Russian Chemical Bulletin

, Volume 57, Issue 2, pp 431–433 | Cite as

Reactions of the paramagnetic quaternary Mannich base in an alkaline medium

  • A. D. Malievskii
  • A. B. Shapiro
Brief Communications


The catalytic action of aqueous NaOH at 20 °C on 2,2,6,6-tetramethyl-3-(N-methyl-piperidiniomethyl)-4-oxopiperidine 1-oxyl iodide rapidly resulted in the formation (k = 57 L mol−1 s−1) of a paramagnetic ketone with an activated double bond: 2,2,6,6-tetramethyl-3-methylidene-4-oxopiperidine 1-oxyl. The latter underwent slow transformation into a nitroxyl biradical containing an activated double bond and a methylene bridge linking positions 3 and 3′.

Key words

paramagnetic Mannich base kinetics rate constants reaction mechanism nitroxyl radicals 


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  1. 1.
    A. B. Shapiro, L. N. Skripchenko, V. M. Chumakov, V. V. Pavlikov, E. G. Rozantsev, Bioorg. Khim., 1977, 3, 707 [Sov. J. Bioorg. Chem., 1977, 3 (Engl. Transl.)].Google Scholar
  2. 2.
    A. B. Shapiro, V. I. Suskina, Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 1900 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986, 35, 1728 (Engl. Transl.)].Google Scholar
  3. 3.
    E. G. Rozantsev, Svobodnye iminoksilr’nye radikaly [Free Iminoxyl Radicals], Khimiya, Moscow, 1970, 216 pp. (in Russian).Google Scholar
  4. 4.
    A. B. Shapiro, L. P. Lebedeva, V. I. Suskina, G. N. Antipina, L. N. Smirnov, P. I. Levin, E. G. Rozantsev, Vysokomol. Soedin., Ser. A, 1973, 15, 2673 [Polym. Sci. USSR, Ser. A, 1973, 15 (Engl. Transl.)].Google Scholar
  5. 5.
    A. V. Fionov, A. F. Sadykov, Izv. Akad. Nauk, Ser. Khim., 2007, 165 [Russ. Chem. Bull., Int. Ed., 2007, 56, 174].Google Scholar
  6. 6.
    A. D. Malievskii, S. V. Koroteev, Izv. Akad. Nauk, Ser. Khim., 1996, 842 [Russ. Chem. Bull., 1996, 45, 797 (Engl. Transl.)].Google Scholar
  7. 7.
    P. I. Dmitriev, A. B. Shapiro, L. G. Kuz’mina, Yu. T. Struchkov, Dokl. Akad. Nauk SSSR, 1983, 271, 645 [Dokl. Chem., 1983 (Engl. Transl.)].Google Scholar
  8. 8.
    P. Sykes, A Guidebook to Mechanism in Organic Chemistry, Longman, London, 1971.Google Scholar

Copyright information

© Springer Science+Business Media, Inc.  2008

Authors and Affiliations

  1. 1.N. M. Emanuel Institute of Biochemical PhysicsRussian Academy of SciencesMoscowRussian Federation

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