(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)acetic acid, ethyl ester → 6-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-2H-1,4-benzoxazin-3(4H)-one

HRID 2395655Notes

Reaction equation

HRID 2395655 reaction equation
[Cl:1][C:2]1[C:3]([C:12]2[C:24]([F:25])=[CH:23][C:15]([O:16][CH2:17][C:18](OCC)=[O:19])=[C:14]([N+:26]([O-])=O)[CH:13]=2)=[N:4][N:5]([CH3:11])[C:6]=1[C:7]([F:10])([F:9])[F:8]>C(O)(=O)C.[Fe]>[Cl:1][C:2]1[C:3]([C:12]2[C:24]([F:25])=[CH:23][C:15]3[O:16][CH2:17][C:18](=[O:19])[NH:26][C:14]=3[CH:13]=2)=[N:4][N:5]([CH3:11])[C:6]=1[C:7]([F:10])([F:9])[F:8]

Participants

4

Reactant 1

HCID 86747521(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)acetic acid, ethyl ester

Product 1

HCID 194367686-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-2H-1,4-benzoxazin-3(4H)-oneYield 80%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 4.5 g (0.0106 mole) (4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)-acetic acid, ethyl ester in 75 mL acetic acid was heated to 80° C. under a nitrogen atmosphere. The heat and nitrogen were removed and 1.8 g (0.033 mole) iron powder was added in 3 portions over 5 min. The solution was stirred at 80° C. for an additional 3 hours. The solution was cooled and filtered through Celite®. The filtrate was diluted with 100 mL water and extracted three times with ethyl acetate. The ethyl acetate extracts were washed with a saturated NaHCO3 solution, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was recrystallized from methylcyclohexane/ethyl acetate to give 2.95 g (80%) of 6-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-2H-1,4-benzoxazin-3(4H)-one as a white solid, mp 207° C.

Workup

  1. temperatureThe heat
  2. customnitrogen were removed
  3. temperatureThe solution was cooled
  4. filtrationfiltered through Celite®
  5. additionThe filtrate was diluted with 100 mL water
  6. extractionextracted three times with ethyl acetate
  7. washThe ethyl acetate extracts were washed with a saturated NaHCO3 solution
  8. dry with materialdried over anhydrous MgSO4
  9. concentrationconcentrated in vacuo
  10. customThe residue was recrystallized from methylcyclohexane/ethyl acetate

Sources & evidence

ORD record
ord-ce32d43beaec4c74b27f60ad35859049
Source dataset
uspto-grants-1996_02
Patent number
US05489571

Reaction notes

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