Izvestiya of Saratov University.

Chemistry. Biology. Ecology

ISSN 1816-9775 (Print)
ISSN 2541-8971 (Online)


For citation:

Inshina T. ., Golikov A. G. Synthesis and structure of polycyclic O-containing systems based on diarylmethylidenepiperidones (cyclanones). Izvestiya of Saratov University. Chemistry. Biology. Ecology, 2022, vol. 22, iss. 2, pp. 122-127. DOI: 10.18500/1816-9775-2022-22-2-122-127

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).
Full text:
(downloads: 179)
Полный текст в формате PDF(En):
(downloads: 63)
Language: 
Russian
Heading: 
Article type: 
Article
UDC: 
547.572.6+547.64

Synthesis and structure of polycyclic O-containing systems based on diarylmethylidenepiperidones (cyclanones)

Autors: 
Inshina Tatiana V. , Saratov State University
Golikov Aleksey G. , Saratov State University
Abstract: 

In this work, the interaction of diarylmethylidene piperidones with acetylacetone and acetoacetic ester has been studied. It has been shown that the transition to piperidone in the basis of dienone does not allow the selective synthesis of products. It has been found that the direction of the reaction with 1,3-C,C-dinucleophilic reagents is infl uenced by the nature of peripheral ylidene substituents, which allows targeted synthesis of O-heterocyclization products (hexahydropyranopyridines) by introducing an NO2 group into the arylmethylidene fragment. Previously unknown substituted deca(octa)hydro(xanthenes)cyclopentachromenes have been synthesized. It has been established that the interaction of diarylmethylidenecyclanones with cyclohexa(penta)ne under conditions of mild basic catalysis (piperidine) proceeds nonselectively, the size of the cycle in the base of the initial substrate plays an important role, and the reaction products are always a mixture of substances (two or more). Based on the experimental data obtained, a scheme has been proposed for the formation of hydroxanthene and hydrocyclopentachromene fragments of the resulting products. It has been found that, while maintaining the general direction of the reaction, the determining role in the structure of the products is played by the size of the cycle (С5 ,С6 ) in the basis of the initial substrates. Six-membered fused fragments promote enolization and intramolecular O-heterocyclization of 1,5-diketone with the formation of polycyclic systems. The composition and structure of the synthesized compounds have been confi rmed by elemental analysis, IR and one-dimensional, two-dimensional NMR spectroscopy.

Reference: 
  1. Vatsadze S. Z., Zyk N. V., Golikov A. G., Kriven’ko A. P. Chemistry of cross-conjugated dienones // Russian Chemical Reviews. 2008. Vol. 77, № 8. P. 661–681. https://doi.org/10.1070/RC2008v077n08ABEH003771
  2. Zakharova G. V., Zyuz’kevich F. S., Gutrov V. N., Plotnikov V. G., Gromov S. P., Chibisov A. K., Gavrilova G. V., Nuriev V. N., Vatsadze S. Z. Effect of substituents on spectral, luminescent and time-resolved characteristics of 2,5-diarylidene derivatives of cyclopentanone // High Energy Chemistry. 2017. Vol. 51, № 2. P. 113–117. https://doi.org/10.1134/S0018143917020126
  3. Пожаров М. В., Захарова Т. В. Синтез и изучение люминисцентных свойств комплекса тербия с 2,6-дибензилиденциклогексаноном // Известия Саратовского университета. Новая серия. Серия: Химия. Биология. Экология. 2015. Т. 15, вып. 4. С. 5–11. https://doi.org/10.18500/1816-9775-2015-15-4-5-11
  4. Chebanov V. A., Desenko S. M., Gurley T. W. Azaheterocycles based on а, в-Unsaturated carbonyls. Berlin ; Heidelberg : Springer-Verlag, 2008. 210 p. https://doi. org/10.1007/978-3-540-68367-4
  5. Vasilkova N. O., Kalugina A. S., Nikulin A. V., Krivenko A. P. Reactions of malononitrile with cross-conjugated dienone derivatives of cyclohexane. Synthesis of substituted partially hydrogenated quinoline- and chromenecarbonitriles // Russian Journal of Organic Chemistry. 2019. Vol. 55, № 7. P. 995–998. https://doi.org/10.1134/S1070428019070145
  6. Gulai T. V., Morozova A. A., Golikov A. G. Condensation of 2,6-diarylmethylidenecyclohexa(penta)nones with acetylacetone and ethyl acetoacetate // Russian Journal of Organic Chemistry. 2011. Vol. 47, № 11. P. 1690–1694. https://doi.org/10.1134/S1070428011110066 
  7. ИсмиевА. И., МагеррамовА. М., СукачВ. А., Вовк М. В. Синтез и реакции диацетил(диалкоксикарбонил) замещенных гидроксициклогексанонов // Журнал органической и фармацевтической химии. 2016. Т. 14, № 4 (56). С. 16–32.
Received: 
11.01.2022
Accepted: 
14.02.2022
Published: 
30.06.2022
Short text (in English):
(downloads: 41)