Binap, (A+-)- → 5-((5-Chloro-4-((1-methylpiperidin-4-yl)amino)pyridin-2-yl)amino)pyrazine-2-carbonitrile

HRID 556840ノート

反応式

HRID 556840 の反応式
[Cl:1][C:2]1[C:3]([NH:9][CH:10]2[CH2:15][CH2:14][N:13]([CH3:16])[CH2:12][CH2:11]2)=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=1.Br[C:18]1[C:23]([C:24]#[N:25])=[N:22][CH:21]=[CH:20][N:19]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+]>O1CCOCC1>[Cl:1][C:2]1[C:3]([NH:9][CH:10]2[CH2:15][CH2:14][N:13]([CH3:16])[CH2:12][CH2:11]2)=[CH:4][C:5]([NH:8][C:20]2[N:19]=[CH:18][C:23]([C:24]#[N:25])=[N:22][CH:21]=2)=[N:6][CH:7]=1

参加物

6

反応物 4

HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 596134945-Chloro-N4-(1-methylpiperidin-4-yl)pyridine-2,4-diamineHCID 626739383-Bromopyrazine-2-carbonitrile

生成物 1

HCID 596134475-((5-Chloro-4-((1-methylpiperidin-4-yl)amino)pyridin-2-yl)amino)pyrazine-2-carbonitrile収率 30.4%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

A solution of 5-chloro-N4-(1-methylpiperidin-4-yl)pyridine-2,4-diamine (0.080 g, 0.33 mmol), 2-bromo-cyanopyrazine (0.040 g, 0.22 mmol), BINAP (0.005 g, 0.02 mmol), sodium tert-butoxide (0.030 g, 0.31 mmol), tris(dibenzylideneacetone)dipalladium chloroform complex (0.009 g, 0.01 mmol) in dioxane (1.6 mL) was stirred at r.t. under nitrogen for 10 min before being heated under microwave irradiation for 30 min at 90° C. The crude reaction mixture was purified by ion exchange on SCX-II acidic resin (1 g) eluting with methanol/dichloromethane (1/1), then 2M ammonia-methanol. The basic fractions were combined and the solvent was removed in vacuo. The crude mixture was purified by preparative thin layer chromatography eluting with methanol/dichloromethane (1/9) to give the title compound as a yellow solid (0.023 g, 30%).

後処理

  1. customThe crude reaction mixture
  2. customwas purified by ion exchange on SCX-II acidic resin (1 g)
  3. washeluting with methanol/dichloromethane (1/1)
  4. customthe solvent was removed in vacuo
  5. customThe crude mixture was purified by preparative thin layer chromatography
  6. washeluting with methanol/dichloromethane (1/9)

出典と根拠

ORDレコード
ord-dfb53ea78a9a447a86dda950beb04cfd
出典データセット
uspto-grants-2011_11
特許番号
US08058045B2

反応ノート

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