Pyrazole → HCID 68804275, compound

HRID 1878664Notes

Reaction equation

HRID 1878664 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([F:8])[CH:7]=1.[NH:9]1[CH:13]=[CH:12][CH:11]=[N:10]1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.[Cu]=O>[F:8][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([N:9]2[CH:13]=[CH:12][CH:11]=[N:10]2)[CH:7]=1

Participants

6

Reactant 3

HCID 1048PyrazoleHCID 10796Cesium carbonateHCID 8202063-Bromo-5-fluoropyridine

Product 1

HCID 68804275HCID 68804275, compound

Reagents, catalysts & solvents 2

HCID 14829Copper oxideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

3-Bromo-5-fluoropyridine (300 mg, 1.705 mmol), 1H-pyrazole (180 mg, 2.64 mmol), ferric acetylacetonate (181 mg, 0.511 mmol), copper(II) oxide (13.6 mg, 0.170 mmol) and cesium carbonate (1.11 g, 3.41 mmol) were suspended in DMF (2.0 mL). The reaction mixture was stirred at 90° C. for 60 hours. After cooling to room temperature, the reaction mixture was partitioned between ethyl acetate (3×30 mL) and water (100 mL). The organic layers were combined, washed with brine (50 mL) and dried (sodium sulfate). It was then concentrated and the residue was purified by silica gel flash chromatography to afford the titled compound: 1H NMR (400 MHz, methanol-D4) δ ppm 6.55-6.65 (m, 1H), 7.80 (d, J=1.2 Hz, 1H), 8.10 (dt, J=9.9, 2.3 Hz, 1H), 8.38 (d, J=2.5 Hz, 1H), 8.42 (d, J=1.5 Hz, 1H), 8.93 (s, 1H). MS (ESI) m/z=163 (M+H)+. Anal. Calcd. for C8H6FN3.0.15CH3OH; C, 61.99; H, 4.48; N, 32.42. Found: C, 62.30; H, 4.12; N, 32.21.

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe reaction mixture was partitioned between ethyl acetate (3×30 mL) and water (100 mL)
  3. washwashed with brine (50 mL)
  4. dry with materialdried (sodium sulfate)
  5. concentrationIt was then concentrated
  6. customthe residue was purified by silica gel flash chromatography

Sources & evidence

ORD record
ord-8ec49281645e4cc4a2c01f83e5355aed
Source dataset
uspto-grants-2012_11
Patent number
US08314119B2

Reaction notes

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