Cesium carbonate → 5-Nitro-2,3'-bipyridin-6-amine

HRID 2264176Notes

Reaction equation

HRID 2264176 reaction equation
Cl[C:2]1[N:7]=[C:6]([NH2:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][CH:3]=1.[N:12]1[CH:17]=[CH:16][CH:15]=[C:14](B(O)O)[CH:13]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1>[N+:9]([C:5]1[CH:4]=[CH:3][C:2]([C:14]2[CH:13]=[N:12][CH:17]=[CH:16][CH:15]=2)=[N:7][C:6]=1[NH2:8])([O-:11])=[O:10]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 27240356-Chloro-3-nitropyridin-2-ylamineHCID 27343783-Pyridinylboronic acid

Product 1

HCID 205503675-Nitro-2,3'-bipyridin-6-amineYield 77.1%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

An oven dried resealable Schlenk tube was charged with 6-chloro-3-nitropyridin-2-amine (5 g, 28.81 mmol), 3-pyridineboronic acid (5.31 g, 43.2 mmol), dioxane (250 mL) and a 2M aqueous solution of cesium carbonate (43 mL, 86.4 mmol). The Schlenk tube was subjected to three cycles of evacuation-backfilling with argon, and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (2.3 g, 2.81 mmol) was added. After three new cycles of evacuation-backfilling with argon, the Schlenk tube was capped and placed in a 100° C. oil bath. After 3 h, the mixture was cooled, partitioned between water and ethyl acetate, the aqueous phase extracted twice with ethyl acetate, the organic layers washed with brine, dried (MgSO4) and evaporated. The residue was purified by silica gel flash chromatography (95:5 dichloromethane/methanol) to give the title compound (4.8 g, 77%) as a solid.

Workup

  1. customAn oven dried resealable Schlenk tube
  2. additionwas added
  3. customAfter three new cycles of evacuation-backfilling with argon, the Schlenk tube was capped
  4. customplaced in a 100° C.
  5. temperaturethe mixture was cooled
  6. custompartitioned between water and ethyl acetate
  7. extractionthe aqueous phase extracted twice with ethyl acetate
  8. washthe organic layers washed with brine
  9. dry with materialdried (MgSO4)
  10. customevaporated
  11. customThe residue was purified by silica gel flash chromatography (95:5 dichloromethane/methanol)

Sources & evidence

ORD record
ord-25d0255f5ad24c6ba3799fb65bb596f6
Source dataset
uspto-grants-2010_12
Patent number
US07855202B2

Reaction notes

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