Grinding Synthesis of Pyrazolyl-Bis Coumarinyl Methanes Using Potassium 2-Oxoimidazolidine-1,3-diide

Author(s): Kazem Hematinezhad, Mohammad Nikpassand*, Leila Zare Fekri.

Journal Name: Current Organic Synthesis

Volume 16 , Issue 2 , 2019

Submit Manuscript
Submit Proposal

Graphical Abstract:


Aim and Objective: Potassium 2-oxoimidazolidine-1,3-diide (POImD) as a novel and reusable catalyst was used for the synthesis of pyrazolyl-bis coumarinyl methanes by a nucleophilic addition reaction of synthetized pyrazolecarbaldehyde and two equivalents of 4-hydroxycoumarin under grinding. The catalyst can be reused and recovered several times without loss of activity. This method provides several advantages such as eco-friendliness, simple work-up and shorter reaction time as well as excellent yields. All of the synthesized compounds were characterized by IR, 1H and 13C NMR spectroscopy and elemental analyses.

Material and Method: Synthetized pyrazole carbaldehyde 1a (1 mmol), 4-hydroxycoumarin 2 (2 mmol), 1 mmol of POImD and 10mL of H2O were ground in a mortar by a pestle for 30-90 minutes. After the completion of the reaction, as monitored by TLC on silica gel using ethyl acetate/n-hexane (1:2), the mixture was allowed to cool to room temperature. After completion of the reaction, we extracted the product with CH2Cl2/H2O. This was followed by separation of phases, evaporation of the organic phase and recrystallization of the residue with 50 mL of ethanol/H2O (1:1). The pure product was then obtained in 87 to 96% yield. The aqueous phase was concentrated under reduced pressure to recover the catalyst for subsequent use.

Results: To continue our ongoing studies to synthesize heterocyclic and pharmaceutical compounds by mild, facile and efficient protocols, herein we wish to report our experimental results on the synthesis of pyrazolylbis coumarinyl methanes, using various synthetized pyrazole carbaldehydes and 4-hydroxycoumarin in the presence of POImD in aqueous media at room temperature.

Conclusion: Finally, we developed an efficient, fast and convenient procedure for the three-component synthesis of pyrazolyl-bis coumarinyl methanes through the reaction of pyrazole carbaldehydes and 4- hydroxycoumarin, using POImD as a novel and reusable catalyst. The remarkable advantage offered by this method is that the catalyst is non-toxic, inexpensive, easy to handle and reusable. A short reaction time, simple work-up procedure, high yields of product with better purity and the green aspect by avoiding a hazardous solvent and a toxic catalyst are the other advantages. To the best of our knowledge, this is the first report on the synthesis of pyrazolyl-bis coumarinylmethane derivatives using potassium 2-oxoimidazolidine-1,3-diide (POImD).

Keywords: Catalyst, solvent-free, grinding, 4-hydroxycoumarin, three-component synthesis, potassium 2-oxoimidazolidine-1, 3-diide.

Borges, F.; Roleira, F.; Milhazes, N.; Santana, L.; Uriarte, E. Simple coumarins and analogues in medicinal chemistry: Occurrence, synthesis and biological activity. Curr. Med. Chem., 2005, 12, 887-916.
Bolognese, A.; Correale, G.; Manfra, M.; Levecchia, A.; Mazzoni, O.; Novellino, E.; Lacolla, P.; Sanna, G.; Loddo, R. Antitumor agents. 3. Design, synthesis, and biological evaluation of new pyridoisoquinolindione and dihydrothienoquinolindione derivatives with potent cytotoxic activity. J. Med. Chem., 2004, 47, 849-858.
Bayer, T.A.; Schafer, S.; Breyh, H.; Breyhan, O.; Wirths, C.; Treiber, G.A. A vicious circle: Role of oxidative stress, intraneuronal Aβ and Cu in Alzheimer’s disease multhaup. Clin. Neuropathol., 2006, 25, 163-171.
Lacy, A.; O’Kennedy, R. Studies on coumarins and coumarin-related compounds to determine their therapeutic role in the treatment of cancer. Curr. Pharm. Des., 2004, 10, 3797-3811.
Foye, W.O. Principidi Chimica Farmaceutica Piccin- Padova, Italy, 1991.
Su, C.X.; Mouscadet, J.F.; Chiang, C.C.; Tsai, H.J.; Hsu, L.Y. HIV-1 integrase inhibition of biscoumarin analogues. Chem. Pharm. Bull., 2006, 54, 682-686.
Trost, B.M. Atom economy-A challenge for organic synthesis: Homogeneous catalysis leads the way. Angew. Chem. Int. Ed. Engl., 1995, 34, 259-281.
Jain, Sh.; Paliwal, P.K.; Babu, G.N.; Bhatewara, A. DABCO promoted one-pot synthesis of dihydropyrano(c)chromene and pyrano [2,3-d]pyrimidine derivatives and their biological activities. J. Saudi Chem. Soc., 2014, 18, 535-540.
Choudhary, M.I.; Fatima, N.; Khan, K.M.; Jalil, S.; Iqbal, S.; Atta-ur, R. New biscoumarin derivatives-cytotoxicity and enzyme inhibitory activities. Bioorg. Med. Chem., 2006, 14, 8066-8072.
Ellis, G.P. The Chemistry of Heterocyclic Compounds. In:Chromenes; Chromenes, and Chromenes; Weissberger; E.C.; Taylor, A.; Eds, John Wiley; NewYork, 11,. , 1977.
Zolfigol, M.A.; Mousavi-Zare, A.R.; Zarei, M. Friedel–Crafts alkylation of 4-hydroxycoumarin catalyzed by sulfonic-acid-functionalized pyridinium chloride as a new ionic liquid. Comp. Rend. Chim., 2014, 17, 1264-1267.
Khurana, J.M.; Kumar, S. Ionic liquid: An efficient and recyclable medium for the synthesis of octahydroquinazolinone and biscoumarin derivatives. Monatsh. Chem., 2010, 141, 561-564.
Tavakoli-Hoseini, N.; Heravi, M.M.; Bamoharram, F.F.; Davoodnia, A.; Ghassemzadeh, M. An unexpected tetracyclic product isolated during the synthesis of biscoumarins catalyzed by [MIM(CH2)4SO3H][HSO4]: Characterization and X-ray crystal structure of 7-(2-hydroxy-4-oxo-4H-chromen-3-yl)-6H,7H-chromeno [4,3-b]chromen-6-one. J. Mol. Liq., 2011, 163, 122-127.
Khan, K.M.; Iqbal, S.; Lodhi, M.A.; Maharvi, G.M.; Zia-Ullah, M.I. Choudhary, Atta-ur-Rahman. S. Perveen, Biscoumarin: New class of urease inhibitors; economical synthesis and activity. Bioorg. Med. Chem., 2004, 12, 1963-1968.
Hagiwara, H.; Miya, S.; Suzuki, T.; Ando, M.; Yamamoto, I.; Kato, M. Et2AlCl promoted coupling reactions of 4-hydroxy-2-pyrone or 4-hydroxycoumarine with aldehydes: Synthesis of methylenebis-(4-hydroxy-2-pyrone) or methylenebis-(4-hydroxycoumarine) derivatives. Heterocycles, 1999, 51, 493-496.
Tabatabaeian, K.; Heidari, H.; Khorshidi, A. mamaghani, M.; Mahmoodi, N.O. Synthesis of biscoumarin derivatives by the reaction of aldehydes and 4-hydroxycoumarin using ruthenium(III) chloride hydrate as a versatile homogeneous catalyst. J. Serb. Chem. Soc., 2012, 77, 407-413.
Khurana, J.M.; Kumar, S. 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 Lett., 2009, 50, 4125-4127.
Padalkar, V.; Phatangare, K.; Takale, S.; Pisal, R.; Chaskar, A. Silica supported sodium hydrogen sulfate and indion 190 resin:an efficient and heterogeneous catalyst for facile synthesis of bis-(4-hydroxycoumarin-3-yl)methanes. J. Saudi Chem. Soc., 2015, 19, 42-45.
Mehrabi, H.; Abusaidi, H. Synthesis of biscoumarin and 3,4-dihydropyrano[c]chromene derivatives catalysed by sodium dodecyl sulfate (SDS) in neat water. J. Iran Chem. Soc., 2010, 7, 890-894.
Yadav, U.N.; Shankarling, G.S. Room temperature ionic liquid choline chloride–oxalic acid: A versatile catalyst for acid-catalyzed transformation in organic reactions. J. Mol. Liq., 2014, 191, 137-141.
Kandasamy, K.; Pachamuthu, M.P.; Muthusamy, M.; Ganesabaskaran, S.; Ramanathan, A. Synthesis of novel pyrazolylbiscoumarin derivatives using FeTUD-1 as a mesoporous solid acid catalyst. RSC Advances, 2013, 3, 25367-25373.
Li, W.; Wang, Y.; Wang, Z.; Dai, L.; Wang, Y. Novel SO3H-functionalized ionic liquids based on benzimidazolium cation: Efficient and recyclable catalysts for one-pot synthesis of biscoumarin derivatives. Catal. Lett., 2011, 141, 1651-1658.
Rodriguez, B.; Bruckmann, A.; Rantanen, T.; Bolm, C. Solvent-free carbon-carbon bond formations in ball mills. Adv. Synth. Catal., 2007, 349, 2213-2233.
Bruckmann, A.; Krebs, A.; Bolm, C. Organocatalytic reactions: Effects of ball milling, microwave and ultrasound irradiation. Green Chem., 2008, 10, 1131-1141.
Shan, Z.X.; Luo, X.X.; Hu, L.; Hu, X.Y. New observation on a class of old reactions: Chemoselectivity for the solvent-free reaction of aromatic aldehydes with alkylketones catalyzed by a double-component inorganic base system. Sci. China Chem., 2010, 53, 1095-1101.
Zare Fekri, L.; Nikpassand, M.; Hasanpour, K. Green aqueous synthesis of mono, bis and trisdihydropyridines using nano Fe3O4 under ultrasound irradiation. Curr. Org. Synth., 2015, 12, 76-79.
Zare Fekri, L.; Nikpassand, M.; Maleki, R. 1, 4-Diazabicyclo [2.22] octanium diacetate: As an effective, new and reusable catalyst for the synthesis of benzo [d] imidazole. J. Mol. Liq., 2016, 222, 77-81.
Nikpassand, M.; Mamaghani, M.; Shirini, F.; Tabatabaeian, K. A convenient ultrasound-promoted regioselective synthesis of fused polycyclic 4-aryl-3-methyl-4,7-dihydro-1H-pyrazolo [3,4-b]pyridines. Ultrason. Sonochem., 2010, 17, 301-305.
Nikpassand, M.; Zare Fekri, L.; Karimian, L.; Rassa, M. Synthesis of biscoumarin derivatives using nanoparticle Fe3O4 as an efficient reusable heterogeneous catalyst in aqueous media and their antimicrobial activity. Curr. Org. Synth., 2015, 12, 358-362.
Nikpassand, M.; Zare Fekri, L.; Farokhian, P. An efficient and green synthesis of novel benzoxazole under ultrasound irradiation. Ultrason. Sonochem., 2016, 28, 341-345.
Kiyani, H.; Ghiasi, M. Potassium phthalimide: An efficient and green organocatalyst for the synthesis of 4-aryl-7-(arylmethylene)-3, 4, 6, 7-tetrahydro-1H-cyclopenta [d] pyrimidin-2 (5H)-ones/thiones under solvent-free conditions. Chin. Chem. Lett., 2014, 25, 313-316.

Rights & PermissionsPrintExport Cite as

Article Details

Year: 2019
Page: [303 - 308]
Pages: 6
DOI: 10.2174/1570179416666190101142542
Price: $58

Article Metrics

PDF: 14