Potassium Carbonate → HCID 87726341, compound

HRID 1912656Notes

Reaction equation

HRID 1912656 reaction equation
FC(F)(F)C([NH:5][CH2:6][CH2:7][S:8][C@@H:9]1[CH2:26][CH2:25][C@@:24]2([CH3:27])[CH:11](/[C:12](=[N:29]/[OH:30])/[CH2:13][C@@H:14]3[C@@H:23]2[CH2:22][CH2:21][C@@:19]2([CH3:20])[C@H:15]3[CH2:16][CH2:17][C:18]2=[O:28])[CH2:10]1)=O.[C:33]([O-:36])([O-:35])=O.[K+].[K+].C[OH:40].O>>[C:18]([OH:28])(=[O:40])/[CH:19]=[CH:21]/[C:33]([OH:36])=[O:35].[NH2:5][CH2:6][CH2:7][S:8][C@@H:9]1[CH2:26][CH2:25][C@@:24]2([CH3:27])[CH:11](/[C:12](=[N:29]/[OH:30])/[CH2:13][C@@H:14]3[C@@H:23]2[CH2:22][CH2:21][C@@:19]2([CH3:20])[C@H:15]3[CH2:16][CH2:17][C:18]2=[O:28])[CH2:10]1

Participants

4

Reactant 3

HCID 11430Potassium CarbonateHCID 22242641Methanol--water (1/1)HCID 87709962HCID 87709962, compound

Product 1

HCID 87726341HCID 87726341, compound

Procedure

To a stirred solution of 3α-(2-trifluoroacetamidoethylthio)-6-(E)-hydroxyiminoandrostan-17-one (Prepn. 78, 115 mg) in MeOH/H2O 95/5 (7 mL), K2CO3 (159 mg) was added. The mixture was refluxed for 1.5 hrs and then concentrated, washed with water, extracted with CH2Cl2 and dried with Na2SO4. Fumaric acid (27 mg) was added and the resulting solution evaporated to dryness. The residue was purified by flash chromatography (SiO2, CH2Cl2/MeOH/NH3 9/1/0.1). To the concentrated fractions a stoichiometric amount of fumaric acid in MeOH was added. The solution was concentrated and the resulting mixture centrifugated. The solid was washed with Et2O/EtOH 9/1 (0.8 mL) to give, after centrifugation, the title compound I-dv (53 mg, 50%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 10.45 (1H, s), 8.10 (3H, m), 6.35 (2H, s), 3.29 (1H, dd), 3.22 (1H, m), 2.86 (2H, t), 2.67 (1H, m), 2.60 (2H, t), 2.50-0.80 (20H, m), 0.76 (3H, s), 0.67 (3H, s).

Workup

  1. temperatureThe mixture was refluxed for 1.5 hrs
  2. concentrationconcentrated
  3. washwashed with water
  4. extractionextracted with CH2Cl2
  5. dry with materialdried with Na2SO4
  6. additionFumaric acid (27 mg) was added
  7. customthe resulting solution evaporated to dryness
  8. customThe residue was purified by flash chromatography (SiO2, CH2Cl2/MeOH/NH3 9/1/0.1)
  9. additionTo the concentrated fractions a stoichiometric amount of fumaric acid in MeOH was added
  10. concentrationThe solution was concentrated
  11. washThe solid was washed with Et2O/EtOH 9/1 (0.8 mL)
  12. customto give

Sources & evidence

ORD record
ord-450c6d9149dd4a549bf7023b29e5b89d
Source dataset
uspto-grants-2013_12
Patent number
US08609644B2

Reaction notes

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