반응 #5521

반응 방정식

(+)-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

용매

diethyl ether

반응 조건

후처리

1. 1
   온도The reaction mixture was refluxed for 16 hr
2. 2
   온도The reaction mixture was cooled
3. 3
   추출The reaction mixture was extracted with ethyl acetate
4. 4
   기타The 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
   추출The basic mixture was extracted twice with ethyl acetate
8. 8
   세척The combined organic solution was washed once with saturated NaCl solution
9. 9
   건조dried over MgSO4
10. 10
    기타The ethyl acetate solution was evaporated

실험 절차

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.

출처