1,4-Dioxane → 5-Amino-4,6-dimethylpicolinonitrile

HRID 1043921Notes

Reaction equation

HRID 1043921 reaction equation
BrC1[C:7]([NH2:8])=[C:6](Br)[N:5]=[C:4]([C:10]#[N:11])[CH:3]=1.[CH3:12]B1OB(C)OB(C)O1.O1[CH2:26][CH2:25]OCC1>O.C(=O)([O-])[O-].[K+].[K+]>[NH2:11][C:10]1[C:25]([CH3:26])=[CH:12][C:6]([C:7]#[N:8])=[N:5][C:4]=1[CH3:3]

Participants

6

Reactant 3

HCID 312751,4-DioxaneHCID 574072TrimethylboroxineHCID 866863455-Amino-4,6-dibromopyridine-2-carbonitrile

Product 1

HCID 866863445-Amino-4,6-dimethylpicolinonitrile

Reagents, catalysts & solvents 2

HCID 11430Potassium CarbonateCatalystHCID 962WaterSolvent

Procedure

4,6-dibromo-5-amino-2-cyanopyridine (1 g) was dissolved in a mixed solvent of 1,4-dioxane (10 mL) and water (1 mL). Trimethylboroxin (1.3 g), Pd(dppf)Cl2-DCM complex (264 mg) and potassium carbonate (1.5 mg) were added to the solution, and the mixture was reacted using a microwave reactor at 140° C. for four hours. The reaction mixture was returned to mom temperature and then partitioned by adding ethyl acetate and water. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/n-heptane, 0% to 100%) to give the title compound (390 mg).

Workup

  1. customthe mixture was reacted
  2. customat 140° C.
  3. customfor four hours
  4. custompartitioned
  5. additionby adding ethyl acetate and water
  6. washThe organic layer was washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe desiccant was removed by filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/n-heptane, 0% to 100%)

Sources & evidence

ORD record
ord-5652ee4f3e8e4718a0412c9949b221ad
Source dataset
uspto-grants-2013_10
Patent number
US08563565B2

Reaction notes

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