Chloroacetonitrile → 2-(5-Bromo-2-chloropyridin-3-yloxy)acetonitrile

HRID 2077590Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2077590
[Br:1][C:2]1[CH:3]=[C:4]([OH:9])[C:5]([Cl:8])=[N:6][CH:7]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Cl[CH2:17][C:18]#[N:19]>CN(C=O)C>[Br:1][C:2]1[CH:3]=[C:4]([O:9][CH2:17][C:18]#[N:19])[C:5]([Cl:8])=[N:6][CH:7]=1

Komponenten

5

Edukt 3

HCID 7856ChloroacetonitrileHCID 10796Cesium carbonateHCID 167481065-Bromo-2-chloropyridin-3-ol

Produkt 1

HCID 866279992-(5-Bromo-2-chloropyridin-3-yloxy)acetonitrileAusbeute 61 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A dry 10 mL, one neck round bottom flask was charged with 5-bromo-2-chloropyridin-3-ol (0.0518 g, 0.249 mmol), cesium carbonate (0.0972 g, 0.298 mmol), a stirbar and 2 mL dry DMF. The stirring slurry was treated with 2-chloroacetonitrile (0.0709 ml, 1.12 mmol) and fitted with an inert atmosphere inlet. The reaction was heated to 80° C. using an oil bath for 3 h, and cooled. The slurry was filtered through a 0.22 μm PTFE filter, and concentrated in vacuo. The residue was purified in one injection using a YMC pack diol-120-NP column (PN DN12S05-2520 wt, 250×20 mm, spherical particle, 5 μm particle size, 120 Å pore size, flow=20 mL/min: A=hexanes; B=THF; 15% B isocratic). A fraction that eluted from 10.0 to 11.8 minutes was isolated. The solvent was removed in vacuo to afford 2-(5-bromo-2-chloropyridin-3-yloxy)acetonitrile (0.0375 g, 61.0% yield). 1H NMR (300 MHz, chloroform-d) δ ppm 4.88 (s, 2H) 7.52 (d, J=1.97 Hz, 1H) 8.25 (d, J=1.97 Hz, 1H). 13C NMR (75 MHz, chloroform-d) δ ppm 54.71 (s, 1 C) 113.51 (s, 1 C) 118.90 (s, 1 C) 125.53 (s, 1 C) 140.63 (s, 1 C) 144.40 (s, 1 C) 148.93 (s, 1 C).

Aufarbeitung

  1. customfitted with an inert atmosphere inlet
  2. customfor 3 h
  3. temperaturecooled
  4. filtrationThe slurry was filtered through a 0.22 μm PTFE
  5. filtrationfilter
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified in one injection
  8. washA fraction that eluted from 10.0 to 11.8 minutes
  9. customwas isolated
  10. customThe solvent was removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-a8c0c00ae3e74257b1c198a667612f76
Quelldatensatz
uspto-grants-2011_04
Patentnummer
US07928140B2

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