卤素-镁交换法合成2-三氟甲基丙烯酸  

Synthesis of 2-Trifluoromethylacrylic Acid Via Halogen-Magnesium Exchange Method

作　　者：赵娟[1] 万洪[1] 冯晓军[1] 徐洪涛[1] 吕剑[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《合成化学》2014年第6期820-823,共4页Chinese Journal of Synthetic Chemistry

基　　金：陕西省工业科技攻关项目(2010K07-06)

摘　　要：以2-溴-3,3,3-三氟丙烯(1)为原料,经卤素-镁交换反应制得中间体三氟异丙烯基格氏试剂(2);2分别与CO2,正丁醛,苯甲醛和苯甲酰氯反应合成了2-三氟甲基丙烯酸(3a),2-三氟甲基-1-己烯-3-醇(3b),1-苯基-2-三氟甲基-2-丙烯-1-醇(3c)和1-苯基-4-三氟甲基-4-丁烯-1-酮(3d),其中3d为新化合物,其结构经1H NMR,13C NMR,IR,MS和元素分析表征。考察了交换试剂、物料比、温度和反应时间对3a产率的影响。在最优反应条件[以i-Pr Mg Br/Li Cl为交换试剂,1 50 mmol,n(2-溴丙烷)∶n(1)=1.25∶1.00,于-60℃反应2 h]下,3a收率64.3%。An intermediate,3,3,3-trifluoroisopropenyl Grignard reagent（ 2）,was prepared by the bromine-magnesium exchange reaction of i-Pr Mg Br with 2-bromo-3,3,3-trifluoropropene（ 1）. 2-Trifluoromethylacrylic acid（ 3a）,2-trifluoromethyl-1-hexene-3-ol（ 3b）,1-phenyl-2-trifluoromethyl-2-propylene-1-ol（ 3c） and 1-phenyl-4-trifluoromethyl-4-buten-1-one（ 3d） were synthesized by addition reaction of 2 with CO2,n-butanal,benzaldehyde and benzoyl chloride,respectively. 3d was a novel compound. The structures were characterized by^1 H NMR,^13 C NMR,IR,GC-MS and elemental analysis. Effects of exchange agent,mole ratio,temperature and reaction time on the yield of 3a were investigated. The optimum reaction conditions of 3a at- 60 ℃ for 2 h were as follows： exchange reagent was i-Pr Mg Br / Li Cl,1 was 50 mmol,n（ 2-bromopropane） ∶ n（ 1） = 1. 25 ∶ 1. 00. The yield of 3a was 64. 3% under the optimum reaction conditions.

关 键 词：卤素-镁交换 2-三氟甲基丙烯酸 三氟异丙烯基格氏试剂 合成 

分 类 号：O622.4[理学—有机化学] O622.5[理学—化学]