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

HRID 238437

Reaction equation

HRID 238437 reaction equation
OS(O)(=O)=O.[C:6]([C:10]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:11]=1N)([CH3:9])([CH3:8])[CH3:7].NC1C=CC=CC=1.N([O-])=[O:28].[Na+].NC(N)=O>O.CCOC(C)=O>[C:6]([C:10]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:11]=1[OH:28])([CH3:9])([CH3:8])[CH3:7]

Participants

8

Reactant 5

HCID 1118Sulfuric Acid5×HCID 1176UreaHCID 6115AnilineHCID 8261032-Tert-butyl-5-nitroanilineHCID 23668193Sodium Nitrite2×

Product 1

HCID 219596172-Tert-butyl-5-nitrophenol

Reagents, catalysts & solvents 2

HCID 962WaterSolvent6×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

In a 250 ml round bottom flask, 20 mL concentrated H2SO4 was added to 2-tert-butyl-5-nitro-aniline (7.15 g) by adding 5 mL aliquots of acid and sonicating with occasional heating until all of the starting aniline went into solution. H2O (84 ml) was added with stirring, then the reaction was cooled to 0° C. forming a yellow-orange suspension. A solution of NaNO2 (2.792 g) in H2O (11.2 mL) was added dropwise to the suspension and stirred for 5 min. Excess NaNO2 was neutralized with urea, then the cloudy solution was transferred to 500 ml 3-necked round bottom flask then added 17 mL of 1:2 H2SO4:H2O solution, and heated at reflux. Two additional 5 mL aliquots of 1:2 H2SO4:H2O solution, a 7 mL aliquot of 1:2 H2SO4:H2O solution and another 10 mL of 1:2 H2SO4:H2O were added while heating at reflux. The mixture was cooled to RT forming a black layer floating on top of the aqueous layer. The black layer was diluted with EtOAc (300 mL) and separated. The organic layer was washed with H2O then brine, dried over Na2SO4 and concentrated in vacuo. Crude oil was purified on silica gel column with 8% EtOAc/Hexanes. Upon drying under vacuum, the 2-tert-butyl-5-nitrophenol was isolated as a brown solid.

Workup

  1. additionby adding 5 mL aliquots of acid
  2. customsonicating
  3. customforming a yellow-orange suspension
  4. stirringstirred for 5 min
  5. customthe cloudy solution was transferred to 500 ml 3-necked round bottom flask
  6. temperatureat reflux
  7. temperaturewhile heating
  8. temperatureat reflux
  9. temperatureThe mixture was cooled to RT
  10. customforming a black layer
  11. customseparated
  12. washThe organic layer was washed with H2O
  13. dry with materialbrine, dried over Na2SO4
  14. concentrationconcentrated in vacuo
  15. customCrude oil was purified on silica gel column with 8% EtOAc/Hexanes
  16. customUpon drying under vacuum

Sources & evidence

ORD record
ord-289140cd4f354c46a3b83e706e0f9f9a
Source dataset
uspto-grants-2014_02
Patent number
US08642624B2

Linked notes

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