Florol synthesis via Prins cyclization over hierarchical beta zeolites

Nataliya Shcherban; Roman Barakov; Basile Lasne; Päivi Mäki-Arvela; Mariya Shamzhy; Igor Bezverkhyy; Johan Wärnå; Dmitry Yu Murzin

doi:10.1016/j.mcat.2022.112683

Florol synthesis via Prins cyclization over hierarchical beta zeolites

Nataliya Shcherban^*
, Roman Barakov
, Basile Lasne
, Päivi Mäki-Arvela
, Mariya Shamzhy
, Igor Bezverkhyy
, Johan Wärnå
, Dmitry Yu Murzin

^*Corresponding author for this work

Laboratory of Industrial Chemistry and Reaction Engineering

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

9 Citations (Scopus)

110 Downloads (Pure)

Abstract

A set of hierarchical beta zeolites with variable Si/Al ratios, nanoparticle sizes, textural and acidic properties was prepared using a hydrothermal treatment of a concentrated alkali metal-free protic acid-containing zeolite gel-precursor. The obtained catalysts were investigated in the Prins cyclization of isovaleraldehyde with isoprenol yielding a commercially valuable tetrahydropyranol (Florol). The highest yield of the desired product (55.4%) was achieved over a zeolite catalyst possessing moderate acidity, developed mesoporosity (V_meso 0.60 cm³/g) and a high external surface area (290 m²/g). Preferable formation of substituted tetrahydropyranol over weak- and medium-strength Brønsted acid sites, on the one hand, and generation of the undesired dehydration products mainly over strong Brønsted acid sites, on the other hand, occurring in parallel routes were supported by the kinetic analysis of the reaction network.

Original language	English
Article number	112683
Number of pages	13
Journal	Molecular Catalysis
Volume	531
DOIs	https://doi.org/10.1016/j.mcat.2022.112683
Publication status	Published - Oct 2022
MoE publication type	A1 Journal article-refereed

Funding

The authors are grateful to Prof. Jiří Čejka and CSc. Maksym Opanasenko (Charles University, Prague) for discussing the results. N.S. and R.B. acknowledge the support of the National Research Foundation of Ukraine to the project “New effective zeolite catalysts for environmentally friendly processes of the conversion of renewable raw materials into valuable organic compounds” (project number 2020.02/0335 ). M.S. acknowledges the Czech Science Foundation for supporting this work through project 20-12099S . The authors express their gratitude to Prof. Roman Bulánek (University of Pardubice) for collecting ICP-OES analysis data and Ph.D. Martin Kubů (Charles University, Prague) for nitrogen adsorption measurements.

Keywords

Florol, Acid sites
Hierarchical zeolite
Prins cyclisation
Tetrahydropyranol

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10.1016/j.mcat.2022.112683

1-s2.0-S2468823122005697-mainFinal published version, 2.14 MBLicence: CC BY

https://urn.fi/URN:NBN:fi-fe2022112266391

Cite this

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title = "Florol synthesis via Prins cyclization over hierarchical beta zeolites",

abstract = "A set of hierarchical beta zeolites with variable Si/Al ratios, nanoparticle sizes, textural and acidic properties was prepared using a hydrothermal treatment of a concentrated alkali metal-free protic acid-containing zeolite gel-precursor. The obtained catalysts were investigated in the Prins cyclization of isovaleraldehyde with isoprenol yielding a commercially valuable tetrahydropyranol (Florol). The highest yield of the desired product (55.4\%) was achieved over a zeolite catalyst possessing moderate acidity, developed mesoporosity (Vmeso 0.60 cm3/g) and a high external surface area (290 m2/g). Preferable formation of substituted tetrahydropyranol over weak- and medium-strength Br{\o}nsted acid sites, on the one hand, and generation of the undesired dehydration products mainly over strong Br{\o}nsted acid sites, on the other hand, occurring in parallel routes were supported by the kinetic analysis of the reaction network.",

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author = "Nataliya Shcherban and Roman Barakov and Basile Lasne and P{\"a}ivi M{\"a}ki-Arvela and Mariya Shamzhy and Igor Bezverkhyy and Johan W{\"a}rn{\aa} and Murzin, \{Dmitry Yu\}",

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doi = "10.1016/j.mcat.2022.112683",

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T1 - Florol synthesis via Prins cyclization over hierarchical beta zeolites

AU - Shcherban, Nataliya

AU - Barakov, Roman

AU - Lasne, Basile

AU - Mäki-Arvela, Päivi

AU - Shamzhy, Mariya

AU - Bezverkhyy, Igor

AU - Wärnå, Johan

AU - Murzin, Dmitry Yu

PY - 2022/10

Y1 - 2022/10

N2 - A set of hierarchical beta zeolites with variable Si/Al ratios, nanoparticle sizes, textural and acidic properties was prepared using a hydrothermal treatment of a concentrated alkali metal-free protic acid-containing zeolite gel-precursor. The obtained catalysts were investigated in the Prins cyclization of isovaleraldehyde with isoprenol yielding a commercially valuable tetrahydropyranol (Florol). The highest yield of the desired product (55.4%) was achieved over a zeolite catalyst possessing moderate acidity, developed mesoporosity (Vmeso 0.60 cm3/g) and a high external surface area (290 m2/g). Preferable formation of substituted tetrahydropyranol over weak- and medium-strength Brønsted acid sites, on the one hand, and generation of the undesired dehydration products mainly over strong Brønsted acid sites, on the other hand, occurring in parallel routes were supported by the kinetic analysis of the reaction network.

AB - A set of hierarchical beta zeolites with variable Si/Al ratios, nanoparticle sizes, textural and acidic properties was prepared using a hydrothermal treatment of a concentrated alkali metal-free protic acid-containing zeolite gel-precursor. The obtained catalysts were investigated in the Prins cyclization of isovaleraldehyde with isoprenol yielding a commercially valuable tetrahydropyranol (Florol). The highest yield of the desired product (55.4%) was achieved over a zeolite catalyst possessing moderate acidity, developed mesoporosity (Vmeso 0.60 cm3/g) and a high external surface area (290 m2/g). Preferable formation of substituted tetrahydropyranol over weak- and medium-strength Brønsted acid sites, on the one hand, and generation of the undesired dehydration products mainly over strong Brønsted acid sites, on the other hand, occurring in parallel routes were supported by the kinetic analysis of the reaction network.

KW - Florol, Acid sites

KW - Hierarchical zeolite

KW - Prins cyclisation

KW - Tetrahydropyranol

UR - https://www.scopus.com/pages/publications/85138173489

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DO - 10.1016/j.mcat.2022.112683

M3 - Article

AN - SCOPUS:85138173489

SN - 2468-8231

VL - 531

JO - Molecular Catalysis

JF - Molecular Catalysis

M1 - 112683

ER -

Florol synthesis via Prins cyclization over hierarchical beta zeolites

Abstract

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Keywords

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