Nickel-based metal organic framework, aniline compound and preparation methods of nickel-based metal organic framework and aniline compound

Abstract

The invention is applicable to the technical field of organic chemistry, and provides a nickel-based metal organic framework, an aniline compound and preparation methods of the nickel-based metal organic framework and the aniline compound, and the preparation method of the nickel-based metal organic framework comprises the following steps: adding metal salt into a solvent, and carrying out sufficient ultrasonic treatment to completely dissolve the metal salt to obtain a solution; adding an organic ligand into a solvent, and carrying out sufficient ultrasonic treatment to completely dissolve the organic ligand to obtain a solution; s2, slowly dropwise adding the solution obtained in the step S2 into the liquid obtained in the step S1, mixing, and heating in an oil bath at the heating temperature of 100-150 DEG C for 24-48 hours; and S3, respectively washing the heating product obtained in the step S3 with N, N-dimethylformamide and acetone for multiple times, and then drying to obtain the nickel-based metal organic framework. According to the method, porphyrin is used as a cocatalyst, and the porphyrin and the nickel-based metal organic framework are jointly used for photocatalytic coupling of aryl bromide and pyrrolidine C-N to synthesize the aniline compound, so that the method has the advantages of high catalytic efficiency, single product, easiness in separation from a reaction system, low cost and simple reaction steps, and can be used for large-scale production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a nickel-based metal organic framework, an aniline compound and a preparation method thereof. Background Art

[0002] As the ultimate source of energy on Earth, solar energy is widely distributed, abundant in reserves, clean and sustainable, and is therefore seen as a new direction for the development of renewable energy. In modern industrial production, using solar energy to drive photocatalytic organic coupling reactions will provide an important green, low-energy and sustainable development solution for the preparation of high-value-added pharmaceutical and chemical intermediates.

[0003] Aniline compounds have great utilization value in the manufacture of dyes, drugs, resins, etc., and can also be used as rubber vulcanization accelerators. They occupy an important market position in various fields and have great market demand. Among the numerous aniline compounds, 1-[4-(trifluoromethyl)phenyl]pyrrolidine is one of the most promising compounds, and its market value is dozens of times that of its synthetic raw material p-bromotrifluorotoluene. The Buchwald-Hartwig CN coupling reaction is a traditional method for synthesizing aniline compounds. This method uses various precious metal palladium and palladium metal complexes as catalysts, and also requires the addition of alkali. The process of the catalytic reaction is complex, the selectivity is low, and the total yield is low. It is necessary to ensure a continuous and stable high temperature to promote the normal reaction, resulting in high energy consumption, high production cost and large amount of three wastes generated in the Buchwald-Hartwig CN coupling reaction.

[0004] Photocatalytic technology converts renewable solar energy into chemical energy, providing an energy basis for the synthesis of aniline compounds. Based on this, the McMillan research group pioneered the use of nickel salts as co-catalysts to generate aniline compounds under visible light drive. However, during the experiment, nickel salts are very easy to absorb water and deliquesce. Most importantly, nickel salts are also easily reduced to nickel black by short-wavelength light irradiation, which wraps on the surface of the photocatalyst, deactivates the catalyst, and thus affects the catalytic reaction. Therefore, designing a new photocatalyst that can be used in the photocatalytic CN coupling reaction without the use of external nickel salts is the key to solving the problem. Summary of the invention

[0005] The purpose of the embodiments of the present invention is to provide a method for preparing a nickel-based metal organic framework, aiming to solve the problems raised in the above background technology.

[0006] The embodiment of the present invention is implemented as follows: a method for preparing a nickel-based metal organic framework comprises the following steps: S1. Add the metal salt into the solvent and fully sonicate it to completely dissolve it to obtain a solution; S2, adding the organic ligand into the solvent, and fully sonicating it to completely dissolve it to obtain a solution; S3, slowly dropwise adding the solution obtained in step S2 to the liquid obtained in step S1, and heating in an oil bath after mixing, the heating temperature is 100-150° C., and the heating time is 24-48 h; S4. Wash the heated product obtained in step S3 with N,N-dimethylformamide and acetone for multiple times, and then dry to obtain a nickel-based metal organic framework.

[0007] Preferably, in step S1, the metal salt is one of nickel perchlorate hexahydrate, nickel acetate tetrahydrate, and nickel nitrate hexahydrate, and the solvent is one or more of N,N-dimethylformamide, methanol, and water, and the concentration of the metal salt in the obtained solution is 0.02-8 mol / L; In step S2, the organic ligand is one of tetrapyrazolylporphyrin, 1, 3, 5-tris((1H-pyrazol-4-yl)phenyl)benzene, 2, 4, 6-tris(4-(1H-pyrazol-4-yl)phenyl)-1,3,5-triazine, 2, 5-dihydroxyterephthalic acid and anthracene-9,10-dicarboxylic acid, the solvent is one or more of N,N-dimethylformamide, methanol, and water, and the concentration of the organic ligand in the obtained solution is 0.02-0.8 mol / L; The molar ratio of the organic ligand to the metal salt is 1:1-6.

[0008] Preferably, in step S1 and step S2, the ultrasonic frequency is 60-120 KHz, and the ultrasonic time is 10-30 min.

[0009] Preferably, in step S3, the dripping rate is 0.1-2 mL / min.

[0010] Another object of an embodiment of the present invention is to provide a nickel-based metal organic framework, which is prepared by the above-mentioned preparation method.

[0011] Another object of the present invention is to provide a method for preparing an aniline compound, comprising the following steps: S1. Adding the nickel-based metal organic framework described in claim 5 into a transparent reaction bottle containing aryl bromide; S2, dissolving the porphyrin molecules in N,N-dimethylacetamide, and completely dissolving them by ultrasound to obtain a solution; S3, bringing the reaction bottle of S1 and the solution obtained in S2 into a glove box, adding the solution obtained in S2 to the reaction bottle of S1, then dropping the tetrahydropyrrole solution, and placing the reaction bottle on a stirrer in the glove box to obtain a mixed solution to be reacted; S4, placing a magnetic stirrer in the reaction bottle containing the reaction mixture in S3 and sealing the bottle mouth, turning on the xenon lamp light source and adjusting the light power density so that the strongest point of light irradiates the wall of the reaction bottle to start the catalytic reaction; S5. After the reaction in step S4 is completed, an internal standard is added to the mixed solution, wherein the internal standard is 1,3,5-trimethoxybenzene. After the mixed solution is fully dissolved, the mixed solution is subjected to high-speed centrifugation to separate the supernatant, which is the aniline compound.

[0012] Preferably, the aryl bromide is one of p-bromobenzonitrile, m-bromobenzonitrile, o-bromobenzonitrile, p-bromotrifluorotoluene, and methyl p-bromobenzoate, and the added amount of the aryl bromide is 0.2-0.6 mmol; and the added amount of the nickel-based metal organic framework is 5-10 mg.

[0013] Preferably, in step S2, the amount of the porphyrin molecule added is 0.25-4 mg, which is a metal porphyrin or a non-metal porphyrin, the metal porphyrin is one of tetraphenylporphyrin nickel, tetraphenylporphyrin cobalt and 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin nickel, the non-metal porphyrin is one of tetraphenylporphyrin, 5,10,15,20-tetrakis-1H-pyrazol-4-yl-21H,23H-porphine and 5,10,15,20-tetraalkyl[4-(2H-tetrazol-5-yl)phenyl]-21H,23Hporphine; the added volume of N,N-dimethylacetamide is 2-6 mL; the frequency of the ultrasound is 60-120 KHz, and the ultrasound duration is 10-30 min.

[0014] Preferably, in step S4, the rotation speed of the magnetic stirrer is 500-1200 r / min, and the optical power density of the xenon lamp is 200-400 mW / cm 2 , the lighting time is 12-24 h.

[0015] In the embodiment of the present invention, a nickel-based metal organic framework material is prepared by high-temperature solvothermal method through high-temperature self-assembly of nickel salt and organic ligand. As the active site of the photoreaction, inspired by plant photosynthesis in nature, porphyrin, a chemical component in chlorophyll, is used as the main light-absorbing unit of the photocatalyst. The porphyrin used in the photocatalytic reaction can be most types of porphyrins, and the two materials are used together to photocatalyze aryl bromide and tetrahydropyrrole to synthesize aniline compounds; the nickel-based metal organic framework material and the porphyrin molecule work together to enhance the photogenerated electron separation ability of the material, promote the adsorption and activation of aryl bromide and tetrahydropyrrole by the material, and reduce the activation energy barrier of the reaction. At the same time, thanks to the high specific surface area of ​​the nickel-based metal organic framework and the excellent charge conduction ability of porphyrin, the photocatalytic efficient synthesis of aniline compounds at room temperature and pressure is realized. In addition, the addition of no exogenous nickel salt makes the entire reaction more stable, the catalyst stability can be better maintained, and ultimately the yield of the product aniline compounds can be greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the X-ray diffraction pattern of the nickel-based metal organic framework material Ni-BTPP prepared in Example 1 of the present invention; Figure 2 This is the X-ray diffraction pattern of the nickel-based metal organic framework material BUT-33-Ni prepared in Example 2 of the present invention; Figure 3 This is a hydrogen nuclear magnetic resonance spectrum analysis diagram of the product prepared in Example 3 of the present invention; Figure 4 This is a hydrogen nuclear magnetic resonance spectrum analysis diagram of the product prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0018] A nickel-based metal organic framework, the preparation method of which comprises the following steps: S1. Add a metal salt to a solvent and fully ultrasonicate (ultrasonic frequency is 60-120 KHz, ultrasonic time is 10-30 min) to completely dissolve it to obtain a solution, wherein the metal salt is one of nickel perchlorate hexahydrate, nickel acetate tetrahydrate, and nickel nitrate hexahydrate, and the solvent is one or more of N,N-dimethylformamide, methanol, and water. The concentration of the metal salt in the obtained solution is 0.02-8 mol / L, and the volume of the solvent is 0.15-6 L; S2, adding an organic ligand to a solvent, fully ultrasonicating (ultrasonic frequency of 60-120 KHz, ultrasonic time of 10-30 min) to completely dissolve it to obtain a solution, wherein the organic ligand is one of tetrapyrazolylporphyrin, 1, 3, 5-tris((1H-pyrazol-4-yl)phenyl)benzene, 2, 4, 6-tris(4-(1H-pyrazol-4-yl)phenyl)-1,3,5-triazine, 2, 5-dihydroxyterephthalic acid and anthracene-9, 10-dicarboxylic acid, and the solvent is one or more of N,N-dimethylformamide, methanol, and water, the concentration of the organic ligand in the obtained solution is 0.02-0.8 mol / L, the volume of the solvent is 0.015-0.6 L, and the molar ratio of the organic ligand to the metal salt is 1:1-6; S3, slowly dripping the solution obtained in step S2 (the dripping rate is 0.1-2 mL / min, specifically 0.1 mL / min) into the liquid obtained in step S1, adding the mixture into a thick-walled pressure-resistant bottle after mixing, placing the thick-walled pressure-resistant bottle in an oil bath, setting the heating temperature to 100-150° C., and heating time to 24-48 h; S4. Wash the heated product obtained in step S3 with N,N-dimethylformamide and acetone three times respectively (the washing method can be centrifugal washing or suction filtration washing, wherein the suction filtration washing uses an organic filter membrane and the washing container is a sand core funnel), and then dry (drying can be normal pressure high drying or reduced pressure drying, the temperature is 60-80°C, the drying time is 8-12 h, specifically, it can be 70°C reduced pressure drying) to obtain a nickel-based metal organic framework.

[0019] An aniline compound, the preparation method of which comprises the following steps: S1. Add the nickel-based metal organic framework prepared above into a transparent reaction bottle containing aryl bromide, the mass of the nickel-based metal organic framework material is 5-10 mg, the aryl bromide is one of p-bromobenzonitrile, m-bromobenzonitrile, o-bromobenzonitrile, p-bromotrifluorotoluene, and methyl p-bromobenzoate, the amount of the aryl bromide added is 0.2-0.6 mmol, and the transparent reaction bottle can be made of a highly light-transmitting material such as quartz, crystal, or glass; S2. Dissolve the porphyrin molecule in N,N-dimethylacetamide, and completely dissolve it by ultrasound (ultrasound frequency is 60-120KHz, ultrasound duration is 10-30 min) to obtain a solution, wherein the amount of the porphyrin molecule added is 0.25-4 mg, and it is a metal porphyrin or a non-metal porphyrin. The metal porphyrin is one of tetraphenylporphyrin nickel, tetraphenylporphyrin cobalt and 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin nickel, and the non-metal porphyrin is one of tetraphenylporphyrin, 5,10,15,20-tetra-1H-pyrazol-4-yl-21H,23H-porphine and 5,10,15,20-tetraalkyl[4-(2H-tetrazol-5-yl)phenyl]-21H,23Hporphine; the added volume of N,N-dimethylacetamide is 2-6 mL; S3, bringing the reaction bottle of S1 and the solution obtained in S2 into the glove box, adding the solution obtained in S2 into the reaction bottle of S1, and then dropping the tetrahydropyrrole solution, the reaction bottle is placed on the stirrer in the glove box for 3-5 minutes, the air dissolved in the reaction bottle and the mixed solution is removed by the inert gas (high-purity argon gas) in the glove box, and finally a mixed solution to be reacted is obtained, wherein the volume of the tetrahydropyrrole is 50-100 μL; S4. Place a magnetic stirrer in the reaction bottle containing the reaction mixture in S3 and seal the bottle mouth (the sealing method is a combination of an aluminum cap and a rubber stopper) to prevent air from entering the reaction bottle during photocatalysis. Set the speed of the magnetic stirrer to 500-1200 r / min, turn on the xenon lamp light source, adjust the light power density, and record the illumination time. Let the strongest light point irradiate the wall of the reaction bottle to start the catalytic reaction. The filter type of the xenon lamp used is JB420, and the light power density is 200-400 mW / cm 2 , the photoperiod is 12-24 h; S5. After the reaction in step S4 is completed, an internal standard is added to the mixed solution, wherein the internal standard is 1,3,5-trimethoxybenzene, and the amount used is 0.2-0.6 mmol (specifically 0.2 mmol). After being fully dissolved, the mixed solution is transferred to a centrifuge tube, and subjected to high-speed centrifugation (speed of 8000-10000 r / min, centrifugation time of 1-3 min) to obtain a supernatant, i.e., a product solution. The supernatant is added dropwise to a deuterated reagent (deuterated dimethyl sulfoxide, volume of 300 μL), and finally detected by a nuclear magnetic resonance spectrometer (the volume of the supernatant taken is 200 μL); S6. Increase the reactants, catalysts and reaction time (the amount of aryl bromide is 10 mmol, the amount of tetrahydropyrrole is 200 μL, the amount of catalyst is 100 mg, and the reaction time is 48 h). After the reaction, extract and rotary evaporate the product (the extraction liquid used is ether, and the rotary evaporation temperature is set to 36 °C). Characterize the purity of the photocatalytically synthesized product by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and X-ray diffraction technology.

[0020] The specific implementation of the present invention is described in detail below in conjunction with specific embodiments.

[0021] Example 1: A nickel-based metal organic framework material Ni-BTPP, the preparation method of which comprises the following steps: S1. Add 108.6 mg of nickel perchlorate hexahydrate into 10 mL of N,N-dimethylacetamide and completely dissolve it by magnetic stirring for 10 min at a stirring rate of 800 r / min. S2. Add 25 mg of 1, 3, 5-tri((1H-pyrazol-4-yl)phenyl)benzene into 5 mL of methanol and completely dissolve it by magnetic stirring for 10 min at a stirring rate of 800 r / min. S3, adding the solution in step S2 dropwise to the solution in step S1 at a dropping speed of 0.1 mL / min. During the dropping process, the solution was continuously stirred on a magnetic stirrer at a stirring rate of 1000 r / min. The mixed solution was then transferred to a 40 mL thick-walled pressure-resistant bottle, and the thick-walled pressure-resistant bottle was reacted in an oil bath pot set at 100 °C for 48 h; S4. The preliminary product obtained in step S3 was washed three times with N,N-dimethylformamide and ethanol respectively, and dried at 80° C. for 24 h to obtain 100 mg of nickel-based metal-organic framework material NiBTPP.

[0022] The X-ray diffraction pattern of the nickel-based metal organic framework material NiBTPP is as follows: Figure 1 As shown, according to Figure 1 It can be seen that the nickel-based metal organic framework material prepared in Example 1 exhibits high purity, and no other impurity peaks are detected.

[0023] Example 2: A nickel-based metal organic framework material BUT-33-Ni, the preparation method of which comprises the following steps: S1. Add 200 mg of 2, 4, 6-tris(4-(1H-pyrazol-4-yl)phenyl)-1,3,5-triazine to 20 mL of N,N-dimethylacetamide and stir magnetically to dissolve it completely. The stirring time is 10 min and the stirring rate is 800 r / min. S2. Add 150 mg of nickel acetate tetrahydrate into 20 mL of N,N-dimethylformamide and completely dissolve it by magnetic stirring for 10 min at a stirring rate of 800 r / min. S3, adding the solution in step S2 dropwise to the solution in step S1 at a dropping speed of 0.1 mL / min. During the dropping process, the solution was continuously stirred on a magnetic stirrer at a stirring rate of 1000 r / min. The mixed solution was then transferred to a 40 mL thick-walled pressure-resistant bottle. After stirring for another five minutes, the thick-walled pressure-resistant bottle was placed in an oil bath pot set at 150 °C for reaction for 2 h. S4. The preliminary product obtained in step S3 was washed three times with N,N-dimethylacetamide and acetone respectively, and dried at 80° C. for 24 h to obtain 300 mg of a nickel-based metal organic framework material, BUT-33-Ni.

[0024] The X-ray diffraction pattern of the nickel-based metal organic framework material BUT-33-Ni is as follows: Figure 2 As shown, according to Figure 2 It can be seen that the nickel-based metal organic framework material prepared in Example 2 exhibits high purity, and no other impurity peaks are detected.

[0025] Example 3: Using nickel-based metal organic framework Ni-BTPP and tetraphenylporphyrin to photocatalyze p-bromotrifluorotoluene and tetrahydropyrrole to directly synthesize 1-[4-(trifluoromethyl)phenyl]pyrrolidine, the specific method comprises the following steps: S1. Add 10 mg of the nickel-based metal organic framework NiBTPP prepared in Example 1 into a transparent quartz bottle containing 1 mL of N,N-dimethylacetamide, and ultrasonicate at a frequency of 100 KHz for 15 min to obtain a uniformly dispersed mixed solution; S2, add 0.5 mg of tetraphenylporphyrin into a centrifuge tube containing 1 mL of N,N-dimethylacetamide, and ultrasonicate at a frequency of 100 KHz for 15 min to obtain a uniformly dispersed mixed solution; S3, bring the transparent quartz bottle of step S1 and the liquid in step S2 into the glove box, then drop the solution in step S2 into the transparent quartz bottle of step S1, the dropping speed is 1 mL / min, during the dropping process, the solution is continuously stirred on a magnetic stirrer, the stirring rate is 1000 r / min, 0.2 mmol of parabromotrifluorotoluene and 50 μL of tetrahydropyrrole are added, and the bottle mouth is sealed to prevent air from entering the reaction bottle during photocatalysis; S4. Set the speed of the magnetic stirrer, turn on the xenon lamp light source, adjust the light power density, and record the illumination time. Let the strongest light point irradiate the wall of the reaction bottle to start the catalytic reaction. The speed is 500 r / min, the filter type of the xenon lamp used is JB420, and the light power density is 400 mW / cm 2 , the photoperiod is 14 h; S5. After the reaction in step S4 is completed, 0.2 mmol of internal standard is added to the mixed solution. After it is fully dissolved, the mixed solution is transferred to a centrifuge tube, and the supernatant, i.e., the product solution, is obtained by high-speed centrifugation at 10,000 r / min for 1 min. The supernatant is added dropwise to the deuterated reagent, and finally detected by a nuclear magnetic resonance spectrometer.

[0026] The yield of the obtained product was analyzed by hydrogen nuclear magnetic resonance spectroscopy. Figure 3 As shown, according to Figure 3 It can be seen that the selectivity of the direct synthesis of 1-[4-(trifluoromethyl)phenyl]pyrrolidine from p-bromotrifluorotoluene and tetrahydropyrrole by the co-photocatalysis of the nickel-based metal-organic framework Ni-BTPP and tetraphenylporphyrin is 100%, and no signal peaks of other by-products are detected. The molar conversion rate of 1-[4-(trifluoromethyl)phenyl]pyrrolidine relative to p-bromotrifluorotoluene is 100%.

[0027] Example 4: A nickel-based metal organic framework BUT-33-Ni and 5,10,15,20-tetrakis(1H-pyrazol-4-yl)porphyrin are used to photocatalyze the direct synthesis of 4-(1-pyrrolidinyl)benzonitrile from bromoxynil and tetrahydropyrrole, wherein the specific method comprises the following steps: S1. Add 10 mg of the nickel-based metal organic framework BUT-33-Ni prepared in Example 2 and 0.2 mmol of p-bromobenzonitrile into a transparent quartz bottle containing 1 mL of N,N-dimethylacetamide, and perform ultrasound at a frequency of 100 KHz for 15 min to obtain a uniformly dispersed mixed solution; S2, adding 0.5 mg of 5,10,15,20-tetrakis(1H-pyrazol-4-yl)porphyrin into a centrifuge tube containing 1 mL of N,N-dimethylacetamide, and ultrasonicating at a frequency of 100 KHz for 15 min to obtain a uniformly dispersed mixed solution; S3, bring the transparent quartz bottle of step S1 and the liquid in step S2 into the glove box, then drop the solution in step S2 into the transparent quartz tube of step S1, the dropping speed is 1 mL / min, during the dropping process, the solution is continuously stirred on a magnetic stirrer, the stirring rate is 1000 r / min, 50 μL of tetrahydropyrrole is added, and the bottle mouth is sealed to prevent air from entering the reaction bottle during photocatalysis; S4. Set the speed of the magnetic stirrer, turn on the xenon lamp light source, adjust the light power density, and record the illumination time. Let the strongest light point irradiate the wall of the reaction bottle to start the catalytic reaction. The speed is 500 r / min, the filter type of the xenon lamp used is JB420, and the light power density is 400 mW / cm 2 , the illumination time is 12 h; S5. After the reaction in step S4 is completed, 0.2 mmol of internal standard is added to the mixed solution. After it is fully dissolved, the mixed solution is transferred to a centrifuge tube, and the supernatant, i.e., the product solution, is obtained by high-speed centrifugation at 10,000 r / min for 1 min. The supernatant is added dropwise to the deuterated reagent, and finally detected by a nuclear magnetic resonance spectrometer.

[0028] The yield of the obtained product was analyzed by hydrogen nuclear magnetic resonance spectrum, and the results were as follows: Figure 4 As shown, according to Figure 4 It can be seen that the selectivity of the direct synthesis of 4-(1-pyrrolidinyl)benzonitrile from bromoxynil and tetrahydropyrrole by the co-photocatalysis of the nickel-based metal organic framework BUT-33-Ni and 5,10,15,20-tetrakis(1H-pyrazol-4-yl)porphyrin is 100%, and no signal peaks of other by-products are detected. The molar conversion rate of 4-(1-pyrrolidinyl)benzonitrile relative to bromoxynil is 100%.

[0029] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a nickel-based metal organic framework, characterized in that: The following steps are involved: S1. Add the metal salt into the solvent and fully sonicate it to completely dissolve it to obtain a solution; S2, adding the organic ligand into the solvent, and fully sonicating it to completely dissolve it to obtain a solution; S3, slowly dropwise adding the solution obtained in step S2 to the liquid obtained in step S1, and heating in an oil bath after mixing, the heating temperature is 100-150° C., and the heating time is 24-48 h; S4. Wash the heated product obtained in step S3 with N,N-dimethylformamide and acetone for multiple times, and then dry to obtain a nickel-based metal organic framework.

2. The method for preparing a nickel-based metal organic framework according to claim 1, characterized in that: In step S1, the metal salt is one of nickel perchlorate hexahydrate, nickel acetate tetrahydrate, and nickel nitrate hexahydrate, and the solvent is one or more of N,N-dimethylformamide, methanol, and water, and the concentration of the metal salt in the obtained solution is 0.02-8 mol / L; In step S2, the organic ligand is one of tetrapyrazolylporphyrin, 1, 3, 5-tris((1H-pyrazol-4-yl)phenyl)benzene, 2,4, 6-tris(4-(1H-pyrazol-4-yl)phenyl)-1,3,5-triazine, 2, 5-dihydroxyterephthalic acid and anthracene-9, 10-dicarboxylic acid, the solvent is one or more of N,N-dimethylformamide, methanol, and water, and the concentration of the organic ligand in the obtained solution is 0.02-0.8 mol / L; The molar ratio of the organic ligand to the metal salt is 1:1-6.

3. The method for preparing a nickel-based metal organic framework according to claim 1, characterized in that: In step S1 and step S2, the ultrasonic frequency is 60-120 KHz, and the ultrasonic time is 10-30 min.

4. The method for preparing a nickel-based metal organic framework according to claim 1, characterized in that: In step S3, the dropping rate is 0.1-2 mL / min.

5. A nickel-based metal organic framework, characterized in that The invention is prepared by the preparation method according to any one of claims 1 to 4.

6. A method for preparing an aniline compound, characterized in that: The following steps are involved: S1. Adding the nickel-based metal organic framework described in claim 5 into a transparent reaction bottle containing aryl bromide; S2, dissolving the porphyrin molecules in N,N-dimethylacetamide, and completely dissolving them by ultrasound to obtain a solution; S3, bringing the reaction bottle of S1 and the solution obtained in S2 into a glove box, adding the solution obtained in S2 to the reaction bottle of S1, then dropping the tetrahydropyrrole solution, and placing the reaction bottle on a stirrer in the glove box to obtain a mixed solution to be reacted; S4, placing a magnetic stirrer in the reaction bottle containing the reaction mixture in S3 and sealing the bottle mouth, turning on the xenon lamp light source and adjusting the light power density so that the strongest point of light irradiates the wall of the reaction bottle to start the catalytic reaction; S5. After the reaction in step S4 is completed, an internal standard is added to the mixed solution, wherein the internal standard is 1,3,5-trimethoxybenzene. After the mixed solution is fully dissolved, the mixed solution is subjected to high-speed centrifugation to separate the supernatant, which is the aniline compound.

7. The method for preparing aniline compounds according to claim 6, characterized in that: In step S1, the aryl bromide is one of p-bromobenzonitrile, m-bromobenzonitrile, o-bromobenzonitrile, p-bromotrifluorotoluene, and methyl p-bromobenzoate, and the amount of the aryl bromide added is 0.2-0.6 mmol; the amount of the nickel-based metal organic framework added is 5-10 mg.

8. The method for preparing aniline compounds according to claim 6, characterized in that: In step S2, the added amount of the porphyrin molecule is 0.25-4 mg, which is a metal porphyrin or a non-metal porphyrin. The metal porphyrin is one of tetraphenylporphyrin nickel, tetraphenylporphyrin cobalt and 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin nickel. The non-metal porphyrin is one of tetraphenylporphyrin, 5,10,15,20-tetrakis-1H-pyrazol-4-yl-21H,23H-porphine and 5,10,15,20-tetraalkyl[4-(2H-tetrazol-5-yl)phenyl]-21H,23Hporphine; the added volume of N,N-dimethylacetamide is 2-6 mL; the frequency of the ultrasound is 60-120 KHz, and the ultrasound duration is 10-30 min.

9. The method for preparing aniline compounds according to claim 6, characterized in that: In step S4, the rotation speed of the magnetic stirrer is 500-1200 r / min, and the optical power density of the xenon lamp is 200-400 mW / cm 2 , the lighting time is 12-24 h.

10. An aniline compound, characterized in that: It is prepared by the preparation method according to any one of claims 6 to 9.

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