Vanillin → 4-(Difluoromethoxy)-3-methoxybenzaldehyde

HRID 468687Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 468687
Cl[C:2]([F:8])([F:7])C(OC)=O.[O:9]=[CH:10][C:11]1[CH:19]=[CH:18][C:16]([OH:17])=[C:13]([O:14][CH3:15])[CH:12]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O>[F:7][CH:2]([F:8])[O:17][C:16]1[CH:18]=[CH:19][C:11]([CH:10]=[O:9])=[CH:12][C:13]=1[O:14][CH3:15]

Komponenten

6

Edukt 3

HCID 1183VanillinHCID 11430Potassium CarbonateHCID 73935Methyl chlorodifluoroacetate

Produkt 1

HCID 31612494-(Difluoromethoxy)-3-methoxybenzaldehydeAusbeute 41 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
67.5 °C

Versuchsvorschrift

Methyl chlorodifluoroacetate (1.4 mL, 13 mmol) was added to a suspension of vanillin (1.0 g, 6.6 mmol) and potassium carbonate (2.0 g, 14 mol) in DMF (10 mL). The suspension was heated to 65-70° C. for 16 h and the suspension was diluted with water. The aqueous phase was extracted with EtOAc and the combined organic fractions were washed with saturated aqueous NaHCO3, water, brine, dried and concentrated. The residue was purified by column chromatography, eluting with 10% EtOAc/petrol to give 4-(difluoromethoxy)-3-methoxybenzaldehyde (0.54 g, 41%) as a colourless oil; δH (400 MHz, CDCl3) 3.95 (s, 3H, OCH3), 6.60 (t, J=74 Hz, 1H, OCHF2), 7.30 (d, J5,6=8.0 Hz, 1H, H5), 7.45 (dd, J5,6=8.0, J2,6=2.0 Hz, 1H, H6), 7.50 (d, J2,6=2.0 Hz, 1H, H2), 9.93 (s, 1H, CHO); δC (100 MHz, CDCl3) 56.2, 110.9, 115.5 (t, J=256 Hz), 121.5, 125.0, 134.5, 144.9, 151.5, 190.8.

Aufarbeitung

  1. extractionThe aqueous phase was extracted with EtOAc
  2. washthe combined organic fractions were washed with saturated aqueous NaHCO3, water, brine
  3. customdried
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography
  6. washeluting with 10% EtOAc/petrol

Quellen und Nachweise

ORD-Eintrag
ord-5abfc0e55060424d91d4c4115a7f979f
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08624056B2

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