Реакция #1869170

Уравнение реакции

2-Methoxyestradiol

Compound 1

2-Methoxyestradiol

Aluminum isopropoxide

cyclohexanone

→

product

Выход 78.0%

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

Выход 78.0%

Растворители

sodium bicarbonate

Условия реакции

Обработка

1. 1
   Другоеthat was equipped with a 25 mL Dean-Stark trap and a reflux condenser
2. 2
   ТемператураThe entire apparatus had been flame
3. 3
   Другоеdried under an argon atmosphere
4. 4
   workup.ADDITIONToluene (400 mL) was added
5. 5
   workup.DISSOLUTIONto dissolve the starting material
6. 6
   Другоеthe entire reaction mixture
7. 7
   Температураwas heated
8. 8
   Температураat reflux (145°-150° C.) for 20 h
9. 9
   ЭкстракцияThe organic material was extracted with dichloromethane (3×300 mL)
10. 10
    Другоеseparated
11. 11
    Экстракцияthe aqueous layer was extracted with ethyl acetate (2×75 mL)
12. 12
    СушкаThe combined organic extracts were dried over magnesium sulfate and condensed
13. 13
    Другоеa rotary evaporator
14. 14
    ДругоеThe cyclohexanone and cyclohexanol were removed by vacuum distillation
15. 15
    ТемператураWhen the distillation pot was cool enough
16. 16
    workup.ADDITIONhexane was added
17. 17
    Другое2-methoxyestrone (Scheme 1, Compound 4) precipitated out of solution

Методика

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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