Expeditious Synthesis of 2-Amino-4H-chromenes and 2-Amino-4H-pyran-3- carboxylates Promoted by Sodium Malonate

Author(s): Mohsen Tazari, Hamzeh Kiyani*.

Journal Name: Current Organic Synthesis

Volume 16 , Issue 5 , 2019

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: Chromenes and pyran annulated heterocycles are the most common frameworks existing in various biologically active molecules. Due to their beneficial and biological properties, they are eyecatching synthetic targets in the arsenal of organic chemistry. Thus, finding green and efficient methods, as well as searching for a new catalyst for the synthesis of these heterocycles is of interest to organic chemistry researchers.

Objective: Sodium malonate as a readily available catalyst was employed aimed at the multicomponent synthesis of numerous 2-amino-4H-chromenes and 2-amino-4H-pyrans in water as a green medium reaction.

Methods: The reaction was performed via treatment of aldehydes (1 mmol) with malononitrile/ethyl cyanoacetate (1 mmol) and β-dicarbonyl compounds (1 mmol)/or resorcinol (1 mmol) in water (4 mL) in the presence of sodium malonate (10 mol %) at 70°C. On completion of the reaction (monitored by TLC analysis), the reaction mixture was gradually cooled at room temperature, and the resulting precipitates were collected by filtration, washed with cold ethanol and air-dried to give the corresponding pure products. The solvent was evaporated from the filtrate to recover the catalyst, and the catalyst was reused for subsequent reactions.

Results: In the initial stages, we explored the best reaction conditions using three-component reaction of benzaldehyde, malononitrile, and dimedone as the model reaction. The effects of catalyst loading, temperature, and solvents were explored for this reaction. It was found that the best results were obtained for the synthesis of 2-amino-4H-chromenes and 2-amino-4H-pyran when the three-component reaction was carried out with equivalent molar quantities of each of the reactants in water containing 10 mol% sodium malonate at 70°C for 15 min in 96% yield. After finding optimal conditions, these conditions apply to other reactants and the target heterocyclic products were obtained with excellent yields.

Conclusion: This study describes an efficient, environmentally benign, and clean one-pot, three-component synthesis of 2-amino-4H-chromenes and 2-amino-4H-pyran-3-carboxylates in the presence of sodium malonate as the commercially available catalyst in an aqueous medium at 70°C. High yields, mild reaction conditions, relatively shorter reaction times, use of simple reagents, and no requirement of the ultrasound, microwave, and ball milling techniques are the salient features and benefits of the present method. In addition, the present process is smooth and green.

Keywords: 2-Amino-4H-chromene, 2-amino-4H-pyran-3-carboxylate, dimedone, nitrile-containing compounds, resorcinol, sodium malonate.

[1]
(a) Brahmachari, G. Green Synthetic Approaches for Biologically Relevant 2-amino-4H-pyrans and 2-amino-4H-pyran-Annulated Heterocycles in Aqueous Media.In: Green Synthetic Approaches for Biologically Relevant Heterocycles; Brahmachari, G., Ed.; Elsevier: Amsterdam, Netherlands, 2015, pp. 185-208.
(b) Kumar, D.; Reddy, V.B.; Sharad, S.; Dube, U.; Kapur, S. A facile one-pot green synthesis and antibacterial activity of 2-amino-4H-pyrans and 2-amino-5-oxo-5,6,7,8- tetrahydro-4H-chromenes. Eur. J. Med. Chem., 2009, 44(9), 3805-3809.
(c) Khodairy, A.; Ali, A.M.; Aboelez, M.O.; El-Wassimy, M.T. One-pot multicomponent synthesis of novel 2-tosyloxyphenylpyrans under green and conventional condition with anti-inflammatory activity. J. Heterocycl. Chem., 2017, 54(2), 1442-1449.
(d) Elinson, M.N.; Ryzhkov, F.V.; Nasybullin, R.F.; Vereshchagin, A.N.; Egorov, M.P. Fast efficient and general PASE approach to medicinally relevant 4H,5H-pyrano[4,3-b]pyran-5-one and 4,6-dihydro-5H-pyrano-[3,2-c]pyridine-5-one scaffolds. Helv. Chim. Acta, 2016, 99(9), 724-731.
(e) Patel, H.B.; Gohil, J.D.; Patel, M.P. Microwave-assisted, solvent-free, one-pot, three-component synthesis of fused pyran derivatives containing benzothiazole nucleus catalyzed by pyrrolidine-acetic acid and their biological evaluation. Monatsh. Chem., 2017, 148(6), 1057-1067.
[2]
(a) Kiyani, H.; Jalali, M.S. Facile and efficient access to tetrahydrobenzo[b]pyrans catalyzed by N,N-dimethylbenzylamine. Heterocycles, 2016, 92(1), 75-85.
(b) Kiyani, H. Recent advances in three-component cyclocondensation of dimedone with aldehydes and malononitrile for construction of tetrahydrobenzo[b]pyrans using organocatalysts. Curr. Org. Synth., 2018, 15(8), 1043-1072.
[3]
Salama, S.K.; Darweesh, A.F.; Abdelhamid, I.A.; Elwahy, A.H.M. Microwave assisted green multicomponent synthesis of novel bis(2-amino-tetrahydro-4H-chromene-3-carbonitrile) derivatives using chitosan as eco-friendly basic catalyst. J. Heterocycl. Chem., 2017, 54(1), 305-312.
[4]
Thomas, N.; Zachariah, S.M.; Ramani, P. 4-Aryl-4H-chromene-3-carbonitrile derivates: Synthesis and preliminary anti-breast cancer studies. J. Heterocycl. Chem., 2016, 53(6), 1778-1782.
[5]
González-Olvera, R.; Román-Rodríguez, V.; Negrón-Silva, G.E.; Espinoza-Vázquez, A.; Rodríguez-Gómez, F.J.; Santillan, R. Multicomponent synthesis and evaluation of new 1,2,3-triazole derivatives of dihydropyri-midinones as acidic corrosion inhibitors for steel. Molecules, 2016, 21(2), 250.
[6]
(a) Dömling, A.; Wang, W.; Wang, K. Chemistry and biology of multicomponent reactions. Chem. Rev., 2012, 112(6), 3083-3135.
(b) Domling, A.; Ugi, I. Multicomponent reactions with isocyanides Angew. Chem. Int. Ed, 2000, 39(18), 3168-3210.
(d) Zhu, J.; Wang, Q.; Wang, M.X. Multicomponent Reactions in Organic Synthesis, Wiley-VCH: Weinheim. 2015.
(c) Kiyani, H.; Ghorbani, F. Expeditious green synthesis of 3,4-disubstituted isoxazole-5(4H)-ones catalyzed by nano-MgO. Res. Chem. Intermed., 2016, 42(9), 6831-6844.
(d) Kiyani, H.; Bamdad, M. One-pot and efficient synthesis of 5-aminopyrazole-4-carbonitriles catalyzed by potassium phthalimide. Heterocycles, 2017, 94(2), 276-285.
(e) Kiyani, H.; Ghorbani, F. Potassium phthalimide as efficient basic organocatalyst for the synthesis of 3,4-disubstituted isoxazol-5(4H)-ones in aqueous medium. J. Saudi Chem. Soc., 2017, 21(Suppl. 1), S112-S119.
(f) Kiyani, H.; Ghorbani, F. Potassium phthalimide: an efficient and simple organocatalyst for the one-pot synthesis of dihydropyrano[3,2-c]chromenes in aqueous media. Res. Chem. Intermed., 2015, 41(6), 4031-4046.
(g) Kiyani, H.; Ghorbani, F. Potassium phthalimide-catalyzed one-pot multicomponent reaction for efficient synthesis of amino-benzochromenes in aqueous media. Chem. Pap., 2014, 68(8), 1104-1112.
(h) Sabbaghan, M.; Sofalgar, P. Ultrasonic assisted synthesis of chromenes catalyzed by sodium carbonate in aqueous media. Comb. Chem. High Throughput Screen., 2015, 18, 901-910.
[7]
(a) Zavar, S. A novel three component synthesis of 2-amino-4H-chromenes derivatives using nano ZnO catalyst. Arab. J. Chem., 2017, 10(Suppl. 1), S67-S70.
(b) Hosseini-Sarvari, M.; Shafiee-Haghighi, S. Nano-ZnO as heterogeneous catalyst for three-component synthesis of tetrahydrobenzo[b]pyrans in water. Chem. Heterocycl. Compd., 2012, 48(9), 1307-1313.
(c) Anandgaonker, P.L.; Jadhav, S.; Gaikwad, S.T.; Rajbhoj, A.S. Nanosized TiO2 as a recyclable heterogeneous catalyst for the synthesis of tetrahydrobenzo[b]pyran derivatives. J. Cluster Sci., 2014, 25(2), 483-493.
(d) Mohammadinezhad, A.; Akhlaghinia, B. Nanofibre sepiolite catalyzed green and rapid synthesis of 2-amino-4H-chromene derivatives. Aust. J. Chem., 2018, 71(1), 32-46.
[8]
(a) 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(6), 1145-1150.
(b) Rostamizadeh, S.; Zekri, N. An efficient, one-pot synthesis of 2-amino-4H-chromenes catalyzed by (α-Fe2O3)-MCM-41-supported dual acidic ionic liquid as a novel and recyclable magnetic nanocatalyst. Res. Chem. Intermed., 2016, 42(3), 2329-2341.
(c) Hu, H.; Qiu, F.; Ying, A.; Yang, J.; Meng, H. An environmentally benign protocol for aqueous synthesis of tetrahydrobenzo[b]pyrans catalyzed by cost-effective ionic liquid. Int. J. Mol. Sci., 2014, 15(4), 6897-6909.
(d) Sharma, P.; Gupta, M.; Kant, R.; Gupta, V.K. One-pot synthesis of various 2-amino-4H-chromene derivatives using a highly active supported ionic liquid catalyst. RSC Advances, 2016, 6(38), 32052-32059.
[9]
(a) 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(3), 411-422.
(b) Pandit, K.S.; Chavan, P.V.; Desai, U.V.; Kukarnia, M.A.; Wadgaonkar, P.P. Tris-hydroxymethylaminomethane (THAM): a novel organocatalyst for an environmentally benign synthesis of medicinally important tetrahydrobenzo[b]pyrans and pyran-annulated heterocycles. New J. Chem., 2015, 39(6), 4452-4463.
(c) Mansoor, S.S.; Logaiya, K.; Aswin, K.; Sudhan, P.N. An appropriate one-pot synthesis of 3,4-dihydro-pyrano[c]chromenes and 6-amino-5-cyano-4-aryl-2-methyl-4H-pyrans with thiourea dioxide as an efficient, reusable organic catalyst in aqueous medium. J. Taibah Univ. Sci, 2015, 9(2), 213-226.
(d) 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(11), 557-563.
(e) Kiyani, H.; Ghorbani, F. Potassium phthalimide promoted green multicomponent tandem synthesis of 2-amino-4H-chromenes and 6-amino-4H-pyran-3-carboxylates. J. Saudi Chem. Soc., 2014, 18(5), 689-701.
(f) Kiyani, H.; Ghorbani, F. Efficient tandem synthesis of a variety of pyran-annulated heterocycles, 3,4-disubstituted isoxazol-5(4H)-ones, and α,β-unsaturated nitriles catalyzed by potassium hydrogen phthalate in water. Res. Chem. Intermed., 2015, 41(10), 7847-7882.
(g) Tahmassebi, D.; Bryson, J.A.; Binz, S.I. 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.
(h) Abaszadeh, M.; Seifi, M. Sodium benzenesulfinates: novel and effective organo catalyst for three component synthesis 5,6,7,8-tetrahydro-4H-chromene derivatives under ultrasound irradiation. Lett. Org. Chem., 2015, 12(4), 271-276.
(i) Khandebharad, A.U.; Sarda, S.R.; Gill, C.H.; Soni, M.G.; Agrawal, B.R. Condition based divergence in synthesis of tetrahydrobenzo[b]pyrans. Res. Chem. Intermed., 2016, 42(6), 5779-5787.
(j) Ahmad, M.G.; Romman, U.K.R.; Akhter, K.; Jahan, K.; Bhuiyan, M.H.H.; Halim, M.E. Synthesis of substituted tetrahydrochromenes by the reactions of α,β-unsaturated cyanoesters with dimedone/1,3-cyclohexanedione. Synth. Commun., 2011, 41(19), 2822-2827.
(k) Ramesh, R.; Jayamathi, J.; Karthika, C.; Malecki, J.G.; Lalitha, A. An organocatalytic newer synthetic strategy toward the access of poly-functionalized 4H-pyrans via multicomponent reactions. Polycycl. Aromat. Compd., 2018.
[http://dx.doi.org/10.1080/10406638.2018.1454968]
[10]
(a) Datta, B.; Pasha, M.A. Glycine catalyzed convenient synthesis of 2-amino-4H-chromenes in aqueous medium under sonic condition. Ultrason. Sonochem., 2012, 19(4), 725-728.
(b) Ahad, A.; Farooqui, M. Organocatalyzed domino reactions: Diversity oriented synthesis of pyran-annulated scaffolds using in situ developed benzylidenemalononitriles. Res. Chem. Intermed., 2017, 43(4), 2445-2455.
[11]
(a) Pratap, U.R.; Jawale, D.V.; Netankar, P.D.; Mane, R.A. Baker’s yeast catalyzed one-pot three-component synthesis of polyfunctionalized 4H-pyrans. Tetrahedron Lett., 2011, 52(44), 5817-5819.
(b) Dekamin, M.G.; Peyman, S.Z.; Karimi, Z.; Javanshir, S.; Naimi-Jamal, M.R.; Barikani, M. Sodium alginate: An efficient biopolymeric catalyst for green synthesis of 2-amino-4H-pyran derivatives. Int. J. Biol. Macromol., 2016, 87, 172-179.
[12]
(a) Hazeri, N.; Maghsoodlou, M.T.; Mir, F.; Kangani, M.; Saravan, H.; Molashahi, E. An efficient one-pot three-component synthesis of tetrahydrobenzo[b]pyran and 3,4-dihydropyrano[c]chromene derivatives using starch solution as catalyst. Chin. J. Catal., 2014, 35(3), 391-395.
(b) Mousavi, M.R.; Maghsoodlou, M.T.; Noori, F.; Hazeri, N. A facile and fficient synthesis of tetrahydrobenzo[b]pyrans using sucrose as green, inexpensive, natural and biodegradable catalyst. Org. Chem. Res, 2015, 1(1), 66-71.
(c) Noori Sadeh, F.; Maghsoodlou, M.T.; Hazeri, N.; Kangani, M. A facile and efficient synthesis of tetrahydrobenzo[b]pyrans using lactose as a green catalyst. Res. Chem. Intermed., 2015, 41(8), 5907-5914.
[13]
(a) Behbahani, F.K.; Naderi, M. One-pot synthesis of 2-amino-4H-chromenes catalyzed by Fe(ClO4)3/SiO2. Russ. J. Gen. Chem., 2016, 86(12), 2804-2806.
(b) Mohammadi, A.A.; Asgharigangeh, M.R.; Hadadzahmatkesh, A. Synthesis of tetrahydrobenzo[b]pyran under catalysis of NH4Al(SO4)2.12H2O (Alum). Arab. J. Chem., 2017, 10(Suppl. 2), S2213-S2216.
(c) Sabitha, G. Arundhathi. K.; Sudhakar, K.; Sastry, B.S.; Yadav, J.S. Cerium(III)chloride–catalyzed one-pot synthesis of tetrahydrobenzo [b]pyrans. Synth. Commun., 2009, 39(3), 433-442.
(d) Rosati, O.; Pelosi, A.; Temperini, A.; Pace, V.; Curini, M. Potassium-exchanged zirconium hydrogen phosphate [α-Zr(KPO4)2]-catalyzed synthesis of 2-amino-4H-pyran derivatives under solvent-free conditions. Synthesis, 2016, 48(10), 1533-1540.
(e) Boumoud, B.; Debbache, A.; Boumoud, T.; Boulcina, R.; Debache, A. Aqua mediated one-pot synthesis of 2-amino-tetrahydrobenzo[b]pyran derivatives catalyzed by Mg(NO3)2•6H2O. Lett. Org. Chem., 2014, 11(7), 475-479.
[14]
Sánchez, A.; Hernández, F.; Cruz, P.C.; Alcaraz, Y.; Tamariz, J.; Delgado, F.; Vázquez, M.A. Infrared irradiation-assisted multicomponent synthesis of 2-amino-3-cyano-4H-pyran derivatives. J. Mex. Chem. Soc., 2012, 56(2), 121-127.
[15]
(a) Kiyani, H.; Darzi Daroonkala, M. A cost-effective and green aqueous synthesis of 3-substituted coumarins catalyzed by potassium phthalimide. Bull. Chem. Soc. Ethiop., 2015, 29(3), 449-456.
(b) Biswas, K.; Ghosh, S.; Ghosh, P.; Basu, B. Cyclic ammonium salts of dithiocarbamic acid: stable alternative reagents for the synthesis of S-alkyl carbodithioates from organyl thiocyanates in water. J. Sulfur Chem., 2016, 37(4), 361-376.
(c) Kiyani, H.; Tazari, M. Aqua one-pot, three-component synthesis of dihydropyrano[3,2-c]chromenes and amino-benzochromenes catalyzed by sodium malonate. Res. Chem. Intermed., 2017, 43(11), 6639-6650.
(d) Kumaravel, K.; Vasuki, G. Multi-component reactions in water. Curr. Org. Chem., 2009, 13(18), 1820-1841.
(e) Kiyani, H.; Bamdad, M. Sodium ascorbate as an expedient catalyst for green synthesis of polysubstituted 5-aminopyrazole-4-carbonitriles and 6-amino-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles. Res. Chem. Intermed., 2018, 44(44), 2761-2788.
(f) Kiyani, H.; Aslanpour, S. Sulfanilic acid-catalyzed green synthesis of 4-arylidene-2-phenyl-5(4H)-oxazolones. Heterocycles, 2018, 96(2), 297-303.
(g) Kiyani, H.; Aslanpour, S. Synthesis of Erlenmeyer-Plöchl azlactones promoted by 5-sulfosalicylic acid. Heterocycles, 2017, 94(7), 1314-1321.
(h) Mosallanezhad, A.; Kiyani, H. KI-Mediated three-component reaction of hydroxylamine hydrochloride with aryl/heteroaryl aldehydes and two β-oxoesters. Orbital: Electron. J. Chem, 2018, 10(2), 133-139.
(i) Kiyani, H.; Mosallanezhad, A. Sulfanilic acid-catalyzed synthesis of 4-arylidene-3-substituted isoxazole-5(4H)-ones. Curr. Org. Synth., 2018, 15(5), 715-772.
[16]
Devi, I.; Bhuyan, P.J. Sodium bromide catalysed one-pot synthesis of tetrahydrobenzo[b]pyrans via a three-component cyclocondensation under microwave irradiation and solvent free conditions. Tetrahedron Lett., 2004, 45(47), 8625-8627.
[17]
Dekamin, M.G.; Eslami, M. Highly efficient organocatalytic synthesis of diverse and densely functionalized 2-amino-3-cyano-4H-pyrans under mechanochemical ball milling. Green Chem., 2014, 16(12), 4914-4921.
[18]
Sarkar, A.; Pandit, B.K.; Sinha, B. Effect of paracetamol in aqueous sodium malonate solutions with reference to volumetric and viscometric measurements. J. Chem. Thermodyn., 2016, 96, 161-168.


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 16
ISSUE: 5
Year: 2019
Page: [793 - 800]
Pages: 8
DOI: 10.2174/1570179416666190415105818
Price: $65

Article Metrics

PDF: 34
HTML: 3