A highly active heterometallic CuIn-MOF catalyst, a preparation method thereof, and a method and application thereof for catalyzing amino synthesis of organic azides

Abstract

The present invention belongs to the field of organic chemistry technology, and in particular to a highly active heterometallic CuIn‑MOF catalyst and a preparation method thereof and a method and application of its catalytic amino synthesis of organic azides, and more particularly to a method for preparing a heterometallic CuIn‑MOF catalyst material based on 3,5-bis(4-carboxylphenyl)pyridine ligands and its catalytic amino compound to prepare an azide compound. The inventive method is as follows: using CuIn‑MOF as a reaction catalyst, an amino compound is added to a reactor, reacted at a specific temperature, and after the reaction is completed, the product is separated and purified to obtain the corresponding organic azide compound. The present invention has the characteristics of simple operation, mild reaction conditions, short reaction time, high reaction purity, and being applicable to highly active amino compounds, is suitable for industrial production, and provides ideas and methods for subsequent highly active natural amino compounds to participate in click chemistry.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic chemistry, and specifically relates to a highly active heterometallic CuIn-MOF catalyst, a preparation method thereof, and a method and application thereof for catalyzing the synthesis of organic azides from amino groups. More specifically, it relates to a heterometallic CuIn-MOF catalyst material constructed based on 3,5-di(4-carboxyphenyl)pyridine, a preparation method thereof, and an application thereof for catalyzing the preparation of organic azides from amino groups. Background Art

[0002] Organic azide compounds are a class of highly active chemical raw materials and important intermediates that can be widely used in organic synthesis, fine chemicals, functional materials, biotechnology, and clinical medicine. Due to their good reactivity, these compounds are often used to efficiently synthesize nitrogen-containing heterocyclic compounds, such as triazole and tetrazole derivatives, in click chemistry reactions, becoming a key intermediate compound in the field of innovative drug research and chemical biology. At the same time, some organic azide compounds themselves can also be used as important clinical drugs, such as zidovudine (ATZ, 1) and adoxicillin (2), which are currently excellent anti-AIDS drugs and antibacterial drugs, respectively. In addition, the azide group is also a good protecting group for amino groups and is often used to protect amino groups. Compared with other protecting groups, it has many advantages, such as good stability, acid and alkali resistance, high temperature resistance, oxidation resistance, and stability to most reducing agents. When reduced with hydrogen under Pd-C catalysis, it can be converted into amino groups with high yield. Therefore, the azide group is an ideal amino protecting group.

[0003]

[0004] There are not many methods reported in the literature for protecting amino groups with azide. The most typical method involves reacting an amino compound with a prepared organic hydrazoic acid using water and acetonitrile as solvents and CuSO₄·5H₂O as a catalyst. This reaction typically requires an ice-water bath followed by prolonged stirring at room temperature, resulting in long reaction times and low yields (Med. Chem. 19 (2011) 30-40).

[0005]

[0006] The above methods have disadvantages such as long reaction time, many steps, high failure rate and low yield. Therefore, finding a synthesis method with efficient catalysis, simple steps and green environmental protection is the goal of many researchers.

[0007] Meanwhile, metal-organic frameworks (MOFs) are a class of organic / inorganic hybrid materials with porous structures constructed from central metal ions and organic ligands through coordination bonds. Due to their highly dispersed catalytic active sites, easily modifiable framework structures, and tunable pore size, they have been widely used in reactions such as catalytic hydrogenation, hydration, coupling, and cyclization. The use of MOFs as heterogeneous catalysts has attracted widespread attention from scientific researchers. However, there are currently no reports on the synthesis of azide groups from amino groups catalyzed by MOFs.

[0008] Therefore, constructing cheap and efficient MOFs catalysts and developing a simple, green and environmentally friendly method to synthesize azide compounds have very important industrial value and research significance. Summary of the Invention

[0009] The purpose of the present invention is to prepare a catalyst with high catalytic activity for the azide protection reaction of amino compounds and to solve the shortcomings of the azide protection reaction of amino compounds, such as harsh conditions, long reaction time, and low yield, so as to provide a simple, efficient and green catalyst preparation method for amino azide protection, especially amino azide protection of highly active substrate compounds.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is:

[0011] The first aspect of the present invention provides a highly active heterometallic CuIn-MOF catalyst, the chemical formula of which is {[(μ2-OH)∙(Cu4I4) 0.25 ∙L∙In]·3DMF} n , wherein L is an organic ligand 3,5-di(4-carboxyphenyl)pyridine, and DMF is N,N-dimethylformamide.

[0012] As a further improvement of the present invention, the framework structure contains two metal ions, Cu I and In Ⅲ , where every four Cu I Respectively with four I - Connected to form a [Cu4I4] cluster, with the cluster as the core and coordinated with the four pyridine N atoms of the four ligands, each ligand is respectively connected to the adjacent In through the carboxyl group at the other end. Ⅲ Coordinate to form a one-dimensional metal In chain, where every two adjacent In Ⅲ At the same time, through μ2-OH - Connection, each In Ⅲ They all form a hexacoordinated octahedral coordination pattern with oxygen atoms, ultimately forming a three-dimensional porous structure.

[0013] As a further improvement of the present invention, the crystal structure belongs to the Pnma space group of the orthorhombic system, and the unit cell parameters are: a=35.3958(5), b=13.4799(2), c=34.3164(5), α=90°, β=90°, γ=90°.

[0014] The second aspect of the present invention provides a method for preparing a highly active heterometallic CuIn-MOF catalyst, comprising the following steps:

[0015] S1: DMF and concentrated nitric acid are added to indium salt, cuprous iodide and 3,5-di(4-carboxyphenyl)pyridine in sequence, stirred evenly, reacted at a constant temperature and then cooled to room temperature;

[0016] S2: The reaction solution is removed by centrifugation, washed with N,N-dimethylformamide, and activated by adding acetonitrile or methanol solution. After activation, the catalyst is centrifuged to remove the upper layer of acetonitrile or methanol solution, and the precipitate is dried to obtain the catalyst;

[0017] The indium salt is hydrated indium nitrate, preferably indium nitrate pentahydrate.

[0018] As a further improvement of the present invention, the molar ratio of the indium salt, the copper salt and 3,5-di(4-carboxyphenyl)pyridine is 4:5:3; the usage ratio of the 3,5-di(4-carboxyphenyl)pyridine, DMF and concentrated nitric acid is 0.03 mmol:3~6 mL:50~150 μL.

[0019] As a further improvement of the present invention, the reaction temperature of the isothermal reaction in step S1 is 80-150° C.; the reaction time is 48-96 hours; and the programmed cooling rate is 0.75-2° C. / hour.

[0020] As a further improvement of the present invention, the activation reaction in step S2 is: activating with acetonitrile or methanol for 3 days, replacing the acetonitrile or methanol solution every 12 hours, and then drying at 60° C. for 6 hours to obtain the product.

[0021] The third aspect of the present invention provides the use of the highly active heterometallic CuIn-MOF catalyst in catalyzing the synthesis of organic azide compounds from amino compounds.

[0022] A fourth aspect of the present invention provides a method for preparing an organic azide compound by catalytic synthesis using the catalyst, comprising the following steps:

[0023] The amino compound, the acid binding agent and the CuIn-MOF catalyst are added to a solvent, mixed evenly, and an organic azide compound is added, and the reaction is carried out at 0°C to 70°C. After the reaction is completed, the product is separated and purified to obtain the corresponding organic azide compound product;

[0024] The chemical reaction formula is as follows:

[0025] ,

[0026] Wherein: R is a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, a nitrogen-containing fused heterocyclic group, a substituted or unsubstituted five-membered or six-membered heteroaryl group, or a substituted or unsubstituted five-membered or six-membered heteroarylmethyl group; or R-NH2 is an aminoglycoside compound, an amino acid compound, or an amino acid alkyl ester compound;

[0027] The acid-binding agent is selected from triethylamine or sodium bicarbonate; the solvent is selected from one or more of dichloromethane, acetonitrile, methanol, and tetrahydrofuran; the organic azide compound is selected from trifluoromethanesulfonic acid azide; trifluoromethanesulfonic acid azide is dissolved in dichloromethane and added in the form of a solution, the concentration of which is 0.97 to 1.94 mol / L, preferably 1 mol / L.

[0028] As a further improvement of the present invention, the molar ratio of the amino compound, the acid binding agent and the organic azide compound is 1:3-20:1.2-6;

[0029] Preferably, the molar number of the organic azide compound is 1.2 times the number of amino groups in the amino compound;

[0030] Preferably, the ratio of the amount of the amino compound to the amount of the catalyst is 1 mmol of the amino compound to 1-10 mg of the catalyst;

[0031] Preferably, 1 mmol of amino compound is added to 2 mg of CuIn-MOF.

[0032] The beneficial effects of adopting the above technical solution are:

[0033] 1. The catalyst structure contains abundant nanocages and pore structures with high porosity, which provides favorable conditions for the diffusion of substrates in the catalytic reaction and their enrichment at the catalytic site.

[0034] 2. The catalyst obtained by the present invention has high chemical stability and thermal stability, and its thermal stability can reach 380°C; its structure remains unchanged after five catalytic cycles, and its powder diffraction peak can still remain consistent with the original powder diffraction peak, indicating that it has good chemical stability.

[0035] 3. The reaction speed of the present invention is fast, and the MOF catalyst greatly increases the reaction rate and the yield is also improved to a certain extent.

[0036] 4. The present invention has simple post-processing, high product purity, mild reaction conditions, and is suitable for large-scale preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1This is the coordination pattern diagram of the CuIn-MOF catalyst obtained in Example 1;

[0038] Figure 2 Schematic diagram of the three-dimensional structure of the CuIn-MOF catalyst obtained in Example 1;

[0039] Figure 3 This is the thermogravimetric diagram of the CuIn-MOF catalyst obtained in Example 1;

[0040] Figure 4 This is the X-ray powder diffraction (XRD) pattern of the CuIn-MOF catalyst obtained in Example 1 after catalytic cycle;

[0041] Figure 5 This is the recycling result of the CuIn-MOF catalyst obtained in Example 1. DETAILED DESCRIPTION

[0042] In order to make the objectives, technical solutions and advantages of the present invention more clear, the invention is clearly and completely described below in conjunction with specific embodiments.

[0043] Example 1

[0044] To indium nitrate pentahydrate (0.04 mmol), cuprous iodide (0.05 mmol), and 3,5-bis(4-carboxyphenyl)pyridine (0.03 mmol) were added 3 mL of N,N-dimethylformamide and 50 μL of concentrated nitric acid, respectively. After stirring, the mixture was placed in a 100°C oven for 72 hours, then cooled to room temperature at a rate of 1.25°C per hour. The reaction solution was removed by centrifugation, washed three times with N,N-dimethylformamide, and activated with methanol for three days, replacing the methanol or acetonitrile every 12 hours. After centrifugation, the supernatant was removed, and the precipitate was dried in a 60°C oven for 6 hours to obtain a green powder, the CuIn-MOF catalyst.

[0045] Structural characterization:

[0046] Its chemical formula is {[(μ2-OH)∙(Cu4I4) 0.25 ∙L∙In]·3DMF} n Where L is the organic ligand 3,5-di(4-carboxyphenyl)pyridine and DMF is N,N-dimethylformamide. The framework structure contains two metal ions, Cu I and In Ⅲ , where every four Cu I Respectively with four I - Connected to form a [Cu4I4] cluster, and with the cluster as the core, it coordinates with the four pyridine N atoms of the four ligands. Each ligand is connected to the adjacent In through the carboxyl group at the other end. Ⅲ Coordinate to form a one-dimensional metal In chain. Every two adjacent InⅢ At the same time, through μ2-OH - Connection, each In Ⅲ They all form a hexacoordinated octahedral coordination pattern with oxygen atoms, ultimately forming a three-dimensional porous structure, such as Figure 1 and 2 As shown in the figure, the framework, viewed along the b-axis, contains a 6.8Å × 12.4Å pore. Also present are octahedral nanocages formed by two [Cu₄I₄] clusters and four In metal chains connected by four ligands, each with a cavity diameter of up to 1nm. Due to the rich nanocage and pore structure within the porous framework, its porosity reaches 63.2%, providing favorable conditions for substrate diffusion and enrichment at the catalytic site during catalytic reactions.

[0047] The obtained crystal structure was determined to belong to the Pnma space group of the orthorhombic system, with unit cell parameters of a=35.3958(5), b=13.4799(2), c=34.3164(5), α=90°, β=90°, γ=90°.

[0048] Thermogravimetric analysis results showed Figure 3 As shown, it proves that it has high stability.

[0049] Example 2

[0050] To cuprous iodide (0.05 mmol) and 3,5-bis(4-carboxyphenyl)pyridine (0.03 mmol) was added 3 mL of N,N-dimethylformamide mixed with indium nitrate pentahydrate (0.04 mmol). 75 μL of concentrated nitric acid was added dropwise to the mixture, stirred evenly, and then placed in a 100°C oven for 72 hours. The temperature was then cooled to room temperature at a rate of 1.25°C per hour. The reaction solution was centrifuged, washed three times with N,N-dimethylformamide, and activated with methanol for three days, replacing the methanol or acetonitrile every 12 hours. After centrifugation, the supernatant was removed, and the precipitate was dried in a 60°C oven for 6 hours to obtain a green powder, the CuIn-MOF heterogeneous catalyst. Its structural characterization was as described in Example 1.

[0051] Example 3

[0052] To indium nitrate pentahydrate (0.04 mmol), cuprous iodide (0.05 mmol), and 3,5-bis(4-carboxyphenyl)pyridine (0.03 mmol) were added 3 mL of N,N-dimethylformamide and 100 μL of concentrated nitric acid, respectively. After stirring, the mixture was placed in a 100°C oven for 72 hours, then cooled to room temperature at a rate of 1°C per hour. The reaction solution was removed by centrifugation, washed three times with N,N-dimethylformamide, and activated with methanol or acetonitrile for three days, replacing the methanol or acetonitrile every 12 hours. After centrifugation, the upper acetonitrile solution was removed, and the precipitate was dried in a 60°C oven for 6 hours to obtain a green powder, the CuIn-MOF heterogeneous catalyst. Its structural characterization is as described in Example 1.

[0053] Example 4

[0054] To indium nitrate pentahydrate (0.08 mmol), cuprous iodide (0.1 mmol), and 3,5-bis(4-carboxyphenyl)pyridine (0.06 mmol) were added 6 mL of N,N-dimethylformamide and 150 μL of concentrated nitric acid, respectively. After stirring, the mixture was placed in an 80°C oven for 96 hours, then cooled to room temperature at a rate of 0.75°C per hour. The reaction solution was centrifuged, washed three times with N,N-dimethylformamide, and activated with methanol for three days, replacing the methanol or acetonitrile every 12 hours. After centrifugation, the supernatant was removed, and the precipitate was dried in a 60°C oven for 6 hours to obtain a green powder, the CuIn-MOF heterogeneous catalyst. Its structural characterization is as described in Example 1.

[0055] Example 5

[0056] To indium nitrate pentahydrate (0.08 mmol), cuprous iodide (0.1 mmol), and 3,5-bis(4-carboxyphenyl)pyridine (0.06 mmol) were added 9 mL of N,N-dimethylformamide and 150 μL of concentrated nitric acid, respectively. After stirring, the mixture was placed in a 150°C oven for 48 hours, then cooled to room temperature at a rate of 2°C per hour. The reaction solution was centrifuged, washed three times with N,N-dimethylformamide, and activated with methanol for three days, replacing the methanol or acetonitrile every 12 hours. After centrifugation, the supernatant was removed, and the precipitate was dried in a 60°C oven for 6 hours to obtain a green powder, the CuIn-MOF heterogeneous catalyst. Its structural characterization is as described in Example 1.

[0057] Example 6

[0058] 1mmol 3-chloroaniline, 3mmol NEt3 (triethylamine), and 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 2h. After the reaction, the product was purified by column chromatography. 石油醚:V 乙酸乙酯 =7:1 to obtain the product, which is a light yellow liquid with a yield of 92%.

[0059] Example 7

[0060] 1mmol 2-chloroaniline, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 50min. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 88%.

[0061] Example 8

[0062] 1mmol benzylamine, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 50min. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 85%.

[0063] Example 9

[0064] 1mmol 4-chloroaniline, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 87%.

[0065] Example 10

[0066] 1mmol 4-methoxyaniline, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 2h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a yellow liquid with a yield of 79%.

[0067] Example 11

[0068] 1mmol 3-methoxyaniline, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a light yellow liquid with a yield of 78%.

[0069] Example 12

[0070] 1mmol 2-thiophenemethylamine, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1.5h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a yellow liquid with a yield of 61%.

[0071] Example 13

[0072] 1mmol 2-aminomethylpyridine, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1.5h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 64%.

[0073] Example 14

[0074] 1mmol 9-aminoacridine, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 2h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a dark brown solid with a yield of 91%.

[0075] Example 15

[0076] 1mmol 2-methylaniline, 3mmol NEt3, 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 2h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 82%.

[0077] Example 16

[0078] 1mmol 3-chloro-o-phenylenediamine, 3mmol NEt3, and 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1.5h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a light yellow liquid with a yield of 86%.

[0079] Example 17

[0080] 1mmol L-phenylalanine ethyl ester hydrochloride, 3mmol NEt3, and 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 2.5h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a colorless liquid with a yield of 76%.

[0081] Example 18

[0082] 1mmol o-phenylenediamine, 3mmol NEt3, and 2mg CuIn-MOF catalyst prepared in Example 1 were added to 2mL CH2Cl2, stirred at room temperature for 15min, and then 1.2mL 1mol / L TfN3 / CH2Cl2 was added and stirred for 1.5h. After the reaction, the product was purified by column chromatography. 石油醚 :V 乙酸乙酯 =7:1 to obtain the product, which is a brown liquid with a yield of 77%.

[0083] Example 19

[0084] 1 mmol of kanamycin monosulfate A, 18.2 mmol of NaHCO3, and 2 mg of the CuIn-MOF catalyst prepared in Example 1 were added to 1 mL of H2O. After stirring in an ice-water bath for 5 minutes, 4.8 mL of 1 mol / L TfN3 / CH2Cl2 was slowly added, followed by 1.7 mL of CH3OH. The mixture was then stirred at room temperature for 6 hours until the reaction was completed. The product was purified by column chromatography using V dichloromethane: V methanol = 4:1 to obtain a pure product as a light yellow colloidal solid with a yield of 91%.

[0085] Example 20

[0086] 1 mmol 3-chloroaniline, 3 mmol NEt3, and 1 mg CuIn-MOF catalyst prepared in Example 2 were added to 2 mL CH2Cl2. After stirring at room temperature for 15 min, 1.2 mL 1 mol / L TfN3 / CH2Cl2 was added and stirring was continued for 2 h. After the reaction was completed, the product was treated by column chromatography with V petroleum ether: V ethyl acetate = 7:1 to obtain the product, which was a light yellow liquid with a yield of 81%.

[0087] Example 21

[0088] 1 mmol 3-chloroaniline, 3 mmol NEt3, and 4 mg CuIn-MOF catalyst prepared in Example 3 were added to 2 mL CH2Cl2. After stirring at room temperature for 15 min, 1.2 mL 1 mol / L TfN3 / CH2Cl2 was added and stirring was continued for 2.5 h. After the reaction was completed, the product was treated by column chromatography with V petroleum ether: V ethyl acetate = 7:1 to obtain the product, which was a light yellow liquid with a yield of 83%.

[0089] Example 22

[0090] 1 mmol 3-chloroaniline, 3 mmol NEt3, and 6 mg CuIn-MOF catalyst prepared in Example 4 were added to 2 mL CH2Cl2. After stirring at room temperature for 15 min, 1.2 mL 1 mol / L TfN3 / CH2Cl2 was added and stirring was continued for 2 h. After the reaction was completed, the product was treated by column chromatography with V petroleum ether: V ethyl acetate = 7:1 to obtain the product, which was a light yellow liquid with a yield of 83%.

[0091] Example 23

[0092] 1 mmol 3-chloroaniline, 3 mmol NEt3, and 8 mg CuIn-MOF catalyst prepared in Example 5 were added to 2 mL CH2Cl2. After ultrasonication at room temperature for 15 min, 1.2 mL 1 mol / L TfN3 / CH2Cl2 was added, and ultrasonication was continued for 2 h. After the reaction was completed, the product was treated by column chromatography with V petroleum ether: V ethyl acetate = 7:1 to obtain the product, which was a light yellow liquid with a yield of 85%.

[0093] Test Example 1

[0094] (1) Catalytic cycle test

[0095] The catalyst prepared in Example 1 was subjected to a catalytic cycle test according to the method for catalytic synthesis of azide compounds in Example 6. The catalyst after the reaction was centrifuged and dried before being reused in the next cycle. The yields of each cycle are shown in Table 1:

[0096] Table 1 Catalytic cycle test results of Example 6

[0097]

[0098] The test results are as follows Figure 5 As shown, the yield of the catalyst catalytic synthesis after the catalytic cycle experiment remains above 85%, indicating that the catalyst obtained by the present invention has good chemical stability.

[0099] (2) X-ray powder diffraction test

[0100] The catalyst prepared in Example 1 was subjected to five catalytic cycles, and the catalyst after each catalytic cycle was subjected to X-ray powder diffraction test. The test results are shown in FIG. Figure 4 As shown, the structure of the catalyst sample after catalytic cycling is consistent with that of the sample without catalytic cycling experiment, indicating that the catalyst obtained by the present invention has good chemical stability.

[0101] Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art may still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A highly active heterometallic CuIn-MOF catalyst, characterized in that: Its chemical formula is {[(μ2-OH)∙(Cu4I4) 0.25 ∙L∙In]·3DMF} n , where L is the organic ligand 3,5-di(4-carboxyphenyl)pyridine, DMF is N,N-dimethylformamide; the framework structure contains two metal ions, Cu I and In Ⅲ , where every four Cu I Respectively with four I - Connected to form a [Cu4I4] cluster, and with the cluster as the core, it coordinates with the four pyridine N atoms of the four ligands. Each ligand is connected to the adjacent In atoms through the carboxyl group at the other end. Ⅲ Coordinate to form a one-dimensional metal In chain, where every two adjacent In Ⅲ At the same time, through μ2-OH - Connection, each In Ⅲ They all form a hexacoordinated octahedral coordination pattern with oxygen atoms, ultimately forming a three-dimensional porous structure.

2. A highly active heterometallic CuIn-MOF catalyst according to claim 1, characterized in that: The crystal structure belongs to the orthorhombic Pnma space group, and the unit cell parameters are: a=35.3958(5), b=13.4799(2), c=34.3164(5), α=90°, β=90°, γ=90°.

3. A method for preparing a highly active heterometallic CuIn-MOF catalyst as claimed in claim 1 or 2, characterized in that: The following steps are involved: S1: DMF and concentrated nitric acid are added to indium salt, cuprous iodide and 3,5-di(4-carboxyphenyl)pyridine in sequence, stirred evenly, reacted at a constant temperature and then cooled to room temperature; S2: The reaction solution is removed by centrifugation, washed with N,N-dimethylformamide, and activated by adding acetonitrile or methanol solution. After activation, the catalyst is centrifuged to remove the upper layer of acetonitrile or methanol solution, and the precipitate is dried to obtain the catalyst; The indium salt is hydrated indium nitrate.

4. The method for preparing a highly active heterometallic CuIn-MOF catalyst according to claim 3, characterized in that: The molar ratio of the indium salt, cuprous iodide and 3,5-bis(4-carboxyphenyl)pyridine is 4:5:3; the usage ratio of 3,5-bis(4-carboxyphenyl)pyridine, DMF and concentrated nitric acid is 0.03 mmol: 3-6 mL: 50-150 μL.

5. The method for preparing a highly active heterometallic CuIn-MOF catalyst according to claim 3, characterized in that: The reaction temperature of the isothermal reaction in step S1 is 80-150° C.; the reaction time is 48-96 hours; and the programmed cooling rate is 0.75-2° C. / hour.

6. The method for preparing a highly active heterometallic CuIn-MOF catalyst according to claim 3, characterized in that: The activation reaction in step S2 is as follows: activating with acetonitrile or methanol for 3 days, replacing the acetonitrile or methanol solution every 12 hours, and then drying at 60° C. for 6 hours to obtain the product.

7. Use of the highly active heterometallic CuIn-MOF catalyst according to claim 1 or 2 in catalyzing the synthesis of organic azide compounds from amino compounds.

8. A method for preparing an organic azide compound by catalytic synthesis using the catalyst according to claim 1 or 2, characterized in that: The following steps are involved: The amino compound, the acid binding agent and the CuIn-MOF catalyst are added to a solvent, mixed evenly, and an organic azide compound is added, and the reaction is carried out at 0°C to 70°C. After the reaction is completed, the product is separated and purified to obtain the corresponding organic azide compound product; The chemical reaction formula is as follows: Wherein: R is a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, a nitrogen-containing fused heterocyclic group, a substituted or unsubstituted five-membered or six-membered heteroaryl group, or a substituted or unsubstituted five-membered or six-membered heteroarylmethyl group; or R-NH2 is an aminoglycoside compound, an amino acid compound, or an amino acid alkyl ester compound; The acid binding agent is selected from triethylamine or sodium bicarbonate; the solvent is selected from one or more of dichloromethane, acetonitrile, methanol, and tetrahydrofuran; and the organic azide compound is selected from trifluoromethanesulfonic acid azide.

9. The method for preparing an organic azide compound according to claim 8, wherein: The molar ratio of the amino compound, the acid binding agent and the organic azide compound is 1:3-20:1.2-6.

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