Cesium carbonate → HCID 57576801, compound

HRID 1777391Notes

Reaction equation

HRID 1777391 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[CH:9][NH:8][N:7]=1)=[O:5])[CH3:2].Br[C:12]1[CH:17]=[CH:16][C:15]([F:18])=[CH:14][N:13]=1.CN[C@@H]1CCCC[C@H]1NC.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.[Cu]I.CCOC(C)=O.O>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[CH:9][N:8]([C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][N:13]=2)[N:7]=1)=[O:5])[CH3:2]

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 27831712-Bromo-5-fluoropyridineHCID 178469268HCID 178469268, compound

Product 1

HCID 57576801HCID 57576801, compoundYield 69.1%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of ethyl-1H-pyrazole-3-carboxylate (25.0 g, 178.4 mmol) and 2-bromo-5-fluoropyridine (47.1 g, 267.6 mmol) in DMF (300 mL), copper(I) iodide (8.5 g, 44.6 mmol), rac-trans-N,N′-dimethylcyclohexane-1,2-diamine (28.1 mL, 178.4 mmol) and Cs2CO3 (116.2 g, 356.8 mmol) were added, and the resulting mixture was stirred for 7 hours at 90° C. The reaction mixture was allowed to cool to room temperature, then water and EtOAc were added thereto, followed by filtration through Celite®. The organic layer was taken out from the filtrate, washed with a saturated aqueous solution of sodium chloride, dried over Na2SO4, then the drying agent was filtered off, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (HP-Sil 50 g, hexane/EtOAc=70/30 to 0/100). The obtained solid was stirred and washed in hexane/EtOAc=4/1 and filtered out to obtain the title compound (29.0 g) (colorless solid).

Workup

  1. temperatureto cool to room temperature
  2. filtrationfollowed by filtration through Celite®
  3. washwashed with a saturated aqueous solution of sodium chloride
  4. dry with materialdried over Na2SO4
  5. filtrationthe drying agent was filtered off
  6. distillationthe solvent was distilled off under reduced pressure
  7. customThe obtained residue was purified by column chromatography (HP-Sil 50 g, hexane/EtOAc=70/30 to 0/100)
  8. stirringThe obtained solid was stirred
  9. washwashed in hexane/EtOAc=4/1
  10. filtrationfiltered out

Sources & evidence

ORD record
ord-0692a8993eff474b8a4d47323ffb7df0
Source dataset
uspto-grants-2016_02
Patent number
US09266870B2

Reaction notes

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