104-80-3Relevant articles and documents
Enzyme-catalyzed asymmetric acylation and hydrolysis of cis-2,5-disubstituted tetrahydrofuran derivatives: Contribution to development of models for reactions catalyzed by porcine liver esterase and porcine pancreatic lipase
Naemura,Fukuda,Takahashi,Konishi,Hirose,Tobe
, p. 911 - 918 (1993)
Pig liver esterase, lipase from porcine pancreas, lipase from Pseudomonas sp. (lipase YS), and lipase from Candida cylindracea catalyzed hydrolyses of the cis-diacetate 1 and the trans-diacetate (±)-4 to give the cis-monoacetate 3 and the trans-monoacetate 6 in optically active forms, respectively. Lipase YS-catalyzed acylations of the cis-diol 2 and the trans-diol (±)-5 with an acylating agent in cyclohexane yielded (-)-3 and (-)-6, respectively. The group adjacent to the R stereogenic center preferentially reacted in lipase YS-catalyzed hydrolyses of 1 and (±)-4 and acylations of 2 and (±)-5, and the enantioselectivites are rationalized by our rule recently proposed for lipase YS.
Catalytic selective hydrogenation and rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water
Zhang, Shujing,Ma, Hong,Sun, Yuxia,Luo, Yang,Liu, Xin,Zhang, Meiyun,Gao, Jin,Xu, Jie
, p. 1702 - 1709 (2019)
The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone (HCPN) were studied over a MOF-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper dramatically improved the efficiency in both the selective hydrogenation of the carbonyl group of 5-HMF and the hydrogenative ring-rearrangement of the C5 ring, affording 70.3% yield for HCPN and 99.8% yield for the rearrangement products. Moreover, it was indicated that water acted as a solvent, reactant, and proton donor by dissociation at an elevated temperature, which supplied slightly acidic conditions and promoted the rearrangement reaction.
Combination of Pd/C and Amberlyst-15 in a single reactor for the acid/hydrogenating catalytic conversion of carbohydrates to 5-hydroxy-2,5- hexanedione
Liu, Fei,Audemar, Maite,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jerome, Francois
, p. 4110 - 4114 (2014)
Here we show that combination of Pd/C and Amberlyst-15 in a single reactor allowed fructose and inulin to be converted to 5-hydroxy-2-5-hexanedione, a valuable chemical platform, in a one-pot process. the Partner Organisations 2014.
Homogeneous catalysed hydrogenation of HMF
Cadu, Alban,Sekine, Kohei,Mormul, Jaroslaw,Ohlmann, Dominik M.,Schaub, Thomas,Hashmi, A. Stephen K.
, p. 3386 - 3393 (2018)
In this report, hydroxymethylfurfural (HMF) is used as a bio-based feedstock for homogeneous metal-catalysed hydrogenation. Several ligand classes and metals are employed to reduce the aldehyde and aromatic ring of HMF. The previously unknown homogeneous catalysed hydrogenation of HMF to tetrahydrofuran-dimethanol (THFDM) was investigated using different catalyst systems. NHCs and phosphites give higher trans/cis ratios (between 1:1.25 and 1:3.95) of the product THFDM, but low conversions of only up to 17% accompanied by up to 92% yield of bis(hydroxymethyl)furan at 10 bar H2 and 120 °C. Conversely, di-phosphine ligated ruthenium catalysts in up to 87% yield lead to the highest overall conversion but only moderate trans/cis ratios of only 1:3.1-1:5.
Biomass into chemicals: One-pot production of furan-based diols from carbohydrates via tandem reactions
Cai, Haile,Li, Changzhi,Wang, Aiqin,Zhang, Tao
, p. 59 - 65 (2014)
In this work, the direct production of furan-based diols from carbohydrates and their upstream raw materials via one-pot tandem reactions in ionic liquid/water system is presented. In this novel reaction system, ionic liquid serves as an advantageous solvent for polysaccharide (cellulose, inulin, sucrose) hydrolysis and hexose dehydration reactions, and heterogeneous Pd, Pt, Ir, Ni, Ru-based catalysts catalyze HMF hydrogenation reaction under relatively mild condition (50 °C, 6 MPa H2) to afford moderate to high yield (34.0-89.3%) of furan-based diols, namely, 2,5-dihydroxymethylfuran (DHMF) and 2,5-dihydroxymethyltetrahydrofuran (DHMTF). Our results show that the metal species strongly affects the selectivity of the products, while the nature of the support influences the activity of the catalysts significantly. By selecting the proper metal species and the support, controllable production of DHMF or DHMTF was realized. Based on the intermediates identified and the conversion results, the proposed reaction pathway, including possible side reactions were presented. Taken together, our catalytic system featured with simple process, mild condition, high yield of diols and adjustable product selectivity. The direct conversion of the carbohydrates and the upstream materials drives our technology nearer to real application for cost-efficient production of chemicals from biomass.
Ru/MnCo2O4 as a catalyst for tunable synthesis of 2,5-bis(hydroxymethyl)furan or 2,5-bis(hydroxymethyl)tetrahydrofuran from hydrogenation of 5-hydroxymethylfurfural
Mishra, Dinesh Kumar,Lee, Hye Jin,Truong, Cong Chien,Kim, Jinsung,Suh, Young-Wong,Baek, Jayeon,Kim, Yong Jin
, (2020)
Manganese and cobalt metals-based mixed oxide (MnCo2O4) spinels supported ruthenium (Ru) nanoparticles, Ru/MnCo2O4, is found to be an active catalyst to execute outstandingly the hydrogenation of 5-hydroxymethylfurfural (HMF) to produce two useful furan diols such as 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) in highly selective fashion without any additive. It could found that Ru/MnCo2O4 was able to catalyze not only the oxidation but also the reduction of HMF due to the redox properties of the MnCo2O4. Moreover, the characterization details responsible for the high activity of this catalyst in the hydrogenation of HMF were investigated by several spectroscopic methods. In order to maximize the products yield and HMF conversion, the effect of reaction variables such as time, temperature, pressure, and various metal oxides supported Ru nanoparticles was also investigated. Furthermore, the reusability tests exhibited that Ru/MnCo2O4 catalyst could be reused at several consecutive cycles, retaining almost its original activity.
Preparation of 1-Hydroxy-2,5-hexanedione from HMF by the Combination of Commercial Pd/C and Acetic Acid
Duan, Ying,Yang, Dexi,Yang, Yanliang,Zhang, Chi,Zheng, Min
, (2020)
The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2 pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.
Selective hydrogenation of biomass-based 5-hydroxymethylfurfural over catalyst of palladium immobilized on amine-functionalized metal-organic frameworks
Chen, Jinzhu,Liu, Ruliang,Guo, Yuanyuan,Chen, Limin,Gao, Hui
, p. 722 - 733 (2015)
A catalyst of palladium [Pd/MIL-101(Al)-NH2] supported on amine-functionalized Metal-Organic Frameworks (MOFs) allows selective hydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethyl-tetrahydrofuran (DHMTHF) with 2,5-dihydroxymethylfuran (DHMF) as an observed "intermediate". The Pd/MIL-101(Al)-NH2 was prepared by using a direct anionic exchange approach and subsequent gentle reduction. The presence of free amine moieties in the frameworks of MIL-101(Al)-NH2 is suggested to play a key role on the formation of uniform and well-dispersed palladium nanoparticles on the support. The adsorption experiments reveal that the amine-functionalized MOF supports show preferential adsorption to hydrogenation intermediate DHMF than in the case of reactant HMF owing to an enhanced hydrophilic nature of DHMF as well as improved hydrogen bonding interactions between DHMF and the MOF support, which promotes a further hydrogenation of DHMF to DHMTHF upon the in situ formation of DHMF over Pd/MIL-101(Al)-NH2. Moreover, our results also indicate that the observed high selectivity toward DHMTHF form HMF is closely related to the cooperation between the metallic site and the free amine moiety on the MOF support. Under the optimal conditions, a maximum DHMTHF yield of 96% with a full conversion of HMF is obtained by using Pd/MIL-101(Al)-NH2 (Pd 3.0 wt %) catalyst at a low reaction temperature of 30 °C in aqueous medium. The research thus highlights new perspectives for aluminum-based and amine-functionalized MOF material for biomass transformation.
Selective hydrogenation of 5-hydroxymethylfurfural and its acetal with 1,3-propanediol to 2,5-bis(hydroxymethyl)furan using supported rhenium-promoted nickel catalysts in water
Wiesfeld, Jan J.,Kim, Minjune,Nakajima, Kiyotaka,Hensen, Emiel J. M.
, p. 1229 - 1238 (2020)
The high reactivity of the formyl group of 5-hydroxymethylfurfural (5-HMF) is problematic, because it leads to undesired oligomerization reactions. This is usually countered by working in dilute non-aqueous solutions. Here, we present a novel approach to convert concentrated aqueous solutions of 5-HMF to 2,5-bishydroxymethylfuran (BHMF), which is a prospective monomer for polyesters and self-healing polymers. Our approach is based on the protection of the formyl group of 5-HMF using acetalization with 1,3-propanediol. Hydrogenation is carried out using an optimized bimetallic Ni-Re catalyst supported on TiO2 at a carefully controlled pH, resulting in balanced rates of deprotection and hydrogenation and high BHMF yield. Under optimized conditions at a benign temperature of 40 °C, hydrogenation of concentrated solutions (10-20 wt%) of protected 5-HMF in water gave 81-89% yields of BHMF without having to resort to platinum-group metals such as palladium or platinum.
Direct synthesis of 1,6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source
Tuteja, Jaya,Choudhary, Hemant,Nishimura, Shun,Ebitani, Kohki
, p. 96 - 100 (2014)
A new approach is developed for hydrogenolytic ring opening of biobased 5-hydroxymethylfurfural (HMF), dehydration product of hexoses, towards 1,6-hexanediol (HDO) under atmospheric pressure. The highest yield of HDO, 43 %, is achieved over reusable Pd/zirconium phosphate (ZrP) catalyst at 413 K in the presence of formic acid as hydrogen source. In comparison with various Bronsted and/or Lewis acidic supports, the specific Bronsted acidity on ZrP support effectively accelerated the cleavage of C-O bond in a furan ring.
Perovskite type oxide-supported Ni catalysts for the production of 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural
Chen, Meng-Yuan,Chen, Chu-Bai,Zada, Bakht,Fu, Yao
, p. 3858 - 3866 (2016)
The hydrogenolysis of C-O and CO in 5-hydroxymethylfurfural for the production of furan biofuel 2,5-dimethylfuran (DMF) is of great importance for biomass refining. However, development of non-noble metal-based catalysts which perform stably for this process is still challenging. Here, perovskite-supported Ni catalysts were used for the hydrogenolysis of 5-hydroxymethylfurfural at 230 °C, with 98.3% yield of DMF being obtained. The effects of reaction conditions such as temperature and pressure were investigated and discussed, and the catalyst could maintain good activity after being used at least 5 times. In order to further explore the reaction mechanism, dynamic experiments at different times were carried out and a possible reaction pathway was proposed. The development of efficient perovskite-supported Ni catalysts verified their great potential in biomass conversion.
Kinetics of Catalytic Hydrogenation of 5-Hydroxymethylfurfural to 2,5-bis-Hydroxymethylfuran in Aqueous Solution over Ru/C
Jain, Anandkumar B.,Vaidya, Prakash D.
, p. 318 - 328 (2016)
5-Hydroxymethylfurfural (5-HMF) is a cellulosic product of the hydrolysis of biomass, and it is widely considered for the production of several interesting chemicals and derivatives. In the present work, catalytic hydrogenation of 5-hydroxymethylfurfural to 2,5-bis-hydroxymethylfuran was investigated using 5% Ru/C in the aqueous phase. Kinetic data were experimentally obtained over a wide range of temperatures (313-343 K), H2 partial pressure (0.69-2.07 MPa), initial HMF concentration (19.8-59.5 mM), and catalyst loading (0.3-0.7 kg/m3) in a three-phase slurry reactor. Disappearance of initial 5-HMF concentrations was modeled using the power law and Langmuir-Hinshelwood-Hougen-Watson models. A model based on the competitive adsorption of molecular H2 and HMF was proposed. It is presumed that surface reaction between nondissociatively chemisorbed H2 and 5-HMF was rate determining. This model provided the best fit for the kinetic data. From the Arrhenius equation, the activation energy for the surface reaction was found to be 104.9 kJ/mol.
Synthesis of 1,6-hexanediol from HMF over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor
Xiao, Bin,Zheng, Mingyuan,Li, Xinsheng,Pang, Jifeng,Sun, Ruiyan,Wang, Hua,Pang, Xiaoli,Wang, Aiqin,Wang, Xiaodong,Zhang, Tao
, p. 2175 - 2184 (2016)
1,6-Hexanediol (1,6-HDO) was effectively prepared from 5-hydroxymethylfurfural (HMF) over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor. Under optimal reaction conditions (373 K, 7.0 MPa H2, in solvent mixtures of 40% water and 60% tetrahydrofuran (THF)), 57.8% yield of 1,6-HDO was obtained. The double-layered catalysts loaded in double-layered beds showed much superior performance compared to that of a single catalyst of Pd-Ir-ReOx/SiO2, even when the same amount of active components were used in the catalysts. The reaction solvent significantly affected product distributions, giving a volcano-shape plot for the 1,6-HDO yield as a function of the ratio of water to THF. Br?nsted acidic sites were generated on the catalyst in the presence of water which played determining roles in 1,6-HDO formation. A high pressure of H2 contributed to 1,6-HDO formation by depressing the over-hydrogenolysis of reaction intermediates and products to form hexane and hexanol. The reaction route was proposed for HMF conversion to 1,6-HDO on the basis of conditional experiments.
Selective conversion of 5-hydroxymethylfurfural to cyclopentanone derivatives over Cu-Al2O3 and Co-Al2O3 catalysts in water
Ramos, Rubén,Grigoropoulos, Alexios,Perret, Noémie,Zanella, Marco,Katsoulidis, Alexandros P.,Manning, Troy D.,Claridge, John B.,Rosseinsky, Matthew J.
, p. 1701 - 1713 (2017)
The production of cyclopentanone derivatives from 5-hydroxymethylfurfural (HMF) using non-noble metal based catalysts is reported for the first time. Five different mixed oxides containing Ni, Cu, Co, Zn and Mg phases on an Al-rich amorphous support were prepared and characterised (XRD, ICP, SEM, TEM, H2-TPR, NH3/CO2-TPD and N2 sorption). The synthesised materials resulted in well-dispersed high metal loadings in a mesoporous network, exhibiting acid/base properties. The catalytic performance was tested in a batch stirred reactor under H2 pressure (20-50 bar) in the range T = 140-180 °C. The Cu-Al2O3 and the Co-Al2O3 catalysts showed a highly selective production of 3-hydroxymethylcyclopentanone (HCPN, 86%) and 3-hydroxymethylcyclopentanol (HCPL, 94%), respectively. A plausible reaction mechanism is proposed, clarifying the role of the reduced metal phases and the acid/basic sites on the main conversion pathways. Both Cu-Al2O3 and Co-Al2O3 catalysts showed a loss of activity after the first run, which can be reversed by a regeneration treatment. The results establish an efficient catalytic route for the production of the diol HCPL (reported for the first time) and the ketone HCPN from bio-derived HMF over 3d transition metals based catalysts in an environmental friendly medium such as water.
Process condition-based tuneable selective catalysis of hydroxymethylfurfural (HMF) hydrogenation reactions to aromatic, saturated cyclic and linear poly-functional alcohols over Ni-Ce/Al2O3
Grilc, M.,Likozar, B.,Pomeroy, Brett
supporting information, p. 7996 - 8002 (2021/11/01)
The related immense versatility of a ceria-promoted transition metal catalyst, utilized for the hydrogenation of 5-hydroxymethylfurfural (HMF), is demonstrated in this research study. We reveal a strategy to achieve considerable selective yields of three important high-value HMF-derived compounds by simply modifying the analysed reaction conditions and/or water-containing process medium.
Preparation method 2 and 5 - tetrahydrofuran dimethanol
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Paragraph 0072-0106, (2021/11/19)
The preparation method of 2-5 - tetrahydrofuran dimethanol (THFDM) comprises the following steps: mixing a solvent containing 5 - hydroxymethylfurfural raw material with a catalyst, and reacting in an atmosphere containing hydrogen to obtain the 2 and 5 - tetrahydrofuran dimethanol. The purity of 5 - hydroxymethyl furfural raw material is 90 - 99%. The catalyst comprises a carrier and an active component. The active component is loaded on the carrier. The active component includes a noble metal element. The carrier comprises a carbon material. The method is simple in synthesis process, and has a great application prospect in the field of a plurality of fields, especially degradable materials.
