Sodium Sulfite → HCID 69216387、化合物

HRID 2221831ノート

反応式

HRID 2221831 の反応式
[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

参加物

8

反応物 5

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

生成物 1

HCID 69216387HCID 69216387、化合物収率 38.8%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-95014949fa4d43bebd626d392d718b02
出典データセット
uspto-grants-2008_05
特許番号
US07368578B2

反応ノート

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