Sodium Carbonate → HCID 66958681, compound

HRID 1984385Notes

Reaction equation

HRID 1984385 reaction equation
Br[C:2]1[C:3]([C:13]#[N:14])=[N:4][N:5]([CH2:9][CH2:10][CH2:11][CH3:12])[C:6]=1[CH2:7][CH3:8].[CH3:15][C:16]([CH3:30])([CH3:29])[C:17]([NH:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1B(O)O)=[O:18].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OC)(C)(C)C.C(O)CC.O>[CH2:7]([C:6]1[N:5]([CH2:9][CH2:10][CH2:11][CH3:12])[N:4]=[C:3]([C:13]#[N:14])[C:2]=1[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=1[NH:19][C:17](=[O:18])[C:16]([CH3:29])([CH3:15])[CH3:30])[CH3:8]

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 41935022-(tert-Butylcarbonylamino)phenylboronic acidHCID 66958379HCID 66958379, compound

Product 1

HCID 66958681HCID 66958681, compoundYield 12.8%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 10311-PropanolSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
100 °C

Procedure

A flask containing a mixture of 4-bromo-1-butyl-5-ethyl-1H-pyrazole-3-carbonitrile (2.56 g, 10 mmol), 2-[(2,2-dimethylpropanoyl)amino]phenylboronic acid (2.87 g, 15 mmol), triphenylphosphine (0.079 g, 0.30 mmol), 2 M aqueous sodium carbonate (15 mL, 30 mmol), water (3 mL) and 1-propanol (20 mL) was placed under vacuum and back-filled with nitrogen three times. Palladium (II) acetate (0.023 g, 0.10 mmol) was added. Again, the flask was placed under vacuum and back-filled with nitrogen. The mixture was heated overnight under a nitrogen atmosphere at 100° C. The reaction was allowed to cool to ambient temperature and methyl tert-butyl ether was added. After the mixture was stirred for about 10 minutes, the layers were separated. The organic layer was dried over magnesium sulfate, filtered, and concentrated to yield a brown oil. Hexanes were added to the brown oil, causing the formation of a tan solid that was isolated by filtration. The filtrate was concentrated to an oil that was purified by chromatography on a HORIZON HPFC system (silica gel, eluted with ethyl acetate/hexanes) to provide 0.45 g of N-[2-(5-ethyl-1-butyl-3-cyano-1H-pyrazol-4-yl)phenyl]-2,2-dimethylpropanamide, which was used in the next step without further purification.

Workup

  1. additionA flask containing
  2. additionback-filled with nitrogen three times
  3. additionback-filled with nitrogen
  4. temperatureto cool to ambient temperature
  5. customthe layers were separated
  6. dry with materialThe organic layer was dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto yield a brown oil
  10. customthat was isolated by filtration
  11. concentrationThe filtrate was concentrated to an oil that
  12. customwas purified by chromatography on a HORIZON HPFC system (silica gel, eluted with ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-151f3b607768485f81fb7ff6aad6e3a9
Source dataset
uspto-grants-2009_06
Patent number
US07544697B2

Reaction notes

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