Toluene → ethyl 4-(4-chloro-9-oxo-9H-fluorene-2-yloxy)butyrate

HRID 579382Notes

Reaction equation

HRID 579382 reaction equation
[Cl:1][C:2]1[C:14]2[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:7](=[O:15])[C:6]=2[CH:5]=[C:4]([OH:16])[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:24][CH2:25][CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28].C1(C)C=CC=CC=1>CN(C)C=O.O>[Cl:1][C:2]1[C:14]2[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:7](=[O:15])[C:6]=2[CH:5]=[C:4]([O:16][CH2:24][CH2:25][CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:3]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 76300Ethyl 4-bromobutyrateHCID 1175991484-Chloro-2-hydroxy-9H-fluoren-9-one

Product 1

HCID 117599125ethyl 4-(4-chloro-9-oxo-9H-fluorene-2-yloxy)butyrate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

4-Chloro-2-hydroxy-9H-fluoren-9-one (48.6 g) was dissolved in N,N-dimethylformamide (150 ml), potassium carbonate (58.3 g) and ethyl 4-bromobutyrate (33.5 ml) were added, and the mixture was stirred at 60° C. for 2 hr. The reaction mixture was cooled to 40° C., and toluene (300 ml) and water (300 ml) were added to allow for layer separation. The obtained aqueous layer was extracted again with toluene (100 ml). The obtained organic layers were combined, washed twice with water (100 ml), anhydrous sodium sulfate and activated carbon (2.5 g) were added, and the mixture was stirred at room temperature for 5 min. The insoluble material was filtered off through celite, and the solvent in the filtrate was evaporated. To the obtained residue was added hexane (220 ml), and the mixture was stirred at 50° C. for 10 min and at room temperature for 1 hr. The precipitated solid was collected by filtration, and washed with hexane. The obtained solid was dried under reduced pressure to give the title compound (66.9 g). In addition, the solvent in the obtained filtrate was evaporated, to the residue were added ethyl acetate (5 ml) and hexane (20 ml), and the mixture was stirred at room temperature for 1 hr. The precipitated solid was collected by filtration, and washed with hexane. The obtained solid was dried under reduced pressure to further give the title compound (2.5 g).

Workup

  1. temperatureThe reaction mixture was cooled to 40° C.
  2. customto allow for layer separation
  3. extractionThe obtained aqueous layer was extracted again with toluene (100 ml)
  4. washwashed twice with water (100 ml), anhydrous sodium sulfate and activated carbon (2.5 g)
  5. additionwere added
  6. stirringthe mixture was stirred at room temperature for 5 min
  7. filtrationThe insoluble material was filtered off through celite
  8. customthe solvent in the filtrate was evaporated
  9. additionTo the obtained residue was added hexane (220 ml)
  10. stirringthe mixture was stirred at 50° C. for 10 min and at room temperature for 1 hr
  11. filtrationThe precipitated solid was collected by filtration
  12. washwashed with hexane
  13. customThe obtained solid was dried under reduced pressure

Sources & evidence

ORD record
ord-099786f5a10b43c28efcb3183abfdf13
Source dataset
uspto-grants-2015_05
Patent number
US09040717B2

Reaction notes

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