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Letters in Organic Chemistry

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ISSN (Print): 1570-1786
ISSN (Online): 1875-6255

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Letter Article

Decomposition Kinetics of 1,1-Dihydroperoxycyclohexane in Some Organic Solvents

Author(s): Nadezhda M. Andriyashina, Stanislav A. Grabovskii* and Rustam L. Safiullin

Volume 20, Issue 3, 2023

Published on: 26 September, 2022

Page: [193 - 196] Pages: 4

DOI: 10.2174/1570178619666220727114411

Price: $65

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Abstract

Background: 1,1-Bishydroperoxides are used as oxidizing agents, radical initiators, in addition, studies of biological activity show the promise of this area of research.

Objective: There are currently no kinetic data on the thermal stability of these peroxides in various solvents. Therefore, we investigated the thermal stability of 1,1-dihydroperoxycyclohexane as the most widely used at present.

Methods: The rate constants and activation parameters were measured at the temperature range of 100- 170°C in the presence of 2-naphthol, which inhibits the induced decomposition of the peroxide by free radicals. Peroxide concentration was determined by iodometric method.

Results: The rate constants of the reaction with the solvents and of the monomolecular decomposition of the peroxide were determined.

Conclusion: The use of DHPC as a radical initiator requires taking into account its reactions with the solvent and/or monomer, in addition to its monomolecular decomposition with the formation of free radicals.

Keywords: Geminal dihydroperoxide, thermolysis, kinetics, inhibition, rate constant, oxidation.

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[1]
Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer; Adam, W., Ed.; Wiley-VCH: Weinheim, Germany, 2000.
[http://dx.doi.org/10.1002/3527600396]
[2]
Jakka, K.; Liu, J.; Zhao, C.G. Tetrahedron Lett., 2007, 48(8), 1395-1398.
[http://dx.doi.org/10.1016/j.tetlet.2006.12.104] [PMID: 18283328]
[3]
McCullough, K.J.; Tokuhara, H.; Masuyama, A.; Nojima, M. Org. Biomol. Chem., 2003, 1(9), 1522-1527.
[http://dx.doi.org/10.1039/b300342f] [PMID: 12926282]
[4]
Terent’ev, A.O.; Platonov, M.M.; Kutkin, A.V. Cent. Eur. J. Chem., 2006, 4(2), 207-215.
[5]
Handbook of Vinyl Polymers: Radical Polymerization, Process, and Technology, 2nd ed; Mishra, M.; Yagci, Y., Eds.; CRC Press: Boca Raton, FL, 2008.
[6]
Sheppard, C.S.; Kamath, V.R. Polym. Eng. Sci., 1979, 19(9), 597-606.
[http://dx.doi.org/10.1002/pen.760190902]
[7]
Tropina, V.I.; Krivykh, O.V.; Sadchikova, N.P.; Terent’ev, A.O.; Krylov, I.B. Pharm. Chem. J., 2010, 44(5), 248-250.
[http://dx.doi.org/10.1007/s11094-010-0441-6]
[8]
Žmitek, K.; Zupan, M. Iskra, J. Org. Biomol. Chem., 2007, 5(24), 3895-3908.
[http://dx.doi.org/10.1039/b711647k] [PMID: 18043792]
[9]
Vil’, V.A.; Bityukov, O.V.; Terent’ev, A.O. Science of Synthesis: Knowledge Updates; Jiang, X.; Paquin, J-F.; Terent’ev, A.; Wang, M., Eds.; George Thieme Verlag: Stuttgart, 2019, 3, pp. 383-431.
[10]
Terent’ev, A.O.; Kutkin, A.V.; Platonov, M.M.; Ogibin, Y.N.; Nikishin, G.I. Tetrahedron Lett., 2003, 44(39), 7359-7363.
[http://dx.doi.org/10.1016/S0040-4039(03)01844-6]
[11]
Capellos, C.; Bielski, B.H.J. Kinetic systems, 1st ed; John Wiley & Sons, Inc.: New York, 1972.
[12]
Denisov, E.T.; Denisova, T.G.; Pokidova, T.S. Handbook of Free Radical Initiators, 1st ed; John Wiley & Sons, Inc.: Hoboken, 2003.
[http://dx.doi.org/10.1002/0471721476]
[13]
Thomas, J.R.; Harle, O.L. J. Phys. Chem., 1959, 63(7), 1027-1032.
[http://dx.doi.org/10.1021/j150577a001]
[14]
Cullis, C.F.; Hirschler, M.M.; Rogers, R.L. Proc. R. Soc. A: Math. Phys. Eng. Sci., 1981, 375(1763), 543-563.
[15]
Terent’ev, A.O.; Platonov, M.M.; Ogibin, Y.N.; Nikishin, G.I. Synth. Commun., 2007, 37(8), 1281-1287.
[http://dx.doi.org/10.1080/00397910701226384]
[16]
Li, Y.; Hao, H.D.; Zhang, Q.; Wu, Y. Org. Lett., 2009, 11(7), 1615-1618.
[http://dx.doi.org/10.1021/ol900262t] [PMID: 19278246]
[17]
Tada, N.; Cui, L.; Okubo, H.; Miura, T.; Itoh, A. Chem. Commun. (Camb.), 2010, 46(10), 1772-1774.
[http://dx.doi.org/10.1039/b917056a]
[18]
Gobert, S.R.L.; Kuhn, S.; Braeken, L.; Thomassen, L.C.J. Org. Process Res. Dev., 2017, 21(4), 531-542.
[http://dx.doi.org/10.1021/acs.oprd.6b00359]
[19]
Islamova, R.M.; Ishkinina, O.I.; Nazarova, S.V.; Chupakhin, O.N.; Utepova, I.A.; Andriyashina, N.M.; Terent’ev, A.O. Russ. Chem. Bull., 2013, 62(5), 1282-1285.
[http://dx.doi.org/10.1007/s11172-013-0177-z]
[20]
Safiullin, R.L.; Enikeeva, L.R.; Serenko, S.Y.; Komissarov, V.D.; Tolstikov, G.A. Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991, 40(2), 280-284.
[http://dx.doi.org/10.1007/BF00965415]
[21]
Benson, S.W.; Spokes, G.N. J. Phys. Chem., 1968, 72(4), 1182-1186.
[http://dx.doi.org/10.1021/j100850a018]

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