Dimethylformamide → HCID 89783710, compound

HRID 58113Notes

Reaction equation

HRID 58113 reaction equation
[Br:1][C:2]1[C:3]([CH3:12])=[N:4][NH:5][C:6]=1[C:7]([O:9][CH2:10][CH3:11])=[O:8].C([O-])([O-])=O.[Cs+].[Cs+].[CH3:19][N:20]([CH:22]=O)C>O>[Br:1][C:2]1[C:3]([CH3:12])=[N:4][N:5]([CH2:6][C:2]2[CH:3]=[N:4][N:20]([CH3:19])[CH:22]=2)[C:6]=1[C:7]([O:9][CH2:10][CH3:11])=[O:8]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 178470421HCID 178470421, compound

Product 1

HCID 89783710HCID 89783710, compoundYield 23%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To ethyl 4-bromo-3-methyl-1H-pyrazole-5-carboxylate (2.56 g, 10.98 mmol) in DMF (30 mL) were added Cs2CO3 (8.94 g, 27.4 mmol) and 4-(chloromethyl)-1-methyl-1H-pyrazole, HCl (2.2 g, 13.17 mmol). The reaction mixture was stirred at room temperature for 20 hours and then diluted with water. The product was extracted into EtOAc. The organic phase was dried over Na2SO4 and concentrated. The crude residue was purified by CombiFlash® chromatography (120 g, column) eluting with a gradient of 10-100% EtOAc in heptane over a period of 180 minutes. The product-containing fractions were combined and concentrated to give the title compound (0.82 g, 23%) and a regioisomer, ethyl 4-bromo-5-methyl-1-((1-methyl-1H-pyrazol-4-yl)methyl)-1H-pyrazole-3-carboxylate (1.32 g, 36.8%).

Workup

  1. extractionThe product was extracted into EtOAc
  2. dry with materialThe organic phase was dried over Na2SO4
  3. concentrationconcentrated
  4. customThe crude residue was purified by CombiFlash® chromatography (120 g, column)
  5. washeluting with a gradient of 10-100% EtOAc in heptane over a period of 180 minutes
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-6c7a2770aa8247009d7f4c32ef950d10
Source dataset
uspto-grants-2016_09
Patent number
US09434743B2

Reaction notes

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