摘要
以2-香豆冉酮为原料、甲酸甲酯/NaH为甲酰化试剂、对甲苯磺酸甲酯为甲基化试剂,通过“一锅”反应得到3-甲氧甲烯基-2-香豆冉酮,进一步以N-羟基丁二酰亚胺(NHSI)为催化剂,3-甲氧甲烯基-2-香豆冉酮在甲醇中与4,6-二氯嘧啶反应得到嘧菌酯中间体2-[2-(6-氯嘧啶-4-基氧基)苯基]-3,3-二甲氧基丙酸甲酯。考察了碱、催化剂用量、反应温度等对产率的影响,优选的最佳反应条件为:反应温度为60℃、反应时间为6 h、n(甲氧甲烯基香豆冉酮)∶n(二氯嘧啶)∶n(碳酸钾)∶n(NHSI)=1∶1∶1.2∶0.2,此时产率为84.5%。相比传统方法,该方法无需低温、无需使用甲醇钠、反应时间较短。初步放大实验中,反应扩大10倍后仍具有较高的产率。
3-Methoxymethyl-2-coumarinone is obtained through a one-pot version by using 2-coumarinone as feedstock,methyl formate/NaH as formylating agent,and methyl p-toluene sulfonate as methylating agent.Then,a reaction between 3-methoxymethyl-2-coumarinone and 4,6-dichloroquine in methanol is catalyzed over N-hydroxybutyl succinimide(NHSI)to prepare methyl 2-(2-((6-chloropyrimidin-4-yl)oxy)phenyl)-3,3-dimethoxypropanoate that is the key intermediate of azoxystrobin.The influences of alkali dosage,catalyst dosage and reaction temperature on the yield are investigated.The optimal reaction conditions are obtained below:the reaction has been carried out at 60℃for 6 h with n(3-methoxymethyl-2-coumarinone)∶n(4,6-dichloroquine)∶n(K;CO;)∶n(NHSI)=1∶1∶1.2∶0.2.Under the optimal conditions,the yield is 84.5%.Comparing with traditional method,this method has the advantages such as the needless of low temperature and sodium methoxide,and a shorter reaction time.A preliminary scale-up experiment is conducted for this method,and the yield is still high after the reaction scale is expanded by 10 times.
作者
蒋达洪
范芳
黄林伟
王煦
张志华
JIANG Da-hong;FAN Fang;HUANG Lin-wei;WANG Xu;ZHANG Zhi-hua(Faculty of Chemistry,Guangdong University of Petrochemical Technology,Maoming 525000,China;Faculty of Biology and Food Engineering,Guangdong University of Petrochemical Technology,Maoming 525000,China;Faculty of Chemical Engineering,Guangdong University of Petrochemical Technology,Maoming 525000,China)
出处
《现代化工》
CAS
CSCD
北大核心
2022年第6期183-186,共4页
Modern Chemical Industry
基金
广东省教育科学规划课题+校企共享分析测试平台协同培养应用型人才机制研究(2017GXJK115)。
关键词
嘧菌酯中间体
N-羟基丁二酰亚胺
活性酯催化
杀菌剂
合成工艺
intermediate of azoxystrobin
N-hydroxybutyl succinimide
active ester catalysis
bactericide
synthetic process
