反应详情

A mixture of Testosterone acetate (available from Steraloids Inc, Wilton, N.H. USA) (3.3 g, 10 mmol.), aqueous formaldehyde (1 mL) and thiophenol (0.9 g, 8 mmol ) is stirred in triethanolamine (30 mL) for 10 h under an atmosphere of argon at 110° C. After 4 h. additional aqueous formaldehyde (0.7 mL) and thiophenol (0.5 mg) are added. After cooling, the mixture is poured in brine and extracted with methylene chloride. The organic phase is washed with dilute sodium hydroxide solution and with water, dried and evaporated. The residue is purified by chromatography on "flash" silica gel using mixtures of ethyl acetate and hexane as eluant. The purified residue in acetone (15 mL) is added to Raney nickel (35 g) in acetone (60 mL) which is heated at reflux since 1 h. The reflux is continued for 15 min. The hot organic phase is decanted and the metal is washed with hot acetone. The combined filtrates were concentrated and purified by chromatography on "flash" silica gel using a mixture of ethyl acetate and hexane as eluant. The purified residue is dissolved in methanolic potassium hydroxide solution (50 mL, 3%) and kept at room temperature for 4 h. under an atmosphere of argon. After concentration, the mixture is poured in water and extracted with methylene chloride. The organic phase is washed with brine, dried and evaporated to dryness. The residue, purified by chromatography on "flash" silica gel using a mixture of ethyl acetate and hexane as eluant, is dissolved in acetone (30 mL) and treated at 0° C. with a slight excess of Jones' reagent (8N chromium trioxide)(until a red color). After 15 min., isopropanol (1 mL) is added and the mixture is poured in brine and extracted with ethyl acetate. The organic phase is washed with brine, dried and evaporated to dryness. Purification of the residue by chromatography on "flash" silica gel using a mixture of ethyl acetate and hexane as eluant give pure 4-methyl-4-androsten-3,17-dione.

1. temperatureAfter cooling
2. extractionextracted with methylene chloride
3. washThe organic phase is washed with dilute sodium hydroxide solution and with water
4. customdried
5. customevaporated
6. customThe residue is purified by chromatography on "flash" silica gel using mixtures of ethyl acetate and hexane as eluant
7. additionThe purified residue in acetone (15 mL) is added to Raney nickel (35 g) in acetone (60 mL) which
8. temperatureis heated
9. temperatureat reflux since 1 h
10. customThe hot organic phase is decanted
11. washthe metal is washed with hot acetone
12. concentrationThe combined filtrates were concentrated
13. custompurified by chromatography on "flash" silica gel using
14. additiona mixture of ethyl acetate and hexane as eluant
15. dissolutionThe purified residue is dissolved in methanolic potassium hydroxide solution (50 mL, 3%)
16. waitkept at room temperature for 4 h. under an atmosphere of argon
17. concentrationAfter concentration
18. additionthe mixture is poured in water
19. extractionextracted with methylene chloride
20. washThe organic phase is washed with brine
21. customdried
22. customevaporated to dryness
23. customThe residue, purified by chromatography on "flash" silica gel using
24. additiona mixture of ethyl acetate and hexane as eluant
25. dissolutionis dissolved in acetone (30 mL)
26. additiontreated at 0° C. with a slight excess of Jones' reagent (8N chromium trioxide)(until a red color)
27. waitAfter 15 min.
28. additionisopropanol (1 mL) is added
29. additionthe mixture is poured in brine
30. extractionextracted with ethyl acetate
31. washThe organic phase is washed with brine
32. customdried
33. customevaporated to dryness
34. customPurification of the residue by chromatography on "flash" silica gel using
35. additiona mixture of ethyl acetate and hexane as eluant