N,N'-Dimethylethylenediamine → HCID 86676843, compound

HRID 1029005Notes

Reaction equation

HRID 1029005 reaction equation
Br[C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:3]=1[NH2:4].[Cl:10][C:11]1[C:12]([CH3:16])=[N:13][NH:14][CH:15]=1.C(=O)([O-])[O-].[K+].[K+].CNCCNC>CCOC(C)=O.[Cl-].[NH4+].[OH-].[NH4+].[Cu]I.C1(C)C=CC=CC=1>[Cl:10][C:11]1[C:12]([CH3:16])=[N:13][N:14]([C:2]2[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:3]=2[NH2:4])[CH:15]=1

Participants

9

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 27562502-Bromo-6-methylanilineHCID 178434543HCID 178434543, compound

Product 1

HCID 86676843HCID 86676843, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 21863491Ammonium chloride ammonium hydroxideSolvent

Conditions

Temperature
110 °C

Procedure

2-Bromo-6-methylaniline (1.080 mL, 8.58 mmol), 4-chloro-3-methyl-1H-pyrazole (1.0 g, 8.58 mmol), potassium carbonate (2.49 g, 18.02 mmol), and copper(I) iodide (0.082 g, 0.429 mmol) were added to a RBF which was evacuated and flushed with N2 3×. Toluene (9 mL) (degassed by bubbling N2 through solution for 10 minutes) and N1,N2-dimethylethane-1,2-diamine (0.185 mL, 1.716 mmol) were added and the mixture was heated in an oil bath at 110° C. After 18 h, the reaction was allowed to cool, diluted with EtOAc, and 10:1 saturated ammonium chloride/ammonium hydroxide. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic extracts were washed with water, saturated sodium chloride, and dried over sodium sulfate. The solution was filtered and concentrated in vacuo to give the crude material. The crude material was purified by silica gel column chromatography eluting with 1:2 EtOAc in hexanes to provide 2-(4-chloro-3-methyl-1H-pyrazol-1-yl)-6-methylaniline.

Workup

  1. customwas evacuated
  2. customflushed with N2 3×
  3. temperatureto cool
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc
  6. washThe combined organic extracts were washed with water, saturated sodium chloride
  7. dry with materialdried over sodium sulfate
  8. filtrationThe solution was filtered
  9. concentrationconcentrated in vacuo
  10. customto give the crude material
  11. customThe crude material was purified by silica gel column chromatography
  12. washeluting with 1:2 EtOAc in hexanes

Sources & evidence

ORD record
ord-bffbc1694fc3430e8e501a2a1c66f462
Source dataset
uspto-grants-2014_05
Patent number
US08735384B2

Reaction notes

Loading…