Nitrogen → 5,6-dihydro-1H-pyrazolo(3,4-c)pyridin-7(4H)-one

HRID 25171Notes

Reaction equation

HRID 25171 reaction equation
C(C1C=C([N:10]2[C:14]3[C:15](=[O:26])[N:16](C4C=CC(Br)=CC=4)[CH2:17][CH2:18][C:13]=3[C:12](C)=[N:11]2)C=CC=1F)#N.N#N.CCOC(C)=O>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].C1C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+].[Cl-].[Na+].O>[NH:10]1[C:14]2[C:15](=[O:26])[NH:16][CH2:17][CH2:18][C:13]=2[CH:12]=[N:11]1

Participants

8

Reactant 3

HCID 947NitrogenHCID 8857Ethyl AcetateHCID 225662481-[3-cyano-4-fluorophenyl]-3-methyl-6-[4-bromophenyl]-1,4,5,6-tetrahydro-7H-pyrazolo[3,4-c]pyridin-7-one

Product 1

HCID 179257945,6-dihydro-1H-pyrazolo(3,4-c)pyridin-7(4H)-one

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 241BenzeneSolventHCID 10340Sodium CarbonateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

1-[3-Cyano-4-fluorophenyl)-3-methyl-6-[4-bromophenyl]-1,4,5,6-tetrahydro-7H-pyrazolo-[3,4-c]-pyridin-7-one (Example 47, Part B; 0.23 g, 0.54 mmol), 2-thiomethylphenylboronic acid (0.13 g, 0.76 mmol) and Bu4NBr (0.011 g) in C6H6 (20 mL) and 2N Na2CO3 (4 mL) was purged with a stream of N2 gas. Palladium tetrakis(triphenyl) phosphine (0.032 g, 0.028 mmol) was added and the mixture heated at reflux for 18 h. To the cooled reaction mixture, brine and EtOAc was added and the layers separated. The organic layer was dried (MgSO4) and evaporated then the residue was purified by silica gel chromatography (100 g of SiO2, eluted with 1:1 hexane:EtOAc) to give 0.17 g (3.2 mmol) of 1-[3-cyano-4-fluorophenyl]-3-methyl-6-[2′-thiomethyl)-[1,1′]-biphen-4-yl]-1,4,5,6-tetrahydro-7H-pyrazolo-[3,4-c]-pyridin-7-one; LRMS (M+H)+: 469.0 m/z.

Workup

  1. temperaturethe mixture heated
  2. temperatureat reflux for 18 h
  3. additionwas added
  4. customthe layers separated
  5. dry with materialThe organic layer was dried (MgSO4)
  6. customevaporated
  7. customthe residue was purified by silica gel chromatography (100 g of SiO2, eluted with 1:1 hexane:EtOAc)

Sources & evidence

ORD record
ord-4f0ea3e3ec9b40418fd3cdda07811602
Source dataset
uspto-grants-2005_02
Patent number
US06858616B2

Reaction notes

Loading…