Skip to main content
SpringerLink
Log in

Efficient mild oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2(5H)-furanone, a versatile chemical intermediate

  • Published:
Research on Chemical Intermediates Aims and scope Submit manuscript

Abstract

The 5-hydroxymethyl-2(5H)-furanone is a versatile chemical intermediate used to produce a variety of products such as unsaturated (+) muscarine, microbial metabolites, (+) trans-burseran, (−) isostegane, (+) steganacin, (−) verrucarinolactone and certain analogues of prostacyclin and chrysanthemic acid. In this study, we have successfully tested a sodium perborate (NaBO3·4H2O) known by its acronym, SPB, in the oxidation of 5-hydroxymethylfurfural (5-HMF) using acetic acid (AcOH) as solvent. SPB has been proven to be an efficient reagent for the oxidation of 5-HMF into 5-hydroxymethyl-2(5H)-furanone in one step. A reaction mechanism has been proposed for this purpose. In this work, a variety of important reaction parameters, such as SPB amount, reaction temperature, and time were explored. The maximum yield to 5-hydroxymethyl-2(5H)-furanone was achieved in 94 % at room temperature in 24 h, with 5-HMF conversion of 100 % being obtained in SPB/5-HMF mol ratio = 1.5 under optimal reaction conditions. Then, it could be obtained in a high yield of 87 % at 50 °C after a short reaction time of 4 h. At high temperature (100 °C), 5-hydroxymethyl-2(5H)-furanone yield decreased dramatically.

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

Scheme 1
Scheme 2
Fig. 1

Similar content being viewed by others

References

  1. J.J. Bozell, G.R. Petersen, Green Chem. 12, 539 (2010)

    Article  CAS  Google Scholar 

  2. J.C. Serrano, R. Luque, Chem. Soc. Rev. 40, 5266 (2011)

    Article  Google Scholar 

  3. A. Corma, S. Iborra, A. Velty, Chem. Rev. 107, 2411 (2007)

    Article  CAS  Google Scholar 

  4. A.M. Balu, V. Budarin, P.S. Shuttleworth, L.A. Pfaltzgraff, K. Waldron, R. Luque, J.H. Clark, ChemSusChem 5, 1694 (2012)

    Article  CAS  Google Scholar 

  5. A. Szabolcs, M. Molnar, G. Dibo, L.T. Mika, Green Chem. 15, 439 (2013)

    Article  CAS  Google Scholar 

  6. J. Ahrenfeldt, H. Egsgaard, W. Stelte, T. Thomsen, U.B. Henriksen, Fuel 112, 662 (2013)

    Article  CAS  Google Scholar 

  7. B. Liu, Z.H. Zhang, RSC Adv. 3, 12313 (2013)

    Article  CAS  Google Scholar 

  8. H. Zohrer, F. Vogel, Biomass Bioenergy 53, 138 (2013)

    Article  CAS  Google Scholar 

  9. A.I. Torres, P. Daoutidis, M. Tsapatsis, Energy Environ. Sci. 3, 1560e72 (2010)

    Article  Google Scholar 

  10. Z.H. Zhang, Z.K. Zhao, Bioresour. Technol. 101, 1111 (2010)

    Article  CAS  Google Scholar 

  11. A.A. Rosatella, S.P. Simeonov, R.F.M. Frade, C.A.M. Afonso, Green Chem. 13, 754 (2011)

    Article  CAS  Google Scholar 

  12. L. Hu, Y. Sun, L. Lin, S.J. Liu, Biomass Bioenergy 47, 289 (2012)

    Article  CAS  Google Scholar 

  13. R.J. Van Putten, J.C. Van der Waal, E. De Jong, C.B. Rasrendra, H.J. Heeres, J.G. De Vries, Chem. Rev. 113, 1499 (2013)

    Article  Google Scholar 

  14. C. Carlini, P. Patrono, A.M.R. Galletti, G. Sbrana, V. Zima, Appl. Catal. A 289, 197 (2005)

    Article  CAS  Google Scholar 

  15. O.C. Navarro, A.C. Canos, S.I. Chornet, Top. Catal. 52, 304 (2009)

    Article  CAS  Google Scholar 

  16. G.A. Halliday, R.J. Young, V.V. Grushin, Org. Lett. 5, 2003 (2003)

    Article  CAS  Google Scholar 

  17. C. Moreau, M.N. Belgacem, A. Gandini, Top. Catal. 27, 11 (2004)

    Article  CAS  Google Scholar 

  18. S.E. Davis, L.R. Houk, E.C. Tamargo, A.K. Datye, R.J. Davis, Catal. Today 160, 55 (2011)

    Article  CAS  Google Scholar 

  19. A. Gandini, A.J.D. Silvestre, C.P. Neto, A.F. Sousa, M. Gomes, J. Polym. Sci., Part A: Polym. Chem. 47, 295 (2008)

    Article  Google Scholar 

  20. Z. Zhang, K. Deng, ACS Catal. 5, 6529 (2015)

    Article  CAS  Google Scholar 

  21. M.J. Climent, A. Corma, S. Iborra, Green Chem. 13, 520 (2011)

    Article  CAS  Google Scholar 

  22. R. Lopes de Souza, H. Yu, F. Rataboul, N. Essayem, Challenges 3, 212 (2012)

    Article  Google Scholar 

  23. P. Verdeguer, N. Merat, A. Gaset, J. Mol. Catal. 85, 327 (1993)

    Article  CAS  Google Scholar 

  24. P. Vinke, H.E. Van Dam, H. Van Bekkum, in New Developments in Selective Oxidation, ed. by G. Centi, F. Trifiro (Spinger, New York, 1990), p. 147

  25. Y.Y. Gorbanev, S.K. Klitgaard, J.M. Woodley, C.H. Christensen, A. Riisager, ChemSusChem 2, 672 (2009)

    Article  CAS  Google Scholar 

  26. O. Casanova, S. Iborra, A. Corma, ChemSusChem 12, 1138 (2009)

    Article  Google Scholar 

  27. M.A. Lilga, R.T. Hallen, M. Gray, Top. Catal. 53, 1264 (2010)

    Article  CAS  Google Scholar 

  28. B. Saha, S. Dutta, M.M. Abu-Omar, Catal. Sci. Technol. 2, 79 (2012)

    Article  CAS  Google Scholar 

  29. W. Partenheimer, V.V. Grushin, Adv. Synth. Catal. 343, 102 (2001)

    Article  CAS  Google Scholar 

  30. A.A. Churchil, J. Jaewon, K. Bora, S. Seunghan, K. Sangyong, L. Kwan-Young, Ch. Jin, Ku. Ind. Eng. Chem. 19, 1056 (2013)

    Article  Google Scholar 

  31. N.-T. Le, P. Lakshmanan, K. Cho, Y. Han, H. Kim, Appl. Catal. A: Gen. 464–465, 305 (2013)

    Article  Google Scholar 

  32. I. Sádaba, Y.Y. Gorbanev, S. Kegnæs, S.S.R. Putluru, R.W. Berg, A. Riisager, ChemCatChem 5, 284 (2013)

    Article  Google Scholar 

  33. Z. Du, J. Ma, F. Wang, J. Liu, J. Xu, Green Chem. 13, 554 (2011)

    Article  CAS  Google Scholar 

  34. J. Lan, J. Lin, Z. Chen, G. Yin, ACS Catal. 5, 2035 (2015)

    Article  CAS  Google Scholar 

  35. A. McKillop, W.R. Sanderson, Tetrahedron 51, 6145 (1995)

    Article  CAS  Google Scholar 

  36. M. Pischetsrieder, Th Severin, J. Agric. Food Chem. 42, 890 (1994)

    Article  CAS  Google Scholar 

  37. K. Tomioka, T. Ishiguro, K. Koga, J. Chem. Soc., Chem. Commun. 652 (1979)

  38. K. Tomioka, T. Ishiguro, K. Koga, Tetrahedron Lett. 2l, 2973 (1980)

    Article  Google Scholar 

  39. K. Tomioka, F. Sate, K. Koga, Heterocvcles 17, 311 (1982)

    Article  CAS  Google Scholar 

  40. J. Mann, A. Thomas, J. Chem. Soc., Chem. Commun. 737 (1985)

  41. K.H. Kang, M.Y. Cha, A.N. Pae, K. Choi, Y.S. Cho, H.Y. Koh, B.Y. Chung, Tetrahedron Lett. 41, 8137 (2000)

    Article  CAS  Google Scholar 

  42. R. Alibésa, J. Fonta, A. Muláa, R.M. Ortuñoa, Synth. Commun. 20, 2607 (1990)

    Article  Google Scholar 

  43. L. Cottier, G. Descotes, L. Eymard, K. Rapp, Synthesis 3, 303 (1995)

    Article  Google Scholar 

  44. J. Mann, N.K. Partlett, A. Thomas, J. Chem. Res. 137, 369 (1987)

    Google Scholar 

  45. J. Cardellach, C. Estopà, J. Font, M. Moreno-Mafias, R.M. Ortufio, F. Sbnchez-Ferrando, S. Valle, L. Vilamajó, Tetrahedron 38, 2377 (1982)

    Article  CAS  Google Scholar 

  46. P. Camps, J. Cardellach, J. Font, R.M. Ortuño, O. Ponsati, Tetrahedron 38, 2395 (1982)

    Article  CAS  Google Scholar 

  47. A. McKillop, W.R. Sanderson, J. Chem. Soc. Perkin Trans. 1(1), 471 (2000)

    Article  Google Scholar 

  48. J. Muzart, Synthesis 11, 1325 (1995)

    Article  Google Scholar 

  49. S.J. Dee, A.T. Bell, ChemSusChem 4, 1166 (2011)

    Article  CAS  Google Scholar 

  50. G. Piancatelli, A. Scettri, S. Barbadoro, Tetrahedron Lett. 17, 3555 (1976)

    Article  Google Scholar 

  51. R. Wojcieszak, F. Santarelli, S. Paul, F. Dumeignil, F. Cavani, R.V. Gonçalves, Sustain. Chem. Process. 3, 9 (2015)

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Laboratory of Natural Substances, Faculty of Sciences, University of Sfax, Route de Soukra Km 3,5, 3038, Sfax, Tunisia

    Khaled Mliki & Mahmoud Trabelsi

Authors
  1. Khaled Mliki
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mahmoud Trabelsi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mahmoud Trabelsi.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mliki, K., Trabelsi, M. Efficient mild oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2(5H)-furanone, a versatile chemical intermediate. Res Chem Intermed 42, 8253–8260 (2016). https://doi.org/10.1007/s11164-016-2593-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11164-016-2593-9

Keywords

Search

Navigation