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.]
Dicarboxyl acid aromatic heterocyclic compound and method for preparing thereof
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Paragraph 0309-0319, (2021/10/15)
The present invention relates to a method for preparing a dicarboxylic acid aromatic heterocyclic compound and a dicarboxylic acid aromatic heterocyclic composition obtained therefrom. To the present invention, a bio-based hydroxyl - free aromatic heterocyclic compound is oxidized under heterogeneous catalysis to produce oxides having improved yield and purity.
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
Method for preparing 2, 5-diformyl furan through glucose three-step cascade reaction
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Paragraph 0039-0065; 0068; 0069, (2021/02/20)
The invention discloses a method for preparing 2, 5-diformyl furan through glucose three-step cascade reaction, which is a three-step cascade reaction and comprises the following steps of: (1) preparing fructose through glucose isomerization; and (2) dehydrating the fructose to generate 5-hydroxymethylfurfural (5-HMF) 3) F, and oxidizing the 5-HM to synthesize DFF. A TiO2 catalyst containing an anatase phase and a rutile phase is selected and used in step (1), a graphene oxide catalyst is selected and used in step (2) to step (3) , so that biomass (glucose) is directly and efficiently converted into a high-added-value platform product (2, 5-diformyl furan).
Method for preparing 2,5-diformyl furan through selective oxidation of 5-hydroxymethylfurfural
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Paragraph 0018-0029, (2021/05/29)
The invention discloses a method for preparing 2,5-diformyl furan through selective oxidation of 5-hydroxymethylfurfural, which comprises the steps of reacting 5-hydroxymethylfurfural serving as a raw material, a four-component molybdenum-based compound Co9Fe3BiMo12O51 serving as a catalyst and oxygen serving as an oxidant in dimethyl sulfoxide under normal pressure and heating conditions for a certain time to obtain 2,5-diformyl furan, wherein the catalyst can be repeatedly used after being centrifugally separated, washed and dried. The conversion rate of the raw material 5-hydroxymethylfurfural is high, the yield of the product 2,5-diformyl furan is high, and the catalyst Co9Fe3BiMo12O51 can be repeatedly used.
