<i>cis</i>-5-Cyclooctene-1,2-dione and its Ethylene Ketals

Abstract

Oxidation of cis-cis-1,5-cyclooctadiene with hydrogen peroxide gives cis-5-cyclooctene-trans-1,2-diol (3) which is converted to cis-5-cyclooctene-1,2-dione (6) on treatment with dimethyl sulfoxide and acetic anhydride. Bromination of 6 is accompanied by transannular bonding to give a dibromo keto ether 9a or b. Ketalization of 6 with ethylene glycol gives a monoketal 11 and two diketals 12 and 13 with 1,3-dioxolane and 1,4-dioxane rings, respectively. Bromination of 12 with bromine or pyridinium perbromide is accompanied by transannular bonding and fission of one of the 1,3-dioxolane rings to give a dibromo monoketal ether 15a (or b). Bromination of 12 with N-bromosuccinimide followed by dehydrobromination gives a cyclooctadiene-1,2-dione diketal 20a (or b).