Kinetic control wins out over thermodynamic control in Friedel-Crafts acyl rearrangements |
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| Authors: | Tahani Mala&rsquo biSergey Pogodin,Israel Agranat |
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| Affiliation: | Organic Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Philadelphia Bldg, #201/205, Edmond J. Safra Campus, Jerusalem 91904, Israel |
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| Abstract: | 1,5-, 1,8- and 9,10-diacetylanthracenes undergo Friedel-Crafts acyl rearrangements in polyphosphoric acid at 130-150 °C to give 3-methylbenz[de]anthracen-1-one via the kinetically-controlled 1,9-diacetylanthracene. The rearrangement mechanism is supported by DFT calculations of diacetylanthracenes, their σ-complexes, O-protonates, and O,O-diprotonates. The importance of kinetic control versus thermodynamic control in Friedel-Crafts acyl rearrangements is highlighted. Certain features of reversibility are also suggested. |
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| Keywords: | Diacetylanthracenes Polyphosphoric acid Reversibility Rearrangement mechanism DFT calculations |
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