Iron Ore Pellet, A Natural and Reusable Catalyst for Synthesis of Pyrano[2,3-d]pyrimidine and Dihydropyrano[c]chromene Derivatives in Aqueous Media

Document Type: Research Article


1 Department of Chemistry, Kerman Branch, Islamic Azad University, P.O. Box 76351-31167 Kerman, I.R. IRAN

2 Department of Chemistry, Jiroft Branch, Islamic Azad University, P.O. Box 78617-36343 Jiroft, I.R. IRAN

3 Department of Biology, Jiroft Branch, Islamic Azad University, P.O. Box 78617-36343 Jiroft, I.R. IRAN


  We wish to report a mild and efficient one-pot three-component reaction of an aryl aldehyde, malononitrile and barbituric acid or 4-hydroxycoumarinfor the synthesis ofpyrano[2,3-d]pyrimidine and dihydropyrano[c]chromene derivatives in the presence of iron ore pellet as a natural and reusable catalyst under heterogeneous and green 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 after six times using the same catalyst with high yields. Use of water as the reaction medium makes the process environmentally benign.


Main Subjects

[1] Grieco P.A., "Organic Synthesis in Water", Thomson Science, London, (1998).

[3] Shaabani A., Ghadari R., Rezayan A.H., Synthesis of Functionalized Coumarins, Iran. J. Chem. Chem. Eng. (IJCCE), 30(4): 19-22 (2011).

[4] Anderson G.L., Shim J.L., Broom A.D., Pyrido[2,3-d] pyrimidines. IV. Synthetic Studies Leading to Various Oxopyrido[2,3-d]pyrimidines,J. Org. Chem., 41(7): 1095-1098 (1976).

[6] Sangani C.B., Mungra D.C., Patel M.P., Patel R.G., Synthesis and Antimicrobial Screening of Pyrano[3,2-c]chromene Derivatives of 1H-Pyrazoles, Cent. Eur. J. Chem., 9(4): 635-647 (2011).

[7] Simon C., Constantieux T., Rodriguez J., Utilisation of 1,3-Dicarbonyl Derivatives in Multicomponent Reactions, Eur. J. Org. Chem., 2004(24): 4957-4980 (2004).

[8] Kempen I., Papapostolou D., Thierry N., Pochet L., Counerotte S., Masereel B., Foidart J.-M., Reboud-Ravaux M., Noel A., Pirotte B.,3-Bromophenyl 6-Acetoxymethyl-2- oxo-2H-1- Benzopyran-3-carboxylate Inhibits Cancer Cell Invasion in Vitro and Tumour Growth in Vivo, Br. J. Cancer, 88: 1111-1118 (2003). 

[9] Shaabani A., Samadi S., Rahmati A., OnePot, ThreeComponent Condensation Reaction in Water: an Efficient and Improved Procedure for the Synthesis of Pyran Annulated Heterocyclic Systems, Synth. Commun., 37(3): 491-499 (2007).

[10] Kefayati H., Valizade M., Islamnehad A., Green Electrosynthesis of Pyrano[2,3-d]pyrimidinones at Room Temperature, Anal. Bioanal. Electrochem., 6(1): 80-90 (2014). 

[11] Mashkouri S., Naimi-Jamal M.R., Mechanochemical Solvent-Free and Catalyst-Free One-Pot Synthesis of Pyrano[2,3-d]pyrimidine-2,4(1H,3H)-diones with Quantitative Yields, Molecules, 14(1): 474-479 (2009).

[12] Jin T.S., Liu L.B., Tu S.J., Zhao Y., Li T.S., A Clean One-Pot Synthesis of 7-Amino-5-aryl-6-cyano-1,5-dihydro-2H-pyrano[2,3-d]pyrimidine -2,4(3H)-diones in Aqueous Media under Ultrasonic Irradiation, J. Chem. Res., 2005(3): 162 (2005).

[13] Devi I., Kumar B.S.D., Bhuyan P.J., A Novel Three-Component One-Pot Synthesis of Pyrano[2,3-d] pyrimidines and Pyrido[2,3-d]pyrimidines Using Microwave Heating in the Solid State,Tetrahedron Lett., 44(45): 8307-8310 (2003).

14] Azizian J., Shameli A., Balalaie S., Ghanbari M.M., Zomorodbakhsh S., Entezari M., Bagheri S., Fakhrpour G., The One-Pot Synthesis of Pyrano[2,3-d] pyrimidinone Derivatives with 1,4-Diazabicyclo[2.2.2]octane in Aqueous Media, Orient. J. Chem., 28(1): 327-332 (2012).

[15] Jain S.,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., 18(5): 535-540 (2014).

[16] Da-Qing S., Jing W., Qi-Ya Z., Xiang-Shan W., Three-Component One-Pot Synthesis of 1,6-dioxa-5-oxo-1,4,5,6-tetrahydrophenanthrene Derivatives in Aqueous Media, Chin. J. Org. Chem., 26(05):643-647 (2006).

[17] Bararjanian M., Balalaie S., Movassagh B., Amani A.M., One-Pot Synthesis of Pyrano[2,3-d]pyrimidinone Derivatives Catalyzed by L-Proline in Aqueous Media, J. Iran. Chem. Soc., 6(2): 436-442 (2009).

[18] Balalaie S., Abdolmohammadi S., Bijanzadeh H.R., Amani A.M., Diammonium Hydrogen Phosphate as a Versatile and Efficient Catalyst for the One-Pot Synthesis of Pyrano[2,3-d]pyrimidinone Derivatives in Aqueous Media, Mol. Divers.,12(2): 85-95 (2008).

[19] Abdolmohammadia S., Balalaie S., Novel and Ecient Catalysts for the One-Pot Synthesis of 3,4-Dihydropyrano[c]chromene Derivatives in Aqueous Media, Tetrahedron Lett., 48(18): 3299-3303 (2007).

[20] Heravi M.M., Zakeri M., Mohammadi N., Morpholine Catalyzed One-Pot Multicomponent Synthesis of Compounds Containing Chromene Core in Water, Chin. J. Chem., 29(6): 1163-1166 (2011).  

[21] Heravi M.M., Ghods A., Derikvand F., Bakhtiari K., Bamoharram F.F.D., H14[NaP5W30O110] Catalyzed One-Pot Three-Component Synthesis of Dihydropyrano [2,3-c]pyrazole and Pyrano[2,3-d]pyrimidine Derivatives, J. Iran. Chem. Soc., 7(3): 615-620 (2010).

[22] Ziarani G.M., Faramarzi S., Asadi S., Badiei A., Bazl R., Three-Component Synthesis of Pyrano[2,3-d]- pyrimidine-dione Derivatives Facilitated by Sulfonic Acid Nanoporous Silica (SBA-Pr-SO3H) and Their Docking and Urease Inhibitory Activity, DARU Journal of Pharmaceutical Sciences, 21(3)(2013).

[23] Mohammad Ziarani G., Badiei A., Azizi M., Zarabadi P., Synthesis of 3,4-Dihydropyrano[c]chromeneDerivatives Using Sulfonic Acid Functionalized Silica (SiO2PrSO3H), Iran. J. Chem. Chem. Eng. (IJCCE), 30(2): 59-65 (2011).

[24] Mobinikhaledi A., Bodaghifard M.A., Tetrabutylammonium Bromide in Water as a Green Media for the Synthesis of Pyrano[2,3-d]Pyrimidinone and Tetrahydrobenzo[b]Pyran Derivatives, Acta Chim. Slov., 57(4): 931-935 (2010).

[25] Mobinikhaledi A., Foroughifar N., Bodaghifard M.A., Eco-Friendly and Efficient Synthesis of Pyrano[2,3-d] pyrimidinone and Tetrahydrobenzo[b]pyran Derivatives in Water, Synth React Inorg, Met-Org, Nano-Met Chem., 40(3): 179-185 (2010).

[26] Mehrabi H., Kazemi-Mireki M., CuO Nanoparticles: An Efficient and Recyclable Nanocatalyst for the Rapid and Green Synthesis of 3,4-Dihydropyrano[c] chromenes, Chin. Chem. Lett., 22(12):1419-1422 (2011).

[27] 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., 7(4): 890-894 (2010).

[28] Shahi M., Foroughifar N., Moradi S., Synthesis and ab Initio Study of Pyrano[2,3-d]pyrimidine Derivatives, Iran. J. Chem. Chem. Eng. (IJCCE),33(1): 1-13 (2014).

[29] Zheng J., Li Y-Q., One-Pot Synthesis of Tetrahydrobenzo[b]pyran and Dihydropyrano[c] chromene Derivatives in Aqueous Media by Using Trisodium Citrate as a Green CatalystArch. Appl. Sci. Res., 3(2):381-388 (2011).

[30] Ranjbar-Karimi R., Hashemi-Uderji S., Mousavi M., Selectfluor Promoted Environmental-Friendly Synthesis of 2H-Chromen-2-ones Derivatives under Various Reaction ConditionsJ. Iran. Chem. Soc., 8(1): 193-197 (2011).

[31] Shaabani A., Samadi S., Badri Z., Ramai A., Ionic Liquid Promoted Efficient and Rapid One-PotSynthesis of Pyran Annulated Heterocyclic Systems, Catal. Lett., 104(1): 39-43 (2005).

[32] Patel D.S., Avalani J.R., Raval D.K., One-Pot Solvent-Free Rapid and Green Synthesis of 3,4-Dihydropyrano[c]chromenes Using Grindstone Chemistry, J. Saudi.  Chem. Soc., (2013) in press

[33] Wang H.-J., Lu J., Zhang Z.-H., Highly Efficient Three-Component, One-Pot Synthesis of Dihydropyrano[3,2-c]chromene Derivatives, Monatsh. Chem., 141(10): 1107-1112 (2010). 

[34] Nagabhushana H., Sandeep Saundalkar S., Muralidhar L., Nagabhushana B.M., Girija C.R., Nagaraja D., Pasha M.A., Jayashankara V.P., α-Fe2O3 Nanoparticles: An Efficient, Inexpensive Catalyst for the One-Pot Preparation of 3,4-Dihydropyrano[c]chromenes, Chin. Chem. Lett., 22(2): 143-146 (2011).

[35] Prasanna, T.S.R., Raju K.M., Silica-gel Promoted Mild, Efficient and Inexpensive Protocol for the Peparation of 3,4-Dihydropyrano[c]chromenes, J. Korean Chem. Soc., 55(4): 662-665 (2011).

[36] Tabatabaeian K., Heidari H., Mamaghani M., Mahmoodi N.O., Ru(II) Complexes Bearing Tertiary Phosphine Ligands: A Novel and Efficient Homogeneous Catalyst for One-Pot Synthesis of Dihydropyrano[3,2-c]chromene and Tetrahydrobenzo[b]pyran Derivatives, Appl. Organometal. Chem., 26(2): 56-61 (2012).

[37] Sheikhhosseini E., Ghazanfari D., Nezamabadi V., A New Method for Synthesis of  Tetrahydrobenzo[b]pyrans  and Dihydropyrano[c]chromenes Using p-Dodecylbenzenesulfonic Acid as Catalyst in Water, Iranian J. Catal., 3(4): 197-201 (2013).

[38] Firoozi M., Baghalha M., Asadi M., Synthesis of ZSM-5 Zeolite as the Catalyst for the Methanol to Propylene Reaction, NashriehShimi va Mohandesi Shimi Iran (NSMSI), 31(2): 21-26 (2012).[in Persian]

[39] Apollo S., Onyongo S.O., Ochieng A., UV/H2O2/TiO2/Zeolite Hybrid System for Treatment of Molasses Wastewater, Iran. J. Chem. Chem. Eng. (IJCCE), 33(2): 107-117 (2014).

[40] Sheikhhosseini E., Faryabi M., A Green Synthesis of Thioxopyrano[2, 3-d]parimidine Using Iron ore Pellet as Natural and Reusable Catalyst, Heterocyclic Letters, 5(1): 37-43 (2015)

[41] Kempen I., Papapostolou D., Thierry N., Pochet L., Counerotte S., Masereel B., Foidart J.-M., Reboud-Ravaux M., Noel A., Pirotte B.,3-Bromophenyl 6-Acetoxymethyl-2- oxo-2H-1- Benzopyran-3-carboxylate Inhibits Cancer Cell Invasion in Vitro and Tumour Growth in Vivo, Br. J. Cancer, 88: 1111-1118 (2003).