Skip to main content
SpringerLink
Log in

Sulfonated litchi exocarp carbon as solid acid catalyst to produce dihydropyrimidinones via Biginelli reaction

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

The sulfonation of a partly carbonized litchi shell with concentrated H2SO4 afforded a carbon solid acid catalyst. Various physicochemical techniques, such as XRD, X-ray photoelectron spectroscopy, FT-IR spectroscopy, scanning electron microscopy (SEM), and N2 physisorption measurements were used to study the structural properties of the prepared materials. It was an amorphous carbon material composed of aromatic carbon in random orientations. The catalytic behavior of the material was examined in the di-carbonyl compounds and urea with aromatic aldehydes for 3,4-dihydropyridine-2 (1H)-ones (DHPMs) production. Sulfonic acid groups were present on the surface at a density of 0.82 mmol/g, which led to a high DHPMs conversion efficiency of 95% at SO3H-CL at 80 °C after 3.5 h. More importantly, SO3H-CL has satisfying recyclable features and could maintain an 83% yield of its initial catalytic activity in the 6th catalytic run.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 1
Fig. 7
Fig. 8
Scheme 2

Similar content being viewed by others

Data availability

Data available in article supplementary material.

References

  1. Cao M, Peng L, Xie Q, Xing K, Lu M, Ji J (2021) Sulfonated Sargassum horneri carbon as solid acid catalyst to produce biodiesel via esterification. Bioresource Technol 324:124614

    Article  CAS  Google Scholar 

  2. Zhang H, Li H, Xu CC, Yang S (2019) Heterogeneously chemo/enzyme-functionalized porous polymeric catalysts of high-performance for efficient biodiesel production. ACS Catal 9:10990–11029

    Article  CAS  Google Scholar 

  3. Tan X, Sudarsanam P, Tan J, Wang A, Zhang H, Li H, Yang S (2021) Sulfonic acid-functionalized heterogeneous catalytic materials for efficient biodiesel production: A review. J Environ Chem Eng 9:104719

    Article  CAS  Google Scholar 

  4. Zhou Z, Liu D, Zhao X (2021) Conversion of lignocellulose to biofuels and chemicals via sugar platform: an updated review on chemistry and mechanisms of acid hydrolysis of lignocellulose. Renew Sust Energ Rev 146:111169

    Article  CAS  Google Scholar 

  5. Lokman IM, Rashid U, Taufiq-Yap YH (2015) Microwave-assisted methyl ester production from palm fatty acid distillate over a heterogeneous carbon-based solid acid catalyst. Chem Eng Technol 38:1837–1844

    Article  CAS  Google Scholar 

  6. Hu S, Zeng Y, Wu D, Lou W (2021) A novel magnetic carbon-based solid acid catalyst suitable for efficient hydrolysis of cellulose. Biomass Convers Biorefin 1–9.

  7. Wang C, Yuan F, Liu L, Niu X, Zhu Y (2015) Transesterification of tributyrin and dehydration of fructose over a carbon-based solid acid prepared by carbonization and sulfonation of glucose. ChemPlusChem 80:1657

    Article  CAS  PubMed  Google Scholar 

  8. Liu Y, Fang Y, Lu X, Wei Z, Li X (2013) Hydrogenation of nitrobenzene to p-aminophenol using Pt/C catalyst and carbon-based solid acid. Chem Eng J 229:105–110

    Article  CAS  Google Scholar 

  9. Liu K, Li C, Zhang X, Hua W, Yang D, Hu J, Yue Y, Gao Z (2010) Poly(styrene sulfonic acid)-grafted carbon nanotube as a stable protonic acid catalyst. Catal Commun 12:217–221

    Article  CAS  Google Scholar 

  10. Sluban M, Cojocaru B, Parvulescu VI, Iskra J, Korošec RC, Umek P (2017) Protonated titanate nanotubes as solid acid catalyst for aldol condensation. J Catal 346:161–169

    Article  CAS  Google Scholar 

  11. Kazemi M (2020) Magnetically reusable nanocatalysts in biginelli synthesis of dihydropyrimidinones (DHPMs). Synth Commun 50:1409–1445

    Article  CAS  Google Scholar 

  12. Patil RV, Chavan JU, Dalal DS, Shinde VS, Beldar AG (2019) Biginelli reaction: Polymer supported catalytic approaches. ACS Comb Sci 21(3):105–148

    Article  CAS  PubMed  Google Scholar 

  13. Tang L, El-Din TMG, Lenaeus MJ, Zheng N, Catterall WA (2019) Structural Basis for diltiazem block of a voltage-gated Ca2+ Channel. Mol Pharmacol 96:485–492

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. Phukan A, Borah SJ, Bordoloi P, Sharma K, Borah BJ, Sarmah PP, Dutta DK (2017) An efficient and robust heterogeneous mesoporous montmorillonite clay catalyst for the Biginelli type reactions. Adv Powder Technol 28:1585–1592

    Article  CAS  Google Scholar 

  15. Bhuyan D, Saikia M, Saikia L (2018) ZnO nanoparticles embedded in SBA-15 as an efficient heterogeneous catalyst for the synthesis of dihydropyrimidinones via Biginelli condensation reaction. Micropor Mesopor Mater 256:39–48

    Article  CAS  Google Scholar 

  16. Haider J, Saeed S, Qyyum MA, Kazmi B, Ahmad R, Muhammad A, Lee M (2020) Simultaneous capture of acid gases from natural gas adopting ionic liquids: Challenges, recent developments, and prospects. Renew Sust Energ Rev 123:109771

    Article  CAS  Google Scholar 

  17. Maleki A, Hajizadeh Z, Firouzi-Haji R (2018) Eco-friendly functionalization of magnetic halloysite nanotube with SO3H for synthesis of dihydropyrimidinones. Micropor Mesopor Mater 259:46–53

    Article  CAS  Google Scholar 

  18. Bureros GMA, Tanjay AA, Cuizon DES, Go AW, Cabatingan LK, Agapay RC, Ju Y (2019) Cacao shell-derived solid acid catalyst for esterification of oleic acid with methanol. Renew Energy 138:489–501

    Article  CAS  Google Scholar 

  19. Wang Y, Fang Z, Zhang F (2019) Esterification of oleic acid to biodiesel catalyzed by a highly acidic carbonaceous catalyst. Catal Today 319:172–181

    Article  CAS  Google Scholar 

  20. Zhang J, Sato H, Noda I, Ozaki Y (2005) Conformation rearrangement and molecular dynamics of poly(3-hydroxybutyrate) during the melt-crystallization process investigated by infrared and two-dimensional infrared correlation spectroscopy. Macromolecules 38:4274–4281

    Article  CAS  Google Scholar 

  21. Hussein MF, Naga AOAE, Saied ME, AbuBaker MM, Shaban SA, Kady FYE (2021) Potato peel waste-derived carbon-based solid acid for the esterification of oleic acid to biodiesel. Environ Technol Innov 21:101355

    Article  CAS  Google Scholar 

  22. Tsyurupa MP, Blinnikova ZK, Davidovich YA, Lyubimov SE, Naumkin AV, Davankov VA (2012) On the nature of “functional groups” in non-functionalized hypercrosslinked polystyrenes. React Funct Polym 72:973–982

    Article  CAS  Google Scholar 

  23. Dutta S, Hartkopf-Fröder C, Witte K, Brocke R, Mann U (2013) Molecular characterization of fossil palynomorphs by transmission micro-FTIR spectroscopy: Implications for hydrocarbon source evaluation. Int J Coal Geol 115:13–23

    Article  CAS  Google Scholar 

  24. Qiu M, Bai C, Yan L, Shen F, Qi X (2018) Efficient mechanochemical-assisted production of glucose from cellulose in aqueous solutions by carbonaceous solid acid catalysts. ACS Sustain Chem Eng 6:13826–13833

    Article  CAS  Google Scholar 

  25. Xue W, Zhao H, Yao J, Li F, Wang Y (2016) Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst. Chin J Catal 37:769–777

    Article  CAS  Google Scholar 

  26. Araujo RO, da Silva Chaar J, Queiroz LS, da Rocha Filho GN, da Costa CEF, da Silva GC, de Souza LK (2019) Low temperature sulfonation of acai stone biomass derived carbons as acid catalysts for esterification reactions. Energy Convers Manag 196:821–830

    Article  CAS  Google Scholar 

  27. Nascimento L, Dias IM, Souza G, Mourão LC, Pereira MB, Viana JCV, Lião LM, Oliveira G, Alonso CG (2022) Sulfonated carbons from agro-industrial residues: simple and efficient catalysts for the Biginelli reaction. New J Chem 46:6091

    Article  Google Scholar 

  28. Tao L, Wang X (2021) Boosting microbial electrocatalysis via localized high electron shuttles concentration by monolithic electrode based on nanostructured nitrogen-doped carbon microtubes. J Power Sources 514:230557

    Article  CAS  Google Scholar 

  29. Li M, Zhang Q, Luo B, Chen C, Wang S, Min D (2020) Lignin-based carbon solid acid catalyst prepared for selectively converting fructose to 5-hydroxymethylfurfural. Ind Crops Prod 145:111920

    Article  CAS  Google Scholar 

  30. Zhang X, Zhang L, Yang Q (2014) Designed synthesis of sulfonated polystyrene/mesoporous silica hollow nanospheres as efficient solid acid catalysts. J Mater Chem A 2:7546

    Article  CAS  Google Scholar 

  31. Zhang B, Gao M, Tang W, Wang X, Wu C, Wang Q, Cheung SM, Chen X (2023) Esterification efficiency improvement of carbon-based solid acid catalysts induced by biomass pretreatments: Intrinsic mechanism. Energy 263:125606

    Article  CAS  Google Scholar 

  32. Zhang K, Zhang Q, Gao X, Chen X, Wang Y, Li W, Wu J (2018) Effect of absorbers’ composition on the microwave absorbing performance of hollow Fe3O4 nanoparticles decorated CNTs/graphene/C composites. J Alloys Compd 748:706–716

    Article  CAS  Google Scholar 

  33. Tang X, Niu S (2019) Preparation of carbon-based solid acid with large surface area to catalyze esterification for biodiesel production. J Ind Eng Chem 69:187–195

    Article  CAS  Google Scholar 

  34. Liu C, Shiliang W, Zhang H, Xiao R (2019) Catalytic oxidation of lignin to valuable biomass-based platform chemicals: a review. Fuel Process Technol 191:181–201

    Article  CAS  Google Scholar 

  35. Yao B, Wu W, Ding L, Dong Y (2021) Sulfonic acid and ionic liquid functionalized covalent organic framework for efficient catalysis of the biginelli reaction. J Org Chem 86:3024–3032

    Article  CAS  PubMed  Google Scholar 

  36. Shi X, Yang H, Tao M, Zhang W (2013) Sulfonic acid-functionalized polypropylene fiber: highly efficient and recyclable heterogeneous Brønsted acid catalyst. RSC Adv 3:3939

    Article  CAS  Google Scholar 

  37. Yao N, Lu M, Liu XB, Tan J, Hu YL (2018) Copper-doped mesoporous silica supported dual acidic ionic liquid as an efficient and cooperative reusability catalyst for Biginelli reaction. J Mol Liq 262:328–335

    Article  CAS  Google Scholar 

  38. Bosica G, Cachia F, Nittis RD, Mariotti N (2021) Efficient one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones via a three-component Biginelli reaction. Molecules 26:3753

    Article  PubMed  PubMed Central  Google Scholar 

  39. Patel HA, Sawant AM, Rao VJ, Patel AL, Bedekar AV (2017) Polyaniline supported FeCl3: an effective heterogeneous catalyst for Biginelli reaction. Catal Lett 147:2306–2312

    Article  CAS  Google Scholar 

  40. Fazaeli R, Tangestaninejad S, Aliyan H (2010) Heterogeneous polyoxometalates: efficient, facile and reusable catalysts for one-pot synthesis of dihydropyrimidinones. Asian J Chem 22:877–887

    CAS  Google Scholar 

  41. Khatri CK, Rekunge DS, Chaturbhuj GU (2016) Sulfated polyborate: a new and eco-friendly catalyst for one-pot multi-component synthesis of 3, 4-dihydropyrimidin-2 (1 H)-ones/thiones via Biginelli reaction. New J Chem 40(12):10412–10417

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Fundamental Research Funds for the Central Universities (Grant No. 31920230150), the National Natural Science Foundation of China (Grant No. 21962017), Gansu Key research and development plan—industrial project (Grant No. 22YF7GA170, 20YF8GA044, 20YF8FA045), the Natural Science Foundation of Gansu Province (22JR5RA215), Postgraduate research innovation team Project of the Northwest Minzu University (Grant No. Yxm2021004), Chemistry innovation team of the Northwest Minzu University (Grant No. 1110130139, 1110130141). We also thank the Key Laboratory for Utility of Environmental-Friendly Composite Materials and Biomass at the University of Gansu Province (Northwest Minzu University), for financial support.

Author information

Author notes

  1. Qiang Hu and Shang Wu have contributed equally to this work and also considered as co-first authors.

Authors and Affiliations

  1. Key Laboratory for Utility of Environmental Friendly Composite Materials and Biomass in the University of Gansu Province, Key Laboratory of Environment Friendly Composites of the State Ethnic Affairs Commission, Gansu Provincial Biomass Function Composites Engineering Research Center, College of Chemical Engineering,, Northwest Minzu University, Lanzhou, 730030, China

    Qiang Hu, Shang Wu, Penghui Zhang, Shuaishuai Fu, Jiajia Wang, Chaoyang Liu, Hong Zhang & Yuzhi Sun

  2. College of Chemical Engineering, Lanzhou University of Arts and Science, Beimiantan 400, Lanzhou, 730000, Gansu, China

    Quanlu Yang

Authors
  1. Qiang Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Penghui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shuaishuai Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jiajia Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chaoyang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yuzhi Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Quanlu Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shang Wu.

Ethics declarations

Conflict of interest

There are no conflicts of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 1877 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hu, Q., Wu, S., Zhang, P. et al. Sulfonated litchi exocarp carbon as solid acid catalyst to produce dihydropyrimidinones via Biginelli reaction. Reac Kinet Mech Cat 136, 2587–2600 (2023). https://doi.org/10.1007/s11144-023-02470-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-023-02470-4

Keywords

Search

Navigation