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.
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).
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.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
B. A. Énglin, B. N. Osipov, and R. Kh. Friedlina, Izv. AN SSSR, Ser. Khim., 2223 (1967).
F. M. Lewis and F. R. Mayo, J. Amer. Chem. Soc.,76, 457 (1954).
B. A. Énglin, B. N. Osipov, V. A. Valovoi, L. G. Zelenskaya, T. A. Babushkina, G. K. Semin, B. V. Bondarev, and R. Kh. Friedlina, Izv. AN SSSR, Ser. Khim., No. 1 (1969).
B. A. Énglin, B. N. Osipov, and R. Kh. Freidlina, Izv. AN SSSR, Ser. Khim., 1736 (1967).
V. I. Vedeneev, L. V. Gurvich, V. N. Kondrat'ev, V. A. Medvedev, and E. D. Frankevich, Cleavage Energies of Chemical Bonds [in Russian], Izd-vo AN SSSR (1962), pp. 69, 74, 136.
C. Walling, Free Radicals in Solution [Russian translation], IL (1960), pp. 45, 190, 203.
F. R. Mayo, J. Amer. Chem. Soc.,70, 3689 (1948).
F. W. Mellows and M. Burton, J. Phys. Chem.,66, 2164 (1962).
B. A. Énglin and R. Kh. Friedlina, Izv. AN SSSR, Ser. Khim., 2097 (1966).
B. A. Énglin, T. A. Onishchenko, and R. Kh. Friedlina, Izv. AN SSSR, Ser. Khim., 2489 (1968).
I. B. Afanas'ev and A. A. Beér, Neftekhimiya,2, 611 (1962).
C. H. Bamford and A. D. Jenkins, Trans. Faraday Soc.,59, 530 (1963).
M. Szwarc, Disc. Faraday Soc.,10, 143 (1951).
B. A. Pal'm, Uspekhi Khimii,30, 1069 (1961).
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2712–2720, December, 1968.
About this article
Cite this article
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
- Transition State