2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 21-Acetoxy-6alpha-chloro-11beta-hydroxy-16alpha-methyl-1,4-pregnadiene-3,20-dione

HRID 1577859Notes

Reaction equation

HRID 1577859 reaction equation
[C:1]([O:4][CH2:5][C:6](=[O:30])[C@@H:7]1[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C@H:21]([C@@H:22]([OH:26])[CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:27])[CH2:17][CH2:18]2)[C@@H:13]([Cl:28])[CH2:12]3)[CH2:9][C@H:8]1[CH3:29])(=[O:3])[CH3:2].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[C:1]([O:4][CH2:5][C:6](=[O:30])[C@@H:7]1[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C@H:21]([C@@H:22]([OH:26])[CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:27])[CH:17]=[CH:18]2)[C@@H:13]([Cl:28])[CH2:12]3)[CH2:9][C@H:8]1[CH3:29])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 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 7051826521-Acetoxy-6alpha-chloro-11beta-hydroxy-16alpha-methyl-1,4-pregnadiene-3,20-dioneYield 54.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

2.0 g of 21-acetoxy-6α-chloro-11β-hydroxy-16α-methyl-4-pregnene-3,20-dione is dissolved in 100 ml of dioxane; 3 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is added thereto and the mixture heated for 24 hours to boiling. After cooling, the mixture is vacuum-filtered from the undissolved matter, washed with dichloromethane, and concentrated under vacuum. The crude product is chromatographed on silica gel. With 37-46% acetone-hexane, after recrystallization from acetone-diisopropyl ether, 1.08 g of 21-acetoxy-6α-chloro-11βhydroxy-16α-methyl-1,4-pregnadiene-3,20-dione is obtained, m.p. 208.5° C. [α]D25 =+90° (chloroform). UV: ε243 =15,700 (methanol).

Workup

  1. temperaturethe mixture heated for 24 hours
  2. temperatureAfter cooling
  3. filtrationthe mixture is vacuum-filtered from the undissolved matter
  4. washwashed with dichloromethane
  5. concentrationconcentrated under vacuum
  6. customThe crude product is chromatographed on silica gel
  7. customWith 37-46% acetone-hexane, after recrystallization from acetone-diisopropyl ether

Sources & evidence

ORD record
ord-890afe1c3c7e428c8bd2494be27401d8
Source dataset
uspto-grants-1981_09
Patent number
US04289763

Reaction notes

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