反应 #1869170

反应方程式

2-Methoxyestradiol

Compound 1

2-Methoxyestradiol

Aluminum isopropoxide

cyclohexanone

→

product

收率 78.0%

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

收率 78.0%

溶剂

sodium bicarbonate

反应条件

后处理

1. 1
   其他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
   其他dried under an argon atmosphere
4. 4
   workup.ADDITIONToluene (400 mL) was added
5. 5
   workup.DISSOLUTIONto dissolve the starting material
6. 6
   其他the entire reaction mixture
7. 7
   温度was heated
8. 8
   温度at reflux (145°-150° C.) for 20 h
9. 9
   萃取The organic material was extracted with dichloromethane (3×300 mL)
10. 10
    其他separated
11. 11
    萃取the aqueous layer was extracted with ethyl acetate (2×75 mL)
12. 12
    干燥The combined organic extracts were dried over magnesium sulfate and condensed
13. 13
    其他a rotary evaporator
14. 14
    其他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
    其他2-methoxyestrone (Scheme 1, Compound 4) precipitated out of solution

实验过程

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).

来源