Sodium Bicarbonate → 6-Hydroximino-4-androstene-3,17-dione

HRID 42134Notes

Reaction equation

HRID 42134 reaction equation
C1CO[C:8]23OCCO[C:3]2([C@:4]2([CH2:27][CH2:26][C@H:25]4[C@@H:15]([CH2:16]/[C:17](=[N:29]\[OH:30])/[C@:18]5(O)[C@:23]4([CH3:24])[CH2:22][CH2:21][CH2:20][CH2:19]5)[C@@H:6]2[CH2:7]3)[CH3:5])[O:2]1.CC1C=CC(S(O)(=O)=[O:39])=CC=1.O.C([O-])(O)=O.[Na+]>CC(C)=O>[OH:30]/[N:29]=[C:17]1\[CH2:16][C@@H:15]2[C@@H:25]([C@:23]3([CH3:24])[C:18]\1=[CH:19][C:20](=[O:39])[CH2:21][CH2:22]3)[CH2:26][CH2:27][C@@:4]1([CH3:5])[C@H:6]2[CH2:7][CH2:8][C:3]1=[O:2]

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 154041431HCID 154041431, compound

Product 1

HCID 111308686-Hydroximino-4-androstene-3,17-dioneYield 67%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent2×

Procedure

A solution of 3,3:17,17-bis(ethylendioxy)-5α-hydroxy-6-(E)-hydroxyimino-androstane (Prepn. 27) (1.05 g) and pTSA H2O (4.00 g) in acetone (100 mL) was stirred at room temperature for 5 h. The solution was neutralized by addition of 5% aqueous NaHCO3 and acetone was evaporated. The aqueous suspension was extracted with CH2Cl2 (3×). The combined organic extracts were washed with H2O, dried over Na2SO4 and evaporated to dryness. The residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 80/10/10) to give the title compound II-bw in 67% yield. 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 11.60 (1H, s), 5.90 (1H, s), 3.36 (1H, d), 2.60-1.15 (16H, m), 1.08 (3H, s), 0.82 (3H, s)

Workup

  1. customwas evaporated
  2. extractionThe aqueous suspension was extracted with CH2Cl2 (3×)
  3. washThe combined organic extracts were washed with H2O
  4. dry with materialdried over Na2SO4
  5. customevaporated to dryness
  6. customThe residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 80/10/10)

Sources & evidence

ORD record
ord-c5f6dbd5ebd84a36bb42d74af68e8ca8
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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