CHEMISTRY OF SINGLET OXYGEN. PART 44: MECHANISM OF PHOTOOXIDATION OF 2,5-DIMETHYLHEXA-2,4-DIENE AND 2-METHYL-2-PENTENE.

Article abstract of DOI:10.1021/ja00352a032

Solvent and temperature effects on the singlet oxygen oxidations of 2,6-dimethyl-2,4-hexadiene (DMHD) and 2-methyl-2-pentene (2M2P) are studied. It is concluded that the initial interaction between 2M2P and **1O//2 (which gives only ene products) and that between DMHD and **1O//2 (which gives ene products, dioxetane, and nonreactive quenching) are identical. It is also suggested that the quenching path for DMHD could involve formation of an intermediate zwitterion or 1,4-biradical, which undergoes intersystem crossing and decays to ground-state oxygen and DMHD.