6,7-Dinitro-2,3-dihydro-1,4-benzodioxine → 7-Nitro-2,3-dihydro-1,4-benzodioxin-6-amine

HRID 1454661Notes

Reaction equation

HRID 1454661 reaction equation
[N+:1]([C:4]1[C:13]([N+:14]([O-])=O)=[CH:12][C:7]2[O:8][CH2:9][CH2:10][O:11][C:6]=2[CH:5]=1)([O-:3])=[O:2]>[Fe].C(O)(=O)C>[N+:1]([C:4]1[C:13]([NH2:14])=[CH:12][C:7]2[O:8][CH2:9][CH2:10][O:11][C:6]=2[CH:5]=1)([O-:3])=[O:2]

Participants

4

Reactant 1

HCID 35898126,7-Dinitro-2,3-dihydro-1,4-benzodioxine

Product 1

HCID 6072087-Nitro-2,3-dihydro-1,4-benzodioxin-6-amineYield 28.4%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

To a mixture of 6,7-dinitro-2,3-dihydrobenzo[1,4]dioxin (Takakis, I. M.; Hadjimihalakis, P. M. J. Heterocyclic. Chem., 1991, 28, 625., 13 g, 57.8 mmol) and acetic acid (150 mL) was added iron powder (9.6 g, 172.5 mmol) at room temperature, then the mixture was refluxed for 30 min. After cooling, the mixture was filtered through a pad of Celite and the filtrate was concentrated. The residue was purified by flash column chromatography on silica gel eluting with hexane/ethyl acetate (gradient elution from 1:1 to 1:2) to afford 3.22 g (28%) of the title compound as orange solid: 1H-NMR (CDCl3) δ 7.67 (1H, s), 6.23 (1H, s), 5,85 (2H, br.s), 4.19-4.33 (4H, m).

Workup

  1. temperaturethe mixture was refluxed for 30 min
  2. temperatureAfter cooling
  3. filtrationthe mixture was filtered through a pad of Celite
  4. concentrationthe filtrate was concentrated
  5. customThe residue was purified by flash column chromatography on silica gel eluting with hexane/ethyl acetate (gradient elution from 1:1 to 1:2)

Sources & evidence

ORD record
ord-9221c8952edc422bb7f18b8008019df9
Source dataset
uspto-grants-2009_01
Patent number
US07479564B2

Reaction notes

Loading…