Water → 4-(Difluoromethoxy)-3,5-dimethoxybenzaldehyde

HRID 468693ノート

反応式

HRID 468693 の反応式
Cl[C:2]([F:8])([F:7])C(OC)=O.O[C:10]1(OC)[CH:17]=[CH:16][C:13]([CH:14]=[O:15])=[CH:12][CH:11]1[O:18][CH3:19].[C:22](=O)([O-])[O-:23].[K+].[K+].[OH2:28]>CN(C=O)C>[F:7][CH:2]([F:8])[O:28][C:10]1[C:11]([O:18][CH3:19])=[CH:12][C:13]([CH:14]=[O:15])=[CH:16][C:17]=1[O:23][CH3:22]

参加物

6

反応物 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 73935Methyl chlorodifluoroacetateHCID 866503554-Hydroxy-3,4-dimethoxybenzaldehyde

生成物 1

HCID 7105984-(Difluoromethoxy)-3,5-dimethoxybenzaldehyde収率 39%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
67.5 °C

実験手順

Methyl chlorodifluoroacetate (0.58 mL, 5.5 mmol) was added to a suspension of 4-hydroxy-3,4-dimethoxybenzaldehyde (0.50 g, 2.7 mmol) and potassium carbonate (0.76 g, 5.5 mol) in DMF (5.0 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 crude product was recrystallised from EtOAc/petrol providing 4-(difluoromethoxy)-3,5-dimethoxybenzaldehyde (0.25 g, 39%) as a colourless crystalline solid; mp 113-115° C.; δH (400 MHz, CDCl3) 3.95 (s, 6H, OCH3), 6.65 (t, J=74 Hz, 1H, OCHF2), 7.15 (s, 2H, H2, H6), 9.91 (s, 1H, CHO); δC (100 MHz, CDCl3) δ6.5, 106.3, 116.2 (t, J=256 Hz), 134.1, 153.5, 190.8; νmax 831, 1048, 1099, 1330, 1600, 1699, 2854 cm−1.

後処理

  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 crude product was recrystallised from EtOAc/petrol

出典と根拠

ORDレコード
ord-82ff59ce80314f98b1f58463600fd8da
出典データセット
uspto-grants-2014_01
特許番号
US08624056B2

反応ノート

読み込み中…