Diethyl Oxalate → HCID 271544, compound

HRID 1387411Notes

Reaction equation

HRID 1387411 reaction equation
[C:1]([O:8]CC)(=[O:7])[C:2]([O:4]CC)=O.[Br:11][C:12]1[CH:17]=[CH:16][C:15]([CH3:18])=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=1.[O-]CC.[Na+].[Na]>O.C(O)C>[Br:11][C:12]1[CH:17]=[CH:16][C:15]([CH2:18][C:2](=[O:4])[C:1]([OH:8])=[O:7])=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=1

Participants

7

Reactant 4

HCID 7268Diethyl OxalateHCID 1235464-Bromo-2-nitrotolueneHCID 2723922Sodium ethoxideHCID 5360545Sodium

Product 1

HCID 271544HCID 271544, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Diethyl oxalate (29.2 g, 0.2 mol) and 4-bromo-2-nitrotoluene (21.6 g, 0.1 mol, Lancaster) were poured into a cooled sodium ethoxide solution, prepared from sodium (4.6 g, 0.2 mol) and absolute ethanol (90 mL). The mixture was stirred overnight at room temperature and then refluxed for 10 minutes at the end of the reaction. Water (30 mL) was added and the reaction refluxed for 2.5 h. The reaction mixture was cooled and concentrated to remove excess ethanol. The precipitate was collected by filtration, washed with ether and dried. The crude sodium salt was dissolved in water and acidified with conc. HCl. The solid precipitated and was collected by filtration. The crude product was recrystallized from hexane and ethyl acetate to give 12.5 g (43%) as a feathery putty-colored solid; 1H-NMR (CDCl3): δ8.40 (d, 1H, J=1.9 Hz). 7,84 (dd, 1H, J=8.0, 2.0 Hz), 7.30 (d, 1H, J=2 Hz) 4.65 (s, 2H).

Workup

  1. temperaturerefluxed for 10 minutes at the end of the reaction
  2. temperaturethe reaction refluxed for 2.5 h
  3. temperatureThe reaction mixture was cooled
  4. concentrationconcentrated
  5. customto remove excess ethanol
  6. filtrationThe precipitate was collected by filtration
  7. washwashed with ether
  8. customdried
  9. dissolutionThe crude sodium salt was dissolved in water
  10. customThe solid precipitated
  11. filtrationwas collected by filtration
  12. customThe crude product was recrystallized from hexane and ethyl acetate
  13. customto give 12.5 g (43%) as a feathery putty-colored solid

Sources & evidence

ORD record
ord-166c1a64ba5d479d8116663ae5e0b339
Source dataset
uspto-grants-2001_07
Patent number
US06268391B1

Reaction notes

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