阅读说明：本技术 一种催化合成2-氰基-4’-甲基联苯的工艺 (Process for catalytically synthesizing 2-cyano-4' -methyl biphenyl ) 是由 黄军 吴明伟 于 2020-12-24 设计创作，主要内容包括：本发明涉及一种催化合成2-氰基-4’-甲基联苯的工艺,先制备含膦材料载体：将膦配体、三苯基苯和二甲氧基甲烷按照比例放入反应釜中,然后加入磷钨酸,在保护气下高温制备含膦聚合物载体；然后催化合成2-氰基-4’-甲基联苯：加入载体、金属钯、和邻氯苯甲腈底物,加入对甲基苯硼酸,加入溶剂,加入碱,在中高温度和反应压力下,得到2-氰基-4’-甲基联苯。本发明的优点有：催化剂可以回收,具有较高的活性和选择性,稳定性好,基本没有金属钯的流失,适宜工业化生产。(The invention relates to a process for catalytically synthesizing 2-cyano-4' -methyl biphenyl, which comprises the following steps of firstly preparing a phosphine-containing material carrier: putting phosphine ligand, triphenylbenzene and dimethoxymethane into a reaction kettle according to a proportion, then adding phosphotungstic acid, and preparing a phosphine-containing polymer carrier at a high temperature under a protective gas; then catalytically synthesizing 2-cyano-4' -methyl biphenyl: adding a carrier, metal palladium and an o-chlorobenzonitrile substrate, adding p-methylbenzeneboronic acid, adding a solvent, adding alkali, and obtaining the 2-cyano-4' -methyl biphenyl at medium-high temperature and reaction pressure. The invention has the advantages that: the catalyst can be recovered, has higher activity and selectivity, good stability and no loss of metal palladium basically, and is suitable for industrial production.)

1. a process for catalytically synthesizing 2-cyano-4' -methyl biphenyl comprises the following specific steps:

(A) preparation of a phosphine ligand-containing support: putting phosphine ligand, triphenylbenzene and dimethoxymethane into a reaction kettle according to a certain proportion, then adding phosphotungstic acid, and heating and reacting under protective gas to prepare a phosphine-containing polymer carrier;

(B) synthesis of 2-cyano-4' -methylbiphenyl:

adding the carrier and palladium metal in the step (A) into a reaction kettle, then adding substrates of o-chlorobenzonitrile and p-methylbenzeneboronic acid, adding a solvent and alkali, introducing protective gas, and heating to react to obtain the 2-cyano-4' -methyl biphenyl.

2. The process according to claim 1, characterized in that the phosphine ligand in step a is 2- (di-tert-butylphosphine) biphenyl, XPhos, XantPhos or S-Phos; the mass ratio of the phosphine ligand to the triphenylbenzene to the dimethoxymethane is 1: (1-4): (20-50); the mass ratio of the phosphine ligand to the phosphotungstic acid is 1: (10-30).

3. The process of claim 1, wherein the heating reaction in step A is carried out at a temperature of 150 ℃ to 190 ℃ for a reaction time of 8 to 15 hours.

4. The process according to claim 1, wherein the mass ratio of the o-chlorobenzonitrile to the carrier in the step B is 0.9-2.2: 1; the molar ratio of the palladium metal to the o-chlorobenzonitrile is 0.6 to 1 percent; the mol ratio of the o-chlorobenzonitrile to the p-methylbenzyl boric acid is 1: (1-1.3); the adding amount of the alkali is that the mol ratio of the alkali to the o-chlorobenzonitrile is 1-3: 1.

5. the process according to claim 1, wherein the solvent in step B is dioxane, toluene, tetrahydrofuran or ethanol; the alkali is Na₂CO₃、K₂CO₃、CSCO₃NaOH or K₃PO₄。

6. The process according to claim 1, wherein the heating reaction in step B is carried out at a temperature of 70 ℃ to 130 ℃ for a reaction time of 5 to 15 hours.

7. The process of claim 1, wherein the shielding gas used in steps a and B is nitrogen or argon.

Technical Field

The invention relates to a process for catalytically synthesizing 2-cyano-4 '-methyl biphenyl, in particular to a process for preparing 2-cyano-4' -methyl biphenyl by catalyzing o-chlorobenzonitrile.

Background

The 2-cyano-4' -methyl biphenyl belongs to aromatic compounds, is a medical intermediate, and can be used for synthesizing novel sartan antihypertensive drugs, such as losartan, valsartan, eprosartan, irbesartan and the like.

The literature (Qi Liang, Wen Yong-ju, Lv Mei-yun. Study on the synthesis of sartanbiphenol [ J ]. Chemical Research And Application 2015,1:1004-1656) also used a one-pot method to prepare 2-cyano-4' -methylbiphenyl, but with a large amount of metallic palladium (2% of the substrate o-chlorobenzonitrile), when the temperature is 80 ℃ the yield is 64%; when the temperature is 120 ℃ the yield drops to 45%, and the recovery can be achieved in the literature (Hermann W A, Brossmer C, OefeleK, et al. Palladacycles as a structured defined catalysts for the recovery of and branched olefins [ J ]. Angew Chem Int Ed Engl,1995,34(17):1844-184), the disadvantage being that higher temperatures are required in comparison with the present invention.

Disclosure of Invention

The invention aims to improve the defects of the prior art and provide a process for catalytically synthesizing 2-cyano-4' -methyl biphenyl.

The technical scheme of the invention is as follows: a process for catalytically synthesizing 2-cyano-4' -methyl biphenyl comprises the following specific steps:

(A) preparation of a phosphine ligand-containing support: putting phosphine ligand, triphenylbenzene and dimethoxymethane into a reaction kettle according to a certain proportion, then adding phosphotungstic acid, and heating and reacting under protective gas to prepare a phosphine-containing polymer carrier;

(B) synthesis of 2-cyano-4' -methylbiphenyl:

adding the phosphine-containing polymer carrier prepared in the step (A) and palladium metal into a reaction kettle, then adding substrates of o-chlorobenzonitrile and p-methylbenzeneboronic acid, then adding a solvent (the addition can dissolve the substrates) and alkali, and introducing protective gas to carry out heating reaction to obtain the 2-cyano-4' -methyl biphenyl.

Preferably, the phosphine ligand in the step A is 2- (di-tert-butylphosphine) biphenyl, XPhos, XantPhos or S-Phos; preferably, the mass ratio of the phosphine ligand to the triphenylbenzene to the dimethoxymethane is 1: (1-4): (20-50); the mass ratio of the phosphine ligand to the phosphotungstic acid is 1: (10-30).

Preferably, the reaction temperature in the step A is 150-190 ℃ and the reaction time is 8-15 hours.

Preferably, the mass ratio of the o-chlorobenzonitrile to the carrier in the step B is 0.9-2.2: 1; the adding amount of the palladium metal is 0.6 to 1 percent of the molar ratio of the palladium metal to the substrate o-chlorobenzonitrile; the mol ratio of the o-chlorobenzonitrile to the p-methylbenzeneboronic acid is 1: (1-1.3); the adding amount of the alkali is 1-3 of the mol ratio of the alkali to the o-chlorobenzonitrile.

Preferably, the solvent in the step B is dioxane, toluene or tetrahydroFuran or ethanol (the addition amount can dissolve the substrate); the alkali is soluble alkali, more preferably Na₂CO₃、K₂CO₃、CSCO₃NaOH or K₃PO₄。

Preferably, the reaction temperature in the step B is 70-130 ℃ and the reaction time is 5-15 hours.

Preferably, the protective gas in the steps A and B is nitrogen or argon (the phosphine ligand is protected from being oxidized).

Has the advantages that:

the synthesis yield of the cyano-4 ' -methyl biphenyl is high, the palladium consumption is low, the cost is greatly saved, the synthesis reaction of the prior art for synthesizing the 2-cyano-4 ' -methyl biphenyl is a Suzuki coupling reaction, and from the aspect of industrial production and application, the 2-cyano-4 ' -methyl biphenyl is synthesized at a medium-high temperature by using a one-pot method under the condition of protective gas. The method has the advantages of simple reaction conditions, high yield, recyclability and the preference, and the conventional Suzuki coupling reaction generally adopts a homogeneous catalyst and cannot be recycled, but the method can be recycled.

The catalyst provided by the invention has the advantages of simple preparation method, higher activity, repeated use and CSCO₃Providing an alkaline environment. The catalyst has high activity and high selectivity for preparing 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile, and is easy to recycle. Has good industrial application prospect.

Detailed Description

Example 1:

reacting 2- (di-tert-butylphosphine) biphenyl and triphenylbenzene 1: adding 1 (the using amount of 2- (di-tert-butylphosphine) biphenyl is 100mg) into a reaction kettle, then adding 2g of dimethoxymethane and 1g of phosphotungstic acid, quickly charging nitrogen, reacting for 8h at 150 ℃ to obtain a phosphorus-containing palladium catalyst carrier, and using the phosphorus-containing palladium catalyst carrier to prepare 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile.

In a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of 2- (di-tert-butylphosphine) biphenyl polymer-containing support together with palladium acetate (1%) and the solvent dioxane 2 mL. Argon gas is filled in to screw up the pressureThe tube is put into an oil bath kettle at 130 ℃ for reaction for 5 hours, after the reaction is finished, the pressure tube is taken out and cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 1 in Table 1.

2- (di-tert-butylphosphine) biphenyl polymer carrier and preparation of 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile under palladium catalysis

Example 2:

XPhos and triphenylbenzene 1: adding 2(XPhos with the dosage of 100mg) into a reaction kettle, then adding 3g of dimethoxymethane and 2g of phosphotungstic acid, rapidly charging argon, reacting for 10 hours at 170 ℃ to obtain a palladium catalyst carrier containing phosphine, and using the palladium catalyst carrier to prepare 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile.

In a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of XPhos-containing polymer support, along with palladium acetate (1%) and the solvent dioxane, 2 mL. Filling nitrogen to tighten the pressure pipe, putting the pressure pipe into an oil bath kettle at 130 ℃ for reaction for 10 hours, taking out the pressure pipe after the reaction is finished, cooling the pressure pipe to room temperature, sampling, and detecting the conversion rate and the selectivity by using gas chromatography, wherein the reaction result is shown in example 2 in Table 1;

xphos polymer carrier and preparation of 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile catalyzed by palladium of Xphos polymer carrier

Example 3:

xanthphos and triphenylbenzene 1: adding 3 (the dosage of XantPhos is 100mg) into a reaction kettle, then adding 4g of dimethoxymethane and 3g of phosphotungstic acid, rapidly charging argon, reacting for 15h at 180 ℃ to obtain a palladium catalyst carrier containing phosphine, and using the palladium catalyst carrier in the preparation of 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile.

137.5mg (1 mm) were added to the pressure tubeoL) o-chlorobenzonitrile, and 163.1mg (1.2mmoL) p-methylbenzylboronic acid and 2 equivalents of CSCO₃100mg of a polymeric support containing XantPhos, together with palladium acetate (1%) and the solvent dioxane 2 mL. Argon is filled into the pressure pipe to tighten the pressure pipe, the pressure pipe is placed into an oil bath kettle at the temperature of 130 ℃ to react for 15 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to the room temperature, a sample is taken, the conversion rate and the selectivity are detected by using gas chromatography, and the reaction result is shown in example 3 in the table 1;

XantPhos polymer carrier and preparation of 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile catalyzed by palladium of XantPhos polymer carrier

Example 4:

mixing S-Phos and triphenylbenzene 1: 4 (the dosage of S-Phos is 100mg) is added into a reaction kettle, then 5g of dimethoxymethane and 2g of phosphotungstic acid are added, argon is rapidly filled, the reaction is carried out for 10h at 190 ℃, and a palladium catalyst carrier containing phosphine is obtained and is used for preparing 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile.

In a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of S-Phos-containing polymer support, as well as palladium acetate (1%) and the solvent dioxane, 2 mL. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 12 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 4 in the table 1.

S-Phos polymer carrier and preparation of 2-cyano-4' -methyl biphenyl from o-chlorobenzonitrile catalyzed by palladium thereof

Table 1:

example 5:

in a pressure pipe, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 1 equivalent of CSCO were charged₃100mg of 2- (di-tert-butylphosphine) -biphenyl polymer-containing carrier (carrier preparation reference example 1) and 2mL of palladium acetate (1%) and tetrahydrofuran solvent. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 5 in the table 2.

Example 6:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃100mg of 2- (di-tert-butylphosphine) -biphenyl polymer-containing support (support preparation reference example 1) and 2ml of palladium acetate (1%) and ethanol solvent. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 6 in the table 2.

Example 7:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 3 equivalents of K are added₂CO₃100mg of 2- (di-tert-butylphosphine) -biphenyl polymer-containing carrier (carrier preparation reference example 1) and palladium acetate (1%) and the solvent toluene 2 mL. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 7 in the table 2.

Example 8:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃100mg of 2- (di-tert-butylphosphine) -biphenyl polymer-containing carrier (carrier preparation reference example 1) and palladium acetate (1%) and the solvent dioxane 2 mL. Argon is filled in and screwed downThe pressure tube is put into an oil bath kettle at 130 ℃ for reaction for 10h, after the reaction is finished, the pressure tube is taken out and cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 8 in Table 2.

Table 2:

example 9:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃62.5mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (1%) and solvent dioxane. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 9 in the table 3.

Example 10:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃80mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (1%) and solvent dioxane. Argon is filled into the reactor to tighten the pressure pipe, the reactor is put into an oil bath kettle at 130 ℃ for reaction for 10 hours, after the reaction is finished, the pressure pipe is taken out and cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 10 in Table 3.

Example 11:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃100mg of XPhos-containing polymer support (support preparation reference example 2) and palladium acetate (1%) and solvent dioxygenSix rings 2 mL. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 11 in Table 3.

Example 12:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃150mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (1%) and solvent dioxane. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 12 in the table 3.

Table 3:

example 13:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (0.6%) and solvent dioxane. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 13 in the table 4.

Example 14:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (0.8%) and solvent dioxane. Argon is filled into the pressure pipe to screw down the pressure pipe, the pressure pipe is put into an oil bath kettle at 130 ℃ for reaction for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, sampling is carried out, and the conversion rate and selection are detected by gas chromatographyThe reaction results are shown in Table 4 as example 14.

Example 15:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium acetate (1%) and solvent dioxane. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 15 in the table 4.

Table 4:

example 16:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of a polymeric support containing XantPhos (support preparation reference example 3) and 2mL of palladium acetate (1%) and dioxane as solvent. Argon is filled into the reactor to tighten the pressure pipe, the reactor is put into an oil bath kettle at 70 ℃ for reaction for 10 hours, after the reaction is finished, the pressure pipe is taken out and cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 16 in Table 5.

Example 17:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of a polymeric support containing XantPhos (support preparation reference example 3) and 2mL of palladium acetate (1%) and dioxane as solvent. Argon is filled into the reactor to tighten the pressure pipe, the reactor is placed into a 90 ℃ oil bath pot to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 17 in Table 5.

Example 18:

137.5mg (1mmoL) of o-chlorobenzonitrile were added to the pressure pipeAnd 163.1mg (1.2mmoL) of p-methylphenylboronic acid and 2 equivalents of CSCO₃100mg of a polymeric support containing XantPhos (support preparation reference example 3) and 2mL of palladium acetate (1%) and dioxane as solvent. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at the temperature of 110 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to the room temperature, a sample is taken, the conversion rate and the selectivity are detected by using gas chromatography, and the reaction result is shown in example 18 in the table 5.

Example 19:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 2 equivalents of CSCO were charged₃100mg of a polymeric support containing XantPhos (support preparation reference example 3) and 2mL of palladium acetate (1%) and dioxane as solvent. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 19 in the table 5.

Table 5:

example 20:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 135.9mg (1.0mmoL) of p-methylbenzylboronic acid and 2 equivalents of K are added₂CO₃100mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium metal (1%) and dioxane solvent. Argon is filled into the reactor to tighten the pressure pipe, the reactor is put into an oil bath kettle at 130 ℃ for reaction for 10 hours, after the reaction is finished, the pressure pipe is taken out and cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 20 in Table 6.

Example 21:

in the pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 1 equivalent of Na were charged₂CO₃100mg of XPhos-containing polymer support (reference example 2 for the preparation of the support) and metallic palladium (1%) and solvent II2mL of oxahexacyclic compound. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 21 in Table 6.

Example 22:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 176.7mg (1.3mmoL) of p-methylbenzylboronic acid and 2 equivalents of NaOH, 100mg of an XPhos-containing polymer carrier (carrier preparation reference example 2) and 2mL of metallic palladium (1%) and dioxane as a solvent were charged. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 22 in the table 6.

Example 23:

in a pressure tube, 137.5mg (1mmoL) of o-chlorobenzonitrile, and 163.1mg (1.2mmoL) of p-methylbenzylboronic acid and 3 equivalents of K are added₃PO₄100mg of XPhos-containing polymer support (support preparation reference example 2) and 2mL of palladium metal (1%) and dioxane solvent. Argon is filled into the pressure pipe to be screwed, the pressure pipe is placed into an oil bath kettle at 130 ℃ to react for 10 hours, after the reaction is finished, the pressure pipe is taken out to be cooled to room temperature, a sample is taken, the conversion rate and the selectivity are detected by gas chromatography, and the reaction result is shown in example 23 in the table 6.

Table 6: