The Preparation of Olefins by the Pyrolysis of Xanthates. The Chugaev Reaction

Nace, Harold R.


In this chapter the Chugaev reaction is defined as the thermal decomposition of the xanthate ester of an alcohol that contains at least one beta-hydrogen atom to produce one or more olefins, carbon oxysulfide and a mercaptan. The formation of olefins by the pyrolysis of xanthates was discovered in 1899 by Chugaev in connection with his studies on the optical properties of xanthates and other compounds. He subsequently employed the reaction in his investigation of terpenes and demonstrated both its utility as an olefin-forming reaction and its usefulness in structural determination. The reaction, which is particularly valuable for the conversion of sensitive alcohols to the corresponding olefins without the rearrangement of the carbon skeleton is analogous to the thermal decomposition of carboxylic esters of alcohols and other derivatives such as carbamates and carbonates, to yield olefins.