反应 #2348110

反应方程式

triphenyl phosphate

dimethylzinc

acetic anhydride

2-cyclopentadecenone

sulfuric acid

→

3-methycyclopentadecene-1-yl acetate

收率 92.0%

溶剂

toluene

toluene

反应条件

后处理

1. 1
   其他Placed in a 2000-mL flask
2. 2
   其他equipped with a stirrer
3. 3
   workup.STIRRINGby further stirring for 10 min
4. 4
   温度The mixture was then cooled to −17° C.
5. 5
   workup.ADDITIONwas added dropwise to the mixture over the period of 1 hour
6. 6
   workup.ADDITIONAfter completion of the dropwise addition
7. 7
   workup.STIRRINGstirring
8. 8
   workup.WAITwas continued at the same temperature for 6 hours
9. 9
   workup.ADDITIONwas added to the reaction mixture
10. 10
    其他for quenching
11. 11
    其他After separation
12. 12
    洗涤the organic layer was washed with water (5 times)
13. 13
    浓缩the resultant organic layer was concentrated under reduced pressure
14. 14
    其他to give 4.93 g of a crude product
15. 15
    其他The crude product was purified by silica-gel column chromatography

实验过程

Placed in a 2000-mL flask equipped with a stirrer, dropping funnel and thermometer were 54.3 mg (0.15 mmol) of Cu(OTf)2, 25 g of toluene and 93.1 mg (0.30 mmol) of triphenyl phosphate, and the inner atmosphere was replaced with nitrogen. After replacement with nitrogen, the mixture was stirred at 25° C. for 20 min. Then, 9 mL (18 mmol) of a toluene solution (2.0 mmol/L) of dimethylzinc was added to the mixture at 25° C., followed by further stirring for 10 min. The mixture was then cooled to −17° C., followed by addition of 1.68 g (16.5 mmol) of acetic anhydride, and 3.34 g (15 mmol) of 2-cyclopentadecenone was added dropwise to the mixture over the period of 1 hour. After completion of the dropwise addition, stirring was continued at the same temperature for 6 hours. After the reaction was completed, 32.5 g of a 5% aqueous sulfuric acid solution as cooled to 0° C. was added to the reaction mixture for quenching. After separation, the organic layer was washed with water (5 times), and the resultant organic layer was concentrated under reduced pressure to give 4.93 g of a crude product. The crude product was purified by silica-gel column chromatography to produce 3.89 g (13.8 mmol, 92% yield) of dl-3-methycyclopentadecene-1-yl acetate.

来源