Methane → 4-Chloro-3-ethynyl-5-nitropyridin-2-amine

HRID 1969556Notes

Reaction equation

HRID 1969556 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH2:11])[C:3]=1[C:12]#[C:13][Si](C)(C)C.[F-].[K+].C>CN(C=O)C>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH2:11])[C:3]=1[C:12]#[CH:13]

Participants

5

Reactant 3

HCID 297MethaneHCID 522689Potassium FluorideHCID 585574594-Chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine

Product 1

HCID 585573334-Chloro-3-ethynyl-5-nitropyridin-2-amineYield 71%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine (1.98 g, 7.34 mmol) in DMF (25 mL) was added potassium fluoride on alumina (40 wt %, 2.67 g, 18.35 mmol). The suspension was stirred at ambient temperature for about 1 h. Activated charcoal (0.3 g) was added and the suspension was filtered through Celite®, washing with DMF (150 mL). The solvent was removed under reduced pressure and the crude material was purified by silica gel chromatography eluting with a gradient of 0-10% MeOH in DCM to afford 4-chloro-3-ethynyl-5-nitropyridin-2-amine (1.03 g, 71%) as a yellow solid: LC/MS (Table 1, Method n) Rt=0.59 min; MS m/z: 196 (M−H)−.

Workup

  1. filtrationthe suspension was filtered through Celite®
  2. washwashing with DMF (150 mL)
  3. customThe solvent was removed under reduced pressure
  4. customthe crude material was purified by silica gel chromatography
  5. washeluting with a gradient of 0-10% MeOH in DCM

Sources & evidence

ORD record
ord-def23f0aa653442cbf3c72637fa8d8cc
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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