Nitrogen → N-(2',4'-difluoro-5-nitrobiphenyl-3-yl)acetamide

HRID 64085

反応式

HRID 64085 の反応式
Br[C:2]1[CH:3]=[C:4]([NH:11][C:12](=[O:14])[CH3:13])[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.N#N.[F:17][C:18]1[CH:23]=[C:22]([F:24])[CH:21]=[CH:20][C:19]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:17][C:18]1[CH:23]=[C:22]([F:24])[CH:21]=[CH:20][C:19]=1[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([NH:11][C:12](=[O:14])[CH3:13])[CH:3]=1

参加物

7

反応物 4

HCID 947NitrogenHCID 10340Sodium CarbonateHCID 27343342,4-Difluorophenylboronic acidHCID 10658908N-(3-bromo-5-nitrophenyl)acetamide

生成物 1

HCID 89500094N-(2',4'-difluoro-5-nitrobiphenyl-3-yl)acetamide収率 80%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
90 °C

実験手順

A solution of N-(3-bromo-5-nitrophenyl)acetamide (1 g, 3.86 mmol) in 1,2-dimethoxyethane (15 ml) was degassed by N2 bubbling for 5 min. 2,4-Difluorophenylboronic acid (0.727 g, 4.63 mmol, 1.2 eq.) was added and the mixture was degassed for another 5 min. Pd(dppf)Cl2 (0.627 g, 0.769 mmol, 0.2 eq.) and aqueous sodium carbonate (1.22 g, 11.5 mmol, 3.0 eq.) were added sequentially and the mixture was further degassed for 5 min and then heated at 90° C. for 2 h. The mixture was quenched with water and extracted with ethyl acetate (3×50 ml). The combined organic layer was washed with water, brine and dried over sodium sulphate. The solvent was distilled off under reduced pressure and the crude residue was purified by column chromatography (60-120 silica gel, 30% ethyl acetate in hexane) to give the product in 80% yield (0.9 g). 1H NMR (300 MHz, DMSO-d6): δ 10.63 (s, 1H), 8.7-8.69 (m, 1H), 8.16 (d, 1H), 8.04 (s, 1H), 7.8-7.67 (m, 1H), 7.53 (m, 1H), 7.34 (m, 1H), 2.19 (s, 3H).

後処理

  1. customthe mixture was degassed for another 5 min
  2. customthe mixture was further degassed for 5 min
  3. customThe mixture was quenched with water
  4. extractionextracted with ethyl acetate (3×50 ml)
  5. washThe combined organic layer was washed with water, brine
  6. dry with materialdried over sodium sulphate
  7. distillationThe solvent was distilled off under reduced pressure
  8. customthe crude residue was purified by column chromatography (60-120 silica gel, 30% ethyl acetate in hexane)
  9. customto give the product in 80% yield (0.9 g)

出典と根拠

ORDレコード
ord-e22b3ee5a0c241e38ce9d93b1983acae
出典データセット
uspto-grants-2016_09
特許番号
US09447091B2

関連ノート

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