Sodium Carbonate → Methyl-4-(6-chloropyrazolo[1,5-a]pyrimidin-3-yl)-5-methylthiophene-2-carboxylate

HRID 1842600ノート

反応式

HRID 1842600 の反応式
O1CCOCC1.Br[C:8]1[CH:9]=[N:10][N:11]2[CH:16]=[C:15]([Cl:17])[CH:14]=[N:13][C:12]=12.[CH3:18][O:19][C:20]([C:22]1[S:23][C:24]([CH3:36])=[C:25](B2OC(C)(C)C(C)(C)O2)[CH:26]=1)=[O:21].C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:18][O:19][C:20]([C:22]1[S:23][C:24]([CH3:36])=[C:25]([C:8]2[CH:9]=[N:10][N:11]3[CH:16]=[C:15]([Cl:17])[CH:14]=[N:13][C:12]=23)[CH:26]=1)=[O:21]

参加物

7

反応物 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 46703107Methyl 5-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxylateHCID 673469363-Bromo-6-chloropyrazolo[1,5-a]pyrimidine

生成物 1

HCID 67348535Methyl-4-(6-chloropyrazolo[1,5-a]pyrimidin-3-yl)-5-methylthiophene-2-carboxylate収率 67.7%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

To a flask containing 1,4-dioxane (58.1 mL) and water (19.4 mL) was added 3-bromo-6-chloropyrazolo[1,5-a]pyrimidine (3.60 g, 15.5 mmol), methyl-5-methyl-4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)-thiophene-2-carboxylate (4.37 g, 15.5 mmol), palladium tetrakis (895 mg, 0.774 mmol), and sodium carbonate (4.92 g, 46.5 mmol). The reaction mixture was sealed and degassed with N2 for 15 min. The reaction mixture was then heated to 100° C. for 2 h. The reaction was cooled to room temperature and partitioned between water and ethyl acetate. The organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by column chromatography (dichloromethane:hexane:ethyl acetate 20:75:5 to 20:60:20) to afford the title compound (3.23 g, 10.5 mmol). LRMS (APCI) calc'd for (C13H10ClN3O2S) [M+H]+, 308.0; found 308.0.

後処理

  1. customThe reaction mixture was sealed
  2. customdegassed with N2 for 15 min
  3. temperatureThe reaction was cooled to room temperature
  4. custompartitioned between water and ethyl acetate
  5. dry with materialThe organic layer was dried with sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude material was purified by column chromatography (dichloromethane:hexane:ethyl acetate 20:75:5 to 20:60:20)

出典と根拠

ORDレコード
ord-90be0aec3c08480d97191f115ef8f4e4
出典データセット
uspto-grants-2015_02
特許番号
US08946237B2

反応ノート

読み込み中…