CN111569883B - Preparation method and application of cellulose-supported nickel catalyst - Google Patents
Preparation method and application of cellulose-supported nickel catalyst Download PDFInfo
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- CN111569883B CN111569883B CN202010435385.XA CN202010435385A CN111569883B CN 111569883 B CN111569883 B CN 111569883B CN 202010435385 A CN202010435385 A CN 202010435385A CN 111569883 B CN111569883 B CN 111569883B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method and application of a cellulose supported nickel catalyst, wherein the preparation method comprises the following steps: (1) refluxing cellulose and nickel salt in a solvent for 8-16 hours, cooling to room temperature, and carrying out vacuum drying on the solid to remove the solvent; (2) under the protection of nitrogen, respectively carbonizing under the protection of nitrogen to obtain catalysts; the cellulose supported nickel catalyst can be applied to the preparation of amine compounds by reducing nitro groups. The catalyst has the advantages of high activity, easy separation, high stability, high activity, long service life, less metal residue, simple operation and simple equipment requirement; the catalyst has high activity after being recycled for many times, and has the advantages of economy, high efficiency, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of metal organic catalysis, and particularly relates to a preparation method of an environment-friendly cellulose-supported nickel catalyst and application of the catalyst in drug synthesis.
Background
Aromatic amines are important raw materials for the manufacture of many fine chemicals, such as pharmaceuticals, pesticides, dyes, surfactants, etc., where the hydrogenation of nitroarenes is a simple and reliable process for the production of aromatic amines. The reduction of the corresponding nitroarenes using sulfides, iron, zinc, etc. in acidic media is the most traditional and most widely used method in industry, but these processes generate large amounts of waste acid and residues, resulting in serious environmental problems. In contrast, noble metal-catalyzed hydrogenation of nitro compounds is an efficient and environmentally friendly method for producing aromatic amines. However, it has some disadvantages such as the use of a noble metal catalyst in a large amount, an organic reaction medium, a harmful or expensive hydride, etc., and even requires severe reaction conditions such as high temperature and high pressure. Homogeneous rare metal supported catalysts are of particular interest because of their presence of expensive or toxic ligands and their difficulty in recycling. In drugs, nitro reduction is also common, which puts higher demands on the efficiency of the catalyst and the residual of heavy metals in the drug. Therefore, there is a need to find more efficient and greener catalytic systems.
In recent years, the development of transition metal catalytic organic synthesis just meets the demand of the current generation, and the preparation of cheap, efficient and nontoxic metal organic catalysts is a key point and a difficulty point for promoting the development of the field. The polysaccharide compound is used as a biomass which is cheap, easy to obtain and nontoxic, and is an ideal raw material for synthesizing the metal organic catalyst ligand. Heterogeneous reactions have many advantages over homogeneous reactions. For example, after the reaction is completed, the catalyst and the product are simple to separate, and can be recycled, so that the cost is greatly reduced, and the reaction stereoselectivity can be better controlled in the reaction. After seeing these great advantages, researchers have focused on the design and synthesis of a wide variety of catalyst supports and the loading of homogeneous catalysts onto a wide variety of supports. Common carriers include silicon dioxide, zeolite, magnetic materials, high molecular polymers and the like, and cellulose is a green and environment-friendly biomass material, so that the cellulose is concerned by people because the cellulose meets the green and environment-friendly requirements and plays an important role in transition metal catalytic reaction.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly cellulose-supported nickel catalyst and application of the catalyst in preparing amine compounds by reducing nitro groups with high selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a cellulose supported nickel catalyst comprises the following steps:
(1) refluxing cellulose and nickel salt in a solvent for 8-16 hours, cooling to room temperature, and carrying out vacuum drying on the solid to remove the solvent;
(2) under the protection of nitrogen, respectively carbonizing under the protection of nitrogen to obtain the catalyst.
The preparation route of the Cellulose supported nickel catalyst (Cellulose @ Ni salts catalyst) is shown in figure 1.
Preferably, the nickel salt is one or any combination of more than two of nickel chloride, nickel acetate, nickel bromide and nickel nitrate; more preferably, the nickel salt is nickel acetate.
Preferably, the solvent is water, ethanol, methanol, or their corresponding polar solvents.
Preferably, the molar ratio of the cellulose to the nickel salt is 5: 1-10: 1; more preferably, the molar ratio of the cellulose to the nickel salt is 9.1: 1.
preferably, the reflux reaction temperature is 50-120 ℃, and the carbonization temperature is 600-800 ℃; more preferably, the reflux reaction temperature is 100 ℃ and the carbonization temperature is 800 ℃.
Preferably, the preparation method of the cellulose supported nickel catalyst comprises the following steps:
(1) adding nickel acetate and water into a four-neck flask, slowly adding cellulose, heating the system to 100 ℃, carrying out reflux reaction for 12 hours, cooling to room temperature, carrying out reduced pressure filtration to remove water, rinsing a filter cake for 3 times by using water, and drying the solid in a vacuum drying oven for 24 hours at 65 ℃;
(2) putting the catalyst solid into a porcelain boat, heating up at 2 ℃ per minute under the protection of nitrogen, and carbonizing at 600 ℃, 700 ℃ and 800 ℃ for 3 hours respectively to obtain the catalyst.
The invention also provides application of the cellulose supported nickel catalyst in preparation of amine compounds by reducing nitro groups.
Preferably, the application of the cellulose supported nickel catalyst in the preparation of amine compounds by reducing nitro groups adopts the following method: adding a nitrobenzene compound, a cellulose supported nickel catalyst, ethanol and water into a hydrogenation reaction kettle, introducing hydrogen, and reacting for 6-18 hours under a heating condition; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, and evaporating the solvent to obtain the aromatic amine compound.
The invention relates to a route for synthesizing aniline compounds by catalyzing Cellulose @ Ni-800, which comprises the following steps:
preferably, the molar ratio of the nitrobenzene compound to the cellulose-supported nickel catalyst is 100: 5-25; more preferably, the molar ratio of the nitrobenzene compound to the cellulose-supported nickel catalyst is 100: 10.
preferably, the molar ratio of ethanol to water is 1: 0.5 to 4; the reaction temperature is 60-90 ℃; more preferably, the molar ratio of ethanol to water is 1: 1; the reaction temperature was 85 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst has the advantages of high activity, easy separation, high stability, high activity, long service life, less metal residue, simple operation and simple equipment requirement; the catalyst has high activity after being recycled for many times, and has the advantages of economy, high efficiency, environmental protection and the like.
Drawings
FIG. 1 is a schematic preparation of a Cellulose supported nickel (Cellulose @ Ni salts) catalyst according to the present invention;
FIG. 2 is a transmission electron micrograph of Cellulose @ Ni-800, a catalyst of the present invention;
FIG. 3 is a graph of the catalytic effect of the catalyst of the present invention after being used under the same catalytic conditions and being recycled for 10 times.
Detailed Description
The invention is further illustrated with reference to specific examples, without however being limited thereto. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the protection scope of the present invention.
The purity grade of the reagent related by the invention is above Chemical Purity (CP), and the nickel salt and cellulose are purchased from Aladdin reagent (Shanghai) Co.
Example 1
Preparation of Cellulose @ Ni-600
Adding nickel acetate and water into a four-neck flask as solvents, slowly adding cellulose, wherein the molar ratio of the cellulose to nickel salt is 9.5: 1, raising the temperature of the system to 100 ℃ and reacting for 12 hours. Cooling to room temperature, filtering under reduced pressure to remove water, rinsing the filter cake with water for 3 times, and drying the solid in a vacuum drying oven at 65 ℃ for 24 hours. And putting the catalyst solid into a porcelain boat, heating at 2 ℃ per minute under the protection of nitrogen, and carbonizing at 600 ℃ for 3 hours to obtain the catalyst.
Example 2
Preparation of Cellulose @ Ni-700
Adding nickel acetate and water into a four-neck flask as solvents, slowly adding cellulose, wherein the molar ratio of the cellulose to nickel salt is 9.5: 1, raising the temperature of the system to 100 ℃ and reacting for 12 hours. Cooling to room temperature, filtering under reduced pressure to remove water, rinsing the filter cake with water for 3 times, and drying the solid in a vacuum drying oven at 65 ℃ for 24 hours. And putting the catalyst solid into a porcelain boat, heating at 2 ℃ per minute under the protection of nitrogen, and carbonizing at 700 ℃ for 3 hours to obtain the catalyst.
Example 3
Preparation of Cellulose @ Ni-800
Adding nickel acetate and water into a four-neck flask as solvents, slowly adding cellulose, wherein the molar ratio of the cellulose to nickel salt is 9.5: 1, raising the temperature of the system to 100 ℃ and reacting for 12 hours. Cooling to room temperature, filtering under reduced pressure to remove water, rinsing the filter cake with water for 3 times, and drying the solid in a vacuum drying oven at 65 ℃ for 24 hours. And putting the catalyst solid into a porcelain boat, heating at 2 ℃ per minute under the protection of nitrogen, and carbonizing at 800 ℃ for 3 hours to obtain the catalyst. A transmission electron micrograph of catalyst Cellulose @ Ni-800 is shown in FIG. 2.
Example 4
Preparation of anilines
80 mmol of nitrobenzene, 8 mmol of Cellulose @ Ni-800, 100 ml of water and 100 ml of ethanol were charged into a 500 ml hydrogenation reactor, and heated under reflux at 85 ℃ for 12 hours. The reaction process is qualitatively monitored by Thin Layer Chromatography (TLC), after the reaction is finished, the reaction liquid is cooled to room temperature, the catalyst is recovered by decompression and suction filtration, the filtrate is used for removing the reaction solvent by a rotary evaporator, and the product aniline is obtained, wherein the yield is 99%.
1 H NMR(500MHz,CDCl 3 )： 1 H NMR(500MHz,CDCl 3 )δ8.47(s,1H),7.57(d, J＝8.5Hz,2H),6.63(d,J＝8.5Hz,2H),5.23(s,1H)。
Example 5
Preparation of N1- [2- (dimethylamino) ethyl ] -5-methoxy-N1-methyl-N4- [4- (1-methyl-1H-indol-3-yl) -2-pyrimidinyl ] -1,2, 4-benzenetriamine
To a 500 ml hydrogenation kettle was added 80 mmol of N- (2-dimethylamino-ethyl) -2-methoxy-N-methyl-N- [4- (1-methyl-1H-indol-3-yl) -pyrimidin-2-yl ] -5-nitro-benzene-1, 4-diamine, 8 mmol of Cellulose @ Ni-800, 100 ml of water and 100 ml of ethanol, and heated at 85 ℃ under reflux for 12 hours. The reaction process is qualitatively monitored by Thin Layer Chromatography (TLC), after the reaction is finished, the reaction liquid is cooled to room temperature, the catalyst is recovered by decompression and suction filtration, the filtrate is used for removing the reaction solvent by a rotary evaporator, and the product aniline is obtained, wherein the yield is 98%.
1 H NMR(500MHz,DMSO d6 )δ8.43(d,J＝8.0Hz,1H),8.29(s,1H),8.27(d,J ＝5.3Hz,1H),7.78(s,1H),7.51(d,J＝6.5Hz,2H),7.28-7.22(m,1H),7.19-7.12(m, 2H),6.76(s,1H),4.58(s,2H),3.88(s,3H),3.74(s,3H),2.89(t,J＝6.7Hz,2H), 2.63(s,3H),2.36(t,J＝6.7Hz,2H),2.17(s,6H)。
Example 6
Cellulose @ Ni-800 can be recycled
The catalyst can be recycled for 10 times when preparing the aniline compound, and the catalytic effect is not obviously reduced, and the specific operation is as follows: 80 mmol of nitrobenzene, 8 mmol of Cellulose @ Ni-800, 100 ml of water and 100 ml of ethanol were charged into a 500 ml hydrogenation reactor, and heated under reflux at 85 ℃ for 12 hours. The reaction process is qualitatively monitored by Thin Layer Chromatography (TLC), after the reaction is finished, the reaction liquid is cooled to room temperature, the catalyst is recovered by decompression and suction filtration, the reaction solvent is removed from the filtrate by a rotary evaporator to obtain the product aniline, the dried catalyst is used under the same catalysis condition, the catalysis effect is shown in figure 3 after the catalyst is circularly used for 10 times, and the result shows that the catalysis effect is not obviously reduced after the catalyst is circularly used for 10 times.
Claims (1)
1. An application of a cellulose supported nickel catalyst in the preparation of amine compounds by reducing nitro groups is characterized in that: the amine compound is N1- [2- (dimethylamino) ethyl ] -5-methoxy-N1-methyl-N4- [4- (1-methyl-1H-indol-3-yl) -2-pyrimidinyl ] -1,2, 4-benzenetriamine, which is prepared by the following method:
80 mmol of N- (2-dimethylamino-ethyl) -2-methoxy-N-methyl-N- [4- (1-methyl-1H-indol-3-yl) -pyrimidin-2-yl ] -5-nitro-benzene-1, 4-diamine, 8 mmol of Cellulose @ Ni-800, 100 ml of water and 100 ml of ethanol were added to a 500 ml hydrogenation reactor and heated under reflux at 85 ℃ for 12 hours; the reaction process is qualitatively monitored by thin layer chromatography, after the reaction is finished, the reaction liquid is cooled to room temperature, the catalyst is recovered by decompression and suction filtration, the reaction solvent is removed from the filtrate by a rotary evaporator, and the product is obtained with the yield of 98 percent;
wherein the catalyst Cellulose @ Ni-800 is prepared by the following method:
adding nickel acetate and water into a four-neck flask as solvents, slowly adding cellulose, wherein the molar ratio of the cellulose to nickel salt is 9.5: 1, heating the system to 100 ℃, and reacting for 12 hours; cooling to room temperature, filtering under reduced pressure to remove water, rinsing the filter cake with water for 3 times, and drying the solid in a vacuum drying oven at 65 ℃ for 24 hours; and putting the catalyst solid into a porcelain boat, heating at 2 ℃ per minute under the protection of nitrogen, and carbonizing at 800 ℃ for 3 hours to obtain the catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10059319A1 (en) * | 2000-06-14 | 2002-02-28 | Kataleuna Gmbh Catalysts | Hydrogenation catalyst for reducing functional groups and process for its preparation |
| CN102413922A (en) * | 2009-02-27 | 2012-04-11 | 巴斯夫公司 | Process for the preparation of metal-carbon containing bodies |
| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
| CN108745333A (en) * | 2018-04-17 | 2018-11-06 | 华南理工大学 | A kind of porous platinum/carbon aerogel catalyst and the preparation method and application thereof |
| CN109772337A (en) * | 2019-03-07 | 2019-05-21 | 河北大学 | A kind of load-type nickel base nano-catalyst and the preparation method and application thereof |
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- 2020-05-21 CN CN202010435385.XA patent/CN111569883B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10059319A1 (en) * | 2000-06-14 | 2002-02-28 | Kataleuna Gmbh Catalysts | Hydrogenation catalyst for reducing functional groups and process for its preparation |
| CN102413922A (en) * | 2009-02-27 | 2012-04-11 | 巴斯夫公司 | Process for the preparation of metal-carbon containing bodies |
| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
| CN108745333A (en) * | 2018-04-17 | 2018-11-06 | 华南理工大学 | A kind of porous platinum/carbon aerogel catalyst and the preparation method and application thereof |
| CN109772337A (en) * | 2019-03-07 | 2019-05-21 | 河北大学 | A kind of load-type nickel base nano-catalyst and the preparation method and application thereof |
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