Aniline → 4-Nitrodiphenylamine

HRID 1995460Notes

Reaction equation

HRID 1995460 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C(C)=CC=CC=1.[N+:16]([C:19]1[CH:24]=[CH:23][C:22](Cl)=[CH:21][CH:20]=1)([O-:18])=[O:17].C(=O)([O-])[O-].[K+].[K+]>N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.O>[CH:5]1[CH:6]=[CH:7][C:2]([NH:1][C:22]2[CH:23]=[CH:24][C:19]([N+:16]([O-:18])=[O:17])=[CH:20][CH:21]=2)=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 6115AnilineHCID 7237O-XyleneHCID 74741-Chloro-4-nitrobenzeneHCID 11430Potassium Carbonate

Product 1

HCID 132714-NitrodiphenylamineYield 129.4%

Reagents, catalysts & solvents 2

HCID 13181,10-PhenanthrolineCatalystHCID 962WaterSolvent

Conditions

Temperature
96 °C

Procedure

186 g of aniline, 60 ml of xylene, 4.5 g of 1,10-phenanthroline, 157.5 g of 4-nitrochlorobenzene, 2 g of CuO and 76.3 g of potassium carbonate are heated to 195° C. for 7 hours in a water separator. The reaction mixture is cooled to 96° C. After the precipitated salts have been separated off by filtration, the filter cake is thoroughly washed with 200 ml of hot xylene. The filtrate and the washing liquid are combined, and after the solution has been cooled to 0° C., 127 g of 4-nitrodiphenylamine of melting point 128°-130° C. crystallize out and are separated off by filtration. 93 g of aniline, 157.5 g of p-nitrochlorobenzene and 76.3 g of potassium carbonate are added to the mother liquor produced in this procedure, and the mixture is freed from excess xylene by distillation, and heated at 195° C. for 11 hours in a water separator. After the salts have again been filtered off, the filtrate is worked up by steam distillation, as described in Example 7. 277 g of 4-nitrodiphenylamine of melting point 107°-111° C. are obtained.

Workup

  1. customAfter the precipitated salts have been separated off by filtration
  2. washthe filter cake is thoroughly washed with 200 ml of hot xylene
  3. temperatureafter the solution has been cooled to 0° C.
  4. custom127 g of 4-nitrodiphenylamine of melting point 128°-130° C. crystallize out
  5. customare separated off by filtration
  6. addition93 g of aniline, 157.5 g of p-nitrochlorobenzene and 76.3 g of potassium carbonate are added to the mother liquor
  7. customproduced in this procedure
  8. distillationthe mixture is freed from excess xylene by distillation
  9. temperatureheated at 195° C. for 11 hours in a water separator
  10. filtrationAfter the salts have again been filtered off
  11. distillationthe filtrate is worked up by steam distillation

Sources & evidence

ORD record
ord-8ec9837f04a0461cb390e178c4f7bfce
Source dataset
uspto-grants-1983_09
Patent number
US04404400

Reaction notes

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