Methyl 2,4-dinitro-5-fluorophenoxyacetate → 7-Fluoro-6-amino-2H-1,4-benzoxazin-3(4H)-one

HRID 2255179Notes

Reaction equation

HRID 2255179 reaction equation
[N+:1]([C:4]1[CH:15]=[C:14]([N+:16]([O-])=O)[C:13]([F:19])=[CH:12][C:5]=1[O:6][CH2:7][C:8](OC)=[O:9])([O-])=O>C(O)(=O)C.CCOC(C)=O.[Fe]>[NH2:16][C:14]1[C:13]([F:19])=[CH:12][C:5]2[O:6][CH2:7][C:8](=[O:9])[NH:1][C:4]=2[CH:15]=1

Participants

5

Reactant 1

HCID 14423669Methyl 2,4-dinitro-5-fluorophenoxyacetate

Product 1

HCID 103133897-Fluoro-6-amino-2H-1,4-benzoxazin-3(4H)-oneYield 60%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 12.2 g (0.22 mol) of iron powder in 100 ml of 5% aqueous acetic acid was added dropwise a solution of 10.0 g (36.5 mmol) of methyl 2,4-dinitro-5-fluorophenoxyacetate in 100 ml of EtOAc and 100 ml of glacial acetic acid. The reaction mixture was stirred at room temperature for 18 hours. The iron was removed by suction filtration through a small pad of Celite® and the filter pad was rinsed with 50 ml of EtOAc. The filtrate was transferred to a separatory funnel and the phases were separated. The aqueous layer was extracted with EtOAc (3×50 ml) and the combined organic phases were washed with sodium bicarbonate (2×50 ml), dried over Na2SO4 and filtered. The solvent was removed from the filtrate in vacuo to yield 3.9 g (60% yield) of 6-amino-7-fluoro-2H-1,4-benzoxazin-3(4H)-one as a brown solid.

Workup

  1. customThe iron was removed by suction filtration through a small pad of Celite®
  2. washthe filter pad was rinsed with 50 ml of EtOAc
  3. customThe filtrate was transferred to a separatory funnel
  4. customthe phases were separated
  5. extractionThe aqueous layer was extracted with EtOAc (3×50 ml)
  6. washthe combined organic phases were washed with sodium bicarbonate (2×50 ml)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customThe solvent was removed from the filtrate in vacuo

Sources & evidence

ORD record
ord-581ebe0867804e2d9a5610259bf7c871
Source dataset
uspto-grants-1993_08
Patent number
US05238908

Reaction notes

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