PHOSPHOTUNGSTIC ACID SUPPORTED ON ACID-LEACHED POROUS KAOLIN FOR FRIEDEL-CRAFTS ACYLATION OF ANISOLE
DOI:
https://doi.org/10.11113/jt.v76.5819Keywords:
Porous clay heterostructure (PCH), phosphotungstic acid, Lewis and Brönsted acids, acylation of anisoleAbstract
Porous clay heterostructures (PCH) was derived from natural kaolin through intercalation with cationic potato starch as the template. Leaching of PCH was performed in concentrated acid solutions consisting of HCl and H2SO4. Phosphotungstic acid (HPW) supported on PCH and modified PCH were synthesized by wet impregnation method. The resulting PCH showed remarkable increase in surface area starting from 15 m2g–1 for the parent kaolin to maximium value of 725 m2g–1 for PCH. Acidity studies by pyridine adsorption and FTIR spectra showed that both natural kaolin and PCH possessed strong Lewis acid sites. In contrast, the surface acidity of HPW supported on PCH was significantly enhanced and comprising mainly Brönsted acid sites. The correlation between the Brönsted to Lewis acid ratios (B/L) and either conversion or selectivity of the catalysts has been studied in Friedel-Crafts acylation of anisole. The PCH/30HPW catalyst with the highest number of Brönsted acid sites showed excellent catalytic activity giving 86% conversion of anisole and high selectivity of 95% toward p-methoxypropiophenone.
References
Olah, G. A. 1973. Friedel-Crafts Chemistry. New York: John Wiley and Sons.
Spagnol, M., Gilbert, L. And Alby, D. 1996. In: J. R. Desmurs, S. Rattoy (Eds.). The Roots of Organic Development. Amsterdam: Elsevier.
Tanabe, K. and Hölderich, W. F. 1999. Industrial Application of Solid Acid–Base Catalysts. Applied Catalysis A: General. 181(2): 399-434.
Clark, J. H. 2002. Solid Acids for Green Chemistry. Acc. Chem. Res. 35(9): 791-797.
Nagendrappa, G. 2011. Organic Synthesis Using Clay and Clay-Supported Catalysts. Applied Clay Science. 53(2): 106-138.
Chen, F., Meng, X. and Xiao, F-S. 2010. Mesoporous Solid Acid Catalysts. Catal Surv Asia. 15: 37-48.
Kumbar, S. M. and Halligudi, S. B. 2007. Tungstophosphoric Acid Supported on Titania: A Solid Acid Catalyst in Benzylation of Phenol with Benzylalcohol. Catalysis Communications. 8(5): 800-806.
Hoelderich, W. F. 1993. New Reactions in Various Fields and Production of Specialty Chemicals. Stud. Surf. Sci. Catal. 75: 127-163.
Parida, K. M., Rana, S., Mallick, S. and D. Rath. 2010. Cesium Salts of Heteropoly Acid Immobilized Mesoporous Silica: An Efficient Catalyst for Acylation of Anisole. Journal of Colloid and Interface Science. 350: 132-139.
Ren, Y., Yue, B., Gu, M. and He, H. 2010. Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides. Materials. 3: 764-785.
Ibrahim, S. M. 2013. Catalytic Activity and Selectivity of Unsupported Dodecatungstophosphoric Acid, and Its Cesium and Potassium Salts Supported on Silica. Modern Research in Catalysis. 2(3): 110-118.
Kozhevnikov, I. V. 1998. Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions. Chem. Rev. 98: 171-198.
Kapustin, G. I., Brueva, T. R., Klyachko, A. L., Timofeeva, M. N., Kulikov, S. M. and Kozhevnikov, I. V. 1990. A Study of the Acidity of Heteropoly Acids. Kinet. Katal. 31: 1017-1020.
Castro, C., Corma, A. and Primo, J. 2002. On the Acylation Reactions of Anisole Using α,β-Unsaturated Organic Acids as Acylating Agents and Solid Acids as Catalysts: A Mechanistic Overview. Journal of Molecular Catalysis A: Chemical. 177(2): 273-280.
Yadav, G. D. and Kamble, S. B. 2012. Atom Efficient Friedel–Crafts Acylation of Toluene with Propionic Anhydride over Solid Mesoporous Superacid UDCaT-5. Applied Catalysis A: General. 433-434: 265-274.
Nguetnkam, J. P., Kamga, R., Villiéras, F., Ekodeck, G. E., Razafitianamaharavo, A. and Yvon, J. 2005. Assessment of the Surface Areas of Silica and Clay in Acid-Leached Clay Materials Using Concepts of Adsorption on Heterogeneous Surfaces. Journal of Colloid and Interface Science. 289(1): 104-115.
Kuźniarska-Biernacka, I., Silva, A. R., Carvalho, A. P., Pires, J. and Freire, C. 2010. Anchoring of Chiral Manganese(III) Salen Complex onto Organo Clay and Porous Clay Heterostructure and Catalytic Activity in Alkene Epoxidation. Catal Lett. 134: 63-71.
Larsson, A. and Wall, S. 1998. Flocculation of Cationic Amylopectin Starch and Colloidal Silicic Acid. The Effect of Various Kinds of Salt. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 139: 259-270.
Zheng, J. Y., Qiu, K. Y., Pang, J. B. and Wei, Y. 2002. Synthesis of Mesoporous Silica Materials via Non-surfactant Templated Sol-Gel Route by Using Mixture of Organic Compounds as Template. J of Sol-Gel Sci. and Techn. 24: 81-88.
Galarneau, A., Barodawalla, A. and Pinnavaia, T. J. 1995. Porous Clay Heterostructures Formed by Gallery-Templated Synthesis. Nature. 374: 529-531.
S. Chandren, Z. Ramli, H. Nur. 2010. Friedel-Crafts Alkylation of Resorcinol over Mesoporous Alumina Loaded with Sulfuric Acid. Int. J. Chem. Reactor Eng. 8: A40.
Madejova, J. 2003. FTIR Techniques in Clay Mineral Studies. Vibrational Spectroscopy. 31: 1-10.
Rocchiccioli-Deltcheff, C., Fournier, M., Franck, R. and Thouvenot, R. 1983. Vibrational Investigations of Polyoxometalates. 2. Evidence for Anion-Anion Interactions in Molybdenum(VI) and Tungsten(VI) Compounds Related to the Keggin Structure. Inorg Chem. 22: 207-216.
Nandi, B. K., Goswami, A. and Purkait, M. K. 2009. Adsorption Characteristics of Brilliant Green Dye on Kaolin. Journal of Hazardous Materials. 161: 387-395.
Konan, K. L., Peyratout, C., Bonnet, J. P., Smith, A., Jacquet, A., Magnoux, P. and Ayrault, P. 2007. Surface Properties of Kaolin and Illite Suspensions in Concentrated Calcium Hydroxide Medium. Journal of Colloid and Interface Science. 307: 101-108.
Madejová, J., Bujdák, J., Janek, M. and Komadel, P. 1998. Comparative FT-IR Study of Structural Modifications during Acid Treatment of Dioctahedral Smectites and Hectorite. Spectrochimica Acta Part A. 54: 1397-1406.
Corma, A., Climent, M. J., Garcia, H. and Primo, J. 1989. Design of Synthetic Zeolites as Catalsyts in Organic Reactions. Acylation of Anisole by Acyl Chlorides or Carboxylic Acids over Acid Zeolites. Appl. Catal., A. 49: 109-123.
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