Addition of Methanesulfenyl Chloride and Sulfur Chloride to 1,4-Dimethyl-3,6-dimethylene-2,5-piperazinedione and Substitution of the Adducts

Abstract

Abstract Addition of methanesulfenyl chloride or sulfur chloride to 3,6-dimethylene-(1a) and 3,6-dibenzylidene-1,4-dimethyl-2,5-piperazinediones (1b) gave the Markownikoff products. The addition of methanesulfenyl chloride to 1a proceeded stepwise within 1 hr, and gave a mixture of (Z,Z)-, (Z,E)-, and (E,E)-isomers of the corresponding 3,6-bis(methylthiomethylene) derivative, accompanied by gradual elimination of hydrogen chloride. 3,6-Di-chloro groups of the adduct were substituted with water, ethanethiol and ethanol to give the corresponding hydroxy, ethylthio, and ethoxy derivatives, respectively. A similar substitution with ethanedithiol and hydrogen sulfide followed by aeration gave 7,9-dimethyl-1,6-bis(methylthiomethyl)-8,10-dioxo-2,5-dithia-7,9-diazabicyclo[4,2,2]-decane and the corresponding 3,6-epitetrathio derivative, respectively. The same mode of reaction of sulfur chloride with 1a and 1b gave a few 1,6-disubstituted-7,9-dimethyl-8,10-dioxo-3,4-dithia-7,9-diazabicyclo[4,2,2]-decanes. Mass fragmentations of new compounds were also described.