反应 #64053

反应方程式

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

收率 84.0%

溶剂

water

ethanol

ethanol

反应条件

后处理

1. 1
   温度the mixture was heated
2. 2
   温度to reflux temperature
3. 3
   workup.ADDITIONwas added over a period of 2 minutes
4. 4
   温度the mixture was heated
5. 5
   温度under reflux for a period of 2 hours
6. 6
   温度the mixture was heated
7. 7
   温度under reflux for a further 41/2 hours
8. 8
   洗涤the aqueous mixture was washed with diethyl ether (2×100 ml)
9. 9
   温度warmed gently until the evolution of carbon dioxide
10. 10
    萃取The aqueous mixture was extracted with ethyl acetate
11. 11
    干燥dried over anhydrous sodium sulfate
12. 12
    其他the solvent was removed by evaporation under reduced pressure

实验过程

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).

来源