Skip to main content
SpringerLink
Log in

Carbazole-based photocatalyst (4CzIPN) as a novel donor-acceptor fluorophore-catalyzed visible-light-induced photosynthesis of dihydropyrano[2,3-c]pyrazole scaffolds via a proton-coupled electron transfer process

  • REGULAR ARTICLE
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

A green radical synthesis method for pyranopyrazole scaffolds catalyzed by a PCET (proton-coupled electron transfer) photocatalyst in an aqueous media in an air environment, at rt, and under a blue LED as a renewable energy source. The goal of this effort is the use of novel, widely available, and affordable donor-acceptor (D-A) fluorophores. The rapid and easy-to-use photocatalyst based on carbazoles; (4CzIPN) produces excellent results, uses little energy, and safeguards the environment. This makes it feasible to study the historical evolution of the environment and its chemical constituents. Gram-scale cyclization further indicates suitability for industrial applications.

Graphical Abstract

Radical Knoevenagel-Michael cyclo condensation reactions were used to create pyranopyrazole scaffolds. The proton-coupled electron transfer method of photosynthesis was employed to catalyze the reaction utilizing the novel donor-acceptor fluorophore; 4CzIPN. A renewable energy source using blue LED in an aqueous medium is used at room temperature and in an air environment.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Scheme 1
Scheme 2
Scheme 3

Similar content being viewed by others

References

  1. Liu Q, Wang L, Yue H, Li J S, Luo Z and Wei W 2019 Recent advances of 1, 2, 3, 5-tetrakis (carbazol-9-yl)-4, 6-dicyanobenzene (4CzIPN) in photocatalytic transformations Chem. Commun. 55 5408

    Article  Google Scholar 

  2. Mohamadpour F 2022 The development of Friedländer heteroannulation through a single electron transfer and energy transfer pathway using methylene blue (MB+) Sci. Rep. 12 7253

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Mohamadpour F 2022 The development of imin-based tandem Michael-Mannich cyclocondensation through a single-electron transfer (SET)/energy transfer (EnT) pathway in the use of methylene blue (MB+) as a photo-redox catalyst RSC Adv. 12 10701

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Mohamadpour F 2021 New role for photoexcited organic dye, Na2 eosin Y via the direct hydrogen atom transfer (HAT) process in photochemical visible-light-induced synthesis of spiroacenaphthylenes and 1H-pyrazolo[1,2-b]phthalazine-5,10-diones under air atmosphere Dyes Pigm. 194 109628

    Article  CAS  Google Scholar 

  5. Mohamadpour F 2022 Visible-Light-Induced Radical Condensation Cyclization to Synthesize 3, 4-Dihydropyrimidin-2-(1H)-ones/thiones Using Photoexcited Na2 Eosin Y as a Direct Hydrogen Atom Transfer (HAT) Catalyst ACS Omega 7 8429

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Leitch J A, Smallman H R and Browne D L 2021 Solvent-Minimized Synthesis of 4CzIPN and Related Organic Fluorophores via Ball Milling J. Org. Chem. 86 14095

    Article  CAS  PubMed  Google Scholar 

  7. Prier C K, Rankic D A and MacMillan D W 2013 Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis Chem. Rev. 113 5322

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Shaw M H, Twilton J and MacMillan D W 2016 Photoredox catalysis in organic chemistry J. Org. Chem. 81 6898

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. BabiolaáAnnes S 2021 Metal-free, regioselective, visible light activation of 4CzIPN for the arylation of 2 H-indazole derivatives RSC Adv. 11 14079

    Article  Google Scholar 

  10. Speckmeier E, Fischer T G and Zeitler K A 2018 A toolbox approach to construct broadly applicable metal-free catalysts for photoredox chemistry: deliberate tuning of redox potentials and importance of halogens in donor–acceptor cyanoarenes J. Am. Chem. Soc. 140 15353

    Article  CAS  PubMed  Google Scholar 

  11. Wang Z, Liu Q, Liu R, Ji Z, Li Y, Zhao X and Wei W 2022 Visible-light-initiated 4CzIPN catalyzed multi-component tandem reactions to assemble sulfonated quinoxalin-2(1H)-ones Chin. Chem. Lett. 33 1479

    Article  CAS  Google Scholar 

  12. Mohamadpour F 2022 Catalyst-Free and Solvent-Free Visible Light Assisted Synthesis of Tetrahydrobenzo[b]Pyran Scaffolds at Room Temperature Polycycl. Aromat. Compd. 42 7607

    Article  CAS  Google Scholar 

  13. 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

    Article  CAS  PubMed  Google Scholar 

  14. Wang J L, Liu D, Zhang Z J, Shan S, Han X, Srinivasula S M, et al. 2000 Structure-based discovery of an organic compound that binds Bcl-2 protein and induces apoptosis of tumor cells Proc. Natl. Acad. Sci. U.S.A. 97 7124

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Kuo S C, Huang L 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

    Article  CAS  Google Scholar 

  16. Abdelrazek F M, Metz P, Kataeva O, Jäger 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

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

  18. Mohamadpour F 2021 A new role for photoexcited Na2 eosin Y as direct hydrogen atom transfer (HAT) photocatalyst in photochemical synthesis of dihydropyrano[2,3-c]pyrazole scaffolds promoted by visible light irradiation under air atmosphere J. Photochem. Photobiol. A: Chem. 418 113428

    Article  CAS  Google Scholar 

  19. Mohamadpour F 2020 Caffeine as a Naturally Green and Biodegradable Catalyst for Preparation of Dihydropyrano[2,3-c]pyrazoles Org. Prep. Proced. Int. 52 453

    Article  CAS  Google Scholar 

  20. 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

    Article  CAS  Google Scholar 

  21. 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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. Gujar J B, Chaudhari M A, Kawade D S and Shingare 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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  26. 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

    Article  CAS  Google Scholar 

  27. 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

    Article  CAS  Google Scholar 

  28. 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 Enzym. 92 24

    Article  CAS  Google Scholar 

  29. 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

    Article  CAS  Google Scholar 

  30. 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

    Article  CAS  Google Scholar 

  31. 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

    Article  CAS  Google Scholar 

  32. Yarie M, Zolfigol M A, Baghery S, Alonso D A, Khoshnood A, Bayat Y and Asgari 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

    Article  CAS  Google Scholar 

  33. 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

    Article  CAS  Google Scholar 

  34. 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 

  35. 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

    Article  CAS  Google Scholar 

  36. Mohamadpour F 2021 Synthesis of Pyran-Annulated Heterocyclic Systems Catalyzed by Theophylline as a Green and Bio-Based Catalyst Polycycl. Aromat. Compd. 41 160

    Article  CAS  Google Scholar 

  37. 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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  39. 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

    Article  CAS  Google Scholar 

  40. Kumar G S, Kurumurthy C, Veeraswamy B, Rao P S, Rao P S and Narsaiah B 2013 An efficient multi-component synthesis of 6-amino-3-methyl-4-aryl-2, 4-dihydropyrano [2,3-c] pyrazole-5-carbonitriles Org. Prep. Proced. Int. 45 429

    Article  CAS  Google Scholar 

  41. Mecadon H, Rohman M R, Rajbangshi M and Myrboh B 2011 γ-Alumina as a recyclable catalyst for the four-component synthesis of 6-amino-4-alkyl/aryl-3-methyl-2, 4-dihydropyrano [2, 3-c] pyrazole-5-carbonitriles in aqueous medium Tetrahedron Lett. 52 2523

    Article  CAS  Google Scholar 

  42. Mohamadpour F 2020 Catalyst-free green synthesis of dihydropyrano[2,3-c]pyrazole scaffolds assisted by ethylene glycol (EG) as a reusable and biodegradable solvent medium J. Chem. Sci. 132 72

    Article  CAS  Google Scholar 

  43. Mohamadpour F 2023 Carbazole-based photocatalyst (4CzIPN) as a novel donor-acceptor (D-A) fluorophore catalyzed gram-scale 2-amino-4H-chromene scaffolds photosynthesis via a proton-coupled electron transfer (PCET) process J. Taiwan Inst. Chem. Eng. 144 104699

    Article  CAS  Google Scholar 

Download references

Acknowledgments

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

Author information

Authors and Affiliations

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

    Farzaneh Mohamadpour

Authors
  1. Farzaneh Mohamadpour
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Farzaneh Mohamadpour.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mohamadpour, F. Carbazole-based photocatalyst (4CzIPN) as a novel donor-acceptor fluorophore-catalyzed visible-light-induced photosynthesis of dihydropyrano[2,3-c]pyrazole scaffolds via a proton-coupled electron transfer process. J Chem Sci 135, 74 (2023). https://doi.org/10.1007/s12039-023-02204-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-023-02204-y

Keywords

Search

Navigation