Sodium Carbonate → 4-[2-Methyl-5-(methyloxy)-4-nitrophenyl]pyridine

HRID 419520Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:8]=[C:7](Br)[C:6]([CH3:10])=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].[N:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:10][C:6]1[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[C:3]([O:2][CH3:1])=[CH:8][C:7]=1[C:17]1[CH:18]=[CH:19][N:14]=[CH:15][CH:16]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A solution of 5-bromo-4-methyl-2-nitrophenyl methyl ether (6.0 g, 24.38 mmol), PdCl2(dppf)*DCM (1.43 g, 1.95 mmol) and 4-pyridylboronic acid (20.4 g, 165.8 mmol) in dioxane was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 2.0 N Na2CO3 (aq) (170 mL, 14.0 equiv.) and the resulting slurry was warmed to 80° C. for 24 h. The dioxane was removed under reduced pressure and the solids were dissolved in EtOAc and washed with H2O, dried (Na2SO4), and purified by flash chromatography to give the title compound of step A (2.81 g, 11.5 mmol, 57%). 1H NMR (400 MHz, CDCl3) δ ppm 8.72 (d, J=4.77 Hz, 2H), 7.79 (s, 1H), 7.22-7.31 (m, 2H), 6.90 (s, 1H), 3.95 (s, 3H), 2.22 (s, 3H).

Workup

customby bubbling with N2 (g) for ca 15 min
additionTo this solution was added
customThe dioxane was removed under reduced pressure
dissolutionthe solids were dissolved in EtOAc
washwashed with H2O
dry with materialdried (Na2SO4)
custompurified by flash chromatography

Sources & evidence

ORD record: ord-463722b9566b486ea014b0a3e8f74ce3
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08093239B2

Reaction notes

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