Skip to main content
SpringerLink
Log in

Methyltrioxorhenium as a Lewis Acid in the Prins Cyclization of Benzaldehyde and Isoprenol

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

Abstract

Methyltrioxorhenium (MTO) as a Lewis acid was used in the acid catalyzed reaction of benzaldehyde and isoprenol leading to the formation of 4-methyl-2-phenyl-tetrahydro-2H-pyran-4-ol. The influence of reaction conditions on the reaction course was investigated. Under optimal reaction conditions (70 °C, a molar ratio of reactants 1:1, 1 wt% of MTO, no solvent, 100 mol% of water) the selectivity to desired product was 76%. The addition of water to the reaction mixture evoked the decrease of the reaction rate and slight increase of selectivity (without water addition the selectivity was approximately 70%). The typical composition of isomers of the desired product was cis:trans = 30:70. The mechanism of Prins cyclization using methyltrioxorhenium as the catalyst was offered. This mechanism explains the low concentration of intermediate hemiacetal in the reaction mixture using MTO as the catalyst. MTO was also heterogenized on silica, alumosilicate and alumina support. Characterization confirmed the successful attachment and homogeneous distribution of MTO on the supports, but kinetic measurement showed high leaching of MTO from pure silica and aluminosilicate support. MTO/alumina was reused with a low decrease of conversion.

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

Similar content being viewed by others

References

  1. Beattie IR, Jones PJ (1979) Inorg Chem 18:2318–2319

    Article  CAS  Google Scholar 

  2. Herrmann WA, Kratzer RM, Fischer RW (1997) Angew Chem Int Ed Engl 23:2652–2654

    Article  Google Scholar 

  3. Kühn FE, Fischer RW, Hermann WA (1999) Chem unserer Zeit 4:192–198

    Article  Google Scholar 

  4. Yin G, Busch DH (2009) Catal Lett 130:52–55

    Article  CAS  Google Scholar 

  5. Zdeňková R, Leitmannová-Vyskočilová E, Červený L (2012) Chem Listy 106:1042–1048

    Google Scholar 

  6. Zhu Z, Espenson JH (1997) J Am Chem Soc 119:3507–3512

    Article  CAS  Google Scholar 

  7. Stekrova M, Matouskova M, Vyskocilova E, Cerveny L (2015) Res Chem Intermed 41:9003–9013

    Article  CAS  Google Scholar 

  8. Wang WD, Espenson JH (1998) J Am Chem Soc 120:11335–11341

    Article  CAS  Google Scholar 

  9. Nabavizadeh SM, Rashidi M (2006) J Am Chem Soc 128:351–357

    Article  CAS  PubMed  Google Scholar 

  10. Stekrova M, Zdenkova R, Vesely M, Vyskocilova E, Cerveny L (2014) Materials 7:2650–2668

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  11. Vyskocilova E, Rezkova L, Vrbkova E, Paterova I, Cerveny L (2016) Res Chem Intermed 42:725–733

    Article  CAS  Google Scholar 

  12. Li G, Gu Y, Ding Y, Yong Z, Hanpeng W, Jianming G, Qiang Y, Liang SL (2004) J Mol Catal A 218:147–152

    Article  CAS  Google Scholar 

  13. Yadav JS, Reddy BVS, Kumar NGGKS, Aravind S (2008) Synthesis 3:395–400

    Article  CAS  Google Scholar 

  14. Yadav JS, Reddy BVS, Chaya DN, Kumar NGGK, Naresh P, Jagadeesh B (2009) Tetrahedron Lett 50:1799–1802

    Article  CAS  Google Scholar 

  15. More GP, Rane M, Bhat SV (2012) Green Chem Lett Rev 5:13–17

    Article  CAS  Google Scholar 

  16. Vyskočilová E, Krátká M, Veselý M, Vrbková E, Červený L (2016) Res Chem Intermed 42(9):6991–7003

    Article  CAS  Google Scholar 

  17. Vyskočilová E, Sekerová L, Paterová I, Krupka J, Veselý M, Červený L (2018) J Porous Mater 25:273–281

    Article  CAS  Google Scholar 

  18. Sekerová L, Vyskočilová E, Červený L (2017) React Kinet Mech Cat 121(1):83–95

    Article  CAS  Google Scholar 

  19. Vyskočilová E, Gruberová A, Shamzhy M, Vrbková E, Krupka J, Červený L (2018) React Kinet Mech Cat 124(2):711–725

    Article  CAS  Google Scholar 

  20. Damera K, Yu B, Wang B (2015) J Org Chem 80:5457–5463

    Article  CAS  PubMed  Google Scholar 

  21. Ghosh AK, Tomaine AJ, Cantwell KE (2017) Synthesis 49:4229–4246

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  22. Breugst M, Grée R, Houk KN (2013) J Org Chem 78:9892–9897

    Article  CAS  PubMed  Google Scholar 

  23. Vyskočilová E, Krátká M, Červený L (2015), 3rd International Conference on Chemical Technology, Česká společnost průmyslové chemie, 27–30

  24. Sekerová L, Vyskočilová E, Fantova JS, Paterová I, Krupka J, Červený L (2017) Res Chem Intermed 43(8):4943–4958

    Article  CAS  Google Scholar 

  25. Tadpetch K, Rychnovsky S (2008) Org Lett 10:4839–4842

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Gisdakis P, Antonczak S, Köstlmeier S, Hermann WA, Rösch N (1998) Angew Chem Int Ed 37(16):2211–2214

    Article  CAS  Google Scholar 

  27. Kuznetsov ML, Pombeiro AJL (2009) Inorg Chem 48:307–318

    Article  CAS  PubMed  Google Scholar 

  28. Herrmann WA, Kühn FE, Fischer RW, Thiel WR, Romao CC (1992) Inorg Chem 31:4431–4432

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This work was realized within the Operational Programme Prague—Competitiveness (CZ.2.16/3.1.00/24501) and “National Program of Sustainability“(NPU I LO1613) MSMT- 43760/2015. We also acknowledge the support from Specific University Research (MSMT NO 21-SVV/2018). Autors thank Eva Vrbková for performing reuse experiment and Jiří Krupka for TPD measurement.

Author information

Authors and Affiliations

  1. Department of Organic Technology, University of Chemistry and Technology, Prague, Czech Republic

    Lada Sekerová, Hana Černá, Eliška Vyskočilová & Libor Červený

Authors
  1. Lada Sekerová
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hana Černá
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Eliška Vyskočilová
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Libor Červený
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Eliška Vyskočilová.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 567 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sekerová, L., Černá, H., Vyskočilová, E. et al. Methyltrioxorhenium as a Lewis Acid in the Prins Cyclization of Benzaldehyde and Isoprenol. Reac Kinet Mech Cat 126, 869–878 (2019). https://doi.org/10.1007/s11144-018-1503-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-018-1503-0

Keywords

Search

Navigation