Water → 3-((2-Chloropyridin-4-yl)oxy)-2-methyl-6-nitropyridine

HRID 1049231ノート

反応式

HRID 1049231 の反応式
Br[C:2]1[C:3]([CH3:11])=[N:4][C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1.C([O-])([O-])=O.[K+].[K+].[Cl:18][C:19]1[CH:24]=[C:23]([OH:25])[CH:22]=[CH:21][N:20]=1.O>CN(C=O)C.CCOC(C)=O>[Cl:18][C:19]1[CH:24]=[C:23]([O:25][C:2]2[C:3]([CH3:11])=[N:4][C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=2)[CH:22]=[CH:21][N:20]=1

参加物

7

反応物 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 674264093-Bromo-2-methyl-6-nitropyridineHCID 178516507HCID 178516507、化合物

生成物 1

HCID 904036213-((2-Chloropyridin-4-yl)oxy)-2-methyl-6-nitropyridine収率 55%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
100 °C

実験手順

A solution of Example A3 (25.59 g, 118 mmol), K2CO3 (48.9 g, 354 mmol) and 2-chloro-4-hydroxy-pyridine (30.6 g, 236 mmol) in DMF (160 mL) was sparged with Ar, heated at 100° C. overnight, then cooled to RT. The mixture was treated with water and EtOAc, the solids removed via filtration through diatomaceous earth and washed with water, EtOAc, then DCM. The aqueous filtrate was extracted with EtOAc (2×) and the organic extracts were combined with the organic filtrates, washed with water, then brine, dried over Na2SO4 and concentrated to dryness. The residue was treated with MTBE, sonicated and the resulting solid collected via filtration to afford 3-((2-chloropyridin-4-yl)oxy)-2-methyl-6-nitropyridine (17.16 g, 55%). 1H NMR (400 MHz, DMSO-d6): δ 8.38 (d, J=5.7 Hz, 1H), 8.25 (d, J=8.7 Hz, 1H), 7.95 (d, J=8.7 Hz, 1H), 7.29 (d, J=2.3 Hz, 1H), 7.16 (dd, J=5.7, 2.3 Hz, 1H), 2.46 (s, 3H); MS (ESI) m/z: 266.0 (M+H+).

後処理

  1. temperaturecooled to RT
  2. customthe solids removed via filtration through diatomaceous earth
  3. washwashed with water, EtOAc
  4. extractionThe aqueous filtrate was extracted with EtOAc (2×)
  5. washwashed with water
  6. dry with materialbrine, dried over Na2SO4
  7. concentrationconcentrated to dryness
  8. additionThe residue was treated with MTBE
  9. customsonicated
  10. filtrationthe resulting solid collected via filtration

出典と根拠

ORDレコード
ord-faa89e6c71df403a8a3ef97ec969f18f
出典データセット
uspto-grants-2016_07
特許番号
US09382228B2

反応ノート

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