Allyl bromide → HCID 20532011, compound

HRID 866763Notes

Reaction equation

HRID 866763 reaction equation
[CH2:1]([O:3][C:4]([C:6]([CH:9]1[C:14](=[O:15])[NH:13][C:12](=[O:16])[NH:11][C:10]1=[O:17])([CH3:8])[CH3:7])=[O:5])[CH3:2].S([O-])([O-])(=O)=O.[Ca+2].[CH2:24](Br)[CH:25]=[CH2:26].[OH-].[Na+]>[Cu].O>[CH2:26]([C:9]1([C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])([CH3:8])[CH3:7])[C:14](=[O:15])[NH:13][C:12](=[O:16])[NH:11][C:10]1=[O:17])[CH:25]=[CH2:24]

Participants

7

Reactant 4

HCID 7841Allyl bromide2×HCID 14798Sodium Hydroxide3×HCID 24497Calcium SulfateHCID 20532005HCID 20532005, compound

Product 1

HCID 20532011HCID 20532011, compound

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 962WaterSolvent

Procedure

Into a one liter three-neck flask equipped with mechanical stirrer, reflux condenser and a dropping funnel, were placed 100 g. of 5-(1-ethoxycarbonylisopropyl)barbituric acid, 100 mg. of calcium sulfate, 50 mg. of copper dust and 500 ml. of water. The mixture was stirred at room temperature for 15 minutes and 53.6 g of allyl bromide were added in one portion followed by the dropwise addition of 125 ml. of 20% sodium hydroxide over 45 minutes at 50°-55°. After stirring at 50°-55° for 3 hours, the reaction mixture was cooled to about 30° and an additional 26.8 g. of allyl bromide were added in one portion. The reaction mixture was heated with stirring, for 90 minutes, and a solution (65-70 ml.) of 20% sodium hydroxide was then added at a rate such that the reaction mixture was always slightly alkaline. The mixture was cooled to room temperature. The pH of the mixture was adjusted to about 9 by the addition of 20% sodium hydroxide and the mixture was extracted with 4 × 250 ml. of ethyl acetate. The combined ethyl acetate extracts were re-extracted with 4 × 300 ml. of 1% sodium hydroxide and the aqueous extracts were added to a mixture of 500 g. of ice and 300 ml. of 6N hydrochloric acid. The precipitate which formed upon standing at room temperature overnight was collected to give 91.0 g. (78%) of the alkylbarbituric acid, m.p. 112°-114°.

Workup

  1. customInto a one liter three-neck flask equipped with mechanical stirrer
  2. temperaturereflux condenser and a dropping funnel
  3. additionfollowed by the dropwise addition of 125 ml
  4. stirringAfter stirring at 50°-55° for 3 hours
  5. temperaturethe reaction mixture was cooled to about 30°
  6. temperatureThe reaction mixture was heated
  7. stirringwith stirring, for 90 minutes
  8. temperatureThe mixture was cooled to room temperature
  9. extractionthe mixture was extracted with 4 × 250 ml
  10. extractionThe combined ethyl acetate extracts were re-extracted with 4 × 300 ml
  11. additionof 1% sodium hydroxide and the aqueous extracts were added to a mixture of 500 g
  12. customThe precipitate which formed
  13. waitupon standing at room temperature overnight
  14. customwas collected
  15. customto give 91.0 g

Sources & evidence

ORD record
ord-2bb9e5412ca544d091ee2a8f0408e2bf
Source dataset
uspto-grants-1978_07
Patent number
US04101549

Reaction notes

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