反応 #5521

反応方程式

(+)-1-trityl-6-cyano-4-(di-n-propylamino)-1,2,2a,3,4,5-hexahydrobenz[cd]indole

methylmagnesium bromide

THF

NH4Cl

→

oil

(+) (2aS,4R)-6-acetyl-4-(di-n-propylamino)-1,2,2a,3,4,5-hexahydrobenz[cd]indol

溶媒

diethyl ether

反応条件

後処理

1. 1
   温度The reaction mixture was refluxed for 16 hr
2. 2
   温度The reaction mixture was cooled
3. 3
   抽出The reaction mixture was extracted with ethyl acetate
4. 4
   その他The organic solution was evaporated to an oil
5. 5
   workup.DISSOLUTIONThe oil was dissolved in 25 mL of 5N HCl
6. 6
   workup.ADDITIONwith the addition of excess concentrated NH4OH solution
7. 7
   抽出The basic mixture was extracted twice with ethyl acetate
8. 8
   洗浄The combined organic solution was washed once with saturated NaCl solution
9. 9
   乾燥dried over MgSO4
10. 10
    その他The ethyl acetate solution was evaporated

実験手順

A solution of 2.4 g (4.6 mmol) (+)-1-trityl-6-cyano-4-(di-n-propylamino)-1,2,2a,3,4,5-hexahydrobenz[cd]indole in 100 mL of THF was treated with 25 mL of 2.0M methylmagnesium bromide in diethyl ether. The reaction mixture was refluxed for 16 hr. The reaction mixture was cooled and excess Grignard reagent was decomposed with addition of saturated NH4Cl solution. The reaction mixture was extracted with ethyl acetate. The organic solution was evaporated to an oil. The oil was dissolved in 25 mL of 5N HCl and the solution was stirred at room temperature for 30 min. The acidic solution was made alkaline with the addition of excess concentrated NH4OH solution. The basic mixture was extracted twice with ethyl acetate. The combined organic solution was washed once with saturated NaCl solution and dried over MgSO4. The ethyl acetate solution was evaporated to yield 1.4 g of an oil. Chromatography of this oil over silicia gel with ethyl acetate as eluent gave 1.2 g (87%) of product. Recrystallization from hexanes yielded 840 mg of the product (+) ketone.

出典