Pyrazole → 6-Methyl-3-(1H-pyrazol-1-yl)picolinonitrile

HRID 61088Notes

Reaction equation

HRID 61088 reaction equation
Br[C:2]1[C:3]([C:9]#[N:10])=[N:4][C:5]([CH3:8])=[CH:6][CH:7]=1.[NH:11]1[CH:15]=[CH:14][CH:13]=[N:12]1.CN[C@H]1CCCC[C@@H]1NC.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.[Cu]I>[CH3:8][C:5]1[N:4]=[C:3]([C:9]#[N:10])[C:2]([N:11]2[CH:15]=[CH:14][CH:13]=[N:12]2)=[CH:7][CH:6]=1

Participants

7

Reactant 4

HCID 1048PyrazoleHCID 10796Cesium carbonateHCID 13822957(1S,2S)-(+)-N,N'-Dimethylcyclohexane-1,2-diamineHCID 219527473-Bromo-6-methylpyridine-2-carbonitrile

Product 1

HCID 1177281526-Methyl-3-(1H-pyrazol-1-yl)picolinonitrileYield 64%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 3-bromo-6-methylpicolinonitrile (1 g, 5.1 mmol), 1H-pyrazole (0.52 ml, 7.61 mmol), (1S,2S)—N1,N2-dimethylcyclohexane-1,2-diamine (0.97 ml, 6.09 mmol), Cs2CO3 (2.48 g, 7.61 mmol) and CuI (97 mg, 0.51 mmol) in DMF (10 mL) was degassed and heated at 120° C. for 1 h in a microwave reactor. The solvent was removed in vacuo to obtain the crude which was purified by silica gel chromatography (0˜100% DCM/EtOAc) to yield the title compound as a yellow oil (600 mg, 64%). MS (ESI) 185 (M+H).

Workup

  1. customwas degassed
  2. customThe solvent was removed in vacuo
  3. customto obtain the crude which
  4. customwas purified by silica gel chromatography (0˜100% DCM/EtOAc)

Sources & evidence

ORD record
ord-3f695cb7893047ccbf9393b06ea224d3
Source dataset
uspto-grants-2016_09
Patent number
US09440982B2

Reaction notes

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