反応 #452439

反応方程式

1-naphthoyl chloride

3,7-dimethyl-1,6-octadien-3-yl acetate

Lithium diisopropylamide

→

desired product

3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate

溶媒

THF

THF

反応条件

後処理

1. 1
   その他fitted with a magnetic stirrer
2. 2
   workup.ADDITIONinternal thermometer, argon inlet, and addition funnel
3. 3
   workup.ADDITIONthe resulting solution added to the flask over 45 min
4. 4
   workup.ADDITIONOnce addition
5. 5
   温度The mixture is warmed to -20° C.
6. 6
   workup.STIRRINGstirred at that temperature for 18 h
7. 7
   温度After warming to 0° C.
8. 8
   その他the mixture is quenched with 20% HCl (53 mL)
9. 9
   workup.ADDITIONThe mixture is poured into a separatory funnel
10. 10
    workup.ADDITIONcontaining ether (150 mL) and water (250 mL)
11. 11
    抽出The aqueous layer is extracted with ether (150 mL)
12. 12
    洗浄The combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL) and brine (150 mL)
13. 13
    乾燥dried over MgSO4
14. 14
    ろ過filtered
15. 15
    その他The solvent is removed by rotary evaporation
16. 16
    その他to give an oil
17. 17
    その他The oil is purified by column chromatography (elution with 2% ethyl acetate/petroleum ether)
18. 18
    その他to yield a colorless oil

実験手順

Lithium diisopropylamide (96.3 mL of a 2.0 M solution, 0.193 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. 3,7-dimethyl-1,6-octadien-3-yl acetate (17.81 g, 0.091 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min. before being treated with a solution of 1-naphthoyl chloride (16.82 g, 0.086 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate/petroleum ether) to yield a colorless oil having 1H and 13C NMR spectra consistent with the desired product.

出典