2-Nitro-5-aminophenol → N-methyl-N-allyl-4-(4'-nitro-3'-hydroxyphenylazo)aniline

HRID 488054Notes

Reaction equation

HRID 488054 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([OH:8])[CH:7]=1.C([O-])(=O)C.[Na+].[CH3:17][N:18]([CH2:25][CH:26]=[CH2:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[N:28]([O-])=O.[Na+].C(=O)(O)[O-].[Na+]>Cl.C1COCC1.O.C(O)(=O)C>[CH3:17][N:18]([CH2:25][CH:26]=[CH2:27])[C:19]1[CH:20]=[CH:21][C:22]([N:28]=[N:1][C:2]2[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([OH:8])[CH:7]=2)=[CH:23][CH:24]=1

Participants

10

Reactant 5

HCID 1554322-Nitro-5-aminophenolHCID 246778N-Allyl-N-methylanilineHCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 23668193Sodium Nitrite2×

Product 1

HCID 19702670N-methyl-N-allyl-4-(4'-nitro-3'-hydroxyphenylazo)anilineYield 98.5%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In a beaker is dissolved 300 mg (1.95 mmol) of recrystallized 5-amino-2-nitrophenol in 2 ml 5N HCl and 1 ml of THF, and the solution is cooled to 0° C. In a separate beaker are combined 2 g sodium acetate, 4 ml of acetic acid and 287 mg (1.95 mmol) of N-methyl-N-allylaniline and the resulting suspension is cooled to as near 0° C. as possible. NaNO2 (140 mg) dissolved in 1 ml of water is added to the first beaker dropwise over 15 minutes while keeping the temperature of the solution below 0° C. When all the sodium nitrite has been added, the solution is stirred for 10 minutes and the contents of the first beaker are added to the second beaker slowly with stirring. After 30 minutes, the contents of the flask are poured into 30 ml of ice water and saturated aqueous sodium bicarbonate solution is added until the foaming stops. The organics are extracted with ethyl acetate, washed with sodium bicarbonate solution, dried over magnesium sulfate, filtered and concentrated to yield 600 mg of N-methyl-N-allyl-4-(4'-nitro-3'-hydroxyphenylazo)aniline, as a dark red viscous oil.

Workup

  1. temperaturethe resulting suspension is cooled to as near 0° C. as possible
  2. additionis added to the first beaker dropwise over 15 minutes
  3. customthe temperature of the solution below 0° C
  4. additionthe contents of the first beaker are added to the second beaker slowly
  5. stirringwith stirring
  6. waitAfter 30 minutes
  7. additionis added until the foaming
  8. extractionThe organics are extracted with ethyl acetate
  9. washwashed with sodium bicarbonate solution
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-c598bbde085f4a29b593b317b40676c3
Source dataset
uspto-grants-1994_03
Patent number
US05298588

Reaction notes

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