Water → 3-(2-Nitrophenyl)pyridine

HRID 2181710Notes

Reaction equation

HRID 2181710 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].C(B(CC)[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1)C.C(=O)([O-])[O-].[Na+].[Na+].O>O1CCCC1.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Cl)Cl.CO>[N+:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1)([O-:10])=[O:9]

Participants

8

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 113411-Bromo-2-nitrobenzeneHCID 6428513-(Diethylboryl)pyridine

Product 1

HCID 51500193-(2-Nitrophenyl)pyridineYield 41%

Reagents, catalysts & solvents 3

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

To a mixture consisting of 1-bromo-2-nitrobenzene (2.12 g, 8.7 mmol), diethyl (3-pyridyl) borane (1.47 g, 10.0 mmol), and bis (triphenylphosphine) palladium (II) chloride (913 mg, 1.3 mmol) in tetrahydrofuran (40 ml), sodium carbonate (4.24 g, 40.0 mmol) was added, and the resulting reaction mixture was heated at reflux for 4 hours. Water (40 ml) was added to the cooled reaction mixture which was then extracted with three 25 ml portions of ethyl acetate. The combined organic extracts were dried (anhydrous sodium sulfate) and concentrated in vacuo to afford a tacky residue. Flash chromatography of the entire sample (silica gel, 47-61 micron mesh; elution initially with methylene chloride and finally with methylene chloride/methanol=98:2 in volume) afforded the title compound as a viscous amber oil (713 mg, 41% yield). Subsequent eluent contained less pure product which was further purified by a similar flash chromatography, eluting with methylene chloride/methanol=99:1 in volume, thus affording an additional 488 mg (28% yield) of the purified title compound, again as a viscous amber oil.

Workup

  1. additionwas added
  2. customthe resulting reaction mixture
  3. temperaturewas heated
  4. temperatureat reflux for 4 hours
  5. extractionwas then extracted with three 25 ml portions of ethyl acetate
  6. dry with materialThe combined organic extracts were dried (anhydrous sodium sulfate)
  7. concentrationconcentrated in vacuo
  8. customto afford a tacky residue
  9. washelution initially with methylene chloride

Sources & evidence

ORD record
ord-105acd0607da4daa858173a73c3bc48e
Source dataset
uspto-grants-2005_05
Patent number
US06894062B1

Reaction notes

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