Hydrochloric Acid → 21-Acetoxy-6-chloro-11beta-hydroxy-16alpha-methyl-1,4,6-pregnatriene-3,20-dione

HRID 2049152Notes

Reaction equation

HRID 2049152 reaction equation
Cl.[C:2]([O:5][CH2:6][C:7](=[O:31])[C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([C@@H:23]([OH:27])[CH2:24]2)[C@:20]2([CH3:21])[C:15](=[CH:16][C:17](=[O:28])[CH2:18][CH2:19]2)[C@@H:14]([Cl:29])[CH2:13]3)[CH2:10][C@H:9]1[CH3:30])(=[O:4])[CH3:3].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[C:2]([O:5][CH2:6][C:7](=[O:31])[C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([C@@H:23]([OH:27])[CH2:24]2)[C@:20]2([CH3:21])[C:15](=[CH:16][C:17](=[O:28])[CH:18]=[CH:19]2)[C:14]([Cl:29])=[CH:13]3)[CH2:10][C@H:9]1[CH3:30])(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7052009321-Acetoxy-6alpha-chloro-11beta-hydroxy-16alpha-methyl-4-pregnene-3,20-dione

Product 1

HCID 7058383021-Acetoxy-6-chloro-11beta-hydroxy-16alpha-methyl-1,4,6-pregnatriene-3,20-dione

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A hydrogen chloride stream is introduced into a solution of 1.0 g. of 21-acetoxy-6α-chloro-11β-hydroxy-16α-methyl-4-pregnene-3,20-dione in 100 ml. of dioxane for 30 minutes at 25° after adding 1.5 g. of dichlorodicyanobenzoquinone. The solution is then heated for 15 hours to 120°. After cooling, the solution is filtered, the filter cake washed with dichloromethane, and the filtrate evaporated under vacuum. The residue of the evaporation is chromatographed on silica gel. With 32-40% acetone-hexane, after recrystallization from acetone-diisopropyl ether, 380 mg. of 21-acetoxy-6-chloro-11β-hydroxy-16α-methyl-1,4,6-pregnatriene-3,20-dione is obtained.

Workup

  1. temperatureThe solution is then heated for 15 hours to 120°
  2. temperatureAfter cooling
  3. filtrationthe solution is filtered
  4. washthe filter cake washed with dichloromethane
  5. customthe filtrate evaporated under vacuum
  6. customThe residue of the evaporation
  7. customis chromatographed on silica gel
  8. customWith 32-40% acetone-hexane, after recrystallization from acetone-diisopropyl ether, 380 mg

Sources & evidence

ORD record
ord-08990c1696d24517aa3f524ff9be6906
Source dataset
uspto-grants-1980_04
Patent number
US04196203

Reaction notes

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