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

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence