4-Nitroaniline → Ethyl (4-aminophenyl)carbamate

HRID 2221107Notes

Reaction equation

HRID 2221107 reaction equation
[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)([O-])=O.C(N(C(C)C)CC)(C)C.[C:20]([O:23][CH2:24][CH3:25])(=[O:22])C>>[CH2:24]([O:23][C:20](=[O:22])[NH:1][C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)[CH3:25]

Participants

4

Reactant 3

HCID 74754-NitroanilineHCID 8857Ethyl Acetate2×HCID 81531Diisopropylethylamine

Product 1

HCID 12731941Ethyl (4-aminophenyl)carbamateYield 90%

Procedure

4-Nitro-aniline (100 g, 0.72 mol) is dissolved in ethyl acetate (800 mL) and diisopropylethylamine (89.6 mL, 0.936 mol) is added. Ethyl chloroformiate (252 mL, 1.45 mol) dissolved in ethyl acetate (200 mL) is added and the solution is stirred for 18 h at ambient temperature. The mixture is washed with 2M HCl (300 mL) and brine (300 mL), dried (MgSO4) and concentrated in vacuo to half of the original volume. To the resulting solution is added palladium on activated carbon (10 g, 5% Pd, 50% H2O) and the mixture is hydrogenated on a Parr apparatus (pH2=3 bar) at ambient temperature for 12 hours. The mixture is filtered through Celite and the solvent evaporated in vacuo to give 118 g (90%) of the title compound as crystalline product.

Workup

  1. additionis added
  2. washThe mixture is washed with 2M HCl (300 mL) and brine (300 mL)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo to half of the original volume
  5. additionTo the resulting solution is added palladium on activated carbon (10 g, 5% Pd, 50% H2O)
  6. waitthe mixture is hydrogenated on a Parr apparatus (pH2=3 bar) at ambient temperature for 12 hours
  7. filtrationThe mixture is filtered through Celite
  8. customthe solvent evaporated in vacuo

Sources & evidence

ORD record
ord-1ab3c4c683044bf58c47ef602758b688
Source dataset
uspto-grants-2008_05
Patent number
US07368472B2

Reaction notes

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