Izvestiya of Saratov University.

Chemistry. Biology. Ecology

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

For citation:

Amalʼchieva O. A., Grinev V. S., Демешко И. А., Yegorova A. Y. Interaction of 3H-furan-2-ones and 4-oxobutanoic acids with 2-(aminophenyl)methanol. Izvestiya of Saratov University. Chemistry. Biology. Ecology, 2022, vol. 22, iss. 3, pp. 244-250. DOI: 10.18500/1816-9775-2022-22-3-244-250

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: 51)
Article type: 
547.415.1’ 435.1’ 484.2’ 745.04:543.422.25

Interaction of 3H-furan-2-ones and 4-oxobutanoic acids with 2-(aminophenyl)methanol

Amalʼchieva Olga A. , Saratov State University
Grinev Vyacheslav Sergeevich, Institute of Biochemistry and Physiology of Plants and Microorganisms of the Russian Academy of Sciences
Yegorova Alevtina Yu., Saratov State University

Reactions of 4-oxobutanoic acids as well as their cyclic analogues 3H-furan-2-ones with 1,3-binucleophilic reagent (2-aminophenyl) methanol lead to the formation of 1-R-5H-benzo[d]pyrrolo[2,1-b][1,3]oxazines and 3a-R-2,3,3a-trihydro-5H-benzo[d]pyrrolo[2,1-b][1,3]oxazin1-ones, respectively. Quantum-chemical calculations of the Fukui reactivity indices and local hardness have substantiated the mechanisms of the reactions carried out. According to the calculated values of the Fukui indices, in the (2-aminophenyl)methanol molecule, compared to the hydroxyl, the amino group has a higher nucleophilicity, which suggests that its initial nucleophilic attack on the electrophilic centers of the substrates is more probable. According to the calculations, the carbonyl carbon atoms in the molecules of 3H-furan-2-ones have much more pronounced local hardness compared to both carbonyl carbon atoms of 4-oxo acids, which suggests an initial attack by a harder nucleophilic center, the hydroxyl group of 2-(aminophenyl)methanol. Thus, it has been shown that the structure of the formed benzopyrroloxazine(one)s depends on the studied substrate.

  1. Katritzky A. R., Qiu G., He H.-Y., Yang B. Novel Syntheses of Hexahydro-1H-pyrrolo[1,2-a]imidazoles and Octahydroimidazo[1,2-a]pyridines // J. Org. Chem. 2000. Vol. 65, iss. 12. P. 3683–3689. https://doi.org/10.1021/jo991881z
  2. Chimirri A., De Sarro A., De Sarro G., Gitto R., Zappala M. Synthesis and anticonvulsant properties of 2,3,3a,4- tetrahydro-1H-pyrrolo[1,2-a]benzimidazol-1-one derivatives // Il Farmaco. 2001. Vol. 56. P. 821–826. https://doi.org/10.1016/s0014-827x(01)01147-83
  3. Lee E. C. Y., Carpino P. A. Melanocortin-4 receptor modulators for the treatment of obesity: A patent analysis (2008–2014) // Pharm. Pat. Anal. 2015. Vol. 4, iss. 2. P. 95–107. https://doi.org/10.4155/PPA.15.1 
  4. Гринёв В. С., Егорова А. Ю. Способы построения (бензо)пирроло[1,2-a]имидазолонов (микрообзор) // Химия гетероциклических соединений. 2016. Т. 52, № 10. С. 785–787. https://doi.org/10.1007/s10593-016- 1966-8
  5. Granovsky A. A. Firefl y version 8. URL: http://classic. chem.msu.su/gran/ gamess/bins/fi refl y820_windows.zip (дата обращения: 18.04.2022).
  6. Becke A. D. Density-functional thermochemistry. III. The role of exact exchange // J. Chem. Phys. 1993. Vol. 98. P. 5648–5652. https://doi.org/10.1063/1.464913
  7. Becke A. D. Density-functional exchange-energy approximation with correct asymptotic behavior // Phys. Rev. A. 1988. Vol. 38. P. 3098–3100. https://doi.org/10.1103/PhysRevA.38.3098
  8. Lee C., Yang Y., Parr R. G. Development of the ColleSalvetti correlation-energy formula into a functional of the electron density // Phys. Rev. B. 1988. Vol. 37. P. 785–789. https://doi.org/10.1103/PhysRevB.37.785
  9. Krishnan R., Binkley J. S., Seeger R., Pople J. A. Selfconsistent molecular orbital methods. XX. A basis set for correlated wave functions // J. Chem. Phys. 1980. Vol. 72. P. 650–654. https://doi.org/10.1063/1.438955
  10. Chattaraj P. K., Maiti B., Sarkar U. Philicity: A unifi ed treatment of chemical reactivity and selectivity // J. Phys. Chem. A. 2003. Vol. 107, № 25. P. 4973–4975. https://doi.org/10.1021/jp034707u
  11. Амальчиева О. А., Егорова А. Ю. Реакции 3Н-фуран2-онов с 1,2-бинуклеофилами // Журн. орг. химии. 2006. Т. 42, № 9. С. 1358–1361. https://doi.org/10.1134/ S1070428006090144
  12. Гринёв В. С., Амальчиева О. А., Егорова А. Ю., Любунь Е. В. Взаимодействие 4-оксокислот и 5-R-3Hфуран-2-онов с 1,2-бинуклеофилами ароматического и алициклического рядов // Журн. орг. химии. 2010. Т. 46, № 9. С. 1376–1379. https://doi.org/10.1134/ S1070428010090198