Iodine → HCID 178452208, compound

HRID 387546Notes

Reaction equation

HRID 387546 reaction equation
[C:1]1([C:7]2[C:8]([N:16]3[CH2:21][CH2:20][N:19]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:18][CH2:17]3)=[C:9]3[CH:15]=[N:14][NH:13][C:10]3=[N:11][CH:12]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[K+].[I:31]I>CN(C=O)C.CCOC(C)=O>[I:31][C:15]1[C:9]2[C:10](=[N:11][CH:12]=[C:7]([C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)[C:8]=2[N:16]2[CH2:17][CH2:18][N:19]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:20][CH2:21]2)[NH:13][N:14]=1

Participants

6

Reactant 3

HCID 807Iodine2×HCID 14797Potassium Hydroxide2×HCID 68758199tert-butyl 4-(5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

Product 1

HCID 178452208HCID 178452208, compoundYield 79.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of tert-butyl 4-(5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (3 g, 7.75 mmol) and powdered potassium hydroxide (1.28 g, 19.4 mmol) in DMF (20 mL) was treated with iodine (3.93 g, 15.5 mmol), and the mixture was heated at 60° C. After 4 hours, the mixture was cooled to room temperature and treated with powdered KOH (700 mg, 10.7 mmol) and I2 (1.97 g, 7.75 mmol). The mixture was stirred at 60° C. for 1 hour. The mixture was cooled to room temperature, diluted with EtOAc (200 mL) and successively washed with saturated Na2S2O3 solution (2×20 mL) and water (2×50 mL). The organic layer was separated, dried (MgSO4), filtered, and concentrated in vacuo. The residue obtained was crystallized from boiling CH3CN to provide tert-butyl 4-(3-iodo-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (3.12 g, 79.7% yield) as a solid. LCMS (APCI+) m/z 506 (M+H)+, Retention time=4.04 minutes.

Workup

  1. temperaturethe mixture was cooled to room temperature
  2. temperatureThe mixture was cooled to room temperature
  3. washsuccessively washed with saturated Na2S2O3 solution (2×20 mL) and water (2×50 mL)
  4. customThe organic layer was separated
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue obtained
  9. customwas crystallized

Sources & evidence

ORD record
ord-010555df074341a89e8b092d643d1dbc
Source dataset
uspto-grants-2013_02
Patent number
US08372842B2

Reaction notes

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