2-Amino-5-bromo-3-nitropyridine → HCID 68462064, compound

HRID 505440Notes

Reaction equation

HRID 505440 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5](Br)=[CH:4][N:3]=1.C(=O)(O)[O-].[Na+].[CH3:17][N:18]([CH3:28])[C:19]1[CH:24]=[CH:23][C:22](B(O)O)=[CH:21][CH:20]=1>O1CCOCC1>[NH2:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([C:22]2[CH:23]=[CH:24][C:19]([N:18]([CH3:28])[CH3:17])=[CH:20][CH:21]=2)=[CH:4][N:3]=1

Participants

5

Reactant 3

HCID 1388782-Amino-5-bromo-3-nitropyridineHCID 516892Sodium BicarbonateHCID 27343444-(Dimethylamino)phenylboronic acid

Product 1

HCID 68462064HCID 68462064, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

4.36 g of 2-amino-5-bromo-3-nitropyridine are dissolved in 73 ml of anoxic dioxane under a nitrogen atmosphere. Subsequently, 60 ml of an aqueous sodium bicarbonate solution (2.0 M), 7.3 g of 4-dimethylaminophenyl-boronic acid, and 0.886 g of trans-dichloro-bis(tricyclohexylphosphane)palladium-(II) are added. The reaction mixture is refluxed at 110° C. for 19 hours. Thereafter, the volatile components are removed in vacuo and the remaining residue is redissolved in 1.0 l of a mixture of water/dichloromethane (1:1). The aqueous phase is extracted four times each with 500 ml of dichloromethane. The organic layer is separated, dried using sodium sulfate, and evaporated to dryness to yield a colorless, crude solid. Subsequently, the residue is purified by flash chromatography on silica gel (eluent: dichloromethane/ethanol 50:1) to afford 3.41 g of the title compound as a colorless solid of m.p. 212° C. MS: 259.2 (MH+). TLC: Rf=0.55 (dichloromethane/ethanol 50:1).

Workup

  1. customThereafter, the volatile components are removed in vacuo
  2. dissolutionthe remaining residue is redissolved in 1.0 l of a mixture of water/dichloromethane (1:1)
  3. extractionThe aqueous phase is extracted four times each with 500 ml of dichloromethane
  4. customThe organic layer is separated
  5. customdried
  6. customevaporated to dryness
  7. customto yield a colorless, crude solid
  8. customSubsequently, the residue is purified by flash chromatography on silica gel (eluent: dichloromethane/ethanol 50:1)

Sources & evidence

ORD record
ord-ca46b1af073c436da1640c46abd339ca
Source dataset
uspto-grants-2010_08
Patent number
US07781453B2

Reaction notes

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