Diisopropylamine → tert-Butyl N-allyl-N-(2-isothiazol-5-yl-2-oxo-ethyl)carbamate

HRID 470206노트

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HRID 470206 반응식
C(NC(C)C)(C)C.C([Li])CCC.[S:13]1[CH:17]=[CH:16][CH:15]=[N:14]1.[CH2:18]([N:21]([CH2:29][C:30](N(OC)C)=[O:31])[C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH:19]=[CH2:20].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[CH2:18]([N:21]([CH2:29][C:30]([C:17]1[S:13][N:14]=[CH:15][CH:16]=1)=[O:31])[C:22](=[O:28])[O:23][C:24]([CH3:25])([CH3:26])[CH3:27])[CH:19]=[CH2:20]

참가 물질

8

반응물 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 67515IsothiazoleHCID 86697892tert-Butyl N-allyl-N-[2-(methoxy(methyl)amino)-2-oxo-ethyl]carbamateHCID 178418339Butyllithium

생성물 1

HCID 86697894tert-Butyl N-allyl-N-(2-isothiazol-5-yl-2-oxo-ethyl)carbamate수율 86.3%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매3회HCID 8857Ethyl Acetate용매

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온도
-78 °C

실험 절차

To a −78° C. solution of diisopropylamine (9.01 mL, 64.01 mmol) in tetrahydrofuran (80 mL) is added n-butyl lithium (30.78 mL, 49.24 mmol, 1.6 M in hexanes) drop wise under nitrogen. The resulting solution is stirred at −78° C. for 20 minutes and then a solution of isothiazole (4.19 g, 49.24 mmol) in tetrahydrofuran (10 mL) is added drop wise. The resultant white slurry is stirred for 30 minutes at −78° C. A solution of tert-butyl N-allyl-N-[2-(methoxy(methyl)amino)-2-oxo-ethyl]carbamate (6.36 g, 24.62 mmol) in tetrahydrofuran (50 mL) is then added to the slurry over a 15 minutes period. The reaction is then stirred for 30 minutes at −78° C., warmed to ambient temperature and is stirred for 30 minutes. Saturated ammonium chloride (200 mL) is then added. The resulting solution is extracted three times with ethyl acetate. The combined organic layers are dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product is purified over silica gel with a 35 minute, 5% to 100% ethyl acetate in hexanes gradient, to give the title compound (6.00 g, 21.25 mmol, 86%). ES/MS (m/e): 283.0 (M+H).

후처리

  1. stirringThe resultant white slurry is stirred for 30 minutes at −78° C
  2. stirringThe reaction is then stirred for 30 minutes at −78° C.
  3. temperaturewarmed to ambient temperature
  4. stirringis stirred for 30 minutes
  5. extractionThe resulting solution is extracted three times with ethyl acetate
  6. dry with materialThe combined organic layers are dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe crude product is purified over silica gel with a 35 minute

출처 및 근거

ORD 기록
ord-94d41e5c8a094ddfaa9efe8f3a7eee71
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08629270B2

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