Triethylamine → Di-tert-butyl(5-bromo-3-pyridinyl)methylimidodicarbonate

HRID 601104ノート

反応式

HRID 601104 の反応式
Cl.[Br:2][C:3]1[CH:4]=[C:5]([CH2:9]Cl)[CH:6]=[NH+:7][CH:8]=1.C(N(CC)CC)C.[C:18]([NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].[K]>CN(C=O)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[Br:2][C:3]1[CH:4]=[C:5]([CH2:9][N:25]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:26]([O:28][C:29]([CH3:30])([CH3:31])[CH3:32])=[O:27])[CH:6]=[N:7][CH:8]=1

参加物

7

反応物 3

HCID 8471TriethylamineHCID 214777755-Bromo-3-chloromethylpyridinium hydrochlorideHCID 86222903Imidodicarbonic acid, bis(1,1-dimethylethyl) ester, potassium salt

生成物 1

HCID 22265925Di-tert-butyl(5-bromo-3-pyridinyl)methylimidodicarbonate収率 60.4%

試薬・触媒・溶媒 3

HCID 74236Tetrabutylammonium Bromide触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of 5-bromo-3-chloromethylpyridinium hydrochloride (716 mg, 4.189 mmol) in anhydrous DMF (15 mL) under nitrogen at 0° C. was treated with triethylamine (0.65 mL, 4.61 mmol), tetrabutylammonium bromide (273 mg, 0.838 mmol), and potassium di-tert-butyl imidodicarbonate (1.284 g, 5.027 mmol). The reaction was heated to 50° C.-55° C. for 3.5 hours, then cooled to room temperature, diluted with ethyl acetate (150 mL), and washed with water (2×50 mL) and saturated aqueous sodium chloride. The combined extracts were dried over anhydrous Na2SO4, filtered, and concentrated by rotary evaporation. The residue was purified by flash column chromatography on silica gel with 6% ethyl acetate/dichloromethane to give the title compound as a colorless oil (0.980 g, 60%). MS (ESI+) m/z 387/389 (M+H)+; 1H NMR (300 MHz, CDCl3) δ 1.49 (s, 18H), 4.75 (s, 2H), 7.83 (t, J=2.02 Hz, 1H), 8.50 (d, J=1.84 Hz, 1H), 8.58 (d, J=2.21 Hz, 1H).

後処理

  1. temperatureThe reaction was heated to 50° C.-55° C. for 3.5 hours
  2. washwashed with water (2×50 mL) and saturated aqueous sodium chloride
  3. dry with materialThe combined extracts were dried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation
  6. customThe residue was purified by flash column chromatography on silica gel with 6% ethyl acetate/dichloromethane

出典と根拠

ORDレコード
ord-1c710ae1f4d245c8a59b81ad892faa77
出典データセット
uspto-grants-2011_03
特許番号
US07902203B2

反応ノート

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