Allyl iodide → HCID 22414838, compound

HRID 1721437Notes

Reaction equation

HRID 1721437 reaction equation
[CH2:1]([N:8]([C:25](=[O:35])[C:26](NC1C=CC=CC=1)=[O:27])[C:9]1[CH:14]=[C:13]([O:15][CH2:16][C:17]2C=CC=C[CH:18]=2)[CH:12]=[C:11](C)[C:10]=1[CH3:24])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[K+].C(=O)([O-])[O-].[K+].[K+].C(I)C=C>C(O)C>[CH2:16]([O:15][C:13]1[CH:12]=[CH:11][C:10]([CH3:24])=[C:9]2[C:14]=1[C:26](=[O:27])[C:25](=[O:35])[N:8]2[CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH:17]=[CH2:18]

Participants

6

Reactant 4

HCID 11166Allyl iodideHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 22414831HCID 22414831, compound

Product 1

HCID 22414838HCID 22414838, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

149.98 g (0.386 mol) of N-benzyl-5'-benzyloxy-2'-methylmethyloxalanilide was dissolve in 900 ml of 90% ethanol aqueous solution. After the addition of 44.0 g (0.786 mol) of potassium hydroxide, the mixture was stirred for 2 hours at 50° C. The reaction mixture was concentrated under reduced pressure, and to the residue were slowly added 400 ml of trifluoroacetic acid and then 400 ml of trifluoroacetic anhydride under cooling with ice. The temperature was raised to 50° C and the mixture was stirred for 1 hour, and for a further 35 hours at 60° C. The reaction mixture was concentrated under reduced pressure and the residue was extracted with chloroform. The organic layer was partitioned by 1N aqueous solution of sodium hydroxide. Hydrochloric acid was added to the basic water layer to adjust pH to about 4, and this layer was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate. The residue obtained by evaporating the solvent under reduced pressure was dissolved in 200 ml of N,N-dimethylformamide, and 100 g (0.725 mol) of potassium carbonate and 50.0 g (0.298 mol) of allyl iodide were added to the solution, followed by stirring for 90 minutes at 60° C. The reaction mixture was concentrated under reduced pressure and the residue was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate. The residue obtained by evaporating the solvent under reduced pressure was recrystallized from benzene to obtain reddish brown crude crystals. The crystals were recrystallized from ethyl acetate-ether-n-hexane to obtain 17.3 g (three steps, 14.2%) of a reddish brown powder of the title compound.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. temperature400 ml of trifluoroacetic anhydride under cooling with ice
  3. temperatureThe temperature was raised to 50° C
  4. stirringthe mixture was stirred for 1 hour
  5. waitfor a further 35 hours at 60° C
  6. concentrationThe reaction mixture was concentrated under reduced pressure
  7. extractionthe residue was extracted with chloroform
  8. customThe organic layer was partitioned by 1N aqueous solution of sodium hydroxide
  9. additionHydrochloric acid was added to the basic water layer
  10. extractionthis layer was extracted with chloroform
  11. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  12. customThe residue obtained
  13. customby evaporating the solvent under reduced pressure
  14. dissolutionwas dissolved in 200 ml of N,N-dimethylformamide
  15. stirringby stirring for 90 minutes at 60° C
  16. concentrationThe reaction mixture was concentrated under reduced pressure
  17. extractionthe residue was extracted with chloroform
  18. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  19. customThe residue obtained
  20. customby evaporating the solvent under reduced pressure
  21. customwas recrystallized from benzene
  22. customto obtain reddish brown crude crystals
  23. customThe crystals were recrystallized from ethyl acetate-ether-n-hexane

Sources & evidence

ORD record
ord-7cd9fc01aa1a4b818f06d54a23b846fc
Source dataset
uspto-grants-1996_04
Patent number
US05510366

Reaction notes

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