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

  • Lada Sekerová
  • Hana Černá
  • Eliška Vyskočilová
  • Libor Červený
Article
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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.

Keywords

Methyltrioxorhenium Prins cyclization Benzaldehyde Isoprenol Lewis acid 

Notes

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.

Supplementary material

11144_2018_1503_MOESM1_ESM.docx (568 kb)
Supplementary material 1 (DOCX 567 kb)

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Lada Sekerová
    • 1
  • Hana Černá
    • 1
  • Eliška Vyskočilová
    • 1
  • Libor Červený
    • 1
  1. 1.Department of Organic TechnologyUniversity of Chemistry and TechnologyPragueCzech Republic

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