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Title: Formaldehyde–isobutene Prins condensation over MFI-type zeolites

Abstract

The liquid phase Prins condensation of formaldehyde with butenes on H-ZSM-5 (MFI) zeolite catalysts was investigated showing that reaction rates follow the order isobutene > 1-butene > cis-2-butene. The catalytic rates for medium-pore zeolite H-ZSM-5 were not only a larger than for H-beta, but also selective for 3-methyl-3-buten-1-ol during formaldehyde condensation with isobutene. Isoprene forms, under the optimal reaction conditions, either in a second dehydration step of the unsaturated alcohol, or in a single step over H-ZSM-5 with optimal Si/Al ratio (Si/Al = 40). Mechanistic studies revealed that sequential Prins cyclization and hetero-Diels–Alder reactions of the desired products, forming six carbon species, occur only at slow rates over H-ZSM-5. Using DFT methods it was determined that the reaction follows a two-step mechanism: protonation of formaldehyde and electrophilic attack to the alkene, and deprotonation of the resulting intermediate carbocation. For isobutene and 1-butene, the electrophilic addition is coordinated with the protonation of the formyl group, but for cis-2-butene, it is coordinated with the proton back-donation step. The rate-limiting step switches from electrophilic addition for isobutene to proton elimination for the other two C4 isomers.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemical and Biomolecular Engineering; Catalysis Center for Energy Innovation; University of Delaware; Newark; USA
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566636
DOE Contract Number:  
SC0001004
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 22; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, hydrogen and fuel cells, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Vasiliadou, Efterpi S., Li, Sha, Caratzoulas, Stavros, and Lobo, Raul F. Formaldehyde–isobutene Prins condensation over MFI-type zeolites. United States: N. p., 2018. Web. doi:10.1039/c8cy01667d.
Vasiliadou, Efterpi S., Li, Sha, Caratzoulas, Stavros, & Lobo, Raul F. Formaldehyde–isobutene Prins condensation over MFI-type zeolites. United States. doi:10.1039/c8cy01667d.
Vasiliadou, Efterpi S., Li, Sha, Caratzoulas, Stavros, and Lobo, Raul F. Mon . "Formaldehyde–isobutene Prins condensation over MFI-type zeolites". United States. doi:10.1039/c8cy01667d.
@article{osti_1566636,
title = {Formaldehyde–isobutene Prins condensation over MFI-type zeolites},
author = {Vasiliadou, Efterpi S. and Li, Sha and Caratzoulas, Stavros and Lobo, Raul F.},
abstractNote = {The liquid phase Prins condensation of formaldehyde with butenes on H-ZSM-5 (MFI) zeolite catalysts was investigated showing that reaction rates follow the order isobutene > 1-butene > cis-2-butene. The catalytic rates for medium-pore zeolite H-ZSM-5 were not only a larger than for H-beta, but also selective for 3-methyl-3-buten-1-ol during formaldehyde condensation with isobutene. Isoprene forms, under the optimal reaction conditions, either in a second dehydration step of the unsaturated alcohol, or in a single step over H-ZSM-5 with optimal Si/Al ratio (Si/Al = 40). Mechanistic studies revealed that sequential Prins cyclization and hetero-Diels–Alder reactions of the desired products, forming six carbon species, occur only at slow rates over H-ZSM-5. Using DFT methods it was determined that the reaction follows a two-step mechanism: protonation of formaldehyde and electrophilic attack to the alkene, and deprotonation of the resulting intermediate carbocation. For isobutene and 1-butene, the electrophilic addition is coordinated with the protonation of the formyl group, but for cis-2-butene, it is coordinated with the proton back-donation step. The rate-limiting step switches from electrophilic addition for isobutene to proton elimination for the other two C4 isomers.},
doi = {10.1039/c8cy01667d},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 22,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
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