Abstract
The conformational isomerization of cis- and trans-isomers of 2,5-dimethyl-1,3-dioxane was investigated by means of ab initio RHF//6-31G(d) and PBE//ccpVDZ quantum-chemical methods. It has been shown that in comparison with cis-form the potential energy surface of trans-isomer has a less number of stationary points and includes the main minimum belonging to the diequatorial chair form. In the case of cisisomer the main minimum corresponds to the C 2e5a chair form. The values of potentional barriers of conformational isomerization were also determined. On the basis of experimental (NMR 1H) and theoretical vicinal coupling constants we determine the value ΔG 0 of chair-chair inversion for the trans-isomer molecule.
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Rakhmankulov, D.l., Karakhanov, R.A., Zlotskii, S.S., Kantor, E.A., Imashev, U.B., and Syrkin, A.M., Itogi nauki i tekhniki. Tekhnologiya organicheskikh veshchestv (Science and Technics Results. Organic Substances Technology), Moscow: VINITI, 1979, vol. 5, p. 6.
Vnutrenneye vrashchenie molekul (Internal Rotation of Molecules), Orwill-Tomas, V.J., Ed., Moscow: Mir, 1975, p. 355.
Kuznetsov, V.V., Khim. Geterotsikl. Soedinin., 2006, no. 5, p. 643.
Kuznetsov, V.V., Izv. Akad. Nauk Ser. Khim., 2005, no. 7, p. 1499.
Freeman, F. and Uyen, Do K., J. Mol. Struct. (Theochem), 2002, vol. 577, no. 1, p. 43.
Kuramshina, A.E., Faizullin, M.G., Bochkor, S.A., and Kuznetsov, V.V., Bashkir. Khim. Zh., 2004, vol. 11, p. 81.
Mazitova, E.G., Kuramshina, A.E., and Kuznetsov, V.V., Zh. Org. Khim., 2004, vol. 40, no. 4, p. 615.
Mamleev, A.Kh., Gunderova, L.N., Galeev, R.V., Shapkin, A.A., Faizullin, M.G., Gorbunova, N.V., Shornikov, D.V., and Kantor, E.A., Zh. Strukt. Khim., 2007, vol. 48, no. 3, p. 501.
Faizullin, M.G., Galeev, R.V., Gunderova, L.N., Shapkin, A.A., and Mamleev, A.Kh., Vestnik Bash. Gos. Univ., 2006, no. 2, p. 29.
Alabugin, I.V., Manoharan, M., and Zeidan T.A., J. Am. Chem. Soc., 2003, vol. 125, no. 46, p. 14014.
Kuramshina, A.E., Bochkor, S.A., and Kuznetsov, V.V., Zh. Org. Khim., 2006, vol. 42, no. 4, p. 629.
Mamleev, A.Kh., Gunderova, L.N., Galeev, R.V., Shapkin, A.A., Faizullin, M.G., Nikitina, A.P., Shornikov, D.V., and Kantor, E.A., Zh. Strukt. Khim., 2007, vol. 48, no. 6, p. 1097.
Mamleev, A.Kh., Galeev, R.V., Gunderova, L.N., Faizullin, M.G., and Shapkin, A.A., Zh. Strukt. Khim., 2008, vol. 49, no. 4, p. 667.
Kuramshina, A.E. and Kuznetsov, V.V., Khim. Geterotsikl. Soedinin., 2009, no. 1, p. 131.
Mamleev, A.Kh., Galeev, R.V., Gunderova, L.N., Faizullin, M.G., and Shapkin, A.A., Zh. Strukt. Khim., 2007, vol.48, no. 5, p. 1020.
Kuramshina, A.E., Tseplin, E.E., Bochkor, S.A., Khvostenko, O.G., and Kuznetsov, V.V., Fizika v Bashkortostane (Physics in Bashkortostan), Ufa: Gilem, 2005, no. 3, p. 161.
Kuznetsov, V.V., Kuramshina, A.E., Tseplin, E.E., Bochkor, S.A., and Khvostenko, O.G., Sovremennye naukoemkie tekhnologii (Contemporary Science Intensive Technology), 2006, no. 2, p. 76.
HyperChem 7.01. Trial version, www.hyper.com.
Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L., Dupuis, M., and Montgomery, J.A., J. Comput. Chem., 1993, vol.14, p. 1347.
Dashevskii, V.G., Konformatsii organicheskikh molekul (Organic Molecules Conformations), Moscow: Khimiya, 1974.
Samitov, Yu.Yu., Atlas spektrov YaMR prostranstvennykh izomerov (NMR Spectral Atlas of Stereoisomers), Kazan: Kazansk. Univ., vol.1, 1978, p. 59.
Eliel, E. and Knoeber, M.C., J. Am. Chem. Soc., 1968, vol.90, no. 13, p. 3444.
Kuramshina, A.E., Bochkor, S.A., and Kuznetsov, V.V., Fundament. Issled., 2008, no. 11, p. 77.
Zefirov, N.S., Blagoveshchenskii, V.S., Kazimirchik, I.V., and Yakovleva, O.P., Zh. Org. Khim., 1971, vol.7, no. 3, p. 594.
Haasnoot, C.A.G., de Leeuw, F.A.A.M., and Altona, C., Tetrahedron, 1980, vol.36, no. 19, p. 2783.
Pihlaja, K., Ann. Univ. Turkuensis. Ser. A-1, 1967, no. 114, p. 109.
Bogatskii, A.V., Samitov, Yu.Yu., and Bogatskaya, Z.D., Zh. Org. Khim., 1969, vol.5, no. 12, p. 2230.
Yuldasheva, L.K., Bogatskii, A.V., Bogatskaya, Z.D., and Arshinova, R.P., Khim. Geterotsikl. Soedin., 1971, no. 5, p. 593.
Kuznetsov, V.V. and Alekseeva, E.A., Khim. Geterotsikl. Soedin., 2003, no. 6, p. 839.
Huggins, M.L., J. Am. Chem. Soc., 1953, vol.75, no. 17, p. 4123.
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Original Russian Text © M.G. Faizullin, A.E. Kuramshina, A.Kh. Mamleev, V.V. Kuznetsov, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 12, pp. 2046–2050.
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Faizullin, M.G., Kuramshina, A.E., Mamleev, A.K. et al. Conformational analysis of cis- and trans-isomers of 2,5-dimethyl-1,3-dioxane. Russ J Gen Chem 79, 2673–2677 (2009). https://doi.org/10.1134/S1070363209120202
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DOI: https://doi.org/10.1134/S1070363209120202