Iodine → HCID 68774908, compound

HRID 2261262Notes

Reaction equation

HRID 2261262 reaction equation
N[C:2]1[CH:3]=[CH:4][C:5]([Cl:27])=[C:6]([C:8]2[C:13](=[O:14])[N:12]([CH3:15])[C:11]3[N:16]([C:19]4[C:24]([F:25])=[CH:23][CH:22]=[CH:21][C:20]=4[F:26])[N:17]=[CH:18][C:10]=3[CH:9]=2)[CH:7]=1.[I:28]I.[I-].[Cs+].N(OCCC(C)C)=O>COCCOC.[Cu]I>[Cl:27][C:5]1[CH:4]=[CH:3][C:2]([I:28])=[CH:7][C:6]=1[C:8]1[C:13](=[O:14])[N:12]([CH3:15])[C:11]2[N:16]([C:19]3[C:24]([F:25])=[CH:23][CH:22]=[CH:21][C:20]=3[F:26])[N:17]=[CH:18][C:10]=2[CH:9]=1

Participants

7

Reactant 4

HCID 807IodineHCID 8053Isoamyl NitriteHCID 24601Cesium iodideHCID 68778431HCID 68778431, compound

Product 1

HCID 68774908HCID 68774908, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

At RT, a mixture of 5-(5-amino-2-chlorophenyl)-1-(2,6-difluorophenyl)-7-methyl-1H-pyrazolo[3,4-b]pyridin-6(7H)-one (230 mg, 0.59 mmol), iodine (151 mg, 0.59 mmol), copper(I) iodide (34 mg, 0.18 mmol) and cesium iodide (154 mg, 0.59 mmol) in DME (4.40 mL) was treated with isoamyl nitrite (0.48 mL, 3.57 mmol) drop wise over 3 min. The reaction mixture was stirred for 4 h, and filtered through a pad of celite washing with EtOAc (100 mL). The organic layer was washed sequentially with ˜2% NH4OH (20 mL), a solution of sodium thiosulfate (20 mL) and brine (20 mL), dried over MgSO4, filtered and concentrated. The crude residue was purified on the ISCO 12 g column (10-60% EtOAc in hexanes) affording the title compound as a white crystalline solid. MS (ESI, pos.ion) m/z: 497.9 (M+1).

Workup

  1. filtrationfiltered through a pad of celite
  2. washwashing with EtOAc (100 mL)
  3. washThe organic layer was washed sequentially with ˜2% NH4OH (20 mL)
  4. dry with materiala solution of sodium thiosulfate (20 mL) and brine (20 mL), dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude residue was purified on the ISCO 12 g column (10-60% EtOAc in hexanes)

Sources & evidence

ORD record
ord-6dab9f65d022497589b8378b702c296d
Source dataset
uspto-grants-2010_12
Patent number
US07846944B2

Reaction notes

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