Application of Green Catalysts for the Esterification of Benzoic Acid with Different Alcohols

In this study, three different catalysts were applied as catalysts for esterification of benzoic acid with ethanol, butanol and hexanol. These catalysts are ionic liquid, deep eutectic solvent, ion exchange resin. Amberlyst 15, ion exchange resin, was used as control catalyst to observe the catalytic activity of new generation solvent, deep eutectic solvent. Deep eutectic solvents show the similar properties with ionic liquids and have great attraction due to ease of preparation, low cost and environmentally friendly nature. They have many advantages such as reusability, stability, catalytically activity and removal of the reaction mixture. Deep eutectic solvents (DES) are composed hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA). It has lower freezing point than that of individual constituents. In this study, p-toluene sulfonic acid (p-TSA) was used as HBD, benzyl tri-ethyl ammonium chloride (BTEAC) was used as HBA. DES formed by p-TSA and BTEAC was used as dual solventcatalyst for esterification of benzoic acid with different alcohols. DES gave high catalytic activity among three different catalysts, 88.3, 87.8 and 67.5% conversion of benzoic acid for ethanol, butanol and hexanol, respectively. The effects of time, temperature, alcohol type and catalyst type were investigated in a batch reactor at specified conditions. It was found that DES provided the simple, efficient and environmentally friendly method for the synthesis of benzoic acid ester

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1. Othmer, K. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; John Wiley & Sons: New York, NY, USA, 1994; p. 797.
2. Pipus, G., Plazl, I., Koloini, T., Esterification of benzoic acid in microwave tubular flow reactor, Chemical Engineering Journal, 2000, 76(3), 239-245.
3. Lilja, J., Yu, D., Murzin, Salmi, T., Aumo, J., Mäki-Arvela, P., Sundell, M., Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the Taft equation, Journal of Molecular Catalysis A: Chemical, 2002, 182, 555-563.
4. Rönnback, R., Salmi, T., Vuori, A., Haario, H., Lehtonen, J., Sundqvist, A., Tirronen, E., Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the Taft equation, Chemical Engineering Science, 1997, 52, 3369- 3381.
5. Liu, Y., Lotero, E., Goodwin Jr. J.G., Effect of water on sulfuric acid catalyzed esterification, Journal of Molecular Catalysis A: Chemical, 2006, 245(1-2), 132-140.
6. Buluklu, A.D., Sert, E., Karakus, S., Atalay, F.S., Development of Kinetic Mechanism for the Esterification of Acrylic Acid with Hexanol Catalyzed by Ion-Exchange Resin, International Journal of Chemical Kinetics, 2014, 46, 197-205.
7. Kirumakki, S. R., Nagaraju, N., Chary, K.V.R., Esterification of alcohols with acetic acid over zeolites Hβ, HY and HZSM5, Applied Catalysis A: General, 2006, 299, 185-192.
8. Sert, E., Atalay, F.S., Esterification of Acrylic Acid with Different Alcohols Catalyzed by Zirconia Supported Tungstophosphoric Acid, Industrial & Chemistry Research, 2012, 51, 6666-6671.
9. Rajabi, F., Abdollahi, M., Luque, R., Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst, Materials, 2016, 9, 557-563.
10. Gaifutdinova, E. K., Beresnev, V. V., Synthesis of Ethyl Benzoate by Ozonolysis of Styrene in the Presence of Ethanol, Russian Journal of Applied Chemistry, 2002, 75(3), 441-443.
11. Cai, Y.Q., Yu, G.Q., Liu, C. D., Xu, Y.Y., Wang, W., Imidazolium ionic liquid-supported sulfonic acids: Efficient and recyclable catalysts for esterification of benzoic acid, Chinese Chemical Letters, 2012, 23, 1-4.
12. Zhang, Q., Vigier, K. O., Royer, S., Jerome, F., Deep eutectic solvents: syntheses, properties and applications, Chemical Society Reviewes, 2012, 41, 7108-7146.
13. Kareem, M. A., Mjalli, F. S., Hashim, M. A., AlNashef, I. M., Phosphonium-Based Ionic Liquids Analogues and Their Physical Properties, Journal of Chemical Engineering Data, 2010, 55, 4632- 4637.
14. De Santi, V., Cardellini, F., Brinchi, L., Germani, R., Novel Brønsted acidic deep eutectic solvent as reaction media for esterification of carboxylic acid with alcohols, Tetrahedron Letters, 2012, 53, 5151-5155.
15. Taysun, M. B., Sert, E., Atalay, F. S., Physical properties of benzyl tri-methyl ammonium chloride based deep eutectic solvents and employment as catalyst, Journal of Molecular Liquids, 2016, 223, 845-852.
16. Taysun, M. B., Sert, E., Atalay, F. S., Effect of Hydrogen Bond Donor on the Physical Properties of Benzyltriethylammonium Chloride Based Deep Eutectic Solvents and Their Usage in 2- Ethyl-Hexyl Acetate Synthesis as a Catalyst, Journal of Chemical & Engineering Data, 2017, 62(4), 1173-1181.
17. Sert, E., Buluklu, A. D., Karakuş, S., Atalay, F.S., Kinetic study of catalytic esterification of acrylic acid with butanol catalyzed by different ion exchange resins, Chemical Engineering & Processing, 2013, 73, 23-28.
18. Marziano, N.C., Tortato, C. Ronchin, L., Bianchi, C., On the acidity of liquid and solid acid catalysts. Part 3. Esterification of benzoic and mesitoic acids, Catalysis Letters, 2000, 64, 15-22.
19. Barbosa, S. L., Ottone, M., Santos, M. C., Junior, G.C., Lima, C. D.,Glososki, G.C., Lopes, N.P., Klein, S.I., Benzyl benzoate and dibenzyl ether from of benzoic acid and benzyl alcohol under microwave irradiation using a SiO2–SO3H catalyst, Catalysis Communications, 2015, 68, 97-100.
20. Wu, M., Guo, J., Li, Y., Zhang, Y., Esterification of benzoic acid using Ti3AlC2 and SO4 2−/Ti3AlC2 ceramic as acid catalysts, Ceramics International, 2013, 39, 9731-9736.