Peculiarities in the Radiolysis of β-Diketones

S. I. Vlasov; Власов С. И.; A. A. Smirnova; Смирнова А. А.; A. V. Ponomarev; Пономарев А. В.; D. A. Uchkina; Учкина Д. А.; A. Yu. Sholokhova; Шолохова А. Ю.; A. A. Mitrofanov; Митрофанов А. А.

doi:10.31857/S0023119323030166

Peculiarities in the Radiolysis of β-Diketones

Authors: Vlasov S.I.¹, Smirnova A.A.², Ponomarev A.V.¹, Uchkina D.A.¹, Sholokhova A.Y.¹, Mitrofanov A.A.²
Affiliations:
1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences
2. Faculty of Chemistry, Moscow State University
Issue: Vol 57, No 3 (2023)
Pages: 218-223
Section: RADIATION CHEMISTRY
URL: https://rjsvd.com/0023-1193/article/view/661508
DOI: https://doi.org/10.31857/S0023119323030166
EDN: https://elibrary.ru/KIFSPQ
ID: 661508

Cite item

Full Text

Open Access
Restricted Access

Access granted
Restricted Access

Subscription Access

Abstract
About the authors
References
Supplementary files
Statistics

Abstract

Intramolecular hydrogen bonding has a significant effect on the radiolytic transformations of β- diketones. Using the radiolysis of acetylacetone as an example, it has been shown that a hydrogen bond between the hydroxyl and carbonyl in an enol prevents proton transfer from the primary radical cation to the neighboring molecule. As a result, the radiolytic formation of a keto alcohol (4-hydroxy-2-pentanone) was not observed at room temperature, but it was effective under boiling conditions. The intramolecular hydrogen
bond contributed to a significant structural stress in the radical cation, which increased the yield of C–OH bond cleavage and the inhomogeneous formation of acetate (4-oxopent-2-en-2-yl acetate) under normal conditions

Keywords

дикетон, енол, ацетилацетон, радиолиз, водородная связь, фрагментация

References

Vlasov S.I., Kholodkova E.M., Ponomarev A.V. // High Energy Chem. 2021. V. 55(5). P. 393.
Ponomarev A.V., Vlasov S.I., Kholodkova E.M. // High Energy Chem. 2019. V. 53(4). P. 314.
Belova N.V., Oberhammer H., Trang N.H., Girichev G.V. // J. Org. Chem. 2014. V. 79. P. 5412.
Morell C., Grand A., Toro-Labbé A. // J. Phys. Chem. A. 2005. V. 109. P. 205
Fukui K. // Science. 1982. V. 218(4574). P. 747.
Smirnova A., Mitrofanov A., Matveev P., Baygildiev T., Petrov V. // Phys. Chem. Chem. Phys. 2020. V. 22. P. 14992.
Matveev P.I., Mitrofanov A.A., Petrov V.G., Zhokhov S.S., Smirnova A.A., Ustynyuk Y.A., Kalmykova S.N. // RSC Adv. 2017. V. 7. P. 55441.
Curran H.J. // Int. J. Chem. Kinet. 2006. V. 38. P. 250.
Huynh L.K., Violi A. // J. Org. Chem. 2008. V. 73. P. 94.
Woods R., Pikaev A. // Applied Radiation Chemistry. Radiation Processing. Wiley. N.Y. 1994.
Hush N., Livett M., Peel J., Willett G. // Aust. J. Chem. 1987. V. 40. P. 599.
Messaadia L., El Dib G., Ferhati A., Chakir A. // Chem. Phys. Lett. 2015. V. 626. P. 73.
Ji Y., Qin D., Zheng J., Shi Q., Wang J., Lin Q., Chen J., Gao Y., Li G., An T. // Sci. Total Environ. 2020. V. 720. P. 137610.
Vlasov S.I., Kholodkova E.M., Ponomarev A.V. // High Energy Chem. 2018. V. 52(4). P. 312.
Ponomarev A.V., Ratner A.M., Pikaev A.K. // High Energy Chem. 1995. V. 29(2). P. 91.
Howard D.L., Kjaergaard H.G., Huang J., Meuwly M. // J. Phys. Chem. A. 2015. V. 119. P. 7980.
Antonov I., Voronova K., Chen M.-W., Sztáray B., Hemberger P., Bodi A., Osborn D.L., Sheps L. // J. Phys. Chem. A. 2019. V. 123. P. 5472.
Guo J.-J., Hu A., Zuo Z. // Tetrahedron Lett. 2018. V. 59. P. 2103.
Dibble T.S., Chai J. // Advances in Atmospheric Chemistry. World Scientific, 2017. P. 185.