Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Alcoholysis of Furfuryl Alcohol to Ethyl Levulinate Catalyzed by a Deep Eutectic Solvent.

ABSTRACT: In this study, the alcoholysis of furfuryl alcohol (FA) into ethyl levulinate (EL) using a deep eutectic solvent (DES) composed of choline chloride (ChCl) and ethanol was investigated by experiments and calculations. Experimental results reveal that the addition of 5-sulfonic acid salicylic acid (5-SSA) can catalyze the alcoholysis of FA to produce EL. The combined presence of ChCl and 5-SSA significantly improved the selectivity for EL. The mechanism of the alcoholysis of FA to EL in acidic DES was investigated by density functional theory (DFT) calculations in Gaussian 03. It was found that hydrogen-bond acceptor ChCl is coupled with hydrogen-bond donor ethanol to form a structure similar to HCl and ethoxy, which facilitates the alcoholysis of FA into EL.

SUBMITTER: Hu A

PROVIDER: S-EPMC9494666 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Alcoholysis of Furfuryl Alcohol to Ethyl Levulinate Catalyzed by a Deep Eutectic Solvent.

Hu Aiyun A Wang Haijun H Ding Jian J

ACS omega 20220908 37

In this study, the alcoholysis of furfuryl alcohol (FA) into ethyl levulinate (EL) using a deep eutectic solvent (DES) composed of choline chloride (ChCl) and ethanol was investigated by experiments and calculations. Experimental results reveal that the addition of 5-sulfonic acid salicylic acid (5-SSA) can catalyze the alcoholysis of FA to produce EL. The combined presence of ChCl and 5-SSA significantly improved the selectivity for EL. The mechanism of the alcoholysis of FA to EL in acidic DES ...[more]

PMID: 36157777

Similar Datasets

Acid-Catalyzed Conversion of Furfuryl Alcohol to Ethyl Levulinate in Liquid Ethanol.

Project description:Reaction pathways for the acid-catalyzed conversion of furfuryl alcohol (FAL) to ethyl levulinate (EL) in ethanol were investigated using liquid chromatography-mass spectrometry (LC-MS), 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, and ab initio high-level quantum chemical (G4MP2) calculations. Our combined studies show that the production of EL at high yields from FAL is not accompanied by stoichiometric production of diethyl either (DEE), indicating that ethoxymethyl furan (EMF) is not an intermediate in the major reaction pathway. Several intermediates were observed using an LC-MS system, and three of these intermediates were isolated and subjected to reaction conditions. The structures of two intermediates were elucidated using 1D and 2D NMR techniques. One of these intermediates is EMF, which forms EL and DEE in a secondary reaction pathway. The second intermediate identified is 4,5,5-triethoxypentan-2-one, which is analogous to one of the intermediates observed in the conversion of FAL to LA in water (i.e. 4,5,5-trihydroxypentan-2-one). Furthermore, conversion of this intermediate to EL again involves the formation of DEE, indicating that it is also part of a secondary pathway. The primary pathway for production of EL involves solvent-assisted transfer of a water molecule from the partially detached protonated hydroxyl group of FAL to a ring carbon, followed by intra-molecular hydrogen shift, where the apparent reaction barrier for the hydrogen shift is relatively smaller in ethanol (21.1 kcal/mol) than that in water (26.6 kcal/mol).

| S-EPMC4097379 | biostudies-literature

Conversion of Furfuryl Alcohol into Ethyl Levulinate over Glucose-Derived Carbon-Based Solid Acid in Ethanol.

Project description:In this study, a carbon-based solid acid was created through the sulfonation of carbon obtained from the hydrothermal pretreatment of glucose. Additionally, ethyl levulinate, a viable liquid biofuel, was produced from furfuryl alcohol using the environmentally benign and low-cost catalyst in ethanol. Studies for optimizing the reaction conditions, such as reaction time, temperature, and catalyst loading, were performed. Under the optimal conditions, a maximum ethyl levulinate yield of 67.1% was obtained. The recovered catalyst activity (Ethyl levulinate yield 57.3%) remained high after being used four times, and it was easily regenerated with a simple sulfonation process. Moreover, the catalyst was characterized using FT-IR, XRD, SEM, elemental analysis, and acid-base titration techniques.

| S-EPMC6572322 | biostudies-literature

Efficient Catalytic Upgradation of Bio-Based Furfuryl Alcohol to Ethyl Levulinate Using Mesoporous Acidic MIL-101(Cr).

Project description:Enlarging the dispersed micropores of metal-organic frameworks to the well-ordered mesostructure can enhance the accessibility of acidic sites for reactants resulting in the improvement of selectivity. With the regulation of cetyltrimethylammonium bromide/Cr3+ and ClSO3H sulfonation, a series of mesoporous MIL-101(Cr)-SO3H (MMSs) with multiple pore sizes and acidic properties were synthesized and explored to further facilitate the furfuryl alcohol (FA) ethanolization to ethyl levulinate (EL) for the first time. The optimal catalytic activity of 83.8% EL yield at full FA conversion demonstrated that the appropriate mesopore size, acidic density, and accessible -SO3H sites contributed to the superior performance of the MMS(0.3)-0.15. The turnover frequency value (14.8 h-1) obtained with MMS(0.3)-0.15 was comparable to the commercial Nafion NR50 (18.3 h-1) and much higher than the classical Amberlyst-15 (1.9 h-1), confirming the predominant catalytic performance. Furthermore, two coexistent reaction paths with 2-ethoxymethylfuran and 4,5,5-triethoxy-pentan-2-one as intermediates indicated the possibility of producing EL from FA.

| S-EPMC6545550 | biostudies-literature

Humin Formation on SBA-15-pr-SO<sub>3</sub>H Catalysts during the Alcoholysis of Furfuryl Alcohol to Ethyl Levulinate: Effect of Pore Size on Catalyst Stability, Transport, and Adsorption.

Project description:Herein, the alcoholysis of furfuryl alcohol in a series of SBA-15-pr-SO3H catalysts with different pore sizes is reported. Elemental analysis and NMR relaxation/diffusion methods show that changes in pore size have a significant effect on catalyst activity and durability. In particular, the decrease in catalyst activity after catalyst reuse is mainly due to carbonaceous deposition, whereas leaching of sulfonic acid groups is not significant. This effect is more pronounced in the largest-pore-size catalyst C3, which rapidly deactivates after one reaction cycle, whereas catalysts with a relatively medium and small average pore size (named, respectively, C2 and C1) deactivate after two reaction cycles and to a lesser extent. CHNS elemental analysis showed that C1 and C3 experience a similar amount of carbonaceous deposition, suggesting that the increased reusability of the small-pore-size catalyst can be attributed to the presence of SO3H groups mostly present on the external surface, as corroborated by results on pore clogging obtained by NMR relaxation measurements. The increased reusability of the C2 catalyst is attributed to a lower amount of humin being formed and, at the same time, reduced pore clogging, which helps to maintain accessible the internal pore space.

| S-EPMC10214382 | biostudies-literature

Deep eutectic solvent-catalyzed arylation of benzoxazoles with aromatic aldehydes.

Project description:A novel and efficient methodology for the arylation of benzoxazoles with aromatic aldehydes catalyzed by deep eutectic solvent has been developed. The reaction smoothly proceeded with a wide range of substrates to give the desired products in high yields within short reaction time. Deep eutectic solvents are easily recovered and reused without significant loss of catalytic activity.

| S-EPMC9078944 | biostudies-literature

Modeling Alcohol Dehydrogenase Catalysis in Deep Eutectic Solvent/Water Mixtures.

Project description:The use of oxidoreductases (EC1) in non-conventional reaction media has been increasingly explored. In particular, deep eutectic solvents (DESs) have emerged as a novel class of solvents. Herein, an in-depth study of bioreduction with an alcohol dehydrogenase (ADH) in the DES glyceline is presented. The activity and stability of ADH in mixtures of glyceline/water with varying water contents were measured. Furthermore, the thermodynamic water activity and viscosity of mixtures of glyceline/water have been determined. For a better understanding of the observations, molecular dynamics simulations were performed to quantify the molecular flexibility, hydration layer, and intraprotein hydrogen bonds of ADH. The behavior of the enzyme in DESs follows the classic dependence of water activity (aW ) in non-conventional media. At low aW values (<0.2), ADH does not show any activity; at higher aW values, the activity was still lower than that in pure water due to the high viscosities of the DES. These findings could be further explained by increased enzyme flexibility with increasing water content.

| S-EPMC7154551 | biostudies-literature

Selective and Efficient Synthesis of Pine Sterol Esters Catalyzed by Deep Eutectic Solvent.

Project description:Phytosterol esters have attracted widespread academic and industrial interests due to their advantages in lowering cholesterol, as antioxidants, and in preventing or treating cancer. However, the generation of by-products limits the application of phytosterol esters in food fields. In this study, deep eutectic solvents (DESs), a series of green, nontoxic, low-cost and biodegradable solvents, were adopted as the catalyst for the synthesis of pine sterol esters. The results showed that the acidic DES which was prepared with choline chloride (ChCl) and p-toluene sulfonic acid monohydrate (PTSA) with a molar ratio of 1:3 performed best in the prescreening experiments. To further improve the efficiency of the pine sterol ester, the molar ratio of substrates, the amount of catalyst, the reaction temperature and the reaction time were optimized, and its yield was improved to 94.1%. Moreover, the by-products of the dehydration side reactions of the sterol can be efficiently inhibited. To make this strategy more universal, other fatty acids were also used as the substrate for the synthesis of pine sterol esters, and a yield of above 92.0% was obtained. In addition, the reusability of DES was also investigated in this study, and the efficiency of DES was well maintained within five recycled uses. Finally, DFT calculations suggested that the suitable H-bonds between ChCl and PTSA decreased the nucleophilic capacity and increased the steric hindrance of the latter, and further prevented the attack on βH and reduced the generation of by-products. This study developed a reliable and eco-friendly strategy for the preparation of high-quality phytosterol esters with low-dosage catalyst usage and high selectivity.

| S-EPMC9921590 | biostudies-literature

High-Strength Double-Network Conductive Hydrogels Based on Polyvinyl Alcohol and Polymerizable Deep Eutectic Solvent.

Project description:Conductive hydrogels feature the flexibility of soft materials plus conductive properties providing functionality for effectively sticking to the epidermis and detecting human activity signals. Their stable electrical conductivity also effectively avoids the problem of uneven distribution of solid conductive fillers inside traditional conductive hydrogels. However, the simultaneous integration of high mechanical strength, stretchability, and transparency through a simple and green fabrication method remains a great challenge. Herein, a polymerizable deep eutectic solvent (PDES) composed of choline chloride and acrylic acid was added to a biocompatible PVA matrix. The double-network hydrogels were then simply prepared by thermal polymerization and one freeze-thaw method. The introduction of the PDES significantly improved the tensile properties (1.1 MPa), ionic conductivity (2.1 S/m), and optical transparency (90%) of the PVA hydrogels. When the gel sensor was fixed to human skin, real-time monitoring of a variety of human activities could be implemented with accuracy and durability. Such a simple preparation method performed by combining a deep eutectic solvent with traditional hydrogels offers a new avenue to construct multifunctional conductive hydrogel sensors with excellent performance.

| S-EPMC10301373 | biostudies-literature

Selective and fast oxidation of alcohol to aldehyde using novel catalytic deep eutectic solvent surfactants.

Project description:Deep eutectic solvent (DES) has been considered as a useful catalyst and reaction medium for various organic transformations. Herein, we report the catalytic application of novel deep eutectic solvent- based surfactant (DES surfactant) for the selective and fast oxidation of alcohols to aldehydes. The readily accessible DES surfactants (FeCl3/BHDC) was prepared using inexpensive ferric chloride (FeCl3) and benzyl hexadecyl dimethyl ammonium chloride in a simple manner. The synthesized FeCl3/BHDC was characterized using various techniques, including, FTIR spectroscopy, thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), and energy- dispersive X-ray spectroscopy (EDS) to determine its structure. The catalytic activity of FeCl3/BHDC in the selective oxidation of various alcohols to corresponding aldehyde derivative was investigated. The results showed the reaction could be completed within very short reaction times ranging from 2 to 15 min, while achieving good to excellent yields. This protocol offers a facile strategy and excellent efficiency in selectively oxidizing various alcohol derivatives to their respective aldehydes and ketones, utilizing hydrogen peroxide in the presence of catalytic DES surfactant.

| S-EPMC11527706 | biostudies-literature

Synthesis of ethyl furfuryl ether <i>via</i> etherification of furfuryl alcohol with ethanol over montmorillonite K10.

Project description:Ethyl furfuryl ether (EFE), which is synthesized via etherification of furfuryl alcohol (FFalc) with ethanol over Brønsted acid catalysts, is used as an additive in gasoline to reduce its consumption and CO2 emission. In this work, we demonstrate that the performance of this synthesis route can be improved by using commercially available, low-cost, and environmentally friendly montmorillonite K10, which produces EFE in a relatively high yield of 45.3% and a FFalc conversion of 94.2% at a low reaction temperature of 393 K within 1 h. Other commercially available clay minerals showing Brønsted acidity, namely, kaolinite and halloysite, were also used in the etherification reaction under identical conditions. The catalytic performance followed the order of montmorillonite K10 > halloysite > kaolinite, which is consistent with that of the Brønsted acidities determined via acid-base titration. The spent montmorillonite K10 showed a catalytic performance comparable to that of the fresh catalyst after calcination.

| S-EPMC11318525 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data