Ammonia → HCID 22296115, compound

HRID 1077203Notes

Reaction equation

HRID 1077203 reaction equation
[CH2:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C:12]4[CH:13]=[CH:14][C:15]([O:20]C)=[CH:16][C:17]=4[CH2:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C@:4]2([C:26](=[O:28])[CH3:27])OC(=O)C)[CH3:2].[Li].N.CO>O1CCOCC1>[CH2:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@@H:12]4[C:17]([CH2:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C@@H:4]2[C:26](=[O:28])[CH3:27])=[CH:16][C:15](=[O:20])[CH2:14][CH2:13]4)[CH3:2]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 887MethanolHCID 3028194Lithium2×HCID 22790398HCID 22790398, compound

Product 1

HCID 22296115HCID 22296115, compoundYield 36.7%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

Add 13β-ethyl-3-methoxy-17α-acetyl-17β-acetoxy-gona-1,3,5(10)-triene (0.24 g.) in dioxan (5 cc.) to a stirred solution of lithium (0.15 g.) in liquid ammonia (100 cc.). After 30 minutes and methanol (8 cc.) followed by lithium (0.5 g.) in small pieces. Add water, extract with ether and work up to a gum (0.218 g.). Reflux this product with 4N hydrochloric acid (5 cc.) and methanol (8 cc.) for 15 minutes. Add water, extract with ether, work up and dissolve the resulting gum in acetone (30 cc.) containing anhydrous magnesium sulphate (0.5 g.) and add 8N-chromic acid dropwise with swirling until the solution assumes a permanent yellowish-orange color. Add excess isopropanol and evaporate the solution almost to dryness. Add water, extract with ether, wash, dry and evaporate the organic solution, filter the product through alumina with benzene-ether and recrystallize the product from ethyl acetate to obtain the title product (0.072 g.), m.p. 138°-142°; infrared absorption peaks at 5.9, 6 μ.

Workup

  1. extractionAdd water, extract with ether
  2. temperatureReflux this product with 4N hydrochloric acid (5 cc.) and methanol (8 cc.) for 15 minutes
  3. extractionAdd water, extract with ether
  4. dissolutiondissolve the resulting gum in acetone (30 cc.)
  5. additioncontaining anhydrous magnesium sulphate (0.5 g.)
  6. additionadd 8N-chromic acid dropwise
  7. customAdd excess isopropanol and evaporate the solution almost to dryness
  8. extractionAdd water, extract with ether
  9. washwash
  10. customdry
  11. customevaporate the organic solution
  12. filtrationfilter the product through alumina with benzene-ether
  13. customrecrystallize the product from ethyl acetate

Sources & evidence

ORD record
ord-36d2c3db03284cfd9a3e818aaf057cf3
Source dataset
uspto-grants-1976_05
Patent number
US03959322

Reaction notes

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