Water → 4-Androstene-3,17-dione, 1alpha-methyl-

HRID 1415844Notes

Reaction equation

HRID 1415844 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])[CH:14]=[CH: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@@H:14]1[C@@:15]2([CH3:16])[C:10]([CH2:9][CH2:8][C@@H:7]3[C@@H:17]2[CH2:18][CH2:19][C@@:2]2([CH3:1])[C@H:6]3[CH2:5][CH2:4][C:3]2=[O:21])=[CH:11][C:12](=[O:20])[CH2:13]1

Participants

7

Reactant 3

HCID 962WaterHCID 13472Androsta-1,4-diene-3,17-dioneHCID 16682925Trimethylaluminum

Product 1

HCID 109575614-Androstene-3,17-dione, 1alpha-methyl-

Reagents, catalysts & solvents 3

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

Conditions

Temperature
25 °C

Procedure

14.2 g (50 mmol) of androsta-1,4-diene-3,17-dione is dissolved under nitrogen atmosphere in 100 ml of anhydrous dioxane. 716 mg (5 mmol) of copper(I) bromide is added and the solution is heated to 25° C. Then 47 ml (55 mmol) of a 10% solution of trimethyl aluminum in toluene is added to the reaction so that the temperature does not rise above 35° C. Then it is stirred for 1.5 hours more at 35° C. For the hydrolysis, 2.5 ml of water mixed with 10 ml of dioxane is added to the reaction and the solution is stirred for 15 minutes more. The inorganic solid is suctioned off and washed again with 30 ml of dioxane. After concentration by evaporation of the dioxane solution, 17 g of crude product is obtained, that is chromatographed on silica gel with an hexane/ethyl acetate mixtures as eluent. After concentration by evaporation of the fractions and recrystallization from diisopropyl ether, 11.66 g of 1α-methylandrost-4-ene-3,17-dione (77% of theory) of a melting point of 154° C. is obtained.

Workup

  1. customdoes not rise above 35° C
  2. additionis added to the reaction
  3. stirringthe solution is stirred for 15 minutes more
  4. washwashed again with 30 ml of dioxane
  5. concentrationAfter concentration
  6. customby evaporation of the dioxane solution

Sources & evidence

ORD record
ord-585589e700a243a7a7179d32480ea120
Source dataset
uspto-grants-1999_06
Patent number
US05908944

Reaction notes

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