Urea → 3-Methyl-4-((4-nitrophenyl)azo)benzenamine

HRID 1656569Notes

Reaction equation

HRID 1656569 reaction equation
[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)([O-:3])=[O:2].N([O-])=O.[Na+].[NH2:15]C(N)=O.[NH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH3:26])[CH:21]=1.Cl.NC1C=CC=C(C)C=1.C(=O)([O-])[O-].[K+].[K+]>Cl.O>[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([N:8]=[N:15][C:23]2[CH:24]=[CH:25][C:20]([NH2:19])=[CH:21][C:22]=2[CH3:26])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

9

Reactant 6

HCID 1176UreaHCID 74754-NitroanilineHCID 7934m-ToluidineHCID 11430Potassium CarbonateHCID 5221053-Methylaniline hydrochlorideHCID 23668193Sodium Nitrite

Product 1

HCID 439913-Methyl-4-((4-nitrophenyl)azo)benzenamineYield 195%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent

Procedure

Recrystallized 4-nitroaniline (16.5 g, 0.12 mol) was dissolved in 10N hydrochloric acid (40 ml) at 75° C. The solution was diluted with water (40 ml), poured over ice (100 g), and cooled in an ice bath. Sodium nitrite solution (64.0 ml, 2M) was added over 5 minutes and the mixture was stirred for 30 minutes. Urea (1.0 g) was added and the mixture was stirred 20 minutes in an ice bath. In a separate beaker distilled m-toluidine (17.1 g, 0.16 mol) was mixed with 5N hydrochloric acid (40 ml) for 5 minutes at room temperature and then cooled in an ice bath. The diazonium salt solution was added all at once to the m-toluidine hydrochloride suspension. The mixture was stirred occasionally over 2 hours at 0°-5° C. The mixture was basified with saturated potassium carbonate and the resulting solid was washed twice with warm water. Recrystallization of the solid twice from tetrahydrofuran (90 ml) and ethanol (200 ml) gave 4-(4-nitrophenylazo)-3-methylaniline as red needles (8.32 g, 28 %): mp 152° C.

Workup

  1. temperaturecooled in an ice bath
  2. stirringthe mixture was stirred 20 minutes in an ice bath
  3. temperaturecooled in an ice bath
  4. stirringThe mixture was stirred occasionally over 2 hours at 0°-5° C
  5. washthe resulting solid was washed twice with warm water
  6. customRecrystallization of the solid twice from tetrahydrofuran (90 ml) and ethanol (200 ml)

Sources & evidence

ORD record
ord-fcd8ab33693e48548237838a08059ed3
Source dataset
uspto-grants-1993_10
Patent number
US05254655

Reaction notes

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