Ammonium Chloride → Gestodene

HRID 2413545Notes

Reaction equation

HRID 2413545 reaction equation
C(O[C@@H:10]1[C@H:16]2[C@H:17]3[C@H:26]([CH2:27][CH2:28][C@:13]2([CH2:14][CH3:15])[C:12](=[O:31])[CH2:11]1)[C@@H:25]1[C:20]([CH:21]=[C:22]([O:29]C)[CH2:23][CH2:24]1)=[CH:19][CH2:18]3)(=O)C1C=CC=CC=1.[C-:32]#[C-:33].[Li+].[Li+].[Cl-].[NH4+]>C(OCC)(=O)C>[C:32]([C@:12]1([OH:31])[CH:11]=[CH:10][C@H:16]2[C@H:17]3[C@H:26]([CH2:27][CH2:28][C@:13]12[CH2:14][CH3:15])[C@@H:25]1[C:20](=[CH:21][C:22](=[O:29])[CH2:23][CH2:24]1)[CH2:19][CH2:18]3)#[CH:33]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 70389428HCID 70389428, compoundHCID 178462446HCID 178462446, compound

Product 1

HCID 3033968Gestodene

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

As described in 1(b), 3.6 g of 15α-benzoyloxy-3-methoxy-18-methyl-3,5-estradien-17-one is reacted with lithium acetylide. After completed reaction, the reaction mixture is combined with saturated ammonium chloride solution, diluted with ethyl acetate, washed with water, and dried over sodium sulfate. The resultant 17α-ethynyl-3-methoxy-18-methyl-3,5,15-estratrien-17β-ol is stirred, in the form of the crude product, in 70 ml of methanol and 6 ml of water with 3 g of oxalic acid for 10 minutes under reflux. The reaction mixture is introduced into ice/water. The thus-precipitated product is suctioned off, dissolved in ethyl acetate, washed with water, and dried over sodium sulfate. Recrystallization from acetone/hexane yields 1.9 g of 17α-ethynyl-17β-hydroxy-18-methyl-4,15-estradien-3-one, melting point 197.8° C.

Workup

  1. customreaction
  2. washwashed with water
  3. dry with materialdried over sodium sulfate
  4. temperature6 ml of water with 3 g of oxalic acid for 10 minutes under reflux
  5. additionThe reaction mixture is introduced into ice/water
  6. dissolutiondissolved in ethyl acetate
  7. washwashed with water
  8. dry with materialdried over sodium sulfate
  9. customRecrystallization from acetone/hexane

Sources & evidence

ORD record
ord-d5bd3f21c7e941fcb262ca8c82366841
Source dataset
uspto-grants-1988_01
Patent number
US04719054

Reaction notes

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