CN111871462B - Iron-cobalt organic catalyst, preparation method thereof and CO conversion method thereof 2 Use of benzazepine for the synthesis of benzazepine - Google Patents
Iron-cobalt organic catalyst, preparation method thereof and CO conversion method thereof 2 Use of benzazepine for the synthesis of benzazepine Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DQFQCHIDRBIESA-UHFFFAOYSA-N 1-benzazepine Chemical compound N1C=CC=CC2=CC=CC=C12 DQFQCHIDRBIESA-UHFFFAOYSA-N 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 8
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 238000005406 washing Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 238000013032 photocatalytic reaction Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910017061 Fe Co Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- -1 o-aminobenzonitrile compound Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 7
- 239000005431 greenhouse gas Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SLIBXRZCKZOXQV-UHFFFAOYSA-N O1CCCC1.NC1=C(C#N)C=CC=C1 Chemical compound O1CCCC1.NC1=C(C#N)C=CC=C1 SLIBXRZCKZOXQV-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical class NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
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Abstract
The invention relates to the field of catalysts and aims at CO 2 The invention provides an iron-cobalt organic catalyst which is a microsphere with the diameter of 200-400nm and has lamellar crystals on the surface. The space formed between the catalyst particles increases the contact area of the reactants with the catalyst. Also provides a preparation method of the iron-cobalt organic catalyst, which comprises the steps of adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol, stirring for dissolving, and then sequentially adding FeCl 3 And Co (NO) 3 ) 2 •6H 2 And O, stirring, reacting for 10-20 hours at 150-200 ℃, washing and drying the product. The preparation method is simple and has high repeatability. Also provides an iron-cobalt organic catalyst for converting CO 2 The application of the benzo-azacyclo is mild in reaction condition, and can effectively fix greenhouse gases to generate a drug intermediate with additional value.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an iron-cobalt organic catalyst, a preparation method thereof and CO conversion by using the iron-cobalt organic catalyst 2 Application of synthesizing benzazepine.
Background
CO 2 Is a greenhouse gas with large amount, no toxicity and stability in nature. With the global industrial development and the dramatic population increase, CO is generated every year 2 The discharge amount is suddenly increased, and the ecological environment is destroyed. Thus, CO is converted 2 Efficient conversion of green to other compounds has been a very hot topic of research. At present, a large amount of CO exists 2 Is sealed at the seabed in a physical mode, although a large amount of greenhouse gas can be stored in a short time, a plurality of disadvantages exist, which are a great hidden danger of the ecological environment, and CO can not be fundamentally solved 2 Excessive discharge problems. It can also be stored or reacted chemically into C1 compounds such as methanol, formic acid, etc., due to CO 2 Chemical potentialThe catalyst has low energy and is difficult to activate, so that the problem of finding a green, environment-friendly and efficient catalyst for catalytic reaction is always a problem in the field. At present, with CO 2 The photocatalytic reaction as a raw material is carried out under relatively severe conditions. Some of them need to be catalyzed at high temperature and high pressure, some are added with expensive rare earth metal elements, and some are added with photosensitizer. For example, chinese patent publication No. CN105749914B discloses a symmetric bifunctional photocatalyst and a corresponding dual-chamber photoreactor, and belongs to the technical field of comprehensive utilization of carbon dioxide, wherein the symmetric bifunctional photocatalyst comprises double-sided TiO 2 And depositing a graphene intermediate electron transport layer on the nanotube array substrate, and depositing narrow-gap semiconductor nanoparticles as a photosensitizer. The symmetrical photocatalyst provided by the invention has the advantages that the photoresponse of the three-way composite photocatalyst is expanded to a visible light region through the introduction of the electron transport layer and the photosensitizer component, meanwhile, the effective separation of a photoproduction electron-hole pair is promoted, and the photocatalytic reduction of CO by the composite photocatalyst is enhanced 2 (ii) ability of; after the double-sided symmetrical ternary composite catalyst is matched with a double-chamber photoreactor, photocatalytic water oxidation and CO are carried out 2 The reduction reactions are respectively carried out in independent areas, so that the occurrence of reverse reactions is reduced, and the photocatalytic CO is further improved 2 The reduction efficiency is high, but the preparation of the photosensitizer is complicated and has requirements on a reactor. Therefore, a simple and efficient new carbon fixation way needs to be found.
Disclosure of Invention
In order to solve the technical problems, the invention provides an iron-cobalt organic catalyst, a preparation method thereof and CO conversion thereof 2 The application of synthesizing benzoazacyclo, uses hydrothermal method to synthesize a novel homogeneous phase photocatalyst, its preparation method is simple, its repeatability is high, said catalyst can make photocatalytic reaction under the moderate condition of normal temp. and normal pressure, and can effectively fix CO 2 And converts it into a more valuable pharmaceutical intermediate.
In order to achieve the purpose, the invention adopts the following technical scheme: an organic Fe-Co catalyst is a microsphere with the diameter of 200-400nm and lamellar crystals on the surface of the microsphere. The microsphere has perfect surface crystallization and regular lattice structure. The microsphere has uniform particle size. Some space formed between catalyst particles increases the contact area of reactants and catalyst, and promotes the reaction.
The invention also provides a preparation method of the iron-cobalt organic catalyst, which comprises the following steps: adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol, stirring for dissolving, and adding FeCl 3 Stirring for 5-15 min, and adding Co (NO) 3 ) 2 · 6H 2 Stirring for 5-15 min with FeCl 3 And Co (NO) 3 ) 2 ·6H 2 The amount of O is 1-10 times of that of aromatic acid, the reaction is carried out for 10-20 hours at 150-200 ℃, and the product is washed and dried in vacuum to obtain the Fe-Co organic catalyst. The invention prepares the iron-cobalt organic catalyst with lamellar crystals on the surface without a template agent, realizes the control of the product morphology, and has simple preparation method and high repeatability.
Preferably, the volume ratio of DMF to absolute ethyl alcohol in the mixed solvent is 1 (0.1-10).
Preferably, the washing is carried out by alternately washing with absolute ethyl alcohol and DMF, and the dosage of each washing liquid is 5-10ml for each mol of the product, and the washing is carried out until the product quality is unchanged. DMF has good solubility to organic solvent, aromatic acid also has good solubility in ethanol, and the alternate washing of the DMF and the aromatic acid can effectively remove redundant aromatic acid and cobalt nitrate in the product and improve the purity of the catalyst. The washing sequence or times of DMF and ethanol is not limited, as long as the washing is ensured to be as complete as possible, the washing effect of a small amount of washing times is better than that of a large amount of washing times, and the effect of washing till the weight is not changed can be achieved by washing for 4-5 times in total.
Preferably, the vacuum drying is carried out at 80-100 deg.C for 5-10 hr. The vacuum drying can reduce the boiling point of the solvent, enhance the volatilization effect of the solvent at the same temperature, ensure the complete volatilization of the organic solvent in the product and shorten the drying time. Drying at 80-100 deg.c for 5-10 hr to volatilize residual organic solvent and to ensure complete volatilization of the organic solvent and no damage to the lamellar crystal on the surface of the catalyst.
The invention also provides a method for converting CO by using the iron-cobalt organic catalyst 2 The application of synthesizing benzoazacyclo is to add 1-10mg of the iron-cobalt organic catalyst into 5-20mL of tetrahydrofuran solution of 0.05-1mmol/L o-aminobenzonitrile compound under normal pressure, and continuously blow CO 2 The gas is subjected to photocatalytic reaction under a sunlight simulator to synthesize the benzoazacycle. The general formula of the o-aminobenzonitrile compounds is as follows:
the catalyst has the mesoporous property and the sea urchin-shaped surface structure, so that the catalyst has large specific surface area and can convert CO 2 More effective contact areas and active sites can be provided in the reaction of synthesizing the benzazepine, which is beneficial to CO 2 The adsorption of gas and high catalytic activity. The method can be carried out under normal pressure, the temperature is not high, the reaction can be carried out at room temperature, the reaction condition is mild, greenhouse gases can be effectively fixed, and a medicine intermediate with additional value is generated.
Preferably, the reaction temperature is 20 to 80 ℃. The organic Fe-Co catalyst of the present invention may be used in converting CO at normal temperature 2 The benzazepine is synthesized, and the conversion rate can be improved by properly increasing the temperature.
Compared with the prior art, the iron-cobalt organic catalyst has simple preparation method and high repeatability; the catalyst has lamellar crystals on the surface and large surface area, and can effectively fix greenhouse gases under mild conditions when being used for photocatalytic reaction to generate a drug intermediate with added value.
Drawings
FIG. 1 is an SEM image of an Fe-Co organic catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of an iron-cobalt organic catalyst comprises the following steps: adding 0.1mmol of terephthalic acid into 50mL of a mixed solvent of DMF and absolute ethanol with the volume ratio of 1 3 Stirred for 10 minutes, then 10mmolCo (NO) was added 3 ) 2 ·6H 2 And O is stirred for 10 minutes and reacts for 15 hours at the temperature of 200 ℃, the product is washed alternately by absolute ethyl alcohol and DMF for 4 times, the mass is not reduced any more, the using amount of the washing liquid for each mole of the product is 8ml, the product is put into a vacuum drying oven to be dried, and the iron-cobalt organic catalyst is obtained after the product is dried for 5 hours at the temperature of 100 ℃.
The SEM image of the iron-cobalt organic catalyst is shown in figure 1, the catalyst is microspheres with the diameter of 200-400nm, and layered crystals are arranged on the surfaces of the microspheres.
The iron-cobalt organic catalyst is applied to converting CO 2 Synthesis of a benzazepine ring: adding 1mg of the iron-cobalt organic catalyst into 5mL of 0.05mmol/L o-aminobenzonitrile tetrahydrofuran solution at 80 ℃ under normal pressure, and continuously blowing CO 2 And (3) carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 86%.
Example 2
A preparation method of an iron-cobalt organic catalyst comprises the following steps: 0.5mmol of 1,4,5, 8-naphthalene tetracarboxylic acid is added into 50mL of a mixed solvent of DMF and absolute ethanol with the volume ratio of 1 3 Stirred for 15 minutes, then 5mmolCo (NO) was added 3 ) 2 ·6H 2 And stirring the mixture for 5 minutes, reacting for 10 hours at 150 ℃, alternately washing the product for 5 times by using absolute ethyl alcohol and DMF (dimethyl formamide), wherein the mass of the product is not reduced any more, the using amount of the washing liquid is 10ml of mixed liquid used for each mole of the product, drying the product in a vacuum drying oven, and drying for 10 hours at 80 ℃ to obtain the iron-cobalt organic catalyst.
The iron-cobalt organic catalyst is a microsphere with the diameter of 300-400nm, and layered crystals are arranged on the surface of the microsphere.
The iron-cobalt organic catalyst is applied to converting CO 2 Synthesis of benzo nitrogensHeterocyclic ring: adding 5mg of the iron-cobalt organic catalyst into 10mL of 1mmol/L o-aminobenzonitrile tetrahydrofuran solution at 20 ℃ under normal pressure, and continuously blowing CO 2 And (3) carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 53%.
Example 3
A preparation method of an iron-cobalt organic catalyst comprises the following steps: 1mmol of 2, 5-dipicolinic acid is added into 50mL of a mixed solvent of DMF and absolute ethanol with the volume ratio of 1 3 Stirred for 5 minutes and then 1mmol Co (NO) was added 3 ) 2 ·6H 2 And stirring the mixture for 5 minutes, reacting for 20 hours at 180 ℃, alternately washing the product for 4 times by using absolute ethyl alcohol and DMF (dimethyl formamide), wherein the mass of the product is not reduced any more, the using amount of the washing liquid is 5ml of mixed liquid used for each mole of the product, drying the product in a vacuum drying oven, and drying for 8 hours at 90 ℃ to obtain the iron-cobalt organic catalyst.
The iron-cobalt organic catalyst is a microsphere with the diameter of 200-400nm, and layered crystals are arranged on the surface of the microsphere.
The iron-cobalt organic catalyst is applied to converting CO 2 Synthesis of a benzoazacycle: at 40 ℃ and normal pressure, adding 10mg of the iron-cobalt organic catalyst into 20mL of 0.1mmol/L o-aminobenzonitrile tetrahydrofuran solution, and continuously blowing CO 2 And carrying out photocatalytic reaction on the gas under a sunlight simulator to obtain a corresponding quinazoline substrate with the yield of 77%.
The iron-cobalt organic catalyst prepared by the invention can perform photocatalytic reaction under mild conditions of normal temperature and normal pressure, and effectively fix CO 2 And the compound is converted into a more valuable drug intermediate with high yield.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. For converting CO 2 The preparation method of the iron-cobalt organic catalyst for synthesizing the benzoazacycle is characterized by comprising the following steps: adding aromatic acid into a mixed solvent of DMF and absolute ethyl alcohol with the volume ratio of 1 (0.1-5), stirring and dissolving, and then adding FeCl 3 Stirring for 5-15 min, and adding Co (NO) 3 ) 2 •6H 2 Stirring for 5-15 min with FeCl 3 And Co (NO) 3 ) 2 •6H 2 The amount of O is 1-10 times of that of aromatic acid, the reaction is carried out for 10-20 hours at 150-200 ℃, the product is washed and dried in vacuum to obtain the iron-cobalt organic catalyst, the catalyst is microspheres with the diameter of 200-400nm, and the surfaces of the microspheres are provided with lamellar crystals.
2. The preparation method of claim 1, wherein the washing is performed by alternately washing with absolute ethanol and DMF, and the amount of washing solution used is 5-10ml per mole of product, and the washing is performed until the product quality is unchanged.
3. The method according to claim 1, wherein the vacuum drying is carried out at 80 to 100 ℃ for 5 to 10 hours.
4. A method for converting CO by using the organic Fe-Co catalyst prepared by the method of any one of claims 1-3 2 The application of synthesizing benzazepine is characterized by that under the condition of normal pressure, in the 5-20mL of 0.05-1mmol/L tetrahydrofuran solution of o-aminobenzonitrile compound 1-10mg of the described iron-cobalt organic catalyst is added, and continuously the CO is blown 2 The gas is subjected to photocatalytic reaction under a sunlight simulator to synthesize the benzoazacycle.
5. Use according to claim 4, wherein the reaction temperature is 20-80 ℃.
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| US7026478B2 (en) * | 2002-05-10 | 2006-04-11 | Studiengesellschaft Kohle Mbh | Iron catalyzed cross coupling reactions of aromatic compounds |
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