Nitrogen → HCID 69260340, compound

HRID 1428347Notes

Reaction equation

HRID 1428347 reaction equation
N#N.[F:3][C:4]1[CH:5]=[C:6]([N:10]2[CH:14]=[C:13]([N:15]([CH3:23])[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[C:12]([CH:24]=[CH2:25])=[N:11]2)[CH:7]=[N:8][CH:9]=1>CO.[Pd]>[CH2:24]([C:12]1[C:13]([N:15]([CH3:23])[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:19])[CH3:20])=[CH:14][N:10]([C:6]2[CH:7]=[N:8][CH:9]=[C:4]([F:3])[CH:5]=2)[N:11]=1)[CH3:25]

Participants

5

Reactant 2

HCID 947NitrogenHCID 68089887HCID 68089887, compound

Product 1

HCID 69260340HCID 69260340, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Conditions

Temperature
50 °C

Procedure

To a N2-purged solution of tert-butyl (1-(5-fluoropyridin-3-yl)-3-vinyl-1H-pyrazol-4-yl)(methyl)carbamate (0.730 g, 2.293 mmol) in methanol (15.29 ml) was added 10% palladium on carbon (0.036 g, 0.339 mmol). The reaction was purged with hydrogen and run under 80 psi of hydrogen at room temperature for 60 hours. The reaction gave less than 20% conversion. The reaction mixture was filtered through celite, concentrated, and redissolved in ethyl acetate (4 mL) and transferred to a bomb. The reaction was heated at 50° C. at 600 psi of hydrogen for 20 hours. The reaction was only 50% complete. Methanol (1 mL) and 10% palladium on carbon (36 mg) were added, and the reaction was heated at 80° C. at 650 psi of hydrogen for 20 hours. The reaction was filtered through celite and concentrated to give tert-butyl (3-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate (616 mg, 1.923 mmol, 84% yield) as yellow oil: IR (thin film) 1692 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.71 (t, J=1.4 Hz, 1H), 8.35 (d, J=2.6 Hz, 1H), 7.83 (dt, J=9.5, 2.3 Hz, 2H), 3.18 (s, 3H), 2.65 (q, J=7.5 Hz, 2H), 1.44 (s, 9H), 1.25 (t, J=7.1 Hz, 3H); EIMS m/z 320.

Workup

  1. customThe reaction was purged with hydrogen
  2. customThe reaction gave less than 20% conversion
  3. filtrationThe reaction mixture was filtered through celite,
  4. concentrationconcentrated
  5. dissolutionredissolved in ethyl acetate (4 mL)
  6. additionMethanol (1 mL) and 10% palladium on carbon (36 mg) were added
  7. temperaturethe reaction was heated at 80° C. at 650 psi of hydrogen for 20 hours
  8. filtrationThe reaction was filtered through celite and
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-50588c8c3dd943338f9a983b3c27bc6d
Source dataset
uspto-grants-2015_01
Patent number
US08937083B2

Reaction notes

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