Sodium Chlorite → 3-[4-(Benzenesulfonylmethyl)-3-tert-butoxycarbonyl-2-hydroxyphenyl]-furan-2-carboxylic acid

HRID 1778349Notes

Reaction equation

HRID 1778349 reaction equation
OP([O-])(O)=O.[Na+].[C:7]1([S:13]([CH2:16][C:17]2[C:22]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[C:21]([OH:30])[C:20]([C:31]3[CH:35]=[CH:34][O:33][C:32]=3[CH:36]=[O:37])=[CH:19][CH:18]=2)(=[O:15])=[O:14])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.Cl([O-])=[O:39].[Na+]>O.C(#N)C.OO>[C:7]1([S:13]([CH2:16][C:17]2[CH:18]=[CH:19][C:20]([C:31]3[CH:35]=[CH:34][O:33][C:32]=3[C:36]([OH:39])=[O:37])=[C:21]([OH:30])[C:22]=2[C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])(=[O:15])=[O:14])[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

7

Reactant 3

HCID 23668197Sodium Chlorite2×HCID 23672064Monosodium phosphate2×HCID 86684731Tert-butyl 6-(benzenesulfonylmethyl)-3-(2-formylfuran-3-yl)-2-hydroxybenzoate2×

Product 1

HCID 666926633-[4-(Benzenesulfonylmethyl)-3-tert-butoxycarbonyl-2-hydroxyphenyl]-furan-2-carboxylic acidYield 25.7%

Reagents, catalysts & solvents 3

HCID 784Hydrogen PeroxideSolvent2×HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Procedure

A solution of sodium phosphate monobasic (0.039 g) in water (1 mL) was added to a solution of tert-butyl 6-(benzenesulfonylmethyl)-3-(2-formylfuran-3-yl)-2-hydroxybenzoate (Intermediate 27, 0.105 g) in acetonitrile (2 mL) at 0° C. Hydrogen peroxide (50% wt. in water, 0.078 mL) and sodium chlorite (0.029 g) were added and the reaction mixture was warmed to room temperature and stirred for 18 hours. The mixture was cooled to 0° C. and further sodium phosphate monobasic (0.028 g) in water (0.5 mL), hydrogen peroxide (50% wt. in water, 0.038 mL) and sodium chlorite (0.052 g) were added and the mixture was warmed to room temperature and stirred for 18 hours. The mixture was poured onto sodium sulfite (10% in water) at 0° C., extracted into ethyl acetate, washed with water, dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of methanol and 1% acetic acid in methanol with a gradient of O-100%. The resultant product was triturated in cyclohexane and ethyl acetate and the solid was collected by filtration and dried in vacuo to give 3-[4-(benzenesulfonylmethyl)-3-tert-butoxycarbonyl-2-hydroxy-phenyl]-furan-2-carboxylic acid (0.028 g) as a white solid.

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. temperaturethe mixture was warmed to room temperature
  3. stirringstirred for 18 hours
  4. additionThe mixture was poured onto sodium sulfite (10% in water) at 0° C.
  5. extractionextracted into ethyl acetate
  6. washwashed with water
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customThe filtrate was evaporated to dryness
  10. customthe residue was purified by chromatography on silica
  11. washeluting with a mixture of methanol and 1% acetic acid in methanol with a gradient of O-100%
  12. customThe resultant product was triturated in cyclohexane
  13. filtrationethyl acetate and the solid was collected by filtration
  14. customdried in vacuo

Sources & evidence

ORD record
ord-3a95b30ccf604127ad147b642f99b05a
Source dataset
uspto-grants-2016_02
Patent number
US09266896B2

Reaction notes

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