Decay kinetics and products of transformation of aromatic nitroso oxides 4-R–C6H4–CH2–C6H4NOO, R = OH, NHCOCH3

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

The optical properties and kinetics of consumption of cis- and trans-isomers of aromatic nitroso oxides 4-R–C6H4–CH2–C6H4NOO (R = OH, NHCOCH3) were studied using pulse photolysis and UV-Vis spectrophotometry. The cis-isomer ArNOO is irreversibly transformed into a nitrile oxide intermediate, which then either participates in the (3 + 2)-cycloaddition reaction to the solvent - acetonitrile, or undergoes intramolecular ipso-ortho-cyclization. The substituent R has virtually no effect on the spectral and kinetic characteristics of ArNOO, but shifts the competition between two product formation channels towards ipso-ortho-transformation, leading to the formation of tricyclic isoxazole. Using DFT calculations in the M06L/6-311+G(d,p) + IEFPCM approximation, the details of the mechanisms of the studied transformations are discussed.

About the authors

A. N Teregulova

Ufa Institute of Chemistry - Subdivision of the Ufa Federal Research Centre RAS

Email: kinetic@anrb.ru
Ufa, Republic of Bashkortostan, Russia

A. R Yarullin

Ufa Institute of Chemistry - Subdivision of the Ufa Federal Research Centre RAS

Ufa, Republic of Bashkortostan, Russia

A. N Lobov

Ufa Institute of Chemistry - Subdivision of the Ufa Federal Research Centre RAS

Ufa, Republic of Bashkortostan, Russia

S. L Khursan

Ufa Institute of Chemistry - Subdivision of the Ufa Federal Research Centre RAS

Ufa, Republic of Bashkortostan, Russia

R. L Safiullin

Ufa Institute of Chemistry - Subdivision of the Ufa Federal Research Centre RAS

Ufa, Republic of Bashkortostan, Russia

References

  1. Chainikova E.M., Khursan S.L., Safiullin R.L. The Chemistry of Nitroso Oxides / The Chemistry of Peroxides. Patai’s Chemistry of Functional Groups. Ed. Z. Rappoport. John Wiley & Sons, 2014. P. 357.
  2. Чайникова Е.М., Хурсан С.Л., Сафиуллин Р.Л. Химия нитрозооксидов. М.: РАН, 2023.
  3. Хурсан С.Л., Сафиуллин Р.Л. // Изв. АН. Сер. хим. 2023. Т. 72. № 11. С. 2576.
  4. Chainikova E.M., Yusupova A.R., Khursan S.L., Teregulova A.N., Lobov A.N., Abdullin M.F., Enikeeva L.V., Gubaydullin I.M., Safiullin R.L. // J. Org. Chem. 2017. V. 82. N. 15. P. 7750.
  5. Khursan S.L., Ovchinnikov M.Yu., Yarullin A.R., Teregulova A.N., Safiullin R.L. // J. Phys. Chem. A. 2022. V. 126. N. 44. P. 8188.
  6. Сафиуллин Р.Л., Терегулова А.Н., Яруллин А.Р., Овчинников М.Ю., Хурсан С.Л. // Кинетика и катализ. 2022. T. 63. N. 2. C. 193.
  7. Teregulova A.N., Yarullin A.R., Chainikova E.M., Lobov A.N., Safiullin R.L., Khursan S.L. // Tetrahedron. 2024. V. 153. Art. 133849.
  8. Hu M., Li J., Q. Yao S. // Org. Lett. 2008. V. 10. N. 24. P. 5529.
  9. Kaslow C.E., Stayner R.D. // J. Am. Chem. Soc. 1946. V. 68. N. 12. P. 2600.
  10. Talrose V., Yermakov A.N., Usov A.A., Goncharova A.A., Leskin A.N., Messineva N.A., Trusova N.V., Efimkina M.V. UV/Visible Spectra / NIST Chemistry Webbook. NIST Standard Reference Database Number 69. Eds P.J. Linstrom, W.G. Mallard. Gaithersburg (MD): National Institute of Standards and Technology, 2012. P. 20899.
  11. Zhao Y., Truhlar D.G. // J. Chem. Phys. 2006. V. 125. N. 19. Art. 194101.
  12. McLean A.D., Chandler G.S. // J. Chem. Phys. 1980. V. 72. N. 10. P. 5639.
  13. Tomasi J., Mennucci B., Cammi R. // Chem. Rev. 2005. V. 105. N. 8. P. 2999.
  14. Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Scalmani G., Barone V., Petersson G.A., Nakatsuji H., Li X., Caricato M., Marenich A.V., Bloino J., Janesko B.G. et al. Gaussian 09. Rev. C.01. Wallingford. CT. 2009.
  15. Chainikova E.M., Khursan S.L., Safiullin R.L. // Kinet. Catal. 2006. V. 47. N. 4. P. 549.
  16. Hansch C., Leo A., Taft R.W. // Chem. Rev. 1991. V. 91. N. 2. P. 165.

Supplementary files

Supplementary Files
Action
1. JATS XML
Download


Согласие на обработку персональных данных

 

Используя сайт https://journals.rcsi.science, я (далее – «Пользователь» или «Субъект персональных данных») даю согласие на обработку персональных данных на этом сайте (текст Согласия) и на обработку персональных данных с помощью сервиса «Яндекс.Метрика» (текст Согласия).