Ethoxalyl chloride → Ethyl [4-(cyclopropylsulfanyl)phenyl](oxo)acetate

HRID 546233Notes

Reaction equation

HRID 546233 reaction equation
[Cl-].[Cl-].[Cl-].[Al+3].[CH2:5]([O:7][C:8](=[O:12])[C:9](Cl)=[O:10])[CH3:6].[CH:13]1([S:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:15][CH2:14]1>C(Cl)Cl>[CH2:5]([O:7][C:8](=[O:12])[C:9]([C:20]1[CH:21]=[CH:22][C:17]([S:16][CH:13]2[CH2:15][CH2:14]2)=[CH:18][CH:19]=1)=[O:10])[CH3:6]

Participants

5

Reactant 3

HCID 20884Ethoxalyl chlorideHCID 123348Benzene, (cyclopropylthio)-HCID 6451240Aluminum(III) Chloride

Product 1

HCID 46856411Ethyl [4-(cyclopropylsulfanyl)phenyl](oxo)acetateYield 91.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

In a round bottom flask was placed methylene chloride (100 mL) and aluminum trichloride (9.87 g, 74.01 mmol) and it was cooled to 0° C. in an ice bath. To this was then added dropwise chloro-oxo-acetic acid ethyl ester (6.46 mL, 58.03 mmol) keeping the temperature of the solution below 5° C. and it was then stirred for 30 min at 0° C. After this time a solution of cyclopropylsulfanyl-benzene (8.00 g, 53.24 mmol) in methylene chloride (5 mL) was added dropwise while keeping the temperature of the solution below 5° C. The ice bath was then removed and the reaction allowed to warm up to 25° C. and stirred for 3 h. The reaction was then cooled back down to 0° C. in an ice bath and added dropwise ice water (20 mL) keeping the temperature of the solution below 20° C. It was then stirred for 15 min and then transferred to a separatory funnel and separated. The organic phase was then washed with water (2×25 mL), saturated aqueous sodium bicarbonate solution (2×25 mL) and water (25 mL) and then dried over magnesium sulfate, filtered and concentrated in vacuo to afford (4-cyclopropylsulfanyl-phenyl)-oxo-acetic acid ethyl ester (12.19 g, 91%) as a yellow oil and used without further purification.

Workup

  1. customIn a round bottom flask was placed
  2. customthe temperature of the solution below 5° C. and it
  3. customthe temperature of the solution below 5° C
  4. customThe ice bath was then removed
  5. temperatureto warm up to 25° C.
  6. stirringstirred for 3 h
  7. temperatureThe reaction was then cooled back down to 0° C. in an ice bath
  8. additionadded dropwise ice water (20 mL)
  9. customthe temperature of the solution below 20° C
  10. stirringIt was then stirred for 15 min
  11. customtransferred to a separatory funnel
  12. customseparated
  13. washThe organic phase was then washed with water (2×25 mL), saturated aqueous sodium bicarbonate solution (2×25 mL) and water (25 mL)
  14. dry with materialdried over magnesium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ac3e8c031ed944d0a80a38170c39ddc8
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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