- Aqueous phase hydrogenation of furfural to tetrahydrofurfuryl alcohol over Pd/UiO-66
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A Pd/UiO-66 catalyst was synthesized with well-dispersed Pd nanoparticles. The obtained catalyst was tested in the hydrogenation of furfural to tetrahydrofurfuryl alcohol in various solvents, Water was found to be the most suitable solvent. Pd/UiO-66 exhibited much higher activity than Pd/SiO2 and Pd/γ-Al2O3, completely converting furfural to tetrahydrofurfuryl alcohol with 100% selectivity under mild conditions. The hydrogenation of C[dbnd]O moiety in tetrahydrofurfural was rate-determining step. Static adsorption measurement indicated that the adsorption of furfural on UiO-66 was significantly stronger than that on SiO2 or γ-Al2O3, suggesting that the adsorption play an important role in the gas-liquid-solid furfural hydrogenation reaction.
- Kogan, Victor M.,Liu, Ying-Ya,Sun, Zhichao,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yu, Zhiquan
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- Sulfamic acid as a cost-effective and recyclable catalyst for protection of carbonyls to acetals and ketals under mild conditions
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An efficient H2NSO3H-catalyzed protection of various carbonyl compounds at room temperature was investigated. The features of mild conditions, cost-efficient catalyst, simple workup, and the recyclability of the catalyst were represented in this process.
- Gong, Weizhong,Wang, Bo,Gu, Yanglong,Yan, Liang,Yang, Liming,Suo, Jishuan
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- Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes
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The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](Z)2 (1, Z = CF3SO3; 2, Z = (3,5-(CF3)2C6H3)4B, i.e. BArF) and cis-[Ru(4,4′-Cl2bpy)2(OH2) 2](Z)2 (3, Z = CF3SO3; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl2bpy)2(CH3CN)2](CF 3SO3)2 (3′) and dimeric cis-[(Ru(4,4′-Cl2bpy)2Cl)2](BArF) 2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl2bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](BArF)2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](CF3SO3)2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds. Copyright
- Gowda, Anitha S.,Parkin, Sean,Ladipo, Folami T.
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- Bronsted acidic ionic liquids as efficient and recyclable catalysts for protection of carbonyls to acetals and ketals under mild conditions
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A series of acidic ionic liquids have been used as efficient catalysts for the protection of various carbonyl compounds at room temperature. The features of mild conditions, satisfactory isolated yield, simple workup, and the recyclability of the catalyst were present in this process. Copyright Taylor & Francis, Inc.
- Du, Yuying,Tian, Fuli
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- Furfural hydrogenation on nickel-promoted Cu-containing catalysts prepared from hydrotalcite-like precursors
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The nickel-promoted Cu-containing catalysts (CuxNi y-MgAlO) for furfural (FFR) hydrogenation were prepared from the hydrotalcite-like precursors, and characterized by X-ray powder diffraction, inductively-coupled plasma atomic emission spectroscopy, N2 adsorption-desorption, UV-Vis diffuse reflectance spectra and temperature-programmed reduction with H2 in the present work. The obtained catalysts were observed to exhibit a better catalytic property than the corresponding Cu-MgAlO or Ni-MgAlO samples in FFR hydrogenation, and the CuNi-MgAlO catalyst with the actual Cu and Ni loadings of 12.5 wt% and 4.5 wt%, respectively, could give the highest FFR conversion (93.2%) and furfuryl alcohol selectivity (89.2%). At the same time, Cu0 species from the reduction of Cu2+ ions in spinel phases were deduced to be more active for FFR hydrogenation. The nickel-promoted Cu-containing catalysts were prepared from hydrotalcite-like precursors. Cu0 species from spinel phase was found to be the best active sites in furfural hydrogenation and the Ni2+ species in catalysts acted as the promoter.
- Xu, Chenghua,Zheng, Liangke,Liu, Jianying,Huang, Zunyu
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- Effect of activation temperature on the surface copper particles and catalytic properties of Cu-Ni-Mg-Al oxides from hydrotalcite-like precursors
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The Cu-Ni-Mg-Al oxides catalysts for furfural hydrogenation were prepared from the hydrotalcite-like precursors, and the effect of activation temperature on the Cu0 particles and catalytic properties of the catalyst was thoroughly investigated. The catalyst activated by H2 at 300 °C was found to exhibit the best catalytic activity, due to the presence of the smallest Cu0 particles with a high dispersion. Moreover, the bigger Cu0 particles were active for furfuralcohol hydrogenolysis to 2-methylfuran in the liquid-phase (ethanolic solution), and the hydrogenation of the furan ring of furfuralcohol and 2-methylfuran on Cu0 particles was easily achieved in the vapour-phase.
- Xu, Chenghua,Zheng, Liangke,Deng, Danfeng,Liu, Jianying,Liu, Shengyu
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- Integrated catalytic process to directly convert furfural to levulinate ester with high selectivity
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Levulinic acid is an important platform molecule from biomass-based renewable resources. A sustainable manufacturing process for this chemical and its derivatives is the enabling factor to harness the renewable resource. An integrated catalytic process to directly convert furfural to levulinate ester was developed based on a bifunctional catalyst of Pt nanoparticles supported on a ZrNb binary phosphate solid acid. The hydrogenation of furfural and the following alcoholysis of furfuryl alcohol were performed over this catalyst in a one-pot conversion model. Mesoporous ZrNb binary phosphate was synthesized by a sol-gel method and had a high surface area of 170.1 m2g-1 and a large average pore size of around 8.0 nm. Pt nanoparticles remained in a monodisperse state on the support, and the reaction over Pt/ZrNbPO4 (Pt loading: 2.0 wt%; Zr/Nb, 1:1) gave a very high selectivity to levulinate derivatives (91 % in total). The sustainability of this conversion was greatly improved by the process intensification based on the new catalyst, mild reaction conditions, cost abatement in separation and purification, and utilization of green reagents and solvents.
- Chen, Bingfeng,Li, Fengbo,Huang, Zhijun,Lu, Tao,Yuan, Yin,Yuan, Guoqing
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- Versatile catalysis of iron: Tunable and selective transformation of biomass-derived furfural in aliphatic alcohol
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An iron-catalyzed efficient valorization of biomass-derived furfural (FUR) in aliphatic alcohols is developed in which product selectivity can be simply regulated by varying the gas atmosphere. In the presence of molecular oxygen, there is oxidative condensation of FUR with ethanol, and the obtained product is furan-2-acrolein in a "FUR-ethanol-O2" system. Under suitable conditions, the conversion of FUR and selectivity of furan-2-acrolein are 84.2% and 82.7%, respectively. In the presence of H2, the selective hydrogenation of FUR is achieved, and the main product is furfuryl alcohol in a "FUR-ethanol-H2" system. Under optimal conditions, a 99.9% conversion of FUR and 93.6% selectivity of furfuryl alcohol are attained. This provides an economic, green and sustainable method for the utilization of biomass-based platform compounds in the chemical industry.
- Zhang, Zhenya,Tong, Xinli,Zhang, Haigang,Li, Yongdan
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- The influence of metal selection on catalyst activity for the liquid phase hydrogenation of furfural to furfuryl alcohol
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In this work the replacement of toxic chromium containing catalysts for the selective hydrogenation of furfural to furfuryl alcohol was investigated. The initial focus was on the synthesis of monometallic catalysts by wet impregnation and concentrated on the employment of metals such as platinum, palladium, copper and nickel. Experiments were conducted using ethanol as the solvent which was found to have a negative effect on the selectivity to the desired product, furfuryl alcohol, with high quantities of 2-Furaldehyde diethyl acetal and difurfuryl ether formed. Consequently, toluene was selected as an alternative solvent facilitating selectivity to furfuryl alcohol only. It was found that platinum was the most promising metal of those studied as it displayed higher selectivity to furfuryl alcohol and was subsequently employed for the synthesis of bimetallic catalysts. The bimetallic catalysts were synthesised by surface reactions using a variety of promoter metals selected according on their electronegativity. It was found that, while the selectivity of all catalysts to furfuryl alcohol was close to 100%, the conversion was influenced significantly by the second metal and followed the order tin > molybdenum > manganese > barium > iron > nickel. The purpose of the research was to produce an active catalyst for the liquid phase hydrogenation under suitable industrial conditions with the results presented here conducted at 100 °C and 20 bar hydrogen pressure. Furfural conversion of 47% and close to 100% selectivity to furfuryl alcohol was achieved using a 0.6%Pt0.4%Sn/SiO2 catalyst.
- O'Driscoll,Leahy,Curtin
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- Tuning catalytic selectivity of liquid-phase hydrogenation of furfural via synergistic effects of supported bimetallic catalysts
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Bimetallic catalysts supported over TiO2-ZrO2 binary oxides were prepared by co-impregnation methods and used for catalyzing liquid-phase hydrogenation of furfural. Highly selective hydrogenation catalysts can be developed based on bimetallic synergistic effect. The coexistence of small proportion of palladium with supported nickel species greatly improves the catalytic performance and transfer the reaction selectivity from partial hydrogenation to total hydrogenation. The catalyst with Ni-Pd mole ratio of 5:1 shows the best performance. The yield of tetrahydrofurfuryl alcohol (THFA) reaches 93.4%. Ni-Pd synergistic effect is interpreted through XPS measurement and a hydrogen-transfer mechanism is proposed. Pt-Re bimetallic catalyst is an excellent partial hydrogenation catalyst for furfural conversion. Furfural can be totally converted and the selectivity of partial hydrogenation product (FA) reaches 95.7%. When rhenium oxide species are located on the Pt surface, the hydrogen species on Pt are transferred to adsorbed C=O bond to achieve selective hydrogenation.
- Chen, Bingfeng,Li, Fengbo,Huang, Zhijun,Yuan, Guoqing
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- A catalytic aldol condensation system enables one pot conversion of biomass saccharides to biofuel intermediates
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Producing bio-intermediates from lignocellulosic biomass with minimal process steps has a far-reaching impact on the biofuel industry. We studied the metal chloride catalyzed aldol condensation of furfural with acetone under conditions compatible with the upstream polysaccharide conversions to furfurals. In situ far infrared spectroscopy (FIR) was applied to guide the screening of aldol condensation catalysts based on the distinguishing characteristics of metal chlorides in their coordination chemistries with carbonyl-containing compounds. NiCl2, CoCl2, CrCl3, VCl3, FeCl3, and CuCl2 were selected as the potential catalysts in this study. The FIR results further helped to rationalize the excellent catalytic performance of VCl3 in furfural condensation with acetone, with 94.7% yield of biofuel intermediates (C8, C13) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solvent. Remarkably, addition of ethanol facilitated the acetal pathway of the condensation reaction, which dramatically increased the desired product selectivity over the furfural pathway. Most significantly, we demonstrate for the first time that VCl3 catalyzed aldol condensation in acidic medium is fully compatible with upstream polysaccharide hydrolysis to monosaccharide and the subsequent monosaccharide isomerization and dehydration to furfurals. Our preliminary results showed that a 44% yield of biofuel intermediates (C8, C13) can be obtained in one-pot conversion of xylose catalyzed by paired metal chlorides, CrCl2 and VCl3. A number of prior works have shown that the biofuel intermediates derived from the one-pot reaction of this work can be readily hydrogenated to biofuels.
- Li, Huixiang,Xu, Zhanwei,Yan, Peifang,Zhang, Z. Conrad
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- Acetalization of furfural with zeolites under benign reaction conditions
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Acetalization is a viable method to protect carbonyl functionalities in organic compounds and offers a potential synthetic strategy for synthesizing derived chemicals. In this work, several families of commercial zeolites have been employed as solid acid catalysts in the acetalization of furfural to form furfural diethyl acetal at room temperature using ethanol as a renewable solvent. Among the tested catalysts, H-USY (6) provided the highest catalytic activity (79% acetal yield), excellent selectivity and reusability in five consecutive reaction runs. Process parameters such as, e.g. reaction time, catalyst loading and applicability of different lower alcohols were evaluated and optimized.
- Rubio-Caballero, Juan Miguel,Saravanamurugan, Shunmugavel,Maireles-Torres, Pedro,Riisager, Anders
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- A kinetic study of heteropolyacid-catalyzed furfural acetalization with methanol at room temperature via ultraviolet spectroscopy
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In this work, the ultraviolet spectroscopy was used as a tool to monitor the kinetics of acetalization reaction of furfural with alkyl alcohols. Among the Bronsted acids evaluated, Keggin heteropolyacids (e.g., H3PW12O40 and H3PMo12O40) were the more active and selective in the acetalization of furfural in reactions carried out at room temperature. The ultraviolet spectroscopy, a simple and inexpensive analytic technique was used to quantify the furfural and acetals during the reaction progress. The influence of main reaction parameters such as temperature, time, and catalyst load were assessed. The reaction scope was extended to the other alcohols. The activation energy of heteropolyacid-catalyzed reactions was determined.
- Teixeira, Milena Galdino,Natalino, Ricardo,da Silva, Márcio José
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- A regulatable oxidative valorization of furfural with aliphatic alcohols catalyzed by functionalized metal-organic frameworks-supported Au nanoparticles
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The oxidative upgrading of furfural (FUR) and aliphatic alcohols is an important way to produce desirable precursor of jet fuel or value-added furanic compound. Therein, developing a highly active catalytic system with switchable product selectivity still remains a challenge. In this work, we report a novel strategy on regulating the oxidative condensation and oxidative esterification of FUR with aliphatic alcohol in the presence of molecular oxygen. Firstly, Au@UiO-66 is prepared using different methods and employed as the catalyst for the oxidative valorization of FUR with methanol. It is found that the impregnation-reduction-H2 (I-H) method is the best where a 100% selectivity of methyl-2-furoate with a complete conversion was obtained using Au@UiO-66 as catalyst. Then, a series of metal-organic frameworks (MOFs) supported Au nanoparticles (Au@UiO-66-X) such as Au@UiO-66, Au@UiO-66-NH2, Au@UiO-66-NO2, Au@UiO-66-COOH and Au@UiO-66-NH3Cl have been prepared with I-H method and employed for oxidative valorization of furfural with ethanol. Experimental results showed that, in “FUR-ethanol-O2” system, the Au@UiO-66-X can efficiently regulate the oxidative condensation and oxidative esterification as two competitive reaction pathways. With Au@UiO-66-COOH as the catalyst, the oxidative condensation process is dominant in which 84.1% selectivity of furan-2-acrolein is attained; Meanwhile, the Au@UiO-66 is beneficial to the occurrence of oxidative esterification and generation of ethyl-2-furoate. At last, based on the catalyst characterization and the numerous control experiments, a possible catalytic reaction mechanism for conversion of FUR is proposed.
- Ning, Liangmin,Liao, Shengyun,Liu, Xuguang,Guo, Pengfei,Zhang, Zhenya,Zhang, Haigang,Tong, Xinli
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- Efficient hydrogenation of concentrated aqueous furfural solutions into furfuryl alcohol under ambient conditions in presence of PtCo bimetallic catalyst
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Furfural (FAL), a major biomass-derived chemical, can be hydrogenated to yield the industrially important platform chemical, furfuryl alcohol (FOL). Although heterogeneous catalyst-based methods are known to yield FOL from dilute solutions of FAL, they mainly operate at high temperatures and/or high pressures of hydrogen and in the presence of organic solvents. In this work, we employ bimetallic PtCo/C catalysts with varying metal concentrations to achieve the maximum possible FOL yield (100%) at 35 °C under 0.1 MPa H2 in water. With concentrated FAL (40 wt%) at 50 °C and under 1 MPa H2 pressure, 86% yield of FOL was observed. Moreover, efficient catalyst recycling was observed over at least four runs with marginal loss in activity due to handling error and isolation of FOL in pure form confirmed by NMR and HPLC. Characterization of catalysts with several physico-chemical techniques (XRD, TEM, XPS, ICP, TPR) reveals the presence of electron-rich Pt and ionic Co species in proximity with each other and these work synergistically to facilitate maximum possible yield of FOL under ambient conditions and in water medium.
- Dohade,Dhepe
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- Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
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A series of functionalized hydrogen sulfate imidazolium ILs were synthesized and applied as catalysts in the reaction of glucose, xylose and fructose with ethanol. In this research, an unexpected selectivity phenomenon was observed. It showed that in this reaction functionalized ILs should be considered as a special type of catalyst. Functionalization of alkyl imidazolium ILs, especially the addition of electronegative OH groups, causes a clear and unexpected effect manifested via visible changes in the selectivity of the reaction studied. In the case of fructose, an increase in the number of OH groups affects an increase in the selectivity towards ethyl levulinate from 14.2% for [bmim]HSO4 to 20.1% for [glymim]HSO4 with an additional increase in selectivity to 5-hydroxymethyfurfural. In turn, for xylose, the introduction of OH groups to the alkyl chain was manifested by a decrease in selectivity to furfural as its ethyl acetal and an increase in selectivity to ethylxylosides. This journal is
- Nowakowska-Bogdan, Ewa,Nowicki, Janusz
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p. 1857 - 1866
(2022/02/05)
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- Practical acetalization and transacetalization of carbonyl compounds catalyzed by recyclable PVP-I
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A novel PVP-I catalyzed acetalizations/transacetalizations of carbonyl compounds has been developed processing with a mild and easy handling fashion. Different types of Acyclic and cyclic acetals were prepared from carbonyl compounds or their acetals successfully. Further applications of newly developed catalytic combination were testified. This protocol featured with simplicity of operation, mild reaction condition, short reaction time, recyclable of catalyst and broad substrates scope with excellent yields.
- Cao, Fu-Rong,Lu, Guangying,Ren, Jiangmeng,Wang, Di,Zeng, Bu-Bing
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- Zeolite-catalyzed acetalization reaction of furfural with alcohol under solvent-free conditions
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Acetalization reactions present a viable method for producing valuable chemicals and protecting carbonyl functionalities in organic compounds. Herein, several commercial zeolites were used as solid acid catalysts in the acetalization of biomass-derived furfural with alcohols under solvent-free conditions. The effects of major reaction parameters such as catalyst concentration, reaction temperature, and reaction time were investigated. Among the tested catalysts, SAPO-34 with appropriate acid sites and textural structure exhibited the highest catalytic activity under optimized reaction conditions. Additionally, the catalyst showed excellent recyclability and no obvious deactivation was observed even after using it six times.
- Jin, Fuxiang,Liu, Hailong,Liu, Qiao,Song, Heyuan
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- Production of Furfural-Diethyl-Acetal as Biofuel Additives for Gasoline by Metal Free Porphyrin Photocatalyst Under Visible Light
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The protocol presents conversion of furfural (FFL) to furfural-diethyl-acetal (FDA), using ionic liquid tangled, sulphonic acid functionalized, porphyrin (ILSAFPc) as a photocatalyst under visible light at ambient conditions. The formation of FDA was achieved by reacting furfural and ethanol (1: 2.2) over ILSAFPc photocatalyst in a home-made photoreactor under 5?W LED light. The product was attained with 92% yield by photocatalytic acetalization in 18?h at room temperature and confirmed by 1H NMR and 13C NMR. The acetal was confirmed by the presence of CH singlet in 1H NMR, at (8.08) ppm and disappearance of CHO proton of the substrate at 18?h. In addition, FDA exhibited as an excellent fuel additive and results presented that both 15 and 20% blending by volume with the gasoline found comparable physicochemical properties including octane number and calorific value. Finally, ILSAFPc displayed reusability for six times under optimized conditions without significant change in the yield and structure. Graphic Abstract: [Figure not available: see fulltext.]
- Bhagat, Pundlik Rambhau,Bhansali, Karan Jeevanlal
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- Etherification of biomass-derived furanyl alcohols with aliphatic alcohols over silica-supported nickel phosphide catalysts: Effect of surplus P species on the acidity
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The acidity of nickel phosphide (Ni2P) catalysts plays a crucial role in producing a desired hydrodeoxygenation molecule from biomass-derived substrates; yet, it has never been explored in acid-catalyzed reactions. Herein, we demonstrated the activity of silica-supported Ni2P catalyst prepared with the nominal P/Ni ratio of 2 (Ni2P/SiO2-2P) in the etherification of furanyl alcohols (particularly, 5-(hydroxymethyl)furfural) with aliphatic alcohols including ethanol. By comparing the characteristics of Ni/SiO2, PxOy/SiO2, and Ni2P/SiO2-xP (x = 0.5 and 1), Ni2P/SiO2-2P was revealed to contain the Br?nsted and Lewis acid sites of which both contributed to the etherification reaction. Notably, the Br?nsted acidity was associated with the surplus P species added to produce the Ni2P phase. Consequently, supported Ni2P catalysts can work in acid-catalyzed reactions if an adequate ratio of Br?nsted to Lewis acid sites is provided by the amount of the surplus P species determined by adjusting the P/Ni ratio.
- Kim, Jinsung,Shin, Mi,Suh, Young-Woong
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- Magnetic Fe3O4 nanoparticles as easily separable catalysts for efficient catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol
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Magnetic Fe3O4-12 nanoparticles, an easily separable heterogeneous catalyst, exhibits high catalytic performance in the catalytic transfer hydrogenation (CTH) reaction of biomass-derived furfural (FAL) to furfuryl alcohol (FOL) with 2-propanol (2-PrOH) as the hydrogen source (90.1 percent FOL yield at 160 °C for 5 h). Comparing Fe3O4 nanoparticles with different particle sizes found that the smaller the nanoparticles, the larger the BET surface area, pore volume and pore diameter, resulting in more acid-base active sites through BET, SEM, TEM, NH3-/CO2-TPD and other characterizations. Moreover, a scaled-up CTH experiment of FAL and a stepwise reaction from xylose to FOL verified that the catalytic system has great industrial application prospects. A feasible flowchart of the chemical process from xylose to FOL was designed, which can realize the regeneration of biomass resources (xylose derived from corncob), the reuse and recycling of catalysts and solvents, and minimize the amount of solvents and pollutant emissions.
- Cao, Jingjie,Feng, Shouhua,Hou, Pan,Liu, Hui,Ma, Mingwei,Tian, Ge,Yue, Huijuan,Zhang, Peng
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- Transposition of Aromaticity from a Furan to a Cyclohexane Ring in Furoisoindoles during the Interaction of 3-(Furyl)allylamines with Bromomaleic Anhydride
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An unexpected four-step reaction sequence was discovered in the course of investigation of the interaction between 3-(furan-2-yl)allylamines and bromomaleic anhydride. This conversion begins with the initial N -acylation of the allylamines by the anhydride, followed by intramolecular Diels-Alder reaction, which is accompanied by a dehydrohalogenation, and ends with the formation of partially unsaturated furo[2,3- f ]isoindoles followed by transposition of aromaticity from the furan moiety to the neighboring cyclohexane ring. The reaction between 3-(furan-3-yl)allylamines and bromomaleic anhydride does not stop at a furo[2,3- f ]isoindole formation step, but proceeds further with the cleavage of the furan ring in a 100percent atom-efficient fashion to provide polysubstituted isoindoline-4-carboxylic acids.
- Alekseeva, Kseniia A.,Eroshkina, Svetlana M.,Khrustalev, Victor N.,Kvyatkovskaya, Elizaveta A.,Nikitina, Eugeniya V.,Shikhaliev, Khidmet S.,Truong, Hieu H.,Zaytsev, Vladimir P.,Zubkov, Fedor I.
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supporting information
p. 255 - 260
(2020/02/18)
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- Formation of Acetals and Ketals from Carbonyl Compounds: A New and Highly Efficient Method Inspired by Cationic Palladium
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The development of a new, highly efficient, and simple method for masking carbonyl groups as acetals and ketals is described. This methodology relies on the nature of the palladium catalyst to direct the acetalization/ketalization reaction. This new protocol is mild and proceed with a very low catalyst loading at ambient temperatures. The method has been extended to a wide variety of different carbonyl compounds with various steric encumbrances to form the corresponding acetals and ketals in excellent yields.
- Green, Shawn D.,Kindoll, Tyler,Lazaro-Martinez, Brenda,Mensah, Enoch A.,West, Jesse
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p. 1810 - 1814
(2019/09/09)
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- Highly selective synthesis under benign reaction conditions of furfural dialkyl acetal using SnCl2 as a recyclable catalyst
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A new and mild route of furfural acetalization with various alkyl alcohols catalyzed by cheap and simple SnCl2 has been developed. This process consists of the conversion of furfural to alkyl acetals under benign and mild reaction conditions (i.e., room temperature, without solvent, recyclable catalyst), achieving a very good selectivity (97-100%) and almost complete conversion of furfural. Various tin(ii) salts were used as catalysts for the upgrading of furfural to alkyl acetal in an alcoholic solution at room temperature. SnCl2 was the most active and selective catalyst toward furfural diethyl acetal. Tin(ii) chloride is a commercially available and water tolerant Lewis acid and was demonstrated to be an efficient and recyclable catalyst for the synthesis of furfural alkyl acetal. The effects of the main variables of the reaction such as the catalyst load, temperature, reaction time and alcohol nature were assessed. SnCl2 was easily recovered and reused without loss of activity and selectivity.
- Da Silva, Márcio José,Teixeira, Milena Galdino,Natalino, Ricardo
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p. 8606 - 8612
(2019/06/14)
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- Facile synthesis of furfuryl ethyl ether in high yield: Via the reductive etherification of furfural in ethanol over Pd/C under mild conditions
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The one-pot synthesis of furfuryl ethyl ether (FEE) over Pd nanoparticles supported on TiO2, Al2O3, SiO2, and active carbon via the catalytic reductive etherification of furfural in ethanol was systematically studied. The Pd nanoparticles supported on SiO2, TiO2 and active carbon are all active for this novel process under mild reaction conditions, with Pd/C showing the highest selectivity to FEE. The effects of palladium loading, reaction temperature, and hydrogen pressure on the activity and selectivity of Pd/C have been investigated in detail. The results demonstrate that suitable Pd amount, low reaction temperature of about 60 °C, and low H2 pressure of about 0.3 MPa are favorable for the formation of the desired ether product. Under the optimized conditions, an unprecedented high yield of up to 81% of FEE was firstly obtained with the major by-products being furfuryl alcohol and 2-methyltetrahydrofuran. Compared with the conventional hydrogenation-etherification route via furfural alcohol as a reaction intermediate, the reductive etherification shows significant advantage in product yield because of its much lower reaction temperature that is required.
- Wang, Yun,Cui, Qianqian,Guan, Yejun,Wu, Peng
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p. 2110 - 2117
(2018/05/24)
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- Facile synthesis of Cu3(BTC)2/cellulose acetate mixed matrix membranes and their catalytic applications in continuous flow process
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Metal-organic framework (MOF)-based mixed matrix membranes (MMMs) were fabricated by a combination of Cu3(BTC)2 MOF and polymer cellulose acetate. The cellulose acetate in the MMMs served as the matrix and the Cu3(BTC)2 MOF as the filler. The as-synthesized MMMs were utilized as a heterogeneous catalyst for aldehyde acetalization. The characterization techniques indicated that the Cu3(BTC)2 crystals were uniformly dispersed in the MMMs. The BET surface area of the Cu3(BTC)2-based MMM was measured to be 459 m2 g-1 at 60 wt% Cu3(BTC)2 loading. Furthermore, the MMMs served as an excellent catalyst under our continuous flow catalytic reaction conditions. The optimal catalytic result of benzaldehyde yield reached 94% with 60 wt% Cu3(BTC)2 loading of the MMMs at room temperature and the benzaldehyde diethyl acetal reached 0.59 mmol min-1 gCu-BTC-1.
- Hou, Junying,Luan, Yi,Huang, Xiubing,Gao, Hongyi,Yang, Mu,Lu, Yunfeng
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p. 9123 - 9129
(2017/08/29)
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- Kinetic analysis and process modeling for cellulose valorization in cooperative ionic liquid pairs
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Studies on kinetic analysis and process modeling are important and necessary for the development of novel and efficient technology for cellulose utilization. In this study, a kinetic model for the batch reactor was described for catalytic cellulose degradation in cooperative ionic liquid pairs based on an intensive analysis of the experimental parameters. Our fitting results show that the proposed model agrees well with the experimental data. The kinetic parameters obtained from the above model were subsequently applied to the continuous stirred tank reactor (CSTR) by constructing a mathematical process model for the continuous operation of cellulose degradation combined with product separation. The effects of reaction temperature, retention time, extract flow rate and distribution coefficients were intensively investigated. The numerical results demonstrate that relatively high temperature and larger retention time are favorable in cellulose conversion, whereas the product distribution coefficient and extract flow rate mainly affect the concentration of the hexane-soluble fraction (volatile chemicals). The findings presented in this work will serve as a beneficial reference for further biomass transformation of industrial purpose.
- Liu, Sijie,Tang, Luo,Long, Jinxing,Guan, Jianyu,Li, Xuehui
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- Au-catalyzed oxidative condensation of renewable furfural and ethanol to produce furan-2-acrolein in the presence of molecular oxygen
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A specialty chemical compound, furan-2-acrolein, can be produced from renewable feedstock via furfural. An efficient catalytic process related to oxidative condensation of furfural and ethanol using supported Au catalyst has been developed. A series of solid catalysts including Au/Al2O3, Au/CeO2, Au/Fe3O4, Au/HTc (hydrotalcite calcined) and Au/Nb2O5 are prepared and their catalytic activities in oxidative condensation of furfural with ethanol are compared. Moreover, the influence of the presence of base promoters, such as K2CO3, on Au catalyst performance is investigated. The physical properties of these catalysts are characterized by XRD, TEM, SEM, UV-vis and BET techniques. The impact of reaction variables on catalyst performance is measured. It has been found that, in the presence of Au/Al2O3 and potassium carbonate, 94.1% conversion of furfural and 75.0% selectivity to furan-2-acrolein are obtained under the conditions of 140 °C, 0.3 MPa of O2 and reaction time of 4 h.
- Tong, Xinli,Liu, Zonghui,Hu, Jianli,Liao, Shengyun
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p. 196 - 203
(2015/12/05)
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- Antiknock properties of furfural derivatives
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Preparative amounts of furfuryl alcohol ethers and furfural acetals were prepared from renewable vegetable raw materials. The blending reseach octane numbers of mixing of furan derivatives in straight-run gasoline were estimated: butyl furfuryl ether, 97.8 ± 7; propyl furfuryl ether, 112 ± 6; furfural diethyl acetal, 105 ± 6, furfural ethylene glycol acetal, 108 ± 7; furfurylamine, 194 ± 4. These results demonstrate prospects for using furan derivatives as available biofuels.
- Tarabanko,Chernyak,Simakova,Kaigorodov,Bezborodov,Orlovskaya
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p. 1778 - 1782
(2016/03/05)
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- One step catalytic conversion of cellulose to sustainable chemicals utilizing cooperative ionic liquid pairs
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A 100% conversion of cellulose to industrially useful chemicals is, for the first time, achieved in a single pot reaction by the use of cooperative ionic liquid pairs for combined dissolution and catalytic degradation of cellulose, which overcomes the long intrinsic phase problem in the conversion of biomass to chemicals.
- Long, Jinxing,Guo, Bin,Li, Xuehui,Jiang, Yanbin,Wang, Furong,Tsang, Shik Chi,Wang, Lefu,Yu, Kai Man K.
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supporting information; experimental part
p. 2334 - 2338
(2011/10/12)
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- A facile procedure for acetalization of aldehydes and ketones catalyzed by cerium(III) trifluoromethanesulfonate
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Aldehydes and ketones are readily protected in the presence of trialkyl orthoformate and a catalytic amount of cerium(III) trifluoromethanesulfonate under mild conditions to give the corresponding acetals in good to excellent yields. Due to the mild reaction conditions, this method is compatible with acid-sensitive substrates. Copyright
- Ono, Fumiaki,Inatomi, Yoshiko,Tada, Yuusuke,Mori, Masaki,Sato, Tsuneo
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experimental part
p. 96 - 97
(2009/11/30)
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- Iron(III) tosylate in the preparation of dimethyl and diethyl acetals from ketones and β-keto enol ethers from cyclic β-diketones
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An efficient method for conversion of ketones to their corresponding dimethyl and diethyl acetals and of cyclic β-diketones into β-keto enol ethers using Fe(OTs)3 as a catalyst is described. Copyright Taylor & Francis Group, LLC.
- Mansilla, Horacio,Afonso, Maria M.
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p. 2607 - 2618
(2008/12/22)
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- Sequential and tandem oxidation/acetalization procedures for the direct generation of acetals from alcohols
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Alcohols are transformed directly into either acyclic or cyclic acetals in both tandem and sequential oxidation/acetalization processes using manganese dioxide, trialkyl orthoformates and catalytic quantities of indium triflate.
- Smith, Brendan M.,Graham, Andrew E.
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p. 4891 - 4894
(2008/02/08)
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- Synthesis of substituted bis(heteroaryl)maleimides
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Substituted bis(fur-2-yl), bis(fur-3-yl) and bis(thien-2-yl) maleimides with potential antidiabetic properties are described. Their synthesis involves, as a key step, a Suzuki cross-coupling between various boron derivatives and the diiodomaleimides. Therefore, a wide range of substituted symmetric and non-symmetric maleimide derivatives can be prepared.
- Dubernet, Mathieu,Caubert, Virginie,Guillard, Jér?me,Viaud-Massuard, Marie-Claude
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p. 4585 - 4593
(2007/10/03)
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- Tetrabutylammonium tribromide (TBATB) as an efficient generator of HBr for an efficient chemoselective reagent for acetalization of carbonyl compounds
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Acyclic and cyclic acetals of various carbonyl compounds were obtained in excellent yields under a mild reaction condition in the presence of trialkyl orthoformate and a catalytic amount of tetrabutylammonium tribromide (TBATB) in absolute alcohol. Chemoselective acetalization of an aldehyde in the presence of ketone, unsymmetrical acetal formation, shorter reaction times, mild reaction conditions, the stability of acid-sensitive protecting groups, high efficiencies, facile isolation of the desired products, and the catalytic nature of the reagent make the present methodology a practical alternative.
- Gopinath, Rangam,Haque, Sk. Jiaul,Patel, Bhisma K.
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p. 5842 - 5845
(2007/10/03)
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- A new molecular iodine-catalyzed acetalization of carbonyl compounds
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A new and facile molecular iodine-catalyzed acetalization of carbonyl compounds has been developed. Useful selectivity has also been demonstrated.
- Basu, Manas K.,Samajdar, Susanta,Becker, Frederick F.,Banik, Bimal K.
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p. 319 - 321
(2007/10/03)
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- The thermally induced synthesis of N-(diethoxyphosphoryl)aldimines
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The reaction of diethyl phosphoroamidate (2) with aromatic aldehyde diethyl acetals (1) carried out at 120-160°C provides a simple, one-step preparation of N-(diethoxyphosphoryl)aldimines (3a-b). The extension of this reaction to aliphatic aldehyde diethyl acetals failed to give the expected imines.
- Zwierzak, Andrzej,Napieraj, Anna
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p. 8789 - 8794
(2007/10/03)
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- Die photochemische Synthese von Feinchemikalien mit Sonnenlicht
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Das Licht der Sonne kann in der Photochemie direkt zur Veraenderung chemischer Strukturen genutzt werden.Die spektrale Photonenverteilung der Sonne sowie die Diskontinuitaet der Einstrahlung durch den Tag-Nacht-Rhythmus und das Wetter sind Randparameter, an denen sich eine technische Nutzung orientieren muss.Ausgehend von der Beschreibung des photochemischen Potentials der Sonne und grundsaetzlicher Ueberlegungen zur Konzeption von mit Sonnenlicht betriebenen Photoreaktoren (kurz: solare Photoreaktoren) werden deren Realisierung in einer ersten Pilotanlage auf der Plataforma Solar de Almeria in Suedspanien sowie andere Aktivitaeten in diesem Bereich zusammenfassend dargestellt.An den experimentellen Daten photochemischer Versuche im Technikumsmassstab werden Moeglichkeiten, Grenzen und Entwicklungspotential der solaren Photochemie dargelegt.Die solare Photochemie ist nach unserer Ansicht eine Technik, die wegen des photochemischen Synthesepotentials, der Abfallvermeidung und der direkten Nutzung der Sonne als Primaerenergiequelle (in diesem Fall eigentlich als Reaktionspartner) einen Beitrag zur Chemie der Zukunft leisten koennte.
- Esser, Peter,Pohlmann, Bettina,Scharf, Hans-Dieter
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p. 2093 - 2108
(2007/10/02)
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- PHASE-TRANSFER CATALYZED ALKOXYLATION OF 2-(DICHLOROMETHYL)FURAN BY ALCOHOLS IN THE PRESENCE OF POTASSIUM HYDROXIDE
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Reaction of 2-(dichloromethyl)furan (I) with KOH in a CH2Cl2 medium and in the presence of alcohols (methanol, ethanol, and n-butanol) and a catalytic amount of triethylbenzylammonium chloride (TEBAC) results in the formation of 2-chloromethylene-5-alkoxy-2,5-dihydrofurans (II) (mixtures of Z- and E-isomers) and 2-dialkoxymethylfurans (III), in overall yields of up to 96percent.Reaction with isopropyl and tert-butyl alcohols gave only corresponding products (II), in 21 and 12percent yield, respectively.
- Shavrin, K. N.,Volotova, I. V.,Kutin, A. A.
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p. 1244 - 1248
(2007/10/02)
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- Selective Acetalization of Aldehydes with Trialkoxystibine using Allyl Bromide
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Trialkoxystibine has been found to be an effective reagent for selective acetalization of aldehydes with the aid of allyl bromide.
- Liao, Yi,Huang, Yao-Zeng,Zhu, Fang-Hua
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p. 493 - 494
(2007/10/02)
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- Practical Synthesis of dl-4-Hydroxymethyl-2-buten-4-olide from Furfural
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dl-4-Hydroxymethyl-2-buten-4-olide(4) has been synthesized from furfural (5) through a sequence of reactions as shown in Scheme of the text.
- Wang, Zhong-Qi,Zhou, Wei-Shan,Chen, Yi,Wy, Yue-Huan,Zhu, Zhou-Yuan
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p. 3267 - 3274
(2007/10/02)
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