Azobisisobutyronitrile → Methyl-2-bromo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carboxylate

HRID 528990ノート

反応式

HRID 528990 の反応式
[CH3:1][Si:2]([CH3:17])([CH3:16])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[N:9]=[CH:8]1.[Br:18]N1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl.CCOC(C)=O>[Br:18][C:8]1[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:16])([CH3:17])[CH3:1])[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[N:9]=1

参加物

6

反応物 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 22954042Methyl 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carboxylate

生成物 1

HCID 58638548Methyl-2-bromo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carboxylate収率 43.6%

試薬・触媒・溶媒 2

HCID 5943Carbon Tetrachloride溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

To a stirred solution of methyl 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carboxylate (5.0 g, 19.5 mmol) in carbon tetrachloride (50 mL) was added N-bromosuccinimide (3.47 g, 19.5 mmol) and AIBN (160 mg, 5 mol %) at room temperature. The reaction mixture was heated at 60° C. for 3 h, cooled to room temperature, and filtered through a small pad of CELITE®. The filtrate was concentrated in vacuo to give light yellow colored residue which was dissolved in EtOAc and washed with 10% NaHCO3 solution. The organic layer was dried over Na2SO4 and concentrated to give crude compound. The crude material was purified by flash chromatography (gradient from 20 to 30% EtOAc/hexanes), to provide the title compound (2.85 g, 43%). 1H NMR (CDCl3) δ 7.76 (s, 1H), 5.30 (s, 2H), 3.90 (s, 3H), 3.55 (t, J=8.0 Hz, 2H), 0.92 (t, J=8.0 Hz, 2H), 0.01 (s, 9H); MS(ESI+) m/z 335.0 (M+H)+.

後処理

  1. temperaturecooled to room temperature
  2. filtrationfiltered through a small pad of CELITE®
  3. concentrationThe filtrate was concentrated in vacuo
  4. customto give light yellow colored residue which
  5. washwashed with 10% NaHCO3 solution
  6. dry with materialThe organic layer was dried over Na2SO4
  7. concentrationconcentrated
  8. customto give crude compound
  9. customThe crude material was purified by flash chromatography (gradient from 20 to 30% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-714aa5e8bce347fea6ab71699a135bc0
出典データセット
uspto-grants-2016_05
特許番号
US09346795B2

反応ノート

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