Conclusions
-
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.
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.
The reaction is selective with respect to the spatial isomers of 2,4-dialkyl-1,3-dioxolanes (the cis-isomer reacts faster).
-
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.
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.
Similar content being viewed by others
Literature cited
M. F. Shostakovskii, A. S. Atavin, and B. A. Trofimov, Zh. obshch. khimii,34, 2088 (1964).
B. A. Trofimov, “Dissertation” [in Russian], Irkutsk (1965).
M. F. Shostakovskii, A. S. Atavin, S. E. Orlova, and B. A. Trofimov, Zh. organ. khimii,1, 1170 (1965).
A. S. Atavin, B. A. Trofimov, and S. E. Orlova, Zh. organ. khimii,2, 206 (1966).
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).
B. A. Trofimov, A. S. Atavin, and S. E. Orlova, Izv. AN SSSR, Ser. khim., 2023 (1966).
B. A. Trofimov, A. S. Atavin, and S. E. Orlova, Zh. organ. khimii, “in press” [in Russian].
P. J. Kruger and H. D. Mettee, J. Molec. Spectr.,18, 131 (1965).
A. Foster, A. Haines, and M. Stacey, Tetrahedron,16, 177 (1961).
L. P. Kuhn and B. A. Wires, J. Amer. Chem. Soc.,86, 2161 (1964).
M. Flett, Spectrochim. acta,10, 21 (1957).
M. I. Batuev and A. D. Matveeva, Izv. AN SSSR, Otd. khim. n., 448 (1951).
K. Nakanisi, “Infrared Spectra and the Structure of Organic Compounds” [in Russian], “Mir” (1965), p. 38.
H. H. Leiss and M. Tsutsui, J. Amer. Chem. Soc.,75, 897 (1953).
Habermehl Gerhard, Angew. Chemie,76, No. 6, 271 (1964).
L. I. Bellami, “Infrared Spectra of Complex Molecules,” [in Russian], IL (1958), p. 470.
N. Sheppard, Trans. Faraday Soc.,46 (7), 533 (1950).
P. Solomaa and A. Kankaanpeä, Acta chem. scand.,15, 871 (1961).
C. Blomberg, A. D. Vrengdenhil, and T. Homsma, Recueil. trav. chim.,82, 355 (1963).
Author information
Authors and Affiliations
Additional information
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 27272–2733, December, 1967.
Rights 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
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00908504