The Reactions of <i>cis, trans, trans</i>-1, 5, 9-Cyclododecatriene. IV. Selective Reactions with <i>cis</i>-Addition Reagents

Abstract

Abstract The addition reactions of cis, trans, trans-1, 5, 9-cyclododecatriene with cis-addition reagents, such as osmium tetroxide, potassium permanganate, diimide, and nitrosyl chloride, have been investigated. It has been shown that the first attack of each reagent preferentially takes place at one of the trans double bonds. The reactions with osmium tetroxide and potassium permanganate at room temperature afforded cis-5, trans-9-cyclododecadiene-trans-1, 2-diol in 89 and 59% yields respectively. The glycol was then further oxidized with osmium tetroxide into cis-y-9-cyclo-dodecene-1, 2, 5, 6-tetrol in a 60% yield. The reduction of the cyclotriene with diimide, generated in situ by the oxidation of hydrazine, afforded cis-cyclododecene in 60—82% yields. The addition of nitrosyl chloride in the presence of hydrochloric acid afforded 2-chlorocyclodode-cadienone oxime in a quantitative yield; this was then reduced into cyclododecanone oxime, obtained in a quantitative yield, by catalytic reduction with palladium-charcoal.