tert-Butanol → N-t-butyloxycarbonyl-3,5-dinitro-4-methylaniline

HRID 1106762Notes

Reaction equation

HRID 1106762 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6](C)[CH:7]=[C:8]([N+:13]([O-:15])=[O:14])[C:9]=1[C:10](O)=O)([O-:3])=[O:2].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:24])C=CC=CC=1.C([N:36]([CH2:39]C)CC)C.[C:41]([OH:45])([CH3:44])([CH3:43])[CH3:42]>>[C:41]([O:45][C:39]([NH:36][C:6]1[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[C:9]([CH3:10])=[C:8]([N+:13]([O-:15])=[O:14])[CH:7]=1)=[O:24])([CH3:44])([CH3:43])[CH3:42]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 120522384-Methyl-2,6-dinitrobenzoic acid

Product 1

HCID 18789671N-t-butyloxycarbonyl-3,5-dinitro-4-methylaniline

Procedure

A mixture of 3,5-dinitro-p-toluic acid (20 g), diphenylphosphoryl azide (29.2 g) and triethyl amine (10.7 g, from Mallinckrodt) in tert-butyl alcohol (200 mL) under nitrogen was heated at reflux for 1 hr. The solvent was evaporated under reduced pressure. The residue was partitioned between ethyl acetate (300 mL) and 1N HCl (300 mL). The ethyl acetate solution was washed with half-saturated sodium chloride solution, 1N sodium hydroxide solution (300 mL), and dried over magnesium sulfate. The solvent was evaporated and the residue was chromatographed on silica gel eluting with ethyl acetate:hexane (1:9) to afford N-t-butyloxycarbonyl-3,5-dinitro-4-methylaniline (7.8 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 hr
  3. customThe solvent was evaporated under reduced pressure
  4. customThe residue was partitioned between ethyl acetate (300 mL) and 1N HCl (300 mL)
  5. washThe ethyl acetate solution was washed with half-saturated sodium chloride solution, 1N sodium hydroxide solution (300 mL)
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent was evaporated
  8. customthe residue was chromatographed on silica gel eluting with ethyl acetate:hexane (1:9)

Sources & evidence

ORD record
ord-4246d1ee73454be9b811c0fb5905fab9
Source dataset
uspto-grants-2000_05
Patent number
US06057349

Reaction notes

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