反应 #77596

反应方程式

sulphuric acid

(3-carboxypropyl)triphenylphosphonium bromide

1-(5-bromo-2-thienyl)ethanone

potassium tert-butoxide

→

Ethyl (E)-5-(Bromo-2-thienyl)-4-hexenoate

溶剂

ethanol

THF

THF

THF

反应条件

后处理

1. 1
   温度cooled to room temperature
2. 2
   workup.STIRRINGthe reaction medium is stirred for 15 hours
3. 3
   萃取After treatment with saturated ammonium chloride solution, extraction with ethyl acetate
4. 4
   其他drying
5. 5
   其他evaporation of the solvents from the organic phase
6. 6
   其他the residue obtained
7. 7
   其他is purified by chromatography on a column of silica
8. 8
   其他An ochre-coloured solid is obtained (m.p.: 62-64° C., m=5.8 g; Y=62%)
9. 9
   温度to reflux
10. 10
    workup.STIRRINGstirred for 2 hours
11. 11
    萃取After treatment with water, the medium is extracted with ethyl acetate
12. 12
    其他dried
13. 13
    浓缩concentrated under reduced pressure
14. 14
    其他The residue obtained
15. 15
    其他is purified by chromatography on a column of silica (eluent: 95 heptane/5 ethyl acetate)
16. 16
    其他to give the pure trans isomer in the form of a yellow oil (m=3.4 g; Y=77%)

实验过程

22.2 g (51.7 mmol) of (3-carboxypropyl)triphenylphosphonium bromide are dried under vacuum for 1 h with heating at 130° C., and then cooled to room temperature and dissolved in 200 mL of anhydrous THF. 11.5 g (102.5 mmol) of potassium tert-butoxide in 100 mL of THF are then added slowly, after which the orange-red mixture is stirred for 15 minutes. A solution of 7 g (34 mmol) of 1-(5-bromo-2-thienyl)ethanone in 100 mL of THF is then added dropwise and the reaction medium is stirred for 15 hours. After treatment with saturated ammonium chloride solution, extraction with ethyl acetate, drying and evaporation of the solvents from the organic phase, the residue obtained is purified by chromatography on a column of silica. An ochre-coloured solid is obtained (m.p.: 62-64° C., m=5.8 g; Y=62%). This product is then dissolved in 100 mL of ethanol and 2 mL of sulphuric acid are then added. The reaction medium is brought to reflux and stirred for 2 hours. After treatment with water, the medium is extracted with ethyl acetate and the organic phases are then combined, dried and concentrated under reduced pressure. The residue obtained is purified by chromatography on a column of silica (eluent: 95 heptane/5 ethyl acetate) to give the pure trans isomer in the form of a yellow oil (m=3.4 g; Y=77%).

来源