Sodium Sulfite → HCID 69216387, compound

HRID 2221831Notes

Reaction equation

HRID 2221831 reaction equation
[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[O:7][C:8]([CH3:36])=[C:9]([CH2:11][O:12][C:13]2[CH:33]=[CH:32][C:16]([CH2:17][O:18][C:19]3[C:23]([CH:24]=O)=[CH:22][N:21]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[N:20]=3)=[CH:15][C:14]=2[O:34][CH3:35])[N:10]=1.[CH3:37][S:38][CH2:39]P(=O)(OCC)OCC.[H-].[Na+].ClC1C=CC=C(C(OO)=[O:58])C=1.S([O-])([O-])=O.[Na+].[Na+]>O1CCCC1.CN(C)C=O>[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[O:7][C:8]([CH3:36])=[C:9]([CH2:11][O:12][C:13]2[CH:33]=[CH:32][C:16]([CH2:17][O:18][C:19]3[C:23](/[CH:24]=[CH:37]/[S:38]([CH3:39])=[O:58])=[CH:22][N:21]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[N:20]=3)=[CH:15][C:14]=2[O:34][CH3:35])[N:10]=1

Participants

8

Reactant 5

HCID 24437Sodium SulfiteHCID 24758Sodium hydrideHCID 70297m-Chloroperbenzoic acidHCID 520377Diethyl methylthiomethylphosphonateHCID 866057753-[(4-{[2-(2-furyl)-5-methyl-1,3-oxazol-4-yl]methoxy}-3-methoxybenzyl)oxy]-1-phenyl-1H-pyrazole-4-carbaldehyde

Product 1

HCID 69216387HCID 69216387, compoundYield 38.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 3-[(4-{[2-(2-furyl)-5-methyl-1,3-oxazol-4-yl]methoxy}-3-methoxybenzyl)oxy]-1-phenyl-1H-pyrazole-4-carbaldehyde (2.0 g), diethyl (methylthio)methylphosphonate (0.89 g) and N,N-dimethylformamide (50 mL) was added sodium hydride (60% in oil, 0.20 g) at room temperature and the mixture was stirred at room temperature for 15 hrs. The reaction mixture was poured into ice water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:2, v/v) to give colorless crystals. To a mixture of the obtained crystal and tetrahydrofuran (50 mL) was added m-chloroperbenzoic acid (0.66 g) at room temperature, and the mixture was stirred at the same temperature for 2 hrs. Saturated sodium sulfite aqueous solution was added to the reaction mixture, and the mixture was stirred at room temperature for 10 min, and extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-methanol (100:1, v/v) to give 2-(2-furyl)-4-({2-methoxy-4-[({4-[(E)-2-(methylsulfinyl)ethenyl]-1-phenyl-1H-pyrazol-3-yl}oxy)methyl]phenoxy}methyl)-5-methyl-1,3-oxazole as colorless crystals (0.81 g, yield 36%). Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 156-157° C.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe organic layer was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated
  5. washeluted with ethyl acetate-hexane (1:2
  6. customv/v) to give colorless crystals
  7. stirringthe mixture was stirred at the same temperature for 2 hrs
  8. stirringthe mixture was stirred at room temperature for 10 min
  9. extractionextracted with ethyl acetate
  10. washThe organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine
  11. dry with materialdried over anhydrous magnesium sulfate
  12. concentrationconcentrated
  13. washeluted with ethyl acetate-methanol (100:1

Sources & evidence

ORD record
ord-95014949fa4d43bebd626d392d718b02
Source dataset
uspto-grants-2008_05
Patent number
US07368578B2

Reaction notes

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