Catalyst for selectively deuterating bromine-containing aromatic hydrocarbon compound as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for selectively deuterating a bromine-containing aromatic hydrocarbon compound as well as a preparation method and application of the catalyst, and belongs to the technical field of metal-containing catalysts. A nitrogen-doped mesoporous carbon material loaded copper monatomic site is used as a heterogeneous catalyst to catalyze debromination and deuteration of a bromine-containing aromatic hydrocarbon compound to obtain a corresponding deuterated aromatic hydrocarbon compound. The catalyst prepared by the invention has ordered mesoporous channel copper single atoms which are uniformly distributed on a carrier, and the coordination environment is adjustable from Cu-N3 to Cu-N4. According to the method, the substrate is wide in application range, and deuteration can be carried out on a specific bromine-containing site. The deuterium source is deuterium water which is low in cost and easy to transport. The reaction can be carried out under mild conditions of relatively low temperature and low-pressure carbon monoxide, and the selectivity and the conversion rate are excellent. In addition, the catalyst can be recycled for multiple times without obvious activity attenuation, and is easy to separate and recover, so that the separation difficulty of the reaction product is reduced, and the synthesis cost is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of metal-containing catalysts, and in particular to a catalyst for selectively deuterating bromine-containing aromatic compounds, and a preparation method and application thereof. Background Art

[0002] Isotope labeling plays a vital role in studying reaction mechanisms, pharmaceuticals, agrochemicals, and bioanalytical characterization. Hydrogen-deuterium exchange reactions are considered to be the simplest method for producing deuterated compounds, but expensive and difficult-to-transport deuterium gas is usually used as a deuterium source, which increases the cost of synthesis and the difficulty of transportation. Dehalogenation, as an alternative transformation to hydrogen-deuterium exchange, can be easily controlled to carry out dehalogenation at specific sites, and the conversion rate and selectivity are significantly improved. Homogeneous catalysts have high chemical selectivity in dehalogenation deuteration reactions, but usually require the addition of additional ligands, strong reducing agents, and strong bases. They are difficult to separate from the reaction system after the reaction, and the metal components used are also difficult to recover. Compared with homogeneous catalysts, heterogeneous catalysts have the advantages of easy separation and recyclability, and have higher economic value.

[0003] Currently, it is still extremely challenging to prepare heterogeneous catalysts with high activity, good selectivity, good cyclic stability, and that can be used under relatively mild reaction conditions. Summary of the invention

[0004] In view of the above-mentioned defects of the prior art, in a first aspect of the present invention, a method for preparing a catalyst for selectively deuterated bromine-containing aromatic compounds with a simple synthesis process and convenient operation is provided, comprising the following steps:

[0005] (1) dispersing a divalent copper salt, a nitrogen-containing organic compound, and a mesoporous silica template in an alcohol-water mixed solvent to obtain a reaction suspension;

[0006] (2) The reaction suspension is subjected to solvent evaporation, and the obtained product is carbonized in an inert gas environment until the carbonization is complete to obtain a carbonized product; the mesoporous silica template in the carbonized product is removed, and then the product is washed, dried, and crushed to obtain a catalyst for selective deuterated bromine-containing aromatic compounds.

[0007] Preferably, in step (1), the divalent copper salt includes one of copper nitrate, copper sulfate, copper chloride and copper acetate.

[0008] Preferably, in step (1), the nitrogen-containing organic compound includes one of 1,10-phenanthroline, 2,2'-bipyridine, 3-aminophenol, dopamine hydrochloride, tryptophan, tyrosine, and o-phenylenediamine.

[0009] Preferably, in step (1), the mesoporous silica template includes one of MCF-OH, KIT-6-OH, and SBA-15-OH.

[0010] Preferably, in step (1), the usage ratio of the divalent copper salt, the nitrogen-containing organic compound and the mesoporous silica template is 0.05-1.0 mmol: 7.0-30.0 mmol: 1.0-2.0 g.

[0011] Preferably, in the step (1), the ratio of the alcohol-water mixed solvent to the mesoporous silica template is 10-200 mL: 1.0 g.

[0012] Preferably, in step (1), the alcohol-water mixed solvent is a mixture of methanol or ethanol and water, wherein the volume ratio of alcohol to water is 0.1 to 10:1.

[0013] Preferably, in step (2), the carbonization temperature is 500-1500°C.

[0014] In the second aspect of the present invention, a catalyst for selective deuterated bromine-containing aromatic compounds with strong selectivity and high conversion rate is provided. The catalyst is a nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst, which is prepared by the preparation method of the first aspect of the present invention; the catalyst has ordered mesoporous channels, and copper is uniformly distributed on the carbon carrier in the form of single-atom sites.

[0015] Preferably, the mass fraction of copper in the catalyst for selective deuteration of bromine-containing aromatic compounds is 0.1 to 20.0 wt.%.

[0016] Further preferably, in the catalyst for selective deuteration of bromine-containing aromatic compounds, the mass fraction of copper is 0.5 to 5.0 wt.%.

[0017] The reason for further preference is that if the loading is too high, it is not easy to form a single atom catalyst, but metal aggregation will occur during the calcination process to obtain a copper nanoparticle catalyst, the metal utilization rate will be reduced, and the catalytic selectivity will also change, so the preferred maximum is 5wt.%; when using carbon material as a carrier, there is a phenomenon that some active sites are covered by the carbon carrier, and in catalysts with too low loading, this phenomenon has a more obvious effect on the reduction of catalytic activity, so the preferred minimum is 0.5wt.%.

[0018] In a third aspect of the present invention, there is provided a use of the catalyst for selectively deuterating bromine-containing aromatic compounds according to the second aspect of the present invention in catalyzing the selective debromination of bromine-containing aromatic compounds, comprising the following steps:

[0019] S1, mixing a catalyst for selectively deuterating bromine-containing aromatic compounds, a bromine-containing aromatic compound, a base, deuterated water and an organic solvent to obtain a deuterated reaction solution;

[0020] S2. The deuterated reaction liquid is subjected to a deuterated reaction in a carbon monoxide atmosphere at a certain temperature, and the deuterated aromatic compound is recovered after the reaction is complete.

[0021] Preferably, in S1, the molar ratio of copper to brominated aromatic compound in the catalyst for selective deuteration of brominated aromatic compound is 0.01-10:100; the molar ratio of brominated aromatic compound to base is 1:0.5-20; the dosage ratio of brominated aromatic compound to deuterated water is 1 g:10-200 mL; the dosage ratio of brominated aromatic compound to organic solvent is 1 g:0.1-50 mL.

[0022] Preferably, in S1, the bromine-containing aromatic compound includes bromine-substituted aromatics and derivatives thereof; the structure of the derivative includes one of naphthalene, anthracene, phenanthrene, quinolinone, phthalide, carbazole, indole, and quinoline, and the derivative contains no or at least one substituent other than the bromine group; the substituent includes at least one of keto, methyl, cyano, hydroxyl, aldehyde, amino, methoxy, ethoxy, halogen, amide, pyridine and morpholine groups.

[0023] Preferably, in S1, the base includes at least one of triethylamine, potassium hydroxide, sodium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, bicyclic amidine, tetramethylethylenediamine, and N,N-diisopropylethylamine.

[0024] Preferably, in S1, the solvent includes at least one of tetrahydrofuran, toluene, methanol, ethanol, 1,4-dioxane, dichloromethane, acetonitrile, N,N-dimethylformamide, deuterated chloroform, and hexafluoroisopropanol.

[0025] Preferably, in S1, the temperature of the deuteration reaction is 30-200° C., the reaction pressure is 0.01-10 MPa, and the reaction time is 0.01-400 h.

[0026] Further preferably, the temperature of the deuteration reaction is 30-200° C., the reaction pressure is 1-5 MPa, and the reaction time is 20-150 h.

[0027] Since there are different substituent groups on the substrate molecules, and both temperature and pressure play an important role in the reaction activity and selectivity, further optimization was carried out after the technical purpose of deuteration was met. When the reaction pressure is reduced, the corresponding reaction time needs to be greatly increased, which is not conducive to the synthesis process, so the preferred minimum pressure is 1MPa; in addition, when the reaction pressure increases, the reaction rate will increase accordingly, so the substrate molecules or intermediates may undergo side reactions in a relatively high energy state, resulting in a significant reduction in the selectivity of the reaction, so the preferred maximum pressure is 5MPa.

[0028] Preferably, in S1, after the deuteration reaction is completed, the reaction liquid is filtered to separate the crude product of the deuterated aromatic compound and the catalyst; the crude product is extracted and purified to obtain the deuterated aromatic compound; the catalyst can be reused after washing, centrifugation and drying.

[0029] Single-atom site catalysts have 100% atomic utilization, relatively determined coordination environment and good cyclic stability, and are excellent heterogeneous catalysts. Compared with homogeneous catalysts with a certain structure, the active sites and structures of heterogeneous catalysts are usually not very clear, which is not conducive to designing synthetic catalysts and understanding the reaction process. Based on these advantages and disadvantages and the technical solution provided by the present invention, the design idea of ​​the present invention is that the present invention uses a simple impregnation and roasting method to synthesize nitrogen-doped mesoporous carbon-supported copper single-atom site materials as heterogeneous catalysts, which have ordered mesoporous channels, large specific surface area and pore volume, and are conducive to the material transport during the reaction process, especially organic molecules with large steric hindrance. When used, copper single atoms are evenly distributed on the carrier, and the coordination environment is adjustable from Cu-N3 to Cu-N4, thereby regulating the temperature of the deuteration reaction, and can achieve selective deuteration of a variety of bromine-containing aromatic compounds under mild conditions to obtain corresponding deuterated aromatic compounds. The coordination environment of the copper single atom site can be adjusted by adjusting the calcination temperature. The ordered mesoporous channels can provide excellent mass transfer channels for organic molecular substrates. The high conversion rate, high selectivity and good cyclic stability of the deuteration reaction can be achieved through the synergistic effect of clear active sites, coordination environment and good mass transfer structure.

[0030] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0031] The invention provides a method for preparing a catalyst for selectively deuterating bromine-containing aromatic compounds. The synthesis process is simple, the operation is convenient, and industrial mass production can be achieved.

[0032] The invention provides a catalyst for selectively deuterating bromine-containing aromatic compounds, which has strong catalytic selectivity, high conversion rate, is easy to separate and recover, and can be recycled for multiple times without obvious activity decay.

[0033] The present invention also provides an application of a catalyst for selectively deuterating bromine-containing aromatic compounds, which can achieve deuteration at specific sites under mild conditions, has a good catalytic effect, and is expected to become a feasible approach for industrial catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is a wide angle X-ray diffraction (WAXRD) pattern of the catalyst for selectively deuterating bromine-containing aromatic compounds of Example 1;

[0035] Figure 2is a small angle X-ray diffraction (SAXRD) pattern of the catalyst for selectively deuterating bromine-containing aromatic compounds of Example 1;

[0036] Figure 3 is a transmission electron microscope (TEM) image of the catalyst for selectively deuterating bromine-containing aromatic compounds of Example 1;

[0037] Figure 4 A high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of the catalyst for selective deuteration of bromine-containing aromatic compounds of Example 1;

[0038] Figure 5 is a synchrotron radiation X-ray absorption near edge structure (XANES) spectrum of the catalyst for selectively deuterating bromine-containing aromatic compounds of Example 1;

[0039] Figure 6 This is a cycle experiment diagram of the catalyst for selective deuteration of bromine-containing aromatic compounds in Example 1. DETAILED DESCRIPTION

[0040] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0041] In the following embodiments:

[0042] Preparation of SBA-15-OH template: Add 20.0g of surfactant P123 to 650mL of distilled water, stir to dissolve, then add 100mL of concentrated hydrochloric acid with a mass fraction of 37wt.%, and stir the resulting solution at 38°C for 2h. Add 41.6g of tetraethyl orthosilicate to the solution and stir for 24h. Then transfer it to an autoclave, place it in an oven at 110°C for hydrothermal treatment for 24h, filter it, and dry it. Weigh 8.0g of the obtained dry sample and disperse it in 120mL of concentrated nitric acid with a mass fraction of 65wt.% and 40mL of aqueous hydrogen peroxide with a mass fraction of 35wt.%, and heat it under reflux at 80°C for 3h; after cooling to room temperature, filter it, wash it with water, and dry it to obtain a mesoporous silica SBA-15-OH template; the specific surface area of ​​the mesoporous template is 731m 2 / g, pore volume 1.30cm 3 / g.

[0043] Example 1

[0044] Preparation method of catalyst for selective deuteration of bromine-containing aromatic compounds:

[0045] (1) Weigh 2 g of o-phenylenediamine and dissolve it in an alcohol-water mixed solvent formed by 20 mL of ethanol and 20 mL of ultrapure water, heat and stir at 70° C. until the o-phenylenediamine is completely dissolved, then add 40 mg of anhydrous copper acetate and 1 g of SBA-15-OH template to the resulting solution, stir for 1 h to evenly disperse the raw materials, and obtain a reaction suspension;

[0046] (2) evaporating the alcohol-water mixed solvent of the reaction suspension at 70° C., recovering the product and transferring it to a 70° C. oven for drying for 24 h; placing the dried product in a tubular furnace, carbonizing it in an argon atmosphere at a high temperature of 800° C., with a carbonization heating rate of 5° C. / min. After the carbonization is complete, cooling it to room temperature and obtaining a carbonized product; removing the SBA-15-OH template with a 2 mol / L sodium hydroxide aqueous solution, dissolving the template in an alkali, filtering and collecting the filter cake, washing, freeze-drying, and grinding the filter cake to obtain a nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst material, i.e., a catalyst for selective deuterated bromine-containing aromatic compounds.

[0047] According to the measurement, in the catalyst of this embodiment, the copper species is evenly distributed on the carrier in the form of single atoms, with a mass fraction of 2.7wt.%, and a specific surface area of ​​520m 2 / g, pore volume 0.50cm 3 / g; Based on these characteristics, the catalyst is beneficial to the material transport during the reaction process, especially the organic molecules with large steric hindrance.

[0048] The catalyst of this example was characterized by wide angle X-ray diffraction (WAXRD), and the corresponding characterization spectrum is shown in Figure 1 As shown in the figure, the prepared nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst has no obvious copper species diffraction peak, indicating that the copper species is highly dispersed on the carrier.

[0049] The catalyst of this example was characterized by small angle X-ray diffraction (SAXRD) patterns. The corresponding characterization patterns are shown in Figure 2 As shown in the figure, the prepared catalyst has three obvious diffraction peaks, indicating that the mesoporous structure of the SBA-15-OH template is completely replicated.

[0050] The microscopic morphology of the catalyst of this example was observed by transmission electron microscopy (TEM), and the corresponding image is shown in FIG. Figure 3 As shown in the figure, the prepared catalyst completely replicates the mesoporous channels of the SBA-15-OH template and has an ordered rod-like structure.

[0051] The microscopic morphology of the catalyst of this example was observed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), and the corresponding image is shown in FIG. Figure 4As shown in the figure, it can be seen from the circled part that in the prepared catalyst, the copper species (i.e. the white dot in the center of the circle) is evenly distributed on the carrier in the form of single atoms.

[0052] The catalyst of this example was characterized by synchrotron X-ray absorption near edge structure (XANES), and the corresponding characterization spectrum is shown in Figure 5 As shown in the figure, it can be seen that the copper in the prepared catalyst exists in the form of a single atom, and the valence state is between +1 and +2.

[0053] Single copper atoms are evenly distributed on the carrier, and the coordination environment is adjustable from Cu-N3 to Cu-N4, thereby achieving the control of the temperature of the deuteration reaction and making the deuteration conditions milder.

[0054] Example 2

[0055] Preparation method of catalyst for selective deuteration of bromine-containing aromatic compounds:

[0056] (1) Weigh 2 g of dopamine hydrochloride and dissolve it in a mixed solvent of 4 mL of ethanol and 40 mL of ultrapure water, heat and stir at 60° C. until the dopamine hydrochloride is completely dissolved, then add 40 mg of anhydrous copper acetate and 1 g of SBA-15-OH template to the resulting solution, stir for 2 h to evenly disperse the raw materials, and obtain a reaction suspension;

[0057] (2) evaporating the alcohol-water mixed solvent of the reaction suspension at 60°C, recovering the product and transferring it into a 60°C oven for drying for 24 hours; placing the dried product in a tubular furnace, carbonizing it in an argon atmosphere at a high temperature of 1100°C, and the carbonization heating rate is 10°C / min. After the carbonization is complete, cooling it to room temperature and obtaining a carbonized product; removing the SBA-15-OH template with a 2 mol / L sodium hydroxide aqueous solution, dissolving the template in an alkali, filtering and collecting the filter cake, washing, freeze-drying, and grinding the filter cake to obtain a nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst material.

[0058] According to the measurement, in the catalyst of this embodiment, the copper species is evenly distributed on the carrier in the form of single atoms, with a mass fraction of 1.0wt.%, and a specific surface area of ​​560m 2 / g, pore volume 0.51cm 3 / g.

[0059] Example 3

[0060] Preparation method of catalyst for selective deuteration of bromine-containing aromatic compounds:

[0061] (1) Weigh 2 g of tryptophan and dissolve it in a mixed solvent of 5 mL of ethanol and 50 mL of ultrapure water, heat and stir at 80° C. until the tryptophan is completely dissolved, then add 40 mg of anhydrous copper acetate and 1 g of SBA-15-OH template to the resulting solution, and stir for 2 h to evenly disperse the raw materials to obtain a reaction suspension;

[0062] (2) evaporating the alcohol-water mixed solvent of the reaction suspension at 80°C, recovering the product and transferring it to an 80°C oven for drying for 24 hours; placing the dried product in a tubular furnace, carbonizing it in an argon atmosphere at a high temperature of 700°C, and the carbonization heating rate is 2°C / min. After the carbonization is complete, cooling it to room temperature and obtaining a carbonized product; removing the SBA-15-OH template with a 2 mol / L sodium hydroxide aqueous solution, dissolving the template in an alkali, and filtering and collecting the filter cake. The filter cake is washed, freeze-dried, and ground to obtain a nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst material.

[0063] According to the measurement, in the catalyst of this embodiment, the copper species is evenly distributed on the carrier in the form of single atoms, with a mass fraction of 2.4wt.%, and a specific surface area of ​​540m 2 / g, pore volume 0.56cm 3 / g.

[0064] Example 4

[0065] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0066]

[0067] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a1, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0068] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 50 hours; after the reaction is completed, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b1, and the yield of this embodiment is 99%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, Chloroform-d) δ7.79-7.74(m,3H),7.45(d,J=8.2Hz,1H),7.18-7.14(m,2H),3.93(s,3H). 13C NMR (151MHz, Chloroform-d) δ 157.72, 134.71, 129.52, 127.68, 126.87, 126.40, 118.85, 105.88, 55.42.

[0069] The cyclic performance of the catalyst of this embodiment was characterized by a catalytic cycle experiment, and the catalytic performance of the catalyst used in this embodiment was tested under different catalytic and recovery cycles. In a heterogeneous catalytic cycle experiment, a similar yield during the cycle can be considered to have good cyclic stability. Therefore, the yields of the reaction under the same conditions for 20 hours were counted and compared. The corresponding characterization spectrum is shown in FIG. Figure 6 As shown in the figure (the number of circles in the figure represents the number of times the catalyst is used, that is, circle number 1 represents the first use, and circle number 2 represents the second use after recycling once). It can be seen from the figure that the prepared catalyst can be circulated for at least 5 cycles without obvious activity decay after simple recycling treatment.

[0070] Example 5

[0071] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0072]

[0073] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a2, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0074] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 150 hours; after the reaction, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b2, and the yield of this embodiment is 99%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR(600MHz,Chloroform-d)δ7.78(dd,J=8.2,1.3Hz,1H),7.75(d,J=8.7Hz,2H),7.45(ddd,J =8.1,6.8,1.3Hz,1H),7.34(ddd,J=8.0,6.7,1.2Hz,1H),7.16(d,J=8.9Hz,1H),3.93(s,3H). 13C NMR (151MHz, Chloroform-d) δ157.68,134.64,129.51,129.08,127.79,126.82,126.50,123.72,118.86,105.88,105.74,105.58,105.42,55.43.

[0075] Example 6

[0076] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0077]

[0078] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a3, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0079] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 150 hours; after the reaction is completed, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b3, and the yield of this embodiment is 89%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR(600MHz,Chloroform-d)δ7.80-7.78(m,1H),7.78-7.74(m,2H),7.46(ddd,J= 8.3, 6.8, 1.3Hz, 1H), 7.36 (ddd, J=8.1, 6.8, 1.2Hz, 1H), 7.16 (s, 1H), 3.94 (s, 3H). 13 C NMR (151MHz, Chloroform-d) δ157.68,134.70,129.41,129.07,127.79,126.87,126.49,123.71,105.89,55.41.

[0080] Example 7

[0081] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0082]

[0083] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a4, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0084] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 150 hours; after the reaction is completed, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b4, and the yield of this embodiment is 84%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, Chloroform-d) δ7.83-7.72(m,3H),7.46(d,J=8.2Hz,1H),7.21-7.13(m,2H),4.17(q,J=7.0Hz,2H),1.51(t,J=7.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ157.04,134.75,129.47,129.02,127.65,126.83,126.32,119.12,106.66,63.56,14.95.

[0085] Example 8

[0086] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0087]

[0088] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a5, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0089] S2, the deuterated reaction liquid is placed in a high-pressure reactor, and 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 50 hours; after the reaction, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b5, and the yield of this embodiment is 99%; nuclear magnetic resonance hydrogen spectrum, carbon spectrum and fluorine spectrum: 1H NMR (600MHz, Chloroform-d) δ7.52 (s, 1H), 7.43 (dd, J = 9.7, 4.8Hz, 1H), 6.99 (t, J = 7.6Hz, 2H), 2.15 (s, 3H). 13 C NMR (151MHz, Chloroform-d) δ168.61,160.31,158.70,133.93,121.96,121.91,115.78,115.70,115.64,115.55,24.48. 19 F NMR (565MHz, Chloroform-d) δ-118.00 (td, J=8.1, 4.3Hz).

[0090] Example 9

[0091] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0092]

[0093] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a6, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0094] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 100 hours; after the reaction, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b6, and the yield of this embodiment is 80%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, DMSO-d6) δ7.31-7.08(m,2H),6.55-6.43(m,2H),3.34(s,4H),1.98-1.90(m,4H). 13 C NMR (151MHz, DMSO-d6) δ147.72,128.81,113.50,111.57,47.32,47.22,24.98,24.94.

[0095] Example 10

[0096] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0097]

[0098] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a7, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0099] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 120 ° C for 50 hours; after the reaction is completed, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b7, and the yield of this embodiment is 80%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, DMSO-d6) δ11.25(s,1H),8.10(t,J=4.1Hz,2H),7.50(d,J=8.1Hz,2H),7.38(dt,J=7.6,3.5Hz,2H),7.16(t,J=7.4Hz,1H). 13 C NMR (151MHz, DMSO-d6) δ140.18,125.94,125.84,122.86,122.84,120.59,120.48,118.92,111.38.

[0100] Embodiment 11

[0101] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0102]

[0103] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a8, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0104] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 100 hours; after the reaction, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b8, and the yield of this embodiment is 90%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1H NMR (600MHz, DMSO-d6) δ8.14(t,J=3.9Hz,2H),7.58(d,J=8.2Hz,2H),7.45(dt,J=7 .8,3.8Hz,2H),7.19(t,J=7.4Hz,1H),4.42(q,J=7.2Hz,2H),1.30(t,J=7.2Hz,3H). 13 C NMR (151MHz, DMSO-d6) δ139.50,125.67,125.58,122.15,122.14,120.32,120.21,118.65,109.03,36.88,13.66.

[0105] Example 12

[0106] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0107]

[0108] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a9, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them to a reaction tube, mix well and obtain a deuterated reaction solution;

[0109] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 120 ° C for 50 hours; after the reaction, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b9, and the yield of this embodiment is 92%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, Chloroform-d) δ8.44 (s, 1H), 8.04-7.99 (m, 4H), 7.47 (dt, J = 6.6, 3.2Hz, 4H). 13 C NMR (151MHz, Chloroform-d) δ131.81,131.73,128.30,128.25,126.34,125.48.

[0110] Example 13

[0111] Catalyst for selective deuteration of bromine-containing aromatic compounds Method for selective debromination of bromine-containing aromatic compounds:

[0112]

[0113] S1, weigh 20 mg of the catalyst prepared in Example 1, 0.25 mmol of substrate a10, 0.5 mmol of triethylamine, 1.5 mL of deuterated water and 0.5 mL of tetrahydrofuran, add them into a reaction tube, mix well and obtain a deuterated reaction solution;

[0114] S2, the deuterated reaction liquid is placed in a high-pressure reactor, 10 bar carbon monoxide is charged into it, and the air is completely exhausted for six times, and finally 2 MPa carbon monoxide is charged, and the reaction is carried out at 80 ° C for 150 hours; after the reaction is completed, the crude product is filtered to separate the crude product of deuterated aromatic compound and the catalyst, and the crude product is extracted with ethyl acetate and separated by column chromatography to obtain the deuterated product b10, and the yield of this embodiment is 95%; nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (600MHz, Chloroform-d) δ8.71 (d, J = 8.2Hz, 2H), 7.91 (d, J = 7.8Hz, 2H), 7.75 (s, 1H), 7.71-7.64 (m, 2H), 7.61 (t, J = 7.4Hz, 2H). 13 C NMR (151MHz, Chloroform-d) δ132.18,132.11,130.43,128.71,128.65,126.93,126.70,122.79.

[0115] It can be seen from the application of the catalyst for selective deuteration of bromine-containing aromatic compounds to catalyze the selective debromination and deuteration of bromine-containing aromatic compounds that the present invention can achieve deuteration at specific sites under mild conditions, and has a good catalytic effect on various derivatives of benzene, naphthalene, anthracene, phenanthrene, quinolinone, phthalide, carbazole, indole, quinoline, etc., achieving high conversion rate, high selectivity and good cyclic stability, and is expected to become a feasible way for industrial catalysis.

[0116] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for preparing a catalyst for selectively deuterating bromine-containing aromatic compounds, characterized in that: The steps include: (1) dispersing a divalent copper salt, a nitrogen-containing organic compound, and a mesoporous silica template in an alcohol-water mixed solvent to obtain a reaction suspension; (2) the reaction suspension is subjected to solvent evaporation, and the obtained product is carbonized in an inert gas environment until the carbonization is complete to obtain a carbonized product; The mesoporous silica template in the carbonized product is removed, and then washed, dried and crushed to obtain a catalyst for selective deuterated bromine-containing aromatic compounds.

2. The method according to claim 1, characterized in that: In the step (1), the divalent copper salt includes one of copper nitrate, copper sulfate, copper chloride, and copper acetate; the nitrogen-containing organic compound includes one of 1,10-phenanthroline, 2,2'-bipyridine, 3-aminophenol, dopamine hydrochloride, tryptophan, tyrosine, and o-phenylenediamine; the mesoporous silica template includes one of MCF-OH, KIT-6-OH, and SBA-15-OH; and the alcohol-water mixed solvent is a mixture of methanol or ethanol and water.

3. The method according to claim 1, characterized in that: In the step (1), the usage ratio of the divalent copper salt, the nitrogen-containing organic compound and the mesoporous silica template is 0.05-1.0 mmol:7.0-30.0 mmol:1.0-2.0 g; the usage ratio of the alcohol-water mixed solvent and the mesoporous silica template is 10-200 mL:1.0 g, and the volume ratio of alcohol to water in the alcohol-water mixed solvent is 0.1-10:

1.

4. The method according to claim 1, characterized in that: In the step (2), the carbonization temperature is 500 to 1500°C.

5. A catalyst for selectively deuterating bromine-containing aromatic compounds, characterized in that: The catalyst is a nitrogen-doped mesoporous carbon-supported copper single-atom site catalyst, which is prepared by the method described in any one of claims 1 to 4, has ordered mesoporous channels, and copper is uniformly distributed on the carbon carrier in the form of single-atom sites.

6. The catalyst for selectively deuterating bromine-containing aromatic compounds according to claim 5, characterized in that: In the catalyst for selectively deuterating bromine-containing aromatic compounds, the mass fraction of copper is 0.1 to 20.0 wt.%.

7. Use of the catalyst for selectively deuterating bromine-containing aromatic compounds as claimed in claim 5 or 6 in catalyzing the selective debromination of bromine-containing aromatic compounds, characterized in that: The steps include: S1, mixing a catalyst for selectively deuterating bromine-containing aromatic compounds, a bromine-containing aromatic compound, a base, deuterated water and an organic solvent to obtain a deuterated reaction solution; S2. The deuterated reaction liquid is subjected to a deuterated reaction in a carbon monoxide atmosphere at a certain temperature, and the deuterated aromatic compound is recovered after the reaction is complete.

8. The use according to claim 7, characterized in that: In S1, the molar ratio of copper to bromine-containing aromatic compound in the catalyst for selective deuteration of bromine-containing aromatic compound is 0.01-10:100; the molar ratio of bromine-containing aromatic compound to base is 1:0.5-20; the dosage ratio of bromine-containing aromatic compound to deuterated water is 1 g:10-200 mL; the dosage ratio of bromine-containing aromatic compound to organic solvent is 1 g:0.1-50 mL.

9. The use according to claim 7, characterized in that: In S1, the bromine-containing aromatic compound includes bromine-substituted aromatics and derivatives thereof, the structure of the derivative includes one of naphthalene, anthracene, phenanthrene, quinolinone, phthalide, carbazole, indole, and quinoline, and the derivative does not contain or contains at least one substituent except the bromine group, and the substituent includes at least one of keto, methyl, cyano, hydroxyl, aldehyde, amino, methoxy, ethoxy, halogen, amide, pyridine and morpholine groups; the base includes at least one of triethylamine, potassium hydroxide, sodium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, bicyclic amidine, tetramethylethylenediamine, and N,N-diisopropylethylamine; the solvent includes at least one of tetrahydrofuran, toluene, methanol, ethanol, 1,4-dioxane, dichloromethane, acetonitrile, N,N-dimethylformamide, deuterated chloroform, and hexafluoroisopropanol.

10. The use according to claim 7, characterized in that: In S1, the temperature of the deuteration reaction is 30-200° C., the reaction pressure is 0.01-10 MPa, and the reaction time is 0.01-400 h.

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