Acetic Acid → 3alpha-Hydroxy-21-methylene-21-morpholinomethyl-5alpha-pregnane-11,20-dione

HRID 1973738Notes

Reaction equation

HRID 1973738 reaction equation
[OH:1][C@@H:2]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[C@@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:18]2[C:17](=[O:23])[CH2:16][C@@:15]2([CH3:24])[C@H:8]3[CH2:9][CH2:10][C@@H:11]2[C:12](=[O:14])[CH3:13])[CH2:3]1.[CH2:25]=O.[NH:27]1[CH2:32]CO[CH2:29][CH2:28]1.Cl.[C:34]([OH:37])(=O)[CH3:35]>>[OH:1][C@@H:2]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[C@@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:18]2[C:17](=[O:23])[CH2:16][C@@:15]2([CH3:24])[C@H:8]3[CH2:9][CH2:10][C@@H:11]2[C:12](=[O:14])[C:13](=[CH2:25])[CH2:32][N:27]2[CH2:35][CH2:34][O:37][CH2:29][CH2:28]2)[CH2:3]1

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 8083MorpholineHCID 104845Alphaxalone

Product 1

HCID 867342893alpha-Hydroxy-21-methylene-21-morpholinomethyl-5alpha-pregnane-11,20-dione

Procedure

3α-Hydroxy-5α-pregnane-11,20-dione (2 g) was dissolved in glacial acetic acid (50 ml). Paraformaldehyde (1.2 g), morpholine (2 ml) and conc. hydrochloric acid (2 ml) were added and the stirred mixture heated between 105°-110° C for 4 hours. The excess acetic acid was removed in vacuo and the red oil obtained partitioned between 0.1 N hydrochloric acid and ethyl acetate. The aqueous layer was basified with saturated sodium bicarbonate solution and the emulsion formed extracted into ethyl acetate. The organic layer was washed with water, dried (Na2SO4) and evaporated to a yellow foam which was purified by preparative t.l.c. (ethyl acetate) to give title compound (550 mg) as a foam [α]D + 100° (c, 0.11).

Workup

  1. temperaturethe stirred mixture heated between 105°-110° C for 4 hours
  2. customThe excess acetic acid was removed in vacuo
  3. customthe red oil obtained
  4. custompartitioned between 0.1 N hydrochloric acid and ethyl acetate
  5. customthe emulsion formed
  6. extractionextracted into ethyl acetate
  7. washThe organic layer was washed with water
  8. dry with materialdried (Na2SO4)
  9. customevaporated to a yellow foam which
  10. customwas purified by preparative t.l.c

Sources & evidence

ORD record
ord-5315588d3cf24233bb917324a68489ed
Source dataset
uspto-grants-1976_12
Patent number
US03998829

Reaction notes

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