反応 #64051

反応方程式

2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one

dichloromethyl methyl ether

→

2-butyryl-3-hydroxy-5-(3-formyl-2,4,6-trimethylphenyl)cyclohex-2-en-1-one

収率 26.7%

溶媒

dichloroethane

dichloroethane

反応条件

後処理

1. 1
   workup.ADDITIONwas added dropwise over a 25 minute period
2. 2
   workup.ADDITIONAfter the addition
3. 3
   workup.STIRRINGthe mixture was stirred for 5 minutes at 0° C., for 30 minutes at room temperature and for 2 hours
4. 4
   温度under reflux
5. 5
   その他The cooled reaction mixture
6. 6
   workup.ADDITIONwas poured into a separatory funnel
7. 7
   workup.ADDITIONcontaining
8. 8
   その他crushed ice
9. 9
   workup.STIRRINGwas shaken thoroughly
10. 10
    その他The organic layer was separated
11. 11
    抽出the aqueous solution was extracted with methylene chloride
12. 12
    洗浄The combined organic solution was washed with water
13. 13
    乾燥dried over anhydrous sodium sulfate
14. 14
    その他evaporated to dryness
15. 15
    その他to give a crude brown oil (0.70 g)
16. 16
    その他Purification by column chromatography over silica gel (eluant dichloromethane)

実験手順

To a solution of 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (1.20 g) in dichloroethane (20 ml) at 0° C. was added titanium tetrachloride (300 g) over a period of 3 minutes. While the solution was stirred and cooled dichloromethyl methyl ether (0.46 g) in dichloroethane(20 ml) was added dropwise over a 25 minute period. After the addition was complete, the mixture was stirred for 5 minutes at 0° C., for 30 minutes at room temperature and for 2 hours under reflux. The cooled reaction mixture was poured into a separatory funnel containing crushed ice and was shaken thoroughly. The organic layer was separated, and the aqueous solution was extracted with methylene chloride. The combined organic solution was washed with water, dried over anhydrous sodium sulfate and evaporated to dryness to give a crude brown oil (0.70 g). Purification by column chromatography over silica gel (eluant dichloromethane) gave 2-butyryl-3-hydroxy-5-(3-formyl-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (0.35 g) as a pale yellow oil. Proton nuclear magnetic resonance spectrum (CDCl3 ; δ in ppm): 1.0 (3H, t); 1.68 (2H, m); 2.43 (3H, s); 2.48 (3H, s); 2.61 (3H, s); 2.65-4.20 (7H, m); 6.94 (1H, s); 10.54 (1H, s); 18.33 (1H, s).

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