Sodium Hydroxide → 3-amino-N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-4-cyanobenzamide

HRID 1970841ノート

反応式

HRID 1970841 の反応式
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([F:20])([C:16]([F:19])([F:18])[F:17])[C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])[CH:5]=[C:4]([Cl:21])[C:3]=1[NH:22][C:23](=[O:35])[C:24]1[CH:29]=[CH:28][C:27]([C:30]#[N:31])=[C:26]([N+:32]([O-])=O)[CH:25]=1.[OH-].[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>O1CCCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[NH2:32][C:26]1[CH:25]=[C:24]([CH:29]=[CH:28][C:27]=1[C:30]#[N:31])[C:23]([NH:22][C:3]1[C:4]([Cl:21])=[CH:5][C:6]([C:8]([F:20])([C:16]([F:17])([F:18])[F:19])[C:9]([F:14])([F:15])[C:10]([F:11])([F:12])[F:13])=[CH:7][C:2]=1[Br:1])=[O:35]

参加物

6

反応物 3

HCID 14798Sodium HydroxideHCID 24489Sodium DithioniteHCID 86665275N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-4-cyano-3-nitrobenzamide

生成物 1

HCID 866652793-amino-N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-4-cyanobenzamide収率 78.4%

試薬・触媒・溶媒 2

HCID 74236Tetrabutylammonium Bromide触媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)phenyl]-4-cyano-3-nitrobenzamide (Example 1.1) (92.7 g, 154.8 mmol) in tetrahydrofuran (800 ml) was added aqueous sodium hydroxide (0.1 M) (270 ml), sodium hydrosulfite (80.9 g, 464.4 mmol) and tetrabutylammonium bromide (“TBAB”) (4.99 g, 15.5 mmol). The reaction mixture was stirred at ambient temperature for 90 minutes. The phases were separated. The aqueous phase was extracted twice with ethyl acetate. The combined organic extracts were washed with water, aqueous sodium hydrogen carbonate (10% w/v) (400 ml) and brine, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent:cyclohexane/ethyl acetate 5:1) to give 3-amino-N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-4-cyanobenzamide (69 g, 78.4% yield). 1H NMR (400 MHz, CDCl3): 7.82 (s, 1H), 7.75 (s, 1H), 7.71 (s, 1H), 7.51 (m, 1H), 7.35 (s, 1H), 7.21 (m, 1H), 4.7 (s, 2H).

後処理

  1. customThe phases were separated
  2. extractionThe aqueous phase was extracted twice with ethyl acetate
  3. washThe combined organic extracts were washed with water, aqueous sodium hydrogen carbonate (10% w/v) (400 ml) and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography on silica gel (eluent:cyclohexane/ethyl acetate 5:1)

出典と根拠

ORDレコード
ord-c16818541bc244f5a1cb4fcb41dc4ba4
出典データセット
uspto-grants-2013_04
特許番号
US08431514B2

反応ノート

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