2-Bromotoluene → Benzenamine, 2-methyl-N-(2-methylphenyl)-

HRID 2405685Notes

Reaction equation

HRID 2405685 reaction equation
C(P(C(C)(C)C)C1C=CC=C[C:7]=1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)(C)(C)C.Br[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[CH3:29].ClC1C=CC=CC=1C.[NH2-:38].[Li+].CC(C)([O-])C.[Na+]>C(OCC)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].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].C1(C)C=CC=CC=1>[C:12]1([CH3:7])[CH:13]=[CH:14][CH:15]=[CH:16][C:17]=1[NH:38][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[CH3:29]

Participants

10

Reactant 5

HCID 72362-BromotolueneHCID 72382-ChlorotolueneHCID 24532Lithium amideHCID 27342152-(Di-tert-butylphosphino)biphenylHCID 23676156Sodium t-butoxide

Product 1

HCID 136423Benzenamine, 2-methyl-N-(2-methylphenyl)-Yield 72%

Reagents, catalysts & solvents 4

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

The following were added to a reaction vessel dried as indicated: One mole percent of Pd2(dba)3 (1.39 g, 1.52 mmol) or Pd(dba)2 (1.38 g, 2.4 mmol, 1.4 mol %), 2-(di-tert-butylphosphino)biphenyl (1.09 g, 3.65 mmoles, 2.4 mole %), 2-bromotoluene (40 mL, 332.1 mmol) or 2-chlorotoluene (39 mL, 332.1 mmol), lithium amide (3.47 g, 151.1 mmol, 45 mol %), sodium t-butoxide 29.5 g, 297.7 mmol, 90 mol %), and then toluene (150 mL). The mixture was then heated at 80° C. under argon overnight. Following the reaction period the mixture was allowed to cool to room temperature, and then diluted with diethyl ether and filtered through a pad of celite. The collected filtrate was concentrated in vacuo. Purify of the resulting residue was accomplished by flash silica gel chromatography in hexane to give the desired product as white crystals with a yellow tint (23.4 g, 118.6 mmol, 72% yield).

Workup

  1. additionThe following were added to a reaction vessel
  2. customdried
  3. customthe reaction period the mixture
  4. temperatureto cool to room temperature
  5. filtrationfiltered through a pad of celite
  6. concentrationThe collected filtrate was concentrated in vacuo
  7. customPurify of the resulting residue

Sources & evidence

ORD record
ord-ed4c0e239a4c4d6a9d317a1e7636e6f3
Source dataset
uspto-grants-2014_08
Patent number
US08809317B2

Reaction notes

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