阅读说明：本技术 甲氧虫酰肼的合成工艺 (Synthesis process of methoxyfenozide ) 是由 李德平 于 2018-06-25 设计创作，主要内容包括：本发明涉及甲氧虫酰肼的合成工艺。按照以下工艺步骤进行：1)反应容器中加入3,5-二甲基苯甲酸即甲苯,滴加亚硫酰氯,保温反应2.5-3.5h,减压脱除溶剂,得到中间体3,5-二甲基苯甲酰氯；2)反应容器中加入叔丁基肼、碱性溶液以及甲苯,冷却,然后加入二碳酸二叔丁酯,分水去层；有机层中加入3,5-二甲基苯甲酰氯和碱性水溶液,反应混合物中加入盐酸,在30-40度条件下反应18-25h得到N-(3,5-二甲基苯甲酰基)-N-叔丁基肼；3)反应容器中加入N-(3,5-二甲基苯甲酰基)-N-叔丁基肼以及二氯乙烷,然后滴加3-甲氧基-2-甲基苯甲酰氯的二氯乙烷溶液；滴加完毕后慢慢升温至18-25度,过滤得到滤饼得到甲氧虫酰肼原药。本发明通过优化,以较高收率合成出高质量的甲氧虫酰肼原料,得出了合成配比和温和的工艺条件,使甲氧虫酰肼原药产品的含量和合成收率均得到了极大的提高；且本发明甲氧虫酰肼高效低毒,对环境友好,能满足各种类型害虫的杀虫需要,具备极好的市场应用前景。(The invention relates to a synthesis process of methoxyfenozide. The method comprises the following steps: 1) adding 3, 5-dimethylbenzoic acid, namely toluene, into a reaction container, dropwise adding thionyl chloride, reacting for 2.5-3.5 hours under the condition of heat preservation, and removing the solvent under reduced pressure to obtain an intermediate 3, 5-dimethylbenzoyl chloride; 2) adding tert-butylhydrazine, an alkaline solution and toluene into a reaction container, cooling, then adding di-tert-butyl dicarbonate, and carrying out water separation and layer removal; adding 3, 5-dimethylbenzoyl chloride and an alkaline aqueous solution into the organic layer, adding hydrochloric acid into the reaction mixture, and reacting for 18-25h at 30-40 ℃ to obtain N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine; 3) adding N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine and dichloroethane into a reaction container, and then dropwise adding an dichloroethane solution of 3-methoxy-2-methylbenzoyl chloride; after the dropwise addition, slowly heating to 18-25 ℃, and filtering to obtain a filter cake to obtain the methoxyfenozide original drug. According to the invention, the high-quality methoxyfenozide raw material is synthesized at a high yield through optimization, the synthesis proportion and mild process conditions are obtained, and the content and the synthesis yield of the original methoxyfenozide product are greatly improved; the methoxyfenozide is efficient, low in toxicity and environment-friendly, can meet the insecticidal requirements of various pests, and has a good market application prospect.)

1. The synthesis process of methoxyfenozide is characterized by comprising the following process steps of:

1) adding 3, 5-dimethylbenzoic acid, namely toluene, into a reaction container, heating to 50-70 ℃, dropwise adding thionyl chloride within 2.5h, reacting for 2.5-3.5h under heat preservation, and removing the solvent under reduced pressure to obtain an intermediate 3, 5-dimethylbenzoyl chloride;

2) adding tert-butylhydrazine, an alkaline solution and toluene into a reaction vessel, cooling, then adding di-tert-butyl dicarbonate, reacting for 8-15h at 0-5 ℃, and carrying out water separation and layer removal; adding 3, 5-dimethylbenzoyl chloride and an alkaline aqueous solution into the organic layer, reacting for 3-6h at 0-3 ℃, filtering the product, then adding a filter cake into methanol, adding hydrochloric acid into the reaction mixture, reacting for 18-25h at 30-40 ℃, filtering the product, washing with water and drying to obtain N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine;

3) adding N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine and dichloroethane into a reaction vessel, and cooling; then dripping dichloroethane solution of 3-methoxy-2-methylbenzoyl chloride; after the dropwise addition, slowly heating to 18-25 ℃, uniformly stirring for 10-15h, then filtering to obtain a filter cake, and washing and drying the filter cake to obtain the methoxyfenozide original drug.

2. The process for synthesizing methoxyfenozide according to claim 1, wherein in the step 1), the molar ratio of the 3, 5-dimethylbenzoic acid (toluene) to the thionyl chloride is 1:1-3, and the reaction temperature is 60 ℃.

3. The process for synthesizing methoxyfenozide according to claim 1, wherein in the step 2), the ratio of tert-butylhydrazine: di-tert-butyl dicarbonate: the mol ratio of the 3, 5-dimethyl benzoyl chloride is 1:0.8-1.3: 0.6-0.9.

4. The process for synthesizing methoxyfenozide according to claim 1, wherein in the step 3), the ratio of N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine: the mol ratio of the 3-methoxy-2-methyl benzoyl chloride is 1: 0.8-1.2.

5. The process for synthesizing methoxyfenozide according to claim 1, wherein the alkaline solution in each reaction step is sodium hydroxide solution.

Technical Field

The invention relates to a synthesis process of methoxyfenozide, belonging to the technical field of pesticides.

Background

Methoxyfenozide is a 2 nd generation diacylhydrazine insect growth regulator, has highly selective insecticidal activity on lepidoptera pests, has no osmosis and phloem systemic activity, is mainly effective through stomach toxicity, and also has certain contact poisoning and ovicidal activity. Like other diacylhydrazine insecticides such as chromafenozide, chlorfenozide and tebufenozide, methoxyfenozide is also an ecdysone agonist, and causes lepidoptera larvae to stop feeding, so that the ecdysis process is accelerated, and the pests die due to early ecdysis before maturity. The action mechanism of the pesticide is opposite to that of a pesticide for inhibiting molting of pests, and the pesticide can be used for preventing and treating the pests in the whole larval stage.

The existing methoxyfenozide synthesis process has the defects of not ideal yield, difficulty in obtaining high-content intermediates, low product yield and content and incapability of meeting the use requirement.

Disclosure of Invention

The invention aims to overcome the defects and provide a synthesis process of methoxyfenozide, which can improve the synthesis yield of the methoxyfenozide.

The technical scheme adopted by the invention is as follows: the synthesis process of the methoxyfenozide comprises the following process steps:

1) adding 3, 5-dimethylbenzoic acid, namely toluene, into a reaction container, heating to 50-70 ℃, dropwise adding thionyl chloride within 2.5h, reacting for 2.5-3.5h under heat preservation, and removing the solvent under reduced pressure to obtain an intermediate 3, 5-dimethylbenzoyl chloride;

2) adding tert-butylhydrazine, an alkaline solution and toluene into a reaction vessel, cooling, then adding di-tert-butyl dicarbonate, reacting for 8-15h at 0-5 ℃, and carrying out water separation and layer removal; adding 3, 5-dimethylbenzoyl chloride and an alkaline aqueous solution into the organic layer, reacting for 3-6h at 0-3 ℃, filtering the product, then adding a filter cake into methanol, adding hydrochloric acid into the reaction mixture, reacting for 18-25h at 30-40 ℃, filtering the product, washing with water and drying to obtain N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine;

3) adding N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine and dichloroethane into a reaction vessel, and cooling; then dripping dichloroethane solution of 3-methoxy-2-methylbenzoyl chloride; after the dropwise addition, slowly heating to 18-25 ℃, uniformly stirring for 10-15h, then filtering to obtain a filter cake, and washing and drying the filter cake to obtain the methoxyfenozide original drug.

In the step 1), the molar ratio of the 3, 5-dimethylbenzoic acid, namely toluene, to thionyl chloride is 1:1-3, and the reaction temperature is 60 ℃.

In the step 2), the tert-butyl hydrazine: di-tert-butyl dicarbonate: the mol ratio of the 3, 5-dimethyl benzoyl chloride is 1:0.8-1.3: 0.6-0.9.

In the step 3), N- (3, 5-dimethylbenzoyl) -N-tert-butylhydrazine: the mol ratio of the 3-methoxy-2-methyl benzoyl chloride is 1: 0.8-1.2.

The alkaline solution in each reaction step is a sodium hydroxide solution.

The invention has the advantages that: according to the invention, the high-quality methoxyfenozide raw material is synthesized at a high yield through optimization, the synthesis proportion and mild process conditions are obtained, and the content and the synthesis yield of the original methoxyfenozide product are greatly improved; the methoxyfenozide is efficient, low in toxicity and environment-friendly, can meet the insecticidal requirements of various pests, and has a good market application prospect.

Detailed Description