Pyridine → N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-bromo-3-nitrobenzamide

HRID 570756

反応式

HRID 570756 の反応式
[CH2:1]([C:3]1[CH:9]=[C:8]([C:10]([F:22])([C:18]([F:21])([F:20])[F:19])[C:11]([F:17])([F:16])[C:12]([F:15])([F:14])[F:13])[CH:7]=[C:6]([CH3:23])[C:4]=1[NH2:5])[CH3:2].N1C=CC=CC=1.[Br:30][C:31]1[C:39]([N+:40]([O-:42])=[O:41])=[CH:38][CH:37]=[CH:36][C:32]=1[C:33](Cl)=[O:34].CN(C)C(=O)C>O1CCCC1>[CH2:1]([C:3]1[CH:9]=[C:8]([C:10]([F:22])([C:18]([F:19])([F:20])[F:21])[C:11]([F:16])([F:17])[C:12]([F:14])([F:15])[F:13])[CH:7]=[C:6]([CH3:23])[C:4]=1[NH:5][C:33](=[O:34])[C:32]1[CH:36]=[CH:37][CH:38]=[C:39]([N+:40]([O-:42])=[O:41])[C:31]=1[Br:30])[CH3:2]

参加物

6

反応物 4

HCID 1049PyridineHCID 31374DimethylacetamideHCID 2229532-Bromo-3-nitrobenzoyl chloride2 回HCID 86665289HCID 86665289、化合物

生成物 1

HCID 86673888N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-bromo-3-nitrobenzamide収率 76.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of 2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylaniline (preparation as described in WO 08/074427) (106 mg, 0.3 mmol) in tetrahydrofuran (0.5 ml) was added pyridine (72.6 μl, 0.9 mmol) at 0 to 5° C. A solution of 2-bromo-3-nitrobenzoic acid chloride (87 mg, 0.33 mmol) in tetrahydrofuran (0.5 ml) was added. The reaction mixture was stirred at ambient temperature for 3 hours, then at reflux for 15 hours. After 15 hours, the reaction was not complete so N,N-dimethylacetamide (“DMA”) (0.1 equivalents) and more 2-bromo-3-nitrobenzoic acid chloride (0.2 equivalents) were added. The reaction mixture was stirred at ambient temperature for 41 hours. After 41 hours, the reaction was quenched by addition of saturated aqueous sodium hydrogen carbonate (10 ml) and the mixture extracted twice with ethyl acetate (2×20 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 6:1) to give N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-bromo-3-nitrobenzamide (0.133 g, 76% yield).

後処理

  1. temperatureat reflux for 15 hours
  2. waitAfter 15 hours
  3. additionwere added
  4. stirringThe reaction mixture was stirred at ambient temperature for 41 hours
  5. waitAfter 41 hours
  6. customthe reaction was quenched by addition of saturated aqueous sodium hydrogen carbonate (10 ml)
  7. extractionthe mixture extracted twice with ethyl acetate (2×20 ml)
  8. dry with materialThe combined organic extracts were dried over sodium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 6:1)

出典と根拠

ORDレコード
ord-e56acf9b309948b58ba75380c0963644
出典データセット
uspto-grants-2015_05
特許番号
US09023873B2

関連ノート

読み込み中…