2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 22875684, compound

HRID 2258011Notes

Reaction equation

HRID 2258011 reaction equation
[CH3:1][C@H:2]1[CH2:21][C@@H:20]2[C@:15]([CH3:23])([CH2:16][CH2:17][C:18](=[O:22])[NH:19]2)[C@@H:14]2[C@@H:3]1[C@H:4]1[C@:11]([CH3:24])([CH2:12][CH2:13]2)[C@@H:7]([C:8](=[O:10])[CH3:9])[CH2:6][CH2:5]1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C[Si](N([Si](C)(C)C)C(=O)C(F)(F)F)(C)C.OS(C(F)(F)F)(=O)=O.C(OC)(=O)CC(C)=O.C(=O)(O)[O-].[Na+].S([O-])([O-])=O.[Na+].[Na+]>O>[CH3:1][C@H:2]1[CH2:21][C@@H:20]2[C@:15]([CH3:23])([CH:16]=[CH:17][C:18](=[O:22])[NH:19]2)[C@@H:14]2[C@@H:3]1[C@H:4]1[C@:11]([CH3:24])([CH2:12][CH2:13]2)[C@@H:7]([C:8](=[O:10])[CH3:9])[CH2:6][CH2:5]1

Participants

9

Reactant 7

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7757Methyl acetoacetateHCID 24437Sodium SulfiteHCID 62406Trifluoromethanesulfonic acidHCID 65279N,N-Bis(trimethylsilyl)trifluoroacetamideHCID 516892Sodium BicarbonateHCID 22875685HCID 22875685, compound

Product 1

HCID 22875684HCID 22875684, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of 7β-methyl-5α-4-azapregnane-3,20-dione (5.5 gm, 16.6 mmol) in dry toulene (100 mL) was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 4.52 gm, 19.92 mmol) followed by bis(trimethylsilyl)trifluoroacetamide (17.6 mL, 66.4 mmol) and triflic acid (0.11 mL, 1.3 mmol). The mixture was stirred under nitrogen for 24 hr at room temperature after which methyl acetoacetate (1.8 mL, 1.66 mmol) was added and stirring continued for 4 hr followed refluxing for 48 hr. The reaction mixture was poured into water (500 mL) containing sodium bicarbonate (8 gm) and sodium sulfite (3 gm). The solution was extracted with methylene chloride (3×250 mL), washed with water, saturated salt solution, and dried over anhydrous sodium sulfate. The solvent was removed by rotoevaporation and the product purified by flash column chromatography on silica gel eluted with 10% isopropanol in hexane as eluent to the title compound (2.47 gm).

Workup

  1. additionwas added
  2. temperaturefollowed refluxing for 48 hr
  3. extractionThe solution was extracted with methylene chloride (3×250 mL)
  4. washwashed with water, saturated salt solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. customThe solvent was removed by rotoevaporation
  7. customthe product purified by flash column chromatography on silica gel
  8. washeluted with 10% isopropanol in hexane as eluent to the title compound (2.47 gm)

Sources & evidence

ORD record
ord-67f676c535794566b48009331c04102d
Source dataset
uspto-grants-1997_08
Patent number
US05658922

Reaction notes

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