Stable gem-trifluoromethyl anionic σ-complexes based on 1,3,5-tris(sulfonyl)benzene derivatives and their transformations |
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Authors: | Oksana M Holovko-Kamoshenkova Vladimir N Boiko Yurii L Yagupolskii |
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Institution: | a Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya Str. 5, UA-02094 Kiev, Ukraine b Fakultät für Chemie der Universität, Postfach 10 01 31, 33501 Bielefeld, Germany |
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Abstract: | A convenient synthetic procedures is described to obtain gem-trifluoromethyl anionic σ-complexes of 1,3,5-tris(fluorosulfonyl)benzene, 1,3,5-tris(β,β,β-trifluoroethoxysulfonyl)benzene, 1,3,5-tris(trifluoromethylsulfonyl)benzene as well as of 1,3,5-trinotrobenzene. Conditions for easy oxidation of these adducts into corresponding 2,4,6-tris(substituted)benzotrifluorides have been found. It is shown that the latter add trifluoromethyl anion to the 1 and 3 positions of the aromatic ring forming new anionic σ-complexes in different ratio. Structures and relative stabilities of the anionic adducts are discussed based on RI-MP2 quantum chemical calculations. |
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Keywords: | Anionic σ-complexes Trifluoromethylation Oxidation Quantum chemical investigation |
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