Cesium carbonate-promoted synthesis of aryl methyl sulfides using S-methylisothiourea sulfate under transition-metal-free conditions

Abstract

In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the substitute for malodorous methanethiol. The gram-scale reaction also proceeds smoothly without the use of column chromatography separation. Similarly, 2-(dimethylamino)ethylthio and cyclopropylmethylthio groups can be easily introduced into the aromatic rings from the corresponding S-[2-(dimethylamino)ethyl]isothiourea dihydrochloride and S-cyclopropylmethylisothiourea hydrobromide. The possible reaction mechanism is proposed. It is believed that this route to aryl alkyl sulfides is well competitive with currently known methods due to its wide substrate scope, excellent yields, easy operation and transition-metal-free conditions.