Hydrochloric Acid → Ethyl 4-thiomethylbenzoylformate

HRID 1358157Notes

Reaction equation

HRID 1358157 reaction equation
[C:1]1([S:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:9]([O:11][C:12](=[O:16])[C:13](Cl)=[O:14])[CH3:10].[Cl-].[Cl-].[Cl-].[Al+3].Cl>ClCCl>[CH2:9]([O:11][C:12](=[O:16])[C:13]([C:4]1[CH:5]=[CH:6][C:1]([S:7][CH3:8])=[CH:2][CH:3]=1)=[O:14])[CH3:10]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7520ThioanisoleHCID 20884Ethoxalyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 2758911Ethyl 4-thiomethylbenzoylformateYield 78%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

37.5 g (0.3 mol) of Thioanisol and 41.4 g (0.3 mol) of chloro-oxo-acetic acid ethyl ester dissolved in 200 ml of dichloromethane are added dropwise to a suspension of 60 g (0.45 mol) of aluminum trichloride in 350 ml of dichloromethane at 0° C. The solution is stirred overnight at room temperature and then heated to reflux for two hours. After cooling to room temperature, the reaction mixture is poured on a mixture of 100 ml conc. HCl and ice/water. After extraction with dichloromethane, the organic phase is washed with water and sodium bicarbonate and dried over magnesium sulfate. The salt is filtered off and the solvent distilled to give 52.3 g (78%) of (4-methylsulfanyl-phenyl)-oxo-acetic acid ethyl ester as a yellow oil. This oil is used for the next step without further purification. The structure is confirmed by the 1H-NMR spectrum (in CDCl3). δ[ppm]: 7.87 (d,2H), 7.24 (d,2H), 4.39 (q,2H), 2.48 (s,2H), 1.37 (t,3H).

Workup

  1. temperatureheated
  2. temperatureto reflux for two hours
  3. temperatureAfter cooling to room temperature
  4. extractionAfter extraction with dichloromethane
  5. washthe organic phase is washed with water and sodium bicarbonate
  6. dry with materialdried over magnesium sulfate
  7. filtrationThe salt is filtered off
  8. distillationthe solvent distilled

Sources & evidence

ORD record
ord-5200da1fd0354bcebd610b27334d1fee
Source dataset
uspto-grants-2003_07
Patent number
US06596445B1

Reaction notes

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