Sodium Chloride → 3-(4-Piperidyl)oxyiminoandrostane-6,17-dione hydrochloride

HRID 42073Notes

Reaction equation

HRID 42073 reaction equation
[ClH:1].Cl.[NH:3]1[CH2:8][CH2:7][CH:6]([O:9][NH2:10])[CH2:5][CH2:4]1.[CH3:11][C@:12]12[CH2:29][CH2:28][C@H:27]3[C@@H:17]([CH2:18][C:19](=[O:31])[CH:20]4[C@:25]3([CH3:26])[CH2:24][CH2:23][C:22](=O)[CH2:21]4)[C@@H:16]1[CH2:15][CH2:14][C:13]2=[O:32].[Na+].[Cl-]>O.C1COCC1>[ClH:1].[NH:3]1[CH2:8][CH2:7][CH:6]([O:9][N:10]=[C:22]2[CH2:23][CH2:24][C@@:25]3([CH3:26])[CH:20]([C:19](=[O:31])[CH2:18][C@@H:17]4[C@@H:27]3[CH2:28][CH2:29][C@@:12]3([CH3:11])[C@H:16]4[CH2:15][CH2:14][C:13]3=[O:32])[CH2:21]2)[CH2:5][CH2:4]1

Participants

6

Reactant 3

HCID 5234Sodium ChlorideHCID 103134494-Piperidyloxyamine dihydrochlorideHCID 54071530Androstane-3,6,17-trione

Product 1

HCID 866355523-(4-Piperidyl)oxyiminoandrostane-6,17-dione hydrochloride

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-piperidyloxyamine dihydrochloride (III-a, Prepn. 1, 100 mg) and Na2HPO4.12H2O (380 mg) in water (1.6 mL), a solution of androstane-3,6,17-trione (160 mg) in THF (3.2 mL) was added. After 2 hours at room temperature, NaCl (150 mg) was added and stirred for 15 min. The mixture was extracted with THF (2×2 mL) and the combined organic phases were washed with brine (3×3 mL), dried over Na2SO4 and evaporated to dryness. The residue was purified by flash chromatography (SiO2, CH2Cl2:MeOH:NH3 9:1:0.1). To the concentrated fractions 5M HCl in EtOAc was added. After dilution with Et2O, the solid was collected by filtration to give the title compound I-aa (140 mg, 60%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 8.68 (2H, bb), 4.17 (1H, m), 3.15-2.90 (5H, m), 2.60-1.10 (23H, m), 0.79 (3H, s), 0.78 (3H, s).

Workup

  1. extractionThe mixture was extracted with THF (2×2 mL)
  2. washthe combined organic phases were washed with brine (3×3 mL)
  3. dry with materialdried over Na2SO4
  4. customevaporated to dryness
  5. customThe residue was purified by flash chromatography (SiO2, CH2Cl2:MeOH:NH3 9:1:0.1)
  6. additionTo the concentrated fractions 5M HCl in EtOAc was added
  7. filtrationAfter dilution with Et2O, the solid was collected by filtration

Sources & evidence

ORD record
ord-4d956ff4faa645609799d2c0ad457803
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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