Hydrochloric Acid → Methyl 4-(2-(2-(acetylthio)-4-methoxyphenyl)-2-oxoethyl)benzoate

HRID 410035Notes

Reaction equation

HRID 410035 reaction equation
[Cl-].[Cl-].[Cl-].[Al+3].[C:5](=[O:16])([S:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH3:15])[CH:9]=1)[CH3:6].Cl[C:18](=[O:30])[CH2:19][C:20]1[CH:29]=[CH:28][C:23]([C:24]([O:26][CH3:27])=[O:25])=[CH:22][CH:21]=1.Cl>C(Cl)Cl>[C:5]([S:7][C:8]1[CH:9]=[C:10]([O:14][CH3:15])[CH:11]=[CH:12][C:13]=1[C:18](=[O:30])[CH2:19][C:20]1[CH:21]=[CH:22][C:23]([C:24]([O:26][CH3:27])=[O:25])=[CH:28][CH:29]=1)(=[O:16])[CH3:6]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 539677S-(3-Methoxyphenyl) ethanethioateHCID 6451240Aluminum(III) ChlorideHCID 19746402Methyl 4-(2-chloro-2-oxoethyl)benzoate

Product 1

HCID 86673619Methyl 4-(2-(2-(acetylthio)-4-methoxyphenyl)-2-oxoethyl)benzoateYield 20.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a suspension of aluminum trichloride (9.9 g, 74.08 mmol) in DCM (100 ml) was added S-3-methoxyphenyl ethanethioate (step 1) (4.5 g, 30.57 mmol) at 0-5° C., followed by a solution of methyl 4-(2-chloro-2-oxoethyl)benzoate (step 2) (4.5 g, crude, 24.69 mmol) in DCM (20 ml). The mixture was stirred at room temperature for 3 days. The mixture was poured carefully into icy 1 N HCl (200 ml) and extracted with EtOAc (50 ml×2). The combined organic layers were washed with water (100 ml×2) and brine (100 ml), dried with anhydrous sodium sulfate, filtered and concentrated. The residue was purified by column chromatography (PE/EtOAc=15/1 to 10/1) to afford Intermediate F as a yellow solid (1.8 g, 14%). MS (ESI): m/z 359.0 [M+1]+.

Workup

  1. extractionextracted with EtOAc (50 ml×2)
  2. washThe combined organic layers were washed with water (100 ml×2) and brine (100 ml)
  3. dry with materialdried with anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (PE/EtOAc=15/1 to 10/1)

Sources & evidence

ORD record
ord-1dfd2c14db4144f5b6a05b3ed6c9b01c
Source dataset
uspto-grants-2014_06
Patent number
US08759548B2

Reaction notes

Loading…