The reductive amination of furfural to furfurylamine is an important and still challenging topic in the field of biomass conversion. In this work, we prepared a series of Ni/Al_(2)O_(3)-LaO_(x) catalysts by co-precipi...The reductive amination of furfural to furfurylamine is an important and still challenging topic in the field of biomass conversion. In this work, we prepared a series of Ni/Al_(2)O_(3)-LaO_(x) catalysts by co-precipitation method, the role of La played in promoting the catalytic performances of reductive amination furfural was discussed based on the changes in the electronic state of Ni species, acidity, and Ni particle size. The catalytic activity and the selectivity of furfurylamine are highly dependent on the surface properties and the structure of the catalyst. The addition of La promoted the amount of strong acidic sites and the H2dissociation and spillover on the surface, thus inducing the improvement of the catalytic activity and furfurylamine selectivity. The Ni/Al_(2)O_(3)-0.5LaO_(x)catalyst with suitable acid sites gave a high yield of furfurylamine (94.9%) under mild reaction conditions. Moreover, the catalyst could be recycled five times without significant loss in activity. The Ni/Al_(2)O_(3)-LaO_(x) catalyst is of great promise in the production of amines via reductive amination reaction.展开更多
The synthesis of primary amines via reductive amination in the presence of NH_(3)and H_(2),as a green and sustainable process,has attracted much attention.In this paper,we prepared series of Ni/SiO_(2)catalysts with d...The synthesis of primary amines via reductive amination in the presence of NH_(3)and H_(2),as a green and sustainable process,has attracted much attention.In this paper,we prepared series of Ni/SiO_(2)catalysts with deposition-precipitation and impregnation methods,and their catalytic performances on the reductive amination of a biomass derived compound of furfural to produce furfurylamine were studied.The catalytic activity and the yield were correlated to the structure and the surface properties of catalysts largely.The Ni/SiO_(2)is of high Lewis acidity and small Ni particle with numerous large Ni flat step surface showed high activity and selectivity,it afforded a reaction rate of 12.8 h^(−1)and a high yield to furfurylamine around 98%.These results are superior to the most non-noble metal catalysts reported so far.Moreover,the reaction route was examined with the unit control reactions of the intermediate.To produce furfurylamine selectively,the most suitable catalyst should have the moderate but not the highest activity in activation of hydrogen and hydrogenation in the reductive amination of furfural.This work provides some useful information for the catalytic reductive amination of aldehydes both in the design of catalyst and the reaction route.展开更多
A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized...A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.展开更多
A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase...A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.展开更多
We report the highly efficient conversion of readily available biomass-derived polyols with amines to valuable furfurylamines orβ-amino alcohols compounds using ruthenium catalysis.The reaction outcome is readily tun...We report the highly efficient conversion of readily available biomass-derived polyols with amines to valuable furfurylamines orβ-amino alcohols compounds using ruthenium catalysis.The reaction outcome is readily tuned by the simple addition of 4Åmolecular sieves(furfurylamines vs.β-amino alcohols)with high chemo-selectivity.The proposed reaction mechanism involves ruthenium-catalyzed hydrogen borrowing for the reduction of the imine intermediate and C–C bond cleavage of polyols via a retro-aldol process.A series of arylamines was suc-cessfully transformed into the desired products with moderate to good yields.展开更多
基金the National Key Research and Development Program of China(No.2022YFA1504901)the National Natural Science Foundation of China(No.NSFC 22072142)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202301ZYTS539).
文摘The reductive amination of furfural to furfurylamine is an important and still challenging topic in the field of biomass conversion. In this work, we prepared a series of Ni/Al_(2)O_(3)-LaO_(x) catalysts by co-precipitation method, the role of La played in promoting the catalytic performances of reductive amination furfural was discussed based on the changes in the electronic state of Ni species, acidity, and Ni particle size. The catalytic activity and the selectivity of furfurylamine are highly dependent on the surface properties and the structure of the catalyst. The addition of La promoted the amount of strong acidic sites and the H2dissociation and spillover on the surface, thus inducing the improvement of the catalytic activity and furfurylamine selectivity. The Ni/Al_(2)O_(3)-0.5LaO_(x)catalyst with suitable acid sites gave a high yield of furfurylamine (94.9%) under mild reaction conditions. Moreover, the catalyst could be recycled five times without significant loss in activity. The Ni/Al_(2)O_(3)-LaO_(x) catalyst is of great promise in the production of amines via reductive amination reaction.
基金the financial support from the National Natural Science Foundation of China(Nos.22172155 and 22072142)the Youth Innovation Promotion Association CAS(No.2016206).
文摘The synthesis of primary amines via reductive amination in the presence of NH_(3)and H_(2),as a green and sustainable process,has attracted much attention.In this paper,we prepared series of Ni/SiO_(2)catalysts with deposition-precipitation and impregnation methods,and their catalytic performances on the reductive amination of a biomass derived compound of furfural to produce furfurylamine were studied.The catalytic activity and the yield were correlated to the structure and the surface properties of catalysts largely.The Ni/SiO_(2)is of high Lewis acidity and small Ni particle with numerous large Ni flat step surface showed high activity and selectivity,it afforded a reaction rate of 12.8 h^(−1)and a high yield to furfurylamine around 98%.These results are superior to the most non-noble metal catalysts reported so far.Moreover,the reaction route was examined with the unit control reactions of the intermediate.To produce furfurylamine selectively,the most suitable catalyst should have the moderate but not the highest activity in activation of hydrogen and hydrogenation in the reductive amination of furfural.This work provides some useful information for the catalytic reductive amination of aldehydes both in the design of catalyst and the reaction route.
文摘A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.
基金the National Natural Science Foundation of China (No. 649620)
文摘A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.
基金support from the National Natural Science Foundation of China(NSFC,Nos.21633013,22022204).
文摘We report the highly efficient conversion of readily available biomass-derived polyols with amines to valuable furfurylamines orβ-amino alcohols compounds using ruthenium catalysis.The reaction outcome is readily tuned by the simple addition of 4Åmolecular sieves(furfurylamines vs.β-amino alcohols)with high chemo-selectivity.The proposed reaction mechanism involves ruthenium-catalyzed hydrogen borrowing for the reduction of the imine intermediate and C–C bond cleavage of polyols via a retro-aldol process.A series of arylamines was suc-cessfully transformed into the desired products with moderate to good yields.
