- Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
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Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
- Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
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supporting information
p. 6807 - 6815
(2021/02/01)
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- Selective aqueous-phase hydrogenation of furfural to cyclopentanol over Ni-based catalysts prepared from Ni-MOF composite
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Metal-organic frameworks (MOFs) as an emerging class of porous materials exhibit some unique advantages, including controllable composition, a large surface area, high porosity, and so on. In this work, the spherical NiMo bimetal catalysts supported on porous carbon matrix were prepared using a simple wet impregnation method and studied for selective hydrogenation of furfural (FFA). Three different catalysts were investigated including Ni/C-Mo-BTC, Ni/C-Mo-DHTA and Ni/C-Mo-PTA. Of the catalysts studied the Ni/C-Mo-BTC catalyst could achieve the highest selectivity of CPL (up to 90%) under moderate reaction conditions (140 °C, 2 MPa, 2 h) in aqueous medium. In addition, other Ni-based catalysts (Ni/C-Fe, Ni/C-Zn, Ni/C-Cu, Ni/C-Ce) were also investigated to achieve yields of 20–70% under the same reaction conditions. The influence of temperature, H2 pressure, time and solvent were investigated for the best performing catalyst. Based on the optimal reaction condition, various of furfural derivatives could also be effectively transferred to produce corresponding products. The detailed physicochemical characterization was carried out by means of XRD, SEM, TEM, XPS, NH3-TPD and Raman analysis. In the end, the optimal Ni/C-Mo0.4 catalyst could be recycled magnetically and efficiently applied in the next run for five consecutive recycling tests in the FFA hydrogenation to CPL. The results suggested Ni/C-Mo0.4 catalyst occurred to increasingly favor the formation of Ni-Mo alloys and suggested a metallic active site in FFA hydrogenation with the addition of element Mo. Mechanism study indicated that water was a key factor contributing to the formation of different desired products, which was responsible for the arrangement of furan compound.
- Chen, Changzhou,Jiang, Jianchun,Li, Jing,Ren, Jurong,Wu, Dichao,Xia, Haihong,Zhou, Minghao
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- Insight into the hydrogenation of pure and crude HMF to furan diols using Ru/C as catalyst
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5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was investigated. Three commercial catalysts, Ru/C, Pd/C and Pt/C, were tested in the hydrogenation of aqueous HMF solutions (2–3 wt%), using a metal loading of 1 wt% respect to HMF content. By appropriate tuning of the process conditions, either BHMF or BHMTHF were obtained in good yields, and Ru/C resulted the best catalyst for this purpose, allowing us to obtain BHMF or BHMTHF yields up to 93.0 and 95.3 mol%, respectively. This catalyst was also tested for in the hydrogenation of a crude HMF-rich hydrolyzate, obtained by one-pot the dehydration of fructose. The influence of each component of this hydrolyzate on the hydrogenation efficiency was investigated, including unconverted fructose, rehydration acids and humins, in order to improve the yields towards each furan diol. Moreover, ICP-OES and TEM analysis showed that the catalyst was not subjected to important leaching and sintering phenomena, as further confirmed by catalyst recycling study.
- Fulignati, Sara,Antonetti, Claudia,Licursi, Domenico,Pieraccioni, Matteo,Wilbers, Erwin,Heeres, Hero Jan,Raspolli Galletti, Anna Maria
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p. 122 - 133
(2019/04/17)
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- Catalytic selective hydrogenation and rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water
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The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone (HCPN) were studied over a MOF-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper dramatically improved the efficiency in both the selective hydrogenation of the carbonyl group of 5-HMF and the hydrogenative ring-rearrangement of the C5 ring, affording 70.3% yield for HCPN and 99.8% yield for the rearrangement products. Moreover, it was indicated that water acted as a solvent, reactant, and proton donor by dissociation at an elevated temperature, which supplied slightly acidic conditions and promoted the rearrangement reaction.
- Zhang, Shujing,Ma, Hong,Sun, Yuxia,Luo, Yang,Liu, Xin,Zhang, Meiyun,Gao, Jin,Xu, Jie
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supporting information
p. 1702 - 1709
(2019/04/08)
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- Rhenium-catalyzed deoxydehydration of renewable triols derived from sugars
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An efficient method for the catalytic deoxydehydration of renewable triols, including those obtained from 5-HMF, is described. The corresponding unsaturated alcohols were obtained in good yields using simple rhenium(vii)oxide under neat conditions and ambient atmosphere at 165 °C.
- Wozniak, Bartosz,Li, Yuehui,Tin, Sergey,De Vries, Johannes G.
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p. 4433 - 4437
(2018/10/17)
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- Hydrogenation of levoglucosenone to renewable chemicals
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We have studied the hydrogenation of levoglucosenone (LGO) to dihydrolevoglucosenone (Cyrene), levoglucosanol (Lgol), and tetrahydrofurandimethanol (THFDM) and elucidated the reaction network over supported palladium catalysts. At low temperature (40 °C) over a Pd/Al2O3 catalyst, LGO is selectively hydrogenated to Cyrene. At intermediate temperatures (100 °C) over a Pd/Al2O3 catalyst, Cyrene is selectively hydrogenated to Lgol, with an excess of the exo-Lgol isomer produced over the endo-Lgol isomer. At higher temperatures (150 °C) over a bifunctional Pd/SiO2-Al2O3 catalyst, Lgol is converted to THFDM in 58% selectivity, with 78% overall selectivity to 1,6-hexanediol precursors. The ratio of cis-THFDM relative to trans-THFDM is approximately 2.5, and this ratio is independent of the Lgol feed stereoisomer ratio. Tetrahydropyran-2-methanol-5-ketone (THP2M5one) and tetrahydropyran-2-methanol-5-hydroxyl (THP2M5H) are side-products of Lgol hydrogenolysis, but neither of these species are precursors to THFDM.
- Krishna, Siddarth H.,McClelland, Daniel J.,Rashke, Quinn A.,Dumesic, James A.,Huber, George W.
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p. 1278 - 1285
(2017/08/15)
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- Application of apatite substance in catalytic hydrogenation and tetrahydrofurfuryl alcohol preparation method
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The invention discloses application of an apatite substance in catalytic hydrogenation and a tetrahydrofurfuryl alcohol preparation method. The method can be used for an alcohol or alkane solvent system, furfural is completely hydrogenated in the hydrogen atmosphere of 0.1-6 MPa at the temperature of 0-200 DEG C under the effects of Pd-HAP prepared from hydroxyapatite and palladium metal by adopting an ion exchange method and other catalysts to generate the tetrahydrofurfuryl alcohol, and the method is provided for efficient utilization of biomass raw materials. The used catalysts can be used for high-conversion-rate and high-yield preparation of tetrahydrofurfuryl alcohol in the alcohol or alkane solvent system, and the conversion rate of the furfural and the yield of the furfural can be up to 100%. The tetrahydrofurfuryl alcohol preparation method is simple, reaction devices are simple, the operation is simple and convenient, a product and the catalysts are easy to separate, the catalysts are cheap and easy to obtain, and the catalysts have good hydrothermal stability and recycling performance, are suitable for industrial production and have a very broad application prospect.
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Paragraph 0099-0101; 0103; 0104
(2017/08/29)
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- SYNTHESIS OF R-GLUCOSIDES, SUGAR ALCOHOLS, REDUCED SUGAR ALCOHOLS, AND FURAN DERIVATIVES OF REDUCED SUGAR ALCOHOLS
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Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.
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Paragraph 0078
(2017/05/31)
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- Tetrahydrofuran compound
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The present invention is a method for producing a tetrahydrofuran compound represented by general formula (2), the method comprising a reaction step for bringing a furan compound represented by general formula (1) into contact with a palladium catalyst in the presence of a hydrogen source. (In formula (1), R is a formyl group or hydroxymethyl group, R1a is a hydrogen atom, C1-5 alkyl group, formyl group, or hydroxymethyl group, R2 and R3 are each independently a hydrogen atom or C1-5 alkyl group, and R1a and R2 or R2 and R3 may bond together to form a ring.) (In formula (2), R1b is a hydrogen atom, C1-5 alkyl group or hydroxymethyl group, R2 and R3 are the same as defined above, and R1b and R2 or R2 and R3 can bond together to form a ring.)
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-
Paragraph 0079; 0080; 0081
(2017/08/30)
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- METHOD FOR PRODUCING TETRAHYDROFURAN COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing a tetrahydrofuran compound having a hydroxymethyl group by suppressing the hydrogenolysis of a hydroxymethyl group in a step of obtaining a tetrahydrofuran compound by reducing a furan compound. SOLUTION: There is obtained a corresponding tetrahydrofuran compound by reducing a furan compound represented by the following general formula (1) by bringing into contact with a palladium catalyst in a hydrogen atmosphere in the coexistence of a base. (wherein, Ra represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group or a hydroxymethyl group; Rb represents a formyl group or a hydroxymethyl group; R1 and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group; and R1 and R2 may be bonded together to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0088; 0090; 0096
(2017/01/17)
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- METHODS OF PRODUCING COMPOUNDS FROM 5-(HALOMETHYL)FURFURAL
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Provided herein are methods of producing compounds, such as cyclohexanone, hexanediamine, hexanediol, hexamethylenediamine, caprolactam and nylon, from 5-(halomethyl)furfural.
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-
Paragraph 0161; 0162
(2016/10/09)
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- Synthesis of 1,6-hexanediol from HMF over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor
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1,6-Hexanediol (1,6-HDO) was effectively prepared from 5-hydroxymethylfurfural (HMF) over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor. Under optimal reaction conditions (373 K, 7.0 MPa H2, in solvent mixtures of 40% water and 60% tetrahydrofuran (THF)), 57.8% yield of 1,6-HDO was obtained. The double-layered catalysts loaded in double-layered beds showed much superior performance compared to that of a single catalyst of Pd-Ir-ReOx/SiO2, even when the same amount of active components were used in the catalysts. The reaction solvent significantly affected product distributions, giving a volcano-shape plot for the 1,6-HDO yield as a function of the ratio of water to THF. Br?nsted acidic sites were generated on the catalyst in the presence of water which played determining roles in 1,6-HDO formation. A high pressure of H2 contributed to 1,6-HDO formation by depressing the over-hydrogenolysis of reaction intermediates and products to form hexane and hexanol. The reaction route was proposed for HMF conversion to 1,6-HDO on the basis of conditional experiments.
- Xiao, Bin,Zheng, Mingyuan,Li, Xinsheng,Pang, Jifeng,Sun, Ruiyan,Wang, Hua,Pang, Xiaoli,Wang, Aiqin,Wang, Xiaodong,Zhang, Tao
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p. 2175 - 2184
(2016/04/19)
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- Production of liquid hydrocarbon fuels with acetoin and platform molecules derived from lignocellulose
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Acetoin, a novel C4 platform molecule derived from new ABE (acetoin-butanol-ethanol) type fermentation via metabolic engineering, was used for the first time as a bio-based building block for the production of liquid hydrocarbon fuels. A series of diesel or jet fuel range C9-C14 straight, branched, or cyclic alkanes were produced in excellent yields by means of C-C coupling followed by hydrodeoxygenation reactions. Hydroxyalkylation/alkylation of acetoin with 2-methylfuran was investigated over a series of solid acid catalysts. Among the investigated candidates, zirconia supported trifluoromethanesulfonic acid showed the highest activity and stability. In the aldol condensation step, a basic ionic liquid [H3N+-CH2-CH2-OH][CH3COO-] was identified as an efficient and recyclable catalyst for the reactions of acetoin with furan based aldehydes. The scope of the process has also been studied by reacting acetoin with other aldehydes, and it was found that abnormal condensation products were formed from the reactions of acetoin with aromatic aldehydes through an aldol condensation-pinacol rearrangement route when amorphous aluminium phosphate was used as a catalyst. And the final hydrodeoxygenation step could be achieved by using a simple and handy Pd/C + H-beta zeolite system, and no or a negligible amount of oxygenates was observed after the reaction. Excellent selectivity was also observed using the present system, and the clean formation of hydrocarbons with a narrow distribution of alkanes occurred in most cases.
- Zhu, Chenjie,Shen, Tao,Liu, Dong,Wu, Jinglan,Chen, Yong,Wang, Linfeng,Guo, Kai,Ying, Hanjie,Ouyang, Pingkai
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supporting information
p. 2165 - 2174
(2016/04/19)
-
- Simultaneous hydrogenation and acid-catalyzed conversion of the biomass-derived furans in solvents with distinct polarities
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Furfural and 5-hydroxymethylfurfural (HMF), the two typical biomass-derived furans, can be converted into biofuels and value-added chemicals via hydrogenation or acid catalysis or both. The potential competition between the hydrogenation and the catalyzed-conversion of HMF and furfural has been investigated with Pd/C and Amberlyst 70 as the catalysts at 170°C in various solvents. In water, the hydrogenation of HMF or the derivatives of HMF could take place, but the acid-catalyzed conversion of HMF to the diketones (2,5-hexanedione) was the dominant reaction pathway. On the contrary, with ethanol as the solvent, the full hydrogenation of HMF to 2,5-tetrahydrofurandimethanol was the dominant route, and the acid-catalyzed routes became insignificant. The efficiency for hydrogenation of HMF was much higher in ethanol than in water. As for furfural, its hydrogenation proceeded more efficiently in the polar solvents (i.e. ethanol, diethyl ether) than in non-polar solvents (i.e. toluene): a polar solvent tended to favor the hydrogenation of the furan ring in furfural over that of the carbonyl group in the same furfural.
- Hu, Xun,Kadarwati, Sri,Song, Yao,Li, Chun-Zhu
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p. 4647 - 4656
(2016/01/29)
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- Upgrading biomass-derived furans via acid-catalysis/hydrogenation: The remarkable difference between water and methanol as the solvent
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In methanol 5-hydroxymethylfurfural (HMF) and furfuryl alcohol (FA) can be selectively converted into methyl levulinate via acidcatalysis, whereas in water polymerization dominates. The hydrogenation of HMF, furan and furfural with the exception of FA is
- Hu, Xun,Westerhof, Roel J. M.,Wu, Liping,Dong, Dehua,Li, Chun-Zhu
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p. 219 - 224
(2018/04/16)
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- METHODS OF PRODUCING COMPOUNDS FROM 5-(HALOMETHYL)FURFURAL
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Provided herein are methods of producing compounds, such as cyclohexanone, hexanediamine, hexanediol, hexamethylenediamine, caprolactam and nylon, from 5- (halomethyl)furfural.
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Paragraph 0162
(2016/04/26)
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- Tailored one-pot production of furan-based fuels from fructose in an ionic liquid biphasic solvent system
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The one-pot catalytic transformation of biomass to useful products is desirable for saving cost and time. The integration of the various reaction steps need to address the presence of incompatible reaction conditions and numerous side reactions. We report a novel process for the one-pot production of furan-based fuels, 2,5-dimethylfuran (DMF) and 2,5-dihmethyltetrahydrofuran (DMTF), from fructose by optimizing the synergic effect of an ionic liquid promoted Ru/C catalyst and the solvent effect. The dehydration of fructose and subsequent in situ hydrodeoxygenation of HMF to DMF and DMTF on Ru/C were enhanced by the use of an ionic liquid and a biphasic [BMIm]Cl/THF solvent. Elemental analysis, X-ray Photoelectron Spectroscopy, Raman spectroscopy and H2-temperature programmed reduction-mass spectroscopy characterization showed that the ionic liquid modified the electronic density of the Ru species to favor HMF in situ hydrodeoxygenation. Moreover, THF served as a reaction-extraction solvent that extracted DMF and DMTF from the reaction layer to avoid further side reactions. A rational design that gave enhancement of the catalytic performance and product protection provides a promising strategy for the one-pot conversion of biomass to desired fuels.
- Li, Changzhi,Cai, Haile,Zhang, Bo,Li, Weizhen,Pei, Guangxian,Dai, Tao,Wang, Aiqin,Zhang, Tao
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p. 1638 - 1646
(2015/09/15)
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- Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-Dimethylfuran
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2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic ZnII and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF.
- Saha, Basudeb,Bohn, Christine M.,Abu-Omar, Mahdi M.
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p. 3095 - 3101
(2015/09/28)
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- Switchable synthesis of 2,5-dimethylfuran and 2,5-dihydroxymethyltetrahydrofuran from 5-hydroxymethylfurfural over Raney Ni catalyst
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Raney-type metals (Cu, Co and Ni) were employed to catalyze hydrogenation of 5-hydroxymethylfurfural. Switchable synthesis of 2,5-dimethylfuran and 2,5-dihydroxymethyltetrahydrofuran was achieved with 96% and 88.5% yield respectively over Raney Ni, demonstrating high feasibility for industrialization. The excellent yields can be explained by the fact that Raney Ni facilitates the hydrogenation reaction but has limited deoxygenation ability at low temperature, while high temperature promotes the deoxygenation step. The reaction pathway was analyzed by time course experiments and HMF hydrogenation over model catalysts was performed. The reaction mechanism related to the respective catalytic sites was discussed and proposed, which has great implications in the design of efficient and non-noble metal catalysts.
- Kong, Xiao,Zhu, Yifeng,Zheng, Hongyan,Dong, Fang,Zhu, Yulei,Li, Yong-Wang
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p. 60467 - 60472
(2015/02/19)
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- CATALYTIC SYNTHESIS OF REDUCED FURAN DERIVATIVES
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The present invention relates to catalytic synthesis of furan derivatives from alkoxymethylfurfural ethers or acyloxymethylfurfural esters. More particularly, the invention pertains to furan derivatives obtained by use of a multifunctional catalyst system to carry out both hydrogenation of furan starting material and hydrolysis of the reduced furan derivative in a single reaction. The process allows recovering and recycling of alcohol or acid from the reaction product.
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Paragraph 0065
(2014/11/13)
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- Palladium/carbon dioxide cooperative catalysis for the production of diketone derivatives from carbohydrates
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The one-pot production of industrially valuable diketone derivatives from carbohydrates is achieved through a bifunctional catalytic process. In particular, Pd/C-catalyzed hydrogenation of HMF in water and under CO 2 affords 1-hydroxypentane-2,5-dione with up to 77 % yield. The process is also eligible starting from fructose and inulin, affording 1-hydroxyhexane-2,5-dione with 36 % and 15 % yield, respectively. The key of the process is reversible in situ formation of carbonic acid, which is capable of assisting Pd/C during the hydrogenation reaction by promoting the dehydration of carbohydrates and the ring-opening of furanic intermediates. Interestingly, by changing the reaction medium from H2O to a H2O/THF mixture (1:9), it is possible to switch the selectivity of the reaction and to produce 2,5-hexanadione with 83 % yield. Within the framework of sustainable chemistry, reactions presented in this report show 100 % carbon economy, involve CO 2 to generate acidity, require water as a solvent, and are conducted under rather low hydrogen pressures (10 bar).
- Liu, Fei,Audemar, Ma?té,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jér?me, Fran?ois
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p. 2089 - 2093
(2014/11/27)
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- Biphasic catalytic conversion of fructose by continuous hydrogenation of HMF over a hydrophobic ruthenium catalyst
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The production of chemicals directly from sugars is an important step in biomass conversion. Herein, tetrahydro-2,5-furandimethanol (THFDM), obtained from fructose, is formed by using a combination of acid and hydrophobic Ru/SiO2 in a water/cyclohexane biphasic system. Two key factors enable the high selectivity towards THFDM: modifying the hydrogenation catalyst so that it has hydrophobic properties, and the continuous hydrogenation of generated 5-(hydroxymethyl)furfural in the cyclohexane phase. Moreover, the selectivity towards THFDM is found to depend strongly on the acid catalyst used. Divide and conquer: A method for direct catalytic conversion of fructose to tetrahydro-2,5-furandimethanol (THFDM) via 5-(hydroxymethyl)furfural (HMF) is reported. High selectivity towards THFDM is achieved by using a catalyst combination of acid and a hydrophobic ruthenium catalyst (Ru/SiO2-TM) in a water/cyclohexane biphasic system by continuous hydrogenation of generated HMF. The use of the hydrophobic Ru/SiO2-TM is the key, as it prevents hydrogenation of fructose to mannitol and sorbitol in the water phase.
- Yang, Yanliang,Du, Zhongtian,Ma, Jiping,Lu, Fang,Zhang, Junjie,Xu, Jie
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p. 1352 - 1356
(2014/06/09)
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- Hydrogenation of 5-hydroxymethylfurfural in supercritical carbon dioxide-water: A tunable approach to dimethylfuran selectivity
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The use of supercritical carbon dioxide-water on the hydrogenation of 5-hydroxymethylfurfural (HMF) was investigated over a Pd/C catalyst. It was possible to achieve a very high yield (100%) of DMF within the reaction time of 2 hours at 80 °C. A significant effect of CO2 pressure was observed on the product distribution. Simply by tuning the CO2 pressure it was possible to achieve various key compound, such as tetrahydro-5-methyl-2-furanmethanol (MTHFM) (10 MPa) with very high selectivity. Optimization of other reaction parameters revealed that H 2 pressure, temperature, as well as the CO2-water mole ratio, played an important role in the selectivity to the targeted DMF. It is interesting to note that a very high yield of DMF was achieved when a combination of CO2 and water was used. For instance, in the absence of water or CO2, the selectivity of DMF was low; similarly, an excess of water against the fixed pressure of CO2 reduced the selectivity to DMF. Hence, an optimized amount of water was mandatory in the presence of CO2 for the formation of DMF with high selectivity. This method was successfully extended to the hydrogenation of furfural, which could afford 100% selectivity to 2-methylfuran with complete conversion within a very short reaction time of 10 min. The studied catalyst could be recycled successfully without significant loss of catalytic activity.
- Chatterjee, Maya,Ishizaka, Takayuki,Kawanami, Hajime
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p. 1543 - 1551
(2014/03/21)
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- Conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts
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The conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts was studied under hydrogen atmosphere. Furfuryl alcohol, 4-hydroxy-2-cyclopentenone and 2-cyclopentenone were verified as three key intermediates. Rearrangement of the furan ring was independent of hydrogenation, starting from furfuryl alcohol rather than furfural. The opening and closure of the furan ring were closely related to the attack of a H2O molecule on the 5-position of furfuryl alcohol. Prior hydrogenation of the aldehyde group accounted for the different reactivity of furfural and furfuryl alcohol. The high selectivity of cyclopentanone was ascribed to the presence of 2-cyclopentenone.
- Yang, Yanliang,Du, Zhongtian,Huang, Yizheng,Lu, Fang,Wang, Feng,Gao, Jin,Xu, Jie
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p. 1932 - 1940
(2013/09/24)
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- Immobilized Ru clusters in nanosized mesoporous zirconium silica for the aqueous hydrogenation of furan derivatives at room temperature
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Ru lonesome tonight? Immobilized ruthenium clusters (50Ru atoms) in nanosized mesoporous zirconium silica were synthesized by using an impregnation method starting from an aqueous solution of RuCl3. The Ru cluster catalysts were thermally stable at 500°C and showed remarkable activity for the hydrogenation of furan derivatives in water at room temperature under 5bar hydrogen pressure.
- Chen, Jiazhi,Lu, Fang,Zhang, Junjie,Yu, Weiqiang,Wang, Feng,Gao, Jin,Xu, Jie
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p. 2822 - 2826
(2013/10/21)
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- Mechanistic study of a one-step catalytic conversion of fructose to 2,5-dimethyltetrahydrofuran
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Carbohydrates, such as fructose, can be fully dehydroxylated to 2,5-dimethyltetrahydrofuran (DMTHF), a valuable chemical and potential gasoline substitute, by the use of a dual catalytic system consisting of HI and RhX 3 (X=Cl, I). A mechanistic study has been carried out to understand the roles that both acid and metal play in the reaction. HI serves a two-fold purpose: HI acts as a dehydration agent (loss of 3 H2O) in the initial step of the reaction, and as a reducing agent for the conjugated carbinol group in a subsequent step. I2 is formed in the reduction step and metal-catalyzed hydrogenation reforms HI. The rhodium catalyst, in addition to catalyzing the reaction of iodine with hydrogen, functions as a hydrogenation catalyst for C=O and C=C bonds. A general mechanistic scheme for the overall reaction is proposed based on identification of intermediates, independent reactions of the intermediates, and deuterium labeling studies. Copyright
- Grochowski, Matthew R.,Yang, Weiran,Sen, Ayusman
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p. 12363 - 12371
(2013/01/14)
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- C-O bond hydrogenolysis of cyclic ethers with OH groups over rhenium-modified supported iridium catalysts
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Hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol and other related substrates such as 3-hydroxytetrahydrofuran and 1,2-cyclohexanediol proceeds over Ir-ReOx/SiO2 catalyst. TOF values are higher than those of Rh-ReOx/SiO2, which has been reported to be an effective catalyst. The selectivity to the product, where the C-O bond neighboring the C-OH group in the substrate is dissociated, is comparable to or higher than that of Rh-ReOx/SiO2. Hydrogenolysis of most substrates except 1,2-cyclohexanediol proceeds via the direct mechanism where hydride species formed from hydrogen molecule attacks the anti-position of C-O bond. In the case of hydrogenolysis of 1,2-cyclohexanediol where attack of anti-position of C-O bond is unfavorable, indirect mechanism involving dehydrogenation to 2-hydroxycyclohexanone is responsible for the formation of cyclohexanol.
- Chen, Kaiyou,Mori, Kazuma,Nakagawa, Yoshinao,Tomishige, Keiichi,Watanabe, Hideo
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p. 171 - 183,13
(2020/07/31)
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- EFFICIENT METHOD FOR PREPARING 2,5-DIMETHYLFURAN
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The present disclosure provides methods to make liquid fuels from renewable, carbon neutral precursors. Specifically, methods to prepare 2,5-dimethylfuran from a source of fructose or other carbohydrates using a one-pot synthesis are provided. In some embodiments, the disclosed methods avoid the isolation of intermediates, and employ “green” reagents like formic acid and acetic acid.
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Page/Page column 14
(2011/11/06)
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- ETHER DERIVATIVES OF BICYCLIC HETEROARYLS
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The invention relates to compounds of formula (I), wherein the substituents are as defined in the specification; to processes for the preparation of such compounds; pharmaceutical compositions comprising such compounds; such compounds as a medicament; such compounds for the treatment of a proliferative disease
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Page/Page column 57
(2011/04/18)
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- Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent
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Three in one: New reagents are needed to generate liquid fuels from biomass, but the reagents must serve multiple roles. For the conversion of fructose into the title compound 1, formic acid serves three roles: assists in the isomerization/dehydration, serves as an H2 source for hydrogenation, and helps deoxygenate the alcohol functional groups.
- Thananatthanachon, Todsapon,Rauchfuss, Thomas B.
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supporting information; experimental part
p. 6616 - 6618
(2010/11/04)
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- CHARACTERISTICS OF THE CATALYTIC HYDROGENATION OF 5-METHYLFURFURAL
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The hydrogenation of 5-methylfurfural in the vapor and liquid phases was studied in the presence of catalysts: Pd/C (KDF), Pd/Al2O3, copper-chromite (GIPKh-105) and Raney-Ni.The chief characteristics of the conversion of the aldehyde group of 5-methylfurfural depending on the nature of the catalyst and the reaction conditions were established.The greater reactivity of 5-methylfurfural in the hydrogenation reaction, compared with furfural, was revealed.
- Stonkus, V. V.,Yuskovets, Zh. G.,Shimanskaya, M. V.
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p. 1214 - 1218
(2007/10/02)
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- Solvomercuration-Demercuration. 9. Oxymercuration-Demercuration of Chloro-, Epoxy-, and Thiomethyl-Substituted Alkenes
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The oxymercuration-demercuration (OM-DM) of allyl, crotyl, 3-buten-1-yl, 4-penten-1-yl, and 5-hexen-1-yl chlorides and methyl sulfides as well as 3,4-epoxy-1-butene, 4,5-epoxy-1-pentene, and 5,6-epoxy-1-hexene has been studied.Allyl chloride undergoes a slow but normal OM to give the Markovnikov oxymarcurial.However, in situ demercuration under the standard conditions (NaOH, NaBH4) gives only allyl alcohol.Fortunately, demercuration with an ethanolic solution of sodium borohydride results in high yields of the chlorohydrin accompanied by small amounts of propylene oxide.In contrast, crotyl chloride fails to give any products resulting from the OM-DM sequence.Thus, 3-buten-2-yl chloride underwent only solvolytic reaction while 2-methylallyl chloride underwent exclusive OM to give, upon DM, the expected Markovnikov chlorohydrin.Similarly, 3-buten-1-yl chloride underwent exclusive hydration under the standard OM-DM conditions.In the case of 4-penten-1-yl chloride, the C1-C5 neighboring-group participation was seen during OM.However, 5-hexen-1-yl chloride showed exclusive hydration to give a 94percent yield of the Markovnikov chlorohydrin.The approximate rates of solvolysis of a series of representative alkyl halides have been determined under the OM conditions.The OM-DM of 3,4-epoxy-1-butene proceeded to give hydrated products although the yield was low, ca. 60percent.On the other hand, 4,5-epoxy-2-pentene gave products arising only from participation of the epoxide ring in the OM stage.Moreover, the yields of these products are very low, only ca. 15percent.By contrast, the OM-DM of 4,5-epoxy-1-pentene proceeds cleanly, giving a 96percent yield of the Markovnikov epoxy alcohol.In the case of 5,6-epoxy-1-hexene, ca. 80percent of the products arise from epoxide participation in the OM stage.With the exception of the crotyl derivative, the (methylthio)alkenes undergo hydration cleanly, although slowly, to give approximately 70-80percent yields of the thio alcohols.The crotyl alkene gave 3-butene-2-ol in only ca. 20percent yield.
- Brown, Herbert C.,Lynch, Gary J.
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p. 930 - 939
(2007/10/02)
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