反応 #1869170

反応方程式

2-Methoxyestradiol

Compound 1

2-Methoxyestradiol

Aluminum isopropoxide

cyclohexanone

→

product

収率 78.0%

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

収率 78.0%

溶媒

sodium bicarbonate

反応条件

後処理

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

実験手順

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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