Trifluoroacetic anhydride → HCID 118598753, compound

HRID 1050338Notes

Reaction equation

HRID 1050338 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([Cl:14])[C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[N+:6]([O-])[CH:7]=1.FC(F)(F)C(OC(=O)C(F)(F)F)=[O:18]>CN(C)C=O>[Br:1][C:2]1[C:7](=[O:18])[NH:6][C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([Cl:14])[CH:3]=1

Participants

4

Reactant 2

HCID 9845Trifluoroacetic anhydrideHCID 118598619HCID 118598619, compound

Product 1

HCID 118598753HCID 118598753, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

To a stirred solution of ethyl 5-bromo-3-chloro-1-oxido-pyridin-1-ium-2-carboxylate (3, 150 g, 534.8 mmol) in dimethylformamide (900 mL) at 0° C. was added trifluoroacetic anhydride (224.63 g, 1.07 mmol). The temperature of the reaction mixture was raised to 50° C. and stirring was continued for 1 h. After the oxidation was complete, the reaction mass was quenched with a saturated aqueous sodium bicarbonate solution and product was extracted with dichloromethane (2×100 mL). The organic layers were separated, combined, dried with magnesium sulfate and concentrated to dryness under vacuum to afford ethyl 5-bromo-3-chloro-6-oxo-1H-pyridine-2-carboxylate (4) as a yellow solid. Yield: 75 g, 50%; MS (ESI) m/z 281.8 [M+1]+; 1H NMR (400 MHz, DMSO-d6) δ 10.44-10.02 (m, 1H), 7.86 (s, 1H), 4.47 (q, J=7.2 Hz, 2H), 1.43 (t, J=5.6 Hz, 3H).

Workup

  1. customthe reaction mass was quenched with a saturated aqueous sodium bicarbonate solution and product
  2. extractionwas extracted with dichloromethane (2×100 mL)
  3. customThe organic layers were separated
  4. dry with materialdried with magnesium sulfate
  5. concentrationconcentrated to dryness under vacuum

Sources & evidence

ORD record
ord-5c090583eab2497e9a16df25cfbc4467
Source dataset
uspto-grants-2016_07
Patent number
US09382248B2

Reaction notes

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