1-Chloro-4-nitrobenzene → 4-Nitrodiphenylamine

HRID 1448753Notes

Reaction equation

HRID 1448753 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7](Cl)=[CH:6][CH:5]=1)([O-:3])=[O:2].C([NH:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=O.[Na].C(NC1C=CC=CC=1)=O.[C]=O>C1(C)C(C)=CC=CC=1>[CH:17]1[CH:18]=[CH:19][C:14]([NH:13][C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)=[CH:15][CH:16]=1

Participants

6

Reactant 4

HCID 74741-Chloro-4-nitrobenzeneHCID 7671FormanilideHCID 86736350HCID 86736350, compoundHCID 178418416HCID 178418416, compound2×

Product 1

HCID 132714-Nitrodiphenylamine

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Conditions

Temperature
10 °C

Procedure

Into a suitable reactor is charged 78.5 parts by weight (0.5 mole) of p-nitrochlorobenzene, 93.8 parts by weight (0.65 mole) of sodium formanilide, 96 parts by weight (0.8 mole) of formanilide. The mixture is gradually heated and stirred; and, at about 134° C., evolution of carbon monoxide begins. Heating is continued until the temperature reaches 180°, at which temperature the reaction mixture becomes self-heating. Stirring is continued at 180°. After about two and one-half hours, 18 parts by weight of carbon monoxide are evolved; and reaction is stopped, xylene added, and the xylene solution washed with 250 parts by weight of water, separated from the water and cooled to 10° C. The crystals of 4-nitrodiphenylamine which form are separated by filtration and washed with a little xylene. From the mother liquor a second crop of 4-nitrodiphenylamine is recovered. The yield of 4-nitrodiphenylamine is 86% and conversion of p-nitrochlorobenzene is 96%. The presence of the formanilide reduces tertiary amine byproduct which becomes excessive in the case of reaction in dimethylformamide, for example.

Workup

  1. temperatureThe mixture is gradually heated
  2. customat about 134° C.
  3. temperatureHeating
  4. customreaches 180°, at which temperature
  5. temperaturebecomes self-heating
  6. stirringStirring
  7. customis continued at 180°
  8. customand reaction
  9. washthe xylene solution washed with 250 parts by weight of water
  10. customseparated from the water
  11. customThe crystals of 4-nitrodiphenylamine which form are separated by filtration
  12. washwashed with a little xylene
  13. customFrom the mother liquor a second crop of 4-nitrodiphenylamine is recovered

Sources & evidence

ORD record
ord-3d93106bacdd48eba04e44cdd3d8506c
Source dataset
uspto-grants-1980_02
Patent number
US04187248

Reaction notes

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