Diethyl Malonate → HCID 18981215, compound

HRID 1657182Notes

Reaction equation

HRID 1657182 reaction equation
[OH:1][CH2:2][CH2:3][NH:4][C:5]([NH:7]C1C=CC([N+]([O-])=O)=CC=1)=[O:6].[C:17]([O:25]CC)(=O)[CH2:18][C:19]([O:21]CC)=O.[O-]CC.[Na+]>C(O)C>[OH:1][CH2:2][CH2:3][N:4]1[C:17](=[O:25])[CH2:18][C:19](=[O:21])[NH:7][C:5]1=[O:6]

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 2723922Sodium ethoxideHCID 4890913HCID 4890913, compound

Product 1

HCID 18981215HCID 18981215, compoundYield 96%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

In a 1 liter round-bottom flask equipped with an overhead stirrer and reflux condenser was placed N-(2-hydroxyethyl)-N'-(4-nitrophenyl)urea (40.0 grams, 0.178 mol), diethyl malonate (71.2 grams, 0.445 mol), and ethanol (560 mL). Sodium ethoxide in ethanol (21 wt %, 69.2 grams, 0.214 mol) was added and the reaction mixture was heated to reflux for 6 hours. The reaction mixture was cooled and the ethanol was removed under vacuum. Methylene chloride (500 mL) and water (500 mL) were added. The layers were separated and the aqueous layer was further washed with a second portion of methylene chloride to extract a by-product, 4-nitroaniline which was discarded. The aqueous layer was acidified with 6N HCl (50 mL) and an oily phase precipitated. The oil layer was separated and stirred with 70 mL of benzene. After several minutes the oil turned into a chunky, aggregated solid. The benzene was decanted off and the chunky solid was broken up and triturated with hot benzene. The solution was cooled and suction filtered to isolate the solid, which was oven-dried yielding N-(2-hydroxyethyl)barbituric acid (29.4 grams). Additional product (6.2 grams) crystallized out of the water layer upon standing overnight. The additional product was collected by suction filtration and dried.

Workup

  1. customIn a 1 liter round-bottom flask equipped with an overhead stirrer
  2. temperaturereflux condenser
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 6 hours
  5. temperatureThe reaction mixture was cooled
  6. customthe ethanol was removed under vacuum
  7. additionMethylene chloride (500 mL) and water (500 mL) were added
  8. customThe layers were separated
  9. washthe aqueous layer was further washed with a second portion of methylene chloride
  10. extractionto extract a by-product, 4-nitroaniline which
  11. customan oily phase precipitated
  12. customThe oil layer was separated
  13. waitAfter several minutes the oil turned
  14. customThe benzene was decanted off
  15. customtriturated with hot benzene
  16. temperatureThe solution was cooled
  17. filtrationsuction filtered
  18. customto isolate the solid, which
  19. customwas oven-dried

Sources & evidence

ORD record
ord-a963c0f007b4488a8548a281994894f5
Source dataset
uspto-grants-1993_10
Patent number
US05256784

Reaction notes

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