O-Xylene → 4-Nitrodiphenylamine

HRID 903520Notes

Reaction equation

HRID 903520 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.C1(C)C(C)=CC=CC=1.[OH-].[Cs+]>O>[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 7237O-XyleneHCID 74741-Chloro-4-nitrobenzene2×HCID 7671FormanilideHCID 62750Cesium hydroxide

Product 1

HCID 132714-Nitrodiphenylamine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

Into the reactor previously described are charged 49.7 grams (0.315 moles) of p-nitrochlorobenzene together with 98.7 grams of a 66.4% solution of formanilide recovered from a previous run (0.54 molecular proportions). The solution also contained 0.07 moles of p-nitrochlorobenzene, bringing the total to 0.385 mole. About 50 milliliters of xylene are added, and the mixture heated to refluxing temperature which is about 195°-198° C. To the hot mixture is added at the rate of about 0.4 ml. per minute 82.5 grams (0.55 mole) of cesium hydroxide as a 50% solution in water (165 grams) during which addition the water is continuously removed. The heating is continued for a total time of about five hours, then 250 ml. of xylene is added and the xylene solution washed twice with 200 ml. portions of 90° C. water. The xylene solution is cooled to 5° C., filtered and the cake washed with 60 ml. of 5° C. xylene. There is obtained 40.7 grams of 4-nitrodiphenylamine. The total yield determined as described in Example 1 is 72%. The conversion of p-nitrodiphenylamine is 99.1%.

Workup

  1. customrecovered from a previous run (0.54 molecular proportions)
  2. temperaturethe mixture heated
  3. temperatureto refluxing temperature which
  4. customis about 195°-198° C
  5. additionTo the hot mixture is added at the rate of about 0.4 ml
  6. customis continuously removed
  7. customis continued for a total time of about five hours
  8. additionof xylene is added
  9. washthe xylene solution washed twice with 200 ml
  10. customportions of 90° C. water
  11. filtrationfiltered
  12. washthe cake washed with 60 ml
  13. customof 5° C.

Sources & evidence

ORD record
ord-7ba1722f1d604567912309a43ec0ab10
Source dataset
uspto-grants-1980_10
Patent number
US04228103

Reaction notes

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