Water → HCID 67557649, compound

HRID 1415853Notes

Reaction equation

HRID 1415853 reaction equation
[C:1]([O:4][CH:5]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:21]2[CH2:20][CH2:19][C@@:18]2([CH3:26])[C@H:11]3[CH2:12][CH:13]=[C:14]2[C:15](=[O:17])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2].C[Al](C)C.O.O1CCO[CH2:34][CH2:33]1>CCCCCC.[Cu]Br>[C:1]([O:4][CH:5]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:21]2[CH2:20][CH2:19][C@@:18]2([CH3:26])[C@H:11]3[CH2:12][C@@H:13]([CH2:33][CH3:34])[C@@H:14]2[C:15](=[O:17])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 962WaterHCID 312751,4-Dioxane2×HCID 109043983-Hydroxypregna-5,16-dien-20-one 3-acetateHCID 16682925Trimethylaluminum

Product 1

HCID 67557649HCID 67557649, compound

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 8058HexaneSolvent

Conditions

Temperature
22 °C

Procedure

3.56 g (10 mmol) of 3-acetoxy-pregna-5,16-dien-20-one is dissolved in 20 ml of dioxane at 20° C. and mixed with 143.3 g (1 mmol) of copper(I) bromide. 11 ml (11 mmol) of a 1 molar solution of trimethyl aluminum in hexane is added to the reaction at room temperature under nitrogen atmosphere and, after completion of the addition, stirred for 3 hours more at 22° C. For hydrolysis of the reaction solution, 1 ml of water dissolved in 5 ml of dioxane is carefully added to the reaction. It is stirred for 10 minutes more and the inorganic precipitate is filtered off with dioxane and washed again. The dioxane solution is concentrated by evaporation on a rotary evaporator and the residue is chromatographed on silica gel with ethyl acetate/hexane as eluent. After concentration by evaporation of the fractions, 1.72 g of 3-acetoxy-16α-ethyl-pregn-5-en-20-one (45% of theory) of a melting point of 114.9° C. is obtained.

Workup

  1. additionafter completion of the addition
  2. additionis carefully added to the reaction
  3. stirringIt is stirred for 10 minutes more
  4. filtrationthe inorganic precipitate is filtered off with dioxane
  5. washwashed again
  6. concentrationThe dioxane solution is concentrated by evaporation on a rotary evaporator
  7. customthe residue is chromatographed on silica gel with ethyl acetate/hexane as eluent
  8. concentrationAfter concentration
  9. customby evaporation of the fractions, 1.72 g of 3-acetoxy-16α-ethyl-pregn-5-en-20-one (45% of theory) of a melting point of 114.9° C.
  10. customis obtained

Sources & evidence

ORD record
ord-8bed8918a56743c38e11d471ec4cb389
Source dataset
uspto-grants-1999_06
Patent number
US05908944

Reaction notes

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