Solvent Free Synthesis of α, á-Bis(substituted-benzylidene)cycloalkanones Using Covalently Anchored Sulfonic Acid on Silica Gel (SiO2-R-SO3H) as an Efficient and Reusable Heterogeneous Catalyst


We wish to report a mild and efficient Crossed-Aldol reaction for the synthesis of α, ?-bis(substituted-ben- zylidene)cycloalkanones in the presence of catalytic amounts of covalently anchored sulfonic acid onto sil- ica gel under heterogeneous and solvent-free conditions. The present methodology offers several advantages such as excellent yields, simple procedure and work up steps, short reaction times and easy recovery of the catalyst. We have also demonstrated that the catalyst can be reused successfully.

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A. Habibi, E. Sheikhhosseini, M. Bigdeli, S. Balalaie and E. Farrokhi, "Solvent Free Synthesis of α, á-Bis(substituted-benzylidene)cycloalkanones Using Covalently Anchored Sulfonic Acid on Silica Gel (SiO2-R-SO3H) as an Efficient and Reusable Heterogeneous Catalyst," International Journal of Organic Chemistry, Vol. 1 No. 4, 2011, pp. 143-147. doi: 10.4236/ijoc.2011.14021.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] D. Choudhary, S. Paul, R. Gupta and J. H. Clark, “Catalytic Properties of Several Palladium Complexes Covalently Anchored onto Silica for the Aerobic Oxidation of Alcohols,” Green Chemistry, Vol. 8, No. 5, 2006, pp. 479-482. doi:10.1039/b601363e
[2] B. Karimi, A. Zamani and J. H. Clark, “A Bipyridyl Palladium Complex Covalently Anchored onto Silica as an Effective and Recoverable Interphase Catalyst for the Aerobic Oxidation of Alcohols,” Organometallics, Vol. 24, No. 19, 2005, pp. 4695-4698. doi:10.1021/om050326m
[3] S. Paul and J. H Clark, “A Highly Active and Reusable Heterogeneous Catalyst for the Suzuki Reaction: Synthesis of Biaryls and Polyaryls,” Green Chemistry, Vol. 5, No. 5, 2003, pp. 635-638. doi:10.1039/b306097g
[4] M. Lagasi and P. Moggi, “Anchor-ing of Pd on Silica Functionalized with Nitrogen Containing Chelating Groups and Applications in Catalysis,” Journal of Molecular Catalysis A: Chemical, Vol. 182-183, 2002, pp. 61-72. doi:10.1016/S1381-1169(01)00478-2
[5] B. Das, K. Venka-teswarlu, H. Holla and M. Krishnaiah, “A Remarkably Efficient Heterogeneous Reusable Catalyst for α-Monobromination of Carbonyl Compounds Using N-Bromosuccinimide,” Journal of Molecular Catalysis A: Chemical, Vol. 253, No. 1-2, 2006, pp. 107- 111. doi:10.1016/j.molcata.2006.03.011
[6] B. Karimi and M, Khalkhali, “Solid Silica-Based Sulfonic Acid as an Efficient and Recoverable Interphase Catalyst for Selective Tetrahydropyranylation of Alcohols and Phenols,” Journal of Molecular Catalysis A: Chemical, Vol. 232, No. 1-2, 2005, pp. 113-117. doi:10.1016/j.molcata.2005.01.028
[7] P. Gupta, V. Kumar and S. Paul, “Silica Functionalized Sulfonic Acid Catalyzed One-pot Synthesis of 4,5,8a- Triarylhexahydropyrimi-do-[4,5-d]pyrimidine-2,7(1H,3H) -diones under Liquid Phase Catalysis,” Journal of Brazilian Chemical Society, Vol. 21, No. 2, 2010, pp. 249- 252. doi:10.1590/S0103-50532010000200022
[8] R. Gupta, S. Paul and R. Gupta, “Covalently Anchored Sulfonic Acid onto Silica as an Efficient and Recoverable Interphase Catalyst for the Synthesis of 3,4-Dihydropyrimidinones/Thiones,” Journal of Molecular Catalysis A: Chemical, Vol. 266, No. 1-2, 2007, pp. 50-54. doi:10.1016/j.molcata.2006.10.039
[9] A. T. Nielsen and W. J. Houlihan, “The Aldol Condensation,” In: R. Adams, A. H. Blatt, V. Boekelheide, T. L. Cairns, D. J. Cram and H. O. House, Eds., Organic Reactions, Wiley, New York, 1968.
[10] T. P. Robinson, R. B. Hubbard, T. J. Ehlers, J. L. Arbiser, D. J. Goldsmith and J. P. Bowen, “Synthesis and Biological Evaluation of Aromatic Enones Related to Curcumin,” Bioorganic & Medicinal Chemistry, Vol. 13, No. 24, 2005, pp. 4007-4013. doi:10.1016/j.bmc.2005.03.054
[11] A. T. Dinko-va-Kostova, C. Abeygunawardana and P. Talalay, “Chemopro-tective Properties of Phenylpropenoids, Bis(benzylidene)cycloalkanones, and Related Michael Reaction Acceptors: Correlation of Potencies as Phase 2 Enzyme Inducers and Radical Scave,” Journal of Medicinal Chemistry, Vol. 41, No. 26, 1998, pp. 5287- 5296. doi:10.1021/jm980424s
[12] A. Modzelewska, C. Pettit, G. Achanta, N. E. Davidson, P. Huang and S. R. Khan, “Anticancer Activities of Novel Chalcone and Bis-Chalcone Derivatives,” Bioorganic & Medicinal Chemistry, Vol. 14, No. 24, 2006, pp. 3491- 3495. doi:10.1016/j.bmc.2006.01.003
[13] C. Piantadosi, I. H. Hall, J. L. Irvine and G. L. Carlson, “Synthesis and Biological Activity of Alpha, Alpha’- dibenzylcycloalkanones,” Journal of Medicinal Chemistry, Vol. 16, No. 7, 1973, pp. 770-775. doi:10.1021/jm00265a006
[14] J. Kawamata, K. Inoue, T. Inabe, M. Kiguchi, M. Kato and Y. Taniguchi, “Large Second-Harmonic Generation Coefficients of Bis(benzylidine) Cycloalkanones Estimated by the Second-Harmonic Wave Generated with the Evanescent Wave Technique,” Chemical Physics Letters, Vol. 249, No. 1-2, 1996, pp. 29-34. doi:10.1016/0009-2614(95)01373-3
[15] J. Deli, T. Lorand, D. Szabo and A. Foldesi, “Potentially Bioactive Pyrimidine Deriva-tives. 1.2-Amino-4-aryl-8-a- ryli-dene-3,4,5,6,7,8-hexahydroquinazoline,” Pharmazie, Vol. 39, No. 8, 1984, pp. 539-540.
[16] N. J. Leonard, L. A. Miller and J. W. Berry, “The Synthesis of 2,7-Disubstituted Tropones via Aromatization,” Journal of the American Chemical Society, Vol. 79, No. 6, 1957, pp. 1482-1485. doi:10.1021/ja01563a056
[17] M. A. Ciufolini and N. E. Byrne. “The Total Synthesis of Cystodytins,” Journal of the American Chemical Society, Vol. 113, No. 21, 1991, pp. 8016-8024. doi:10.1021/ja00021a031
[18] B. A. Hathaway, “An Aldol Condensation Experiment Using a Number of Aldehydes and Ketones,” Journal of Chemical Education, Vol. 64, No. 4, 1987, p. 367. doi:10.1021/ed064p367
[19] T. Nakano, S. Irifune, S. Umano, A. Inada, Y. Ishii and M. Ogawa, “Cross-Condensation Reac-tions of Cycloalkanones with Aldehydes and Primary Alcohols under the Influence of Zirconocene Complexes,” The Journal of Organic Chemistry, Vol. 52, No. 11, 1987, pp. 2239- 2244. doi:10.1021/jo00387a025
[20] K. Irie and K. Watanabe, “Aldol Condensations with Metal(II) Complex Catalysts,” Bul-letin of the Chemical Society of Japan, Vol. 53, No. 5, 1980, pp. 1366-1371. doi:10.1246/bcsj.53.1366
[21] K. Li-Qin, S. Gong-Hua, W. Jia-Yi and W. Bang-Guo, “Synthesis of α, ? -Bis(substituted benzylidene)cycl- oalkanones Catalyzed by Ami-no-Functionalized Ionic Li- quid,” Journal of the Chinese Chemical Society, Vol. 55, No. 5, 2008, pp. 1125-1128.
[22] D. Song, Y. Chen, R. Wang, C. Liu, H. Jiang and G. Luo, “Crossed-Aldol Condensation of Cycloalkanones with Aromatic Aldehydes Catalyzed by Copper(II) Trifluoroacetate,” Preparative Biochemistry & Biotechnology, Vol. 39, No. 2, 2009, pp. 201-207. doi:10.1080/10826060902800874
[23] M. A. Bigdeli, G. H. Mahdavinia and H. Hazarkhani, “Wet 2,4,6-Trichloro[1,3,5]triazine (TCT) an Efficient Catalyst for Synthesis of α, ? -Bis(substituted-benzylidene) cycloalkanones under Solvent-Free Conditions,” Catalysis Communications, Vol. 8, No. 12, 2007, pp. 2228-2230.
[24] P. Salehi, M. Dabiri, M. A. Zolfigol and M. A. B. Fard, “Silica Sulfuric Acid as an Efficient and Reusable Reagent for Crossed-Aldol Condensation of Ketones with Aromatic Aldehydes under Solvent-Free Conditions,” Journal of Brazilian Chemical Society, Vol. 15, No. 5, 2004, pp. 773-777. doi:10.1590/S0103-50532004000500026
[25] M. G. Ziarani, A. Badiei, A. Abbasi and Z. Farahani, “Cross-Aldol Condensation of Cycloalkanones and Aromatic Aldehydes in the Presence of Nanoporous Silica- Based Sulfonic Acid (SiO2-Pr-SO3H) under Solvent Free Conditions,” Chinese Journal of Chemistry, Vol. 27, No. 8, 2009, pp. 1537-1542. doi:10.1002/cjoc.200990259
[26] L.-T. An, J.-P. Zou and L.-L. Zang, “Polymer-Supported Sulphonic Acid Catalyzed Cross-Aldol Condensation: An Expeditious Synthesis of α, ? -Bis(substituted benzyli- dene)cycloalkanones,” Catalysis Communications, Vol. 9, No. 3, 2008, pp. 349-354. doi:10.1016/j.catcom.2007.06.004
[27] G. H. Mahdavinia, M. A. Bigdeli and S. Y. Hayeniaz, “Covalently Anchored Sulfonic Acid on Silicagel (SiO2- R-SO3H) as an Efficient and Reusable Heterogeneous Catalyst for the One-Pot Synthesis of 1,8-Dioxo-octahy- droxanthenes under Solvent-Free Condi-tions,” Chinese Chemical Letters, Vol. 20, No. 5, 2009, pp. 539-541. doi:10.1016/j.cclet.2008.12.026
[28] G. A. Ziarani, A. Badiei, M. Hassanzadeh and S. Mousavi, “Synthesis of 1,8-Dioxo-decahydroacridine Derivatives Using Sulfonic Acid Functionalized Silica (SiO2- Pr-SO3H) under Solvent-Free Conditions,” Arabian Jour- nal of Chemistry, 2011, in press.

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