ChemInform Abstract: Reversible Friedel—Crafts Acylations of Phenanthrene: Rearrangements of Acetylphenanthrenes.

Abstract

Phenanthrene derivatives Q 1090Reversible Friedel-Crafts Acylations of Phenanthrene: Rearrangements of Acetylphenanthrenes. -Studies on Friedel-Crafts acetylation of phenanthrene, along with rearrangements and deacetylations of acetylphenanthrene isomers, indicate its reversibility. In accordance with experimental data, PM3 calculations predict that 9-acetylphenanthrene is the kinetically controlled and 2-and 3-acetylphenanthrene are thermodynamically controlled products. -(LEVY, L.; POGODIN, S.; COHEN, S.; AGRANAT*, I.; Lett.

Polycyclic Aromatic Ketones – A Crystallographic and Theoretical Study of Acetyl Anthracenes

“…The Haworth synthesis of PAHs, which previously had allowed access to angularly annelated PAHs could thus be applied to the synthesis of linearly annelated PAHs [Agranat & Shih, 1974b]. Further experimental evidence in support of true reversibility of Friedel-Crafts acylation is limited [Frangopol et al, 1964;Balaban, 1966;Nenitzescu & Balaban, 1964;Effenberger et al, 1973;Levy et al, 2007;Mala'bi et al,. 2009;Titinchi et al, 2008;Adams et al, 1998;Okamoto & Yonezawa, 2009].…”

“…Notable cases are the report by Balaban [Frangopol et al, 1964;Balaban, 1966;Nenitzescu & Balaban, 1964] on the reversibility of Friedel-Crafts acetylation of olefins to -chloroketones, the report by Effenberger [Effenberger et al, 1973] of the retro-Fries rearrangement of phenyl benzoates (CF 3 SO 3 H, 170 °C) and the reversible ArS E aroylation of naphthalene derivatives [Okamoto & Yonezawa, 2009]. Additional examples are the acyl rearrangements of acetylphenanthrenes [Levy et al, 2007] and acetylanthracenes [Mala'bi et al, 2009] in PPA, the acetylation of fluorene [Titinchi et al, 2008], the disproportionation of 9-acetylanthracene into 1,5-and 1,8-diacetylanthracenes in an ionic liquid systems [Adams et al, 1998]. Complete reversibility of Friedel-Crafts acylation was established in the intramolecular para ortho acyl rearrangements of fluorofluorenones in PPA (Fig.…”

“…2) [Agranat et al, 1977]. Friedel-Crafts acyl rearrangement of polycyclic aromatic ketones (PAKs) has been referred to as the Agranat-Gore rearrangement [Levy et al, 2007;Mala'bi et al, 2009]. The Friedel-Crafts acylation can be adjusted to give a kinetically controlled ketone or a thermodynamically controlled ketone [Buehler & Pearson, 1970].…”