Stannane, tributyl(1-ethoxyethenyl)- → 6-(4-Acetyl-phenyl)-5-(4-chloro-phenyl)-1-phenyl-1,5-dihydro-pyrazolo[3,4-d]pyrimidin-4-one

HRID 1693514Notes

Reaction equation

HRID 1693514 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]([C:24]3[CH:29]=[CH:28][C:27]([Cl:30])=[CH:26][CH:25]=3)[C:10](=[O:23])[C:11]3[CH:16]=[N:15][N:14]([C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)[C:12]=3[N:13]=2)=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:36]([O:38]CC)=[CH2:37])CCC>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.C1(C)C=CC=CC=1>[C:36]([C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]([C:24]3[CH:25]=[CH:26][C:27]([Cl:30])=[CH:28][CH:29]=3)[C:10](=[O:23])[C:11]3[CH:16]=[N:15][N:14]([C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)[C:12]=3[N:13]=2)=[CH:4][CH:3]=1)(=[O:38])[CH3:37]

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 20472026-(4-Bromophenyl)-5-(4-chlorophenyl)-1-phenyl-1H,4H,5H-pyrazolo[3,4-D]pyrimidin-4-one

Product 1

HCID 116765606-(4-Acetyl-phenyl)-5-(4-chloro-phenyl)-1-phenyl-1,5-dihydro-pyrazolo[3,4-d]pyrimidin-4-oneYield 97.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a reaction vessel charged with 6-(4-bromo-phenyl)-5-(4-chloro-phenyl)-1-phenyl-1,5-dihydro-pyrazolo[3,4-d]pyrimidin-4-one (0.5 g, 1.05 mmol), tributyl-(1-ethoxy-vinyl)-stannane (0.49 g, 1.36 mmol), Pd (PPh3)4 (0.061 g, 0.053 mmol) and toluene (5 mL) is purged with N2 and heated to 100° C. for 2 h. After cooling down to room temperature, the solvent is removed under vacuum and the residue is treated with acetonitrile (10 mL) and 1 N HCl (40 mL) for 1 h. The mixture is then extracted with EtOAc (3×30 mL) and the combined organic layer is washed with saturated aqueous KF solution (20 mL). The resulted precipitate is removed by filtration and washed with EtOAc (2×10 mL). The organic layer is washed with brine and dried (MgSO4). After filtering off the drying agent, the solvent is removed under vacuum and the residue is purified by flash column chromatography (silica gel, 0%˜50% EtOAc/hexane) to provide the titled compound 6-(4-acetyl-phenyl)-5-(4-chloro-phenyl)-1-phenyl-1,5-dihydro-pyrazolo[3,4-d]pyrimidin-4-one (450 mg, 95%). HPLC-MS calculated for C25H17ClN4O2 (M+1+): 441.1. Found: 441.1.

Workup

  1. customis purged with N2
  2. temperatureAfter cooling down to room temperature
  3. customthe solvent is removed under vacuum
  4. additionthe residue is treated with acetonitrile (10 mL) and 1 N HCl (40 mL) for 1 h
  5. extractionThe mixture is then extracted with EtOAc (3×30 mL)
  6. washthe combined organic layer is washed with saturated aqueous KF solution (20 mL)
  7. customThe resulted precipitate is removed by filtration
  8. washwashed with EtOAc (2×10 mL)
  9. washThe organic layer is washed with brine
  10. dry with materialdried (MgSO4)
  11. filtrationAfter filtering off the drying agent
  12. customthe solvent is removed under vacuum
  13. customthe residue is purified by flash column chromatography (silica gel, 0%˜50% EtOAc/hexane)

Sources & evidence

ORD record
ord-bf371265a4d74ccf999e64f2bfe9dfb4
Source dataset
uspto-grants-2012_04
Patent number
US08158634B2

Reaction notes

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