67-47-0Relevant articles and documents
Synthesis of hydroxymethylfurfural from sucrose using Br?nsted-Lewis acidic ionic liquid
Yao, Lin,Liu, Shiwei,Li, Lu,Yu, Shitao,Liu, Fusheng,Song, Zhanqian
, p. 283 - 288 (2016)
The synthesis of 5-hydroxymethylfurfural (HMF) from sucrose was investigated in the presence of the Br?nsted-Lewis acidic ionic liquids (ILs). It was concluded that IL 1-(3-sulfonic acid)-propyl-3-methylimidazole chlorochrominate [HO3S-(CH2)3-mim]Cl-CrCl3 (molar fraction of CrCl3 x = 0.55) had a good catalytic performance with 78.8% yield of HMF. The acid type of IL played a significant role in the reaction. Lewis acid site acted more effectively than its Br?nsted counterpart and a synergetic effect of Br?nsted and Lewis acid sites enhanced the IL catalytic performance. The reusability of IL was good.
Practical synthesis of mumefural, a component of Japanese apricot juice concentrate
Sugimura, Hideyuki,Kikuchi, Mao,Kato, Saori,Sekita, Wataru,Sasaki, Ikuo
, p. 7638 - 7641 (2016)
A practical four-step method for the synthesis of mumefural from malic acid is described. The key step of this method involves the alkylation of acetal-protected malic acid with bromoacetate, followed by condensation with 5-(hydroxymethyl)furfural. Some of the13C NMR data for our products differed from those previously reported, and further analysis indicated that the previously reported assignments were partly erroneous.
Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose
Yong, Gen,Zhang, Yugen,Ying, Jackie Y.
, p. 9345 - 9348 (2008)
(Chemical Equation Presented) A sweet conversion! A NHC-Cr/ionic liquid system has achieved excellent efficiency and the highest 5-hydroxymethylfurfural (1; see scheme; NHC=N-heterocyclic carbene) yields reported thus far for both fructose and glucose feedstocks. The catalyst and ionic liquid are tolerant of high substrate loading and can be recycled after extraction of the product.
Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems
Shi, Xian-Lei,Lin, Huikun,Tao, Minli,Zhang, Wenqin,Zhang, Min,Li, Yongdan
, p. 572 - 578 (2015)
A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxyme-thylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor.
A selective and economic carbon catalyst from waste for aqueous conversion of fructose into 5-hydroxymethylfurfural
Deng, Tiansheng,Li, Jiangong,Yang, Qiqi,Yang, Yongxing,Lv, Guangqiang,Yao, Ying,Qin, Limin,Zhao, Xianlong,Cui, Xiaojing,Hou, Xianglin
, p. 30160 - 30165 (2016)
It is of vital importance to design stable and selective heterocatalysts for aqueous production of platforms from biomass-derived sugars. This paper describes a selective aqueous conversion of fructose to HMF using carbon catalysts from pulping waste sodium ligninsulfonate (SLS). The effect of carbonization atmospheres (N2 flow, static air and air flow) on the structure, porosity, compositions and acidic properties of carbon catalysts were investigated by thermogravimetry-mass spectrum analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Boehm titrations, N2 adsorption–desorption isotherms and elemental analysis. The carbonization in air flow favored the formation of more oxygen-containing functional groups and micropores, while more sulfonic groups and meso-/macro-pores were formed during carbonization in a static air atmosphere. Both oxygen- and sulfur-containing groups were acid sites, and their total amount was the largest when carbonized in air flow, followed by static air and N2 flow. The positive correlation between the acid amounts and fructose conversion of carbon catalysts clearly demonstrated the catalytic effect of the acid sites. The steric hindrance of micropores in carbon catalysts restricted the formation of humins and promoted the HMF selectivity compared with meso-/macro-pores.
Aluminum doped solid acid with suitable ratio of Br?nsted and Lewis acid sites synthesized by electric-flocculation of phosphotungstic acid via hydrothermal treatment for producing 5-hydroxymethylfurfural from glucose
Wang, Xin,Lv, Tao,Wu, Minghui,Sui, Junwei,Liu, Qing,Liu, Huan,Huang, Jiaojiao,Jia, Lishan
, p. 87 - 96 (2019)
Novel solid acid catalyst PWAl-200 was synthesized by a new green method of electric-flocculation of phosphotungstic acid (PW) with aluminum as electrodes to transform glucose to 5-hydroxymethylfurfural (5-HMF). Through electric-flocculation, PW was deposited in the hydrated aluminum received from electrolysis. Then the obtained floc was treated by hydrothermal process to get solid acid. Characterization results showed that after electric-flocculation, the electron-withdrawing influence of terminal W[dbnd]O in the PW on hydrated aluminum formed Lewis (L) acid sites on these six-coordinated aluminum. The H+ derived from PW could supply Br?nsted (B) acid sites. In the further hydrothermal treatment, hydrated aluminum dehydrated to produce reformed six-coordinated aluminum. It was linked to heteropoly anions ligands through oxygen bridges, producing more L acid center. Besides, four-coordinated aluminum formed from the hydrated aluminum. The positive charge it produced increased L acid sites due to the strong effect of nearby tungsten species, further adjusting to a moderate ratio of Lewis/Br?nsted (L/B) on solid acid for catalytic synthesis 5-HMF from glucose. The highest yield was 61.7% at 170 ℃ for 4 h and the catalyst could be recycled for four times and tend to stabilize.
Levulinic Acid as a Catalyst for the Production of 5-Hydroxymethylfurfural and Furfural from Lignocellulose Biomass
Seemala, Bhogeswararao,Haritos, Victoria,Tanksale, Akshat
, p. 640 - 647 (2016)
Levulinic acid (LA) was used as a catalyst for the first time to produce 5-hydroxymethylfurfural (5-HMF) and furfural (FAL) from pinewood and eucalyptus sawdust in a mono- or biphasic solvent system. 2-Methyltetrahydrofuran was used as a co-solvent with water in different ratios and temperatures (140-200 °C). Highest yields of 5-HMF and FAL were obtained at 180 °C and 2 h reaction time; however, at 160 °C, high yields of C6 and C5 sugars were obtained. Both hydrolysis and dehydration steps were accelerated in the MTHF/water biphasic system compared to pure aqueous phase. In particular, 1:2 w/w ratio of MTHF/water resulted in the highest yield of 5-HMF and FAL, whereas 2:1 w/w ratio showed highest yield of C6 and C5 sugars. Increasing the ratio of MTHF/water resulted in a higher fraction of dehydrated products extracted into the organic phase. LA as a catalyst is beneficial because it is miscible in both the phases and the presence of LA favours the equilibrium towards 5-HMF production.
Efficient process for the direct transformation of cellulose and carbohydrates to 5-(hydroxymenthyl)furfural with dual-core sulfonic acid ionic liquids and co-catalysts
Shi, Jincai,Gao, Haiyan,Xia, Yongmei,Li, Wei,Wang, Haijun,Zheng, Changge
, p. 7782 - 7790 (2013)
The direct transformation of cellulose and carbohydrates into 5-(hydroxymethyl)furfural (HMF) in the solvent [BMIM]Cl using dual-core sulfonic acid ionic liquids (ILs) as catalysts and metal salts as co-catalysts was investigated, aiming at a more environmentally friendly process not involving chromium. From the high throughput screening of various metal salts, a combination of [bi-C3SO3HMIM][CH3SO 3] (IL-2) and manganese chloride (MnCl2) was found to be the most effective catalyst. HMF was directly afforded from cellulose in 66.5% yield. Thus, synthesis of HMF was successfully performed from cellulose using ILs and MnCl2. Following the principles of green engineering, we recycled the catalyst in our system for cellulose hydrolysis and this catalyst maintained its good performance even after four runs. Furthermore, various sugars and lignocellulosic raw materials could be directly converted into HMF in reasonable yields under these conditions. The mechanism that explains the high activity of ILs in combination with MnCl2 is also proposed.
Conversion of carbohydrates into 5-hydroxymethylfurfural in an advanced single-phase reaction system consisting of water and 1,2-dimethoxyethane
Wang, Shurong,Lin, Haizhou,Chen, Jingping,Zhao, Yuan,Ru, Bin,Qiu, Kunzan,Zhou, Jinsong
, p. 84014 - 84021 (2015)
5-Hydroxymethylfurfural (HMF) is a bio-based platform chemical that may be converted into various chemicals and fuels. In the present study, we developed an advanced low-boiling single-phase reaction system for producing HMF from glucose. It consists of water and 1,2-dimethoxyethane (DMOE) and uses AlCl3 as catalyst. Our results show that introduction of DMOE can substantially enhance HMF production because of the polar aprotic solvent effect provided by DMOE. Under optimal conditions, a high HMF yield (58.56%) was obtained. GC-MS of the liquid-phase products revealed that HMF and furans comprised 80% and ～90% of the detected products. Formation of liquid-phase products, including furans, oxygenated aliphatics, cyclopenten-1-ones, and pyrans is discussed. Further study of the humins formed during glucose conversion showed the effective inhibition of humin formation by DMOE. The structure of humins was characterized by FTIR spectroscopy. Finally, HMF production from disaccharides (sucrose, maltose and cellobiose) and polysaccharide (cellulose) using the water-DMOE system resulted in good yields, demonstrating that our single-phase water-DMOE solvent system has good potential use in HMF production from glucose and complex carbohydrates.
Synthesis of 5-hydroxymethylfurural from carbohydrates using large-pore mesoporous tin phosphate
Dutta, Arghya,Gupta, Dinesh,Patra, Astam K.,Saha, Basudeb,Bhaumik, Asim
, p. 925 - 933 (2014)
A large-pore mesoporous tin phosphate (LPSnP-1) material has been synthesized hydrothermally by using Pluronic P123 as the structure-directing agent. The material is composed of aggregated nanoparticles of 10-15nm in diameter and has a BET surface area of 216m2 g-1 with an average pore diameter of 10.4nm. This pore diameter is twice as large as that of mesoporous tin phosphate materials synthesized through the surfactant- templating pathways reported previously. LPSnP-1 shows excellent catalytic activity for the conversion of fructose, glucose, sucrose, cellobiose, and cellulose to 5-hydroxymethylfurfural (HMF) in a water/methyl isobutyl ketone biphasic solvent to give maximum yields of HMF of 77, 50, 51, 39, and 32mol %, respectively, under microwave-assisted heating at 423K. Under comparable reaction conditions, LPSnP-1 gives 12 % more HMF yield than a small-pore mesoporous tin phosphate catalyst that has an identical framework composition. This confirms the beneficial role of large mesopores and nanoscale particle morphology in catalytic reactions that involve bulky natural carbohydrate molecules. Sugar to fuel: A large-pore mesoporous tin phosphate material is synthesized hydrothermally by using Pluronic triblock copolymer as the template. This material shows high thermal stability and catalyzes naturally abundant carbohydrates in the aqueous phase to 5-hydroxymethylfurfural, which is a potential bio-based platform chemical to produce a broad range of chemicals and liquid transportation fuels.
