摘要
[目的]改进丙硫菌唑合成工艺,降低合成风险,提高合成效率。[方法]以γ-丁内酯为起始原料,经氯化、醇解及环化反应合成1-氯-1-甲酸甲酯环丙烷后,依次通过与邻氯苯乙酸甲酯进行缩合反应得到1-(1-氯环丙基)-2-邻氯苯基乙酮,与硫酸二甲酯发生环氧化反应得到2-(1-氯环丙基)-2-邻氯苄基环氧乙烷,与水合肼发生肼解反应得到1-邻氯苯基-2-(1-氯环丙基)-2-羟基-3-肼基丙烷,与硫氰化钠进行环化反应获得2-[2-(1-氯环丙基)-3-邻氯苄基-2-羟丙基]-1,2,4-三唑烷-3-硫酮,最后经过氧化反应得到丙硫菌唑。[结果]通过改进的合成工艺获得了纯度99%丙硫菌唑原药。[结论]改进的合成工艺有效的避免了合成中带来的危险,并提高了合成收率。
[Aims]This study aims to improve the synthesis process of prothioconazole,reduce the synthesis risk and increase the synthesis efficiency.[Methods]Usingγ-butyrolactone as the startingmaterial,methyl 1-chlorocyclopropane-1-carboxylate was obtained through the process of chlorination and alcoholysis and cyclization ofγ-butyrolactone,followed by the condensation reaction with methyl o-chlorophenylacetate to obtain 1-(1-chlorocyclopropyl)-2-(2-chlorophenyl)ethan-1-one,epoxidation reaction with dimethyl sulfate to obtain 2-(2-chlorobenzyl)-2-(1-chlorocyclopropyl)oxirane,hydrazinolysis reaction with hydrazine hydrate obtain 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-hydrazinylpropan-2-o1,cyclozation reaction with sodium hydrosulfinde to obtain 2-(2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl)-1,2,4-triazolidine-3-thione with thiocyanate,and then through oxidation reaction to obtain prothioconazole.[Results]Prothioconazole was successfully synthesized with 99%purity.[Conclusions]The improved synthesis process effectively avoids the dangers in the synthesis and improves the synthesis yield.
作者
沈运河
熊国银
高全
肖金京
祝玉超
SHEN Yun-he;XIONG Guo-yin;GAO Quan;XIAO Jin-jing;ZHU Yu-chao(Anhui Jiuyi Agrochemical Co.,Ltd.,Hefei 230088,China;School of Plant Protection,Anhui Agricultural University,Hefei 230036,China;Anhui Province Key Laboratory of Integrated Pest Management on Crops,Hefei 230036,China)
出处
《农药》
CAS
CSCD
北大核心
2020年第11期794-796,共3页
Agrochemicals
基金
安徽省科技重大专项(17030701050)。
关键词
三唑硫酮
杀菌剂
丙硫菌唑
trizolethione
fungicide
prothioconazole
