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

HRID 601104노트

반응식

HRID 601104 반응식
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

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 74236Tetrabutylammonium Bromide촉매HCID 6228Dimethylformamide용매HCID 8857Ethyl Acetate용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-1c710ae1f4d245c8a59b81ad892faa77
출처 데이터셋
uspto-grants-2011_03
특허 번호
US07902203B2

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