Methyl chlorodifluoroacetate → 1-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene

HRID 74008

Reaktionsgleichung

Reaktionsgleichung von HRID 74008
[C:1]([C:5]1[CH:10]=[C:9](Br)[C:8]([N+:12]([O-:14])=[O:13])=[CH:7][C:6]=1[O:15][CH3:16])([CH3:4])([CH3:3])[CH3:2].[F-:17].[K+].[K+].[Br-].Cl[C:22]([F:28])([F:27])C(OC)=O>CN(C=O)C.O.[Cu]I>[C:1]([C:5]1[CH:10]=[C:9]([C:22]([F:28])([F:17])[F:27])[C:8]([N+:12]([O-:14])=[O:13])=[CH:7][C:6]=1[O:15][CH3:16])([CH3:4])([CH3:3])[CH3:2]

Komponenten

8

Edukt 4

HCID 73935Methyl chlorodifluoroacetateHCID 253877Potassium BromideHCID 522689Potassium FluorideHCID 574702451-Bromo-5-(tert-butyl)-4-methoxy-2-nitrobenzene

Produkt 1

HCID 574702461-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzeneAusbeute 61,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
125 °C

Versuchsvorschrift

A mixture of 1-tert-butyl-2-methoxy-5-bromo-4-nitrobenzene (867 mg, 3.0 mmol), KF (348 mg, 6 mmol), KBr (714 mg, 6 mmol), CuI (684 mg, 3.6 mmol), methyl chlorodifluoroacetate (2.2 mL, 21.0 mmol) in DMF (5 mL) was stirred at 125° C. in a sealed tube overnight, cooled to room temperature, diluted with water and extracted three times with EtOAc. The combined organic layers were washed with brine and dried over anhydrous MgSO4. After removal of the solvent, the residue was purified by column chromatography (0-5% EtOAc-Hexane) to yield 1-tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene (512 mg, 61%). 1H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), 7.29 (s, 1H), 3.90 (s, 3H), 1.33 (s, 9H).

Aufarbeitung

  1. temperaturecooled to room temperature
  2. extractionextracted three times with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. customAfter removal of the solvent
  6. customthe residue was purified by column chromatography (0-5% EtOAc-Hexane)

Quellen und Nachweise

ORD-Eintrag
ord-e77fe0383fc346d59ce7a71dd0be2d9e
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08829204B2

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