Sodium Carbonate → 4-[2-Methyl-5-(methyloxy)-4-nitrophenyl]pyridine

HRID 419520ノート

反応式

HRID 419520 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[C:7](Br)[C:6]([CH3:10])=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].[N:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.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]>[CH3:10][C:6]1[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[C:3]([O:2][CH3:1])=[CH:8][C:7]=1[C:17]1[CH:18]=[CH:19][N:14]=[CH:15][CH:16]=1

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 59441753HCID 59441753、化合物

生成物 1

HCID 594526494-[2-Methyl-5-(methyloxy)-4-nitrophenyl]pyridine収率 57%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

A solution of 5-bromo-4-methyl-2-nitrophenyl methyl ether (6.0 g, 24.38 mmol), PdCl2(dppf)*DCM (1.43 g, 1.95 mmol) and 4-pyridylboronic acid (20.4 g, 165.8 mmol) in dioxane was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 2.0 N Na2CO3 (aq) (170 mL, 14.0 equiv.) and the resulting slurry was warmed to 80° C. for 24 h. The dioxane was removed under reduced pressure and the solids were dissolved in EtOAc and washed with H2O, dried (Na2SO4), and purified by flash chromatography to give the title compound of step A (2.81 g, 11.5 mmol, 57%). 1H NMR (400 MHz, CDCl3) δ ppm 8.72 (d, J=4.77 Hz, 2H), 7.79 (s, 1H), 7.22-7.31 (m, 2H), 6.90 (s, 1H), 3.95 (s, 3H), 2.22 (s, 3H).

後処理

  1. customby bubbling with N2 (g) for ca 15 min
  2. additionTo this solution was added
  3. customThe dioxane was removed under reduced pressure
  4. dissolutionthe solids were dissolved in EtOAc
  5. washwashed with H2O
  6. dry with materialdried (Na2SO4)
  7. custompurified by flash chromatography

出典と根拠

ORDレコード
ord-463722b9566b486ea014b0a3e8f74ce3
出典データセット
uspto-grants-2012_01
特許番号
US08093239B2

反応ノート

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