Dimethyl Sulfoxide → 2-[(Methylsulfanyl)methyl]aniline

HRID 483276Notes

Reaction equation

HRID 483276 reaction equation
[CH3:1][S:2]([CH3:4])=O.S(=O)(=O)(O)O.[C:10]1([N:16]=C=O)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[OH-].[Na+]>C(O)(=O)C>[NH2:16][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[CH3:1][S:2][CH2:4][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=1[NH2:16]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 1118Sulfuric AcidHCID 7672Phenyl isocyanateHCID 14798Sodium Hydroxide

Product 2

HCID 6115AnilineYield 22.4%HCID 123574872-[(Methylsulfanyl)methyl]anilineYield 55.8%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 7.60 g (0.0974 moles) of dry dimethyl sulfoxide in 70 ml of dry acetic acid at 0° C. and under a nitrogen atmosphere, was slowly added 9.76 g (0.0959 moles) of 100% sulfuric acid. The temperature rose to 15° C. The ice bath was removed and 9.9843 g (0.0838 moles) of phenyl isocyanate was added dropwise. An immediate evolution of gas began, which subsided after approximately fifteen minutes. After thirty minutes at room temperature, the reaction mixture was warmed to 50° C. for an additional hour. The entire solution was then poured into 100 ml of 10% aqueous sodium hydroxide solution and this was extracted with methylene chloride. The organic layer was dried over anhydrous sodium carbonate and filtered. Due to the instability of this sulfilimine, 0.33 g of succnimide was added and the solution was then concentrated to 150 ml and refluxed for sixteen hours. The solution was then washed with 10% aqueous sodium hydroxide, dried over anhydrous magnesium sulfate and filtered. To this was added dodecane as an internal standard and the solution was analyzed by gas chromatography. In this manner, there was obtained 1.751 g (22.4%) of aniline and 7.166 g (55.8%) of 2-methylthiomethylaniline. Other examples of the preparation and rearrangement of unstable N-aryl-S,S-dimethylsulfilimines were performed and these results can be found in Table II.

Workup

  1. customat 0° C.
  2. customrose to 15° C
  3. customThe ice bath was removed
  4. waitwhich subsided after approximately fifteen minutes
  5. waitAfter thirty minutes at room temperature
  6. extractionthis was extracted with methylene chloride
  7. dry with materialThe organic layer was dried over anhydrous sodium carbonate
  8. filtrationfiltered
  9. additionDue to the instability of this sulfilimine, 0.33 g of succnimide was added
  10. concentrationthe solution was then concentrated to 150 ml
  11. temperaturerefluxed for sixteen hours
  12. washThe solution was then washed with 10% aqueous sodium hydroxide
  13. dry with materialdried over anhydrous magnesium sulfate
  14. filtrationfiltered
  15. additionTo this was added dodecane as an internal standard

Sources & evidence

ORD record
ord-b1a5d3c108214d048262cf5bec3f9c9d
Source dataset
uspto-grants-1986_03
Patent number
US04578514

Reaction notes

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