氯嘧啶基氧基苯基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实验小结王一军（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互换、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映得（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映得嘧菌酯。总收率46.2%，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；ProcessExperimentonSynthesisofMethyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylateWANGYi-jun(YabangChemicalGroupCo.,Ltd(Liangyungang),Liangyungang,222523,China)Abstract:In0.65Mpa,2-chlorophenylaceticacidandNaOHprepared2-hydroxyphenylaceticacidbycatalytichydrolysisofcopper8-quinolinolate.Thenbenzofuran-2(3H)-one(Ⅰ)wascyclizedbydehydrationandesterification,(Ⅰ)reactedwithCH(OCH3)3and(CH3CO)2Otoform3-(α-methoxy)methylene-benzofuran-2(3H)-one(Ⅱ)viamethoxymethlenation;(Ⅱ)catalyzedbyCH3ONa,interesterificationbyCH3OH,acidificationbyCH3COOHto3，3-dimethoxy-2-(2-hydroxyphenyl)-propanoate(Ⅲ)；(Ⅲ)reactdwith4,6-DichloropyrimidineandK2CO3tosynthesis（E）-methyl-2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Ⅳ)viaullmannreaction;(Ⅳ)reactedwithself-made2-cyanophenolviaullmannreactiontoproduceazoxystrobin(amistar).Eachstep’soperationconditionswereoptimizedandsidereactionswererestrained.Thetotalyieldreached47.4%.Keywords:2-Hydroxyphenylaceticacid;Trimethylorthoformate;4,6-Dichloropyrimidine;2-Hydroxybenzonitrile;Benzofuran-2(3H)-one;Azoxystrobin;Processtechnology;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-methoxyacrylate，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，CASNo：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