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A “universal” catalyst for aerobic oxidations to synthesize (hetero)aromatic aldehydes, ketones, esters, acids, nitriles, and amides
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.
Bartling, Stephan,Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Rabeah, Jabor,Rockstroh, Nils,Senthamarai, Thirusangumurugan
supporting information
p. 508 - 531
(2022/02/11)

Effective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by an Acetal Protection Strategy
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.
Asakawa, Miyuki,Boonyakarn, Tat,Chen, Lulu,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka,Wiesfeld, Jan J.
(2022/02/25)

Hydroxyapatite Supported Manganese Oxide as a Heterogeneous Catalyst for the Synthesis of 2, 5-Diformylfuran
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.]
Chen, Hong,Li, Yingying,Li, Yongdan,Ma, Xueli,Wang, Can,Wang, Sen,Yu, Linhao
(2022/02/16)

Hydroxyapatite-Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5-Hydroxymethylfurfural or Glucose to 2,5-Diformylfuran under Atmospheric Pressure
(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.
Guan, Hongyu,Li, Ying,Wang, Qiwen,Wang, Xiaohong,Yu, Hang
p. 997 - 1005
(2021/08/06)

Highly selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over an α-MnO2 catalyst
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.
Yu, Linhao,Chen, Hong,Wen, Zhe,Jin, Mengmeng,Ma, Zewei,Ma, Xueli,Sang, Yushuai,Chen, Mengmeng,Li, Yongdan
p. 9 - 15
(2020/11/20)

Electro-catalytic oxidation of HMF to FDCA over RuO2/MnO2/CNT catalysts in base-free solution
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
Dai, Yihu,Jin, Yuguang,Song, Yu,Wan, Xiaoyue,Wang, Tianci,Yang, Yanhui,Zhao, Wanna,Zhou, Chunmei
p. 21285 - 21292
(2021/12/09)

Synthesis of amides and esters containing furan rings under microwave-assisted conditions
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.
Janczewski, ?ukasz,Zieliński, Dariusz,Kolesińska, Beata
p. 265 - 280
(2021/03/17)

Method for preparing 2,5-diformyl furan through selective oxidation of 5-hydroxymethylfurfural
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.
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Paragraph 0018-0029

(2021/05/29)

Synthesis and characterization of an α-MoO3nanobelt catalyst and its application in one-step conversion of fructose to 2,5-diformylfuran
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.
Yang, Zhenzhen,Zhu, Bangchong,He, Yuhan,Zhang, Genlei,Cui, Peng,He, Jianbo
p. 16482 - 16489
(2021/09/28)

Preparation method 2-5 -dimethoxyfuran
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.
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Paragraph 0062-0094

(2021/11/26)

Imidazole-Functionalized Polyoxometalate Catalysts for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Using Atmospheric O2
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.
Liu, Dan,Chen, Baokuan,Li, Jie,Lin, Zhengguo,Li, Peihe,Zhen, Ni,Chi, Yingnan,Hu, Changwen
p. 3909 - 3916
(2021/03/08)

SBA-15 Supported 1-Methyl-2-azaadamanane N-Oxyl (1-Me-AZADO) as Recyclable Catalyst for Oxidation of Alcohol
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.
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)

Highly efficient and tunable visible-light-catalytic synthesis of 2,5-diformylfuran using HBr and molecular oxygen
This paper discloses that inexpensive hydrobromic acid (HBr) is active and highly selective to the photo-oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with dioxygen (O2) or even with water under visible light illumination, which can achieve the highest 89.1% DFF yield in DMSO at 80 °C under pure O2atmosphere. More importantly, under bifunctional acid-photooxidation catalysis of HBr, fructose can be directly converted to DFF and its two-step cascade conversion in DMSO provides a far higher DFF yield (80.2%) than the one-step cascade conversion in MeCN (42.1%). The results of HMF photooxidation catalyzed by hydrohalic acids, free radical quenching tests and EPR spectrum support that the Br atom and superoxide (O2?˙) anion radicals generated by HBr photolysis in O2are active species for the oxidation of HMF to DFF and their activities are adjusted by the reaction medium. This photo-synthetic protocol is very simple and practical, especially with low operating costs, showing a good industrial application prospect.
Fu, Zaihui,Hu, Wenwei,Jiang, Dabo,She, Jialuo,Yang, Bo,Zhang, Huanhuan
p. 23365 - 23373
(2021/07/13)

Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials
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.
Ibrahim, Nagham,Moussallem, Chady,Allain, Magali,Segut, Olivier,Gohier, Frédéric,Frère, Pierre
p. 475 - 482
(2021/03/31)

Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by Visible Light-Driven Photocatalysis over In Situ Substrate-Sensitized Titania
Solar energy-driven processes for biomass valorization are priority for the growing industrialized society. To address this challenge, efficient visible light-active photocatalyst for the selective oxidation of biomass-derived platform chemical is highly desirable. Herein, selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was achieved by visible light-driven photocatalysis over titania. Pristine titania is photocatalytically inactive under visible light, so an unconventional approach was employed for the visible light (λ=515 nm) sensitization of titania via a formation of a visible light-absorbing complex of HMF (substrate) on the titania surface. Surface-complexation of HMF on titania mediated ligand-to-metal charge transfer (LMCT) under visible light, which efficiently catalyzed the oxidation of HMF to DFF. A high DFF selectivity of 87 % was achieved with 59 % HMF conversion after 4 h of illumination. The apparent quantum yield obtained for DFF production was calculated to be 6.3 %. It was proposed that the dissociative interaction of hydroxyl groups of HMF and the titania surface is responsible for the surface-complex formation. When the hydroxyl groups of titania were modified via surface-fluorination or calcination the oxidation of HMF was inhibited under visible light, signifying that hydroxyl groups are decisive for photocatalytic activity.
Khan, Ayesha,Goepel, Michael,Kubas, Adam,?omot, Dariusz,Lisowski, Wojciech,Lisovytskiy, Dmytro,Nowicka, Ariadna,Colmenares, Juan Carlos,Gl?ser, Roger
p. 1351 - 1362
(2021/02/05)

CLEAVABLE MULTI-ALCOHOL-BASED MICROCAPSULES
The present invention relates to a new process for the preparation of microcapsules based on cleavable multi-alcohols. Cleavable multi-alcohol-based microcapsules are also an object of the invention. Perfuming compositions and consumer products comprising
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Page/Page column 42

(2021/02/12)

Symmetric 32π(1.0.1.0.1.0.1) core-modified heptaphyrins from asymmetric building block
An asymmetrical precursor with three thiophene subunits on condensation with a thiophene/furan diol yield a symmetrical 32πheptaphyrin. Here are the first examples of pyrrole-free antiaromatic heptaphyrin synthesized by the acid assisted condensation reaction, followed by an oxidative α-α coupling between the terminal thiophene rings. The macrocycles attains a slightly bent configuration, which undergoes reversible two-electron oxidation between a neutral 4nπand (4n + 2)πdication state.
Anand, Venkataramanarao G.,Gupta, Prachi
supporting information
p. 3481 - 3485
(2021/05/31)

Facile Production of 2,5-Furandicarboxylic Acid via Oxidation of Industrially Sourced Crude 5-Hydroxymethylfurfural
The oxidation of 5-hydroxymethylfurfural (HMF) produces value-added chemicals such as 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). In this work, FDCA production was achieved by oxidation of crude HMF solution containing around 45 % HMF a
Martin, Kevin J.,Subramaniam, Bala,Venkitasubramanian, Padmesh,Zuo, Xiaobin
(2022/01/13)

An efficient approach to synthesizing 2,5-bis(: N -methyl-aminomethyl)furan from 5-hydroxymethylfurfural via 2,5-bis(N -methyl-iminomethyl)furan using a two-step reaction in one pot
In this study, an amination-oxidation-amination-reduction (AOAR) strategy was proposed for the synthesis of 2,5-bis(N-methyl-aminomethyl)furan (BMAF) from HMF via the intermediate 2,5-bis(N-methyl-iminomethyl)furan (BMIF). Firstly, an efficient synthesis of BMIF from HMF using a one-pot amination-oxidation-amination reaction was developed over α-MnO2 under an air atmosphere. A BMIF yield of 98.3% was obtained under mild reaction conditions. The conversion of HMF to BMIF underwent the fast amination of HMF to 5-(methyl-iminomethyl)furfuryl alcohol (MIFA), the subsequent rate-limiting oxidation of MIFA to 5-(methyl-iminomethyl)furfural (MIFF) and the final fast amination of MIFF to BMIF. The quick amination of MIFF to BMIF drove the oxidation reaction equilibrium toward MIFF from MIFA, which ensured the highly efficient conversion of HMF to BMIF. The investigation of the catalytic mechanism showed better lattice oxygen donating ability and oxygen coordination capacity, which made α-MnO2 retain the structural stability in the reaction. The higher ratio and better mobility of the lattice oxygen endowed α-MnO2 with excellent catalytic performance in the oxidation of MIFA to MIFF by the redox cycling of Mn4+/Mn3+, facilitating the conversion of HMF to BMIF. Eventually, a BMAF yield of 96.1% was achieved by the reduction of BMIF with Ru/C after the AOA reaction, realizing the synthesis of BMAF from HMF using a two-step reaction in one pot. This journal is
Jia, Wenlong,Lin, Lu,Sun, Yong,Tang, Xing,Yang, Shuliang,Zeng, Xianhai,Zhang, Jie
p. 5656 - 5664
(2021/08/16)

Iodine-catalyzed alcohol disproportionation method
The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
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Paragraph 0032-0033

(2021/06/13)

Insights into the catalytic mechanism of 5-hydroxymethfurfural to phthalic anhydride with MoO3/Cu(NO3)2in one-pot
Recently, we reported a synthetic approach to obtain renewable phthalic anhydride (PA) from 5-hydroxymethfurfural (HMF) with a yield of 63.2% using MoO3/Cu(NO3)2 as a catalyst in one pot, for the first time. The reaction pathway has been elucidated in our previous study. Herein, the synergistic catalytic mechanism of MoO3/Cu(NO3)2 for the oxidation of HMF to PA was investigated. The commercially available MoO3 (c-MoO3) with superior characteristics, including more lattice oxygen and better oxygen-donating capacity, provides higher activity for the oxidation of HMF to PA. More importantly, the synergy between c-MoO3 and Cu(NO3)2 ensured the high yield of PA through the Mo6+/Mo4+ redox couple facilitated by the redox cycling of Cu2+/Cu+ with the assistance of oxygen.
Feng, Yunchao,Jia, Wenlong,Li, Weile,Lin, Lu,Sun, Yong,Tang, Xing,Zeng, Xianhai,Zhao, Xiaoyu,Zuo, Miao
p. 5656 - 5662
(2021/08/24)

Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information
p. 8108 - 8115
(2021/10/29)

Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid
Encapsulating noble metal nanoparticles (NPs) within the zeolite framework enhances the stability and accessibility of active sites; however, direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions. Herein, beta zeolite-encapsulated Pt NPs (Pt?Beta) were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step. The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species. Thus, the resultant 0.2%Pt?Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDCA) under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield (90%) associated with a large turnover number of 176. The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.
Chen, Lei,Jiang, Shi,Liu, Xiaoling,Wang, Jun,Xu, Hongzhong,Zhou, Yu
p. 994 - 1003
(2020/12/14)

Nitrogen doped carbon spheres with wrinkled cages for the selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancarboxylic acid
Nitrogen doped carbon spheres with wrinkled cages (NCSWCs), which were used for the first time as metal-free catalysts, exhibited high catalytic activity and selectivity in the oxidation of 5-hydroxymethylfurfural (HMF) to 5-formyl-2-furancarboxylic acid
Zhu, Jiaping,Yao, Chaojian,Maity, Ayan,Xu, Jielai,Zhan, Tong,Liu, Weibing,Sun, Mingtai,Wang, Suhua,Polshettiwar, Vivek,Tan, Hua
supporting information
p. 2005 - 2008
(2021/03/01)

Selective Oxidation of 5-Hydroxymethylfurfural to 2, 5-Diformylfuran Over a Vanadium Manganese Oxide Catalyst
5-Hydroxymethylfurfural (HMF) is a major feedstock derived from biomass which could be converted to various high-value-added chemicals. However, it is a challenge to obtain a target product with high selectivity under mild conditions using a heterogeneous non-noble catalyst. In this study, a vanadium manganese oxide catalyst was prepared by a simple chemical synthesis method. Detailed characterization was performed to reveal that the catalyst phase composition is V2O5 and Mn(VO3)2. The catalyst showed good catalytic activity in the selective oxidation of HMF to produce 2,5-diformylfuran (DFF) at atmospheric oxygen pressure. Under optimal conditions, DFF selectivity of 97.8% was obtained at 80?°C with acetonitrile as the solvent. Furthermore, the catalyst could be recovered conveniently and reused for several runs without significant loss of the catalytic activity. Graphic Abstract: The vanadium manganese oxide catalyst was developed for the selective oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran under atmospheric pressure of molecular oxygen. [Figure not available: see fulltext.].
Cheng, Feng,Liu, Xianxiang,Wang, Fei,Wen, Sha,Zhu, Jie
(2021/10/05)

Mechanistic Studies on the Photooxidation of 5-Hydroxymethylfurfural by Polyoxometalate Catalysts and Atmospheric Oxygen
Efficient oxidation of 5-hydroxymethylfurfural (HMF) to corresponding furanic products represents an important research focus of biomass valorization, recent research on polyoxometalates (POMs)-catalyzed aerobic oxidation of HMF usually requires high temperature and sometimes high O2/air pressure. In this work, we report a mild and green approach to photocatalytically transform HMF into various furanic products using atmospheric oxygen as oxidant and POMs as photocatalysts. The influence of different POMs, light sources, and additives were systematically investigated by various experimental and spectroscopic results. Under minimally optimized conditions, 88.0 % HMF can be efficiently photooxidized with as high as 70.2 % furanic yield by TBA-W10 catalyst after 2 h irradiation of 365 nm UV light when coupling with TEMPO and Na2CO3 as additives. Finally, detailed mechanistic pathways of HMF photooxidation have been proposed to illustrate the transformation of HMF to various furanic products. This work provides some insightful guidelines for photooxidation of biomass-derived platform chemicals to value-added products under efficient, mild, and green conditions, exhibiting potential practical applications in the future.
Li, Zheng,Zhang, Mo,Xin, Xing,Lv, Hongjin
p. 1389 - 1395
(2021/02/01)

Understanding the Roles of Electrogenerated Co3+ and Co4+ in Selectivity-Tuned 5-Hydroxymethylfurfural Oxidation
The Co-based electrocatalyst is among the most promising candidates for electrochemical oxidation of 5-hydroxymethylfurfural (HMF). However, the intrinsic active sites and detailed mechanism of this catalyst remains unclear. We combine experimental evidence and a theoretical study to show that electrogenerated Co3+ and Co4+ species act as chemical oxidants but with distinct roles in selective HMF oxidation. It is found that Co3+ is only capable of oxidizing formyl group to produce carboxylate while Co4+ is required for the initial oxidation of hydroxyl group with significantly faster kinetics. As a result, the product distribution shows explicit dependence on the Co oxidation states and selective production of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) and 2,5-furandicarboxylic acid (FDCA) are achieved by tuning the applied potential. This work offers essential mechanistic insight on Co-catalyzed organic oxidation reactions and might guide the design of more efficient electrocatalysts.
Deng, Xiaohui,Fu, Xian-Zhu,Li, Jian-Feng,Luo, Jing-Li,Wang, Lei,Xu, Ge-Yang,Zhang, Jiujun,Zhang, Yue-Jiao
supporting information
p. 20535 - 20542
(2021/08/12)

Dicarboxyl acid aromatic heterocyclic compound and method for preparing thereof
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.
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Paragraph 0309-0319

(2021/10/15)

Method for preparing 2, 5-furandicarboxaldehyde by degrading carbohydrate
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.
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Paragraph 0019-0048

(2021/06/22)

Method for preparing 2, 5-diformyl furan through glucose three-step cascade reaction
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).
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Paragraph 0039-0065; 0068; 0069

(2021/02/20)

Selective valorization of 5-hydroxymethylfurfural to 2,5-diformylfuran using atmospheric O2 and MAPBBr3 perovskite under visible light
Selective production of value-added platform chemicals from renewable biomass feedstocks and their derivatives has attracted tremendous attention with high potential in addressing global problems of energy and sustainability. In this work, a lead-halide perovskite (MAPbBr3, MA = methylammonium) is utilized as a photocatalyst for selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) using atmospheric O2 upon visible-light irradiation. Under minimally optimized conditions, the photocatalytic conversion of HMF in acetonitrile solvent reaches 100% with a DFF selectivity of over 90%, achieving an overall furanic carbon yield of over 96%. A detailed catalytic mechanism was proposed based on various spectroscopic and experimental results, revealing that the atmospheric O2, photogenerated electrons (e?), holes (h+), ?O2?, and 1O2 species together play crucial roles in the effective and selective photo-oxidation of HMF to DFF. In addition, our present photocatalytic system is also applicable for photo-oxidation of benzyl alcohol with approximately 100% conversion and benzaldehyde selectivity, providing insights for future exploration of the present catalytic system.
Zhang, Mo,Li, Zheng,Xin, Xing,Zhang, Junhao,Feng, Yeqin,Lv, Hongjin
p. 14793 - 14800
(2020/12/21)

Aerobic oxidation of 5-(hydroxymethyl)furfural into 2,5-diformylfuran catalyzed by starch supported aluminum nitrate
Al(NO3)3 immobilized on expanded corn starch catalyst (ECS-IL-Al(NO3)3) was prepared by silane-modified imidazolium ionic liquid reacting with expanded corn starch (ECS) and coordination of Al(NO3)3 with the imidazolium chloride grafted on the surface, as proved by FT-IR, NMR, SEM/EDS, and XPS. The catalytic activity of ECS-IL-Al(NO3)3 was evaluated in the 5-hydroxymethylfurfural (HMF) oxidation under mild conditions with 98% of 2,5-diformylfuran (DFF) production at 99% HMF conversion after 5 h at 50 °C, using molecular oxygen as the oxidant. Furthermore, this catalyst was found to exhibit excellent recyclability, making it an attractive catalytic system from economic and environmental points of view.
Hong, Mei,Wu, Shuangyan,Li, Jiatong,Wang, Jing,Wei, Lifen,Li, Kun
(2019/12/25)

Non-metallic Aerobic Oxidation of Alcohols over Anthraquinone Based Compounds
The catalytic performances of substituted anthraquinones were investigated in catalytic oxidation of alcohols like cyclohexanol, benzyl alcohol and 5-hydroxymethylfurfural (HMF) to carbonyl compounds (cyclohexanone, benzyl aldehyde and diformylfuran). The reduction potential of anthraquinone plays the key role in the oxidation reactions. TOF numbers and selectivities to carbonyl compounds pass through the maximum with increase of the reduction potential. The maximum activity and selectivity (>80 %) is observed for sulfonated and carboxylated anthraquinones having intermediate reduction potentials (≈ 0.1-0.2 V vs SHE). Grafted 2-carboxyanthraquinone catalyst has demonstrated comparable catalytic performance to the parent molecule and might be used as heterogeneous catalyst. The oxidation reaction was found to have radical character with transfer of hydrogen from alcohol to anthraquinone and subsequent oxidation of hydrogenated anthraquinone by oxygen.
Zhao, Jingpeng,Wu, Dan,Hernández, Willinton Yesid,Zhou, Wen-Juan,Capron, Mickael,Ordomsky, Vitaly V.
(2019/11/14)

Synthesis of 2,5-furandicarboxylic acid by a TEMPO/laccase system coupled withPseudomonas putidaKT2440
As a useful and renewable chemical building block from biomass, 2,5-furandicarboxylic acid (FDCA) has become an increasingly desirable platform chemical as a terephthalic acid replacement for polymerization. In this work, an efficient and highly selective biocatalytic approach for the synthesis of FDCA from 5-hydroxymethylfurfural (HMF) was successfully developed using a TEMPO/laccase system coupled withPseudomonas putidaKT2440. TEMPO/laccase afforded the selective oxidation of the hydroxymethyl group of HMF to form 5-formyl-2-furancarboxylic acid as a major product, which was subsequently oxidized to FDCA byP. putidaKT2440. Manipulating the reaction conditions resulted in a good conversion of HMF (100percent) and an excellent selectivity of FDCA (100percent) at substrate concentrations up to 150 mM within 50 h. The cascade catalytic process established in this work offers a promising approach for the green production of FDCA.
Ouyang, Jia,Tan, Huanghong,Xu, Qianqian,Zheng, Zhaojuan,Zou, Lihua
p. 21781 - 21788
(2020/07/03)

Green synthesis method for preparing 2,5-diformyl furan by catalyzing 5-hydroxymethylfurfural
The invention provides a green synthesis method for preparing 2, 5-diformyl furan by catalyzing 5hydroxymethylfurfural, which comprises the following steps: oxidizing 5-hydroxymethylfurfural under mild conditions to prepare 2,5-diformyl furan under the catalytic action of a Mn-based composite oxide MxMnOy and the oxidation action of an oxidant; the synthesis method comprises the following specificsteps: (1) adding 5-hydroxymethylfurfural (HMF), a reaction medium and a Mn-based composite oxide into a reaction tube; (2) introducing oxygen, wherein the speed of the oxygen is 5-20mL/min; and stirring the reaction mixture in the reaction tube at the temperature of 20 DEG C and 40 DEG C at the stirring speed of 500-1200rpm to react for 30 minutes and 640 minutes. The method overcomes the defectof higher reaction activity of aldehyde groups in the 5-hydroxymethylfurfural, enhances the selectivity of the 2, 5-diformyl furan, enables the reaction to be more economical, milder and greener, andcan implement large-scale application.
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Paragraph 0020; 0041-0043; 0044-0045; 0046-0047; 0048-0077

(2020/12/30)

Method for preparing 2,5-furandicarboxaldehyde from 5-hydroxymethylfurfural
The invention relates to a method for preparing 2,5-furandicarboxaldehyde through oxidation of 5-hydroxymethylfurfural, particularly a method for catalyzing oxidation of 5-hydroxymethylfurfural (HMF)by adopting an Anderson type CeCu(OH)6Mo6O18 heteropolyacid salt as a catalyst to prepare 2,5-furandicarboxaldehyde (DFF). The method comprises the following steps: 1) adding 0.0504 g of HMF into 7 mLof an aromatic hydrocarbon solvent solution, stirring, then adding 40-120 mg of the Anderson type heteropolyacid salt CeCu(OH)6Mo6O18 catalyst; 2) introducing oxygen, carrying out an HMF oxidation reaction at the temperature of 110 to 150 DEG C to obtain a liquid mixture containing DFF; (3) diluting the liquid mixture and analyzing a product by using a high performance liquid chromatograph. The DFF can be efficiently synthesized by the method (the yield is up to 99%), the reaction conditions are mild, and the catalyst can be recycled, so that the method is a cheap and efficient DFF preparation method. Moreover, compared with a catalyst in the prior art, the catalyst used in the method has higher DFF selectivity and is more economical.
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Paragraph 0023-0039

(2020/05/14)

Functionalized expanded corn starch-anchored Cu(I): An efficient and recyclable catalyst for oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran
The development of new strategies for the synthesis of biomass-based non-precious metal heterogeneous catalysts has recently received great interest from chemists because of the advantages of these catalytic systems being sustainable, low cost and green. An expanded corn starch-supported CuBr catalyst (ECS-SB-CuBr) has been successfully prepared and well characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Further, ECS-SB-CuBr was used as a heterogeneous catalyst for the selective oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-diformylfuran (DFF) and a full HMF conversion is obtained with 98% DFF yield in acetonitrile under ambient pressure of dioxygen at 50°C. The catalyst also showed good reusability, could be easily recovered through filtration and washing and was reused in at least six consecutive runs with virtually no loss of catalytic performance.
Hong, Mei,Min, Jie,Wu, Shuangyan,Li, Jiatong,Wang, Jing,Wei, Lifen,Ling, Zhi,Li, Kun,Wang, Shifa
(2020/01/08)

Preparation method of 2, 5-furandicarboxaldehyde under illumination condition
The invention discloses a preparation method of 2, 5-furandicarboxaldehyde under an illumination condition. The process of a magnetic nanoparticle-loaded TEMPO catalyst comprises the following steps:dissolving FeCl3, citric acid and urea in diglycerol, carrying out a heating reaction, cooling, carrying out magnetic separation, washing with ethanol, and drying to obtain citric acid functionalizedmagnetic nanoparticles; mixing the citric acid functionalized magnetic nanoparticles, 4-amine-2, 2, 6, 6-tetramethyldiphenylpiperidine and dichloromethane and stirring the mixture at room temperature,then adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and carrying out a stirring reaction; and carrying out suction filtration, washing and freeze drying to obtain the magnetic nanoparticle-loaded TEMPO catalyst. The catalyst carrier prepared by the method is low in raw material price, wide in source, easy to recycle, green and environment-friendly; the catalyst catalyzes and oxidizes HMF under the illumination condition, and the oxidation product DFF obtained at high yield can be used for synthesizing many useful compounds and novel high polymer materials.
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Paragraph 0039-0047

(2020/07/02)

2D/2D MXene/g-C3N4 for photocatalytic selective oxidation of 5-hydroxymethylfurfural into 2,5-formylfuran
The selective oxidation of 5-hydroxyfurfural (HMF) into the corresponding aldehyde is one of the key reactions in the production of chemical products. Here, we prepared the MXene/g-C3N4 composite (MX/CN) for photocatalytic selective oxidation of HMF into 2,5-diformylfuran (DFF). At the mild reaction conditions, both DFF selectivity and yield can reach up to ≥ 90% over 6% MX/CN. In addition, the MX/CN also shows high activity for selective oxidation of other non-aromatic and aromatic alcohols. Moreover, the reaction conditions are surveyed and the mechanism has been studied. This study provides a way for HMF conversion under mild conditions.
Wang, Xiang-Xiang,Meng, Sugang,Zhang, Sujuan,Zheng, Xiuzhen,Chen, Shifu
(2020/09/09)

A gram scale selective oxidation of 5-hydroxymethylfurfural to diformylfuran in the presence of oxone and catalyzed by 2-iodobenzenesulfonic acid
In the present work, an alternative system of 5-hydroxymethylfurfural (HMF) oxidation was studied, in an attempt to avoid the use of expensive metal catalysts, polluting systems and high pressures. In this context, the partial oxidation of the hydroxyl gr
Ayoub, Nadim,Bergère, Carla,Toufaily, Joumana,Guénin, Erwann,Enderlin, Gérald
supporting information
p. 11577 - 11583
(2020/07/27)

Hydrothermal polymerization towards fully biobased polyazomethines
Microwave assisted polycondensation for the synthesis of (partially) biobased polyazomethines in water (hydrothermal polymerization) was investigated for the first time in this study. The polyazomethines prepared via this environmentally friendly and simple method show comparable characteristics as the polymers prepared via traditional methods in organic solvents.
Bernaerts, Katrien V.,Gebben, Bert,Li, Guotai,Meeusen-Wierts, Monique H. M.,Noordijk, Jurrie,Oude Lohuis, Petra A. M.,Schotman, Anton H. M.,Yu, Kui
supporting information
p. 9194 - 9197
(2020/08/26)

Work-hardening Photopolymer from Renewable Photoactive 3,3’-(2,5-Furandiyl)bisacrylic Acid
The design of a photopolymer around a renewable furan-derived chromophore is presented herein. An optimised semi-continuous oxidation method using MnO2 affords 2,5-diformylfuran from 5-(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’-(2,5-furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD-DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo- and enzyme-catalysed polycondensation. The latter enzyme-catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator-free UV curing leads to an impressive increase in the material stiffness, with work-hardening characteristics observed during tensile strength testing.
Farmer, Thomas J.,Funes-Ardoiz, Ignacio,Lie, Yann,Macquarrie, Duncan J.,Pellis, Alessandro,Sampedro, Diego
(2020/08/03)

One-step synthesis of 2,5-diformylfuran from monosaccharides by using lanthanum(iii) triflate, sulfur, and DMSO
The combination of lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide prompted a facile, direct preparation of 2,5-diformylfuran from glucose and fructose. The one-step dehydration/oxidation of fructose afforded 2,5-diformylfuran in an excellent yield with high selectivity. The proposed mechanism, large-scale synthesis, and product separation were presented. This approach represents a straightforward and eco-friendly pathway, which can be applied in the large-scale production of 2,5-diformylfuran from fructose. This journal is
Nguyen, Quynh Nhu Ba,Le, Hao Anh Nguyen,Ly, Phat Duc,Phan, Ha Bich,Tran, Phuong Hoang
supporting information
p. 13005 - 13008
(2020/11/07)

Method for preparing 2,5-furandicarboxaldehyde from fructose
The invention provides a method for preparing 2,5-furandicarboxaldehyd from fructose. Fructose is adopted as a raw material, dehydration and oxidation are carried out through a one-pot method under mild conditions to obtain DFF, the separation difficulty of HMF is avoided, piperidine nitroxide free radicals are used on the catalyst, no metal ions are contained in the reaction process, and the whole synthesis method has obvious economic advantages and better conforms to the green chemical target.
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Paragraph 0020-0033

(2020/08/30)

The one-step transformation of fructose to 2,5-diformylfuran over Ru metal supported on montmorillonite
In this work, the synthesis of a catalyst with Ru metal supported on a montmorillonite (MMT) support was performed and the prepared catalyst was characterized via different characterization techniques such as: SEM, XRD, XPS, EDX, TEM, and TGA. The catalytic effect of the prepared Ru-MMT with various wt% of Ru metal were determined for the dehydration reaction of fructose to 5-hydroxymethylfurfural (HMF), and for the efficient oxidation of HMF into 2,5-diformylfuran (DFF). HMF conversion occurred completely in 4 h of reaction time to obtain DFF with a 96% yield at 120 °C and an oxygen pressure of 3 bar in dimethyl sulfoxide (DMSO) solvent with 2 wt% of the Ru-MMT catalyst. A one-pot, two-step reaction produced a yield of 89% DFF with 100% conversion of fructose, however an 81% yield of DFF was achieved from a one-pot, one-step reaction using the 2 wt% Ru-MMT catalyst. The catalyst can be isolated easily after the completion of the reaction and successfully reused up to five times with no substantial loss of catalyst activity. The practical applicability of the developed catalyst was successfully demonstrated for the direct transformation of various carbohydrates (glucose, inulin, sucrose, starch, raffinose, and maltose) to DFF in moderate to good yields (35-64% yield). Overall, the 2 wt% Ru-MMT catalyst demonstrated excellent catalytic activity for the one-pot transformation of fructose to DFF showing an excellent yield of DFF in a short reaction time, and afforded wide substrate applicability, good recyclability and catalyst stability. This journal is
Raut, Amol B.,Shende, Vaishali S.,Bhanage, Bhalchandra M.
supporting information
p. 13659 - 13668
(2020/09/07)

Oxidative Esterification of 5-Hydroxymethylfurfural under Flow Conditions Using a Bimetallic Co/Ru Catalyst
Furanic di-carboxylate derivatives of 5-Hydroxymethylfurfural (HMF) are nowadays important in the polymer industry as they are used as building blocks for bio-based polyesters. The high reactivity of HMF compels to avoid harsh synthetic conditions. Therefore, developing mild catalytic processes for its selective oxidation is a challenging task. Herein, we report the first oxidative esterification of HMF to dimethyl furan-2,5-dicarboxylate (FDCM) under flow conditions using oxygen as oxidant. For that purpose, a new series of nitrogen-doped carbon-supported bimetallic Co/Ru heterogeneous catalysts were prepared and characterized by XRD, XPS and N2 physisorption. These analyses revealed that the porosity of the materials and order of impregnation of the metals to the carbon supports lead to varying catalytic activities. Under optimized conditions the flow reactor showed a 15-fold increase on the production of FDCM compared to batch conditions.
Salazar, Abel,Linke, Alexander,Eckelt, Reinhard,Quade, Antje,Kragl, Udo,Mejía, Esteban
p. 3504 - 3511
(2020/05/16)

One-Pot Synthesis of Renewable Phthalic Anhydride from 5-Hydroxymethfurfural by using MoO3/Cu(NO3)2 as Catalyst
Herein, a synthetic pathway to renewable phthalic anhydride (PA) from 5-hydroxymethfurfural (HMF) in one pot is reported. The commonly available catalysts MoO3 and Cu(NO3)2 play a crucial role in integrating the multiple steps of the reaction, namely decarbonylation of HMF to active furyl intermediate (AFI), oxidation of HMF to maleic anhydride (MA), Diels–Alder cycloaddition of AFI and MA, and subsequent dehydration, in one pot. Under mild reaction conditions, a 63.2 % yield of PA is obtained from HMF. Compared with the currently reported route to renewable PA based on the Diels–Alder cycloaddition of biomass-derived MA and furan, this convenient one-pot synthesis represents a great improvement in efficiency.
Jia, Wenlong,Sun, Yong,Zuo, Miao,Feng, Yunchao,Tang, Xing,Zeng, Xianhai,Lin, Lu
p. 640 - 646
(2020/01/22)

Insights into the active sites and catalytic mechanism of oxidative esterification of 5-hydroxymethylfurfural by metal-organic frameworks-derived N-doped carbon
Directly oxidative esterification of Biomass-derived 5-hydroxymethylfurfural (HMF) into dimethyl furan dicarboxylate (DMFDCA) is a promising route for the replacement of petroleum-derived commodity chemical terephthalic acid (TPA) extensively employed in polyester synthesis. Co-based N-doped carbon materials are one of the most promising applied catalysts for oxidative esterification reaction, however, the active sites and reaction pathway of these catalysts have not been clearly clarified, which is crucial to the practical application. Herein, we report that ZIF-67 (a zeolitic imidazolate framework (ZIF)-type cobalt-containing MOF) derived Co@C-N material is a highly effective catalyst for the selective conversion of HMF into DMFDCA in 95% yield. The high activity of the ZIF-67 derived nanocarbon composites Co@C-N can be attributed to the electron transfer between nitrogen-doped carbon shells and Co nanoparticles. The appropriate graphitic N and pyridinic N doping increases the electronic mobility and active sites. Density functional theory (DFT) simulations indicated that oxygen, HMF and methanol molecules are adsorbed and activated on C-N materials. Furthermore, no 2, 5-diformylfuran (DFF) was captured as an intermediate because the oxidative esterification of aldehyde preferentially occurred than the oxidation of hydroxyl group in HMF. We anticipate that these results can drive progress in the bio-based polymers sector and oxidative esterification reaction.
Feng, Yunchao,Jia, Wenlong,Yan, Guihua,Zeng, Xianhai,Sperry, Jonathan,Xu, Binbin,Sun, Yong,Tang, Xing,Lei, Tingzhou,Lin, Lu
p. 570 - 578
(2019/12/25)

Efficient and Selective Oxidation of 5-Hydroxymethylfurfural into 2, 5-Diformylfuran Catalyzed by Magnetic Vanadium-Based Catalysts with Air as Oxidant
Abstract: In this study, a new kind of magnetic vanadium-based catalyst was successfully prepared and employed to produce 2, 5-diformylfuran (DFF) in the liquid phase through selective oxidation of biomass-derived 5-hydroxymethylfurfur (HMF) with air as oxidant. It was found that magnetic Fe3O4 nanoparticles supported NH4·V3O8 showed excellent catalytic performance with the achievement of 95.5% HMF conversion along with 82.9% selectivity to DFF under optimal reaction conditions. More importantly, the catalyst could be readily separated from the reaction mixture by a permanent magnet, and recycled several times without the loss of its catalytic activity. Graphic Abstract: The NH4·V3O8/Fe3O4 catalyst showed high activity for selective oxidation of 5-hydroxymethylfurfural into 2, 5-diformylfuran.[Figure not available: see fulltext.]
Lai, Jinhua,Zhou, Shuolin,Cheng, Feng,Guo, Dongwen,Liu, Xianxiang,Xu, Qiong,Yin, Dulin
p. 1301 - 1308
(2019/11/29)

Production of 5-(formyloxymethyl)furfural from biomass-derived sugars using mixed acid catalysts and upgrading into value-added chemicals
In this work, 5-(formyloxymethyl)furfural (FMF) has been produced from biomass-derived hexose sugars within a biphasic reaction mixture consisting of aqueous formic acid (85%), a strong Br?nsted acid catalyst, and 1,2-dichloroethane as an organic extractant. Using a combination of aqueous hydrobromic acid and formic acid, under optimized condition (80 °C, 8 h, 10 wt% substrate loading), 68% isolated yield of FMF was obtained from fructose. FMF has been demonstrated as a renewable chemical building block for the synthesis of renewable chemicals of commercial significance such as 5-methylfurfural, 2,5-diformylfuran, and 2,5-furandicarboxylic acid in good to excellent isolated yields.
Dutta, Saikat
(2020/10/02)