Yaroslavl, Yaroslavl, Russian Federation
Yaroslavl, Yaroslavl, Russian Federation
Yaroslavl, Yaroslavl, Russian Federation
Yaroslavl, Yaroslavl, Russian Federation
The paper examines the contents of products of liquid-phase oxidation of cyclohexylbenzene. The study proves the existence of tertiary and secondary hydroperoxide in the oxidation products of cyclohexylbenzene. The hydroperoxides were determined directly by NMR1H-spectroscopy and indirectly by their products of reduction to ketones and alcohols. By comparing integral intensities of tertiary and secondary cyclohexylbenzene hydroperoxide proton signals, we can assume that the content of the latter is approximately 15-20% of the total hydroperoxide content present in the cyclohexylbenzene oxidation products. The general scheme of oxidative transformations of cyclohexylbenzene is compiled based on the experimental data obtained and the existing knowledge of the essence of liquid-phase oxidation of alkylsubstituted aromatic and cycloaliphatic hydrocarbons. The study shows a considerable decrease in selectivity of oxidation process when cyclohexylbenzene conversion increases up to 40-50%.
cyclohexylbenzene, liquid-phase oxidation, tertiary cyclohexylbenzene hydroperoxide, secondary cyclohexylbenzene hydroperoxide
1. Harlampovich G.D., Churkin Yu.V. Fenoly. M.: Himiya, 1974. 376 s.
2. Furman M.S., Gol'dman A.M. Proizvodstvo ciklogeksanona i adipinovoy kisloty okisleniem ciklogeksana. M.: Himiya, 1967. 240 s.
3. Kruzhalov B.D., Golovanenko B.I. Sovmestnoe poluchenie fenola i acetona. M.: Nauka. 1963. 200 s.
4. Zakoshanskiy V.M. Fenol i aceton: Analiz tehnologiy, kinetiki i mehanizma osnovnyh reakciy. SPb: Himizdat, 2009. C. 149-189.
5. Lebedev N.N. Himiya i tehnologiya osnovnogo organicheskogo i neftehimicheskogo sinteza. M.: Al'yanS, 2013. 588 c.
6. Zavgorodniy S.V., Nasyr I.A. Sintez i avtookislenie metilciklogeksilbenzola. Ukrainskiy himicheskiy zhurnal. 1964. T. 30. № 8. S. 862-868.
7. Arendsa I.W.C.E, Sasidharan M., Kühnle A., Duda M., Jost C., Sheldon R.A. Selective catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide: a coproduct-free route to phenol. Tetrahedron. 2002. Vol. 58. N 44. P. 9055-9061. DOI:https://doi.org/10.1016/S0040-4020(02)01131-6.
8. Aoki Y., Sakaguci S., Ishii Y. One-pot synthesis of phenol and cyclohexanone from cyclohexylbenzene catalyzed by N-Hydroxyphtalimide (NHPI). Tetrahedron. 2005. Vol. 61, N 22. R. 5219-5222. DOI: 10.1016/ j.tet.2005. 03.079.
9. Rong H. Yuhua S., Haixia S., Qiumin G., Mohong L., Mingshi L. Synthesis of Phenol and Cyclohexanone from Catalytic Oxidation of Cyclohexylbenzene. Petrochemical Technology. 2012. Vol. 41. N 9. P. 1023-1027.
10. Kurganova E.A., Sapunov V.N., Koshel' G.N., Frolov A.S.Selektivnoe aerobnoe okislenie ciklogeksil- i vtor-alkilarenov do gidroperoksidov v prisutstvii N-gidroksiftalimida. Izvestiya akademii nauk. Seriya himicheskaya. 2016. № 9. S. 2115-2128.
11. Havkins E. Organicheskie perekisi, ih poluchenie i reakcii. Per. s angl.; pod red. L.F. Efroma. M-L.: Himiya, 1964. 536 s.
12. Sneering R., Stenberg V. The quantitative determination of hydroperoxides, alcohols and ketones in hydrocarbon solvents. Annal. Lett. 1971. Vol.4. P. 458-490.
13. Neu D.H., Stirling G.J.M., Williams G.H. The decomposition of 1-phenylcyclohexylperoxides. J. Chem. Soce. 1957. P. 1054-1060.
14. Rieche A. Über Peroxyde der Äther, der Carbonyl‐Verbindungen und die Ozonide. Angewan. Chem. 1958. Vol. 70. N 9. P. 251-278. DOI:https://doi.org/10.1002/ange.19580700902.
15. Selivanov N.T., Potehin V.M., Proskuryakov V.A. Izuchenie sostava produktov okisleniya metilciklogeksana kislorodom vozduha. Zhurnal prikladnoy himii, 1971. T. 44. C. 394-399.
16. Eventova M.S., Meylanova D.Sh. Vysokotemperaturnoe okislenie fenilciklogeksana. Vestnik MGU. Seriya fiz.-mat. i estest. nauk. 1955. № 10. S.103-106.
17. Sapunov V.N., Kurganova E.A., Koshel G.N. Kinetics and Mechanism of Cumene Oxidation Initiated by N-Hydroxyphthalimide. International Journal of Chemical Kinetics. 2018. Vol.50. N 1. P. 3-14. DOI:https://doi.org/10.1002/kin.21135.
18. Sosnovskih V.Ya. Reakciya Grin'yara. Sorosovskiy obrazovatel'nyy zhurnal. 1999. № 6. S. 47-53.
19. Vacuro K.V., Mischenko G.L. Imennye reakcii v organicheskoy himii. M.: Himiya, 1976. 528 s.
20. Belen'kiy M.S., Vorob'eva V.A., Chernysheva L.I. Poluchenie alkilaromaticheskih gidroperekisey okisleniem dimetilfenilkarbinola i dioksidiizopropilbenzolov. Himicheskaya promyshlennost'. 1972. № 1. S. 24-26.
21. Newman N.S., Farman M.D. The synthesis of hydroaromatic compounds containing angular groups. Journal of the American Chemical Society. 1944. Vol. 66. N 9. P. 1550-1552. DOI:https://doi.org/10.1021/ja01237a042
