3,5-Dimethylaniline → 4-[4'-(4"-Nitrophenylazo)phenylazo]-3,5-dimethylaniline

HRID 1858874

Reaction equation

HRID 1858874 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]=[N:9][C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.[N:19]([O-])=O.[Na+].[CH3:23][C:24]1[CH:25]=[C:26]([CH:28]=[C:29]([CH3:31])[CH:30]=1)[NH2:27].C([O-])(=O)C.[Na+].[OH-].[Na+]>O.C(O)(=O)C>[N+:16]([C:13]1[CH:14]=[CH:15][C:10]([N:9]=[N:8][C:5]2[CH:6]=[CH:7][C:2]([N:1]=[N:19][C:30]3[C:29]([CH3:31])=[CH:28][C:26]([NH2:27])=[CH:25][C:24]=3[CH3:23])=[CH:3][CH:4]=2)=[CH:11][CH:12]=1)([O-:18])=[O:17]

Participants

8

Reactant 5

HCID 79493,5-DimethylanilineHCID 12896Disperse orange 3HCID 14798Sodium HydroxideHCID 517045Sodium AcetateHCID 23668193Sodium Nitrite

Product 1

HCID 543938214-[4'-(4"-Nitrophenylazo)phenylazo]-3,5-dimethylanilineYield 61%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

A 4 g (16.53 mmol) amount of 4-amino-4'-nitroazobenzene (Disperse Orange 3) was dissolved in ice-cooled acetic acid (100 mL) containing 8 mL of 98% sulfuriic acid. Sodium nitrite (1.48 g, 21.40 mmol) dissolved in a small amount of water (less than 2 mL) was added dropwise to the stirred solution. The reaction temperature was maintained at 5° C. After 6 h of stirring, 3,5-dimethylaniline (5.0 g, 41.30 mmol) in 10 mL of acetic acid was added followed by slow addition of sodium acetate (4.10 g, 50.0 mmol). The resulting red solution was stirred at 5° C. for an additional 16 h. A 10% sodium hydroxide solution was slowly added to neutralize the reaction mixture. The precipitates formed were collected by filtration, washed with water several times, dissolved in THF, and dried over magnesium sulfate. Solvent was evaporated, and a dark red powder was obtained by precipitation in n-hexane. The solid was further purified by column chromatography (silica gel; THF: n-hexane=4 6), affording 3.51 g (61%) of 4-[4'-(4"-nitrophenylazo)phenylazo]-3,5-dimethylaniline as a dark red solid product.

Workup

  1. additionwas added dropwise to the stirred solution
  2. stirringThe resulting red solution was stirred at 5° C. for an additional 16 h
  3. customThe precipitates formed
  4. filtrationwere collected by filtration
  5. washwashed with water several times
  6. dissolutiondissolved in THF
  7. dry with materialdried over magnesium sulfate
  8. customSolvent was evaporated
  9. customa dark red powder was obtained by precipitation in n-hexane
  10. customThe solid was further purified by column chromatography (silica gel; THF: n-hexane=4 6)

Sources & evidence

ORD record
ord-f4627ddeb8094052b45573f08384758d
Source dataset
uspto-grants-2000_11
Patent number
US06153272

Linked notes

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