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.
The Vilsmeier reaction: A new synthetic method for 5-(chloromethyl)-2-furaldehyde
Sanda,Rigal,Delmas,Gaset
, p. 541 - 542 (1992)
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%).
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.
AN IMPROVED METHOD FOR THE CONVERSION OF SACCHARIDES INTO FURFURAL DERIVATIVES
Hamada, Kazuhiko,Yoshihara, Hiroshi,Suzukamo, Gohfu
, p. 617 - 618 (1982)
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.
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.
The potential of microwave technology for the recovery, synthesis and manufacturing of chemicals from bio-wastes
Budarin, Vitaliy L.,Shuttleworth, Peter S.,De Bruyn, Mario,Farmer, Thomas J.,Gronnow, Mark J.,Pfaltzgraff, Lucie,Macquarrie, Duncan J.,Clark, James H.
, p. 80 - 89 (2015)
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.
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.
Microwave heating for rapid conversion of sugars and polysaccharides to 5-chloromethyl furfural
Breeden,Clark,Farmer,MacQuarrie,Meimoun,Nonne,Reid
, p. 72 - 75 (2013)
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.
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.
Processed Lignin as a Byproduct of the Generation of 5-(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material
Budarin, Vitaliy L.,Clark, James H.,Henschen, Jonatan,Farmer, Thomas J.,Macquarrie, Duncan J.,Mascal, Mark,Nagaraja, Gundibasappa K.,Petchey, Tabitha H. M.
, p. 4172 - 4179 (2015)
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.
