Acetic Acid → HCID 13578833, compound

HRID 1649332Notes

Reaction equation

HRID 1649332 reaction equation
[CH3:1][C@:2]12[CH2:19][CH:18]=[C: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].C[O-].[Na+].[C:25](O)(=O)C.C=O>C1COCC1.CO.O.C(N(CC)CC)C>[CH2:25]=[C:4]1[CH2:5][C@H:6]2[C@H:7]3[C:17](=[CH:18][CH2:19][C@:2]2([CH3:1])[C:3]1=[O:21])[C@:15]1([CH3:16])[C:10](=[CH:11][C:12](=[O:20])[CH:13]=[CH:14]1)[CH2:9][CH2:8]3

Participants

9

Reactant 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 10265807Androsta-1,4,9(11)-triene-3,17-dioneHCID 10942334Sodium Methoxide

Product 1

HCID 13578833HCID 13578833, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolvent2×HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

Androsta-1,4,9(11)-triene-3,17-dione (I, 0.7 g) in THF (8 ml) and dimethyloxylate (0.44 g) were combined and cooled to 3° in an ice bath. Sodium methoxide in methanol (25%, 0.685 ml) was added dropwise with no temperature rise. TLC after about 1/2 hr showed the reaction was nearly completed. Acetic acid (0.05 ml), triethylamine (0.26 ml) and methanol (1 ml) were added. Formaldehyde (37%, 0.28 ml) was added and the reaction mixture stirred at 20°-25°. TLC, after approximately 11/2 hrs. showed the reaction was complete. The reaction mixture was added to water and extracted with ethyl acetate. The layers were separated, the aqueous layer was extracted with ethyl acetate and combined with the organic extract. The combined organic extract was washed with water and separated from the organic layer. Methylene chloride was added and the mixture dried over sodium sulfate. The mixture was filtered and the filtrate was concentrated under reduced pressure to an oil. Acetone was added and the title compound was obtained upon crystallization.

Workup

  1. temperaturecooled to 3° in an ice bath
  2. custom2 hrs
  3. extractionextracted with ethyl acetate
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate
  6. extractionThe combined organic extract
  7. washwas washed with water
  8. customseparated from the organic layer
  9. additionMethylene chloride was added
  10. dry with materialthe mixture dried over sodium sulfate
  11. filtrationThe mixture was filtered
  12. concentrationthe filtrate was concentrated under reduced pressure to an oil
  13. additionAcetone was added

Sources & evidence

ORD record
ord-3796293c6e984ce8b3d34f63b151cb76
Source dataset
uspto-grants-1983_11
Patent number
US04416821

Reaction notes

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