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December 17, 2017 23:26 MSK  
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Section of Unstable Molecules and Small-Sized Cyclic Compounds
Section of Unstable Molecules and Small-Sized Cyclic Compounds
Head: Full Member of RAS Oleg M. Nefedov

The Section was established in 2004 and includes four laboratories:

  • Laboratory of Carbene Chemistry and Small-Sized Cyclic Compounds (N5)
    Head: Full Member of RAS Oleg M. Nefedov (e-mail: nefedovatioc.ac.ru)
    The Laboratory was established in 1968 by its present Head.
  • Laboratory of Carbene Analogs and Related Intermediates (N1)
    Head: Corresponding Member of RAS Mikhail P. Egorov (e-mail: mpeatioc.ac.ru)
    The Laboratory was established in 2004.
  • Laboratory of Chemistry of Diazo Compounds (N6)
    Head: Yuri V. Tomilov, ScD (Chem.) (e-mail: tomatioc.ac.ru)
    The Laboratory was established in 2004.
  • Laboratory of Organic Electrosynthesis (N37)
    Head: Vladimir A. Petrosyan, Prof. (e-mail: petrosatioc.ac.ru)
    The laboratory was established in 1986 by its present Head.

Research Areas:
  • Usage of the modern computational and experimental methods for the comprehensive studies of the generation, structure, reactivity and chemical transformations of carbenes, their analogs, free radicals, and other unstable molecules with chemical bonds of unusual types, including multiple bonds E=X (E = Si, Ge; X = C, O, S);
  • Systematic study of the reactions of diazo alkanes and diazo esters both as carbene precursors and as reagents of 1,3-dipolar cycloaddition to multiple bonds, as well as non-conventional diazo components in processes similar to azo coupling reactions;
  • Development of fundamentally new methods for the synthesis of important organofluorine and other synthons;
  • Organization of manufacture of the compounds with practically useful properties.
Main results:
  • The method of IR and UV spectroscopic investigation of intermediates and other unstable molecules at their low-temperature stabilization in inert matrices has been developed;
  • Considerable contribution was made to the study of double bonds involving silicon and germanium atoms; in particular, Si=C was observed experimentally and studied for the first time;
  • Original systematic investigations of the role of labile complexes and electron-transfer stages in reactions of carbene analogs and radicals were carried out;
  • New methods for the synthesis of fluoroarenes based on [1+2] and [2+2] cycloaddition of available fluorocarbenes, fluoroolefines and fluorodienes to unsaturated compounds were developed;
  • Regularities of catalytic cyclopropanation of broad series of unsaturated compounds with aliphatic diazo compounds were established, particularly, this implies the first technologically compatible method for cyclopropanation of strained olefins under the conditions of simultaneous generation and catalytic destruction of diazomethane;
  • The ability of cyclopropyldiazonium ions to exhibit properties of both aliphatic and aromatic diazo compounds was discovered, with diazocyclopropane and cyclopropyldiazonium being trapped under direct nitrozation of cyclopropylamine with alkyl nitrites.
  • Manufacture of unique hydrocarbon fuel Cyclin and other high-energy polycyclic hydrocarbons was arranged in collaboration with other organizations. The first domestic manufacture of synthetic pyrethroids was started.
  • The studies on the directed synthesis and property investigation of new biologically active nitrogen-containing polycyclic compounds are in progress.
Labs 1, 5, 6