Abstract
A method of synthesis of aminobicycloheptanols by the hydroxyhalogenation of bicyclo[2.2.1]- heptene and its alkyl derivatives in a cycloolefin‒oxidant‒hydrogen halide system to induce electrophilic intermediates followed by substitution of the halogen atoms by amino groups of different compositions and structures. It was found that the selectivity of the reaction depends on the formation/consumption rate ratio for the electrophilic intermediate. A high selectivity with respect to hydroxyhalides takes place, when the consumption rate of the latter intermediate is higher than its formation rate. An increase in the pH of the medium becomes higher than 10.5 decreases the yield of amino alcohols and changes the reaction direction due to acceleration of dehydrohalogenation and formation of the corresponding epoxides.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Cervery, L., Harhoul, A., Berkas, S., and Ruzicka, V., Sb.VSCHT Praze, 1980, vol. 26, p. 58.
Kas’yan, L.I., Kas’yan, A.O., Okocityi S.I., and Tarabara I.N., Alitsiklicheskie epoksidnye soedineniya. Reaktsionnaya sposobnost’ (Alicyclic Epoxide Compounds. Reactivity), Dnepropetrovsk: Dnepropetrovsk. Nats. Univ., 2003.
Kas’yan, L.I. and Pal’chikov, V.A., Russ. J. Org. Chem., 2010, vol. 46, no. 1, p. 1. doi 1134/S107042801001001X
Okovityi, S.I., and Kas’yan, A.O., Russ. J. Org. Chem., 2004, vol. 440, no. 1, p. 1. doi 10.1023/B:RUJO.0000034906.46654.ff
Bergmeier, S.C., Tetrahedron, 2000, vol. 56, no. 17, p. 2561. doi 10.1016/S0040-4020(00)00149-6
Dryuk, V.G., Kartsev, V.G., and Voitsekhovskaya, M.A., Oksirany: sintez and biologicheskaya aktivnost’ (Oxiranes: Synthesis and Biological Activity), Moscow: Bogorodskii Pechatnik, 1997.
Karpf, M. and Trussardi, R., J. Org. Chem., 2001, vol. 66, no. 6, p. 2044. doi 10.1021/jo0057021
Inaba, T., Yamada, X., Abe, H., Segawa, S., and Cho, H., J. Org. Chem., 2000, vol. 65, no. 6, p.1623. doi 10.1021/jo991793e
Saiz, C., Villamil, V., González, M.M., Rossi, M.A., Martínez, L., Suescun, L., Vila, A.J., and Mahler, G., Tetrahedron: Asymmetry, 2017, vol. 28, no. 1, p. 110. doi 10.1016/j.tetasy.2016.11.002
De Souza Fernandes, F., Fernandes, T.S., Da Silveira, L.S., Caneschi, W., Lourenço, M.C.S., Diniz, C.G., De Olivera, P.F., Martins, S.D.P.L., Periera, D.E., Tavares, D.C., Le Hyaric, M., De Almeida, M.V., and Couri, M.R.C., Eur. J. Med. Chem., 2016, vol. 108, p. 203. doi 10.1016/j.ejmech.2015.11.037
Liu, X., Tang, M., Wang, L., and Chao, R., ommun. Mass Spectrom., 2016, vol. 30, no. 1, p. 161. doi 10.1002/rcm.7402
Sadygov, O.A., Alimardanov, Kh.M., and Abbasov, M.F., Russ. J. Gen. Chem., 2009, vol. 79, no. 8, p. 1698. doi 10.1134/S1070363209080192
Veliyev, M.G., Sadygov, O.A., Shatirova, M.I., and Alimardanov, Kh.M., Russ. J. Org. Chem., 2008, vol. 44, no. 9, p. 1282. doi 10.1134/S1070428008090066
Dobroserdova, I.B. and Anisimov, A.B., Praktikum po neftekhimicheskomu sintezu (Manual on Petrochemical Synthesis), Moscow: Mosl. Gos. Univ., 1981.
Babko, A.K. and Pyatnitskii, I.V., Kolichestvennyi analiz (Quantitative Analysis), Moscow: Vysshaya Shkola, 1962.
Colthup, N.B., Daiy, L.H., and Wiberiey, S.E., Introduction to Infrared and Raman Spectroscopy, Boston: Academic, 1990.
Derome, A.E., Modern NMR Techniques for Chemistry Research, Oxford: Pergamon, 1987.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © O.A. Sadygov, Kh.M. Alimardanov, Sh.I. Ismailova, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 5, pp. 717–723.
Rights and permissions
About this article
Cite this article
Sadygov, O.A., Alimardanov, K.M. & Ismailova, S.I. Inductive Hydroxyhalogenation of Bicyclo[2.2.1]heptenes and Synthesis of Amino Alcohols from the Reaction Products. Russ J Gen Chem 88, 862–868 (2018). https://doi.org/10.1134/S1070363218050031
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1070363218050031