1,8-Diazabicyclo(5.4.0)undec-7-ene → Ethyl 3-(3-nitropyridin-4-yl)-2-oxopropanoate

HRID 2358153Notes

Reaction equation

HRID 2358153 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[C:11]([O:16][CH2:17][CH3:18])(=[O:15])[C:12]([O-])=[O:13].N12CCCN=C1CCCCC2>C(OCC)(=O)C.O.C(O)(=O)C>[N+:8]([C:3]1[CH:4]=[N:5][CH:6]=[CH:7][C:2]=1[CH2:1][C:12](=[O:13])[C:11]([O:16][CH2:17][CH3:18])=[O:15])([O-:10])=[O:9]

Participants

7

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 5218284-Methyl-3-nitropyridineHCID 21943339Ethanedioic acid, monoethyl ester

Product 1

HCID 23269548Ethyl 3-(3-nitropyridin-4-yl)-2-oxopropanoateYield 73%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

3.1 g (22.44 mmol) of 4-methyl-3-nitropyridine and 16.39 g (112.22 mmol) of ethyl oxalate are placed in a 100 ml three-necked flask equipped with a magnetic stirrer and maintained under a flush of nitrogen. 3.69 ml (24.69 mmol) of 1,8-diaza-bicyclo[5.4.0]undec-7-ene are then added to the reaction medium stirred at room temperature. The reaction mixture is then stirred at room temperature for 1 hour and then diluted with a mixture of ethyl acetate (150 ml), water (100 ml) and acetic acid (4 ml). The mixture is extracted twice with ethyl acetate. The combined organic phases are washed with 100 ml of water, with 100 ml of saturated aqueous sodium chloride solution, dried over sodium sulfate and then concentrated under reduced pressure. The crude reaction product is then triturated from pentane, filtered and then heated in petroleum ether, filtered and dried under reduced pressure. 3.9 g (16.37 mmol) of product are thus isolated, and are used without further purification in the following step.

Workup

  1. customequipped with a magnetic stirrer
  2. temperaturemaintained under
  3. customa flush of nitrogen
  4. stirringThe reaction mixture is then stirred at room temperature for 1 hour
  5. extractionThe mixture is extracted twice with ethyl acetate
  6. washThe combined organic phases are washed with 100 ml of water, with 100 ml of saturated aqueous sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe crude reaction product
  10. customis then triturated from pentane
  11. filtrationfiltered
  12. temperatureheated in petroleum ether
  13. filtrationfiltered
  14. customdried under reduced pressure

Sources & evidence

ORD record
ord-38d802305f1f4abc9a8ef6195faf6e4d
Source dataset
uspto-grants-2010_07
Patent number
US07763636B2

Reaction notes

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