823-82-5Relevant academic research and scientific papers
A “universal” catalyst for aerobic oxidations to synthesize (hetero)aromatic aldehydes, ketones, esters, acids, nitriles, and amides
Bartling, Stephan,Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Rabeah, Jabor,Rockstroh, Nils,Senthamarai, Thirusangumurugan
supporting information, p. 508 - 531 (2022/02/11)
Functionalized (hetero)aromatic compounds are indispensable chemicals widely used in basic and applied sciences. Among these, especially aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides represent valuable fine and bulk chemicals, which are used in chemical, pharmaceutical, agrochemical, and material industries. For their synthesis, catalytic aerobic oxidation of alcohols constitutes a green, sustainable, and cost-effective process, which should ideally make use of active and selective 3D metals. Here, we report the preparation of graphitic layers encapsulated in Co-nanoparticles by pyrolysis of cobalt-piperazine-tartaric acid complex on carbon as a most general oxidation catalyst. This unique material allows for the synthesis of simple, functionalized, and structurally diverse (hetero)aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides from alcohols in excellent yields in the presence of air.
Effective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by an Acetal Protection Strategy
Asakawa, Miyuki,Boonyakarn, Tat,Chen, Lulu,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka,Wiesfeld, Jan J.
, (2022/02/25)
An acetal protection strategy for 5-hydroxymethylfurfural (HMF) was used to obtain 2,5-diformyfuran (DFF) using concentrated HMF solutions and a γ-Al2O3-supported Ru catalyst (Ru/γ-Al2O3). The HMF-acetal with 1,3-propanediol can be oxidized to DFF-acetal with a yield of 84.0 % at an HMF conversion of 94.2 % from a 50 wt % solution. In contrast, aerobic oxidation of nonprotected HMF using a 10 wt % solution afforded DFF only in a moderate yield (52.3 %). Kinetic studies indicated that the six-membered ring acetal group not only prevents side reactions but also accelerates aerobic oxidation of the ?CH2OH moiety to ?CHO under retention of the acetal functionality. Organic deposits formed during the reaction explained the significant decrease in the activity of the Ru/γ-Al2O3 catalyst, which could be recovered neither by washing in water or organic solvents, nor by a calcination-reduction treatment. Sonication of the used Ru/γ-Al2O3 catalyst in an aqueous NaOH solution successfully removed the deposits and allowed reuse of the catalyst for at least four times without activity loss.
Hydroxyapatite Supported Manganese Oxide as a Heterogeneous Catalyst for the Synthesis of 2, 5-Diformylfuran
Chen, Hong,Li, Yingying,Li, Yongdan,Ma, Xueli,Wang, Can,Wang, Sen,Yu, Linhao
, (2022/02/16)
A series of hydroxyapatite (HAP) supports with different Ca/P ratios were synthesized to prepare the MnOx/HAP catalysts. A MnOx/HAP catalyst showed highly efficient conversion of 5-hydroxymethylfurfural (HMF) into 2, 5-diformylfuran (DFF) in toluene solvent under no-alkali condition. 86.4% conversion of HMF with 90.9% selectivity of DFF at 120?°C for 12?h under 1.0?MPa O2 over the MnOx/HAP-10.0-400 were obtained. The redox of Mn4+/Mn3+ improved the oxidation of 5-HMF to DFF by the lattice oxygen, and the lattice oxygen was replenished by adsorbing O2 molecules. The reusability tests were found the catalyst could be reused up to four cycles without notable loss of catalytic activity. The MnOx/HAP-10.0-400 was a stable and reusable material for further industrial exploration of DFF in an environmentally friendly way. Graphical Abstract: [Figure not available: see fulltext.]
Method for preparing 2, 5-furandicarboxaldehyde by degrading carbohydrate
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Paragraph 0019-0048, (2021/06/22)
The invention relates to a method for preparing 2, 5-furandicarboxaldehyde by degrading carbohydrate. The method comprises the following steps: 1) placing 20-40 parts by weight of cane sugar or glucose, 0.2-0.5 part by weight of a catalyst, 1-2 parts by weight of a dispersing agent and 80-100 parts by weight of an organic solvent in a reaction kettle, sealing, and uniformly stirring to form a mixed solution, wherein the catalyst is cerium dioxide with a particle size of less than 100 nm; and 2) introducing air into the reaction kettle under the condition of continuously stirring, keeping the pressure in the reaction kettle at 2-5 MPa and the temperature at 70-90 DEG C, reacting for 1-2 hours, then stopping the reaction, and naturally cooling to room temperature to obtain a mixed solution with 2, 5-furandicarboxaldehyde as a main component. The method has the advantages of mild reaction conditions, no need of high temperature and high pressure, high yield of 2, 5-furandicarboxaldehyde, no need of a complicated HMF separation step, cost reduction, and better conformity to the target of green chemistry.
Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials
Ibrahim, Nagham,Moussallem, Chady,Allain, Magali,Segut, Olivier,Gohier, Frédéric,Frère, Pierre
, p. 475 - 482 (2021/03/31)
Two series of linear extended benzofuran derivatives associating cyanovinyl unit and phenyl or furan moieties obtained from benzaldehyde-lignocellulosic (Be series) or furaldehyde –saccharide (Fu series) platforms were prepared in order to investigate their emission and electrochemical properties. For the fluorescence in solution and solid states, contrasting results between the two series were demonstrated. For Be series a net aggregation induced emission effect was observed with high fluorescence quantum yield for the solid state. A [2+2] cycloaddition under irradiation at 350 nm was also revealed for one derivative of Be series. In contrast, for Fu series the fluorescence in solution is higher than in the solid state. The X-ray crystallography studies for the compounds reveal the formation of strong π-π stacking for the derivatives without emissive property in the solid state and the presence of essentially lateral contacts for emissive compounds. Taking advantage of the propensity to develop 2D π-stacking mode for the more extended derivative with a central furan cycle, organic field effect transistors presenting hole mobility have been made.
Synthesis and characterization of an α-MoO3nanobelt catalyst and its application in one-step conversion of fructose to 2,5-diformylfuran
Cui, Peng,He, Jianbo,He, Yuhan,Yang, Zhenzhen,Zhang, Genlei,Zhu, Bangchong
supporting information, p. 16482 - 16489 (2021/09/28)
In this study, α-MoO3nanobelts were successfully synthesized by a simple, green and economic hydrothermal method and applied as a bifunctional catalyst for one-step conversion of fructose to DFF under atmospheric air. The structure of the as-prepared α-MoO3catalyst was characterized in detail by SEM, TEM, EDS, XRD, XPS, H2-TPR and NH3-TPD to better understand the relationship between structure and performance. α-MoO3nanobelts exhibited high catalytic activities for production of DFF from HMF and fructose in atmospheric air. Under optimized reaction conditions, high DFF yields of 97.2% and 78.3% were obtained by using HMF and fructose as raw materials, respectively. Furthermore, a plausible reaction pathway was proposed for the selective oxidation of HMF to DFF according to the experimental and catalyst characterization results. Importantly, α-MoO3is a robust catalyst that can be used at least five times without obvious loss in its catalytic activity. In brief, α-MoO3is an easily-prepared, eco-friendly, low cost and highly effective catalyst which has potential application in one-step conversion of fructose to DFF under atmospheric air.
Synthesis of amides and esters containing furan rings under microwave-assisted conditions
Janczewski, ?ukasz,Zieliński, Dariusz,Kolesińska, Beata
, p. 265 - 280 (2021/03/17)
In this work, we present a novel method for the synthesis of ester and amide derivatives containing furan rings (furfural derivatives) under mild synthetic conditions supported by microwave radiation. N-(Furan-2-ylmethyl)furan-2-carboxamide and furan-2-ylmethyl furan-2-carboxylate were produced using 2-furoic acid, furfurylamine, and furfuryl alcohol. The reactions were carried out in a microwave reactor in the presence of effective coupling reagents: DMT/NMM/TsO? or EDC. The reaction time, the solvent, and the amounts of the substrates were optimized. After crystallization or flash chromatography, the final compounds were isolated with good or very good yields. Our method allows for the synthesis of N-blocked amides using N-blocked amino acids (Boc, Cbz, Fmoc) and amine. As well as compounds with a monoamide and ester moiety, products with diamides and diester bonds (N,N-bis(furan-2-ylmethyl) furan-2,5-dicarboxamide, bis(furan-2-ylmethyl) furan-2,5dicarboxylate, and furan-3,4-diylbis(methylene) bis(furan-2-carboxylate)) were synthesized with moderate yields in the presence of DMT/NMM/TsO– or EDC, using 2,5-furan-dicarboxylic acid and 3,4-bis(hydroxymethyl)furan as substrates.
Hydroxyapatite-Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5-Hydroxymethylfurfural or Glucose to 2,5-Diformylfuran under Atmospheric Pressure
Guan, Hongyu,Li, Ying,Wang, Qiwen,Wang, Xiaohong,Yu, Hang
, p. 997 - 1005 (2021/08/06)
(NH4)5H6PV8Mo4O40 supported on hydroxyapatite (HAP) (PMo4V8/HAP (n)) was prepared through the ion exchange of hydroxy groups. This ion exchange favored the oxidative conversion of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF) in a one-pot cascade reaction with 96.0 % conversion and 83.8 % yield under 10 mL/min of O2 flow. PMo4V8/HAP (31) was used to explore the production of DFF directly from glucose with the highest yield of 47.9 % so far under atmospheric oxygen, whereas the yield of DFF increased to 54.7 % in a one-pot and two-step reaction. These results indicated that the active sites in PMo4V8/HAP (31) retained their activities without any interference toward one another, which enabled the production of DFF in a more cost-saving way by only using oxygen and one catalyst in a one-step reaction. Meanwhile, the rigid structure of HAP and strong interaction in PMo4V8/HAP (31) allowed this catalyst to be reused for at least six times with high stability and duration.
Highly selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over an α-MnO2 catalyst
Yu, Linhao,Chen, Hong,Wen, Zhe,Jin, Mengmeng,Ma, Zewei,Ma, Xueli,Sang, Yushuai,Chen, Mengmeng,Li, Yongdan
, p. 9 - 15 (2020/11/20)
Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-diformylfuran (DFF) with molecular oxygen is realized with an α-MnO2 catalyst under mild conditions. In this work, α-MnO2 exhibited the best performance among the samples examined. Meanwhile, solvent shows a significant effect on the product selectivity and isopropanol is found good for improving the selectivity of DFF. 93.2 % conversion of HMF was achieved at 140 °C for 4 h with 84.3 % selectivity of DFF. Moreover, α-MnO2 catalyst keeps good reusability in recycling for five times. The reaction pathway indicated that the lattice oxygen species on α-MnO2 is involved in the selective oxidation of hydroxyl group in HMF molecule.
Electro-catalytic oxidation of HMF to FDCA over RuO2/MnO2/CNT catalysts in base-free solution
Dai, Yihu,Jin, Yuguang,Song, Yu,Wan, Xiaoyue,Wang, Tianci,Yang, Yanhui,Zhao, Wanna,Zhou, Chunmei
, p. 21285 - 21292 (2021/12/09)
The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the most attractive reactions to establish a sustainable chemical process based on biomass resources. In this work, a CNT-supported ruthenium-manganese oxide nano-catalyst (RuO2/MnO2/CNT) was employed for the electro-catalytic oxidation of HMF in base-free aqueous solution. The activity test showed that α-MnO2 can effectively promote the activity of RuO2 in the oxidation of HMF. In comparison with RuO2/CNT, RuO2/MnO2/CNT possessed a lower activation energy and more than twice the FDCA formation rate. Under the optimized reaction conditions, the RuO2/MnO2/CNT catalyst afforded a FDCA yield of 72.1% in a 0.1 M K2SO4 aqueous solution at a 0.9 V (vs. Ag/AgCl) applied potential. To our knowledge, this is the first demonstration of FDCA formation as the primary product with high yield in an initially neutral electrolyte. The product FDCA can be easily separated after cooling the reaction solution to room temperature. This journal is
