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

HRID 408107

Reaction equation

HRID 408107 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

Procedure

A round-bottom flask was heated, and then allow to cool to room temperature under argon. To the flask were added Pd2(dba)3 (1.39 g, 1.52 mmol, 1.0 mol %) or Pd(dba)2 (1.38 g, 2.4 mmol, 1.4 mol %), 2-(di-tert-butylphosphino)biphenyl (1.09 g, 3.65 mmol, 2.4 mol %), 2-bromotoluene (12, 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 %), then toluene (150 mL). The reaction mixture was heated at 80° C. under argon overnight, then allowed to cool to room temperature. The resulting liquid was diluted with diethyl ether, and then filtered through a pad of celite. The resulting cocnentrte was filtered in vacuo and used in the next reaction without purification. The crude material was purified by column chromatography with hexane to give the product as white crystals with a yellow tint (23.4 g, 118.6 mmol, 72% yield).

Workup

  1. temperatureA round-bottom flask was heated
  2. temperatureThe reaction mixture was heated at 80° C. under argon overnight
  3. temperatureto cool to room temperature
  4. filtrationfiltered through a pad of celite
  5. filtrationThe resulting cocnentrte was filtered in vacuo
  6. customused in the next reaction without purification
  7. customThe crude material was purified by column chromatography with hexane

Sources & evidence

ORD record
ord-0845e1f1662e420f99af65bf52af23eb
Source dataset
uspto-grants-2014_06
Patent number
US08759336B2

Linked notes

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