반응 #6496

반응 방정식

lithium cyanide

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

diethyl cyanophosphonate

water

→

title compound

수율 64.2%

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

수율 64.2%

용매

DMF

THF

반응 조건

후처리

1. 1
   추출The aqueous mixture was extracted with three portions of diethyl ether
2. 2
   건조The ether extracts were dried over anhydrous magnesium sulfate
3. 3
   여과filtered
4. 4
   농축concentrated under reduced pressure
5. 5
   workup.DISSOLUTIONThe residue was dissolved in 400 mL of toluene
6. 6
   workup.ADDITION20 g of p-toluenesulfonic acid was added
7. 7
   온도The reaction mixture was heated
8. 8
   온도at reflux for 3 h
9. 9
   온도to cool to ambient temperature
10. 10
    세척The toluene solution was washed with 5% aqueous sodium bicarbonate
11. 11
    건조dried over anhydrous magnesium sulfate
12. 12
    여과filtered
13. 13
    농축concentrated in vacuo
14. 14
    기타The residue was purified by chromatography on silica gel
15. 15
    세척eluted with 10% ethyl acetate in hexane

실험 절차

2-(2-Ethoxycarbonylethyl)-3,4-dihydro-1(2H)-naphthalenone (19.7 g, 80 mmol), from Step 1, was dissolved in 200 mL of dry THF and diethyl cyanophosphonate (23.6 mL, 160 mmol), commercially available from Aldrich Chemical Company, was added, followed by 160 mL of a 0.5M solution of lithium cyanide 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. The ether extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in 400 mL of toluene and 20 g of p-toluenesulfonic acid was added. The reaction mixture was heated at reflux for 3 h and allowed to cool to ambient temperature. The toluene solution was washed with 5% aqueous sodium bicarbonate, 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 13.1 g (64.2% yield) of the title compound; MS DCl--NH3 M/Z: 273 (M+NH4)+.

출처