Synthesis of Florol via Prins cyclization over heterogeneous catalysts

Basile Lasne; Päivi Mäki-Arvela; Atte Aho; Zuzana Vajglova; Kari Eränen; Narendra Kumar; Julián E. Sánchez-Velandia; Markus Peurla; Cecilia Mondelli; Javier Pérez-Ramírez; Dmitry Yu Murzin

doi:10.1016/j.jcat.2021.12.008

Synthesis of Florol via Prins cyclization over heterogeneous catalysts

Basile Lasne
, Päivi Mäki-Arvela
, Atte Aho
, Zuzana Vajglova
, Kari Eränen
, Narendra Kumar
, Julián E. Sánchez-Velandia
, Markus Peurla
, Cecilia Mondelli
, Javier Pérez-Ramírez
, Dmitry Yu Murzin^*

^*Corresponding author for this work

Laboratory of Industrial Chemistry and Reaction Engineering

Research output: Contribution to journal › Article › Scientific › peer-review

10 Citations (Scopus)

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Abstract

In this work, several heterogeneous micro- and mesoporous, acidic catalysts were tested for the selective synthesis of Florol®, an industrial product formed via condensation and rehydration starting from isoprenol and isovaleraldehyde in dimethylcarbonate as a solvent. The results showed that a mildly acidic, microporous H-Beta-300 with SiO₂/Al₂O₃ ratio of 300 was the best catalyst, giving 72% selectivity with 99% conversion at 40 °C when using the molar ratio isoprenol to isovaleraldehyde of 1:5. More acidic zeolites gave slightly lower selectivity, while the lowest selectivity (up to 52%) was obtained with mesoporous catalysts exhibiting mild acidity and no strong Brønsted acid sites. Selectivity to pyranols was nearly constant when changing temperature, while a larger excess of isovaleraldehyde promoted formation of tetrahydropyranol. H-Beta-300 catalyst was successfully after calcination at 400 °C. DFT calculations pointed out on the parallel formation of tetrahydro pyranols and dihydropyrans, which are the corresponding dehydration products.

Original language	English
Pages (from-to)	288-302
Number of pages	15
Journal	Journal of Catalysis
Volume	405
Early online date	Dec 2021
DOIs	https://doi.org/10.1016/j.jcat.2021.12.008
Publication status	Published - Jan 2022
MoE publication type	A1 Journal article-refereed

Funding

Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the “Apoyo a Estancias Postdoctorales” (2020-2021) program. Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the ?Apoyo a Estancias Postdoctorales? (2020-2021) program.

Keywords

DFT
Florol
Isoprenol
Isovaleraldehyde
Mesoporous materials
Prins cyclization
Zeolites

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10.1016/j.jcat.2021.12.008Licence: CC BY

Synthesis of Florol via Prins cyclization over heterogeneous catalystsFinal published version, 2.16 MBLicence: CC BY

https://urn.fi/URN:NBN:fi-fe2023030329317

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@article{c5cb5ef2038c4a559dc2413916163f51,

title = "Synthesis of Florol via Prins cyclization over heterogeneous catalysts",

abstract = "In this work, several heterogeneous micro- and mesoporous, acidic catalysts were tested for the selective synthesis of Florol{\textregistered}, an industrial product formed via condensation and rehydration starting from isoprenol and isovaleraldehyde in dimethylcarbonate as a solvent. The results showed that a mildly acidic, microporous H-Beta-300 with SiO2/Al2O3 ratio of 300 was the best catalyst, giving 72\% selectivity with 99\% conversion at 40 °C when using the molar ratio isoprenol to isovaleraldehyde of 1:5. More acidic zeolites gave slightly lower selectivity, while the lowest selectivity (up to 52\%) was obtained with mesoporous catalysts exhibiting mild acidity and no strong Br{\o}nsted acid sites. Selectivity to pyranols was nearly constant when changing temperature, while a larger excess of isovaleraldehyde promoted formation of tetrahydropyranol. H-Beta-300 catalyst was successfully after calcination at 400 °C. DFT calculations pointed out on the parallel formation of tetrahydro pyranols and dihydropyrans, which are the corresponding dehydration products.",

keywords = "DFT, Florol, Isoprenol, Isovaleraldehyde, Mesoporous materials, Prins cyclization, Zeolites",

author = "Basile Lasne and P{\"a}ivi M{\"a}ki-Arvela and Atte Aho and Zuzana Vajglova and Kari Er{\"a}nen and Narendra Kumar and S{\'a}nchez-Velandia, \{Juli{\'a}n E.\} and Markus Peurla and Cecilia Mondelli and Javier P{\'e}rez-Ram{\'i}rez and Murzin, \{Dmitry Yu\}",

note = "Funding Information: Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the “Apoyo a Estancias Postdoctorales” (2020-2021) program. Funding Information: Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the ?Apoyo a Estancias Postdoctorales? (2020-2021) program. Publisher Copyright: {\textcopyright} 2021 Elsevier Inc.",

year = "2022",

month = jan,

doi = "10.1016/j.jcat.2021.12.008",

language = "English",

volume = "405",

pages = "288--302",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Elsevier",

}

TY - JOUR

T1 - Synthesis of Florol via Prins cyclization over heterogeneous catalysts

AU - Lasne, Basile

AU - Mäki-Arvela, Päivi

AU - Aho, Atte

AU - Vajglova, Zuzana

AU - Eränen, Kari

AU - Kumar, Narendra

AU - Sánchez-Velandia, Julián E.

AU - Peurla, Markus

AU - Mondelli, Cecilia

AU - Pérez-Ramírez, Javier

AU - Murzin, Dmitry Yu

N1 - Funding Information: Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the “Apoyo a Estancias Postdoctorales” (2020-2021) program. Funding Information: Electron microscopy samples were processed and analyzed in the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland. J.E. S-V is grateful Pontificia Universidad Javeriana for the ?Apoyo a Estancias Postdoctorales? (2020-2021) program. Publisher Copyright: © 2021 Elsevier Inc.

PY - 2022/1

Y1 - 2022/1

N2 - In this work, several heterogeneous micro- and mesoporous, acidic catalysts were tested for the selective synthesis of Florol®, an industrial product formed via condensation and rehydration starting from isoprenol and isovaleraldehyde in dimethylcarbonate as a solvent. The results showed that a mildly acidic, microporous H-Beta-300 with SiO2/Al2O3 ratio of 300 was the best catalyst, giving 72% selectivity with 99% conversion at 40 °C when using the molar ratio isoprenol to isovaleraldehyde of 1:5. More acidic zeolites gave slightly lower selectivity, while the lowest selectivity (up to 52%) was obtained with mesoporous catalysts exhibiting mild acidity and no strong Brønsted acid sites. Selectivity to pyranols was nearly constant when changing temperature, while a larger excess of isovaleraldehyde promoted formation of tetrahydropyranol. H-Beta-300 catalyst was successfully after calcination at 400 °C. DFT calculations pointed out on the parallel formation of tetrahydro pyranols and dihydropyrans, which are the corresponding dehydration products.

AB - In this work, several heterogeneous micro- and mesoporous, acidic catalysts were tested for the selective synthesis of Florol®, an industrial product formed via condensation and rehydration starting from isoprenol and isovaleraldehyde in dimethylcarbonate as a solvent. The results showed that a mildly acidic, microporous H-Beta-300 with SiO2/Al2O3 ratio of 300 was the best catalyst, giving 72% selectivity with 99% conversion at 40 °C when using the molar ratio isoprenol to isovaleraldehyde of 1:5. More acidic zeolites gave slightly lower selectivity, while the lowest selectivity (up to 52%) was obtained with mesoporous catalysts exhibiting mild acidity and no strong Brønsted acid sites. Selectivity to pyranols was nearly constant when changing temperature, while a larger excess of isovaleraldehyde promoted formation of tetrahydropyranol. H-Beta-300 catalyst was successfully after calcination at 400 °C. DFT calculations pointed out on the parallel formation of tetrahydro pyranols and dihydropyrans, which are the corresponding dehydration products.

KW - DFT

KW - Florol

KW - Isoprenol

KW - Isovaleraldehyde

KW - Mesoporous materials

KW - Prins cyclization

KW - Zeolites

UR - http://dx.doi.org/10.1016/j.jcat.2021.12.008

U2 - 10.1016/j.jcat.2021.12.008

DO - 10.1016/j.jcat.2021.12.008

M3 - Article

AN - SCOPUS:85121906463

SN - 0021-9517

VL - 405

SP - 288

EP - 302

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Synthesis of Florol via Prins cyclization over heterogeneous catalysts

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Keywords

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