4-Chlorophenol → 2-[5-(4-Chlorophenoxy)-2-trifluoromethoxyphenyl]cyclopentane-1,3-dione

HRID 339471Notes

Reaction equation

HRID 339471 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:16]1[CH:17]=[CH:18][C:19]([O:29][C:30]([F:33])([F:32])[F:31])=[C:20]([CH:22]2[C:26](=[O:27])[CH2:25][CH2:24][C:23]2=[O:28])[CH:21]=1>C1(C)C=CC=CC=1.[O-]S(C(F)(F)F)(=O)=O.[Cu+2].[O-]S(C(F)(F)F)(=O)=O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:16]2[CH:17]=[CH:18][C:19]([O:29][C:30]([F:31])([F:32])[F:33])=[C:20]([CH:22]3[C:26](=[O:27])[CH2:25][CH2:24][C:23]3=[O:28])[CH:21]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 46844-ChlorophenolHCID 10796Cesium carbonateHCID 666778042-(5-Bromo-2-trifluoromethoxyphenyl)cyclopentane-1,3-dione

Product 1

HCID 666779502-[5-(4-Chlorophenoxy)-2-trifluoromethoxyphenyl]cyclopentane-1,3-dione

Reagents, catalysts & solvents 2

HCID 2734996copper(II) trifluoromethanesulfonateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
160 °C

Procedure

To a mixture of 4-chlorophenol (0.473 g, 3.69 mmol), cesium carbonate (0.521 g, 1.48 mmol), copper triflate (0.013 g, 0.04 mmol) and powdered 5 Å molecular sieves (0.400 g) is added a solution of 2-(5-bromo-2-trifluoromethoxyphenyl)cyclopentane-1,3-dione (0.249 g, 0.74 mmol) in anhydrous toluene (3.5 ml). The mixture is flushed with nitrogen and heated at 160° C. for 1 hour under microwave radiation, then for a further 1 h at 170° C. After cooling to room temperature the crude product is partitioned between dichloromethane (5 ml) and 2M hydrochloric acid (5 ml), and the organic phase is separated then concentrated in vacuo. The residue is then purified by flash column chromatography on silica gel (ethyl acetate/iso-hexane eluant) to afford 2-[5-(4-chlorophenoxy)-2-trifluoromethoxyphenyl]cyclopentane-1,3-dione as a white solid.

Workup

  1. customThe mixture is flushed with nitrogen
  2. temperatureAfter cooling to room temperature the crude product
  3. customis partitioned between dichloromethane (5 ml) and 2M hydrochloric acid (5 ml)
  4. customthe organic phase is separated
  5. concentrationthen concentrated in vacuo
  6. customThe residue is then purified by flash column chromatography on silica gel (ethyl acetate/iso-hexane eluant)

Sources & evidence

ORD record
ord-af09a8cffd5a4e75982d29490f4cbe5b
Source dataset
uspto-grants-2014_11
Patent number
US08895474B2

Reaction notes

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