Singlet oxygen cyclic hydrocarbons

One may well ask why the isomerization of alkenes discussed in the preceding section requires a sensitizer. Why cannot the same result be achieved by direct irradiation One reason is that a tt — tt singlet excited state (5,) produced by direct irradiation of an alkene or arene crosses over to the triplet state (Ij) inefficiently (compared to n —> it excitation of ketones). Also, the Si state leads to other reactions beside isomerization which, in the case of 1,2-diphenyl-ethene and other conjugated hydrocarbons, produce cyclic products. For example, cw-l,2-diphenylethene irradiated in the presence of oxygen gives phenanthrene by the sequence of Equation 28-8. The primary photoreaction is cyclization to a dihydrophenanthrene intermediate, 6, which, in the presence of oxygen, is converted to phenanthrene ... 

Aromatic hydrocarbons 50 and 51 react with oxygen under the influence of light to give cyclic peroxides. Oxygen in its singlet state serves as a dienophile. 

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