Trifluoroacetic anhydride → HCID 86727384, compound

HRID 519024Notes

Reaction equation

HRID 519024 reaction equation
C([O-])(O)=O.[Na+].OO.NC(N)=O.C([C:15]1[C:32]([F:33])=[CH:31][C:18]2[O:19][CH2:20][C:21](=[O:30])[N:22]([CH:23]([CH3:29])[C:24]([O:26][CH2:27][CH3:28])=[O:25])[C:17]=2[CH:16]=1)(=O)C.[C:34]([O:40]C(C(F)(F)F)=O)([C:36](F)(F)F)=[O:35]>C(Cl)Cl>[C:34]([O:40][C:15]1[C:32]([F:33])=[CH:31][C:18]2[O:19][CH2:20][C:21](=[O:30])[N:22]([CH:23]([CH3:29])[C:24]([O:26][CH2:27][CH3:28])=[O:25])[C:17]=2[CH:16]=1)(=[O:35])[CH3:36]

Participants

6

Reactant 4

HCID 9845Trifluoroacetic anhydrideHCID 31294Carbamide PeroxideHCID 516892Sodium BicarbonateHCID 86727382HCID 86727382, compound

Product 1

HCID 86727384HCID 86727384, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of NaHCO3 (5.38 g, 64.0 mmol) and urea hydrogen peroxide (6.02 g, 64.0 mmol) in DCM (60 mL) at 0° C. was added ethyl 2-(6-acetyl-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl)propanoate (6.6 g, 21.34 mmol). The reaction mixture was stirred for 10 min then TFAA (5.94 mL, 42.7 mmol) was added dropwise. The reaction mixture was stirred at 0° C. for 1 h and then allowed to warm to ambient temperature and stirred for 3 days. The reaction mixture was diluted with DCM (30 mL) and washed with water (30 mL). The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 15% EtOAc in petroleum ether) to give ethyl 2-(6-acetoxy-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl)propanoate and starting material as a white solid (5.9 g, 85%). 1H NMR (CDCl3, 400 MHz): δ 6.85 (d, J=10 Hz, 1H), 6.59 (d, J=6.8 Hz, 1H), 5.23 (m, 1H), 4.57 (q, J1=15.2 Hz, J2=14.8 Hz, 2H), 4.17 (m, 2H), 2.29 (s, 3H), 1.58 (d, J=7.2 Hz, 3H), 1.17 (t, 3H).

Workup

  1. stirringThe reaction mixture was stirred at 0° C. for 1 h
  2. stirringstirred for 3 days
  3. washwashed with water (30 mL)
  4. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography on silica gel (eluting with 15% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-7cc2c2b391584ffaab1ccbf771ebdb9b
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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