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A Straightforward Selective Acylation of Phenols over ZSM-5 towards Making Paracetamol Precursors

1Organic Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Bandung Institute of Technology, Jalan Ganesha 10, Bandung 40132, Indonesia

2Inorganic and Physical Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Bandung Institute of Technology, Jalan Ganesha 10, Bandung 40132, Indonesia

Received: 29 Jun 2018; Revised: 1 Aug 2018; Accepted: 5 Aug 2018; Published: 4 Dec 2018; Available online: 14 Nov 2018.
Open Access Copyright (c) 2018 by Authors, Published by BCREC Group under http://creativecommons.org/licenses/by-sa/4.0.

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Abstract

Commercially available ZSM-5 was minimally treated as the catalyst to selectively acylate phenols. The ZSM-5 was simply immersed in ammonium nitrate in order to fill the pores with Brönsted acid to concentrate the catalytic reactions inside the pores. The reactions were carried out in liquid phase at 383 K. Acetic acid and propionic acid were chosen as the acyl substrate. Gas chromatography reveals two products which are phenyl acetate and almost exclusively para-hydroxyacetophenone meaning no ortho product observed. This para selectivity can be attributed to the pores of ZSM-5 where the reaction is assumed to be happening via intermolecular reaction. It is a relatively straightforward method in making para-hydroxyacetophenone which is known as paracetamol precursor. 

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Keywords: Acylation of Phenol; ZSM-5; Regioselectivity; Para-hydroxhyacetophenone
Funding: Riset Peningkatan Kapasitas ITB program

Article Metrics:

  1. Guisnet, M., Guidotti, M. (2006). Aromatic Acetylation in Catalysts for Fine Chemical Synthesis, John Wiley & Sons, Ltd. pp. 69-94
  2. Fritch, J.R., Fruchey, S.O., Horlenko, T., Aguilar, D.A., Hilton, C.B., Snyder, P.S., Seeliger, W.J. (1992). Production of Acetaminophen. U.S. Patent 5,155,273
  3. Commarieu, A., Hoelderich, W., Laffitte, J.A., Dupont, M.-P. (2002). Fries Rearrangement in Methane Sulfonic Acid, an Environmental Friendly Acid. Journal of Molecular Catalysis A: Chemical, 182–183: 137-141
  4. Uwaydah, I.M., Aslam, M., Brown II, C.H., Fitzhenry, S.R., Mcdonough, J.A. (1997). Syntheses Based on 2-Hydroxyacetophenone. U.S. Patent 5,696,274
  5. Drexler, M.T., Amiridis, M.D. (2003). The Effect of Solvents on the Heterogeneous Synthesis of Flavanone over MgO. Journal of Catalysis, 214: 136-145
  6. Climent, M.J., Corma, A., Iborra, S., Primo, J. (1995). Base Catalysis for Fine Chemicals Production: Claisen-Schmidt Condensation on Zeolites and Hydrotalcites for the Production of Chalcones and Flavanones of Pharmaceutical Interest. Journal of Catalysis, 151: 60-66
  7. Sartori, G., Maggi, R. (2011). Update 1 of: Use of Solid Catalysts in Friedel−Crafts Acylation Reactions. Chemical Reviews, 111: PR181-PR214
  8. Padró, C.L., Apesteguía, C.R. (2005). Acylation of Phenol on Solid Acids: Study of the Deactivation Mechanism. Catalysis Today, 107-108: 258-265
  9. Ashforth, R., Desmurs, J.-R., (1996). Friedel-crafts Acylation: Interactions Between Lewis Acids/Acyl Chlorides and Lewis Acids/Aryl Ketones. in Industrial Chemistry Library, Jean-Roger, D., Serge, R., Eds. Elsevier. 8: 3-14
  10. Das, D., Cheng, S. (2000). Friedel–Crafts Acylation of 2-Methoxynaphthalene over Zeolite Catalysts. Applied Catalysis A: General, 201: 159-168
  11. Arata, K. (1991). Synthesis of Solid Superacids by Metal Oxides and their Catalytic Action. Trends in Physical Chemistry, 2: 1-24
  12. Cundy, C.S., Higgins, R., Kibby, S.A.M., Lowe, B.M., Michael Paton, R. (1989). Para-selective Fries Rearrangement of Phenyl Acetate in the Presence of Zeolite Molecular Sieves. Tetrahedron Letters, 30: 2281-2284
  13. Borzatta, V., Poluzzi, E., Vaccari, A. (2002). In Science and Technology in Catalysis, Anpo, M.; Onaka, M., Yamashita, H., Eds. Elsevier: Amsterdam. p 439
  14. Subba Rao, Y.V., Kulkarni, S.J., Subrahmanyam, M., Rama Rao, A.V. (1995). An Improved Acylation of Phenol over Modified ZSM-5 Catalysts. Applied Catalysis A: General, 133: L1-L6
  15. Neves, I., Jayat, F., Magnoux, P., Pérot, G., Ribeiro, F.R., Gubelmann, M., Guisnet, M. (1994). Acylation of Phenol with Acetic Acid over a HZSM5 Zeolite, Reaction Scheme. Journal of Molecular Catalysis, 93: 169-179
  16. Chaube, V.D., Moreau, P., Finiels, A., Ramaswamy, A.V., Singh, A.P. (2002). A Novel Single Step Selective Synthesis of 4-Hydroxybenzophenone (4-HBP) Using Zeolite H-Beta. Catalysis Letters, 79: 89-94
  17. Padró, C.L., Sad, M.E., Apesteguía, C.R. (2006). Acid Site Requirements for the Synthesis of o-Hydroxyacetophenone by Acylation of Phenol with Acetic Acid. Catalysis Today, 116: 184-190
  18. Armaroli, T., Bevilacqua, M., Trombetta, M., Alejandre, A.d.G., Ramirez, J., Busca, G. (2001). An FT-IR Study of the Adsorption of Aromatic Hydrocarbons and of 2,6-Lutidine on H-FER and H-ZSM-5 Zeolites. Applied Catalysis A: General, 220: 181-190
  19. Pouilloux, Y., Bodibo, J.P., Neves, I., Gubelmann, M., Perot, G., Guisnet, M. (1991). Mechanism of Phenylacetate Transformation on Zeolites. In Studies in Surface Science and Catalysis, M. Guisnet, J.B.C.B.D.D.G.P.R.M., Montassier, C., Eds. Elsevier. 59: 513-522
  20. Chaube, V.D., Moreau, P., Finiels, A., Ramaswamy, A.V., Singh, A.P. (2001). Propionylation of Phenol to 4-Hydroxypropiophenone over Zeolite H-beta. Journal of Molecular Catalysis A: Chemical, 174: 255-264

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Last update: 2021-07-25 09:08:27

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