Rate constants of the reaction of cumyl peroxide radicals with 2-arylindan-1, 3-diones
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The rate constant K(7) of the interaction of cumyl peroxide radicals with 2-arylindan-1,3-diones (ΦH), the activation energies of these reactions (Eact), and the stoichiometric coefficients of inhibition (f) were determined.
The values of k7 and f are determined to a substantial degree by the nature of the substituents and their position in the 2-phenyl ring.
For the p-substituted 2-phenylidan-1,3-diones a correlation equation logk7/k7.st=0.28σ + 1.01 ER was established. The value of the rate constants of stripping of a H atom from the CH bonds of φH by peroxide radicals is influenced by the polarity of the substituent (σ) and the resonance factor (ER), considering the contribution of the substituents to the delocalization of the unpaired electron in the radical Ф formed.
KeywordsPeroxide Activation Energy Diones Unpaired Electron Correlation Equation
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- 1.V. V. Moiseev and I. M. Poluéktov, Uspekhi Khimii,42, 471 (1973).Google Scholar
- 2.A. B. Gagarina, L. M. Pisarenko, and N. M. Émanuél', Dokl. Akad. Nauk SSSR,212, 653 (1973).Google Scholar
- 3.I. R. Yanson, V. P. Karlivan, V. F. Griks, O. Ya. Neiland, and A. K. Aren, Uch. Zap. Rizhsk. Politekhn. In-ta,27, 19 (1967).Google Scholar
- 4.F. M. Beringer, S. A. Galton, and S. J. Huang, Tetrahedron,18, 809 (1963).Google Scholar
- 5.V. Ya. Shlyapintokh, O. N. Karpukhin, L. M. Postnikov, I. V. Zakharov, A. A. Vichutinskii, and V. F. Tsepalov, Chemiluminescence Methods of Investigation of Slow Chemical Processes [in Russian], “Nauka” (1966), p. 40.Google Scholar
- 6.N. M. Émanuél', E. T. Denisov, and Z. K. Maizus, Chain Reactions of liquid-Phase Oxidation of Hydrocarbons [in Russian], “Nauka” (1965), p. 32.Google Scholar
- 7.V. V. Moiseev and L. P. Zalukaev, Zh. Organ. Khimii,3, 731, 734 (1967).Google Scholar
- 8.F. M. Beringer and S. A. Galton, J. Organ. Chem.,28, 3417 (1963).Google Scholar
- 9.J. E. Leffler and E. Grunwald, Rates and Equilibria of Organic Reactions, J. Wiley, New York (1963), Chap. 6.Google Scholar
- 10.T. Jamamoto, Chemistry and Industry, 787 (1967).Google Scholar
- 11.L. M. Pisarenko, A. B. Gagarina, G. N. Bogdanov, and V. V. Moiseev, Dokl. Akad. Nauk SSSR,213, 638 (1973).Google Scholar