CN111097421A - Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same - Google Patents
Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same Download PDFInfo
- Publication number
- CN111097421A CN111097421A CN201811269883.0A CN201811269883A CN111097421A CN 111097421 A CN111097421 A CN 111097421A CN 201811269883 A CN201811269883 A CN 201811269883A CN 111097421 A CN111097421 A CN 111097421A
- Authority
- CN
- China
- Prior art keywords
- aldehyde compound
- reaction
- active metal
- organic amine
- primary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- 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
- B01J23/745—Iron
-
- 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing primary amine by catalytic conversion of aldehyde compounds, which at least comprises the following steps: i) reacting aldehyde compounds with organic amine to obtain an intermediate; ii) in the presence of a supported metal catalyst, the intermediate is in contact reaction with ammonia and hydrogen to prepare the primary amine compound. The method has the advantages of high selectivity of primary amine, no secondary amine, tertiary amine and other byproducts in the product, mild reaction conditions and easy implementation, and is a novel method for synthesizing the primary amine from the aldehyde compound with high selectivity.
Description
Technical Field
The application relates to a supported metal catalyst and a method for preparing primary amine by catalyzing aldehyde compounds with the supported metal catalyst, belonging to the field of chemical engineering.
Background
The primary amine compound has wide application in the fields of medicine, pesticide, organic synthesis, polymer material and the like, for example, a condensation product of furfuryl amine and 2, 4-dichloro-5-sulfamoylphthalein benzoic acid is an essential drug for treating severe edema; the benzylamine is an important intermediate for preparing pesticides imidacloprid, acetamiprid and medicinal mafenide; ethanolamine is widely used to absorb acidic components in various gases. Primary amines are also important raw materials for the synthesis of higher amines such as secondary amines and tertiary amines.
Reductive amination of aldehyde compounds is one of the common methods for preparing primary amine compounds. The main problems exist that the product primary amine is easy to further react to generate corresponding secondary amine, tertiary amine and other byproducts, and the selectivity of the primary amine is difficult to control.
Disclosure of Invention
According to one aspect of the application, a method for preparing primary amine by catalytic conversion of an aldehyde compound is provided, wherein organic amine is used as a medium, and the aldehyde compound and the organic amine are reacted to generate relatively stable imine; then adding ammonia and hydrogen to prepare primary amine with high selectivity under the action of the supported metal catalyst. The product of the method does not contain secondary amine, tertiary amine and other byproducts, and the primary amine selectivity is high; the reaction condition is mild and easy to implement.
The method for preparing primary amine by catalytic conversion of the aldehyde compound at least comprises the following steps:
i) reacting aldehyde compounds with organic amine to obtain an intermediate;
ii) in the presence of a supported metal catalyst, the intermediate is in contact reaction with ammonia and hydrogen to prepare the primary amine compound.
Preferably, the supported metal catalyst in step ii) comprises an active metal component and a support, wherein,
the active metal component comprises an active metal element, and the active metal element is selected from at least one of zero-valent Fe, Co, Ni, Cu, Pt, Rh, Ru, Pd and Re;
the carrier is selected from activated carbon and C3N4、TiO2、MgO、Al2O3Hydrotalcite, CeO2、SiO2And mayenite.
Preferably, the mass ratio of the active metal component to the support in step ii) is (10)-50.5) 1; wherein the mass of the active metal component is based on the mass of the active metal element contained in the active metal component; the mass of the carrier is based on the mass of the carrier itself.
Preferably, the aldehyde compound in step I) is at least one selected from compounds having the formula shown in formula I:
wherein R is1Is selected from C1～C10A hydrocarbon group of1～C10Substituted hydrocarbyl of (2), C3～C10Heteroaryl of (A), C3～C10At least one of substituted heteroaryl groups of (a).
Further preferably, the aldehyde compound in step i) is selected from at least one of the following compounds:
preferably, the organic amine is selected from at least one of the compounds having the formula shown in formula II:
R2—NH2formula II
R2Is selected from C1～C10A hydrocarbon group of1～C10Substituted hydrocarbyl of (2), C3～C10Heteroaryl of (A), C3～C10At least one of substituted heteroaryl groups of (a).
Further preferably, the organic amine is selected from at least one of the following compounds:
the substituent in the substituted alkyl and the substituted heteroaryl is a non-hydrocarbon substituent.
Preferably, the non-hydrocarbon substituent is selected from at least one of oxygen, halogen, a group having a structural formula shown in formula (1), a group having a structural formula shown in formula (2):
R3-O-formula (1)
In the formula (1), R3Selected from hydrogen, C1～C5Alkyl groups of (a);
R4-O-A1- (O) formula (2)
In the formula (1), R4Selected from hydrogen, C1～C5Alkyl groups of (a); a. the1Is selected from C1～C10An alkylene group of (a).
The proportion of the aldehyde compound to the organic amine in step i) can be selected by those skilled in the art according to the actual need.
Preferably, the molar ratio of the aldehyde compound to the organic amine in step i) is (10)-3～1)：1。
Further preferably, the mass ratio of the aldehyde compound to the organic amine in step i) is:
the aldehyde compound: the organic amine is (60-126): (457-940).
Preferably, the reaction temperature of the aldehyde compound and the organic amine in the step i) is 0 ℃ to 250 ℃, and the reaction time is 0.5h to 72 h.
Further preferably, the reaction temperature of the aldehyde compound and the organic amine in the step i) is 40 ℃ to 190 ℃, and the reaction time is 0.5h to 24 h.
Preferably, the reaction temperature of the contact reaction of the intermediate in the step ii) with ammonia and hydrogen is 30 ℃ to 250 ℃, and the reaction time is 0.5h to 72 h.
Further preferably, the reaction temperature of the contact reaction of the intermediate in the step ii) with ammonia and hydrogen is 60 ℃ to 200 ℃, and the reaction time is 2h to 7 h.
Alternatively, the reaction of the aldehyde compound with the organic amine in step i) is carried out in the presence of a solvent.
Preferably, the solvent is at least one selected from methanol, ethanol, water, tetrahydrofuran, dichloromethane, N-dimethylformamide, and 1, 4-dioxane.
More preferably, the mass ratio of the aldehyde compound to the solvent is (10)-5～3)：1。
More preferably, the volume ratio g/L of the aldehyde compound to the solvent is (60-126): (3-10).
As a specific embodiment, the method for preparing primary amine by catalytic conversion of the aldehyde compound at least comprises the following steps:
i) adding the aldehyde compound and the organic amine into a solvent, and reacting at 40-190 ℃ for 0.5-24 h to obtain an intermediate;
ii) adding the supported metal catalyst and ammonia water into the intermediate obtained in the step i), introducing hydrogen, and reacting at 60-200 ℃ for 2-7 h to obtain the primary amine compound.
Preferably, the mass ratio of the supported metal catalyst in the step ii) to the aldehyde compound in the step i) is (10)-5～0.5):1；
The mass ratio of the ammonia in the step ii) to the aldehyde compound in the step i) is 1-100: 1;
the pressure of the hydrogen in step ii) is from 0.1MPa to 7.0 MPa.
Further preferably, the mass ratio of the supported metal catalyst in the step ii) to the aldehyde compound in the step i) is (60-126): (15-30).
Further preferably, the ammonia NH in the ammonia water in step ii)3The mass ratio of the aldehyde compound to the aldehyde compound in the step i) is (2.8-5.6): (5-10.5).
In this application, C1～C10、C3～C10And the like refer to the number of carbon atoms that the group contains. The carbon atoms of the "substituted hydrocarbon group", "substituted aromatic hydrocarbon group" and "substituted heteroaryl group" are defined to mean the number of carbon atoms contained in the hydrocarbon group, aromatic hydrocarbon group and heteroaryl group, not the number of carbon atoms after substitution. Such as C1～C10The substituted hydrocarbyl refers to hydrocarbyl with 1-10 carbon atoms, and at least one hydrogen atom is substituted by a substituent.
As used herein, a "hydrocarbyl group" is a group formed by the loss of any hydrogen atom from a hydrocarbon compound molecule; the hydrocarbon compounds include alkane compounds, alkene compounds, alkyne compounds, and aromatic hydrocarbon compounds. Such as p-tolyl group in which toluene loses the hydrogen atom para to the methyl group on the phenyl ring, or benzyl group in which toluene loses any of the hydrogen atoms on the methyl group, and the like.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound. The alkane compound comprises straight-chain alkane, branched-chain alkane, cycloalkane and cycloalkane with branched chain.
In the present application, an "alkylene group" is a group formed by losing any two hydrogen atoms on the molecule of an alkane compound.
In the present application, the "heteroaryl" is a group formed by removing any one hydrogen atom from an aromatic compound (referred to as a "heteroaryl compound" for short) having O, N, S heteroatoms in an aromatic ring.
As used herein, a "substituted hydrocarbyl group" is a group in which at least one hydrogen atom of the hydrocarbyl group has been replaced with a non-hydrocarbon substituent.
As used herein, a "substituted heteroaryl" is a group formed by substituting at least one hydrogen atom on a heteroaryl group with a non-hydrocarbon substituent.
In the present application, when the substituent is oxygen, it means that two H atoms on any one C atom in the group are replaced with O to form a C ═ O bond.
The beneficial effects that this application can produce include:
1) compared with the traditional reductive amination method, the method provided by the application has the advantages that the selectivity of the primary amine is high, the secondary amine, the tertiary amine and other byproducts are not contained in the product, and the separation and the purification are easy.
2) The method provided by the application has the advantages of mild reaction conditions, easiness in implementation, high catalyst activity, easiness in separation, recyclability and good application prospect.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The conversion of the raw material and the yield of the product of the reaction were analyzed by an Agilent-7890 gas chromatograph.
In the examples of the present application, the conversion of the aldehyde compound and the selectivity for the primary amine were calculated on the basis of the number of moles of carbon.
Preparation of supported metal catalyst
The catalysts in the examples were prepared by an equivalent volume impregnation method according to the proportions in Table 1. The method comprises the following specific steps:
soaking the carrier in nitrate solution of active metal element in the same volume, keeping at room temperature for 2 hours, drying at 120 ℃, and roasting at 500 ℃ to obtain the supported metal catalyst.
Adding nitrate solution of active metal elements into the carrier, and stirring while adding until the solid just absorbs the metal salt solution completely. And continuously stirring for 30min-3h, standing overnight, naturally drying, then placing in a 120 ℃ oven for continuously drying for 8h, and then keeping at 500 ℃ for 6h to obtain the supported metal catalyst.
TABLE 1
| Active metal element/carrier | Mass ratio of active metal element to carrier |
| Ni/TiO2 | 0.05：1 |
| Pt/Al2O3 | 10-3：1 |
| Cu/MgO | 0.13：1 |
| Fe/activated carbon | 0.48：1 |
| Rh/hydrotalcite | 10-5：1 |
| Ru/CeO2 | 0.01：1 |
| Co/C3N4 | 0.25：1 |
| Re/mayenite | 10-4：1 |
Example 1
60mg of glycolaldehyde, 885mg of propylamine and 5mL of water were put into a 10mL reaction vessel, stirred and heated to 140 ℃ for reaction for 0.5 h. After cooling, 20mg of Ni/TiO was added to the reaction mixture2And 120mg of ammonia water with the mass fraction of 28 percent, introducing hydrogen to the pressure of 2.5MPa, stirring and heating to 150 ℃, reacting for 5 hours, centrifuging the reaction solution, and taking the supernatant for gas chromatography analysis. The conversion of glycolaldehyde was 99% and the selectivity of ethanolamine was 97%.
Example 2
90mg of 2, 3-dihydroxypropanal, 730mg of butylamine, and 3mL of dichloromethane were added to a 10mL reaction vessel, stirred and heated to 40 ℃ for 2.5 hours. After cooling, 25mg of Pt/Al was added to the reaction mixture2O3Introducing hydrogen into the catalyst and 240mg of ammonia water with the mass fraction of 28% until the pressure is 6MPa, stirring and heating the mixture to 60 ℃, reacting for 5 hours, centrifuging the reaction solution, and taking the supernatant for gas chromatography analysis. The conversion of 2, 3-dihydroxypropanal was 99%, and the selectivity of 2, 3-dihydroxypropylamine was 95%.
Example 3
72mg of butylaldehyde, 472mg of isopropylamine and 2.5mL of tetrahydrofuran were put into a 10mL reaction vessel, stirred and heated to 80 ℃ for 2 hours. After cooling, adding 30mg of Cu/MgO catalyst and 180mg of ammonia water with the mass fraction of 28% into the reaction solution, introducing hydrogen to the pressure of 4MPa, stirring and heating to 90 ℃, reacting for 8 hours, centrifuging the reaction solution, and taking the supernatant for gas chromatography analysis. Butyraldehyde conversion was 99% and butylamine selectivity was 95%.
Example 4
96mg of furfural, 963mg of benzylamine and 3.5mL of methanol were added to a 10mL reaction kettle, stirred and heated to 90 ℃ for reaction for 0.5 h. After cooling, 15mg of Fe/activated carbon catalyst and 120mg of ammonia water with the mass fraction of 28% are added into the reaction liquid, hydrogen is introduced until the pressure is 1MPa, the reaction liquid is stirred and heated to 150 ℃, after 2 hours of reaction, the reaction liquid is centrifuged, and the supernatant liquid is taken for gas chromatography analysis. The furfural conversion rate was 99% and the selectivity of furfurylamine was 95%.
Example 5
110mg of 5-methylfurfural, 570mg of isopropylamine and 5.5mL of N, N-dimethylformamide were added to a 10mL reaction vessel, stirred and heated to 160 ℃ for reaction for 3.5 hours. After cooling, adding 20mg of Rh/hydrotalcite catalyst and 150mg of ammonia water with the mass fraction of 28% into the reaction solution, introducing hydrogen to the pressure of 3MPa, stirring and heating to 180 ℃, reacting for 6 hours, centrifuging the reaction solution, and taking the supernatant for gas chromatography analysis. The conversion rate of 5-methylfurfural is 99%, and the selectivity of 5-methylfurfurylamine is 97%.
Example 6
126mg of 5-hydroxymethylfurfural, 570mg of propylamine and 4mL of N, N-dimethylformamide were added to a 10mL reaction vessel, stirred and heated to 160 ℃ for reaction for 3.5 hours. After cooling, adding 20mg of Rh/hydrotalcite catalyst and 150mg of ammonia water with the mass fraction of 28% into the reaction solution, introducing hydrogen to the pressure of 3MPa, stirring and heating to 180 ℃, reacting for 6 hours, centrifuging the reaction solution, and taking the supernatant for gas chromatography analysis. The conversion rate of 5-hydroxymethyl furfural is 99%, and the selectivity of 5-hydroxymethyl furfuryl amine is 97%.
Example 7
124mg of 2, 5-diformylfuran, 787mg of n-hexylamine and 5mL of 1, 4-dioxane are added into a 10mL reaction kettle, stirred and heated to 190 ℃ to react for 4 DEGh. After cooling, 30mg of Ru/CeO were added to the reaction mixture2Introducing hydrogen into a catalyst and 210mg of ammonia water with the mass fraction of 28% until the pressure is 2.5MPa, stirring and heating to 200 ℃, reacting for 7 hours, centrifuging reaction liquid, and taking supernatant liquid for gas chromatography analysis. The conversion of 2, 5-diformylfuran was 99% and the selectivity of 2, 5-diaminomethylfuran was 95%.
Example 8
106mg of benzaldehyde, 679mg of furfuryl amine, and 6.5mL of ethanol were put into a 10mL reaction vessel, stirred and heated to 110 ℃ to react for 1 hour. After cooling, 10mg of Co/C was added to the reaction mixture3N4Introducing hydrogen into catalyst and 180mg of 28 mass percent ammonia water until the pressure is 0.8MPa, stirring and heating to 130 ℃, reacting for 3 hours, centrifuging reaction liquid, and taking supernatant liquid for gas chromatography analysis. The conversion of benzaldehyde was 99% and the selectivity to benzylamine was 96%.
Example 9
106mg of benzaldehyde, 457mg of ethanolamine, and 5mL of tetrahydrofuran were added to a 10mL reaction vessel, stirred, and heated to 100 ℃ to react for 24 hours. After cooling, 20mg of Re/mayenite catalyst and 150mg of ammonia water with the mass fraction of 28% are added into the reaction liquid, hydrogen is introduced to the reaction liquid until the pressure is 6MPa, the reaction liquid is stirred and heated to 100 ℃, after 3 hours of reaction, the reaction liquid is centrifuged, and the supernatant liquid is taken for gas chromatography analysis. The conversion of benzaldehyde was 99% and the selectivity of benzylamine was 98%.
Example 10
106mg of m-methoxybenzaldehyde, 790mg of furfuryl amine, and 6.5mL of ethanol were added to a 10mL reaction vessel, stirred and heated to 110 ℃ for reaction for 1 hour. After cooling, 10mg of Co/C was added to the reaction mixture3N4Introducing hydrogen into catalyst and 180mg of 28 mass percent ammonia water until the pressure is 0.8MPa, stirring and heating to 130 ℃, reacting for 3 hours, centrifuging reaction liquid, and taking supernatant liquid for gas chromatography analysis. The conversion rate of m-methoxybenzaldehyde is 99%, and the selectivity of m-methoxybenzylamine is 96%.
Example 11
106mg of p-chlorobenzaldehyde, 940mg of furfuryl amine, 6.5mL of water were added to 10mL of the reaction solutionIn a kettle, stirring and heating to 110 ℃, and reacting for 1 h. After cooling, 10mg of Co/C was added to the reaction mixture3N4Introducing hydrogen into catalyst and 180mg of 28 mass percent ammonia water until the pressure is 0.8MPa, stirring and heating to 130 ℃, reacting for 3 hours, centrifuging reaction liquid, and taking supernatant liquid for gas chromatography analysis. The conversion rate of p-chlorobenzaldehyde is 99 percent, and the selectivity of p-chlorobenzylamine is 97 percent.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing primary amine by catalytic conversion of aldehyde compound, characterized in that the method at least comprises the following steps:
i) reacting aldehyde compounds with organic amine to obtain an intermediate;
ii) in the presence of a supported metal catalyst, the intermediate is in contact reaction with ammonia and hydrogen to prepare the primary amine compound.
2. The process of claim 1 wherein the supported metal catalyst in step ii) comprises an active metal component and a support, wherein,
the active metal component comprises an active metal element, and the active metal element is selected from at least one of zero-valent Fe, Co, Ni, Cu, Pt, Rh, Ru, Pd and Re;
the carrier is selected from activated carbon and C3N4、TiO2、MgO、Al2O3Hydrotalcite, CeO2、SiO2And mayenite.
3. The method of claim 1,the mass ratio of the active metal component to the carrier in step ii) is (10)-5～0.5):1；
Wherein the mass of the active metal component is based on the mass of the active metal element contained in the active metal component; the mass of the carrier is based on the mass of the carrier itself.
4. The process according to claim 1, wherein the aldehyde compound in step I) is at least one selected from the group consisting of compounds having the formula shown in formula I:
wherein R is1Is selected from C1～C10A hydrocarbon group of1～C10Substituted hydrocarbyl of (2), C3～C10Heteroaryl of (A), C3～C10At least one of substituted heteroaryl groups of (a);
the organic amine is at least one selected from compounds having a structural formula shown in formula II:
R2—NH2formula II
R2Is selected from C1～C10A hydrocarbon group of1～C10Substituted hydrocarbyl of (2), C3～C10Heteroaryl of (A), C3～C10At least one of substituted heteroaryl groups of (a).
5. The process according to claim 1, characterized in that the aldehyde compound in step i) is selected from at least one of the following compounds:
the organic amine is selected from at least one of the following compounds:
6. the process according to claim 1, characterized in that the molar ratio of the aldehyde compound to the organic amine in step i) is (10)-3～1)：1。
7. The process according to claim 1, wherein the aldehyde compound is reacted with the organic amine in step i) at a reaction temperature of 0 ℃ to 250 ℃ for a reaction time of 0.5h to 72 h;
the reaction temperature of the contact reaction of the intermediate in the step ii) with ammonia and hydrogen is 30-250 ℃, and the reaction time is 0.5-72 h.
8. The process according to claim 1, characterized in that the reaction of the aldehyde compound with the organic amine in step i) is carried out in the presence of a solvent;
the solvent is at least one selected from methanol, ethanol, water, tetrahydrofuran, dichloromethane, N-dimethylformamide and 1, 4-dioxane;
the mass ratio of the aldehyde compound to the solvent is (10)-5～3)：1。
9. Method according to claim 8, characterized in that it comprises at least the following steps:
i) adding the aldehyde compound and the organic amine into a solvent, and reacting at 40-190 ℃ for 0.5-24 h to obtain an intermediate;
ii) adding the supported metal catalyst and ammonia water into the intermediate obtained in the step i), introducing hydrogen, and reacting at 60-200 ℃ for 2-7 h to obtain the primary amine compound.
10. The method according to claim 3, wherein the mass ratio of the supported metal catalyst in step ii) to the aldehyde compound in step i) is (10)-5～0.5):1；
The mass ratio of the ammonia in the step ii) to the aldehyde compound in the step i) is 1-100: 1;
the pressure of the hydrogen in step ii) is from 0.1MPa to 7.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811269883.0A CN111097421A (en) | 2018-10-29 | 2018-10-29 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811269883.0A CN111097421A (en) | 2018-10-29 | 2018-10-29 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111097421A true CN111097421A (en) | 2020-05-05 |
Family
ID=70419338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811269883.0A Pending CN111097421A (en) | 2018-10-29 | 2018-10-29 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111097421A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731443A (en) * | 2021-09-22 | 2021-12-03 | 西北工业大学 | Pt/CoFe-LDH supported nano solid catalyst and preparation method and application thereof |
| CN114230469A (en) * | 2021-12-15 | 2022-03-25 | 中国科学院大连化学物理研究所 | Synthesis of load type nano ruthenium zirconium tin composite oxide and application of load type nano ruthenium zirconium tin composite oxide in benzylamine synthesis through benzaldehyde amination |
| CN114805098A (en) * | 2022-04-13 | 2022-07-29 | 河北工业大学 | Method for synthesizing 5-amino-1-pentanol by taking furfural as initial raw material |
| CN114849761A (en) * | 2022-06-09 | 2022-08-05 | 东莞理工学院 | Photocatalytic material and preparation method and application thereof |
| WO2023017199A1 (en) | 2021-08-10 | 2023-02-16 | Advanced Thermal Devices S.L. | Cathode based on the material c12a7:e− (electride) for thermionic electron emission and method for using same |
| CN115739083A (en) * | 2022-10-17 | 2023-03-07 | 东南大学 | Hydrothermal carbon catalyst, preparation method thereof and preparation method of primary imine compound |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101658A (en) * | 1987-03-26 | 1988-12-14 | Bp化学有限公司 | Produce the method for amine |
| CN1062677A (en) * | 1992-01-05 | 1992-07-15 | 湖北省化学研究所 | Be used for alcohol, ketoamine catalyst for reaction and preparation |
| CN1151984A (en) * | 1995-12-15 | 1997-06-18 | 化学工业部北京化工研究院 | Catalyst for ammoniation reaction |
| CN1186453A (en) * | 1995-06-02 | 1998-07-01 | 陶氏化学公司 | Catalyst and process for producing amides |
| CN103097336A (en) * | 2010-09-11 | 2013-05-08 | 奥克塞有限公司 | Method for producing primary aliphatic amines from aldehydes |
| CN103145974A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Method of preparing primary amine by ammonification of alcoholic hydroxyl group |
| CN104710325A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for one step synthesis of imine through catalyzing alcohol and amine by supported manganese oxide |
| CN106488905A (en) * | 2014-07-10 | 2017-03-08 | 罗地亚经营管理公司 | The method producing Aromatic primary diamines |
-
2018
- 2018-10-29 CN CN201811269883.0A patent/CN111097421A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101658A (en) * | 1987-03-26 | 1988-12-14 | Bp化学有限公司 | Produce the method for amine |
| US4912260A (en) * | 1987-03-26 | 1990-03-27 | Bp Chemicals Limited | Process for the production of amines |
| CN1062677A (en) * | 1992-01-05 | 1992-07-15 | 湖北省化学研究所 | Be used for alcohol, ketoamine catalyst for reaction and preparation |
| CN1186453A (en) * | 1995-06-02 | 1998-07-01 | 陶氏化学公司 | Catalyst and process for producing amides |
| CN1151984A (en) * | 1995-12-15 | 1997-06-18 | 化学工业部北京化工研究院 | Catalyst for ammoniation reaction |
| CN103097336A (en) * | 2010-09-11 | 2013-05-08 | 奥克塞有限公司 | Method for producing primary aliphatic amines from aldehydes |
| CN103145974A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Method of preparing primary amine by ammonification of alcoholic hydroxyl group |
| CN104710325A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for one step synthesis of imine through catalyzing alcohol and amine by supported manganese oxide |
| CN106488905A (en) * | 2014-07-10 | 2017-03-08 | 罗地亚经营管理公司 | The method producing Aromatic primary diamines |
Non-Patent Citations (1)
| Title |
|---|
| 尹志刚 主编: "《有机化学》", 28 February 2010, 河南科学技术出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023017199A1 (en) | 2021-08-10 | 2023-02-16 | Advanced Thermal Devices S.L. | Cathode based on the material c12a7:e− (electride) for thermionic electron emission and method for using same |
| CN113731443A (en) * | 2021-09-22 | 2021-12-03 | 西北工业大学 | Pt/CoFe-LDH supported nano solid catalyst and preparation method and application thereof |
| CN113731443B (en) * | 2021-09-22 | 2023-08-01 | 西北工业大学 | Pt/CoFe-LDH supported nano solid catalyst and preparation method and application thereof |
| CN114230469A (en) * | 2021-12-15 | 2022-03-25 | 中国科学院大连化学物理研究所 | Synthesis of load type nano ruthenium zirconium tin composite oxide and application of load type nano ruthenium zirconium tin composite oxide in benzylamine synthesis through benzaldehyde amination |
| CN114805098A (en) * | 2022-04-13 | 2022-07-29 | 河北工业大学 | Method for synthesizing 5-amino-1-pentanol by taking furfural as initial raw material |
| CN114805098B (en) * | 2022-04-13 | 2023-08-04 | 河北工业大学 | Method for synthesizing 5-amino-1-amyl alcohol by using furfural as initial raw material |
| CN114849761A (en) * | 2022-06-09 | 2022-08-05 | 东莞理工学院 | Photocatalytic material and preparation method and application thereof |
| CN114849761B (en) * | 2022-06-09 | 2024-04-12 | 东莞理工学院 | Photocatalytic material and preparation method and application thereof |
| CN115739083A (en) * | 2022-10-17 | 2023-03-07 | 东南大学 | Hydrothermal carbon catalyst, preparation method thereof and preparation method of primary imine compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111097421A (en) | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same | |
| CN113149883B (en) | Process for preparing pyrrole compounds | |
| TW200936541A (en) | Process for preparing an amine | |
| JP2009526801A (en) | Process for producing ethyleneamine and ethanolamine from monoethylene glycol (MEG) | |
| TW200936547A (en) | Process for preparing an amine | |
| JP2009526810A (en) | Process for producing ethyleneamine and ethanolamine by hydroamination of monoethylene glycol and ammonia in the presence of a catalyst | |
| CN105636930B (en) | The method to form primary amine, secondary amine or tertiary amine is reacted via direct aminatin | |
| JP2004516308A (en) | Method for producing primary and secondary amines by hydrogenation of nitriles and imines | |
| CN111229320B (en) | Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof | |
| KR101701973B1 (en) | Method for preparing ferrite metal oxide catalyst | |
| US8642811B2 (en) | Preparation of primary diamines having a linear main chain for polyamide syntheses | |
| JP6130298B2 (en) | Amino group transfer of nitrogen-containing compounds to high molecular weight polyalkyleneamines. | |
| JPS6094947A (en) | Reducing alkylation of aromatic nitro compound and ketone or aldehyde | |
| JP5514218B2 (en) | Process for preparing cinacalcet | |
| JPH0152381B2 (en) | ||
| CN115028537A (en) | Preparation method of aminopropyl alicyclic secondary amine | |
| Querard et al. | Direct synthesis of indenes via a rhodium-catalyzed multicomponent C sp2–H annulation reaction | |
| CN101260044B (en) | Method for preparing arylamines compounds by arene nitro compound catalysis hydrogenation in H2O-CO2 system | |
| US4263175A (en) | Catalyst for the production of pyrrolidone | |
| WO2019174221A1 (en) | Process for producing an amine in a solvent system containing water | |
| CN113372303B (en) | Method for preparing tetrahydrofuran dimethanol dialkyl ether | |
| JPS6160636A (en) | Manufacture of amine | |
| CN107801392B (en) | Direct amination of hydrocarbons | |
| CN111100015B (en) | Method for preparing aliphatic amine compound | |
| JPS6362525B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200505 |
|
| WD01 | Invention patent application deemed withdrawn after publication |