- Fe/FeOx embedded in LDH catalyzing C-C bond forming reactions of furfural with alcohols in the absence of a homogeneous base
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Fe/FeOx embedded in LDH was prepared by reducing the pre-synthesized [Fe(C2O4)3]3? anions intercalated LDH and used as a multi-functional catalyst for synthesis of C7-C9 compound via transfer hydrogenation between furfural (C5) and short-chain alcohols (C2-C4) and a subsequent aldol reaction of furfural with intermediate short-chain aldehydes in the absence of a homogeneous base with furfuryl alcohol as a byproduct. Screening reaction conditions, evaluation and improvement of the cyclic catalytic performance, and determination of catalytically active components were performed, and the results demonstrated that both high conversion and high selectivity to the C[sbnd]C bond forming product can be obtained under a non-oxidizing atmosphere of Ar or H2/Ar mixed gas, a reaction temperature of 140 °C and a reaction time of 4 h; the catalyst was easily deactivated during the cycle experiments, however, its catalytic stability can be effectively improved by depositing Ni with weak reducibility on the surface of Fe nanoparticles at the cost of reducing partial catalytic activity. Fe/FeOx together with LDH as a whole proved to be effective in catalyzing the transfer hydrogenation reaction and the support LDH imparted basic catalytic function to the composite realizing the aldol reaction in the absence of a homogeneous base.
- Wang, Lijun,Zhong, Yang,Zhou, Bo
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- Selective carbon-chain increasing of renewable furfural utilizing oxidative condensation reaction catalyzed by mono-dispersed palladium oxide
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A novel carbon-chain increasing valorization of furfural (FUR), a cheap bio-based platform compound, has been successfully performed via the catalytic oxidative condensation process with mono-dispersed palladium oxide catalyst. For the reaction of furfural, n-propanol and O2, the PdO?TiO2 exhibited a prominent catalytic activity in which a 77.8% conversion of FUR with 89.2% selectivity of 3-(furan-2-yl)-2-methylacrylaldehyde was obtained. Based on the XRD, SEM, TEM, HRTEM, XPS, and UV–vis results of catalysts, it was concluded that high activity is associated with particle size, uniform distribution of palladium oxide and surface area of the support. Moreover, the recycling experiments confirmed that mono-dispersed palladium oxide catalyst was stable, in which it still kept a good catalytic performance after being recycled for five times. This provided a new route for the selective transformation of the hemicellulose-derived platform compounds.
- Tong,Zhang, Zhenya,Gao, Yiqi,Zhang, Yue,Yu, Linhao,Li, Yongdan
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- A method for utilizing high-efficiency catalytic oxidation of furfural and fatty alcohol preparation furan for fluoro method
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The invention discloses a method for preparing furyl aldehyde by using efficient catalytic oxidation of furfural and fatty alcohol. Furyl aldehyde is prepared from furfural as a substrate and supported nano gold as a catalyst. The method comprises the following specific steps: dissolving furfural into an organic solvent, adding to the supported nano gold and an assistant, and reacting at 25-170 DEG C for 1-15 hours in a 0.01-05MPa oxygen atmosphere under the condition that the stirring speed is 100-5,000r/min; and carrying out selective catalytic oxidation on furfural and fatty alcohol through the supported nano gold, so as to prepare furyl aldehyde. The preparation method is simple and easy to operate, generates few by-products and is friendly to environment. A supported nano gold catalyst is adopted, is mild in condition, good in catalysis effect, easy to recover, and can be repeatedly used; the supported nano gold catalyst can be used for efficiently catalyzing oxidation of furfural with high selectivity to generate furyl aldehyde; and the product is easy to separate, the production cost is low, and technical and economic effects are remarkable, and therefore the method has a good application prospect.
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Paragraph 0020; 0021; 0023; 0025; 0027
(2018/04/20)
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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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p. 3092 - 3100
(2018/07/13)
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- Efficient and selective transformation of biomass-derived furfural with aliphatic alcohols catalyzed by a binary Cu-Ce oxide
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The efficient transformation of furfural (FUR) with aliphatic alcohols to achieve the carbon-chain growth has been developed using a binary Cu-Ce oxide as the catalyst. In the presence of molecular oxygen, the tandem oxidative condensation of FUR with n-propanol is successfully performed, in which an 85.4% conversion of FUR in 95.3% selectivity of 3-(furan-2-yl-)-2-methylacryaldehyde was obtained. The effects of different Cu/Ce ratios and base additives were investigated in detail. As a result, it is found that the CuO-CeO2 (1: 9) catalyst is optimal and potassium carbonate is a suitable additive. Next, the recycling of CuO-CeO2 catalyst was tested and there is no obvious activity loss after being reused five times. Moreover, the oxidative condensation of FUR with various aliphatic alcohols including ethanol, isopropanol, n-butanol and n-hexanol was studied where the long chain alcoholic molecule hinders the proceeding of reaction. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the oxidative condensation of FUR with n-propanol-O2 is proposed.
- Tong, Xinli,Yu, Linhao,Luo, Xuan,Zhuang, Xuli,Liao, Shengyun,Xue, Song
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p. 175 - 180
(2017/09/30)
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- Selective transformation of renewable furfural catalyzed by diverse active species derived from 2D co-based metal-organic frameworks
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We report a facile method for gaining two different types of highly active species from the same 2D Co-based MOFs, which can effectively catalyze the selective transformation of biomass-derived furfural (FUR) in alcohols. Removal of the coordinated water molecules from the Co-based MOFs at 300?°C creates the open metal centers as catalytic active species (designated as ACS-I catalyst). Increasing the pyrolysis temperature to 700?°C, the derived multi-element carbon-matrix nanocomposite from the MOFs (designated as ACS-II catalyst) also shows highly catalytic performance. Both catalyst ACS-I and ACS-II exhibit high reactivity (84.9% conv.) and excellent selectivity (ca. 99.0%) in the oxidative condensation of FUR with n-propanol to produce 3-(furan-2-yl-)-2-methylacrylaldehyde (2) in the presence of molecular oxygen. The particular evidence for the role of metal Co centers in ACS-I and ACS-II is originated from the catalyst characterization and control experiments, in which Ni-I and Ni-II catalysts derived from isomorphrous 2D Ni-based MOFs show no catalytic activity on the transformation of FUR under the similar conditions.
- Ning, Liangmin,Liao, Shengyun,Liu, Xuguang,Yu, Linhao,Zhuang, Xuli,Tong, Xinli
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p. 480 - 490
(2017/07/11)
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- Pd/Al2O3-catalysed redox isomerisation of allyl alcohol: Application in aldol condensation and oxidative heterocyclization reactions
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The application of the Pd/Al2O3 catalyst in allyl alcohol isomerization and subsequent aldol condensation and heterocyclization reactions is described. The activity of Pd/Al2O3 in these transformations is suggested to be due to the participation of the Lewis acidic sites of the support in the activation of the alcohol towards oxidative dehydrogenation by the metal and subsequent hydride transfer. The resulting enol(ate)/aldehyde could undergo further reactions promoted by the acid-base properties of the support. In the aldol condensation reactions of the isomerization product, electron poor aromatic aldehydes and heteroaromatic aldehydes showed the highest activity, while aromatic aldehydes bearing electron donating substituents reacted after transformation to the corresponding N-tosyl imines. 1,2-Disubstituted aromatics gave heterocyclic products in one-pot multistep reaction sequences.
- Zsolnai, Dániel,Mayer, Péter,Szori, Kornél,London, Gábor
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p. 3814 - 3820
(2016/06/13)
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- A smart catalyst system for the valorization of renewable furfural in aliphatic alcohols
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A highly efficient and selective oxidative condensation-hydrogenation process of renewable furfural with aliphatic alcohols catalyzed by metallic platinum in a one-pot reactor is developed. A series of supported platinum catalysts including Pt/FH, Pt/H, Pt/HT, Pt/Fe3O4, Pt/Al2O3 and Pt/ZrO2 are prepared and employed for the polarization of furfural in ethanol and n-propanol. It is found that, in the presence of Pt/FH and potassium carbonate, 93.9% conversion of furfural and 67.9% selectivity to furan-2-acrolein were obtained via oxidative condensation in the furfural-ethanol-O2 (FEO) system, and 90.1% conversion of furfural and 90% selectivity to 3-(furan-2-yl-)-2-methylacrylaldehyde were obtained via oxidative condensation in the furfural-n-propanol-O2 (FPO) system. Moreover, the oxygen in the FPO system is completely replaced by molecular hydrogen to allow the further conversion of 3-(furan-2-yl-)-2-methylacrylaldehyde, while the catalytic system was kept unchanged. During this process, 87.3% conversion of 3-(furan-2-yl-)-2-methylacrylaldehyde and 73.2% selectivity to 3-(furan-2-yl-)-2-methylpropanol were obtained via a hydrogenation reaction with the Pt/FH catalyst. Moreover, several common bases as promoters were investigated in detail. All the catalysts were characterized by XRD, TEM, SEM, TPD and BET methods to reveal their catalytic nature in the reaction.
- Liu, Zonghui,Tong, Xinli,Liu, Jinbiao,Xue, Song
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p. 1214 - 1221
(2016/02/27)
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- A tunable process: Catalytic transformation of renewable furfural with aliphatic alcohols in the presence of molecular oxygen
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The tunable transformation of renewable furfural with aliphatic alcohols in the presence of O2 is developed. Based on a nano Au catalyst and potassium carbonate, a 91.8% yield of methyl 2-furoate with 98.7% selectivity is obtained via the oxidative esterification in a furfural-methanol-O2 system; while a 91.4% yield of 3-(furan-2-yl-)-2-methylacrylaldehyde with 97.2% selectivity is attained via the oxidative condensation in a furfural-n-propanol-O2 system. This journal is
- Tong, Xinli,Liu, Zonghui,Yu, Linhao,Li, Yongdan
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supporting information
p. 3674 - 3677
(2015/03/18)
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- Assembly of indenamine derivatives through in situ formed N-sulfonyliminium ion initiated cyclization
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An expedient route to structurally diverse indenamine derivatives through condensation of the readily accessible substituted cinnamylaldehydes and sulfonylamines under the catalysis of FeCl3 has been developed, featuring high efficiency in the generation of two bonds and one ring in a single-step and water as the only by-product. This journal is the Partner Organisations 2014.
- Fan, Xiaohui,Lv, Hao,Guan, Yong-Hong,Zhu, Hong-Bo,Cui, Xiao-Meng,Guo, Kun
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supporting information
p. 4119 - 4122
(2014/04/03)
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- One-pot synthesis of furfural derivatives from pentoses using solid acid and base catalysts
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One-pot synthesis of (2-furanylmethylene)malononitrile, a Knoevenagel product of furfural with malononitrile, from xylose efficiently proceeded by combined use of acid Amberlyst-15 and acid-base Cr/hydrotalcites in 44% yield. Structural characterization was carried out using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy, and nitrogen adsorption measurements. The Lewis acidic properties of the highly active Cr/HT were investigated using the Meerwein-Ponndorf-Verley (MPV) reaction. It was confirmed that the prepared Cr/HT possessed the Lewis acid Cr2O 3 on the HT surface. Thus, combined use of the dispersed Lewis acid Cr2O3 and the Bronsted base HT facilitated the isomerization step of aldose into ketose and strongly promoted activity for the synthesis of furfural derivatives from aldoses through isomerization, dehydration and Knoevenagel condensation reactions in a one-pot manner. This journal is the Partner Organisations 2014.
- Shirotori, Mahiro,Nishimura, Shun,Ebitani, Kohki
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p. 971 - 978
(2014/04/03)
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- Neutral nazarov-type cyclization catalyzed by palladium(0)
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Joining the circle: The first Pd0 catalyzed Nazarov-type cyclization of diketoesters (see scheme) proceeds in 70 % to 95 % yield under strictly neutral pH conditions. Aryl substitution of the diketoesters is not required, so the reaction shows great versatility and can also proceed with aliphatic substrates. Copyright
- Shimada, Naoyuki,Stewart, Craig,Bow, William F.,Jolit, Anais,Wong, Kahoano,Zhou, Zhe,Tius, Marcus A.
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supporting information; experimental part
p. 5727 - 5729
(2012/08/07)
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- Liquid phase aldol condensation reactions with MgO-ZrO2 and shape-selective nitrogen-substituted NaY
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The aldol condensation reactions of furfural/hydroxymethylfurfural (furfurals) with acetone/propanal in water-methanol solvents were studied over the solid base catalysts MgO-ZrO2, NaY and nitrogen-substituted NaY (Nit-NaY). The reactions were conducted at 120°C and 750 psig of He in batch reactors. Nit-NaY exhibited catalytic activity for aldol condensation comparable to MgO-ZrO2 and much higher than that of NaY, indicative of the increased base strength after replacing the bridging oxygen with the lower electronegativity nitrogen over Nit-NaY. The aldol condensation of furfurals with acetone produces two different products, the monomer and the dimer. The monomer is formed from reaction of furfurals with acetone. The dimer is formed from reaction of the monomer with furfurals. MgO-ZrO2 had a higher selectivity towards dimer formation. In contrast, Nit-NaY was more selective towards the monomer product due to the cage size in the FAU structure, indicating that Nit-NaY is a shape selective base catalyst. Increasing the water concentration in the feed solution or increasing the feed concentration led to both increased catalytic activity and dimer selectivity. The Nit-NaY catalyst was not stable and lost catalytic activity when recycled due to leaching of the framework nitrogen. Different characterization techniques, including XRD, high resolution Ar adsorption isotherm, basic sites titration, CO2 TPD-MS, TGA and 29Si SP MAS NMR, were used here to characterize the fresh and spent catalysts. The results show that Nit-NaY maintains only part of the FAU-type crystal structure. Furthermore, the base strength over Nit-NaY was found to be between that of Mg2+-O 2- pair and Mg(OH)2. The reaction mechanism over Nit-NaY was discussed.
- Shen, Wenqin,Tompsett, Geoffrey A.,Hammond, Karl D.,Xing, Rong,Dogan, Fulya,Grey, Clare P.,Conner Jr., W. Curtis,Auerbach, Scott M.,Huber, George W.
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experimental part
p. 57 - 68
(2011/11/05)
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- An organocatalytic asymmetric nazarov cyclization
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An organocatalytic asymmetric Nazarov cyclization of diketoesters that proceeds by means of a dual activation mechanism has been developed. Screening of a number of catalysts led to a new thiourea that incorporates a primary amino group. The method gives rise to cyclic products with two adjacent quaternary asymmetric carbon atoms, one of which is an all-carbon stereocenter, with complete or nearly complete diastereoselectivity and in high or very high enantiomeric excess. A brief and very convenient synthesis of the acyclic diketoester starting materials through nucleophilic addition to a ketene is also described.
- Basak, Ashok K.,Shimada, Naoyuki,Bow, William F.,Vicic, David A.,Tius, Marcus A.
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supporting information; experimental part
p. 8266 - 8267
(2010/08/04)
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- A general route to α-alkyl (E)-α,β-unsaturated aldehydes
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Bis(trimethylsilyl)-tert-butylaldimines 3 react with aldehydes in the presence of zinc bromide at room temperature to give, after hydrolysis, the desired α-alkyl α,β-ethylenic aldehydes in good yield and with very high E stereoselectivity. The reaction was believed to proceed via the α-silyl β-siloxyimines 4.
- Lahmar, Nour,Aatar, Jamaa,Ayed, Ta?cir Ben,Amri, Hassen,Bellassoued, Moncef
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p. 3018 - 3026
(2007/10/03)
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- Tetraalkylammonium and 1,3-dialkylimidazolium salts with fluorinated anions as recoverable phase-transfer catalysts in solid base-promoted cross-aldol condensations
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Tetraalkylammonium and 1,3-dialkylimidazolium tetrafluoroborates and hexafluorophosphates were employed for the first time as recoverable phase-transfer catalysts in multiphase reactions of CH-acids, in particular in solid base-pro-moted cross-aldol condensations. The catalysts retained their catalytic activity over several reaction cycles.
- Kryshtal, Galina V.,Zhdankina, Galina M.,Zlotin, Sergei G.
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p. 2822 - 2827
(2007/10/03)
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- Aldol Condensation of Aromatic nd Heterocyclic Aldehydes with Alkanals in Heterophase Systems
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The aldol condensation of aromatic and heterocyclic aldehydes with propionaldehyde and valeraldehyde was realized in the two-phase systems consisting of solid potassium hydroxide, benzene, and benzyltriethylammonium chloride or solid potassium hydroxide and DMFA.The three-substituted 2-alkyl-2-propenals were obtained with high selectivity and high yields.
- Kryshtal', G. V.,Zhdankina, G. M.,Serebryakov, E. P.
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p. 777 - 779
(2007/10/02)
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- Reactions Of Ruran Aldehydes 4. Oxidation-Reduction Reactions Of Furfural with Monohydric Alcohols
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Furfural oxidizes aliphatic and alicyclic alcohols at 70-100 deg C under the action of sodium alcoholate to aldehydes and ketones, and then participates in a crotonate condensation.At 0-10 deg C the alcohol is not oxidized but the adduct with alkoxide ion is oxidized to form an alkyl furoate.
- Shapiro, Yu. M.
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