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

HRID 601104Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 601104
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

Komponenten

7

Edukt 3

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

Produkt 1

HCID 22265925Di-tert-butyl(5-bromo-3-pyridinyl)methylimidodicarbonateAusbeute 60,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-1c710ae1f4d245c8a59b81ad892faa77
Quelldatensatz
uspto-grants-2011_03
Patentnummer
US07902203B2

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