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Cesium carbonate → 3,5-Dichloro-4-[7-chloro-4-(6-methylpyrimidin-4-ylamino)pyrazolo[4,3-c]pyridin-2-yl]benzonitrile

HRID 626708
ノート
印刷プレビュー

反応式

HRID 626708 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([Cl:21])[C:9]=1[N:10]1[CH:20]=[C:13]2[C:14](Cl)=[N:15][CH:16]=[C:17]([Cl:18])[C:12]2=[N:11]1)[C:5]#[N:6].[CH3:22][C:23]1[N:28]=[CH:27][N:26]=[C:25]([NH2:29])[CH:24]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.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]>[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([Cl:21])[C:9]=1[N:10]1[CH:20]=[C:13]2[C:14]([NH:29][C:25]3[CH:24]=[C:23]([CH3:22])[N:28]=[CH:27][N:26]=3)=[N:15][CH:16]=[C:17]([Cl:18])[C:12]2=[N:11]1)[C:5]#[N:6]
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 5728526-Methylpyrimidin-4-amineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 866970503,5-Dichloro-4-(4,7-dichloropyrazolo[4,3-c]pyridin-2-yl)benzonitrile

生成物 1

HCID 696715103,5-Dichloro-4-[7-chloro-4-(6-methylpyrimidin-4-ylamino)pyrazolo[4,3-c]pyridin-2-yl]benzonitrile
収率 43%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒

実験手順

A suspension of 3,5-dichloro-4-(4,7-dichloropyrazolo[4,3-c]pyridin-2-yl)benzonitrile (70 mg, 0.20 mmol), 6-methylpyrimidin-4-ylamine (23 mg, 0.22 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), Xantphos (12 mg, 0.02 mmol) and cesium carbonate (130 mg, 0.40 mmol) in dioxane (3 mL) was sealed in a microwave vial, purged with nitrogen and irradiated at 150° C. for 30 minutes in the microwave. The reaction mixture was cooled and partitioned between ethyl acetate and water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (0-80% ethyl acetate in pentane), then further triturated with ethyl acetate to afford the title compound as a yellow solid (37 mg, 43% yield). 1H NMR (400 MHz, DMSO-d6): δ 10.90 (s, 1H), 9.33 (s, 1H), 8.71 (d, J=1.2 Hz, 1H), 8.51 (s, 2H), 8.37 (s, 1H), 8.08 (s, 1H), 2.45 (s, 3H). LCMS (Method B): RT=3.69 min, m/z: 430 [M+H+].

後処理

  1. customwas sealed in a microwave vial
  2. custompurged with nitrogen
  3. customirradiated at 150° C. for 30 minutes in the microwave
  4. temperatureThe reaction mixture was cooled
  5. custompartitioned between ethyl acetate and water
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel flash chromatography (0-80% ethyl acetate in pentane)
  9. customfurther triturated with ethyl acetate

出典と根拠

ORDレコード
ord-9d1724df7d93457680b57e2aa35034a9
出典データセット
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09309240B2

反応ノート

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