Tin Pyrophosphate (SnP2O7): As a Novel Heterogeneous and Highly Efficient Catalyst for the One Pot-Three Component Synthesis of Tetrahydrobenzo[b]Pyran and Dihydropyran[c]Chromene Derivatives

Document Type : Research Article


1 Laboratory of Organic Chemistry, Catalysis, and Environment. University of Ibn Tofail, Faculty of Science, Kenitra, MOROCCO

2 Laboratory of Organic Chemistry, Catalysis, and Environment. University of Ibn Tofail, Faculty of Science, Po Box 133, 14000. Kenitra, Morocco


The tin pyrophosphate (SnP2O7) was synthesized from the modification of mono-ammonium phosphate (MAP) by tin chloride (SnCl2). This solid was used as a heterogeneous catalyst for the one-pot multicomponent synthesis of tetrahydrobenzo[b]pyran and dihydropyrano[3,2-c]chromenes derivatives under green reaction conditions. This synthetic protocol offers several advantages such as short reaction times (8-15 min), high product yields (85-97%), easy work‐up procedure, and easy catalyst separation from the reaction mixture. In addition, SnP2O7 can be recycled for up to five cycles without a significant loss of catalytic reactivity. The XRD and IR spectra confirm the stability and heterogeneity of SnP2O7 in the reaction medium even after its reuse.


Main Subjects

 [1] Tang Q., Yin X., Kuchukulla R.R., Zeng Q., Recent Advances in Multicomponent Reactions with Organic and Inorganic Sulfur Compounds, Chem. Rec., 21: 893–905 (2021).
[2] Ardeshir K., Ahmad Reza M.Z., Hadis A. H., Vahid K., Programming of Fe-Catalyzed Cascade Knoevenagel-Michael-Cyclocondensation Reaction: Create out Pseudo Acridine Derivatives under Solvent Free Conditions, Eurasian Chem. Commun., 2: 27–34 (2020).
[5] Nikpassand M., Zare Fekri L., Catalyst-Free Synthesis of Mono and Bis Spiro Pyrazolopyridines in DSDABCO as a Novel Media, Chem. Methodol., 4: 437–446 (2020).
[8]     Maleki B., Taimazi F., One-Pot Synthesis of 1-Amidoalkyl-2-Naphthols under Solvent-Free Conditions, Organic Preparations and Procedures International, 46: 252–260 (2014).
[9]   Ahmad Reza M.Z., Hadis A. H., Vahid K., Application of [Pyridine-1-SO3H-2-COOH]Cl as an Efficient Catalyst for the Preparation of Hexahyroquinolines, Eurasian Chem. Commun., 2: 465-474 (2020).
[10] Maleki B., Sheikh S., One-Pot Synthesis of 2-Amino-2-Chromene and 2-Amino-3-Cyano-4H-Pyran Derivatives Promoted by Potassium Fluoride, Organic Preparations and Procedures International, 47: 368–378 (2015).
[13] Samaneh Z., Masoud M., Mogharab T., L-Proline Catalyzed Synthesis of Betti Bases and Biscoumarin Derivatives, Iran. J. of Cat., 5: 149-153 (2015).
[17] Maleki B., Green Synthesis of Bis-Coumarin and Dihydropyrano[3,2-c]Chromene Derivatives Catalyzed by o-Benzenedisulfonimide, Organic Preparations and Procedures International, 48: 303–318 (2016).
[21] El-Agrody A.M., Fouda A.M., Assiri M.A., Mora A., Ali T.E., Alam M.M., Alfaifi M.Y., In vitro anti-Cancer Activity of Pyrano[3,2-c]Chromene Derivatives with Both Cell Cycle Arrest and Apoptosis Induction, Med. Chem. Res., 29: 617–629 (2020).
[23] Ilyina I.V., Patrusheva O.S., Zarubaev V.V., Misiurina M.A., Slita A.V., Esaulkova I.L., Korchagina D.V., Gatilov Y.V., Borisevich S.S., Volcho K.P., Salakhutdinov N.F., Influenza Antiviral Activity of F- and OH-Containing Isopulegol-Derived Octahydro-2H-Chromenes, Bioorganic. Med. Chem. Lett., 31: 127677 (2021).
[24] Kalaria P.N., Karad S.C., Raval D.K., A Review on Diverse Heterocyclic Compounds as the Privileged Scaffolds in Antimalarial Drug Discovery, Eur. J. Med. Chem., 158: 917–936 (2018).
[25] Ahmed E.M., Khalil N.A., Zaher A.F., Alhamaky S.M., El-Zoghbi S.M., Synthesis, Molecular Modeling and Biological Evaluation of New Benzo[4,5]Thieno[3,2-b]Pyran Derivatives as Topoisomerase I-DNA Binary Complex Poisons, Bioorg. Chem., 112: 104915 (2021).
[26] Santra S., Gogoi S., Gopishetty B., Antonio T., Zhen J., Reith M.E.A., Dutta A.K., Structural Exploration of (3S,6S)  -6-Benzhydryl-N-benzyltetrahydro-2H-pyran-3-Amine Analogues: Identification of Potent Triple Monoamine Reuptake Inhibitors as Potential Antidepressants, ChemMedChem., 7: 2093–2100 (2012).
[27] Renuka C.G., Nadaf Y.F., Sriprakash G., Rajendra P.S., Solvent Dependence on Structure and Electronic Properties of 7-(Diethylamino) - 2H -1- Benzopyran-2- one (C-466) Laser Dye, J. Fluoresc., 28: 839–854 (2018).
[28] Baghernejad B., Fiuzat M., Ninhydrin as a Novel and Efficient Catalyst for the Synthesis of 2-Amino-4H-Pyran Derivatives in Aqueous Media Using, J. Appl. Organomet. Chem., 1: 17-21 (2021).
[29] Birkbeck A.A., Brkic Z., Giles R.G.F., Stereoselective Syntheses of Enantiopure 2-benzopyran-5,8-Quinones Related to the Aphid Insect Pigments, the Protoaphins, Tetrahedron Lett., 45: 6147–6150 (2004).
[31] Pund G., Dhumal S., Hebade M., Farooqui M., Dobhal B., Meglumine Catalysed Green Synthesis of Ethyl-6-Amino-5-Cyano-2-Methyl-4-Phenyl-4H-Pyran-3-Carboxylate Derivatives, J. Appl. Organomet. Chem., 2: 15-23 (2022).
[32] Shekhar A.C., Kumar A.R., Sathaiah G., Raju K., Rao P.S., Sridhar M., Narsaiah B., Srinivas P.V.S.S., Sridhar B., An Efficient One-Pot Synthesis of Substituted 1H-Naphtho[2,1-b]pyrans and 4H-1-Benzopyrans (=Chromenes) under Solvent-Free Microwave-Irradiation Conditions, Helv. Chim. Acta., 95: 502–508 (2012).
[33] Abdel Hamid A., Abd-Elmonem M., Hayallah A.M., Abo Elsoud F.A., Sadek K.U., Glycerol: A Promising Benign Solvent for Catalyst Free One-Pot Multi-Component Synthesis of Pyrano[2,3-c]pyrazoles and Tetrahydro-benzo[b]pyrans at Ambient Temperature, ChemistrySelect., 2: 10689–10693 (2017).
[34] Tiwari J., Saquib M., Singh S., Tufail F., Singh M., Singh J., Visible Light Promoted Synthesis of Dihydropyrano [2,3-c]Chromenes Via A Multicomponent- Tandem Strategy under Solvent and Catalyst Free Conditions, Green. Chem., 18: 3221–3231 (2016).
[35] Pendalwar S.S., Chakrawar A.V., Chavan A.S., Bhusare S.R., An Efficient Synthesis of Dihydropyrano[3,2-c] Chromene Derivatives via Green Approach, Der Pharma Chemica, 8: 143–145 (2016).
[40] Nesaragi A.R., Kamble R.R., Hoolageri S.R., Mavazzan A., Madar S.F., Anand A., Joshi S.D., A Natural Catalyst of Alkali and Alkaline Earth Metals for the Facile Synthesis of Tetrahydrobenzo[ b ]Pyrans and Pyrano[2,3‐ d ]Pyrimidinones as Inhibitors of SARS‐CoV‐2, Appl. Organomet. Chem., 36: (2022).
[41] Mehravar M., Mirjalili B.B.F., Babaei E., Bamoniri A., Nano-SiO2/DBN: an Efficacious and Reusable Catalyst for One-Pot Synthesis of Tetrahydrobenzo[B]Pyran Derivatives, B.M.C. Chem., 15: 34 (2021).
[43] Kamble R., Gaikwad M., Tapare M., Hese S., Kadam S., Ambhore A., Dawane, B., DTP/SiO2: An Efficient And Reusable Heterogeneous Catalyst For Synthesis of Dihydropyrano [3,2-c] Chromene-3-Carbonitrile Derivatives, J. Appl. Organomet., Chem., 1: 22-28 (2021).
[45] Vajar S., Mokhtary M., Nano-CuFe2O4@SO3H Catalyzed Efficient One-Pot Cyclo-Dehydration of Dimedone and Synthesis of Chromeno[4,3-b]Chromenes, Polycycl. Aromat. Compound., 39: 111–123 (2019).
[49] Fallah-Mehrjardi M., Shirzadi M., Banitaba S.H.,  A New Basic Ionic Liquid Supported on Magnetite Nanoparticles: An Efficient Phase-Transfer Catalyst for the Green Synthesis of 2-Amino-3-Cyano-4 H -Pyrans, Polycycl. Aromat. Compound., 42: 2198–2209 (2022).
[50] Altass H.M., Khder A.S., Ahmed A.S., Morad M., Alsabei A.A., Jassas R.S., Althagafy K., Ahmed A.I., Salama R.S., Highly Efficient, Recyclable Cerium-Phosphate Solid Acid Catalysts for the Synthesis of Tetrahydrocarbazole Derivatives by Borsche–Drechsel Cyclization, Reac. Kinet. Mech. Cat., 134: 143–161 (2021).
[52] Chehab S., Merroun Y., Ghailane R., Boukhris S., Souizi A., Na2Ca(HPO4)2, an Efficient, Reusable Eco-Friendly Catalyst for the Synthesis of 1,8-Dioxo-Octahydroxanthenes and Biscoumarin Derivatives, Polycycl. Aromat. Compound., 1:1–18 (2022).
[53] Chehab S., Merroun Y., Ghailane T., Habbadi N., Boukhris S., Hassikou A., Ghailane R., Akhazzane M., Kerbal A., Daich A., Souizi A., A new process for Na2Ca(HPO4)2 Synthesis and its Application as a Heterogeneous Catalyst in Knoevenagel Condensation, Mediterr. J. Chem., 7: 56–67 (2018).
[54] Chehab S., Merroun Y., Ghailane T., Ghailane R., Boukhris S., Souizi A., A Green and Efficient Method for The Synthesis of 3,4-Dihydropyrano[c]Chromene Using Phosphate Fertilizers (MAP, DAP and TSP) as Heterogeneous Catalysts, J. Turk. Chem. Soc. A: Chem., 5: 355–370 (2018).
[55] Chehab S., Merroun Y., Ghailane T., Ghailane R., Boukhris S., Lakhrissi B., Souizi A., A Facile and Efficient Synthesis of Tetrahydrobenzo[b]Pyrans and Dihydropyrano[4,3-b]Pyrans Derivatives Using Phosphate Fertilizers MAP, DAP, and TSP as Heterogeneous Catalysts, J. Iran. Chem. Soc., 18: 2665–2678 (2021).
[56] Chehab S., Merroun Y., Ghailane T., Ghailane R., Boukhris S., Souizi A., Mono-Ammonium Phosphate Fertilizer Modified by Cadmium: An Efficient and Recyclable Catalyst for 2,3-Dihydroquinazolin-4(1H)-One Derivatives Synthesis, Polycycl. Aromat. Compound., 1: 1–16 (2021).
[57] Merroun Y., Chehab S., Ghailane T., Boukhris S., Ghailane R., Habbadi N., Hassikou A., Lakhrissi B., Souizi A., An Effective Method to Synthesize 2,3-Dihydroquinazolin-4(1H)-One Using Phosphate Fertilizers (MAP, DAP and TSP) as Green Heterogeneous Catalysts, J. Turk. Chem. Soc. A: Chem., 1: 303–316 (2018).
[58] El Hallaoui A., Chehab S., Malek B., Zimou O., Ghailane T., Boukhris S., Souizi A., Ghailane R., Valorization of the Modified Mono Ammonium Phosphate by Cobalt in the Synthesise of 3,4‐Dihydropyrano [c] Chromene Derivatives, Chemistry Select., 4: 3062–3070 (2019).
[59] Hallaoui A.E., Chehab S., Ghailane T., Malek B., Zimou O., Boukhriss S., Souizi A., Ghailane R., Application of Phosphate Fertilizer Modified by Zinc as a Reusable Efficient Heterogeneous Catalyst for the Synthesis of Biscoumarins and Dihydropyrano [3,2-c]Chromene-3-Carbonitriles under Green Conditions, Polycycl. Aromat. Compound., 41: 2083–2102 (2021).
[60] Malek B., Bahammou İ., Zimou O., El Hallaoui A., Ghailane R., Boukhri̇s S., Souizi A., Eco-friendly Synthesis of Quinoxaline Derivatives Using Mineral Fertilizers as Heterogeneous Catalysts, J. Turk. Chem. Soc. A: Chem., 1: 427–440 (2020).
[61] Bahammou I., Malek B., Ghailane T., Ghailane R., Boukhris S., Souizi A., A Green and Efficient Process for the Synthesis of Benzothiazinones Using Phosphate Fertilizers MAP, DAP and TSP as Heterogeneous Catalysts, J. Turk. Chem. Soc. A: Chem., 1: 349–354 (2019).
[62] Merroun Y., Chehab S., Ghailane T., Akhazzane M., Souizi A., Ghailane R., Preparation of tin-Modified Mono-Ammonium Phosphate Fertilizer and its Application as Heterogeneous Catalyst
in the Benzimidazoles and Benzothiazoles Synthesis
, Reac. Kinet. Mech. Cat., 126: 249–264 (2019).
[64] Rupnar B.D., Bhagat S.S., Sirsat A.J., Pawar R.P., Microwave Assisted, LTyrosine Catalyzed Efficient Synthesis of Tetrahydrobenzo[b] Pyrans, Int. J. Sci. Res. Sci. Eng. Technol., 4: 30–33 (2018).
[65] Joshi V.M., Magar R.L., Throat P.B., Tekale S.U., Patil B.R., Kale M.P., Pawar R.P., Novel One-Pot Synthesis of 4H-Chromene Derivatives Using Amino Functionalized Silica Gel Catalyst, Chin. Chem. Lett., 25: 455–458 (2014).
[66] Achagar R., Elmakssoudi A., Dakir M., Elamrani A., Zouheir Y., Zahouily M., Jamaleddine J., A Green and Efficient Protocol for the Synthesis of Phenylhydrazone Derivatives Catalyzed by Nanostructured Diphosphate Na2CaP2O7 and Screening of Their Antibacterial Activity, ChemistrySelect, 6: 1366–1371 (2021).
[75]  Mokhtari S., Sheikhhosseini E., Faryabi M., Rafiepour A., Soltaninejad S., Iron Ore Pellet, A Natural and Reusable Catalyst for Synthesis of Pyrano[2,3-d] Pyrimidine and Dihydropyrano [c] Chromene Derivatives in Aqueous Media, Iran. J. Chem. Chem. Eng. (IJCCE), 35: 43-50 (2016).
[77] Noroozi Pesyan N., Rezanejade Bardajee G., Kashani E., Mohammadi M., Batmani H., Ni(II)-Schiff Base/SBA-15: A Nanostructure and Reusable Catalyst for one-Pot three-Component Green Synthesis of 3,4-Dihydropyrano[3,2-c] Chromene Derivatives, Res. Chem. Intermed., 46: 347–367 (2020).