Carbon-oxygen alkyl ether fragmentation in the radical anions of phenyl and nitrophenyl methyl ethers. An AM1 study

Alkyl ether fragmentations of radical anions of several phenyl and nitrophenyl methyl ethers have been theoretically studied by means of the AM1 semiempirical method. The cleavage occurs through a π*-σ* intramolecular electron transfer process, that is made possible by the lengthening of the C-O alkyl ether bond. The C-O scission is slowed down by the introduction of substituents that increase the σ*-π* energy gap.