Reaktion #2348110

Reaktionsgleichung

triphenyl phosphate

dimethylzinc

acetic anhydride

2-cyclopentadecenone

sulfuric acid

→

3-methycyclopentadecene-1-yl acetate

Ausbeute 92.0%

Lösungsmittel

toluene

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigePlaced in a 2000-mL flask
2. 2
   Sonstigeequipped with a stirrer
3. 3
   workup.STIRRINGby further stirring for 10 min
4. 4
   TemperaturThe 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
    Sonstigefor quenching
11. 11
    SonstigeAfter separation
12. 12
    Waschenthe organic layer was washed with water (5 times)
13. 13
    Einengenthe resultant organic layer was concentrated under reduced pressure
14. 14
    Sonstigeto give 4.93 g of a crude product
15. 15
    SonstigeThe crude product was purified by silica-gel column chromatography

Vorschrift

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.

Quelle