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

HRID 335073Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 335073
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

Komponenten

7

Edukt 4

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

Produkt 1

HCID 187528795-Chloro-3-phenoxy-2-pyridinamineAusbeute 15 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178419072HCID 178419072, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-e103d3f542a046f7a035fd939ea83912
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08883828B2

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