- Green Process for 5-(Chloromethyl)furfural Production from Biomass in Three-Constituent Deep Eutectic Solvent
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5-(Chloromethyl)furfural (CMF), a versatile bio-platform molecule, was first synthesized in a three-constituent deep eutectic solvent (3c-DES) including choline chloride, AlCl3 ? 6H2O, and oxalic acid. In particular, 3c-DES was conducive for the production of CMF from glucose and provided a CMF yield of 70 % at 120 °C within 30 min. In addition, CMF yields reached up to 86, 80, 30, 29, and 35 % from fructose, sucrose, cellulose, bamboo, and bamboo pulp, respectively. This study opens new avenues for the preparation of CMF.
- Chen, Binglin,Li, Zheng,Feng, Yunchao,Hao, Weiwei,Sun, Yong,Tang, Xing,Zeng, Xianhai,Lin, Lu
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- The Vilsmeier reaction: A new synthetic method for 5-(chloromethyl)-2-furaldehyde
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Phosphorus or sulfur chlorides were screened for the chlorination of 5-(hydroxymethyl)-2-furaldehyde (1) to 5-(chloromethyl)-2-furaldehyde (2), with dimethylformamide or N-methylpyrrolidone as solvents. Preparative scale experiments were carried out with suitable phosphorus oxychloride, sulfurylchloride or methanesulfonyl chloride in the presence of dimethylformamide to give 5-(chloromethyl)-2-furaldehyde in good yields (77 to 83%).
- Sanda,Rigal,Delmas,Gaset
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- Preparation of halogenated furfurals as intermediates in the carbohydrates to biofuel process
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Lignocellulose derived halogenated furfurals are important chemicals that can serve as starting materials for diverse products such as drugs, polymers and fuels, including fuel additives. In this paper a protocol for the synthesis of 5-chloromethyl furfural (CMF) and 5-bromomethyl furfural (BMF) is put forward. The proposed process is based on a two liquid phases reaction composed of an aqueous hydrochloric or hydrobromic acid phase and 1,2-dichloroethane (DCE) organic phase. We have optimized and compared the yields of CMF and BMF in an open flask and in a closed reaction vessels. Utilization of the close reaction vessel resulted in not only higher yields in a shorter reaction time but also eliminated the necessity of the customary lithium salts additives previously advocated for this process. These additives were required in the open reaction systems in order to achieve reasonable yields. While a closed reaction vessel was previously reported for the production of CMF, and in this work its production was further improved, it is the first time a close vessel protocol for the production of BMF has been reported. In addition, improvement of the substrate to organic solvent ratio has been carried while yields of halogenated furfurals were maintained almost intact. NMR and UV-vis spectroscopy were used for identification and quantification of the products.
- Meller, Elad,Aviv, Avishay,Aizenshtat, Zeev,Sasson, Yoel
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- AN IMPROVED METHOD FOR THE CONVERSION OF SACCHARIDES INTO FURFURAL DERIVATIVES
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An improved method for the preparation of furan compounds by dehydrating saccharides with hydrochloric acid either in a mixture containing water, organic solvent and a catalytic amount of a surface active agent or in the presence of magnesium halide is described.
- Hamada, Kazuhiko,Yoshihara, Hiroshi,Suzukamo, Gohfu
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- The Dehydration of Ketohexoses into 5-Chloromethyl-2-furaldehyde. The isolation of Diketohexose Dianhydrides
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The isolation of diketohexose dianhydrides, produced during the dehydration of D(-)-fructose and L(-)-sorbose with concentrated hydrochloric acid, in a mixture containing water, an organic solvent and a catalytic amount of a surface-active agent is described.
- Hamada, Kazuhiko,Yoshihara, Hiroshi,Suzukamo, Gohfu,Hiroaki, Osamu
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- The potential of microwave technology for the recovery, synthesis and manufacturing of chemicals from bio-wastes
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Through a series of case studies it is demonstrated that microwave dielectric heating can be a powerfultool to recover and synthesize valuable molecules from a wide range of biomass types. In addition, undermicrowave irradiation the production of chemicals from biomass proceeds at markedly lower temper-atures (up to 150?C) compared to conventional heating. This has a secondary benefit in that moleculeswith a high degree of functionality are produced while conventional heating tends to produce a greatproportion of lower value gases. Furthermore, the technical set-up of a microwave reactor can easilyaccommodate for an in-situ separation of acids and valuable products therewith improving the shelf lifeof the latter. The benefits of combining hydrothermal conditions with microwave irradiation are alsoillustrated. In addition, a specialized case of selective heating in a biphasic reaction system is discussed,allowing for improved yields and selectivity.
- Budarin, Vitaliy L.,Shuttleworth, Peter S.,De Bruyn, Mario,Farmer, Thomas J.,Gronnow, Mark J.,Pfaltzgraff, Lucie,Macquarrie, Duncan J.,Clark, James H.
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- Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)
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2,5-Diformylfuran (DFF) is an important biorenewable building block, namely for the manufacture of new polymers that may replace existing materials derived from limited fossil fuel resources. The current reported methods for the preparation of DFF are mainly derived from the oxidation of 5-hydroxymethylfurfural (HMF) and, to a lesser extent, directly from fructose. 5-Chloromethylfurfural (CMF) has been considered an alternative to HMF as an intermediate building block due to its advantages regarding stability, polarity, and availability from glucose and cellulose. The only reported method for the transformation of CMF to DFF is restricted to the use of DMSO as the solvent and oxidant. We envisioned that the transformation could be performed using more attractive conditions. To that end, we explored the oxidation of CMF to DFF by screening several oxidants such as H2O2, oxone, and pyridine N-oxide (PNO); different heating methods, namely thermal and microwave irradiation (MWI); and also flow conditions. The combination of PNO (4 equiv.) and Cu(OTf)2 (0.5 equiv.) in acetonitrile was identified as the best system, which lead to the formation of DFF in 54% yield under MWI for 5 min at 160°C. Consequently, a range of different heterogeneous copper catalysts were tested, which allowed for catalyst reuse. Similar results were also observed under flow conditions using copper immobilized on silica under thermal heating at 160°C for a residence time of 2.7 min. Finally, HMF and 5,5′-oxybis(5-methylene-2-furaldehyde) (OBMF) were the only byproducts identified under the reaction conditions studied.
- Vicente, Ana I.,Coelho, Jaime A. S.,Simeonov, Svilen P.,Lazarova, Hristina I.,Popova, Margarita D.,Afonso, Carlos A. M.
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- Microwave heating for rapid conversion of sugars and polysaccharides to 5-chloromethyl furfural
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A range of carbohydrates has been rapidly and selectively converted to 5-chloromethyl furfural using microwave heating in a biphasic reaction system with a range of organic solvents. Fructose and inulin were especially effective for production of this valuable bio-platform molecule, with yields of >70% obtained in 15 minutes under microwave heating. Yields from cellulose were dramatically increased with ball mill pre-treatment, this being associated with a reduction in polysaccharide crystallinity.
- Breeden,Clark,Farmer,MacQuarrie,Meimoun,Nonne,Reid
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- Efficient one-pot synthesis of 5-chloromethylfurfural (CMF) from carbohydrates in mild biphasic systems
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5-Halomethylfurfurals can be considered as platform chemicals of high reactivity making them useful for the preparation of a variety of important compounds. In this study, a one-pot route for the conversion of carbohydrates into 5-chloromethylfurfural (CMF) in a simple and efficient (HCl-H 3PO4/CHCl3) biphasic system has been investigated. Monosaccharides such as D-fructose, D-glucose and sorbose, disaccharides such as sucrose and cellobiose and polysaccharides such as cellulose were successfully converted into CMF in satisfactory yields under mild conditions. Our data shows that when using D-fructose the optimum yield of CMF was about 47%. This understanding allowed us to extent our work to biomaterials, such as wood powder and wood pulps with yields of CMF obtained being comparable to those seen with some of the enumerated mono and disaccharides. Overall, the proposed (HCl-H3PO4/CHCl3) optimized biphasic system provides a simple, mild, and cost-effective means to prepare CMF from renewable resources.
- Gao, Wenhua,Li, Yiqun,Xiang, Zhouyang,Chen, Kefu,Yang, Rendang,Argyropoulos, Dimitris S.
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- Processed Lignin as a Byproduct of the Generation of 5-(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material
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The lignin by-product of the conversion of lignocellulosic biomass to 5-(chloromethyl)furfural (CMF) has been characterised by thermogravimetric analysis, N2 physisorption porosimetry, attenuated internal reflectance IR spectroscopy, elemental analysis and solid-state NMR spectroscopy. The lignin (LCMF) has a moderate level of mesoporosity before thermal treatment and a surface area of 63 m2g-1, which increases dramatically on pyrolysis at temperatures above 400 °C. An assessment of the functionality and textural properties of the material was achieved by analysing LCMF treated thermally over a range of pyrolysis temperatures. Samples were sulfonated to test their potential as heterogeneous acid catalysts in the esterification of levulinic acid. It was shown that unpyrolysed catalysts gave the highest ester yields of up to 93%. To the best of our knowledge, this is the first example of mesoporous lignin with an appreciable surface area that is produced directly from a bio-refinery process and with further textural modification of the material demonstrated.
- Budarin, Vitaliy L.,Clark, James H.,Henschen, Jonatan,Farmer, Thomas J.,Macquarrie, Duncan J.,Mascal, Mark,Nagaraja, Gundibasappa K.,Petchey, Tabitha H. M.
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- Green catalytic conversion of bio-based sugars to 5-chloromethyl furfural in deep eutectic solvent, catalyzed by metal chlorides
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5-Chloromethylfurfural (5-CMF), a biomass-derived platform chemical with great potential applications, was synthesized by a novel method from sugars, using metal chlorides as catalysts in a deep eutectic solvent (DES). AlCl3·6H2O was verified as the most effective catalyst among various metal chlorides, and provided a 5-CMF yield of 50.3% along with 8.1% 5-HMF yield at 120°C in 5 h. By this green, mild and cost-effective approach, the dependence of 5-CMF production on the large amount and high concentration of hydrochloric acid in previous studies was eliminated.
- Zuo, Miao,Li, Zheng,Jiang, Yetao,Tang, Xing,Zeng, Xianhai,Sun, Yong,Lin, Lu
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- Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural
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The influence of different parameters on the conversion of carbohydrates and biomass into the potential biofuel intermediate 5-bromomethylfurfural (BMF) has been studied. Our optimized conditions avoid the use of lithium salt additives, making this method cheaper and environmentally more benign compared to previously reported methods. Different wood species and their potential as a raw material in BMF and furfural production have also been evaluated. In addition, we report a very simple and efficient procedure for conversion of 5-hydroxymethylfurfural (HMF) into BMF or 5-chloromethylfurfural (CMF).
- Bredihhin, Aleksei,M?eorg, Uno,Vares, Lauri
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- Synthese du 5-bromomethyl- et du 5-chloromethyl-2-furannecarboxaldehyde
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The action of hydrogen halides, sulfur and phosphorous halides, and halotrimethylsilanes on 5-(hydroxymethyl)-2-furancarboxaldehyde (1) led to the corresponding 5-(chloromethyl)- (2) or 5-(bromomethyl)-2-furancarboxaldehyde (3).Thus, treatment of 1 in diethyl ether solution with gaseous dry hydrogen chloride under very mild experimental conditions led to high yields of 2.The selective and quantitative conversion of 1 into 3 was achieved with bromotrimethylsilane.In the same manner, chlorotrimethylsilane gave high yields of 2 from 1.The latter compound was obtained by acid-catalyzed dehydration of D-fructose in dimethyl sulfoxide, and then converted into 2 without prior purification.
- Sanda, Komla,Rigal, Luc,Gaset, Antoine
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- 3-deoxy-glucosone is an intermediate in the formation of furfurals from D-glucose.
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The acid-catalyzed dehydration of glucose to hydroxymethylfurfural (6) can occur via two possible mechanisms. 3-deoxy-D-erythro-hex-2-ulose (3) is found to be an intermediate in the formation of 6 from glucose (1). This finding implies that elimination of the glucose 3-OH group is the important step, rather than isomerization of the carbonyl group.
- Jadhav, Harishchandra,Pedersen, Christian Marcus,S?lling, Theis,Bols, Mikael
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- Synthesis of 2-Azidomethyl-5-ethynylfuran: A New Bio-Derived Self-Clickable Building Block
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2-Azidomethyl-5-ethynylfuran, a new ambivalent compound with both azide and alkyne moieties that can be used as a self-clickable monomer, is synthesized starting directly from renewable biomass. The reactivity of the azide group linked to furfural is tested via the efficient preparation of a broad range of furfural-containing triazoles in good to excellent yields using a 'green' copper(I)-catalyzed azide-alkyne cycloaddition procedure. Access to new bio-based chemicals and oligomeric materials via a click-chemistry approach is also demonstrated using this bio-derived building block.
- Karlinskii, Bogdan Ya.,Romashov, Leonid V.,Galkin, Konstantin I.,Kislitsyn, Pavel G.,Ananikov, Valentine P.
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- Preparation method of 5-halogenated methylfurfural
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The invention discloses a preparation method of 5-halogenated methylfurfural, which comprises the steps of (1) adding raw materials, choline chloride/choline bromide, an organic acid as a hydrogen bond donor, a metal salt and dichloroethane into a reactor, and carrying out stirring reaction at the temperature of 80-150 DEG C for 5-300 minutes to obtain a reaction phase composed of an upper layer and a lower layer, wherein the lower layer is an eutectic solvent phase, and the upper layer is a dichloroethane phase; and (2) enabling the eutectic solvent phase to be subjected to dichloroethane extraction and separation purification so as to obtain a product containing 5-halogenated methylfurfural. The selected raw materials are wide in source, low in price and easy to obtain; the reaction conditions are mild, and the reaction yield is high; and a novel thought is provided for researching the 5-halogenated methylfurfural and downstream products thereof in the future.
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Paragraph 0027-0028; 0051-0052
(2021/01/30)
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- 5-(Chloromethyl)furfural production from glucose: A pioneer kinetic model development exploring the mechanism
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Conversion of glucose to 5-(chloromethyl)furfural (CMF) is one of the well-known high yield unit processes in lignocellulosic biomass valorization. A kinetic modeling study was not reported for the reaction, owing to the complexity in quantification of CMF. Herein we have successfully developed a rapid, sensitive, and specific HPLC method (reverse phase) to quantify the generated CMF (range: 10–650?μg/mL) in a dichloroethane solvent. The Box–Behnken design of experiment method employed for the statistical optimization. A kinetic model was developed based on the homogeneous first-order kinetic model, and the results are in good agreement with the experiment data. The formation of CMF, 5-(hydroxymethyl)furfural, formic acid, levulinic acid, and humins from glucose and HCl were modeled using a serial parallel reaction mechanism. The apparent activation energy (Ea) for glucose decomposition and CMF formation is 99 and 31 kJ/mol.
- Antonyraj, Churchil A.,Chennattussery, Amal J.,Haridas, Ajit
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supporting information
p. 825 - 833
(2021/03/18)
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- Process for preparing 5-chloromethylfurfural from fructose
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The invention discloses a process for preparing 5-chloromethylfurfural from fructose. The process includes preparing an eutectic solvent from the fructose and choline chloride at a certain temperature, taking a certain amount of hydrochloric acid as a catalyst and a chlorinating reagent, carrying out a reaction at 70-110 DEG C, cooling down to room temperature after reaction, dissolving a reactionmixture in deionized water, extracting a reaction product by an organic solvent, and performing organic phase separation to obtain a target product, the 5-chloromethylfurfural. The maximum yield of the process can reach 90%. The process for preparing the 5-chloromethylfurfural from the biomass-derived fructose has the advantages of simplicity, mild condition, high yield, low cost and easy availability of catalysts, non-toxicity, harmlessness, environmental friendliness and the like, providing a new approach to production of biomass-based high-value-added products.
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Paragraph 0016-0027
(2019/10/17)
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- A SINGLE STEP PROCESS FOR THE SYNTHESIS OF FURAN DERIVATIVES FROM CARBOHYDRATES
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The present invention discloses a single step process for the synthesis of furan derivative from carbohydrate comprises stirring the reaction mixture of carbohydrate in solvent in presence of catalyst at temperature in the range of 170 to 190°C for the period in the range of 23 to 25 hrs to afford corresponding furan derivative.
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Page/Page column 9-11
(2018/12/13)
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- Critical Influence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis
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Spectral studies revealed the presence of a specific arrangement of 5-hydroxymethylfurfural (5-HMF) molecules in solution as a result of a hydrogen–bonding network, and this arrangement readily facilitates the aging of 5-HMF. Deterioration of the quality of this platform chemical limits its practical applications, especially in synthesis/pharma areas. The model drug Ranitidine (Zantac) was synthesized with only 15 % yield starting from 5-HMF which was isolated and stored as an oil after a biomass conversion process. In contrast, a much higher yield of 65 % was obtained by using 5-HMF isolated in crystalline state from an optimized biomass conversion process. The molecular mechanisms responsible for 5-HMF decomposition in solution were established by NMR and ESI-MS studies. A highly selective synthesis of a 5-HMF derivative from glucose was achieved using a protecting group at O(6) position.
- Galkin, Konstantin I.,Krivodaeva, Elena A.,Romashov, Leonid V.,Zalesskiy, Sergey S.,Kachala, Vadim V.,Burykina, Julia V.,Ananikov, Valentine P.
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supporting information
p. 8338 - 8342
(2016/07/19)
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- Synthesis of HIV-1 capsid protein assembly inhibitor (CAP-1) and its analogues based on a biomass approach
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A biomass-derived platform chemical was utilized to access a demanded pharmaceutical substance with anti-HIV activity (HIV, human immunodeficiency virus) and a variety of structural analogues. Step economy in the synthesis of the drug core (single stage from cellulose) is studied including flexible variability of four structural units. The first synthesis and X-ray structure of the inhibitor of HIV-1 capsid protein assembly (CAP-1) is described.
- Romashov, Leonid V.,Ananikov, Valentine P.
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p. 10593 - 10598
(2016/11/30)
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- A 5-chloro methyl furfural method for the preparation of
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The invention belongs to the field of synthesis of chemical materials and in particular discloses a method for preparing 5-chloromethyl furfural. The method comprises the following steps: preparing 5-chloromethyl furfural in a metal chloride/concentrated hydrochloric acid solution-organic solvent heterogeneous system by adopting a carbohydrate raw material or biomass raw material. The composition structure of the synthetic 5-chloromethyl furfural is detected by adopting gas chromatography-mass spectrometer (GC-MS), wherein the highest yield of the obtained 5-chloromethyl furfural can be 71.67mol% (mol/mol). The method has reference significance for improving the yield of the biomass energy intermediate product 5-chloromethyl furfural, reducing the production cost, increasing the industry value and realizing industrialization and commercialization of the technology of preparing the biomass energy intermediate in the carbohydrate heterogeneous system.
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Paragraph 0020-0022; 0023-0026; 0028-0034
(2019/02/02)
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- OXIMINO DERIVATIVES FOR THE TREATMENT OF DYSLIPIDEMIA
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Compounds of the general formula (I), including their tautomeric forms, their stereoisomers, their pharmaceutically acceptable salts, pharmaceutical compositions containing them, methods for their preparation, use of these compounds and the intermediates involved in their preparation.
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Paragraph 0277; 0278
(2016/04/19)
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- The effects of emulsion on sugar dehydration to 5-hydroxymethylfurfural in a biphasic system
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Alkyl/amino functionalized silica nanoparticles to create an emulsion in a biphasic system for sugar dehydration to HMF were successfully developed. As a proof-of-concept, more than 10% increase of HMF yield and 20% increase of selectivity were achieved for both fructose and glucose dehydrations in the emulsion system as compared to the conventional biphasic system. The excellent recyclability of the nanoparticles also further widens the potential of the biphasic system to be scaled up for industrial application.
- Teong, Siew Ping,Yi, Guangshun,Zeng, Huaqiang,Zhang, Yugen
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supporting information
p. 3751 - 3755
(2015/07/15)
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- Facile synthesis of 5-hydroxymethylfurfural: A sustainable raw material for the synthesis of key intermediates toward 21,23-dioxaporphyrins
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In a simple and conceptually designed method for the dehydration of fructose on a solid support, 5-hydroxymethylfurfural (HMF) was synthesized in more than 95% isolated yield from fructose under very mild conditions at room temperature. The loading of fructose on the solid support reduced the intermolecular interactions between fructose/intermediates, diminished the formation of polymeric material (humin) and increased the selectivity towards HMF formation. The synthesized HMF was readily converted into key intermediates toward the simpler synthesis of 21,23-dioxaporphyrins.
- Rajmohan, Rajamani,Gayathri, Subramaniyan,Vairaprakash, Pothiappan
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p. 100401 - 100407
(2015/12/04)
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- METHODS FOR PRODUCING 5-(HALOMETHYL) FURFURAL
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The present disclosure provides methods to produce 5-(halomethyl)furfural, including 5- (chloromethyl)furfural, by acid-catalyzed conversion of C6 saccharides, including isomers thereof, polymers thereof, and certain derivatives thereof. The methods make use of acids with lower concentrations, and allows for conversion of sugars into 5-(halomethyl)furfural at higher temperatures and faster reaction or residence times.
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Paragraph 0156-0160
(2015/04/15)
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- Trienamines derived from 5-substituted furfurals: Remote ε-functionalization of 2,4-dienals
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The selective ε-functionalization of 5-substituted furfurals via trienamine intermediates is reported herein. This methodology was successfully applied to several 5-substituted furfurals with different amines via formation of a trienamine through the furan ring. The rationalized reaction mechanism involves the addition of the trienamine intermediate to its corresponding iminium-ion producing new furan-containing scaffolds.
- Coelho, Jaime A. S.,Trindade, Alexandre F.,Andr, Vnia,Teresa Duarte,Veiros, Luis F.,Afonso, Carlos A.M.
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supporting information
p. 9324 - 9328
(2014/12/11)
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- METHOD FOR PREPARING 5-CHLOROMETHYL-2-FURFURAL USING GALACTAN DERIVED FROM SEAWEED IN TWO COMPONENT PHASE
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The present disclosure relates to an acid catalyst composition for producing 5-chloromethyl-2-furfural from galactan derived from seaweed and a method for producing 5-chloromethyl-2-furfural from galactan derived from seaweed on a two component phase using the acid catalyst, the acid catalyst composition for producing 5-chloromethyl-2-furfural from galactan derived from seaweed including organic solvent and dilute hydrochloric acid, a concentration of the dilute hydrochloric acid being 4N to 8N (normal). According to the present disclosure, there is an advantage of converting 5-chloromethyl-2-furfural from galactan derived from seaweed by means of a single process by mixing dilute hydrochloric acid and organic solvent by an optimal ratio, unlike conventional methods for producing 5-chloromethyl-2-furfural that had to go through a multi-phase process of preconditioning and saccharification.
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Paragraph 0089; 0092
(2014/03/25)
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- Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent
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We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl3 as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH2Cl2 and MeNO2 solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural. Copyright
- Zhou, Xiaoyuan,Rauchfuss, Thomas B.
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p. 383 - 388
(2013/04/24)
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- η3-furfuryl and η3-thienyl complexes of palladium and platinum of relevance to the functionalization of biomass-derived furans
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A number of cationic and neutral η3-furfuryl complexes of palladium and platinum were prepared, including one with a ligand derived from fructose, 5-chloromethylfurfural. The complexes were studied by variable-temperature and heteronuclear correlation NMR spectroscopy, as well as single-crystal X-ray crystallography. Analogous η3-thienyl complexes could be prepared and detected in solution by NMR, but could not be isolated due to facile decomposition.
- Shi, Yang,Brenner, Peter,Bertsch, Stefanie,Radacki, Krzysztof,Dewhurst, Rian D.
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p. 5599 - 5605
(2012/11/13)
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- Total synthesis of naturally occurring furan compounds 5-{[(4- hydroxybenzyl)oxy]methyl}-2-furaldehyde and pichiafuran C
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The synthesis of the natural furan derivatives 5-{[(4-hydroxybenzyl)oxy] methyl}-2-furaldehyde and pichiafuran C is described. Diverse alternative synthetic approaches were developed for the preparation of these natural products. They were prepared through an etherification reaction of the key furan precursor 5-(hydroxymethyl)-2-furaldehyde (HMF), which can be readily obtained from d-fructose, d-glucose, or sucrose, with the corresponding alcohols. 5-{[(4-Hydroxybenzyl)oxy]methyl}-2-furaldehyde was not only obtained in a two-step methodology but also by a biomimetic single-step synthesis. Similarly, pichiafuran C was prepared by three different syntheses, each one by a two-step procedure, also including a biomimetic approach. Georg Thieme Verlag Stuttgart.
- Quiroz-Florentino, Hector,Hernandez-Benitez, R. Israel,Avina, Judit A.,Burgueno-Tapia, Eleuterio,Tamariz, Joaquin
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experimental part
p. 1106 - 1112
(2011/06/20)
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- Highly efficient dehydration of carbohydrates to 5-(chloromethyl)furfural (CMF), 5-(hydroxymethyl)furfural (HMF) and levulinic acid by biphasic continuous flow processing
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Using a continuous flow reactor, the dehydration of d-fructose and other carbohydrates to 5-(chloromethyl)furfural (1) is achieved in reaction times as short as 60 s. The biphasic flow process allows for high-yielding multigram scale production of CMF (1) which is obtained with excellent purity after a simple extractive work-up. Efficient conversion of d-fructose into 5-(hydroxymethyl)furfural (2) and levulinic acid (6) is also demonstrated using flow reactor techniques.
- Brasholz, Malte,Von Kaenel, Karin,Hornung, Christian H.,Saubern, Simon,Tsanaktsidis, John
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supporting information; experimental part
p. 1114 - 1117
(2011/06/22)
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- Synthesis of 5-bromomethylfurfural from cellulose as a potential intermediate for biofuel
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Cellulose can be converted into 5-bromomethylfurfural (BMF), a brand new biofuel or biofuel intermediate, in 80 yield by treatment with HBr and LiBr and continuous extraction with toluene. From other carbohydrates and straw, BMF was also obtained in high yields. The mechanism of BMF formation was investigated, and the results indicate that this furfural is formed during the depolymerization of cellulose and that glucose is not an intermediate.
- Kumari, Nitee,Olesen, Jens Kruse,Pedersen, Christian M.,Bols, Mikael
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experimental part
p. 1266 - 1270
(2011/04/17)
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- A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids
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Lignocellulosic biomass is an attractive resource for producing transportation fuels, and consequently novel approaches are being sought for transforming the lignin and cellulosic constituents of biomass to fuels or fuel additives. Glucose, the monomer of cellulose, is a good starting material for exploring such chemistries. We report here the results of an investigation aimed at identifying catalysts for the dehydration of glucose to 5- hydroxymethylfurfural (HMF) dissolved in ionic liquids and the subsequent conversion of HMF to 2,5-dimethylfuran (DMF), a high-energy content product that could be used as a fuel or fuel additive. Heteropoly acids were found to be exceptionally active and selective catalysts for the dehydration of glucose. Nearly 100% yield of HMF could be achieved using 12-molybdophosphoric acid (12-MPA) in a solution of 1-ethyl-3-methylimidazolium chloride (EMIMCl) and acetonitrile. The addition of acetonitrile to EMIMCl suppressed the formation of humins from glucose. The high HMF selectivity achievable with heteropoly acid catalysts is ascribed to stabilization of 1,2-enediol and other intermediates involved in the dehydration of glucose and the avoidance of forming the 2,3-enediol intermediate leading to furylhydroxymethyl ketone (FHMK). Carbon-supported metals, and in particular Pd/C, were effective in promoting the hydrogenation of HMF dissolved in EMIMCl and acetonitrile to DMF. The following intermediates were observed in the hydrogenation of HMF to DMF: 5-methylfurfural (MF), 5-methylfurfyl alcohol (MFA), and 2,5- dihydroxymethylfuran (DHMF). The relative rate of formation and consumption of these compounds was explored by using each of them as a reactant in order to identify the reaction pathway from HMF to DMF. It was also observed that HMF produced via glucose dehydration could be converted to DMF without isolation, if the dehydration catalyst, 12 MPA, was replaced by the hydrogenation catalyst, Pd/C. This two-step catalytic approach provides the basis for completely converting glucose to HMF and further converting HMF to DMF. The Royal Society of Chemistry 2010.
- Chidambaram, Mandan,Bell, Alexis T.
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experimental part
p. 1253 - 1262
(2010/10/03)
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- HIGH-YIELD CONVERSION OF CELLULOSIC BIOMASS INTO FURANIC BIOFUELS AND VALUE-ADDED PRODUCTS
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Paper, cotton, corn stover, straw, and wood are converted into furanic products in high yields (based on their cellulose content) using a simple, inexpensive process involving concurrent hydrolysis, dehydration, and substitution reactions coupled with continuous extraction into an organic phase. In a simultaneous process, the hemicellulose fraction of these substrates is converted into furfural, and together these constitute an efficient means for the total exploitation of the carbohydrate content of biomass.
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Page/Page column 7
(2009/09/28)
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- Direct, high-yield conversion of cellulose into biofuel
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(Chemical Equation Presented) Fueling up with furans: Cellulose can be converted into furanic biofuels in unprecedented yields using an inexpensive, simple process involving concurrent hydrolysis, dehydration, and chlorine substitution reactions coupled with continuous extraction into an organic phase (see scheme). Furanic ethers, such as those that can be derived from the products above, are known diesel additives.
- Mascal, Mark,Nikitin, Edward B.
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supporting information; experimental part
p. 7924 - 7926
(2009/04/18)
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- Novel peptides comprising furanoid sugar amino acids for the treatment of cancer
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Anticancer peptides which incorporate furanoid sugar amino acids and compositions made using these peptides are described. Methods for synthesis of the peptides and for preparing the furanoid sugar amino acids are disclosed. The peptides and compositions made using the peptides have pharmacological applications of these peptides especially in the treatment and prevention of cancer and tumors.
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Page/Page column 4
(2010/02/10)
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- 2 - SUBSTITUTED HETEROCYCLIC COMPOUNDS AND ANTITUMOR COMPOSITION COMPRISING THE SAME
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The present invention relates with 2-substituted heterocyclic compounds and antitumor composition comprising the same. The compound according to the present invention exhibits superior effect as telomerase inhibitor based on new mechanism (terlomere-terlomerase) which can resolve the problems occurring at the time of using chemotherapeutics, i.e side effects and cross resistance between related mechanism on using chemotherapeutics. In addition, the antitumor composition comprising the compound of the present invention exhibits superior effect in inhibiting the growth of cancer cell.
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- Cyclic trimer of 5-(aminomethyl)-2-furancarboxylic acid as a novel synthetic receptor for carboxylate recognition
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A novel 18-membered cyclic oligopeptide 1 based on 5-(aminomethyl)-2-furancarboxylic acid (2), is developed as an excellent receptor for carboxylate binding having an association constant of 8.64×103 M-1 for tetrabutylammonium acetate in CD3CN. The synthesis of 1 was achieved by a high-yielding cyclotrimerization reaction of the unfunctionalized furan amino acid 2.
- Chakraborty, Tushar K,Tapadar, Subhasish,Kiran Kumar
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p. 1317 - 1320
(2007/10/03)
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- Action of boron trifluoride etherate and stannic chloride on heterocyclic aromatic acetals
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Twelve heterocyclic aromatic acetals (1a-12a) have been synthesised and their reactions with Lewis acids, viz. boron trifluoride etherate (BTE) and stannic chloride (STC) have been studied.The acetals yield ethers, esters and aldehydes with BTE, but only esters and aldehydes with STC.Interestingly, pyridine-2-aldehyde acetal (12a), yields aldehyde alone, that too in low yield.Probable mechanisms have been suggested for the product formation.
- Raja, S.,Xavier, N.,Arulraj, S. J.
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p. 687 - 689
(2007/10/02)
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- Process for producing 5-halomethylfurfural
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A process for producing 5-halomethylfurfural represented by the formula, STR1 wherein X is Cl or Br, which comprises carrying out a acid-decomposition of saccharide in a water/organic solvent/magnesium halide system with hydrochloric acid, sulfuric acid, hydrogen chloride or other mineral acid in the presence or absence of surface active agent as a catalyst. The 5-halomethylfurfural is useful as an intermediate of medicines, agricultural chemicals, perfumes and the like.
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- Inhibitors for furfurals
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Furfural or derivatives thereof, especially 5-chloromethyl furfural, is inhibited against the formation of resinous decomposition products by addition of epoxy compounds such as the reaction product of epichlorohydrin and bisphenol A.
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- NOUVELLE METHODE DE PREPARATION DU 5-HYDROXYMETHYL-2-FURALDEHYDE PAR ACTION DE SELS D'AMMONIUM OU D'IMMONIUM SUR LES MONO-, OLIGO- ET POLY-SACCHARIDES. ACCES DIRECT AUX 5-HALOGENOMETHYL-2-FURALDEHYDES
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In a new and simple process for preparing 5-hydroxymethyl-2-furaldehyde from mono-, oligo- and poly-saccharides, which uses immonium or ammonium salts, direct heating of the reagent and the starting material, both in solid phase, gave directly 5-hydroxymethyl-2-furaldehyde with a good purity, avoiding production of secondary products.The use of a polymeric form of the reagent constitutes an extension of the method toward an eventual industrial application.Under special conditions, a one-pot dehydration-halogenation sequence gave 5-bromomethyl-(or 5-chloromethyl)-2-furaldehyde.
- Fayet, Catherine,Gelas, Jacques
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- Process for producing a furan derivative
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A process for producing furan derivatives of the formula, STR1 wherein R is hydrogen, methyl or chloromethyl, which comprises reacting a mono- or a disaccharide with hydrochloric acid in a mixture containing water, an organic solvent and a catalytic amount of a surface active agent.
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