4-Bromo-2-nitroaniline → HCID 10353230, compound

HRID 730233Notes

Reaction equation

HRID 730233 reaction equation
[N:1]1[CH:6]=[CH:5][C:4](B(O)O)=[CH:3][CH:2]=1.Br[C:11]1[CH:16]=[CH:15][C:14]([NH2:17])=[C:13]([N+:18]([O-:20])=[O:19])[CH:12]=1>COCCOC.C([O-])([O-])=O.[Na+].[Na+].C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:18]([C:13]1[CH:12]=[C:11]([C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)[CH:16]=[CH:15][C:14]=1[NH2:17])([O-:20])=[O:19]

Participants

7

Reactant 2

HCID 701324-Bromo-2-nitroanilineHCID 2734379(Pyridin-4-yl)boronic acid

Product 1

HCID 10353230HCID 10353230, compoundYield 119.9%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolventHCID 10340Sodium CarbonateSolvent

Procedure

To a mixture of pyridine-4-boronic acid (3 mmol), 4-bromo-2-nitrophenylamine (2 mmol), and Pd(PPh3)4 (20 mg) in DME (10 mL), 2 M aqueous Na2CO3 was added. The suspension was then refluxed under nitrogen for 36 h. After cooling to the room temperature, the reaction mixture was diluted with ethyl acetate (150 mL). The organic phase was washed with brine (50 mL), dried over sodium sulfate, and concentrated under vacuum. The residue obtained was purified by column chromatography eluting with hexanes/ethyl acetate (1:1) then ethyl acetate/methanol (10:1) to give 516 mg of 2-nitro-4-pyridin-4-ylphenylamine. 1H NMR (DMSO-d6, 400 MHz): LC: Tr 0.44 min, MS: 216.1 (M+1)+. 1H NMR (DMSO-d6, 400 MHz): δ 7.13 (d, 1H), 7.60 (d, 2H), 7.69 (bs, 2H), 7.88 (dd, 1H), 8.37 (d, 1H), 8.55 (d, 2H) ppm.

Workup

  1. additionwas added
  2. temperatureThe suspension was then refluxed under nitrogen for 36 h
  3. washThe organic phase was washed with brine (50 mL)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under vacuum
  6. customThe residue obtained
  7. customwas purified by column chromatography
  8. washeluting with hexanes/ethyl acetate (1:1)

Sources & evidence

ORD record
ord-71a4331336504c27b746f1b401715061
Source dataset
uspto-grants-2009_09
Patent number
US07582673B2

Reaction notes

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