Dimethyl Sulfoxide → 2-Methoxy-6-[(methylsulfanyl)methyl]aniline

HRID 483277Notes

Reaction equation

HRID 483277 reaction equation
[CH3:1][S:2]([CH3:4])=O.C(S(O)(=O)=O)CCC.[CH3:13][O:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[N:21]=C=O>C(Cl)(Cl)Cl>[CH3:13][O:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[NH2:21].[CH3:13][O:14][C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH2:1][S:2][CH3:4])[C:16]=1[NH2:21]

Participants

6

Reactant 3

HCID 679Dimethyl SulfoxideHCID 499351-Butanesulfonic acidHCID 69695Benzene, 1-isocyanato-2-methoxy-

Product 2

HCID 70002-MethoxyanilineYield 22.4%HCID 123574922-Methoxy-6-[(methylsulfanyl)methyl]anilineYield 67.6%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 1.429 g (0.018 moles) of dry dimethyl sulfoxide and 2.27 g (0.015 moles) of dry n-butanesulfonic acid in 13 ml of dry chloroform, was added 2.2110 g (0.0148 moles) of o-methoxyphenyl isocyanate. After thirty minutes at room temperature, the reaction mixture was refluxed for three and a half hours. After cooling to room temperature, the reaction mixture was poured into 180 ml of ice-cold 10% aqueous sodium hydroxide solution. After extracting with methylene chloride, the organic layer was dried over anhydrous sodium carbonate, filtered and 0.10 g of succinimide was added. The resulting solution was concentrated to 100 ml and then refluxed for twenty hours. This solution was cooled, extracted with 10% aqueous sodium hydroxide solution and the organic layer dried over anhydrous magnesium sulfate and filtered. At this point, tridecane was added as an internal standard and the solution was analyzed by gas chromatography. In this manner, there was obtained 0.338 g (22.4%) of o-methoxyaniline and 1.8319 g (67.6%) of 2 -methoxy-6-(methylthiomethyl)aniline. The results are included in Table II.

Workup

  1. waitAfter thirty minutes at room temperature
  2. temperaturethe reaction mixture was refluxed for three and a half hours
  3. extractionAfter extracting with methylene chloride
  4. dry with materialthe organic layer was dried over anhydrous sodium carbonate
  5. filtrationfiltered
  6. addition0.10 g of succinimide was added
  7. concentrationThe resulting solution was concentrated to 100 ml
  8. temperaturerefluxed for twenty hours
  9. temperatureThis solution was cooled
  10. extractionextracted with 10% aqueous sodium hydroxide solution
  11. dry with materialthe organic layer dried over anhydrous magnesium sulfate
  12. filtrationfiltered
  13. additionAt this point, tridecane was added as an internal standard

Sources & evidence

ORD record
ord-5566842dd11441b3a1c62a255d521972
Source dataset
uspto-grants-1986_03
Patent number
US04578514

Reaction notes

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