Reaction of quinaldine with 4,6-di(tert-butyl)-3-nitro-1,2-benzoquinone. Dependence of the outcome on the reaction conditions and a deeper insight into the mechanism
Tatyana A. Krasnikova,
Yurii A. Sayapin,
Inna O. Tupaeva,
Eugeny A. Gusakov,
Ilya V. Ozhogin,
Anton V. Lisovin,
Mikhail V. Nikogosov,
Oleg P. Demidov,
Duong Nghia Bang,
Tran Dai Lam,
Nguyen Thi Thu Trang,
Alexander D. Dubonosov,
Vladimir I. Minkin
Affiliations
Tatyana A. Krasnikova
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Yurii A. Sayapin
Federal Research Centre the Southern Scientific Centre of the Russian Academy of Sciences, Rostov on Don 344006, Russian Federation; Corresponding author.
Inna O. Tupaeva
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Eugeny A. Gusakov
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Ilya V. Ozhogin
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Anton V. Lisovin
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Mikhail V. Nikogosov
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Oleg P. Demidov
North Caucasus Federal University, Stavropol 355009, Russian Federation
Duong Nghia Bang
Office of the State Council for Professorship, Ministry of Education and Training, Hanoi, 10000, Viet Nam
Tran Dai Lam
Institute for Tropical Technology, Vietnam Academy of Science and Technology, Hanoi, 10000, Viet Nam
Nguyen Thi Thu Trang
Institute for Tropical Technology, Vietnam Academy of Science and Technology, Hanoi, 10000, Viet Nam; Corresponding author.
Alexander D. Dubonosov
Federal Research Centre the Southern Scientific Centre of the Russian Academy of Sciences, Rostov on Don 344006, Russian Federation
Vladimir I. Minkin
Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian Federation
Condensation of quinaldine with 4,6-di (tert-butyl)-3-nitro-1,2-benzoquinone results in the formation of 5,7-di (tert-butyl)-2-(quinoline-2-yl)-1,3-tropolone, 5,7-di (tert-butyl)-4-nitro-2-(quinoline-2-yl)-1,3-tropolone, 3,3-dimethyl-2-(5-hydroxy-4-nitro-3-tert-butyl-6-quinoline-2-yl-pyridine-2-yl)butanoic acid, 6-(2,2-dimethylprop-3-yl)-5-tert-butyl-4-nitro-2-(quinoline-2-yl)-pyridine-3-ol, 1,7-di (tert-butyl)-3-(quinoline-2-yl)-2-azabicyclo-[3.3.0]octa-2,7-diene-4,6-dione-N-oxide. The formation of 1,3-tropolone and pyridine-2-yl butanoic acid derivatives proceeds through a ring expansion and 2-azabicyclo [3.3.0]octa-2,7-diene-4,6-dione-N-oxide via the contraction of the o-quinone ring. The structure of the heterocyclic compounds obtained was justified by X-ray diffraction analysis, NMR spectroscopy, IR- and HRMS-spectrometry, and the proposed mechanisms of their formation include the participation of an intermediate product of the expansion reaction of the o-quinone cycle - 5,7-di (tert-butyl)-4-nitro-2-(quinoline-2-yl)-cyclohepta-1,3,5-triene-1,3-diol, which was first isolated preparatively. The DFT/B3LYP/6–311++G** methods were used to determine the thermodynamic stability of tautomeric forms of intermediate products, as well as the relative stability of NH and OH tautomers of 5,7-di (tert-butyl)-2-(quinolin-2-yl)-1,3-tropolone and 5,7-di (tert-butyl)-4-nitro-2-(quinolin-2-yl)-1,3-tropolone.
