Bromine → ethyl 3-(benzyloxy)-9-bromo-4-oxo-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate

HRID 346487Notes

Reaction equation

HRID 346487 reaction equation
[CH2:1]([O:8][C:9]1[C:14](=[O:15])[N:13]2[CH2:16][CH2:17][CH2:18][CH2:19][C:12]2=[N:11][C:10]=1[C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])(=O)C.[Na+].[Br:30]Br>C(O)(=O)C>[CH2:1]([O:8][C:9]1[C:14](=[O:15])[N:13]2[CH2:16][CH2:17][CH:18]=[C:19]([Br:30])[C:12]2=[N:11][C:10]=1[C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 21080169Ethyl 3-benzyloxy-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate

Product 1

HCID 21080172ethyl 3-(benzyloxy)-9-bromo-4-oxo-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylateYield 43%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

A mixture intermediate 14, ethyl 3-benzyloxy-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate, (1.00 g, 3.05 mmol) and sodium acetate (1.50 g) in acetic acid (20 ml) was heated at 120° C. and then treated with a solution of bromine (1.5 g, 9.2 mmol) in acetic acid (5 ml). After 1 h at 120° C., the reaction mixture was cooled and concentrated in vacuo. The residue was diluted with ethyl acetate, washed with water and brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent and chromatography of the residue on silica gel (elution gradient of ethyl acetate in hexane) gave 0.531 g (43% yield) of the title material as a white solid. 1HNMR 400 MHz (CDCl3) δ (ppm): 1.34 (3H, t, J=7.1 Hz, CH3), 2.60 (2H, m, CH2), 4.28 (2H, t, J=7.3 Hz, CH2), 4.38 (2H, q, J=7.1 Hz, OCH2), 5.34 (2H, s, OCH2), 7.05 (1H, t, J=4.8 Hz, CH), 7.3–7.52 (5H, m, aromatics).

Workup

  1. temperaturethe reaction mixture was cooled
  2. concentrationconcentrated in vacuo
  3. additionThe residue was diluted with ethyl acetate
  4. washwashed with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customEvaporation of the solvent and chromatography of the residue on silica gel (elution gradient of ethyl acetate in hexane)

Sources & evidence

ORD record
ord-f1ada8fb93d14d528340a522452fff53
Source dataset
uspto-grants-2007_02
Patent number
US07173022B2

Reaction notes

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