65313-46-4Relevant articles and documents
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
, (2020/06/17)
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.
Highly efficient hydrogenative ring-rearrangement of furanic aldehydes to cyclopentanone compounds catalyzed by noble metals/MIL-MOFs
Li, Xiang,Deng, Qiang,Zhang, Likang,Wang, Jun,Wang, Rong,Zeng, Zheling,Deng, Shuguang
, p. 152 - 158 (2019/02/26)
Hydrogenative ring-rearrangement reaction of biomass-derived furanic aldehydes to cyclopentanone compounds catalyzed by metal/support bifunctional catalysts suffers a low selectivity of target product and serious carbon loss because of the Br?nsted acid catalysis. Herein, a series of pure Lewis acid sites MIL-MOFs (Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101) with different crystal topology structures and metals are synthesized. Then the nanoparticles of Ru, Pt, Pd and Au are uniformly dispersed on the internal surface of the MOF support. The hydrogenation rate catalyzed by the noble metals/Fe-MIL-100 is three times faster than those obtained with Fe-MIL-101 and Cr-MIL-101-based catalysts due to the higher dispersion of nanoparticles on the former to make it more accessible to reactants. Meanwhile, both of the noble metals on Fe-MIL-100 and Fe-MIL-101 have a higher selectivity of cyclopentanone compounds than that on Cr-MIL-101, since the Fe ions in the MOF host with a higher oxophilicity will promote the adsorption and hydrolysis of the intermediate furanic alcohols (furfural alcohol or 2,5-bis(hydroxymethyl)furan). Furthermore, the noble metals/MIL-MOFs catalyst can maintain a good activity and stability after recycling for five runs. The current work will present an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural and 5-hydroxymethyl furfural to synthesize cyclopentanone compounds.
Selective conversion of 5-hydroxymethylfurfural to diketone derivatives over Beta zeolite-supported Pd catalysts in water
Ramos, Rubén,Grigoropoulos, Alexios,Griffiths, Ben L.,Katsoulidis, Alexandros P.,Zanella, Marco,Manning, Troy D.,Blanc, Frédéric,Claridge, John B.,Rosseinsky, Matthew J.
, p. 224 - 233 (2019/06/19)
Conversion of 5-hydroxymethylfurfural (HMF) in water to the linear diketone derivatives 1-hydroxyhexane-2,5-dione (HHD) and 2,5-hexanedione (HXD) was investigated over a series of Beta zeolite-supported transition metal catalysts (Co, Ni, Cu, Ru, Pd). Their catalytic performance was tested in a batch stirred reactor (T = 110 °C, PH2 = 20 bar) with Pd showing the highest activity and selectivity to HHD and HXD. The effects of Pd particle size, zeolite Si/Al ratio and reaction conditions (T = 80–155 °C, PH2 = 5–60 bar) were also investigated. The incorporation of Pd into Beta zeolite by the deposition-coprecipitation method produced the most efficient catalyst, affording complete HMF conversion (T = 110 °C, PH2 = 60 bar) predominantly to HHD (68% selectivity) and HXD (8% selectivity). The combination of a bifunctional acid/redox solid catalyst and water enhances the hydrolytic ring-opening and subsequent hydrogenation of the furan ring. Catalytic activity can be partially restored by a simple regeneration treatment. This work establishes a catalytic route to produce valuable diketone derivatives from renewable furanic platform sources in water.
Cyclopentadienyl-Ru(II)-Pyridylamine Complexes: Synthesis, X-ray Structure, and Application in Catalytic Transformation of Bio-Derived Furans to Levulinic Acid and Diketones in Water
Dwivedi, Ambikesh D.,Sahu, Vinod K.,Mobin, Shaikh M.,Singh, Sanjay K.
, p. 4777 - 4787 (2018/04/25)
A series of cationic half-sandwich cyclopentadienyl-ruthenium(II)-pyridylamine complexes, [(η5-C5H5)Ru(κ2-L)(PPh3)]+ (L = Namine-substituted pyridylamine ligands) ([Ru]-1-[Ru]-6), along with the analogous cyclopentadienyl-ruthenium(II)-N-isopropylpyridylimine complex [(η5-C5H5)Ru(κ2-L)(PPh3)]+ (L = N-isopropylpyridylimine) ([Ru]-7), have been synthesized in good yields. Structural identities of all the complexes have been authenticated by 1H, 13C, and 31P NMR, mass spectrometry, and X-ray crystallography. The synthesized complexes exhibited high catalytic activity for the transformation of the bio-derived furans, 2-furfural (furfural), 5-methyl-2-furfural (5-MF), and 5-hydroxymethyl-2-furfural (5-HMF) to levulinic acid (LA) and the diketones, 3-hydroxyhexane-2,5-dione (3-HHD), 1-hydroxyhexane-2,5-dione (1-HHD), and hexane-2,5-dione (HD) in water. Efficient transformation of furfural to LA over a range of η5-Cp-Ru-pyridylamine complexes is substantially affected by the Namine-substituents, where a η5-Cp-Ru-N-propylpyridylamine complex ([Ru]-2) exhibited higher catalytic activity in comparison to other η5-Cp-Ru-pyridylamine and η5-Cp-Ru-pyridylimine complexes. The relative catalytic activity of the studied complexes demonstrated a substantial structure-activity relationship which is governed by the basicity of Namine, steric hindrance at Namine, and the hemilabile nature of the coordinated pyridylamine ligands.
Conversion of HMF to methyl cyclopentenolone using Pd/Nb2O5 and Ca-Al catalysts: Via a two-step procedure
Duan, Ying,Zheng, Min,Li, Dongmi,Deng, Dongsheng,Ma, Lu-Fang,Yang, Yanliang
, p. 5103 - 5113 (2017/11/09)
The catalytic conversion of HMF to 2-hydroxy-3-methyl-2-cyclopenten-1-one (MCP), which is a valuable edible essence that has traditionally been obtained from adipic acid, was achieved with an isolated yield of 58%. This procedure comprised two steps: the hydrogenation of 5-hydroxymethylfurfural (HMF) to 1-hydroxy-2,5-hexanedione (HHD) in water on Pd/Nb2O5 catalysts and then the isomerization of HHD to MCP in the presence of a base. The Nb2O5 supports, which were acidic, were characterized by FTIR, XRD and NH3-TPD. The supported Pd/Nb2O5 catalysts, in which Pd was highly dispersed, were synthesized employing cyclohexene as a reductant and were characterized by XRD, TEM, ICP-AES, XPS, EDX and CO pulse chemisorption. The high conversion of HMF was attributed to the high dispersion of Pd, and the acidity of the supports led to high selectivity for HHD. The conversion of HHD to MCP was an intramolecular aldol condensation reaction, and the protonic solvent favored this reaction. Ca-Al was proved to be an effective solid base for the conversion of HHD to MCP in water.
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 (2017/06/07)
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.
Electrochemical reductive biomass conversion: Direct conversion of 5-hydroxymethylfurfural (HMF) to 2,5-hexanedione (HD): Via reductive ring-opening
Roylance, John J.,Choi, Kyoung-Shin
supporting information, p. 2956 - 2960 (2016/06/06)
2,5-Hexanedione (HD), which can be produced by reduction of 5-hydroxymethylfurfural (HMF), one of the most important biomass intermediates, can serve as a precursor to produce various biofuels and key building block chemicals. The conversion of HMF to HD requires reduction of both the alcohol and aldehyde groups to alkane groups as well as opening of the furan ring. In this study, a direct electrochemical conversion of HMF to HD at ambient pressure and temperature was demonstrated without using H2 or precious metal catalysts. Water was used as the hydrogen source and zinc was used as the catalytic electrode, which enabled hydrogenolysis and Clemmensen reduction coupled with furan ring opening. Optimum conditions to achieve high Faradaic efficiency (FE) and selectivity for HD production were investigated and plausible mechanisms were proposed. The environmentally benign one-step procedure to produce HD reported in this study will serve as a new route to valorize biomass intermediates.
Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water
Perret, Noémie,Grigoropoulos, Alexios,Zanella, Marco,Manning, Troy D.,Claridge, John B.,Rosseinsky, Matthew J.
, p. 521 - 531 (2016/03/09)
The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni2+ to Ni0. Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt %) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water.
Ruthenium and Formic Acid Based Tandem Catalytic Transformation of Bioderived Furans to Levulinic Acid and Diketones in Water
Dwivedi, Ambikesh D.,Gupta, Kavita,Tyagi, Deepika,Rai, Rohit K.,Mobin, Shaikh M.,Singh, Sanjay K.
, p. 4050 - 4058 (2015/12/26)
Efficient tandem catalytic transformations of bioderived furans, such as furfural, 5-hydroxymethylfurfural (5-HMF), and 5-methylfurfural (5-MF), to levulinic acid (LA) and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione (3-HHD), and hexane-2,5-dione (2,5-HD), was achieved by using water-soluble arene-RuII complexes, containing ethylenediamine-based ligands, as catalysts in the presence of formic acid. The catalytic conversion of furans depends on the catalyst, ligand, formic acid concentration, reaction temperature, and time. Experimental evidence, including time-resolved 1H NMR spectral studies, indicate that the catalytic reaction proceeds first with formyl hydrogenation followed by hydrolytic ring opening of furans. The ruthenium-formic acid tandem catalytic transformation of fructose to diketones and LA was also achieved. Finally, the molecular structures of the four representative arene-RuII catalysts were established by single-crystal X-ray diffraction studies.
Catalytic transformation of bio-derived furans to valuable ketoacids and diketones by water-soluble ruthenium catalysts
Gupta, Kavita,Tyagi, Deepika,Dwivedi, Ambikesh D.,Mobin, Shaikh M.,Singh, Sanjay K.
supporting information, p. 4618 - 4627 (2015/09/15)
Bio-derived furans such as 2-furfural (furfural), 5-hydroxymethyl-2-furfural (5-HMF) and 5-methyl-2-furfural (5-MF) were successfully transformed to a ketoacid, levulinic acid (LA), and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione (3-HHD) and hexane-2,5-dione (HD), under moderate reaction conditions using water soluble and recyclable 8-aminoquinoline coordinated arene-ruthenium(ii) complexes. Under the optimized reaction conditions using 1 mol% catalyst in the presence of 12 equivalents of formic acid at 80-100 °C, complete conversion of furfural to LA with high selectivity was achieved. Several experiments along with 1H NMR spectral studies are described which provide more insights into the mechanism underlying the transformation of furans to open ring components. Experiments performed using structural analogues of the active catalyst inferred a structure-activity relationship for the observed superior catalytic activity of the 8-aminoquinoline coordinated arene-ruthenium(ii) complex. Furthermore, due to the high aqueous solubility of the studied complexes, high recyclability, up to 4 catalytic runs, was achieved without any significant loss of activity. Molecular identities of the studied 8-aminoquinoline coordinated arene-ruthenium(ii) complex were also confirmed using single-crystal X-ray diffraction studies.
