Published 4 issues per year
ISSN Print: 2572-9896
ISSN Online: 2572-990X
Indexed in
COMPUTATIONAL MODELING STUDY OF ACYLATION OF PHENOL OVER ZEOLITES TO HYDROXYACETOPHENONES
Get access
ABSTRACT
Ortho- (o-HAP) and para-hydroxyacetophenone (p-HPA) isomers are intermediate compounds for the synthesis of fragrances and pharmaceuticals. In this study, molecular modeling was done to study the acylation of phenol on four potential zeolites, namely, MOR, beta-A, BETAPA, and ZSM-5 catalysts. The grand canonical Monte Carlo method was used, along with the NVT simulation techniques and force field-based calculations to investigate the adsorption, diffusion, and surface reaction, respectively. From this fundamental simulation study, it is concluded that this method can be applied to screen the potential zeolite catalysts. DMol3 was used to carry out the energy minimization and geometrical optimization at various stages by using the density functional theory. An investigation of the comparative sorption, diffusion, and surface binding of all the reacting, product, and intermediate species on these four zeolites was done. Diffusion was studied by making use of the Discover Module, which makes use of molecular dynamics to carry out the calculations. Much more particular properties are studied from the simulation, such as the energy and density distribution of components in silicalite crystal, the diffusivities of each component in the zeolites, the porosity, and accessible surface area of the zeolites, which are difficult to be explained by experiments.
-
Borzatta, V., Busca, G., Poluzzi, E., Rossetti, V., Trombetta, M., and Vaccari, A., As to the Reasons of the High Activity of a Commercial Pentasil-Type Zeolite in the Vapor-Phase Fries Rearrangement, Appl. Catal. A, vol. 257, pp. 85-95, 2004.
-
Bussai, C., Vasenkov, S., Liu, H., Bohlmann, W., Fritzsche, S., Hannongbua, S., Haberlandt, R., and Karger, J., On the Diffusion of Water in Silicalite-1: MD Simulations Using Ab Initio Fitted Potential and PFG NMR Measurements, Appl. Catal. A, vol. 232, pp. 59-66,2002.
-
Chen, N.Y. and Garwood, W.E., Industrial Application of Shape Selective Catalysis, Catal. Rev. Sci. Eng., vol. 28, pp. 185-264, 1986.
-
Choudary, B.M., Bhaskar, V., Lakshmi Kantam, M., Rao, K.K., and Raghavan, K.V., Acylation of Alcohols with Carboxylic Acids via the Evolution of Compatible Acidic Sites in Montmorillonites, Green Chem., vol. 2, pp. 67-70, 2000.
-
Commarieu, A., Holderich, W., Laffitee, J.A., and Dupont, M., Fries Rearrangement in Methane Sulfonic Acid, an Environmental Friendly Acid, J. Mol. Catal. A, vol. 182, pp. 137-141,2002.
-
Cybulski, A., Moulijn, J., Sharma, M.M., and Sheldon, R.A., Fine Chemicals Manufacture: Technology and Engineering, 1st Ed., Netherlands: Elsevier Science, 2001.
-
Davenport, K.G. and Hilton, C.B., Process for Producing N-Acyl-Hydroxy Aromatic Amines. US Patent 4,524,217, filed June 8, 1984, and issued June 18,1985.
-
Ferriz, J.M. and Vinsova, J., Prodrug Design of Phenolic Drugs, Curr. Pharmaceutical Des., vol. 16, no. 18, pp. 2033-2052,2010.
-
Fleys, M. and Thompson, R.W., Monte Carlo Simulations of Water Adsorption Isotherms in Silicalite and Dealuminated Zeolite Y, J. Chem. Theory Comput., vol. 1, pp. 453-458, 2005.
-
Friis, G.J. and Bundgaard, H., A Textbook of Drug Design and Development, 2nd Ed., P. Krogsgaard-Larsen, T. Liljefors, and U. Madsen, Eds., Amsterdam: Harwood Academic, 1996.
-
Frenkel, D. and Smit, B., Understanding Molecular Simulation: From Algorithm to Applications, San Diego: Academic Press, 2002.
-
Fritch, J., Fruchey, O.S., andHorlenko, T., Production of Acetaminophen. US Patent 4,954,652, filed December 7,1988 and issued September 4, 1990.
-
Ghiaci, M., Abbaspur, A., and Kalbasi, R.J., Internal versus External Surface Active Sites in ZSM-5 Zeolite Part 1. Fries Rearrangement Catalyzed by Modified and Unmodified H3PO4/ZSM-5, Appl. Catal. A., vol. 298, pp. 32-39, 2006.
-
Horsley, J.A., Fallmann, J.D., Derouane, E.G., and Freeman, C.M., Computer-Assisted Screening of Zeolite Catalysts for the Selective Isopropylation ofNaphthalene, J. Catal., vol. 147, pp. 231-240, 1994.
-
Hou, T.J., Zhu, L.L., and Xu, X.J., Adsorption and Diffusion of Benzene in ITQ-1 Type Zeolite: Grand Canonical Monte Carlo and Molecular Dynamics Simulation Study, J. Phys. Chem. B, vol. 104, pp. 9356-9364, 2000.
-
Jankovic, L. and Komadel, P., Metal Cation-Exchanged Montmorillonite Catalyzed Protection of Aromatic Aldehydes with Ac2O, J. Catal., vol. 218, pp. 227-233, 2003.
-
Kaeding, W.W., Chu, C., Young, L.B., Weinstein, B., and Butter, S.A., Selective Alkylation of Toluene with Methanol to Produce para-Xylene, J. Catal., vol. 67, pp. 159-174, 1981.
-
Kozhevnikova, E.F., Quartararo, J., and Kozhevnikov, I.V., Fries Rearrangement of Aryl Esters Catalysed by Heteropoly Acid, Appl. Catal. A, vol. 245, pp. 69-78, 2003.
-
Kozhevnikov, I.V., Friedel-Crafts Acylation and Related Reactions Catalyzed by Heteropoly Acids, Appl. Catal. A, vol. 256, pp. 3-18,2003.
-
Louis, A.C., Amit, G., and Randall, Q.S., Siting and Segregation Effects of Simple Molecules in Zeolites MFI, MOR, and BOG, J. Phys. Chem. B, vol. 102, pp. 6720-6731,1998.
-
Martyna, G.J., Explicit Reversible Integrators for Extended Systems Dynamics,Mol. Phys., vol. 87, pp. 1117-1157,1996.
-
Mouhtady, O., Iloughmane, H.G., Roques, N., and Roux, C.L., Metal Trifiates-Methanesulfonic Acid as New Catalytic Systems: Application to the Fries Rearrangement, Tetrahedron Lett., vol. 44, pp. 6379-6382, 2003.
-
Olah, G.A., Friedel-Crafts and Related Reactions, New York: Wiley-Interscience, 1964.
-
Padro, C.L. and Apesteguia, C.R., Gas-Phase Synthesis of Hydroxyacetophenones by Acylation of Phenol with Acetic Acid, J. Catal., vol. 226, pp. 308-320,2004.
-
Subba Rao, Y.V., Kulkarni, S.J., Subrahmanyam, M., and Rama Rao, A.V., Highly Selective Fries Rearrangement over Modified ZSM-5 Catalysts, Tetrahedron Lett., vol. 34, pp. 7799-7800,1993.
-
Uwaydah, I.M., Aslam, M., Brown, C.H., Fitzhenry, S.R., and McDonough, J.A., Syntheses based on 2-Hydroxyacetophenone. US Patent 5,696,274, filed May 22, 1996, and issued December 9,1997.
-
Veronique, L., Boutin, A., Tavitian, B., and Fuchs, A.H., Molecular Simulation of p-Xylene and m-Xylene Adsorption in Y Zeolites. Single Components and Binary Mixtures Study, Langmuir, vol. 15, pp. 8678-8685, 1999.
-
Wang, H. and Zou, Y., Modified Beta Zeolite as Catalyst for Fries Rearrangement Reaction, Catal. Lett., vol. 86, no. 4, pp. 163.
-
Yadav, G.D. and Patil, S.P., Selective Acylation of 2-Methoxynaphthalene by Large Pore Zeolites: Catalyst Selection through Molecular Modeling, Comput. Biol. Chem., vol. 27, pp. 393-404, 2003.