Skip to main content
Log in

Structural features of cleavage of nonsymmetrically substituted 1,3-dioxolanes by the Grignard reagent

  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    The reaction between 4-methyl- and 2,4-dialkyl-1,3-dioxolanes and the Grignard reagent shows specific structural features, since only one of the possible hydroxyl ethers is formed.

  2. 2.

    IR spectroscopy and GLCH analysis were used to determine the structures of the hydroxy ethers; based on these findings, it was shown that the Grignard reagent splits the nonsymmetrically substituted dioxolanes under study at the O1-C2 bond.

  3. 3.

    The reaction is selective with respect to the spatial isomers of 2,4-dialkyl-1,3-dioxolanes (the cis-isomer reacts faster).

  4. 4.

    The reaction of 4-methyl-1,3-dioxolane with ethylmagnesium bromide was used as an example to show that insoluble solvates form at the first reaction stage; these consist mainly of a complex of cyclic acetal with magnesium bromide.

  5. 5.

    The findings agree with a mechanism involving cyclic migration of electrons in the six-membered ring formed by the complex “acetal-magnesium bromide” and magnesium diethyl.

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

Access this article

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

Literature cited

  1. M. F. Shostakovskii, A. S. Atavin, and B. A. Trofimov, Zh. obshch. khimii,34, 2088 (1964).

    Google Scholar 

  2. B. A. Trofimov, “Dissertation” [in Russian], Irkutsk (1965).

  3. M. F. Shostakovskii, A. S. Atavin, S. E. Orlova, and B. A. Trofimov, Zh. organ. khimii,1, 1170 (1965).

    Google Scholar 

  4. A. S. Atavin, B. A. Trofimov, and S. E. Orlova, Zh. organ. khimii,2, 206 (1966).

    Google Scholar 

  5. M. F. Shostakovskii, A. S. Atavin, E. P. Vyalykh, B. A. Trofimov, N. A. Vodbol'skaya, and V. V. Keiko, Izv. AN SSSR, Ser. khim., 1283 (1966).

  6. B. A. Trofimov, A. S. Atavin, and S. E. Orlova, Izv. AN SSSR, Ser. khim., 2023 (1966).

  7. B. A. Trofimov, A. S. Atavin, and S. E. Orlova, Zh. organ. khimii, “in press” [in Russian].

  8. P. J. Kruger and H. D. Mettee, J. Molec. Spectr.,18, 131 (1965).

    Google Scholar 

  9. A. Foster, A. Haines, and M. Stacey, Tetrahedron,16, 177 (1961).

    Google Scholar 

  10. L. P. Kuhn and B. A. Wires, J. Amer. Chem. Soc.,86, 2161 (1964).

    Google Scholar 

  11. M. Flett, Spectrochim. acta,10, 21 (1957).

    Google Scholar 

  12. M. I. Batuev and A. D. Matveeva, Izv. AN SSSR, Otd. khim. n., 448 (1951).

  13. K. Nakanisi, “Infrared Spectra and the Structure of Organic Compounds” [in Russian], “Mir” (1965), p. 38.

  14. H. H. Leiss and M. Tsutsui, J. Amer. Chem. Soc.,75, 897 (1953).

    Google Scholar 

  15. Habermehl Gerhard, Angew. Chemie,76, No. 6, 271 (1964).

    Google Scholar 

  16. L. I. Bellami, “Infrared Spectra of Complex Molecules,” [in Russian], IL (1958), p. 470.

  17. N. Sheppard, Trans. Faraday Soc.,46 (7), 533 (1950).

    Google Scholar 

  18. P. Solomaa and A. Kankaanpeä, Acta chem. scand.,15, 871 (1961).

    Google Scholar 

  19. C. Blomberg, A. D. Vrengdenhil, and T. Homsma, Recueil. trav. chim.,82, 355 (1963).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 27272–2733, December, 1967.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Trofimov, B.A., Atavin, A.S., Orlova, S.E. et al. Structural features of cleavage of nonsymmetrically substituted 1,3-dioxolanes by the Grignard reagent. Russ Chem Bull 16, 2596–2600 (1967). https://doi.org/10.1007/BF00908504

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00908504

Keywords

Navigation