Synchronous and zwitter-ion channels of (R)-5-methyl2-(1-methylethylidene)-cyclohexanone reaction with 4-phenyl-4H-1,2,4-triazoline-3,5-dione
- Autores: Bodrikov I.1, Kurskii Y.1, Chiyanov A.1, Subbotin A.1, Kuropatov V.2
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Afiliações:
- R.E. Alekseev Nizhny Novgorod State Technical University
- Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences
- Edição: Volume 59, Nº 12 (2023)
- Páginas: 1644-1652
- Seção: Articles
- URL: https://journals.rcsi.science/0514-7492/article/view/247264
- DOI: https://doi.org/10.31857/S0514749223120091
- EDN: https://elibrary.ru/OETCSM
- ID: 247264
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Resumo
The interaction of pulegone with enophil - 4-phenyl-4 H -1,2,4-triazoline-3,5-dione leads to the formation of two described earlier epimers: 1-[(1 R ,4 R )-4-methyl-1-(1-methylethenyl)-2-oxocyclohexyl]-4-phenyl-1,2,4-triazolidine-3,5-dione ( RR -isomer) and 1-[(1 S ,4 R )-4-methyl-1-(1-methylethenyl)-2-oxocyclohexyl]-4-phenyl-1,2,4-triazolidine-3,5-dione ( SR -isomer). Along with these epimers, we found another isomer - 1-{1-methyl-1-[(4 R )-4methyl-6-oxocyclohex-1-en-1-yl]ethyl}-4-phenyl-1,2,4-triazolidine-3,5-dione. Quantum chemical modeling has established that isomeric products of hydrogen substitution in pulegone by enophil are formed along three routes. In the SR -isomer formation route, the ene reaction proceeds consistently. The other two routes are implemented with the enophil approach from the R -side of the pulegon. These routes consist of two consecutive stages. At the first stage, an intermediate of the type of asymmetric cyclic aziridine cation is formed. Elimination of a proton from one of the geminal methyl groups of the intermediate leads to an RR -isomer with a terminal double bond. When a proton is eliminated from the methylene group of the pulegog ring, an internal unsaturated compound is formed. The ratio of the yield of the isomer with an internal double binding and the RR -isomer depends on the polarity of the aprotic solvents.
Sobre autores
I. Bodrikov
R.E. Alekseev Nizhny Novgorod State Technical University
Yu. Kurskii
R.E. Alekseev Nizhny Novgorod State Technical University
Email: orgchim@nntu.ru
A. Chiyanov
R.E. Alekseev Nizhny Novgorod State Technical University
A. Subbotin
R.E. Alekseev Nizhny Novgorod State Technical University
V. Kuropatov
Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences
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