ACID-CATALYZED SOLVOLYSIS OF POLYENOL ETHERS .3. EFFECT OF THE ALKOXYMOIETY

The dependence of the solvolysis of polyenol ethers on the nature of t he alkoxy moiety has been studied. A new reaction path, leading to the formation of omega-hydroxy (methoxy) substituted aldehydes and -ester s, was established. The proposed reaction pathway (scheme 6) is initia ted by an electron transfer from the polyenol ether to molecular oxyge n, followed by combination of the two radicals to a peroxide zwitterio n. Upon protonation, solvent adds to the omega-carbon atom of the poly ene to give an intermediate that can either loose water to form an est er, or loose the alkoxy moiety to give an aldehyde. This mechanism is believed to be involved in the strong mutagenic activity displayed by many polyenol ethers, including the natural mutagen fecapentaene-12.