Dehydrative Etherification Reactions of Glycerol with Alcohols Catalyzed by Recyclable Nanoporous Aluminosilicates: Telescoped Routes to Glyceryl Ethers

Abstract

Catalytic strategies for the efficient transformation of abundant sustainable bioderived molecules, like glycerol, into higher value more useful products is an important research goal. In this study, we demonstrate that atom efficient dehydrative etherification reactions of glycerol with 2 activated alcohols are effectively catalyzed by nanoporous aluminosilicate materials in dimethylcarbonate (DMC) to produce the corresponding 1-substituted glyceryl ethers in high yield. By carrying out the reaction in acetone, it is possible to capitalize on the ability of these materials to catalyze the corresponding acetalization reaction allowing for the development of novel, telescoped acetalization-dehydrative etherification reaction sequences to selectively produce protected solketal derivatives. These materials also catalyze the telescoped reaction of glycerol with tert-butanol (TBA) in acetone to produce the corresponding solketal mono tert-butyl ether product in high yield, providing a potential route to convert glycerol directly into a useful and sustainable fuel additive. washed with dimethyl carbonate (2  2 mL), and the combined solvents were removed under reduced pressure to afford the crude product as a colorless oil. 48 ASSOCIATED CONTENT Supplementary Information General methods, experimental procedures, catalyst characterization methods, catalyst characterization data and spectroscopic data for ether products. This material is available free of charge via the Internet at http://pubs.acs.org.

Nanoporous Aluminosilicate-Catalyzed Telescoped Acetalization-Direct Aldol Reactions of Acetals with 1,3-Dicarbonyl Compounds

“…In line with our previous studies, the nanoporous material could also be isolated from the reaction mixtures and reused either directly or after a short recalcination step without loss of catalytic activity (entry 9). 36,37…”

Synthesis of Monoalkyl Glyceryl Ethers by Ring Opening of Glycidol with Alcohols in the Presence of Lewis Acids

“…Notably, among the investigated synthetic routes to obtain high‐value chemicals (e.g., surfactant, diols, acrolein, carbonates) through glycerol conversion, the synthesis of monoalkyl glyceryl ethers (MAGEs) is an active task of research. MAGEs have found application in several fields and can be used, for example, in the formulation of inks, polymers, lubricants, and liquid detergents .…”

“…Moreover, this molecule has also served as as tarting material for the productiono ff ine specialty and bulk chemicals for various industrial sectors. [10][11][12] Notably,a mong the investigated synthetic routest oo btain high-value chemicals (e.g.,s urfactant, diols, acrolein, carbonates) [13][14][15] through glycerolconversion,the synthesis of monoalkyl glyceryl ethers( MAGEs) is an active task of research.…”

Thermodynamic equilibrium analysis on the dehydration of glycerol with monohydric alcohols to alkyl glyceryl ethers

“…Most of the researchers concentrated on the corresponding catalysts, reaction processes, and reactors, while few researchers focus on comprehensive comparisons of the reaction routes of various alcohols. [11][12][13][14][15][16][17][18][19][20] The boiling point of glycerol is 564 K, while those of methanol, ethanol, isopropanol, and tert-butanol are 337.9, 351.2, 355.6, and 357.8 K, respectively. If the reaction temperature is set to be greater than 564 K, the self-polymerization process of glycerol is likely to occur.…”

“…Taking into account the differences in the structure and physicochemical properties of raw materials and products, there are some differences in the synthesis processes of alkyl glycerol ethers. Most of the researchers concentrated on the corresponding catalysts, reaction processes, and reactors, while few researchers focus on comprehensive comparisons of the reaction routes of various alcohols 11–20 …”