KF-Al2O3 as an Efficient and Recyclable Basic Catalyst for the Synthesis of 4H-Pyran-3-carboxylates and 5-Acetyl-4H-pyrans


KF-Al2O3 as a recyclable basic catalyst for the three-component synthesis of 4H-pyran derivatives by the reaction of aldehydes, malononitrile and active methylene dicarbonyl compounds in ethanol at room temperature is described. The protocol is environmentally benign and offers rapid access to a wide array of 4H-pyran heterocycles in good to excellent yields.

Share and Cite:

I. Kharbangar, M. Rohman, H. Mecadon and B. Myrboh, "KF-Al2O3 as an Efficient and Recyclable Basic Catalyst for the Synthesis of 4H-Pyran-3-carboxylates and 5-Acetyl-4H-pyrans," International Journal of Organic Chemistry, Vol. 2 No. 3, 2012, pp. 282-286. doi: 10.4236/ijoc.2012.23038.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] G. R. Green, J. M. Evans and A. K. Vong, “Comprehensive Heterocyclic Chemistry II,” In: A. R. Katritsky, C. Rees and E. F. V. Scriven, Eds., Pergamon Press, Oxford, 1995, pp. 469.
[2] W. O. Foye, “Prinicipi di Chemico Farmaceutica,” Piccin, Padora, 1991.
[3] L. Bonsignore, G. Loy, D. Secci and A. Calignano, “Synthesis and Pharmacological Activity of 2-Oxo-(2H)1-benzopyran-3-carboxamide Derivatives,” Euro-pean Journal of Medicinal Chemistry, Vol. 28, No. 6, 1993, pp. 517-520. Hdoi:10.1016/0223-5234(93)90020-F
[4] S. Hatakeyama, N. Ochi, H. Numata and S. Takano, “A New Route to Substituted 3-Methoxycarbonyldi-hydro-pyrans; En-antioselective Synthesis of (-)-Methyl Elenolate,” Journal of the Chemical Society, Chemical Communications, No. 17, 1988, pp. 1202-1204. Hdoi:10.1039/c39880001202
[5] R. Gonzalez, N. Martin, C. Seoane, J. L. Marco, A. Albert and F. H. Cano, “The First Asymmetric Synthesis of Poly- functionalized 4H-pyrans via Michael Addition to Malo- nonitrile to 2-Acyl Acrylates,” Tet-rahedron Letters, Vol. 33, No. 26, 1992, pp. 3809-3812.
[6] T. S. Jin, J. C. Xiao, S. J. Wang, T. S. Li and X. R. Song, “An Efficient and Convenient Approach to the Synthesis of Benzopyrans by a Three-Component Coupling of One-Pot Reaction,” Synlett, No. 13, 2003, pp. 2001-2004. Hdoi:10.1055/s-2003-42030
[7] S. Balalaie, M. Bararjanian, A. M. Amani and B. Movassagh, “(S)-Proline as a Neutral and Efficient Catalyst for the One-Pot Synthesis Tetrahydro-benzo[b]pyran Derivatives in Aqueous Media,” Synlett, Vol. 2, 2006, pp. 263- 266. Hdoi:10.1055/s-2006-926227
[8] T. S. Jin, A. Q. Wang, X. Wang, J. S. Zhang and T. S. Li, “A Clean One-Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives Catalyzed by Hexadecyltrimethyl Ammonium Bromide in Aqueous Media,” Synlett, No. 5, 2004, pp. 871-873. Hdoi:10.1055/s-2004-820025
[9] K. Singh, J. Singh and H. Singh, “A Synthetic Entry into Fused Pyran Derivatives through Carbon Transfer Reactions of 1,3-Oxazinanes and Oxazolidines with Carbon Nucleophiles,” Tetrahedron, Vol. 52, No. 45, 1996, pp. 14273-14280. Hdoi:10.1016/0040-4020(96)00879-4
[10] S. T. Tu, Y. Gao, C. Guo, D. Shi and Z. Lu, “A Conven- ient Synthesis of 2-Amino-5,6,7,8-tetrahydro-5-oxo-4- aryl-7,7-dimethyl-4H-benzo-[b]-pyran-3-carbonitrile under Microwave Irradiation,” Synthetic Communications, Vol. 32, No. 14, 2002, pp. 2137-2141. Hdoi:10.1081/SCC-120005420
[11] X. S. Wang, D. Q. Shi, S. J. Tu and C. S. Yao, “A Convenient Synthesis of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]pyran Derivatives Catalyzed by KF-Alumina,” Syn- thetic Communications, Vol. 33, No. 1, 2003, pp. 119-126. Hdoi:10.1081/SCC-120015567
[12] Z. Q. Jiang, S. J. Ji, J. Lu and J. M. Yang, “A Mild and Efficient Synthesis of 5-Oxo-5,6,7,8-tetrahydro-4H-benzo- [b]-pyran Derivatives in Room Temperature Ionic Liq- uids,” Chinese Journal of Chemistry, Vol. 23, No. 8, 2005, pp. 1085-1089. Hdoi:10.1002/cjoc.200591085
[13] B. C. Ranu and S. Banerjee, “A Task Specific Basic Ionic Liquid, [bmIm]OH-Promoted Efficient, Green and One- Pot Synthesis of Tetrahydro-benzo[b]pyran Derivatives,” Indian Journal of Chemistry, Vol. 47, No. 7, 2008, pp. 1108-1112.
[14] L.-Q. Yu, F. Liu and Q.-D. You, “One-Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives Catalyzed by Amines in Aqueous Media,” Organic Preparations and Proce- dures International: The New Journal for Organic Synthesis, Vol. 41, No. 1, 2009, pp. 77-82.
[15] D. M. Pore, K. A. Undale, B. B. Dongare and U. V. Desai, “Potas-sium Phosphate Catalyzed a Rapid Three-Compo- nent Synthesis of Tetrahydrobenzo[b]pyran at Ambient Temperature,” Catalysis Letters, Vol. 132, No. 1-2, 2009, pp. 104-108. Hdoi:10.1007/s10562-009-0074-0
[16] N. S. Babu, N. Pasha, K. T. Venkateswara Rao, P. S. S. Prasad and N. Lingaiah, “A Het-erogeneous Strong Basic Mg/La Mixed Oxide Catalyst for Efficient Synthesis of Polyfunctionalized Pyrans,” Tetrahedron Letters, Vol. 49, No. 17, 2008, pp. 2730-2733. Hdoi:10.1016/j.tetlet.2008.02.154
[17] B. E. Blass, “KF/Al2O3 Mediated Organic Synthesis,” Tetrahedron, Vol. 58, No. 46, 2002, pp. 9301-9320.
[18] B. A. Bunin, “The Combinatorial Index,” Academic, New York, 1998; (b) A. W. Czarnik and S. H. DeWitt, “A Practical Guide to Combinatorial Chemistry,” American Chemical Society, Washington, DC, 1997.
[19] K. C. Nicolaou, R. Hanko and W. Hartwig, “Handbook of Combina-torial Chemistry: Drugs, Catalysts, Materials,” Wiley-VCH, Weinheim, 2002. Hdoi:10.1002/3527603034
[20] M. R. Roh-man and B. Myrboh, “KF-Alumina Mediated Bargellini Reac-tion,” Tetrahedron Letters, Vol. 51, No. 36, 2010, pp. 4772-4775. Hdoi:10.1016/j.tetlet.2010.07.029
[21] M. R. Roh-man, M. Rajbangshi, B. M. Laloo, P. R. Sahu and B. Myrboh, “Iodine-Alumina as an Efficient and Useful Catalyst for the Regeneration of Carbonyl Functional- ity from the Corre-sponding 1,3-Oxathiolanes and 1,3- Dithiolanes in Aqueous System,” Tetrahedron Letters, Vol. 51, No. 26, 2010, pp. 2862-2864. Hdoi:10.1016/j.tetlet.2010.03.084
[22] G.-P. Lu and C. Cai, “A Facile, One-Pot, Green Synthesis of Polysubstituted 4H-Pyrans via Piperidine-Catalyzed Three-Component Condensation in Aqueous Medium,” Journal of Heterocyclic Chemistry, Vol. 48, No. 1, 2011, pp. 124-128. Hdoi:10.1002/jhet.528
[23] H. Valizadeh and A. A. Azimi, “ZnO/MgO Containing ZnO Nanopar-ticles as a Highly Effective Heterogeneous Base Catalyst for the Synthesis of 4H-Pyrans and Coumarins in [bmim]BF4,” Journal of the Iranian Chemical Society, Vol. 8, No. 1, 2011, pp. 123-130. Hdoi:10.1007/BF03246209

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.