Acetone → 4-Fluorobiphenyl

HRID 571448

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HRID 571448 반응식
[OH-].[Na+].[C:3]1([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.CC(C)=O.[F:22][BH-](F)F.F[BH-](F)F.ClC[N+]12CC[N+](F)(CC1)CC2>CO.C(S([O-])(=O)=O)(F)(F)F.[Ag+]>[F:22][C:6]1[CH:7]=[CH:8][C:3]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:4][CH:5]=1

참가 물질

7

반응물 4

HCID 180AcetoneHCID 14798Sodium HydroxideHCID 1512531,1'-Biphenyl-4-yl-boronic acidHCID 1317328221-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(trifluoroborate)

생성물 1

HCID 94614-Fluorobiphenyl수율 94.1%

시약·촉매·용매 2

HCID 76223Silver(I) trifluoromethanesulfonate촉매HCID 887Methanol용매

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온도
23 °C

실험 절차

To NaOH (480 mg, 12.0 mmol, 1.20 equiv) in MeOH (20 mL) at 23° C. was added 4-biphenylboronic acid (1.98 g, 10.0 mmol, 1.00 equiv). After stirring for 15 min at 23° C., the reaction mixture was cooled to 0° C. and was added to AgOTf (7.71 g, 30.0 mmol, 3.00 equiv). After stirring for 30 min at 0° C., the solvent was removed under reduced pressure at 0° C. and the residual MeOH was completely removed by co-evaporation with acetone (20 mL×2). To the residue was added acetone (50 mL), MS3 Å (5.0 g), and 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(trifluoroborate) (1) (3.72 g, 10.5 mmol, 1.05 equiv) and the reaction mixture was stirred for 30 min and concentrated in vacuo. The residue was dissolved in CH2Cl2 and filtered through a plug of Celite. After the removal of CH2Cl2, to the residue was added H2O (30 mL) and Et2O (30 mL) and the phases were separated. The aqueous phase was extracted with Et2O (2×20 mL). The combined organic phases are washed with brine (30 mL) and dried (Na2SO4). The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica gel eluting with hexanes to afford 1.62 g of 4-fluorobiphenyl as a colorless solid (94% yield).

후처리

  1. temperaturethe reaction mixture was cooled to 0° C.
  2. stirringAfter stirring for 30 min at 0° C.
  3. customthe solvent was removed under reduced pressure at 0° C.
  4. customthe residual MeOH was completely removed by co-evaporation with acetone (20 mL×2)
  5. stirringthe reaction mixture was stirred for 30 min
  6. concentrationconcentrated in vacuo
  7. dissolutionThe residue was dissolved in CH2Cl2
  8. filtrationfiltered through a plug of Celite
  9. customAfter the removal of CH2Cl2
  10. additionto the residue was added H2O (30 mL) and Et2O (30 mL)
  11. customthe phases were separated
  12. extractionThe aqueous phase was extracted with Et2O (2×20 mL)
  13. washThe combined organic phases are washed with brine (30 mL)
  14. dry with materialdried (Na2SO4)
  15. concentrationThe filtrate was concentrated in vacuo
  16. customthe residue was purified by chromatography on silica gel eluting with hexanes

출처 및 근거

ORD 기록
ord-9402b9119c624e60bd23531423334d89
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09024093B2

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