Allyl bromide → HCID 20532011, compound

HRID 1759365Notes

Reaction equation

HRID 1759365 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-ethoxycarbonyl-isopropyl)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 6 N 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 upon-standing at room temperature overnight
  13. customwas collected
  14. customto give 91.0 g

Sources & evidence

ORD record
ord-5baaaf4bee444369a135c91807a65e60
Source dataset
uspto-grants-1982_07
Patent number
US04340736

Reaction notes

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