Cesium carbonate → [2-(2,6-Dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridin-4-yl]-(2,6-dimethylpyrimidin-4-yl)amine

HRID 626686ノート

反応式

HRID 626686 の反応式
Cl[C:2]1[C:7]2=[CH:8][N:9]([C:11]3[C:16]([Cl:17])=[CH:15][C:14]([S:18]([CH3:21])(=[O:20])=[O:19])=[CH:13][C:12]=3[Cl:22])[N:10]=[C:6]2[CH:5]=[CH:4][N:3]=1.[NH2:23][C:24]1[CH:29]=[C:28]([CH3:30])[N:27]=[C:26]([CH3:31])[N:25]=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:17][C:16]1[CH:15]=[C:14]([S:18]([CH3:21])(=[O:20])=[O:19])[CH:13]=[C:12]([Cl:22])[C:11]=1[N:9]1[CH:8]=[C:7]2[C:2]([NH:23][C:24]3[CH:29]=[C:28]([CH3:30])[N:27]=[C:26]([CH3:31])[N:25]=3)=[N:3][CH:4]=[CH:5][C:6]2=[N:10]1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 680392,6-Dimethyl-4-aminopyrimidineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 866970454-Chloro-2-(2,6-dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine

生成物 1

HCID 69671279[2-(2,6-Dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridin-4-yl]-(2,6-dimethylpyrimidin-4-yl)amine収率 59.4%

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 4-chloro-2-(2,6-dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine (75 mg, 0.20 mmol), 4-amino-2,6-dimethylpyrimidine (27 mg, 0.22 mmol), Pd2(dba)3 (5 mg, 0.005 mmol), Xantphos (12 mg, 0.02 mmol) and cesium carbonate (130 mg, 0.40 mmol) in dioxane (2 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 washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (0-1% methanol in ethyl acetate) to afford the title compound as a yellow solid (55 mg, 59% yield). 1H NMR (400 MHz, DMSO-d6): δ 10.60 (br s, 1H), 9.21 (s, 1H), 8.32 (s, 2H), 8.30 (s, 1H), 7.99 (d, J=6.4 Hz, 1H), 7.21 (d, J=6.4 Hz, 1H), 3.48 (s, 3H), 2.49 (s, 3H), 2.40 (s, 3H). LCMS (Method B): RT=2.80 min, m/z: 463 [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. washThe organic layer was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel flash chromatography (0-1% methanol in ethyl acetate)

出典と根拠

ORDレコード
ord-5ab35d177b434488a1a8f3077fc02bd1
出典データセット
uspto-grants-2016_04
特許番号
US09309240B2

反応ノート

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