Clothianidin synthesis process

Abstract

The invention aims to provide a clothianidin synthesis process, which is characterized by comprising the following steps of: after 1-methyl-5-propyl-2-nitroimino-hexahydric-1,3,5-triazine and 2-chloro-5-chloromethylthiazole is completely reacted, adding a saline solution and an organic solvent into the obtained object, stirring the obtained mixture so as to extract and separate the mixture; carrying out organic phase filtration; cooling filter liquor to a temperature below zero DEG C so as to crystallize the filter liquor; and carrying out suction filtration on the obtained object so as to obtain 1-(2-chlorothiazole-5-methyl)-2-nitroamino-3-methyl-5-n-propyl-hexahydric-1,3,5-triazine; and decomposing the 1-(2-chlorothiazole-5-methyl)-2-nitroamino-3-methyl-5-n-propyl-hexahydric-1,3,5-triazine in a diluted hydrochloric acid so as to obtain clothianidin. According to the process disclosed by the invention, after an intermediate 1-(2-chlorothiazole-5-methyl)-2-nitroamino-3-methyl-5-n-propyl-hexahydric-1,3,5-triazine coarse product is obtained, in the process of treating the coarse product, the problem of recrystallization or column chromatographic refining required in the prior art is solved by using a mixed solution extraction method, thereby facilitating the expanding production.

Description

technical field

[0001] The invention relates to the industrial production of a pesticide and insecticide, in particular to a clothianidin synthesis process. technical background

[0002] The structure of the insecticide clothianidin (English name: Clothianidin) is as follows:

[0003]

[0004] It is a neonicotinoid insecticide, which is a broad-spectrum insecticide with high activity, systemic, contact and stomach toxicity. (Yoshiaki Nakagawa. Nicotinoid insecticides and the nicotinic acetylcholine receptor, Pest ManagSci, 2001, 57, 102) is the fourth generation of novel insecticides following organophosphorus, carbamates, and pyrethroids. It is an invention of great significance in the field of pesticide research. It is safe to mammals and aquatic organisms, has good system properties and environmental friendliness, and has no cross-resistance with traditional pesticides, so it is currently the most important category to replace highly toxic pesticides. (CN20111019473...

Examples

Embodiment 1

[0029] In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and dichloromethane (volume ratio 4.1:1) to the filtrate at 20-25°C, stir, extract and separate, filter the organic phase, cool the filtrate to crystallize below 0°C, and obtain 1-( 2-chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine 21.86g, yield 91.0%, purity 99.3% (HPLC), and then generate clothianidin under the action of dilute hydrochloric acid, wi...

Embodiment 2

[0031] In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and ethyl acetate (volume ratio 4.1:1) to the filtrate at 20-25°C, stir, extract and separate, filter the organic phase, and cool the filtrate to crystallize below 0°C, and obtain 1-( 2-chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine 24.01g, yield 95.5%, purity 99.7% (HPLC), and then generate Clothianidin under the action of dilute hydrochloric acid, ...

Embodiment 3

[0033]In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and petroleum ether (volume ratio 4.1:1) to the filtrate at 20-25°C, stir for extraction and separation, filter the organic phase, cool the filtrate to crystallize below 0°C, and suction filter to obtain 1-(2 -Chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine yield 23.15g, 92.14%, purity 99.3 % (HPLC), and then generate clothianidin under the effect of d...

technical field

[0001] The invention relates to the industrial production of a pesticide and insecticide, in particular to a clothianidin synthesis process. technical background

[0002] The structure of the insecticide clothianidin (English name: Clothianidin) is as follows:

[0003]

[0004] It is a neonicotinoid insecticide, which is a broad-spectrum insecticide with high activity, systemic, contact and stomach toxicity. (Yoshiaki Nakagawa. Nicotinoid insecticides and the nicotinic acetylcholine receptor, Pest ManagSci, 2001, 57, 102) is the fourth generation of novel insecticides following organophosphorus, carbamates, and pyrethroids. It is an invention of great significance in the field of pesticide research. It is safe to mammals and aquatic organisms, has good system properties and environmental friendliness, and has no cross-resistance with traditional pesticides, so it is currently the most important category to replace highly toxic pesticides. (CN20111019473...

Examples

Embodiment 1

[0029] In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and dichloromethane (volume ratio 4.1:1) to the filtrate at 20-25°C, stir, extract and separate, filter the organic phase, cool the filtrate to crystallize below 0°C, and obtain 1-( 2-chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine 21.86g, yield 91.0%, purity 99.3% (HPLC), and then generate clothianidin under the action of dilute hydrochloric acid, wi...

Embodiment 2

[0031] In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and ethyl acetate (volume ratio 4.1:1) to the filtrate at 20-25°C, stir, extract and separate, filter the organic phase, and cool the filtrate to crystallize below 0°C, and obtain 1-( 2-chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine 24.01g, yield 95.5%, purity 99.7% (HPLC), and then generate Clothianidin under the action of dilute hydrochloric acid, ...

Embodiment 3

[0033]In a 250ml four-necked flask, add DMF (150ml), 1-methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine (15.97g , 79mmol), potassium carbonate (27.08g, 196mmol), control the temperature at 20~25°C, add dropwise 2-chloro-5-chloromethylthiazole (13.35g, 79mmol) dissolved in DMF within 30min, after the dropwise addition, add The temperature rises slowly to 40-50°C, traced by high performance liquid chromatography - the content of methyl-5-n-propyl-2-nitroimino-hexahydro-1,3,5-hexahydro-triazine is less than 1.0% , stop the reaction. After filtering while hot, add saturated brine and petroleum ether (volume ratio 4.1:1) to the filtrate at 20-25°C, stir for extraction and separation, filter the organic phase, cool the filtrate to crystallize below 0°C, and suction filter to obtain 1-(2 -Chlorothiazole-5-methyl)-2-nitroimino-3-methyl-5-n-propyl-hexahydro-1,3,5-triazine yield 23.15g, 92.14%, purity 99.3 % (HPLC), and then generate clothianidin under the effect of d...

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