Skip to main content
SpringerLink
Log in

Oxidation of cyclohexanone and/or cyclohexanol catalyzed by Dawson-type polyoxometalates using hydrogen peroxide

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

The oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture using as catalyst, Dawson-type polyoxometalates (POMs) of formula, α- and β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 and hydrogen peroxide, carried out at 90 °C with a reaction time of 20 h, led to a high number of mono- and di-acids which were identified by GC-MS. Levulinic, 6-hydroxyhexanoic, adipic, glutaric and succinic acids, major products were evaluated by HPLC. Regardless of the substrate nature, all POMs exhibited high catalytic activity with 94–99% of conversion, whereas the formation of the different products is sensitively related to both the composition and symmetry of the POMs and the substrate nature. The main products are adipic acid in the presence of α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62, levulinic acid in the presence of α1-K7P2Mo5VW12O62 and β-K6P2W18O62 and 6-hydroxyhexanoic acid in the presence of α- and β-K6P2W18O62.

Graphical abstract

High catalytic activity was observed with α- and β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 Dawson-type for the oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture, in the hydrogen peroxide presence, to several oxygenated products. Adipic, levulinic and 6-hydroxyhexanoic acids are the main products. The peroxo- species formed in situ could be the active sites.

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

Similar content being viewed by others

References

  1. Venturello C, Alneri E and Ricci M 1983 A New Effective Catalytic System for Epoxidation of Olefins by Hydrogen Peroxide under Phase-Transfer Conditions J. Org. Chem. 48 3831

    Article  CAS  Google Scholar 

  2. Venturello C and Ricci M 1986 Oxidative Cleavage of 1,2-Diols to Carboxylic Acids by Hydrogen Peroxide J. Org. Chem. 51 1599

    Article  CAS  Google Scholar 

  3. Venturello C, D’Aloisio R, Bart JCJ and Ricci M 1985 A new peroxotungsten heteropoly anion with special oxidizing properties: synthesis and structure of tetrahexylammonium tetra (dipewroxotungsto) phosphate(3-) J. Mol. Catal. 32 107

    Article  CAS  Google Scholar 

  4. Ramos ML, Justino LLG and Burrows HD 2011 Structural considerations and reactivity of peroxocomplexes of V(V), Mo(VI) and W(VI) Dalton Trans. 40 4374

    Article  CAS  Google Scholar 

  5. Aubry C, Chottard G, Platzer N, Bregeault JM, Thowenot R, Chauveau F, et al. 1991 Reinvestigation of epoxidation using tungsten-based precursors and hydrogen peroxide in a biphase medium Inorg. Chem. 30 4409

    Article  CAS  Google Scholar 

  6. Bregeault J M, Thouvenot R, Zoughebi S, Salles L, Atlamani A, Duprey E, et al. 1994 Novel tungsten catalysts grafted onto polymeric materials: a comparison with phase transfer catalysis Stud. Surf. Sci. Catal. 82 571

    Article  CAS  Google Scholar 

  7. Bregeault J M, Vennat M, Salles L, Piquemal J Y, Yahdih M, Briot E, et al. 2006 From polyoxometalates to polyoxoperoxometalates and back again; potential applications Rev. J. Mol. Catal A: Chem. 250 177

    Article  CAS  Google Scholar 

  8. Ishii Y, Yamawaki K, Yoshida T, Ura T and Ogawa M 1987 Oxidation of Olefins and Alcohols by Peroxo-Molybdenum Complex Derived from Tris(cety1pyridinium) 12-Molybdophosphate and Hydrogen Peroxide J. Org. Chem. 52 1868

    Article  CAS  Google Scholar 

  9. Ishii Y and Sakata Y 1990 A Novel Oxidation of Internal Alkynes with Hydrogen Peroxide Catalyzed by Peroxotungsten Compounds J. Org. Chem 55 5545

    Article  CAS  Google Scholar 

  10. Duncan D C, Chambers R C, Hecht E and Hill C L 1995 Mechanism and Dynamics in the H3[PW12O40]-Catalyzed Selective Epoxidation of Terminal Olefins by H2O2 Formation, Reactivity, and Stability of {PO4[WO(O2)2]4}3- J. Am. Chem. Soc. I17 681

    Article  Google Scholar 

  11. Su H and Yang C 2014 Selective oxidation of benzyl alcohol catalyzed by (TEAH)nH3-n PW12O40 and its reaction mechanism Chin. J. Catal. 35 1224

    Article  CAS  Google Scholar 

  12. Kozhevnikov I V, Mulder G P, Steverink-de Zoete M C and Oostwal M G 1998 Epoxidation of oleic acid catalyzed by peroxo phosphotungstate in a two-phase system J. Mol. Catal A: Chem. 134 223

    Article  CAS  Google Scholar 

  13. Julião D, Gomes A C, Cunha-Silva L, Valença R, Ribeiro J C, Pillinger M, et al. 2020 A sustainable peroxophosphomolybdate/H2O2 system for the oxidative removal of organosulfur compounds from simulated and real high-sulfur diesels Appl. Catal. A 589 117154

    Article  Google Scholar 

  14. Mazari T, Benadji S, Tahar A, Dermeche L and Rabia C 2013 Liquid-Phase Synthesis of Adipic Acid Using Keggin-Type Phosphomolybdates Catalysts J. Mater. Sci. Eng. B 3 146

    CAS  Google Scholar 

  15. Benadji S, Mazari T, Dermeche L, Salhi N, Cadot E and Rabia C 2013 Clean Alternative for Adipic Acid Synthesis Via Liquid-Phase Oxidation of Cyclohexanone and Cyclohexanol Over H3–2xCoxPMo12O40 Catalysts with Hydrogen Peroxide Catal. Lett. 143(8) 749

    Article  CAS  Google Scholar 

  16. Tahar A, Benadji S, Mazari T, Dermeche L, Marchal-Roch C and Rabia C 2015 Preparation, characterization and reactivity of Keggin type phosphomolybdates, H3–2xNixPMo12O40 and (NH4)3–2xNixPMo12O40, for adipic acid synthesis Catal. Lett. 145 569

    Article  CAS  Google Scholar 

  17. Mouanni S, Mazari T, Amitouche D, Benadji S, Dermeche L, Catherine Roch-Marchal C and Rabia C 2018 Simple and green adipic acid synthesis from cyclohexanone and/or cyclohexanol oxidation with efficient (NH4)xHyMzPMo12O40 (M: Fe Co, Ni) Catalysts Bull. Chem. React. Eng. Catal. 13 386

    Article  CAS  Google Scholar 

  18. Mouanni S, Mazari T, Amitouche D, Benadji S, Dermeche L, Catherine Roch-Marchal C and Rabia C 2019 Preparation and characterization of H3–2(x+y)MnxCoyPMo12O40 heteropolysalts. Application to adipic acid green synthesis from cyclohexanone oxidation with hydrogen peroxide C. R. Chim. 22 327

    Article  CAS  Google Scholar 

  19. Mouanni S, Amitouche D, Mazari T and Rabia C 2019 Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production Appl. Petrochem. Res. 9 67

    Article  CAS  Google Scholar 

  20. Mouheb L, Dermeche L, Mazari T, Benadji S, Essayem N and Rabia C 2018 Clean adipic acid synthesis from liquid-phase oxidation of cyclohexanone and cyclohexanol using (NH4)xAyPMo12O40 (A: Sb, Sn, Bi) mixed heteropolysalts and hydrogen peroxide in free solvent Catal. Lett. 148 612

    Article  CAS  Google Scholar 

  21. Mouheb L, Dermeche L, Essayem N and Rabia C 2020 Keggin-type mixed polyoxomolybdates catalyzed cyclohexanone oxidation by hydrogen peroxide: in Situ IR pyridine adsorption Catal. Lett. 150 3327

    Article  CAS  Google Scholar 

  22. Moudjahed M, Dermeche L, Benadji S, Mazari T and Rabia C 2016 Dawson-type polyoxometalates as green catalysts for adipic acid synthesis J. Mol. Catal A: Chem. 414 7

    Article  Google Scholar 

  23. Guerroudj M R, Dermeche L, Mouheb L, Mazari T, Benadji S and Rabia C 2019 Preparation, characterization, and catalytic activity of tin (antimony) substituted and lacunar Dawson phosphotungstomolybdates for synthesis of adipic acid Bull. Chem. React. Eng. Catal. 14 283

    Article  CAS  Google Scholar 

  24. Nomiya K, Miwa M and Sugaya Y 1984 Catalysis by heteropolyacid-VII. Catalytic oxidation of cyclohexanol by dodecamolybdate Polyhedron. 3 607

    Article  CAS  Google Scholar 

  25. Amitouche D, Haouas M, Mazari T, Mouanni S, Canioni R, Rabia C and Marchal-Roch C 2018 The primary stages of polyoxomolybdate catalyzed cyclohexanone oxidation by hydrogen peroxide as investigated by in situ NMR Substrate activation and evolution of the working catalyst Appl. Catal A 561 104

    Article  CAS  Google Scholar 

  26. Dai J, Zhong W, Yi W, Liu M, Mao L, Xu Q and Yin D 2016 Bifunctional H2WO4/TS-1 catalysts for direct conversion of cyclohexane to adipic acid: Active sites and reaction steps Appl. Catal B: Env. 192 325

    Article  CAS  Google Scholar 

  27. Dermeche L, Salhi N, Hocine S, Thouvenot R and Rabia C 2012 Effective Dawson type polyoxometallate catalysts for methanol oxidation J. Mol. Catal A: Chem. 356 29

    Article  CAS  Google Scholar 

  28. Randall W J, Lyon D K, Domaille P J and Finke R G 1998 Inorganic Syntheses M Y Darensbourg (Ed.) (New York: Wiley) Vol. 32 p. 242

  29. Contant R, Abbessi M, Thouvenot R and Hervé G 2004 Dawson Type Heteropolyanions. 3. Syntheses and 31P, 51V, and 183W NMR Structural Investigation of Octadeca (molybdo-tungsto-vanado)diphosphates Related to the [H2P2W12O48]12- Anion Inorg. Chem. 43 3597

    Article  CAS  Google Scholar 

  30. Terent’ev A O, Platonov M M, Kashin A S and Nikishin G I 2008 Oxidation of cycloalkanones with hydrogen peroxide: an alternative route to the Baeyer-Villiger reaction. Synthesis of dicarboxylic acid esters Tetrahedron 64 7944

    Article  CAS  Google Scholar 

  31. Steffen R A, Teixeira S, Sepulveda J and Rinaldi R 2008 Alumina-catalyzed Baeyer–Villiger oxidation of cyclohexanone with hydrogen peroxide J. Mol. Catal A: Chem. 287 41

    Article  CAS  Google Scholar 

  32. Blasco T, Corma A, Fornés V and Jensen R 2002 Selective and Shape-Selective Baeyer-Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2 Chem. A Eur. J. 8 4708

    Article  Google Scholar 

Download references

Acknowledgment

Ministry of Higher Education and Scientific Research and Directorate General of Scientific Research and Technological Development for financial support.

Author information

Authors and Affiliations

  1. Laboratoire de Chimie du Gaz Naturel, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène (USTHB), BP 32, 16111, El Alia, Bab Ezzouar, Alger, Algeria

    Mohammed Moudjahed, Leila Dermeche, Yasmina Idrissou, Tassadit Mazari & Cherifa Rabia

  2. Laboratoire de Chimie Appliquée et de Génie Chimique, Hasnaoua I, Université Mouloud Mammeri, B.P.17 RP, 15000, Tizi-Ouzou, Algeria

    Leila Dermeche & Tassadit Mazari

  3. Ecole Normale Supérieure Kouba (ENS), Alger, Algeria

    Yasmina Idrissou

Authors
  1. Mohammed Moudjahed
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Leila Dermeche
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yasmina Idrissou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tassadit Mazari
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Cherifa Rabia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Leila Dermeche.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 693 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Moudjahed, M., Dermeche, L., Idrissou, Y. et al. Oxidation of cyclohexanone and/or cyclohexanol catalyzed by Dawson-type polyoxometalates using hydrogen peroxide. J Chem Sci 134, 31 (2022). https://doi.org/10.1007/s12039-022-02028-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-022-02028-2

Keywords

Search

Navigation