Ab initio study of the mechanism of the formation of p-rosolic acid from trifluoromethoxybenzene under HF/Lewis acid conditions |
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Authors: | Randolph K Belter Cheri A McFerrin |
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Institution: | a Y-Not Chemical Consulting, Zachary, LA 70791, USA b Dept. of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA |
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Abstract: | The mechanism of the formation of p-rosolic acid from trifluoromethoxybenzene under HF/Lewis acid conditions was studied using ab initio methods. A series of cationic intermediates is initiated by the expulsion of a fluorine atom of trifluoromethoxybenzene with anomeric assistance of the trifluoromethoxy oxygen. The resulting difluorocarbonium ion is attacked by a second trifluoromethoxybenzene to generate the first carbon-carbon bond on what will be the central carbon of p-rosolic acid. Elimination of phenol results in the formation of cationic intermediate 4 which is susceptible to carbon-alkylation by the same phenol to form the second carbon-carbon bond. Attack on subsequent difluorocarbonium ions by trifluoromethoxybenzene strips trifluoromethyl groups from the downstream intermediates, eventually leading to p-rosolic acid, and continues the generation of 4, each of which initiate a fresh mechanistic series toward another p-rosolic acid molecule. |
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Keywords: | Trifluoromethoxy benzene p-Rosolic acid Fries rearrangement Lewis acid catalysis Friedel-Crafts |
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