Ammonium → 3-Methoxy-4-(6-methylpyridazin-4-yl)aniline

HRID 59124

反応式

HRID 59124 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([CH3:14])[N:11]=[N:12][CH:13]=2)=[C:4]([O:15][CH3:16])[CH:3]=1.CC(C)([O-])C.[Na+].C(=[NH:36])(C1C=CC=CC=1)C1C=CC=CC=1.CC([O-])=O.[Na+].[NH4+].C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[CH3:16][O:15][C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][C:5]=1[C:8]1[CH:9]=[C:10]([CH3:14])[N:11]=[N:12][CH:13]=1)[NH2:36]

参加物

10

反応物 6

HCID 223AmmoniumHCID 10340Sodium CarbonateHCID 136809Benzophenone imineHCID 517045Sodium AcetateHCID 23676156Sodium t-butoxideHCID 1178214665-(4-Bromo-2-methoxyphenyl)-3-methylpyridazine

生成物 1

HCID 668590663-Methoxy-4-(6-methylpyridazin-4-yl)aniline収率 93%

試薬・触媒・溶媒 3

HCID 634876Binap, (A+-)-触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

5-(4-Bromo-2-methoxyphenyl)-3-methylpyridazine (1.72 g, 6.20 mmol), Pd2(dba)3 (57 mg, 0.062 mmol), BINAP (116 mg, 0.19 mmol), sodium tert-butoxide (833 mg, 8.68 mmol), benzophenone imine (1.25 mL, 7.44 mmol) and toluene (30 mL) were added into a sealed tube. The flask was purged with N2 three times. The reaction was stirred at 80° C. overnight and then cooled down, filtered through a pad of diatomaceous earth and the filter was washed with MTBE. The filtrate was concentrated. The residue was dissolved in MeOH (60 mL). NaOAc (1.22 g, 14.90 mmol) and ammonium hyxroxide hydrochloride (776 mg, 11.2 mmol) was added. The mixture was stirred at room temperature for 1 hour. Sodium carbonate (1.23 g, 11.60 mmol) was added, and the mixture was stirred at room temperature for 10 minutes and then concentrated under reduced pressure. The residue was taken up in dichloromethane. The organic phase was washed with water, brine, dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by flash chromatography on silica gel, eluting with 0% to 1% methanol in ethyl acetate to afford the title compound 1.24 g (93%) as a solid.

後処理

  1. customThe flask was purged with N2 three times
  2. temperaturecooled down
  3. filtrationfiltered through a pad of diatomaceous earth
  4. washthe filter was washed with MTBE
  5. concentrationThe filtrate was concentrated
  6. dissolutionThe residue was dissolved in MeOH (60 mL)
  7. stirringThe mixture was stirred at room temperature for 1 hour
  8. stirringthe mixture was stirred at room temperature for 10 minutes
  9. concentrationconcentrated under reduced pressure
  10. washThe organic phase was washed with water, brine
  11. dry with materialdried over sodium sulfate
  12. customthe solvent was removed under reduced pressure
  13. customThe residue was purified by flash chromatography on silica gel
  14. washeluting with 0% to 1% methanol in ethyl acetate

出典と根拠

ORDレコード
ord-7769ddb901f04ee8a320d5418ebd8ce3
出典データセット
uspto-grants-2016_09
特許番号
US09439904B2

関連ノート

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