반응 #64053

반응 방정식

Diethyl malonate

sodium

1-(3-acetyl-2,4,6-trimethylphenyl)but-1-en-3-one

sodium hydroxide

→

5-(3-acetyl-2,4,6-trimethylphenyl)-3-hydroxycyclohex-2-en-1-one

수율 84.0%

용매

water

ethanol

ethanol

반응 조건

후처리

1. 1
   온도the mixture was heated
2. 2
   온도to reflux temperature
3. 3
   workup.ADDITIONwas added over a period of 2 minutes
4. 4
   온도the mixture was heated
5. 5
   온도under reflux for a period of 2 hours
6. 6
   온도the mixture was heated
7. 7
   온도under reflux for a further 41/2 hours
8. 8
   세척the aqueous mixture was washed with diethyl ether (2×100 ml)
9. 9
   온도warmed gently until the evolution of carbon dioxide
10. 10
    추출The aqueous mixture was extracted with ethyl acetate
11. 11
    건조dried over anhydrous sodium sulfate
12. 12
    기타the solvent was removed by evaporation under reduced pressure

실험 절차

Diethyl malonate (10.16 g; 69 mmole) was added to a solution of sodium metal (1.46 g; 63 mmole) in anhydrous absolute ethanol (50 ml) and the mixture was heated to reflux temperature. A mixture of 1-(3-acetyl-2,4,6-trimethylphenyl)but-1-en-3-one (14.60 g; 63 mmole) in anhydrous absolute ethanol (50 ml) was added over a period of 2 minutes and the mixture was heated under reflux for a period of 2 hours. A 30% aqueous solution of sodium hydroxide (100 ml) was added and the mixture was heated under reflux for a further 41/2 hours. The solution was poured into water (200 ml) and the aqueous mixture was washed with diethyl ether (2×100 ml). The aqueous phase was acidified with concentrated hydrochloric acid and warmed gently until the evolution of carbon dioxide ceased. The aqueous mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under reduced pressure. The product, 5-(3-acetyl-2,4,6-trimethylphenyl)-3-hydroxycyclohex-2-en-1-one (13.55 g; 84.0%), was obtained as a glassy solid. Proton magnetic resonance spectrum (D6 -dimethylsulfoxide; δ in ppm): 2.20 (3H, s); 2.24 (3H, s); 2.38 (3H, s); 2.45 (3H, s); 2.45-3.40 (4H, m); 3.90 (1H, m); 5.25 (1H, s); 6.85 (1H, s); 11.0 (1h, br.s).

출처