Potassium Hydroxide → HCID 19741667, compound

HRID 2255199Notes

Reaction equation

HRID 2255199 reaction equation
[CH2:1]([C:4]1[C:5]([OH:13])=[C:6]([C:10](=[O:12])[CH3:11])[CH:7]=[CH:8][CH:9]=1)[CH:2]=[CH2:3].[F:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[F:24])[C:18](Cl)=O.[OH-].[K+].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC=CC=1>[CH2:1]([C:4]1[C:5]2[O:13][C:18]([C:17]3[CH:21]=[CH:22][C:23]([F:24])=[C:15]([F:14])[CH:16]=3)=[CH:11][C:10](=[O:12])[C:6]=2[CH:7]=[CH:8][CH:9]=1)[CH:2]=[CH2:3]

Participants

7

Reactant 4

HCID 14797Potassium HydroxideHCID 521998p-Toluenesulfonic acid monohydrateHCID 27245193,4-Difluorobenzoyl chlorideHCID 130269161-(3-Allyl-2-hydroxyphenyl)ethanone

Product 1

HCID 19741667HCID 19741667, compoundYield 57.8%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 241BenzeneSolvent2×

Conditions

Temperature
60 °C

Procedure

A mixture of 1.7 g (9.4 mmol) of 3'-allyl-2'-hydroxyacetophenone, 2.0 g (11 mmol) of 3,4-difluorobenzoyl chloride, 1.6 g (4.7 mmol) of tetra-n-butylammonium bisulfate, 60 ml of 10% aqueous potassium hydroxide and 60 ml of benzene was heated at 60° C. for 4 hours, cooled and the phases separated. The organic phase was washed with three 60 ml portions of water, treated with 5.6 g (28 mmol) of p-toluenesulfonic acid monohydrate and an additional 60 ml of benzene and refluxed for 3 hours, using a Dean-Stark trap to remove the water in the reaction. The resulting mixture was washed with 150 ml of 8% aqueous sodium bicarbonate and then with three 60 ml portions of water. The organic phase was then concentrated in vacuo; treated with 25 ml of methanol and cooled to -20° C. After four hours the resulting solid was filtered, washed with three 5 ml portions of methanol and dried to give 1.62 g (56%) of 8-allyl-2-(3,4-difluorophenyl)-4H-benzopyran-4-one as a solid: m.p. 127°-130° C.; TLC Rf 0.48 in 3:1 toluene-methyl isobutyl ketone.

Workup

  1. temperaturecooled
  2. customthe phases separated
  3. washThe organic phase was washed with three 60 ml portions of water
  4. customto remove the water
  5. customin the reaction
  6. washThe resulting mixture was washed with 150 ml of 8% aqueous sodium bicarbonate
  7. concentrationThe organic phase was then concentrated in vacuo
  8. additiontreated with 25 ml of methanol
  9. temperaturecooled to -20° C
  10. filtrationAfter four hours the resulting solid was filtered
  11. washwashed with three 5 ml portions of methanol
  12. customdried

Sources & evidence

ORD record
ord-6b27fd0d6fd14c529bf150a6209ab4c1
Source dataset
uspto-grants-1993_08
Patent number
US05238954

Reaction notes

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