e-2-2-6-氯嘧啶-4-基氧基苯基-3-甲氧基丙烯酸甲酯合成工艺试验小结.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 、 8- 羟基喹啉铜催化下水解自制邻羟基苯乙酸在乙酸下催化内酯化成环得苯并呋喃-2(3H)- 酮(Ⅰ) 在醋酐下与原甲酸三甲酯脱醇、加成甲氧甲烯化得 3-( α- 甲氧基)- 甲烯基苯并呋喃-2(3H)- 酮(Ⅱ) 后在甲醇钠催化下与甲醇酯交换、乙酸酸化得 3,3- 二甲氧基-2-(2- 羟基苯基) 丙酸甲酯(Ⅲ); 与4, 6- 二氯嘧啶在碳酸钾下经乌尔门反应得(E) -2-[2-(6- 氯嘧啶-4- 基氧) 苯基]-3- 甲氧基丙烯酸甲酯(Ⅳ); 在碳酸钾下 DMF 为溶剂, 与水杨醛与盐酸羟胺肟化得水杨醛肟, 用乙酸酐脱水和酰化得乙酰水杨腈水解、酸化自制的邻羟基苯甲腈再经催化下乌尔门反应得嘧菌酯。总收率 % ,产品纯度≥ 95% 。关键词: (E)-[2-[6-(2- 氰基苯氧基) 嘧啶-4- 基氧] 苯基]-3- 甲氧基丙烯酸甲酯; 邻羟基苯乙酸; 原甲酸三甲酯; 4, 6- 二氯嘧啶;邻羟基苯甲腈;苯并呋喃-2(3H)- 酮;嘧菌酯;合成工艺; P rocess Experiment on Synthesis ofM ethyl(E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3- m ethoxyacrylate WANG Yi-jun (Yabang Chemical Group Co., Ltd(Liangyungang), Liangyungang, 222523, China) Abstract: In0. 65Mpa,2- c hlorophenylacetic acid and NaOH prepared 2-h ydroxyphenylacetic acid by catalytic hydrolysis of copper 8-quinolinolate . Then benzofuran-2(3H)-one (Ⅰ) was cyclized by dehydration and esterification, (Ⅰ) reacted with CH(OCH 3) 3 and (CH 3 CO) 2O to form 3-( α-methoxy)methylene-benzofuran- 2(3H)-one( Ⅱ) via methoxymethlenation; (Ⅱ) catalyzed by CH 3 ONa, interesterification by CH 3 OH, acidification by CH 3 COOH to3, 3-dimethoxy-2-(2-hydroxyphenyl)-propanoate( Ⅲ);(Ⅲ) reactd with 4,6-Dichloropyrimidine and K 2 CO 3 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 %. Key words: 2 -Hydroxyphenylacetic acid ; Trimethyl orthoformate ; 4,6- D ichloropyrimidine ; 2 -Hydroxybenzonitrile ; Benzofuran-2(3H)-one ; Azoxystrobin; P rocess 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; Aboun