Thiophenol → Benzo(b)thiophene-2,3-dione

HRID 2064765Notes

Reaction equation

HRID 2064765 reaction equation
[C:1](Cl)(=[O:5])[C:2](Cl)=[O:3].[C:7]1([SH:13])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[Cl-].[Al+3].[Cl-].[Cl-]>CCOCC>[S:13]1[C:2](=[O:3])[C:1](=[O:5])[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]1=2

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 65578Oxalyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 97303Benzo(b)thiophene-2,3-dione

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of oxalyl chloride (73.1 mmol) in ether (14 mL) is added to a solution of thiophenol (45.4 mmol) in ether (20 mL). The mixture is heated to reflux for 90 min, cooled to RT and concentrated in vacuo. The residue is dissolved in DCM (85 mL), cooled to 0° C. and treated portionwise with aluminum chloride (54.5 mmol). The mixture is heated to reflux for 30 min, cooled to RT and poured with stirring into ice-water. The layers are separated and the organic layer is washed with aqueous NaHCO3 solution, water and brine. After drying over MgSO4 the solvents are removed in vacuo and the residue is purified by flash chromatography (gradient: EtOAc/heptane 1/9 to 1/1) to give the desired product. 1H-NMR (CDCl3): δ=7.37 (t, J=7.62 Hz, 1H); 7.42 (d, J=7.62 Hz, 1H); 7.68 (t, J=7.62 Hz, 1H); 7.82 (d, J=7.62 Hz, 1H).

Workup

  1. temperatureThe mixture is heated
  2. temperatureto reflux for 90 min
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue is dissolved in DCM (85 mL)
  5. temperaturecooled to 0° C.
  6. temperatureThe mixture is heated
  7. temperatureto reflux for 30 min
  8. temperaturecooled to RT
  9. additionpoured
  10. customThe layers are separated
  11. washthe organic layer is washed with aqueous NaHCO3 solution, water and brine
  12. dry with materialAfter drying over MgSO4 the solvents
  13. customare removed in vacuo
  14. customthe residue is purified by flash chromatography (gradient: EtOAc/heptane 1/9 to 1/1)

Sources & evidence

ORD record
ord-6045f759553547fca28dae2c3b126cc1
Source dataset
uspto-grants-2012_10
Patent number
US08288435B2

Reaction notes

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