Recyclable Nanocrystalline Copper Based on MoO3/SiO2 as an Efficient Catalyst for Acylation of Amines
This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
Various loadings of copper supported on MoO3/SiO2 (CMS) were prepared by sol-gel method and used for the synthesis of substituted benzimidazole. Further it was characterized by using X‐ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX), Transmission Electron Microscopy (TEM), and acidity measurement by potentiometric method. XRD results indicated that Cu is present on the support primarily as CuO. The SEM and TEM results showed dispersion of cubic CuO nanoparticles on the surface. These mixed oxides were studied for the acylation of o-phenylene diamine with acetic acid in liquid phase. 10 wt. % CMS gave best results at 110 ºC with 94.81 % conversion of o-phenylene diamine and 100 % selectivity of substituted benzimidazole. Different parameters were studied for optimization of acylation, such as: temperature, acylating agents, solvents, amount of catalyst, and different catalysts. The CMS catalyst could also be recovered and reused at three times without any discernible decrease in its catalytic activity. Copyright © 2018 BCREC Group. All rights reserved
- Williams, C.C., Ekerdt, J.G., Jehng, J.M., Hardcastle, F.D., Turek, A.M., Wachs, I.E. (1991). J. Phys. Chem., 95: 8781-8791
- Carbucicchio, M., Trifiro, F. (1980). J. Catal., 62: 13-18
- Bruckman, K., Grzybowska, B., Che, M., Tatibouet, J.M. (1993). Appl. Catal. A., 96: 279-288
- Ono, T., Miyata, H., Kubokawa, Y. (1987). J. Chem. Soc. Faraday Trans., 183: 1761-1770
- Ma, X., Gong, J., Wang, S., Gao, N., Wang, D., Yang, X., He, F. (2004). Catal. Commun., 5: 101-106
- Patel, R.M. (2012). Synthesis, Characterization and Application of Mesoporous Materials, PhD Dissertation, Applied Chemistry Department, The Maharaja Sayajirao, University of Baroda.
- Auroux, A., Gervasini, A. (1990). J. Phys. Chem., 94: 6371-6379
- Kawai, M., Tsukuda, M., Tamaru, K. (1981). Surf. Sci., 111: L716-L720
- Preston, P.N., Stevens, M.F.G., Tennant, G. (1980). Benzimidazoles and Congeneric Tricyclic Compounds, Part 2, John Wiley and Sons, New York.
- Spasov, A.A., Yozhitsa, I.N., Bugaeva, L.I., Anisimova, V.A. (1999). Rearrangement Strategy for the Syntheses of 2-Amino Anilines. Pharm. Chem. J., 33: 232-243.
- Porcari, A.R., Devivar, R.V., Kucera, L.S., Drach, J.C., Townsend, L.B. (1998). Design, Synthesis and Antiviral Evaluation of 1-(Substituted Benzyl)-2-Substituted-5,6-Dichloro-Benzimidazoles as Non Nucleoside Analogues of 2,5,6-trichloral-((-D-Ribofuranosyl) Benzimidazole. J. Med. Chem., 41: 1252-1262.
- Roth, M., Morningstar, M.L., Boyer, P.L., Hughes, S.H., Bukheit, R.W., Michejda, C.J. (1997). Synthesis and Biological Activity of Novel Nonnucleosides Inhibitors of HIV-1 Reverse Transcriptase, 2-Aryl Substituted Benzimidazoles. J. Med. Chem., 40: 4199-4207
- Singh, N., Pandurangan, A., Rana, K., Anand, P., Ahmad, A., Tiwari, A.K. (2012). Benzimidazole: A Short Review of their Antimicrobial Activities. Int. Curr. Pharm. J., 1: 119-127.
- Walia, R., Hedaitullah, M.D., Naaz, S.F., Iqbal, K., Lamba, H.S. (2011). Benzimidazole Derivatives – An Overview, Int. J. Res. Pharm. hem., 1: 565-574
- Kedar, M.S., Dighe, N.S., Pattan, S.R., Musmade, D.S., Thakur, D., Bhosale, M., Gaware, V.M. (2010). Benzimidazole in Medicinal Chemistry: An Overview. Der Pharma Chem.. 2: 249-256.
- Yerragunta, V., Patil, P., Srujana, S., Devi, R., Gayathri, R., Aary, S.D. (2014). Benzimidazole Derivatives and Its Biological Importance: A Review, PharmaTutor., 2: 109-113.
- Kadhim, A.J., Kazim, A.C. (2018). Synthesis and Characterization of Benzimidazole by Using o-Phenylenediamine with Different Aldehydes and Carboxylic Acids in the Presence of ρ-TSOH as a Catalyst. Orient. J. Chem., 34: 2131-2136
- Mohammad, S., Avijit, S., Mohammad, M., Abdullah, M. (2017). Synthesis, Characterization and Antimicrobial Activity of 1,3,4-Oxadiazole Bearing 1H-Benzimidazole Derivatives. Arabian Journal of Chemistry, 10: 503-508.
- Jubie, S., Rajeshkumar, R1, Yellareddy, B., Siddhartha, G., Sandeep, M., Surendrareddy, K. (2010) Microwave Assisted Synthesis of some Novel Benzimidazole Substituted Fluoroquinolones and their Antimicrobial Evaluation. J. Pharm. Sci. & Res., 2: 69-76
- Curini, M., Epifano, F., Montanari, F., Rosati, O., Taccone, S. (2004). Ytterbium Triflate Promoted Synthesis of Benzimidazole Derivatives, Synlett., 10: 1832-1834.
- Patil, V.D., Medha, G., Shramesha, M., Aarti, J. (2010). A Mild and Efficient Synthesis of Benzimidazole by using Lead Peroxide under Solvent Free Condition, Der Chemica Sinica., 1: 125-129.
- Kathirvelan, D., Yuvaraj, P., Babu, K., Nagarajan, A.S., Reddy, B.S.R. (2013). A Green Synthesis of Benzimidazoles, Indian J. Chem.. 52B: 1152-1156.
- Tushar, M., Kaneria, D.M., Kapse, G.K., Gaikwad, T.V., Sarvaiya, J.A. (2013). Mild and Efficient Synthesis of Benzimidazole by Using Zinc Chloride under Solvent Free Condition, IJPRS, 2: 90-98.
- Swami, M.B., Patil, S.G., Mathapati, S.R., Ghuge, H.G., Jadhav, A.H. (2015). Ecofriendly One Pot Synthesis of 2-Substituted Benzimidazole. Der Pharma Chem., 7: 533-535.
- Chari, M.A., Mosaa, Z-A., Shobha, D., Malayalama, S. (2013). Synthesis of Multifunctionalised 2-Substituted Benzimidazoles using Copper (II) Hydroxide as Efficient Solid Catalyst. Int. J. Org. Chem., 3: 243-250.
- Mukhopadhyay, C., Ghosh, S., Butcher, R.J. (2010). An Efficient and Versatile Synthesis of 2,2’-(alkanediyl)-bis-1H- Benzimidazoles Employing Aqueous Fluoroboric Acid as Catalyst: Density Functional Theory Calculations and Fluorescence Studies, ARKIVOC, 11: 75-96.
- Karimi-Jaberi, Z., Amiri, M. (2012). An Efficient and Inexpensive Synthesis of 2-Substituted Benzimidazoles in Water Using Boric Acid at Room Temperature E- J. Chem., 9: 167-170.
- Srinivasulu, R., Kumar, K.R., Veera, P., Satyanarayana, V. (2014). Facile and Efficient Method for Synthesis of Benzimidazole Derivatives Catalyzed by Zinc Triflate. Green Sustainable Chem., 4: 33-37.
- Kidwai, M., Jahan, N., 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.
- Patil, V.D., Patil, K.P. (2015). Synthesis of Benzimidazole and Benzoxazole Derivatives Catalyzed by Nickel Acetate as Organometallic Catalyst. Int. J. Chem. Tech. Res., 8: 457-465.
- Aliyan, H., Fazaeli, R., Fazaeli, N., Mssah, A.R., Naghash, H.J., Alizadeh, M., Emami, G. (2009). Facile Route for the Synthesis of Benzothiazoles and Benzimidazoles in the Presence of Tungstophosphoric Acid Impregnated Zirconium Phosphate under Solvent-Free Conditions, Heteroat. Chem., 20: 202-207.
- Zhang, Z.H., Yin, L., Wang, Y.M. (2007). An Expeditious Synthesis of Benzimidazole Derivatives Catalyzed by Lewis Acids. Catal. Commun., 8: 1126–1131.
- Chakrabarty, M., Karmakar, S., Ajanta, M., Arima, S., Harigaya, Y. (2006). Application of Sulfamic Acid as an Eco-Friendly Catalyst in an Expedient Synthesis of Benzimidazoles, Heterocycles, 68: 967-974.
- Vidhate, K.N., Waghmare, R.A. (2015). An Efficient and Ecofriendly RuO2-MoO3 Solid Heterogeneous Catalyst for the Synthesis of Benzimidazole from Aldehydes, Adv. Appl. Sci. Res., 6: 167-170.
- Kannan, V., Sreekumar, K. (2013). Clay Supported Titanium Catalyst for the Solvent Free Synthesis of Tetra Substituted Imidazoles and Benzimidazoles. J. Mol. Catal. A: Chemical, 376: 34–39.
- Ziarani, I.M., Badiei, A., Hassanzadeh, M. (2011). One-pot Synthesis of 2-
- Aryl-1-arylmethyl-1h-1,3-benzimidazole Derivatives using Sulfonic Acid Functionlized Silica (SiO2-Pr-SO3H) under Solvent Free Conditions. Int. J. Appl. Biol. Pharm., 2: 48-54.
- Ziarani, G.M., Badiei, A., Nahad, M.S., Alizadeh, S.G. (2012). Synthesis of 1,2-Disubstituted Benzimidazoles in the Presence of SBA-Pr-SO3H as a Nano Solid Acid Catalyst. JNS, 2: 213-220
- Kumar, P., Pandey, R.K., Bodas, M.S., Dagade, S.P., Dongare, M.K., Ramaswamy, A.V. (2002). Acylation of Alcohols, Thiols and Amines with Carboxylic Acids Catalyzed by Yttria–Zirconia-Based Lewis Acid. J. Mol. Catal. A: Chemical, 181: 207-213
- Pandey, R.K., Dagade, S.P., Malase, K.M., Songire, S.B., Kumar, P. (2006). Synthesis of Ceria-Yttria based Strong Lewis Acid Heterogeneous Catalyst: Application for Chemoselective Acylation and Ene Reaction. J. Mol. Catal. A: Chemical, 245: 255-259.
- Tarpada, U.P., Thummar, B.B., Raval, D.K. (2012). Polymer Supported Sulphanilic Acid – A Novel Green Heterogeneous Catalyst for Synthesis of Benzimidazole Derivatives. J. Saudi Chem. Soc., 20: 530-535
- Shen, M-G., Cai, C. (2007). Ytterbium Perfluorooctane Sulfonates Catalyzed Synthesis of Benzimidazole Derivatives in Fluorous Solvents. J. Fluorine Chem., 128: 232–235.
- Rathod, S.B., Lande, M.K., and Arbad, B.R. (2010) Synthesis, Characterization and Catalytic Application of MoO3/CeO2-ZrO2 Solid Heterogeneous Catalyst for the Synthesis of Benzimidazole Derivatives. Bull. Korean Chem. Soc., 31(10): 2835-2840.
- Chen, G-F., Dong, X-Y., Meng, F-Z., Chen, B-H., Li, J-T., Wang, S-X., Bai, G-Y. (2011). Synthesis of 2-Substituted Benzimidazoles Catalyzed by FeCl3/Al2O3 Under Ultrasonic Irradiation, Lett. Org. Chem., 8: 464-469.
- Pardeshi, S.D., Sonar, J.P., Pawar, S.S., Dekhane, D., Gupta, S., Zine, A.M., Thore, S.N. (2014). Sonicated Assisted Synthesis of Benzimidazoles, Benzoxazoles and Benzothiazoles in Aqueous Media, J. Chil. Chem. Soc., 59: 2335-2340
- Bougrin, K., Soufiaoui, M.. Nouvelle voie de. (1995). Synthese Des Arylimidazole Sous Irradiation Micro-Ondes En Milieu Sec. Tetrahedron Lett.36: 3683-3686.
- VanVilet, D.S., Gillespie, P., Scicinski, J.J. (2005). Rapid One-Pot Preparation of 2-Substituted Benzimidazoles from 2-Nitroanilines using Microwave Conditions. Tetrahedron Lett., 46: 6741-6743.
- Mobinikhaledi, A., Zendehdel, M., Jamshidi, F.H. (2007). Zeolite-catalyzed Synthesis of Substituted Benzimidazoles under Solvent-Free Condition and Microwave Irradiation. Synth. React. Inorg. Met.-Org. Chem., 37: 175-177.
- Kotbagi, T.V., Biradar, A.V., Umbarkar, S.B., Dongare, M.K. (2013). Isolation, Characterization, and Identification of Catalytically Active Species in the MoO3/SiO2 Catalyst during Solid Acid Catalyzed Reactions, ChemCatChem., 5: 1531-1537.
- El-Sharkawy, E.A., Khder A.S., Ahmed, A.I. (2007). Structural Characterization and Catalytic Activity of Molybdenum Oxide Supported Zirconia Catalysts. Micropor. Mesopor. Mater., 102: 128-137.
- Rao, K.N., Reddy, K.M., Lingaiah, N., Suryanarayana, I., Prasad, P.S. (2006). Structure and Reactivity of Zirconium Oxide-Supported Ammonium Salt of 12-Molybdophosphoric Acid Catalysts. J. Appl.Catal. A: Gen., 300: 139-146.
- Cid, R., Pecci, G. (1985). Potentiometric Method for Determining the Number and Relative Strength of Acid Sites in Colored Catalysts. J. Appl. Catal. A: Gen. 14: 15-21.
- Deshmukh, J.M., Dagade, S.P. (2018), Study of Structural and Catalytic Properties of Copper Supported Mixed Oxide Catalysts. International Journal of Current Advanced Research, 7: 13231-13235.
- Chari, M.A., Shobha, D., Sasaki, T. (2011). Room Temperature Synthesis of Benzimidazole Derivatives Using Re-usable Cobalt Hydroxide and Cobalt Oxide as an Efficient Solid Catalysts. Tetrahedron Lett., 52: 5575-5580.
- Chaudhari, C., Hakim Siddiki, S.M.A., Shimizu, K. (2015). Acceptorless Dehydrogenative Synthesis of Benzothiazoles and Benzimidazoles from Alcohols or Aldehydes by Heterogeneous Pt Catalysts under Neutral Conditions, Tetrahedron Lett., 56 (34): 4885-4888
- de Noronha, R.G., Ferrandes, A.C., Roao, C. (2009). MoO2Cl2 as a novel catalyst for Friedel craft acylation and sulfonylation. Tetrahedron Lett., 50: 1407-1410.
- Posternak, A.G., Garlyauskayte, R.Y., Yagupolskii, L.M. (2009). A novel Brønsted acid catalyst for Friedel–Crafts acylation, Tetrahedron Lett. 50: 446.
- Reichardt, C., Welton, T. (2011). Solvents and Solvent Effects in Organic Chemistry. 4th Ed. New York: Wiley-VCH, 303.
- Debecker, D.P., Mutin, P.H. (2012). Non-hydrolytic sol–gel routes to heterogeneous catalysts, Chem. Soc. Rev., 41: 3624.
- Gesser, H.D., Goswami, P.C. (1989). Aerogels and related porous materials, Chem. Rev. 89: 765
This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
As a journal Author, you have rights for a large range of uses of your article, including use by your employing institute or company. These Author rights can be exercised without the need to obtain specific permission.
Authors publishing in BCREC journals have wide rights to use their works for teaching and scholarly purposes without needing to seek permission, including: use for classroom teaching by Author or Author's institutionand presentation at a meeting or conference and distributing copies to attendees; use for internal training by author's company; distribution to colleagues for their reseearch use; use in a subsequent compilation of the author's works; inclusion in a thesis or dissertation; reuse of portions or extrcats from the article in other works (with full acknowledgement of final article); preparation of derivative works (other than commercial purposes) (with full acknowledgement of final article); voluntary posting on open web sites operated by author or author’s institution for scholarly purposes (follow CC by SA License).
Authors and readers can copy and redistribute the material in any medium or format, as well as remix, transform, and build upon the material for any purpose, even commercially, but they must give appropriate credit (cite to the article or content), provide a link to the license, and indicate if changes were made. If you remix, transform, or build upon the material, you must distribute your contributions under the same license as the original.
Copyright Transfer Agreement
The Authors submitting a manuscript do so on the understanding that if accepted for publication, copyright publishing of the article shall be assigned to Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University as publisher of the journal.
Copyright encompasses exclusive rights to reproduce and deliver the article in all form and media, including reprints, photographs, microfilms and any other similar reproductions, as well as translations. The reproduction of any part of this journal, its storage in databases and its transmission by any form or media, such as electronic, electrostatic and mechanical copies, photocopies, recordings, magnetic media, etc., will be allowed only with a written permission from Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University.
Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University, the Editors and the Advisory International Editorial Board make every effort to ensure that no wrong or misleading data, opinions or statements be published in the journal. In any way, the contents of the articles and advertisements published in the Bulletin of Chemical Reaction Engineering & Catalysis are sole and exclusive responsibility of their respective authors and advertisers.
Remember, even though we ask for a transfer of copyright, our journal authors retain (or are granted back) significant scholarly rights.
The Copyright Transfer Form can be downloaded here: [Copyright Transfer Form BCREC 2016]
The copyright form should be signed originally and send to the Editorial Office in the form of original mail, scanned document or fax :
Prof. Dr. I. Istadi (Editor-in-Chief)
Editorial Office of Bulletin of Chemical Reaction Engineering and Catalysis
Department of Chemical Engineering, Diponegoro University
Jl. Prof. Soedarto, Kampus Undip Tembalang, Semarang, Central Java, Indonesia 50275
Telp.: +62-24-7460058, Fax.: +62-24-76480675