Preparation method of chlorantraniliprole and intermediate thereof

Abstract

The invention discloses a preparation method of chlorantraniliprole and an intermediate of chlorantraniliprole, which comprises the following steps: in the presence of an alkali and a solvent, mixing3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid and 2-amino-5-chloro-3-methylbenzoic acid together to form a material I; and mixing the methylsulfonyl chloride with the material I, and carrying out a reaction so as to obtain a 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3, 1-benzoxazine-4-one intermediate, i.e., a chlorantraniliprole intermediate. The method is easy to operate, the benzoxazinone intermediate generated in the reaction process does not need to be further treated, can be adopted in a next step of reaction directly without drying for preparation of chlorantraniliprole; the method has the advantages that the method is simple in process and high in total yield and product quality, a filtrate can be used by the aid of synchronous and continuous application processes, accordingly, the usage amount of the solvent can be reduced to a great extent, and the method is suitable for industrial production.

Description

technical field

[0001] The invention belongs to the chemical technology field of insecticide synthesis, and more specifically relates to a preparation method of chlorantraniliprole and an intermediate thereof. Background technique

[0002] Chlorantraniliprole is a broad-spectrum insecticide with a new type of o-formamidobenzamide chemical structure first successfully developed by DuPont of the United States. It has the advantages of strong insecticidal activity, excellent field performance, less toxicity to mammals and good environmental compatibility. The compound has excellent control effects on Lepidoptera pests, acts on ryanodine receptors and has the characteristics of high efficiency, low toxicity, safety to non-target organisms, and no cross-resistance to existing insecticides, so it has attracted widespread attention. Attention, has a huge market prospect.

[0003] The chlorantraniliprole intermediate can be synthesized through various routes, as disclosed in DuPon...

Examples

preparation example Construction

[0024] According to an exemplary embodiment of the present invention, the preparation method of the chlorantraniliprole intermediate mainly comprises: in the presence of a base and a solvent, formula I compound 2-amino-5-chloro-3-methylbenzoic acid (hereinafter Hereinafter abbreviated as B-2) and formula II compound 3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (hereinafter referred to as K acid) are mixed together to form material one ; Methanesulfonyl chloride (hereinafter referred to as MsCl) is mixed with material one reaction again, obtains formula III compound 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl] -6-Chloro-8-methyl-4H-3,1-benzoxazin-4-one (abbreviated as BCPP hereinafter), which is the intermediate of chlorantraniliprole (III).

[0025] Among them, the preparation method of chlorantraniliprole intermediate BCPP also includes a post-treatment step of filtration, the resulting filter cake is crude BCPP, and the filtrate continues to be used as ...

Embodiment 1

[0036] Step A: Preparation of BCPP

[0037] Add K acid (200.0 g, 0.66 mol), B-2 (122.7 g, 0.66 mol) and 1 L of acetonitrile into a 2 L three-necked flask, and start mechanical stirring. Weigh 3-methylpyridine (320.2 g, 3.44 mol) into it, and stir at room temperature for about 5-10 min. The system was moved to a low temperature bath to start cooling down. When the internal temperature of the system is 0-2°C, start to slowly add MsCl (181.8g, 1.59mol) dropwise in total, keeping the internal temperature of the system not exceeding 5°C. After the dropwise addition, the temperature was naturally raised to room temperature, and the stirring reaction was continued until the reaction was complete. The filter cake and filtrate are obtained by filtration, the filter cake is the crude product of BCPP, and the filtrate is used as solvent recovery.

[0038] Step B: Preparation of Crude Chlorantraniliprole

[0039]Add 1 L of acetonitrile to the reaction flask containing the above-mentio...

Embodiment 2

[0043] Step A: Preparation of BCPP

[0044] Add K acid (200.0g, 0.66mol), B-2 (122.7g, 0.66mol) and solvent 1L respectively in 2L there-necked flask, this solvent is made up of filtrate 0.95L and acetonitrile 0.05L in step A among the embodiment 1, Turn on mechanical agitation. Weigh 3-methylpyridine (320.2 g, 3.44 mol) into it, and stir at room temperature for about 5-10 min. The system was moved to a low temperature bath to start cooling down. When the internal temperature of the system is 0-2°C, start to slowly add MsCl (181.8g, 1.59mol) dropwise in total, keeping the internal temperature of the system not exceeding 5°C. After the dropwise addition, the temperature was naturally raised to room temperature, and the stirring reaction was continued until the reaction was complete. The filter cake and filtrate are obtained by filtration, the filter cake is BCPP crude product, and the filtrate can still be used as a solvent for the recovery of the next batch.

[0045] Step B...

technical field

[0001] The invention belongs to the chemical technology field of insecticide synthesis, and more specifically relates to a preparation method of chlorantraniliprole and an intermediate thereof. Background technique

[0002] Chlorantraniliprole is a broad-spectrum insecticide with a new type of o-formamidobenzamide chemical structure first successfully developed by DuPont of the United States. It has the advantages of strong insecticidal activity, excellent field performance, less toxicity to mammals and good environmental compatibility. The compound has excellent control effects on Lepidoptera pests, acts on ryanodine receptors and has the characteristics of high efficiency, low toxicity, safety to non-target organisms, and no cross-resistance to existing insecticides, so it has attracted widespread attention. Attention, has a huge market prospect.

[0003] The chlorantraniliprole intermediate can be synthesized through various routes, as disclosed in DuPon...

Examples

preparation example Construction

[0024] According to an exemplary embodiment of the present invention, the preparation method of the chlorantraniliprole intermediate mainly comprises: in the presence of a base and a solvent, formula I compound 2-amino-5-chloro-3-methylbenzoic acid (hereinafter Hereinafter abbreviated as B-2) and formula II compound 3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (hereinafter referred to as K acid) are mixed together to form material one ; Methanesulfonyl chloride (hereinafter referred to as MsCl) is mixed with material one reaction again, obtains formula III compound 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl] -6-Chloro-8-methyl-4H-3,1-benzoxazin-4-one (abbreviated as BCPP hereinafter), which is the intermediate of chlorantraniliprole (III).

[0025] Among them, the preparation method of chlorantraniliprole intermediate BCPP also includes a post-treatment step of filtration, the resulting filter cake is crude BCPP, and the filtrate continues to be used as ...

Embodiment 1

[0036] Step A: Preparation of BCPP

[0037] Add K acid (200.0 g, 0.66 mol), B-2 (122.7 g, 0.66 mol) and 1 L of acetonitrile into a 2 L three-necked flask, and start mechanical stirring. Weigh 3-methylpyridine (320.2 g, 3.44 mol) into it, and stir at room temperature for about 5-10 min. The system was moved to a low temperature bath to start cooling down. When the internal temperature of the system is 0-2°C, start to slowly add MsCl (181.8g, 1.59mol) dropwise in total, keeping the internal temperature of the system not exceeding 5°C. After the dropwise addition, the temperature was naturally raised to room temperature, and the stirring reaction was continued until the reaction was complete. The filter cake and filtrate are obtained by filtration, the filter cake is the crude product of BCPP, and the filtrate is used as solvent recovery.

[0038] Step B: Preparation of Crude Chlorantraniliprole

[0039]Add 1 L of acetonitrile to the reaction flask containing the above-mentio...

Embodiment 2

[0043] Step A: Preparation of BCPP

[0044] Add K acid (200.0g, 0.66mol), B-2 (122.7g, 0.66mol) and solvent 1L respectively in 2L there-necked flask, this solvent is made up of filtrate 0.95L and acetonitrile 0.05L in step A among the embodiment 1, Turn on mechanical agitation. Weigh 3-methylpyridine (320.2 g, 3.44 mol) into it, and stir at room temperature for about 5-10 min. The system was moved to a low temperature bath to start cooling down. When the internal temperature of the system is 0-2°C, start to slowly add MsCl (181.8g, 1.59mol) dropwise in total, keeping the internal temperature of the system not exceeding 5°C. After the dropwise addition, the temperature was naturally raised to room temperature, and the stirring reaction was continued until the reaction was complete. The filter cake and filtrate are obtained by filtration, the filter cake is BCPP crude product, and the filtrate can still be used as a solvent for the recovery of the next batch.

[0045] Step B...

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