M. Heravi, F. Derikvand and F. F. Bamoharramb, “Highly Efficient, Four-Component One-Pot Synthesis of Tetrasubstituted Imidazoles Using Keggin-Type Heteropolyacids as Green and Reusable Catalysts,” Journal of Molecular Catalysis A: Chemical, Vol. 263, No. 1-2, 2007, pp. 112-114. http://dx.doi.org/10.1016/j.molcata.2006.08.048
[29]	M. R. Manafi, P. Manafi and M. R. Kalaee, “Versatile Microwave-Assisted and Lanthanum Chloride Catalysed Synthesis of Polysubstituted Imidazoles Using Urea/ Thiourea as Benign Source of Ammonia,” E-Journal of Chemistry, Vol. 9, No. 4, 2012, pp. 1773-1777. http://dx.doi.org/10.1155/2012/396127
[30]	H. R. Shaterian and M. Ranjbar, “An Environmental Friendly Approach for the Synthesis of Highly Substituted Imidazoles Using Bronsted Acidic Ionic Liquid, N-Methyl-2-Pyrrolidonium Hydrogen Sulphate, as Reusable Catalyst,” Journal of Molecular Liquids, Vol. 160, No. 1, 2011, pp. 40-49. http://dx.doi.org/10.1016/j.molliq.2011.02.012
[31]	P. Wasserscheid and T. Welton, “Ionic Liquids in Synthesis,” 2nd Edition, Wiley-VCH, Weinheim, 2007. http://dx.doi.org/10.1002/9783527621194
[32]	Y. Izumi, K. Urabe and M. Onaka, “Zeolite, Clay and Heteropolyacid in Organic Reactions,” Kodansha/VCH, Tokyo, 1992.
[33]	T. Okuhara, N. Mizuno and M. Misono, “Catalytic Che mistry of Heteropoly Compounds,” Advances in Catalysis, Vol. 41, 1996, pp. 113-252. http://dx.doi.org/10.1016/S0360-0564(08)60041-3
[34]	P. J. Das and J. Das, “Synthesis of Aryl/alkyl(2,2’-bis-3- methylindolyl)methanes and Aryl(3,3’-bisindolyl)Methanes Promoted by Secondary Amine Based Ionic Liquids and Microwave Irradiation,” Tetrahedron Letters, Vol. 53, No. 35, 2012, pp. 4718-4720. http://dx.doi.org/10.1016/j.tetlet.2012.06.106
[35]	I. V. Kozhevnikov, “Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions,” Chemical Review, Vol. 98, No. 1, 1998, pp. 171- 198. http://dx.doi.org/10.1021/cr960400y