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-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).
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.
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.
Synthesis and characterization of an α-MoO3nanobelt catalyst and its application in one-step conversion of fructose to 2,5-diformylfuran
Yang, Zhenzhen,Zhu, Bangchong,He, Yuhan,Zhang, Genlei,Cui, Peng,He, Jianbo
, 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.
Preparation method 2-5 -dimethoxyfuran
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Paragraph 0062-0094, (2021/11/26)
The method at least comprises the following steps: taking oxygen or air as an oxidizing agent, reacting materials containing 2 hydroxymethyl furfural, reacting in the presence of a two-component catalytic system and an organic additive, and preparing 5 - 2-5 - 5 -dimethoxyfuran. The method is a high yield. Low cost, catalyst easy separation, low pollution, no solvent's bulk oxidation new technology to molecular oxygen or air is oxidant, oxidation 5 - hydroxymethyl furfural preparation 2, 5 - dibenzoyl furan. The method has a wide application prospect.
Imidazole-Functionalized Polyoxometalate Catalysts for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Using Atmospheric O2
Liu, Dan,Chen, Baokuan,Li, Jie,Lin, Zhengguo,Li, Peihe,Zhen, Ni,Chi, Yingnan,Hu, Changwen
, p. 3909 - 3916 (2021/03/08)
Biomass as a sustainable and abundant carbon source has attracted considerable attention as a potential alternative to petroleum resources. The selective oxidation of 5-hydroxymethylfurfural (HMF), a versatile platform molecule, to value-added 2,5-diformylfuran (DFF) provides an efficient pathway for biomass valorization. Herein, three discrete imidazole-functionalized polyoxometalates (POMs), HPMo8VVI4O40(VVO)2[(VIVO)(IM)4]2·nH2O·(IM)m (IM = 1-methylimidazole, n = 4, m = 8 for 1; IM = 1-ethylimidazole, n = 4, m = 9 for 2; IM = 1-propylimidazole, n = 0, m = 4 for 3), have been successfully synthesized by a facile solvothermal method and thoroughly characterized by routine techniques. Compounds 1-3 contain a bi-capped pseudo-Keggin {HPMo8V4O40(VO)2} and two imidazole-functionalized {(VO)(IM)4} groups, which, to our knowledge, represent the first examples of organic-functionalized Mo-V clusters. Compounds 1-3 as heterogeneous catalysts can effectively promote the transformation of HMF to DFF using atmospheric O2 as oxidant. Under minimally optimized conditions, 95% of HMF was converted by 1 with 95% selectivity for DFF and its catalytic activity was basically maintained after five cycles. Moreover, the important roles of the bi-capped pseudo-Keggin cluster and the functionalized V groups in the selective oxidation of HMF have been explored. According to experimental and spectroscopic results, a three-step oxidation mechanism of HMF to DFF has been proposed.
SBA-15 Supported 1-Methyl-2-azaadamanane N-Oxyl (1-Me-AZADO) as Recyclable Catalyst for Oxidation of Alcohol
Tian, Yangwu,Guo, Xiaqun,Li, Meichao,Li, Chunmei,Hu, Xinquan,Jin, Liqun,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu
supporting information, p. 3928 - 3932 (2021/05/26)
Herein, we designed and synthesized an SBA-15 supported 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO) and investigated its catalytic performance for selective oxidation of alcohols under Anelli's conditions. The first example of immobilization of 1-Me-AZADO was very important to advance the oxgenation effectively because this supported N-oxyl has excellent catalytic activity for oxidation of alcohols to carbonyl compounds, and more importantly, it can be conveniently recovered and reused at least 6 times without significant effect on its catalytic efficiency.
