Ethyl Acetate → 3-Bromo-5-(4-methoxyphenyl)-4-methylpyridine

HRID 2076677Notes

Reaction equation

HRID 2076677 reaction equation
C(=O)([O-])[O-].[K+].[K+].Br[C:8]1[CH:9]=[N:10][CH:11]=[C:12]([Br:15])[C:13]=1[CH3:14].[CH3:16][O:17][C:18]1[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][CH:19]=1.C(OCC)(=O)C>CN(C)C(=O)C.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:15][C:12]1[CH:11]=[N:10][CH:9]=[C:8]([C:21]2[CH:22]=[CH:23][C:18]([O:17][CH3:16])=[CH:19][CH:20]=2)[C:13]=1[CH3:14]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 201262(4-Methoxyphenyl)boronic acidHCID 8193383,5-Dibromo-4-methylpyridine

Product 1

HCID 671193413-Bromo-5-(4-methoxyphenyl)-4-methylpyridineYield 46.3%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 21534740N,N-Dimethylacetamide--water (1/1)Solvent

Conditions

Temperature
80 °C

Procedure

Tetrakis(triphenylphosphine)palladium (0) (1.03 g, 0.89 mmol) and potassium carbonate (8.22 g, 59.5 mmol) were added to a solution of 3,5-dibromo-4-methylpyridine (7.46 g, 29.73 mmol) which was synthesized according to the method described in literature (Gu, Y. G. and Bayburt, E. K., Tetrahedron Lett., vol.: 37, 1966, pp. 2565-2568) and 4-methoxyphenylboronic acid (4.52 g, 29.73 mmol) in a mixture of N,N-dimethylacetamide-water (20:1, 100 ml), and the mixture was stirred at 80° C. for 4 hours. After the temperature of the reaction mixture was set to room temperature and ethyl acetate was added thereto, the insolubles were removed by filtration. The obtained filtrate was successively washed with water (twice) and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The residue obtained by removing the solvent under reduced pressure was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=4/1) to give 3-bromo-5-(4-methoxyphenyl)-4-methylpyridine (3.83 g, yield: 46%).

Workup

  1. customwas synthesized
  2. customwas set to room temperature
  3. customthe insolubles were removed by filtration
  4. washThe obtained filtrate was successively washed with water (twice) and a saturated aqueous NaCl solution
  5. dry with materialdried with anhydrous sodium sulfate
  6. customThe residue obtained
  7. customby removing the solvent under reduced pressure
  8. customwas purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-285c19bfba664234bd39dcea2b180395
Source dataset
uspto-grants-2011_04
Patent number
US07923573B2

Reaction notes

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