反応 #2348110

反応方程式

triphenyl phosphate

dimethylzinc

acetic anhydride

2-cyclopentadecenone

sulfuric acid

→

3-methycyclopentadecene-1-yl acetate

収率 92.0%

溶媒

toluene

toluene

反応条件

後処理

1. 1
   その他Placed in a 2000-mL flask
2. 2
   その他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
    その他for quenching
11. 11
    その他After separation
12. 12
    洗浄the organic layer was washed with water (5 times)
13. 13
    濃縮the resultant organic layer was concentrated under reduced pressure
14. 14
    その他to give 4.93 g of a crude product
15. 15
    その他The crude product was purified by silica-gel column chromatography

実験手順

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.

出典