Dimethylformamide → HCID 67499832, compound

HRID 921580Notes

Reaction equation

HRID 921580 reaction equation
N[C:2]1[CH:3]=[C:4]([CH:7]=C[C:9]=1[N:10]1[C:14]2=[N:15][CH:16]=[CH:17][C:18]([I:19])=[C:13]2[C:12]([C:20]([F:23])([F:22])[F:21])=[N:11]1)[C:5]#[N:6].IC.[H-].[Na+].C(OCC)(=O)C.[CH3:34][N:35]([CH:37]=O)[CH3:36]>O>[CH3:34][N:35]([CH3:36])[C:37]1[CH:7]=[C:4]([CH:3]=[CH:2][C:9]=1[N:10]1[C:14]2=[N:15][CH:16]=[CH:17][C:18]([I:19])=[C:13]2[C:12]([C:20]([F:23])([F:21])[F:22])=[N:11]1)[C:5]#[N:6]

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 67500719HCID 67500719, compound

Product 1

HCID 67499832HCID 67499832, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Compound (158a) (0.100 g) and iodomethane (0.18 mL) were dissolved in DMF (6.0 mL), and sodium hydride (0.038 g, a 55% dispersion in paraffin liquid) was added to the resulting solution under ice cooling, followed by stirring for 1 hr. The reaction solution was distributed between ethyl acetate and water, and the organic layer was washed with saturated saline. The organic layer after the washing was dried over anhydrous sodium sulfate, and then the solvent was distilled away to obtain 3-(dimethylamino)-4-{4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl}benzonitrile, which was used in the subsequent reaction without being purified. This 3-(dimethylamino)-4-{4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl}benzonitrile was dissolved in DMSO (3.0 mL), and a hydrogen peroxide solution (30 wt %) (0.060 mL) and a 4 mol % aqueous sodium hydroxide solution (0.15 mL) were added to the resulting solution, followed by stirring at room temperature for 20 min. Water was added to the reaction solution, and the precipitate was collected by filtration and dried under reduced pressure to obtain 3-(dimethylamino)-4-{4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl}benzamide. Lastly, according to Example 99(2), compound (159) (0.025 g, the third stage yield: 17%) was prepared using 3-(dimethylamino)-4-{4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl}benzamide instead of compound (99a).

Workup

  1. washthe organic layer was washed with saturated saline
  2. dry with materialThe organic layer after the washing was dried over anhydrous sodium sulfate
  3. distillationthe solvent was distilled away

Sources & evidence

ORD record
ord-3df0079bd29649b18a3b92ed7cd6bc00
Source dataset
uspto-grants-2016_03
Patent number
US09273045B2

Reaction notes

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