4,4,4-三氟-2-丁炔酸乙酯.doc

项目实施方案 项目说明： 中文名称：4,4,4-三氟-2-丁炔酸乙酯 英文名称： ethyl 4,4,4-trifluorobut-2-ynoate 结构式： 分子式：?C6H5F3O2 分子量：166.10 Cas: 79424-03-6 合成路线流程图： 三、路线制定说明： 实验方案： （一）、次项目一 （1）、中间体1 1、中间体1说明： 中文名称:溴化乙氧羰基亚甲基三苯基膦 英文名称：(2-ethoxy-2-oxoethyl)triphenylphosphonium bromide 分子式：BrC22H22O2P 结构式： 分子量：429.29 Cas : 1530-45-6 2、实验方案： 反应物 分子量 添加量 摩尔量 当量数 溴乙酸乙酯 167 25 g 0.149 mol 1 三苯基膦 262.29 39.04 g 0.149 mol 1 甲苯 1 L 实验步骤： 方案一： To a solution of triphenylphosphine (39.04 gm, 0.149 moles) in toluene (700 ml), a solution of ethyl-2-bromo acetate (25 g, 0.149 moles, 1 eq in 300 ml toluene) was added and heated at 100 0C for 1 hr. The reaction mixture was then cooled to room temperature and the precipitated Wittig salt was filtered, washed with hexane and dried under high vacuum to give 60 gm of 1 (93.8percent yield) as a white solid. 方案二： [(ETHOXYCARBONYL) METHYLENE] TRIPHENYLPHOSPHORANE (4) 2 (ACL-G29-1) Triphenyl phosphine (235.6 g, 0.90 mol) was dissolved in EtOAc (540 mL). Approximately 30 min was required for all of the solids to dissolve. The process was endothermic (solution cooled to 13 .deg.C when the ambient temperature was 20 .deg.C). A solution of ethyl bromoacetate (100 mL, 0.90 mol) in EtOAc (400 mL) was added dropwise over a 1.5 h period. A white precipitate formed during the addition.Stirred overnight (20 h) at ambient temperature (18 .deg.C). The solids were collected by vacuum filtration rinsing with copious amounts OF ET20. Dried overnight in vacuo at 45 .deg.C to give 3 as a white solid 356.3 G, 92.6percent yield (0.83 MOL). H NMR was consistent with literature values. in ethyl acetate, Time= 21.5h, T= 18 °C （2）、中间体2 1、中间体2说明： 中文名称： 4，4，4-三氟-2-三苯基膦叶立德乙酰乙酸乙酯 英文名称：Ethyl 4,4,4-trifluoro-2- (triphenylphosphoranylidene) acetoacetate ethyl 4,4,4- trifluoro-3-oxo-2- (triphenyl phosphoranylidene) butanoate 分子式：C24H20F3O3P 结构式： 分子量：444.38 Cas : 83961-56-2 2、实验方案： 反应物 分子量 添加量 摩尔量 当量数 溴化乙氧羰基亚甲基三苯基膦 429.29 100 g 0.228 mol 1 三氟乙酸酐 210.03 35.7 mL 0.251 mol 1.1 三乙胺 101.19 64