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Статья
2000

Studying the dimerization reaction during the abstraction of halogen from organohalides by laser photoemission, controlled-potential electrolysis, and voltammetry


V. A. Kurmaz V. A. Kurmaz , A. G. Krivenko A. G. Krivenko , A. P. Tomilov A. P. Tomilov , V. V. Turygin V. V. Turygin , A. V. Khudenko A. V. Khudenko , N. N. Shalashova N. N. Shalashova , A. S. Kotkin A. S. Kotkin
Российский электрохимический журнал
https://doi.org/10.1007/BF02827975
Abstract / Full Text

To continue earlier investigations into the dimerization reaction during the cathodic cleavage of a carbon-halogen bond and, in particular, to find an accessible way for synthesizing 1,4-butanediol, a comparative study of the dimerization of ethylene halohydrins and butyl and allyl halides is performed. On the basis of the data obtained by the laser photoemission (LPE), controlled-potential electrolysis, and voltammetry techniques, a general mechanism of the electrode reactions involving these compounds and their intermediates is proposed and recommendations on the optimization of the 1,4-butanediol synthesis are elaborated. According to LPE data, at pH < 8.1, the Β-hydroxyethyl radical reduction occurs with a preceding formation of a complex with a proton donor, whereas a direct electron transfer is characteristic of the butyl radical. This difference in mechanisms is offered as the main reason for the lesser capability of ethylene halohydrins to electrochemical dimerization as compared with butyl halides, where the octane yield reached up to 80–84%. The earlier assumption about a high electrocatalytic activity of the copper cathode in dimerization of ethylene halohydrins is confirmed, and possibilities of an iron cathode in this process are revealed. The dimer yield is found to increase in alkaline solutions and at lowered temperatures, specifically, at pH 11 and temperatures of 0–5°C., the 1,4-butanediol yield reached ∼17%.

Author information
  • Institute of Problems of Chemical Physics, Chernogolovka Branch, Russian Academy of Sciences, p/o Chernogolovka, Noginsk raion, 142432, Moscow oblast, Russia

    V. A. Kurmaz, A. G. Krivenko & A. S. Kotkin

  • Russian Research Institute of Organic Chemistry and Technology, sh. Entuziastov 23, 111024, Moscow, Russia

    A. P. Tomilov, V. V. Turygin, A. V. Khudenko & N. N. Shalashova

References
  1. Feoktistov, L.G.,Organicheskaya elektrokhimiya (Organic Electrochemistry), Moscow: Khimiya, 1988, p. 270.
  2. Tomilov, A.P., Mairanovskii, S.G., Fioshin, M.Ya., and Smirnov, V.A.,Elektrokhimiya organicheskikh soedinenii (The Electrochemistry of Organic Compounds), Leningrad: Khimiya, 1968.
  3. Kharlamova, T.A., Chernykh, I.N., and Tomilov, A.P.,Khim. Prom-st., 1979, no. 10, p. 589.
  4. Itov, G.V. and Avrutskaya, I.A.,Elektrokhimiya, 1995, vol. 31, p. 1245.
  5. Gul’tyai, V.P., Korotaeva, L.M., Mikhal’chenko, L.V., and Leonova, M.Yu.,Elektrokhimiya, 1991, vol. 27, p. 1635.
  6. Vatsuro, K.V. and Mishchenko, G.L.,Imennye reaktsii v organicheskoi khimii (Nominal Reactions in Organic Chemistry), Moscow: Khimiya, 1976.
  7. Elving, P.J. and Tang Ch.-S.,Anal, Chem., 1951, vol. 23, p. 341.
  8. Tomilov, A.P., Chernykh, I.N., and Kargin, Yu.M.,Elektwkhimiya elementoorganicheskikh soedinenii: elementyl, II, i III grupp periodicheskoi sistemy i perekhodnye metally (The Electrochemistry of Organometallic Compounds: Elements of Groups I, II, and III of the Periodic Table and the Transition Metals), Moscow: Nauka, 1985.
  9. Benderskii, V.A. and Krivenko, A.G.,Usp. Khim., 1990, vol. 59, p. 3.
  10. Benderskii, V.A., Krivenko, A.G., Kurmaz, V.A., and Simbirtseva, G.V.,Elektrokhimiya, 1988, vol. 24, p. 158.
  11. Krivenko, A.G. and Kurmaz, V.A., Abstracts of Papers,XIV Soveshchanie po elektrokhimii organicheskikh soedinenii (XIV Meet. on the Electrochemistry of Organic Compounds), Novocherkassk, 1998, p. 14.
  12. Krivenko, A.G., Kotkin, A.S., and Kurmaz, V.A.,Mendeleev Commun., 1998, no. 2, p. 56.
  13. Benderskii, V.A., Kotkin, A.S., Krivenko, A.G., and Kurmaz, V.A.,Elektrokhimiya, 1993, vol. 29, p. 246.
  14. Krivenko, A.G., Benderskii, V.A., Kotkin, A.S., and Kurmaz, V.A.,Elektrokhimiya, 1993, vol. 29, p. 869.
  15. Krivenko, A.G., Kotkin, A.S., and Kurmaz, V.A.,Mendeleev Commun., 2000, no. 2, p. 81.
  16. Eletskii, V.V. and Pleskov, Yu.V.,Elektrokhimiya, 1978, vol. 14, p. 1323.
  17. Rufman, N.M. and Rotenberg, Z.A.,Elektrokhimiya, 1980, vol. 16, p. 1548.
  18. Konovalov, V.V., Bil’kis, I.I., Raitsimring, A.M., and Tsvetkov, Yu.D.,Dokl. Akad. Nauk SSSR, 1988, vol. 302, p. 859.
  19. Rufman, N.M. and Rotenberg, Z.A.,Elektrokhimiya, 1980, vol. 16, p. 364.
  20. Wayner, D.D.M. and Parker, V.D.,Acc. Chem. Res., 1993, vol. 26, p. 287.
  21. Smith, D.K., Strohben, W.E., and Evans, D.G.,J. Electroanal. Chem., 1990, vol. 288, p. 111.
  22. Jones, W.R., Jr. and Fox, M.A.,J. Phys. Chem., 1994, vol. 98, p. 5095.
  23. Henglein, A.,Electroanalytical Chemistry: A Series of Advances, Bard, A.J., Ed., New York: Marcel Dekker, 1976, vol. 9, p. 163.
  24. Toffel, P. and Henglein, A.,Disc. Faraday Soc., 1978, vol. 63, p. 124.
  25. Occialini, D., Kristensen, J.S., Daasbjerg, K., and Lund, H.,Acta Chem. Scand., 1992, vol. 46, p. 474.
  26. Lund, Kh., Daasb’erg, K., Ochiallini, D., and Pedersen, O.U.,Elektrokhimiya, 1995, vol. 31, p. 939.
  27. Ershler, A.B., Kurmaz, V.A., and Strelets, V.V.,Elektrokhimiya, 1981, vol. 17, p. 186.
  28. Casado, J., Gullere, J., Julia, M., and Brillas, E.,Collect. Czech. Chem. Commun., 1993, vol. 58, p. 2875.
  29. Feoktistov, L.G., Tomilov, A.P., and Gol’din, M.M.,Izv. Akad. Nauk SSSR, Ser. Khim., 1963, p. 1352.
  30. Krivenko, A.G., Tomilov, A.P., Smirnov, Yu.D.,et al., Zh. Obshch. Khim., 1998, vol. 68, p. 292.
  31. Krivenko, A.G., Tomilov, A.P., Khudenko, A.V.,et al., Abstracts of Papers,XIV Soveshchanie po elektrokhimii organicheskikh soedinenii (XIV Meet. on the Electrochemistry of Organic Compounds), Novocherkassk, 1998, p. 16.
  32. Tomilov, A.P., Chernykh, I.N., and Khudenko, A.V.,Elektrokhimiya, 1999, vol. 35, p. 773.
  33. Andryushchenko, F.K. and Orekhova, V.V.,Ukr. Khim. Zh. (Russ. Ed.), 1962, vol. 28, p. 269.
  34. Feoktistov, L.G., Tomilov, A.P., Smirnov, Yu.D., and Gol’din, M.M.,Elektrokhimiya, 1965, vol. 1, p. 887.
  35. Plump, R. and Hammet, L.,Trans. Electrochem. Soc., 1938, vol. 23, p. 523.
  36. Brown, O.R. and Taylor, K.,J. Electroanal. Chem., 1974, vol. 50, p. 211.
  37. Elving, P.J.,Record. Chem. Progr., 1953, vol. 14, p. 99.
  38. Brand-Gie\en, K.,Z. Elektrochem., 1910, vol. 16, p. 669.
  39. Brand, K. and Masui, M.,Ber. Bunsen-Ges. Phys. Chem., 1913, vol. 40, p. 2949.
  40. Brand, K. and Kricke-Amelung, D.,Ber. Bunsen-Ges. Phys. Chem., 1939, vol. 70, p. 1029.
  41. Peregudova, S.M., Denisovich, L.I., Ustynyuk, N.A.,et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1995, no. 10, p. 2055.
  42. Vyaseleva, T.Ya., Torsuev, D.M., and Barabanov, V.P.,Zh. Obshch. Khim., 1998, vol. 68, p. 1736.
  43. Petrosyan, V.A.,Elektrokhimiya, 1996, vol. 32, p. 53.
  44. Andrieux, C.P., Gallardo, J., Saveant, J.-M., and Su, Kh.-B.,J. Am. Chem. Soc., 1986, vol. 108, p. 4638.
  45. Dale Hawley, M.,Encyclopedia of Electrochemistry of the Elements, Bard, A.J. and Lund, H., Eds., New York: Marcel Dekker, 1980, vol. 14, p. 2.
  46. Butler, A.L. and Peters, D.G.,J. Electrochem. Soc., 1997, vol. 144, p. 4212.
  47. Cypris, D.,J. Appl. Electrochem., 1978, vol. 8, p. 537.
  48. Cypris, D.,J. Appl. Electrochem., 1978, vol. 8, p. 545.
  49. Zimakov, P.V., Dyment, O.N., Bogoslovskii, N.A.,et al., Okis’ etilena (Ethylene Oxide), Moscow: Khimiya, 1967, p. 158.
  50. Buxton, G.V., Greenstock, C.L., Helman, W.Ph., and Ross, A.R.,J. Phys. Chem. Ref. Data, 1988, vol. 17, p. 513.
  51. Brown, O.R. and Taylor, K.,J. Electroanal. Chem., 1974, vol. 53, p. 281.
  52. Feoktistov, L.G.,Uspekhi elektrokhimii organicheskikh soedinenii (Advances in the Electrochemistry of Organic Compounds), Moscow: Nauka, 1966, p. 135.
  53. Bard, A.J. and Merz, A.,J. Am. Chem. Soc., 1979, vol. 101, p. 2959.
  54. Malinovskii, S.M.,Okisi olefinov i ikh proizvodnye (Olefine Oxides and Their Derivatives), Moscow: Goskhimizdat, 1961.