CN113735823A

CN113735823A - Preparation method of chlorantraniliprole intermediate

Info

Publication number: CN113735823A
Application number: CN202010459306.9A
Authority: CN
Inventors: 张虎; 刘玉超; 刘鹏飞; 姚中伟; 盛莹盈
Original assignee: Jiangsu Sevencontinent Green Chemical Co Ltd
Current assignee: Jiangsu Sevencontinent Green Chemical Co Ltd
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2021-12-03

Abstract

The invention relates to a preparation method of a chlorantraniliprole intermediate, which is characterized in that a raw material A is oxidized into an intermediate B in the presence of an oxidant and a catalyst. The method has the advantages of relatively simple process, low cost, less three wastes, clean system, high content and yield of the target product and stable process, and is suitable for industrial production.

Description

Preparation method of chlorantraniliprole intermediate

Technical Field

The invention relates to a preparation method of a chlorantraniliprole intermediate.

Background

Chlorantraniliprole, developed and marketed by dupont in 2008, is a ryanodine receptor (calcium ion release control) inhibitor. Under the recommended dosage of 35-50g/ha, lepidoptera, coleopteran, dipteran, hemiptera and termite insects can be effectively controlled. Is safe to mammals, has low toxicity to fish, shrimp and crab, and has good safety to natural enemies. At present, 20 kinds of domestic registered crops are provided, including: the vegetable soybean, tomato, cabbage, sugarcane, cauliflower, ginger, pepper, potato, cotton, apple tree, rice, watermelon, pakchoi, small green vegetable seedbed, tobacco, corn, cane shoot, cowpea and the like, and has very wide application prospect.

The production process of chlorantraniliprole is very important because the chlorantraniliprole plays an important role in agricultural production. In the prior art, potassium persulfate is used as an oxidant for synthesizing the chlorantraniliprole intermediate, the ton consumption is high, the solid waste is more, and most importantly, the reaction in the step can only be industrially amplified to 2000L, cannot be further amplified, and severely limits the productivity of the chlorantraniliprole intermediate. Therefore, the prior art needs to be improved, and a more efficient, green and stable method for synthesizing the intermediate is urgently needed to be found.

Disclosure of Invention

The invention aims to provide a novel method for preparing a chlorantraniliprole intermediate efficiently, greenly and stably.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a chlorantraniliprole intermediate comprises the step of generating the chlorantraniliprole intermediate by oxidation reaction of a raw material A under the conditions of an oxidant and a catalyst, wherein the oxidant is one or more of ozone, oxygen, air, hydrogen peroxide, peroxyacetic acid and tert-butyl peroxide, and the structural formula of the raw material A is shown in the specification

The structural formula of the chlorantraniliprole intermediate is shown in the specification

Preferably, the catalyst includes but is not limited to one or a mixture of more of cupric chloride, cuprous chloride, cupric iodide, zinc chloride, ferric chloride, ferrous chloride, zinc chloride and manganese dioxide.

Further preferably, the feeding mass of the catalyst is 1-5% of the feeding mass of the raw material A.

Preferably, the oxidation reaction is carried out in a solvent.

Further preferably, the solvent includes, but is not limited to, chlorobenzene, toluene, xylene, 1, 2-dichloroethane, acetonitrile, one or more of methylcyclohexane.

Further preferably, the feeding mass ratio of the raw material A to the solvent is 1: 1-5.

Preferably, the reaction temperature is in the range of 60 to 150 ℃.

Preferably, the reaction time is 3 to 6 hours.

According to a specific and preferred embodiment, the preparation method comprises the following specific operating steps: adding the raw material A, the catalyst and the solvent into a reaction vessel, heating to 60-150 ℃, introducing and/or adding an oxidant into the reaction vessel, reacting for 3-6h under heat preservation till the raw material A completely reacts, stopping the reaction, filtering to remove solids, and removing the solvent to obtain a solid chlorantraniliprole intermediate.

Wherein the heat preservation reaction is always kept at 60-150 ℃ in the reaction process. The reaction equation is as follows:

due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:

the preparation method of the chlorantraniliprole intermediate has the advantages of relatively simple operation, low cost, less three wastes, clean system, high content and yield of the target product and stable process, and is suitable for industrial production.

Detailed Description

The technical solution of the present invention is further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.

Example 1

200g of toluene are placed in a 500ml round-bottom flask, 100g of starting material A and 5g of catalytic copper chloride are added with stirring, air is introduced at 80 ℃ and the reaction is maintained for about 5 hours until the reaction is complete. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 89.1 g of a solid chlorantraniliprole intermediate with the yield of 89.6%.

Example 2

200g of acetonitrile are introduced into a 500ml round-bottom flask, 100g of starting material A, 3g of catalytic copper chloride are added with stirring, air is introduced at 60 ℃ and the reaction is maintained for about 4 hours until the reaction is complete. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 90.5 g of solid chlorantraniliprole intermediate with the yield of 91.1%.

Example 3

200g of acetonitrile is added into a 500ml round bottom flask, 100g of raw material A and 3g of cuprous chloride catalyst are added under stirring, oxygen is introduced at 60 ℃, and the temperature is kept for about 4 hours until the reaction is completed. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 91.0 g of solid chlorantraniliprole intermediate with the yield of 91.6%.

Example 4

200g of 1, 2-dichloroethane are added to a 500ml round-bottom flask, 100g of the starting material A and 3g of the catalyst iron chloride are added with stirring, air is introduced at 60 ℃ and the temperature is maintained for about 4 hours until the reaction is complete. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 90.8 g of solid chlorantraniliprole intermediate with the yield of 91.4%.

Example 5

200g of acetonitrile are added to a 500ml round-bottom flask, 100g of the starting material A, 3g of the catalyst iron chloride are added with stirring, air is introduced at 60 ℃ and the temperature is maintained for about 4 hours until the reaction is complete. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 91.4 g of a solid chlorantraniliprole intermediate with a yield of 92.0%.

Example 6

200g of acetonitrile are added to a 500ml round-bottom flask, 100g of the starting material A, 2g of the catalyst iron chloride are added with stirring, oxygen is introduced at 60 ℃ and the temperature is maintained for about 4 hours until the reaction is complete. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain the solid chlorantraniliprole intermediate 94.0 g with the yield of 94.6%.

Example 7

200g of acetonitrile is added into a 500ml round-bottom flask, 100g of raw material A and 2g of catalyst ferrous chloride are added under stirring, oxygen is introduced at 60 ℃, and the temperature is kept for about 4 hours until the reaction is completed. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain 93.2 g of solid chlorantraniliprole intermediate with yield of 93.8%.

Example 8

200g of acetonitrile is added into a 500ml round-bottom flask, 100g of raw material A and 2g of catalyst ferrous chloride are added under stirring, ozone is introduced at 60 ℃, and the temperature is kept for about 4 hours until the reaction is completed. Stopping reaction, filtering to remove solid, desolventizing to remove solvent, separating out solid, filtering, and drying to obtain a solid chlorantraniliprole intermediate 94.4 g with a yield of 95.0%.

The present invention is described in detail in order to make those skilled in the art understand the content and practice the present invention, and the present invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of chlorantraniliprole intermediate is characterized in that a raw material A is subjected to oxidation reaction under the conditions of an oxidant and a catalyst to generate the chlorantraniliprole intermediate, and the preparation method comprises the following steps: the oxidant is one or more of ozone, oxygen, air, hydrogen peroxide, peroxyacetic acid and tert-butyl peroxide, wherein the structural formula of the raw material A is shown in the specification

2. The process for preparing a chlorantraniliprole intermediate as claimed in claim 1, wherein: the catalyst is one or more of copper chloride, cuprous chloride, copper iodide, zinc chloride, ferric chloride, ferrous chloride, zinc chloride and manganese dioxide.

3. The process for producing a chlorantraniliprole intermediate as claimed in any one of claims 1 to 2, wherein: the feeding mass of the catalyst is 1-5% of that of the raw material A.

4. The process for preparing a chlorantraniliprole intermediate as claimed in claim 1, wherein: the oxidation reaction is carried out in a solvent.

5. The process for preparing a chlorantraniliprole intermediate as claimed in claim 4, wherein: the solvent is one or more of chlorobenzene, toluene, xylene, 1, 2-dichloroethane, acetonitrile and methylcyclohexane.

6. The process for producing a chlorantraniliprole intermediate as claimed in claim 4 or 5, wherein: the feeding mass ratio of the raw material A to the solvent is 1: 1-5.

7. The process for preparing a chlorantraniliprole intermediate as claimed in claim 1, wherein: the reaction temperature range is 60-150 ℃.

8. The process for producing a chlorantraniliprole intermediate as claimed in claim 1 or 7, wherein: the reaction time is 3-6 h.

9. The process for preparing a chlorantraniliprole intermediate as claimed in claim 1, wherein: the preparation method comprises the following specific operation steps: adding the raw material A, the catalyst and the solvent into a reaction vessel, heating to 60-150 ℃, introducing and/or adding an oxidant into the reaction vessel, reacting for 3-6h under heat preservation till the raw material A completely reacts, stopping the reaction, filtering to remove solids, and removing the solvent to obtain a solid chlorantraniliprole intermediate.