Sodium hydride → 1-Bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzene

HRID 495019Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 495019
[Br:1][C:2]1[C:3]([F:10])=[C:4]([OH:9])[C:5]([Cl:8])=[CH:6][CH:7]=1.[H-].[Na+].[F:13][CH:14]([F:21])[CH2:15]OS(C)(=O)=O>CN(C)C=O.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([O:9][CH2:15][CH:14]([F:21])[F:13])[C:3]=1[F:10]

Komponenten

6

Edukt 3

HCID 24758Sodium hydrideHCID 567764922,2-Difluoroethyl methanesulfonateHCID 666010023-Bromo-6-chloro-2-fluorophenol

Produkt 1

HCID 866138401-Bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzeneAusbeute 45,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel3×

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

A solution of 3-bromo-6-chloro-2-fluorophenol (15.4 g, 0.068 mol) in dimethylformamide (DMF; 25 mL) was slowly added to a suspension of sodium hydride (60% dispersion in mineral oil) (4.0 g, 0.10 mol) in DMF (100 mL) and the reaction mixture was stirred one hour. A solution of methanesulfonic acid 2,2-difluoroethyl ester (17.5 g, 0.109 mol) in DMF (10 mL) was slowly added. The resulting solution was heated at 70° C. for eighteen hours. The cooled solution was diluted with water (200 mL) and extracted with ethyl ether. The combined organic phases were dried and concentrated. The residual oil was purified by column chromatography (in hexanes) to give 1-bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzene (9.0 g, 0.031 mol): 1H NMR (CDCl3): δ 7.26 (m, 1H), 7.09 (m, 1H), 6.12 (tt, 1H), 4.30 (td, 2H).

Aufarbeitung

  1. extractionextracted with ethyl ether
  2. customThe combined organic phases were dried
  3. concentrationconcentrated
  4. customThe residual oil was purified by column chromatography (in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-934d211430f648cbaa088f2b537ca9f1
Quelldatensatz
uspto-grants-2009_05
Patentnummer
US07538214B2

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