Hydrogen Peroxide → 3-Acetoxyestra-1,3,5(10)-trien-17-one-2-carboxylic acid

HRID 1003183Notes

Reaction equation

HRID 1003183 reaction equation
[C:1]([O:4][C:5]1[C:22]([CH:23]=[O:24])=[CH:21][C:20]2[C@@H:19]3[C@H:10]([C@H:11]4[C@@:15]([CH2:17][CH2:18]3)([CH3:16])[C:14](=[O:25])[CH2:13][CH2:12]4)[CH2:9][CH2:8][C:7]=2[CH:6]=1)(=[O:3])[CH3:2].OO.[OH:28]P([O-])(O)=O.[Na+].Cl([O-])=O.[Na+]>C(#N)C.O>[C:1]([O:4][C:5]1[C:22]([C:23]([OH:28])=[O:24])=[CH:21][C:20]2[C@@H:19]3[C@H:10]([C@H:11]4[C@@:15]([CH2:17][CH2:18]3)([CH3:16])[C:14](=[O:25])[CH2:13][CH2:12]4)[CH2:9][CH2:8][C:7]=2[CH:6]=1)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 219678063-Acetoxyestra-1,3,5(10)-trien-17-one-2-carboxaldehydeHCID 23668197Sodium ChloriteHCID 23672064Monosodium phosphate

Product 1

HCID 219678073-Acetoxyestra-1,3,5(10)-trien-17-one-2-carboxylic acidYield 85%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Procedure

To a suspension of 3-acetoxyestra-1,3,5(10)-trien-17-one-2-carboxaldehyde (61, 1.20 g, 3.5 mmol) in acetonitrile (17 mL) and H2O (2.1 mL) were added 30% hydrogen peroxide (0.53 mL) and sodium phosphate monobasic (1.79 g) at room temperature. Sodium chlorite (0.935 g in a H2O (7.0 mL) solution) was added dropwise to the reaction mixture over a 1 h period, and stirring continued for an additional 2 h at room temperature. The reaction mixture was quenched with sodium sulfite, acidified with 10% HCl, and extracted with EtOAc. The combined organic layers were washed with H2O, saturated aqueous NaCl, and then dried (Na2SO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was washed with Et2O to afford 1.06 g of 62 (85% yield) mp: 180-181° C.

Workup

  1. customThe reaction mixture was quenched with sodium sulfite
  2. extractionextracted with EtOAc
  3. washThe combined organic layers were washed with H2O, saturated aqueous NaCl
  4. dry with materialdried (Na2SO4)
  5. filtrationThe desiccant was filtered
  6. customthe solvent was evaporated at reduced pressure
  7. washThe residue was washed with Et2O

Sources & evidence

ORD record
ord-642af89248494250ae66c48382be48c8
Source dataset
uspto-grants-2000_04
Patent number
US06046186

Reaction notes

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