1623-88-7Relevant articles and documents
Green Process for 5-(Chloromethyl)furfural Production from Biomass in Three-Constituent Deep Eutectic Solvent
Chen, Binglin,Li, Zheng,Feng, Yunchao,Hao, Weiwei,Sun, Yong,Tang, Xing,Zeng, Xianhai,Lin, Lu
, p. 847 - 851 (2021)
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.
Preparation of halogenated furfurals as intermediates in the carbohydrates to biofuel process
Meller, Elad,Aviv, Avishay,Aizenshtat, Zeev,Sasson, Yoel
, p. 36069 - 36076 (2016)
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.
The Dehydration of Ketohexoses into 5-Chloromethyl-2-furaldehyde. The isolation of Diketohexose Dianhydrides
Hamada, Kazuhiko,Yoshihara, Hiroshi,Suzukamo, Gohfu,Hiroaki, Osamu
, p. 307 - 308 (1984)
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.
Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)
Vicente, Ana I.,Coelho, Jaime A. S.,Simeonov, Svilen P.,Lazarova, Hristina I.,Popova, Margarita D.,Afonso, Carlos A. M.
, (2017)
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.
Efficient one-pot synthesis of 5-chloromethylfurfural (CMF) from carbohydrates in mild biphasic systems
Gao, Wenhua,Li, Yiqun,Xiang, Zhouyang,Chen, Kefu,Yang, Rendang,Argyropoulos, Dimitris S.
, p. 7675 - 7685 (2013)
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.
Green catalytic conversion of bio-based sugars to 5-chloromethyl furfural in deep eutectic solvent, catalyzed by metal chlorides
Zuo, Miao,Li, Zheng,Jiang, Yetao,Tang, Xing,Zeng, Xianhai,Sun, Yong,Lin, Lu
, p. 27004 - 27007 (2016)
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.
Synthese du 5-bromomethyl- et du 5-chloromethyl-2-furannecarboxaldehyde
Sanda, Komla,Rigal, Luc,Gaset, Antoine
, p. 15 - 24 (1989)
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.
Synthesis of 2-Azidomethyl-5-ethynylfuran: A New Bio-Derived Self-Clickable Building Block
Karlinskii, Bogdan Ya.,Romashov, Leonid V.,Galkin, Konstantin I.,Kislitsyn, Pavel G.,Ananikov, Valentine P.
, p. 1235 - 1242 (2019)
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.
5-(Chloromethyl)furfural production from glucose: A pioneer kinetic model development exploring the mechanism
Antonyraj, Churchil A.,Chennattussery, Amal J.,Haridas, Ajit
supporting information, p. 825 - 833 (2021/03/18)
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.
