除草剂氟吡草酮关键中间体的改进合成  

Improved synthesis of key intermediate of herbicide bicyclopyrone

作　　者：刘长春[1] 周鑫鑫[1] 窦佳沪 LIU Changchun;ZHOU Xinxin;DOU Jiahu(School of Pharmaceutical Engineering,Jiangsu Food and Pharmaceutical Science College,Huai'an 223003,Jiangsu,China)

机构地区：[1]江苏食品药品职业技术学院制药工程学院,江苏淮安223003

出　　处：《农药》2024年第9期643-647,共5页Agrochemicals

摘　　要：[目的]改进除草剂氟吡草酮关键中间体2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)吡啶-3-甲酸的合成方法。[方法]从多个廉价易得的原料出发,通过醚化、多组分串联反应和水解反应合成2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)吡啶-3-甲酸,优化醚化和串联反应条件。[结果]氯乙腈和乙二醇单甲醚发生醚化反应得到2-(2-甲氧基乙氧基)乙腈,收率91%;接着与2-溴乙酸乙酯、多聚甲醛、1,1,1-三氟丙酮发生多组分串联反应“一锅”合成2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)吡啶-3-甲酸乙酯,收率82%;然后水解得到2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)吡啶-3-甲酸,收率93%;产物结构用^(1)H NMR和^(13)C NMR确证。[结论]该方法操作简单、后处理简便、收率高,适合工业化生产。[Aims]To improve the synthetic method of 2-((2-methoxyethoxy)methyl)-6-(trifluoromethyl)pyridine-3-carboxylic acid,a key intermediate for the synthesis of herbicide bicyclopyrone.[Methods]2-((2-Methoxyethoxy)methyl)-6-(trifluoromethyl)pyridine-3-carboxylic acid was synthesized from several cheap and easily available raw materials by etherification,multicomponent tandem reactions and hydrolysis.The conditions of etherification and tandem reaction were optimized.[Results]2-(2-Methoxyethoxy)acetonitrile was obtained with a yield of 91%by etherification reaction of chloroacetonitrile with 2-methoxyethanol.Ethyl 2-((2-methoxyethoxy)methyl)-6-(trifluoromethyl)pyridine-3-carboxylate in 82%yield was synthesized by one-pot tandem reaction of etherification product with ethyl 2-bromoacetate,paraformaldehyde and 1,1,1-trifluoroacetone.Hydrolysis of tandem reaction product was processed to give 2-((2-methoxyethoxy)methyl)-6-(trifluoromethyl)pyridine-3-carboxylic acid with a yield of 93%.The structures of the target compounds were confirmed by^(1)H NMR and^(13)C NMR.[Conclusions]This method has simple operation,easy post-treatment and high yield,which is suitable for industrial production.

关 键 词：氟吡草酮 除草剂 串联反应 醚化 中间体 

分 类 号：TQ457[化学工程—农药化工]