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

HRID 1293268노트

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HRID 1293268 반응식
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]

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 180Acetone용매HCID 313Hydrochloric Acid용매HCID 962Water용매3회

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온도
0 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-d0efa75d49124d738fc9228d49ec26f0
출처 데이터셋
uspto-grants-2007_07
특허 번호
US07238714B2

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