Ethyl Acetate → Ethyl 1-bromo-4-oxo-4H-quinolizine-3-carboxylate

HRID 48907Notes

Reaction equation

HRID 48907 reaction equation
[O:1]=[C:2]1[N:11]2[C:6]([CH:7]=[CH:8][CH:9]=[CH:10]2)=[CH:5][CH:4]=[C:3]1[C:12]([O:14][CH2:15][CH3:16])=[O:13].[Br:17]Br.C(OCC)(=O)C>C(O)(=O)C>[Br:17][C:5]1[CH:4]=[C:3]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:2](=[O:1])[N:11]2[C:6]=1[CH:7]=[CH:8][CH:9]=[CH:10]2

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 24408BromineHCID 4615166Ethyl 4-oxo-4H-quinolizine-3-carboxylate

Product 1

HCID 20634149Ethyl 1-bromo-4-oxo-4H-quinolizine-3-carboxylateYield 71%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

To a solution of ethyl 4-oxo-4H-quinolizine-3-carboxylate (1) (2.33 g, 10.7 mmol) in 20 ml acetic acid was rapidly added a solution of bromine (1.9 g, 12 mmol) in 10 ml acetic acid. The reaction was complete after 5 min, as indicated by thin layer chromatography (ethyl acetate). The solvent was evaporated in vacuo and the remaining yellow solid was dissolved in 20 ml dichloromethane. To this solution, silica gel (3 g) was added and the solvent was evaporated in vacuo. The silica gel was poured on a prepacked column and eluted with ethyl acetate to give ethyl 1-bromo-4-oxo-4H-quinolizine-3-carboxylate (9) as a bright yellow solid (2.1 g, 71%). M.p. 156-158° C. 1H NMR (δ, CDCl3): 1.43 (t, J=7 Hz, 3H), 4.43 (q, J=7 Hz, 2H), 7.03 (dd, J=7 Hz, J=7 Hz, 1H), 7.30 (dd, J=7 Hz, 2H), 7.80 (dd, J=7 Hz, J=7 Hz, 1H), 8.63 (s, 1H), 9.49 (d, J=7 Hz). MS: m/z 294.9839; required for C12H10BrNO3: 294.9843.

Workup

  1. customThe solvent was evaporated in vacuo
  2. dissolutionthe remaining yellow solid was dissolved in 20 ml dichloromethane
  3. additionTo this solution, silica gel (3 g) was added
  4. customthe solvent was evaporated in vacuo
  5. additionThe silica gel was poured on a prepacked column
  6. washeluted with ethyl acetate

Sources & evidence

ORD record
ord-d3178d8e91d04267aa1ceb80d6bc1c57
Source dataset
uspto-grants-2004_03
Patent number
US06706528B2

Reaction notes

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