1,2-Dimethoxyethane → 7-bromo-2-(1-methyl-1H-pyrazol-4-yl)quinoxaline

HRID 927315Notes

Reaction equation

HRID 927315 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([N:6]=[CH:7][C:8](Cl)=[N:9]2)=[CH:4][CH:3]=1.[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-].[Na+].[Na+].COCCOC>O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([N:6]=[CH:7][C:8]([C:17]3[CH:16]=[N:15][N:14]([CH3:13])[CH:18]=3)=[N:9]2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole2×HCID 49132537-Bromo-2-chloroquinoxaline

Product 1

HCID 578432587-bromo-2-(1-methyl-1H-pyrazol-4-yl)quinoxalineYield 89.4%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×

Procedure

7-bromo-2-chloro-quinoxaline (502 g; 2.06 mol), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (450.42 g; 2.16 mol), triphenylphosphine (10.82 g; 0.041 mol) and palladium(II)acetate were added to a mixture of sodium carbonate (240.37 g; 2.267 mol), 1,2-dimethoxyethane (5.48 L) and water (1.13 L). The reaction mixture was stirred at reflux for 20 hours, then 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (42.9 g; 0.206 mol) was added and the reaction mixture refluxed until complete conversion (4 hours). The reaction mixture was poured out in water, stirred for 2 hours at room temperature, filtered and the precipitate was washed with water. The precipitate was then triturated in methanol and filtered. The precipitate was washed with methanol and dried to give 532.2 g (89%) of 7-Bromo-2-(1-methyl-1H-pyrazol-4-yl)-quinoxaline (off-white powder).

Workup

  1. temperatureat reflux for 20 hours
  2. temperaturethe reaction mixture refluxed until complete conversion (4 hours)
  3. stirringstirred for 2 hours at room temperature
  4. filtrationfiltered
  5. washthe precipitate was washed with water
  6. customThe precipitate was then triturated in methanol
  7. filtrationfiltered
  8. washThe precipitate was washed with methanol
  9. customdried

Sources & evidence

ORD record
ord-fee35952035745d294326b1310caa1d1
Source dataset
uspto-grants-2016_03
Patent number
US09290478B2

Reaction notes

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