阅读说明：本技术 芳基吡咯类化合物的制备方法 (Preparation method of arylpyrrole compound ) 是由 兰世林 刘卫东 杜升华 刘源 陈郭芹 虞孝云 杨自力 于 2020-11-20 设计创作，主要内容包括：本发明公开了一种芳基吡咯类化合物的制备方法,该方法以4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈和1,2-二氯-1-甲氧基乙烷为原料,以四丁基溴化铵、四乙基溴化铵、苄基三甲基氯化铵或苄基三乙基氯化铵为催化剂,以有机碱二乙胺或三乙胺为缚酸剂,以二氯乙烷、二氯甲烷或氯仿为溶剂,通过反应制备得到芳基吡咯类化合物,即(R/S)1-(2-氯-1-甲氧基乙基)-4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈。本发明的方法大幅提高了反应速度,缩短了反应时间,提高了反应收率及纯度,且操作简单,成本低。(The invention discloses a preparation method of aryl pyrrole compounds, which takes 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile and 1, 2-dichloro-1-methoxy ethane as raw materials, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride are used as catalysts, preparing aryl pyrrole compounds by taking organic base diethylamine or triethylamine as an acid-binding agent and dichloroethane, dichloromethane or chloroform as a solvent through reaction, i.e. (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The method greatly improves the reaction speed, shortens the reaction time, improves the reaction yield and purity, and has simple operation and low cost.)

1. A preparation method of aryl pyrrole compounds is characterized in that 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile and 1, 2-dichloro-1-methoxy ethane are used as raw materials, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride are used as catalysts, organic base diethylamine or triethylamine is taken as an acid-binding agent, dichloroethane, dichloromethane or chloroform is taken as a solvent, preparing an arylpyrrole compound through reaction, wherein the arylpyrrole compound is (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile.

2. The method for preparing arylpyrrole compound according to claim 1, wherein the molar ratio of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile to 1, 2-dichloro-1-methoxyethane is 1.0: 1.05-1.2.

3. The method for preparing arylpyrrole compounds according to claim 1, wherein the ratio of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile to the organic solvent is 1.0 mol: 1000 mL-1200 mL.

4. The method for preparing arylpyrrole compound according to claim 1, wherein the molar ratio of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile to the organic base is 1.0: 1.3-1.5.

5. The preparation method of the arylpyrrole compound according to claim 1, wherein the feeding temperature of the acid-binding agent is 10-20 ℃, the reaction temperature is 35-45 ℃, and the reaction time is 2-3 h.

6. The preparation method of the arylpyrrole compound according to any one of claims 1 to 5, wherein the reaction is completed, cooling and water adding are carried out, layering is carried out, triethylamine is recovered from a water layer, the solvent is removed under reduced pressure by an organic phase, the obtained solvent is recovered and reused, and the obtained crude product is recrystallized to obtain (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile.

7. The method for preparing arylpyrrole compounds according to any one of claims 1 to 5, comprising the steps of: mixing 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 1, 2-dichloro-1-methoxyethane, a solvent and a catalyst, dropwise adding an acid binding agent at 10-20 ℃, heating to 35-45 ℃ after dropwise adding for reaction, cooling and adding water after the reaction is finished, layering, recovering triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the obtained solvent, and recrystallizing the obtained crude product to obtain the arylpyrrole compound (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile.

8. The method for preparing arylpyrrole compounds according to any one of claims 1 to 5, wherein the yield of (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile is not less than 90%, and the product content is not less than 98%.

Technical Field

The invention belongs to the technical field of organic chemical industry, relates to a preparation method of an aryl pyrrole compound, and particularly relates to a preparation method of an aryl pyrrole compound (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl pyrrole-3-nitrile.

Background

The arylpyrrole compound (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile is a novel spectral pesticide independently designed and synthesized by Hunan chemical research institute Limited company. It has low toxicity to human and livestock, is safe to fish, and has ideal insecticidal and acaricidal effect and even ideal bactericidal effect. The similar compound has been granted by Chinese patent with patent grant number ZL201110432946.1, and the structural formula of the compound is as follows:

the preparation method of (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile disclosed in the above patent is: and (2) sequentially dropwise adding a solution consisting of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile and anhydrous tetrahydrofuran and 1, 2-dichloro-1-methoxyethane into an anhydrous tetrahydrofuran solution of sodium hydride, carrying out reflux reaction for 7-8 hours after dropwise adding, cooling, pouring the reaction mixture into ice water, extracting twice with ethyl acetate, washing the combined extract with water for 2-3 times, drying and concentrating to obtain a crude product, and carrying out column chromatography by using a mixed solution of ethyl acetate and petroleum ether as an eluent to obtain a target compound with the content of 96% and the yield of 38.5%. The reaction formula is as follows:

in the method, the defects of low reaction yield, high raw material consumption and cost, complex operation and the like exist, particularly, in the post-treatment, the tetrahydrofuran reaction mother liquor is poured into water to extract products, the solvent is difficult to recover, and simultaneously, a large amount of waste water is generated, so that the industrialization is difficult to realize.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide the preparation method of the aryl pyrrole compound, which has the advantages of simple operation and low cost, can improve the reaction speed, shorten the reaction time, improve the reaction yield and purity and reduce the three wastes.

In order to solve the technical problems, the invention adopts the following technical scheme.

A preparation method of aryl pyrrole compounds takes 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile and 1, 2-dichloro-1-methoxy ethane as raw materials, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride are used as catalysts, organic base diethylamine or triethylamine is taken as an acid-binding agent, dichloroethane, dichloromethane or chloroform is taken as a solvent, preparing an arylpyrrole compound through reaction, wherein the arylpyrrole compound is (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile.

The chemical reaction formula is as follows:

in the method for preparing the arylpyrrole compound, the molar ratio of the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile to the 1, 2-dichloro-1-methoxyethane is preferably 1.0: 1.05-1.2.

In the method for preparing the arylpyrrole compound, the ratio of the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile to the organic solvent is preferably 1.0 mol: 1000 mL-1200 mL.

In the preparation method of the aryl pyrrole compound, the preferable molar ratio of the 4-bromo-2- (4-chlorophenyl) -5-trifluoromethyl pyrrole-3-nitrile to the organic base is 1.0: 1.3-1.5.

In the preparation method of the arylpyrrole compound, preferably, the feeding temperature of the acid-binding agent is 10-20 ℃, the reaction temperature is 35-45 ℃, and the reaction time is 2-3 h.

Preferably, after the reaction is finished, cooling, adding water, layering, recovering triethylamine from a water layer, removing the solvent by organic phase under reduced pressure, recycling the obtained solvent, and recrystallizing the obtained crude product to obtain (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile.

Preferably, the preparation method of the arylpyrrole compound comprises the following steps: mixing 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 1, 2-dichloro-1-methoxyethane, a solvent and a catalyst, dropwise adding an acid binding agent at 10-20 ℃, heating to 35-45 ℃ after dropwise adding for reaction, cooling and adding water after the reaction is finished, layering, recovering triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the obtained solvent, and recrystallizing the obtained crude product to obtain the arylpyrrole compound (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile.

In the preparation method of the arylpyrrole compound, the yield of the (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile is preferably not less than 90%, and the product content is preferably not less than 98%.

Compared with the prior art, the invention has the advantages that:

the preparation method of the invention takes 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile and 1, 2-dichloro-1-methoxy ethane as raw materials, takes organic alkali diethylamine or triethylamine (more preferably triethylamine) as an acid-binding agent, takes low boiling point non-polar solvent dichloroethane, dichloromethane or chloroform as a solvent, and synthesizes aryl pyrrole compound (R/S)1- (2-chloro-1-methoxy ethyl) -4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile under the action of catalysts tetrabutylammonium bromide, tetraethylammonium bromide or benzyltrimethylammonium chloride and benzyltriethylammonium chloride. Compared with the prior art, the method has the advantages that reaction raw materials are unchanged, a reaction solvent and an acid binding agent are changed, a catalyst is added, a low-boiling-point nonpolar solvent is selected as the reaction solvent, so that the desolventizing temperature of a product can be reduced, the thermal decomposition of the product is avoided, the solvent is easy to recover and apply, organic base triethylamine is selected as the acid binding agent and easy to recover and apply, the catalyst is added, the reaction is more complete, the reaction speed is greatly improved, the reaction time is shortened, and the reaction yield and the product purity are improved. The whole process flow of the invention has simple operation, low cost, high reaction yield and purity, and easy recovery and reuse of the solvent and the acid-binding agent, solves the technical problems of low yield, high cost, and large amount of three wastes, especially waste water, of the prior art, and has high industrial application value.

Detailed Description

The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention. Unless otherwise specified, materials and instruments used in the following examples are commercially available.

Example 1:

the preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent) of dichloroethane and 3.23g (0.01mol) of tetrabutylammonium bromide serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying the crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.9g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.0 percent by liquid chromatography quantitative analysis, and the yield is 90.2 percent.¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):3.463(s,3H,CH₃),3.580～3.641(q,2H,CH₂) 5.419-5.464 (q,1H, CH) and 7.368-7.528 (m,4H, ph H), which prove that the arylpyrrole compound (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile is successfully prepared.

Example 2

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent) of dichloroethane and 2.14g (0.01mol) of catalyst tetraethylammonium bromide into a 3L three-mouth reaction bottle with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing a solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.0g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.1 percent by liquid chromatography quantitative analysis, and the yield is 90.1 percent.

Example 3

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 1.87g (0.01mol) of benzyltrimethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- 404.9g of bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.2 percent by liquid chromatography quantitative analysis, and the yield is 90.0 percent.

Example 4

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 2.28g (0.01mol) of benzyltriethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- Bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 405.9 g. The content of the product is 98.0 percent by liquid chromatography quantitative analysis, and the yield is 90.0 percent.

Example 5

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 157.9g (98.0 percent, 1.2mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.2 mol) of dichloroethane and 3.23g (0.01mol) of tetrabutylammonium bromide serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying the crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.7g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.3 percent by liquid chromatography quantitative analysis, and the yield is 90.4 percent.

Example 6

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 157.9g (98.0 percent, 1.2mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.2 mol) of dichloroethane and 2.14g (0.01mol) of catalyst tetraethylammonium bromide into a 3L three-mouth reaction bottle with a mechanical stirring pipe, a condensing pipe, a constant pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing a solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.0g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.4% by liquid chromatography quantitative analysis, and the yield is 90.3%.

Example 7

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethylpyrrole-3-nitrile, 157.9g (98.0 percent, 1.2mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.2mol) of dichloroethane and 1.87g (0.01mol) of benzyltrimethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- Bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 405.9 g. The content of the product is 98.5% by liquid chromatography quantitative analysis, and the yield is 90.4%.

Example 8

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile, 157.9g (98.0 percent, 1.2mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.2mol) of dichloroethane and 2.28g (0.01mol) of benzyltriethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 35 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- Bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 406.5 g. The content of the product is 98.2 percent by liquid chromatography quantitative analysis, and the yield is 90.3 percent.

Example 9

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent) of dichloroethane and 3.23g (0.01mol) of tetrabutylammonium bromide serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying the crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.5g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.0 percent by liquid chromatography quantitative analysis, and the yield is 90.1 percent.

Example 10

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent) of dichloroethane and 2.14g (0.01mol) of catalyst tetraethylammonium bromide into a 3L three-mouth reaction bottle with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing a solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.2g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.1 percent by liquid chromatography quantitative analysis, and the yield is 90.1 percent.

Example 11

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 1.87(0.01mol) of benzyltrimethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering triethylamine from a water layer, decompressing and removing a solvent by organic phase, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromine -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 405.9 g. The content of the product is 98.0 percent by liquid chromatography quantitative analysis, and the yield is 90.0 percent.

Example 12

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 2.28g (0.01mol) of benzyltriethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 132.9g (99.0 percent, 1.3mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- 406.3g of bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.1 percent by liquid chromatography quantitative analysis, and the yield is 90.1 percent.

Example 13

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent) of dichloroethane and 3.23g (0.01mol) of tetrabutylammonium bromide serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 153.3g (99.0 percent, 1.5mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying the crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.1g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.2 percent by liquid chromatography quantitative analysis, and the yield is 90.2 percent.

Example 14

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (1.0 percent, 1.05mol) of dichloroethane and 2.14g (0.01mol) of catalyst tetraethylammonium bromide into a 3L three-mouth reaction bottle with a mechanical stirring pipe, a constant pressure dropping funnel and a thermometer, starting stirring, dropwise adding 153.3g (99.0 percent, 1.5mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering triethylamine from a water layer, removing a solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4-bromo 406.0g of (E) -2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. The content of the product is 98.2 percent by liquid chromatography quantitative analysis, and the yield is 90.2 percent.

Example 15

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethylpyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 1.87g (0.01mol) of benzyltrimethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 153.3g (99.0 percent, 1.5mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- Bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 405.9 g. The content of the product is 98.3 percent by liquid chromatography quantitative analysis, and the yield is 90.2 percent.

Example 16

The preparation method of the aryl pyrrole compound comprises the following steps:

adding 356.7g (98.0 percent, 1.0mol) of 4-bromo-2- (4-chlorphenyl) -5-trifluoromethyl pyrrole-3-nitrile, 138.2g (98.0 percent, 1.05mol) of 1, 2-dichloro-1-methoxyethane, 1000mL (98.0 percent, 1.05mol) of dichloroethane and 2.28g (0.01mol) of benzyltriethylammonium chloride serving as a catalyst into a 3L three-mouth reaction bottle provided with a mechanical stirring pipe, a condensing pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, dropwise adding 153.3g (99.0 percent, 1.5mol) of triethylamine at 10-20 ℃, heating and raising the temperature, controlling the temperature to react at 45 ℃ for 3 hours, cooling and adding water after the reaction is finished, layering, recovering the triethylamine from a water layer, removing the solvent by organic phase decompression, recycling the solvent, recrystallizing, filtering and drying a crude product to obtain a light yellow solid product (R/S)1- (2-chloro-1-methoxyethyl) -4- Bromo-2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile 406.2 g. The content of the product is 98.2 percent by liquid chromatography quantitative analysis, and the yield is 90.2 percent.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.