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JOURNAL OF ORGANIC CHEMISTRY · 2021 · IF 4.354

Preparation of 4-(Nitromethyl)furan Derivatives and Their Application in the Syntheses of Bis(furan-2-yl)oximes

Yinbo Wan,Yang Zhu,Haiyun Peng,Guisheng Deng

An efficient method for the preparation of tetrasubstituted furans, which contains a nitromethyl group at the 4-position, has been developed. The applications of 4-(nitromethyl)furans on the synthesis of highly functionalized bis(furyl)oxime were explored for the first time.

研究领域: 有机化学 · 药物化学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2018 ·Vol. 36 ·期 6 ·720-727 · IF 2.016

From Furan to High Quality Bio-based Poly(ethylene furandicarboxylate)

Wang Jing-Gang,Liu Xiao-Qing,Zhu Jin

2,5-Furandicarboxylic acid (2,5-FDCA) has been regarded as the ideal bio-based alternative to terephthalic acid (TPA). In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods: (1) oxidation of 5-hydroxymethylfurfural (HMF) in the presence of complex biocatalyst or metallic catalyst; (2) conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly(ethylene furandicarboxylate) (PEF) of high quality in terms of high molecular weight and good appearance.

研究领域: 化学工程 · 材料科学 · 生物技术
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FOOD CHEMISTRY · 2020 · IF 6.306

Furfuryl alcohol is a precursor for furfurylthiol in coffee

Christoph Cerny,Hedwig Schlichtherle-Cerny,Romelo Gibe,Yuan Yuan

This study investigated the role of furfuryl alcohol (FFA) in the formation of furfurylthiol (FFT), the most important odorant in roasted coffee, using in-bean and spiking experiments. Green beans were spiked with FFA, and after roasting FFT was quantified by stable isotope dilution analysis. The FFT level in the roasted beans increased dose-dependently with addition of FFA. Additionally, beans were spiked with isotopically labelled d 2 -FFA which generated isotopically labelled d 2 -FFT after roasting. However, no labelled furfural was observed. The results unambiguously show that FFA serves as a precursor of FFT in coffee. On the other hand, the data indicate that furfural stems not from oxidation of FFA and plays no major role as precursor for FFT formation during coffee roasting. The suggested formation pathway leads from FFA to the furfuryl cation, then protein-bound S-furfuryl- l -cysteine and by subsequent elimination to FFT.

CAS / MDL: 14128-54-2
研究领域: 食品科学 · 化学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2023 · IF 5.2

Selective hydrogenation of furfural to furfuryl alcohol through hydrogenation spillover over amorphized HA zeolite encapsulated platinum clusters

Pai Peng,Yaning Yue,Mengxi Han,Jun Shi,Jing Yang,Junwen Chen,Qiang Chen

Design of heterogeneous catalyst to achieve efficient conversion of biomass to high added-value chemicals is still very attractive. Herein, taking industrially important selective hydrogenation of furfural to furfuryl alcohol as an example, the designed amorphized HA zeolite encapsulation of platinum clusters (denoted as Pt@HA) exhibited excellent catalytic selectivity at totally conversion of the reactant furfural, along with good reusability and poison resistance ability. The selected amorphized HA zeolite with very small pore size constrained the reactant furfural to be reacted through hydrogen spillover process at zeolite surface, instead of to be adsorbed and activated onto Pt surface. Resulting from the stronger interaction between nucleophilic oxygen atom of aldehyde group and acid site at HA zeolite surface than that of furan ring group, furfural preferred to adsorb onto Pt@HA surface with the end of aldehyde group rather than the end of furan ring group, thus facilitating the spilled H atom to react with aldehyde group to give desired furfuryl alcohol product exclusively.

研究领域: 催化化学 · 生物质转化 · 材料科学
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FUEL · 2015 · IF 3.52

Catalytic upgrading of renewable furfuryl alcohol to alkyl levulinates using AlCl3 as a facile, efficient, and reusable catalyst

Lincai Peng,Xueying Gao,Keli Chen

The use of various aluminum salts as acid catalysts was compared in terms of catalytic upgrading of renewable furfuryl alcohol in hot ethanol medium. The commercially available AlCl 3 was emerged as a simple, cheap, and efficient catalyst for the synthesis of ethyl levulinate. From this study, four significant parameters including AlCl 3 dosage, furfuryl alcohol concentration, temperature, and time were evaluated and modeled to determine the optimal combination via response surface methodology with a central composite rotatable design. All parameters influenced the formation of ethyl levulinate—the maximum yield was 95.7% (100% furfuryl alcohol conversion). AlCl 3 could be recovered efficiently and reused multiple times without substantial loss of its catalytic activity. Moreover, AlCl 3 as the catalyst with optimized conditions was appropriate for the alcoholysis of furfuryl alcohol in other linear alcohols to afford equally high yields of the corresponding alkyl levulinates.

CAS / MDL: 7446-70-0
研究领域: 化学工程 · 可再生能源 · 催化科学
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FLUID PHASE EQUILIBRIA · 2021 · IF 2.775

Research on the liquid thermal conductivity of three alternative fuels: Tetrahydrofuran, 2-methylfuran and 2,5- dimethylfuran

Jing Fan,Peng Liu,Zhiqiang Gao,Fenhong Song

As renewable clean bio-fuels, furan fuels, which are usually named the second generation biodiesel, have attracted the extensive attention from the academic world. This work, the experiment research on the thermal conductivity of three furan fuels (Tetrahydrofuran, 2-Methylfuran, 2,5-Dimethylfuran) in the liquid phase has been completed, and the experimental thermal conductivity data of three chemicals are reported under the pressure up to 15 MPa for the first time. The experimental results had a combined expanded uncertainty of better than ± 2.0 % (in the 0.95 confidence level).

研究领域: 化学工程 · 可再生能源 · 热力学
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ACS Sustainable Chemistry & Engineering · 2017 · IF 5.951

Efficient Synthesis of Furfuryl Alcohol from H2-Hydrogenation/Transfer Hydrogenation of Furfural Using Sulfonate Group Modified Cu Catalyst

Wanbing Gong,Chun Chen,Yong Zhang,Hongjian Zhou,Huimin Wang,Haimin Zhang,Yunxia Zhang,Guozhong Wang,Huijun Zhao

A copper-based catalyst, which was supported by sulfonate group (−SO3H) grafted active carbon (AC), was prepared and activated simultaneously by liquid phase chemical reduction method. The modified copper catalyst, Cu/AC–SO3H, displayed an enhanced catalytic performance for selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) in liquid phase, in which almost 100% FOL yield was obtained at 378 K and 0.4 MPa of hydrogen pressure after 120 min reaction. The effect of −SO3H was evaluated and illustrated by the combination of reaction performance and physicochemical characterizations, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectrometer (XPS) measurements. Through grafting sulfonate group on the support, better dispersion of nanoparticles, higher reduction degree of Cu, and stronger adsorption of FAL can be attained to contribute high hydrogenation performance. In addition, the effects of reaction conditions (such as reaction temperature, H2 pressure, reaction time, solvent, and catalyst to FAL mass ratio) were evaluated intensively. Also, the Cu/AC–SO3H catalyst showed an excellent catalytic performance for transfer hydrogenation of FAL, in which 2-propanol was utilized as the solvent and hydrogen donor concurrently. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reduced catalytic activity of hydrogenation.

研究领域: 化学工程 · 催化科学
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Frontiers in Bioengineering and Biotechnology · 2023 · IF 5.7

Efficient synthesis of furfurylamine from biomass via a hybrid strategy in an EaCl:Gly–water medium

He Wei,He Yu-Cai,Ye Jianren

The objective of this work was to develop an efficient approach for chemoenzymatically transforming biomass to furfurylamine by bridging chemocatalysis and biocatalysis in a deep eutectic solvent of EaCl:Gly–water. Using hydroxyapatite (HAP) as support, heterogeneous catalyst SO42−/SnO2–HAP was synthesized for transforming lignocellulosic biomass into furfural using organic acid as a co-catalyst. The turnover frequency (TOF) was correlated with the pKa value of the used organic acid. Corncob was transformed by oxalic acid (pKa = 1.25) (0.4 wt%) plus SO42−/SnO2–HAP (2.0 wt%) to produce furfural with a yield of 48.2% and a TOF of 6.33 h-1 in water. In deep eutectic solvent EaCl:Gly–water (1:2, v/v), co-catalysis with SO42−/SnO2–HAP and oxalic acid was utilized to transform corncob, rice straw, reed leaf, and sugarcane bagasse for the production of furfural with the yield of 42.4%–59.3% (based on the xylan content) at 180°C after 10 min. The formed furfural could be efficiently aminated to furfurylamine with E. coli CCZU-XLS160 cells in the presence of NH4Cl (as an amine donor). As a result of the biological amination of furfural derived from corncob, rice straw, reed leaf, and sugarcane bagasse for 24 h, the yields of furfurylamine reached >99%, with a productivity of 0.31–0.43 g furfurylamine per g xylan. In EaCl:Gly–water, an efficient chemoenzymatic catalysis strategy was employed to valorize lignocellulosic biomass into valuable furan chemicals.

研究领域: 生物化学 · 催化化学
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CATALYSIS LETTERS · 2020 ·Vol. 151 ·期 6 ·1834-1841 · IF 2.482

A Hybrid Catalytic Conversion of Corncob to Furfurylamine in Tandem Reaction with Aluminium-Based Alkaline-Treated Graphite and ω-Transaminase Biocatalyst in γ-Valerolactone–Water

Feng Xiaoqing,Zhang Lin,Zhu Xuan,Xia Yan,Ma Cuiluan,Liang Jianguang,He Yu-Cai

Furfurylamine is an important furfural-upgrading biobased chemical for the production of pharmaceuticals, biofuels, fibers, additives, polymers, etc. In one-pot reaction system, biomass was tandemly catalyzed to furfurylamine with aluminium-based alkaline-treated graphite (Al-AG) catalyst and recombinant ω-transaminase biocatalyst. Al-AG (3.6 wt%) catalyzed corncob (75.0 g/L) to 110.0 mM furfural at 56.8% yield (based on xylan in corncob) in γ-valerolactone–water (1:4, v:v; pH 1.0) for 40 min at 180 °C. The pH-adjusted corncob-slurry (pH 7.5) containing furfural were catalyzed to furfurylamine at high yield with γ-valerolactone-tolerant Aspergillus terreus ω-transaminase biocatalyst at 35 °C using isopropylamine (3 mol isopropylamine/mol furfural) as amine donor. Such an efficient and sustainable approach for catalytic conversion of biomass to high-value-added biobased furfurylamine was successfully established in tandem reaction with Al-AG and ω-transaminase biocatalyst. Graphic Abstract

研究领域: 生物化学 · 催化化学 · 可再生资源
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Frontiers in Chemistry · 2020 · IF 3.693

Selective Biosynthesis of Furoic Acid From Furfural by Pseudomonas Putida and Identification of Molybdate Transporter Involvement in Furfural Oxidation

Zheng Zhaojuan,Xu Qianqian,Tan Huanghong,Zhou Feng,Ouyang Jia

Upgrading of furanic aldehydes to their corresponding furancarboxylic acids has received considerable interest recently. Herein we reported selective oxidation of furfural (FAL) to furoic acid (FA) with quantitative yield using whole-cells of Pseudomonas putida KT2440. The biocatalytic capacity could be substantially promoted through adding 5-hydroxymethylfurfural into media at the middle exponential growth phase. The reaction pH and cell dosage had notable impacts on both FA titer and selectivity. Based on the validation of key factors for FAL conversion, the capacity of P. putida KT2440 to produce FAL was substantially improved. In batch bioconversion, 170 mM FA was produced with selectivity nearly 100% in 2 h, whereas 204 mM FA was produced with selectivity above 97% in 3 h in fed-batch bioconversion. Particularly, the role of molybdate transporter in oxidation of FAL and 5-hydroxymethylfurfural was demonstrated for the first time. The furancarboxylic acids synthesis was repressed markedly by destroying molybdate transporter, which implied Mo-dependent enzyme/molybdoenzyme played pivotal role in such oxidation reactions. This research further highlights the potential of P. putida KT2440 as next generation industrial workhorse and provides a novel understanding of molybdoenzyme in oxidation of furanic aldehydes.

CAS / MDL: 7789-75-5 59-30-3
研究领域: 微生物学 · 生物化学 · 工业生物技术
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Microorganisms · 2020 ·Vol. 8 ·期 8 ·1190 · IF 4.152

Biodegradation of Tetrahydrofuran by the Newly Isolated Filamentous Fungus Pseudallescheria boydii ZM01

Hao Ren,Hanbo Li,Haixia Wang,Hui Huang,Zhenmei Lu

Tetrahydrofuran (THF) is widely used as a precursor for polymer syntheses and a versatile solvent in industries. THF is an environmental hazard and carcinogenic to humans. In the present study, a new THF-degrading filamentous fungus,Pseudallescheria boydiiZM01, was isolated and characterized. Strain ZM01 can tolerate a maximum THF concentration of 260 mM and can completely degrade 5 mM THF in 48 h, with a maximum THF degradation rate of 133.40 mg THF h−1g−1dry weight. Growth inhibition was not observed when the initial THF concentration was below 150 mM, and the maximum THF degradation rate was still maintained at 118.21 mg THF h−1g−1dry weight at 50 mM THF, indicating the great potential of this strain to degrade THF at high concentrations. The initial key metabolic intermediate 2-hydroxytetrahydrofuran was detected and identified by gas chromatography (GC) analyses for the first time during the THF degradation process. Analyses of the effects of initial pH, incubation temperature, and heavy metal ions on THF degradation revealed that strain ZM01 can degrade THF under a relatively wide range of conditions and has good degradation ability under low pH and Cu2+stress, suggesting its adaptability and applicability for industrial wastewater treatment.Keywords:tetrahydrofuran;Pseudallescheria boydii;2-hydroxytetrahydrofuran;biodegradation

研究领域: 环境科学 · 微生物学
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Reaction Chemistry & Engineering · 2022 ·Vol. 8 ·期 2 ·377-388 · IF 5.2

Continuous conversion of furfural to furfuryl alcohol by transfer hydrogenation catalyzed by copper deposited in a monolith reactor

Tiefu Li,Jiaming Liu,Zipeng Li,Peng Zhang,Yunlong Yao,Zhichao Sun,Yao Wang,Ying-Ya Liu,Anjie Wang

A monolith reactor was fabricated by growing carbonaceous fibers in a copper tube (i.d. 2 mm) via copper-catalyzed acetylene polymerization. The fibers were oxidized with air to convert CC bonds to CO bonds and to improve hydrophilicity. –SO3H groups were anchored on the surface by amination. Cu species were introduced by deposition and subsequent reduction. The resultant Cu/CF-SO3H monolith reactor was used to continuously and selectively convert furfural to furfuryl alcohol. At 180 °C, the monolith catalytic reactor performed significantly and stably in a 500 h run, maintaining a 100% conversion with a >99% selectivity. Additionally, the monolith reactor also performed well in continuous transfer hydrogenation of other α,β-unsaturated compounds, including 5-hydroxymethyl-2-furaldehyde, benzaldehyde, and cyclohexanone.

研究领域: 化学工程 · 催化科学
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