Periodic acid, a novel oxidant of polycyclic, aromatic hydrocarbons

Abstract

Ce rtain polycyc li c , aro mat ic hydrocarbons can be ox idi zed with periodi c acid in aprotic so lvent s co nta inin g a s mall p roportion of water. A uniqu e, two· fold cha rac te r of respo nse to pe riodi c acid by these hydroca rbon s has been fo und: (1) prod uc ti on of a co uplin g reac tion throu gh a radi ca l in te rme diate [co nve rsion of pyre ne into l,l ' -b ipyrene, and fluore ne into 1,2-b is(2,2' -biph e ny lylene)ethy le neJ or (2) co nvers io n into qui no nes by a two-equiv alent ox id ation mec hani s m that does not involve a radical int erm edi a te [ace naphth e ne, anthracene, a nthrone , be nz[alanthrace ne, naphthace ne, naphthalen e, a nd ph e nanthre ne]. Little or no reac ti on was observed whe n ox idati on was attempted wi th sodium me taperiodate in s tead of pe riodi c ac id .Electron-s pin reso nan ce revea led no radi cal inte rmediate in th e ox id a ti on of malonic ac id with e ither periodic acid o r sodium periodate.Key Word s: Aproti c so lvents ; aromatic hydroca rbon s; maloni c acid ; periodic acid ; pyrene radical; quinon es; reacti on mecha ni s m; sodium metape ri oda te.

Biasing Divergent Polycyclic Aromatic Hydrocarbon Oxidation Pathway by Solvent-Free Mechanochemistry

“…It is noteworthy to point out that LAG with AcOH (0.076 μL/mg) (Table , entry 11) gave similar result as LAG with EtOH (Table , entry 10). When the solution reaction between 1 and 2 was run in AcOH, Fatiadi observed an exclusive formation of 1,1′-bipyrene, where they detected the involvement of the pyrene radical, followed by oxygen-induced (oxygen generated in situ from H 5 IO 6 ) radical coupling . To rule out a radical pathway, the ball-mill reaction was repeated under a N 2 atmosphere.…”