Phenol → 5-Chloro-3-phenoxy-2-pyridinamine

HRID 1806006ノート

反応式

HRID 1806006 の反応式
Br[C:2]1[C:3]([NH2:9])=[N:4][CH:5]=[C:6]([Cl:8])[CH:7]=1.[C:10]1([OH:16])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.OC1C=CC=CC=1/C=N/O.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.[Cu-]=O>[Cl:8][C:6]1[CH:7]=[C:2]([O:16][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:3]([NH2:9])=[N:4][CH:5]=1

参加物

7

反応物 4

HCID 996PhenolHCID 10796Cesium carbonateHCID 27639713-Bromo-5-chloropyridin-2-amineHCID 135408751Salicylaldoxime

生成物 1

HCID 187528795-Chloro-3-phenoxy-2-pyridinamine収率 15%

試薬・触媒・溶媒 2

HCID 178419072HCID 178419072、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

3-Bromo-5-chloropyridin-2-amine (50.0 g, 241 mmol), phenol (45.4 g, 482 mmol), copper(I) oxide (1.72 g, 12.1 mmol), (E)-2-hydroxybenzaldehyde oxime (6.61 g, 48.2 mmol), Cs2CO3 (157 g, 482 mmol), and 3A powdered molecular (72.3 g) sieves were placed in DMF (300 mL) and heated at 110° C. for 3 days. Reaction was cooled, then filtered through celite. Reaction was then partitioned between water and ether. An emulsion was formed and was filtered through a plug of celite. Water was extracted with ether then dried, filtered, and concentrated. Crude material was purified on a first silica gel chromatography (5-10% EtOAc in hexanes), and then on a second column to provide the title compound (8.00 g, 15.0% yield). 1H NMR (CDCl3) δ 7.80 (d, 1H), 7.39 (t, 2H), 7.19 (t, 1H), 7.03 (d, 2H), 6.94 (d, 1H), 4.76 (bs, 2H); Mass spectrum (apci) m/z=221 (100).

後処理

  1. customReaction
  2. temperaturewas cooled
  3. filtrationfiltered through celite
  4. customReaction
  5. customwas then partitioned between water and ether
  6. customAn emulsion was formed
  7. filtrationwas filtered through a plug of celite
  8. extractionWater was extracted with ether
  9. customthen dried
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customCrude material was purified on a first silica gel chromatography (5-10% EtOAc in hexanes)

出典と根拠

ORDレコード
ord-9ee44d14ef5642d9b0cfe94f53d84a22
出典データセット
uspto-grants-2013_01
特許番号
US08354540B2

反応ノート

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