Stable gem-trifluoromethyl anionic sigma-complexes based on 1,3,5-tris(sulfonyl)benzene derivatives and their transformations

作者：Holovko Kamoshenkova Oksana M; Kirij Nataliia V^*; Boiko Vladimir N; Rozhenko Alexander B; Yagupolskii Yurii L

来源：Journal of Fluorine Chemistry, 2010, 131(12): 1344-1352.

DOI：10.1016/j.jfluchem.2010.09.005

• Anionic sigma-complexes
• Trifluoromethylation
• Oxidation
• Quantum chemical investigation

A convenient synthetic procedures is described to obtain gem-trifluoromethyl anionic a-complexes of 1,3,5-tris(fluorosulfonyl)benzene, 1,3,5-tris(beta,beta,beta-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 sigma-complexes in different ratio. Structures and relative stabilities of the anionic adducts are discussed based on RI-MP2 quantum chemical calculations.

• 出版日期2010-12