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Effects of the medium on kinetics of transannular addition of iodine to dienes of the bicyclo[3.3.1]nonane series

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The kinetics of the transannular iodination of 3, 7-dimethylene- and 3-methylene-7-isopropylidenebicyclo[3.3.1]nonane in benzene, toluene, dioxane, diethyl ether, and tetrahydrofuran have been investigated. The reactions obey a kinetic equation of the form w = k3[diene][I2]2. The reaction rate is determined by both the electrostatic and electron-donor parameters of the medium. A dependence of the effect of specific solvation with a maximum has been observed due to the different directions of the effects of electron donors of different strength. The results obtained have been described in the framework of a scheme of a molecular-ionic mechanism.

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Literature cited

  1. 1.

    F. Freeman, “Possible criteria for distinguishing between cyclic and acyclic activated complexes among cyclic activated complexes in addition reactions,” Chem. Rev.,75, No. 4, 439–490 (1975).

  2. 2.

    P. A. Krasutskii, Yu. A. Serguchev, A. G. Yurchenko, and A. B. Khotkevich, “Kinetics and mechanism of the iodocyclization reaction of 3, 7-dimethylenebicyclo[3.3.1]nonane,” Teor. Éksp. Khim.,19, No. 2, 229–232 (1983).

  3. 3.

    Yu. A. Serguchev, A. B. Khotkevich, V. B. Barabash, et al., “Kinetics and mechanism of the iodination of diolefins with a bicyclo[3.3.1]nonane structure,” ibid.,20, No. 6, 732–737 (1984).

  4. 4.

    P. A. Krasutskii, A. B. Khotkevich, Yu. A. Serguchev, and A. G. Yurchenko, “Mechanism of the transannular bromination of diolefins of the bicyclo[3.3.1]nonane series,” ibid.,21, No. 1, 52–56 (1985).

  5. 5.

    Yu. A. Serguchev, P. A. Krasutskii, A. B. Khotkevich, and A. G. Yurchenko, “Mechanism of the transannular iodination of derivatives of 3, 7-dimethylenebicyclo[3.3.1]nonane,” ibid., No. 6, 743–747 (1986).

  6. 6.

    Yu. A. Serguchev, A. B. Khotkevich, and P. A. Krasutskii, “Transannular bromination of 3,-7-dimethylenebicyclo[3.3.1]nonane under the conditions of mixed addition,” Dokl. Akad. Nauk UkrSSR, Ser. B, No. 11, 51–54 (1985).

  7. 8.

    E. A. Shilov, Yu. A. Serguchev, G. B. Sergeev, et al., “Influence of solvents on the rate of the addition of bromine to olefins,” Dokl. Akad. Nauk SSSR,197, No. 5, 1096–1099 (1971).

  8. 9.

    Yu. A. Serguchev and E. A. Shilov, “Reactivity of π- and n-donor complexes of bromine in reactions with 1-hexene in benzene,” Teor. Éksp. Khim.,8, No. 1, 44–48 (1972).

  9. 10.

    E. N. Gur'yanova, I. P. Gol'dshtein, and I. P. Romm, Donor-Acceptor Bonds [in Russian], Khimiya, Moscow (1973).

  10. 11.

    G. I. Likhtenshtein, “Principle of ‘optimal motion’ in elementary acts of chemical and biochemical processes,” Kinet. Katal.,18, No. 4, 878–882 (1977).

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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 249–253, March–April, 1989.

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Khotkevich, A.B., Serguchev, Y.A., Krasutskii, P.A. et al. Effects of the medium on kinetics of transannular addition of iodine to dienes of the bicyclo[3.3.1]nonane series. Theor Exp Chem 25, 227–231 (1989).

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  • Ether
  • Benzene
  • Toluene
  • Iodine
  • Diethyl