IJOC  Vol.3 No.3 , September 2013
Regioselective Direct Carboxylation of 2-Naphthol with Supercritical CO2 in the Presence of K2CO3
Abstract: A direct regioselective preparation of 2-hydroxynaphthalene-6-carboxylic acid, a useful industrial intermediate of aro-matic polyester from 2-naphthol was conducted by use of excess amount of K2CO3 (10-fold molar to 2-naphthol) under supercritical CO2 at 10 MPa and 473 K. The obtained yield under this condition was ca. 20 mol% to 2-naphthol. The further investigations may provide an alternative process to the conventional Kolbe-Schmitt reaction, because of no use of strong alkali and recoverability of K2CO3. Theoretical explanation about the regioselectivity was achieved by means of DFT calculations.
Cite this paper: S. Furukawa, K. Otokawa, O. Sasaki, K. Nakayasu and T. Yamaguchi, "Regioselective Direct Carboxylation of 2-Naphthol with Supercritical CO2 in the Presence of K2CO3," International Journal of Organic Chemistry, Vol. 3 No. 3, 2013, pp. 210-213. doi: 10.4236/ijoc.2013.33028.

[1]   S. A. Lindsey and H. Jesky, “The Kolbe-Schmitt Reaction,” Chemical Reviews, Vol. 57, No. 4, 1957, pp. 583-620. doi:10.1021/cr50016a001

[2]   F. Seidel, L. Wolf and H. Krause, “über die Bildungsweise der 2-Oxynaphthoesaure-(3),” Journal für Praktische Chemie, Vol. 91, No. 1-2, 1955, pp. 53-83. doi:10.1002/prac.19550020105

[3]   W. H. Meek and C. H. Fuchsmann, “Carboxylation of Substituted Phenols in N,N-Dimethylamide Solvents at Atmospheric Pressure,” Journal of Chemical & Engineering Data, Vol. 14, No. 4, 1968, pp. 388-391. doi:10.1021/je60042a005

[4]   T. Yamaguchi, N. Nagaoka and K. Takahashi, “The Carboxylation of Naphthols by Kolbe-Schmitt Reaction in the Homogeneous Solution,” The Chemical Society of Japan, No. 7, 1989, pp. 1164-1165.

[5]   T. Iijima, T. Iwase and T. Yamaguchi, “Carboxylation of 2-Naphthol with Carbon Dioxide in Anisole,” Journal of the Japan Petroleum Institute, Vol. 49, No. 4, 2006, pp. 206-209. doi:10.1627/jpi.49.206

[6]   T. Iijima, D. Takagi and T. Yamaguchi, “Carboxylation of 2-Naphthol in Kerosene,” Journal of the Japan Petroleum Institute, Vol. 31, No. 1, 2008, pp. 65-69. doi:10.1627/jpi.51.65

[7]   J. Baxter and T. Yamaguhi, “Effect of Cation Capture by Crown Ether and Polar Solvent in the Carboxylation with CO2 of Alkali Metal 2-Naphtholate under Ordinary Conditions,” Journal of Chemical Research (S), 1997, pp. 374-375. doi:10.1039/A703432F

[8]   T. Iijima and T. Yamaguchi, “The Improved Kolbe— Schmitt Reaction Using Supercritical Carbon Dioxide,” Tetahedron Letters, Vol. 48, No. 30, 2007, pp. 5309-5311. doi:10.1016/j.tetlet.2007.05.132

[9]   T. Iijima and T. Yamaguchi, “Efficient Regioselective Carboxylation of Phenol to Salicylic Acid with Supercritical CO2 in the Presence of Aluminum Bromide,” Journal of Molecular Catalysis A: Chemical, Vol. 295, 2008, pp. 52-56. doi:10.1016/j.molcata.2008.07.017

[10]   T. Iijima and T. Yamaguchi, “K2CO3-Catalyzed Direct Synthesis of Salicylic Acid from Phenol and Supercritical CO2,” Applied Catalysis A: General, Vol. 345, No. 1, 2008, pp. 12-17. doi:10.1016/j.apcata.2008.03.037

[11]   S. Fujita, B. M. Bhanage, Y. Ikushima and M. Arai, “Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol in the Presence of Methyl Iodide and Base Catalysts under Mild Conditions: Effect of Reaction Conditions and Reaction Mechanism,” Green Chemistry, Vol. 3, No. 2, 2001, pp. 87-91. doi:10.1039/b100363l

[12]   T. Sakakura, Y. Saito, M. Okano, J. Choi and C. T. Sako, “Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis,” The Journal of Organic Chemistry, Vol. 63, No. 20, 1998, pp. 7095-7096. doi:10.1021/jo980460z

[13]   J. F. Brennkeand and J. E. Chateauneuf, “Homogeneous Organic Reactions as Mechanistic Probes in Supercritical Fluids,” Chemical Reviews, Vol. 99, No. 2, 1999, pp. 433-452. doi:10.1021/cr970035q

[14]   Y. Du, F.Cai, D.-L.Kong and L.-N. He, “Organic Solvent-Free Process for the Synthesis of Propylene Carbonate from Supercritical Carbon Dioxide and Propylene Oxide Catalyzed by Insoluble Ion Exchange Resins,” Green Chemistry, Vol. 7, No. 7, 2005, pp. 518-523. doi:10.1039/b500074b

[15]   G. Steinebrunner, A. J. Dyson, B. Kirchner and H. Hanspeter, “Structural and Thermodynamic Properties of Fluid Carbon Dioxide from a New ab initio Potential Energy Surface,” Journal of Chemical Physics, Vol. 109, 1998, Article ID. 3153. doi:10.1063/1.476922

[16]   K. Rah and B. Eu, “Density Fluctuations and Shear Viscosity of Molecular Liquids: Carbon Dioxide and Nitrogen,” Journal of Chemical Physics, Vol. 112, No. 16, 2000, pp. 7118-7138. doi: 0.1063/1.481306

[17]   Z. Markovic, J. P. Engelbrecht and S. Markovic and Z. Naturforch, “Theoretical Study of the Kolbe-Schmitt Reaction Mechanism,” Zeitschrift für Naturforchung, Vol. 57a, 2002, pp. 812-818.

[18]   Y. Kosugi, Y. Imaoka, F. Gotoh, M. A. Rahim, Y. Matsui and K. Sakanishi, “Carboxylations of Alkali Metal Phenoxides with Carbon Dioxide,” Organic & Biomolecular Chemistry, Vol. 1, No. 5, 2003, pp. 817-821. doi:10.1039/b210793g