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

HRID 1061772ノート

反応式

HRID 1061772 の反応式
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

参加物

6

反応物 2

HCID 881004-Bromopyridinium chlorideHCID 27343542-Fluorophenylboronic acid

生成物 1

HCID 132706464-(2-Fluorophenyl)pyridine

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒HCID 10340Sodium Carbonate溶媒

実験手順

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 organics were washed with water and saturated sodium hydrogencarbonate, dried over anhydrous magnesium sulfate, filtered and pre-adsorbed onto silica. Purification by chromatography on silica eluting with isohexane (containing 0.5% triethylamine) on a gradient of ethyl acetate (20-40%) afforded 4-(2-fluorophenyl)pyridine as a yellow oil that crystallised on standing (6.26 g, 94%): δH (400 MHz, CDCl3) 7.17-7.22 (1H, m), 7.26 (1H, ddd, J 8, 8 and 1), 7.38-7.44 (1H, m), 7.47-7.50 (3H, m), 8.68 (2H, d, J 4); m/z (ES+) 174 (M++H).

後処理

  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 organics were washed with water and saturated sodium hydrogencarbonate
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered and pre-adsorbed onto silica
  8. customPurification by chromatography on silica eluting with isohexane (containing 0.5% triethylamine) on a gradient of ethyl acetate (20-40%)

出典と根拠

ORDレコード
ord-a68cd858c7f74569ac5f5f288b36656d
出典データセット
uspto-grants-2005_11
特許番号
US06960598B2

反応ノート

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