Catalyst-free green synthesis of dihydropyrano[2,3-c]pyrazole scaffolds assisted by ethylene glycol (E-G) as a reusable and biodegradable solvent medium

Journal of Chemical Sciences volume 132, Article number: 72 (2020) Cite this article

Abstract

We revealed a catalyst-free, green and rapid one-pot four-component tandem strategy for the preparation of dihydropyrano[2,3-c]pyrazoles – a biologically significant scaffold – via Knoevenagel-Michael cyclocondensation based on green chemistry principles. Highlights of the current practice are the application of non-hazardous reaction circumstances, catalyst-free, operational simplicity, use of inexpensive initiating substances, isolation of pure product via easy filtration thus preventing the requirement for column chromatography, metal-free, excellent yields, time-saving aspects of the reaction. However, the green ethylene glycol (E-G) can be recycled at least six times with no considerable reduction in activity making it greatly advantageous in addressing the industrial requirements and environmental worries.

Graphic Abstract

The catalyst-free and environmentally friendly synthesis of dihydropyrano[2,3-c]pyrazole scaffolds are reported via ethylene glycol (E-G) as a green, reusable and biodegradable promoting media via tandem Knoevenagel-Michael cyclocondensation reaction of ethyl acetoacetate, hydrazine hydrate/phenylhydrazine, aromatic/aliphatic aldehydes and malononitrile provided the anticipated products in outstanding yields and short reaction times which might solve some cost problems in industry

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References

  1. 1.

    Ibad A, Waseem M A, Ibad F, Ansari K, Lone A M, Watal G and Siddiqui I R 2017 A Green Access to Tetrahydro‐1H‐pyrano [2, 3‐d] pyrimidines: Visible‐Light‐Triggered and Ethylene‐Glycol‐Mediated Multicomponent One‐Pot Process Chem. Select. 2 4587

    CAS  Google Scholar 

  2. 2.

    Chauhan P, Mahajan S and Enders D 2015 Asymmetric synthesis of pyrazoles and pyrazolones employing the reactivity of pyrazolin-5-one derivatives Chem. Commun. 51 12890

    CAS  Google Scholar 

  3. 3.

    (a) Junek H and Aigner H 1973 Synthesen mit Nitrilen, XXXV. Reaktionen von tetracyanäthylen mit heterocyclen Chem. Ber. 106 914; (b) Wamhoff H, Kroth E and Strauch K 1993 Dihalogentriphenylphosphorane in der Heterocyclensynthese; 271: Heterokondensierte 1, 2, 4-Triazolo [1, 5-c] pyrimidine aus Enaminonitrilen via O-Ethylformimide Synthesis 11 1129

  4. 4.

    Foloppe N, Fisher L M, Howes R, Potter A, Robertson A G and Surgenor A E 2006 Identification of chemically diverse Chk1 inhibitors by receptor-based virtual screening Bioorg. Med. Chem. 14 4792

    CAS  Google Scholar 

  5. 5.

    (a) Wang J L, Liu D, Zheng Z J, Shan S, Han X, Srinivasula S M, Croce C M, Alnemri E S and Huang Z 2000 Structure-based discovery of an organic compound that binds Bcl-2 protein and induces apoptosis of tumor cells Proc. Natl. Acad. Sci. 97 7124; (b) Kuo C, Huang J and Nakamura H 1984 Studies on heterocyclic compounds. 6. Synthesis and analgesic and antiinflammatory activities of 3, 4-dimethylpyrano [2, 3-c] pyrazol-6-one derivatives Med. Chem. 27 539

  6. 6.

    Abdelrazek F M, Metz P, Kataeva O, Jaeger A and El-Mahrouky S F 2007 Synthesis and Molluscicidal Activity of New Chromene and Pyrano[2,3‐c]pyrazole Derivatives Arch. Pharm. 340 543

    CAS  Google Scholar 

  7. 7.

    El-Tamany E S, El-Shahed F A and Mohamed B H 1999 Synthesis and bilogical activity of some pyrazole derivatives J. Serb. Chem. Soc. 64 9

    CAS  Google Scholar 

  8. 8.

    Saha A, Payra S and Banerjee S 2015 One-pot multicomponent synthesis of highly functionalized bio-active pyrano[2,3-c]pyrazole and benzylpyrazolyl coumarin derivatives using ZrO2 nanoparticles as a reusable catalyst Green Chem. 17 2859

  9. 9.

    Moshtaghi Zonouz A and Moghani D 2016 Green and highly efficient synthesis of pyranopyrazoles in choline chloride/urea deep eutectic solvent Synth. Commun. 46 220

    CAS  Google Scholar 

  10. 10.

    Zolfigol M A, Tavasoli M, Moosavi-Zare A R, Moosavi P, Grehardus Kruger H, Shiri M and Khakyzadeh V 2013 Synthesis of pyranopyrazoles using isonicotinic acid as a dual and biological organocatalyst RSC Adv. 3 25681

    CAS  Google Scholar 

  11. 11.

    Gujar J B, Chaudhari M A, Kawade D S and Shingara M S 2014 Molecular sieves: an efficient and reusable catalyst for multi-component synthesis of dihydropyrano [2, 3-c] pyrazole derivatives Tetrahedron Lett. 55 6030

  12. 12.

    Guo R Y, An Z M, Mo L P, Yang S T, Liu H X and Wang S X 2013 Meglumine promoted one-pot, four-component synthesis of pyranopyrazole derivatives Tetrahedron 69 9931

  13. 13.

    Tamaddon F and Alizadeh M A 2014 A four-component synthesis of dihydropyrano [2, 3-c] pyrazoles in a new water-based worm-like micellar medium Tetrahedron Lett. 55 3588

  14. 14.

    Mecadon H, Rohman M R, Kharbangar I, Laloo B M, Kharkongor I, Rajbangshi M and Myrboh B 2011 l-Proline as an efficicent catalyst for the multi-component synthesis of 6-amino-4-alkyl/aryl-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles in water Tetrahedron Lett. 52 3228

  15. 15.

    Wu M, Feng Q, Wan D and Ma J 2013 CTACl as catalyst for four-component, one-pot synthesis of pyranopyrazole derivatives in aqueous medium Synth. Commun. 43 1721

    CAS  Google Scholar 

  16. 16.

    Bora P P, Bihani M and Bez G 2013 Multicomponent synthesis of dihydropyrano [2, 3-c] pyrazoles catalyzed by lipase from Aspergillus niger J Mol. Catal. B 92 24

    CAS  Article  Google Scholar 

  17. 17.

    Dalal K S, Tayade Y A, Wagh Y B, Trivedi D R, Dalal D S and Chaudhari B L 2016 Bovine serum albumin catalyzed one-pot, three-component synthesis of dihydropyrano [2, 3-c] pyrazole derivatives in aqueous ethanol RSC Adv. 6 14868

  18. 18.

    Tayade Y A, Padvi S A, Wagh Y B and Dalal D S 2015 β-Cyclodextrin as a supramolecular catalyst for the synthesis of dihydropyrano [2, 3-c] pyrazole and spiro [indoline-3, 4′-pyrano [2, 3-c] pyrazole] in aqueous medium Tetrahedron Lett. 56 2441

  19. 19.

    Zhou C F, Li J J and Su W K 2016 Morpholine triflate promoted one-pot, four-component synthesis of dihydropyrano [2, 3-c] pyrazoles Chin. Chem. Lett. 27 1686

    CAS  Google Scholar 

  20. 20.

    Yarie M, Zolfigol M A, Baghery S, Alonso D A, Khoshnood A, Bayat Y and Asgar A 2018 Triphenyl (3-sulfopropyl) phosphonium trinitromethanide as a novel nanosized molten salt: Catalytic activity at the preparation of dihydropyrano [2, 3-c] pyrazoles J. Mol. Liq. 271 872

    CAS  Article  Google Scholar 

  21. 21.

    Liu T, Lai Y H, Yu Y Q and Xu D Z 2018 A facile and efficient procedure for one-pot four-component synthesis of polysubstituted spiro pyrano[2,3-c]pyrazole and spiro 1,4-dihydropyridine catalyzed by a Dabco-based ionic liquid under mild conditions New. J. Chem. 42 1046

    CAS  Google Scholar 

  22. 22.

    Ghorbani-Vaghei R, Mahmoodi J, Shahriari A and Maghbooli Y 2017 Synthesis of pyrano[2,3‐c]pyrazole derivatives using Fe3O4@SiO2@piperidinium benzene‐1,3‐disulfonate (Fe3O4@SiO2 nanoparticle‐supported IL) as a novel, green and heterogeneous catalyst Appl. Organomet. Chem. 31 e3816

    Article  Google Scholar 

  23. 23.

    Kiyani H and Bamdad M 2018 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. 44 2761

    CAS  Article  Google Scholar 

  24. 24.

    Salehi N and Mirjalili F B B 2018 Green Synthesis of Pyrano[2,3-c]pyrazoles and Spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles] Using Nano-silica Supported 1,4-Diazabicyclo[2.2.2]octane as a Novel Catalyst Org. Prep. Proced. Int. 50 578

  25. 25.

    Konakanchi R, Gondru R, Bharat Nishtala V and Reddy Kotha L NaF-catalyzed efficient one-pot synthesis of dihydropyrano[2,3-c]pyrazoles under ultrasonic irradiation via MCR approach 2018 Synth. Commun. 48 1994

  26. 26.

    Patel K G, Misra N M, Vekariya R H and Shettigar R R 2018 One-pot multicomponent synthesis in aqueous medium of 1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile and derivatives using a green and reusable nano-SiO2 catalyst from agricultural waste Res. Chem. Intermed. 44 289

    CAS  Article  Google Scholar 

  27. 27.

    Mohamadpour F 2019 Synthesis of Pyran-Annulated Heterocyclic Systems Catalyzed by Theophylline as a Green and Bio-Based Catalyst Polycycl. Aromat. Comp. doi: https://doi.org/10.1080/10406638.2019.1575246

    Google Scholar 

  28. 28.

    Zolfigol M A, Afsharnadery F, Baghery S, Salehzadeh S and Maleki F 2015 Catalytic applications of {[HMIM]C(NO2)3}: as a nano ionic liquid for the synthesis of pyrazole derivatives under green conditions and a mechanistic investigation with a new approach RSC Adv. 5 75555

  29. 29.

    Mohamadpour F and Lashkari M 2018 Three-component reaction of β-keto esters, aromatic aldehydes and urea/thiourea promoted by caffeine: A green and natural, biodegradable catalyst for eco-safe Biginelli synthesis of 3,4-dihydropyrimidin-2-(1H)-ones/tiones derivatives under solvent-free conditions J. Serb. Chem. Soc. 83 673

    CAS  Article  Google Scholar 

  30. 30.

    Mohamadpour F 2018 Green and Convenient One-Pot Access to Polyfunctionalized Piperidine Scaffolds via Glutamic Acid Catalyzed Knoevenagel- Intramolecular [4+2] aza-Diels-Alder Imin-Based Multi-Component Reaction Under Ambient Temperature Polycycl. Aromat. Comp. doi: https://doi.org/10.1080/10406638.2018.1472111

    Google Scholar 

  31. 31.

    Mohamadpour F 2019 Glutamic acid as green and bio-based α-amino acid catalyst promoted one-pot access to polyfunctionalized dihydro-2-oxypyrroles J. Serb. Chem. Soc. 84 1083

    CAS  Article  Google Scholar 

  32. 32.

    Mohamadpour F 2019 Theophylline as a Green Catalyst for the Synthesis of 1H-Pyrazolo[1,2-b]phthalazine-5,10-dione Org. Prep. Proced. Int. doi: https://doi.org/10.1080/00304948.2019.1697611

    Google Scholar 

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Acknowledgements

We gratefully acknowledge the financial support from the Research Council of the Apadana Institute of Higher Education.

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  1. School of Engineering, Apadana Institute of Higher Education, Shiraz, Iran

    Farzaneh Mohamadpour

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  1. Farzaneh Mohamadpour
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Correspondence to Farzaneh Mohamadpour.

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Mohamadpour, F. Catalyst-free green synthesis of dihydropyrano[2,3-c]pyrazole scaffolds assisted by ethylene glycol (E-G) as a reusable and biodegradable solvent medium. J Chem Sci 132, 72 (2020). https://doi.org/10.1007/s12039-020-01775-4

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Keywords

  • Catalyst-free
  • ethylene glycol (E-G)
  • green protocol
  • reusable solvent medium
  • dihydropyrano[2,3-c]pyrazoles