Prins cyclization in 4-methyl-2-phenyl-tetrahydro-2H-pyran-4-ol preparation using smectite clay as catalyst
Prins cyclization of isoprenol with benzaldehyde as a model aldehyde was performed using montmorillonite K10 as an acid catalyst. Various reaction conditions were used including catalyst modification by mineral acids and calcination. Both treatments influenced the selectivity to substituted tetrahydropyranol negatively. Due to the increased specific surface of the catalyst the reaction rate increased. Both addition of water and methanol to the reaction mixture prevented dehydration but the selectivity to desired product remained the same. Chosen reaction conditions (70 °C, ratio aldehyde:isoprenol 0.9:1, catalyst amount 110 wt%, solvent toluene) were used in Prins cyclization of other aldehydes with the similar results. Montmorillonite K10 may be used in preparation of substituted tetrahydropyranols with selectivity ranging from 59 to 69% (depending on aldehyde), which is comparable with or higher than heterogeneous catalysts used previously. This catalyst may be also used repeatedly with slight decrease in the reaction rate and no loss of selectivity.
KeywordsPrins cyclization Isoprenol Montmorillonite K10 Tetrahydropyranol
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.
- 7.Vyskočilová E, Krátká M and Červený L (2015) Prins cyclization of isovaleraldehyde and isoprenol 3rd International Conference on Chemical Technology, Česká společnost průmyslové chemie, pp 27–30Google Scholar
- 10.Akira U, Yochiharu A, Shigeyoshi T, Kazuki N and Koji M (2005) Process for producing a pyran compound. European Patent 1493737Google Scholar
- 12.Li G, Gu Y, Ding Y, Yong Z, Hanpeng W, Jianming G, Qiang Y, Liang SL (2004) Wells-Dawson type molybdovanadophosphoric heteropolyacids catalyzed Prins cyclization of alkenes with paraformaldehyde under mild conditions—a facile and efficient method to 1,3-dioxane derivatives. J Mol Catal A 218:147–152CrossRefGoogle Scholar
- 16.Telalović S, Ramanthan A, Fei Ng J, Maheswari R, Kwakernaak C, Soulimani F, Brouwer HC, Chuah GK, Weckhuzsen BM, Hanefeld U (2011) On the synergistic catalytic properties of bimetallic mesoporous materials containing aluminum and zirconium: the Prins cyclisation of citronellal. Chem Eur J 17:2077–2088CrossRefGoogle Scholar
- 23.Kaur N, Kishore D (2012) Montmorillonite: an efficient, heterogeneous and green catalyst for organic synthesis. J Chem Pharm Res 4(2):991–1015Google Scholar