Isomerization of verbenol oxide to a diol with para-menthane structure exhibiting anti-Parkinson activity
- 143 Downloads
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.
KeywordsIsomerization Zeolite Verbenol oxide Para-menthane Oxetane Cyclopentylhydroxyketone
The authors are grateful to Mr. Linus Silvander from Johan Gadolin Process Chemistry Centre at Åbo Akademi University for performing SEM-EDX analysis.
- 1.Ardashov OV, Pavlova AV, Il’ina IV, Morozova EA, Korchagina DV, Karpova EV, Volcho KP, Tolstikova TG, Salakhutdinov NF (2011) Highly potent activity of (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol in animal models of Parkinson’s disease. J Med Chem 54(11): 3866–3874CrossRefGoogle Scholar
- 3.Gainer I, Zorca M (2005) New highly active anticonvulsant agent - (4s, 5r, 6r) -p-Mentha-1,8-dien-5,6-diol. Analele Universitatii din Bucaresti-Chimie, Anul XIV, vol I-II: 287-290Google Scholar
- 5.Zvereva TI, Kykovinets OS, Kasradze VG, Abdullin MI, Galin FZ (2006) Catalytic oxidation of α-pinene in the presence of Co II and Cu II polyphtalocyanines. Bashk Chem J 13:58–59Google Scholar
- 6.Frolova LL, Kuchin AV, Dreval’ IV, Panteleeva MV, Alekseev IN, (2005) Verbenone preparation method. Patent RU2003121762Google Scholar
- 10.Baerlocher Ch, Meler WM, Olson DH (2001) Atlas of Zeolite Framework types, 5th edn. Elsevier, LondonGoogle Scholar
- 12.Chen NY, Degnan TF Jr, Smith CM (1994) Molecular transport and reaction in zeolites: design and application of shape selective catalysis. Wiley, New Yoek, p. 41Google Scholar
- 14.MAUD program (2015) http://www.ing.unitn.it/. Accessed 13 May 2015
- 15.IZA (2015) http://www.iza-online.org/. Accessed 13 May 2015
- 17.Faten Diaz S, (2012) Isomerization of pinene epoxides to fine chemicals over metal modified zeolites, Master of Science Thesis, Åbo Akademi University, TurkuGoogle Scholar
- 20.Torozova A, Mäki-Arvela P, Aho A, Kumara N, Smeds A, Peurla M, Sjöholm R, Heinmaa I, Korchagina DV, Volcho KP, Salakhutdinov NF, Murzin DYu (2015) Heterogeneous catalysis for transformation of biomass derived compounds beyond fuels: Synthesis of monoterpenoid dioxinols with analgesic activity. J Mol Cat 397:48–55CrossRefGoogle Scholar