Acetic Acid → 6-Nitro-1,3-benzodioxol-5-amine

HRID 1669163Notes

Reaction equation

HRID 1669163 reaction equation
C[O-].[Na+].[N+:4]([C:7]1[C:8]([NH:16]C(=O)C)=[CH:9][C:10]2[O:14][CH2:13][O:12][C:11]=2[CH:15]=1)([O-:6])=[O:5].CC(O)=O>CO>[N+:4]([C:7]1[C:8]([NH2:16])=[CH:9][C:10]2[O:14][CH2:13][O:12][C:11]=2[CH:15]=1)([O-:6])=[O:5]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 540215N-(6-Nitro-1,3-benzodioxol-5-yl)acetamideHCID 10942334Sodium Methoxide

Product 1

HCID 6026656-Nitro-1,3-benzodioxol-5-amineYield 80%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

NaOMe (4.82 g, 89.2 mmol) was added to a stirred solution of nitroacetamide 219 (5.0 g, 22.3 mmol) in MeOH (100 mL) at reflux temperature and the mixture stirred at reflux temperature for 15 min. HOAc (25 mL, 446 mmol) was added to quench the reaction and the solvent evaporated. Toluene (2×50 mL) was added and the azeotrope evaporated. The residue was dissolved in DCM (100 mL) and filtered through a short column of silica to give nitroaniline 220 (3.25 g, 80%) as an orange solid: mp 199-201° C. [lit (Krasso, A. & Ramuz, H., U.S. Pat. No. 4,599,347, 1986) mp (iPrOH) 203-204° C.]; 1H NMR δ 7.53 (s, 1H, H-7), 6.30 (br s, 2H, NH2), 6.22 (s, 1H, H-4), 5.98 (s, 2H, H-2).

Workup

  1. temperatureat reflux temperature
  2. temperatureat reflux temperature for 15 min
  3. customto quench
  4. customthe reaction
  5. customthe solvent evaporated
  6. additionToluene (2×50 mL) was added
  7. customthe azeotrope evaporated
  8. dissolutionThe residue was dissolved in DCM (100 mL)
  9. filtrationfiltered through a short column of silica

Sources & evidence

ORD record
ord-a041fbd99dab4403b2389fc175da0443
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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