Potassium sodium tartarate → 17beta-Acetoxy-17alpha-methyl-3-oxoandrost-4-ene-7alpha-carbonitrile

HRID 274312Notes

Reaction equation

HRID 274312 reaction equation
[C:1]([O:4][C@@:5]1([CH3:25])[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:6]12[CH3:7])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH2:17][CH2:18]1)[CH:13]=[CH:12]3)(=[O:3])[CH3:2].[C-:26]#[N:27].C([Al+]CC)C.C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[C:1]([O:4][C@@:5]1([CH3:25])[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:6]12[CH3:7])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH2:17][CH2:18]1)[CH2:13][C@H:12]3[C:26]#[N:27])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 9855836Potassium sodium tartarateHCID 1283221417beta-Acetoxy-17alpha-methylandrosta-4,6-dien-3-oneHCID 16686413Diethyl aluminum cyanide

Product 1

HCID 6778118617beta-Acetoxy-17alpha-methyl-3-oxoandrost-4-ene-7alpha-carbonitrileYield 70.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

At room temperature, 17.1 g of 17β-acetoxy-17α-methylandrosta-4,6-dien-3-one [U.S. Pat. No. 3,033,752 (1962)] in 170 ml of toluene is combined with 100 ml of diethyl aluminum cyanide solution (1 mole in toluene). After 24 hours, the reaction mixture is introduced into a potassium sodium tartrate solution, diluted with ethyl acetate, and the mixture is stirred for 1 hour at room temperature, extracted with ethyl acetate, the organic phase is washed with water, dried, and concentrated under vacuum. The resultant crude product is allowed to react in 500 ml of methanol at room temperature with 360 mg of potassium carbonate, the mixture is concentrated under vacuum after 2.5 hours, diluted with ethyl acetate, washed with water, and dried. After the crude product has been chromatographed on silica gel with a methylene chloride (tert-butyl methyl ether) gradient, 13 g of 17β-acetoxy-17α-methyl-3-oxoandrost-4-ene-7α-carbonitrile is obtained, mp 211°-216° C. (from isopropyl ether).

Workup

  1. customAt room temperature
  2. extractionextracted with ethyl acetate
  3. washthe organic phase is washed with water
  4. customdried
  5. concentrationconcentrated under vacuum
  6. customto react in 500 ml of methanol at room temperature with 360 mg of potassium carbonate
  7. concentrationthe mixture is concentrated under vacuum after 2.5 hours
  8. additiondiluted with ethyl acetate
  9. washwashed with water
  10. customdried
  11. customAfter the crude product has been chromatographed on silica gel with a methylene chloride (tert-butyl methyl ether) gradient

Sources & evidence

ORD record
ord-79d2cf88f12b4039943ec4436ef804db
Source dataset
uspto-grants-1995_02
Patent number
US05389624

Reaction notes

Loading…