HCID 13990933, compound → HCID 13990935, compound

HRID 1658710Notes

Reaction equation

HRID 1658710 reaction equation
[H-].C(O[Al](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+].[F:19][C@H:20]1[CH2:37][C@@:35]2([CH3:36])[C@@H:31]([CH2:32][CH2:33][C:34]2=[O:38])[C@H:30]2[C@H:21]1[C@:22]1([CH3:40])[C:27]([CH2:28][CH2:29]2)=[CH:26][C:25](=[O:39])[CH2:24][CH2:23]1>O1CCCC1>[F:19][C@H:20]1[CH2:37][C@@:35]2([CH3:36])[C@@H:31]([CH2:32][CH2:33][C@@H:34]2[OH:38])[C@H:30]2[C@H:21]1[C@:22]1([CH3:40])[C:27]([CH2:28][CH2:29]2)=[CH:26][C:25](=[O:39])[CH2:24][CH2:23]1

Participants

4

Reactant 2

HCID 13990933HCID 13990933, compoundHCID 16710494Lithium tri-tert-butoxyaluminohydride

Product 1

HCID 13990935HCID 13990935, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 3.0 g. of lithium tri-(tert.-butoxy)-aluminum hydride in 15 ml. of tetrahydrofuran is introduced into 2.0 g. of 11β-fluoro-4-androstene-3,17-dione in 5 ml. of tetrahydrofuran. After 45 minutes, the solution is poured into sulfuric ice water and extracted with methylene chloride. The crude product (1.5 g.) representing a mixture of 11β-fluoro-17β-hydroxy-4-androsten-3-one and 11β-fluoro-4-androstene-3β,17β-diol is stirred for 4 hours at room temperature with 1.8 g. of 2,3-dichloro-4,5-dicyano-1,4-benzoquinone in 50 ml. of dioxane. The solution is diluted with ether, washed repeatedly with 2N sodium hydroxide solution and water, and dried over sodium sulfate. After chromatography on silica gel with acetone/hexane, 1.2 g. of 11β-fluoro-17β-hydroxy-4-androsten-3-one is obtained; m.p. 160°-162°. UV: ε239 = 16,500 (methanol).

Workup

  1. extractionextracted with methylene chloride
  2. additiona mixture of 11β-fluoro-17β-hydroxy-4-androsten-3-one and 11β-fluoro-4-androstene-3β,17β-diol
  3. additionThe solution is diluted with ether
  4. washwashed repeatedly with 2N sodium hydroxide solution and water
  5. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-16725a65a02a4131930a53f2f10543bb
Source dataset
uspto-grants-1976_06
Patent number
US03966713

Reaction notes

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