SYNTHESIS OF MESOCYCLIC AND MACROCYCLIC THIACROWN ETHERS CONTAINING -SCH2SCH2S- UNITS USING THIO(BISCHLOROMETHANE)

Oxidative cleavage of 1,3,5-trithiane 1 by thionyl chloride is promoted by a catalytic quantity of a Lewis acid like zinc bromide or aluminum chloride and results in the formation of pure thiobis(chloromethane) (2). This reagent has been successfully employed in the straight-forward synthesis of a novel series of thiacrown ethers possessing methylene bridges between the heteroatoms. These molecules have chemical and physical properties that differ considerably in their solubilities from those of their ethylenic or propylenic counterparts