반응 #1869170

반응 방정식

2-Methoxyestradiol

Compound 1

2-Methoxyestradiol

Aluminum isopropoxide

cyclohexanone

→

product

수율 78.0%

2-methoxyestra-1,3,5(10)-trien-17-one

수율 78.0%

용매

sodium bicarbonate

반응 조건

후처리

1. 1
   기타that was equipped with a 25 mL Dean-Stark trap and a reflux condenser
2. 2
   온도The entire apparatus had been flame
3. 3
   기타dried under an argon atmosphere
4. 4
   workup.ADDITIONToluene (400 mL) was added
5. 5
   workup.DISSOLUTIONto dissolve the starting material
6. 6
   기타the entire reaction mixture
7. 7
   온도was heated
8. 8
   온도at reflux (145°-150° C.) for 20 h
9. 9
   추출The organic material was extracted with dichloromethane (3×300 mL)
10. 10
    기타separated
11. 11
    추출the aqueous layer was extracted with ethyl acetate (2×75 mL)
12. 12
    건조The combined organic extracts were dried over magnesium sulfate and condensed
13. 13
    기타a rotary evaporator
14. 14
    기타The cyclohexanone and cyclohexanol were removed by vacuum distillation
15. 15
    온도When the distillation pot was cool enough
16. 16
    workup.ADDITIONhexane was added
17. 17
    기타2-methoxyestrone (Scheme 1, Compound 4) precipitated out of solution

실험 절차

2-Methoxyestradiol (Scheme 1, Compound 1) (10 g, 33.1 mmol) was placed in a 1 L round bottom flask that was equipped with a 25 mL Dean-Stark trap and a reflux condenser. The entire apparatus had been flame dried under an argon atmosphere. Toluene (400 mL) was added to dissolve the starting material. Aluminum isopropoxide (34.6 g, 169 mmol) and cyclohexanone (135 mL, 1.3 mol) were added and the entire reaction mixture was heated at reflux (145°-150° C.) for 20 h. Saturated aqueous sodium bicarbonate solution (200 mL) was added after the reaction mixture was allowed to cool to room temperature. The organic material was extracted with dichloromethane (3×300 mL). The aqueous emulsion was acidified with 3 N HCl (˜20 mL) until the emulsion separated and the aqueous layer was extracted with ethyl acetate (2×75 mL). The combined organic extracts were dried over magnesium sulfate and condensed using a rotary evaporator. The cyclohexanone and cyclohexanol were removed by vacuum distillation. When the distillation pot was cool enough, hexane was added and 2-methoxyestrone (Scheme 1, Compound 4) precipitated out of solution. 7.72 g (25.7 mmol, 78%) of product was obtained. 1H NMR (300 MHz, CDCl3) δ 6.81 (s, 1H), 6.68 (s, 1H), 5.46 (s, 1H), 3.88 (s, 3H), 2.89-2.76 (m,2H), 2.61-1.24 (m, 13H), 0.94 (s, 3H).

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