Water → HCID 11077519, compound

HRID 1415845Notes

Reaction equation

HRID 1415845 reaction equation
[CH3:1][C@:2]12[CH2:19][CH2:18][C@H:17]3[C@@H:7]([CH2:8][CH2:9][C:10]4[C@:15]3([CH3:16])[CH2:14][CH2:13][C:12](=[O:20])[CH:11]=4)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:21].[CH3:22][Al](C)C.O>O1CCOCC1.C1(C)C=CC=CC=1.[Cu]Br>[CH3:22][C@@:10]12[CH2:11][C:12](=[O:20])[CH2:13][CH2:14][C@:15]1([CH3:16])[C@@H:17]1[C@H:7]([C@H:6]3[C@@:2]([CH2:19][CH2:18]1)([CH3:1])[C:3](=[O:21])[CH2:4][CH2:5]3)[CH2:8][CH2:9]2

Participants

7

Reactant 3

HCID 962WaterHCID 6128AndrostenedioneHCID 16682925Trimethylaluminum

Product 1

HCID 11077519HCID 11077519, compound

Reagents, catalysts & solvents 3

HCID 24593copper(I) bromideCatalystHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
30 °C

Procedure

2.86 g (10 mmol) of androst-4-ene-3,17-dione and 143.3 mg (1 mmol) of copper(I) bromide are dissolved in 20 ml of dry dioxane. 9.4 ml (11 mmol) of a 10% solution of trimethyl aluminum in toluene is added to the reaction for 10 minutes at room temperature under nitrogen atmosphere so that the temperature does not rise above 30° C. Then it is stirred for 2 hours more at 30° C. For hydrolysis, 0.54 ml of water dissolved in 5 ml of dioxane is added to the reaction and stirred for 10 minutes more. The solid is suctioned off on diatomaceous earth and washed again with 20 ml of dioxane. The filtrate is concentrated by evaporation and the crude product (3.0 g) is chromatographed on silica gel with hexane/ethyl acetate as eluent and an increasing part of ethyl acetate. After concentration by evaporation of the fractions, 2.3 g of 5β-methyl-androsta-3,17-dione (76% of theory) of a melting point of 135° C. is obtained.

Workup

  1. customdoes not rise above 30° C
  2. additionis added to the reaction
  3. stirringstirred for 10 minutes more
  4. washwashed again with 20 ml of dioxane
  5. concentrationThe filtrate is concentrated by evaporation
  6. customthe crude product (3.0 g) is chromatographed on silica gel with hexane/ethyl acetate as eluent
  7. concentrationAfter concentration
  8. customby evaporation of the fractions, 2.3 g of 5β-methyl-androsta-3,17-dione (76% of theory) of a melting point of 135° C.
  9. customis obtained

Sources & evidence

ORD record
ord-070352997417474c935af9dc6d3013a7
Source dataset
uspto-grants-1999_06
Patent number
US05908944

Reaction notes

Loading…