Skip to main content
SpringerLink
Log in

The nature of ferrocenylalkylating agent in the acid-catalyzed reactions with ferrocenyl(phenyl)methanol

  • Full Article
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

The reaction of α-ferrocenyl(phenyl)methanol with various azoles under the phase transfer catalysis conditions afforded a series of ferrocenyl(alkyl)azoles in high yields. The structure of ferrocenyl(phenylmethyl)-3-trifluoromethyl-5-(2-thienyl)pyrazole was established by X-ray diffraction. The formation of a biradical cation from the intermediately formed ferrocenyl(phenyl)-carbenium ion, FcCH(Ph)+, was detected by ESR spin trap technique. Despite the demonstrated possibility of the formation of biradical cations, no products characteristic of the radical reaction pathway were found, which may serve as an indirect evidence that the reaction follows the SN1-mechanism.

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

Similar content being viewed by others

References

  1. V. I. Boev, L. V. Snegur, V. N. Babin, Yu. S. Nekrasov, Russ. Chem. Rev., 1997, 66, 613; DOI: https://doi.org/10.1070/RC1997v066n07ABEH000305.

    Article  Google Scholar 

  2. E. V. Shevaldina, S. K. Moiseev, INEOS OPEN, 2021, 4, 42; DOI: https://doi.org/10.32931/io2107r.

    Google Scholar 

  3. R. A. Benkeser, W. P. Fitzgerald, Jr., J. Org. Chem., 1961, 26, 4179; DOI: https://doi.org/10.1021/jo01068a110.

    Article  CAS  Google Scholar 

  4. A. A. Simenel, V. I. Dyachenko, S. M. Igumnov, Fluorine Notes, 2019, 125, 3; DOI: https://doi.org/10.17677/fn20714807.2019.04.02.

    Google Scholar 

  5. V. A. Mironov, M. D. Reshetova, N. I. Vorona, J. Gen. Chem. USSR, 1979, 49, 2521.

    CAS  Google Scholar 

  6. V. P. Tverdokhlebov, I. V. Tselinskii, B. V. Gidaspov, N. Yu. Vasileva, J. Org. Chem. USSR, 1978, 14, 1320.

    CAS  Google Scholar 

  7. U. Burckhardt, L. Hintermann, A. Schnyder, A. Togni, Organometallics, 1995, 14, 5415; DOI: https://doi.org/10.1021/om00011a069.

    Article  CAS  Google Scholar 

  8. A. A. Simenel, E. A. Morozova, L. V. Snegur, S. I. Zykova, V. V. Kachala, L. A. Ostrovskaya, N. V. Bluchterova, M. M. Fomina, Appl. Organomet. Chem., 2009, 23, 219; DOI: https://doi.org/10.1002/aoc.1500.

    Article  CAS  Google Scholar 

  9. P. G. Cozzi, L. Zoli, Green Chem., 2007, 9, 1292; DOI: https://doi.org/10.1039/B711523G.

    Article  CAS  Google Scholar 

  10. R. Jiang, Y. Shen, Y. Zhang, X.-Q. Xu, J. Shao, S.-J. Ji, Chin. J. Chem., 2011, 29, 1887; DOI: https://doi.org/10.1002/cjoc.201180329.

    Article  CAS  Google Scholar 

  11. A. N. Rodionov, K. Y. Zherebker, L. V. Snegur, A. A. Korlyukov, D. E. Arhipov, A. S. Peregudov M. M. Ilyin, Jr., O. M. Nikitin, N. B. Morozova, A. A. Simenel, J. Organomet. Chem., 2015, 783, 83; DOI: https://doi.org/10.1016/j.jorganchem.2015.01.031.

    Article  CAS  Google Scholar 

  12. R. Jiang, X.-Q. Chu, X. Xu, B. Wu, S.-J. Ji, Aust. J. Chem., 2011, 64, 1530; DOI: https://doi.org/10.1071/CH11167.

    Article  CAS  Google Scholar 

  13. R. Jiang, C.-X. Yuan, X.-P. Xu, S.-J. Ji, Appl. Organomet. Chem., 2012, 26, 62; DOI: https://doi.org/10.1002/aoc.1867.

    Article  CAS  Google Scholar 

  14. E. V. Shevaldina, K. A. Opredelennova, O. A. Chichvarina, Yu. Ya. Spiridonov, A. F. Smol’yakov, P. V. Dorovatovskii, S. K. Moiseev, Appl. Organomet. Chem., 2019, 33, e5228; DOI: https://doi.org/10.1002/aoc.5228.

    Article  CAS  Google Scholar 

  15. E. V. Shevaldina, A. D. Shagina, V. N. Kalinin, A. B. Ponomaryov, A. F. Smol’yakov, S. K. Moiseev, J. Organomet. Chem., 2017, 836–837, 1; DOI: https://doi.org/10.1016/j.jorganchem.2017.02.044.

    Article  CAS  Google Scholar 

  16. E. V. Shevaldina, A. D. Shagina, A. B. Ponomaryov, S. K. Moiseev, J. Organomet. Chem., 2019, 880, 29; DOI: https://doi.org/10.1016/j.jorganchem.2018.10.021.

    Article  CAS  Google Scholar 

  17. F. S. Arimoto, A. S. Haven, J. Am. Chem. Soc., 1955, 77, 6295; DOI: https://doi.org/10.1021/ja01628a068.

    Article  CAS  Google Scholar 

  18. J. Wright, L. Frambes, P. Reeves, J. Organomet. Chem., 1994, 476, 215; DOI: https://doi.org/10.1016/0022-328X(94)87084-5.

    Article  CAS  Google Scholar 

  19. K. Schlogl, A. Monar, Monatsh. Chem., 1961, 92, 219; DOI: https://doi.org/10.1007/BF01153875.

    Article  CAS  Google Scholar 

  20. B. Misterkiewicz, J. Organomet. Chem., 1982, 224, 43; DOI: https://doi.org/10.1016/S0022-328X(00)82565-6.

    Article  CAS  Google Scholar 

  21. V. A. Ol’shevskaya, A. V. Makarenkov, Yu. A. Borisov, I. V. Ananyev, E. G. Kononova, V. N. Kalinin, A. B. Ponomaryev, Polyhedron, 2018, 141, 181; DOI: https://doi.org/10.1016/j.poly.2017.11.034.

    Article  CAS  Google Scholar 

  22. R. P. Shekurov, L. Kh. Gil’manova, A. A. Zagidullin, V. A. Milyukov, Russ. Chem. Bull., 2021, 70, 1415.

    Article  CAS  Google Scholar 

  23. A. N. Nesmeyanov, L. G. Bogomolova, N. S. Kochetkova, V. D. Vilchevskaya, N. P. Palitsyn, I. G. Andrianova, O. P. Belozerova, USSR Pat. 263807, December 29, 1966.

  24. A. A. Simenel, S. V. Samarina, L. V. Snegur, Z. A. Starikova, L. A. Ostrovskaya, N. V. Bluchterova, M. M. Fomina, Appl. Organomet. Chem., 2008, 22, 276; DOI: https://doi.org/10.1002/aoc.1397.

    Article  CAS  Google Scholar 

  25. P. Kopf-Maier, H. Kopf, E. W. Neuse, Angew. Chem., Int. Ed., 1984, 23, 456; DOI: https://doi.org/10.1002/anie.198404561.

    Article  Google Scholar 

  26. V. N. Babin, Yu. A. Belousov, V. I. Borisov, V. V. Gumenyuk, Yu. S. Nekrasov, L. A. Ostrovskaya, I. K. Sviridova, N. S. Sergeeva, A. A. Simenel, L. V. Snegur, Russ. Chem. Bull., 2014, 63, 2405; DOI: https://doi.org/10.1007/s11172-014-0756-7.

    Article  CAS  Google Scholar 

  27. E. W. Neuse, F. Kanzava, Appl. Organomet. Chem., 1990, 4, 19; DOI: https://doi.org/10.1002/aoc.590040105.

    Article  CAS  Google Scholar 

  28. D. Scutaru, L. Tataru, I. Mazilu, E. Diaconu, T. Lixandru, C. Simionescu, J. Organomet. Chem. 1991, 401, 81; DOI: https://doi.org/10.1016/0022-328X(91)86197-X.

    Article  CAS  Google Scholar 

  29. C. Biot, G. Glorian, L. A. Maciejewski, J. S. Brocard, J. Med. Chem., 1997, 40, 3715; DOI: https://doi.org/10.1021/jm970401y.

    Article  CAS  PubMed  Google Scholar 

  30. A. N. Rodionov, L. V. Snegur, Y. V. Dobryakova, M. M. Ilyin, V. A. Markevich, A. A. Simenel, Appl. Organomet. Chem., 2020, 34, e5276; DOI: https://doi.org/10.1002/aoc.5276.

    Article  CAS  Google Scholar 

  31. A. N. Rodionov, L. V. Snegur, A. A. Simenel, Yu. V. Dobryakova, V. A. Markevich, Russ. Chem. Bull., 2017, 66, 136; DOI: https://doi.org/10.1007/s11172-017-1711-1.

    Article  CAS  Google Scholar 

  32. E. Yu. Osipova, A. N. Rodionov, Yu. A. Belousov, M. M. Il’in, A. L. Nikolaev, A. V. Gopin, S. E. Mazina, A. A. Simenel, Russ. J. Org. Chem., 2016, 52, 127; DOI: https://doi.org/10.1134/S1070428016010243.

    Article  CAS  Google Scholar 

  33. K. Kowalski, Coord. Chem. Rev., 2016, 317, 132; DOI: https://doi.org/10.1016/j.ccr.2016.02.008.

    Article  CAS  Google Scholar 

  34. C. Ornelas, New J. Chem., 2011, 35, 1973; DOI: https://doi.org/10.1039/C1NJ20172G.

    Article  CAS  Google Scholar 

  35. L. V. Snegur, A. A. Simenel, A. N. Rodionov, V. I. Boev, Russ. Chem. Bull., 2014, 63, 26; DOI: https://doi.org/10.1007/s11172-0140390-4.

    Article  CAS  Google Scholar 

  36. A. A. Musikhina, I. A. Utepova, O. N. Chupakhin, A. I. Suvorova and E. Yu. Zyryanova, Mendeleev Commun., 2020, 30, 209; DOI: https://doi.org/10.1016/j.mencom.2020.03.026.

    Article  CAS  Google Scholar 

  37. A. A. Simenel, Yu. V. Kuzmenko, M. M. Ilyin, V. V. Gumenyuk, L. V. Snegur, Yu. S. Nekrasov, Russ. Chem. Bull., 2004, 53, 939; DOI: https://doi.org/10.1023/B:RUCB.0000037868.08052.23.

    Article  CAS  Google Scholar 

  38. Comprehensive Heterocyclic Chemistry, Eds A. R. Katritzky, Ch. W. Rees, Pergamon Press, New York, 1984, 5, 169.

    Google Scholar 

  39. Yu. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom., 1991, 26, 733; DOI: https://doi.org/10.1002/oms.1210260903.

    Article  CAS  Google Scholar 

  40. Y. S. Nekrasov, R. S. Skazov, A. A. Simenel, L. V. Snegur, V. V. Gumenyuk, Russ. Chem. Bull., 2005, 54, 2460; DOI: https://doi.org/10.1007/s11172-006-0138-x.

    Article  CAS  Google Scholar 

  41. J. Muller, Angew. Chem., Int. Ed., 1972, 11, 653; DOI: https://doi.org/10.1002/anie.197206531.

    Article  Google Scholar 

  42. S. Allenmark, Tetrahedron Lett., 1974, 15, 371; DOI: https://doi.org/10.1016/S0040-4039(01)82217-6.

    Article  Google Scholar 

  43. M. Hisatome, K. Yamakawa, Tetrahedron, 1971, 27, 2101; DOI: https://doi.org/10.1016/S0040-4020(01)91608-4.

    Article  CAS  Google Scholar 

  44. K. L. Rinehart, C. J. Michejda, P. A. Kittl, J. Am. Chem. Soc., 1959, 81, 3162; DOI: https://doi.org/10.1021/ja01521a082.

    Article  CAS  Google Scholar 

  45. M. Cais, A. Modiano, A. Raveh, J. Am. Chem. Soc., 1965, 87, 5607; DOI: https://doi.org/10.1021/ja00952a017.

    Article  CAS  Google Scholar 

  46. P. Askenazi, M. Cais, Angew. Chem., Int. Ed., 1972, 11, 1027; DOI: https://doi.org/10.1002/anie.197206921.

    Article  Google Scholar 

  47. M. Cais, P. Askenazi, S. Dani, J. Gottlieb, J. Organomet. Chem., 1977, 124, 49; DOI: https://doi.org/10.1016/S0022-328X(00)90048-2.

    Article  CAS  Google Scholar 

  48. A. Z. Kreindlin, F. M. Dolgushin, A. I. Yanovskii, Z. A. Kerzina, P. V. Petrovskii, M. I. Rybinskaya, J. Organomet. Chem., 2000, 616, 106; DOI: https://doi.org/10.1016/S0022-328X(00)00566-0.

    Article  CAS  Google Scholar 

  49. M. I. Rybinskaya, Yu. S. Nekrasov, Yu. A. Borisov, A. I. Belokon’, A. Z. Kreindlin, A. A. Kamyshova, N. V. Kruglova, J. Organomet. Chem., 2001, 631, 9; DOI: https://doi.org/10.1016/S0022-328X(01)00848-8.

    Article  CAS  Google Scholar 

  50. S. P. Solodovnikov, A. Z. Kreindlin, L. S. Shilovtseva, M. I. Rybinskaya, Organomet. Chem. USSR, 1991, 4, 142.

    Google Scholar 

  51. L. V. Snegur, Dr. Sci. Thesis (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Moscow, 2002, 192 pp. (in Russian).

    Google Scholar 

  52. Yu. A. Belousov, Dr. Sci. Thesis (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Moscow, 2008, 231 pp. (in Russian).

    Google Scholar 

  53. V. N. Babin, Yu. A. Belousov, T. A. Belousova, Yu. A. Borisov, V. V. Gumenyuk, Yu. S. Nekrasov, Russ. Chem. Bull., 2011, 60, 2081; DOI: https://doi.org/10.1007/s11172-011-0318-1.

    Article  CAS  Google Scholar 

  54. R. S. Skazov, Y. S. Nekrasov, S. A. Kuklin, A. A. Simenel, Eur. J. Mass Spectrom., 2006, 12, 137; DOI: https://doi.org/10.1255/ejms.795.

    Article  CAS  Google Scholar 

  55. G. M. Sheldrick, Acta Crystallogr., 2015, A71, 3; DOI: https://doi.org/10.1107/S2053273314026370.

    Google Scholar 

  56. G. M. Sheldrick, Acta Crystallogr., 2015, C71, 3; DOI: https://doi.org/10.1107/S2053229614024218.

    Google Scholar 

  57. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Crystallogr., 2009, 42, 339; DOI: https://doi.org/10.1107/S0021889808042726.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    A. N. Rodionov, L. V. Snegur, Yu. A. Belousov, A. A. Korlyukov & A. A. Simenel

Authors
  1. A. N. Rodionov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. V. Snegur
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yu. A. Belousov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. A. Korlyukov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. A. Simenel
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. A. Simenel.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1900–1907, October, 2021.

Single crystal X-ray diffraction study of 3d was carried out in the X-Ray Structural Center of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences.

This work was financially supported by the Ministry of Science and Higher Education of the Russian Federation using the equipment of the X-Ray Structural Center of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Moscow.

This paper does not contain descriptions of studies on animals or humans.

The authors declare no competing interests.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rodionov, A.N., Snegur, L.V., Belousov, Y.A. et al. The nature of ferrocenylalkylating agent in the acid-catalyzed reactions with ferrocenyl(phenyl)methanol. Russ Chem Bull 70, 1900–1907 (2021). https://doi.org/10.1007/s11172-021-3294-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11172-021-3294-0

Key words

Search

Navigation