Hydrogen Peroxide → 3-Acetoxy-1,3,5(10),15-estratetraen-17alpha-ol

HRID 328211

Reaction equation

HRID 328211 reaction equation
C1([SeH-](C2C=CC=CC=2)=[Se])C=CC=CC=1.[BH4-].[Na+].[C:17]([O:20][C:21]1[CH:38]=[CH:37][C:36]2[C@@H:35]3[C@H:26]([C@H:27]4[C@@:31]([CH2:33][CH2:34]3)([CH3:32])[C@@H:30]3[O:39][C@@H:29]3[CH2:28]4)[CH2:25][CH2:24][C:23]=2[CH:22]=1)(=[O:19])[CH3:18].OO.C(OC(=O)C)(=O)C>N1C=CC=CC=1.C(O)C>[C:17]([O:20][C:21]1[CH:38]=[CH:37][C:36]2[C@@H:35]3[C@H:26]([C@H:27]4[C@@:31]([CH2:33][CH2:34]3)([CH3:32])[C@H:30]([OH:39])[CH:29]=[CH:28]4)[CH2:25][CH2:24][C:23]=2[CH:22]=1)(=[O:19])[CH3:18]

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 7918Acetic AnhydrideHCID 4311764Sodium borohydrideHCID 227968363-Acetoxy-16alpha,17alpha-epoxy-1,3,5(10)-estratrieneHCID 178528034HCID 178528034, compound

Product 1

HCID 227968353-Acetoxy-1,3,5(10),15-estratetraen-17alpha-ol

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 1049PyridineSolvent

Conditions

Temperature
0 °C

Procedure

1.7 g. of diphenyldiselenide is dissolved in 90 ml. of absolute ethanol and mixed at room temperature with 480 mg. of sodium borohydride. After decolorization of the yellow solution, 2.2 g. of 3-acetoxy-16α,17α-epoxy-1,3,5(10)-estratriene [V. Prelog et al., Helv. 28, 250 (1945)] is added thereto and the mixture heated for 20 hours under reflux. After cooling to 0° C., 5 ml. of 30% H2O2 is added dropwise, and the solution is gradually warmed to 50° C. The product is worked up in accordance with Example 3, and then an after-acetylation is carried out in 5 ml. of pyridine with 2.5 ml. of acetic anhydride. The reaction solution is introduced into ice water. The thusprecipitated product is vacuum-filtered, washed with water, dissolved in methylene chloride, and dried over sodium sulfate. By chromatography of the crude product on silica gel with acetone/hexane, 930 mg. of 3-acetoxy-1,3,5(10),15-estratetraen- 17α-ol is obtained.

Workup

  1. temperaturethe mixture heated for 20 hours
  2. temperatureunder reflux
  3. temperaturethe solution is gradually warmed to 50° C
  4. filtrationThe thusprecipitated product is vacuum-filtered
  5. washwashed with water
  6. dissolutiondissolved in methylene chloride
  7. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-3a53b1c9d5d9446396137f3bc65b4bf9
Source dataset
uspto-grants-1977_04
Patent number
US04016269

Linked notes

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