Palladium-containing catalysts, methods for their preparation and use, and methods for suzuki-miyaura reactions

Abstract

The application relates to the field of material preparation, and discloses a palladium-containing catalyst, a preparation method and application thereof, and a Suzuki-Miyaura reaction method. The structural general formula of the palladium-containing catalyst is shown in formula (1); in formula (1), Q1, Q2, Q3 and Q4 are each independently selected from metal elements; R is selected from H, halogen or an alkyl group; R1 and R2 are each independently selected from C1-C6 alkyl, substituted C1-C6 alkyl, C6-C18 aryl or substituted C6-C18 aryl; the substituents in the substituted C1-C6 alkyl are each independently selected from halogen or a nitro group; and the substituents in the substituted C6-C18 aryl are each independently selected from halogen or a nitro group. The palladium-containing catalyst is stable in structure, simple in preparation method, short in synthesis period, high in catalytic activity when used for the Suzuki-Miyaura reaction, easy to separate from a product, capable of being repeatedly used for many times, green and environment-friendly, and low in cost.

Description

Technical Field

[0001] This invention relates to the field of materials preparation, specifically to a palladium-containing catalyst, its preparation method and application, and a method for the Suzuki-Miyaura reaction. Background Technology

[0002] The Suzuki-Miyaura reaction involves the cross-coupling of an organoboron reagent and an aromatic or alkenyl halide in the presence of a base under zero-valent palladium catalysis. First reported by A. Suzuki and N. Miyaura in 1979, this reaction exhibits very strong substrate adaptability and functional group tolerance, and is commonly used to synthesize polyenes, styrene, and biphenyl derivatives, showing broad application prospects in the synthesis of natural products and organic materials. Zero-valent palladium catalysts typically use monodentate phosphine ligands, including triphenylphosphine, tri-m-tolylphosphine, tributylphosphine, trimethylphosphine, triphenyl phosphite, triphenyl phosphite, and tributyl phosphite. Catalysts used in the Suzuki-Miyaura reaction are prone to ligand and metal loss, especially palladium, which is usually a single-reaction process, difficult to recover, costly, and unsuitable for large-scale production.

[0003] Metal-organic frameworks (MOFs) are coordination polymers generated through the self-assembly of multidentate organic structural units and inorganic clusters. They not only possess designable MOF catalytic structures, playing a crucial role in the regioselectivity and chirality selection of organic chemical reactions, but also participate in reactions as solids and are easily separated from liquid or gaseous products after the reaction, showing broad application prospects in the field of catalysis. Therefore, research on catalysts based on MOFs is of great significance to the field of organic catalysis. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of easy loss and aggregation of ligands and metals in existing palladium-containing catalysts, complex post-processing, and difficulty in separating them from the product. This invention provides a palladium-containing catalyst, its preparation method, its application, and a method for the Suzuki-Miyaura reaction. The palladium-containing catalyst provided by this invention has a stable structure, and its ligands and metals are tightly connected to the benzene ring and uniformly distributed, without agglomeration after the reaction. The catalytically active sites can coordinate with catalytically active metals through organometallic bonds. The preparation method of this catalyst is simple and has a short synthesis cycle. When used in the Suzuki-Miyaura reaction, the catalyst exhibits higher catalytic activity than industrial homogeneous catalysts, effectively improving the conversion rate of reactants (up to 99.8%) and the yield of the target product (up to 99.6%). Furthermore, it is easily separated from the product, can be reused multiple times with essentially unchanged catalytic activity, is environmentally friendly, has low industrial costs, and is conducive to large-scale industrial use.

[0005] To achieve the above objectives, the first aspect of the present invention provides a palladium-containing catalyst, the general structural formula of which is shown in formula (1);

[0006]

[0007] In equation (1),

[0008] Q1, Q2, Q3, and Q4 are each independently selected from metallic elements;

[0009] R is selected from H, halogen, or alkyl;

[0010] R1 and R2 are each independently selected from C1-C6 alkyl, substituted C1-C6 alkyl, C6-C18 aryl, or substituted C6-C18 aryl;

[0011] The substituents in the substituted C1-C6 alkyl groups are each independently selected from halogens or nitro groups;

[0012] The substituents in the substituted C6-C18 aryl groups are each independently selected from halogens or nitro groups.

[0013] The second aspect of the present invention provides a method for preparing a palladium-containing catalyst, the method comprising: in the presence of a solvent, a palladium metal compound undergoes a complexation reaction with a metal-organic framework material having the structure shown in formula (2) to obtain a palladium-containing catalyst having the structure shown in formula (1);

[0014]

[0015] In equation (2), the definitions of Q1, Q2, Q3, Q4, R, R1 and R2 are the same as those of Q1, Q2, Q3, Q4, R, R1 and R2 in the palladium-containing catalyst.

[0016] A third aspect of the present invention provides the application of a palladium-containing catalyst in the Suzuki-Miyaura reaction.

[0017] The fourth aspect of the present invention provides a method for a Suzuki-Miyaura reaction, the method comprising: cross-coupling an aryl or alkenylboronic acid or boronic ester with a chlorinated, bromine, iodoaryl or olefinic hydrocarbon in the presence of a solvent, a Lewis base and a palladium-containing catalyst, wherein the palladium-containing catalyst is the palladium-containing catalyst described in the first aspect of the present invention.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] (1) The palladium-containing catalyst provided by the present invention has a stable structure, its ligands and metals are tightly connected to the benzene ring and are evenly distributed, and do not agglomerate after the reaction. The catalytic active sites can coordinate with catalytically active metals through organometallic bonds. The preparation method is simple, the synthesis cycle is short, and the yield is high.

[0020] (2) The palladium-containing catalyst provided by the present invention has excellent catalytic effect on the Suzuki-Miyaura reaction, which can effectively improve the conversion rate of reactants and the yield of target products. Moreover, it is easy to separate from the product, can be reused multiple times, and the catalytic activity remains basically unchanged. It is green and environmentally friendly, has low industrial cost, and is conducive to large-scale industrial use.

[0021] (3) The Suzuki-Miyaura reaction method provided by the present invention can effectively improve the conversion rate of reactants and the yield of target products by using the palladium-containing catalyst prepared by the present invention. Attached Figure Description

[0022] Figure 1 This is the 1H NMR spectrum of 2-diphenylphosphino-terephthalic acid from Example 2;

[0023] Figure 2 This is the phosphine NMR spectrum of 2-diphenylphosphino-terephthalic acid in Example 2;

[0024] Figure 3 This is the 1H NMR spectrum of 5-bromo-2-diphenylphosphino-terephthalic acid in Example 3;

[0025] Figure 4 This is the phosphine NMR spectrum of 5-bromo-2-diphenylphosphino-terephthalic acid from Example 3. Detailed Implementation

[0026] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0027] According to a first aspect of the present invention, the present invention provides a palladium-containing catalyst, the general structural formula of which is shown in formula (1);

[0028]

[0029] In equation (1),

[0030] Q1, Q2, Q3, and Q4 are each independently selected from metallic elements;

[0031] R is selected from H, halogen, or alkyl;

[0032] R1 and R2 are each independently selected from C1-C6 alkyl, substituted C1-C6 alkyl, C6-C18 aryl, or substituted C6-C18 aryl;

[0033] The substituents in the substituted C1-C6 alkyl groups are each independently selected from halogens or nitro groups;

[0034] The substituents in the substituted C6-C18 aryl groups are each independently selected from halogens or nitro groups.

[0035] In this invention, the palladium-containing catalyst has a stable structure, and its ligands and metals are tightly connected to the benzene ring and evenly distributed, and do not agglomerate after the reaction. The catalytic active sites can coordinate with catalytically active metals through organometallic bonds, which can overcome the defects of easy loss and agglomeration of ligands and metals in the Suzuki-Miyaura reaction, and has excellent catalytic effect on the Suzuki-Miyaura reaction.

[0036] According to a preferred embodiment of the present invention, Q1, Q2, Q3, and Q4 are each independently selected from Group IIA, Group IIB, Group IVB, or Group VIII metal elements; preferably, Q1, Q2, Q3, and Q4 are each independently selected from Mg, Zn, Zr, Fe, or Co. By employing the aforementioned embodiments, a palladium-containing catalyst with stable structure, tight and uniform distribution of ligands and metals with the benzene ring can be obtained, improving the coordination performance between the catalytic active sites and the catalytically active metal. In particular, when Q1, Q2, Q3, and Q4 are each independently selected from Mg, Zn, Zr, Fe, or Co, the catalytic effect of the palladium-containing catalyst on the Suzuki-Miyaura reaction can be effectively improved.

[0037] According to a particularly preferred embodiment of the present invention, Y1 and Y2 are each independently selected from Mg, Zn, or Co. By employing the aforementioned embodiment, a palladium-containing catalyst with a more stable structure, a tighter and more uniform distribution of ligands and metals connected to the benzene ring can be obtained. This improves the coordination performance between the catalytically active sites and the catalytically active metal, further enhancing the catalytic effect of the palladium-containing catalyst on the Suzuki-Miyaura reaction.

[0038] According to a preferred embodiment of the present invention, R is selected from H, halogens, or C1-C3 alkyl groups, preferably H or halogens. By employing the aforementioned embodiment, the stability of the palladium-containing catalyst structure can be effectively improved, the connectivity and distribution uniformity of ligands and metals with the benzene ring can be enhanced, and the coordination performance between the catalytic active sites and the catalytically active metal can be improved, thereby effectively enhancing the catalytic activity of the catalyst in the Suzuki-Miyaura reaction.

[0039] According to a preferred embodiment of the present invention, R1 and R2 are each independently selected from C1-C5 alkyl, substituted C1-C5 alkyl, C6-C15 aryl, or substituted C6-C15 aryl; preferably, R1 and R2 are each independently selected from C6-C15 aryl or substituted C6-C15 aryl. By employing the aforementioned embodiment, the stability of the palladium-containing catalyst structure can be improved, resulting in a tighter and more uniform connection and distribution of the ligands and metal with the benzene ring, thereby enhancing the coordination performance between the catalytically active sites and the catalytically active metal. In particular, when R1 and R2 are each independently selected from C6-C15 aryl or substituted C6-C15 aryl, the catalytic activity of the catalyst in the Suzuki-Miyaura reaction can be effectively improved.

[0040] According to a particularly preferred embodiment of the present invention, R1 and R2 are each independently selected from C6-C15 aryl groups. By employing the aforementioned embodiment, the stability of the palladium-containing catalyst structure can be improved more effectively, the tight connection and uniform distribution of ligands and metals with the benzene ring can be enhanced, the coordination performance between the catalytic active sites and the catalytically active metal can be effectively improved, and the catalytic activity of the catalyst in the Suzuki-Miyaura reaction can be more effectively enhanced.

[0041] According to a more preferred embodiment of the present invention, R1 and R2 are each independently phenyl. By employing the aforementioned embodiments, the stability of the palladium-containing catalyst structure can be further improved, the tight connection and uniform distribution of ligands and metals with the benzene ring can be enhanced, the coordination performance between the catalytic active sites and the catalytically active metal can be effectively improved, and the catalytic activity of the catalyst in the Suzuki-Miyaura reaction can be further enhanced.

[0042] According to a preferred embodiment of the present invention, the palladium-containing catalyst has a porosity of 0.2-1.8 ml / g and a specific surface area of ​​500-2000 m². 2 / g, with a pore size of 0.2-4nm. Using the aforementioned embodiments, the catalytic activity of palladium-containing catalysts in the Suzuki-Miyaura reaction can be effectively improved.

[0043] According to a second aspect of the present invention, the present invention provides a method for preparing a palladium-containing catalyst, the method comprising: in the presence of a solvent, a palladium metal compound undergoes a complexation reaction with a metal-organic framework material having the structure shown in formula (2) to obtain a palladium-containing catalyst having the structure shown in formula (1);

[0044]

[0045] In equation (2), the definitions of Q1, Q2, Q3, Q4, R, R1 and R2 are the same as those of Q1, Q2, Q3, Q4, R, R1 and R2 in the palladium-containing catalyst described in the first aspect of the present invention.

[0046] In this invention, the preparation method of the palladium-containing catalyst is simple, has a short preparation cycle, is environmentally friendly, and has low production cost, making it suitable for large-scale industrial production. Using this preparation method, palladium-containing catalysts with stable structures, uniform distribution of ligands and metals linked to benzene rings, no aggregation after reaction, and catalytic active sites coordinated with catalytically active metals through organometallic bonds can be prepared. When this catalyst is used in the Suzuki-Miyaura reaction, it exhibits high catalytic activity, can be reused multiple times with essentially unchanged activity, and can be separated from the target product through simple filtration.

[0047] The present invention does not impose any particular limitation on the type of solvent in the second aspect. According to a preferred embodiment of the present invention, the solvent is selected from at least one of toluene, chlorobenzene, 1,2-dichloroethane, and dioxane, preferably toluene and / or dioxane. Using the aforementioned embodiments, the complexation reaction between metal-organic framework materials and palladium metal compounds can be effectively promoted, the complexation reaction time can be shortened, and the efficiency of preparing palladium-containing catalysts can be improved.

[0048] According to a preferred embodiment of the present invention, the palladium metal compound is selected from at least one of Pd(PPh3)4, Pd(OAc)2, and Pd(PPh3)2Cl2, preferably Pd(PPh3)4 and / or Pd(OAc)2. By employing the aforementioned embodiment, the structural stability of the palladium-containing catalyst can be improved. In particular, when the palladium metal compound is selected from Pd(PPh3)4 and / or Pd(OAc)2, the structural stability of the palladium-containing catalyst can be effectively improved, enhancing the ligand and metal-benzene ring linkage and distribution uniformity, and effectively improving the catalytic activity of the palladium-containing catalyst in the Suzuki-Miyaura reaction.

[0049] According to a preferred embodiment of the present invention, the conditions for the complexation reaction include: a reaction temperature of 5-65°C and a reaction time of 0.1-30 h. By employing the aforementioned embodiment, the rate of complexation reaction between the metal-organic framework material and the palladium metal compound can be effectively increased, the complexation reaction time can be shortened, and the efficiency of preparing palladium-containing catalysts and the catalytic activity of the catalyst in the Suzuki-Miyaura reaction can be effectively improved.

[0050] According to a particularly preferred embodiment of the present invention, the conditions for the complexation reaction include: a reaction temperature of 10-40°C and a reaction time of 1-15 h. By employing the aforementioned embodiment, the rate of complexation reaction between the metal-organic framework material and the palladium metal compound can be further increased, the complexation reaction time can be significantly shortened, and the efficiency of preparing palladium-containing catalysts and the catalytic activity of the catalyst in the Suzuki-Miyaura reaction can be further improved.

[0051] According to a preferred embodiment of the present invention, the mass ratio of the metal-organic framework material to the palladium metal compound is (0.01-0.1):1. By employing the aforementioned embodiment, a palladium-containing catalyst with stable structure, high catalytic activity, reusability, and essentially unchanged activity can be obtained, and it is easily separated from the target product.

[0052] According to a preferred embodiment of the present invention, the mass ratio of the solvent to the palladium metal compound is (8-35):1. Using the aforementioned embodiments, a palladium-containing catalyst with stable structure, high catalytic activity, reusability with substantially unchanged activity, and easy separation from the target product can be obtained.

[0053] According to a preferred embodiment of the present invention, the method for preparing the metal-organic framework material specifically includes the following steps:

[0054] (1) The compound represented by formula (3) and the compound represented by formula (4) undergo a substitution reaction in the presence of an inorganic base, a first catalyst and a first solvent, and then the compound represented by formula (5) is obtained after first purification and separation.

[0055] (2) In an inert atmosphere, the compound represented by formula (5) undergoes a reduction reaction with a reducing agent in the presence of a second catalyst and a second solvent, and then the compound represented by formula (6) is obtained after a second purification and separation.

[0056] (3) The compound represented by formula (6) is subjected to a hydrothermal synthesis reaction with a metal salt in the presence of acid and a third solvent, and then purified and separated to obtain a metal-organic framework material with the structure shown in formula (2).

[0057]

[0058] In formulas (3), (4), (5) and (6), X is a halogen, and the definitions of R, R1 and R2 are the same as those of R, R1 and R2 in the palladium-containing catalyst described in the first aspect of the present invention.

[0059] Using the aforementioned embodiments, the palladium-containing catalyst synthesized based on metal-organic framework materials has a stable structure and exhibits excellent catalytic performance for the Suzuki-Miyaura reaction.

[0060] According to a preferred embodiment of the present invention, the inorganic base is selected from bicarbonates and / or carbonates, preferably potassium carbonate. By employing the aforementioned embodiment, the substituent X on the benzene ring of the compound represented by formula (3) can be effectively removed, promoting the substitution reaction between the compound represented by formula (3) and the compound represented by formula (4), shortening the reaction time, increasing the yield of the compound represented by formula (5), and thus improving the yield of the metal-organic framework material.

[0061] According to a preferred embodiment of the present invention, the first catalyst is selected from at least one of Pd / C, Ru / C, Ni / C, Pd / SiO2, and Ru / Al2O3, preferably at least one of Pd / C, Ni / C, and Ru / C. By employing the aforementioned embodiment, the rate of substitution reaction between the compound represented by formula (3) and the compound represented by formula (4) can be effectively increased, the substitution reaction time can be shortened, the yield of the compound represented by (5) can be increased, and thus the yield of the metal-organic framework material can be improved.

[0062] The present invention does not impose any particular limitation on the type of the first solvent. According to a preferred embodiment of the present invention, the first solvent is selected from at least one of tetrahydrofuran, ethanol, distilled water, N,N-dimethylformamide, dimethyl sulfoxide, methanol, and butanol, preferably distilled water. By adopting the foregoing embodiments, the substitution reaction between the compound represented by formula (3) and the compound represented by formula (4) can be effectively promoted, the substitution reaction time can be shortened, and the yield of metal-organic framework materials can be improved.

[0063] According to a preferred embodiment of the present invention, the mass ratio of the compound represented by formula (3), the compound represented by formula (4), the carbonate, the first catalyst, and the first solvent is (1-8):(1.5-6):(2-13):(0.04-0.3):100. Using the aforementioned embodiment, the compound represented by formula (3) and the compound represented by formula (4) can undergo a substitution reaction to obtain the compound represented by formula (5), thereby obtaining a metal-organic framework material with stable structure and excellent metal coordination properties.

[0064] According to a preferred embodiment of the present invention, the conditions for the substitution reaction include: a reaction temperature of 50-200°C and a reaction time of 0.5-24 h. By employing the aforementioned embodiment, the catalytic activity of the first catalyst can be effectively improved, thereby increasing the rate of the substitution reaction between the compound represented by formula (3) and the compound represented by formula (4), shortening the reaction time, increasing the yield of the compound represented by formula (5), and further improving the yield of the metal-organic framework material.

[0065] According to a particularly preferred embodiment of the present invention, the conditions for the substitution reaction include: a reaction temperature of 100-200°C and a reaction time of 4-12 h. By employing the aforementioned embodiment, the catalytic activity of the first catalyst can be further improved, the rate of substitution reaction between the compound represented by formula (3) and the compound represented by formula (4) can be increased, the reaction time can be significantly shortened, the yield of the compound represented by formula (5) can be increased, and the yield of the metal-organic framework material can be further improved.

[0066] The present invention does not specifically limit the type of inert atmosphere in the second step. According to a preferred embodiment of the present invention, the inert atmosphere may be selected from any one of nitrogen, helium, neon, argon, krypton or xenon, preferably nitrogen. Using the aforementioned embodiment, in a nitrogen atmosphere, the compound represented by formula (5) can better undergo a reduction reaction with the reducing agent.

[0067] According to a preferred embodiment of the present invention, the reducing agent is selected from at least one of methyldiethoxysilane, (chloromethyl)methyldiethoxysilane, and diethoxyphenylsilane, preferably methyldiethoxysilane and / or (chloromethyl)methyldiethoxysilane. Using the aforementioned embodiment, the reduction reaction with the compound represented by formula (5) can be performed more effectively, the reaction time can be shortened, the yield of the compound represented by formula (6) can be increased, and thus the yield of the metal-organic framework material can be improved.

[0068] According to a preferred embodiment of the present invention, the second catalyst is selected from at least one of diphenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, and dioctyl phosphate, preferably diphenyl phosphate and / or dibutyl phosphate. By employing the aforementioned embodiments, the rate of reduction reaction between the compound represented by formula (5) and the reducing agent can be effectively increased, the reduction reaction time can be shortened, the yield of the compound represented by formula (6) can be increased, and thus the yield of the metal-organic framework material can be effectively improved.

[0069] The present invention does not impose any particular limitation on the type of the second solvent. According to a preferred embodiment of the present invention, the second solvent is selected from at least one of toluene, xylene, chlorobenzene, and 1,2-dichloroethane, preferably toluene. By adopting the aforementioned embodiments, the reduction reaction between the compound represented by formula (5) and the reducing agent can be effectively promoted, the reduction reaction time can be shortened, the yield of the compound represented by formula (6) can be increased, and thus the yield of metal-organic framework materials can be improved.

[0070] According to a preferred embodiment of the present invention, the mass ratio of the compound represented by formula (5), the reducing agent, the second catalyst, and the second solvent is (3-18):(5-25):(0.3-3):(130-880). Using the aforementioned embodiment, the compound represented by formula (5) can be reduced with the reducing agent to obtain the compound represented by formula (6), thereby obtaining a metal-organic framework material with stable structure and excellent metal coordination properties.

[0071] According to a preferred embodiment of the present invention, the conditions for the reduction reaction include: a reaction temperature of 50-180°C and a reaction time of 12-40 h. By employing the aforementioned embodiment, the catalytic activity of the second catalyst can be effectively improved, the rate of reduction reaction between the compound represented by formula (5) and the reducing agent can be increased, the reduction reaction time can be shortened, the yield of the compound represented by formula (6) can be increased, and thus the yield of the metal-organic framework material can be effectively improved.

[0072] According to a particularly preferred embodiment of the present invention, the conditions for the reduction reaction include: a reaction temperature of 70-150°C and a reaction time of 18-30 h. By employing the aforementioned embodiment, the catalytic activity of the second catalyst can be further improved, the rate of reduction reaction between the compound represented by formula (5) and the reducing agent can be increased, the reaction time can be significantly shortened, the yield of the compound represented by formula (6) can be increased, and the yield of the metal-organic framework material can be further improved.

[0073] According to a preferred embodiment of the present invention, the metal salt is selected from at least one of zinc salts, magnesium salts, zirconium salts, chromium salts, and aluminum salts, preferably at least one of Zn(acac)2, Zn(NO3)2·6H2O, Mg(NO3)2·2H2O, ZrCl4, Co(NO3)3·6H2O, and AlO4(OH)2, more preferably at least one of Co(NO3)3·6H2O, Zn(acac)2, and Mg(NO3)2·2H2O. Using the aforementioned embodiments, metal elements can be provided for the preparation of metal-organic framework materials. In particular, when the metal salt is selected from at least one of Co(NO3)3·6H2O, Zn(acac)2, and Mg(NO3)2·2H2O, metal-organic framework materials with stable structures and excellent metal coordination properties can be obtained.

[0074] According to a preferred embodiment of the present invention, the acid is selected from at least one of acetic acid, formic acid, benzoic acid, and phenylacetic acid, preferably acetic acid and / or benzoic acid. By employing the aforementioned embodiment, the surface roughness of the metal-organic framework material can be effectively increased, exposing more catalytic active sites and effectively improving the catalytic activity of palladium-containing catalysts prepared based on metal-organic framework materials in the Suzuki-Miyaura reaction.

[0075] The present invention does not impose any particular limitation on the type of the third solvent. According to a preferred embodiment of the present invention, the third solvent is selected from at least one of N,N-dimethylformamide, dioxane, dimethyl sulfoxide, and N-methylpyrrolidone, preferably at least one of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. Using the aforementioned embodiments, the hydrothermal synthesis reaction of the compound represented by formula (6) with the metal salt can be effectively promoted, shortening the reaction time and increasing the yield of metal-organic framework materials.

[0076] According to a preferred embodiment of the present invention, the mass ratio of the compound represented by formula (6), the metal salt, the acid, and the third solvent is (1-9):(1-6):(0.5-5):(230-950). Using the aforementioned embodiment, a metal-organic framework material with stable structure and excellent metal coordination properties can be obtained by hydrothermal synthesis reaction of the compound represented by formula (6) and the metal salt.

[0077] According to a preferred embodiment of the present invention, the conditions for the hydrothermal synthesis reaction include: a reaction temperature of 60-200°C and a reaction time of 12-36 h. By employing the aforementioned embodiment, the rate of the hydrothermal synthesis reaction between the compound represented by formula (6) and the metal salt can be effectively increased, the reaction time can be effectively shortened, and the yield of the metal-organic framework material can be effectively improved.

[0078] According to a particularly preferred embodiment of the present invention, the conditions for the hydrothermal synthesis reaction include: a reaction temperature of 90-150°C and a reaction time of 18-30 h. By employing the aforementioned embodiment, the rate of hydrothermal synthesis of the compound represented by formula (6) with the metal salt can be further increased, the reaction time can be significantly shortened, and the yield of the metal-organic framework material can be further improved.

[0079] In this invention, the purification and separation are routine operations familiar to those skilled in the art. The purpose is to purify and separate the obtained products during the preparation of metal-organic framework materials to improve the yield of metal-organic framework materials. According to a preferred embodiment of the present invention, the first purification and separation method includes: cooling, filtering, washing, and drying. In this invention, the materials after the substitution reaction can be purified and separated as needed to obtain the compound represented by formula (5), and the present invention has no special limitation on this. According to a preferred embodiment of the present invention, the second purification and separation method includes: extraction, filtering, and drying. In this invention, the materials after the reduction reaction can be purified and separated as needed to obtain the compound represented by formula (6), and the present invention has no special limitation on this. According to a preferred embodiment of the present invention, the third purification and separation method includes: cooling, filtering, washing, and drying. In this invention, the materials after the hydrothermal synthesis reaction can be purified and separated as needed to obtain metal-organic framework materials with the structure shown in formula (2), and the present invention has no special limitation on this. However, the present invention is not limited to this purification and separation method.

[0080] According to a preferred embodiment of the present invention, the porosity of the metal-organic framework material is 0.1-2.0 ml / g, and the specific surface area is 500-2000 m². 2 / g, with a pore size of 0.1-5nm. By using the aforementioned embodiments, palladium-containing catalysts with more stable structures, tighter and more uniform connections and distributions between ligands and metals and benzene rings can be obtained, resulting in higher catalytic activity.

[0081] According to a third aspect of the present invention, the present invention provides the application of a palladium-containing catalyst in the Suzuki-Miyaura reaction.

[0082] In this invention, a palladium-containing catalyst is used in the Suzuki-Miyaura reaction. The catalytic activity is higher than that of industrial homogeneous catalysts, which can effectively improve the conversion rate of reactants and the yield of target products. Moreover, it is easy to separate from the products, can be reused multiple times, and the catalytic activity remains basically unchanged. It is green and environmentally friendly, has low industrial cost, and is conducive to large-scale industrial use.

[0083] According to a fourth aspect of the present invention, a method for a Suzuki-Miyaura reaction is provided, the method comprising: cross-coupling an aryl or alkenylboronic acid or boronic ester with a chlorinated, bromine, iodoaryl or olefinic hydrocarbon in the presence of a solvent, a Lewis base and a palladium-containing catalyst, wherein the palladium-containing catalyst is the palladium-containing catalyst described in the first aspect of the present invention.

[0084] In this invention, the palladium-containing catalyst prepared by this invention has a good catalytic effect on the Suzuki-Miyaura reaction, which can effectively improve the conversion rate of the reactants. Moreover, the catalyst is easy to separate from the target product and can be reused multiple times, which can effectively improve the yield of the target product.

[0085] According to a preferred embodiment of the present invention, the conditions for the Suzuki-Miyaura reaction include: a reaction temperature of 50-300°C and a reaction time of 0.1-30 h. By employing the aforementioned embodiment, the catalytic activity of the palladium-containing catalyst can be effectively enhanced, promoting the Suzuki-Miyaura reaction and improving the conversion rate of reactants and the yield of the target product.

[0086] According to a particularly preferred embodiment of the present invention, the conditions for the Suzuki-Miyaura reaction include: a reaction temperature of 60-200°C and a reaction time of 3-15 h. By employing the aforementioned embodiment, the catalytic activity of the palladium-containing catalyst can be further enhanced, promoting the Suzuki-Miyaura reaction and improving the conversion rate of the reactants and the yield of the target product.

[0087] The present invention does not impose any particular limitation on the aryl or alkenyl boric acid or borate ester. According to a preferred embodiment of the present invention, the aryl or alkenyl boric acid or borate ester is selected from at least one of p-methylphenylboronic acid, o-methylphenylboronic acid, p-ethylphenylboronic acid, o-ethylphenylboronic acid, p-isopropylphenylboronic acid, o-isopropylphenylboronic acid, p-chlorophenylboronic acid, o-chlorophenylboronic acid, p-bromophenylboronic acid, o-bromophenylboronic acid, p-methylo-chlorophenylboronic acid, and p-chloroo-methylphenylboronic acid, preferably p-methylphenylboronic acid and / or phenylboronic acid.

[0088] The present invention does not specifically limit the chlorine, bromine, iodoaromatic hydrocarbons or hydrocarbons mentioned herein. According to a preferred embodiment of the present invention, the chlorine, bromine, iodoaromatic hydrocarbons or hydrocarbons are selected from at least one of chlorobenzene, bromobenzene, iodobenzene, p-methylchlorobenzene, p-methylbromobenzene, p-ethylchlorobenzene, p-isopropylchlorobenzene, p-ethylbromobenzene, p-isopropylchlorobenzene, p-methyliodobenzene, p-methyliodobenzene, p-ethyliodobenzene, p-isopropyliodobenzene, p-ethyliodobenzene, and p-isopropyliodobenzene, preferably at least one of chlorobenzene, p-methylchlorobenzene, and p-methylbromobenzene.

[0089] According to a preferred embodiment of the present invention, the Lewis base is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, bis(trimethylsilyl)aminolithium, potassium bicarbonate, and sodium bicarbonate, preferably at least one of potassium carbonate, sodium carbonate, and bis(trimethylsilyl)aminolithium. Using the aforementioned embodiment, the Suzuki-Miyaura reaction can be effectively promoted.

[0090] This invention does not impose any particular limitation on the type of solvent used in the Suzuki-Miyaura reaction. According to a preferred embodiment of the invention, the solvent is selected from at least one of toluene, chlorobenzene, 1,2-dichloroethane, and dioxane, preferably toluene and / or dioxane. Using the aforementioned embodiment, the reactants can be dissolved, effectively promoting the Suzuki-Miyaura reaction.

[0091] According to a preferred embodiment of the present invention, the mass ratio of the aryl or alkenylboronic acid or borate ester to chlorinated, bromine, iodoaromatic or olefinic hydrocarbons is (9-45):(5-30). Using the aforementioned embodiments, a high yield of the target product can be obtained.

[0092] According to a preferred embodiment of the present invention, the mass ratio of the palladium-containing catalyst to chlorine, bromine, iodoaromatic hydrocarbons or olefins is (0.03-0.2):1. Using the aforementioned embodiment, a high yield of the target product can be obtained.

[0093] According to a preferred embodiment of the present invention, the mass ratio of the Lewis base to a chlorine, bromine, iodoaryl hydrocarbon, or olefin is (1-5):1. Using the aforementioned embodiment, a high-yield target product can be obtained.

[0094] According to a preferred embodiment of the present invention, the mass ratio of the solvent to chlorine, bromine, iodoaromatic hydrocarbons or olefins is (5-35):1. Using the aforementioned embodiments, a high yield of the target product can be obtained.

[0095] The present invention will be described in detail below through embodiments.

[0096] In the following examples, all raw materials were commercially available products from Innovent Biologics; the conversion rate of olefins and the selectivity of aldehydes were measured using an Agilent gas chromatograph (7890A, Beijing Xibi Instrument Co., Ltd.); the specific surface area, pore size, and porosity of the metal-organic framework materials and hydroformylation catalysts were measured using an Autosorb-iQ physical adsorption analyzer (Anton Paar, Anton Paar (Shanghai) Trading Co., Ltd.); and the 1H NMR spectrum and phosphine NMR spectrum were measured using a nuclear magnetic resonance spectrometer (Bruker 300M, Bruker (Beijing) Technology Co., Ltd.).

[0097] Example 1

[0098] 1. Preparation of metal-organic framework materials

[0099] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 90mg of 8wt% Ru / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 100℃ for 12h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside.

[0100] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 70 °C for 30 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0101] (3) Take 3.5g of 2-diphenylphosphino-terephthalic acid, 2.9g of Co(NO3)2·6H2O, 1.9g of acetic acid and 500ml of N,N-dimethylformamide and add them to a hydrothermal synthesis reactor. Heat at 90℃ for 30h, cool to room temperature, perform post-treatment, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Co metal-organic framework material.

[0102] 2. Preparation of palladium-containing catalysts

[0103] 5g of 2-diphenylphosphino-terephthalic acid-Co metal-organic framework material and 150mg of Pd(OAc)2 were added to 100ml of toluene solution, stirred at 10℃ for 15h, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Co(Pd) catalyst.

[0104] 3. Performance testing of palladium-containing catalysts

[0105] The 2-diphenylphosphino-terephthalic acid-Co(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0106] In a nitrogen-protected atmosphere, 11.2 g of chlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Co(Pd) and 27.6 g of potassium carbonate were added to 200 mL of toluene solution. The mixture was heated to 60 °C and reacted for 15 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.5% and the biphenyl yield was 99.4%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0107] Example 2

[0108] 1. Preparation of metal-organic framework materials

[0109] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0110] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0111] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0112] 2. Preparation of palladium-containing catalysts

[0113] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0114] 3. Performance testing of palladium-containing catalysts

[0115] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0116] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.8% and the biphenyl yield was 99.6%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0117] In this embodiment, the 1H NMR spectrum of 2-diphenylphosphino-terephthalic acid is as follows: Figure 1 As shown; the NMR spectrum of phosphine for 2-diphenylphosphino-terephthalic acid is as follows. Figure 2 As shown.

[0118] Example 3

[0119] 1. Preparation of metal-organic framework materials

[0120] (1) Take 3.6g of 2,5-bromo-terephthalic acid, 2.9g of diphenylphosphine oxide, 6.10g of potassium carbonate, 110mg of 8wt% Ni / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 200℃ for 4h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 5-bromo-2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0121] (2) Under nitrogen protection, 8.5 g of 5-bromo-2-diphenylphosphino-terephthalic acid, 11.4 g of (chloromethyl)methyldiethoxysilane, 1.5 g of dibutyl phosphate and 500 ml of toluene were reacted at 150 °C for 18 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The mixture was extracted three times with 300 ml of ethyl acetate, and the aqueous phase was collected. The aqueous phase was neutralized with 10 wt% hydrochloric acid to pH <3, and a white solid precipitated. The white solid 5-bromo-2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0122] (3) Take 4.3g of 5-bromo-2-diphenylphosphino-terephthalic acid, 3.0g of Zn(NO3)2·6H2O, 2.3g of acetic acid and 500ml of dimethyl sulfoxide and add them to a hydrothermal synthesis reactor. Heat at 150℃ for 18h, cool to room temperature, perform post-treatment, filter, wash with ethanol, and dry to obtain a white 5-bromo-2-diphenylphosphino-terephthalic acid-Zn metal-organic framework material.

[0123] 2. Preparation of palladium-containing catalysts

[0124] 5 g of 5-bromo-2-diphenylphosphino-terephthalic acid-Zn metal-organic framework material and 4200 mg of Pd(PPh3) were added to 100 ml of dioxane solution, stirred at 40 °C for 1 h, filtered, washed with toluene, and dried at 110 °C to obtain 5-bromo-2-diphenylphosphino-terephthalic acid-Zn(Pd) catalyst.

[0125] 3. Performance testing of palladium-containing catalysts

[0126] The 5-bromo-2-diphenylphosphino-terephthalic acid-Zn(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0127] Under a nitrogen-protected atmosphere, 12.6 g of p-methylchlorobenzene, 20.4 g of p-methylphenylboronic acid, 1.0 g of 5-bromo-2-diphenylphosphino-terephthalic acid-Zn(Pd) and 27.6 g of lithium bis(trimethylsilyl)aminoamino were added to 200 mL of dioxane solution. The mixture was heated to 200 °C and reacted for 3 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.6% and the biphenyl yield was 99.5%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0128] In this embodiment, the 1H NMR spectrum of 5-bromo-2-diphenylphosphino-terephthalic acid is as follows: Figure 3 As shown; the NMR spectrum of phosphine for 5-bromo-2-diphenylphosphino-terephthalic acid is as follows. Figure 4 As shown.

[0129] Example 4

[0130] 1. Preparation of metal-organic framework materials

[0131] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 4.68g of potassium bicarbonate, 110mg of 8wt% Ru / Al2O3 and 100ml of butanol and put them into a hydrothermal synthesis reactor. Heat at 50℃ for 24h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside;

[0132] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0133] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0134] 2. Preparation of palladium-containing catalysts

[0135] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0136] 3. Performance testing of palladium-containing catalysts

[0137] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0138] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 95.6%, and the biphenyl yield was 94.2%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0139] Example 5

[0140] 1. Preparation of metal-organic framework materials

[0141] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 4.66g of potassium bicarbonate, 110mg of 8wt% Ru / Al2O3 and 100ml of butanol and put them into a hydrothermal synthesis reactor. Heat at 200℃ for 0.5h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside.

[0142] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0143] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0144] 2. Preparation of palladium-containing catalysts

[0145] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0146] 3. Performance testing of palladium-containing catalysts

[0147] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0148] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 96.7% and the biphenyl yield was 94.6%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0149] Example 6

[0150] 1. Preparation of metal-organic framework materials

[0151] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0152] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphoxy-terephthalic acid, 10.7 g of diethoxyphenylsilane, 750 mg of diethyl phosphate and 300 ml of dichlorobenzene were reacted at 50 °C for 40 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphoxy-terephthalic acid was collected, dried at 105 °C and stored for later use.

[0153] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0154] 2. Preparation of palladium-containing catalysts

[0155] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0156] 3. Performance testing of palladium-containing catalysts

[0157] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0158] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 94.1% and the biphenyl yield was 93.5%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0159] Example 7

[0160] 1. Preparation of metal-organic framework materials

[0161] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0162] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphoxy-terephthalic acid, 10.7 g of diethoxyphenylsilane, 750 mg of diethyl phosphate and 300 ml of dichlorobenzene were reacted at 180 °C for 12 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphoxy-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0163] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0164] 2. Preparation of palladium-containing catalysts

[0165] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0166] 3. Performance testing of palladium-containing catalysts

[0167] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0168] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 92.7%, and the biphenyl yield was 90.8%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0169] Example 8

[0170] 1. Preparation of metal-organic framework materials

[0171] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0172] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0173] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of ZrCl4, 1.2g of formic acid and 500ml of dioxane and add them to a hydrothermal synthesis reactor. Heat at 60℃ for 36h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0174] 2. Preparation of palladium-containing catalysts

[0175] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0176] 3. Performance testing of palladium-containing catalysts

[0177] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0178] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 93.6% and the biphenyl yield was 92.8%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0179] Example 9

[0180] 1. Preparation of metal-organic framework materials

[0181] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0182] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0183] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of ZrCl4, 1.2g of formic acid and 500ml of dioxane and add them to a hydrothermal synthesis reactor. Heat at 200℃ for 12h, cool to room temperature, perform post-treatment, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0184] 2. Preparation of palladium-containing catalysts

[0185] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0186] 3. Performance testing of palladium-containing catalysts

[0187] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0188] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 94.7% and the biphenyl yield was 91.9%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0189] Example 10

[0190] 1. Preparation of metal-organic framework materials

[0191] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0192] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0193] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0194] 2. Preparation of palladium-containing catalysts

[0195] 5 g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 220 mg of Pd(PPh3)2Cl2 were added to 100 ml of chlorobenzene solution, stirred at 65 °C for 0.1 h, filtered, washed with toluene, and dried at 110 °C to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0196] 3. Performance testing of palladium-containing catalysts

[0197] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0198] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 90.1% and the biphenyl yield was 86.7%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0199] Example 11

[0200] 1. Preparation of metal-organic framework materials

[0201] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0202] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0203] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0204] 2. Preparation of palladium-containing catalysts

[0205] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 220mg of Pd(PPh3)2Cl2 were added to 100ml of chlorobenzene solution, stirred at 5℃ for 30h, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0206] 3. Performance testing of palladium-containing catalysts

[0207] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0208] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 91.1%, and the biphenyl yield was 87.5%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0209] Example 12

[0210] 1. Preparation of metal-organic framework materials

[0211] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0212] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0213] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0214] 2. Preparation of palladium-containing catalysts

[0215] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0216] 3. Performance testing of palladium-containing catalysts

[0217] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0218] Under a nitrogen-protected atmosphere, 12.6 g of p-bromobenzene, 18.2 g of p-ethylphenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium bicarbonate were added to 200 mL of dioxane solution. The mixture was heated to 50 °C and reacted for 30 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 90.3%, and the biphenyl yield was 85.8%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0219] Example 13

[0220] 1. Preparation of metal-organic framework materials

[0221] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 150℃ for 8h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside for later use;

[0222] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 110 °C for 24 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0223] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 120℃ for 24h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0224] 2. Preparation of palladium-containing catalysts

[0225] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 25℃ for 8 hours, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0226] 3. Performance testing of palladium-containing catalysts

[0227] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0228] Under a nitrogen-protected atmosphere, 12.6 g of p-bromobenzene, 18.2 g of p-ethylphenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium bicarbonate were added to 200 mL of dioxane solution. The mixture was heated to 300 °C and reacted for 0.1 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 90.8%, and the biphenyl yield was 87.4%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0229] Example 14

[0230] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst recovered once in Example 2 was used to catalyze the Suzuki-Miyaura reaction.

[0231] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) recovered once, and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.7%, and the biphenyl yield was 99.5%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0232] Example 15

[0233] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst recovered in Example 2 was used to catalyze the Suzuki-Miyaura reaction.

[0234] Under a nitrogen-protected atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of recovered secondary 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.6% and the biphenyl yield was 99.3%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0235] Example 16

[0236] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst recovered three times in Example 2 was used to catalyze the Suzuki-Miyaura reaction.

[0237] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) recovered three times, and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 99.5%, and the biphenyl yield was 99.1%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0238] Comparative Example 1

[0239] Pd(PPh3)4 catalyst was used in the Suzuki-Miyaura reaction.

[0240] Under a nitrogen-protected atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of Pd(PPh3)4, and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 130 °C and reacted for 9 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 89.7%, and the biphenyl yield was 83.4%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0241] Comparative Example 2

[0242] 1. Preparation of metal-organic framework materials

[0243] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 25℃ for 48h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside.

[0244] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 20 °C for 72 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0245] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 25℃ for 60h, cool to room temperature, post-process, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0246] 2. Preparation of palladium-containing catalysts

[0247] 5g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230mg of Pd(PPh3) were added to 100ml of toluene solution, stirred at 2℃ for 45h, filtered, washed with toluene, and dried at 110℃ to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0248] 3. Performance testing of palladium-containing catalysts

[0249] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0250] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution and reacted at 25 °C for 45 h. After the reaction was completed, the temperature was lowered to room temperature, and the filtered solution was subjected to GC analysis. The chlorobenzene conversion rate was 70.9%, and the biphenyl yield was 66.7%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0251] Comparative Example 3

[0252] 1. Preparation of metal-organic framework materials

[0253] (1) Take 2.7g of 2-bromoterephthalic acid, 2.9g of diphenylphosphine oxide, 6.08g of potassium carbonate, 120mg of 6wt% Pd / C and 100ml of distilled water and put them into a hydrothermal synthesis reactor. Heat at 300℃ for 0.1h, cool to room temperature, post-process, filter, neutralize the liquid with 10wt% hydrochloric acid to pH=1, a white solid precipitates, filter, wash with distilled water to obtain white solid 2-diphenylphosphineoxy-terephthalic acid, evaporate to dryness at 105℃ and set aside;

[0254] (2) Under nitrogen protection, 6.9 g of 2-diphenylphosphino-terephthalic acid, 10.7 g of methyldiethoxysilane, 750 mg of diphenyl phosphate and 300 ml of toluene were reacted at 300 °C for 5 h. After the reaction was completed, 3 N NaOH aqueous solution was added to the reaction system to adjust the pH to >10. The system was extracted three times with 300 ml of ethyl acetate. The aqueous phase was collected and neutralized with 10 wt% hydrochloric acid to pH <3. A white solid precipitated out. The white solid 2-diphenylphosphino-terephthalic acid was collected, dried at 105 °C and set aside for later use.

[0255] (3) Take 2.6g of 2-diphenylphosphino-terephthalic acid, 2.6g of Mg(NO3)2·2H2O, 1.2g of benzoic acid and 500ml of N-methylpyrrolidone and add them to a hydrothermal synthesis reactor. Heat at 280℃ for 6h, cool to room temperature, perform post-treatment, filter, wash with ethanol, and dry to obtain white 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material.

[0256] 2. Preparation of palladium-containing catalysts

[0257] 5 g of 2-diphenylphosphino-terephthalic acid-Mg metal-organic framework material and 4230 mg of Pd(PPh3) were added to 100 ml of toluene solution, stirred at 120 °C for 0.05 h, filtered, washed with toluene, and dried at 110 °C to obtain 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst.

[0258] 3. Performance testing of palladium-containing catalysts

[0259] The 2-diphenylphosphino-terephthalic acid-Mg(Pd) catalyst prepared above was used in the Suzuki-Miyaura reaction.

[0260] Under a nitrogen-containing atmosphere, 12.6 g of p-methylchlorobenzene, 18.2 g of phenylboronic acid, 1.0 g of 2-diphenylphosphino-terephthalic acid-Mg(Pd) and 27.6 g of sodium carbonate were added to 200 mL of dioxane solution. The mixture was heated to 350 °C and reacted for 0.06 h. After the reaction was complete, the mixture was cooled to room temperature. The filtered solution was subjected to GC analysis, and the chlorobenzene conversion rate was 68.4%, and the biphenyl yield was 65.2%. The obtained metal-organic framework material was washed with ethyl acetate and distilled water, and then dried at 105 °C.

[0261] The GC test results show that the palladium-containing catalyst provided by this invention has high catalytic activity in the Suzuki-Miyaura reaction, with a chlorobenzene conversion rate of up to 99.8% and a biphenyl yield of more than 99.6%. Moreover, the catalyst is easy to separate from the product, can be reused multiple times with its activity remaining basically unchanged, is environmentally friendly, has low industrial cost, and is conducive to large-scale industrial use.

[0262] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A palladium-containing catalyst, characterized in that, The general structural formula of the palladium-containing catalyst is shown in formula (1); (1) In equation (1), Q1, Q2, Q3, and Q4 are each independently selected from metallic elements; R is selected from H, halogen, or alkyl; R1 and R2 are each independently selected from C1-C6 alkyl, substituted C1-C6 alkyl, C6-C18 aryl, or substituted C6-C18 aryl; The substituents in the substituted C1-C6 alkyl groups are each independently selected from halogens or nitro groups; The substituents in the substituted C6-C18 aryl groups are each independently selected from halogens or nitro groups; The method for preparing the palladium-containing catalyst includes: in the presence of a solvent, a palladium metal compound undergoes a complexation reaction with a metal-organic framework material having the structure shown in formula (2) to obtain a palladium-containing catalyst having the structure shown in formula (1); (2) In equation (2), the definitions of Q1, Q2, Q3, Q4, R, R1 and R2 are the same as those of Q1, Q2, Q3, Q4, R, R1 and R2 in the palladium-containing catalyst described above; The preparation method of the metal-organic framework material specifically includes the following steps: (1) The compound represented by formula (3) and the compound represented by formula (4) undergo a substitution reaction in the presence of an inorganic base, a first catalyst and a first solvent, and then the compound represented by formula (5) is obtained after first purification and separation. (2) In an inert atmosphere, the compound represented by formula (5) undergoes a reduction reaction with a reducing agent in the presence of a second catalyst and a second solvent, and then the compound represented by formula (6) is obtained after a second purification and separation. (3) The compound represented by formula (6) is subjected to a hydrothermal synthesis reaction with a metal salt in the presence of acid and a third solvent, and then purified and separated to obtain a metal-organic framework material with the structure shown in formula (2). (3) (4) (5) (6) In equations (3), (4), (5), and (6), X is a halogen, and the definitions of R, R1, and R2 are the same as those of R, R1, and R2 in the palladium-containing catalyst.

2. The palladium-containing catalyst according to claim 1, wherein, Q1, Q2, Q3 and Q4 are each independently selected from Group IIA, Group IIB, Group IVB or Group VIII metal elements; and / or The R is selected from H, halogens, or C1-C3 alkyl groups.

3. The palladium-containing catalyst according to claim 2, wherein, Q1, Q2, Q3, and Q4 are each independently selected from Mg, Zn, Zr, Fe, or Co; and / or The R is selected from H or halogen.

4. The palladium-containing catalyst according to claim 3, wherein, Q1 and Q2 are each independently selected from Mg, Zn or Co.

5. The palladium-containing catalyst according to claim 1, wherein, R1 and R2 are each independently selected from C1-C5 alkyl, substituted C1-C5 alkyl, C6-C15 aryl, or substituted C6-C15 aryl; and / or The palladium-containing catalyst has a porosity of 0.2-1.8 ml / g and a specific surface area of ​​500-2000 m². 2 / g, with a pore size of 0.2-4nm.

6. The palladium-containing catalyst according to claim 5, wherein, R1 and R2 are each independently selected from C6-C15 aryl or substituted C6-C15 aryl.

7. The palladium-containing catalyst according to claim 6, wherein, R1 and R2 are each independently selected from C6-C15 aryl groups.

8. The palladium-containing catalyst according to claim 7, wherein, R1 and R2 are each independently phenyl.

9. The palladium-containing catalyst according to claim 1, wherein, The solvent is selected from at least one of toluene, chlorobenzene, 1,2-dichloroethane, and dioxane; and / or The palladium metal compound is selected from at least one of Pd(PPh3)4, Pd(OAc)2, and Pd(PPh3)2Cl2; and / or The conditions for the complexation reaction include: The reaction temperature is 5-65℃; The reaction time is 0.1-30 hours. and / or The mass ratio of the metal-organic framework material to the palladium metal compound is (0.01-0.1):1; and / or The mass ratio of the solvent to the palladium metal compound is (8-35):

1.

10. The palladium-containing catalyst according to claim 9, wherein, The solvent is toluene and / or dioxane; and / or The palladium metal compound is Pd(PPh3)4 and / or Pd(OAc)2; and / or The conditions for the complexation reaction include: The reaction temperature is 10-40℃; The reaction time is 1-15 hours.

11. The palladium-containing catalyst according to claim 1, wherein, The first catalyst is selected from at least one of Pd / C, Ru / C, Ni / C, Pd / SiO2, and Ru / Al2O3; and / or The second catalyst is selected from at least one of diphenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, and dioctyl phosphate; and / or The porosity of the metal-organic framework material is 0.1-2.0 ml / g, and the specific surface area is 500-2000 m². 2 / g, with a pore size of 0.1-5nm.

12. The palladium-containing catalyst according to claim 11, wherein, The first catalyst is selected from at least one of Pd / C, Ni / C, and Ru / C; and / or The second catalyst is diphenyl phosphate and / or dibutyl phosphate.

13. The use of the palladium-containing catalyst according to any one of claims 1-12 in the Suzuki-Miyaura reaction.

14. A method for the Suzuki-Miyaura reaction, characterized in that, The method comprises: in the presence of a solvent, a Lewis base, and a palladium-containing catalyst, cross-coupling an aryl or alkenyl boronic acid or boronic ester with a chlorinated, bromine, iodoaryl or olefinic hydrocarbon, wherein the palladium-containing catalyst is any one of the palladium-containing catalysts described in claims 1-12.

15. The method according to claim 14, wherein, The conditions for the Suzuki-Miyaura reaction include: The reaction temperature is 50-300℃; The reaction time is 0.1-30 hours. and / or The aryl or alkenyl boronic acid or boronic ester is selected from at least one of p-methylphenylboronic acid, o-methylphenylboronic acid, p-ethylphenylboronic acid, o-ethylphenylboronic acid, phenylboronic acid, p-isopropylphenylboronic acid, o-isopropylphenylboronic acid, p-chlorophenylboronic acid, o-chlorophenylboronic acid, p-bromophenylboronic acid, o-bromophenylboronic acid, p-methylo-chlorophenylboronic acid, and p-chloroo-methylphenylboronic acid; and / or The chlorine, bromine, or iodophore or hydrocarbon is selected from at least one of chlorobenzene, bromobenzene, iodobenzene, p-methylchlorobenzene, p-methylbromobenzene, p-ethylchlorobenzene, p-ethylbromobenzene, p-isopropylchlorobenzene, p-methyliodobenzene, p-ethyliodobenzene, and p-isopropyliodobenzene; and / or The Lewis base is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, bis(trimethylsilyl)aminolithium, potassium bicarbonate, and sodium bicarbonate; and / or The solvent is selected from at least one of toluene, chlorobenzene, 1,2-dichloroethane, and dioxane.

16. The method according to claim 15, wherein, The conditions for the Suzuki-Miyaura reaction include: The reaction temperature is 60-200℃; The reaction time is 3-15 hours; and / or The aryl or alkenyl boronic acid or boronic ester is p-methylphenylboronic acid and / or phenylboronic acid; and / or The chlorine, bromine, or iodoaromatic hydrocarbon or hydrocarbon is at least one of chlorobenzene, p-methylchlorobenzene, and p-methylbromobenzene; and / or The Lewis base is selected from at least one of potassium carbonate, sodium carbonate, and bis(trimethylsilyl)aminolithium; and / or The solvent is toluene and / or dioxane.

17. The method of claim 14, wherein, The mass ratio of the aryl or alkenylboronic acid or borate ester to chlorinated, bromine, iodoaromatic or olefinic hydrocarbons is (9-45): (5-30); and / or The mass ratio of the palladium-containing catalyst to chlorinated, bromine, iodoaromatic or olefinic hydrocarbons (0.03-0.2):1; and / or The mass ratio of the Lewis base to a chlorinated, bromine, iodoaromatic, or olefin is (1-5):1; and / or The mass ratio of the solvent to chlorine, bromine, iodoaromatic hydrocarbons or olefins is (5-35):1.

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