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[目的]旨在探索一条适合工业化生产唑啉草酯的工艺路线。[方法]一缩二乙二醇与甲烷磺酰氯反应,生成甘二醇二甲烷磺酸酯,再与叠氮二羧酸二叔丁酯环化得到4,5-双-叔丁氧基羰基-[1,4,5]氧杂二氮杂草,然后在乙酸溴化氢溶液中脱羧得到中间体[1,4,5]-氧杂二氮杂草二氢溴酸盐;2,6-二乙基-4-甲基苯胺经过Sandmeyer反应,得到2,6-二乙基-4-甲基溴苯,与丙二腈在碘化亚铜催化下偶合,得到2,6-二-乙基-4-甲基苯基丙二腈,最后在过氧化氢溶液中水解得到2,6-二乙基-4-甲基苯基丙二酰胺;在三乙胺的作用下,2,6-二-乙基-4-甲基苯基丙二腈与[1,4,5]-氧杂二氮杂草二氢溴酸盐反应得到8-(2,6-二乙基-4-甲基苯)四氢吡唑[1,2d][1,4,5]-氧杂二氮杂草-7,9-二酮,在4-二甲氨基吡啶的催化下,与新戊酰氯反应,得到目的产物唑啉草酯。[结果]经1H NMR光谱鉴定,产品结构与唑啉草酯结构一致。[结论]该工艺简单经济、条件温和、适合工业化生产。
[Objective] The aim is to explore a process route suitable for the industrial production of pinoxaden. [Method] Diethylene glycol was reacted with methanesulfonyl chloride to give the glycols dimethanesulfonate which was cyclized with di-tert-butyl azido dicarboxylate to give 4,5-bis-tert-butoxycarbonyl - [1,4,5] oxadiazepine, followed by decarboxylation in a solution of hydrogen bromide in acetic acid to give the intermediate [1,4,5] -oxadiazole dihydrobromide; 2,6 - diethyl-4-methylaniline Sandmeyer reaction to give 2,6-diethyl-4-methyl-bromobenzene, and malononitrile coupling under cuprous iodide catalysis to give 2,6-di- Ethyl-4-methylphenyl malononitrile, and finally hydrolyzing in a hydrogen peroxide solution to obtain 2,6-diethyl-4-methylphenyl malonamide; under the action of triethylamine, Reaction of 6-di-ethyl-4-methylphenyl malononitrile with [1,4,5] -oxadiazepine dihydrobromide gave 8- (2,6-diethyl-4 -methylbenzene) tetrahydropyrazol [1,2d] [1,4,5] -oxadiazol-7,9-dione catalyzed by 4-dimethylaminopyridine with neopentyl The acid chloride is reacted to give the target product pinoxaden. [Result] The product structure was consistent with that of pinoxatilide by 1H NMR. [Conclusion] The process is simple and economical, mild conditions, suitable for industrial production.