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

HRID 350617Notes

Reaction equation

HRID 350617 reaction equation
OS(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 NitrateHCID 805742-tert-Butylaniline

Product 1

HCID 8261032-Tert-butyl-5-nitroanilineYield 63%

Procedure

To H2SO4 (50.0 g, 509.79 mmol) was slowly added 2-tert-Butylaniline (5.0 g, 33.50 mmol). The mixture was stirred at room temperature until it became Homogeneous, then was cooled to −10° C. before slow addition of KNO3 in small portions (5.00 g, 49.45 mmol) via a powder addition funnel. After stirring at −10° C. for an hour, the reaction mixture was poured over a small portion of ice in a 250 mL beaker, allowed to stand for 10 min, then filtered and discarded white precipitate. The aqueous solution was neutralized with NH4OH until pH 8–9 (Litmus pH paper) and partitioned between EtOAc/water. The organic phase was washed with water, and saturated NaCl solutions, dried over anhydrous Na2SO4 and evaporated to a dryness (brown oil). The brown residue was recrystallized from methanol/water to give the desired compound (4.1 g, 63%) as dark brown crystals. TLC (20% EtOAc/Hexane) Rf=0.66; 1HNMR (CDCl3) δ 7.55 (dd, J=8.4, 2.4 Hz, 1H), 7.46 (d, J=2.7 Hz, 1H), 7.35–7.33 (d, J=8.7 Hz), 4.16 (br.s, 2H), 1.44 (s, 9H).

Workup

  1. stirringAfter stirring at −10° C. for an hour
  2. additionthe reaction mixture was poured over a small portion of ice in a 250 mL beaker
  3. filtrationfiltered
  4. custompartitioned between EtOAc/water
  5. washThe organic phase was washed with water, and saturated NaCl solutions
  6. dry with materialdried over anhydrous Na2SO4
  7. customevaporated to a dryness (brown oil)
  8. customThe brown residue was recrystallized from methanol/water

Sources & evidence

ORD record
ord-562a32c059e14aacbbc1b9608650b21d
Source dataset
uspto-grants-2007_02
Patent number
US07183260B2

Reaction notes

Loading…