2,2'-Bipyridine → (E)-4-(3-(3,5-dichloro-4-fluorophenyl)-4,4,4-trifluorobut-1-enyl)-2-(trifluoromethoxy)benzoic acid

HRID 1503515노트

반응식

HRID 1503515 반응식
[F:1][C:2]([F:16])([F:15])[O:3][C:4]1[CH:12]=[C:11]([CH:13]=[CH2:14])[CH:10]=[CH:9][C:5]=1[C:6]([OH:8])=[O:7].Br[CH:18]([C:23]1[CH:28]=[C:27]([Cl:29])[C:26]([F:30])=[C:25]([Cl:31])[CH:24]=1)[C:19]([F:22])([F:21])[F:20].N1C=CC=CC=1C1C=CC=CN=1>CN1CCCC1.O.[Cu]Cl>[Cl:29][C:27]1[CH:28]=[C:23]([CH:18]([C:19]([F:22])([F:21])[F:20])/[CH:14]=[CH:13]/[C:11]2[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([O:3][C:2]([F:15])([F:16])[F:1])[CH:12]=2)[CH:24]=[C:25]([Cl:31])[C:26]=1[F:30]

참가 물질

7

반응물 3

HCID 14742,2'-BipyridineHCID 866751625-(1-Bromo-2,2,2-trifluoroethyl)-1,3-dichloro-2-fluorobenzeneHCID 893063732-(Trifluoromethoxy)-4-vinylbenzoic acid

생성물 1

HCID 86675151(E)-4-(3-(3,5-dichloro-4-fluorophenyl)-4,4,4-trifluorobut-1-enyl)-2-(trifluoromethoxy)benzoic acid수율 41.1%

시약·촉매·용매 3

HCID 62652Cuprous chloride촉매HCID 962Water용매HCID 84541-Methylpyrrolidine용매

반응 조건

온도
150 °C

실험 절차

To a stirred solution of 2-(trifluoromethoxy)-4-vinylbenzoic acid (0.356 g, 1.53 mmol) in 1N methyl pyrrolidine (5.0 mL) was added 1-(1-bromo-2,2,2-trifluoroethyl)-3,5-dichloro 4-fluorobenzene (1.0 g, 3.07 mmol), copper(I) chloride (CuCl; 0.03 g, 0.307 mmol) and 2,2 bipyridyl (0.095 g, 0.614 mmol). The reaction mixture was stirred at 150° C. for 1 h. After the reaction was complete by TLC, the reaction mixture was diluted with water (100 mL) and extracted with ethyl acetate (2×50 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure to obtain the crude compound which was purified by flash column chromatography to afford the product as pale yellow gummy material (0.3 g, 21%): 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J=8.0 Hz, 1H), 7.45 (d, J=1.6 Hz, 1H), 7.35 (s, 3H), 6.63 (d, J=16.0 Hz, 1H), 6.50 (dd, J=16.0, 8.0 Hz, 1H), 4.15 (m, 1H); ESIMS m/z 474.81 ([M−H]−).

후처리

  1. extractionextracted with ethyl acetate (2×50 mL)
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. customto obtain the crude compound which
  6. customwas purified by flash column chromatography

출처 및 근거

ORD 기록
ord-ffae36ffdaca4d1f85adda6c1028f51f
출처 데이터셋
uspto-grants-2015_12
특허 번호
US09212163B2

반응 노트

불러오는 중…