Benzoyl Peroxide → HCID 22875686, compound

HRID 963170Notes

Reaction equation

HRID 963170 reaction equation
[C:1]([O:4][CH:5]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:33])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2].[OH:34]N1C(=O)C2=CC=CC=C2C1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(C(C)=O)C>[C:1]([O:4][CH:5]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C:7](=[CH:8][C:9](=[O:34])[C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:33])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([O:17][Si:18]([C:21]([CH3:22])([CH3:23])[CH3:24])([CH3:20])[CH3:19])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 10665N-HydroxyphthalimideHCID 54232237HCID 54232237, compound2×

Product 1

HCID 22875686HCID 22875686, compound

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent

Procedure

To a solution of 3-acetoxy-20-tert-butyldimethylsilyloxy-pregn-5-ene (337 gm, 0.71 mol, product of Step 2) in methyl ethyl ketone (4 L) was added N-hydroxyphthalimide (115.8 gm, 0.71 mol) and dibenzoyl peroxide (1.1 gm, 4.4 mmol). Air was bubbled through the reaction as the reaction was refluxed for 7.5 hr. Additional N-hydroxyphthalimide (9 gm) and dibenzoyl peroxide (0.1 gm) were added and reflux continued for 5 hr. The solvent was removed by rotoevaporation and methylene chloride (0.7 L) was added and warmned to 40° C. Upon cooling to room temperature, the suspension was filtered and the filtrate washed with methylene chloride (0.2 L). The filtrate was rotoevaporated and treated with pyridine (1.35 L) and acetic anhydride (135 mL). After stirring overnight, the solvent was removed by rotoevaporation and the dark orange oil dissolved in methanol (0.6 L). The mixture was heated to 50° C. and then cooled to room temperature. The solution was allowed to stand for 3 days and then cooled in an ice bath. The precipitate was filtered, washed with methanol, and dried to yield the title compound. The filtrate was rotoevaporated to a dry gum to yield the crude product.

Workup

  1. customAir was bubbled through the reaction as the reaction
  2. temperaturewas refluxed for 7.5 hr
  3. additionAdditional N-hydroxyphthalimide (9 gm) and dibenzoyl peroxide (0.1 gm) were added
  4. temperaturereflux
  5. customThe solvent was removed by rotoevaporation and methylene chloride (0.7 L)
  6. additionwas added
  7. customwarmned to 40° C
  8. filtrationthe suspension was filtered
  9. washthe filtrate washed with methylene chloride (0.2 L)
  10. additiontreated with pyridine (1.35 L) and acetic anhydride (135 mL)
  11. customthe solvent was removed by rotoevaporation
  12. dissolutionthe dark orange oil dissolved in methanol (0.6 L)
  13. temperatureThe mixture was heated to 50° C.
  14. temperaturecooled to room temperature
  15. waitto stand for 3 days
  16. temperaturecooled in an ice bath
  17. filtrationThe precipitate was filtered
  18. washwashed with methanol
  19. customdried

Sources & evidence

ORD record
ord-d33056da75af444592d15f8843f100f9
Source dataset
uspto-grants-1998_06
Patent number
US05763361

Reaction notes

Loading…