Conclusions
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1.
Secondary aromatic amines are catalysts in the reaction of sterically hindered aroxyl radicals with hydroperoxides. The rate of the catalytic reaction v is proportional to [ArO′], [ROOH], [AmH], and inversely proportional to [ArOH].
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2.
Values of kcat have been found for eleven aromatic amines in reaction with 2,4,6-tri-t-butylphenoxyl radical with cumyl hydroperoxide in CCl4 over the temperature range 298,2–341.6 K. The values of E and ΔF≠ fall with increasing electron-donor properties of the substituents on the aromatic ring of the amine. On the basis of the values of k which were obtained, several parameters have been estimated including the strength of the N-H bond in the amine molecule.
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3.
For diphenylamines with electron-donor substituents there is a linear relationship between log k and the σ+ function.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 549–557, March 1989.
The authors express their thanks to E. T, Denisov for advice and comments.
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Varlamov, V.T. Activity of secondary aromatic amines as catalysts in the reaction of sterically hindered aroxyl radicals with hydroperoxides. Russ Chem Bull 38, 482–490 (1989). https://doi.org/10.1007/BF00958037
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DOI: https://doi.org/10.1007/BF00958037