Hydrochloric Acid → HCID 15383033, compound

HRID 1416215Notes

Reaction equation

HRID 1416215 reaction equation
[OH:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8]CC)=[O:7])=[CH:4][CH:3]=1.[CH2:13](Cl)[C:14](=[CH2:16])[CH3:15].C(=O)([O-])[O-].[K+].[K+].Cl.[H][H].[F:27][C:28]1[CH:35]=[CH:34][C:31]([CH2:32]Br)=[CH:30][CH:29]=1>CC(C)=O.CN(C)C1C=CC=CC=1.C(O)C.[Pd].O>[F:27][C:28]1[CH:35]=[CH:34][C:31]([CH2:32][O:1][C:2]2[CH:3]=[CH:4][C:5]([C:6]([OH:8])=[O:7])=[CH:11][C:12]=2[CH2:13][CH:14]([CH3:16])[CH3:15])=[CH:30][CH:29]=1

Participants

12

Reactant 6

HCID 313Hydrochloric AcidHCID 8434EthylparabenHCID 112413-Chloro-2-methyl-1-propeneHCID 11430Potassium Carbonate2×HCID 680214-Fluorobenzyl bromideHCID 178418361HCID 178418361, compound

Product 1

HCID 15383033HCID 15383033, compoundYield 78.6%

Reagents, catalysts & solvents 5

HCID 23938PalladiumCatalystHCID 180AcetoneSolvent2×HCID 702EthanolSolventHCID 949N,N-DimethylanilineSolventHCID 962WaterSolvent

Procedure

Ethyl 4-hydroxybenzoate (50.0 g), methallyl chloride (32.6 g), and potassium carbonate (45.6 g) were refluxed in acetone (150 ml) with stirring for 40 hours. The reaction mixture was filtered, and then the filtrate was concentrated under a vacuum. The residue, with toluene (150 ml) added thereto, was washed with 2% sodium hydroxide aqueous solution and water successively, dried over sodium sulfate anhydride, and then concentrated under a vacuum to yield an oil. The oil was dissolved in N,N-dimethylaniline (80 ml) and the solution was refluxed with stirring for approximate 10 hours. The reaction mixture was acidified with concentrated hydrochloric acid while being cooled with ice, and then extracted with toluene. The extract was further extracted with 10% sodium hydroxide aqueous solution. The resulting water layer was acidified with concentrated hydrochloric acid , and then extracted with toluene. The extract was washed with water, dried over sodium sulfate anhydride, and then concentrated under a vacuum, thereby yielding a solid. The solid was dissolved in ethanol (580 ml) and the solution, with 10% palladium-charcoal (6.0 g) added thereto, was subjected to catalytic reduction in a hydrogen gas atmosphere. After the reaction mixture was filtered, the filtrate was concentrated under a vacuum, thereby yielding a solid. The solid was dissolved in acetone (350 ml) and the solution, with potassium carbonate (73.8 g) and 4-fluorobenzyl bromide (60.6 g) added thereto, was refluxed with stirring for 4 hours. The reaction mixture, with water added thereto, was extracted with ethyl acetate and concentrated under a vacuum. The residue, with water (120 ml), potassium hydroxide (29.9 g), and ethanol (250 ml) added thereto, was refluxed with stirring for 2 hours. The reaction mixture, with water added thereto, was neutralized with hydrochloric acid, and then extracted with ethyl acetate. The extract was washed with 10% hydrochloric acid and water successively, dried over sodium sulfate anhydride, and then concentrated under a vacuum. The resulting solid was recrystallized from n-hexane/ethanol to yield 71.5 g of the aimed compound.

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationthe filtrate was concentrated under a vacuum
  3. additionThe residue, with toluene (150 ml) added
  4. washwas washed with 2% sodium hydroxide aqueous solution and water successively
  5. dry with materialdried over sodium sulfate anhydride
  6. concentrationconcentrated under a vacuum
  7. customto yield an oil
  8. temperaturethe solution was refluxed
  9. stirringwith stirring for approximate 10 hours
  10. temperaturewhile being cooled with ice
  11. extractionextracted with toluene
  12. extractionThe extract was further extracted with 10% sodium hydroxide aqueous solution
  13. extractionextracted with toluene
  14. washThe extract was washed with water
  15. dry with materialdried over sodium sulfate anhydride
  16. concentrationconcentrated under a vacuum
  17. customyielding a solid
  18. filtrationAfter the reaction mixture was filtered
  19. concentrationthe filtrate was concentrated under a vacuum
  20. customyielding a solid
  21. temperaturewas refluxed
  22. stirringwith stirring for 4 hours
  23. extractionwas extracted with ethyl acetate
  24. concentrationconcentrated under a vacuum
  25. additionThe residue, with water (120 ml), potassium hydroxide (29.9 g), and ethanol (250 ml) added
  26. temperaturewas refluxed
  27. stirringwith stirring for 2 hours
  28. additionThe reaction mixture, with water added
  29. extractionextracted with ethyl acetate
  30. washThe extract was washed with 10% hydrochloric acid and water successively
  31. dry with materialdried over sodium sulfate anhydride
  32. concentrationconcentrated under a vacuum
  33. customThe resulting solid was recrystallized from n-hexane/ethanol

Sources & evidence

ORD record
ord-c7c9202d6ee847da92387cfb08717773
Source dataset
uspto-grants-1999_06
Patent number
US05912258

Reaction notes

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