4-Methylpyrazole → 5-(4-Methyl-1H-pyrazol-1-yl)-3-pyridinamine

HRID 2171259Notes

Reaction equation

HRID 2171259 reaction equation
[CH3:1][C:2]1[CH:3]=[N:4][NH:5][CH:6]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C[NH:14][C@@H:15]1[CH2:20][CH2:19]CC[C@H:16]1[NH:21][CH3:22].BrC1C=C(N)C=NC=1>[Cu](I)I.O.CC(N(C)C)=O>[CH3:1][C:2]1[CH:3]=[N:4][N:5]([C:19]2[CH:20]=[C:15]([NH2:14])[CH:16]=[N:21][CH:22]=2)[CH:6]=1

Participants

8

Reactant 4

HCID 34064-MethylpyrazoleHCID 10796Cesium carbonateHCID 8176813-Amino-5-bromopyridineHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamine

Product 1

HCID 665212525-(4-Methyl-1H-pyrazol-1-yl)-3-pyridinamineYield 86.1%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 962WaterSolventHCID 31374DimethylacetamideSolvent

Procedure

4-Methyl-1H-pyrazole (114 mg), cesium carbonate (753 mg), trans-N,N′-dimethylcyclohexan-1,2-diamine (164 mg), and copper iodide (110 mg) were added to a DMAc (5 ml) solution containing 5-bromopyridin-3-amine (200 mg) in a nitrogen atmosphere, followed by microwave irradiation (Initiator™, 170° C., 0.5 hours, 2.45 GHz, 0-240 W). Water was added to the reaction solution and the reaction solution was filtered through Celite and the filtrate was extracted with ethyl acetate. The organic layers were washed with saturated saline and dried over sodium sulfate. The solvent was distilled away under reduced pressure. The obtained residue was purified by silica gel chromatography (n-hexane:ethyl acetate=4:1 to 0:1). 5-(4-Methylpyrazol-1-yl)pyridin-3-amine (173 mg) was thus obtained.

Workup

  1. customfollowed by microwave irradiation (Initiator™, 170° C., 0.5 hours, 2.45 GHz, 0-240 W)
  2. filtrationthe reaction solution was filtered through Celite
  3. extractionthe filtrate was extracted with ethyl acetate
  4. washThe organic layers were washed with saturated saline
  5. dry with materialdried over sodium sulfate
  6. distillationThe solvent was distilled away under reduced pressure
  7. customThe obtained residue was purified by silica gel chromatography (n-hexane:ethyl acetate=4:1 to 0:1)

Sources & evidence

ORD record
ord-6b808c05664c48939a0d139bf28e0d9b
Source dataset
uspto-grants-2015_06
Patent number
US09051310B2

Reaction notes

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