Potassium Carbonate → 1-((6-isopropylpyridin-2-yl)methyl)-3-methyl-4-nitro-1H-indazole

HRID 706622Notes

Reaction equation

HRID 706622 reaction equation
C([O-])([O-])=O.[K+].[K+].Br[C:8]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][C:15]=2[N+:17]([O-:19])=[O:18])[N:10]([CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([CH:27]([CH3:29])[CH3:28])[N:22]=2)[N:9]=1.[CH3:30]B(O)O.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=C(S([O-])(=O)=O)C=2OC)CCCCC1.[Na+]>C(O[Pd]OC(=O)C)(=O)C.O1CCOCC1.O>[CH:27]([C:23]1[N:22]=[C:21]([CH2:20][N:10]2[C:11]3[C:16](=[C:15]([N+:17]([O-:19])=[O:18])[CH:14]=[CH:13][CH:12]=3)[C:8]([CH3:30])=[N:9]2)[CH:26]=[CH:25][CH:24]=1)([CH3:29])[CH3:28]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 139377Methylboronic AcidHCID 23677046Sodium 2'-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonateHCID 679758823-bromo-1-((6-isopropylpyridin-2-yl)methyl)-4-nitro-1H-indazole

Product 1

HCID 679762021-((6-isopropylpyridin-2-yl)methyl)-3-methyl-4-nitro-1H-indazole

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

A first flask was charged with 1,4-dioxane/H2O (30 mL/5 mL). The flask was cooled to 0° C. and vacuum was applied for 20 minutes. A second flask was charged with K2CO3 (2.92 g, 21.1 mmol), 3-bromo-1-((6-isopropylpyridin-2-yl)methyl)-4-nitro-1H-indazole (1.98 g, 5.28 mmol), diacetoxypalladium (0.0592 g, 0.264 mmol), methylboronic acid (0.948 g, 15.8 mmol) and sodium 2′-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonate (0.270 g, 0.528 mmol). The second flask was evacuated with vacuum and back filled with N2 for 3 times. The cold degassed dioxane/H2O was then added to the second flask, which was again evacuated with vacuum and back filled with argon 5 times. The reaction mixture was heated to 80° C. for 3 hours. The reaction was cooled to ambient temperature, filtered and concentrated under reduced pressure. The residue was diluted with EtOAc (200 mL). The organic layer was washed with saturated NaHCO3, dried (Na2SO4) and concentrated to give the desired product, which was used without further purification.

Workup

  1. customThe second flask was evacuated with vacuum
  2. additionback filled with N2 for 3 times
  3. customThe cold degassed dioxane/H2O
  4. additionwas then added to the second flask, which
  5. customwas again evacuated with vacuum
  6. additionback filled with argon 5 times
  7. temperatureThe reaction mixture was heated to 80° C. for 3 hours
  8. temperatureThe reaction was cooled to ambient temperature
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. additionThe residue was diluted with EtOAc (200 mL)
  12. washThe organic layer was washed with saturated NaHCO3
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-7cdaa48bab6847eeb04d4ca55910ede7
Source dataset
uspto-grants-2015_11
Patent number
US09174981B2

Reaction notes

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