Sodium Carbonate → 1,2-dimethyl-2H-pyrazolo[3,4-c]quinolin-4-amine

HRID 1360440

反応式

HRID 1360440 の反応式
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl.[NH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1B(O)O.Br[C:32]1[C:33]([C:39]#[N:40])=[N:34][N:35]([CH3:38])[C:36]=1[CH3:37].C(=O)([O-])[O-].[Na+].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.ClCCl.C(O)CC>[CH3:37][C:36]1[N:35]([CH3:38])[N:34]=[C:33]2[C:32]=1[C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][C:22]=1[N:21]=[C:39]2[NH2:40]

参加物

9

反応物 4

HCID 10340Sodium Carbonate2 回HCID 11776TriphenylphosphineHCID 164270902-Aminophenylboronic acid hydrochloride2 回HCID 669589664-bromo-1,5-dimethyl-1H-pyrazole-3-carbonitrile

生成物 1

HCID 577175181,2-dimethyl-2H-pyrazolo[3,4-c]quinolin-4-amine収率 20%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒2 回HCID 962Water溶媒3 回HCID 10311-Propanol溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
100 °C

実験手順

Triphenylphosphine (0.10 g, 0.45 mmol), 2-aminophenylboronic acid hydrochloride (3.89 g, 22.0 mmol), and 4-bromo-1,5-dimethyl-1H-pyrazole-3-carbonitrile (prepared as described in Parts A-C of Example 5, 3.00 g, 15.0 mmol) were placed in a flask. After 1-propanol was added (22 mL), the flask was placed under vacuum and back-filled with nitrogen three times. Palladium (II) acetate (30 mg, 0.15 mmol) was added, followed by aqueous sodium carbonate (22.5 mL of 2 M) and water (4.4 mL). The reaction was heated overnight under a nitrogen atmosphere at 100° C. Additional 2-aminophenylboronic acid hydrochloride (1.0 g), palladium (II) acetate (approximately 10 mg), aqueous sodium carbonate (10 mL of 2 M), and water (5 mL) were added. The reaction was heated at 100° C. for 8 hours, then was allowed to cool to ambient temperature. The reaction mixture was partioned between dichloromethane and water. The organic layer was concentrated under reduced pressure and the crude product was purified by chromatography on a HORIZON HPFC system (silica gel, gradient elution with 0-30% CMA in chloroform). The appropriate fractions were combined and concentrated under reduced pressure. The residue was dissolved in dichloromethane and concentrated under reduced pressure, which resulted in the formation of a solid. Hexanes were added to the solid, which was isolated by filtration and crystallized from acetonitrile to yield 0.637 g of 1,2-dimethyl-2H-pyrazolo[3,4-c]quinolin-4-amine as white needles, mp>250° C.

後処理

  1. additionback-filled with nitrogen three times
  2. temperatureThe reaction was heated at 100° C. for 8 hours
  3. temperatureto cool to ambient temperature
  4. concentrationThe organic layer was concentrated under reduced pressure
  5. customthe crude product was purified by chromatography on a HORIZON HPFC system (silica gel, gradient elution with 0-30% CMA in chloroform)
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe residue was dissolved in dichloromethane
  8. concentrationconcentrated under reduced pressure, which
  9. customresulted in the formation of a solid
  10. customwhich was isolated by filtration
  11. customcrystallized from acetonitrile

出典と根拠

ORDレコード
ord-3c29e927913b46a68c051655143cef0c
出典データセット
uspto-grants-2011_02
特許番号
US07879849B2

関連ノート

読み込み中…