Hydrogen Peroxide → 5-[5-Methyl-1-(4-methylbenzyl)-1H-pyrazol-3-yl]-3-[4-(phenylsulfinyl)-phenyl]-1,2,4-oxadiazole

HRID 2400592ノート

反応式

HRID 2400592 の反応式
[CH3:1][C:2]1[N:6]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)[N:5]=[C:4]([C:15]2[O:19][N:18]=[C:17]([C:20]3[CH:25]=[CH:24][C:23]([S:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[CH:22][CH:21]=3)[N:16]=2)[CH:3]=1.[OH:33]O.O>C1COCC1.[Cl-].[Cl-].[Cl-].[V+3]>[CH3:1][C:2]1[N:6]([CH2:7][C:8]2[CH:9]=[CH:10][C:11]([CH3:14])=[CH:12][CH:13]=2)[N:5]=[C:4]([C:15]2[O:19][N:18]=[C:17]([C:20]3[CH:25]=[CH:24][C:23]([S:26]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[O:33])=[CH:22][CH:21]=3)[N:16]=2)[CH:3]=1

参加物

6

反応物 3

HCID 784Hydrogen Peroxide2 回HCID 962WaterHCID 595047135-[5-methyl-1-(4-methylbenzyl)-1H-pyrazol-3-yl]-3-[4-(phenylsulfanyl)phenyl]-1,2,4-oxadiazole

生成物 1

HCID 595047045-[5-Methyl-1-(4-methylbenzyl)-1H-pyrazol-3-yl]-3-[4-(phenylsulfinyl)-phenyl]-1,2,4-oxadiazole

試薬・触媒・溶媒 2

HCID 178478626HCID 178478626、化合物触媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a mechanically stirred solution of 5-[5-methyl-1-(4-methylbenzyl)-1H-pyrazol-3-yl]-3-[4-(phenylsulfanyl)phenyl]-1,2,4-oxadiazole (Example 114, 350 mg, 0.798 mmol) in THF (3 mL) was added vanadium trichloride (6 mg, 0.04 mmol) and hydrogen peroxide (30% in water, 82 μL, 0.798 mmol). The reaction mixture was stirred at rt for 5 h, before another 40 μL (0.4 mmol) of the hydrogen peroxide solution were added. Stirring was continued at rt over night. Then water (30 mL) was added, and the mixture was extracted with ethyl acetate (3×30 mL). The combined organic extracts were dried over anhydrous sodium sulfate. After filtration and evaporation of the solvent, the crude product was purified by MPLC (silica, cyclohexane/ethyl acetate 3:1), followed by precipitation using acetonitril/water 3:1 affording a first crop of the title compound (29 mg, 8%). A second crop was obtained from the mother liquor after preparative HPLC (26 mg, 7%): 1H NMR (400 MHz, DMSO-d6) 8.39 (s, 1H), 8.18 (d, 1H), 7.96 (d, 1H), 7.81 (d, 2H), 7.78-7.74 (m, 1H), 7.60-7.50 (m, 3H), 7.18 (d, 2H), 7.12 (d, 2H), 6.94 (s, 1H), 5.44 (s, 2H), 2.32 (s, 3H), 2.28 (s, 3H); ES-MS m/z 455, HPLC RT (Method D) 2.78 min.

後処理

  1. additionwere added
  2. waitwas continued at rt over night
  3. extractionthe mixture was extracted with ethyl acetate (3×30 mL)
  4. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  5. filtrationAfter filtration and evaporation of the solvent
  6. customthe crude product was purified by MPLC (silica, cyclohexane/ethyl acetate 3:1)
  7. customfollowed by precipitation
  8. customA second crop was obtained from the mother liquor after preparative HPLC (26 mg, 7%)
  9. customES-MS m/z 455, HPLC RT (Method D) 2.78 min.

出典と根拠

ORDレコード
ord-ef18a28ec0534a288c8c85083fa42e3c
出典データセット
uspto-grants-2014_08
特許番号
US08796253B2

反応ノート

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