Carbon Tetrachloride → HCID 22800141, compound

HRID 1439186Notes

Reaction equation

HRID 1439186 reaction equation
[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C@@H:15]([O:21][C:22](=[O:27])[C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:14][CH2:13]4)=[CH:10][CH2:9][C:8]1=[CH:7][C:6](=[O:28])[CH2:5][CH2:4]2.C(Cl)(Cl)(Cl)Cl.ClC1C=CC=C(C(OO)=[O:42])C=1.[OH-].[K+]>C(OCC)(=O)C.C(O)(=O)C>[OH:42][C@:11]12[CH:10]=[CH:9][C:8]3[C@:3]([CH2:2][OH:1])([CH2:4][CH2:5][C:6](=[O:28])[CH:7]=3)[C@H:20]1[CH2:19][CH2:18][C@@:16]1([CH3:17])[C@H:12]2[CH2:13][CH2:14][C@@H:15]1[O:21][C:22](=[O:27])[C:23]([CH3:24])([CH3:26])[CH3:25]

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 14797Potassium HydroxideHCID 70297m-Chloroperbenzoic acid2×HCID 22800129HCID 22800129, compound

Product 1

HCID 22800141HCID 22800141, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 2 g. of 19-hydroxy-17β-pivaloxyandrosta-4,7-dien-3-one in 2000 ml. of carbon tetrachloride was left to stand with 1.5 g. of meta-chloroperbenzoic acid for two and a half days, whereupon an additional 0.5 g. of meta-chloroperbenzoic acid was added. After five days the solution was repeatedly extracted with 2% aqueous potassium hydroxide until the extracts were alkaline. The solution was then extracted with water and evaporated. The residue obtained was treated with 9 ml. of 0.2 N methanolic potassium hydroxide for 30 minutes. Then 9 ml. of 0.2 N acetic acid in ethyl acetate was added and the mixture was concentrated at reduced pressure. Recrystallization of the residue combined with thick layer chromatography yielded 7-hydroxy-8,19-oxido-17β-pivaloxyandrost-4-en-3-one, mp. 211°-212° C. λ max 246 mμ, 8α,19-dihydroxy-17β-pivaloxyandrost-4,6-dien-3-one, mp 202°-203° C., λ max 280 mμ, as well as 8β,19-dihydroxy-17β-pivaloxyandrost-4,6-dien-3-one, mp. 218°-220° C., λ max 282 mμ. The structure of these compounds was confirmed by ir and nmr spectroscopy.

Workup

  1. extractionAfter five days the solution was repeatedly extracted with 2% aqueous potassium hydroxide until the extracts
  2. extractionThe solution was then extracted with water
  3. customevaporated
  4. customThe residue obtained
  5. additionwas treated with 9 ml
  6. concentrationthe mixture was concentrated at reduced pressure
  7. customRecrystallization of the residue

Sources & evidence

ORD record
ord-c7adbe6c43534d0a8380828ed555ef2d
Source dataset
uspto-grants-1977_11
Patent number
US04058539

Reaction notes

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