Cesium carbonate → 5-(2-chloro-4-fluorophenyl)-1,3-dimethyl-4-nitro-1H-pyrazole

HRID 2276003

Reaction equation

HRID 2276003 reaction equation
Cl[C:2]1[N:6]([CH3:7])[N:5]=[C:4]([CH3:8])[C:3]=1[N+:9]([O-:11])=[O:10].[Cl:12][C:13]1[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=1B(O)O.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1>[Cl:12][C:13]1[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=1[C:2]1[N:6]([CH3:7])[N:5]=[C:4]([CH3:8])[C:3]=1[N+:9]([O-:11])=[O:10]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 2795155-Chloro-1,3-dimethyl-4-nitro-1H-pyrazoleHCID 177502292-Chloro-4-fluorobenzeneboronic acid

Product 1

HCID 666141515-(2-chloro-4-fluorophenyl)-1,3-dimethyl-4-nitro-1H-pyrazoleYield 8.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 5-chloro-1,3-dimethyl-4-nitro-1H-pyrazole (2.50 g, 14.3 mmol), 2-chloro-4-fluorophenylboronic acid (2.98 g, 17.2 mmol), cesium carbonate (5.58 g, 17.2 mmol) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane complex (1:1) (1.16 g, 1.43 mmol) in dioxane (50 mL) was heated at 100° C. for approximately 2.5 days. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite® (diatomaceous earth) on a sintered glass frit funnel and the filtrate was concentrated under reduced pressure. The resulting material was dissolved in ethyl acetate and filtered through a plug of silica on a sintered glass frit funnel and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (5 to 40% gradient of ethyl acetate in hexanes as eluant) to provide the title compound (0.32 g).

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationthe reaction mixture was filtered through a pad of Celite® (diatomaceous earth) on a sintered glass frit funnel
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. dissolutionThe resulting material was dissolved in ethyl acetate
  5. filtrationfiltered through a plug of silica on a sintered glass frit funnel
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customThe resulting material was purified by silica gel column chromatography (5 to 40% gradient of ethyl acetate in hexanes as eluant)

Sources & evidence

ORD record
ord-7ce02eb009144ece8734fd6bd0e6ef55
Source dataset
uspto-grants-2015_09
Patent number
US09131693B2

Linked notes

Loading…