Bromine → Ethyl (3-oxo-2,3,-dihydropyridazin-6-yl)-propionate

HRID 987906Notes

Reaction equation

HRID 987906 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][C:5]([CH:8]([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[N:4][NH:3]1.BrBr.C([O-])(O)=O.[Na+]>C(O)C>[O:1]=[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[N:4][NH:3]1

Participants

5

Reactant 3

HCID 24408BromineHCID 516892Sodium BicarbonateHCID 86759212Ethyl (3-oxo-2,3,4,5-Tetrahydropyridazin-6-yl)propionate

Product 1

HCID 131724097Ethyl (3-oxo-2,3,-dihydropyridazin-6-yl)-propionateYield 34.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of ethyl (3-oxo-2,3,4,5-tetrahydropyridazin-6-yl)-propionate (50.0 mmol, 9.90 g) in ethanol (50 mL) was added bromine (75.0 mmol, 11.99 g). The mixture was stirred at rt for 14 h and the mixture was poored into NaHCO3 (sat. aqueous) (500 mL). The resulting mixture was extracted exhaustively with diethylether (5×500 mL). The combined organic fractions were dried over MgSO4 and evaporated in vacuo. The crude product was recrystallized from toluene to give the title compound (3.35 g, 34.1%) as colorless needles of high purity (HPLC at 260 nm). UV λmax 228 nm and 285 nm. 1H NMR (CDCl3): δ 11.62 (s br, 1H, NH), 7.18 (d, J=9.7 Hz, 1H, arom.), 7.88 (d, J=9.7 Hz, 1H, arom.), 4.11 (q, J=7.1 Hz, 2H, CH2), 2.90 (t, J=7.0 Hz, 2H, CH2), 2.64 (t, J=7.0 Hz, 2H, CH2), 1.25 (t, J=7.1 Hz, 3H, CH3). 13C NMR (CDCl3): δ 172.20, 161.50, 146.73, 134.06, 129.74, 60.45, 31.47, 25.89, 13.97. FAB+ MS: 197.10 (M+H+, calc. for C9H12N2O3+H+ 197.0926).

Workup

  1. extractionThe resulting mixture was extracted exhaustively with diethylether (5×500 mL)
  2. dry with materialThe combined organic fractions were dried over MgSO4
  3. customevaporated in vacuo
  4. customThe crude product was recrystallized from toluene

Sources & evidence

ORD record
ord-ee23abcbeb7d4a8a873a2346500c537f
Source dataset
uspto-grants-2003_10
Patent number
US06632919B1

Reaction notes

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