[Fesipmim]Cl as highly efficient and reusable catalyst for solventless synthesis of dihydropyridine derivatives through Hantzsch reaction

Abstract

In the present investigation, magnetic ferrite nanoparticles (ferrite NPs) were synthesized and coated with silica (ferrite@SiO2NPs) by using the sol-gel method. After that, silica propylmethylimidazolium chloride ionic liquid [Sipmim]Cl was prepared and linked with the above-prepared ferrite@SiO2NPs to synthesize ferrite silica propylmethylimidazolium chloride [Fesipmim]Cl catalyst. The formation of [Fesipmim]Cl catalyst was confirmed by Fourier-transform infrared (FT-IR) spectroscopy analysis. X-ray diffraction (XRD) analysis confirmed the structure of ferrite NPs and ferrite@SiO2 NPs. Transmission electron microscopy (TEM) evidenced the successful formation of ferrite NPs and ferrite@SiO2 NPs. Scanning electron microscopy (SEM) results revealed the change in morphology of ferrite NPs, ferrite@SiO2NPs and [Fesipmim]Cl. The magnetic properties of [Fesipmim]Cl catalyst were measured by vibrating sample magnetometer (VSM). The efficiency of the [Fesipmim]Cl catalyst was checked by using it for the synthesis of different derivatives of dihydropyridine through Hantzsch reaction via a three-component coupling reaction of substituted benzaldehydes, ethyl/ methyl acetoacetate and ammonium acetate. The formation and structures of all the synthesized compounds were confirmed by FT-IR, 1HNMR, 13C NMR spectral analyses. The reusability of the catalyst [Fesipmim]Cl was checked up to seven cycles and found to have excellent activity up to five cycles.

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References

  1. 1.

    Bagheri S, Muhd J N and Bee A H S 2014 Titanium dioxide as a catalyst support in heterogeneous catalysis Sci. World J. 2014 727496

    Google Scholar 

  2. 2.

    Liu R, Jin R, An J, Zhao Q, Cheng T and Liu G 2014 Hollow-shell-structured nanospheres: A recoverable heterogeneous catalyst for rhodium-catalyzed tandem reduction/lactonization of ethyl 2-acylarylcarboxylates to chiral phthalides Chem. - An Asian J. 9 1388

    CAS  Google Scholar 

  3. 3.

    Singh S B and Tandon P K 2016 Catalysis: A brief review on Nano-Catalyst J. Energy Chem. Eng. 2 106

    Google Scholar 

  4. 4.

    Chaturvedi S, Dave P and Shah N 2012 Applications of nano-catalyst in new era J. Saudi Chem. Soc. 16 307

    CAS  Google Scholar 

  5. 5.

    Nejadshafiee V and Naeimi H 2018 Molecular Ionic Liquid Supported on Mesoporous Silica Nanoparticles-Imprinted Iron Metal: A Recyclable Heterogeneous Catalyst for One-Pot, Three-Component Synthesis of a Library of Benzodiazepines Curr. Org. Synth. 16 136

    Google Scholar 

  6. 6.

    Korupolu R B, Maripi S, Madasu S B, Majji R K, Ganta R K and Chilla P N 2017 Nano nickel-cobalt ferrite catalyzed one pot synthesis of 14-Aryl-14H-dibenzo[a, j]xanthenes and 12-Aryl-8, 9, 10, 12-tetrahydrobenzo[a]xanthene-11-one derivatives Orient. J. Chem. 33 122

    CAS  Google Scholar 

  7. 7.

    Safaei-Ghomi J, Enayat-Mehri N and Eshteghal F 2018 4-(4′-Diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous Fe3O4@SiO2 NPs: As a reusable and efficient catalyst for the synthesis of ethyl 2-amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates J. Saudi Chem. Soc. 22 485

    CAS  Google Scholar 

  8. 8.

    Kumari A, Kaur B, Srivastava R and Sangwan R S 2015 Isolation and immobilization of alkaline protease on mesoporous silica and mesoporous ZSM-5 zeolite materials for improved catalytic properties Biochem. Biophys. Rep. 2 108

    PubMed  PubMed Central  Google Scholar 

  9. 9.

    Saghanezhad S J, Nazari Y and Davod F 2016 Cucurbit[6]uril-OSO3H: A novel acidic nanocatalyst for the one-pot preparation of 14-aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-octahydro-xanthenes RSC Adv. 6 25525

    CAS  Google Scholar 

  10. 10.

    Ferlin N, Courty M, Van Nhien A N, Gatard S, Pour M, Quilty B, Ghavre M, Haib A, Kummerer K, Gathergoog N and Bouquillon S 2013 Tetrabutylammonium prolinate-based ionic liquids: A combined asymmetric catalysis, antimicrobial toxicity and biodegradation assessment RSC Adv. 3 26241

    CAS  Google Scholar 

  11. 11.

    Litschauer M and Neouze M A 2008 Nanoparticles connected through an ionic liquid-like network J. Mater. Chem. 18 640

    CAS  Google Scholar 

  12. 12.

    Heravi M M, Zakeri M, Karimi N, Saeedi M, Oskooie H A and Tavakoli-Hosieni N 2010 Acidic ionic liquid [(CH2)4SO3HMIM] [HSO4]: A green media for the simple and straightforward synthesis of 2,4,5-trisubstituted imidazoles Synth. Commun. 40 1998

    CAS  Google Scholar 

  13. 13.

    Bonne D, Coquerel Y, Constantieux T and Rodriguez J 2010 1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions Tetrahedron Asymm. 21 1085

    CAS  Google Scholar 

  14. 14.

    Choudhury L H and Parvin T 2011 Recent advances in the chemistry of imine-based multicomponent reactions (MCRs) Tetrahedron 67 8213

    CAS  PubMed  PubMed Central  Google Scholar 

  15. 15.

    Biggs-Houck J E, Younai A and Shaw J T 2010 Recent advances in multicomponent reactions for diversity-oriented synthesis Curr. Opin. Chem. Biol. 14 371

    CAS  PubMed  Google Scholar 

  16. 16.

    Triggle D J 2007 Calcium channel antagonists: Clinical uses-Past, present and future Biochem. Pharmacol. 74 1

    CAS  PubMed  Google Scholar 

  17. 17.

    Gekeler R 1995 Chemosensitizers in tumor therapy: new compounds promise better efficacy Drugs Future 20 499

    Google Scholar 

  18. 18.

    Shinde S 2002 Synthesis and anti-inflammatory activity of 1,4-dihydropyridines Acta Pharm. 52 281

    Google Scholar 

  19. 19.

    Gullapalli S and Ramarao P 2002 L-type Ca2+ channel modulation by dihydropyridines potentiates κ-opioid receptor agonist induced acute analgesia and inhibits development of tolerance in rats Neuropharmacology 42 467

    CAS  PubMed  Google Scholar 

  20. 20.

    Bossert F, Meyer H and Wehinger E 1981 4-Aryldihydropyridines, a New Class of Highly Active Calcium Antagonists Angew. Chemie Int. Ed. English 20 762

    Google Scholar 

  21. 21.

    Gilpin R K and Pachla L A 1999 Pharmaceuticals and Related Drugs Anal. Chem. 71 217

    Google Scholar 

  22. 22.

    Cosconati S, Marinelli L, Lavecchia A and Novellino E 2007 Characterizing the 1,4-dihydropyridines binding interactions in the L-type Ca2+ channel: Model construction and docking calculations J. Med. Chem. 50 1504

    CAS  PubMed  Google Scholar 

  23. 23.

    Kidwai M, Saxena S, Mohan R and Venkataramanan R 2002 A novel one pot synthesis of nitrogen containing heterocycles: An alternate methodology to the Biginelli and Hantzsch reactions J. Chem. Soc. Perkin 1 2 1845

    Google Scholar 

  24. 24.

    Anniyappan M, Muralidharan D and Perumal P T 2002 Synthesis of hantzsch 1,4-dihydropyridines under microwave irradiation Synth. Commun. 32 659

    CAS  Google Scholar 

  25. 25.

    Öhberg L and Westman J 2001 An Efficient and Fast Procedure for the Hantzsch Dihydropyridine Synthesis under Microwave Conditions Synlett 2001 1296

    Google Scholar 

  26. 26.

    Lee Y A and Kim S C 2011 Synthesis of 1,4-dihydropyridine using microwave-assisted aza-Diels-Alder reaction and its application to Amlodipine J. Ind. Eng. Chem. 17 401

    CAS  Google Scholar 

  27. 27.

    Khadilkar B M, Gaikar V G and Chitnavis A A 1995 Aqueous hydrotrope solution as a safer medium for microwave enhanced hantzsch dihydropyridine ester synthesis Tetrahedron Lett. 36 8083

    CAS  Google Scholar 

  28. 28.

    Vanden Eynde J and Mayence A 2003 Synthesis and aromatization of Hantzsch 1,4-dihydropyridines under microwave irradiation. An overview Molecules 8 381

    CAS  PubMed Central  Google Scholar 

  29. 29.

    Yadav J S, Subba Reddy, B V and Reddy P T 2001 Unprecedented synthesis of hantzsch 1,4-dihydropyridines under biginelli reaction conditions Synth. Commun. 31 425

    CAS  Google Scholar 

  30. 30.

    Shaabani A, Rezayan A H, Rahmati A and Sharifi M 2006 Ultrasound-accelerated synthesis of 1,4-dihydropyridines in an ionic liquid Monatsh. Chem. 137 77

    CAS  Google Scholar 

  31. 31.

    Mekheimer R A, Hameed A A and Sadek K U 2008 Solar thermochemical reactions: Four-component synthesis of polyhydroquinoline derivatives induced by solar thermal energy Green Chem. 10 592

    CAS  Google Scholar 

  32. 32.

    Legeay J C, Vanden Eynde J J and Bazureau J P 2005 Ionic liquid phase technology supported the three component synthesis of Hantzsch 1,4-dihydropyridines and Biginelli 3,4-dihydropyrimidin-2(1H)-ones under microwave dielectric heating Tetrahedron 61 12386

    CAS  Google Scholar 

  33. 33.

    Yadav J S, Reddy B V S, Basak A K and Narsaiah A V 2003 Three-component coupling reactions in ionic liquids: An improved protocol for the synthesis of 1,4-dihydropyridines Green Chem. 5 60

    CAS  Google Scholar 

  34. 34.

    Jin T S, Zhang J S, Xiao J C, Wang A Q and Li T S 2004 Clean Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives Catalyzed by p -Dodecylbenezenesulfonic Acid in Aqueous Media Synlett. 2004 0866

    Google Scholar 

  35. 35.

    Zonouz, A M and Sahranavard N 2010 Synthesis of 1,4-Dihydropyridine Derivatives Under Aqueous Media E-Journal Chem. 7 372

    Google Scholar 

  36. 36.

    Tamaddon F, Razmi Z and Jafari A A 2010 Synthesis of 3,4-dihydropyrimidin-2(1H)-ones and 1,4-dihydropyridines using ammonium carbonate in water Tetrahedron Lett. 51 1187

    CAS  Google Scholar 

  37. 37.

    Evdokimov N M, Magedov I V, Kireev A S and Kornienko A 2006 One-Step, Three-Component Synthesis of Pyridines and 1,4-Dihydropyridines with Manifold Medicinal Utility Org. Lett. 8 899

    CAS  PubMed  Google Scholar 

  38. 38.

    Adharvana C M and Syamasundar K 2005 Silica gel/NaHSo4 catalyzed one-pot synthesis of Hantzsch 1,4-dihydropyridines at ambient temperature Catal. Commun. 6 624

    Google Scholar 

  39. 39.

    Gordeev M F, Patel D V and Gordon E M 1996 Approaches to combinatorial synthesis of heterocycles: A solid-phase synthesis of 1,4-dihydropyridines J. Org. Chem. 61 924

    CAS  Google Scholar 

  40. 40.

    Ghosh S, Saikh F, Das J and Pramanik A K 2013 Hantzsch 1,4-dihydropyridine synthesis in aqueous ethanol by visible light Tetrahedron Lett. 54 58

    CAS  Google Scholar 

  41. 41.

    Tamaddon F and Moradi S 2013 Controllable selectivity in Biginelli and Hantzsch reactions using nanoZnO as a structure base catalyst J. Mol. Catal. A Chem. 370 117

    CAS  Google Scholar 

  42. 42.

    Debache A, Ghalem W, Boulcina R, Belfaitah A, Rhouati S and Carboni B 2009 An efficient one-step synthesis of 1,4-dihydropyridines via a triphenylphosphine-catalyzed three-component Hantzsch reaction under mild conditions Tetrahedron Lett. 50 5248

    CAS  Google Scholar 

  43. 43.

    Debache A, Boulcina R, Belfaitah A, Rhouati S and Carboni B 2008 One-pot synthesis of 1,4-dihydropyridines via a phenylboronic acid catalyzed Hantzsch three-component reaction Synlett. 2008 509

    Google Scholar 

  44. 44.

    Ko S, Sastry M N V, Lin C and Yao C F 2005 Molecular iodine-catalyzed one-pot synthesis of 4-substituted-1,4- dihydropyridine derivatives via Hantzsch reaction Tetrahedron Lett. 46 5771

    CAS  Google Scholar 

  45. 45.

    Ko S and Yao C F 2006 Ceric Ammonium Nitrate (CAN) catalyzes the one-pot synthesis of polyhydroquinoline via the Hantzsch reaction Tetrahedron 62 7292

    Google Scholar 

  46. 46.

    Tewari N, Dwivedi N and Tripathi R P 2004 Tetrabutylammonium hydrogen sulfate catalyzed eco-friendly and efficient synthesis of glycosyl 1,4-dihydropyridines Tetrahedron Lett. 45 9011

    CAS  Google Scholar 

  47. 47.

    Lee J H 2005 Synthesis of Hantsch 1,4-dihydropyridines by fermenting bakers’ yeast Tetrahedron Lett. 46 7329

    CAS  Google Scholar 

  48. 48.

    Kumar A and Maurya R A 2007 Synthesis of polyhydroquinoline derivatives through unsymmetric Hantzsch reaction using organocatalysts Tetrahedron 63 1946

    CAS  Google Scholar 

  49. 49.

    Wang L M, Sheng J, Zhang L, Han J W, Fan Z Y, Tian H and Chan T Q 2005 Facile Yb(OTf)3 promoted one-pot synthesis of polyhydroquinoline derivatives through Hantzsch reaction Tetrahedron 61 1539

    CAS  Google Scholar 

  50. 50.

    Azgomi N and Mokhtary M 2015 Nano-Fe3O4@SiO2 supported ionic liquid as an efficient catalyst for the synthesis of 1,3-thiazolidin-4-ones under solvent-free conditions J. Mol. Catal. A Chem. 398 58

    CAS  Google Scholar 

  51. 51.

    Deng M, Zhao H, Zhang S, Tian C, Zhang D, Du P, Liu C, Cao H and Li H 1970 High catalytic activity of immobilized laccase on core–shell magnetic nanoparticles by dopamine self-polymerization J. Mol. Catal. B Enzym. 112 15

    Google Scholar 

  52. 52.

    Wang Y, Zhu Q and Tao L 2011 Fabrication and growth mechanism of hierarchical porous Fe3O4 hollow sub-microspheres and their magnetic properties CrystEngComm 13 4652

    CAS  Google Scholar 

  53. 53.

    Sabitha G, Reddy G S K K, Reddy C S and Yadav J S 2003 A novel TMSI-mediated synthesis of Hantzsch 1,4-dihydropyridines at ambient temperature Tetrahedron Lett. 44 4129

    CAS  Google Scholar 

  54. 54.

    Sridhar R and Perumal P T 2005 A new protocol to synthesize 1,4-dihydropyridines by using 3,4,5-trifluorobenzeneboronic acid as a catalyst in ionic liquid: Synthesis of novel 4-(3-carboxyl-1H-pyrazol-4-yl)-1,4-dihydropyridines Tetrahedron 61 2465

    CAS  Google Scholar 

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Acknowledgements

The authors wish to thank Govind Ballabh Pant University of Agriculture& Technology, Pantnagar for providing necessary research facilities and KIET Group of Institutions for time to time help and support for completing the research work. Authors also thank AIRF-JNU Delhi and IIT Ropar for providing NMR spectra and ISFAL, Moga for Providing IR spectra and IIT Roorkee for TEM, SEM, XRD and VSM analysis.

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Correspondence to Akansha Agrwal.

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Agrwal, A., Kasana, V. [Fesipmim]Cl as highly efficient and reusable catalyst for solventless synthesis of dihydropyridine derivatives through Hantzsch reaction. J Chem Sci 132, 67 (2020). https://doi.org/10.1007/s12039-020-01770-9

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Keywords

  • 1, 4-Dihydropyridine
  • Hantzsch reaction
  • ferrite nanoparticles (NPs)
  • [Sipmim]Cl,[Fesipmim]Cl