1,3-Dibromo-5,5-dimethylhydantoin → Androst-5,7-diene-3beta,17beta-diol diacetate

Temperatur

0 °C

A mixture of androst-5-ene -3β,17β-diol diacetate (3.75 g, 10 mmol), dibromantin (2.03 g, 7 mmol), and sodium bicarbonate (4.54 g, 54 mmol) in hexane (200 ml) is heated under reflux for 0.5 hours. The mixture is then cooled and filtered and the filtrate evaporated to dryness. The residue is dissolved in 50 ml toluene and treated with lithium bromide (2 g) in 5 ml of acetone. The mixture is stirred at 0° C. for 2 hours and then treated with 2 ml triethylamine and 1.5 ml benzenethiol. After stirring at room temperature for 1.5 hours, 100 ml ethyl acetate is added and the organic solution is washed with 1N hydrochloric acid and water. The organic phase is dried and concentrated. The residue is then redissolved in 75 ml ethyl acetate, cooled to 0° C. and treated with 2.6 g of m chloroperbenzoic acid for 2 hours. The mixture is washed with 10% sodium bicarbonate solution and then concentrated. The residue is dissolved in 100 ml toluene, treated with triethylamine (3.6 ml), heated at 70° C. for 24 hours, cooled, and washed with water. The organic solution was concentrated and chromatographed to yield androst-5,7-diene-3β,17β-diol diacetate. The diacetate is treated with K2CO3 in a 10:1 methanol:water solution overnight to yield, after extractive workup, androst-5,7-diene-3β,17β-diol.

1. temperatureis heated
2. temperatureunder reflux for 0.5 hours
3. temperatureThe mixture is then cooled
4. filtrationfiltered
5. customthe filtrate evaporated to dryness
6. dissolutionThe residue is dissolved in 50 ml toluene
7. additiontreated with lithium bromide (2 g) in 5 ml of acetone
8. additiontreated with 2 ml triethylamine and 1.5 ml benzenethiol
9. stirringAfter stirring at room temperature for 1.5 hours
10. addition100 ml ethyl acetate is added
11. washthe organic solution is washed with 1N hydrochloric acid and water
12. customThe organic phase is dried
13. concentrationconcentrated
14. dissolutionThe residue is then redissolved in 75 ml ethyl acetate
15. temperaturecooled to 0° C.
16. additiontreated with 2.6 g of m chloroperbenzoic acid for 2 hours
17. washThe mixture is washed with 10% sodium bicarbonate solution
18. concentrationconcentrated
19. dissolutionThe residue is dissolved in 100 ml toluene
20. additiontreated with triethylamine (3.6 ml)
21. temperatureheated at 70° C. for 24 hours
22. temperaturecooled
23. washwashed with water
24. concentrationThe organic solution was concentrated
25. customchromatographed

ORD-Eintrag

ord-feeecd539265444a92948ac8753c1771

Quelldatensatz

uspto-grants-1990_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US04910226