Toluene → 2'-Fluoro-4'-(hydroxymethyl)biphenyl-2-carbonitrile

HRID 519540노트

반응식

HRID 519540 반응식
[F:1][C:2]1[CH:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][C:3]=1B(O)O.[C:13]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O)#[N:14].C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:1][C:2]1[CH:7]=[C:6]([CH2:8][OH:9])[CH:5]=[CH:4][C:3]=1[C:16]1[C:15]([C:13]#[N:14])=[CH:20][CH:19]=[CH:18][CH:17]=1

참가 물질

8

반응물 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 27346102-Cyanophenylboronic acidHCID 162180452-Fluoro-4-formylbenzeneboronic acid

생성물 1

HCID 670099902'-Fluoro-4'-(hydroxymethyl)biphenyl-2-carbonitrile수율 30%

시약·촉매·용매 3

HCID 74236Tetrabutylammonium Bromide촉매HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 8857Ethyl Acetate용매

반응 조건

온도
100 °C

실험 절차

A mixture of (2-fluoro-4-formylphenyl)boronic acid (35.3 g), 2-cyano-phenylboronic acid (40.0 g), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (1.7 g), tetrabutylammonium bromide (0.68 g), 2M aqueous sodium carbonate solution (200 mL) and toluene (600 mL) was stirred at 100° C. for 72 hr under an argon atmosphere. The reaction mixture was diluted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The obtained residue was dissolved in tetrahydrofuran (150 mL) and methanol (150 mL), sodium borohydride (8.7 g) was added, and the mixture was stirred at room temperature for 1 hr. After evaporation of the solvent under reduced pressure, the residue was extracted with water and ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography to give the title compound as a colorless solid (14.1 g, 30%).

후처리

  1. washwashed with saturated brine
  2. dry with materialdried over anhydrous magnesium sulfate
  3. customThe solvent was evaporated under reduced pressure
  4. dissolutionThe obtained residue was dissolved in tetrahydrofuran (150 mL)
  5. additionmethanol (150 mL), sodium borohydride (8.7 g) was added
  6. stirringthe mixture was stirred at room temperature for 1 hr
  7. customAfter evaporation of the solvent under reduced pressure
  8. extractionthe residue was extracted with water and ethyl acetate
  9. washThe obtained ethyl acetate layer was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customThe solvent was evaporated under reduced pressure
  12. customthe residue was purified by silica gel column chromatography

출처 및 근거

ORD 기록
ord-e972dbf813b44734907bc4b81c53e022
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09115136B2

반응 노트

불러오는 중…