Triphenylphosphine → Ethyl 2-((3-nitro-5-phenylpyridin-2-yl)oxy)acetate

HRID 1509272ノート

反応式

HRID 1509272 の反応式
Br[C:2]1[CH:3]=[C:4]([N+:15]([O-:17])=[O:16])[C:5]([O:8][CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[N:6][CH:7]=1.[C:18]1(B(O)O)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F-].[Cs+]>COCCOC.ClCCl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:15]([C:4]1[C:5]([O:8][CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[N:6][CH:7]=[C:2]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:3]=1)([O-:17])=[O:16]

参加物

8

反応物 4

HCID 11776TriphenylphosphineHCID 25953Cesium fluorideHCID 66827Phenylboronic AcidHCID 4647502Ethyl 2-((5-bromo-3-nitropyridin-2-yl)oxy)acetate

生成物 1

HCID 67255179Ethyl 2-((3-nitro-5-phenylpyridin-2-yl)oxy)acetate収率 38%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 6344Dichloromethane溶媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
75 °C

実験手順

In a 1 l round-bottomed flask was added ethyl 2-(5-bromo-3-nitropyridin-2-yloxy)acetate (18.33 g, 60.1 mmol), phenylboronic acid (10.99 g, 90 mmol), triphenylphosphine (4.73 g, 18.02 mmol) and cesium fluoride (45.6 g, 300 mmol) in 1,2-dimethoxyethane (300 ml) to give a yellow solution. The reaction mixture was degassed by bubbling nitrogen for 30 minutes. Palladium(II)acetate (2.023 g, 9.01 mmol) was added and the mixture was heated to 75° C. under a nitrogen atmosphere overnight. The reaction mixture was allowed to cool to room temperature and concentrated to dryness under reduced pressure to give a brown solid. This was re-dissolved in dichloromethane, filtered and concentrated to dryness under reduced pressure to give a brown solid The crude residue was purified via Biotage chromatography (gradient 5% to 60% ethyl acetate in n-hexanes) to give the title compound (6.9 g, 38%). 1H NMR (500 MHz, CDCl3) δ 8.58 (1H, s), 8.56 (1H, s), 7.59-7.52 (2H, m), 7.48-7.46 (2H, m), 7.45-7.43 (1H, m), 5.13 (2H, s), 4.30-4.26 (2H, q), 1.33-1.30 (3H, t).

後処理

  1. customto give a yellow solution
  2. customThe reaction mixture was degassed
  3. customby bubbling nitrogen for 30 minutes
  4. temperatureto cool to room temperature
  5. concentrationconcentrated to dryness under reduced pressure
  6. customto give a brown solid
  7. filtrationfiltered
  8. concentrationconcentrated to dryness under reduced pressure
  9. customto give a brown solid The crude residue
  10. customwas purified via Biotage chromatography (gradient 5% to 60% ethyl acetate in n-hexanes)

出典と根拠

ORDレコード
ord-59c1898b21b748b9854d257a0fe3b009
出典データセット
uspto-grants-2015_12
特許番号
US09221838B2

反応ノート

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