Methanol → (17alpha)-17-Hydroxy-3-oxoandrosta-4,9(11)-diene-17-carbonitrile

HRID 1381068Notes

Reaction equation

HRID 1381068 reaction equation
CC(C)(O)[C:3]#[N:4].[C-]#N.[K+].[CH3:10][C@:11]12[CH2:28][CH:27]=[C:26]3[C@@H:16]([CH2:17][CH2:18][C:19]4[C@:24]3([CH3:25])[CH2:23][CH2:22][C:21](=[O:29])[CH:20]=4)[C@@H:15]1[CH2:14][CH2:13][C:12]2=[O:30].CO>O>[C:3]([C@@:12]1([OH:30])[CH2:13][CH2:14][C@H:15]2[C@H:16]3[C:26](=[CH:27][CH2:28][C@:11]12[CH3:10])[C@:24]1([CH3:25])[C:19](=[CH:20][C:21](=[O:29])[CH2:22][CH2:23]1)[CH2:18][CH2:17]3)#[N:4]

Participants

6

Reactant 4

HCID 887MethanolHCID 6406Acetone CyanohydrinHCID 9032Potassium CyanideHCID 2395959-Dehydroandrostenedione

Product 1

HCID 10859900(17alpha)-17-Hydroxy-3-oxoandrosta-4,9(11)-diene-17-carbonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Acetone cyanohydrin (5 ml) and sufficient potassium cyanide to adjust the pH to 9.9 is added to a slurry of androst-4,9(11)-dien-3,17-dione (0,5 g), methanol (40 ml) and water (2.5 g) at 40°. The reaction becomes homogeneous followed by precipitation of the product. After 3.5 hours, water (7.5 ml) is added dropwise and the reaction is allowed slowly to stir at 20°-25° overnight. The slurry is cooled on an ice bath, filtered, the solids washed with methanol/water (1/1) and dried under reduced pressure to give the title compound (4.54 g); [α]D (c=1, CHCl3)=+118°; MS=311, 296 and 284 m/e; NMR (CDCl3)=0.97, 1.37, 2.9, 5.5 and 5.70 δ.

Workup

  1. customThe reaction becomes homogeneous followed by precipitation of the product
  2. additionwater (7.5 ml) is added dropwise
  3. temperatureThe slurry is cooled on an ice bath
  4. filtrationfiltered
  5. washthe solids washed with methanol/water (1/1)
  6. customdried under reduced pressure

Sources & evidence

ORD record
ord-e613c8c1057e4266b83488d7f54fcbb2
Source dataset
uspto-grants-1986_04
Patent number
US04585590

Reaction notes

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