Facile and Rapid Synthesis of 3,4-Dihydropyrimidin-2(1H)-one Derivatives Using [Et3NH][HSO4] as Environmentally Benign and Green Catalyst

Document Type : Research Article

Authors

Department of Chemistry, Shahid Bahonar University of Kerman, Kerman 76169, I.R. IRAN

Abstract

5-acetyl-6-methyl-4-aryl-3,4-dihydropyrimidin-2(1H)-ones were synthesized in good to excellent by one-pot three-component Biginelli condensation in the presence of ammonium salt [Et3NH][HSO4] as an inexpensive and green catalyst under solvent-free conditions. High yields, short reaction time, easy work-up, a green environment which requires no toxic organic solvents and reusability of the catalyst are the advantages of this procedure. A broad range of structurally diverse aldehydes (aromatic aldehydes bearing electron withdrawing and electron releasing groups) was applied successfully, and corresponding products were obtained in good to excellent yields without any by-product. In addition, this catalyst was stable during the reaction process and could also be reused several times with consistent activity.

Keywords

Main Subjects


[1] Clark J.H., Solid Acids for Green Chemistry, Accounts of Chemical Research, 35(9):791-797 (2002).
[2] Saeedi M., Jeiroudi M., Ma’mani L., Mahdavi M, Alipour S., Shafiee A., Foroumadi A.R., Brønsted Acidic Phosphonium Based Ionic Liquid Functionalized SBA-15 [HO3S-PhospIL@SBA-15]: Green, Recyclable, and Efficient Catalyst for the Synthesis of Pyrano[3,2-c]Chromenone Derivatives, Iran. J. Chem. Chem. Eng. (IJCCE), 34(4):39-45 (2015).
[3]  Martins M.A.P., Teixeira M.V.M., Cunico W., Scapin E., Mayer R., Pereira C. M.P., Zanatta N., Bonacorso H.G., Peppe C., Yuan Y.F., Indium(III) Bromide Catalyzed One-Pot Synthesis of Trichloromethylated Tetrahydropyrimidinones, Tetrahedron Letters, 45(49):8991-8994 (2004).
[5] Shaabani, A., Farhangi, E., Shaabani, S., A Rapid Combinatorial Library Synthesis of Benzazolo[2,1-b]quinazolinones and Triazolo[2,1-b]quinazolinones, Iran. J. Chem. Chem. Eng. (IJCCE), 32(1):3-6 (2013).
[6] Earle M.J., Katdare S.P., Seddon K.R., Paradigm Confirmed: the First Use of Ionic Liquids to Dramatically Influence the Outcome of Chemical Reactions, Org. Lett., 6(5):707-710 (2004).
[9] Klingshirn M.A., Rogers, R.S., Shaughnessy, K.H., Palladium-Catalyzed Hydroesterification of Styrene Derivatives in the Presence of Ionic Liquids, J. Organomet. Chem., 690(15):3620- 3626 (2005).
[10] Yadav J.S., Reddy B.V.S., Baishya G., Reddy K.V., Narsaiah A.V., Conjugate Addition of Indoles to α, β-Unsaturated Ketones Using Cu (OTf)2 Immobilized in Ionic Liquids, Tetrahedron, 61(40):9541-9544 (2005). 
[11] Picquet M., Stutzmann S., Tkatchenko I., Tommasi I., Zimmermann J., Wasserscheid P., Selective Palladium-Catalysed Dimerisation of Methyl Acrylate in Ionic Liquids: Towards a Continuous Process, Green. Chem., 5(2):153-162 (2003).
[12] Wilkes J.S., A Short History of Ionic Liquids from Molten Salts to Neoteric Solvents, Green. Chem., 4(2):73-80(2002).
[13] Sheldon R., Green Solvents for Sustainable Organic Synthesis: State of the Art, Green Chem., 7(5):267- 278 (2005).
[14] Ma Y., Qian C., Wang L., Yang M., Lanthanide Triflate Catalyzed Biginelli Reaction. One-pot Synthesis of Dihydropyrimidinones Under Solvent-Free Conditions, J. Org. Chem., 65(12):3864-3868 (2000).
[18] Atwal K.S., Swanson B.N., Unger S.E., Floyd D.M., Mereland S., Hedberg A., O’Reilly B.C., Dihydropyrimidine Calcium Channel Blockers. 3. 3-Carbamoyl-4-aryl-1, 2, 3, 4-tetrahydro-6-methyl-5-Pyrimidinecarboxylic Acid Esters as Orally Effective Antihypertensive Agents, J. Med. Chem., 34(2): 806-811 (1991).
[19] Bigi F., Carloni S., Frullanti B., Maggi R., Sartori G.,
A Revision of the Biginelli Reaction under Solid Acid Catalysis. Solvent-Free Synthesis of Dihydropyrimidines over Montmorillonite KSF, Tetrahedron Lett., 40(17):3465-3468(1999).
[21] Yadav J.S., Praveen Kumar S., Kondaji G., Srinivasa Rao R., Nagaiah K.,  A Novel L-Proline Catalyzed Biginelli Reaction: One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones under Solvent-Free Conditions, Chem. Lett., 33(9):1168-1169 (2004).
[22] Adib M., Ghanbary K., Mostofi M., Ganjali, M.R., Efficient Ce (NO3)3· 6H2O-Catalyzed Solvent-Free Synthesis of 3, 4-dihydropyrimidin-2(1H)-ones, Molecules, 11(8):649-654 (2006).
[24]Kassaee, M.Z., Masrouri, H., Movahedi F., Mohammadi R., TiO2 as a Reusable Catalyst for the One‐Pot Synthesis of 3, 4‐Dihydropyrimidin‐2 (1H)‐ones under Solvent‐Free Conditions, Helv. Chim. Acta., 93(2):261-264(2010).
[25] Khodaei M.M., Khosropour A.R., Beygzadeh M., An Efficient and Environmentally Friendly Method for Synthesis of 3, 4‐Dihydropyrimidin‐2 (1H)‐ones Catalyzed by Bi(NO3)3·5H2O, Synth. Commun., 34(9):1551-1557 (2004).
[29] Ahn B.J., Gang M.S., Chae K., Oh Y., Shin, J., Chang W., A Microwave-Assisted Synthesis of 3,4-Dihydro-pyrimidin-2-(1H)-ones Catalyzed by FeCl3-Supported Nanopore Silica under Solvent-Free Conditions, J. Ind. Eng. Chem., 14 (3): 401-405 (2008).
[33] Khabazzadeh H., Tavakolinejad Kermani E., Jazinizadeh T., An Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Catalyzed by Molten [Et3NH][HSO4], Arab. J. Chem., 5(4):485-488 (2012).
[35] Wang C., Guo L., Li H., Wang Y., Weng J., Wu L., Preparation of Simple Ammonium Ionic Liquids and Their Application in the Cracking of Dialkoxypropanes, Green Chem., 8(7):603-607(2006).
[38] Ramalingan C., Kwak Y-W., Tetrachlorosilane Catalyzed Multicomponent One-Step Fusion of Biopertinent Pyrimidine Heterocycles, Tetrahedron, 64(22): 5023-5031(2008).
[39] Nazari S., Saadat Sh, Kazemian Fard P., Gorjizadeh M., Rezaee Nezhad E., Afshari M., Imidazole Functionalized Magnetic Fe3O4 Nanoparticles as a Novel Heterogeneous and Efficient Catalyst for Synthesis of Dihydropyrimidinones by Biginelli Reaction, Monatsh. Chem., 144(12):1877-1882 (2013).
[40] Mirjalili F.B., Bamoniri A., Akbari A., One-Pot Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones (thiones) Promoted by Nano-BF3. SiO2, J. Iran. Chem. Soc., 8(1):135-140 (2011).
[42] Shirini F., Abedini M., Pourhasan-Kisomi R., N-Sulfonic Acid Poly (4-vinylpyridinium) Chloride as a Highly Efficient and Reusable Catalyst for the Biginelli Reaction, Chin. Chem. Lett., 25(1): 111-114, (2014)
[43] Debache A., Amimour M., Belfaitah A., Rhouati S., Carboni B., A One-Pot Biginelli Synthesis of 3,
4-Dihydropyrimidin-2-(1H)-ones/thiones Catalyzed by Triphenylphosphine as Lewis Base
, Tetrahedron Lett., 49(42):6119-6121(2008).
[44] Yadav J.S., Kumar  S.P., Kondaji G., Rao R.S., Nagaiah K., A Novel L-Proline Catalyzed Biginelli Reaction: One-Pot Synthesis of 3, 4-Dihydropyrimidin-2 (1H)-ones under Solvent-Free Conditions, Chem. Lett., 33(9):1168-1169 (2004).
[45] Deshmukh M.B., Anbhule P.V., Jadhav S.D., Mali A.R., Jagtap S.S., Deshmukh S.A., An Efficient, Simple, One Pot Synthesis of Dihydropyrimidine-2 (1H) Ones Using Phosphorus Pentoxide, Indi. J. Chem. Sec. B, 46(9):1545-1548 (2007).
[46] Salehi P., Dabiri M., Zolfigol M.A., Bodaghi Fard M.A., Efficient Synthesis of 3, 4-dihydropyrimidin-2 (1H)-Ones Over Silica Sulfuric Acid as a Reusable Catalyst under Solvent-Free Conditions, Heterocycles, 60(11):2435-2440 (2003). 
[48] Zhou X., Cheng T., Zheng X., Ke Q., Wang X.,  Boron Trioxide–Alumina as a Heterogeneous Catalyst in a Facile Solvent Free One-Pot Synthesis of 3, 4-Dihydropyrimidin-2 (1H)-ones, J. Chem. Res., 36(4):213-215 (2012)
[49] Gui J., Liu D., Wang C., Lu F., Lian J., Jiang H., Sun Z., One-Pot Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones Catalyzed by Acidic Ionic Liquids under Solvent-Free Conditions, Synth. Commun., 39(19):3436-3443(2009).
[50] Niknam K., Daneshvar N., H4SiW12O40·xH2O as a New Catalyst for the Synthesis of 3,4-Dihydropyrimidin-2(1H)-one, Heterocycles, 71(2): 373-378(2007).
[51] Yu Y., Liu D., Liu C., Luo G., One-Pot Synthesis of 3,4-dihydropyrimidin-2(1H)-ones Using Chloroacetic Acid as Catalyst, Bioorg. Med. Chem. Lett., 17(12):3508-3510 (2007).