Sodium Carbonate → 4-[4-Fluoro-3-(trifluoromethyl)phenyl]pyridine

HRID 1246839ノート

反応式

HRID 1246839 の反応式
[N:1]1[CH:6]=[CH:5][C:4](B(O)O)=[CH:3][CH:2]=1.Br[C:11]1[CH:12]=[CH:13][C:14]([F:21])=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:16]=1.C(=O)([O-])[O-].[Na+].[Na+]>C(O)CC.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:21][C:14]1[CH:13]=[CH:12][C:11]([C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)=[CH:16][C:15]=1[C:17]([F:18])([F:19])[F:20]

参加物

8

反応物 3

HCID 10340Sodium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 27363255-Bromo-2-fluorobenzotrifluoride

生成物 1

HCID 219067584-[4-Fluoro-3-(trifluoromethyl)phenyl]pyridine収率 54%

試薬・触媒・溶媒 4

HCID 11776Triphenylphosphine触媒HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 10311-Propanol溶媒

実験手順

First, 4-(4-fluoro-3-trifluoromethyl-phenyl)-pyridine 73 was prepared as follows. To a suspension of pyridine-4-boronic acid (2.59 g, 21.1 mmol) in 1-propanol (60 mL) was added 5-bromo-2-fluorobenzotrifluoride (5.12 g, 21.1 mmol) and triphenylphosphine (0.160 g, 0.610 mmol), followed by sodium carbonate in water (2.0 M, 12 mL). The mixture was purged with nitrogen gas for 10 minutes. To it was added palladium(II) acetate (0.044 g, 0.196 mmol) and it was then heated under reflux for 4 hours. The reaction mixture was partitioned between ethyl acetate (200 mL) and water (200 mL). The organic layer was separated, washed with brine (3×200 mL), dried over MgSO4, then filtered. After evaporating the solvent, the crude material was loaded to a silica gel column, eluting with 60% ethyl acetate in hexane to give a white solid 73 (2.73 g, 54%). 1H-NMR (CDCl3, 400 MHz) δ 7.34–7.42 (m, 1H), 7.61–7.65 (m, 2H), 7.80–7.93 (m, 2H), 8.73–8.84 (m, 2H); MS (DCI) m/z 242, 243 (M+H)+.

後処理

  1. customFirst, 4-(4-fluoro-3-trifluoromethyl-phenyl)-pyridine 73 was prepared
  2. customThe mixture was purged with nitrogen gas for 10 minutes
  3. temperaturewas then heated
  4. temperatureunder reflux for 4 hours
  5. customThe reaction mixture was partitioned between ethyl acetate (200 mL) and water (200 mL)
  6. customThe organic layer was separated
  7. washwashed with brine (3×200 mL)
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customAfter evaporating the solvent
  11. washeluting with 60% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-ae6eb645e3574b97b200556e8c2dd704
出典データセット
uspto-grants-2006_10
特許番号
US07129247B2

反応ノート

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