Continuous preparation method of buprofezin

Abstract

The invention relates to the field of insecticide synthesis, and discloses a continuous preparation method of buprofezin, which comprises: 1) carrying out first mixing on an organic solvent and N-chloromethyl-N-phenylaminoformyl chloride, adding Butyl Propylthiourea, and carrying out second mixing to obtain a solution A; 2) obtaining an alkali solution B; (3) feeding the solution A and the alkali solution B are simultaneously into more than two reaction kettles connected in series for a reaction, wherein in the step (1), the molar ratio of N-chloromethyl-N-phenylamino formyl chloride to Butyl Propylthiourea is 1: (0.9-1.2), the feeding speed of the solution A and the alkali solution B into the reaction kettle enables the molar ratio of alkali in the alkali solution B to N-chloromethyl-N-phenylamino formyl chloride in the solution A to be (1-5): 1, and the total retention time of the reaction solution in the reaction kettle is more than 150 minutes. According to the continuous preparation method of buprofezin, provided by the invention, the investment of equipment and manpower is greatly reduced, and the product quality is stable and safe.

Description

Technical field

[0001] The present invention relates to synthetic insecticides, and in particular relates to a continuous method for preparing a thiazine ketone. Background technique

[0002] Buprofezin, also known as buprofezin, is an insect growth regulator insecticides. By inhibiting chitin synthesis and metabolism disturbance, so that pests can not with normal moulting and metamorphosis gradually died. It has high activity, high selectivity and long residual lifetime characteristics. The present synthesis method has been reported mainly used -N- chloromethyl-N- phenylcarbamoyl chloride (acid chloride intermediate) and tert-butyl N- -N'- isopropyl-thiourea (buprenorphine thiourea) in diethyl ethyl chloride, or toluene, made alkaline ammonium bicarbonate, prepared ring closing reaction.

[0003] For example, CN101863859A discloses the two materials prepared in aqueous ammonium bicarbonate was added dropwise buprofezin. CN101973962A discloses the use of a reaction solvent chloro...

Examples

preparation example Construction

[0023] The present invention provides a buprofezin continuous production method, wherein the method comprises the steps of:

[0024] After 1) and the organic solvent N- methyl -N- chloro-phenylamino a first mixed chloride, propionyl butyryl thiourea second mixed to obtain a solution A;

[0025] 2) obtaining an alkali solution B;

[0026] 3) The solution A and the solution B are simultaneously fed to the base two or more series-connected reactor in the reaction,

[0027] Wherein, in step 1), N- methyl -N- chloro-phenylamino chloride and thiourea molar ratio of buprenorphine is 1: 0.9-1.2, the solution A and the solution B is fed to the reactor base such that the speed of the vessel base solution B in solution a in the base and the N- methyl -N- chloro-phenylamino chloride molar ratio of 1-5: 1, said reaction fluid in the reactor the total residence time in the reactor is 150 minutes.

[0028] According to the present invention, the inventors of the present invention, many experimen...

preparation example 1

[0046] Chloromethyl-N- -N- phenylamino-carbonyl chloride preparation.

[0047] Photochemical reaction: To a 300mL chlorobenzene actinic kettle temperature was controlled at 15 ℃, while introducing phosgene 100g, N- dimethylaniline was added dropwise 80g, then slowly warmed to 50 ℃, maintain a small period into phosgene, and then with nitrogen off excess phosgene and hydrogen chloride, the reaction mass after distillation under reduced pressure, the solvent was removed to give N- chlorobenzene chloride-methylphenyl group;

[0048] Chlorination reaction: the aforementioned N- methyl-phenylamino chloride dissolved in 100g of chlorobenzene, was added azobisisobutyronitrile catalyst 1.5g, the photochemical reactor temperature was controlled at 55 ℃ chlorine gas 63g, detecting N - dichlorophenyl methylphenyl group i.e. greater than 0.5% chloride was purged with nitrogen and the excess chlorine gas by-product hydrogen chloride, to give after solvent removal -N- chloromethyl-N- phenylcarbam...

Embodiment 1

[0051] A solution is prepared: 50 parts by weight of N- methyl -N- chloro-phenylamino chloride (content 93 wt%) was added to 143 parts by weight of toluene and stirred at 25 ℃ 20 minutes, then 40 parts by weight of buprenorphine thiourea, stirring was continued for 20 minutes to obtain solution A.

[0052] Formulation of the alkali solution B: 437 parts by weight was added to 42 parts by weight of sodium carbonate in water, under stirring 20 ℃ 30 minutes to obtain an alkali solution B.

[0053] Thiazine-one: A solution and alkali solution B was added dropwise while the first stage reactor, a two reactor series, adjusting the dropping speed so that the sodium bicarbonate-chloromethyl-N- -N- phenylamine the molar ratio of acid chloride groups is 2.2: 1, the reaction temperature of each reactor is 45 ℃, the total residence time of the reaction liquid in the reaction vessel was 200 minutes. After the reaction smoothly, every 6 hours and post-treatment samples, the sampling time is 1 h...

Technical field

[0001] The present invention relates to synthetic insecticides, and in particular relates to a continuous method for preparing a thiazine ketone. Background technique

[0002] Buprofezin, also known as buprofezin, is an insect growth regulator insecticides. By inhibiting chitin synthesis and metabolism disturbance, so that pests can not with normal moulting and metamorphosis gradually died. It has high activity, high selectivity and long residual lifetime characteristics. The present synthesis method has been reported mainly used -N- chloromethyl-N- phenylcarbamoyl chloride (acid chloride intermediate) and tert-butyl N- -N'- isopropyl-thiourea (buprenorphine thiourea) in diethyl ethyl chloride, or toluene, made alkaline ammonium bicarbonate, prepared ring closing reaction.

[0003] For example, CN101863859A discloses the two materials prepared in aqueous ammonium bicarbonate was added dropwise buprofezin. CN101973962A discloses the use of a reaction solvent chloro...

Examples

preparation example Construction

[0023] The present invention provides a buprofezin continuous production method, wherein the method comprises the steps of:

[0024] After 1) and the organic solvent N- methyl -N- chloro-phenylamino a first mixed chloride, propionyl butyryl thiourea second mixed to obtain a solution A;

[0025] 2) obtaining an alkali solution B;

[0026] 3) The solution A and the solution B are simultaneously fed to the base two or more series-connected reactor in the reaction,

[0027] Wherein, in step 1), N- methyl -N- chloro-phenylamino chloride and thiourea molar ratio of buprenorphine is 1: 0.9-1.2, the solution A and the solution B is fed to the reactor base such that the speed of the vessel base solution B in solution a in the base and the N- methyl -N- chloro-phenylamino chloride molar ratio of 1-5: 1, said reaction fluid in the reactor the total residence time in the reactor is 150 minutes.

[0028] According to the present invention, the inventors of the present invention, many experimen...

preparation example 1

[0046] Chloromethyl-N- -N- phenylamino-carbonyl chloride preparation.

[0047] Photochemical reaction: To a 300mL chlorobenzene actinic kettle temperature was controlled at 15 ℃, while introducing phosgene 100g, N- dimethylaniline was added dropwise 80g, then slowly warmed to 50 ℃, maintain a small period into phosgene, and then with nitrogen off excess phosgene and hydrogen chloride, the reaction mass after distillation under reduced pressure, the solvent was removed to give N- chlorobenzene chloride-methylphenyl group;

[0048] Chlorination reaction: the aforementioned N- methyl-phenylamino chloride dissolved in 100g of chlorobenzene, was added azobisisobutyronitrile catalyst 1.5g, the photochemical reactor temperature was controlled at 55 ℃ chlorine gas 63g, detecting N - dichlorophenyl methylphenyl group i.e. greater than 0.5% chloride was purged with nitrogen and the excess chlorine gas by-product hydrogen chloride, to give after solvent removal -N- chloromethyl-N- phenylcarbam...

Embodiment 1

[0051] A solution is prepared: 50 parts by weight of N- methyl -N- chloro-phenylamino chloride (content 93 wt%) was added to 143 parts by weight of toluene and stirred at 25 ℃ 20 minutes, then 40 parts by weight of buprenorphine thiourea, stirring was continued for 20 minutes to obtain solution A.

[0052] Formulation of the alkali solution B: 437 parts by weight was added to 42 parts by weight of sodium carbonate in water, under stirring 20 ℃ 30 minutes to obtain an alkali solution B.

[0053] Thiazine-one: A solution and alkali solution B was added dropwise while the first stage reactor, a two reactor series, adjusting the dropping speed so that the sodium bicarbonate-chloromethyl-N- -N- phenylamine the molar ratio of acid chloride groups is 2.2: 1, the reaction temperature of each reactor is 45 ℃, the total residence time of the reaction liquid in the reaction vessel was 200 minutes. After the reaction smoothly, every 6 hours and post-treatment samples, the sampling time is 1 h...