One Pot Synthesis of Biscoumarins and Pyranocoumarins by Coconut Juice as a Natural Catalyst

Author(s): Bipasa Halder, Himadri S. Maity, Ahindra Nag*

Journal Name: Current Organocatalysis

Volume 6 , Issue 1 , 2019

Become EABM
Become Reviewer

Graphical Abstract:


Background: The conception of ‘Green chemistry’ is the much inventive chemistry which is potent and more environmentally benign. It is notable that many organic reactions take place in conventional organic solvents, known as volatile organic compounds. Being concerned about the environmental impact, we report a promoting medium, coconut juice (ACC) for one-pot synthesis of biscoumarins and pyranocoumarins which is safe, harmless, green and environmentally benign.

Methods and Results: Substituted biscoumarins have been achieved by the reaction of biscoumarin and substituted aromatic aldehydes in presence of ACC which acts as a green catalyst cum solvent. Each reaction showed good to excellent yield in presence of both electron donating as well as electron withdrawing group on aromatic aldehyde without formation of any by-products. Similarly, pyranocoumarins have been achieved by the reaction of biscoumarin, substituted aromatic aldehydes, active methylene nitrile in presence of ACC. All the reactions proceed smoothly and gave higher yields in case of malononitrile in comparison of ethyl-2-cyanoacetate.

Conclusion: A simple, eco-friendly and novel procedure was demonstrated for the synthesis of biscoumarins and pyranocoumarins using natural feedstock coconut juice. The major importance of using ACC juice is higher yields, no work-up and no column chromatography.

Keywords: 4-hydroxycoumarin, ACC, active methylene nitrile, aromatic aldehydes, biscoumarins, pyranocoumarins.

Safaei, H.R.; Shekouhy, M.; Rahmanpur, S.; Shirinfeshan, A. Glycerol as a biodegradable and reusable promoting medium for the catalyst-free one-pot three component synthesis of 4H-pyrans. Green Chem., 2012, 14, 1696-1704.
Zhou, B.; Yang, J.; Li, M.; Gu, Y. Gluconic acid aqueous solution as a sustainable and recyclable promoting medium for organic reactions. Green Chem., 2011, 13, 2204-2211.
Azizi, N. dezfooli, S.; Hashemi, M.M. Greener synthesis of spirooxindole in deep eutectic solvent. J. Mol. Liq., 2014, 194, 62-67.
Li, C-J.; Chan, T-H. Organic Reactions in Aqueous Media; J. Wiley & Sons: New York, NY, 1997.
Lindstrom, U.M. Stereoselective Organic reactions in water. Chem. Rev., 2002, 102, 2751-2772.
Kitanosono, T.; Masuda, K.; Xu, P.; Kobayashi, S. Catalytic organic reactions in water toward sustainable society. Chem. Rev., 2018, 118, 679-746.
Knochel, P. Modern Solvents in Organic Synthesis; Springer: Germany, 1999.
Giri, A.; Dhingra, V.; Giri, C.C.; Singh, A.; Ward, O.P.; Narasu, M.L. Biotransformations using plant cells, organ cultures and enzyme systems: current trends and future prospects. Biotechnol. Adv., 2001, 19, 175-199.
Maity, H.S.; Misra, K.; Mahata, T.; Nag, A. CSJ acting as a versatile highly efficient greener resource for organic transformations. RSC Advances, 2016, 6, 24446-24450.
Saikia, B.; Borah, P.; Barua, N.C.H. 2O2 in WEB: a highly efficient catalyst system for the Dakin reaction. Green Chem., 2015, 17, 4533-4536.
Boruah, P.R.; Ali, A.A.; Saikia, B.; Sarma, D. A novel green protocol for ligand free Suzuki- Miyaura cross-coupling reactions in WEB at room temperature. Green Chem., 2015, 17, 1442-1445.
Boruah, P.R.; Ali, A.A.; Chetia, M.; Saikia, B.; Sarma, D. Pd(OAc)2 in WERSA: a novel green catalytic system for Suzuki-Miyaura cross-coupling reactions at room temperature. Chem. Commun. , 2015, 51, 11489-11492.
Yong, J.W.H.; Ge, L.; Ng, Y.F.; Tan, S.N. The chemical composition and biological properties of coconut (Cocos nucifera L.) water. Molecules, 2009, 14, 5144-5164.
Fonseca, A.M.; Monte, F.J.Q.; de Oliveira, M.C.F.; de Mattos, M.C.; Cordell, G.A.; Braz-Filho, R.; Lemos, T.L.G. Coconut water (Cocos nucifera L.)-A new biocatalyst system for organic synthesis. J. Mol. Catal., B Enzym., 2009, 57, 78-82.
Misra, K.; Maity, H.S.; Chanda, S.; Nag, A. New greener alternatives for bioreduction ofaromatic aldehydes and decarboxylation of aromatic acids using juice of fruits. J. Mol. Catal., B Enzym., 2012, 82, 92-95.
Martins, P.; Jesus, J.; Santos, S.; Raposo, L.R.; Roma-Rodrigues, C.; Baptista, P.V.; Fernandes, A.R. Heterocyclic anticancer compounds: recent advances and the paradigm shift towards the use of nanomedicine’s tool box. Molecules, 2015, 20, 16852-16891.
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.
Karmakar, B.; Nayak, A.; Banerji, J. Sulfated titania catalyzed water mediated efficient synthesis of dicoumarols-a green approach. Tetrahedron Lett., 2012, 53, 4343-4346.
Karimian, R.; Piri, F.; Safari, A.A.; Davarpanah, S.J. One-pot and chemoselective synthesis of bis(4-hydroxycoumarin) derivatives catalyzed by nano silica chloride. J. Nanostructure Chem., 2013, 3, 52-57.
Boroujeni, K.P.; Ghasemi, P. Synthesis and application of a novel strong and stable supported ionic liquid catalyst with both Lewis and Brønsted acid sites. Catal. Commun., 2013, 37, 50-54.
Kidwai, M.; Bansal, V.; Mothsra, P.; Saxena, S.; Somvanshi, R.K.; Dey, S.; Singh, T.P. Molecular iodine: A versatile catalyst for the synthesis of bis(4-hydroxycoumarin) methanes in water. J. Mol. Catal.A Chem., 2007, 268, 76-81.
Khan, K.M.; Iqbal, S.; Lodhi, M.A.; Maharvi, G.M. Zia-Ullah; Choudhary, M.I.; Atta-ur-Rahman; Perveen, S. Biscoumarin: new class of urease inhibitors; economical synthesis and activity. Bioorg. Med. Chem., 2004, 12, 1963-1968.
Manolov, I.; Maichle-Moessmer, C.; Danchev, N. Synthesis, structure, toxicological and pharmacological investigations of 4-hydroxycoumarin derivatives. Eur. J. Med. Chem., 2006, 41, 882-890.
Siddiqui, Z.N.; Farooq, F. Zn(Proline)2: a novel catalyst for the synthesis of dicoumarols. Catal. Sci. Technol., 2011, 1, 810-816.
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.
Seddighi, M.; Shirini, F.; Mamaghani, M. Sulfonated rice husk ash (RHA-SO3H) as a highly efficient and reusable catalyst for the synthesis of some bis-heterocyclic compounds. Rsc. Adv., 2013, 3, 24046-24053.
Bonsignore, L.; Loy, G.; Secci, D.; Calignano, A. Synthesis and pharmacological activity of 2-oxo-(2H) 1-benzopyran-3-carboxamide derivatives. Eur. J. Med. Chem., 1993, 28, 517-520.
Gong, K.; Wang, H-L.; Luo, J.; Liu, Z-L. One-pot synthesis of polyfunctionalized pyrans catalyzed by basic ionic liquid in aqueous media. J. Heterocycl. Chem., 2009, 46, 1145-1150.
Azizi, K.; Heydari, A. A simple, green, one-pot of magnetic-nanoparticle-supported proline without any source of supplemental linkers and application as a highly efficient base catalyst. Rsc Adv., 2014, 4, 6508-6512.
Karami, B.; Khodabakhshi, S.; Eskandari, K. A new application of mohr’s salt as a cheap and powerful catalyst for synthesis of novel pyranocoumarins. Lett. Org. Chem., 2013, 10, 105-110.
Guo, R-Y.; An, Z-M.; Mo, L-P.; Wang, R-Z.; Liu, H-X.; Wang, S-X.; Zhang, Z-H. Meglumine: A Novel and Efficient Catalyst for One-Pot, Three-Component Combinatorial Synthesis of Functionalized 2-Amino-4H-pyrans. ACS Comb. Sci., 2013, 15, 557-563.
Brahmachari, G.; Banerjee, B. Facile and one-pot access to diverse and densely functionalized 2-amino-3- cyano-4h-pyrans and pyran-annulated heterocyclic scaffolds via an eco-friendly multicomponent reaction at room temperature using urea as a novel organo- catalyst. ACS Sustain. Chem.& Eng., 2014, 2, 411-422.
Esmaeilpour, M.; Javidi, J.; Dehghani, F.; Dodeji, F.N. A green one-pot three-component synthesis of tetrahydrobenzo[b]pyran and 3,4-dihydropyrano[c]-chromene derivatives using a Fe3O4@SiO2-imid-PMAn magnetic nanocatalyst under ultrasonic irradiation or reflux conditions. RSC Advances, 2015, 5, 26625-26633.
Zolfigol, M.A.; Bahrami-Nejad, N.; Afsharnadery, F.; Baghery, S. 1-Methylimidazolium tricyanomethanide [HMIM]C(CN)3 as a nano structure and reusable molten salt catalyst for the synthesis of tetrahydrobenzo[b]pyrans via tandem Knoevenagel-Michael cyclocondensation and 3,4-dihydropyrano[c]chromene derivatives. J. Mol. Liq., 2016, 221, 851-859.
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.
Tu, S.; Jiang, H.; Fang, F.; Feng, Y.; Zhu, S.; Li, T.; Zhang, X.; Shi, D. Synthesis of 2-amino-3-ethoxycarbonyl-4-aryl-4H,5H-pyrano-[3,2-c]benzopyran-5-one. J. Chem. Res., 2004, 2004, 396-398.
Patel, J.P.; Avalani, J.R.; Raval, D.K. Polymer supported sulphanilic acid: A highly efficient and recyclable green heterogeneous catalyst for the construction of 4,5-dihydropyrano [3,2-c]chromenes under solvent-free conditions. J. Chem. Sci., 2013, 125, 531-536.
Li, J.; Lv, C-W.; Li, X-J.; Qu, D.; Hou, Z.; Jia, M.; Luo, X-X.; Li, X.; Li, M-K. Synthesis of biscoumarin and dihydropyran derivatives and evaluation of their antibacterial activity. Molecules, 2015, 20, 17469-17482.

open access plus

Rights & PermissionsPrintExport Cite as

Article Details

Year: 2019
Published on: 24 April, 2019
Page: [20 - 27]
Pages: 8
DOI: 10.2174/2213337206666190219142408

Article Metrics

PDF: 29