Ethyl Acetate → 2-Fluoro-N,N-dimethyl-4-(pyridin-4-yl)aniline

HRID 240226노트

반응식

HRID 240226 반응식
Br[C:2]1[CH:10]=[CH:9][C:5]([N:6]([CH3:8])[CH3:7])=[C:4]([F:11])[CH:3]=1.C(B(CC)[C:15]1[CH:20]=[CH:19][N:18]=[CH:17][CH:16]=1)C.[OH-].[K+].C(OCC)(=O)C>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O1CCCC1.[Cl-].[Na+].O>[F:11][C:4]1[CH:3]=[C:2]([C:15]2[CH:20]=[CH:19][N:18]=[CH:17][CH:16]=2)[CH:10]=[CH:9][C:5]=1[N:6]([CH3:8])[CH3:7]

참가 물질

8

반응물 4

HCID 8857Ethyl AcetateHCID 14797Potassium HydroxideHCID 133188714-(Diethylboranyl)pyridineHCID 404253644-bromo-2-fluoro-N,N-dimethylaniline

생성물 1

HCID 672021852-Fluoro-N,N-dimethyl-4-(pyridin-4-yl)aniline수율 46.2%

시약·촉매·용매 3

HCID 74236Tetrabutylammonium Bromide촉매HCID 8028Tetrahydrofuran용매HCID 57417360Sodium chloride; water용매

실험 절차

4-Bromo-2-fluoro-N,N-dimethyl aniline (2.83 g, 13 mmols), tetrakis triphenyl palladium (0) (0.508 g, 0.4 mmols), diethyl (4-pyridyl borane) (1.3 g, 9 mmols), potassium hydroxide (2.81 g, 50 mmols) and tetrabutylammonium bromide (1.42 g, 4 mmols) were combined in tetrahydrofuran (50 ml). The resulting mixture was heated at reflux for 18 hrs under nitrogen then cooled to ambient temperature. Ethyl acetate (100 ml) and brine (50 ml) were added and the organic solution was separated. This was dried over magnesium sulfate filtered and evaporated to yield a yellow solid. The product was purified by column chromatography on silica eluted with ethyl acetate:hexanes 50:50 to give 0.9 g of 2-Fluoro-N,N-dimethyl-4-(pyridin-4-yl)aniline (XII) in a 44% yield as a pale yellow solid.

후처리

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 18 hrs under nitrogen
  3. customthe organic solution was separated
  4. dry with materialThis was dried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customto yield a yellow solid
  8. customThe product was purified by column chromatography on silica
  9. washeluted with ethyl acetate:hexanes 50:50

출처 및 근거

ORD 기록
ord-679ebbcbb9de42268d302d621ffbe7de
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08647827B2

반응 노트

불러오는 중…