Silica-Grafted Ionic Liquids as Recyclable Catalysts for the Synthesis of 3,4-Dihydropyrano[c]chromenes and Pyra-no[2,3-c]pyrazoles


Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.

Share and Cite:

K. Niknam and A. Piran, "Silica-Grafted Ionic Liquids as Recyclable Catalysts for the Synthesis of 3,4-Dihydropyrano[c]chromenes and Pyra-no[2,3-c]pyrazoles," Green and Sustainable Chemistry, Vol. 3 No. 2A, 2013, pp. 1-8. doi: 10.4236/gsc.2013.32A001.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] P. Wasserscheid and T. Welton, “Ionic Liquids in Synthesis,” 2nd Edition, Wiley-VCH, Weinheim, 2007. doi:10.1002/9783527621194
[2] W. Keim, W. Korth and P. Wasserscheid, “Ionic Liquids,” Patent WO/2000/016902, March 30, 2000.
[3] P. Wasserscheid, M. Sesing and W. Korth, “Hydrogensulfate and Tetrakis(Hydrogensulfato)borate Ionic Liquids: Synthesis and Catalytic Application in Highly Bronsted-Acidic Systems for Friedel-Crafts Alkylation,” Green Chemistry, Vol. 4, No. 2, 2002, pp. 134-138. doi:10.1039/b109845b
[4] N. Gupta, G. L. Sonu, J. Kad and Singh, “Acidic Ionic Liquid [bmim]HSO4: An Efficient Catalyst for Acetalization and Thioacetalization of Carbonyl Compounds and Their Subsequent Deprotection,” Catalysis Communications, Vol. 8, No. 9, 2007, pp. 1323-1328. doi:10.1016/j.catcom.2006.11.030
[5] D. Q. Xu, W. L. Yang, S. P. Luo, B. T. Wang, M. Wu and Z. Y. Xu, “Fischer Indole Synthesis in Bronsted Acidic Ionic Liquids: A Green, Mild, and Regiospecific Reaction System,” European Journal of Organic Chemistry, No. 6, 2007, pp. 1007-1012. doi:10.1002/ejoc.200600886
[6] W. Wang, W. Cheng, L. Shao and J. Yang, “[TMBSA] [HSO4] Ionic Liquid as Novel Catalyst for the Rapid Acetylation of Alcohols, Hydroxyesters and Phenols under Solvent-Free Conditions,” Catalysis Letters, Vol. 121, No. 1-2, 2008, pp. 77-80. doi:10.1007/s10562-007-9295-2
[7] A. R. Hajipour, A. Rajaei and A. E. Ruoho, “A Mild and Efficient Method for Preparation of Azides from Alcohols Using Acidic Ionic Liquid [H-NMP]HSO4,” Tetrahedron Letters, Vol. 50, No. 6, 2009, pp. 708-711. doi:10.1016/j.tetlet.2008.11.111
[8] H. Tajik, K. Niknam and F. Parsa, “Using Acidic Ionic Liquid 1-Butyl-3-Methylimidazolium Hydrogen Sulfate in Selective Nitration of Phenols under Mild Conditions,” Journal of the Iranian Chemical Society, Vol. 6, No. 1, 2009, pp. 159-164.
[9] K. Niknam and M. Damya, “1-Butyl-3-Methylimidazolium Hydrogen Sulfate [bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Synthesis of 1,8-Dioxo-Octahydroxanthenes,” Journal of the Chinese Chemical Society, Vol. 56, No. 3, 2009, pp. 659-665.
[10] K. Niknam, M. A. Zolfigol, D. Saberi and M. Khonbazi, “1-Butyl-3-Methylimidazolium Hydrogen Sulfate [bmim] HSO4: An Efficient Reusable Acidic Ionic Liquid for the Formylation of Alcohols,” Chinese Journal of Chemistry, Vol. 27, No. 8, 2009, pp. 1548-1552. doi:10.1002/cjoc.200990261
[11] H. Tajik, K. Niknam and M. Sarrafan, “1-Butyl-3-Methylimidazolium Hydrogen Sulfate ([bmim]-HSO4) Mediated Synthesis of Polysubstituted Quinolines,” Synthetic Communications, Vol. 41, No. 14, 2011, pp. 2103-2114. doi:10.1080/00397911.2010.497596
[12] K. Qiao, H. Hagiwara and C. Yokoyama, “Acidic Ionic Liquid Modified Silica Gel as Novel Solid Catalysts for Esterification and Nitration Reactions,” Journal of Molecular Catalyst A: Chemicals, Vol. 246, No. 1-2, 2006, pp. 65-69. doi:10.1016/j.molcata.2005.07.031
[13] R. Sugimura, K. Qiao, D. Tomida and C. Yokoyama, “Immobilization of Acidic Ionic Liquids by Copolymerization with Styrene and Their Catalytic Use for Acetal formation,” Catalysis Communications, Vol. 8, No. 5, 2007, pp. 770-772. doi:10.1016/j.catcom.2006.08.049
[14] A. Chrobok, S. Baj, W. Pudlo and A. Jarzebski, “Supported Hydrogensulfate Ionic Liquid Catalysis in Baeyer-Villiger Reaction,” Applied Catalysis A: General, Vol. 366, No. 1, 2009, pp. 22-28. doi:10.1016/j.apcata.2009.06.040
[15] M. N. Sefat, D. Saberi and K. Niknam, “Preparation of Silica-Based Ionic Liquid an Efficient and Recyclable Catalyst for One-Pot Synthesis of a-Aminonitriles,” Catalysis Letters, Vol. 141, No. 11, 2011, pp. 1713-1720. doi:10.1007/s10562-011-0696-x
[16] M. Baghernejad and K. Niknam, “Synthesis of 4,4’-(Arylmethylene)bis(1H-pyrazol-5-ols) Using Silica-Bonded Ionic Liquid as Recyclable Catalyst,” International Journal of Chemistry, Vol. 4, No. 3, 2012, pp. 52-60. doi:10.5539/ijc.v4n3p52
[17] G. R. Green, J. M. Evans and A. K. Vong, “Comprehensive Heterocyclic Chemistry II,” Pergamon Press, Oxford, 1995, p. 469.
[18] W. O. Foye, “Principi di Chemico Farmaceutica,” Piccin, Padova, 1991, p. 416.
[19] L. Bonsignore, G. Loy, D. Secci and A. Calignano, “Synthesis and Pharmacological Activity of 2-Oxo-(2H) 1-benzopyran-3-Carboxamide Derivatives,” European Journal of Medicinal Chemistry, Vol. 28, No. 6, 1993, pp. 517-520. doi:10.1016/0223-5234(93)90020-F
[20] C. S. Konkoy, D. B. Fick, S. X. Cai, N. C. Lan and J. F. W. Keana, PCT Int Appl, WO 0075123, 2000, [Chem Abstr, Vol. 134, 2001, 29313a].
[21] D. Arnesto, W. M. Horspool, N. Martin, A. Ramos and C. Seaone, “Synthesis of Cyclobutenes by the Novel Photo-Chemical Ring Contraction of 4-Substituted 2-Amino-3,5-Dicyano-6-Phenyl-4H-Pyrans,” The Journal of Organic Chemistry, Vol. 54, No. 13, 1989, pp. 3069-3072. doi:10.1021/jo00274a021
[22] R. M. Shaker, “Synthesis and Reactions of Some New 4H-Pyranol[3,2-c]benzopyran-5-One Derivatives and Their Potential Biological Activities,” Pharmazie, Vol. 51, No. 3, 1996, pp. 148-151.
[23] M. Kidwai and S. Saxena, “Convenient Preparation of Pyrano Benzopyranes in Aqueous Media,” Synthetic Communications, Vol. 36, No. 18, 2006, pp. 2737-2742. doi:10.1080/00397910600764774
[24] S. Abdolmohammadi and S. Balalaie, “Novel and Efficient Catalysts for the One-Pot Synthesis of 3,4-Dihydropyrano[c]chromene Derivatives in Aqueous Media,” Tetrahedron Letters, Vol. 48, No. 18, 2007, pp. 3299-3303. doi:10.1016/j.tetlet.2007.02.135
[25] J. M. Khurana and S. Kumar, “Tetrabutylammonium Bromide (TBAB): A Neutral and Efficient Catalyst for the Synthesis of Biscoumarin and 3,4-Dihydropyrano[c]-Chromene Derivatives in Water and Solvent-Free Conditions,” Tetrahedron Letters, Vol. 50, No. 28, 2009, pp. 4125- 4127. doi:10.1016/j.tetlet.2009.04.125
[26] H. Mehrabi and H. Abusaidi, “Synthesis of Biscoumarin and 3,4-Dihydropyrano[c]chromene Derivatives Catalysed by Sodium Dodecyl Sulfate (SDS) in Neat Water,” Journal of the Iranian Chemical Society, Vol. 7, No. 4, 2010, pp. 890-894.
[27] J. M. Khurana, B. Nand and P. Saluja, “DBU: A Highly Efficient Catalyst for One-Pot Synthesis of Substituted 3,4-dihydropyrano[3,2-c]chromenes, Dihydropyrano- [4,3-b] pyranes, 2-Amino-4Hbenzo[h]chromenes and 2-Amino-4H benzo[g]chromenes in Aqueous Medium,” Tetrahedron, Vol. 66, No. 30, 2010, pp. 5637-5641. doi:10.1016/j.tet.2010.05.082
[28] M. M. Heravi, M. Zakeri and N. Mohammadi, “Morpholine Catalyzed One-pot Multicomponent Synthesis of Compounds Containing Chromene Core in Water,” Chinese Journal of Chemistry, Vol. 29, No. 6, 2011, pp. 1163-1166. doi:10.1002/cjoc.201190217
[29] H. Nagabhushana, S. S. Saundalkar, L. Muralidhar, B. M. Nagabhushana, C. R. Girija, D. Nagaraja, M. A. Pasha and V. P. Jayashankara, “a-Fe2O3 Nanoparticles: An Efficient, Inexpensive Catalyst for the One-Pot Preparation of 3,4-Dihydropyrano[c]chromenes,” Chinese Chemical Letters, Vol. 22, No. 2, 2011, pp. 143-146. doi:10.1016/j.cclet.2010.09.020
[30] H. Mehrabi and M. Kazemi-Mireki, “CuO Nanoparticles: An Efficient and Recyclable Nanocatalyst for the Rapid and Green Synthesis of 3,4-Dihydropyrano[c]chromenes,” Chinese Chemical Letters, Vol. 22, No. 12, 2011, pp. 1419-1422. doi:10.1016/j.cclet.2011.06.003
[31] K. Niknam and A. Jamali, “Silica-Bonded N-Propylpiperazine Sodium n-Propionate as Recyclable Basic Catalyst for Synthesis of 3,4-Dihydropyrano[c]chromene Derivatives and Biscoumarins,“ Chinese Journal of Catalysis, Vol. 33, No. 11, 2012, pp. 1840-1849. doi:10.1016/S1872-2067(11)60457-9
[32] M. H. Elnagdi, M. R. H. Elmaoghayer and G. E. H. Elgemeie, “Chemistry of Pyrazolopyrimidines,” Advance in Heterocyclic Chemistry, Vol. 41, 1987, pp. 319-376. doi:10.1016/S0065-2725(08)60164-6
[33] F. Karci and F. Karci, “Synthesis of Some Novel Pyrazolo[5,1-c][1,2,4]triazine Derivatives and Investigation of Their Absorption Spectra,” Dyes and Pigments, Vol. 76, No. 1, 2008, pp. 97-103. doi:10.1016/j.dyepig.2006.08.011
[34] S. G. Kuo, L. J. Huang and H. Nakamura, “Studies on Heterocyclic Compounds. 6. Synthesis and Analgesic and Antiinflammatory Activities of 3,4-Dimethylpyrano-[2,3-c] pyrazol-6-one Derivatives,” Journal of Medicinal Chemistry, Vol. 27, No. 4, 1984, pp. 539-544. doi:10.1021/jm00370a020
[35] A. A. Fadda, A. A. H. Abdel-Rahman, E. A. Hamed and E. H. Khalil, “Utility of Enaminonitriles in Heterocyclic Synthesis: Synthesis and Antimicrobial Activity of Some New Azole and Azine Derivatives,” American Journal of Organic Chemistry, Vol. 2, No. 2, 2012, pp. 7-13. doi:10.5923/j.ajoc.20120202.02
[36] N. M. Abunada, H. M. Hassaneen, N. G. Kandile and O. A. Miqdad, “Synthesis and Antimicrobial Activity of Some New Pyrazole, Fused Pyrazolo[3,4-d]-pyrimidine and Pyrazolo[4,3-e][1,2,4]-triazolo[1,5-c]pyrimidine Derivatives,” Molecules, Vol. 13, No. 7, 2008, pp. 1501-1517. doi:10.3390/molecules13071501
[37] N. J. Thumar and M. P. Patel, “Synthesis and in Vitro Antimicrobial Evaluation of 4H-Pyrazolopyran, Benzopyran and Naphthopyran Derivatives of 1H-Pyrazole,” Arkivoc, No. 13, 2009, pp. 363-380.
[38] D. Shi, J. Mou, Q. Zhuang, L. Niu, N. Wu and X. Wang, “Three-Component One-Pot Synthesis of 1,4-Dihydropyrano[2,3-c]pyrazole Derivatives in Aqueous Media,” Synthetic Communications, Vol. 34, No. 24, 2004, pp. 4557-4563. doi:10.1081/SCC-200043224
[39] T. S. Jin, A. Q. Wang, Z. L. Cheng, J. S. Zhang and T. S. Li, “A Clean and Simple Synthesis of 6-Amino-4-Aryl-5-Cyano-3-Methyl-1-Phenyl-1,4-Dihydropyrano[2,3-c]Pyrazole in Water,” Synthetic Communications, Vol. 35, No. 1, 2005, pp. 137-143. doi:10.1081/SCC-200046527
[40] S. B. Guo, S. X. Wang and J. T. Li, “D,L-Proline-Catalyzed One-Pot Synthesis of Pyrans and Pyrano[2,3-c]pyrazole Derivatives by a Grinding Method under Solvent-Free Conditions,” Synthetic Communications, Vol. 37, No. 13, 2007, pp. 2111-2120. doi:10.1080/00397910701396906
[41] F. Lehmann, M. Holm and S. Laufer, “Three-Component Combinatorial Synthesis of Novel Dihydropyrano[2,3-c] pyrazoles,” Journal of Combinatorial Chemistry, Vol. 10, No. 3, 2008, pp. 364-367. doi:10.1021/cc800028m
[42] H. M. Al-Matar, K. D. Khalil, A. Y. Adam and M. H. Elnagdi, “Green One Pot Solvent-Free Synthesis of Pyrano[2,3-c]-Pyrazoles and Pyrazolo[1,5-a]Pyrimidines,” Molecules, Vol. 15, No. 9, 2010, pp. 6619-6629. doi:10.3390/molecules15096619
[43] M. M. Heravi, A. Ghods, F. Derikvand, K. Bakhiari and F. F. Bamoharram, “H14[NaP5W30O110] Catalyzed One-Pot Three-Component Synthesis of Dihydropyrano[2,3-c]pyrazole and pyrano[2,3-d]pyrimidine Derivatives,” Journal of the Iranian Chemical Society, Vol. 7, No. 3, 2010, pp. 615-620.
[44] A. Siddekha, A. Nizam and M. A. Pasha, “An Efficient and Simple Approach for the Synthesis of Pyranopyrazoles Using Imidazole (Catalytic) in Aqueous Medium, and the Vibrational Spectroscopic Studies on 6-Amino-4-(4’Methoxyphenyl)-5-Cyano-3-Methyl-1-Phenyl-1,4-Dihydropyrano[2,3-c]pyrazole Using Density Functional Theory,” Spectrochimica Acta Part A: Molecular and Bio- molecular Spectroscopy, Vol. 81, No. 1, 2011, pp. 431-440. doi:10.1016/j.saa.2011.06.033
[45] A. Hasaninejad, M. Shekouhy, N. Golzar, A. Zare and M. M. Doroodmand, “Silica Bonded n-Propyl-4-Aza-1-Azoniabicyclo[2.2.2]octane chloride (SB-DABCO): A Highly Efficient, Reusable and New Heterogeneous Catalyst for the Synthesis of 4H-Benzo[b]pyran Derivatives,” Applied Catalysis A: General, Vol. 402, No. 1-2, 2011, pp. 11-22. doi:10.1016/j.apcata.2011.04.012
[46] H. Mecadon, M. R. Rohman, M. Rajbangshi and B. Myrboh, “γ-Alumina as a Recyclable Catalyst for the Four-Component Synthesis of 6-Amino-4-Alkyl/Aryl-3-methyl-2,4-Dihydropyrano[2,3-c]pyrazole-5-carbonitriles in aqueous medium,” Tetrahedron Letters, Vol. 52, No. 19, 2011, pp. 2523-2525.
[47] S. R. Mandha, S. Siliveri, M. Alla, V. R. Bommena, M. R. Bommineni and S. Balasubramanian, “Eco-Friendly Synthesis and Biological Evaluation of Substituted Pyrano [2,3-c]pyrazoles,” Bioorganic and Medicinal Chemistry Letters, Vol. 22, No. 16, 2012, pp. 5272-5278. doi:10.1016/j.tetlet.2011.03.036
[48] S. H. S. Azzam and M. A. Pasha, “Simple and Efficient Protocol for the Synthesis of Novel Dihydro-1H-pyrano [2,3-c]pyrazol-6-Ones via a One-Pot Four-Component Reaction,” Tetrahedron Letters, Vol. 53, No. 50, 2012, pp. 6834-6837.

Copyright © 2020 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.