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Title: The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity

Abstract

This report describes a new a continuous method for forming ethers, acetals and ketals using solid acid catalysts, DELOXAN ASP or AMBERLYST 15, and supercritical fluid solvents. In the case of ether formation, the authors observe a high selectivity for linear alkyl ethers with little rearrangement to give branches ethers. Such rearrangement is common in conventional synthesis. The approach is effective for a range of n-alcohols up to n-octanol and also for the secondary alcohol 2-propanol. In the reaction of phenol with an alkylating agent, the continuous reaction can be tuned to give preferential O- or C-alkylation with up to 49% O-alkylation with supercritical propene. The authors also investigate the synthesis of a range of cyclic ethers and show an improved method for the synthesis of THF from 1,4-butandiol under very mild conditions.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Univ. of Nottingham (GB)
OSTI Identifier:
20013693
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 46; Other Information: PBD: 24 Nov 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; SUPERCRITICAL STATE; CARBON DIOXIDE; ALCOHOLS; DEHYDRATION; SYNTHESIS; ACETALS; ETHERS; CATALYSTS

Citation Formats

Gray, W K, Smail, F R, Hitzler, M G, Ross, S K, and Poliakoff, M. The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity. United States: N. p., 1999. Web. doi:10.1021/ja991562p.
Gray, W K, Smail, F R, Hitzler, M G, Ross, S K, & Poliakoff, M. The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity. United States. https://doi.org/10.1021/ja991562p
Gray, W K, Smail, F R, Hitzler, M G, Ross, S K, and Poliakoff, M. 1999. "The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity". United States. https://doi.org/10.1021/ja991562p.
@article{osti_20013693,
title = {The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity},
author = {Gray, W K and Smail, F R and Hitzler, M G and Ross, S K and Poliakoff, M},
abstractNote = {This report describes a new a continuous method for forming ethers, acetals and ketals using solid acid catalysts, DELOXAN ASP or AMBERLYST 15, and supercritical fluid solvents. In the case of ether formation, the authors observe a high selectivity for linear alkyl ethers with little rearrangement to give branches ethers. Such rearrangement is common in conventional synthesis. The approach is effective for a range of n-alcohols up to n-octanol and also for the secondary alcohol 2-propanol. In the reaction of phenol with an alkylating agent, the continuous reaction can be tuned to give preferential O- or C-alkylation with up to 49% O-alkylation with supercritical propene. The authors also investigate the synthesis of a range of cyclic ethers and show an improved method for the synthesis of THF from 1,4-butandiol under very mild conditions.},
doi = {10.1021/ja991562p},
url = {https://www.osti.gov/biblio/20013693}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 46,
volume = 121,
place = {United States},
year = {Wed Nov 24 00:00:00 EST 1999},
month = {Wed Nov 24 00:00:00 EST 1999}
}