Treatment of peroxycyclohexanecarboxylic acid with ferrous perchlorate in acetonitrile has been found to afford a 25% yield of cyclohexanol. Similar treatment of cis- or trans-3-hydroxyperoxycyclohexanecarboxylic acid yields largely cis-1,3-cyclohexanediol, revealing a directive effect for free radical oxidation by iron(III) analogous to that observed for the stereospecific cis-1,3 hydroxylation of cyclohexanol by ferrous ion-hydrogen peroxide. Preference for cis diol formation is also observed for w-4-hydroxyperoxycyclohexanecarboxylic acid, but the cis- and trans-1,2 isomers give a cis/trans diol ratio near unity. Analysis of the stereoisomeric mixture of 1,2-cyclohexanediols from the reaction of cyclohexene with ferrous ion-hydrogen peroxide leads to the conclusion that, in acetonitrile, the predominant mode of olefin hydroxylation does not proceed via addition of hydroxyl radical to the double bond.
All Science Journal Classification (ASJC) codes
- General Chemistry
- Colloid and Surface Chemistry