Sodium Carbonate → 1-Methyl-6-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine

HRID 1504761Notes

Reaction equation

HRID 1504761 reaction equation
Cl[C:2]1[N:7]=[C:6]2[N:8]([CH3:11])[N:9]=[CH:10][C:5]2=[C:4]([NH2:12])[N:3]=1.[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.O1CCOCC1.C(=O)([O-])[O-].[Na+].[Na+]>O>[CH3:11][N:8]1[C:6]2=[N:7][C:2]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)=[N:3][C:4]([NH2:12])=[C:5]2[CH:10]=[N:9]1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 66827Phenylboronic AcidHCID 2222506-chloro-1-methyl-1h-pyrazolo[3,4-d]pyrimidin-4-amine

Product 1

HCID 2426261-Methyl-6-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
170 °C

Procedure

A suspension of 6-chloro-1-methyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine (68 mg, 0.37 mmol), phenyl boronic acid (68 mg, 0.56 mmol), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride-dichloromethane complex (30 mg, 0.037 mmol), 1,4-dioxane (3 ml), water (0.2 ml), and aqueous sodium carbonate solution (2.0 M, 0.740 ml, 1.5 mmol) in a 5 mL microwave vial was deoxygenated using 10 alternate vacuum/argon flush cycles. The reaction mixture was then heated via microwave irradiation to 170° C. for 10 minutes. After cooling to room temperature, the reaction mixture was partitioned between ethyl acetate (40 mL) and saturated aqueous sodium bicarbonate solution (10 mL). The layers were separated and the organic layer was washed with brine (10 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (0.5-6.5% methanol/dichloromethane, linear gradient) to afford 1-methyl-6-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine. MS ESI calc'd. for C12H12N5 [M+H]+ 226. found 226.

Workup

  1. customwas deoxygenated
  2. customflush cycles
  3. temperatureAfter cooling to room temperature
  4. customthe reaction mixture was partitioned between ethyl acetate (40 mL) and saturated aqueous sodium bicarbonate solution (10 mL)
  5. customThe layers were separated
  6. washthe organic layer was washed with brine (10 mL)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by chromatography on silica gel (0.5-6.5% methanol/dichloromethane, linear gradient)

Sources & evidence

ORD record
ord-818049ffa0c94f6caf093063fc31ca4e
Source dataset
uspto-grants-2015_12
Patent number
US09216173B2

Reaction notes

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