Formaldehyde → HCID 13314920, compound

HRID 1649331Notes

Reaction equation

HRID 1649331 reaction equation
[CH3:1][O:2][C:3]1[CH2:20][CH2:19][C@@:18]2([CH3:21])[C:5](=[CH:6][CH2:7][C@@H:8]3[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C:12]2=[O:22])[CH:4]=1.[CH2:23]1COCC1.C[O-].[Na+].C=O>C(OCC)(=O)C.O.CO.C(N(CC)CC)C.C(O)(=O)C>[CH3:1][O:2][C:3]1[CH2:20][CH2:19][C@@:18]2([CH3:21])[C:5](=[CH:6][CH2:7][C@@H:8]3[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][C:11](=[CH2:23])[C:12]2=[O:22])[CH:4]=1

Participants

10

Reactant 4

HCID 712Formaldehyde2×HCID 8028TetrahydrofuranHCID 926873-Methoxyandrosta-3,5-dien-17-oneHCID 10942334Sodium Methoxide

Product 1

HCID 13314920HCID 13314920, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Methoxyandrosta-3,5-diene-17-one (I, 2.0 g) was mixed with THF (22 ml). Diethyloxylate (1.45 ml) was added and the mixture cooled in an ice bath. Sodium methoxide (25%, 1.83 ml) was added dropwise with stirring. The mixture was stirred, and after removing the ice bath for one hour TLC showed the reaction to be complete. The reaction mixture was cooled in an ice bath, acetic acid (0.1 ml) was added, followed by triethylamine (0.7 ml) and methanol (2.8 ml). Formaldehyde (37%, 0.3 g) was added and the mixture stirred for 40 min. Then formaldehyde (37% aqueous, 0.61 g) was added and the mixture stirred at 20°-25° for about 45 minutes. TLC showed the reaction to be done. Water (10 ml) and ethyl acetate (10 ml) were added and the mixture stored at about -20° overnight. The mixture was warmed, the layers are separated, and the organic layer was washed twice with saline. The aqueous layer was extracted with ethyl acetate, the ethyl acetate washed with saline, and the organic extracts combined and dried over sodium sulfate, filtered and concentrated under reduced pressure to give the title compound.

Workup

  1. additionDiethyloxylate (1.45 ml) was added
  2. temperaturethe mixture cooled in an ice bath
  3. stirringThe mixture was stirred
  4. customafter removing the ice bath for one hour TLC
  5. customthe reaction
  6. temperatureThe reaction mixture was cooled in an ice bath
  7. stirringthe mixture stirred for 40 min
  8. stirringthe mixture stirred at 20°-25° for about 45 minutes
  9. customthe reaction
  10. temperatureThe mixture was warmed
  11. customthe layers are separated
  12. washthe organic layer was washed twice with saline
  13. extractionThe aqueous layer was extracted with ethyl acetate
  14. washthe ethyl acetate washed with saline
  15. dry with materialdried over sodium sulfate
  16. filtrationfiltered
  17. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-c4c9eb9d66a54b06984171c41eb000f7
Source dataset
uspto-grants-1983_11
Patent number
US04416821

Reaction notes

Loading…