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

HRID 2077729Notes

Reaction equation

HRID 2077729 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-e4dd782e349749ab9e3c088b5f30c980
Source dataset
uspto-grants-2011_04
Patent number
US07928119B2

Reaction notes

Loading…