Conclusions
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1.
Chain propagation in the oxidation of esters proceeds via a reaction of the RH + O2→ R. + HO2 . type. The rate constant for initiation of the chains at 423 K is (3.4 ± 0.4)·10−6 liter/mole·sec for CR4, (5.2 ± 0.4)·10−7 liter/mole·sec for C2H5CR3, (2.2 ± 0.7)·10−10 liter/ mole·sec for (CH3)2CR2 (R=CH2OCOCH2CH3), and (9.4 ± 1.0)·10−7 liter/mole·sec for C(CH2-OCOCH3)4. A multidipole-interaction effect is manifested in this reaction. The greater the number of ester groups in the molecule, the more readily each of them reacts with O2.
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2.
In pentaerythritol tetrapropionate O2 reacts at the α-C-H bond of the acid residue with k=3.1·10−7 liter/mole·sec and at the α-C-H bond of the alcohol residue with k=1.2 × 10−7 liter/mole·sec (423 K).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2681–2686, December, 1987.
The authors thank A. L. Aleksandrov for his advice and valuable comments.
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Pozdeeva, N.N., Denisov, E.T. Multidipole interaction in reactions of oxygen with esters of polyhydric alcohols. Russ Chem Bull 36, 2485–2489 (1987). https://doi.org/10.1007/BF00957216
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DOI: https://doi.org/10.1007/BF00957216