4-Bromopyridinium chloride → 4-(2-Fluorophenyl)pyridine

HRID 586267노트

반응식

HRID 586267 반응식
Cl.Br[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.[F:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1B(O)O>O1CCCC1.C(=O)([O-])[O-].[Na+].[Na+].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1

참가 물질

6

반응물 2

HCID 881004-Bromopyridinium chlorideHCID 27343542-Fluorophenylboronic acid

생성물 1

HCID 132706464-(2-Fluorophenyl)pyridine

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 8028Tetrahydrofuran용매HCID 10340Sodium Carbonate용매

실험 절차

A mixture of 4-bromopyridine hydrochloride (7.5 g, 38.6 mmol) and 2-fluorobenzeneboronic acid (6.75 g, 48 mmol) in tetrahydrofuran (80 ml) and 2 M sodium carbonate (58 ml) was degassed with nitrogen for 20 min then tetrakis(triphenylphosphine)palladium(0) (1.34 g, 1.2 mmol) was added and the reaction heated at reflux for 24 h. The mixture was cooled to ambient temperature then partitioned between ethyl acetate and 10% sodium carbonate. The organic layer was washed with water, then saturated sodium hydrogencarbonate, dried over anhydrous magnesium sulfate, filtered and pre-adsorbed onto silica. Purification by chromatography [silica gel, 20-40% EtOAc/isohexane (containing 0.5% triethylamine)] afforded 4-(2-fluorophenyl)pyridine as a yellow oil that crystallised on standing (6.26 g, 94%): 1H NMR (400 MHz, CDCl3) δ 7.17-7.22 (1H, m), 7.26 (1H, ddd, J 8, 8, 1 Hz), 7.38-7.44 (1H, m), 7.47-7.50 (3H, m), 8.68 (2H, d, J 4 Hz); MS (ES+) m/z 174 [M+H]+.

후처리

  1. customwas degassed with nitrogen for 20 min
  2. temperaturethe reaction heated
  3. temperatureat reflux for 24 h
  4. customthen partitioned between ethyl acetate and 10% sodium carbonate
  5. washThe organic layer was washed with water
  6. dry with materialsaturated sodium hydrogencarbonate, dried over anhydrous magnesium sulfate
  7. filtrationfiltered and pre-adsorbed onto silica
  8. customPurification by chromatography [silica gel, 20-40% EtOAc/isohexane (containing 0.5% triethylamine)]

출처 및 근거

ORD 기록
ord-d86505800a154de1a11d60824fea7e46
출처 데이터셋
uspto-grants-2005_08
특허 번호
US06936608B2

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