Ethyl Acetate → Ethyl 2-(3-fluoro-4-(methylthio)phenyl)-2-oxoacetate

HRID 1843001Notes

Reaction equation

HRID 1843001 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].Cl[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[O:7].[F:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20][CH3:21].C(OCC)(=O)C>C(Cl)(Cl)Cl.CCCCCC>[F:13][C:14]1[CH:19]=[C:18]([C:6](=[O:7])[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:17]=[CH:16][C:15]=1[S:20][CH3:21]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 20884Ethoxalyl chlorideHCID 27747622-FluorothioanisoleHCID 6451240Aluminum(III) Chloride

Product 1

HCID 70816483Ethyl 2-(3-fluoro-4-(methylthio)phenyl)-2-oxoacetateYield 64.6%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8058HexaneSolvent

Procedure

To a solution of AlCl3 (9.2 g, 0.06 mol, 2 eq) in chloroform (50 mL) cooled at 0° C., ethyl (chlorocarbonyl)formate (7.3 g, 0.05 mol, 1.6 eq) was added drop wise and the reaction mixture was stirred for 30-45 min at the same temperature. (2-fluorophenyl)(methyl)sulfane (5 g, crude) was added at 0° C. and the reaction mixture was stirred for 4 h at room temperature. Progress of the reaction was monitored by TLC (5% ethyl acetate in n-hexane, Rf˜0.5). On completion of the reaction, crushed ice was added and the mixture was stirred for some time. The organic layer was separated and the aqueous layer was extracted with DCM (2×50 mL). The combined extract was washed with NaHCO3 solution, dried over sodium sulfate and concentrated under reduced pressure to yield ethyl 2-(3-fluoro-4-(methylthio)phenyl)-2-oxoacetate as an yellow colored liquid (5.5 g).

Workup

  1. stirringthe reaction mixture was stirred for 4 h at room temperature
  2. customOn completion of the reaction
  3. customcrushed ice
  4. additionwas added
  5. stirringthe mixture was stirred for some time
  6. customThe organic layer was separated
  7. extractionthe aqueous layer was extracted with DCM (2×50 mL)
  8. extractionThe combined extract
  9. washwas washed with NaHCO3 solution
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-c9df38cf5c4142c6ada9906d18c3c7a8
Source dataset
uspto-grants-2015_02
Patent number
US08946204B2

Reaction notes

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