Sulfuric Acid → HCID 54225476, compound

HRID 972357Notes

Reaction equation

HRID 972357 reaction equation
[C:1](C1C=CC(C2C=CC(F)=CC=2F)=C(F)C=1)(=O)[CH3:2].[S].N1CCOCC1.S(=O)(=O)(O)O.[F:31][C:32]1[CH:37]=[C:36]([CH2:38][C:39]([OH:41])=[O:40])[CH:35]=[CH:34][C:33]=1[C:42]1[CH:47]=[CH:46][C:45]([F:48])=[CH:44][C:43]=1[F:49]>O.C(O)(=O)C>[F:31][C:32]1[CH:37]=[C:36]([CH2:38][C:39]([O:41][CH2:1][CH3:2])=[O:40])[CH:35]=[CH:34][C:33]=1[C:42]1[CH:47]=[CH:46][C:45]([F:48])=[CH:44][C:43]=1[F:49]

Participants

8

Reactant 5

HCID 1118Sulfuric Acid2×HCID 8083MorpholineHCID 5362487SulfurHCID 21406751HCID 21406751, compoundHCID 21406771HCID 21406771, compound

Product 1

HCID 54225476HCID 54225476, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

A mixture of 4-acetyl-2,2',4'-trifluorobiphenyl (4.4 g., 17.6 m.moles), sulphur (1 g.) and morpholine (5 ml.) was stirred under reflux for 16 hours to give the thiomorpholide. After cooling, and the addition of acetic acid (glacial, 25 ml.), concentrated sulphuric acid (4 ml.) and water (10 ml.) the mixture was stirred and refluxed for 24 hours. Ice-water was added to precipitate a crude solid. This was taken up in ether and back-extracted with aqueous potassium carbonate. The extracts were washed with ether, acidified, and re-extracted with ether. Evaporation gave 4.2 g. of crude 2,2',4'-trifluoro-4-biphenylylacetic acid. This was then mixed with absolute alcohol (65 ml.) and concentrated sulphuric acid (3 ml.) and the mixture refluxed overnight. Excess alcohol was distilled off and the residue diluted with water (100 ml.). The product was isolated with ether, washed with aqueous sodium bicarbonate, dried, evaporated and distilled (b.p. 130°-136°/0.4 mm.) to give 3.2 g. of pale yellow oil which solidified on standing. This was recrystallised from 40-60 petroleum ether to give ethyl 2,2',4'-trifluoro-4-biphenylylacetate having a m.p. of 50°-52° C.

Workup

  1. temperatureunder reflux for 16 hours
  2. customto give the thiomorpholide
  3. temperatureAfter cooling
  4. stirringwas stirred
  5. temperaturerefluxed for 24 hours
  6. customto precipitate a crude solid
  7. extractionback-extracted with aqueous potassium carbonate
  8. washThe extracts were washed with ether
  9. extractionre-extracted with ether
  10. customEvaporation
  11. customgave 4.2 g
  12. temperaturethe mixture refluxed overnight
  13. distillationExcess alcohol was distilled off
  14. additionthe residue diluted with water (100 ml.)
  15. customThe product was isolated with ether
  16. washwashed with aqueous sodium bicarbonate
  17. customdried
  18. customevaporated
  19. distillationdistilled (b.p. 130°-136°/0.4 mm.)
  20. customto give 3.2 g
  21. customThis was recrystallised from 40-60 petroleum ether

Sources & evidence

ORD record
ord-3faa698944c14ed6a0f21f973ff1d50f
Source dataset
uspto-grants-1977_10
Patent number
US04052514

Reaction notes

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