Oxidation and Reduction Reactions of cis-9,10,11-Trithiabicyclo[6.3.0]undecane Synthesized by Reaction of cis-Cyclooctene with S₈O

Abstract

cis-Cyclooctene reacted with S ₈ O in refluxing carbon disulfide to give cis-9,10,11-trithiabicyclo[6.3.0]undecane (1,2,3-trithiolane). Oxidation of the 1,2,3-trithiolane with m-chloroperbenzoic acid (MCPBA) or dimethyldioxirane (DMD) yielded the corresponding 1-exo-oxide, 1-endo-oxide, 2-endo-oxide, 2-exo-oxide, 1-endo,3-exo-dioxide, 1-exo,3-exo-dioxide, 1,1,3-exo-trioxide, and 1,1,3,3-tetraoxide, depending on the amount of the oxidants. Formation of another 1,3-dioxide assignable to the 1-endo,3-endo-dioxide was observed in the oxidation of the 1-endo-oxide with MCPBA. Oxidation of the 2-exo-oxide with DMD gave the 1,1,3,3-tetraoxide in low yield. Reduction of the 1,2,3-trithiolane and its trans isomer with LiAlH ₄ gave cis- and trans-cyclooctane-1,2-dithiol, respectively, in high yields. Oxidation of the sodium salt of the cis-1,2-dithiol with MCPBA provided the corresponding 1,2,5,6-tetrathiocane in low yield as the only identifiable product.

Keywords:

• Cyclooctene
• 1,2-dithiol
• oxidation
• reduction
• sulfuration
• 1,2,3-trithiolane

Dedicated to Professor Marian Mikołajczyk, CBMiM PAN in Łódź, Poland, on the occasion of his 70th birthday.