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Reaction Kinetics, Mechanisms and Catalysis

, Volume 116, Issue 2, pp 299–314 | Cite as

Isomerization of verbenol oxide to a diol with para-menthane structure exhibiting anti-Parkinson activity

  • Alexandra Torozova
  • Päivi Mäki-Arvela
  • Narendra Kumar
  • Atte Aho
  • Annika Smeds
  • Markus Peurla
  • Rainer Sjöholm
  • Ivo Heinmaa
  • Konstantin P. Volcho
  • Nariman F. Salakhutdinov
  • Dmitry Yu. MurzinEmail author
Article

Abstract

Isomerization of verbenol oxide to (1R, 2R, 6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol, which exhibits anti-Parkinson activity, has been investigated with large and medium pore zeolites, namely H-USY and H-ZSM-5 types of catalysts with different SiO2 to Al2O3 ratio in dimethylacetamide as a solvent. The catalysts were characterized with nitrogen adsorption, 27Al MAS NMR, pyridine desorption, XRD, SEM and TEM techniques. The main reaction product was the target diol with the highest selectivity of 52 % achieved with H-ZSM-5-23 (the last number corresponds to SiO2/Al2O3 ratio) at 49 % conversion of verbenol oxide. The catalyst deactivation was, however, extensive with medium pore zeolites, compared to large pore zeolites. The second highest selectivities to diol with H-USY-80 and H-ZSM-5-80 were about 47–50 mol% at 100 and 78 % of conversion, respectively, achieved at 140 °C within 3 and 5 h. The other main products were the corresponding cyclopentylhydroxyketone and oxetane. A reaction mechanism was proposed.

Keywords

Isomerization Zeolite Verbenol oxide Para-menthane Oxetane Cyclopentylhydroxyketone 

Notes

Acknowledgments

The authors are grateful to Mr. Linus Silvander from Johan Gadolin Process Chemistry Centre at Åbo Akademi University for performing SEM-EDX analysis.

Supplementary material

11144_2015_903_MOESM1_ESM.pdf (514 kb)
Supplementary material 1 (pdf 514 kb)

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2015

Authors and Affiliations

  • Alexandra Torozova
    • 1
    • 2
  • Päivi Mäki-Arvela
    • 1
  • Narendra Kumar
    • 1
  • Atte Aho
    • 1
  • Annika Smeds
    • 1
  • Markus Peurla
    • 3
  • Rainer Sjöholm
    • 1
  • Ivo Heinmaa
    • 4
  • Konstantin P. Volcho
    • 5
    • 6
  • Nariman F. Salakhutdinov
    • 5
    • 6
  • Dmitry Yu. Murzin
    • 1
    Email author
  1. 1.Johan Gadolin Process Chemistry CentreÅbo Akademi UniversityTurku/ÅboFinland
  2. 2.Tver State Technical UniversityTverRussia
  3. 3.University of TurkuTurkuFinland
  4. 4.Institute of Chemical Physics and BiophysicsTallinnEstonia
  5. 5.N. N. Vorozhtsov Institute of Organic ChemistryRussian Academy of SciencesNovosibirskRussia
  6. 6.Novosibirsk State UniversityNovosibirskRussia

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