Reaction #1396

Reaction equation

1,10-phenanthroline

bis(3,4-dimethylphenyl)amine

4-iodobiphenyl

potassium hydroxide

→

product

N,N-bis(3,4-dimethylphenyl)-4-biphenylamine

Solvents

toluene

Conditions

Workup

1. 1
   OtherIn a 500 milliliter round bottomed flask equipped with mechanical stirrer
2. 2
   Otherfitted with a Dean-Stark trap under a reflux condenser
3. 3
   Temperaturemaintained at this temperature for 4 hours after which time chromatographic analysis
4. 4
   Otherthe reaction
5. 5
   TemperatureThe reaction was cooled to room temperature, about 25° C.
6. 6
   Otherpartitioned between 200 milliliters of toluene and 150 milliliters of deionized water
7. 7
   OtherThe resulting organic layer was separated
8. 8
   Otherwater removed by azeotropic distillation of the solvent under a Dean-Stark trap
9. 9
   workup.ADDITIONtreating the toluene solution with 10 grams of Filtrol-24™
10. 10
    Washan acid washed clay, and 10 grams of Alcoa CG-20 alumina
11. 11
    Temperatureat reflux
12. 12
    Filtrationthe solution was hot filtered
13. 13
    Otherto remove the clay and alumina
14. 14
    Temperaturecooled to room temperature
15. 15
    OtherEvaporation of the solvent and recrystallization from octane

Procedure

In a 500 milliliter round bottomed flask equipped with mechanical stirrer and fitted with a Dean-Stark trap under a reflux condenser were placed 12.39 grams (0.055 mole) of bis(3,4-dimethylphenyl)amine, 14 grams (0.050 mole) of 4-iodobiphenyl, 0.25 gram (0.0025 mole) of cuprous chloride, 0.45 gram (0,0025 mole) of 1,10-phenanthroline, 22.44 grams (0.4 mole) of flake potassium hydroxide and 20 milliliters of toluene solvent. The reaction was heated quickly to a reflux temperature of 120° C. and maintained at this temperature for 4 hours after which time chromatographic analysis revealed the reaction to be complete. The reaction was cooled to room temperature, about 25° C., and partitioned between 200 milliliters of toluene and 150 milliliters of deionized water. The resulting organic layer was separated and water removed by azeotropic distillation of the solvent under a Dean-Stark trap. The product was decolorized by slurry treating the toluene solution with 10 grams of Filtrol-24™, an acid washed clay, and 10 grams of Alcoa CG-20 alumina. After 3 hours stirring at reflux, the solution was hot filtered to remove the clay and alumina, and cooled to room temperature. Evaporation of the solvent and recrystallization from octane provided the above product compound in a yield of 10.2 grams (76 percent) and which product melted at 113.8° C. This product of N,N-bis(3,4-dimethylphenyl)-4-biphenylamine was suitable for further purification by conventional means to afford electronic grade, about 99 percent pure, product. The above total reaction time was an accelerated 4 hours.

Source