Toluene → N,N'-dianisyl-1,4-phenylenediamine

HRID 50462

Reaction equation

HRID 50462 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.[C:10]1([NH2:17])[CH:15]=[CH:14][C:13]([NH2:16])=[CH:12][CH:11]=1.C[C:19](C)([O-:21])C.[Na+].[C:24]1([CH3:30])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[CH3:31]CCCCC>C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].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]>[CH2:31]([NH:16][C:13]1[CH:14]=[CH:15][C:10]([NH:17][CH2:30][C:24]2[CH:29]=[CH:28][C:27]([O:21][CH3:19])=[CH:26][CH:25]=2)=[CH:11][CH:12]=1)[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 1140TolueneHCID 77304-BromoanisoleHCID 7814P-PhenylenediamineHCID 8058HexaneHCID 23676156Sodium t-butoxide

Product 1

HCID 21301606N,N'-dianisyl-1,4-phenylenediamineYield 72%

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
90 °C

Procedure

A flame-dried one liter three neck round bottom flask was charged with 4-bromoanisole (50.4 g, 0.26 mole), 1,4-phenylenediamine (12.0 g, 0.11 mole), 1,1 ′-bis(diphenylphosphino)ferrocene (1.776 g, 0.0032 mole), tris(dibenzylideneacetone)dipalladium(0) (0.98 g, 0.001 mole), sodium tert-butoxide (31.2 g, 0.32 mole), and anhydrous toluene (350 ml). The reaction mixture was heated to 90° C. for 48 hours. The reaction mixture was cooled to room temperature and hexane (400 ml) was added. The solid was filtered and dissolved in ethanol (400 ml). Sodium dithionite (20.0 g) was dissolved in 300 ml water and added to the ethanol solution. This was heated to reflux for 30 minutes. After the solution was cooled to room temperature, the solid was filtered off and washed with water to give 25.7 g (72%) of N,N′-dianisyl-1,4-phenylenediamine.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationThe solid was filtered
  3. dissolutiondissolved in ethanol (400 ml)
  4. dissolutionSodium dithionite (20.0 g) was dissolved in 300 ml water
  5. additionadded to the ethanol solution
  6. temperatureThis was heated
  7. temperatureto reflux for 30 minutes
  8. temperatureAfter the solution was cooled to room temperature
  9. filtrationthe solid was filtered off
  10. washwashed with water

Sources & evidence

ORD record
ord-361d3f1358d749a78e0447ed25911790
Source dataset
uspto-grants-2004_03
Patent number
US06710906B2

Linked notes

Loading…