Toluene → Benzenamine, 4-methyl-N-(4-methylphenyl)-

HRID 324714Notes

Reaction equation

HRID 324714 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[Cl-].[Ca+2].[Cl-].[Cl-].[Al+3].[Cl-].[Cl-].[C:16]1([CH3:22])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1C2C(=CC=CC=2)CCC1>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([NH:1][C:19]2[CH:20]=[CH:21][C:16]([CH3:22])=[CH:17][CH:18]=2)=[CH:3][CH:4]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 7813p-ToluidineHCID 5284359Calcium ChlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 69293Benzenamine, 4-methyl-N-(4-methylphenyl)-Yield 69.8%

Reagents, catalysts & solvents 1

HCID 8404TetralinSolvent

Procedure

In a 500-ml four-necked flask were charged 56 ml of 1,2,3,4-tetrahydronaphthalene (boiling point: 207° C.) as a solvent and 91.1 g (0.83 mol) of p-toluidine, followed by the addition of 25.6 g (0.23 mol) of anhydrous calcium chloride and 30.8 g (0.23 mol) of anhydrous aluminum chloride under stirring. The resulting mixture was reacted at 210 to 220° C. for 3 hours under a nitrogen atmosphere. After cooling, the reaction mixture was added with 126 ml of toluene, followed by charging in 160 g of ice water. The resulting mixture was stirred and allowed to stand, and then the resulting water layer was separate out. The organic layer was washed successively with 150 ml of a 5% aqueous solution of hydrochloric acid, 100 ml of a 5% aqueous solution of sodium bicarbonate and 100 ml of water. After removal of the organic solvent by distillation under reduced pressure, 80 ml of methanol was added to the residue and the mixture was crystallized overnight at −3 to −8° C. The resulting crystals were collected by filtration, washed with 30 ml of methanol and then dried, whereby 57.1 g (yield: 69.8%) of the title compound was obtained as white crystals. As a result of HPLC. analysis (column: YMC-A-312, detection UV: 280 nm, flow rate: 1.0 ml/min, eluent: acetonitrile/water=8/2), the compound was found to have a purity of 99.8%.

Workup

  1. customThe resulting mixture was reacted at 210 to 220° C. for 3 hours under a nitrogen atmosphere
  2. temperatureAfter cooling
  3. stirringThe resulting mixture was stirred
  4. customthe resulting water layer was separate out
  5. washThe organic layer was washed successively with 150 ml of a 5% aqueous solution of hydrochloric acid, 100 ml of a 5% aqueous solution of sodium bicarbonate and 100 ml of water
  6. customAfter removal of the organic solvent
  7. distillationby distillation under reduced pressure, 80 ml of methanol
  8. additionwas added to the residue
  9. customthe mixture was crystallized overnight at −3 to −8° C
  10. filtrationThe resulting crystals were collected by filtration
  11. washwashed with 30 ml of methanol
  12. customdried

Sources & evidence

ORD record
ord-bdf608f6fa834e619eb0696c0b0032de
Source dataset
uspto-grants-2001_04
Patent number
US06218576B1

Reaction notes

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