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. Kharlampovich G.D., Churkin Yu.V. Phenols. Moscow: Khimiya Publ., 1974. 376 p. (in Russian).
2. Furman M.S., Goldman A.M. The production of cyclohexanone and adipic acid by oxidation of cyclohexane. Moscow: Khimiya Publ., 1967. 240 p. (in Russian).
3. Kruzhalov B.D., Golovanenko B.I. Simultaneous Production of Phenol and Acetone. Moscow: Nauka Publ., 1963. 200 p. (in Russian).
4. Zakoshanskii, V.M. Phenol andAcetone: Analysis of the Technology, Kinetics, and Mechanism of the Main Reactions. St. Petersburg: Khimizdat, 2009. P. 149–189 (in Russian).
5. Lebedev N.N. Chemistry and technology of basic organic and petrochemical synthesis. Moscow: AllianS Publ., 2013. 588 p. (in Russian).
6. Zavgorodnij S.V., Nasyr I.A. Metylcyclobenzene synthesis and autooxidation. Ukrainskij himicheskij zhurnal. – 1964. Vol. 30. N 8. P. 862-868 (in Russian).
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., Sakaguchi S., Ishii Y. One-pot synthesis of phenol and yclohexanone from yclohexylbenzene catalyzed by N-Hydroxyphtalimide (NHPI) Tetrahedron, 2005. Vol. 61. N 22. P. 5219-5222. DOI:https://doi.org/10.1016/j.tet.2005.03.079.
9. Rong, H. Yuhua S., Haixia C., 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. Selective aerobic oxidation of cyclohexyl- and sec-alkylarenes to hydroperoxides in the presence of N-hydroxyphthalimide. Russian Chemical Bulletin. 2016. Vol. 65. N 9. P. 2115-2128. DOIhttps://doi.org/10.1007/s11172-016-1560-3.
11. Hawkins E.G.E. Organic Peroxides: Their Formation and Reactions. Van Nostrand Publ., 1961. 434 p.
12. Sneering P., Stenberg V. The quantitative determination of hydroperoxides, alcohols and ketones in hydrocarbon solvents. Annal. Lett. 1971. Vol. 4. P. 458-490.
13. Hey 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., Potekhin V.M., Proskuryakov V.A. Study of the composition of the oxidation products of methylcyclohexane with atmospheric oxygen. Zhurnal prikladnoj himii, 1971. Vol. 44. P. 394-399 (in Russian).
16. Eventova M.S., Mejlanova D.SH. High temperature oxidation of phenylcyclohexane. Vestnik MGU, seriya fiz.-mat. i estest. Nauk. 1955. N 10. P. 103-106 (in Russian). 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/
17. Sosnovskih V.YA. Grignard reaction. Sorosovskij obrazovatel'nyj zhurnal. 1999. N 6. Pp. 47-53 (in Russian).
18. Vacuro K.V., Mishchenko G.L. Named reactions in organic chemistry. Moscow: Khimiya Publ., 1976. 528 p. (in Russian).
19. Belen'kij M.S., Vorob'yova V.A. Preparation of alkylaromatic hydroperoxides by oxidation of Dimethylphenylcarbinol and dioxydisopropylbenzenes. Himicheskaya promyshlennost'. 1972. N 1. Pp. 24-26 (in Russian).
20. 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. Pp. 1550-1552. DOI:https://doi.org/10.1021/ja01237a042.
