Bromine → methyl 3-bromo-1-(4-methylphenyl)-1H-indazole-6-carboxylate

HRID 1047623Notes

Reaction equation

HRID 1047623 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:16]3[C:11](=[CH:12][CH:13]=[C:14]([C:17]([O:19][CH3:20])=[O:18])[CH:15]=3)[CH:10]=[N:9]2)=[CH:4][CH:3]=1.[Br:21]Br>C(#N)C>[Br:21][C:10]1[C:11]2[C:16](=[CH:15][C:14]([C:17]([O:19][CH3:20])=[O:18])=[CH:13][CH:12]=2)[N:8]([C:5]2[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][CH:6]=2)[N:9]=1

Participants

4

Reactant 2

HCID 24408BromineHCID 66661292Methyl 1-(4-methylphenyl)-1H-indazole-6-carboxylate

Product 1

HCID 66661548methyl 3-bromo-1-(4-methylphenyl)-1H-indazole-6-carboxylateYield 74.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Methyl 1-(4-methylphenyl)-1H-indazole-6-carboxylate (2.7075 g, 10.17 mmol) was dissolved in acetonitrile (102 ml) at 25° C. under Ar. Bromine (1.886 ml, 36.60 mmol) was added. The reaction mixture was allowed to stir for 60 h. The reaction was stopped, quenched by addition of saturated aqueous sodium bicarbonate (40 mL), and the mixture extracted with ethyl acetate (3×35 mL). The combined organic phases were washed with saturated aqueous sodium chloride (1×25 mL), dried (sodium sulfate), filtered, and the solvent evaporated under reduced pressure. The crude product was purified by flash chromatography (RediSep SiO2, 330 g column) on a CombiFlash Rf purification system eluting with ethyl acetate-hexanes (0-5%). The title compound (2.8006 g, 7.55 mmol, 74.2% yield) was recovered as a white solid. LC-MS [M+1]=346.1.

Workup

  1. customquenched by addition of saturated aqueous sodium bicarbonate (40 mL)
  2. extractionthe mixture extracted with ethyl acetate (3×35 mL)
  3. washThe combined organic phases were washed with saturated aqueous sodium chloride (1×25 mL)
  4. dry with materialdried (sodium sulfate)
  5. filtrationfiltered
  6. customthe solvent evaporated under reduced pressure
  7. customThe crude product was purified by flash chromatography (RediSep SiO2, 330 g column) on a CombiFlash Rf purification system
  8. washeluting with ethyl acetate-hexanes (0-5%)

Sources & evidence

ORD record
ord-ea5d45fc7af84c999b37ef74aa40b058
Source dataset
uspto-grants-2013_10
Patent number
US08569512B2

Reaction notes

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