Acetic Acid → (3beta,17Z)-(1,1,2-trimethylpropyl)(pregna-5,7,17(20)-trien-3-yloxy)dimethylsilane

A mixture of 240.2 g (647 mmol) (ethyl)triphenyl-phosphonium bromide, 72.5 g (647 mmol) potassium t-butoxide, and toluene (1 L) was stirred at room temperature for 1 hr. Then, 185 g (430 mmol) (3β)-3-[[(1,1,2-trimethylpropyl)dimethylsilyl]-oxy]androsta-5,7-dien-17-one was added with the aid of 50 mL of toluene. The temperature was kept below 25° C. by water cooling. After stirring at room temperature overnight, the reaction was quenched with 24.5 mL (430 mmol) of acetic acid. After stirring for 1 hr, the solid was removed by filtration and washed with 600 mL of toluene. The combined filtrate and washes were concentrated. Then 200 mL of methanol was added and the mixture was concentrated again. The residue was dissolved in a mixture of 650 mL methanol, 65 mL water and 650 mL hexane. The methanol/water layer was back-extracted with 325 mL of hexane. The combined hexane layers were concentrated. Then, 200 mL of methanol was added and the mixture was concentrated again. The resulting solid was suspended in 800 mL of methanol containing 8 mL of triethylamine, and the suspension was refluxed for 30 minutes. After cooling in a refrigerator overnight, the precipitate was filtered, washed with 300 mL of cold methanol, and dried by suction for 4 hr. Further drying at 50° C. under high vacuum afforded, 178.1 g (93.7% yield) of (3β,17Z)-(1,1,2-trimethylpropyl)(pregna-5,7,17(20)-trien-3-yloxy)dimethylsilane as a yellow solid: mp 94°-97° C. [α]D -62.8° (c 0.94, ethanol); Anal. Calcd for C29H48OSi: C, 79.02; H, 10.98; Si, 6.37. Found C, 78.74; H, 11.23; Si, 6.50.

1. stirringAfter stirring at room temperature overnight
2. stirringAfter stirring for 1 hr
3. customthe solid was removed by filtration
4. washwashed with 600 mL of toluene
5. concentrationThe combined filtrate and washes were concentrated
6. additionThen 200 mL of methanol was added
7. concentrationthe mixture was concentrated again
8. dissolutionThe residue was dissolved in a mixture of 650 mL methanol, 65 mL water and 650 mL hexane
9. extractionThe methanol/water layer was back-extracted with 325 mL of hexane
10. concentrationThe combined hexane layers were concentrated
11. additionThen, 200 mL of methanol was added
12. concentrationthe mixture was concentrated again
13. temperaturethe suspension was refluxed for 30 minutes
14. temperatureAfter cooling in a refrigerator overnight
15. filtrationthe precipitate was filtered
16. washwashed with 300 mL of cold methanol
17. customdried by suction for 4 hr
18. customFurther drying at 50° C. under high vacuum
19. customafforded

ORD 기록

ord-07f7ba0937864a6c8f70fdb0a3a87e24

출처 데이터셋

uspto-grants-1995_02

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US05393900