Tetrahydrofuran → tert-Butyl (2-chloro-4-formylpyridin-3-yl)carbamate

HRID 1914820노트

반응식

HRID 1914820 반응식
[Cl:1][C:2]1[C:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:6][CH:5]=[CH:4][N:3]=1.CN(CCN(C)C)C.C([Li])CCC.[NH4+].[Cl-].C1C[O:34][CH2:33]C1>CCCCCC.CCOC(C)=O.CN(C=O)C>[Cl:1][C:2]1[C:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:14])[CH3:13])=[C:6]([CH:33]=[O:34])[CH:5]=[CH:4][N:3]=1

참가 물질

9

반응물 5

HCID 8028TetrahydrofuranHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 25517Ammonium ChlorideHCID 11961738tert-Butyl (2-chloropyridin-3-yl)carbamateHCID 178418339Butyllithium

생성물 1

HCID 58034339tert-Butyl (2-chloro-4-formylpyridin-3-yl)carbamate

시약·촉매·용매 3

HCID 6228Dimethylformamide용매HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

반응 조건

온도
-10 °C

실험 절차

To a solution of tert-butyl (2-chloropyridin-3-yl)carbamate (7-2) (3.01 g, 13.2 mmol) and TMEDA (3.37 g, 29 mmol) in THF (50 mL) at −78° C. was added a 2.5 M solution of n-butyllithium in hexane (11.6 mL) dropwise over 10 minutes and the mixture was stirred for 1 hour. The mixture was warmed up to −10° C. and then cooled to −78° C. DMF (3.06 mL) was added to the mixture and then the mixture was warmed to ambient temperature over 3 hours. Saturated aq. NH4Cl and EtOAc were added to the mixture and the organic layer was washed with H2O and brine, dried over MgSO4, filtered, concentrated in vacuo, and purified by silica gel chromatography (0-80% EtOAc/hexane) to give tert-butyl (2-chloro-4-formylpyridin-3-yl)carbamate (7-3) as a yellow solid.

후처리

  1. temperaturecooled to −78° C
  2. temperaturethe mixture was warmed to ambient temperature over 3 hours
  3. washthe organic layer was washed with H2O and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. custompurified by silica gel chromatography (0-80% EtOAc/hexane)

출처 및 근거

ORD 기록
ord-842791954b584bc2b78e77663e4a401e
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08614221B2

반응 노트

불러오는 중…