Abstract
A new method was developed for the synthesis of functionalized β-tropolones based on acid-catalyzed condensation of 2-methylquinoline derivatives with 3,5-di(tert-butyl)-1,2-benzoquinone and 4,6-di(tert-butyl)-3-nitro-1,2-benzoquinone (14). The mechanism of the multistep reaction giving rise to β-tropolones and their tautomerism were studied by quantum chemical methods (DFT B3LYP/6-31G**). The reaction of 2-methylquinoline derivatives containing the tertiary amino group at position 4 with quinone 14 is accompanied by the formation of derivatives of a new heterocyclic system, viz., 4,6-dioxo-2-azabicyclo[3.3.0]octa-2,7-diene N-oxide. The molecular and crystal structures of two 5,7-di(tert-butyl)-3-hydroxy-2-(quinolin-2-yl)tropolones and two dioxoazabicyclooctadiene N-oxides, as well as of the preparatively isolated intermediate of the first condensation step and of the by-product of the reaction were established by X-ray diffraction.
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Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1956–1977, November, 2006.
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Minkin, V.I., Aldoshin, S.M., Komissarov, V.N. et al. New method for the synthesis of β-tropolones: Structures of condensation products of o-quinones with 2-methylquinolines and the mechanism of their formation. Russ Chem Bull 55, 2032–2055 (2006). https://doi.org/10.1007/s11172-006-0547-x
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DOI: https://doi.org/10.1007/s11172-006-0547-x