Diethyl Oxalate → Ethyl 3-{2-[2-(dipropylamino)ethyl]-6-nitrophenyl}-2-oxopropanoate

HRID 280269Notes

Reaction equation

HRID 280269 reaction equation
[Na].[CH3:2][C:3]1[C:8]([N+:9]([O-:11])=[O:10])=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:12][C:13]([N:15]([CH2:19][CH2:20][CH3:21])[CH2:16][CH2:17][CH3:18])=O.[C:22](OCC)(=[O:28])[C:23]([O:25][CH2:26][CH3:27])=[O:24]>C(O)C>[CH2:16]([N:15]([CH2:19][CH2:20][CH3:21])[CH2:13][CH2:12][C:4]1[C:3]([CH2:2][C:22](=[O:28])[C:23]([O:25][CH2:26][CH3:27])=[O:24])=[C:8]([N+:9]([O-:11])=[O:10])[CH:7]=[CH:6][CH:5]=1)[CH2:17][CH3:18]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 5360545SodiumHCID 135308982-(2-Methyl-3-nitrophenyl)-N,N-dipropylacetamide

Product 1

HCID 23322030Ethyl 3-{2-[2-(dipropylamino)ethyl]-6-nitrophenyl}-2-oxopropanoateYield 23.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 2.38 g (0.103 gram atoms) of sodium metal in 52 cc of absolute ethanol at room temperature was added 18.51 g (0.07 mole) of the nitro compound in one portion, with stirring, followed by 15.42 g (0.103 mole) of diethyl oxalate. The reaction was refluxed under nitrogen for about 20 minutes, cooled, quenched on 700 cc of ice-water and acidified with 3N hydrochloric acid. This aqueous solution was washed with a small volume of ether, basified to pH 8.5 with solid sodium carbonate and extracted with 3 portions of ether. The combined ether extract was washed with saturated brine, dried over anhydrous magnesium sulfate, clarified with charcoal and concentrated in vacuo. The residue was triturated with cold petroleum ether, filtered and air-dried to give 6.0 g of ethyl 6-(2-di-n-propylaminoethyl)-2-nitrophenylpyruvate as a yellow powder. The triturate was concentrated in vacuo and distilled to give 7.3 g of recovered starting material which was recycled. In the same manner, a total of three recycles provided 11.0 g of ethyl-6-(2-di-n-propylaminoethyl)-2-nitrophenylpyruvate.

Workup

  1. temperatureThe reaction was refluxed under nitrogen for about 20 minutes
  2. temperaturecooled
  3. customquenched on 700 cc of ice-water
  4. washThis aqueous solution was washed with a small volume of ether
  5. extractionextracted with 3 portions of ether
  6. extractionThe combined ether extract
  7. washwas washed with saturated brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe residue was triturated with cold petroleum ether
  11. filtrationfiltered
  12. customair-dried

Sources & evidence

ORD record
ord-e7fe0aea860a4598b846358c5c3caa7b
Source dataset
uspto-grants-1986_05
Patent number
US04588740

Reaction notes

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