[DBN][HSO4]-Promoted facile and green synthesis of 2-Amino-4H-pyrans derivatives under microwave irradiation
Abstract
The [DBN][HSO4] -promoted Knoevenagel condensation followed by cyclization protocol has been developed for the first time by a successive reaction of aldehydes, dimedone and malononitrile to afford 2-Amino-4H-pyrans derivatives in high to excellent yields at room temperature. The synergic couple of microwave and ionic liquid provided the capability to allow a variability of functional groups, short reaction times, easy workup, high yields, recyclability of the catalyst, and solvent-free conditions, thus providing economic and environmental advantages.
Keywords: [DBN][HSO4], Environmentally benign, 2-Amino-4H-pyrans, Knoevenagel condensation, Microwave irradiation
Keywords:
[DBN][HSO4], Environmentally benign, 2-Amino-4H-pyrans, Knoevenagel condensation, Microwave irradiationDOI
https://doi.org/10.22270/jddt.v11i2-S.4824References
Morinaka Y, Takahashi K, Jpn. Patent 1977; JP52017498
Witte EC, Neubert P, Roesch A, Ger. Offen. 1986; DE3427985.
Hafez EA, Elnagdi MH, Elagamey AG, El-Taweel, FMA, Nitriles in heterocyclic synthesis: novel synthesis of benzo[c]coumarin and of benzo[c]pyrano[3,2-cc]quinoline derivatives, Heterocycles 1987; (26) 903-907
Kuthan J, Pyrans, Thiopyrans, and Selenopyrans, Adv. Heterocycl. Chem. 1983; (34): 145-303
Hatakeyama S, Ochi N, Numata H, Takano S, A new route to substituted 3-methoxycarbonyldihydropyrans; enantioselective synthesis of (–)-methyl elenolate, J. Chem. Soc. Chem. Commun. 1988; (17): 1202-1204
Zamocka J, Misikova E, Durinda J, Pharmazie 1991; (46): 610-611
Wang JL, Liu D, Zhang ZJ, Shan S, Han X, Srinivasula SM, Croce CM, Alnemri ES, Huang Z, Structure-based discovery of an organic compound that bind Bc1-2 protein and induces apoptosis of tumor cells. Proc. Natl. Acad. Sci. U. S. A. 2007; (97): 7124-7129
El-Saghier AMMM, Naili B, Rammash BK, Saleh NA, Kreddan KM, Synthesis and antibacterial activity of some new fused chromenes, Arkivoc 2007; (16): 83-91
Kumar RR, Perumal S, Senthilkumar P, Yogeeswari P, Sriram D, An atom efficient, solvent-free, green synthesis and antimycobacterial evaluation of 2-amino-6-methyl-4-aryl-8-[(E)-arylmethylidene]-5,6,7,8-tetrahydro-4H-pyrano[3,2-c]pyridine-3-carbonitriles, Bioorg. Med. Chem. Lett. 2007; 23(17): 6459-6462
Fairlamb IJSL, Marrison R, Dickinson JM, Lu FJ, Schmidt JP, 2-pyrones possessing antimicrobial and cytotoxic activities, Bioorg. Med. Chem. 2004; 12(15): 4285-4299
Aytemir MD; Erol DD, Hider RC, Synthesis and Evaluation of Antimicrobial Activity of New 3-Hydroxy-6-methyl-4-oxo-4H -pyran-2-carboxamide Derivatives, Turk. J. Chem. 2003; (27): 757-764
Kidwai M, Saxena S, Khan MKR, Thukral SS, Aqua mediated synthesis of substituted 2-amino-4H-chromenes and in vitro study as antibacterial agents, Bioorg. Med. Chem. Lett. 2005; 15(19): 4295-4298
Suarez M, Salfran E, Verdecia Y, Ochoa E, Alba L, Martin N, Martinez R, Quinteiro M, Seoane C, Novoa H, Blaton N, Peeters OM, De RC, X-Ray and theoretical structural study of novel 5,6,7,8-tetrahydrobenzo-4H-pyrans, Tetrahedron 2002; (58): 953-960
Kumari G, Nutan, Modi M, Gupta SK, Singh R.K, Rhodium(II) acetate-catalyzed stereoselective synthesis, SAR and anti-HIV activity of novel oxindoles bearing cyclopropane ring, Eur. J. Med. Chem., 2011; (46): 1181-1188
Vintonyak VV, Warburg K, Kruse H, Grimme S, Hubel K, Rauh, D, Waldmann H, Identification of Thiazolidinones Spiro‐Fused to Indolin‐2‐ones as Potent and Selective Inhibitors of the Mycobacterium tuberculosis Protein Tyrosine Phosphatase B, Angew. Chem., Int. Ed., 2010; 49(34): 5902-5905
Yeung BKS, Zou B, Rottmann MS, Lakshminarayana B, Ang SH, Leong SY, Tan J, Wong J, Keller-Maerki S, Fischli C, Goh A, Schmitt EK, Krastel P, Francotte E, Kuhen K, Plouffe D, Henson K, Wagner T, Winzeler EA, Petersen F, Brun R, Dartois V, Diagana TT, Keller TH, Spirotetrahydro β-Carbolines (Spiroindolones): A New Class of Potent and Orally Efficacious Compounds for the Treatment of Malaria, J. Med. Chem., 2010; 53(14): 5155-5164
Ding K, Lu Y, Nikolovska-Coleska Z, Qiu S, Ding Y, Gao W, Stuckey J, Krajewski K, Roller PP, Tomita Y, Parrish DA, Deschamps JR, Wang S, Structure-based design of potent non-peptide MDM2 inhibitors. J. Am. Chem. Soc., 2005; 127(29): 10130-10131
Cioc RC, Ruijter E, Orru RVA, Multicomponent reactions: advanced tools for sustainable organic synthesis, Green Chem., 2014; 16(6): 2958-2975
Isambert N, Duque MMS, Plaquevent JC, Genisson Y, Rodriguez J, Constantieux T, Multicomponent reactions and ionic liquids: a perfect synergy for eco-compatible heterocyclic synthesis. Chem. Soc. Rev., 2011; 40(3): 1347-1357
Norouzi F, Javanshir S, Magnetic γFe2O3@Sh@Cu2O: an efficient solid-phase catalyst for reducing agent and base-free click synthesis of 1,4-disubstituted-1,2,3-triazoles, BMC Chem. 2020; (14): 1
Welton T, Ionic Liquids in Green Chemistry, Green Chem. 2011; (13): 225
Wang C, Guo L, Li H, Wang Y, Weng J, Wu L, Preparation of simple ammonium ionic liquids and their application in the cracking of dialkoxypropanes, Green Chem. 2006; 8(7): 603-607
Wang C, Zhao W, Li H, Guo L, Solvent-free synthesis of unsaturated ketones by the Saucy–Marbet reaction using simple ammonium ionic liquid as a catalyst, Green Chem. 2009; 11(8): 843-847
Weng J, Wang C, Li H, Wang Y, Novel quaternary ammonium ionic liquids and their use as dual solvent-catalysts in the hydrolytic reaction, Green Chem. 2006; 8(1): 96-99
Dupont J, de Souza RF, Suarez PAZ, Ionic Liquid (Molten Salt) Phase Organometallic Catalysis, Chem. Rev. 2002; 102(10): 3667-3692
Sheldon R, Catalytic reactions in ionic liquids, Chem. Commun. 2001: (23): 2399-2407
Dolzhenko AV, Dolzhenko AV, Green Solvents for Eco-Friendly Synthesis of Bioactive Heterocyclic Compounds. Green Synthetic Approaches for Biologically Relevant Heterocycles, Elsevier: Perth, WA, Australia, 2015; 101-139
Jiang T, Gao H, Han B, Zhao G, Chang Y, Wu W, Gao L, Yang G, Ionic liquid catalyzed Henry reactions, Tetrahedron Lett. 2004; 45(12): 2699-2701
Wilkes JS, A short history of ionic liquids-from molten salts to neoteric solvents, Green Chem. 2002; 4(2): 73-80
Zhu X, Song M, Xu Y, DBU-Based Protic Ionic Liquids for CO2 Capture, ACS Sustain. Chem. Eng. 2017; 5(9): 8192-8198
Carta A, Loriga M, Zanetti S, Sechi LA, Quinoxalin-2-ones. Part 5. Synthesis and antimicrobial evaluation of 3-alkyl-, 3 halomethyl-and 3-carboxyethylquinoxaline-2-ones variously substituted on the benzo-moiety. IL Farmaco 2003; (58): 1251-1255
Wei L, Cheng W, Xia Y, Synthesis of Cyclic Carbonate Catalyzed by DBU Derived Basic Ionic Liquids, Chin. J. Chem. 2018; 36(4): 293-298
Cole AC, Jensen JL, Ntai I, Tran KLT, Weave KJ, Novel Brønsted acidic ionic liquids and their use as dual solvent-catalysts, J. Am. Chem. Soc. 2002; 124(21): 5962-5963
Shi H, Zhu W, Li H, Liu H, Zhang M, Yan Y, Wang Z, Microwave-accelerated esterification of salicylic acid using Brönsted acidic ionic liquids as catalysts. Catal. Commun. 2010; 11(7): 588-591
Jin TS, Wang AQ, Wang X, Zhang JS, Li TS, A Clean One-pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives Catalyzed by Hexadecyltrimethyl Ammonium Bromide in Aqueous Media, Synlett 2004; (5): 871-873
Jin TS, Xiao JC, Wang SJ, Li TS, Song XR, An Efficient and Convenient Approach to the Synthesis of Benzopyrans by a Three-Component Coupling of One-Pot Reaction, Synlett 2003; (13): 2001-2004
Babu NS, Pasha N; Venkateswara KT, Prasad PS, Lingaiah N, A heterogeneous strong basic Mg/La mixed oxide catalyst for efficient synthesis of poly functionalized pyrans. Tetrahedron Lett. 2008; 49(17): 2730-2733
Balalaie S, Bararjanian M, Amani AM, Movassagh B, (S)-Proline as a neutral and efficient catalyst for the one-pot synthesis of tetrahydrobenzo [b] pyran derivatives in aqueous media, Synlett 2006; (2): 263-266
Peng Y, Song G, Huang F, Tetramethylguanidine-[bmim][BF4]. An Efficient and Recyclable Catalytic System for One-Pot Synthesis of 4H-Pyrans, Monatsh. Chem. 2005; (136): 727-731
Kumar D, Reddy VB, Mishra BG, Rana RK, Nadagouda MN, Varma RS, Nanosized magnesium oxide as catalyst for the rapid and green synthesis of substituted 2-amino-2-chromenes, Tetrahedron 2007; 63(15): 3093-3097
Maddila SN, Maddila S, van Zyl WE, Jonnalagadda SB, Ceria–Vanadia/Silica‐Catalyzed Cascade for C-C and C-O Bond Activation: Green One‐Pot Synthesis of 2‐Amino‐3‐cyano‐4H‐pyrans, Chemistry Open 2016; 5(1): 38-42
Molla A, Hussain S, Base free synthesis of iron oxide supported on boron nitride for the construction of highly functionalized pyrans and spirooxindoles, RSC Adv. 2016; 6(7): 5491-5502
Ramadoss H, Kiyani H, Mansoor SS, Triphenylphosphine Catalysed Facile Multicomponent Synthesis of 2-Amino-3-Cyano-6-Methyl-4-Aryl- 4H-Pyrans, Iran. J. Chem. Chem. Eng. 2017; 36(1): 19-26
Maleki A, Varzi Z, Hassanzadeh-Afruzi F, Preparation and characterization of an eco-friendly ZnFe2O4@ alginic acid nanocomposite catalyst and its application in the synthesis of 2-amino-3-cyano-4H-pyran derivatives, Polyhedron 2019; (171): 193-202
Pan S, Li P, Xu G, Guo J, Ke L, Xie C, Zhang Z, Hui Y, MCM-41@Schiff base-Co(OAc)2 as an efficient catalyst for the synthesis of pyran derivatives, Res. Chem. Intermed. 2020; (46): 1353-1371
Khazaei A, Gholami F, Khakyzadeh V, Moosavi-Zare AR, Afsar J, Magnetic core-shell titanium dioxide nanoparticles as an efficient catalyst for domino Knoevenagel-Michael-cyclocondensation reaction of malononitrile, various aldehydes and dimedone, RSC Adv. 2015; 5(19): 14305
Esmaeili MS, Khodabakhshi MR, Maleki A, Varzi Z, Green, Natural and Low Cost Xanthum Gum Supported Fe3O4 as a Robust Biopolymer Nanocatalyst for the One-Pot Synthesis of 2-Amino-3-Cyano-4H-Pyran Derivatives, Polycycl. Aromat. Compd. 2020; https://doi.org/10.1080/10406638.2019.1708418.
Maghsoodlou, MT, Hazeri N, Lashkari M, Shahrokhabadi FN, Naghshbandi B, Kazemidoost MS, Rashidi M, Mir F, Kangani M, Salahi S, Saccharose as a new, natural, and highly efficient catalyst for the one-pot synthesis of 4,5-dihydropyrano[3,2-c]chromenes, 2-amino-3-cyano-4H-chromenes, 1,8 dioxodeca hydroacridine, and 2-substituted benzimidazole derivatives, Res. Chem. Intermed. 2015; (41): 6985-6997
Hiremath PB, Kantharaju K, An Efficient and Facile Synthesis of 2‐Amino‐4H‐pyrans &Tetrahydrobenzo[b]pyrans Catalysed by WEMFSA at Room Temperature, Chemistry Select. 2020; 5(6): 1896-1906
Fihri A, Len C, Varma RS, Solhy A, Hydroxyapatite: A review of syntheses, structure and applications in heterogeneous catalysis, Coord. Chem. Rev. 2017; 347 (48): 61
Dangolani SK, Panahi F, Nourisefat M, Khalafi-Nezhad A, 4-Dialkylaminopyridine modified magnetic nanoparticles: as an efficient nano-organocatalyst for one-pot synthesis of 2-amino-4H-chromene-3-carbonitrile derivatives in water, RSC Adv. 2016; (6): 92316-92324
Najmedin A, Ahooie TS, Hashemi MM, Yavari I, Magnetic Graphitic Carbon Nitride-Catalyzed Highly Efficient Construction of Functionalized 4H-Pyrans, Synlett 2018; 29(05): 645-649
Kharbangar I, Rohman R, Mecadon H, Myrboh B, KFAl2O3 as an Efficient and Recyclable Basic Catalyst for the Synthesis of 4H-Pyran-3-Carboxylates and 5-Acetyl-4H Pyrans. Int. J. Org. Chem. 2012; (2): 282-286
Smits R, Belyakov S, Plotniece A, Duburs G, Synthesis of 4H-Pyran Derivatives Under Solvent-Free and Grinding Conditions, Synth. Commun. 2013; 43(4): 465-475
Bhattacharyya P, Pradhan K, Paul S, Das AR, One-pot synthesis of dihydropyrano[2,3-c]chromenes via a three component coupling of aromatic aldehydes, malononitrile, and 3-hydroxycoumarin catalyzed by nano-structured ZnO in water: a green protocol, Tetrahedron Lett. 2012; 52(36): 4687-4641
Gao S.; Tsai CH, Tseng C, Yao C, Fluoride ion catalyzed multicomponent reactions for efficient synthesis of 4H-chromene and N-arylquinoline derivatives in aqueous media, Tetrahedron 2008; 64(38): 9143-9149
Tahmassebi D, Bryson JA, Binz SI, 1,4-Diazabicyclo[2.2.2]octane as an Efficient Catalyst for a Clean, One-Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives via Multicomponent Reaction in Aqueous Media, Synth. Commun. 2011; 41(18): 2701-2711
Zhi H, Lu C, Zhang Q, Luo J, A new PEG-1000-based dicationic ionic liquid exhibiting temperature-dependent phase behavior with toluene and its application in one-pot synthesis of benzopyrans, Chem. Commun. 2009; (20): 2878-2880
Shirini F, Goli-Jolodar O, Akbari M, Seddighi M, Preparation, characterization, and use of poly(vinylpyrrolidonium) hydrogen phosphate ([PVP-H]H2PO4) as a new heterogeneous catalyst for efficient synthesis of 2-amino-tetrahydro-4H-pyrans, Res Chem Inter. 2016; (42): 4733-4749
Amirnejat S, • Nosrati A, • Peymanfar R, • Javanshir S, Synthesis and antibacterial study of 2-amino-4H-pyrans and pyrans annulated heterocycles catalyzed by sulfated polysaccharide-coated BaFe12O19 nanoparticles, Res. Chem. Inter. 2020; (46): 3683-3701
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