Carbon Dioxide → 2-Tert-butyl-5-nitroaniline

HRID 2247220Notes

Reaction equation

HRID 2247220 reaction equation
OS(O)(=O)=O.C(=O)=O.[C:9]([C:13]1[CH:19]=[CH:18][CH:17]=[CH:16][C:14]=1[NH2:15])([CH3:12])([CH3:11])[CH3:10].[N+:20]([O-])([O-:22])=[O:21].[K+]>>[C:9]([C:13]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][C:14]=1[NH2:15])([CH3:12])([CH3:10])[CH3:11]

Participants

5

Reactant 4

HCID 280Carbon DioxideHCID 1118Sulfuric AcidHCID 24434Potassium Nitrate2×HCID 805742-tert-Butylaniline

Product 1

HCID 8261032-Tert-butyl-5-nitroaniline

Procedure

Concentrated H2SO4 (1 L) was cooled to −10° C. with a dry ice IpOH bath in a 2 L 3-neck round bottom flask fitted with a mechanical stirrer and temperature probe. 2-t-Butylaniline (109 g, 730 mmol) was added, giving a clumpy solid. Once the temperature of the mixture was stabilized at −10° C., KNO3 (101 g, 1001 mmol) was added portion-wise, as the solid, over 4 h, maintaining the temperature between −20 and −5° C. Once all of the KNO3 was added, the reaction was stirred overnight with gradual warming to RT. The reaction was quenched by diluting with H2O and extracting 3× with EtOAc. The EtOAc extracts were washed multiple times with saturated NaHCO3(aq), until gas evolution ceased, then with brine. The EtOAc extracts were combined, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure giving a black oil. The oil was eluted through a 36×7 cm column of silica gel with a 5%; 10%; 15%; 25%; and 50% EtOAc:Hexanes step gradient (2 L each step) giving 2-tert-butyl-5-nitro-phenylamine as a red solid.

Workup

  1. customfitted with a mechanical stirrer
  2. customgiving a clumpy solid
  3. customwas stabilized at −10° C.
  4. temperaturemaintaining the temperature between −20 and −5° C
  5. customThe reaction was quenched
  6. additionby diluting with H2O
  7. extractionextracting 3× with EtOAc
  8. washThe EtOAc extracts were washed multiple times with saturated NaHCO3(aq)
  9. dry with materialdried over anhydrous Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customgiving a black oil
  13. washThe oil was eluted through a 36×7 cm column of silica gel with a 5%

Sources & evidence

ORD record
ord-f36f81e740a745b5978fdaa5712b3c74
Source dataset
uspto-grants-2010_03
Patent number
US07687643B2

Reaction notes

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