Ethoxalyl chloride → Ethyl 2-(3-chloro-4-(methylthio)phenyl)-2-oxoacetate

HRID 1843009Notes

Reaction equation

HRID 1843009 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].Cl[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[O:7].[Cl:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20][CH3:21].C(OCC)(=O)C.CCCCCC>C(Cl)(Cl)Cl>[Cl: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

6

Reactant 4

HCID 20884Ethoxalyl chlorideHCID 27373632-Chlorophenyl methyl sulfideHCID 6451240Aluminum(III) ChlorideHCID 21226206Ethyl acetate hexane

Product 1

HCID 53981255Ethyl 2-(3-chloro-4-(methylthio)phenyl)-2-oxoacetateYield 77.3%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a well stirred solution of AlCl3 (16.58 g, 2 eq) in chloroform (100 mL), ethyl (chlorocarbonyl)formate (10.02 g (8.35 mL), 1.6 eq) was added at 0° C. and the contents were allowed to stir for 30 min. Then (2-chlorophenyl)(methyl)sulfane (10 g (8.33 mL), 0.06 mol) was added at 0° C. and the overall reaction mass was allowed to stir for 3-4 h at room temperature. Progress of the reaction was monitored by TLC (5% ethyl acetate/hexane, Rf˜0.3). On completion of the reaction, crushed ice was added and the contents were allowed to stir for 10 min. The organic layer was separated and the aqueous layer was extracted with DCM (2×100 mL). The combined extract was dried over sodium sulfate and concentrated under reduced pressure to yield ethyl 2-(3-chloro-4-(methylthio)phenyl)-2-oxoacetate as a pale yellow colored liquid (12 g, 73%).

Workup

  1. stirringto stir for 3-4 h at room temperature
  2. customOn completion of the reaction
  3. customcrushed ice
  4. additionwas added
  5. stirringto stir for 10 min
  6. customThe organic layer was separated
  7. extractionthe aqueous layer was extracted with DCM (2×100 mL)
  8. extractionThe combined extract
  9. dry with materialwas dried over sodium sulfate
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-f0008d74c42740fab664b287bf76d505
Source dataset
uspto-grants-2015_02
Patent number
US08946204B2

Reaction notes

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