Perchloric Acid → HCID 13477358, compound

HRID 868170Notes

Reaction equation

HRID 868170 reaction equation
C(O[C@:5]1([C@:25]2(C)[C@H:11]([C@H:12]3[C:22](=C[CH2:24]2)[C@:20]2([CH3:21])[C:15](=[CH:16][C:17](=[O:27])[CH2:18][CH2:19]2)[C@@H:14]([CH3:28])[CH2:13]3)[CH2:10][C@@H:9]1[CH3:29])[C:6](=[O:8])[CH3:7])(=O)C.[Br:30]N1C(=O)CCC1=O.Cl(O)(=O)(=O)=O.[C:43]([O-:46])(=[O:45])[CH3:44].[Na+].S([O-])([O-])=O.[Na+].[Na+].[O:54]1[CH2:59][CH2:58]OCC1>O.CO>[C:43]([O:46][C@:5]1([C@:25]2([CH3:24])[C@H:11]([C@H:12]3[C@:22]([Br:30])([C@@H:59]([OH:54])[CH2:58]2)[C@:20]2([CH3:21])[C:15](=[CH:16][C:17](=[O:27])[CH2:18][CH2:19]2)[C@@H:14]([CH3:28])[CH2:13]3)[CH2:10][C@@H:9]1[CH3:29])[C:6](=[O:8])[CH3:7])(=[O:45])[CH3:44]

Participants

9

Reactant 6

HCID 24247Perchloric AcidHCID 24437Sodium SulfiteHCID 312751,4-DioxaneHCID 67184N-bromobutanimideHCID 517045Sodium AcetateHCID 22840081HCID 22840081, compound

Product 1

HCID 13477358HCID 13477358, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent4×

Conditions

Temperature
20 °C

Procedure

A solution of 0.5 g of 17α-acetoxy-6α,16β-dimethyl-4,9(11)-pregnadiene-3,20-dione in 7.7 ml of dioxane and 0.5 ml of water is combined, after adding 380 mg of N-bromosuccinimide, at 20° C. dropwise with a solution of 0.04 ml of 70% strength perchloric acid in 0.6 ml of water. The mixture is agitated for one hour at an internal temperature of 20° C., cooled down to 15° C., and neutralized dropwise with a solution of 1.6 g of sodium acetate and 1.0 g of sodium sulfite in 9.7 ml of water. In this process, the internal temperature must not rise beyond 23° C. After the addition of 5 ml of methanol, the reaction mixture is stirred for 15 minutes at room temperature and, after adding 20 ml of water, for 3 hours at 0° C. Finally, the precipitate is suctioned off, the residue is washed neutral with water and dried at 70° C. in a vacuum-drying cabinet. The crude product is recrystallized from acetone/hexane, thus isolating 380 mg of 17α-acetoxy-9α-bromo-11β-hydroxy-6α,16β-dimethyl-4-pregnene-3,20-dione, mp 162° C. (decomposition).

Workup

  1. customat 20° C.
  2. temperaturecooled down to 15° C.
  3. customrise beyond 23° C
  4. stirringthe reaction mixture is stirred for 15 minutes at room temperature
  5. waitfor 3 hours at 0° C
  6. washthe residue is washed neutral with water
  7. customdried at 70° C. in a vacuum-drying cabinet
  8. customThe crude product is recrystallized from acetone/hexane

Sources & evidence

ORD record
ord-89e5efcc067d4e348fd8bdfebc1b2426
Source dataset
uspto-grants-1988_10
Patent number
US04777165

Reaction notes

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