Reaction #78740

Reaction equation

4-bromoanisole

1,4-phenylenediamine

sodium tert-butoxide

toluene

hexane

→

N,N′-dianisyl-1,4-phenylenediamine

Yield 72.0%

Conditions

Workup

1. 1
   TemperatureThe reaction mixture was cooled to room temperature
2. 2
   FiltrationThe solid was filtered
3. 3
   workup.DISSOLUTIONdissolved in ethanol (400 ml)
4. 4
   workup.DISSOLUTIONSodium dithionite (20.0 g) was dissolved in 300 ml water
5. 5
   workup.ADDITIONadded to the ethanol solution
6. 6
   TemperatureThis was heated
7. 7
   Temperatureto reflux for 30 minutes
8. 8
   TemperatureAfter the solution was cooled to room temperature
9. 9
   Filtrationthe solid was filtered off
10. 10
    Washwashed with water

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.

Source