Abstract
The kinetics of oxidation (323 K) of bicycloolefins from the norbornene series: norbornene, vinylnorbornene, ethylidenenorbornene, and norbornadiene, inhibited by phenols (PhOH), aromatic amines (AmH), transition metal compounds (Men), or stable nitroxyl radicals of the piperidine series (>NO·), in chlorobenzene solutions have been studied. It has been found that the phenols are single-action inhibitors, whereas the amines, the transition metals, and the nitroxyl radicals repeatedly terminate oxidation chains. The results are explained in terms of phenomenology of the bicycloolefin oxidation process associated with the fact that peroxide radicals attack different reaction centers (π- and α-CH bonds), thereby resulting in the formation of different types of chain carrier radicals: low-molecular-weight hydroperoxide and polyperoxide radicals.
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References
V. V. Voronenkov and L. F. Titova, Dokl. Akad. Nauk SSSR 191, 601 (1971).
G. V. Filippova, E. A. Blyumberg, and L. Kas’yan, Dokl. Akad. Nauk SSSR (1973).
V. V. Voronenkov, Yu. V. Shapiro, V. D. Sukhov, and E. A. Lazurin, Dokl. Akad. Nauk SSSR 215, 101 (1974).
V. V. Voronenkov, Yu. G. Osokin, V. N. Baidin, and A. I. Rusakov, Teor. Eksp. Khim. 21(4), 72 (1985).
V. V. Voronenkov, V. N. Baidin, V. A. Machtin, et al., Zh. Org. Khim. 21, 302 (1985).
T. A. Kulikova, V. A. Machtin, and E. M. Pliss, Bashkir. Khim. Zh. 14(3), 132 (2007).
T. A. Kulikova, V. A. Machtin, and E. M. Pliss, Bashkir. Khim. Zh. 14(4), 15 (2007).
E. M. Pliss, R. B. Safiullin, and S. S. Zlotskii, Inhibited Oxidation of Unsaturated Compounds: Kinetics, Mechanism, and Structure-Reactivity Relation (LAP LAMBERT Academic Publishing, Saarbruken, 2012) [in Russian].
E. T. Denisov and I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and Biology (CRC, Boca Raton, 2005).
M. van Duin, R. Orza, R. Peters, and V. Chechik, Macromol. Symp. 291, 66 (2010).
D. Loshadkin, V. Roginsky, and E. Pliss, Int. J. Chem. Kinet. 34, 162 (2002).
A. V. Sokolov, S. V. Popov, E. M. Pliss, and D. V. Loshadkin, Certificate of State Registration of Computer Program No. 612187 (2013).
E. M. Pliss, I. V. Tikhonov, and A. I. Rusakov, Nitroxides—Theory, Experiment and Applications, Ed. by A. I. Kokorin (InTech, Rijeka, Croatia, 2012), p. 263.
E. M. Pliss, V. D. Sen’, and I. V. Tikhonov, Nitroxide Radicals in Chemical and Biological Processes (LAP LAMBERT Academic Publishing, Saarbruken, 2013) [in Russian].
NIST Standard Reference Database 17: NIST Chemical Kinetics Database, Version 7.0 (Web Version), Release 1.6.5 (Gaithersburg, 2012).
E. T. Denisov and V. V. Azatyan, Inhibition of Chain Reactions (Chernogolovka, 1996) [in Russian].
T. A. Kulikova, Candidate’s Dissertation in Chemistry (Ivanovo, 2009).
E. T. Denisov, Usp. Khim. 65, 547 (1996).
E. M. Pliss, I. V. Tikhonov, and A. I. Rusakov, Russ. J. Phys. Chem. B 6, 376 (2012).
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Original Russian Text © R.E. Pliss, V.A. Machtin, D.V. Loshadkin, A.I. Rusakov, E.M. Pliss, 2014, published in Neftekhimiya, 2014, Vol. 54, No. 5, pp. 388–393.
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Pliss, R.E., Machtin, V.A., Loshadkin, D.V. et al. The mechanism of inhibited oxidation of norbornene series bicycloolefins. Pet. Chem. 54, 382–386 (2014). https://doi.org/10.1134/S0965544114050089
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DOI: https://doi.org/10.1134/S0965544114050089