2,4-Dimethylaniline → Aniline

HRID 598056Notes

Reaction equation

HRID 598056 reaction equation
Br[C:2]1[C:3](=[O:12])[N:4]([CH3:11])[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.[CH3:13][C:14]1[CH:20]=[C:19]([CH3:21])[CH:18]=[CH:17][C:15]=1[NH2:16].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C(OCC)(=O)C.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]>[CH3:13][C:14]1[CH:20]=[C:19]([CH3:21])[CH:18]=[CH:17][C:15]=1[NH:16][C:2]1[C:3](=[O:12])[N:4]([CH3:11])[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.[NH2:16][C:15]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:14]=1

Participants

9

Reactant 4

HCID 72502,4-DimethylanilineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 672674813-Bromo-1-methyl-5-nitro-2(1H)-pyridinone

Product 2

HCID 6115AnilineHCID 672679503-[(2,4-Dimethylphenyl)amino]-1-methyl-5-nitropyridin-2(1H)-one

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
95 °C

Procedure

To a solution containing 0.60 g (2.57 mmol) of 3-bromo-1-methyl-5-nitropyridin-2(1H)-one in 120 ml of toluene under a nitrogen atmosphere was added 0.64 ml (5.15 mmol) of 2,4-dimethylaniline, 1.61 g (2.57 mmol) of rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic BINAP), 0.37 g (3.85 mmol) of sodium t-butoxide and 1.20 g (1.31 mmol) of tris(dibenzylideneacetone)dipalladium (0). The reaction was heated to 95° C. overnight. The reaction was cooled to room temperature, diluted with ethyl acetate and washed with saturated sodium bicarbonate. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and purification of the residue via biotage eluting with 60% ethyl acetate/hexanes gave the desired product with some starting aniline. The material was triturated with hexanes and the solids filtered and dried to afford 0.154 g (21.9%) of product.

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. washwashed with saturated sodium bicarbonate
  3. dry with materialThe organic phase was dried over magnesium sulfate
  4. filtrationFiltration, removal of solvent and purification of the residue via biotage
  5. washeluting with 60% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-6f11ef843c1843bf979f4d549fc34825
Source dataset
uspto-grants-2011_03
Patent number
US07897607B2

Reaction notes

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