Dimethylformamide → 6-bromocinnoline

HRID 661123Notes

Reaction equation

HRID 661123 reaction equation
B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.C([O-])(=O)C.[K+].[Br:24][C:25]1[CH:26]=[C:27]2[C:32](=[CH:33][CH:34]=1)[N:31]=[N:30][CH:29]=[C:28]2Cl.CN(C=O)C>C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe]>[Br:24][C:25]1[CH:26]=[C:27]2[C:32](=[CH:33][CH:34]=1)[N:31]=[N:30][CH:29]=[CH:28]2

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 124480786-Bromo-4-chlorocinnoline

Product 1

HCID 112295606-bromocinnolineYield 31%

Reagents, catalysts & solvents 1

HCID 53485975CID 53485975Catalyst

Conditions

Temperature
80 °C

Procedure

To a stirred mixture of bis(pinacolato)diboron (6.4 g, 25 mmol), potassium acetate (6.8 g, 69 mmol), dichloro[1,1′bis(diphenylphoshino)ferrocene]palladium(II) dichloromethane adduct (0.50 g, 0.69 mmol), and 6-bromo-4-chlorocinnoline (5.60 g, 23 mmol), was added DMF (50.00 mL, 646 mmol) and the overall mixture was heated at 80° C. overnight. After cooling and checking by LC-MS, the overall mixture was concentrated with silica and purified with ISCO (40 g, hexanes/EA, 1:0 to 1:1) to provide the title compound 6-bromocinnoline (1.48, 31%) as a yellow solid. LCMS (API-ES) m/z (%): 210.0 (100%, M++H).

Workup

  1. temperatureAfter cooling
  2. concentrationthe overall mixture was concentrated with silica
  3. custompurified with ISCO (40 g, hexanes/EA, 1:0 to 1:1)

Sources & evidence

ORD record
ord-6784a1d3e4594a8f991799e898eaf835
Source dataset
uspto-grants-2011_12
Patent number
US08084479B2

Reaction notes

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