An efficient protocol for the addition reaction of thiols to vinyl ethers has been developed under solvent- and catalyst-free conditions. The influence factors of the structure of thiol and vinyl ether, temperature, molar ratio were investigated. The regioselectivity of the addition reaction can be controlled by the molar ratio of material so that both the anti-Markovnikov (1∶1.2) and the Markovnikov products (1∶8) are now easily accessible in excellent selectivities. The work synthesized 18 kinds of alkyl oxy thioether compounds, including 12 anti-Markovnikov adducts and 6 Markovnikov adducts. The reaction process to avoid the use of any organic solvents, excess vinyl ether recovered by vacuum distillation and can be recycled. It was a green method for synthesizing alkyloxy thioether which was simple and typical, possess the potential industrial application.

Key words: thiol, alkyloxy thioether, solvent-free, catalyst-free, selective control