Clean 3,4-Dihydropyrimidones Synthesis via Biginelli Reaction over Supported Molybdenum: Structural and Textural Characteristic of αMoO3

*Ouzna Kheffache  -  Laboratoire de Chimie du Gaz Naturel, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène, Algeria
Cristina Lopez-Olmos  -  Instituto de Catálisis y Petroleoquímica, Spain
Inmaculada Rodriguez-Ramos  -  Instituto de Catálisis y Petroleoquímica, Spain
Ouiza Cherifi  -  Laboratoire de Chimie du Gaz Naturel, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène, Algeria
Received: 5 Jul 2020; Revised: 14 Aug 2020; Accepted: 15 Aug 2020; Published: 28 Dec 2020; Available online: 15 Sep 2020.
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Abstract

A one-pot three-component synthesis of dihydropyrimidinones (DHPMs) via Biginelli reaction was carried out at 100 °C using benzaldehyde, ethyl acetoacetate and urea as reactants, in the presence of ethanol and free solvent, in heterogeneous catalytic medium. The Mo (30 wt%) metal oxides (Al2O3, SiO2 or MgO) used catalysts were prepared by sol-gel, impregnation and microemulsion methods and characterized by X-Ray Diffraction (XRD), Fourier Transform Infra Red (FTIR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray (EDX), Nitrogen Adsorption - Brunauer-Emmett-Teller (BET), and NH3-Temperature Programmed Desorption (TPD) methods. The Mo-SiO2 sample prepared by the sol-gel method exhibited the highest DHPM yield (87%), in free solvent with a reaction time of 30 min. The high efficiency, in the Biginelli reaction, of the Mo-SiO2 catalyst is due to its structural, textural and acid properties. Highly dispersed αMoO3 species of orthorhombic structure having a high contribution of strong acidic sites would be the active species in the Biginelli synthesis  Copyright © 2020 BCREC Group. All rights reserved

 

Keywords: Heterogeneous catalysis; Biginelli reaction; Green chemistry; αMoO3; SiO2
Funding: Ministère de l'Enseignement Supérieur et de la Recherche Scientifique (MESRS), Algérie under contract Spanish Agencia Estatal de Investigación (AEI) y el Fondo Europeo de Desar

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Section: Original Research Articles
Language: EN
In 2020: BCREC Volume 15 Issue 3 Year 2020 (SCOPUS and Web of Science Indexed,December 2020)
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  1. Kappe, C.O. (1993). 100 years of the Biginelli dihydropyrimidine synthesis. Tetrahedron, 49, 6937-6963
  2. Kappe, C.O., Fabian, W.M.F., Semones, M.A. (1997). Tonformational analysis of 4-aryl-d dihydropyrimidine calcium channel modulators. a comparison of Ab lnitio, semiempirical and x-ray crystallographic studies. Tetrahedron, 53, 2803–2816.
  3. Kappe, C.O. (2000). Recent advances in the Biginelli dihydropyrimidine synthesis. New tricks from an old dog. Accounts of Chemical Research, 33, 879-888.
  4. Atwal, K.S., Rovnyak, G.C., Kimball, S.D., Floyd, D.M., Moreland, S., Swanson, B.N., Malley, M.F. (1990). Dihydropyrimidine calcium channel blockers. II. 3-Substituted-4-aryl-1,4-dihydro-6-methyl-5-pyrimidinecarboxylic acid esters as potent mimics of dihydropyridines. Journal of Medicinal Chemistry, 33, 2629-2635.
  5. Atwal, K.S., Rovnyak, G.C., O'Reilly, B.C., Schwartz, J. (1989). Substituted 1, 4-dihydropyrimidines. 3. Synthesis of selectively functionalized 2-hetero-1, 4-dihydropyrimidines. The Journal of Organic Chemistry, 54, 5898-5907.
  6. Biginelli, P. (1893). Aldehyde-urea derivatives of aceto-and oxaloacetic acids. Gazz. Chim. Ital., 23 , 360-413.
  7. Liu, C., Wang, J., Li, Y. (2006). One-pot synthesis of 3, 4-dihydropyrimidin-2 (1H)-(thio) ones using strontium (II) nitrate as a catalyst. Journal of Molecular Catalysis A: Chemical, 258, 367-370.
  8. Hu, E.H., Sidler, D.R., Dolling, U.-H. (1998). Unprecedented catalytic three component one-pot condensation reaction: an efficient synthesis of 5-alkoxycarbonyl-4-aryl-3, 4-dihydropyrimidin-2 (1H)-ones. The Journal of Organic Chemistry, 63, 3454-3457.
  9. Suzuki, I., Suzumura, Y., Takeda, K. (2006). Metal triflimide as a Lewis acid catalyst for Biginelli reactions in water. Tetrahedron Letters, 47(45), 7861-7864.
  10. Zhao, S.-Y., Chen, Z.-Y., Wei, N., Liu, L., Han, Z.-B. (2019). Highly Efficient Cooperative Catalysis of Single-Site Lewis Acid and Brønsted Acid in a Metal–Organic Framework for the Biginelli Reaction. Inorganic Chemistry, 58(12), 7657-7661.
  11. Zhang, H., Zhou, Z., Yao, Z., Xu, F., Shen, Q. (2009). Efficient synthesis of pyrimidinone derivatives by ytterbium chloride catalyzed Biginelli-type reaction under solvent-free conditions. Tetrahedron Letters, 50, 1622-1624.
  12. Heravi, M.M., Behbahani, F.K., Oskooie, H.A. (2008). Ferric Perchlorate Catalyzed One‐pot Synthesis of 1, 2, 3, 4‐Tetrahydro‐2‐pyrimidinones and‐thiones: an Expedient Protocol for the Biginelli Reaction. Chinese Journal of Chemistry, 26, 2203-2206.
  13. Narsaiah, A.V., Reddy, A.R., Yadav, J. (2011). Samarium triflate–catalyzed Biginelli condensation: An improved method for the synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. Synthetic Communications, 41, 2794-2799.
  14. Narsaiah, A.V., Reddy, A.R., Yadav, J. (2011). Samarium triflate–catalyzed Biginelli condensation: An improved method for the synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. Synthetic Communications, 41(18), 2794-2799.
  15. Nagarajan, S., Shaikh, T. M., Kandasamy, E. (2015). Synthesis of 1-alkyl triazolium triflate room temperature ionic liquids and their catalytic studies in multi-component Biginelli reaction. Journal of Chemical Sciences, 127, 1539-1545.
  16. Wang, Y., Yu, J., Yang, H., Miao, Z., Chen, R. (2011). Solvent-free Biginelli reaction: A green method for the synthesis of 3, 4-dihydropyrimidin-2-ones catalyzed by protic acids in large-scale. Letters in Organic Chemistry, 8(4), 264-267.
  17. Takale, S., Parab, S., Phatangare, K., Pisal, R., Chaskar, A. (2011). IBX in aqueous medium: a green protocol for the Biginelli reaction. Catalysis Science & Technology, 1, 1128-1132.
  18. Fazaeli, R., Tangestaninejad, S., Aliyan, H., Moghadam, M. (2006). One-pot synthesis of dihydropyrimidinones using facile and reusable polyoxometalate catalysts for the Biginelli reaction. Applied Catalysis A: General, 309, 44-51.
  19. Rafiee, E., Shahbazi, F. (2006). One-pot synthesis of dihydropyrimidones using silica-supported heteropoly acid as an efficient and reusable catalyst: Improved protocol conditions for the Biginelli reaction. Journal of Molecular Catalysis A: Chemical, 250, 57-61.
  20. Shen, Z.-L., Xu, X.-P., Ji, S.-J. (2010). Brønsted base-catalyzed one-pot three-component Biginelli-type reaction: An efficient synthesis of 4, 5, 6-triaryl-3, 4-dihydropyrimidin-2 (1H)-one and mechanistic study. The Journal of Organic Chemistry, 75, 1162-1167.
  21. Tamaddon, F., Razmi, Z., Jafari, A.A. (2010). Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones and 1,4-dihydropyridines using ammonium carbonate in water. Tetrahedron Letters, 51, 1187-1189.
  22. Heravi, M.M., Bakhtiari, K., Bamoharram, F.F. (2006). 12-Molybdophosphoric acid: A recyclable catalyst for the synthesis of Biginelli-type 3,4-dihydropyrimidine-2 (1H)-ones. Catalysis Communications, 7, 373-376.
  23. Khabazzadeh, H., Saidi, K., Sheibani, H. (2008). Highly efficient conversion of aromatic acylals to 3,4-dihydropyrimidinones: a new protocol for the Biginelli reaction. Arkivoc, 15, 34-41
  24. Ahmed, B., Khan, R.A., Keshari, M. (2009). An improved synthesis of Biginelli-type compounds via phase-transfer catalysis. Tetrahedron Letters, 50, 2889-2892.
  25. Dadhania, A. N., Patel, V. K., & Raval, D. K. (2012). A facile approach for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones using a microwave promoted Biginelli protocol in ionic liquid. Journal of Chemical Sciences, 124, 921-926.
  26. Mahato, B.N., Krithiga, T. (2019). Mesoporous ZnO/AlSBA-15 (7) Nanocomposite as An Efficient Catalyst for Synthesis of 3,4-dihydropyrimidin-2 (1H)-one via Biginelli Reaction and Their Biological Activity Study. Bulletin of Chemical Reaction Engineering & Catalysis, 14, 634-645.
  27. Chaudhary, G.R., Bansal, P., Mehta, S. (2014). Recyclable CuS quantum dots as heterogeneous catalyst for Biginelli reaction under solvent free conditions. Chemical Engineering Journal, 243, 217-224.
  28. Gupta, R., Paul, S., Gupta, R. (2007). Covalently anchored sulfonic acid onto silica as an efficient and recoverable interphase catalyst for the synthesis of 3, 4-dihydropyrimidinones/thiones. Journal of Molecular Catalysis A: Chemical, 266, 50-54.
  29. Umbarkar, S., Biradar, A., Mathew, S., Shelke, S., Malshe, K., Patil, P., Dagde, S., Niphadkar, S., Dongare, M. (2006). Vapor phase nitration of benzene using mesoporous MoO3/SiO2 solid acid catalyst. Green Chemistry, 8, 488-493.
  30. Amrute, A.P., Bordoloi, A., Lucas, N., Palraj, K., Halligudi, S. (2008). Sol–Gel Synthesis of MoO3/SiO2 Composite for Catalytic Application in Condensation of Anisole with Paraformaldehyde. Catalysis Letters, 126, 286–292.
  31. Klicpera, T., Zdražil, M. (2001). High surface area MoO3/MgO: preparation by reaction of MoO3 and MgO in methanol or ethanol slurry and activity in hydrodesulfurization of benzothiophene. Applied Catalysis A: General, 216, 41-50.
  32. Ma, X., Gong, J., Wang, S., Gao, N., Wang, D., Yang, X., He, F. (2004). Reactivity and surface properties of silica supported molybdenum oxide catalysts for the transesterification of dimethyl oxalate with phenol. Catalysis Communications, 5, 101-106.
  33. Jain, S.L., Prasad, V., Sain, B. (2008). Alumina supported MoO3: An efficient and reusable heterogeneous catalyst for synthesis of 3, 4-dihydropyridine-2 (1H)-ones under solvent free conditions. Catalysis Communications, 9, 499-503
  34. Jadhav, S., Anandgaonker, P.L., Kulkarni, G., Gaikwad, S.T., Rajbhoj, A.S. (2014). Microwave-assisted one-pot synthesis of octahydroquinazolinone derivatives using molybdenum oxide nanoparticles in solvent-free condition. Journal of Cluster Science, 25, 1389-1399.
  35. Thuadaij, N., Nuntiya, A. (2008). Preparation of nanosilica powder from rice husk ash by precipitation method. Chiang Mai Journal of Science, 35(1), 206-211.
  36. Lietti, L., Ramis, G., Busca, G., Bregani, F., Forzatti, P. (2000). Characterization and reactivity of MoO3/SiO2 catalysts in the selective catalytic oxidation of ammonia to N2. Catalysis Today, 61, 187-195.
  37. Biermann, J., Janssen, F., De Boer, M., Van Dillen, A., Geus, J., Vogt, E. (1990). Molybdena on silica catalysts: selective catalytic oxidation of ammonia to nitrogen over MoO3 on SiO2 catalysts. Journal of Molecular Catalysis, 60, 229-238.
  38. Jia, C., Massiani, P., Barthomeuf, D. (1993). Characterization by infrared and nuclear magnetic resonance spectroscopies of calcined beta zeolite. Journal of the Chemical Society, Faraday Transactions, 89, 3659-3665.
  39. Kido, A., Iwamoto, H., Azuma, N., Ueno, A. (2002). Effects of catalyst heating rates upon the activity of silica-supported silicomolybdic acid catalysts for methane partial oxidation. Catalysis Surveys from Asia, 6(1-2), 45-53
  40. Lippincott, E.R., Van Valkenburg, A., Weir, C.E. Bunting, E.N. (1958). Infrared studies on polymorphs of silicon dioxide and germanium dioxide. J. Res. Nat. Bureau of Standards, 61, 61-70.
  41. Rocchiccioli-Deltcheff, C., Amirouche, M., Hervé, G., Fournier, M., Che, M., Tatibouët, J.-M. (1990). Structure and catalytic properties of silica-supported polyoxomolybdates: II. Thermal behavior of unsupported and silica-supported 12-molybdosilicic acid catalysts from IR and catalytic reactivity studies. Journal of Catalysis, 126, 591-599
  42. Skupiński, W., Malesa, M. (2002). An infrared study on the MoO3/SiO2 catalytic system employed in toluene nitration. Appl. Catal. A: Gen. 236223-234.
  43. El Shafei, G.M., Mokhtar, M. (1995). Interaction between molybdena and silica: FT-IR/PA studies of surface hydroxyl groups and pore structure assessment. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 94(2-3), 267-277
  44. Nasrollahzadeh, M., Issaabadi, Z., Sajadi, S. M. (2018). Green synthesis of a Cu/MgO nanocomposite by Cassytha filiformis L. extract and investigation of its catalytic activity in the reduction of methylene blue, congo red and nitro compounds in aqueous media. RSC Advances, 8, 3723-3735.
  45. Nyquist, R.A., Ronald, O. (1971). Kagel, Infrared Spectra of Inorganic Compounds. Academic Press, New York and London-1971 (971), 64, 65.
  46. Smith, M., Zhang, L., Driscoll, S., Ozkan, U. (1993). Effect of surface species on activity and selectivity of MoO3/SiO2 catalysts in partial oxidation of methane to formaldehyde. Catalysis Letters, 19, 1-15.
  47. Xu, S., Zhao, R., Wang, X. (2004). Highly coking resistant and stable Ni/Al2O3 catalysts prepared by W/O microemulsion for partial oxidation of methane. Fuel Process. Technol., 86, 123-133
  48. Yahi, N., Menad, S., Rodríguez-Ramos, I. (2015). Dry reforming of methane over Ni/CeO2 catalysts prepared by three different methods. Green Pocess. Synth., 4, 479-486.
  49. Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P., Rodriguez-Reinoso, F., Rouquerol, J., Sing, K.S. (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 87(9-10), 1051-1069.
  50. Chen, Y., Lu, C., Xu, L., Ma, Y., Hou, W., Zhu, J.-J. (2010). Single-crystalline orthorhombic molybdenum oxide nanobelts: synthesis and photocatalytic properties. Cryst EngComm, 12, 3740-3747.
  51. Bouzidi, A., Benramdane, N., Tabet-Derraz, H., Mathieu, C., Khelifa, B., Desfeux, R. (2003). Effect of substrate temperature on the structural and optical properties of MoO3 thin films prepared by spray pyrolysis technique. Materials Science and Engineering: B, 97, 5-8.
  52. Rao, M., Ravindranadh, K., Kasturi, A., Shekhawat, M. (2013). Structural stoichiometry and phase transitions of MoO3 thin films for solid state microbatteries. Research Journal of Recent Sciences, 2277, 67-73
  53. Lima, D.S., Perez-Lopez, O.W. (2019). Catalytic conversion of glycerol to olefins over Fe, Mo, and Nb catalysts supported on zeolite ZSM-5. Renewable Energy, 136, 828-836.
  54. Obeso-Estrella, R., Fierro, J., De Leon, J.D., Fuentes, S., Alonso-Nuñez, G., Lugo-Medina, E., Zepeda, T. (2018). Effect of partial Mo substitution by W on HDS activity using sulfide CoMoW/Al2O3–TiO2 catalysts. Fuel, 233, 644-657.
  55. Tamaddon, F., Moradi, S. (2013). Controllable selectivity in Biginelli and Hantzsch reactions using nano-ZnO as a structure base catalyst. Journal of Molecular Catalysis A: Chemical, 370, 117-122.
  56. Kouachi, K., Lafaye, G., Pronier, S., Bennini, L., Menad, S. (2014). Mo/γ-Al2O3 catalysts for the Biginelli reaction. Effect of Mo loading. Journal of Molecular Catalysis A: Chemical , 395, 210-216.
  57. Hassani, Z., Islami, M.R., Kalantari, M. (2006). An efficient one-pot synthesis of octahydroquinazolinone derivatives using catalytic amount of H2SO4 in water. Bioorganic & Medicinal Chemistry Letters, 16, 4479-4482.
  58. Kour, G., Gupta, M., Paul, S., Gupta, V.K. (2014). SiO2–CuCl2: An efficient and recyclable heterogeneous catalyst for one-pot synthesis of 3,4-dihydropyrimidin-2 (1H)-ones. Journal of Molecular Catalysis A: Chemical, 392, 260-269.

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