Hydrochloric Acid → 5-Acetyl-2-(methylsulfanyl)phenyl acetate

HRID 514364Notes

Reaction equation

HRID 514364 reaction equation
[CH3:1][S:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[OH:9].[C:10](Cl)(=[O:12])[CH3:11].[Al+3].[Cl-].[Cl-].[Cl-].Cl.C(N([CH2:24][CH3:25])CC)C.[OH2:26]>C(=S)=S>[C:10]([O:9][C:4]1[CH:5]=[C:6]([C:24](=[O:26])[CH3:25])[CH:7]=[CH:8][C:3]=1[S:2][CH3:1])(=[O:12])[CH3:11]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 962WaterHCID 6367Acetyl chloride2×HCID 8471TriethylamineHCID 61261o-(Methylthio)phenolHCID 6451240Aluminum(III) Chloride

Product 1

HCID 139610745-Acetyl-2-(methylsulfanyl)phenyl acetateYield 37%

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Procedure

To a solution of 2-(methylsulfanyl)phenol (4.2 g, 30 mmol) in CS2 (50 mL) was added dropwise acetyl chloride (5.2 g, 66 mmol) at 0° C. for 10 min. The resulting mixture was stirred for 20 min at rt. Then AlCl3 (10.8 g, 81 mmol) was added, and the reaction mixture was heated under reflux conditions for 3 h. The reaction mixture was poured into ice water, conc. HCl (5 mL) was added, and the reaction mixture was extracted with CH2Cl2. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The residue was dissolved in CH2Cl2 (50 mL), cooled to 0° C. and treated successively with acetyl chloride (1.2 g, 15 mmol) and triethylamine (1.5 g, 15 mmol). The mixture was stirred at rt for 2 h and poured into water. After separation of the layers, the organic phase was washed successively with water, 3 N HCl and 10% aq. KHCO3, dried over Na2SO4, and evaporated to dryness. Recrystallization of the resulting solid from benzene-hexane afforded the title compound (2.5 g, 37%). 1H NMR (400 MHz, CDCl3): δ 2.08 (3H, s), 2.47 (3H, s), 2.55 (3H, s), 7.26 (1H, d, J=4.8 Hz), 7.57 (1H, d, J=4.8 Hz), 7.60 (1H, s).

Workup

  1. temperaturethe reaction mixture was heated under reflux conditions for 3 h
  2. additionwas added
  3. extractionthe reaction mixture was extracted with CH2Cl2
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. dissolutionThe residue was dissolved in CH2Cl2 (50 mL)
  8. temperaturecooled to 0° C.
  9. stirringThe mixture was stirred at rt for 2 h
  10. customAfter separation of the layers
  11. washthe organic phase was washed successively with water, 3 N HCl and 10% aq. KHCO3
  12. dry with materialdried over Na2SO4
  13. customevaporated to dryness
  14. customRecrystallization of the resulting solid from benzene-hexane

Sources & evidence

ORD record
ord-06ba3ee69237433eb2f794169a7ad922
Source dataset
uspto-grants-2015_08
Patent number
US09107916B2

Reaction notes

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