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38.11.1 A History of Geminal Bisperoxide Synthesis

DOI: 10.1055/sos-SD-138-00067

Vil, V. A.; Bityukov, O. V.; Terentev, A. O.Science of Synthesis Knowledge Updates, (20193385.

By the middle of the 20th century, organic peroxides were already well known to the chemical community. By that time, such important classes of organic peroxides as peracids, hydroperoxides, and diacyl peroxides had been prepared.[‌39‌] Although numerous cyclic di- and triperoxides were known, acyclic geminal bisperoxides and bishydroperoxides had not been isolated in their individual state, but only mentioned as unstable intermediates. Wittig and Pieper synthesized geminal bishydroperoxide 7 from fluoren-9-one for the first time in 1940 (Scheme 4).[‌53‌] Using elemental analysis and the cryoscopic method (evaluation of molecular weight), they were not able to correctly define the structure of the obtained compound; instead, they suggested the formation of oxonium salt 8. The true structure of the synthesized compound was established by Criegee and co-workers in 1949[‌54‌] based on results of additional reactions with lead(IV) acetate and benzoyl chloride. This gave them reason to believe that the compound obtained by Wittig and Pieper contained a hydroperoxy group. The values of molecular weight, melting point, and the content of active oxygen and hydrogen indicated that the prepared compound 7 was a mixture of two molecules of fluoren-9-one with one bishydroperoxide molecule.

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