Potassium Carbonate → 4-(2-methoxy-4-nitrophenyl)-1-methyl-1H-pyrazole

HRID 1803142Notes

Reaction equation

HRID 1803142 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[O:11][CH3:12].[CH3:13][N:14]1[CH:18]=[C:17](B2OC(C)(C)C(C)(C)O2)[CH:16]=[N:15]1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:12][O:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[C:17]1[CH:16]=[N:15][N:14]([CH3:13])[CH:18]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 1012932-Bromo-5-nitroanisoleHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole

Product 1

HCID 668604724-(2-methoxy-4-nitrophenyl)-1-methyl-1H-pyrazoleYield 70%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

Step K (1): [1,1′-Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (1:1 complex with dichloromethane, 7.0 g, 8.62 mmol) was added to a degassed mixture of 1-bromo-2-methoxy-4-nitrobenzene (20 g, 86.2 mmol), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (23.3 g, 112 mmol), and potassium carbonate (23.6 g, 122 mmol) in DMF (200 mL). The mixture was heated at 150° C. for 18 h. The crude reaction mixture was cooled to rt and filtered through diatomaceous earth (Celite®). The reaction mixture was diluted with EtOAc (200 mL) and washed with water and then brine. The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified using silica gel column chromatography (EtOAc/hexane) to afford 4-(2-methoxy-4-nitrophenyl)-1-methyl-1H-pyrazole (14 g, 70% yield).

Workup

  1. customThe crude reaction mixture
  2. temperaturewas cooled to rt
  3. filtrationfiltered through diatomaceous earth (Celite®)
  4. additionThe reaction mixture was diluted with EtOAc (200 mL)
  5. washwashed with water
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified

Sources & evidence

ORD record
ord-adb0826affb44dbe8dadcc885db26074
Source dataset
uspto-grants-2013_01
Patent number
US08349880B2

Reaction notes

Loading…