Cesium carbonate → Ethyl 6'-{[(ethylamino)carbonyl]amino}-4'-(4-phenyl-1,3-thiazol-2-yl)-3,3'-bipyridine-5-carboxylate

HRID 2243036ノート

反応式

HRID 2243036 の反応式
Br[C:2]1[C:3]([C:14]2[S:15][CH:16]=[C:17]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[N:18]=2)=[CH:4][C:5]([NH:8][C:9]([NH:11][CH2:12][CH3:13])=[O:10])=[N:6][CH:7]=1.CC1(C)C(C)(C)OB([C:33]2[CH:34]=[N:35][CH:36]=[C:37]([CH:43]=2)[C:38]([O:40][CH2:41][CH3:42])=[O:39])O1.C(=O)([O-])[O-].[Cs+].[Cs+]>>[CH2:12]([NH:11][C:9]([NH:8][C:5]1[N:6]=[CH:7][C:2]([C:33]2[CH:34]=[N:35][CH:36]=[C:37]([C:38]([O:40][CH2:41][CH3:42])=[O:39])[CH:43]=2)=[C:3]([C:14]2[S:15][CH:16]=[C:17]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[N:18]=2)[CH:4]=1)=[O:10])[CH3:13]

参加物

4

反応物 3

HCID 10796Cesium carbonateHCID 3816953Ethyl 5-(tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-3-carboxylateHCID 592085041-(5-Bromo-4-(4-phenylthiazol-2-yl)pyridin-2-yl)-3-ethylurea2 回

生成物 1

HCID 59208481Ethyl 6'-{[(ethylamino)carbonyl]amino}-4'-(4-phenyl-1,3-thiazol-2-yl)-3,3'-bipyridine-5-carboxylate収率 100.6%

反応条件

温度
100 °C

実験手順

N-[5-bromo-4-(4-phenyl-1,3-thiazol-2-yl)pyridin-2-yl]-N′-ethylurea (Intermediate 69, 0.17 g, 0.42 mmol), ethyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nicotinate (0.14 g, 0.51 mmol), tetrakis triphenyl phosphine palladium (0.024 g, 0.02 mmol), and cesium carbonate (0.165 g, 0.51 mmol) were combined in a microwave vial and degassed with nitrogen. 1,4-dioxane:water (4:1, 2.5 mL) was added to the mixture and the reaction mixture was heated to 100° C. for 60 minutes. The reaction mixture was partitioned between water and ethyl acetate and the layers separated. The organic layer was washed with saturated NaHCO3, water, and brine, then dried over magnesium sulfate. The organic layer was concentrated to form a precipitate, and the resulting solids were filtered and then washed with acetonitrile followed by chloroform to yield 200 mg of the title compound as an off-white solid. LC/MS (ES+)[(M+H)+]: 474 for C25H23N5O3S. 1H NMR (300 MHz, CHCl3): 1.28 (t, 3H), 1.39 (t, 3H), 3.44-3.49 (m, 2H), 4.41 (q, 2H), 7.31-7.39 (m, 2H), 7.52 (s, 1H), 7.62 (d, 2H), 8.17 (s, 1H), 8.28 (t, 1H), 8.32 (t, 1H), 8.4 (s, 1H), 8.71 (d, 1H), 8.73 (d, 1H), 9.23 (d, 1H), 9.27 (s, 1H).

後処理

  1. customdegassed with nitrogen
  2. addition1,4-dioxane:water (4:1, 2.5 mL) was added to the mixture
  3. customThe reaction mixture was partitioned between water and ethyl acetate
  4. customthe layers separated
  5. washThe organic layer was washed with saturated NaHCO3, water, and brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationThe organic layer was concentrated
  8. customto form a precipitate
  9. filtrationthe resulting solids were filtered
  10. washwashed with acetonitrile

出典と根拠

ORDレコード
ord-ac4df2b0165d4e2aa519a8944164f906
出典データセット
uspto-grants-2010_03
特許番号
US07674801B2

反応ノート

読み込み中…