Sodium Carbonate → 4-(3-Methoxy-4-nitrophenyl)pyridine

HRID 419472Notes

Reaction equation

HRID 419472 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([O:11][CH3:12])[CH:3]=1.[N:13]1[CH:18]=[CH:17][C:16](B(O)O)=[CH:15][CH:14]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:12][O:11][C:4]1[CH:3]=[C:2]([C:16]2[CH:17]=[CH:18][N:13]=[CH:14][CH:15]=2)[CH:7]=[CH:6][C:5]=1[N+:8]([O-:10])=[O:9]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 811105-Chloro-2-nitroanisoleHCID 2734379(Pyridin-4-yl)boronic acid

Product 1

HCID 137288334-(3-Methoxy-4-nitrophenyl)pyridineYield 80%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
102 °C

Procedure

A solution of 4-chloro-2-(methyloxy)-1-nitrobenzene (34.7 g, 184.8 mmol), PdCl2(PPh3)2 (6.5 g, 9.24 mmol) and 4-pyridylboronic acid (25.0 g, 203.2 mmol) in dioxane was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 3.0 N Na2CO3 (aq) (203 mL, 3.0 equiv.) and the resulting slurry was warmed to 102° C. for 4 h. The dioxane was removed under reduced pressure and the solids were dissolved in EtOAc and washed twice with brine. The organic layer was dried over Na2SO4, taken to a residue under reduced pressure, and the residue purified by trituration with diethyl ether to afford 4-[3-(methyloxy)-4-nitrophenyl]pyridine as a brown solid (34.0 g, 147.68 mmol, 80%) of sufficient purity for use in subsequent transformations. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.64-8.73 (m, 2H), 8.00 (d, J=8.43 Hz, 1H), 7.78-7.85 (m, 2H), 7.67 (d, J=1.83 Hz, 1H), 7.51 (dd, J=8.43, 1.83 Hz, 1H), 4.03 (s, 3H).

Workup

  1. customby bubbling with N2 (g) for ca 15 min
  2. additionTo this solution was added
  3. customThe dioxane was removed under reduced pressure
  4. dissolutionthe solids were dissolved in EtOAc
  5. washwashed twice with brine
  6. dry with materialThe organic layer was dried over Na2SO4
  7. customthe residue purified by trituration with diethyl ether

Sources & evidence

ORD record
ord-c7c66a560c174b638ea0f34a90185d96
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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