Cesium carbonate → N-(6-methoxypyridin-3-yl)-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)-2-(pyridin-4-yl)pyrimidin-4-amine

HRID 1811945ノート

反応式

HRID 1811945 の反応式
Cl[C:2]1[N:7]=[C:6]([NH:8][C:9]2[CH:10]=[N:11][C:12]([O:15][CH3:16])=[CH:13][CH:14]=2)[C:5]([C:17]2[N:22]=[C:21]([CH3:23])[N:20]=[C:19]([S:24][CH3:25])[N:18]=2)=[CH:4][N:3]=1.[N:26]1[CH:31]=[CH:30][C:29](B(O)O)=[CH:28][CH:27]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.[NH4+].[Cl-].[Pd+2].ClC1C=C[C-](P(C2C=CC=CC=2)C2C=CC=CC=2)C=1Cl.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:16][O:15][C:12]1[N:11]=[CH:10][C:9]([NH:8][C:6]2[C:5]([C:17]3[N:22]=[C:21]([CH3:23])[N:20]=[C:19]([S:24][CH3:25])[N:18]=3)=[CH:4][N:3]=[C:2]([C:29]3[CH:30]=[CH:31][N:26]=[CH:27][CH:28]=3)[N:7]=2)=[CH:14][CH:13]=1

参加物

7

反応物 3

HCID 10796Cesium carbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 866470542-chloro-N-(6-methoxypyridin-3-yl)-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)pyrimidin-4-amine

生成物 1

HCID 66611390N-(6-methoxypyridin-3-yl)-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)-2-(pyridin-4-yl)pyrimidin-4-amine収率 26%

試薬・触媒・溶媒 3

HCID 178478230HCID 178478230、化合物触媒HCID 25517Ammonium Chloride溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

A mixture of 2-chloro-N-(6-methoxypyridin-3-yl)-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)pyrimidin-4-amine (38 mg, 0.101 mmol), pyridine-4-boronic acid (14.91 mg, 0.121 mmol), dichloro 1,1′-bis(diphenylphosphino)ferrocene palladium(II) (8.26 mg, 10.11 μmol) and cesium carbonate (39 mg, 0.121 mmol) in dioxane (1 mL) was stirred at 100° C. for 1 h. The mixture was cooled down to room temperature. The reaction mixture was diluted with saturated NH4Cl (10 mL) and extracted with EtOAc (2×20 mL). The organic extract was washed with saturated NaCl (5 mL) and dried over Na2SO4. The solution was filtered and concentrated in vacuo to give the crude product as an orange solid. The crude product was purified by silica gel chromatography eluting with 10% MeOH/EtOAc to give N-(6-methoxypyridin-3-yl)-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)-2-(pyridin-4-yl)pyrimidin-4-amine (11 mg, 0.026 mmol, 26.0% yield). 1H NMR (300 MHz, CDCl3) δ 11.69 (s, 1H); 9.78 (s, 1H); 8.62-9.02 (m, 2H); 8.46 (s, 1H); 8.29-8.43 (m, 1H); 8.24 (d, J=4.53 Hz, 1H); 8.04-8.14 (m, 1H); 6.79-6.93 (m, 1H); 5.30 (s, 2H); 4.00 (s, 3H); 2.69 (s, 3H); 2.67 (s, 3H). m/z (ESI, +ve ion) 419.1 (M+H)+.

後処理

  1. temperatureThe mixture was cooled down to room temperature
  2. extractionextracted with EtOAc (2×20 mL)
  3. extractionThe organic extract
  4. washwas washed with saturated NaCl (5 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationThe solution was filtered
  7. concentrationconcentrated in vacuo
  8. customto give the crude product as an orange solid
  9. customThe crude product was purified by silica gel chromatography
  10. washeluting with 10% MeOH/EtOAc

出典と根拠

ORDレコード
ord-8eab79a67b79420b9b3444a23c81de3e
出典データセット
uspto-grants-2013_01
特許番号
US08362241B2

反応ノート

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