Vanillin → 4-(Difluoromethoxy)-3-methoxybenzaldehyde

HRID 468687노트

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HRID 468687 반응식
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]

참가 물질

6

반응물 3

HCID 1183VanillinHCID 11430Potassium CarbonateHCID 73935Methyl chlorodifluoroacetate

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매

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온도
67.5 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-5abfc0e55060424d91d4c4115a7f979f
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08624056B2

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