Potassium Carbonate → Methyl 3-[imino(methyl)oxo-lambda6-sulfanyl]benzoate

HRID 607439Notes

Reaction equation

HRID 607439 reaction equation
[CH3:1][S:2]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=1)[C:7]([O:9][CH3:10])=[O:8])=[O:3].FC(F)(F)C([NH2:18])=O.[O-2].[Mg+2].C(O)(=O)C.C(O)(=O)C.IC1C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>ClCCl.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[CH3:1][S:2]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=1)[C:7]([O:9][CH3:10])=[O:8])(=[NH:18])=[O:3]

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 67717TrifluoroacetamideHCID 6850729Magnesium monoxideHCID 12217721Iodo benzene diacetateHCID 57657958Methyl 3-(methylsulfinyl)benzoate

Product 1

HCID 57657957Methyl 3-[imino(methyl)oxo-lambda6-sulfanyl]benzoateYield 74.2%

Reagents, catalysts & solvents 2

HCID 152122Dirhodium tetraacetateCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of methyl 3-(methylsulfinyl)benzoate (3.23 g, 16.3 mmol), 2,2,2-trifluoroacetamide (3.69 g, 32.6 mmol), magnesium oxide (1.97 g, 48.9 mmol), rhodium(II) acetate dimer (0.18 g, 0.408 mmol), and iodobenzene diacetate (7.88 g, 24.5 mmol) in 150 ml dichloromethane was stirred at room temperature. After 16 hours, the mixture was filtered past filter agent (Celite), rinsed with chloroform, and rotary evaporated. The sample was dissolved in EtOAc, washed with brine/dilute HCl, brine, dried with anhydrous Na2SO4 and rotary evaporated. The yellow-orange oil was dissolved in 60 ml MeOH, K2CO3 (6.76 g, 48.9 mmol) added, and the mixture stirred at room temperature for 12 minutes. The MeOH filtrate was decanted from the solids, which were then rinsed with MeOH and EtOAc. The pH of the combined organic filtrates were adjusted to pH 2 using 4% HCl, then the aqueous layer diluted by adding H2O. The aqueous layer was washed with 30% EtOAc in hexane, then the pH adjusted to pH 9 with saturated Na2CO3. The aqueous layer was extracted with CHCl3, the combined CHCl3 layers washed with brine, dried with anhydrous Na2SO4 and rotary evaporated to give the title compound as a light tan solid (2.58 g, 74%).

Workup

  1. filtrationthe mixture was filtered
  2. filtrationpast filter agent (Celite)
  3. washrinsed with chloroform, and rotary evaporated
  4. dissolutionThe sample was dissolved in EtOAc
  5. washwashed with brine/dilute HCl, brine
  6. dry with materialdried with anhydrous Na2SO4 and rotary evaporated
  7. dissolutionThe yellow-orange oil was dissolved in 60 ml MeOH
  8. customThe MeOH filtrate was decanted from the solids, which
  9. washwere then rinsed with MeOH and EtOAc
  10. additionthe aqueous layer diluted
  11. additionby adding H2O
  12. washThe aqueous layer was washed with 30% EtOAc in hexane
  13. extractionThe aqueous layer was extracted with CHCl3
  14. washthe combined CHCl3 layers washed with brine
  15. dry with materialdried with anhydrous Na2SO4
  16. customrotary evaporated

Sources & evidence

ORD record
ord-6bb5605bd8fd4275bda37cc72a772ca4
Source dataset
uspto-grants-2011_03
Patent number
US07915443B2

Reaction notes

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