Ammonia → Methyl 5-chloro-2-[(5-chloropyridin-2-yl)oxy]benzoate

HRID 1293268ノート

反応式

HRID 1293268 の反応式
N[C:2]1[CH:3]=[CH:4][C:5]([O:8][C:9]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:10]=2[C:11]([O:13][CH3:14])=[O:12])=[N:6][CH:7]=1.N([O-])=O.[Na+].[Cl-:24].N>Cl.O.CC(C)=O>[Cl:19][C:16]1[CH:17]=[CH:18][C:9]([O:8][C:5]2[CH:4]=[CH:3][C:2]([Cl:24])=[CH:7][N:6]=2)=[C:10]([CH:15]=1)[C:11]([O:13][CH3:14])=[O:12]

参加物

8

反応物 4

HCID 222AmmoniaHCID 312ChlorideHCID 23668193Sodium NitriteHCID 69415937Methyl 2-[(5-aminopyridin-2-yl)oxy]-5-chlorobenzoate

生成物 1

HCID 69418235Methyl 5-chloro-2-[(5-chloropyridin-2-yl)oxy]benzoate収率 32.3%

試薬・触媒・溶媒 3

HCID 180Acetone溶媒HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒3 回

反応条件

温度
0 °C

実験手順

To a solution of methyl 2-[(5-aminopyridin-2-yl)oxy]-5-chlorobenzoate (step 2 of Example 101, 1.00 g, 3.6 mmol) in 0.66 M hydrochloric acid (11 mL) was added sodium nitrite (252 mg, 3.6 mmol) in water (5 mL) at 0° C. The reaction mixture was stirred for 30 mim at 0° C. The mixture was added dropwise to a stirred suspension of cupper(II) chloride (1.21 g, 9.0 mmol) in acetone (18 mL) and water (5.4 mL). The whole was stirred at 50° C. for 30 min. Then the reaction mixture was poured into water and it was added ammonia solution. The aqueous mixture was extracted with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate, and concentrated. The residue was purified by flush column chromatography on silica gel eluting with hexane/ethyl acetate (20/1) to afford 347 mg (32%) of the title compound: 1H-NMR (CDCl3) δ 8.00 (1H, d, J=2.8 Hz), 7.99 (1H, d, J=2.8 Hz), 7.67 (1H, dd, J=8.7, 2.8 Hz), 7.55 (1H, dd, J=8.6, 2.8 Hz), 7.14 (1H, d, J=8.6 Hz), 6.97 (1H, d, J=8.7 Hz), 3.72 (3H, s).

後処理

  1. stirringThe whole was stirred at 50° C. for 30 min
  2. extractionThe aqueous mixture was extracted with ethyl acetate
  3. washThe organic phase was washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified
  7. customby flush column chromatography on silica gel eluting with hexane/ethyl acetate (20/1)

出典と根拠

ORDレコード
ord-d0efa75d49124d738fc9228d49ec26f0
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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