N-methyl-2-pyrrolidone → Methyl 3-iodo-2-(1,1-dimethyl-2-methylsulfinylethylaminocarbonyl)-benzoate

HRID 1828368Notes

Reaction equation

HRID 1828368 reaction equation
[I:1]N1C(C)(C)C(=O)N(I)C1=O.[CH3:12][C:13]([NH:19][C:20]([C:22]1[CH:31]=[CH:30][CH:29]=[CH:28][C:23]=1[C:24]([O:26][CH3:27])=[O:25])=[O:21])([CH3:18])[CH2:14][S:15]([CH3:17])=[O:16].CN1CCCC1=O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[I:1][C:31]1[C:22]([C:20]([NH:19][C:13]([CH3:12])([CH3:18])[CH2:14][S:15]([CH3:17])=[O:16])=[O:21])=[C:23]([CH:28]=[CH:29][CH:30]=1)[C:24]([O:26][CH3:27])=[O:25]

Participants

6

Reactant 3

HCID 13387N-methyl-2-pyrrolidoneHCID 2005341,3-Diiodo-5,5-dimethylimidazolidine-2,4-dioneHCID 69343931Methyl 2-(1,1-dimethyl-2-methylsulfinylethylaminocarbonyl)benzoate

Product 1

HCID 12010603Methyl 3-iodo-2-(1,1-dimethyl-2-methylsulfinylethylaminocarbonyl)-benzoateYield 137.3%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

Into the same reactor as in Example 1 were charged 1.5 mg of palladium acetate, 0.83 g of 1,3-diiodo-5,5-dimethylhydantoin, 1.0 g of methyl 2-(1,1-dimethyl-2-methylsulfinylethylaminocarbonyl)benzoate and 5 ml of N-methylpyrrolidone. The mixture thus obtained was heated with stirring at 90° C. for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into water, and the objective product was extracted with ethyl acetate. The organic layer was washed successively with aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. By distilling off the solvent under reduced pressure, a crude product was obtained. Purification of the crude product by silica gel column chromatography (ethyl acetate/n-hexane=1/3) gave 1.27 g of methyl 3-iodo-2-(1,1-dimethyl-2-methylsulfinylethylaminocarbonyl)-benzoate (yield 89.1%, melting point 150.7–151.8° C.).

Workup

  1. customThe mixture thus obtained
  2. temperaturewas heated
  3. customAfter completion of the reaction
  4. temperaturethe reaction mixture was cooled to room temperature
  5. extractionthe objective product was extracted with ethyl acetate
  6. washThe organic layer was washed successively with aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationBy distilling off the solvent under reduced pressure
  9. customa crude product was obtained
  10. customPurification of the crude product by silica gel column chromatography (ethyl acetate/n-hexane=1/3)

Sources & evidence

ORD record
ord-7f8e1646f0e34531846a954fcc0b286f
Source dataset
uspto-grants-2006_06
Patent number
US07057067B2

Reaction notes

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