A covalent organic framework material containing a quinazoline group, its preparation method and application

Abstract

This invention discloses a covalent organic framework material containing a quinazoline group, its preparation method, and its applications. This covalent organic framework material is prepared by polymerization of 1,3,6,8-tetra(4-formylphenyl)pyrene and 3,3”-dibenzoyl-4,4”-diaminoterphenyl as monomers under oxygen conditions. The quinazoline-containing covalent organic framework material prepared by this invention exhibits high crystallinity and stability, and under visible light conditions, it can selectively synthesize sulfoxide compounds from styrene and thiophenol with a yield of up to 98%, showing high application potential in the field of photocatalytic organic synthesis.

Description

Technical Field

[0001] This invention belongs to the field of porous organic materials technology, specifically relating to a covalent organic framework material containing quinazoline groups, its preparation method, and its application in the selective synthesis of sulfoxides from olefins and thiols under photocatalysis. Background Technology

[0002] Sulfoxides, as highly valuable organic compounds, are typically found in natural products and pharmacologically active organic molecules, attracting considerable attention from chemists. Traditionally, the synthesis of sulfoxides largely relies on the use of oxidants. The photocatalytic oxidation of anisole and its derivatives to sulfoxides under light irradiation offers advantages in terms of high atom economy and environmental friendliness. Although various photocatalysts have been developed and applied to this reaction in recent years, their application in the selective synthesis of sulfoxides from styrene and thiophenols is rarely reported, and the reported photocatalysts also suffer from problems such as difficult catalyst recovery and poor cycle stability due to structural instability. Therefore, developing efficient and reusable photocatalysts remains a crucial and far-reaching task.

[0003] Covalent organic frameworks (COFs) are porous organic polymers primarily composed of light elements such as C, H, O, N, and B linked by covalent bonds. They possess advantages such as low density, high structural stability, tunable structural units, and insolubility in most organic solvents, giving them a certain edge in heterogeneous catalysis. However, currently, most COF monomers are linked by imine bonds to construct the COF. But imines can cause structural collapse under harsh conditions such as strong acids and bases, leading to structural destruction. Therefore, constructing COFs with more stable linkage structures remains an important direction for development. Summary of the Invention

[0004] The purpose of this invention is to provide a covalent organic framework material containing a quinazoline group, its preparation method, and its application in the selective synthesis of sulfoxide from styrene and thiophenol under photocatalysis.

[0005] To achieve the above technical objectives, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a covalent organic framework material containing a quinazoline group.

[0007] The covalent organic framework material containing quinazoline groups provided by this invention has structural units as shown in formula (I):

[0008]

[0009] In a second aspect, the present invention provides a method for preparing the above-mentioned covalent organic framework material containing quinazoline groups.

[0010] The method for preparing the covalent organic framework material containing a quinazoline group as shown in formula (I) provided by the present invention includes the following steps:

[0011] (1) Dissolve 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPy) (CAS: 1415238-25-3) and 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) in an organic solvent, add ammonium salt, mix well, and place the mixed solution in air to carry out a solvothermal reaction to obtain a covalent organic framework material intermediate containing quinazoline group;

[0012] (2) Dissolve the intermediate of covalent organic framework material containing quinazoline group obtained in step (1) in an organic solvent, add ammonium acetate, place the mixed solution in oxygen, and carry out a solvothermal reaction to obtain the covalent organic framework material containing quinazoline group.

[0013] In step (1) of the above method, the molar ratio of 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPy) to 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) is 1.0:2.0 to 2.5, preferably 1.0:2.0.

[0014] In step (1) of the above method, the organic solvent is selected from any of the following mixed solvents: o-dichlorobenzene and 1,4-dioxane, o-dichlorobenzene and n-butanol, o-dichlorobenzene and n-pentanol, n-butanol and 1,4-dioxane, preferably a mixed solvent of o-dichlorobenzene and n-pentanol, with a volume ratio of 0.5 to 1.5:0.5 to 1.5, preferably 1:1.

[0015] In step (1) of the above method, the ammonium salt is selected from any one of the following: ammonium acetate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, preferably ammonium acetate; the ammonium salt is added in the form of an ammonium salt aqueous solution, and the concentration of the ammonium salt aqueous solution can be 2.0 to 9.0 mol / L, preferably 3.0 mol / L.

[0016] In step (1) of the above method, the molar ratio of 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) to the ammonium salt is 0.1 to 0.5:1, preferably 0.1:1.

[0017] In step (1) of the above method, the concentration of 1,3,6,8-tetrakis(4-formylphenyl)pyrene in the organic solvent is 0.01-0.04 mol / L, preferably 0.03 mol / L.

[0018] In step (1) of the above method, the reaction temperature of the solvothermal reaction is 90-150℃, preferably 120℃, and the reaction time is 1-3 days, preferably 2 days.

[0019] In step (2) of the above method, the concentration of the covalent organic framework material intermediate containing the quinazoline group in the organic solvent is 10 mg to 60 mg / mL, preferably 30 mg.

[0020] In step (2) of the above method, the ammonium salt is selected from any one of the following: ammonium acetate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, preferably ammonium acetate.

[0021] In step (2) of the above method, the mass ratio of the covalent organic framework material intermediate containing the quinazoline group to the ammonium salt is 0.06 to 0.1:1, preferably 0.03:1.

[0022] In step (2) of the above method, the organic solvent is selected from any one of the following: 1,4-dioxane, n-butanol, n-pentanol, o-dichlorobenzene, mesitylene, preferably 1,4-dioxane.

[0023] In step (2) of the above method, the temperature of the solvothermal reaction is 90-150℃, preferably 120℃, and the reaction time is 2-5 days, preferably 3 days.

[0024] The 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) used in the above method is also within the scope of protection of this invention.

[0025] The structural formula of 3,3”-dibenzoyl-4,4”-diaminoterphenyl is shown in formula (Ⅲ):

[0026]

[0027] The 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) can be prepared by the following method:

[0028] (a) Under an inert atmosphere, 2-benzoyl-4-bromoaniline, pinacol diboronic acid ester and potassium acetate were added to 1,4-dioxane, followed by the addition of catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride. The mixture was heated under reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate, and the ethyl acetate was rotary evaporated to obtain the compound 3-benzoyl-4-aminophenylboronic acid pinacol diboronic acid ester after purification.

[0029] (b) Under an inert atmosphere, 1,4-dibromobenzene, 3-benzoyl-4-aminophenylboronic acid pinacol ester and potassium carbonate were added to a 1,4-dioxane solution, followed by the addition of tetra(triphenylphosphine)palladium catalyst. The mixture was heated under reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and the dichloromethane was rotary evaporated. The purified solution yielded compound 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B).

[0030] In step (a) of the above method, the molar ratio of 2-benzoyl-4-bromoaniline to pinacol diboronic acid ester is 1:1 to 3, preferably 1:1.2.

[0031] In step (a) of the above method, the molar ratio of 2-benzoyl-4-bromoaniline to 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride is 1:0.01 to 0.05, preferably 1:0.02.

[0032] In step (a) of the above method, the molar ratio of pinacol diboronate to potassium acetate is 1:2 to 3, preferably 1:2.4.

[0033] In step (a) of the above method, the temperature of the reflux reaction is 70-120°C, preferably 95°C, and the reaction time is 14-29 h, preferably 19 h.

[0034] In step (b) of the above method, the molar ratio of 3-benzoyl-4-aminophenylboronic acid pinacol ester, 1,4-dibromobenzene, potassium carbonate, and catalyst tetrakis(triphenylphosphine)palladium is 2.0-3.0:1.0-1.2:4.0-7:0.01-0.1, preferably 2.1:1.0:4.0:0.04.

[0035] In step (b) of the above method, the 1,4-dioxane solution is an aqueous solution of 1,4-dioxane, wherein the volume ratio of 1,4-dioxane to water is 3:1 to 3, preferably 3:1 or 2:1.

[0036] In step (b) of the above method, the temperature of the heating reflux reaction is 100-120°C, preferably 115°C, and the reaction time is 15-30 h, preferably 21 h.

[0037] A third aspect of the present invention provides the application of the above-described covalent organic framework material containing a quinazoline group.

[0038] The application provided by this invention is the use of covalent organic framework materials containing quinazoline groups in the preparation of photocatalysts.

[0039] Furthermore, the photocatalyst is used to catalyze the selective synthesis of sulfoxide from styrene and thiophenol under illumination.

[0040] This invention introduces two complementary donor-acceptor (DA) structures, pyrene and quinazoline, into covalent organic framework materials via imine post-modification, thereby preparing covalent organic framework materials containing quinazoline groups. These materials exhibit high crystallinity and stability, while the intralayer charge transfer effect between the bulk and acceptor units promotes charge separation and electron transfer, thus improving photocatalytic efficiency. This material allows for the selective synthesis of sulfoxides from styrene and thiophenol at room temperature under visible light irradiation.

[0041] Compared with the prior art, the present invention has the following significant advantages:

[0042] (1) The covalent organic framework material containing quinazoline group prepared in this invention has good visible light response and excellent catalytic performance in the selective synthesis of sulfoxide from styrene and thiophenol.

[0043] (2) The covalent organic framework material containing quinazoline group prepared by the present invention has high crystallinity and good chemical stability, and can be recycled and reused multiple times. Attached Figure Description

[0044] Figure 1 The 3,3”-dibenzoyl-4,4”-diaminoterphenyl obtained in Example 1 1 H-NMR spectrum.

[0045] Figure 2 The Fourier transform infrared spectra of the 3,3”-dibenzoyl-4,4”-diaminoterphenyl and the covalent organic framework material containing quinazoline groups obtained in Example 1 are shown.

[0046] Figure 3 The image shows the X-ray powder diffraction pattern of the covalent organic framework material containing quinazoline groups obtained in Example 1.

[0047] Figure 4 This is a scanning electron microscope image of the covalent organic framework material containing quinazoline groups obtained in Example 1.

[0048] Figure 5 This is the UV-Vis diffuse reflectance image of the covalent organic framework material containing quinazoline groups obtained in Example 1.

[0049] Figure 6 This is a comparative performance graph of photocatalytic oxidation of 5-hydroxymethylfurfural using different covalent organic framework materials with different structures in Example 3.

[0050] Figure 7 This is a reaction activity diagram of the porphyrin-containing covalent organic framework material in Example 4 after multiple recycling. Detailed Implementation

[0051] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0052] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0053] Example 1

[0054] Synthesis of 3-benzoyl-4-aminophenylboronic acid pinacol ester: Under an inert atmosphere, 2-benzoyl-4-bromoaniline (7.0 g, 25.2 mmol), pinacol ester of pinacol diboronic acid (7.84 g, 30.45 mmol), and potassium acetate (7.36 g, 75 mmol) were added to 1,4-dioxane (100 mL), followed by 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (400 mg, 0.5 mmol). The reaction mixture (54 mmol) was heated under reflux at 95 °C for 19 h. After the reaction was completed, the reaction solution was cooled to room temperature and extracted with ethyl acetate (100 mL × 3). The organic phase was collected, dried with anhydrous sodium sulfate, and purified by rotary evaporation of ethyl acetate and column chromatography. The eluent was a mixture of ethyl acetate and petroleum ether (1:25, v / v) to give 3-benzoyl-4-aminophenylboronic acid pinacol ester (5.69 g, yield 69.83%).

[0055] Synthesis of 3,3”-Dibenzoyl-4,4”-Diaminoterphenyl (ligand B): 1,4-Dibromobenzene (0.368 g, 1.56 mmol) and pinacol ester of 3-benzoyl-4-aminophenylboronic acid (1.0 g, 3.28 mmol) were mixed, followed by the addition of (0.863 g, 6.25 mmol) potassium carbonate and 40 mL of [unspecified substance]. 1,4-Dioxane and 20 mL of water were bubbled with Ar for 15 min, and then 0.06 mmol of tetra(triphenylphosphine)palladium was added under an Ar atmosphere. The mixture was heated and stirred under reflux for 21 hours. After the reaction mixture was cooled to room temperature, it was evaporated to dryness and extracted with dichloromethane (100 mL × 3). The organic phase was collected, dried with anhydrous sodium sulfate, and the dichloromethane was evaporated by rotary evaporation. The mixture was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:10, v / v) as the eluent to give a yellow solid powder, which was 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) (0.71 g, yield 97.3%).

[0056] Weigh 1,3,6,8-tetra(4-formylphenyl)pyrene (18.6 mg, 0.03 mmol) and 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) (28.1 mg, 0.06 mmol) into a test tube, and then add 0.5 mL of o-dichlorobenzene, 0.5 mL of n-pentanol, and 0.1 mL of 3 mol / L ammonium acetate solution. After ultrasonic mixing, heat at 120 °C for 2 days under air conditions. After cooling to room temperature, filter and collect the solid sample. Then wash with water, anhydrous methanol, N,N-dimethylformamide, and chloroform in sequence, and dry under vacuum to obtain a covalent organic framework material intermediate containing a quinazoline group.

[0057] 30 mg of the obtained covalent organic framework material intermediate containing quinazoline group was added to a 10 mL sealed tube. 1.0 g of ammonium acetate and 1.0 mL of 1,4-dioxane were added, oxygen was bubbled in, the stopcock was tightened, and the mixture was heated at 120 °C for 72 h under oxygen conditions. After cooling to room temperature, the solid sample was collected by filtration and then washed sequentially with anhydrous methanol, N,N-dimethylformamide, and chloroform. After vacuum drying, the yellow covalent organic framework material containing quinazoline group was obtained.

[0058] Figure 1 The resulting 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) 1 The 1H-NMR spectrum shows that the doublet at 6.97-7.00 ppm corresponds to the protons on the ortho-carbon of the amino group, the singlet at 7.18 ppm corresponds to the protons on both amino groups, the singlet at 7.31 ppm corresponds to the proton signal on the ortho-benzene ring of the meta-carbonyl group of the amino group, and the multiplet at 7.44-7.68 ppm corresponds to the proton signals on other carbons of the benzene ring.

[0059] Figure 2 The Fourier transform infrared spectra of the obtained 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B) and the covalent organic framework material containing the quinazoline group are shown in the figure. It can be seen from the figure that 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPy) has a peak value of 1703 cm⁻¹. -1 The characteristic peak at this location corresponds to the aldehyde group in the molecule, 3,3”-benzoyl-4,4”-diaminoterphenyl (ligand B), at 1624 cm⁻¹. -1 The characteristic peak at 1662 cm⁻¹ corresponds to the carbonyl group in the molecule, and is the intermediate of the covalent organic framework material containing the quinazoline group. -1 The characteristic peak at 1662 cm⁻¹ corresponds to the carbonyl group in the molecule, while the covalent organic framework containing the quinazoline group is at 1662 cm⁻¹. -1 The characteristic peak disappeared, and a characteristic peak corresponding to the quinazoline structure appeared at 1540 cm⁻¹.

[0060] Figure 3The image shows the XRD pattern of the obtained covalent organic framework material containing quinazoline groups. A broad peak at 23.9° is observed, indicating that the synthesized covalent organic framework material has a partially stacked structure. Sharp peaks appear at 2.8°, 4.3°, 5.7°, and 8.6°, which are characteristic peaks of covalent organic frameworks containing quinazoline groups.

[0061] Figure 4 The image shows a SEM image of the obtained covalent organic framework material containing quinazoline groups. As can be seen from the image, the covalent organic framework material containing quinazoline groups has a porous structure. BET analysis confirms that this material is specifically a mesoporous material with a specific surface area of ​​1256 m². 2 / g, with a pore size of 4.4707nm.

[0062] Figure 5 The image shows the UV-Vis diffuse reflectance of the obtained covalent organic framework material containing quinazoline groups.

[0063] Example 2

[0064] By replacing 3,3”-dibenzoyl-4,4”-biphenyldiamine (ligand A) (1) with 1,3,6,8-tetra(4-formylphenyl)pyrene (ligand B) (2) in Example 1, covalent organic framework materials containing quinazoline groups with different structures were prepared.

[0065]

[0066] The preparation method of ligand A is as follows:

[0067] In a 250 mL double-necked flask, 1.65 g (6.0 mmol) of 2-amino-5-bromobenzophenone, 1.62 g (5 mmol) of 3-benzoyl-4-aminophenylboronic acid pinacol ester, and 2.76 g (20 mmol) of potassium carbonate were added, followed by 25 mL of dioxane and 10 mL of water. The system was purged with argon gas for 15 minutes to remove oxygen. Then, 0.231 g (0.20 mmol) of tetraphenylphosphine palladium was added under argon gas. After the addition was complete, the system was heated in an oil bath at 110 °C for 14 hours under argon protection. After cooling, the system was diluted with 100 mL of water, filtered, and the filtrate was extracted with 100 mL (3 times) of ethyl acetate and washed with 100 mL (2 times) of water. The organic phase was collected, concentrated by rotary evaporation, and the crude product was separated by silica gel column chromatography (ethyl acetate:petroleum ether = 1:50-2:3) to give 1.54 g of a pale yellow solid, with a yield of 78.73%.

[0068] The 3-benzoyl-4-aminophenylboronic acid pinacol ester used above was prepared using the method described in Example 1.

[0069] Example 3

[0070] Eight milligrams of the covalent organic framework material containing a quinazoline group prepared in Example 1 or Example 2 were placed in a 10 mL glass reaction tube, along with 1 mL of water, 1 mL of acetonitrile, 0.1 mmol of styrene, and 0.2 mmol of 4-methylbenzenethiophenol. Oxygen was then introduced, and the reaction was carried out at room temperature under blue LED illumination for 3 hours. The yield was determined by NMR. Using the covalent organic framework material containing a quinazoline group prepared in Example 1 as a catalyst, 23.91 mg of 4-methyl-1-(phenethylsulfinyl)benzene was obtained, with a yield of 98%. Using the covalent organic framework material containing a quinazoline group prepared in Example 2 as a catalyst, 9.03 mg of the product was obtained, with a yield of 37%.

[0071] Figure 6 This is a comparison of the photocatalytic selective synthesis of sulfoxide from styrene and thiophenol using two different covalent organic framework materials containing quinazoline groups. The figure shows that the covalent organic framework prepared using 3,3”-dibenzoyl-4,4”-diaminoterphenyl as a linker exhibits the best photocatalytic performance in the selective synthesis of sulfoxide from styrene and thiophenol.

[0072] Example 4

[0073] The reaction solution after the reaction in Example 3 was filtered, the catalyst was collected and washed three times with ethyl acetate and ethanol (5 ml each time), and then dried under vacuum for 2 hours using an oil pump. The reaction was then repeated as in Example 3.

[0074] Figure 7 The graph shows the activity of the catalyst (a covalent organic framework material containing a quinazoline group prepared in Example 1) after five cycles. As can be seen from the graph, the catalyst maintains a stable and good yield even after five cycles, indicating that this heterogeneous catalyst has good stability and the advantage of being reusable.

[0075] The present invention has been described in detail above. For those skilled in the art, the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. Although specific embodiments have been given, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein. Some of the essential features can be applied within the scope of the following appended claims.

Claims

1. A covalent organic framework material containing a quinazoline group, the structural unit of which is shown in formula (I):

2. The method for preparing the covalent organic framework material containing a quinazoline group according to claim 1, comprising the following steps: (1) Dissolve 1,3,6,8-tetra(4-formylphenyl)pyrene and 3,3”-dibenzoyl-4,4”-diaminoterphenyl in an organic solvent, add ammonium salt, mix well, and place the mixed solution in air to carry out a solvothermal reaction to obtain a covalent organic framework material intermediate containing quinazoline group. (2) Dissolve the intermediate of covalent organic framework material containing quinazoline group obtained in step (1) in an organic solvent, add ammonium acetate, place the mixed solution in oxygen, and carry out a solvothermal reaction to obtain the covalent organic framework material containing quinazoline group. The 3,3”-dibenzoyl-4,4”-diaminoterphenyl has the structural formula shown in formula (Ⅲ):

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to 3,3”-dibenzoyl-4,4”-diaminoterphenyl is 1.0:2.0-2.5; And / or, in step (1), the molar ratio of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to the ammonium salt is 0.1 to 0.5:1; And / or, in step (1), the reaction temperature of the solvothermal reaction is 90-150°C and the reaction time is 1-3 days.

4. The preparation method according to claim 2 or 3, characterized in that: In step (1), the organic solvent is selected from any of the following mixed solvents: o-dichlorobenzene and 1,4-dioxane, o-dichlorobenzene and n-butanol, o-dichlorobenzene and n-pentanol, n-butanol and 1,4-dioxane, preferably a mixed solvent of o-dichlorobenzene and n-pentanol, with a volume ratio of 0.5-1.5:0.5-1.5; And / or, in step (1), the concentration of 1,3,6,8-tetrakis(4-formylphenyl)pyrene in the organic solvent is 0.01 to 0.04 mol / L; And / or, in step (1), the ammonium salt is selected from any one of the following: ammonium acetate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, preferably ammonium acetate; the ammonium salt is added in the form of an aqueous solution of the ammonium salt, and the concentration of the aqueous solution of the ammonium salt is 2.0 to 9.0 mol / L.

5. The preparation method according to any one of claims 2-4, characterized in that: In step (2), the mass ratio of the covalent organic framework material intermediate containing the quinazoline group to the ammonium salt is 0.06 to 0.1:

1. And / or, in step (2), the ammonium salt is selected from any one of the following: ammonium acetate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, preferably ammonium acetate; And / or, in step (2), the temperature of the solvothermal reaction is 90-150°C and the reaction time is 2-5 days; And / or, in step (2), the concentration of the covalent organic framework material intermediate containing the quinazoline group in the organic solvent is 10 mg to 60 mg / mL; And / or, in step (2), the organic solvent is selected from any of the following: 1,4-dioxane, n-butanol, n-pentanol, o-dichlorobenzene, mesitylene, preferably 1,4-dioxane. 6.3,3”-Dibenzoyl-4,4”-Diaminoterphenyl, the structural formula of which is shown in formula (Ⅲ):

7. The method for preparing the 3,3”-dibenzoyl-4,4”-diaminoterphenyl according to claim 6, comprising the following steps: (a) Under an inert atmosphere, 2-benzoyl-4-bromoaniline, pinacol diboronic acid ester and potassium acetate were added to 1,4-dioxane, followed by the addition of catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride. The mixture was heated under reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate, and the ethyl acetate was rotary evaporated to obtain the compound 3-benzoyl-4-aminophenylboronic acid pinacol diboronic acid ester after purification. (b) Under an inert atmosphere, 1,4-dibromobenzene, 3-benzoyl-4-aminophenylboronic acid pinacol ester and potassium carbonate were added to a 1,4-dioxane solution, followed by the addition of tetra(triphenylphosphine)palladium catalyst. The mixture was heated under reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and the dichloromethane was rotary evaporated. The purified solution yielded compound 3,3”-dibenzoyl-4,4”-diaminoterphenyl (ligand B).

8. The preparation method according to claim 7, characterized in that: In step (a), the molar ratio of 2-benzoyl-4-bromoaniline to pinacol diboronic acid ester is 1:1 to 3; And / or, in step (a), the molar ratio of 2-benzoyl-4-bromoaniline to 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride is 1:0.01 to 0.05; And / or, in step (a), the molar ratio of pinacol diboronate to potassium acetate is 1:2 to 3; And / or, in step (a), the temperature of the heating reflux reaction is 70–120°C, and the reaction time is 14–29 h; And / or, in step (b), the molar ratio of 3-benzoyl-4-aminophenylboronic acid pinacol ester, 1,4-dibromobenzene, potassium carbonate, and catalyst tetrakis(triphenylphosphine)palladium is 2.0–3.0:1.0–1.2:4.0–7:0.01–0.1, preferably 2.1:1.0:4.0:0.04; And / or, in step (b), the 1,4-dioxane solution is an aqueous solution of 1,4-dioxane, wherein the volume ratio of 1,4-dioxane to water is 3:1 to 3; And / or, in step (b), the temperature of the heating reflux reaction is 100–120°C, and the reaction time is 15–30 h.

9. The application of the covalent organic framework material containing quinazoline groups as described in claim 1 or the covalent organic framework material containing quinazoline groups prepared by any one of claims 2-5 in the preparation of photocatalysts.

10. The application according to claim 9, characterized in that: The photocatalyst is used to catalyze the selective synthesis of sulfoxide from styrene and thiophenol under illumination.

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