10551-58-3Relevant articles and documents
Trienamines derived from 5-substituted furfurals: Remote ε-functionalization of 2,4-dienals
Coelho, Jaime A. S.,Trindade, Alexandre F.,Andr, Vnia,Teresa Duarte,Veiros, Luis F.,Afonso, Carlos A.M.
, p. 9324 - 9328 (2014)
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.
Selective oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by polymer-supported IBX amide
Yoon, Hyo-Jin,Choi, Jung-Woo,Jang, Hyung-Seok,Cho, Jin Ku,Byun, Jang-Woong,Chung, Woo-Jae,Lee, Sang-Myung,Lee, Yoon-Sik
, p. 165 - 168 (2011)
5-Hydroxymethyl-2-furfural (HMF) was selectively converted to 2,5-diformylfuran (DFF) under mild conditions by polymer-supported IBX amide reagent, thus providing a new platform for the production of highly valuable chemicals from biomass. Georg Thieme Verlag Stuttgart New York.
Design, Synthesis, and Biological Evaluation of Ester and Ether Derivatives of Antisickling Agent 5-HMF for the Treatment of Sickle Cell Disease
Xu, Guoyan G.,Pagare, Piyusha P.,Ghatge, Mohini S.,Safo, Ronni P.,Gazi, Aheema,Chen, Qiukan,David, Tanya,Alabbas, Alhumaidi B.,Musayev, Faik N.,Venitz, Jürgen,Zhang, Yan,Safo, Martin K.,Abdulmalik, Osheiza
, p. 3499 - 3511 (2017)
Candidate drugs to counter intracellular polymerization of deoxygenated sickle hemoglobin (Hb S) continue to represent a promising approach to mitigating the primary cause of the pathophysiology associated with sickle cell disease (SCD). One such compound is the naturally occurring antisickling agent, 5-hydroxymethyl-2-furfural (5-HMF), which has been studied in the clinic for the treatment of SCD. As part of our efforts to develop novel efficacious drugs with improved pharmacologic properties, we structurally modified 5-HMF into 12 ether and ester derivatives. The choice of 5-HMF as a pharmacophore was influenced by a combination of its demonstrated attractive hemoglobin modifying and antisickling properties, well-known safety profiles, and its reported nontoxic major metabolites. The derivatives were investigated for their time- and/or dose-dependent effects on important antisickling parameters, such as modification of hemoglobin, corresponding changes in oxygen affinity, and inhibition of red blood cell sickling. The novel test compounds bound and modified Hb and concomitantly increased the protein affinity for oxygen. Five of the derivatives exhibited 1.5- to 4.0-fold higher antisickling effects than 5-HMF. The binding mode of the compounds with Hb was confirmed by X-ray crystallography and, in part, helps explain their observed biochemical properties. Our findings, in addition to the potential therapeutic application, provide valuable insights and potential guidance for further modifications of these (and similar) compounds to enhance their pharmacologic properties.
Cellulose acetate as a convenient intermediate for the preparation of 5-acetoxymethylfurfural from biomass
Gavilà, Lloren?,Esposito, Davide
, p. 2496 - 2500 (2017)
5-Acetoxymethylfurfural (AMF) is an important biomass derived platform chemical related to 5-hydroxymethylfurfural. Such furanic compounds can be produced via the hydrolysis of cellulose followed by dehydration of the resulting glucose units. However, the integration of these reactions in a single process remains technically challenging, and the direct use of monosaccharides is often preferred. In this work we report a new method for the synthesis of AMF based on the acetolysis of cellulose acetate in the presence of sulfuric acid. The strategy was optimized for both batch and continuous processing. Furthermore, cellulose acetate prepared by direct wood acetylation could be successfully applied as a precursor, proving the method as a robust solution for integrated biomass processing.
From lignocellulosic biomass to furans via 5-acetoxymethylfurfural as an alternative to 5-hydroxymethylfurfural
Kang, Eun-Sil,Hong, Yeon-Woo,Chae, Da Won,Kim, Bora,Kim, Baekjin,Kim, Yong Jin,Cho, Jin Ku,Kim, Young Gyu
, p. 1179 - 1188 (2015)
A facile pathway to furan derivatives from lignocellulosic biomass via 5-acetoxymethylfurfural (AMF) was developed. AMF possesses advantageous properties due to its less-hydrophilic acetoxymethyl group relative to the hydroxymethyl group of 5-hydroxymethylfurfural (HMF). The hydrophobicity and chemical stability of AMF allowed practical isolation and purification to afford a highly pure product of up to 99.9 %. AMF was produced in good to excellent yields under mild conditions from 5-chloromethylfurfural (CMF) and alkylammonium acetates, both of which could be obtained directly from lignocellulosic biomass. Heterogeneous reactions with polymer-supported alkylammonium acetates were also established; this showed the feasibility of a continuous process for this pathway. AMF could be transformed into various promising furanic compounds, such as 2,5-furandicarboxylic acid (FDCA), 2,5-furandimethanol (FDM), and 5-hydroxymethyl-2-furanoic acid (HFA), in high yields.
Diversified upgrading of HMF via acetylation, aldol condensation, carboxymethylation, vinylation and reductive amination reactions
Perosa, Alvise,Polidoro, Daniele,Rigo, Davide,Selva, Maurizio
, (2021)
Multiple sustainable methodologies were developed for the chemical upgrading of HMF: i) at 30–90 °C, highly selective base-catalyzed acetylation and carboxymethylation reactions of HMF with nontoxic reagents as isopropenyl acetate (iPAc) and dimethyl carbonate (DMC) were achieved to prepare the corresponding ester and carbonate products, (5-formylfuran-2-yl)methyl acetate (5-formylfuran-2-yl) methyl carbonate, respectively; ii) based on the combined use of iPAc/DMC with acetone, a tandem protocol of acetylation/transcarbonation and aldol condensation was designed to synthesize a variety of HMF-derived α,β-unsaturated carbonyl compounds; iii) in water as a solvent, a chemoselective Pd-catalysed reductive amination of HMF with amino-alcohols also including glycerol derivatives, was developed using H2 at atmospheric pressure; iv) finally, both HMF and its ester and carbonate products successfully underwent Wittig vinylation reactions promoted by a methyl carbonate phosphonium salt ( [Ph3PCH3] [CH3OCO2]), to obtain the corresponding olefins. The vinylation reagent (the salt) was a DMC derivative. In all cases i-iv), not only processes occurred under mild conditions, but post-reaction procedures (work-up and purification) were optimized to isolate final products in high yields of 85–98%.
Conversion of D-fructose to 5-acetoxymethyl-2-furfural Using Immobilized Lipase and Cation Exchange Resin
Huynh, Nhan Thanh Thien,Lee, Kyung Won,Cho, Jin Ku,Kim, Yong Jin,Bae, Se Won,Shin, Jong Shik,Shin, Seunghan
, (2019)
5-Acetoxymethyl-2-furfural (AMF) was prepared from D-fructose via 1,6-diacetylfructose (DAF) through a simple two-step reaction pathway. Immobilized enzyme (Novozym 435) was found to be the best enzymatic catalyst for the trans-esterification step (yielding 94.6% DAF). In the dehydration step, while soluble H2SO4 was found to be the best acidic catalyst (yielding 86.6% AMF), we opted to utilize heterogeneous cation exchange resin (Amberlyst 15) together with recyclable industrial solvents (1,4-dioxane) for a more sustainable AMF synthesis procedure. Although the total yield of AMF was a little lower, both the enzyme and the solid acid catalyst could be recycled for five cycles without a significant loss of activity, which has a major contribution to the cost-efficient aspect of the entire process.
Conversion of Furfural Derivatives to 1,4-Pentanediol and Cyclopentanol in Aqueous Medium Catalyzed by trans-[(2,9-Dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2
Banz Chung, Elise M.-J.,Da Cunha, Igor Tadeu,Magee, Megan,Moore, Cameron M.,Schlaf, Marcel,Soltanipanah, Parnian,Stones, Maryanne K.,Sullivan, Ryan J.,Sutton, Andrew D.,Umphrey, Gary J.
, p. 2667 - 2683 (2020)
The complex trans-[(2,9-dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2 was synthesized and tested as a homogeneous hydrodeoxygenation catalyst for the conversion of biomass-derived furfuryl alcohol and furfuryl acetate to 1,4-pentanediol (as the primary target compound) and cyclopentanol (formed by the competing Piancatelli rearrangement) in aqueous reaction medium at elevated temperature (150-200 °C) and hydrogen pressure (800 psi = 5.12 MPa). Catalytic reactions using furfuryl alcohol as a substrate were limited by the formation of solid resins with the product yields showing a strong negative correlation with increasing substrate concentration and maximum yields of 1,4-pentanediol and cyclopentanol being 23 and 41%, respectively. A two-level full factorial design of experiments study with four independent input variables (temp., time, [cat.], [substrate]) and a center point was carried out for the conversion of furfuryl acetate, showing good reproducibility between replicates and no humin formation. This enabled a full statistical analysis of the input variable impact on product distribution and yield. The maximum yields of 1,4-pentanediol and cyclopentanol using furfuryl acetate as a substrate are 68 and 35%, respectively. The decreased self-reactivity of furfuryl acetate versus furfuryl alcohol dramatically increases the yields of target products but still shows a strong negative correlation of the yield of the desired products with increasing substrate concentration.
Method For Manufacturing 2,5-Furan dicarboxylic acid using 5-Acetoxymethyl-2-furaldehyde
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Paragraph 0090; 0094-0097, (2021/07/01)
The present invention relates to a method for producing fructose acetoxymethyl 5 - furfuraldehyde (5-2 -2-acetoxymethyl, furaldehyde) using an intermediate produced through a dehydration reaction of fructosins (AMF). And/or) of 5 - acetoxymethyl -2 - furfuraldehyde (AMF) to prepare 2, 5 - furandicarboxylic acid (2, 5-Furan dicarboxylic acid, FDCA). A method for preparing 5 -furandicarboxylic acid (-2 -) using AMF acetoxymethyl 2, 5 - furfuraldehyde (FDCA) is provided.
Dicarboxyl acid aromatic heterocyclic compound and method for preparing thereof
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Paragraph 0299-0307; 0324-0333, (2021/10/15)
The present invention relates to a method for preparing a dicarboxylic acid aromatic heterocyclic compound and a dicarboxylic acid aromatic heterocyclic composition obtained therefrom. To the present invention, a bio-based hydroxyl - free aromatic heterocyclic compound is oxidized under heterogeneous catalysis to produce oxides having improved yield and purity.
