Furan Diol Research Articles

A Preliminary Study of Thermosets from Epoxy Resins Made Using Low-Toxicity Furan-Based Diols.

Glycidyl ethers are prepared from a series of furan-based diols and cured with a diamine to form thermosets. The furan diols demonstrate lower toxicity than bisphenol-A in a prior study. The diglycidyl ethers show improved thermal stability compared to the parent diols. Cured thermosets are prepared at elevated temperature using isophorone diamine (IPDA). Glass transition temperatures are in the range of 30-54 °C and depend on the structure of the furan diol. Coatings are prepared on steel substrates and show very high hardness, good adhesion, and a range of flexibility. Properties compare favorably with a control based on a bisphenol-A epoxy resin. The study demonstrates that epoxy resins based on furan diols, which have been shown to have lower toxicity than bisphenol-A, can form thermosets having properties comparable to a standard epoxy resin system; and thus, are viable as replacements for bisphenol-A epoxy resins.

Synthesis of pyranobenzopyrans from D-glucal using ionic liquids

Imidazolium room temperature ionic liquids (RTILs) were used as solvents in the Lewis acid-catalyzed cycloaddition reactions of D-glucal with substituted salicylaldehydes. These reactions selectively led to various, novel, cis-pyrano [4,3-b]benzopyrans in modest yields, different products than those isolated from analogous solution studies. Furan diol was isolated as the major byproduct from all the reactions. The use of RTILs facilitated the use of unprotected sugars in these reactions.

Novel noble metal-free and recyclable Co-CoOx-FeNiCo/γ-Al2O3 catalyst for selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran or 2,5-Bis(hydroxymethyl)furan

The efficient production of the liquid fuel 2,5-dimethylfuran (DMF) from biomass-derived 5-hydroxymethylfurfural (HMF) is very complicated because of the presence of the aldehyde group, hydroxyl group, and CC bond. In this study, a novel Co-CoOx –FeNiCo/γ-Al2O3 catalyst was developed for selective hydrogenation of HMF to DMF. The catalyst was characterized by using XRD, TEM, SAED, BET, XPS, NH3-TPD, and H2-TPR techniques. The catalyst reduced at 500 °C exhibited excellent catalytic performance and the highest DMF yield (>99.9%) was obtained at 190 °C and 4 h. During the reaction, metal sites selectively hydrogenated the CO bond while acid sites (CoOx acid sites) selectively hydrogenolyzed CO bond. Appropriate surface acidity of the catalyst and the balance between metal and metal oxide species are the main factors for achieving a high yield of DMF. At reaction temperatures below 150 °C, DMF was not produced and HMF has completely converted into 2,5-Bis(hydroxymethyl)furan (BHMF), an important furan diol for polymers production. 100% BHMF yield was also obtained for the HMF hydrogenation over 300 °C reduced catalysts due to the high concentration of strong acid sites. The catalyst recyclability exhibited excellent stability and the original activity was maintained after six reuses. A reaction mechanism was also proposed.

Catalyst structure-based hydroxymethylfurfural (HMF) hydrogenation mechanisms, activity and selectivity over Ni

Catalytic hydrodeoxygenation of hydroxymethylfurfural was investigated in a three-phase batch reactor over a range of reaction temperatures (170–230 °C), under 5 MPa of hydrogen, and tetrahydrofuran solvent. Nickel-based carbon-supported catalysts were also promoted by lanthanum and niobium, despite promoters alone demonstrated no activity. Based on experimentally-obtained liquid products, a reaction pathway was proposed and a microkinetic model was established, by considering adsorption, desorption and surface reaction kinetics, mass transfer and thermodynamics. An unpromoted Ni/C resulted in primarily unsaturated furan diol, a highly desirable intermediate in the polymer industry. As reaction temperatures increased > 200 °C, dehydration yielded deoxygenated products suitable for solvents and biofuel. In spite of enhancements to reducibility, La-promotion significantly decreased both hydrogenation (8-times) and deoxygenation (25-times) rate constants. Alternatively, Nb-incorporation offered additional acidity, while lower activation energies resulted in 200% higher deoxygenation rates via dehydration reactions and humin formation at lower temperatures. It exhibited the highest deoxygenation activity.

Facile Solid-State Mechanochemical Synthesis of Eco-Friendly Thermoplastic Polyurethanes and Copolymers Using a Biomass-Derived Furan Diol

Herein, we report a facile, one-pot, green, and solvent-less (solid-state) mechanochemical approach toward the synthesis of eco-friendly polyurethanes (PUs) at room temperature using biomass-derive...

Insight into the hydrogenation of pure and crude HMF to furan diols using Ru/C as catalyst

5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was investigated. Three commercial catalysts, Ru/C, Pd/C and Pt/C, were tested in the hydrogenation of aqueous HMF solutions (2–3 wt%), using a metal loading of 1 wt% respect to HMF content. By appropriate tuning of the process conditions, either BHMF or BHMTHF were obtained in good yields, and Ru/C resulted the best catalyst for this purpose, allowing us to obtain BHMF or BHMTHF yields up to 93.0 and 95.3 mol%, respectively. This catalyst was also tested for in the hydrogenation of a crude HMF-rich hydrolyzate, obtained by one-pot the dehydration of fructose. The influence of each component of this hydrolyzate on the hydrogenation efficiency was investigated, including unconverted fructose, rehydration acids and humins, in order to improve the yields towards each furan diol. Moreover, ICP-OES and TEM analysis showed that the catalyst was not subjected to important leaching and sintering phenomena, as further confirmed by catalyst recycling study.

Hydroxylation of Eleuthoside Synthetic Intermediates by P450BM3 (CYP102A1)

A seven‐step synthesis of the first tricyclic intermediate in Danishefsky's total synthesis of eleutherobin is reported with Wittig homologation and sequential additions of metallated furan derivatives to aldehydes as key steps. Aiming to prepare hydroxylated eleutherobin analogues for cytotoxicity screening, the furan diol epimers 6 and precursors 1 and 2 were exposed to a 48‐member panel of engineered cytochrome P450BM3 variants. Both furan‐containing substrates reacted solely at the furan ring, one resulting in overall biocatalytic Achmatowicz reaction. Selective hydroxylation at four separate sp3 C–H centres was achieved in the substrates lacking the furan component. P450BM3‐catalysed hydroxylation of racemic substrates can proceed with kinetic resolution; in the case reported here, the 2°‐allylic alcohol product 10 was generated with an 82:18 enantiomeric ratio.

Concise asymmetric total synthesis of catunaregin

The asymmetric total synthesis of the optically pure catunaregin was accomplished in 7 steps from a known methyl ester using an asymmetric syn-selective aldol reaction and the successive ketalization of a furan diol derivative under acidic conditions.

First total synthesis of (4R,5R,11S) and (4R,5R,11R)-isocladospolide B

The two enantiomers of natural products (4 S , 5 S , 11 R )-and (4 S , 5 S , 11 S )- iso -cladospolide B have been synthesized and their structures unambiguously confirmed by X-ray crystallographic analysis. Key steps of the synthesis include the use of tri-O-acetyl-D-glucal as precursor for a chiral furan diol which, after side chain transformation, underwent singlet oxygen oxidation to afford the target butenolides

Divergent Synthesis of the Co-isolated Mycotoxins Longianone, Isopatulin, and (Z)-Ascladiol via Furan Oxidation

Longianone and the biosynthetically related mycotoxins isopatulin and (Z)-ascladiol were prepared following a divergent route from a readily available furan diol. The route toward longianone features an unprecedented TBAF-promoted intramolecular oxa-Michael reaction to a conjugated keto enoate, and the oxidation of dihydrolongianone to longianone with stabilized IBX. The route to isopatulin features a chemoenzymatic synthesis of (Z)-ascladiol, and the regioselective oxidation of (Z)-ascladiol to isopatulin with MnO(2).

Efficient and rapid experimental procedure for the synthesis of furan diol from d-glucal using ionic liquid

A new efficient and rapid experimental method and product isolation procedure as well as easy recyclable reaction media is expected to contribute to the development of a green strategy for the synthesis of furan diol from d-glucal. We determine the best conditions of reaction, minimizing the toxicity and finding an environmentally more acceptable process, using [Bmim][MSO 4]/InCl 3·3H 2O as a new solvent system under extremely mild conditions, providing high yields with a dramatic enhancement of reaction rate.

Protic Acid (HClO4 Supported on Silica Gel)‐Mediated Synthesis of 2,3‐Unsaturated‐O‐glucosides and a Chiral Furan Diol from 2,3‐Glycals.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Montmorillonite KSF clay as novel and recyclable heterogeneous solid acid for the conversion of d-glycals into furan diol

A simple, efficient and environmentally benign protocol has been developed for the conversion of glycals into 2-( d-glycero-1,2-dihydroxy ethyl) furan derivatives using montmorillonite KSF as inexpensive and environmentally benign solid acid to afford excellent yields with high selectivity.

Protic acid (HClO4 supported on silica gel)-mediated synthesis of 2,3-unsaturated-O-glucosides and a chiral furan diol from 2,3-glycals.

Perchloric acid supported on silica gel acts as an excellent reagent system in converting glucals into 2,3-unsaturated-O-glucosides in good to excellent yields in short reaction time with good alpha selectivity. Primary, secondary, and allylic alcohols, phenols, and thiols react with 3,4,6-tri-O-acetyl glucal with equal ease. In addition to this, a chiral furan diol is obtained from unprotected D-glucal or D-galactal in good yields.

A facile synthesis of a chiral furan diol from glycals catalyzed by indium trichloride

ADVERTISEMENT RETURN TO ISSUEPREVNoteNEXTA Facile Synthesis of a Chiral Furan Diol from Glycals Catalyzed by Indium Trichloride†B. Sobhana Babu and K. K. BalasubramanianView Author Information Indian Institute of Technology, Madras, Chennai - 600 036, India Cite this: J. Org. Chem. 2000, 65, 13, 4198–4199Publication Date (Web):June 2, 2000Publication History Received19 January 2000Published online2 June 2000Published inissue 1 June 2000https://doi.org/10.1021/jo000074tCopyright © 2000 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views634Altmetric-Citations28LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (67 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Aldol reactions,Catalysts,Diols,Mixtures,Transfer reactions Get e-Alerts

Metal-catalyzed transformation of D-glucal to optically active furan diol

The treatment of D-glucal with a catalytic amount of Sm(OTf)3 or RuCl2(PPh3)3 in the presence of 1 equiv. of H2O afforded optically active furan diol in good yield under mild conditions.