(E)-2-[2-(6-氯嘧啶-4-基氧基)苯基]-3-甲氧基丙.doc

(E)-2-{2-[6-(2-氰基苯氧基)嘧啶-4-基氧]苯基}-3-甲氧基丙烯酸甲酯 合成工艺试验小结 王一军 （亚邦化工连云港有限公司，连云港，222523） 摘 要：邻氯苯乙酸在0.85Mpa、8-羟基喹啉铜催化下水解自制邻羟基苯乙酸在乙酸成环甲氧甲烯化rocess Experiment on Synthesis of Methyl(E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate WANG Yi-jun (Yabang Chemical Group Co., Ltd(Liangyungang), Liangyungang, 222523, China) Abstract: In 0.65Mpa,2-chlorophenylacetic acid and NaOH prepared 2-hydroxyphenylacetic acid by catalytic hydrolysis of copper 8-quinolinolate.Then benzofuran-2(3H)-one(Ⅰ) was cyclized by dehydration and esterification, (Ⅰ) reacted with CH(OCH3)3 and (CH3CO)2O to form 3-(α-methoxy)methylene-benzofuran- 2(3H)-one(Ⅱ) via methoxymethlenation; (Ⅱ) catalyzed by CH3ONa, interesterification by CH3OH, acidification by CH3COOH to 3，3-dimethoxy-2-(2-hydroxyphenyl)-propanoate(Ⅲ)；(Ⅲ) reactd with 4,6-Dichloropyrimidine and K2CO3 to synthesis（E）-methyl-2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Ⅳ) via ullmann reaction; (Ⅳ)reacted with self-made 2-cyanophenol via ullmann reaction to produce azoxystrobin(amistar). Each step’s operation conditions were optimized and side reactions were restrained. The total yield reached 47.4%. Key words:2-Hydroxyphenylacetic acid; Trimethyl orthoformate; 4,6-Dichloropyrimidine; 2-Hydroxybenzonitrile;Benzofuran-2(3H)-one; Azoxystrobin; Process technology; 1 概 述 (E)-2-{2-[6-(2-氰基苯氧基)嘧啶-4-基氧]苯基}-3-甲氧基丙烯酸甲酯，又称阿米西达、嘧菌酯、恶霜菌酯、安灭达等，英文名称为：(methyl(E)-2-(2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl)-3- methoxy acrylate，简称Azoxystrobin;Amistar;Heritage;Quadris; Abound;Admire。纯品为白色结晶固体，分子式为：C22H17N3O5，分子量：403.4，CAS No：131860-33-8，原药一般为类白色至淡黄色浅棕色固体，无特殊气味，熔点：115-118.5℃，沸点：纯品在360℃左右热分解，密度：1.33-1.34g/cm3 (20℃)，蒸汽压：1.1×10-7Mpa (25℃)，溶解度(20℃,pH5.2, g/L)：水6-10、甲醇20、甲苯55、丙酮86、乙酸乙酯130、二氯甲烷400，水中光解半衰期11-17天，对水解稳定，分配系数(正辛醇/水)440(LogP=2.64)。易溶于乙腈，微溶于正已烷 —————————————————— 收稿日期：2012年月1日; 作者简介：王一军(1969.5-)，男，亚邦化工连云港有限公司，从事氯/碱/氢/酸/硫/光/氨产品、农/医药/染料及中间体研究开发工作。联系方式zjhzwangyijun@163.com (0.057)、正辛醇，与二甲苯混合发生化学反应。大小鼠急