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

HRID 1786333Notes

Reaction equation

HRID 1786333 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 AcidHCID 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 1:2H2SO4:H2O solution, and heated at reflux. Two additional 5 mL aliquots of 1:2H2SO4:H2O solution, a 7 mL aliquot of 1:2H2SO4:H2O solution and another 10 mL of 1:2H2SO4: 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. additionthen added 17 mL of 1:2H2SO4
  7. temperatureat reflux
  8. temperaturewhile heating
  9. temperatureat reflux
  10. temperatureThe mixture was cooled to RT
  11. customforming a black layer
  12. customseparated
  13. washThe organic layer was washed with H2O
  14. dry with materialbrine, dried over Na2SO4
  15. concentrationconcentrated in vacuo
  16. customCrude oil was purified on silica gel column with 8% EtOAc/Hexanes
  17. customUpon drying under vacuum

Sources & evidence

ORD record
ord-87e7bf417e8b4a33a1f5548ab4869f94
Source dataset
uspto-grants-2009_03
Patent number
US07507748B2

Reaction notes

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