Tetrafluoroboric acid → Methyl 5-chloro-2-[(5-fluoropyridin-2-yl)oxy]benzoate

HRID 1293265ノート

反応式

HRID 1293265 の反応式
N([O-])=O.[Na+].N[C:6]1[CH:7]=[CH:8][C:9]([O:12][C:13]2[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][C:14]=2[C:15]([O:17][CH3:18])=[O:16])=[N:10][CH:11]=1.[F:24][B-](F)(F)F.[H+]>O>[Cl:23][C:20]1[CH:21]=[CH:22][C:13]([O:12][C:9]2[CH:8]=[CH:7][C:6]([F:24])=[CH:11][N:10]=2)=[C:14]([CH:19]=1)[C:15]([O:17][CH3:18])=[O:16]

参加物

5

反応物 3

HCID 28118Tetrafluoroboric acidHCID 23668193Sodium NitriteHCID 69415937Methyl 2-[(5-aminopyridin-2-yl)oxy]-5-chlorobenzoate

生成物 1

HCID 69418811Methyl 5-chloro-2-[(5-fluoropyridin-2-yl)oxy]benzoate収率 42%

試薬・触媒・溶媒 1

HCID 962Water溶媒2 回

反応条件

温度
140 °C

実験手順

To a solution of sodium nitrite (224 mg, 3.25 mmol) in water (5 mL) was added methyl 2-[(5-aminopyridin-2-yl)oxy]-5-chlorobenzoate (907 mg, 3.25 mmol) and 48% tetrafluoroboric acid in water (5 mL) at 0° C. The reaction mixture was stirred for 5 h. The resulting precipitate was collected by filtration and dried under reduced pressure at room temperature. To the solids of tetrafluoroborate were added chlorobenzene (5 mL) and the mixture was heated at 140° C. for 40 min. The reaction mixture was diluted with ethyl acetate. The solution was washed with brine and concentrated. The residue was purified by flush column chromatography on silica gel eluting with hexane/ethyl acetate (8/1) to afford 382 mg (42%) of the title compound: 1H-NMR (CDCl3) δ 7.98 (1H, d, J=2.8 Hz), 7.90 (1H, d, J=3.1 Hz), 7.59–7.41 (2H, m), 7.14 (1H, d, J=8.6 Hz), 6.99 (1H, dd, J=8.9, 3.5 Hz), 3.72 (3H, s).

後処理

  1. filtrationThe resulting precipitate was collected by filtration
  2. customdried under reduced pressure at room temperature
  3. additionTo the solids of tetrafluoroborate were added chlorobenzene (5 mL)
  4. additionThe reaction mixture was diluted with ethyl acetate
  5. washThe solution was washed with brine
  6. concentrationconcentrated
  7. customThe residue was purified
  8. customby flush column chromatography on silica gel eluting with hexane/ethyl acetate (8/1)

出典と根拠

ORDレコード
ord-a82fe8ed802d46da97da38b58e32a54e
出典データセット
uspto-grants-2007_07
特許番号
US07238714B2

反応ノート

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