- 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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- 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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Read Online
- Preparation method of furfuryl ester (by machine translation)
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The preparation method comprises the following steps: uniformly mixing furfural, an oxidation esterification catalyst, a cocatalyst and a solvent, and reacting under the condition of an oxygen source for a period of time under a certain temperature and pressure to obtain the furfuryl ester. The method is high in selectivity, few in byproducts and mild in reaction condition, and has a certain industrial application prospect. (by machine translation)
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Paragraph 0023-0025; 0057-0059
(2020/06/22)
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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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- Zinc-Catalyzed Esterification of N-β-Hydroxyethylamides: Removal of Directing Groups under Mild Conditions
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Amide transformations involving C–N bond cleavage are recognized as difficult reactions owing to the inert nature of amides resulting from resonance. Accordingly, a strong inductive effect and geometrical distortion reasonably decrease the resonance stabilization to attenuate the C–N linkage. Although the conversion of such activated amides has been studied intensively, reaction systems for “unactivated” amides are underdeveloped. We herein report that a zinc(II) trifluoromethanesulfonate [Zn(OTf)2] catalyst achieves the esterification of a wide range of unactivated tertiary amides with the assistance of intramolecular acyl rearrangement. The reaction was applied to the one-pot removal of various amide-based directing groups under mild reaction conditions to afford the corresponding esters in high yields.
- Nishii, Yuji,Hirai, Takahiro,Fernandez, Sarah,Knochel, Paul,Mashima, Kazushi
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p. 5010 - 5014
(2017/09/21)
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- Furfural derivatives as a vehicle
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The present invention concerns the use of a furfural derivative of formula (I) in which R represents (i) a —CH═CR′1—COR1 group, a group a group a group or a —CHO and R′ represents a hydrogen atom or a (C1-C4)alkyl group, as a chemical vehicle, as a solvent, co-solvent, coalescing agent, crystallization inhibitor, plasticising agent, degreasing agent, etchant, cleaning agent or agent for increasing biological activity, and more particularly as a solvent. It also concerns phytosanitary formulations or resin-solubilising formulations comprising at least one such furfural derivative of formula (I).
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Paragraph 0253; 0254; 0255; 0256; 0257; 0258; 0259
(2016/01/30)
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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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- Combined catalytic system of scandium triflate and boronic ester for amide bond cleavage
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We have found that the combination of scandium with boronic ester enables the cleavage of amide bonds. Primary amides were converted to the corresponding esters in the presence of catalytic amounts of scandium triflate and boronic ester under mild and neutral conditions. This unique catalytic system can be applied to the deprotection of acetylaniline derivatives. In addition, control NMR experiments were carried out to examine the effect of the boronic esters. Copyright
- Kita, Yusuke,Nishii, Yuji,Onoue, Akihiro,Mashima, Kazushi
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supporting information
p. 3391 - 3395
(2013/12/04)
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- Solvent-free esterification of carboxylic acids and alcohols in the presence of silphos [PCl3-n(SiO2)n] as a heterogeneous phosphine reagent
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An efficient solvent-free method for the preparation of esters from various aromatic and aliphatic acids with primary, secondary, and tertiary alcohols using a heterogeneous phosphine reagent, silphos [PCl3-n(SiO 2)n], in good yields is reported.
- Rao, Ambati Narasimha,Ganesan, Kumaran,Shinde, Chandra Kant
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experimental part
p. 2299 - 2308
(2012/06/18)
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- Action of boron trifluoride etherate and stannic chloride on heterocyclic aromatic acetals
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Twelve heterocyclic aromatic acetals (1a-12a) have been synthesised and their reactions with Lewis acids, viz. boron trifluoride etherate (BTE) and stannic chloride (STC) have been studied.The acetals yield ethers, esters and aldehydes with BTE, but only esters and aldehydes with STC.Interestingly, pyridine-2-aldehyde acetal (12a), yields aldehyde alone, that too in low yield.Probable mechanisms have been suggested for the product formation.
- Raja, S.,Xavier, N.,Arulraj, S. J.
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p. 687 - 689
(2007/10/02)
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