Sodium Carbonate → 3-(2-Chloro-5-nitrophenyl)pyridine

HRID 586303Notes

Reaction equation

HRID 586303 reaction equation
Br[C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:6][C:7]=1[Cl:8].B1([C:18]2[CH:23]=[CH:22][CH:21]=[N:20][CH:19]=2)OCCCO1.C([O-])([O-])=O.[Na+].[Na+]>C(O)C.C1(C)C=CC=CC=1.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>[Cl:8][C:7]1[CH:6]=[CH:5][C:4]([N+:9]([O-:11])=[O:10])=[CH:3][C:2]=1[C:18]1[CH:19]=[N:20][CH:21]=[CH:22][CH:23]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27355492-Bromo-1-chloro-4-nitrobenzeneHCID 41980053-(1,3,2-Dioxaborinan-2-yl)pyridine

Product 1

HCID 223295393-(2-Chloro-5-nitrophenyl)pyridineYield 69%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

A mixture of 3-bromo-4-chloronitrobenzene (5.17 g, 21.9 mmol) and pyridine-3-boronic acid 1,3-propanediol cyclic ester (4.27 g, 26.2 mmol) in ethanol (30 ml) and toluene (30 ml) together with 2 N Na2CO3 solution (13.9 ml) was degassed with a stream of nitrogen for 10 min. Tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.26 mmol) was added and the reaction was heated at reflux for over 24 h. The mixture was concentrated under reduced pressure to remove the organic solvents and water (100 ml) was added. This was extracted with ethyl acetate (200 ml) and then washed with brine (75 ml), dried (MgSO4), and concentrated under reduced pressure while dry loading onto silica. The resulting crude residue was purified by column chromatography (silica gel, 50% Et2O/CH2Cl2), to yield the title compound (3.53 g, 69%): 1H NMR (360 MHz, CDCl3) δ 7.42-7.48 (1H, m), 7.70 (1H, d, J 8.7 Hz), 7.81 (1H, dt, J 8.0, 1.8 Hz), 8.17-8.27 (2H, m), 8.68-8.77 (2H, m).

Workup

  1. customwas degassed with a stream of nitrogen for 10 min
  2. temperaturethe reaction was heated
  3. temperatureat reflux for over 24 h
  4. concentrationThe mixture was concentrated under reduced pressure
  5. customto remove the organic solvents and water (100 ml)
  6. additionwas added
  7. extractionThis was extracted with ethyl acetate (200 ml)
  8. washwashed with brine (75 ml)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated under reduced pressure
  11. customwhile dry loading onto silica
  12. customThe resulting crude residue was purified by column chromatography (silica gel, 50% Et2O/CH2Cl2)

Sources & evidence

ORD record
ord-5d81ba80b27c4c67a0b4b11fdd25b41e
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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