Sulfuric Acid → 2-Tert-butyl-5-nitroaniline

HRID 502722Notes

Reaction equation

HRID 502722 reaction equation
S(=O)(=O)(O)O.[C:6]([C:10]1[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=1[NH2:12])([CH3:9])([CH3:8])[CH3:7].[N+:17]([O-])([O-:19])=[O:18].[K+]>>[C:6]([C:10]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:11]=1[NH2:12])([CH3:9])([CH3:7])[CH3:8]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 24434Potassium Nitrate2×HCID 805742-tert-Butylaniline

Product 1

HCID 8261032-Tert-butyl-5-nitroaniline

Procedure

Concentrated sulfuric acid (1 L) was cooled to −10° C. with a dry ice-isopropanol bath in a 2 L 3-necked round bottom flask fitted with a mechanical stirrer and temperature probe. The 2-t-butylaniline (109 g, 730 mmol) was added, giving a clumpy solid. Once the temperature of the mixture was stabilized at −10° C., the potassium nitrate (101 g, 1001 mmol) was added portion wise, as a solid, over a 4-hour period, maintaining the temperature between −20 and −5° C. Once all of the potassium nitrate was added, the reaction was left to stir overnight with gradual warming to room temperature. The reaction was quenched by diluting with water and then extracting three times with EtOAc. The EtOAc extracts were washed multiple times with saturated NaHCO3, until gas evolution ceased, then with brine. The ethyl acetate extracts were then combined, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure giving a black oil. The oil was eluted through a column of silica gel with EtOAc: hexanes gradient 5-50%. Solvent evaporation afforded 2-tert-butyl-5-nitrobenzenamine as a red solid.

Workup

  1. customfitted with a mechanical stirrer
  2. customgiving a clumpy solid
  3. customwas stabilized at −10° C.
  4. waitas a solid, over a 4-hour period
  5. temperaturemaintaining the temperature between −20 and −5° C
  6. waitthe reaction was left
  7. customThe reaction was quenched
  8. additionby diluting with water
  9. extractionextracting three times with EtOAc
  10. washThe EtOAc extracts were washed multiple times with saturated NaHCO3
  11. dry with materialdried over anhydrous Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure
  14. customgiving a black oil
  15. washThe oil was eluted through a column of silica gel with EtOAc
  16. customSolvent evaporation

Sources & evidence

ORD record
ord-2bdb0893f7eb456da6ee04100e0446f4
Source dataset
uspto-grants-2010_08
Patent number
US07776869B2

Reaction notes

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