Toluene → 3-{[4-(1-Methylethyl)phenoxy]methyl}pyridin-2-amine

HRID 2035795ノート

反応式

HRID 2035795 の反応式
CC(C)([O-])C.[Na+].C1(C(C2C=CC=CC=2)=[NH:14])C=CC=CC=1.Cl[C:22]1[C:27]([CH2:28][O:29][C:30]2[CH:35]=[CH:34][C:33]([CH:36]([CH3:38])[CH3:37])=[CH:32][CH:31]=2)=[CH:26][CH:25]=[CH:24][N:23]=1.C1(C)C=CC=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1COCC1>[CH3:37][CH:36]([C:33]1[CH:34]=[CH:35][C:30]([O:29][CH2:28][C:27]2[C:22]([NH2:14])=[N:23][CH:24]=[CH:25][CH:26]=2)=[CH:31][CH:32]=1)[CH3:38]

参加物

8

反応物 4

HCID 1140TolueneHCID 136809Benzophenone imineHCID 23676156Sodium t-butoxideHCID 624715482-Chloro-3-{[4-(1-methylethyl)phenoxy]methyl}pyridine

生成物 1

HCID 150356783-{[4-(1-Methylethyl)phenoxy]methyl}pyridin-2-amine収率 87%

試薬・触媒・溶媒 3

HCID 634876Binap, (A+-)-触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
110 °C

実験手順

A mixture of sodium tert-butoxide (0.617 g), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.160 g), 1,1-diphenylmethanimine (1.008 g), 2-chloro-3-{[4-(1-methylethyl)phenoxy]methyl}pyridine (1.12 g), tris(dibenzylideneacetone)dipalladium(0) (0.118 g) and toluene (20 mL) was stirred at 110° C. for 6 hr. To the reaction mixture was added THF, and the mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. To the residue were added THF (25 mL) and 1M hydrochloric acid (25 mL) at room temperature, and the mixture was stirred overnight. The reaction mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution, and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (ethyl acetate/hexane) to give the title compound (902.2 mg) containing impurity as a pale-yellow oil.

後処理

  1. filtrationthe mixture was filtered through celite
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. additionTo the residue were added THF (25 mL) and 1M hydrochloric acid (25 mL) at room temperature
  4. stirringthe mixture was stirred overnight
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with water and saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by basic silica gel column chromatography (ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-a63b3febe86f4bdbb46040cd0dd8c9d2
出典データセット
uspto-grants-2013_11
特許番号
US08575154B2

反応ノート

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