p-Bromochlorobenzene → HCID 11185482, compound

HRID 2187256Notes

Reaction equation

HRID 2187256 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(C)([O-])C.[Na+].[NH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH3:21])[CH:16]=1.[CH:22]1[C:27]([Cl:28])=[CH:26][CH:25]=[C:24](Br)[CH:23]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.O>[Cl:28][C:27]1[CH:26]=[CH:25][C:24]([N:14]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:15]2[CH:16]=[C:17]([CH3:21])[CH:18]=[CH:19][CH:20]=2)=[CH:23][CH:22]=1

Participants

8

Reactant 4

HCID 7806p-BromochlorobenzeneHCID 7934m-ToluidineHCID 7961BromobenzeneHCID 23676156Sodium t-butoxide2×

Product 1

HCID 11185482HCID 11185482, compoundYield 85.1%

Reagents, catalysts & solvents 3

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent

Procedure

Under nitrogen, a flask is charged with 138 mg (0.0006 mol) of palladium acetate, 0.48 g (0.002 mol) of tri-tert-butylphosphine, 180 grams of dry, deoxygenated toluene. The solution is stirred for 5 minutes until the pale yellow color changed to a red color. The other reagents are added sequentially under nitrogen: 22 mL (0.2 mol) of bromobenzene, 25.3 g (0.26 mol) of sodium t-butoxide and m-toluidine (22 mL, 0.2 mol). The reaction is heated with stirring to reflux for 2.5 hours, at the end of which it was cooled down and analyzed by GC/MS to contain 95-97% of m-methyldiphenylamine. 25.8 g (0.26 mol) of sodium t-butoxide and 38.8 g (0.2 mol) of 1,4-bromochlorobenzene are added; the reaction is filled with nitrogen, and heated to reflux with stirring for 18 hours. The reaction is cooled, water is added, extract the aqueous with toluene. The combined organic layers are dried over sodium sulfate, filtered through a pad of neutral alumina, and the filtrate is distilled to remove the bulk of the solvent. The concentrated solution is treated with MeOH slowly with stirring. The solid is collected to afford 50 g (83%) of (4-chloro-phenyl)-phenyl-m-tolyl amine as an off-white solid.

Workup

  1. customof dry
  2. customdeoxygenated toluene
  3. additionThe other reagents are added sequentially under nitrogen
  4. temperatureThe reaction is heated
  5. stirringwith stirring
  6. temperatureto reflux for 2.5 hours, at the end of which it
  7. temperaturewas cooled down
  8. additionthe reaction is filled with nitrogen
  9. temperatureheated
  10. temperatureto reflux
  11. stirringwith stirring for 18 hours
  12. temperatureThe reaction is cooled
  13. extractionextract the aqueous with toluene
  14. dry with materialThe combined organic layers are dried over sodium sulfate
  15. filtrationfiltered through a pad of neutral alumina
  16. distillationthe filtrate is distilled
  17. customto remove the bulk of the solvent
  18. additionThe concentrated solution is treated with MeOH slowly
  19. stirringwith stirring
  20. customThe solid is collected

Sources & evidence

ORD record
ord-4ae94ee86e944b918c3d40f692fab073
Source dataset
uspto-grants-2002_06
Patent number
US06407289B1

Reaction notes

Loading…