Skip to main content
SpringerLink
Log in

Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides*

  • Published:
Chemistry of Heterocyclic Compounds Aims and scope

The reaction of amides RSO2-Pro-NHMe with ClCH2SiMe2Cl in the presence of (Me3Si)2NH gave pentacoordinated chlorosilanes RSO2-Pro-N(Me)CH2SiMe2Cl with an organosulfonyl group (R = Me, Ph, 4-ClC6H4, 4-BrC6H4, 4-MeC6H4, and 4-O2NC6H4) attached to the proline nitrogen atom. An alternative method for the preparation of these compounds comprises the cyclosilylmethylation of proline methylamide by dimethylchloromethylchlorosilane to give the previously unreported heterocyclic 2-sila-5-piperazinone system in the first step. The bicyclic silacyclane synthesized is 2-sila5-piperazinone condensed with a proline residue. The action of sulfonyl chlorides RSO2Cl leads to cleavage of the sila ring Si–N bond to give the desired chlorosilanes. The hydrolysis of these products, depending on the reaction conditions, gives either silyloxonium chlorides [RSO2-ProN(Me)CH2SiMe2OH2]Cl or disiloxanes [RSO2-Pro-N(Me)CH2SiMe2]2O. X-ray diffraction structural analysis showed that the silicon atom in the chlorides and silyloxonium chlorides is pentacoordinated due to an intramolecular O → Si bond and has distorted trigonal-bipyrimidal configuration. 29Si NMR spectroscopy showed that the disiloxanes and bicyclic sila-5-piperazinone have a tetracoordinated silicon atom.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. D. Kost and I. Kalikhman, in: Z. Rappoport and Y. Apeloig (editors), The Chemistry of Organic Silicon Compounds, Vol. 2, Part 1, J. Wiley, Chichester (1998), p. 1339.

    Chapter  Google Scholar 

  2. M. G. Voronkov, V. A. Pestunovich, and Yu. I. Baukov, Metalloorg. Khim., 4, 1210 (1991).

    CAS  Google Scholar 

  3. C. Chuit, R. J. P. Corriu, C. Reyé, and J. C. Young, Chem. Rev., 93, 1371 (1993).

    Article  CAS  Google Scholar 

  4. V. V. Negrebetsky and Yu. I. Baukov, Izv. Akad. Nauk, Ser. Khim., 11, 1912 (1997).

    Google Scholar 

  5. A. A. Macharashvili, V. E. Shklover, Yu. T. Struchkov, G. I. Oleneva, E. P. Kramarova, A. G. Shipov, and Yu. I. Baukov, J. Chem. Soc., Chem. Commun., 683 (1988).

  6. D. Kummer and S. H. Abdel Halim, Z. Anorg. Allg. Chem., 622, 57 (1996).

    Article  CAS  Google Scholar 

  7. V. F. Sidorkin, V. V. Vladimirov, M. G. Voronkov, and V. A. Pestunovich, J. Mol. Struct. (Theochem.), 228, 1 (1991).

    Article  Google Scholar 

  8. Yu. E. Ovchinnikov, A. A. Macharashvili, Yu. T. Struchkov, A. G. Shipov, and Yu. I. Baukov, Zh. Strukt. Khim., 35, 1 (1994).

    Google Scholar 

  9. A. R. Bassindale, M. Borbaruah, S. J. Glynn, D. J. Parker, and P. G. Taylor, J. Organomet. Chem., 606, 125 (2000).

    Article  CAS  Google Scholar 

  10. A. R. Bassindale, D. J. Parker, P. G. Taylor, N. Auner, and B. Herrschaft, J. Organomet. Chem., 667, 66 (2003).

    Article  CAS  Google Scholar 

  11. B. Gostevskii, G. Silbert, K. Adear, A. Sivaramakrishna, D. Stalke, S. Deuerlein, N. Kocher, M. G. Voronkov, I. Kalikhman, and D. Kost, Organometallics, 24, 2913 (2005).

    Article  CAS  Google Scholar 

  12. K. D. Onan, A. T. McPhail, C. H. Yoder, and R. W. Hillyard, J. Chem. Soc., Chem. Commun., 209 (1978).

  13. R. W. Hillyard, C. M. Ryan, and C. H. Yoder, J. Organomet. Chem., 153, 369 (1978).

    Article  CAS  Google Scholar 

  14. C. H. Yoder, C. M. Ryan, G. F. Martin, and P. S. Ho, J. Organomet. Chem., 190, 1 (1980).

    Article  CAS  Google Scholar 

  15. Yu. I. Baukov, E. P. Kramarova, A. G. Shipov, G. I. Oleneva, O. B. Artamkina, A. I. Albanov, M. G. Voronkov, and V. A. Pestunovich, Zh. Obshch. Khim., 59, 127 (1989).

    CAS  Google Scholar 

  16. V. V. Negrebetsky, P. G. Taylor, E. P. Kramarova, S. Yu. Bylikin, I. Yu. Belavin, A. G. Shipov, A. R. Bassindale, and Yu. I. Baukov, J. Organomet. Chem., 691, 3976 (2006).

    Article  CAS  Google Scholar 

  17. A. G. Shipov, E. P. Kramarova, and Yu. I. Baukov, Zh. Obshch. Khim., 64, 1220 (1994).

    CAS  Google Scholar 

  18. V. F. Sidorkin, E. F. Belogolova, and V. A. Pestunovich, J. Mol. Struct., 538, 59 (2001).

    CAS  Google Scholar 

  19. V. A. Pestunovich, V. F. Sidorkin, and M. G. Voronkov, in: Progress in Organosilicon Chemistry, Gordon and Breach, New York (1995), p. 69.

    Google Scholar 

  20. A. R. Bassindale, M. Borbaruah, S. J. Glynn, D. J. Parker, and P. G. Taylor, J. Chem. Soc., Perkin Trans. 2, 2099 (1999).

  21. A. R. Bassindale, S. J. Glynn, P. G. Taylor, N. Auner, and B. Herrschaft, J. Organomet. Chem., 619, 132 (2001).

    Article  CAS  Google Scholar 

  22. Cambridge Structural Database (CSD), Release 2010.

  23. A. O Mozzhukhin, M. Yu. Antipin, Yu. T. Struchkov, A. G. Shipov, E. P. Kramarova, and Yu. I. Baukov, Metalloorg. Khim., 5, 906 (1992).

    CAS  Google Scholar 

  24. I. D. Kalikhman, A. I. Albanov, O. B. Bannikova, L. I. Belousova, M. G. Voronkov, V. A. Pestunovich, A. G. Shipov, E. P. Kramarova, and Yu. I. Baukov, J. Organomet. Chem., 361, 147 (1989).

    Article  CAS  Google Scholar 

  25. V. A. Pestunovich, S. V. Kirpichenko, N. F. Lazareva, A. I. Albanov, and M. G. Voronkov, J. Organomet. Chem., 692, 2160 (2007).

    Article  CAS  Google Scholar 

  26. V. A. Pestunovich, Author's Abstract of Chem. Sci. Doct. Diss., Irkutsk (1985).

  27. V. V. Negrebetsky, S. N. Tandura, and Yu. I. Baukov, Usp. Khim., 78, 24 (2009).

    Google Scholar 

  28. A. A. Korlyukov, S. A. Pogozhikh, Yu. E. Ovchinnikov, K. A. Lyssenko, M. Yu. Antipin, A. G. Shipov, O. A. Zamyshlyaeva, E. P. Kramarova, Vad. V. Negrebetsky, I. P. Yakovlev, and Yu. I. Baukov, J. Organom. Chem., 691, 3962 (2006).

    Article  CAS  Google Scholar 

  29. Vad. V. Negrebetsky, A. G. Shipov, E. P. Kramarova, V. V. Negrebetsky, and Yu. I. Baukov, J. Organomet. Chem., 530, 1 (1997).

    Article  CAS  Google Scholar 

  30. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, and R. Taylor, J. Chem. Soc., Perkin Trans. 2, S1 (1987).

  31. R. R. Holmes and J. A. Deiters, J. Am. Chem. Soc., 99, 3318 (1977).

    Article  CAS  Google Scholar 

  32. W. S. Brey, Pulse Methods in 1D and 2D Liquid-Phase NMR, Academic Press, New York (1988), p. 561.

    Google Scholar 

  33. N. Izumiya, Bull. Chem. Soc. Japan, 26, 53 (1953).

    Article  CAS  Google Scholar 

  34. J. De Ruiter, A. N. Brubaker, M. A. Garner, J. M. Barksdale, and C. A. Mayfield, J. Pharm. Sci., 76, 149 (1987).

    Article  Google Scholar 

  35. R. Korukonda, N. Guan, J. T. Dalton, J. Liu, and I. O. Donkor, J. Med. Chem., 49, 5282 (2006).

    Article  CAS  Google Scholar 

  36. J. K. Chang, H. Sievertsson, B. Currie, and K. Folkers, J. Med. Chem., 14, 484 (1971).

    Article  CAS  Google Scholar 

  37. G. M. Sheldrick, Acta Crystallogr. A64, 112 (2008).

    CAS  Google Scholar 

  38. A. A. Potekhin, Handbook of Properties of Organic Compounds [in Russian], Khimiya, Leningrad (1984), p. 298.

    Google Scholar 

  39. R. R. Hill, S. A. Moore, and D. R. Roberts, Photochem. Photobiol., 81, 1439 (2005).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Russian State Medical University, 1 Ostrovityanova St, Moscow, 117997, Russia

    A. A. Nikolin, A. G. Shipov, E. P. Kramarova, V. V. Negrebetsky, Yu. I. Baukov & S. Yu. Bylikin

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St., Moscow, 119991, Russia

    D. E. Arkhipov, N. A. Koval˙ˈchuk & A. A. Korlyukov

  3. Open University, Walton Hall, Milton Keynes, MK7 6AA, Great Britain, UK

    A. R. Bassindale, P. G. Taylor, A. Bowden & S. Yu. Bylikin

Authors
  1. A. A. Nikolin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. E. Arkhipov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. G. Shipov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. E. P. Kramarova
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. N. A. Koval˙ˈchuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. A. Korlyukov
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. V. V. Negrebetsky
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yu. I. Baukov
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. A. R. Bassindale
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. P. G. Taylor
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. A. Bowden
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. S. Yu. Bylikin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to A. A. Korlyukov or Yu. I. Baukov.

Additional information

*Dedicated to the shining memory of our friend, Edmunds Lukevics, whom we knew, appreciated, and loved, a bright, energetic, multifaceted personality, a scientist with a capital S, brilliant leader, highly erudite chemist, who made a definitive contribution to the creation and development of a new area in silicon chemistry, namely, silicon bioorganic chemistry.

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1869–1890, December, 2011.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Nikolin, A.A., Arkhipov, D.E., Shipov, A.G. et al. Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides*. Chem Heterocycl Comp 47, 1565–1583 (2012). https://doi.org/10.1007/s10593-012-0949-7

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10593-012-0949-7

Keywords

Search

Navigation