반응 #6497

반응 방정식

lithium cyanide

2-(2-Ethoxycarbonylethyl)-3,4-dihydro-5-methoxy-1(2H)-naphthalenone

Diethyl cyanophosphonate

water

→

title compound

수율 70.1%

1-Cyano-2-(2-ethoxycarbonylethyl)-5-methoxy-3,4-dihydronaphthalene

수율 70.1%

용매

DMF

THF

반응 조건

후처리

1. 1
   추출The aqueous mixture was extracted with three portions of diethyl ether/ethyl acetate
2. 2
   세척The organic extracts were washed with brine
3. 3
   건조dried over anhydrous magnesium sulfate
4. 4
   여과filtered
5. 5
   농축concentrated under reduced pressure
6. 6
   workup.DISSOLUTIONThe residue was dissolved in 100 mL of toluene
7. 7
   workup.ADDITION1.1 g of p-toluenesulfonic acid was added
8. 8
   온도The reaction mixture was heated
9. 9
   온도at reflux for 2 h
10. 10
    온도to cool to ambient temperature
11. 11
    workup.ADDITIONThe toluene solution was poured into 5% aqueous sodium bicarbonate
12. 12
    추출the aqueous mixture was extracted with ethyl acetate
13. 13
    건조The combined organic layers were dried over anhydrous magnesium sulfate
14. 14
    여과filtered
15. 15
    농축concentrated in vacuo
16. 16
    기타The residue was purified by chromatography on silica gel
17. 17
    세척eluted with 10% ethyl acetate in hexane

실험 절차

2-(2-Ethoxycarbonylethyl)-3,4-dihydro-5-methoxy-1(2H)-naphthalenone (1.1 g, 4 mmol), from Step 1, was dissolved in 15 mL of dry THF and cooled to 0° C. Diethyl cyanophosphonate (1.18 mL, 8 mmol), commercially available from Aldrich Chemical Company, was added, followed by 8 mL of a 0.5M solution of lithium cyanide (4 mmol) in DMF. The reaction mixture was stirred at ambient temperature overnight and then poured into water. The aqueous mixture was extracted with three portions of diethyl ether/ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in 100 mL of toluene and 1.1 g of p-toluenesulfonic acid was added. The reaction mixture was heated at reflux for 2 h and allowed to cool to ambient temperature. The toluene solution was poured into 5% aqueous sodium bicarbonate and the aqueous mixture was extracted with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel eluted with 10% ethyl acetate in hexane to give 0.8 g (70% yield) of the title compound; MS DCl--NH3 M/Z: 286 (M+H)+, 303 (M+NH4)+.

출처