Sulfuric Acid → 4-((2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)aniline

HRID 1748929

Reaction equation

HRID 1748929 reaction equation
[N+:1]([C:4]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].[N:14](OS(=O)(=O)O)=O.S(=O)(=O)(O)O.[CH2:26]([CH:28]([CH2:47][CH2:48][CH2:49][CH3:50])[CH2:29][O:30][C:31]1[CH:37]=[CH:36][C:35]([O:38][CH2:39][CH:40]([CH2:45][CH3:46])[CH2:41][CH2:42][CH2:43][CH3:44])=[CH:34][C:32]=1[NH2:33])[CH3:27]>C(O)(=O)C.C(O)(=O)CC.S(=O)(=O)(O)N>[N+:1]([C:4]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:5]=1[N:6]=[N:14][C:36]1[C:35]([O:38][CH2:39][CH:40]([CH2:45][CH3:46])[CH2:41][CH2:42][CH2:43][CH3:44])=[CH:34][C:32]([NH2:33])=[C:31]([O:30][CH2:29][CH:28]([CH2:26][CH3:27])[CH2:47][CH2:48][CH2:49][CH3:50])[CH:37]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 73212,4-DinitroanilineHCID 82157Nitrosylsulfuric acidHCID 896017572,5-Bis(2-ethylhexyloxy)aniline

Product 1

HCID 896020744-((2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)anilineYield 39%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 1032Propionic AcidSolventHCID 5987Sulfamic AcidSolvent

Conditions

Temperature
3 °C

Procedure

2,4-Dinitroaniline (3.7 g, 0.02 mol) is suspended in a mixture of acetic acid (20 ml) and propionic acid (10 ml) and cooled to 3° C. 40% (w/w) nitrosyl sulfuric acid in sulfuric acid (6.4 g, 0.02 mol) is added dropwise and stirring continued for 30 minutes to give a pale yellow solution. Crude 2,5-bis(2-ethylhexyloxy)aniline (0.02 mol) solution is diluted with IMS (200 ml) and 10% sulfamic acid solution (20 ml) added, followed by ice (200 g). The above pale yellow diazonium salt solution is slowly added with stirring and a dark oil rapidly separated. The mixture is stirred overnight and the water is decanted off. The crude product (8.3 g) is dissolved in 25/75 dichloromethane/hexane and purified over silica gel, the required product eluting with 50/50 hexane/dichloromethane. Evaporation and trituration with methanol gave 4-((2,4-dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)-aniline as a violet-blue crystalline solid (4.2 g, 39%).

Workup

  1. customto give a pale yellow solution
  2. additionadded
  3. stirringwith stirring
  4. customa dark oil rapidly separated
  5. stirringThe mixture is stirred overnight
  6. customthe water is decanted off
  7. dissolutionThe crude product (8.3 g) is dissolved in 25/75 dichloromethane/hexane
  8. custompurified over silica gel
  9. washthe required product eluting with 50/50 hexane/dichloromethane
  10. customEvaporation and trituration with methanol

Sources & evidence

ORD record
ord-9ea3fab324ba47348ba0abb0452255c9
Source dataset
uspto-grants-2015_10
Patent number
US09152006B2

Linked notes

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