2-Bromo-1-fluoro-4-nitrobenzene → 4-Difluoromethoxy-3-(4-nitro-2-bromophenoxy)benzaldehyde

HRID 2039659ノート

反応式

HRID 2039659 の反応式
[F:1][CH:2]([F:13])[O:3][C:4]1[CH:11]=[CH:10][C:7]([CH:8]=[O:9])=[CH:6][C:5]=1[OH:12].[F-].[K+].[Br:16][C:17]1[CH:22]=[C:21]([N+:23]([O-:25])=[O:24])[CH:20]=[CH:19][C:18]=1F>CS(C)=O.C(OCC)(=O)C>[Br:16][C:17]1[CH:22]=[C:21]([N+:23]([O-:25])=[O:24])[CH:20]=[CH:19][C:18]=1[O:12][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][C:4]=1[O:3][CH:2]([F:13])[F:1])[CH:8]=[O:9]

参加物

6

反応物 3

HCID 696992-Bromo-1-fluoro-4-nitrobenzeneHCID 522689Potassium FluorideHCID 27582954-(Difluoromethoxy)-3-hydroxybenzaldehyde

生成物 1

HCID 247582824-Difluoromethoxy-3-(4-nitro-2-bromophenoxy)benzaldehyde収率 66%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
110 °C

実験手順

To a solution of 4-(difluoromethoxy)-3-hydroxy benzaldehyde (8.6 g, 0.046 mol) in dimethylsulphoxide (15 mL) was added potassium fluoride (5.36 g, 0.092 mol) at room temperature. Then it was refluxed to 100-120° C. To this 2-bromo-1-fluoro-4-nitrobenzene (20.3 g, 0.093 mol) in dimethylsulphoxide (10 mL) was added dropwise at 100-120° C. The heating was continued for 5 hours. The reaction mixture was poured into the crushed ice and stirred for 1 hour. Then the aqueous layer was decanted. The solid obtained was dissolved in ethyl acetate (500 mL). The organic layer was washed with water (3×200 mL). The organics were dried over sodium sulphate and filtered. The solvents were removed in vacuum to give the crude product. The product was purified by column chromatography by using gradient (0-2) % of ethyl acetate in hexane. The solid obtained was washed with hexane and dried. Yield—66%. 1H-NMR (DMSO-d6) δ: 7.06 (d, 1H), 7.23-7.41-7.59 (t, 1H), 7.67 (d, 1H), 7.82 (d, 1H), 7.96-7.98 (m, 1H), 8.20-8.23 (m, 1H), 8.61 (d, 1H), 9.97 (s, 1H); HPLC (purity): 99.5%; Mass calculated for C14H8BrF2NO5-388.1, observed—388.1; Rf—0.47 (Ethyl acetate:Hexane (3:7).

後処理

  1. customThen the aqueous layer was decanted
  2. customThe solid obtained
  3. washThe organic layer was washed with water (3×200 mL)
  4. dry with materialThe organics were dried over sodium sulphate
  5. filtrationfiltered
  6. customThe solvents were removed in vacuum

出典と根拠

ORDレコード
ord-4925fa359c7a464794b95cefd8490d7a
出典データセット
uspto-grants-2013_11
特許番号
US08580795B2

反応ノート

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