有机合成课件1.pptxVIP

? （三）.烯胺的烃化反应 1963年, G. Stork使用醛和叔丁基胺形成烯胺 sichiff碱 p-TsOH, 甲苯带水(Dean and Stark apparatus), 或用无水K2CO3 除水 ;;;优点(1)不需要碱或其他催化剂,减少羰基的自身缩合 (2)可以制备单烷基化产物 (3)对于不对称的酮,取代发生在取代基较少的位置 ;;;6-甲氧基-1-甲基-2-四氢萘酮的制备： 1.烯胺的制备 N2，17.6g(0.1mol) 6-甲氧基-2-四氢萘酮 10.6g(0.15mol) 四氢吡咯（除水） 300mL 苯, 回流分水（约2mL） 减压蒸去溶剂，用正己烷重结晶得无色晶体（空气中存放1-2天）。;6-甲氧基-1-甲基-2-四氢萘酮的制备： 2.烯胺的反应 N2，18.6g(0.08mol) 2-四氢吡咯基-1,3-二氢-6-甲氧基萘 30mL CH3I 75mL 1，4- 二噁烷（除水）, 回流18h 加35mL水和1.5mL乙酸，回流5h. 减压蒸去溶剂，加200mL水，乙醚萃取，干燥，蒸去溶剂，减压蒸出6-甲氧基-1-甲基-2-四氢萘酮（113-115oC）。(81%);? ;酰基化:可在碳上酰基化,并用于增长碳链 ;合成昆虫激素的中间体-ω-乙酰基己酸 ? ;三、麦克尔Michael 反应 (一)概述 碱性条件,活泼亚甲基化合物与a, b-不饱和羰基化合物发生1,4-加成反应 ;2. 亲核试剂：活泼甲基和亚甲基化合物 乙酰乙酸乙酯 丙二酸酯 乙酰丙酮 b-酮酸酯 醛 酮 腈 硝基化合物 ;;（二）应用 ;;2．Robinson环化 ;A. 2-Methyl-2-(3-oxobutyl)-1,3-cyclopentanedione. A 1.0-L, three-necked, round-bottomed flask equipped with a condenser, magnetic stirring bar, and thermometer is charged with 112.1 g (1.0 mol) of 2-methyl-1,3-cyclopentanedione 230 mL of deionized water, 3.0 mL of glacial acetic acid, and 140 mL (120.96 g, 1.72 mol) of methyl vinyl ketone. The system is shielded from light with aluminum foil and placed under a slight positive pressure of nitrogen. The flask is placed in an oil bath and the temperature is raised to 70°C. The reaction is monitored by gas chromatography (GLC) until complete (1–2 hr). ;The mixture is cooled, transferred to a separatory funnel, and extracted with 500 mL and then two 100-ml portions of dichloromethane. The combined extracts are washed with 500 and 100 mL of saturated brine. The combined brine wash is extracted with a further two 100-mL portions of dichloromethane. The total dichloromethane extract is dried over sodium sulfate and filtered. The solvent is removed on a rotary evaporator at 45°C (70 mm). Drying on the rotary evaporator at 40–45°C (0.03 mm) for 16 hr gives 181.8 g (100%) of the desired triketone as an orange oil .;B. ( + )-(3aS,7aS)-2,3,3a,4,7,7a-Hexahydro-3a-hydroxy-7a-methyl-1 H-indene-1,5(6H)-dione. A 500-mL, three-ne