Pyridine → 3-amino-4-bromo-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide

HRID 1943094ノート

反応式

HRID 1943094 の反応式
Cl[C:2]1[CH:7]=[C:6]([C:8]([F:17])([C:13]([F:16])([F:15])[F:14])[C:9]([F:12])([F:11])[F:10])[CH:5]=[C:4](Cl)[C:3]=1N.N1C=CC=C[CH:21]=1.S(=[N:28][C:29]1[CH:30]=[C:31]([CH:35]=[CH:36][C:37]=1[Br:38])[C:32](Cl)=[O:33])=O.C[N:40]([CH3:43])C=O>ClCCl>[NH2:28][C:29]1[CH:30]=[C:31]([CH:35]=[CH:36][C:37]=1[Br:38])[C:32]([NH:40][C:43]1[C:4]([CH3:3])=[CH:5][C:6]([C:8]([F:17])([C:13]([F:15])([F:14])[F:16])[C:9]([F:10])([F:12])[F:11])=[CH:7][C:2]=1[CH3:21])=[O:33]

参加物

6

反応物 4

HCID 1049PyridineHCID 6228DimethylformamideHCID 100194962,6-Dichloro-4-(perfluoropropan-2-yl)anilineHCID 594448243-Sulfinylamino-4-bromo-benzoyl chloride

生成物 1

HCID 594448253-amino-4-bromo-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide収率 100%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of 2,6-dichloro-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenylamine (1.02 g, 3.1 mmol) (Example 6.3) in anhydrous dichloromethane (25 ml), at 20° C., was added sequentially pyridine (0.74 g, 2.0 mmol) and 4-bromo-3-sulfinylamino-benzoyl chloride (0.94 g, 9.30 mmol) (Example 1.2). The reaction mixture was stirred at ambient temperature for one hour. The reaction mixture was then heated to 50° C. for 16 hours. The reaction mixture was allowed to cool to ambient temperature before adding dimethylformamide (50 ml). The dichloromethane was distilled off and the reaction mixture was heated to 130° C. for 16 hours. The reaction was quenched by addition of aqueous sodium hydrogen carbonate (saturated) (10 ml). After separation of the phases, the aqueous layer was extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:5 to 1:0) to give 3-amino-4-bromo-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide (quantitative, 100% yield). 1H-NMR (CDCl3, 400 MHz): 7.73 (m, 3H), 7.27 (m, 3H), 6.91 (m, 1H), 3.9 (s, 2H) ppm.

後処理

  1. temperatureThe reaction mixture was then heated to 50° C. for 16 hours
  2. temperatureto cool to ambient temperature
  3. distillationThe dichloromethane was distilled off
  4. temperaturethe reaction mixture was heated to 130° C. for 16 hours
  5. customThe reaction was quenched by addition of aqueous sodium hydrogen carbonate (saturated) (10 ml)
  6. customAfter separation of the phases
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. dry with materialThe combined organic phases were dried over sodium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:5 to 1:0)

出典と根拠

ORDレコード
ord-247be295ece74cfa8b50c64459aefb13
出典データセット
uspto-grants-2013_03
特許番号
US08389767B2

反応ノート

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