Aniline → 4-Nitrodiphenylamine

HRID 1995459Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N12CCCN=C1CCCCC2.[N+:19]([C:22]1[CH:27]=[CH:26][C:25](Cl)=[CH:24][CH:23]=1)([O-:21])=[O:20].C(=O)([O-])[O-].[Na+].[Na+]>[Cu]=O.O.C1(C)C(C)=CC=CC=1>[CH:5]1[CH:6]=[CH:7][C:2]([NH:1][C:25]2[CH:26]=[CH:27][C:22]([N+:19]([O-:21])=[O:20])=[CH:23][CH:24]=2)=[CH:3][CH:4]=1

Participants

Conditions

Temperature: 95 °C

Procedure

93 g of aniline, 3.8 g of 1,8-diazabicyclo[5,4,0]undec-7-ene, 2 g of copper(II)oxide and 40 ml of xylene are heated together to 150° C. for 20 minutes in a water separator. 157.5 g of 4-nitrochlorobenzene, 93 g of aniline and 76 g of calcined sodium carbonate (light) are then added. After 12 hours at 193°-196° C., 10 ml of water have collected in the water separator. The weight ratio of nitrobenzene:4-nitrochlorobenzene:4-nitrodiphenylamine in the reaction mixture is 1.5:2.0:96.5. The reaction mixture is cooled to 95° C. and filtered, and the filter cake is washed with 100 ml of hot xylene. Water is added to the filtrate, and unreacted 4-nitrochlorobenzene and aniline are expelled with steam, the 4-nitrodiphenylamine being obtained as granules. It is isolated by filtration, washed with hot water and dried: 210 g of 4-nitrodiphenylamine, purity (HPLC) 91.3%, yield 89.6 % of theory, relative to p-nitrochlorobenzene employed.

Workup

custom10 ml of water have collected in the water separator
filtrationfiltered
washthe filter cake is washed with 100 ml of hot xylene
additionWater is added to the filtrate, and unreacted 4-nitrochlorobenzene and aniline

Sources & evidence

ORD record: ord-7557be37a55e4af18501f2718726f1f1
Source dataset: uspto-grants-1983_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04404400

Reaction notes

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