Anthracene transannular peroxide

Although thiophene derivatives, e.g., tetraphenylthiophene XXI and XXII70 do not appear to form photoperoxides sulfurated 9,10-diphenyl-anthracenes XXIII and cerothiene XXIV derivatives have been reported to form transannular peroxides of the type A on irradiation in the presence of oxygen.209,210... 

Figure 4.61 Peroxide and hydroperoxide formation in photo-oxygenation reactions addition of molecular oxygen to anthracene to form the transannular peroxide, and insertion into an olefin...

Photolysis, in the presence of oxygen, of alkenes containing an ally lie hydrogen atom leads to the formation of hydroperoxides. The sensitized process is more efficient, and often yields photoproducts different in structure from those obtained by nonsensitized photooxidation. Cyclohexadiene and related dienes on photolysis in the presence of oxygen yield the transannular peroxides. Thus, on photosensitized oxidation, a-terpinene (410) is converted into ascaridole (411).435 The equivalent process is not, in general, observed in acyclic dienes. Certain polynuclear aromatic hydrocarbons, such as anthracene and naphthacene and including the heterocycles 5,10-diphenyl-1-... 

Transannular peroxides of anthracene and its derivatives, preparation, properties, applications of 90CLY582. 

Polycyclic aromatic hydrocarbons such as anthracenes, tetracenes, and pentacenes, as well as cyclopentadienes, cyclohexa-l,3-dienes, cyclo-hepta-l,3-dienes, and furans, have been found to be suitable diene systems to which the singlet oxygen adds as a dienophile in a 1,4-cycloaddition reaction. Thus, endoperoxides (transannular peroxides) and, in the case of furans, ozonides of the corresponding cyclobutadienes are the primarily produced, more or less stable addition products (2, 21, 22). 

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