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Constants of chain transfer and telomerization of propylene by chloroform; influence of the bond dissociation energy and stability of the radicals formed on the rate of the substitution reaction

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Conclusions

  1. 1.

    In the telomerization of C3H6 with CHC13, the rate constants of chain transfer with respect to the C-H and C-Cl bonds of radicals with n=1−3 were calculated at 70, 105, and 150°, with a broad variation of the reagent ratios.

  2. 2.

    The mechanism of the reaction was discussed, with an evaluation of the relative contribution of ionic structures to the transition states of reactions of chain transfer, depending on the polar properties of the reagents (determined using the Bamford correlation scheme).

  3. 3.

    In the telomerization of C3H6 with CCl4 and CHCl3, the value of the rate constant of chain transfer with cleavage of the C-Cl bond is determined by the stability of the radical formed, whereas the contribution of polar structures to the decrease in the level of the transition state depends chiefly on the nature of the bond being broken — its dissociation energy and the electronegativity of the atom being stripped off.

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Literature cited

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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2712–2720, December, 1968.

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Énglin, B.A., Osipov, B.N. Constants of chain transfer and telomerization of propylene by chloroform; influence of the bond dissociation energy and stability of the radicals formed on the rate of the substitution reaction. Russ Chem Bull 17, 2572–2578 (1968). https://doi.org/10.1007/BF00907776

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Keywords

  • Chloroform
  • Propylene
  • Transition State
  • CHCl3
  • CCl4