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

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Abstract

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%.

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References

  1. Feoktistov, L.G.,Organicheskaya elektrokhimiya (Organic Electrochemistry), Moscow: Khimiya, 1988, p. 270.

    Google Scholar 

  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.

    Google Scholar 

  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.

    Google Scholar 

  5. Gul’tyai, V.P., Korotaeva, L.M., Mikhal’chenko, L.V., and Leonova, M.Yu.,Elektrokhimiya, 1991, vol. 27, p. 1635.

    CAS  Google Scholar 

  6. Vatsuro, K.V. and Mishchenko, G.L.,Imennye reaktsii v organicheskoi khimii (Nominal Reactions in Organic Chemistry), Moscow: Khimiya, 1976.

    Google Scholar 

  7. Elving, P.J. and Tang Ch.-S.,Anal, Chem., 1951, vol. 23, p. 341.

    Article  CAS  Google Scholar 

  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.

    Google Scholar 

  9. Benderskii, V.A. and Krivenko, A.G.,Usp. Khim., 1990, vol. 59, p. 3.

    CAS  Google Scholar 

  10. Benderskii, V.A., Krivenko, A.G., Kurmaz, V.A., and Simbirtseva, G.V.,Elektrokhimiya, 1988, vol. 24, p. 158.

    CAS  Google Scholar 

  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.

    CAS  Google Scholar 

  14. Krivenko, A.G., Benderskii, V.A., Kotkin, A.S., and Kurmaz, V.A.,Elektrokhimiya, 1993, vol. 29, p. 869.

    CAS  Google Scholar 

  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.

    CAS  Google Scholar 

  17. Rufman, N.M. and Rotenberg, Z.A.,Elektrokhimiya, 1980, vol. 16, p. 1548.

    CAS  Google Scholar 

  18. Konovalov, V.V., Bil’kis, I.I., Raitsimring, A.M., and Tsvetkov, Yu.D.,Dokl. Akad. Nauk SSSR, 1988, vol. 302, p. 859.

    CAS  Google Scholar 

  19. Rufman, N.M. and Rotenberg, Z.A.,Elektrokhimiya, 1980, vol. 16, p. 364.

    CAS  Google Scholar 

  20. Wayner, D.D.M. and Parker, V.D.,Acc. Chem. Res., 1993, vol. 26, p. 287.

    Article  CAS  Google Scholar 

  21. Smith, D.K., Strohben, W.E., and Evans, D.G.,J. Electroanal. Chem., 1990, vol. 288, p. 111.

    Article  CAS  Google Scholar 

  22. Jones, W.R., Jr. and Fox, M.A.,J. Phys. Chem., 1994, vol. 98, p. 5095.

    Article  CAS  Google Scholar 

  23. Henglein, A.,Electroanalytical Chemistry: A Series of Advances, Bard, A.J., Ed., New York: Marcel Dekker, 1976, vol. 9, p. 163.

    Google Scholar 

  24. Toffel, P. and Henglein, A.,Disc. Faraday Soc., 1978, vol. 63, p. 124.

    Google Scholar 

  25. Occialini, D., Kristensen, J.S., Daasbjerg, K., and Lund, H.,Acta Chem. Scand., 1992, vol. 46, p. 474.

    Google Scholar 

  26. Lund, Kh., Daasb’erg, K., Ochiallini, D., and Pedersen, O.U.,Elektrokhimiya, 1995, vol. 31, p. 939.

    Google Scholar 

  27. Ershler, A.B., Kurmaz, V.A., and Strelets, V.V.,Elektrokhimiya, 1981, vol. 17, p. 186.

    CAS  Google Scholar 

  28. Casado, J., Gullere, J., Julia, M., and Brillas, E.,Collect. Czech. Chem. Commun., 1993, vol. 58, p. 2875.

    Article  CAS  Google Scholar 

  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.

    Google Scholar 

  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.

    Google Scholar 

  33. Andryushchenko, F.K. and Orekhova, V.V.,Ukr. Khim. Zh. (Russ. Ed.), 1962, vol. 28, p. 269.

    CAS  Google Scholar 

  34. Feoktistov, L.G., Tomilov, A.P., Smirnov, Yu.D., and Gol’din, M.M.,Elektrokhimiya, 1965, vol. 1, p. 887.

    CAS  Google Scholar 

  35. Plump, R. and Hammet, L.,Trans. Electrochem. Soc., 1938, vol. 23, p. 523.

    Google Scholar 

  36. Brown, O.R. and Taylor, K.,J. Electroanal. Chem., 1974, vol. 50, p. 211.

    CAS  Google Scholar 

  37. Elving, P.J.,Record. Chem. Progr., 1953, vol. 14, p. 99.

    CAS  Google Scholar 

  38. Brand-Gie\en, K.,Z. Elektrochem., 1910, vol. 16, p. 669.

    Google Scholar 

  39. Brand, K. and Masui, M.,Ber. Bunsen-Ges. Phys. Chem., 1913, vol. 40, p. 2949.

    Google Scholar 

  40. Brand, K. and Kricke-Amelung, D.,Ber. Bunsen-Ges. Phys. Chem., 1939, vol. 70, p. 1029.

    Article  Google Scholar 

  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.

    Google Scholar 

  43. Petrosyan, V.A.,Elektrokhimiya, 1996, vol. 32, p. 53.

    Google Scholar 

  44. Andrieux, C.P., Gallardo, J., Saveant, J.-M., and Su, Kh.-B.,J. Am. Chem. Soc., 1986, vol. 108, p. 4638.

    Google Scholar 

  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.

    Google Scholar 

  46. Butler, A.L. and Peters, D.G.,J. Electrochem. Soc., 1997, vol. 144, p. 4212.

    Article  CAS  Google Scholar 

  47. Cypris, D.,J. Appl. Electrochem., 1978, vol. 8, p. 537.

    Article  Google Scholar 

  48. Cypris, D.,J. Appl. Electrochem., 1978, vol. 8, p. 545.

    Article  Google Scholar 

  49. Zimakov, P.V., Dyment, O.N., Bogoslovskii, N.A.,et al., Okis’ etilena (Ethylene Oxide), Moscow: Khimiya, 1967, p. 158.

    Google Scholar 

  50. Buxton, G.V., Greenstock, C.L., Helman, W.Ph., and Ross, A.R.,J. Phys. Chem. Ref. Data, 1988, vol. 17, p. 513.

    CAS  Google Scholar 

  51. Brown, O.R. and Taylor, K.,J. Electroanal. Chem., 1974, vol. 53, p. 281.

    Article  Google Scholar 

  52. Feoktistov, L.G.,Uspekhi elektrokhimii organicheskikh soedinenii (Advances in the Electrochemistry of Organic Compounds), Moscow: Nauka, 1966, p. 135.

    Google Scholar 

  53. Bard, A.J. and Merz, A.,J. Am. Chem. Soc., 1979, vol. 101, p. 2959.

    Article  CAS  Google Scholar 

  54. Malinovskii, S.M.,Okisi olefinov i ikh proizvodnye (Olefine Oxides and Their Derivatives), Moscow: Goskhimizdat, 1961.

    Google Scholar 

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Authors and Affiliations

  1. 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

  2. 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

Authors
  1. V. A. Kurmaz
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  2. A. G. Krivenko
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  3. A. P. Tomilov
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  4. V. V. Turygin
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  5. A. V. Khudenko
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  6. N. N. Shalashova
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  7. A. S. Kotkin
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Kurmaz, V.A., Krivenko, A.G., Tomilov, A.P. et al. Studying the dimerization reaction during the abstraction of halogen from organohalides by laser photoemission, controlled-potential electrolysis, and voltammetry. Russ J Electrochem 36, 308–315 (2000). https://doi.org/10.1007/BF02827975

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  • DOI: https://doi.org/10.1007/BF02827975

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